HCID 13564274, compound → HCID 70478112, compound

HRID 637621Notes

Reaction equation

HRID 637621 reaction equation
[F:1]/[CH:2]=[C:3]1/[C@H:4]2[C@H:13]([C@H:14]3[C@@:18]([CH2:20]/1)([CH3:19])[C:17](=[O:21])[CH2:16][CH2:15]3)[CH2:12][CH2:11][C:10]1[C@@H:5]2[CH2:6][CH2:7][CH2:8][CH:9]=1.[C:22]([Mg]Br)#[C:23][CH3:24]>O>[F:1]/[CH:2]=[C:3]1/[C@H:4]2[C@H:13]([C@H:14]3[C@@:18]([CH2:20]/1)([CH3:19])[C@:17]([OH:21])([C:22]#[C:23][CH3:24])[CH2:16][CH2:15]3)[CH2:12][CH2:11][C:10]1[C@@H:5]2[CH2:6][CH2:7][CH2:8][CH:9]=1

Participants

4

Reactant 2

HCID 13564274HCID 13564274, compoundHCID 178419101HCID 178419101, compound

Product 1

HCID 70478112HCID 70478112, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

(E)-11-(Fluoromethylene)estr-4-en-17-one (XII, Example 55, 382 ml) is cooled on an ice bath. Propynyl magnesium bromide (about 0.5M, 4.24 ml is THF) is added and the mixture stirred. After 2 hr TLC shows a small amount of starting material and an additional Grignard reagent is added (0.5 ml). After another 0.5 hr ice and water are added and the product extracted with ether, washed several times with water, dried over sodium sulfate, filtered, and concentrated. The residue is chromatographed over a silica gel column using ethyl acetate/hexane (10/90) as the irrigant. Fractions 39 to 45 are pooled and concentrated to give a solid which is crystallized from methanol/water to give the title compound; NMR (CDCl3) 0.83, 1.86, 5.47, 6.53 δ; MS (m/e) 328, 313, 295 and 246; IR (mull) 3428, 1677 cm-1.

Workup

  1. extractionthe product extracted with ether
  2. washwashed several times with water
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue is chromatographed over a silica gel column
  7. concentrationconcentrated
  8. customto give a solid which
  9. customis crystallized from methanol/water

Sources & evidence

ORD record
ord-0b5143e1db594861a7eb250b19358a92
Source dataset
uspto-grants-1985_12
Patent number
US04557867

Reaction notes

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