Ethanol → HCID 73508908, compound

HRID 2253693Notes

Reaction equation

HRID 2253693 reaction equation
[O:1]=[C:2]1[CH2:7][CH:6]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[C:5](=O)[CH:4]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[NH:3]1.C(O)C.Cl.[NH2:25][OH:26].C([O-])(=O)C.[Na+]>O>[C:8]1([CH:6]2[C:5](=[N:25][OH:26])[CH:4]([C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=3)[NH:3][C:2](=[O:1])[CH2:7]2)[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1

Participants

6

Reactant 4

HCID 702EthanolHCID 443297Hydroxyamine hydrochlorideHCID 517045Sodium AcetateHCID 19012803HCID 19012803, compound

Product 1

HCID 73508908HCID 73508908, compoundYield 13.6%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

In a round-bottom flask were placed 15 g (50.6 mmol) of the nitro lactam 4,6-diphenyl-5-nitro-2-oxopiperidine and 85 mL of methylene chloride. Potassium tert-butoxide (5.72 g, 50.6 mmol) was added and the mixture was stirred for 15 min. To this system was added 85 mL of methanol. The mixture was stirred for 15 min and the system was cooled to -78° C. Ozone was bubbled through the reaction mixture for 4 hours, nitrogen was bubbled through the mixture, 10 mL of dimethyl sulfide was added and nitrogen was bubbled through the mixture overnight. A mixture of water and methylene chloride was added to the system and the resulting solid (8.8 g of a mixture of the nitro lactam 4,6-diphenyl-5-nitro-2-oxopiperidine and 2,5-dioxo-4,6-diphenyl-piperidine was collected by suction filtration. The filtrate was concentrated with a rotary evaporator and the residue was partitioned between methylene chloride and water. The layers were separated, and the aqueous phase was extracted with two portions of methylene chloride. The combined organic fractions were dried (sodium sulfate) and concentrated to afford 5.14 g of crude 2,5-dioxo-4,6-diphenylpiperidine which was used immediately without further purification. Under a nitrogen atmosphere in a round-bottom flask were placed 2,5-dioxo-4,6-diphenylpiperidine (5.14 g, 19 mmol) and 75 mL of ethanol. A solution of 3.96 g (57 mmol) of hydroxylamine hydrochloride and 7.74 g (95 mmol) of sodium acetate in 25 mL of water were added and the reaction mixture was stirred at room temperature. The reaction mixture was concentrated to ca. 1/2 its initial volume, and the resulting precipitate was collected by suction filtration. This precipitate (1.5 g) was washed with saturated aqueous sodium bicarbonate, water and ether to afford 722 mg of 4,6-diphenyl-5-oximino-2-oxopiperidine as a white solid.

Workup

  1. customwas used immediately without further purification
  2. customUnder a nitrogen atmosphere in a round-bottom flask were placed
  3. concentrationThe reaction mixture was concentrated to ca. 1/2 its initial volume
  4. filtrationthe resulting precipitate was collected by suction filtration
  5. washThis precipitate (1.5 g) was washed with saturated aqueous sodium bicarbonate, water and ether

Sources & evidence

ORD record
ord-8182d608b80a4eb0a04d48a29b6b8bf4
Source dataset
uspto-grants-1993_08
Patent number
US05232929

Reaction notes

Loading…