2-(4-Fluoro-3-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane → 2-Fluoro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline
Reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([B:8]2[O:12][C:11]([CH3:14])([CH3:13])[C:10]([CH3:16])([CH3:15])[O:9]2)=[CH:4][C:3]=1[N+:17]([O-])=O>[Pd].C(OCC)(=O)C>[F:1][C:2]1[CH:7]=[CH:6][C:5]([B:8]2[O:12][C:11]([CH3:14])([CH3:13])[C:10]([CH3:16])([CH3:15])[O:9]2)=[CH:4][C:3]=1[NH2:17]Participants
Procedure
A 500-mL Parr reactor bottle was purged with nitrogen and charged with 13 (6.92 g, 25.9 mmol), ethyl acetate (150 mL) and 10% palladium on carbon (50% wet, 150 mg dry weight). The bottle was attached to Parr hydrogenator, evacuated, charged with hydrogen gas to a pressure of 50 psi and shaken for 2 h. After this time the hydrogen was evacuated and nitrogen charged into the reactor. The catalyst was removed by filtration through a pad of Celite 521 and the filter cake washed with methylene chloride (400 mL). The resulting solution was concentrated under reduced pressure to afford 14 in 100% yield (6.34 g) as a yellow oil: 1H NMR (500 MHz, CDCl3) δ 7.22 (dd, 1H, J=8.5, 1.0 Hz), 7.16 (m, 1H), 6.97 (dd, 1H, J=11.5, 8.0 Hz), 3.68 (br s, 2H), 1.33 (m, 12H); MS (ESI+) m/z 238.2 (M+H).
Workup
- customA 500-mL Parr reactor bottle was purged with nitrogen
- customevacuated
- additioncharged with hydrogen gas to a pressure of 50 psi
- customAfter this time the hydrogen was evacuated
- additionnitrogen charged into the reactor
- customThe catalyst was removed by filtration through a pad of Celite 521
- washthe filter cake washed with methylene chloride (400 mL)
- concentrationThe resulting solution was concentrated under reduced pressure
Sources & evidence
- ORD record
- ord-5be152da5d064a53a67feae13ba544c3
- Source dataset
- uspto-grants-2013_12
- Patent number
- US08598174B2
Reaction notes
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