Water → tert-Butyl 4-(3-fluoro-4-nitrobenzylidene)piperidine-1-carboxylate

HRID 515288Notes

Reaction equation

HRID 515288 reaction equation
O=[C:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:4][CH2:3]1.[F:15][C:16]1[CH:17]=[C:18]([CH:28]=[CH:29][C:30]=1[N+:31]([O-:33])=[O:32])[CH2:19]P(=O)(OCC)OCC.[H-].[Na+].O>O1CCCC1>[F:15][C:16]1[CH:17]=[C:18]([CH:28]=[CH:29][C:30]=1[N+:31]([O-:33])=[O:32])[CH:19]=[C:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:4][CH2:3]1

Participants

6

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylateHCID 86670944HCID 86670944, compound

Product 1

HCID 67192635tert-Butyl 4-(3-fluoro-4-nitrobenzylidene)piperidine-1-carboxylateYield 64.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

tert-Butyl 4-oxopiperidine-1-carboxylate (126 mmol, 25.04 g) and diethyl 3-fluoro-4-nitrobenzylphosphonate (126 mmol, 36.6 g) in tetrahydrofuran (220 mL) were stirred and sodium hydride (163 mmol, 6.54 g, 60% in oil) was added. The reaction was stirred for 4 hours and then water was added. The reaction was extracted with dichloromethane and the organics were dried (magnesium sulfate), filtered and concentrated under reduced pressure. The residue was purified by silica column chromatography eluting with dichloromethane to give a bright yellow solid. This solid was filtered, washed with heptane and vacuum dried to afford the title compound (27.47 g). 1H NMR (CDCl3, 400 MHz): δ 8.1 (t, 1H), 7.1 (s, 1H), 7.05 (s, 1H), 6.35 (s, 1H), 3.55 (m, 2H), 3.45 (m, 2H), 2.52 (m, 2H), 2.4 (m, 2H), 1.49 (s, 9H)

Workup

  1. extractionThe reaction was extracted with dichloromethane
  2. dry with materialthe organics were dried (magnesium sulfate)
  3. filtrationfiltered
  4. concentrationconcentrated under reduced pressure
  5. customThe residue was purified by silica column chromatography
  6. washeluting with dichloromethane
  7. customto give a bright yellow solid
  8. filtrationThis solid was filtered
  9. washwashed with heptane and vacuum
  10. customdried

Sources & evidence

ORD record
ord-2a2c943105aa4e928bd38f4beb79cb9c
Source dataset
uspto-grants-2015_08
Patent number
US09108939B2

Reaction notes

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