phosphenous acid → 1-Phenyl-4-piperidinone

HRID 37848Notes

Reaction equation

HRID 37848 reaction equation
N[C:2]1[CH:7]=[CH:6][C:5]([N:8]2[CH2:13][CH2:12][C:11](=[O:14])[CH2:10][CH2:9]2)=[CH:4][CH:3]=1.N([O-])=O.[Na+].OP=O.C(=O)(O)[O-].[Na+]>Cl.O>[C:5]1([N:8]2[CH2:9][CH2:10][C:11](=[O:14])[CH2:12][CH2:13]2)[CH:6]=[CH:7][CH:2]=[CH:3][CH:4]=1

Participants

7

Reactant 4

HCID 22497phosphenous acidHCID 516892Sodium BicarbonateHCID 222202411-(4-Aminophenyl)piperidin-4-oneHCID 23668193Sodium Nitrite

Product 1

HCID 4130091-Phenyl-4-piperidinoneYield 15%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 1-(4-amino-phenyl)-piperidin-4-one (1.34 g, 7.05 mmol) in 50% hydrochloric acid (10 mL) was stirred at ambient temperature for 15 min. The reaction mixture was cooled to 0° C. and a solution of sodium nitrite (1.46 g) in water (5 mL) added and stirred for 30 min. To this reaction mixture was added cold 30-32% hypophosphorus acid (10 mL), the mixture then being warmed to ambient temperature and stirred for 2 h. The reaction mixture was neutralised with saturated sodium bicarbonate solution and extracted with ethyl acetate. The organic layer was washed with water, brine solution, dried over anhydrous sodium sulfate and concentrated to give a residue which was purified by column chromatography over silica gel (60-120 mesh) using 17% ethyl acetate in petroleum ether as eluent to afford 1-phenyl-piperidin-4-one (0.18 g, 15%) as a liquid.

Workup

  1. temperaturethe mixture then being warmed to ambient temperature
  2. stirringstirred for 2 h
  3. extractionextracted with ethyl acetate
  4. washThe organic layer was washed with water, brine solution
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated
  7. customto give a residue which
  8. customwas purified by column chromatography over silica gel (60-120 mesh)

Sources & evidence

ORD record
ord-2b5006584e654cc9807556c13c9ffec1
Source dataset
uspto-grants-2013_09
Patent number
US08524705B2

Reaction notes

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