N-bromobutanimide → Ethyl 6-(bromomethyl)picolinate

HRID 2112995

反応式

HRID 2112995 の反応式
[Br:1]N1C(=O)CCC1=O.[CH2:9]([O:11][C:12]([C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([CH3:20])[N:15]=1)=[O:13])[CH3:10]>C(Cl)(Cl)(Cl)Cl.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[CH2:9]([O:11][C:12]([C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([CH2:20][Br:1])[N:15]=1)=[O:13])[CH3:10]

参加物

5

反応物 2

HCID 67184N-bromobutanimide2 回HCID 564597Ethyl 6-methylpyridine-2-carboxylate

生成物 1

HCID 23033755Ethyl 6-(bromomethyl)picolinate収率 32.2%

試薬・触媒・溶媒 2

HCID 7187Benzoyl Peroxide触媒2 回HCID 5943Carbon Tetrachloride溶媒

実験手順

Finely ground N-bromo-succinimide (29.4 g, 165.2 mmol) was added in several portions to a solution of 6-methyl-pyridine-2-carboxylic acid ethyl ester (24.7 g, 150.0 mmol; available from Aldrich Chemical Company, Inc., Milwaukee, Wis.) in carbon tetrachloride (500 mL), and then benzoyl peroxide (100 mg, 0.4 mmol) was added. The mixture was heated at 84 degrees under nitrogen for approximately 40 h. Further portions of N-bromo-succinimide (14.8 g, 83.2 mmol) and then benzoyl peroxide (100 mg, 0.4 mmol) were added and heating was continued overnight. The reaction mixture was cooled to room temperature, filtered, evaporated, and purified by chromatography on silica gel using a Biotage system, eluting with 1:1 dichloromethane/hexane and dichloromethane to give 6-bromomethyl-pyridine-2-carboxylic acid ethyl ester (11.8 g, 32%) as a pale yellow oil. MS (MH+): 244/246. From HPLC, the purity was estimated at 85-90% and the material was used in the next step without further purification.

後処理

  1. temperatureThe mixture was heated at 84 degrees under nitrogen for approximately 40 h
  2. temperatureheating
  3. filtrationfiltered
  4. customevaporated
  5. custompurified by chromatography on silica gel using a Biotage system
  6. washeluting with 1:1 dichloromethane/hexane and dichloromethane

出典と根拠

ORDレコード
ord-782978d24abb48a3b96654c63a9d5596
出典データセット
uspto-grants-2009_04
特許番号
US07524870B2

関連ノート

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