Trifluoromethanesulfonic acid → 5-Iodo-2,2-dimethyl-7-nitro-2h-1,4-benzoxazin-3(4h)-one

HRID 1929453Notes

Reaction equation

HRID 1929453 reaction equation
[CH3:1][C:2]1([CH3:16])[C:7](=[O:8])[NH:6][C:5]2[CH:9]=[CH:10][C:11]([N+:13]([O-:15])=[O:14])=[CH:12][C:4]=2[O:3]1.[B-](F)(F)(F)F.C1C=CN=CC=1.C1C=CN=CC=1.[IH2+:34].FC(F)(F)S(O)(=O)=O>ClCCl>[I:34][C:9]1[C:5]2[NH:6][C:7](=[O:8])[C:2]([CH3:16])([CH3:1])[O:3][C:4]=2[CH:12]=[C:11]([N+:13]([O-:15])=[O:14])[CH:10]=1

Participants

5

Reactant 3

HCID 62406Trifluoromethanesulfonic acidHCID 10883201Bis(pyridine)iodonium tetrafluoroborate2×HCID 127935432,2-Dimethyl-7-nitro-2H-benzo[b][1,4]oxazin-3(4H)-one

Product 1

HCID 667897445-Iodo-2,2-dimethyl-7-nitro-2h-1,4-benzoxazin-3(4h)-oneYield 57.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a suspension of 2,2-dimethyl-7-nitro-2H-1,4-benzoxazin-3(4H)-one (compound obtained in Reference Example 1(1), 1.00 g) in dichloromethane (50 mL) was added bis(pyridine)iodonium tetrafluoroborate (1.68 g), and the mixture was stirred at room temperature for 1 hour. To the reaction mixture were further added bis(pyridine)-iodonium tetrafluoroborate (0.84 g) and trifluoromethanesulfonic acid (1.2 mL), and the mixture was stirred at room temperature for 15 hours. The reaction mixture was concentrated in vacuo. The resultant residue was diluted with ethyl acetate, tetrahydrofuran and water, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with an aqueous saturated sodium hydrogencarbonate solution, an aqueous 15% sodium thiosulfate solution, water and brine, dried over sodium sulfate and concentrated in vacuo. The resultant residue was triturated in n-hexane/ethyl acetate to give 5-iodo-2,2-dimethyl-7-nitro-2H-1,4-benzoxazin-3(4H)-one (0.90 g) as a pale brown powder.

Workup

  1. stirringthe mixture was stirred at room temperature for 15 hours
  2. concentrationThe reaction mixture was concentrated in vacuo
  3. additionThe resultant residue was diluted with ethyl acetate, tetrahydrofuran and water
  4. extractionthe mixture was extracted with ethyl acetate
  5. washThe organic layer was washed successively with an aqueous saturated sodium hydrogencarbonate solution
  6. dry with materialan aqueous 15% sodium thiosulfate solution, water and brine, dried over sodium sulfate
  7. concentrationconcentrated in vacuo
  8. customThe resultant residue was triturated in n-hexane/ethyl acetate

Sources & evidence

ORD record
ord-80c831b77b754d6dadd7e2a33eb982d9
Source dataset
uspto-grants-2012_05
Patent number
US08188073B2

Reaction notes

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