Acetic Acid → HCID 86605393, compound

HRID 1180426Notes

Reaction equation

HRID 1180426 reaction equation
[I-].[CH3:2][O:3][C:4]([C@@H:6]([O:11][C@H:12]([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[C:13]1[CH:18]=[CH:17][C:16]([C:19]2[CH:20]=[N+:21]([CH3:25])[CH:22]=[CH:23][CH:24]=2)=[CH:15][CH:14]=1)[CH2:7][CH:8]([CH3:10])[CH3:9])=[O:5].S(S([O-])=O)([O-])(=O)=O.[Na+].[Na+].CO.C(O)(=O)C>ClCCl.[Pt]=O>[CH3:9][CH:8]([CH3:10])[CH2:7][C@H:6]([O:11][C@@H:12]([C:13]1[CH:18]=[CH:17][C:16]([CH:19]2[CH2:24][CH2:23][CH2:22][N:21]([CH3:25])[CH2:20]2)=[CH:15][CH:14]=1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[C:4]([O:3][CH3:2])=[O:5]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 887MethanolHCID 656671Sodium PyrosulfiteHCID 69473245HCID 69473245, compound

Product 1

HCID 86605393HCID 86605393, compound

Reagents, catalysts & solvents 2

HCID 82844Platinum oxide (PtO)CatalystHCID 6344DichloromethaneSolvent

Procedure

To avoid catalytic poisoning during the hydrogenation, the quaternary pyridinium salt was first washed to remove free iodide. 3-{4-[(R)-{[(1S)-1-(methoxycarbonyl)-3-methylbutyl]oxy}(phenyl)methyl]phenyl}-1-methylpyridinium iodide from step 3 in example 36 (3.58 g, 6.6 mmol) was dissolved in dichloromethane (100 mL) and shaken with 5% sodium metabisulfite (30 mL) until the heavy red color dissipated. The organic layer was separated, dried (Na2SO4), filtered and concentrated to recover 3.2 g. of starting material. A mixture of the quaternary salt (3.2 g, 6.0 mmol), methanol (150 mL), acetic acid (800 mg, 12 mmol) and platinum oxide (hydrated) 79-84% (250 mg) was hydrogenated at 60 psi for 48 hours. The mixture was filtered, concentrated and then concentrated 2 times with n-heptane. The residue was chromatographed on silica gel using 5% methanol in dichloromethane to obtain the title compound as a foam.

Workup

  1. washthe quaternary pyridinium salt was first washed
  2. customto remove free iodide
  3. customThe organic layer was separated
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto recover 3.2 g
  8. filtrationThe mixture was filtered
  9. concentrationconcentrated
  10. concentrationconcentrated 2 times with n-heptane
  11. customThe residue was chromatographed on silica gel using 5% methanol in dichloromethane

Sources & evidence

ORD record
ord-634e083376b243cd8bfebed2df8994aa
Source dataset
uspto-grants-2007_10
Patent number
US07279478B2

Reaction notes

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