Sodium Thiosulfate → Methyl 7-bromo-1,1-dioxo-2,3-dihydro-1-benzothiepine-4-carboxylate

HRID 1978562Notes

Reaction equation

HRID 1978562 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2S[CH2:10][CH2:9][C:8]([C:12]([O:14][CH3:15])=[O:13])=[CH:7][C:6]=2[CH:16]=1.ClC1C=CC=C(C(OO)=O)C=1.[S:28]([O-:32])([O-])(=[O:30])=S.[Na+].[Na+]>C1COCC1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[S:28](=[O:32])(=[O:30])[CH2:10][CH2:9][C:8]([C:12]([O:14][CH3:15])=[O:13])=[CH:7][C:6]=2[CH:16]=1

Participants

5

Reactant 3

HCID 24477Sodium ThiosulfateHCID 70297m-Chloroperbenzoic acidHCID 18472606HCID 18472606, compound

Product 1

HCID 21995732Methyl 7-bromo-1,1-dioxo-2,3-dihydro-1-benzothiepine-4-carboxylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of methyl 7-bromo-2,3-dihydro-1-benzothiepine-4-carboxylate (0.8 g) in THF (10 ml) was added at 0° C. 70% 3-chloroperbenzoic acid (1.45 g), and the mixture was stirred at 0° C. for 30 minutes and further at room temperature for 1 hour. To the mixture was added an aqueous solution of sodium thiosulfate, and the mixture was stirred for a few minutes and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried with magnesium sulfate and concentrated under reduced pressure, and the residue was purified with column chromatography (ethyl acetate/hexane=1:1) and recrystallized from ethyl acetate/hexane to give pale yellow crystals of methyl 7-bromo-1,1-dioxo-2,3-dihydro-1-benzothiepine-4-carboxylate (827 mg). 1H-NMR (200 MHz, CDCl3) δ 3.11 (2H, t, J=6.5 Hz), 3.62 (2H, t, J=6.5 Hz), 3.87 (3H, s), 7.64-7.76 (3H, m), 8.03 (1H, d, J=8.4 Hz). IR (KBr) 1718, 1288, 1263, 1165, 1128, 1090, 797, 748 cm−1; Anal. for C12H11O4SBr; Calcd. C, 43.52; H, 3.35; Found. C, 43.39; H, 3.38.

Workup

  1. extractionextracted with ethyl acetate
  2. washThe organic layer was washed with saturated brine
  3. dry with materialdried with magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customthe residue was purified with column chromatography (ethyl acetate/hexane=1:1)
  6. customrecrystallized from ethyl acetate/hexane

Sources & evidence

ORD record
ord-402b477cc438481db20cb06586e0a44e
Source dataset
uspto-grants-2001_05
Patent number
US06235771B1

Reaction notes

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