Water → 2H-3,1-Benzoxazine-2,4(1H)-dione, 6-chloro-1-methyl-

HRID 2244346Notes

Reaction equation

HRID 2244346 reaction equation
[Cl:1][C:2]1[CH:13]=[CH:12][C:5]2[NH:6][C:7](=[O:11])[O:8][C:9](=[O:10])[C:4]=2[CH:3]=1.[H-].[Na+].[CH3:16]I.O>CN(C=O)C>[Cl:1][C:2]1[CH:13]=[CH:12][C:5]2[N:6]([CH3:16])[C:7](=[O:11])[O:8][C:9](=[O:10])[C:4]=2[CH:3]=1

Participants

6

Reactant 4

HCID 962WaterHCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 784805-Chloroisatoic anhydride

Product 1

HCID 267242H-3,1-Benzoxazine-2,4(1H)-dione, 6-chloro-1-methyl-

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 1 g of 6-chloro-1H-benzo[d][1,3]oxazine-2,4-dione (5.06 mmol) in DMF (20 ml) were carefully added 265 mg of sodium hydride (55% dispersion in oil, 6.07 mmol) at 0° C. and the mixture was stirred at RT for 30 min. Then 0.47 ml of methyl iodide (7.60 mmol) were added and stirring at RT was continued over night. Water was added and the resulting mixture was extracted with ethyl acetate. The combined organic extracts were washed with brine, dried (MgSO4), filtered and concentrated and the remaining residue was purified by crystallization from heptane. This yielded 513 mg of 6-chloro-1-methyl-1H-benzo[d][1,3]oxazine-2,4-dione (48%) as an off-white solid. 1HNMR (DMSO-d6, 300 MHz): δ 3.45 (s, 3H), 7.47 (d, J=8.9 Hz, 1H), 7.89 (dd, J=8.9 and 2.7 Hz, 1H), 7.95 (d, J=2.7 Hz, 1H).

Workup

  1. customat 0° C.
  2. stirringstirring at RT
  3. waitwas continued over night
  4. extractionthe resulting mixture was extracted with ethyl acetate
  5. washThe combined organic extracts were washed with brine
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customthe remaining residue was purified by crystallization from heptane

Sources & evidence

ORD record
ord-dbda843fd2544ac1a50f65a1b6b458aa
Source dataset
uspto-grants-2010_03
Patent number
US07678818B2

Reaction notes

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