tert-Butanol → Tert-butyl (6-bromoquinolin-3-yl)carbamate
Reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N:8]=[CH:7][C:6](C(O)=O)=[CH:5]2.C([N:17]([CH2:20]C)CC)C.C1C=CC(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:29])=CC=1.[C:39]([OH:43])([CH3:42])([CH3:41])[CH3:40]>>[C:39]([O:43][C:20](=[O:29])[NH:17][C:6]1[CH:7]=[N:8][C:9]2[C:4]([CH:5]=1)=[CH:3][C:2]([Br:1])=[CH:11][CH:10]=2)([CH3:42])([CH3:41])[CH3:40]Participants
Procedure
A solution of 6-bromo-quinoline-3-carboxylic acid (500 mg, 1.98 mmol) and triethylamine (3.97 mmol) in tertbutanol (2 mL) was degassed by bubbling nitrogen for 5 min, and DPPA (3.97 mmol, 858 mg) was added. The reaction mixture was stirred at reflux for 4 h. The solvent was removed in vacuo, and the residue was partitioned between water and ethyl acetate. The aqueous layer was extracted with ethyl acetate (2×), and the combined organics were washed sequentially with a saturated aqueous solution of sodium bicarbonate and brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was by flash chromatography using a gradient of 0-10% methanol/dichloromethane to afford 347 mg of (6-bromo-quinolin-3-yl)-carbamic acid tert-butyl ester (54% yield): 1H NMR (DMSO-d6) δ 1.53 (s, 9H), 7.69 (dd, 1H), 7.85 (d, 1H), 8.21 (d, 1H), 8.48 (s, 1H), 8.85 (d, 1H), 10.00 (bs, 1H); MS (m/z) 325 [M+H]+.
Workup
- customby bubbling nitrogen for 5 min
- temperatureat reflux for 4 h
- customThe solvent was removed in vacuo
- customthe residue was partitioned between water and ethyl acetate
- extractionThe aqueous layer was extracted with ethyl acetate (2×)
- washthe combined organics were washed sequentially with a saturated aqueous solution of sodium bicarbonate and brine
- dry with materialdried over sodium sulfate
- filtrationfiltered
- concentrationconcentrated in vacuo
Sources & evidence
- ORD record
- ord-1d2c16c2634f46b8bb7063994ea626b9
- Source dataset
- uspto-grants-2013_08
- Patent number
- US08507489B2
Reaction notes
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