Sodium Iodide → Methyl 3-methoxy-4-(6-nitro-2,3-di-hydrobenz-1,4-oxazin-4-ylmethyl)benzoate

HRID 1086545Notes

Reaction equation

HRID 1086545 reaction equation
[N+:1]([C:4]1[CH:5]=[CH:6][C:7]2[O:12][CH2:11][CH2:10][NH:9][C:8]=2[CH:13]=1)([O-:3])=[O:2].Br[CH2:15][C:16]1[CH:25]=[CH:24][C:19]([C:20]([O:22][CH3:23])=[O:21])=[CH:18][C:17]=1[O:26][CH3:27].C(=O)([O-])[O-].[K+].[K+].[I-].[Na+]>CC(C)=O>[CH3:27][O:26][C:17]1[CH:18]=[C:19]([CH:24]=[CH:25][C:16]=1[CH2:15][N:9]1[C:8]2[CH:13]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=[CH:6][C:7]=2[O:12][CH2:11][CH2:10]1)[C:20]([O:22][CH3:23])=[O:21]

Participants

6

Reactant 4

HCID 5238Sodium IodideHCID 11430Potassium CarbonateHCID 2759828Methyl 4-(bromomethyl)-3-methoxybenzoateHCID 70622256-nitro-3,4-dihydro-2H-1,4-benzoxazine

Product 1

HCID 14763125Methyl 3-methoxy-4-(6-nitro-2,3-di-hydrobenz-1,4-oxazin-4-ylmethyl)benzoateYield 84%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

A mixture of 6-nitro-2,3-dihydrobenz-1,4-oxazine (0.45 g.), methyl 4-bromomethyl-3-methoxybenzoate (B) (0.65 g.), anhydrous potassium carbonate (0.35 g.), sodium iodide (0.38 g.) and acetone (25 ml.) was stirred and heated under reflux for 48 hours, under an atmosphere of nitrogen. The cooled reaction mixture was separated by filtration. The residue was washed with acetone, and the filtrate and washings were evaporated. The resulting solid was dissolved in dichloromethane and residual solid removed by filtration. The filtrate was evaporated. The product was purified by flash chromatography on silica gel (3 cm. diameter column), eluting with 1:10 v/v ethyl acetate: toluene, to give methyl 3-methoxy-4-(6-nitro-2,3-dihydrobenz-1,4-oxazin-4-ylmethyl)benzoate (G) (0.75 g., 84%), m.p. 130°-132° C: NMR (80 MHz, CDCl3) 3.0(t,2H, OCH2.CH2N), 3.8(s,3H, OCH3), 3.95(s,3H, OCH3), 4.3(t, 2H, OCH2.CH2N), 4.5(s,2H, CH2.Ar), 6.8(d,1H), 7.5(m, 5H).

Workup

  1. temperatureheated
  2. temperatureunder reflux for 48 hours, under an atmosphere of nitrogen
  3. customThe cooled reaction mixture
  4. customwas separated by filtration
  5. washThe residue was washed with acetone
  6. customthe filtrate and washings were evaporated
  7. dissolutionThe resulting solid was dissolved in dichloromethane
  8. customresidual solid removed by filtration
  9. customThe filtrate was evaporated
  10. customThe product was purified by flash chromatography on silica gel (3 cm. diameter column)
  11. washeluting with 1:10 v/v ethyl acetate

Sources & evidence

ORD record
ord-693c7cdc06b04e0eab56cd1ae8af56ef
Source dataset
uspto-grants-1991_07
Patent number
US05030643

Reaction notes

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