Nitromethane → (E)-3,3-dimethyl-6-(2-nitrovinyl)benzo[c][1,2]oxaborol-1(3H)-ol

HRID 1037036Notes

Reaction equation

[OH:1][B:2]1[C:6]2[CH:7]=[C:8]([CH:11]=O)[CH:9]=[CH:10][C:5]=2[C:4]([CH3:14])([CH3:13])[O:3]1.[CH3:15][N+:16]([O-:18])=[O:17].CC(=O)OCC>CC(O)=O.O>[CH3:13][C:4]1([CH3:14])[O:3][B:2]([OH:1])[C:6]2[CH:7]=[C:8](/[CH:11]=[CH:15]/[N+:16]([O-:18])=[O:17])[CH:9]=[CH:10][C:5]1=2

Participants

Conditions

Temperature: 100 °C

Procedure

To a solution of 1-hydroxy-3,3-dimethyl-1,3-dihydrobenzo[c][1,2]oxaborole-6-carbaldehyde (1.14 g, 6 mmol) and NH4OAc (47 mg, 0.6 mmol) in AcOH (10 mL) at rt was added CH3NO2 (10 mL). The reaction mixture was stirred at 100° C. for 3 h and diluted with H2O. The mixture was extracted with EA and the organic layer was separated. The organic solution was washed with brine, dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel by elution with PE:EA (2:1 to 1:1) to give (E)-3,3-dimethyl-6-(2-nitrovinyl)benzo[c][1,2]oxaborol-1(3H)-ol as a yellow solid (750 mg, yield 53%). 1F1 NMR (500 MHz, CDCl3) δ 9.18 (s, 1H), 8.18 (s, 2H), 8.01 (s, 1 H), 7.99 (d, J=8.0 Hz, 1 H), 7.57 (d, J=8.0 Hz, 1 H), 1.46 (s, 6H) ppm; MS: m/z=234.1 (M+1, ESI+).

Workup

extractionThe mixture was extracted with EA
customthe organic layer was separated
washThe organic solution was washed with brine
dry with materialdried over Na2SO4
filtrationfiltered
concentrationconcentrated under reduced pressure
customThe residue was purified by column chromatography on silica gel by elution with PE

Sources & evidence

ORD record: ord-c63d5eb0d7874dd3a6473a850f8aaf31
Source dataset: uspto-grants-2013_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08546357B2

Reaction notes

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