Aniline → 1-Phenoxy-2,2,6,6-tetramethylpiperidine

Participants

Reaction Steps

To a suspension of 1.95 g (12.5 mmol) of 2,2,6,6-tetramethylpiperidine-1-oxyl, 3.09 g (30.0 mmol) of tert-butylnitrite and 378 mg (˜0.125 mmol) of iron polyoxometallate (K7PFeW11O39•H2O) in 100 mL of pyridine at 70° C. under a nitrogen atmosphere is added dropwise over 5 minutes 2.32 g (25 mmol) of aniline in 5 mL of pyridine. Evolution of gas is observed during the addition of aniline. The dark red reaction mixture is kept at 70° C. until evolution of gas subsided. Upon cooling to ambient temperature, the reaction mixture is then concentrated to an thick oil. The residue is purified by vacuum flash chromatography (heptane) to give 2.10 g of a colorless oil in 72.2% yield: 1H NMR (CDCL3) (300.08 MHz) d 1.42, 1.29, 1.12 (overlapping m, CH2, 6 H), 1.16 (s, CH3, 6 H), 1.017 (s, CH3, 6 H), 7.25 (d, CH, 2H, 3JHH′=8.2 Hz), 7.12 (dd, CH, 2H, 3JHH′=8.3 Hz, 3JHH′=8.2 Hz), 6.78 (tt, CH, 1 H, 3JHH′=7.2 Hz, 4JHH″=1.2 Hz); MS [M+1]234.

Provenance & Evidence