N-bromobutanimide → Methyl 6-(bromomethyl)pyridine-2-carboxylate

HRID 2112999Notes

Reaction equation

HRID 2112999 reaction equation
[Br:1]N1C(=O)CCC1=O.[CH3:9][O:10][C:11]([C:13]1[CH:18]=[CH:17][CH:16]=[C:15]([CH3:19])[N:14]=1)=[O:12]>C(Cl)(Cl)(Cl)Cl.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[CH3:9][O:10][C:11]([C:13]1[CH:18]=[CH:17][CH:16]=[C:15]([CH2:19][Br:1])[N:14]=1)=[O:12]

Participants

5

Reactant 2

HCID 67184N-bromobutanimide2×HCID 73022Methyl 6-methylpyridine-2-carboxylate

Product 1

HCID 21471714Methyl 6-(bromomethyl)pyridine-2-carboxylateYield 38.2%

Reagents, catalysts & solvents 2

HCID 7187Benzoyl PeroxideCatalyst2×HCID 5943Carbon TetrachlorideSolvent

Procedure

N-Bromosuccinimide (4.9 g, 27.3 mmol) was added in portions to a stirred solution of 6-methyl-pyridine-2-carboxylic acid methyl ester (3.90 g, 25.8 mmol) in carbon tetrachloride (100 mL). Dibenzoyl peroxide (20 mg) was added and the mixture was heated in an oil bath at 85 degrees for two days. TLC (eluting with dichloromethane) showed that there was unreacted starting material in addition to two new spots, so further quantities of N-bromosuccinimide (1.1 g, 6.1 mmol) and dibenzoyl peroxide (20 mg) were added and the reaction mixture was heated at reflux for 24 hours, and then filtered to remove succinimide. The filtrate was evaporated to give an oil that was chromatographed on silica gel (Biotage 90) eluting with 0-100% dichloromethane/hexanes to give 6-bromomethyl-pyridine-2-carboxylic acid methyl ester (2.27 g, 38%) as a crystalline solid. Mass spectrum m/z 230/232.

Workup

  1. temperaturethe mixture was heated in an oil bath at 85 degrees for two days
  2. washTLC (eluting with dichloromethane)
  3. additionwere added
  4. temperaturethe reaction mixture was heated
  5. temperatureat reflux for 24 hours
  6. filtrationfiltered
  7. customto remove succinimide
  8. customThe filtrate was evaporated
  9. customto give an oil that
  10. customwas chromatographed on silica gel (Biotage 90)
  11. washeluting with 0-100% dichloromethane/hexanes

Sources & evidence

ORD record
ord-b4eded7f3e8a4701a24b1d31a706b2c1
Source dataset
uspto-grants-2009_04
Patent number
US07524870B2

Reaction notes

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