HCID 67692824, compound → HCID 68842047, compound

HRID 1033082Notes

Reaction equation

HRID 1033082 reaction equation
[C:1]([NH:4][CH:5]1[CH2:10][CH:9]([CH2:11][CH2:12][O:13][CH3:14])[S:8](=[O:16])(=[O:15])[C:7]2[S:17][C:18]([S:20]([NH2:23])(=[O:22])=[O:21])=[CH:19][C:6]1=2)(=O)[CH3:2]>O1CCCC1.CCOCC>[CH2:1]([NH:4][CH:5]1[CH2:10][CH:9]([CH2:11][CH2:12][O:13][CH3:14])[S:8](=[O:16])(=[O:15])[C:7]2[S:17][C:18]([S:20]([NH2:23])(=[O:22])=[O:21])=[CH:19][C:6]1=2)[CH3:2]

Participants

4

Reactant 1

HCID 67692824HCID 67692824, compound

Product 1

HCID 68842047HCID 68842047, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of 4-acetamido-5,6-dihydro-6-(2-methoxyethyl)-4H-thieno[2,3-b]thiopyran-2-sulfonamide-7,7-dioxide (4.4 g, 0.0115 mol) in tetrahydrofuran (45 ml) under nitrogen and heated to reflux was added borane dimethylsulfide complex (5 ml, 0.05 mol of a 10 M complex) over about 20 minutes. Stirring was continued at reflux for 3 hours, then at room temperature overnight and another 5 hours and then concentrated in vacuo at room temperature. Methanol (50 ml) was carefully added to the white residue. The resulting solution was saturated with anhydrous HCl gas and then was stirred at reflux for 1 hour. The solution was concentrated in vacuo and the residue was taken up in ethyl acetate (50 ml) and saturated sodium bicarbonate (20 ml). The ethyl acetate solution was separated and washed with saturated NaCl, dried, filtered and concentrated in vacuo. The procedure gave a mixture of cis and trans isomers (3.2 g) as a white gummy foam which was chromatographed on silica gel (300 g) using 7.5% methanol-chloroform. Mixed fractions (0.87 g) were chromatographed again using 5% methanol-ether. There was obtained 1.62 g of the a-isomer, mp 132°-134° C. and 0.35 g of the β-isomer, mp 167°-169° C. The hydrochloride salts of the α (trans) and β-isomer (cis) racemates were prepared using ethanolic-HCl and diluting with ether. MP's were 173°-175° C. and 264.5°-266° C., respectively.

Workup

  1. temperatureto reflux
  2. temperatureat reflux for 3 hours
  3. concentrationat room temperature overnight and another 5 hours and then concentrated in vacuo at room temperature
  4. additionMethanol (50 ml) was carefully added to the white residue
  5. stirringwas stirred
  6. temperatureat reflux for 1 hour
  7. concentrationThe solution was concentrated in vacuo
  8. customThe ethyl acetate solution was separated
  9. washwashed with saturated NaCl
  10. customdried
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo
  13. customThe procedure gave
  14. additiona mixture of cis and trans isomers (3.2 g) as a white gummy foam which
  15. customwas chromatographed on silica gel (300 g)
  16. customMixed fractions (0.87 g) were chromatographed again
  17. customThere was obtained 1.62 g of the a-isomer, mp 132°-134° C. and 0.35 g of the β-isomer, mp 167°-169° C
  18. customwere prepared
  19. customwere 173°-175° C. and 264.5°-266° C.

Sources & evidence

ORD record
ord-0742eeac835a4c8a86398b3662ed89f3
Source dataset
uspto-grants-1994_05
Patent number
US05308863

Reaction notes

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