Methanol → HCID 70561763, compound

HRID 1076280Notes

Reaction equation

HRID 1076280 reaction equation
[F:1][C@:2]12[C@@H:22]([OH:23])[CH2:21][C@@:20]3([CH3:24])[C@@H:12]([CH2:13][C@@H:14]([CH3:25])[C@@H:15]3[C:16](=[O:19])[CH2:17][OH:18])[C@@H:11]1[CH2:10][CH2:9][C:8]1[C@:3]2([CH3:27])[CH:4]=[CH:5][C:6](=[O:26])[CH:7]=1.C[OH:29]>C([O-])(=O)C.[Cu+2].C([O-])(=O)C.C(Cl)Cl>[F:1][C@:2]12[C@@H:22]([OH:23])[CH2:21][C@@:20]3([CH3:24])[C@@H:12]([CH2:13][C@@H:14]([CH3:25])[C@@H:15]3[C:16](=[O:19])[C:17]([OH:29])=[O:18])[C@@H:11]1[CH2:10][CH2:9][C:8]1[C@:3]2([CH3:27])[CH:4]=[CH:5][C:6](=[O:26])[CH:7]=1

Participants

5

Reactant 2

HCID 887Methanol2×HCID 5311067Desoximetasone

Product 1

HCID 70561763HCID 70561763, compound

Reagents, catalysts & solvents 2

HCID 8895Cupric acetateCatalystHCID 6344DichloromethaneSolvent

Procedure

One gram of 9α-fluoro-11β,21-dihydroxy-16α-methyl-1.4-pregnadiene-3,20-dione is dissolved in 125 ml. of methanol and combined with a solution of 250 mg. of copper(II) acetate in 125 ml. of methanol. The mixture is stirred for 15 minutes at room temperature while passing air therethrough, and then is combined with methylene chloride, washed with 5% ammonium chloride solution and water, and concentrated under vacuum. The thus-obtained product is dissolved in 50 ml. of methanol. The solution is mixed with 165 mg. of potassium cyanide, 1.0 ml. of acetic acid, and 5 g. of manganese(IV) oxide and agitated for 30 minutes at room temperature. Then the mixture is filtered, the filtrate diluted with methylene chloride, washed with water, dried, and concentrated under vacuum. The residue is chromatographed over a silica gel column, recrystallized from acetone/hexane, and the methyl ester of 9α-fluoro-11β-hydroxy-3,20-dioxo-16α-methyl-1,4-pregnadiene-21-oic acid is thus produced, m.p. 215° C.

Workup

  1. washwashed with 5% ammonium chloride solution and water
  2. concentrationconcentrated under vacuum
  3. dissolutionThe thus-obtained product is dissolved in 50 ml
  4. additionThe solution is mixed with 165 mg
  5. stirringof manganese(IV) oxide and agitated for 30 minutes at room temperature
  6. filtrationThen the mixture is filtered
  7. additionthe filtrate diluted with methylene chloride
  8. washwashed with water
  9. customdried
  10. concentrationconcentrated under vacuum
  11. customThe residue is chromatographed over a silica gel column
  12. customrecrystallized from acetone/hexane

Sources & evidence

ORD record
ord-8d41a99ce9f448298db02ad27e127564
Source dataset
uspto-grants-1976_05
Patent number
US03956347

Reaction notes

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