Sodium hydride → HCID 59316597, compound

HRID 1845922Notes

Reaction equation

HRID 1845922 reaction equation
[H-].[Na+].[Br:3][C:4]1[CH:5]=[C:6]2[C:11](=[CH:12][CH:13]=1)[NH:10][C:9](=[O:14])[CH2:8][CH2:7]2.Br[CH2:16][C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18]>CN(C)C=O>[Br:3][C:4]1[CH:5]=[C:6]2[C:11](=[CH:12][CH:13]=1)[N:10]([CH2:16][C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[C:9](=[O:14])[CH2:8][CH2:7]2

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 79177tert-Butyl bromoacetateHCID 143732816-Bromo-3,4-dihydroquinolin-2(1H)-one

Product 1

HCID 59316597HCID 59316597, compoundYield 72%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Procedure

To a mixture of 95% dry sodium hydride (834 mg, 33.0 mmol) in anhydrous N,N-dimethylformamide (30 mL) at room temperature was added a solution of 6-bromo-3,4-dihydroquinolin-2(1H)-one (6.780 g, 30.00 mmol) in anhydrous N,N-dimethylformamide (10 mL). The reaction mixture was stirred for 30 minutes under an atmosphere of dry N2, followed by addition of a solution of tert-butyl 2-bromoacetate (7.5 mL, 49.7 mmol) in N,N-dimethylformamide (10 mL). The reaction mixture was stirred at room temperature until the majority of the starting material was converted (confirmed by LCMS). The reaction mixture was quenched with methanol (40 mL), the mixture concentrated under reduced pressure, then diluted with ethyl acetate (150 mL). The organic phase was washed with water (100 mL), 30% ammonium chloride (100 mL) and brine (100 mL), dried, and concentrated under reduced pressure. Ethyl ether (20 mL) was added, and the mixture sonicated, filtered, washed with ether (20 mL), and dried to afford tert-butyl 2-(6-bromo-2-oxo-3,4-dihydroquinolin-1(2H)-yl)acetate (7.348 g, 21.6 mmol, 72%). LCMS mz 285.9 (M-56+H), 363.9 (M+Na), anal HPLC >97% in purity. 1H NMR (400 MHz; CDCl3) δ 7.30-7.40 (m, 2H); 7.50-6.70 (m, 1H); 4.54 (s, 2H); 2.92 (m, 2H); 2.69 (m, 2H), 1.44 (s, 9H).

Workup

  1. stirringThe reaction mixture was stirred at room temperature until the majority of the starting material
  2. customThe reaction mixture was quenched with methanol (40 mL)
  3. concentrationthe mixture concentrated under reduced pressure
  4. additiondiluted with ethyl acetate (150 mL)
  5. washThe organic phase was washed with water (100 mL), 30% ammonium chloride (100 mL) and brine (100 mL)
  6. customdried
  7. concentrationconcentrated under reduced pressure
  8. additionEthyl ether (20 mL) was added
  9. customthe mixture sonicated
  10. filtrationfiltered
  11. washwashed with ether (20 mL)
  12. customdried

Sources & evidence

ORD record
ord-f20a54a0257441f18512247b4b68e794
Source dataset
uspto-grants-2015_02
Patent number
US08952007B2

Reaction notes

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