Ethyl Acetate → 10-Benzyl-4-methyl-3,5,10-triaza-tricyclo[6.3.1.02,7]dodeca-2(7),3,5-triene

HRID 272617Notes

Reaction equation

HRID 272617 reaction equation
[CH2:1]([N:8]1[CH2:14][CH:13]2[CH2:15][CH:10]([C:11](=[CH:17]N(C)C)[C:12]2=O)[CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(=O)([O-])[O-].[K+].[K+].Cl.[C:28]([NH2:31])(=[NH:30])[CH3:29].C(OCC)(=O)C>C(O)C>[CH2:1]([N:8]1[CH2:14][CH:13]2[CH2:15][CH:10]([C:11]3[CH:17]=[N:30][C:28]([CH3:29])=[N:31][C:12]=32)[CH2:9]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 67170Acetamidine monohydrochlorideHCID 688083373-Benzyl-7-dimethylaminomethylene-3-aza-bicyclo[3.2.1]octan-6-one

Product 1

HCID 5983782510-Benzyl-4-methyl-3,5,10-triaza-tricyclo[6.3.1.02,7]dodeca-2(7),3,5-triene

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a solution of 3-benzyl-7-dimethylaminomethylene-3-aza-bicyclo[3.2.1]octan-6-one (1.42 mmol) in ethanol was added potassium carbonate (3.8 mmol) and acetamidine hydrochloride (1.6 mmol). The reaction mixture was heated under reflux overnight. After cooling the solvents were removed and dichloromethane and aqueous sodium bicarbonate solution were added. The dichloromethane layer was separated and dried to and oil. Purification by flash chromatography on silica gel eluted with ethyl acetate yielded product (0.23 mmol). 1H NMR (CD3OD, 400 MHz) δ 8.25 (s, 1H), 7.18 (br s, 3H), 6.85 (br s, 2H), 3.60–3.40 (m, 2H), 3.10 (s, 1H), 3.00 (m, 2H), 2.79 (m, 1H), 2.70 (s, 3H), 2.5 (m, 1H), 2.45 (m, 1H), 2.25 (m, 1H), 1.70 (m, 1H); APCl MS m/z 266.2 (M+H)+.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureunder reflux overnight
  3. temperatureAfter cooling the solvents
  4. customwere removed
  5. additiondichloromethane and aqueous sodium bicarbonate solution were added
  6. customThe dichloromethane layer was separated
  7. customdried to and oil
  8. customPurification by flash chromatography on silica gel

Sources & evidence

ORD record
ord-67951e79aedc46408223bca439b775d6
Source dataset
uspto-grants-2008_11
Patent number
US07456177B2

Reaction notes

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