N-Nitroso-N-methylurethane → 1-Benzyl-hexahydro-4H-azepin-4-one

HRID 1269781Notes

Reaction equation

HRID 1269781 reaction equation
CN(N=O)C([O:5][CH2:6][CH3:7])=O.[CH2:10]([N:17]1[CH2:22][CH2:21]C(=O)[CH2:19][CH2:18]1)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[O-2].[Ba+2]>CO>[CH2:10]([N:17]1[CH2:22][CH2:21][CH2:7][C:6](=[O:5])[CH2:19][CH2:18]1)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Participants

5

Reactant 3

HCID 12001N-Nitroso-N-methylurethaneHCID 192201-Benzyl-4-piperidoneHCID 9855530Barium Oxide Nanoparticle Dispersion

Product 1

HCID 15143501-Benzyl-hexahydro-4H-azepin-4-oneYield 31%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
-5 °C

Procedure

N-methyl-N-nitrosourethane (1.39 ml, 10.8 mmol) was added dropwise to a solution of 1-benzyl-4-piperidone (2.0 g, 10.6 mmol) in methanol (4 ml) at −15° C. over a period of 30 minutes while maintaining the temperature at −5° C. or lower. During the addition, barium oxide (65 mg, 0.423 mmol) was added thereto in small portions. The resulting mixture was stirred overnight at −15° C. and then filtered, and the filtrate was distilled under reduced pressure to remove the solvent and diethyl ether was added to the residue. The insoluble material was filtered off and a saturated aqueous sodium hydrogencarbonate solution was added to the filtrate, followed by extraction with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate and distilled under reduced pressure to remove the solvent, and the resulting residue was purified by a silica gel column chromatography (eluent: hexane/ethyl acetate=2/1) to obtain 1-benzyl-4-azepanone (662 mg, 31%).

Workup

  1. additionwas added
  2. filtrationfiltered
  3. distillationthe filtrate was distilled under reduced pressure
  4. customto remove the solvent and diethyl ether
  5. additionwas added to the residue
  6. filtrationThe insoluble material was filtered off
  7. additiona saturated aqueous sodium hydrogencarbonate solution was added to the filtrate
  8. extractionfollowed by extraction with diethyl ether
  9. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  10. distillationdistilled under reduced pressure
  11. customto remove the solvent
  12. customthe resulting residue was purified by a silica gel column chromatography (eluent: hexane/ethyl acetate=2/1)

Sources & evidence

ORD record
ord-958dee58b0b04d8585504f8781da97ba
Source dataset
uspto-grants-2007_04
Patent number
US07199147B2

Reaction notes

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