Nitric Acid → 1-(2-(Dimethylamino)ethyl)-8-fluoro-6-nitro-3,4-dihydroquinolin-2(1H)-one

HRID 1922431Notes

Reaction equation

[CH3:1][N:2]([CH3:17])[CH2:3][CH2:4][N:5]1[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][C:13]=2[F:15])[CH2:8][CH2:7][C:6]1=[O:16].[N+:18]([O-])([OH:20])=[O:19]>S(=O)(=O)(O)O>[CH3:1][N:2]([CH3:17])[CH2:3][CH2:4][N:5]1[C:14]2[C:9](=[CH:10][C:11]([N+:18]([O-:20])=[O:19])=[CH:12][C:13]=2[F:15])[CH2:8][CH2:7][C:6]1=[O:16]

Participants

Conditions

Temperature: -5 °C

Procedure

1-(2-(Dimethylamino)ethyl)-8-fluoro-3,4-dihydroquinolin-2(1H)-one (2.86 g, 12.11 mmol) was weighed into a round bottom flask equipped a stir bar. To this was added concentrated sulfuric acid (30 mL) and the flask was cooled to −5° C. in an ice/salt bath. To this stirring solution was added nitric acid (90%, 615.5 μL, 13.2 mmol) and the resulting mixture was stirred for 30 min. The reaction mixture was then quenched with ice and NaOH(aq). The product was extracted with CH2Cl2 (3×). The combined organics were dried, filtered and concentrated then chromatographed on silica using 0-10% (2M NH3 in MeOH) in dichloromethane, giving the desired product. Yield: 1.1 g, 32%, product still contains some impurities). 1H NMR (CDCl3) δ 2.20 (s, 6H), 2.48 (t, 2H, J=7.0 Hz), 2.67 (t, 2H, J=7.0 Hz), 2.98 (t, 2H, J=7.0 Hz), 4.16 (t, 2H, J=7.0 Hz), 7.89 (m, 2H). ESI-MS: 282 (MH+, 100), 237 (50), 192 (27).

Workup

customequipped a stir bar
customThe reaction mixture was then quenched with ice and NaOH(aq)
extractionThe product was extracted with CH2Cl2 (3×)
customThe combined organics were dried
filtrationfiltered
concentrationconcentrated
customthen chromatographed on silica using 0-10% (2M NH3 in MeOH) in dichloromethane

Sources & evidence

ORD record: ord-988b7676d1394468a60f3b4fcb450e1d
Source dataset: uspto-grants-2012_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08173813B2

Reaction notes

Loading…