Benzoyl Peroxide → 4-Bromo-3-(4-fluoro-phenyl)-7-hydroxy-thieno[3,2-c]pyridine-6-carboxylic acid methyl ester

HRID 1465953Notes

Reaction equation

HRID 1465953 reaction equation
[CH3:1][O:2][C:3]([C:5]1[N:10]=[CH:9][C:8]2[C:11]([C:14]3[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=3)=[CH:12][S:13][C:7]=2[C:6]=1[OH:21])=[O:4].[Br:22]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl>[CH3:1][O:2][C:3]([C:5]1[N:10]=[C:9]([Br:22])[C:8]2[C:11]([C:14]3[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=3)=[CH:12][S:13][C:7]=2[C:6]=1[OH:21])=[O:4]

Participants

5

Reactant 3

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 672328323-(4-Fluoro-phenyl)-7-hydroxy-thieno[3,2-c]pyridine-6-carboxylic acid methyl ester

Product 1

HCID 866075134-Bromo-3-(4-fluoro-phenyl)-7-hydroxy-thieno[3,2-c]pyridine-6-carboxylic acid methyl esterYield 61.8%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

A suspension of 3-(4-fluoro-phenyl)-7-hydroxy-thieno[3,2-c]pyridine-6-carboxylic acid methyl ester (100 mg, 0.33 mmol), example 31-f, N-bromosuccinimide (61.6 mg, 0.346 mmol), and benzoyl peroxide (8.0 mg, 0.033 mmol) in 0.83 mL of carbon tetrachloride was heated at reflux temperature for 5 hours. The reaction mixture was washed successively with saturated sodium bicarbonate, brine, saturated ammonium chloride solution, and brine. The organic solution was dried, filtered, and concentrated. The crude product was purified by flash chromatography eluting from silica gel with a gradient of 0-50% ethyl acetate in methylene chloride to produce 77.9 mg of a light yellow solid. MS: (−) m/z 380.3, 382.1 (M−1, 79Br/81Br).

Workup

  1. temperaturewas heated
  2. temperatureat reflux temperature for 5 hours
  3. washThe reaction mixture was washed successively with saturated sodium bicarbonate, brine, saturated ammonium chloride solution, and brine
  4. customThe organic solution was dried
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude product was purified by flash chromatography
  8. washeluting from silica gel with a gradient of 0-50% ethyl acetate in methylene chloride

Sources & evidence

ORD record
ord-5ecfebe9b7f54640a46948c26996d2e0
Source dataset
uspto-grants-2015_04
Patent number
US09000006B2

Reaction notes

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