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

HRID 899500Notes

Reaction equation

HRID 899500 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([CH3:11])[N:6]=1)=[O:4].C1C(=O)N([Br:19])C(=O)C1>C(Cl)(Cl)(Cl)Cl.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([CH2:11][Br:19])[N:6]=1)=[O:4]

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 73022Methyl 6-methylpyridine-2-carboxylate

Product 1

HCID 21471714Methyl 6-(bromomethyl)pyridine-2-carboxylateYield 20.2%

Reagents, catalysts & solvents 2

HCID 7187Benzoyl PeroxideCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

6-Bromomethyl-pyridine-2-carboxylic acid methyl ester was prepared according to Wells, G. J. et al. (WO 94/11398): A mixture of 6-methyl-pyridine-2-carboxylic acid methyl ester (6.5 g, 43.0 mmol), benzoyl peroxide (25 mg, 0.1 mmol) and NBS (8.5 g, 47.8 mmol) in carbon tetrachloride (250 mL) was heated at reflux overnight. The reaction mixture was cooled to room temperature, filtered, evaporated, and purified by chromatography on flash silica gel, eluting with 15% ethyl acetate/hexane to give 6-bromomethyl-pyridine-2-carboxylic acid methyl ester (2.0 g, 20%) as a white solid. 1HNMR (CDCl3): 6 8.06 (d, J=8.0 Hz, 1H), 7.87 (dd, J=8.0 Hz, 1H), 7.70 (d, J=8.0 Hz, 1H), 4.65 (s, 2H MS (APCI+): 231 (45), 235 (42).

Workup

  1. custom6-Bromomethyl-pyridine-2-carboxylic acid methyl ester was prepared
  2. temperaturewas heated
  3. temperatureat reflux overnight
  4. filtrationfiltered
  5. customevaporated
  6. custompurified by chromatography on flash silica gel
  7. washeluting with 15% ethyl acetate/hexane

Sources & evidence

ORD record
ord-1d7b259dd06740e08cb6f08f6644e98a
Source dataset
uspto-grants-2008_04
Patent number
US07355049B2

Reaction notes

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