Sulfuric Acid → HCID 9943709, compound

HRID 2414464Notes

Reaction equation

HRID 2414464 reaction equation
S(=O)(=O)(O)O.O[C@@:7]12[C@@H:24]3[C@H:15]([C@H:16]4[C@@:20]([CH2:22][CH2:23]3)([CH3:21])[C:19](=[O:25])[CH2:18][CH2:17]4)[C@H:14]([CH3:26])[CH2:13][C:12]1=[CH:11][C:10](=[O:27])[CH2:9][CH2:8]2.C(OCC)(=O)C.CCCCCC>C(Cl)Cl>[CH3:26][C@@H:14]1[CH2:13][C:12]2[C:7]([CH2:8][CH2:9][C:10](=[O:27])[CH:11]=2)=[C:24]2[C@@H:15]1[C@H:16]1[C@@:20]([CH2:22][CH2:23]2)([CH3:21])[C:19](=[O:25])[CH2:18][CH2:17]1

Participants

5

Reactant 3

HCID 1118Sulfuric AcidHCID 21226206Ethyl acetate hexaneHCID 69609360HCID 69609360, compound

Product 1

HCID 9943709HCID 9943709, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To 15 ml of concentrated sulfuric acid (98%) cooled to ˜5° C. was added dropwise ˜20 Mm of a mixture containing 10-hydroxy-7α-methyl-estra-4-ene-3,17-dione (III) and 5,10-dihydroxy-7α-methyl-estra-3,17-dione (IV) from example 2 dissolved in 15 ml of methylene chloride. About 20 minutes after the addition was complete, TLC ({fraction (1/1)} ethyl acetate/hexane, Rf 0.4) showed that the reaction was complete. The deep red reaction mixture was poured over ice, washed in with methylene chloride, partially neutralized with potassium carbonate, and the phases separated. The organic phase was washed with dilute aqueous potassium carbonate, brine, and dried over sodium sulfate, and concentrated under vacuum to a solid product. This material was column chromatographed on 150 g of silica gel with gradient elution from ⅓ to {fraction (1/1)} ethyl acetate/hexane. Fractions 6-9 were combined to give a solid which was recrystallized from ethyl acetate to provide the title product. Mp 208-209° C.

Workup

  1. additionwas added dropwise ˜20 Mm of a mixture
  2. additionAbout 20 minutes after the addition
  3. customThe deep red reaction mixture
  4. additionwas poured over ice
  5. washwashed in with methylene chloride
  6. customthe phases separated
  7. washThe organic phase was washed with dilute aqueous potassium carbonate, brine
  8. dry with materialdried over sodium sulfate
  9. concentrationconcentrated under vacuum to a solid product
  10. customchromatographed on 150 g of silica gel with gradient elution from ⅓
  11. customto give a solid which
  12. customwas recrystallized from ethyl acetate

Sources & evidence

ORD record
ord-641fa7084ebe48b2bcdb6335dab7071b
Source dataset
uspto-grants-2004_11
Patent number
US06812358B2

Reaction notes

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