Phosphate → 16-(Phenylsulfinylmethyl)pregn-1,4,9(11),16-tetraene-3,20-dione

HRID 1285315Notes

Reaction equation

HRID 1285315 reaction equation
[C:1]1([S:7](Cl)=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:10]([C@:13]1(O)[C:18](=[CH2:19])[CH2:17][C@H:16]2[C@H:20]3[C:30](=[CH:31][CH2:32][C@:14]12[CH3:15])[C@:28]1([CH3:29])[C:23](=[CH:24][C:25](=[O:33])[CH:26]=[CH:27]1)[CH2:22][CH2:21]3)(=[O:12])[CH3:11].P([O-])([O-])([O-])=O>C(Cl)Cl.C(N(CC)CC)C>[C:1]1([S:7]([CH2:19][C:18]2[CH2:17][C@@H:16]3[C@:14]([CH3:15])([CH2:32][CH:31]=[C:30]4[C@H:20]3[CH2:21][CH2:22][C:23]3[C@:28]4([CH3:29])[CH:27]=[CH:26][C:25](=[O:33])[CH:24]=3)[C:13]=2[C:10](=[O:12])[CH3:11])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

6

Reactant 3

HCID 1061PhosphateHCID 4190003Benzenesulfinyl chlorideHCID 1357883717beta-Hydroxy-16-methylenepregna-1,4,9(11)-triene-3,20-dione

Product 1

HCID 5718204716-(Phenylsulfinylmethyl)pregn-1,4,9(11),16-tetraene-3,20-dione

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 8471TriethylamineSolvent

Procedure

Phenylsulfinyl chloride in methylene chloride (2.5N, 2.4 ml) was added to a mixture of 17α-acetyl-17β-hydroxy-16-methyleneandrost-1,4,9(11)-trien-3-one (VB, Example 17, 1 g) in methylene chloride (10 ml) and triethylamine (0.82 ml) previously cooled to -30° over a period of 2 hrs. The reaction is plunged into phosphate buffer (pH 7, 10 ml); the phases are separated; the aqueous phase is extracted with methylene chloride; the organic phases are combined and dried over sodium sulfate and concentrated under reduced presure to an isomeric mixture of the title compound. The isomers are separated by chromatography on silica gel (50 g), eluting with acetone/hexane: 5/95 to give the title compound, NMR (CDCl3) 0.89, 1.42, 2.10, 4.03, 5.5, 6.0, 6.27, 7.20 δ.

Workup

  1. temperaturepreviously cooled to -30° over a period of 2 hrs
  2. customthe phases are separated
  3. extractionthe aqueous phase is extracted with methylene chloride
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated under reduced presure to an isomeric mixture of the title compound
  6. customThe isomers are separated by chromatography on silica gel (50 g)
  7. washeluting with acetone/hexane

Sources & evidence

ORD record
ord-f7977debaa2e407ebe39837cb647285f
Source dataset
uspto-grants-1986_01
Patent number
US04567001

Reaction notes

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