N-bromobutanimide → 2-[(3-Bromo-5-chlorophenyl)oxy]-4-(bromomethyl)-1-chloro-3-fluorobenzene

HRID 1874937Notes

Reaction equation

[Br:1]N1C(=O)CCC1=O.[Br:9][C:10]1[CH:11]=[C:12]([O:17][C:18]2[C:23]([F:24])=[C:22]([CH3:25])[CH:21]=[CH:20][C:19]=2[Cl:26])[CH:13]=[C:14]([Cl:16])[CH:15]=1>C(Cl)(Cl)(Cl)Cl.CC(N=NC(C#N)(C)C)(C#N)C>[Br:9][C:10]1[CH:11]=[C:12]([O:17][C:18]2[C:23]([F:24])=[C:22]([CH2:25][Br:1])[CH:21]=[CH:20][C:19]=2[Cl:26])[CH:13]=[C:14]([Cl:16])[CH:15]=1

Participants

Conditions

Temperature: 90 °C

Procedure

N-bromosuccinimide (1.95 g, 10.94 mmol) was added to a solution of 2-[(3-bromo-5-chlorophenyl)oxy]-1-chloro-3-fluoro-4-methylbenzene (3.20 g, 9.12 mmol) in CCl4 (300 mL) at RT. The solution was heated to 90° C. for 5 min under N2 and AIBN (0.070 g, 0.46 mmol) was added. After 4 h, more AIBN (0.070 g, 0.46 mmol) was added and the solution was heated at 90° C. for an additional 2 h. The solution was cooled to 0° C., filtered through Celite and concentrated. The yellow oil was purified by column chromatography (0% to 30% EtOAc/hexanes gradient) to afford the title compound (3.2 g, 60%) as a clear oil 1H NMR (400 MHz, DMSO-d6): δ ppm 7.58-7.49 (m, 3H), 7.13-7.12 (m, 1H), 7.06-7.05 (m, 1H), 4.73 (s, 2H). In addition, 2.25 g (48%) of the di-brominated material, 12-[(3-bromo-5-chlorophenyl)oxy]-1-chloro-4-(dibromomethyl)-3-fluorobenzene was also obtained as a clear oil. 1H NMR (400 MHz, DMSO-d6): δ ppm 7.72-7.68 (m, 1H), 7.61 (dd, 1H), 7.51 (t, 1H), 7.47 (s, 1H), 7.19-7.18 (m, 1H), 7.11 (t, 1H).

Workup

temperaturethe solution was heated at 90° C. for an additional 2 h
temperatureThe solution was cooled to 0° C.
filtrationfiltered through Celite
concentrationconcentrated
customThe yellow oil was purified by column chromatography (0% to 30% EtOAc/hexanes gradient)

Sources & evidence

ORD record: ord-a604b70fc37343d2999acd741f37eac1
Source dataset: uspto-grants-2012_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08304419B2

Reaction notes

Loading…