Dimethyl Sulfoxide → 4-Fluoro-2-methylsulfinylbenzaldehyde

HRID 2214670Notes

Reaction equation

HRID 2214670 reaction equation
[F:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[C:4]([S:10][CH3:11])[CH:3]=1.ClC1C=CC=C(C(OO)=[O:20])C=1.[CH3:23][S:24]([CH3:26])=[O:25].C([O-])(O)=[O:28].[Na+]>C(Cl)Cl>[F:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[C:23]([S:24]([CH3:26])(=[O:20])=[O:25])[CH:3]=1.[F:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[C:4]([S:10]([CH3:11])=[O:28])[CH:3]=1

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 70297m-Chloroperbenzoic acidHCID 516892Sodium BicarbonateHCID 219474094-Fluoro-2-(methylthio)benzaldehyde

Product 2

HCID 219474744-Fluoro-2-methylsulfinylbenzaldehydeYield 53%HCID 219474804-Fluoro-2-methylsulfonylbenzaldehydeYield 33%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 4-fluoro-2-methylsulfanylbenzaldehyde (9.7 g, 57 mmol) in CH2Cl2 (300 mL) was added in small portions m-chloroperbenzoic acid (60%, 20.71 g, 120 mmol) over 20 minutes. After 24 h, mL of dimethylsulfoxide followed by saturated NaHCO3 (100 mL) was added and stirred for additional 2 h. The organic layer separated and washed with saturated NaHCO3 (2×100 mL). The combined aqueous layers were saturated with NaCl and extracted with CH2Cl2 (2×100 mL). The combined organic phases were dried over anhydrous Na2SO4, filtered and concentrated to give a viscous yellow oil. This residue was purified by flash chromatography on a silica gel column using hexanes/ether/ethyl acetate (gradient elution). The fractions containing the desired product are combined and concentrated to give 4-fluoro-2-methylsulfonylbenzaldehyde (3.85 g, 33%) and 4-fluoro-2-methylsulfinylbenzaldehyde (5.61 g, 53% yield) as a white solid. 4-fluoro-2-methylsulfonylbenzaldehyde: 1HNMR (500 MHz, CDCl3) δ: 10.41 (1H, s), 8.08–8.06 (1H, M), 7.85–7.71 (2H, m), 3.09 (3H, s). HRMS calcd for C8H6FO3S (M−H): 201.0022. found: 201.0025. 4-fluoro-2-methylsulfinyl-benzaldehyde: 1HNMR (500 MHz, CDCl3) δ: 9.97 (1H, s), 8.07–8.05 (1H, M), 7.99–7.94 (1H, m), 7.36–7.33 (1H, m), 2.80 (3H, s). MS calcd for C8H8FO2S (M+H): 187.02. found: 187.02.

Workup

  1. additionwas added
  2. customThe organic layer separated
  3. washwashed with saturated NaHCO3 (2×100 mL)
  4. extractionextracted with CH2Cl2 (2×100 mL)
  5. dry with materialThe combined organic phases were dried over anhydrous Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto give a viscous yellow oil
  9. customThis residue was purified by flash chromatography on a silica gel column
  10. additionThe fractions containing the desired product
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-61c01fbfeebe4241992787bc4e9925df
Source dataset
uspto-grants-2006_09
Patent number
US07109186B2

Reaction notes

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