Diiodomethane → (7alpha,14beta,15beta,17beta)-3-Methoxy-7-methyl-14,15-methyleneestra-1,3,5(10)-trien-17-ol

HRID 49409Notes

Reaction equation

HRID 49409 reaction equation
[CH3:1][O:2][C:3]1[CH:20]=[CH:19][C:18]2[C@@H:17]3[C@H:8]([C:9]4[C@@:13]([CH2:15][CH2:16]3)([CH3:14])[C@@H:12]([OH:21])[CH2:11][CH:10]=4)[C@H:7]([CH3:22])[CH2:6][C:5]=2[CH:4]=1.I[CH2:24]I.C([Zn]CC)C.[Cl-].[NH4+]>ClCCl.CCCCCC>[CH3:1][O:2][C:3]1[CH:20]=[CH:19][C:18]2[C@@H:17]3[C@H:8]([C@@:9]45[CH2:24][C@@H:10]4[CH2:11][C@H:12]([OH:21])[C@:13]5([CH2:15][CH2:16]3)[CH3:14])[C@H:7]([CH3:22])[CH2:6][C:5]=2[CH:4]=1

Participants

7

Reactant 4

HCID 6346DiiodomethaneHCID 25517Ammonium ChlorideHCID 69624986(7alpha,17beta)-3-Methoxy-7-methylestr-1,3,5(10),14-tetraen-17-olHCID 178418750HCID 178418750, compound

Product 1

HCID 69625229(7alpha,14beta,15beta,17beta)-3-Methoxy-7-methyl-14,15-methyleneestra-1,3,5(10)-trien-17-ol

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8058HexaneSolvent

Procedure

i)—A solution of (7α,17β)-3-methoxy-7-methylestra-1,3,5(10),14-tetraen-17-ol [Segaloff, A. et al, Steroids 22, 99 (1973); 25.4 g] and diiodomethane (27 ml) in dry dichloromethane (500 ml) was cooled to 0° C. A solution of diethylzinc in hexane (15% wt., 300 ml) was added in 1 h and the reaction mixture was stirred for 21 h at room temperature. Ice was added and the mixture was poured into a saturated aqueous solution of ammonium chloride. The product was extracted into diethyl ether; the combined organic phases were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. Column chromatography afforded (7α,14β,15β,17β)-3-methoxy-7-methyl-14,15-methyleneestra-1,3,5(10)-trien-17-ol (6.50 g).

Workup

  1. additionIce was added
  2. extractionThe product was extracted into diethyl ether
  3. washthe combined organic phases were washed with brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-f7cc4a8ed7da41c39310ee738b6eff68
Source dataset
uspto-grants-2004_03
Patent number
US06706700B2

Reaction notes

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