Oxygen → 58551-69-2

HRID 437893Notes

Reaction equation

HRID 437893 reaction equation
[CH3:1][CH2:2][CH2:3][CH2:4][CH2:5][C@:6]([OH:26])(/[CH:8]=[CH:9]/[C@@H:10]1[C@@H:14]([CH2:15]/[CH:16]=[CH:17]/[CH2:18][CH2:19][CH2:20][C:21]([OH:23])=[O:22])[C@@H:13]([OH:24])[CH2:12][C@H:11]1[OH:25])[CH3:7].O=O.C1C=C(SSC2N=CC=CC=2)N=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(OCC)(=O)C.CCOC(C)=O.CCCCCC.C1(C)C(C)=CC=CC=1>[CH3:1][CH2:2][CH2:3][CH2:4][CH2:5][C@:6]([OH:26])(/[CH:8]=[CH:9]/[C@@H:10]1[C@@H:14]([CH2:15]/[CH:16]=[CH:17]\[CH2:18][CH2:19][CH2:20][C:21]([OH:23])=[O:22])[C@@H:13]([OH:24])[CH2:12][C@@H:11]1[OH:25])[CH3:7]

Participants

8

Reactant 4

HCID 977OxygenHCID 11776TriphenylphosphineHCID 650932,2'-Dipyridyl disulfideHCID 5284525trans-Carboprost

Product 1

HCID 3502317758551-69-2

Reagents, catalysts & solvents 3

HCID 7237O-XyleneSolventHCID 8857Ethyl AcetateSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

A solution of 15-methyl-PGF2α (185 mg.) in 2.5 ml. of an anhydrous, oxygen-free xylene containing 2,2'-dipyridyl disulfide (165 mg.) and triphenylphosphine (196 mg.) is stirred under nitrogen for 2.5 hr. at 25° C. The mixture is diluted with 150 ml. of xylene and heated at reflux for 3 hr. TLC (80 percent EtOAc/hexane) shows essentially a single, less polar product. The xylene is removed by evaporation at reduced pressure to afford a residue which is diluted with ice/water/sodium bicarbonate and ethyl acetate and extracted thoroughly with ethyl acetate. The ethyl acetate extract is washed with brine, dried over anhydrous sodium sulfate and concentrated to afford a residue of (15S)-15-methyl PGF2α, 1,9-lactone. The residue is purified by chromatography on 50 g. of neutral silica packed with 10 percent acetone/methylene chloride and eluted (5 ml. fractions) with 200 ml. of 10 percent acetone/methylene chloride, 1500 ml. of 20 percent acetone/methylene chloride and 1000 ml. of 35 percent acetone/methylene chloride.

Workup

  1. customat 25° C
  2. additionThe mixture is diluted with 150 ml
  3. temperatureat reflux for 3 hr
  4. customThe xylene is removed by evaporation at reduced pressure
  5. customto afford a residue which
  6. extractionextracted thoroughly with ethyl acetate
  7. extractionThe ethyl acetate extract
  8. washis washed with brine
  9. dry with materialdried over anhydrous sodium sulfate
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-e0b4d23c2be344eb85ff2488554c9617
Source dataset
uspto-grants-1977_06
Patent number
US04032543

Reaction notes

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