Water → 3,5-Difluoro-4-(methylthio)benzaldehyde

HRID 47644Notes

Reaction equation

HRID 47644 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([F:11])[C:9]=1F)[CH:5]=[O:6].[CH3:12][S-:13].[Na+].O>C1COCC1>[F:1][C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([F:11])[C:9]=1[S:13][CH3:12])[CH:5]=[O:6]

Participants

5

Reactant 3

HCID 962WaterHCID 27769543,4,5-TrifluorobenzaldehydeHCID 4378561Sodium methanethiolate

Product 1

HCID 227466823,5-Difluoro-4-(methylthio)benzaldehydeYield 62.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 3,4,5-trifluorobenzaldehyde (30.0 g, 0.187 mol) in anhydrous THF (400 mL) cooled in a cold water bath was added sodium thiomethoxide (14.4 g, 0.20 mol) in portions over 30 minutes. The mixture was stirred at room temperature for 18 hours, then poured into water and extracted with dichloromethane (1×500 mL, 2×200 mL). The combined extracts were washed with water, dried using magnesium sulfate, and concentrated. Purification of the product by silica gel chromatography using 2% dichloromethane/5% ethyl acetate in hexanes gave the 3,5-difluoro-4-(methylthio)-benzaldehyde as a clear colorless liquid (22.0 g, 62%). 1H NMR (CDCl3/400 MHz) 9.86 (t, J=1.5, 1H), 7.34-7.39 (m, 2H), 2.55 (s, 3H). HRMS m/z 188.0099 (M+, calcd 188.0107).

Workup

  1. extractionextracted with dichloromethane (1×500 mL, 2×200 mL)
  2. washThe combined extracts were washed with water
  3. customdried
  4. concentrationconcentrated
  5. customPurification of the product by silica gel chromatography

Sources & evidence

ORD record
ord-5d227b58a8c147cabad50cee31c465e7
Source dataset
uspto-grants-2004_03
Patent number
US06699884B2

Reaction notes

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