Ethyl Acetate → 6-Bromo-2-methoxycarbonylmethyltetrahydroquinoline

HRID 52482Notes

Reaction equation

HRID 52482 reaction equation
C(=O)([O-])[O-].[K+].[K+].C(OCC)(=O)C.Cl.[CH3:14][O:15][C:16]([CH2:18][CH:19]1[CH2:28][CH2:27][C:26]2[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=2)[NH:20]1)=[O:17].[Br:29]N1C(=O)CCC1=O>CN(C=O)C.O>[Br:29][C:24]1[CH:25]=[C:26]2[C:21](=[CH:22][CH:23]=1)[NH:20][CH:19]([CH2:18][C:16]([O:15][CH3:14])=[O:17])[CH2:28][CH2:27]2

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 67184N-bromobutanimideHCID 196983852-Methoxycarbonylmethyltetrahydroquinoline hydrochloride

Product 1

HCID 104016006-Bromo-2-methoxycarbonylmethyltetrahydroquinoline

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

In a mixture of aqueous solution of potassium carbonate (30 g) and ethyl acetate was dispersed 2-methoxycarbonylmethyltetrahydroquinoline hydrochloride (24.8 g, 0.1 mol). The organic layer was separated, dried over magnesium sulfate, and concentrated. The residue was dissolved in DMF (400 mL) and a solution of N-bromosuccinimide (21.36 g, 0.12 mol)in DMF (400 mL) was added dropwise at 0° C. The mixture was stirred for 5 h at room temperature, poured into water (250 mL), and extracted with ether (250 mL). The organic layer was washed with water, dried over magnesium sulfate, and concentrated to give 36 g of the crude title compound (quant) which was used for the next step without purification. The specimen for characterization was obtained by silica gel column chromatography of the crude compound with 1:1 dichloromethane/hexane to 100% dichloromethane: 1H NMR (270 MHz, CDCl3) δ7.02~7.06 (m, 2H), 6.38 (dd, 1H, J=1.7, 7.3 Hz), 4.53 (br, 1H), 3.75 (s, 3H), 3.72~3.75 (m, 4H), 2.70~2.85 (m, 2H), 2.49~2.53 (m, 1H), 1.89~1.99 (m, 1H), 1.61~1.75 (m, 1H),

Workup

  1. customThe organic layer was separated
  2. dry with materialdried over magnesium sulfate
  3. concentrationconcentrated
  4. dissolutionThe residue was dissolved in DMF (400 mL)
  5. extractionextracted with ether (250 mL)
  6. washThe organic layer was washed with water
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated
  9. customto give 36 g of the crude title compound (quant) which
  10. customwas used for the next step without purification

Sources & evidence

ORD record
ord-1d6527708a754f6da2330fb9181d69c5
Source dataset
uspto-grants-1997_04
Patent number
US05616586

Reaction notes

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