Sodium hydride → 6-bromo-1-{[2-(trimethylsilyl)ethoxy]methyl}-1,4-dihydro-2H-3,1-benzoxazin-2-one

HRID 1468765

Reaction equation

HRID 1468765 reaction equation
[H-].[Na+].[Br:3][C:4]1[CH:5]=[CH:6][C:7]2[NH:12][C:11](=[O:13])[O:10][CH2:9][C:8]=2[CH:14]=1.Cl[CH2:16][O:17][CH2:18][CH2:19][Si:20]([CH3:23])([CH3:22])[CH3:21]>CN(C)C=O>[Br:3][C:4]1[CH:5]=[CH:6][C:7]2[N:12]([CH2:16][O:17][CH2:18][CH2:19][Si:20]([CH3:23])([CH3:22])[CH3:21])[C:11](=[O:13])[O:10][CH2:9][C:8]=2[CH:14]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 27242712-Chloromethyl 2-(trimethylsilyl)ethyl etherHCID 259189636-Bromo-1,4-dihydro-2H-3,1-benzoxazin-2-one

Product 1

HCID 679776606-bromo-1-{[2-(trimethylsilyl)ethoxy]methyl}-1,4-dihydro-2H-3,1-benzoxazin-2-oneYield 85.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

To a solution of sodium hydride (55 wt % in mineral oil, 1.36 g, 31.2 mmol) in N,N-dimethylformamide (37 ml) was added 6-bromo-1,4-dihydro-2H-3,1-benzoxazin-2-one (5.93 g, 26.0 mmol) in N,N-dimethylformamide (37 ml) at 0° C. The mixture was stirred at room temperature for one hour, then 2-(chloromethoxy)ethyltrimethylsilane (4.77 g, 28.6 mmol) was added at 0° C. The mixture was stirred at room temperature overnight. The mixture was partitioned between water and ethyl acetate. The organic layer was washed with water (four times), dried over sodium sulfate, and concentrated in vacuo. The residue was purified by silica gel column chromatography (eluent; hexane/ethyl acetate=90/10 to 60/40) to afford 6-bromo-1-{[2-(trimethylsilyl)ethoxy]methyl}-1,4-dihydro-2H-3,1-benzoxazin-2-one as a pale yellow solid (7.96 g, 22.2 mmol, 85%).

Workup

  1. stirringThe mixture was stirred at room temperature overnight
  2. customThe mixture was partitioned between water and ethyl acetate
  3. washThe organic layer was washed with water (four times)
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by silica gel column chromatography (eluent; hexane/ethyl acetate=90/10 to 60/40)

Sources & evidence

ORD record
ord-0f78bfe11bc6498e94617a705081500e
Source dataset
uspto-grants-2015_04
Patent number
US09006232B2

Linked notes

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