N-bromobutanimide → 2-Bromomethyl-5-chloro-4-nitrobenzonitrile

HRID 1739835Notes

Reaction equation

[Cl:1][C:2]1[C:3]([N+:11]([O-:13])=[O:12])=[CH:4][C:5]([CH3:10])=[C:6]([CH:9]=1)[C:7]#[N:8].C1C(=O)N([Br:21])C(=O)C1>ClC1C=CC=CC=1.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[Br:21][CH2:10][C:5]1[CH:4]=[C:3]([N+:11]([O-:13])=[O:12])[C:2]([Cl:1])=[CH:9][C:6]=1[C:7]#[N:8]

Participants

Conditions

Temperature: 130 °C

Procedure

A mixture of 5-chloro-4-nitro-2-methylbenzonitrile (32.0 g, 0.16 mol), NBS (54.0 g, 0.30 mol) and benzoyl peroxide (200 mg, catalytic amount) in chlorobenzene was heated at 130° C. and irradiated with a sunlamp for 15 h. More NBS (30.0 g, 0.17 mol) and benzoyl peroxide (200 mg) were added. The mixture was further reacted for 24 h. After cooling, the precipitate formed was filtered off and washed with CH2Cl2. The combined filtrates were washed with H2O (2×), dried over anhydrous MgSO4 and concentrated in vacuo. The residue was then chromatographed over silica gel and eluted with hexanes:EtOAc (9:1) to give 2-bromomethyl-5-chloro-4-nitrobenzonitrile (48 g, contaminated with starting material and dibrominated product) as a pale yellow solid.

Workup

customirradiated with a sunlamp for 15 h
customThe mixture was further reacted for 24 h
temperatureAfter cooling
customthe precipitate formed
filtrationwas filtered off
washwashed with CH2Cl2
washThe combined filtrates were washed with H2O (2×)
dry with materialdried over anhydrous MgSO4
concentrationconcentrated in vacuo
customThe residue was then chromatographed over silica gel
washeluted with hexanes:EtOAc (9:1)

Sources & evidence

ORD record: ord-154b6c551aee4eeaa57aabc2ee6bcb65
Source dataset: uspto-grants-1999_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05968958

Reaction notes

Loading…