Azobisisobutyronitrile → Methyl 2-(bromomethyl)-3-nitrobenzoate

HRID 718730Notes

Reaction equation

[CH3:1][C:2]1[C:11]([N+:12]([O-:14])=[O:13])=[CH:10][CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].C1C(=O)N([Br:22])C(=O)C1.CC(N=NC(C#N)(C)C)(C#N)C>C(Cl)Cl>[Br:22][CH2:1][C:2]1[C:11]([N+:12]([O-:14])=[O:13])=[CH:10][CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Participants

Conditions

Temperature: 60 °C

Procedure

To a solution of methyl 2-methyl-3-nitrobenzoate (5 g, 25.6 mmol) in dry DCM (20 mL) were added NBS (4.56 g, 25.6 mmol) and AIBN (0.421 g, 2.56 mmol) and the mixture was stirred at 60° C. After 20 h, additional AIBN (0.42 g) was added and the mixture continued to be stirred at 60° C. After 72 h, the mixture was filtered and concentrated. Purification by flash chromatography (100% hexanes to 10% EtOAC/hexanes) afforded 18 (5.2 g, 74%) as a light yellow solid. Rf=0.3 (9:1 hexanes:ethyl acetate). 1H NMR (400 MHz, CDCl3) δ 8.11 (dd, J=7.9, 1.4 Hz, 1H), 8.03-7.91 (m, 1H), 7.54 (dd, J=8.0 Hz, 8.0 Hz, 1H), 5.24-5.03 (s, 2H), 4.08-3.88 (s, 3H). MS (ESI) m/z calcd for C9H9BrNO4 [M+H]+ 275.1, found 275.5.

Workup

stirringto be stirred at 60° C
waitAfter 72 h
filtrationthe mixture was filtered
concentrationconcentrated
customPurification by flash chromatography (100% hexanes to 10% EtOAC/hexanes)

Sources & evidence

ORD record: ord-53c8bf18301c4da58f0af2061a9f3f04
Source dataset: uspto-grants-2015_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09193989B2

Reaction notes

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