Carbon Tetrachloride → 2-(Bromomethyl)-5-chloro-3-(2-(trifluoromethyl)-phenyl)quinoxaline

反応式

[Cl:1][C:2]1[CH:11]=[CH:10][CH:9]=[C:8]2[C:3]=1[N:4]=[C:5]([C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[C:19]([F:22])([F:21])[F:20])[C:6]([CH3:12])=[N:7]2.[Br:23]N1C(C)(C)C(=O)N(Br)C1=O.C(Cl)(Cl)(Cl)Cl.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>>[Br:23][CH2:12][C:6]1[C:5]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=2[C:19]([F:22])([F:20])[F:21])=[N:4][C:3]2[C:8](=[CH:9][CH:10]=[CH:11][C:2]=2[Cl:1])[N:7]=1

参加物

反応物 4

HCID 5943Carbon Tetrachloride

HCID 64791,3-Dibromo-5,5-dimethylhydantoin

HCID 7187Benzoyl Peroxide

HCID 577079875-Chloro-2-methyl-3-(2-(trifluoromethyl)phenyl)quinoxaline

生成物 1

HCID 577078262-(Bromomethyl)-5-chloro-3-(2-(trifluoromethyl)-phenyl)quinoxaline

実験手順

5-Chloro-2-methyl-3-(2-(trifluoromethyl)phenyl)quinoxaline (1.4455 g, 4.479 mmol) and 1,3-dibromo-5,5-dimethylhydantoin (0.6404 g, 2.240 mmol) were suspended in carbon tetrachloride (44.79 mL, 4.479 mmol). To the mixture was added benzoyl peroxide (0.1447 g, 0.4479 mmol) and the mixture was heated at reflux. After 21.5 h, the mixture was cooled to room temperature and concentrated under reduced pressure. The residue was purified by silica gel column chromatography on a 80 g of Redi-Sep™ column using 0 to 9% gradient of EtOAc in hexane over 2 min, then 9% isocratic of EtOAc for 13 min, then 9 to 100% gradient of EtOAc in hexane over 23 min, then 100% isocratic of EtOAc for 4 min as eluent to give 2-(bromomethyl)-5-chloro-3-(2-(trifluoromethyl)-phenyl)quinoxaline as a yellow solid: 1H NMR (400 MHz, DMSO-d6) δ ppm 8.18 (1 H, dd, J=8.4, 1.4 Hz), 8.13 (1 H, dd, J=7.8, 1.2 Hz), 7.81-8.03 (5 H, m), 4.69 (2 H, dd, J=88.4, 10.2 Hz); LC-MS (ESI) m/z 400.9 and 403.0 [M+H]+.