Azobisisobutyronitrile → 2-Bromomethyl-3-fluoro-6-nitro-benzoic acid methyl ester

HRID 604263Notes

Reaction equation

[CH3:1][O:2][C:3](=[O:15])[C:4]1[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][CH:7]=[C:6]([F:13])[C:5]=1[CH3:14].[Br:16]N1C(=O)CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N>C(Cl)(Cl)(Cl)Cl>[CH3:1][O:2][C:3](=[O:15])[C:4]1[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][CH:7]=[C:6]([F:13])[C:5]=1[CH2:14][Br:16]

Participants

Conditions

Temperature: 85 °C

Procedure

To a suspension of 3-fluoro-2-methyl-6-nitro-benzoic acid methyl ester (6.1 g, 28.6 mmol) and N-bromosuccinimide in 70 mL of CCl4 is added 2,2′-azobisisobutyronitrile at room temperature under nitrogen atmosphere. The reaction mixture is stirred at 85° C. for 6 hours under N2, then cooled to room temperature and filtrated. The filtrate is extracted with CH2Cl2 and washed with aqueous NaHCO3 solution followed by brine, dried over Na2SO4, filtered and evaporated in vacuo. The residue is purified by silica gel column chromatography (n-hexane:ethyl acetate=4:1) to afford the 2-bromomethyl-3-fluoro-6-nitro-benzoic acid methyl ester (4.48 g, 15.3 mmol, 54%) as yellow oil. 1H-NMR (400 MHz, δ, ppm) CDCl3: 4.01 (s, 3H), 4.53 (d, 2H), 7.31 (dd, 1H), 8.17 (dd, 1H).

Workup

temperaturecooled to room temperature
filtrationfiltrated
extractionThe filtrate is extracted with CH2Cl2
washwashed with aqueous NaHCO3 solution
dry with materialdried over Na2SO4
filtrationfiltered
customevaporated in vacuo
customThe residue is purified by silica gel column chromatography (n-hexane:ethyl acetate=4:1)

Sources & evidence

ORD record: ord-80d4feb0551e4a54aecb612d0f5cd661
Source dataset: uspto-grants-2011_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07910585B2

Reaction notes

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