Iodine → HCID 56633654, compound

HRID 848444Notes

Reaction equation

HRID 848444 reaction equation
[Cl:1][C:2]1[C:21]2[C@:16]([CH3:24])([C@H:17]3[CH2:23][C@H:18]3[C:19](=[O:22])[CH:20]=2)[C@@H:15]2[C@H:4]([C@H:5]3[C@:12]([CH3:25])([CH2:13][CH2:14]2)[C@@:8]([OH:26])([C:9](=[O:11])[CH3:10])[CH2:7][CH2:6]3)[CH:3]=1.[O-2:27].[Ca+2].II.ClC1C2[C@](C)([C@H]3C[C@H]3[C:50](=[O:53])[CH:51]=2)[C@@H]2[C@H]([C@H]3[C@](C)(CC2)[C@@](O)(C(=O)CI)CC3)C=1>C(N(CC)CC)C.C(O)(=O)C.CC(C)=O.CO.O1CCCC1>[C:50]([O:53][CH2:10][C:9](=[O:11])[C@:8]1([OH:26])[C@:12]2([CH3:25])[C@H:5]([C@H:4]3[C@H:15]([CH2:14][CH2:13]2)[C@:16]2([CH3:24])[C:21](=[CH:20][C:19](=[O:22])[C@@H:18]4[CH2:23][C@@H:17]42)[C:2]([Cl:1])=[CH:3]3)[CH2:6][CH2:7]1)(=[O:27])[CH3:51]

Participants

10

Reactant 4

HCID 807Iodine2×HCID 5284537CyproteroneHCID 6850728CalciumoxideHCID 56632733HCID 56632733, compound

Product 1

HCID 56633654HCID 56633654, compound

Reagents, catalysts & solvents 5

HCID 176Acetic AcidSolventHCID 180AcetoneSolventHCID 887MethanolSolvent2×HCID 8028TetrahydrofuranSolvent2×HCID 8471TriethylamineSolvent

Procedure

A solution of 10 g. of 6-chloro-17-hydroxy-1α,2α-methylene-4,6-pregnadiene-3,20-dione in 75 ml. of methanol and 75 ml. of tetrahydrofuran is combined with 15 g. of calcium oxide and 500 mg. of azoisobutyronitrile. Several milliliters of a solution of 10 g. of iodine in 50 ml. of tetrahydrofuran and 30 ml. of methanol are added dropwise to the reaction mixture. After an induction time of 60 minutes, the solution loses its color; the residual iodine solution is added dropwise within 8 hours. The reaction mixture is diluted with 500 ml. of dichloromethane, the calcium oxide is filtered off, and the filtrate is washed with sodium thiosulfate solution and water, dried over sodium sulfate, and concentrated under vacuum at 35° C., thus obtaining 13 g. of 6-chloro-17-hydroxy-21-iodo-1α,2α-methylene-4,6-pregnadiene-3,20-dione. This product is dissolved in 130 ml. of acetone and 45 ml. of acetic acid, combined with 69 ml. of triethylamine, and refluxed for 90 minutes. The solution is stirred into ice water. The thus-obtained precipitate is isolated and chromatographed on silica gel. With 16-20% acetone-pentane, 6.1 g. of 21-acetoxy-6-chloro-17-hydroxy-1α,2α-methylene-4,6-pregnadiene-3,20-dione is obtained, m.p. 224° C.

Workup

  1. customAfter an induction time of 60 minutes
  2. additionThe reaction mixture is diluted with 500 ml
  3. filtrationof dichloromethane, the calcium oxide is filtered off
  4. washthe filtrate is washed with sodium thiosulfate solution and water
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated under vacuum at 35° C.
  7. customthus obtaining 13 g
  8. dissolutionThis product is dissolved in 130 ml
  9. customThe thus-obtained precipitate is isolated
  10. customchromatographed on silica gel

Sources & evidence

ORD record
ord-85611ac782b447efa27f406ef50639c5
Source dataset
uspto-grants-1981_10
Patent number
US04296109

Reaction notes

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