Benzoic acid, 2-bromo-4-ethenyl-, 1,1-dimethylethyl ester → HCID 86675120, compound

HRID 1504613Notes

Reaction equation

Br[C:2]1[CH:14]=[C:13]([CH:15]=[CH2:16])[CH:12]=[CH:11][C:3]=1[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5].[Cu][C:18]#[N:19]>CN(C=O)C.O>[C:18]([C:2]1[CH:14]=[C:13]([CH:15]=[CH2:16])[CH:12]=[CH:11][C:3]=1[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5])#[N:19]

Participants

Conditions

Temperature: 140 °C

Procedure

To a stirred solution of tert-butyl 2-bromo-4-vinylbenzoate (0.5 g, 1.77 mmol) in DMF (20 mL) was added copper(I) cyanide (CuCN; 0.23 g, 2.65 mmol), and the reaction mixture was heated at 140° C. for 3 h. The reaction mixture was cooled to 25° C., diluted with H2O, and extracted with EtOAc. The combined organic layer was washed with brine, dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by flash chromatography (SiO2, 100-200 mesh; eluting with 15% EtOAc in n-hexane) to afford the title compound as a white solid (0.3 g, 72%): mp 51-53° C.; 1H NMR (400 MHz, CDCl3) δ 8.03 (s, 1H), 7.77 (s, 1H), 7.64 (d, J=8.4 Hz, 1H), 6.75 (dd, J=17.6, 10.8 Hz, 1H), 5.93 (d, J=17.6 Hz, 1H), 5.51 (d, J=10.8 Hz, 1H), 1.65 (s, 9H); ESIMS m/z 229.84 ([M+H]+); IR (thin film) 2370, 1709, 1142 cm−1.

Workup

temperatureThe reaction mixture was cooled to 25° C.
extractionextracted with EtOAc
washThe combined organic layer was washed with brine
dry with materialdried over Na2SO4
concentrationconcentrated under reduced pressure
customThe residue was purified by flash chromatography (SiO2, 100-200 mesh; eluting with 15% EtOAc in n-hexane)

Sources & evidence

ORD record: ord-c692837a6cb94455a26688c23462e02c
Source dataset: uspto-grants-2015_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09215870B2

Reaction notes

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