Ethanol → 4-(2-tert-Butyl-1,1-dioxido-3-oxoisothiazolidin-5-yl)-3-fluorobenzaldehyde

HRID 724733

Reaction equation

HRID 724733 reaction equation
[C:1]([N:5]1[C:9](=[O:10])[CH2:8][CH:7]([C:11]2[CH:16]=[CH:15][C:14]([CH:17](Br)Br)=[CH:13][C:12]=2[F:20])[S:6]1(=[O:22])=[O:21])([CH3:4])([CH3:3])[CH3:2].C([OH:25])C>O.[N+]([O-])([O-])=O.[Ag+]>[C:1]([N:5]1[C:9](=[O:10])[CH2:8][CH:7]([C:11]2[CH:16]=[CH:15][C:14]([CH:17]=[O:25])=[CH:13][C:12]=2[F:20])[S:6]1(=[O:22])=[O:21])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 2

HCID 702EthanolHCID 116339232-tert-Butyl-5-[4-(dibromomethyl)-2-fluorophenyl]isothiazolidin-3-one 1,1-dioxide

Product 1

HCID 116166194-(2-tert-Butyl-1,1-dioxido-3-oxoisothiazolidin-5-yl)-3-fluorobenzaldehydeYield 83%

Reagents, catalysts & solvents 2

HCID 24470Silver NitrateCatalystHCID 962WaterSolvent

Procedure

2-tert-Butyl-5-[4-(dibromomethyl)-2-fluorophenyl]isothiazolidin-3-one 1,1-dioxide (4.2 g, 9.2 mmol) and silver nitrate (3.12 g, 18.4 mmol) in ethanol (200 mL) and water (50 mL) were heated at reflux for 0.5 h. The solution was cooled to rt, filtered to remove precipitate, and concentrated to remove most of the ethanol. The residue was diluted with ethyl acetate (200 mL). The organic layer was washed with water (200 mL) and then dried over sodium sulfate. Concentration in vacuo followed by purification by silica gel chromatography (30% ethyl acetate:hexanes) afforded product as a white solid (2.4 g, 83%). 1H NMR (400 MHz, CDCl3): δ 10.0 (d, J=2.0 Hz, 1H), 7.78–7.75 (m,1H), 7.70–7.65 (m, 1H), 7.56–7.52 (m, 1H), 5.13 (dd, J=8.9, 6.6 Hz, 1H), 3.35 (dd, J=17.2, 8.9 Hz, 1H), 3.15 (dd, J=17.2, 6.6 Hz, 1H), 1.66 (s, 9H). LCMS found for C14H17FNNaO4S (M+Na)+: m/z=336.

Workup

  1. temperatureat reflux for 0.5 h
  2. filtrationfiltered
  3. customto remove precipitate
  4. concentrationconcentrated
  5. customto remove most of the ethanol
  6. additionThe residue was diluted with ethyl acetate (200 mL)
  7. washThe organic layer was washed with water (200 mL)
  8. dry with materialdried over sodium sulfate
  9. concentrationConcentration in vacuo
  10. customfollowed by purification by silica gel chromatography (30% ethyl acetate:hexanes)

Sources & evidence

ORD record
ord-6b74ef2a632e4fca8b875eb97718274f
Source dataset
uspto-grants-2006_11
Patent number
US07141596B2

Linked notes

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