Benzoyl Peroxide → 4-Bromomethyl-2-(methyl-phenyl-amino)-thiazole-5-carboxylic acid ethyl ester

HRID 642308Notes

Reaction equation

HRID 642308 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[S:10][C:9]([N:11]([CH3:18])[C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[N:8][C:7]=1[CH3:19])=[O:5])[CH3:2].[Br:20]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]([C:6]1[S:10][C:9]([N:11]([CH3:18])[C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[N:8][C:7]=1[CH2:19][Br:20])=[O:5])[CH3:2]

Participants

5

Reactant 3

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 130483514-Methyl-2-(methyl-phenyl-amino)-thiazole-5-carboxylic acid ethyl ester

Product 1

HCID 684285544-Bromomethyl-2-(methyl-phenyl-amino)-thiazole-5-carboxylic acid ethyl ester

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

A mixture of 4-methyl-2-(methyl-phenyl-amino)-thiazole-5-carboxylic acid ethyl ester (3.32 g, 12.0 mmol), N-bromosuccinimide (2.35 g, 13.2 mol) and benzoyl peroxide (291 mg, 1.2 mmol) in carbon tetrachloride (45 mL) was refluxed for 17 h before it was cooled to room temperature and partitioned between dichloromethane and water. The organic layer was washed with saturated aqueous sodium bicarbonate solution, brine, dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel with a gradient of ethyl acetate and hexanes to give the title compound as a yellow oil: MS: (+) m/z 354.9, 356.9 (M+1, 79Br/81Br).

Workup

  1. temperaturewas refluxed for 17 h before it
  2. custompartitioned between dichloromethane and water
  3. washThe organic layer was washed with saturated aqueous sodium bicarbonate solution, brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by flash column chromatography on silica gel with a gradient of ethyl acetate and hexanes

Sources & evidence

ORD record
ord-94cea0566fd2428cb074f5c836b91187
Source dataset
uspto-grants-2010_04
Patent number
US07696223B2

Reaction notes

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