p-Fluoronitrobenzene → HCID 22220480, compound

HRID 1061424Notes

Reaction equation

HRID 1061424 reaction equation
C([O-])=O.[NH4+].[CH:5]([N:18]1[CH2:21][CH:20]([O:22][Si](C(C)(C)C)(C)C)[CH2:19]1)([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14]C=1)C1C=CC=CC=1.FC1C=CC([N+:37]([O-:39])=[O:38])=CC=1>CO.N1C=CC=CC=1.[Pd]>[N+:37]([C:16]1[CH:17]=[CH:12][C:5]([N:18]2[CH2:19][CH:20]([OH:22])[CH2:21]2)=[CH:14][CH:15]=1)([O-:39])=[O:38]

Participants

7

Reactant 3

HCID 9590p-FluoronitrobenzeneHCID 2723923Ammonium formateHCID 22220462HCID 22220462, compound

Product 1

HCID 22220480HCID 22220480, compoundYield 81.9%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 887MethanolSolventHCID 1049PyridineSolvent

Procedure

Ammonium formate (15.1 g, 246 mmol) was added to a solution of 1-benzhydryl-3-(tert-butyl-dimethyl-silanyloxy)-azetidine (which was obtained in Example 395) (8.7 g, 24.6 mmol) and 10%Pd/C (1 g) in methanol (100 mL). The reaction was stirred for 3 hours at room temperature. The solution was passed through celite and concentrated to afford a crude solid. The crude solid was taken up in pyridine (75 mL) and the salts were removed by filtration. 4-Fluoronitrobenzene (2.9 mL, 27.1 mmol) was added to the above solution and the reaction was stirred at reflux overnight. Pyridine was removed by vacuum distillation and the resultant crude was treated with water (100 mL), followed by extraction with ethyl acetate (3×25 mL). The organic layers were combined, dried (Na2SO4), filtered, and passed through a plug of silica. The solvent was evaporated and triturated with hexanes to give 3.91 g of the desired product as red solid; 1H NMR (300 MHz, CDCl3) δ 1.62 (s, 1H), 3.89(m, 2H), 4.31 (m, 2H), 4.87 (m, 1H), 6.31 (d, 2H, J=7.14), 8.09 (d, 2H, J=7.14 Hz); MS (ES) m/z: 194.8 (MH+); Anal. Calcd. for C9H10N2O3: C, 55.67; H, 5.19; N, 14.43. Found: C, 55.67; H, 5.05; N, 14.59.

Workup

  1. concentrationconcentrated
  2. customto afford a crude solid
  3. customthe salts were removed by filtration
  4. stirringthe reaction was stirred
  5. temperatureat reflux overnight
  6. customPyridine was removed by vacuum distillation
  7. additionthe resultant crude was treated with water (100 mL)
  8. extractionfollowed by extraction with ethyl acetate (3×25 mL)
  9. dry with materialdried (Na2SO4)
  10. filtrationfiltered
  11. customThe solvent was evaporated
  12. customtriturated with hexanes

Sources & evidence

ORD record
ord-4518ba59b59e4dab9df800898fdfc44c
Source dataset
uspto-grants-2003_02
Patent number
US06525202B2

Reaction notes

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