Methanol → 2-(1,2-Epoxy-1,5-dimethyl-4-hexenyl)-3-methoxy-1-phenylthiomethyl-1,4-cyclohexanediol

HRID 1646640Notes

Reaction equation

HRID 1646640 reaction equation
CO.[H-].[Na+].[C:5]1([SH:11])[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.[CH3:12][C:13]([CH3:31])=[CH:14][CH2:15][C@H:16]1[O:18][C@@:17]1([C@@H:20]1[C@:25]2([O:27][CH2:26]2)[CH2:24][CH2:23][C@@H:22]([OH:28])[C@H:21]1[O:29][CH3:30])[CH3:19]>O>[O:18]1[CH:16]([CH2:15][CH:14]=[C:13]([CH3:31])[CH3:12])[C:17]1([CH:20]1[CH:21]([O:29][CH3:30])[CH:22]([OH:28])[CH2:23][CH2:24][C:25]1([CH2:26][S:11][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)[OH:27])[CH3:19]

Participants

6

Reactant 4

HCID 887MethanolHCID 7969ThiophenolHCID 24758Sodium hydrideHCID 222778Fumagillol

Product 1

HCID 198010622-(1,2-Epoxy-1,5-dimethyl-4-hexenyl)-3-methoxy-1-phenylthiomethyl-1,4-cyclohexanediolYield 95%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To methanol (5 ml) was added, under ice-cooling, 60% sodium hydride (213 mg), and the mixture was stirred for 5 minutes at room temperatures, to which was then added thiophenol (0.55 ml), followed by stirring for 15 hours. To the resultant mixture was added fumagillol (500 mg), which was stirred for 30 minutes, followed by adding water to suspend the reaction. The product was extracted with ethyl acetate, and the extract solution was washed with a saturated aqueous solution of sodium hydrogencarbonate and a saturated aqueous saline solution, followed by drying over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by means of a silica gel column chromatography (carrier 25 g, developing solvent: ethyl acetate-hexane=1:2), followed by crystallization from isopropylether to afford 2-(1,2-epoxy-1,5-dimethyl-4-hexenyl)- 3-methoxy-1-phenylthiomethyl-1,4-cyclohexanediol (660 mg: yield 95%) as colorless crystals, m.p. 94° to 96° C.

Workup

  1. temperaturecooling
  2. stirringwas stirred for 30 minutes
  3. customthe reaction
  4. extractionThe product was extracted with ethyl acetate
  5. washthe extract solution was washed with a saturated aqueous solution of sodium hydrogencarbonate
  6. dry with materialby drying over anhydrous magnesium sulfate
  7. distillationThe solvent was distilled off under reduced pressure
  8. customthe residue was purified by means of a silica gel column chromatography (carrier 25 g, developing solvent: ethyl acetate-hexane=1:2)
  9. customfollowed by crystallization from isopropylether

Sources & evidence

ORD record
ord-c139406a316c4257ac6e73d4e94ccda5
Source dataset
uspto-grants-1993_01
Patent number
US05180735

Reaction notes

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