Azobisisobutyronitrile → Methyl 3-(bromomethyl)-1-benzothiophene-2-carboxylate

HRID 1918793Notes

Reaction equation

HRID 1918793 reaction equation
[CH3:1][C:2]1[C:3]2[CH:14]=[CH:13][CH:12]=[CH:11][C:4]=2[S:5][C:6]=1[C:7]([O:9][CH3:10])=[O:8].[Br:15]N1C(=O)CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N>C1C=CC=CC=1>[Br:15][CH2:1][C:2]1[C:3]2[CH:14]=[CH:13][CH:12]=[CH:11][C:4]=2[S:5][C:6]=1[C:7]([O:9][CH3:10])=[O:8]

Participants

5

Reactant 3

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 268658Methyl 3-methylbenzo[b]thiophene-2-carboxylate

Product 1

HCID 21251535Methyl 3-(bromomethyl)-1-benzothiophene-2-carboxylateYield 82%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A 250-mL single-neck round-bottomed flask equipped with a magnetic stirrer, nitrogen inlet and reflux condenser was purged with nitrogen and charged with methyl 3-methylbenzo[b]thiophene-2-carboxylate (2.00 g, 9.70 mmol) and benzene (20 mL). N-bromosuccinimide (1.72 g, 9.70 mmol) and 2,2′-azobisisobutyronitrile (160 mg, 1.00 mmol) were added, and the mixture was refluxed for 2 h. After this time, the mixture was cooled to room temperature and filtered. The filter cake was rinsed with carbon tetrachloride (20 mL) and the filtrate was concentrated under reduced pressure. The resulting residue was purified by column chromatography to afford 103a in 82% yield (2.27 g) as a white solid: mp 101-102° C.; 1H NMR (500 MHz, CDCl3) d 7.97 (m, 1H), 7.86 (m, 1H), 7.51 (m, 2H), 5.22 (s, 2H), 3.97 (s, 3H).

Workup

  1. customA 250-mL single-neck round-bottomed flask equipped with a magnetic stirrer, nitrogen inlet
  2. temperaturereflux condenser
  3. customwas purged with nitrogen
  4. temperaturethe mixture was refluxed for 2 h
  5. filtrationfiltered
  6. washThe filter cake was rinsed with carbon tetrachloride (20 mL)
  7. concentrationthe filtrate was concentrated under reduced pressure
  8. customThe resulting residue was purified by column chromatography

Sources & evidence

ORD record
ord-4daa65e403d249bc8eb62e862bde1df3
Source dataset
uspto-grants-2013_12
Patent number
US08618107B2

Reaction notes

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