Ethyl Acetate → 5-(5-Bromo-3-pyridinyl)-1-methyl-2-pyrrolidinone

HRID 724907

Reaction equation

HRID 724907 reaction equation
[BH4-].[Na+].[Te].[Br:4][C:5]1[CH:6]=[C:7]([CH:11]2[N:15]([CH3:16])[C:14](=[O:17])[C:13](Br)(Br)[CH2:12]2)[CH:8]=[N:9][CH:10]=1.C(OCC)(=O)C>C(O)C>[Br:4][C:5]1[CH:6]=[C:7]([CH:11]2[N:15]([CH3:16])[C:14](=[O:17])[CH2:13][CH2:12]2)[CH:8]=[N:9][CH:10]=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 4311764Sodium borohydrideHCID 6327182TelluriumHCID 196943305-Bromo-3-(3,3-dibromo-1-methyl-5-pyrrolidin-2-onyl)pyridine

Product 1

HCID 196943295-(5-Bromo-3-pyridinyl)-1-methyl-2-pyrrolidinoneYield 68%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Sodium borohydride (862 mg, 22.8 mmol) was dissolved in ethanol (20 mL) and tellurium metal powder (1.45 g, 11.4 mmol) was added in portions. The mixture was heated under reflux for 0.25 h and 5-bromo-3-(3,3-dibromo-1-methyl-5-pyrrolidin-2-onyl)pyridine (775 mg, 1.9 mmol) was added to the solution at 25° C. After stirring for 2 h, ethyl acetate (50 mL) was added and the solution was filtered through Celite and concentrated in vacuo. 1M HCl (10 mL) was added to the residue and the solution was adjusted to pH 11 with solid potassium carbonate. After extraction with ethyl acetate (50 mL) the organic phase was separated. The aqueous phase was extracted with ethyl acetate (2×50 mL) and the combined organic phases were washed with brine (30 mL), dried (MgSO4) and concentrated. This material was chromatographed on silica gel with ethyl acetate:hexane (1:1) as eluant to afford 5-bromo-3-(1-methyl-5-pyrrolidin-2-onyl)pyridine as a solid (329 mg, 68%). M.p. 85°-87° C.; 1H NMR (CDCl3, 300 MHz): δ 8.66 (d, J=2 Hz, 1H), 8.42 (d, J=2 Hz, 1H), 7.68 (t, J=2 Hz, 1H), 4.56 (t, J=7 Hz, 1H), 2.71 (s, 3H), 2.45-2.65 (m, 2H), 1.80-1.95 (m, 2H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 0.25 h
  3. filtrationthe solution was filtered through Celite
  4. concentrationconcentrated in vacuo
  5. addition1M HCl (10 mL) was added to the residue
  6. extractionAfter extraction with ethyl acetate (50 mL) the organic phase
  7. customwas separated
  8. extractionThe aqueous phase was extracted with ethyl acetate (2×50 mL)
  9. washthe combined organic phases were washed with brine (30 mL)
  10. dry with materialdried (MgSO4)
  11. concentrationconcentrated
  12. customThis material was chromatographed on silica gel with ethyl acetate:hexane (1:1) as eluant

Sources & evidence

ORD record
ord-dc50d1f4c0a04586a835e53b3f02b86d
Source dataset
uspto-grants-1998_01
Patent number
US05705512

Linked notes

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