Chloroacetyl chloride → Methyl 3-oxo-3,4-dihydro-2H-1,4-benzoxazine-6-carboxylate

HRID 2261101Notes

Reaction equation

HRID 2261101 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([OH:10])=[C:6]([NH2:11])[CH:5]=1.C([O-])(O)=O.[Na+].Cl[CH2:19][C:20](Cl)=[O:21]>[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1.C(Cl)(Cl)Cl>[CH3:1][O:2][C:3]([C:4]1[CH:9]=[CH:8][C:7]2[O:10][CH2:19][C:20](=[O:21])[NH:11][C:6]=2[CH:5]=1)=[O:12]

Participants

6

Reactant 3

HCID 6577Chloroacetyl chlorideHCID 10815Methyl 3-amino-4-hydroxybenzoateHCID 516892Sodium Bicarbonate

Product 1

HCID 2974054Methyl 3-oxo-3,4-dihydro-2H-1,4-benzoxazine-6-carboxylateYield 84.1%

Reagents, catalysts & solvents 2

HCID 66133Benzyl triethylammonium chlorideCatalystHCID 6212ChloroformSolvent2×

Conditions

Temperature
-5 °C

Procedure

To a mixture of methyl-3-amino-4-hydroxybenzoate (105 g, 0.62 mol) and benzyltriethylammonium chloride (142 g, 0.62 mol) in dry CHCl3 (1.5 L) was added NaHCO3 (211 g, 2.5 mol) with stirring. The reaction mixture was cooled to −5° C., added chloroacetylchloride (85 g, 0.75 mol) in dry CHCl3 (350 mL) over a period of 1.5 h at the same temperature. The reaction mixture was then heated to 55° C. for 16 h. The solvent was removed under vacuum, added water (3 L) and filtered off the solid. The solid product was dried and recrystallised from ethanol to give methyl-3-oxo-3,4-dihydro-2H-1,4-benzoxazin-6-carboxylate (108 g, 83%).

Workup

  1. temperatureThe reaction mixture was then heated to 55° C. for 16 h
  2. customThe solvent was removed under vacuum
  3. additionadded water (3 L)
  4. filtrationfiltered off the solid
  5. customThe solid product was dried
  6. customrecrystallised from ethanol

Sources & evidence

ORD record
ord-f35491cda79b452aa29993b097748b9e
Source dataset
uspto-grants-2010_12
Patent number
US07846925B2

Reaction notes

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