Ethyl Acetate → HCID 21099413, compound

HRID 2376950Notes

Reaction equation

HRID 2376950 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([C:11]2[CH:12]=[CH:13][C:14](/[CH:17]=[CH:18]/[C:19]3[CH:24]=[CH:23][C:22]([F:25])=[CH:21][CH:20]=3)=[N:15][CH:16]=2)(=[O:10])=[O:9])=[CH:4][CH:3]=1.C(OCC)(=O)C.[H][H]>C(O)C.[Pd]>[F:25][C:22]1[CH:21]=[CH:20][C:19]([CH2:18][CH2:17][C:14]2[CH:13]=[CH:12][C:11]([S:8]([C:5]3[CH:4]=[CH:3][C:2]([F:1])=[CH:7][CH:6]=3)(=[O:10])=[O:9])=[CH:16][N:15]=2)=[CH:24][CH:23]=1

Participants

6

Reactant 3

HCID 8857Ethyl AcetateHCID 21099515HCID 21099515, compoundHCID 178418361HCID 178418361, compound2×

Product 1

HCID 21099413HCID 21099413, compoundYield 61.3%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

5-[(4-fluorophenyl)sulfonyl]-2-[(E)-2-(4-fluorophenyl)vinyl]-pyridine (Example 2, 0.42 g, 1.18 mmol) was taken up in ethanol (5 mL) and ethyl acetate (5 mL) and palladium (10% wt. on activated carbon, 60 mg) was added. The suspension was shaken in a Parr apparatus at 20 psi hydrogen for 6 hours, followed by 40 psi hydrogen for 3 days. The catalyst was removed by filtration and the solvent removed in vacuo. The residue was taken up in acetic acid (25 mL) and platinum(IV) oxide (20 mg) was added. The suspension was stirred under a balloon of hydrogen for 20 hours. Further platinum(IV) oxide (20 mg) was added and stirring under hydrogen continued for 24 hours. The catalyst was removed by filtration and most of the solvent removed in vacuo. The residue was partitioned between ethyl acetate and 4N sodium hydroxide solution. The organic phase was dried over MgSO4 and concentrated in vacuo while loading onto silica. Eluting through a plug of silica using 20% ethyl acetate/isohexane gave the title compound as a yellow solid (0.26 g, 61%). δH (500 MHz, d6 DMSO): 9.04 (1H, d, J=2.2 Hz), 8.23 (1H, dd, J=2.4, 8.3 Hz), 8.09-8.07 (2H, m), 7.49-7.45 (3H, m), 7.22-7.19 (2H, m), 7.04 (2H, t, J=8.8 Hz), 3.11-3.09 (2H, m), 2.98-2.95 (2H, m); m/z (ES+) 360 [MH+].

Workup

  1. customThe catalyst was removed by filtration
  2. customthe solvent removed in vacuo
  3. additionplatinum(IV) oxide (20 mg) was added
  4. additionFurther platinum(IV) oxide (20 mg) was added
  5. stirringstirring under hydrogen
  6. waitcontinued for 24 hours
  7. customThe catalyst was removed by filtration and most of the solvent
  8. customremoved in vacuo
  9. customThe residue was partitioned between ethyl acetate and 4N sodium hydroxide solution
  10. dry with materialThe organic phase was dried over MgSO4
  11. concentrationconcentrated in vacuo
  12. washEluting through a plug of silica using 20% ethyl acetate/isohexane

Sources & evidence

ORD record
ord-f9a723e6b2f94a7f98e9e3377225b871
Source dataset
uspto-grants-2008_12
Patent number
US07468393B2

Reaction notes

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