Methyl benzenesulfonate → 3-Bromo-5-(1-methyl-1,2,3,6-tetrahydropyridin-2-yl)-1-phenyl-1,2-dihydropyridin-2-one

HRID 229689Notes

Reaction equation

HRID 229689 reaction equation
[Br:1][C:2]1[C:3](=[O:20])[N:4]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[CH:5]=[C:6]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][N:9]=2)[CH:7]=1.[C:21]1(S(OC)(=O)=O)C=CC=CC=1>C(#N)C>[Br:1][C:2]1[C:3](=[O:20])[N:4]([C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=2)[CH:5]=[C:6]([CH:8]2[CH2:13][CH:12]=[CH:11][CH2:10][N:9]2[CH3:21])[CH:7]=1

Participants

4

Reactant 2

HCID 6630Methyl benzenesulfonateHCID 223190653-Bromo-1-phenyl-5-(pyridin-2-yl)-1,2-dihydropyridin-2-one

Product 1

HCID 223191043-Bromo-5-(1-methyl-1,2,3,6-tetrahydropyridin-2-yl)-1-phenyl-1,2-dihydropyridin-2-one

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
100 °C

Procedure

99 mg of 3-bromo-5-(2-pyridyl)-1-phenyl-1,2-dihydropyridin-2-one was dissolved in 10 ml of acetonitrile. 2 ml of methyl benzenesulfonate was added thereto, followed by stirring at 100° C. for 2 nights. After cooling to room temperature, the solvent was evaporated. The residue was dissolved in 10 ml of methanol, followed by cooled to 0° C. under stirring. Sodium borohydride was added 5 times at intervals of 5 hours, 1 g for each time, followed by further stirring at 0° C. overnight. Then the solvent was evaporated and a saturated aqueous solution of ammonium chloride was added to the residue, followed by extracting with ethyl acetate. The organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was evaporated, and the residue was purified by silica gel chromatography (hexane/ethyl acetate system), to give 107 mg of 3-bromo-5-(1-methyl-1,2,3,6-tetrahydropyridin-2-yl)-1-phenyl-1,2-dihydropyridin-2-one. The product was dissolved in 10 ml of dimethylformamide. 81 mg of 2-(2-cyanophenyl)-1,3,2-dioxaborinate, 142 mg of cesium carbonate and 7 mg of tetrakistriphenylphosphine palladium were added thereto, followed by stirring at 140° C. for 2 hours. After cooling to room temperature, water was added thereto, followed by extracting with ethyl acetate. The organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was evaporated, and the residue was purified by silica gel chromatography (hexane/ethyl acetate system), to give 41 mg of the title compound.

Workup

  1. temperatureAfter cooling to room temperature
  2. customthe solvent was evaporated
  3. dissolutionThe residue was dissolved in 10 ml of methanol
  4. temperatureby cooled to 0° C.
  5. stirringunder stirring
  6. additionSodium borohydride was added 5 times at intervals of 5 hours, 1 g for each time
  7. stirringby further stirring at 0° C. overnight
  8. customThen the solvent was evaporated
  9. additiona saturated aqueous solution of ammonium chloride was added to the residue
  10. extractionby extracting with ethyl acetate
  11. washThe organic layer was washed with brine
  12. dry with materialdried over anhydrous magnesium sulfate
  13. customThe solvent was evaporated
  14. customthe residue was purified by silica gel chromatography (hexane/ethyl acetate system)

Sources & evidence

ORD record
ord-88af30b5b9aa4091946f3e6c51a6606f
Source dataset
uspto-grants-2009_07
Patent number
US07563811B2

Reaction notes

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