1,2-Dichloroethane → HCID 70626296, compound

HRID 616351Notes

Reaction equation

HRID 616351 reaction equation
[Cl:1]C1C=CC=C(C(OO)=O)C=1.C(O)(C)(C)C.[C:17]([O:20][C@:21]1([C@:41]2([CH3:42])[C@H:27]([C@H:28]3[C@H:38]([C@@H:39]([F:43])[CH2:40]2)[C@:36]2(C)[C:31](=[CH:32][C:33](=[O:45])[C@@H:34]4C[C@@H:35]42)[CH:30]=[CH:29]3)[CH2:26][CH2:25]1)[C:22](=[O:24])[CH3:23])(=[O:19])[CH3:18].[CH2:46]([Cl:49])[CH2:47]Cl>C(OCC)(=O)C>[C:17]([O:20][C@:21]1([C@:41]2([CH3:42])[C@H:27]([C@H:28]3[C@H:38]([C@@H:39]([F:43])[CH2:40]2)[C@:36]2([CH3:35])[C:31](=[CH:32][C:33](=[O:45])[CH2:34][C@@H:47]2[CH2:46][Cl:49])[C:30]([Cl:1])=[CH:29]3)[CH2:26][CH2:25]1)[C:22](=[O:24])[CH3:23])(=[O:19])[CH3:18]

Participants

6

Reactant 4

HCID 111,2-DichloroethaneHCID 6386tert-ButanolHCID 70297m-Chloroperbenzoic acidHCID 70626310HCID 70626310, compound

Product 1

HCID 70626296HCID 70626296, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

A solution of 4.0 g. of m-chloroperbenzoic acid in 10 ml. of tert.-butanol is combined with 700 mg. of 17-acetoxy-11β-fluoro-1α,2α -methylene-4,6-pregnadiene-3,20-dione in 60 ml. of ethylene chloride. The solution is allowed to stand for 48 hours at room temperature, then diluted with ethyl acetate, and washed in succession with sodium bisulfite solution and water. Yield: 510 mg. of 17-acetoxy-6α,7α -epoxy-11β-fluoro-1α,2α -methylene-4-pregnene-3,20dione, which is introduced into 10 ml. of glacial acetic acid saturated with gaseous hydrogen chloride. After 22 hours, the solution is poured into ice/water. The thus-precipitated product is vacuum-filtered, washed with water, taken up in methylene chloride, and dried over sodium sulfate. The thus-produced crude 17-acetoxy-6-chloro-1α-chloromethyl-11β-fluoro-4,6-pregnadiene-3,20-dione (380 mg.) is agitated in 5 ml. of collidine for 6 hours at 140° C. After cooling, the solution is diluted with ether and washed repeatedly in succession with 2N hydrochloric acid and water. The ether phase is dried over sodium sulfate. The crude product is purified by preparative layer chromatography (system: ether/chloroform 8+2), thus obtaining 175 mg. of 17-acetoxy-6-chloro-11β-fluoro-1α,2α -methylene-4,6-pregnadiene-3,20-dione; m.p. 250°-252° C. UV: ε282 = 16,650.

Workup

  1. washwashed in succession with sodium bisulfite solution and water
  2. additionof 17-acetoxy-6α,7α -epoxy-11β-fluoro-1α,2α -methylene-4-pregnene-3,20dione, which is introduced into 10 ml
  3. waitAfter 22 hours
  4. additionthe solution is poured into ice/water
  5. filtrationThe thus-precipitated product is vacuum-filtered
  6. washwashed with water
  7. dry with materialdried over sodium sulfate

Sources & evidence

ORD record
ord-901f20c4aa74430ca65770b103f7b068
Source dataset
uspto-grants-1978_02
Patent number
US04073900

Reaction notes

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