Hydrochloric Acid → 4a-Methyl-6-(phenylsulfonyl)-1,2,3,4,4a,9a-hexahydro[1]benzofuro[2,3-c]pyridine hydrochloride

HRID 1616874Notes

Reaction equation

HRID 1616874 reaction equation
C(O[C:6]([N:8]1C[CH2:12][C:11]2(C)[C:14]3[CH:20]=[C:19]([S:21][C:22]4[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=4)[CH:18]=[CH:17][C:15]=3O[CH:10]2[CH2:9]1)=O)(C)(C)C.[CH3:29][OH:30].[OH2:31].[OH:32]OS([O-])=O.[K+].O1CCOCC1.[ClH:44]>C(OCC)(=O)C>[ClH:44].[CH3:12][C:11]12[C:14]3[CH:20]=[C:19]([S:21]([C:22]4[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=4)(=[O:32])=[O:31])[CH:18]=[CH:17][C:15]=3[O:30][CH:29]1[CH2:6][NH:8][CH2:9][CH2:10]2

Participants

8

Reactant 6

HCID 313Hydrochloric AcidHCID 887MethanolHCID 962WaterHCID 312751,4-DioxaneHCID 23707502Potassium hydroxy sulfiteHCID 673240934a-Methyl-6-(phenylsulfanyl)-1,2,3,4,4a,9-hexahydro[1]benzofuro[2,3-c]pyridine-2-carboxylic acid tert-butyl ester

Product 1

HCID 673251544a-Methyl-6-(phenylsulfonyl)-1,2,3,4,4a,9a-hexahydro[1]benzofuro[2,3-c]pyridine hydrochloride

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 4a-methyl-6-(phenylsulfanyl)-1,2,3,4,4a,9a-hexahydro[1]benzofuro[2,3-c]pyridine-2-carboxylic acid tert-butyl ester (0.327 g, 0.82 mmol) in methanol (10 mL, 0.2 mol) was added water (0.5 mL, 0.03 mol) and Oxone® (2.0 g, 0.0032 mol). The reaction was stirred overnight at room temperature. The reaction mixture was filtered and the filtrate concentrated. The residue was dissolved in DCM and washed with brine, dried, filtered and concentrated. The crude product was purified on a 12 g silica gel column eluting with hexanes to 2:1 hexanes:ethyl acetate and then stirred in 4 M HCl in dioxane (5 mL, 0.04 mol) for 30 min. The product was precipitated by addition of DCM and ether. The solid was filtered, washed with ether and dried under house vacuum to afford the title compound. mp 236-238° C. dec.; MS m/z 330 [M+H]+. 1H-NMR (400 MHz, DMSO): δ 1.45 (s, 3H), 1.75 (m, 1H), 1.90 (m, 1H), 2.82 (m, 1H), 3.03 (m, 1H), 3.35-3.56 (m, 2H), 4.63 (s, 1H), 7.08 (d, J=8.9 Hz, 1H), 7.58-7.70 (m, 3H), 7.81 (d, J=8.85 Hz, 1H), 7.91-7.96 (m, 3H), 8.91 (bs, 1H), 9.91 (bs, 1H).

Workup

  1. filtrationThe reaction mixture was filtered
  2. concentrationthe filtrate concentrated
  3. dissolutionThe residue was dissolved in DCM
  4. washwashed with brine
  5. customdried
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe crude product was purified on a 12 g silica gel column
  9. washeluting with hexanes to 2:1 hexanes
  10. customThe product was precipitated by addition of DCM and ether
  11. filtrationThe solid was filtered
  12. washwashed with ether
  13. customdried under house vacuum

Sources & evidence

ORD record
ord-808b9f79a43048718126be74b1ef64b9
Source dataset
uspto-grants-2014_07
Patent number
US08765779B2

Reaction notes

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