Potassium Carbonate → HCID 67239172, compound

HRID 1912348Notes

Reaction equation

HRID 1912348 reaction equation
C([O-])([O-])=O.[K+].[K+].C[N:8]1[CH:14]2[CH2:15][CH2:16][CH:9]1[CH2:10][N:11]([CH:17]([C:29]1[CH:34]=[CH:33][CH:32]=[C:31]([O:35][CH3:36])[CH:30]=1)[C:18]1[CH:28]=[CH:27][C:21]([C:22]([N:24]([CH3:26])[CH3:25])=[O:23])=[CH:20][CH:19]=1)[CH2:12][CH2:13]2>C1(C)C=CC=CC=1.C(O)(=O)C.[Zn]>[CH:9]12[NH:8][CH:14]([CH2:15][CH2:16]1)[CH2:13][CH2:12][N:11]([CH:17]([C:29]1[CH:34]=[CH:33][CH:32]=[C:31]([O:35][CH3:36])[CH:30]=1)[C:18]1[CH:28]=[CH:27][C:21]([C:22]([N:24]([CH3:26])[CH3:25])=[O:23])=[CH:20][CH:19]=1)[CH2:10]2

Participants

6

Reactant 2

HCID 11430Potassium CarbonateHCID 67239312HCID 67239312, compound

Product 1

HCID 67239172HCID 67239172, compoundYield 62%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 176Acetic AcidSolventHCID 1140TolueneSolvent2×

Procedure

0.4 ml of 2,2,2-trichloroethylchloro formate and 0.52 g of K2CO3 were added to a solution of the compound obtained in Example 4.10 (1.02 g) in toluene (25 ml), kept under argon inert atmosphere. The mixture was heated at reflux for 16 hours and at the end cooled at room temperature. The mixture is washed in sequence with water, with an aqueous solution of 15% citric acid and then with brine. At the end of the washings the organic phase was recovered and dehydrated on sodium sulphate. After solvent evaporation 1.21 g of a light yellow oil (carbamate) were obtained. The oil was dissolved in 25 ml of glacial acetic acid. To the solution 0.82 g of zinc in powder were added. The mixture was kept under stirring at room temperature for 16 hours and at the end diluted with about 25 ml of toluene. The solvent was evaporated under vacuum. The residue was dissolved in the minimum volume of dichloromethane. The solution was extracted three times with an aqueous solution of 15% w citric acid. The aqueous phases were shaken with dichloromethane, then brought to an alkaline pH with conc. NH4OH and extracted again with dichloromethane. The pooled organic phases were dehydrated with sodium sulphate and the solvent evaporated. 0.52 g of the compound 4-[(3,9-diazabicyclo[4.2.1]non-3-yyl)-(3-methoxy-phenyl)methyl]-N,N-dimethylbenzamide were obtained. Yield: 62%; IR (nujol) (λ=cm−1) 1646 (C═O), 3120 (NH); 1H-NMR (CDCl3): δ 1.39-1.65 (m, 3H), 1.74-1.97 (m, 1H), 2.11-2.30 (m, 2H), 2.66 (bs, 1H), 2.75 (dd, 1H, J=2.2 and 11.0 Hz), 2.81-3.04 (m, 3H), 3.05 (s, 6H), 3.11-3.32 (m, 2H), 3.81 (s, 3H), 4.27 (s, 1H), 6.63-6.79 (m, 1H), 7.00-7.20 (m, 5H), 7.55 (d, 2H, J=8.1 Hz). Anal. calc. for C24H31N3O2: C, 73.25; H, 7.94; N, 10.68. Found: C, 73.11; H, 7.92; N, 10.65.

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 16 hours and at the end
  3. washThe mixture is washed in sequence with water, with an aqueous solution of 15% citric acid
  4. customAt the end of the washings the organic phase was recovered
  5. customAfter solvent evaporation 1.21 g of a light yellow oil (carbamate)
  6. customwere obtained
  7. customThe solvent was evaporated under vacuum
  8. dissolutionThe residue was dissolved in the minimum volume of dichloromethane
  9. extractionThe solution was extracted three times with an aqueous solution of 15%
  10. stirringThe aqueous phases were shaken with dichloromethane
  11. extractionextracted again with dichloromethane
  12. customthe solvent evaporated

Sources & evidence

ORD record
ord-ad001349178b4425857056f486261a11
Source dataset
uspto-grants-2013_12
Patent number
US08609659B2

Reaction notes

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