Hydrochloric Acid → 5-Bromo-3-[5-(1-ethylamino-1-methyl-ethyl)-pyridin-2-ylamino]-1-methyl-1H-pyridin-2-one

HRID 2069868Notes

Reaction equation

HRID 2069868 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([NH:10][C:11]2[N:16]=[CH:15][C:14]([C:17]([NH:20][C:21](=O)[CH3:22])([CH3:19])[CH3:18])=[CH:13][CH:12]=2)[C:5](=[O:9])[N:6]([CH3:8])[CH:7]=1.Cl.[OH-].[Na+].O>C1COCC1>[Br:1][C:2]1[CH:3]=[C:4]([NH:10][C:11]2[CH:12]=[CH:13][C:14]([C:17]([NH:20][CH2:21][CH3:22])([CH3:19])[CH3:18])=[CH:15][N:16]=2)[C:5](=[O:9])[N:6]([CH3:8])[CH:7]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 14798Sodium HydroxideHCID 59473804N-(2-(6-(5-bromo-1-methyl-2-oxo-1,2-dihydropyridin-3-ylamino)pyridin-3-yl)propan-2-yl)acetamide

Product 1

HCID 594738195-Bromo-3-[5-(1-ethylamino-1-methyl-ethyl)-pyridin-2-ylamino]-1-methyl-1H-pyridin-2-oneYield 18.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

N-(2-(6-(5-bromo-1-methyl-2-oxo-1,2-dihydropyridin-3-ylamino)pyridin-3-yl)propan-2-yl)acetamide (417 mg, 1.1 mmol) was dissolved in THF (40 ml). This solution was refluxed and 10 M borane dimethyl sulfide complex (165 μl, 1.65 mmol) was added slowly to the refluxing mixture. The reaction mixture was refluxed for 2.5 hr. Next, 0.5 ml 6 M hydrochloric acid solution was added and after stirring at reflux for 5 min it was cooled to room temperature. Next 3M sodium hydroxide solution was added, followed by water and the material was extracted with ethyl acetate. It was washed with brine, dried over sodium sulfate, filtered and concentrated. The crude was purified by silica gel chromatography 0-10% MeOH in DCM to give 5-Bromo-3-[5-(1-ethylamino-1-methyl-ethyl)-pyridin-2-ylamino]-1-methyl-1H-pyridin-2-one (73 mg, 18%). 1H NMR (300 MHz, DMSO-d6) δ ppm 1.14 (t, J=7.18 Hz, 3 H) 1.70 (s, 6 H) 2.67 (m, 2 H) 3.52 (s, 3 H) 7.44 (d, J=9.06 Hz, 1 H) 7.58 (d, J=2.27 Hz, 1 H) 7.86 (dd, J=8.69, 2.64 Hz, 1 H) 8.45 (d, J=2.64 Hz, 1 H) 8.73 (d, J=2.64 Hz, 1 H) 8.76-8.88 (m, 1 H) 8.99 (s, 1 H).

Workup

  1. temperatureThis solution was refluxed
  2. addition10 M borane dimethyl sulfide complex (165 μl, 1.65 mmol) was added slowly to the refluxing mixture
  3. temperatureThe reaction mixture was refluxed for 2.5 hr
  4. temperatureat reflux for 5 min it
  5. extractionthe material was extracted with ethyl acetate
  6. washIt was washed with brine
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe crude was purified by silica gel chromatography 0-10% MeOH in DCM

Sources & evidence

ORD record
ord-a4100ee0f4c643a0a5ef1a79a2f02a0a
Source dataset
uspto-grants-2012_10
Patent number
US08299077B2

Reaction notes

Loading…