Water → 2-Fluoro-4-(3-trifluoromethylphenylthio)benzaldehyde

HRID 445422

Reaction equation

HRID 445422 reaction equation
C(N(C(C)C)C(C)C)C.[F:10][C:11]([F:20])([F:19])[C:12]1[CH:13]=[C:14]([SH:18])[CH:15]=[CH:16][CH:17]=1.Br[C:22]1[CH:29]=[CH:28][C:25]([CH:26]=[O:27])=[C:24]([F:30])[CH:23]=1.O>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C(Cl)(Cl)Cl.[Pd].[Pd].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>[F:30][C:24]1[CH:23]=[C:22]([S:18][C:14]2[CH:15]=[CH:16][CH:17]=[C:12]([C:11]([F:10])([F:19])[F:20])[CH:13]=2)[CH:29]=[CH:28][C:25]=1[CH:26]=[O:27]

Participants

8

Reactant 4

HCID 962WaterHCID 81531DiisopropylethylamineHCID 1367513-(Trifluoromethyl)benzenethiolHCID 1435174-Bromo-2-fluorobenzaldehyde

Product 1

HCID 580226012-Fluoro-4-(3-trifluoromethylphenylthio)benzaldehydeYield 68%

Reagents, catalysts & solvents 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 11029508Palladium, tris[mu-[(1,2-eta:4,5-eta)-(1E,4E)-1,5-diphenyl-1,4-pentadien-3-one]]di-, compd. with trichloromethane (1:1)CatalystHCID 312751,4-DioxaneSolvent

Procedure

Under an argon atmosphere, ethyldiisopropylamine (7.0 mL), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (518 mg), xantphos (578 mg), and 3-trifluoromethylthiophenol (3.56 g) were added at room temperature into a solution of 4-bromo-2-fluorobenzaldehyde (4.06 g) in 1,4-dioxane (42 mL), and the resultant solution was heated to reflux for 5 hours. To the reaction solution added water, extracted with ethyl acetate, washed with water and saturated brine in that order, and then dried over anhydrous sodium sulfate. The solvent was evaporated, and the resultant residue was purified by silica gel column chromatography (hexane:ethyl acetate=30:1) to obtain the target product (4.08 g) as a colorless oil.

Workup

  1. temperatureto reflux for 5 hours
  2. extractionextracted with ethyl acetate
  3. washwashed with water and saturated brine in that order
  4. dry with materialdried over anhydrous sodium sulfate
  5. customThe solvent was evaporated
  6. customthe resultant residue was purified by silica gel column chromatography (hexane:ethyl acetate=30:1)

Sources & evidence

ORD record
ord-ba81324ddb7f4c3b85a8c5cb1aea8a62
Source dataset
uspto-grants-2013_07
Patent number
US08476305B2

Linked notes

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