Sodium hydride → tert-Butyl 4-(4-nitrobenzylidene)piperidine-1-carboxylate

HRID 515277Notes

Reaction equation

HRID 515277 reaction equation
[N+:1]([C:4]1[CH:18]=[CH:17][C:7]([CH2:8]P(=O)(OCC)OCC)=[CH:6][CH:5]=1)([O-:3])=[O:2].O=[C:20]1[CH2:25][CH2:24][N:23]([C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[CH2:22][CH2:21]1.[H-].[Na+]>O1CCCC1>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([CH:8]=[C:20]2[CH2:25][CH2:24][N:23]([C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[CH2:22][CH2:21]2)=[CH:17][CH:18]=1)([O-:3])=[O:2]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 256065Diethyl 4-nitrobenzylphosphonateHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylate

Product 1

HCID 86670935tert-Butyl 4-(4-nitrobenzylidene)piperidine-1-carboxylateYield 81.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Diethyl 4-nitrobenzylphosphonate (36 g, 132 mmol) and tert-butyl 4-oxopiperidine-1-carboxylate (26.3 g, 132 mmol) were stirred in tetrahydrofuran (230 mL) and cooled in an ice bath. Sodium hydride was added (6.85 g, 171 mmol) and the reaction was taken off the ice bath and stirred for 3 hours at room temperature. The reaction was quenched with water and extracted with dichloromethane, dried (magnesium sulphate), filtered and evaporated under reduced pressure. The crude material was purified by silica chromatography using a dichloromethane solvent system. The oil obtained was triturated with heptane and filtered to give the title compound as a yellow solid (34.24 g). 1H NMR (CDCl3, 400 MHz): δ 8.18 (d, 2H), 7.33 (d, 2H), 6.40 (s, 1H), 3.54 (t, 2H), 3.43 (t, 2H), 2.46 (t, 2H), 2.38 (t, 2H), 1.48 (s, 9H)

Workup

  1. temperaturecooled in an ice bath
  2. customThe reaction was quenched with water
  3. extractionextracted with dichloromethane
  4. dry with materialdried (magnesium sulphate)
  5. filtrationfiltered
  6. customevaporated under reduced pressure
  7. customThe crude material was purified by silica chromatography
  8. customThe oil obtained
  9. customwas triturated with heptane
  10. filtrationfiltered

Sources & evidence

ORD record
ord-8cc60bf3ebd947fba9da60b4689b8dc4
Source dataset
uspto-grants-2015_08
Patent number
US09108939B2

Reaction notes

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