Azobisisobutyronitrile → 2-Bromo-5-(chloromethyl)-3-fluoropyridine

反応式

[Br:1][C:2]1[N:7]=[CH:6][C:5]([CH3:8])=[CH:4][C:3]=1[F:9].BrN1C(=O)CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N.[Cl:30]C1C=CC=CC=1>>[Br:1][C:2]1[N:7]=[CH:6][C:5]([CH2:8][Cl:30])=[CH:4][C:3]=1[F:9]

参加物

反応物 4

HCID 6547Azobisisobutyronitrile

HCID 7964Chlorobenzene

HCID 67184N-bromobutanimide

HCID 135375362-Bromo-3-fluoro-5-methylpyridine

生成物 1

HCID 190020622-Bromo-5-(chloromethyl)-3-fluoropyridine収率 42%

実験手順

10.00 g (52.63 mmol) of 6-bromo-5-fluoro-3-methylpyridin (cf. F. L. Setliff, Organic Preparations and Procedures International 1971, 3, 217-222), 12.18 g (68.42 mmol) of N-bromosuccinimide and 0.86 g (5.26 mmol) of 2,2′-azobis(2-methylpropanenitrile) in 1 of chlorobenzene are boiled under reflux for 6 hours. The reaction mixture is washed with saturated aqueous sodium sulphite solution and sodium bicarbonate solution and then dried over sodium sulphate and concentrated under reduced pressure. Column chromatography of the residue on silica gel (silica gel 60-Merck, particle size: 0.04 to 0.063 mm) using the mobile phase mixture ethyl acetate:cyclohexane (1:20) gives 6.0 g (42% of theory) of 6-bromo-3-chloromethyl-5-fluoropyridine.