Water → HCID 13731306, compound

HRID 1780640Notes

Reaction equation

HRID 1780640 reaction equation
[H-].[Na+].[NH2:3][C:4]1[C:5]([F:16])=[CH:6][C:7]2[O:12][CH:11]([CH3:13])[C:10](=[O:14])[NH:9][C:8]=2[CH:15]=1.[CH2:17](Br)[C:18]#[CH:19].O>CN(C)C=O>[NH2:3][C:4]1[C:5]([F:16])=[CH:6][C:7]2[O:12][CH:11]([CH3:13])[C:10](=[O:14])[N:9]([CH2:19][C:18]#[CH:17])[C:8]=2[CH:15]=1

Participants

6

Reactant 4

HCID 962WaterHCID 7842Propargyl bromideHCID 24758Sodium hydride2×HCID 15839682HCID 15839682, compound

Product 1

HCID 13731306HCID 13731306, compoundYield 40.8%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

While kept under N2, 0.30 g (7.4 mmol) of sodium hydride (60% dispersion in oil) was washed with 1 ml pentanes and then suspended in 2 ml anhydrous dimethylformamide. A solution of 1.36 g (6.9 mmol) of 6-amino-7-fluoro-2-methyl-2H-1,4-benzoxazin-3(4H)-one in 10 ml of dimethylformamide was added to the sodium hydride slurry slowly by syringe with ice cooling and the reaction mixture was stirred at room temperature for 0.5 hr. There was then added 0.77 ml (8.6 mmol) of propargyl bromide by syringe with ice bath cooling. The reaction mixture was allowed to warm to room temperature, stirred for 84 hours and then poured into 50 ml of water. The resulting mixture was extracted with EtOAc (2×50 ml) and the organic layers were combined and washed with water (3×50 ml), dried over MgSO4 and filtered. The solvent was removed in vacuo to yield a golden solid which was recrystallized from chloroform to yield 0.66 g of 6-amino-7-fluoro-2-methyl-4-propargyl-2H-1,4-benzoxazin-3(4H)-one as a brown solid, m.p. 142°-145° C.

Workup

  1. temperaturecooling
  2. temperatureto warm to room temperature
  3. stirringstirred for 84 hours
  4. extractionThe resulting mixture was extracted with EtOAc (2×50 ml)
  5. washwashed with water (3×50 ml)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. customThe solvent was removed in vacuo
  9. customto yield a golden solid which
  10. customwas recrystallized from chloroform

Sources & evidence

ORD record
ord-0033a6a9fd3940968bd7e0009805da43
Source dataset
uspto-grants-1997_05
Patent number
US05631209

Reaction notes

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