HCID 91285444, compound → HCID 70018658, compound

HRID 47662Notes

Reaction equation

HRID 47662 reaction equation
CS[CH:3]([C:9]1[CH:10]=[C:11]2[C:16](=[CH:17][CH:18]=1)[O:15][C@@H:14]([CH2:19][C:20](=[O:25])[C:21]([F:24])([F:23])[F:22])[CH2:13][CH2:12]2)[C:4]([O:6][CH2:7][CH3:8])=[O:5]>C(O)C.[Ni]>[F:24][C:21]([F:22])([F:23])[C:20](=[O:25])[CH2:19][C@H:14]1[CH2:13][CH2:12][C:11]2[C:16](=[CH:17][CH:18]=[C:9]([CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5])[CH:10]=2)[O:15]1

Participants

4

Reactant 1

HCID 91285444HCID 91285444, compound

Product 1

HCID 70018658HCID 70018658, compoundYield 83%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 702EthanolSolvent

Procedure

The above crude thiomethyl compound of Example 4 was dissolved in absolute ethanol (340 mL) under argon and mixed with Raney nickel (17 teaspoons) freshly washed with water and ethanol (3 times). The resulting mixture was stirred vigorously at room temperature for 1 hours. Stirring was stopped, and the liquid layer was removed by decanting. The catalyst was then washed with ethanol (250 mL) and dichloromethane (250 mL). The liquid was removed by decanting in each case. The combined liquid layer was concentrated in vacuo. The residue was dissolved in methyl t-butyl ether (300 mL), washed with water (200 mL), and brine (200 mL) and dried over anhydrous sodium sulfate. Removal of solvent in vacuo afforded the crude product as a colorless oil (14.3 g, 83%): 1H NMR (CDCl3) δ1.26 (t, J=7.2 Hz, 3H), 1.80 (m, 1H), 2.00 (m, 1H), 2.70-2.95 (m, 2H), 3.50 (m, 3H), 3.80-3.85 (m, 1H), 4.15 (m, 4H), 6.76 (d, J=8.4 Hz, 1H), 6.98 (s,1H), 7.02 (d, J=8.7 Hz, 1H); CI-MS m/z 346 (M+H+). The crude was used for next step without further purification.

Workup

  1. washfreshly washed with water and ethanol (3 times)
  2. stirringStirring
  3. customthe liquid layer was removed
  4. customby decanting
  5. washThe catalyst was then washed with ethanol (250 mL) and dichloromethane (250 mL)
  6. customThe liquid was removed
  7. customby decanting in each case
  8. concentrationThe combined liquid layer was concentrated in vacuo
  9. dissolutionThe residue was dissolved in methyl t-butyl ether (300 mL)
  10. washwashed with water (200 mL), and brine (200 mL)
  11. dry with materialdried over anhydrous sodium sulfate
  12. customRemoval of solvent in vacuo

Sources & evidence

ORD record
ord-185874cb2766442ab06ceebfdc0f5104
Source dataset
uspto-grants-2004_03
Patent number
US06699860B2

Reaction notes

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