Hydrochloric Acid → 1-Tert-butyl-2-fluoro-4-nitrobenzene

HRID 471976Notes

Reaction equation

[C:1]([C:5]1[CH:11]=[CH:10][C:9]([N+:12]([O-:14])=[O:13])=[CH:8][C:6]=1N)([CH3:4])([CH3:3])[CH3:2].Cl.N([O-])=O.[Na+].[H+].[F:21][P-](F)(F)(F)(F)F>O>[C:1]([C:5]1[CH:11]=[CH:10][C:9]([N+:12]([O-:14])=[O:13])=[CH:8][C:6]=1[F:21])([CH3:4])([CH3:3])[CH3:2]

Participants

Conditions

Temperature: 0 °C

Procedure

To a stirred solution of 2-tert-butyl-5-nitroaniline (5.0 g, 25.8 mmol) in H2O (20 mL) was added conc.HCl (10 mL). After a solution was observed, the mixture was cooled to 0° C. followed by the slow addition of NaNO2 (1.78 g, 25.8 mmol) in H2O (10 mL). The reaction mixture was stirred at 0° C. for another 0.5 hours. Then HPF6 solution (40 mL) was added in two batches. The precipitate obtained by filtration was then heated under infrared light about 130-150° C. while grey solid slowly burned to dark viscous oil. The reaction process was monitored by TLC. The obtained dark oil was purified by chromatography on silica gel to afford 1-tert-butyl-2-fluoro-4-nitrobenzene (600 mg, 12.0% yield). 1H NMR (400 MHz, CDCl3) δ 7.96 (dd, J=2.4, 8.8 Hz, 1H), 7.87 (dd, J=2.4, 12.0 Hz, 1H), 7.48 (t, J=8.0 Hz, 1H), 1.43 (s, 9H).

Workup

customThe precipitate obtained by filtration
temperaturewas then heated
customunder infrared light about 130-150° C. while grey solid slowly burned to dark viscous oil
customThe obtained dark oil was purified by chromatography on silica gel

Sources & evidence

ORD record: ord-6fda8932d6034966ba90ac20433497d1
Source dataset: uspto-grants-2014_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08633189B2

Reaction notes

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