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

HRID 2394259Notes

Reaction equation

HRID 2394259 reaction equation
[NH2:1][C:2]1[CH:3]=[C:4]([CH:9]=[CH:10][C:11]=1[OH:12])[C:5]([O:7][CH3:8])=[O:6].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>[O:12]1[C:11]2[CH:10]=[CH:9][C:4]([C:5]([O:7][CH3:8])=[O:6])=[CH:3][C:2]=2[NH:1][C:20](=[O:21])[CH2:19]1

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-carboxylate

Reagents, catalysts & solvents 2

HCID 66133Benzyl triethylammonium chlorideCatalystHCID 6212ChloroformSolvent2×

Conditions

Temperature
0 °C

Procedure

In a 250 ml three-necked round-bottomed flask were placed methyl 3-amino-4-hydroxybenzoate (5 g, 30 mmole), benzyltriethylammonium chloride (6.8 g, 30 mmole), chloroform (75 ml) and powdered sodium bicarbonate (10.1 g, 120 mmole). The resulting mixture was cooled down to 0° C. and a solution of chloroacetyl chloride (4.1 g, 36 mmole) in chloroform (20 ml) was added dropwise at such a rate as to keep the reaction temperature between 0° C. to 3° C. After the addition was complete the reaction mixture was stirred at 0° C. for another 90 minutes, followed by slow heating to 55° C., kept at that temperature for 8 hours, and finally stirred at room temperature overnight. The solvent was removed in a rotary evaporator, the resulting crude product was taken up in water, shaken and filtered yielding, after drying in a vacuum oven, 5.8 g of the expected methyl 1,4-benzoxazine-3-one-6-carboxylate which was used in the next step without further purification.

Workup

  1. customIn a 250 ml three-necked round-bottomed flask were placed
  2. custombetween 0° C. to 3° C
  3. additionAfter the addition
  4. temperatureby slow heating to 55° C.
  5. waitkept at that temperature for 8 hours
  6. stirringfinally stirred at room temperature overnight
  7. customThe solvent was removed in a rotary evaporator
  8. stirringshaken
  9. filtrationfiltered
  10. customyielding
  11. dry with materialafter drying in a vacuum oven, 5.8 g of the expected methyl 1,4-benzoxazine-3-one-6-carboxylate which
  12. customwas used in the next step without further purification

Sources & evidence

ORD record
ord-313d536c43e04368ab504ad2b7478147
Source dataset
uspto-grants-1998_09
Patent number
US05811427

Reaction notes

Loading…