Ammonium formate → HCID 11157748, compound

HRID 2374645Notes

Reaction equation

HRID 2374645 reaction equation
C([O:8][C:9]1[CH:10]=[C:11]2[C:16](=[CH:17][CH:18]=1)[C:15]([O:19][C:20]1[CH:25]=[CH:24][C:23]([O:26][CH2:27][CH2:28][CH2:29][CH2:30][S:31][CH2:32][CH2:33][CH2:34][C:35]([F:41])([F:40])[C:36]([F:39])([F:38])[F:37])=[CH:22][CH:21]=1)=[C:14]([C:42]1[CH:47]=[CH:46][C:45]([O:48][CH3:49])=[CH:44][CH:43]=1)[CH:13]=[CH:12]2)C1C=CC=CC=1.C([O-])=O.[NH4+]>[Pd].CCO>[CH3:49][O:48][C:45]1[CH:44]=[CH:43][C:42]([C:14]2[C:15]([O:19][C:20]3[CH:25]=[CH:24][C:23]([O:26][CH2:27][CH2:28][CH2:29][CH2:30][S:31][CH2:32][CH2:33][CH2:34][C:35]([F:40])([F:41])[C:36]([F:39])([F:38])[F:37])=[CH:22][CH:21]=3)=[C:16]3[C:11](=[CH:12][CH:13]=2)[CH:10]=[C:9]([OH:8])[CH:18]=[CH:17]3)=[CH:47][CH:46]=1

Participants

5

Reactant 2

HCID 2723923Ammonium formate2×HCID 58830669HCID 58830669, compound

Product 1

HCID 11157748HCID 11157748, compoundYield 62%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalyst2×HCID 702EthanolSolvent

Procedure

Add dry Pd/C (0.110 g, 0.104 mmol) to 6-benzyloxy-2-(4-methoxy-phenyl)-1-{4-[4-(4,4,5,5,5-pentafluoro-pentylsulfanyl)-butoxy]phenoxy}-naphtalene (0.590 g, 0.847 mmol). Add EtOH (25 mL), followed by ammonium formate (0.382 g, 6.058 mmol). Heat to reflux and stirred for 1.5 hours. Cool to room temperature and add additional Pd/C (0.610 g, 0.547 mmol), and ammonium formate (0.385 g, 6.105 mmol). Heat to reflux and stirred for 3 hours. Add celite (10 g) and filter washing with CH2Cl2 and CH3OH. Concentrate the solution in vacuo. Dissolve the resulting residue in CH2Cl2 (20 mL) and wash the solution with H2O (2×15 mL). Separate the layers and dry the organic (Na2SO4), filter and concentrate in vacuo. Purify by radial chromatography (eluting with 30% EtOAc in hexanes) to afford 0.318 g (62%) of the desired 6-(4-methoxy-phenyl)-5-{4-[4-(4,4,5,5,5-pentafluoro-pentylsulfanyl)-butoxy]-phenoxy}-naphthalen-2-ol as a white solid. 1H NMR (400 MHz, CDCl3): δ 7.83 (t, J=9.3 Hz, 1H), 7.58 (d, J=8.3 Hz, 1H), 7.47 (m, 3H), 7.16 (d, J=2.4 Hz, 1H), 7.0 (m, 1H), 6.83 (dd, J=2.0, 6.8 Hz, 2H), 6.58 (m, 4H), 3.81 (t, J=5.9 Hz, 2H), 3.76 (s, 3H), 2.65-2.75 (m, 2H), 2.54 (m, 2H), 2.06-2.29 (m, 3H), 1.68-1.93 (m, 5H).

Workup

  1. temperatureHeat
  2. temperatureto reflux
  3. temperatureHeat
  4. temperatureto reflux
  5. stirringstirred for 3 hours
  6. additionAdd celite (10 g)
  7. filtrationfilter
  8. washwashing with CH2Cl2 and CH3OH
  9. concentrationConcentrate the solution in vacuo
  10. dissolutionDissolve the resulting residue in CH2Cl2 (20 mL)
  11. washwash the solution with H2O (2×15 mL)
  12. customSeparate the layers
  13. dry with materialdry the organic (Na2SO4)
  14. filtrationfilter
  15. concentrationconcentrate in vacuo
  16. customPurify by radial chromatography (eluting with 30% EtOAc in hexanes)

Sources & evidence

ORD record
ord-f37ae7ee021a49c29219e3996631b07a
Source dataset
uspto-grants-2008_12
Patent number
US07462647B2

Reaction notes

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