Di-tert-butyl dicarbonate → 7-bromo-6-methoxy-2-methyl-4H-3,1-benzoxazin-4-one

HRID 454502Notes

Reaction equation

HRID 454502 reaction equation
[C:1]([NH:4][C:5]1[CH:13]=[C:12]([Br:14])[C:11]([O:15][CH3:16])=[CH:10][C:6]=1[C:7]([OH:9])=[O:8])(=O)[CH3:2].C(OC(OC(C)(C)C)=O)(OC(C)(C)C)=O>CN(C)C1C=CN=CC=1.O1CCCC1>[Br:14][C:12]1[C:11]([O:15][CH3:16])=[CH:10][C:6]2[C:7](=[O:9])[O:8][C:1]([CH3:2])=[N:4][C:5]=2[CH:13]=1

Participants

5

Reactant 2

HCID 90495Di-tert-butyl dicarbonate2×HCID 669903374-Bromo-2-acetamido-5-methoxybenzoic acid

Product 1

HCID 669902127-bromo-6-methoxy-2-methyl-4H-3,1-benzoxazin-4-oneYield 87.1%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

4-(Dimethylamino)pyridine (63 mg) and 2-(acetamido)-4-bromo-5-methoxybenzoic acid (0.49 g) were added to a tetrahydrofuran (1.5 mL) solution of di-tert-butyl dicarbonate (0.75 g) at room temperature, followed by stirring at the same temperature for 4 hours and 15 minutes. Tetrahydrofuran (2 mL) was added to the reaction mixture at room temperature, followed by stirring at the same temperature for 3 days. (Di-tert-butyl)dicarbonate (0.37 g) was added to the reaction mixture at room temperature, followed by stirring at the same temperature for one day. The solvent was evaporated under reduced pressure, and ethyl acetate and a saturated aqueous solution of sodium bicarbonate were added to the residue. The organic layer was separated, washed with a 10% aqueous solution of citric acid and a saturated aqueous solution of sodium chloride sequentially, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. Hexane and diisopropyl ether were added to the obtained residue, and the solid substance was collected by filtration to obtain 0.40 g of 7-bromo-6-methoxy-2-methyl-4H-3,1-benzoxazin-4-one as a brown solid.

Workup

  1. stirringby stirring at the same temperature for 3 days
  2. stirringby stirring at the same temperature for one day
  3. customThe solvent was evaporated under reduced pressure, and ethyl acetate
  4. additiona saturated aqueous solution of sodium bicarbonate were added to the residue
  5. customThe organic layer was separated
  6. washwashed with a 10% aqueous solution of citric acid
  7. dry with materiala saturated aqueous solution of sodium chloride sequentially, and dried over anhydrous magnesium sulfate
  8. customthe solvent was evaporated under reduced pressure
  9. additionHexane and diisopropyl ether were added to the obtained residue
  10. filtrationthe solid substance was collected by filtration

Sources & evidence

ORD record
ord-b58aec6c666447418fba8bd375815e04
Source dataset
uspto-grants-2013_07
Patent number
US08492582B2

Reaction notes

Loading…