Sodium Hydroxide → HCID 67745318, compound

HRID 375473Notes

Reaction equation

HRID 375473 reaction equation
O[C:2]1([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH:10]2[CH:6]([CH2:7][N:8]([CH2:11][C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)[CH2:9]2)[S:5][CH2:4][CH2:3]1.[OH-].[Na+]>C1C=CC=CC=1.ClCCl.[Cl-].[Cl-].[Cl-].[Cl-].[Zr+4]>[CH2:11]([N:8]1[CH2:9][CH:10]2[C:2]([C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[CH2:3][CH2:4][S:5][CH:6]2[CH2:7]1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

6

Reactant 2

HCID 14798Sodium HydroxideHCID 67745319HCID 67745319, compound

Product 1

HCID 67745318HCID 67745318, compoundYield 85.8%

Reagents, catalysts & solvents 3

HCID 9856075Zirconium chloride (ZrCl4), (T-4)-CatalystHCID 241BenzeneSolventHCID 6344DichloromethaneSolvent

Procedure

43.7 g of zirconium tetrachloride are added to a solution of 12.2 g of (4RS,4aSR,7aRS)-4-hydroxy4-phenyl-6-benzylperhydrothiopyrano[2,3-c]pyrrole in 180 cm3 of benzene. The reaction mixture is refluxed for 1 hour and then brought to 20° C. and diluted with 200 cm3 of dichloromethane. 150 cm3 of a 4N aqueous solution of sodium hydroxide are added to the resulting cooled solution. The suspension obtained is filtered, the filtrate is decanted, the organic phase is washed with 200 cm3 of a saturated aqueous solution of sodium chloride, dried over magnesium sulphate and concentrated to dryness under reduced pressure (2.7 kPa). The oil obtained is chromatographed on a silica gel column (0.04 mm-0.06 mm, diameter 5.2 cm, height 39 cm), eluting under a nitrogen pressure of 0.6 bar, with a cyclohexane and ethyl acetate mixture (90/10 by volume) and collecting fractions of 125 cm 3. Fractions 19 to 32 are pooled and concentrated to dryness under reduced pressure (2.7 kPa). The oil obtained is crystallized from 200 cm3 of diisopropyl oxide, the crystals are drained and dried. 6.2 g of (4aRS,7aRS)-6-benzyl-4,4-diphenylperhydrothiopyrano[2,3-c]pyrrole are obtained in the form of orange-colored crystals; melting point 130° C.

Workup

  1. temperatureThe reaction mixture is refluxed for 1 hour
  2. custombrought to 20° C.
  3. temperaturecooled solution
  4. customThe suspension obtained
  5. filtrationis filtered
  6. customthe filtrate is decanted
  7. washthe organic phase is washed with 200 cm3 of a saturated aqueous solution of sodium chloride
  8. dry with materialdried over magnesium sulphate
  9. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)
  10. customThe oil obtained
  11. customis chromatographed on a silica gel column (0.04 mm-0.06 mm, diameter 5.2 cm, height 39 cm)
  12. washeluting under a nitrogen pressure of 0.6 bar
  13. customwith a cyclohexane and ethyl acetate mixture (90/10 by volume) and collecting fractions of 125 cm 3
  14. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)
  15. customThe oil obtained
  16. customis crystallized from 200 cm3 of diisopropyl oxide
  17. customdried

Sources & evidence

ORD record
ord-ff95f58f1cdb4626b6f8c14edf928ddb
Source dataset
uspto-grants-1996_01
Patent number
US05484942

Reaction notes

Loading…