Pivalic acid → 2-(tert-Butyl)isonicotinonitrile

Beteiligte Stoffe

Reaktionsbedingungen

Reaktionsschritte

p-cyanopyridine (4.00 g, 38.4 mmol) was added to a 1:1 mixture of chlorobenzene/water (750 mL) in a 1 L round-bottom flask. Trimethylacetic acid (10.88 g, 106-5 mmol), (NH4)2S2O8 (17.53 g, 76.8 mmol), trifluoroacetic acid (4.390 g, 38.5 mmol) and AgNO3 (0.521 g, 3.1 mmol) were added and the heterogeneous mixture was vigorously stirred at 50° C. for 2 h. The reaction was cooled down to 0° C. and 8 M NaOH was added slowly until pH 9-10. The mixture was filtered through Celite and extracted with EtOAc (×3). The combined organic extracts were dried with MgSO4 and the solvent removed in vacuo. The dark-brown oil was purified via flash chromatography (1:6 EtOAc/Hexane) to afford a brown solid (4.305 g, 70%); 1H NMR (400 MHz, CDCl3): δ 1.39 (s, 9H), 7.38 (d, J=5.2 Hz, 1H), 7.63 (s, 1H), 8.73 (d, J=4.4 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 29.2, 37.3, 116.4, 119.9, 120.4, 121.6, 149.1, 170.3; HRMS-EI (m/z): [M+H+] calcd for [C10H13N2]+, 161.1079. found 161.1070.

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