Thiophenol → Acetic acid, difluoro(phenylthio)-, ethyl ester

HRID 520423Notes

Reaction equation

HRID 520423 reaction equation
[H-].[Na+].[C:3]1([SH:9])[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.Br[C:11]([F:18])([F:17])[C:12]([O:14][CH2:15][CH3:16])=[O:13]>CS(C)=O>[F:17][C:11]([F:18])([S:9][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1)[C:12]([O:14][CH2:15][CH3:16])=[O:13]

Participants

5

Reactant 3

HCID 7969ThiophenolHCID 24758Sodium hydrideHCID 69585Ethyl bromodifluoroacetate

Product 1

HCID 10775925Acetic acid, difluoro(phenylthio)-, ethyl esterYield 84%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

60% NaH (0.233 g, 5.81 mmol) was added to a cold (0° C.) solution of thiophenol (0.566 mL, 5.54 mmol) in DMSO (6 mL) and the reaction mixture was allowed to warm to rt over 30 min. Then neat ethyl 2-bromo-2,2-difluoroacetate (1.236 g, 6.09 mmol) was added and the mixture was stirred at rt overnight. The reaction was quenched with satd. NH4Cl and extracted with ether, washed with water, brine and dried (MgSO4). The crude isolate was purified by silica gel FCC (1:1 DCM-hexanes) to afford ethyl 2,2-difluoro-2-(phenylthio)acetate as a clear oil (1.076 g, 84%): 1H NMR (500 MHz, CHLOROFORM-d) δ 7.67-7.62 (m, 2H), 7.52-7.46 (m, 1H), 7.45-7.39 (m, 2H), 4.27 (q, J=7.2 Hz, 2H), 1.28 (t, J=7.2 Hz, 3H).

Workup

  1. customThe reaction was quenched with satd
  2. extractionNH4Cl and extracted with ether
  3. washwashed with water, brine
  4. dry with materialdried (MgSO4)
  5. customThe crude isolate
  6. customwas purified by silica gel FCC (1:1 DCM-hexanes)

Sources & evidence

ORD record
ord-b1a5376ce90041fe86ea4f000ead76db
Source dataset
uspto-grants-2016_05
Patent number
US09326973B2

Reaction notes

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