Benzoyl Peroxide → (E)-4-bromo-3-(2-methylsulfanyl-phenoxy)-but-2-enoic acid ethyl ester

HRID 19212Notes

Reaction equation

HRID 19212 reaction equation
[CH2:1]([O:3][C:4](=[O:17])/[CH:5]=[C:6](/[O:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[S:15][CH3:16])\[CH3:7])[CH3:2].[Br:18]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl>[CH2:1]([O:3][C:4](=[O:17])/[CH:5]=[C:6](/[O:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[S:15][CH3:16])\[CH2:7][Br:18])[CH3:2]

Participants

5

Reactant 3

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 66893823(E)-3-(2-methylsulfanyl-phenoxy)-but-2-enoic acid ethyl ester

Product 1

HCID 66893646(E)-4-bromo-3-(2-methylsulfanyl-phenoxy)-but-2-enoic acid ethyl esterYield 38%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

To a stirred mixture of (E)-3-(2-methylsulfanyl-phenoxy)-but-2-enoic acid ethyl ester (1.00 g, 0.004 mol) in carbon tetrachloride (15 mL) under a nitrogen atmosphere was added N-bromosuccinimide (1.00 g, 0.006 mol) and benzoyl peroxide (0.13 g, 0.001 mol). Nitrogen gas was bubbled through the mixture for 5 min, and the resulting mixture was heated to reflux for 4 h. The reaction mixture was then placed in the refrigerator overnight. The solids formed were removed by filtration and the filtrate concentrated in vacuo. The crude product obtained was purified using flash column chromatography (silica gel (100-200 mesh), ethyl acetate/hexanes) to afford (E)-4-bromo-3-(2-methylsulfanyl-phenoxy)-but-2-enoic acid ethyl ester (0.50 g, 38%) as a yellow oil: LR-ES-MS m/z calculated for C13H15BrO3S [M]+ 330, observed 333.

Workup

  1. customNitrogen gas was bubbled through the mixture for 5 min
  2. temperaturethe resulting mixture was heated
  3. temperatureto reflux for 4 h
  4. customwas then placed in the refrigerator overnight
  5. customThe solids formed
  6. customwere removed by filtration
  7. concentrationthe filtrate concentrated in vacuo
  8. customThe crude product obtained
  9. customwas purified

Sources & evidence

ORD record
ord-4f76b157534c4055aaf0e30f37a48f33
Source dataset
uspto-grants-2010_06
Patent number
US07741327B2

Reaction notes

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