N-bromobutanimide → 1-Benzyl-5-bromo-2-methyl-6-oxo-1,6-dihydro-pyridine-3-carboxylic acid methyl ester

HRID 919653Notes

Reaction equation

HRID 919653 reaction equation
C[O:2][C:3](=O)[CH:4]=[CH:5][C:6](=[C:11]([NH:13][CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[CH3:12])[C:7]([O:9][CH3:10])=[O:8].C[O-].[Na+].[Br:25]N1C(=O)CCC1=O>CO>[CH3:10][O:9][C:7]([C:6]1[CH:5]=[C:4]([Br:25])[C:3](=[O:2])[N:13]([CH2:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[C:11]=1[CH3:12])=[O:8]

Participants

5

Reactant 3

HCID 67184N-bromobutanimideHCID 10942334Sodium MethoxideHCID 728337734-(1-Benzylamino-ethylidene)-pent-2-enedioic acid dimethyl ester

Product 1

HCID 120086331-Benzyl-5-bromo-2-methyl-6-oxo-1,6-dihydro-pyridine-3-carboxylic acid methyl esterYield 66.2%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

MeOH (28 mL) was added to a flask containing 4-(1-benzylamino-ethylidene)-pent-2-enedioic acid dimethyl ester (1.0 g, 3.46 mmol). NaOMe solution (7 mL, 3.46 mmol, 0.5M in MeOH) and N-bromosuccinimide (0.74 g, 4.15 mmol) were added. The resulting mixture was refluxed for 1 h. After cooling to r.t., the solvent was evaporated in vacuo. The residue was partitioned between saturated NH4Cl (50 mL) and CH2Cl2 (50 mL). The aqueous layer was extracted with additional CH2Cl2 and the organic layers were combined, dried over MgSO4, and concentrated. The crude product was chromatographed (0-40% EtOAc/hexanes) to give 0.77 g of the title compound. MS: (+) m/z 357.95, 359.92 (M+Na, 79/81Br).

Workup

  1. temperatureThe resulting mixture was refluxed for 1 h
  2. customthe solvent was evaporated in vacuo
  3. customThe residue was partitioned between saturated NH4Cl (50 mL) and CH2Cl2 (50 mL)
  4. extractionThe aqueous layer was extracted with additional CH2Cl2
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated
  7. customThe crude product was chromatographed (0-40% EtOAc/hexanes)

Sources & evidence

ORD record
ord-9c08dafcfcf24ed8a67550109d0ef1da
Source dataset
uspto-grants-2016_03
Patent number
US09271970B2

Reaction notes

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