Hydrochloric Acid → HCID 137078800, compound

Participants

Reaction Conditions

Reaction Steps

4-(8-Bromooctyloxy)aniline (2.30 g, 7.7 mmol) was suspended in a mixture of concentrated hydrochloric acid (mL) and water (75 mL). The resulting solution was cooled to 0° C. in an ice bath. Sodium nitrite (0.83 g, 12.1 mmol) in water (10 mL) was added dropwise to the reaction mixture with rapid stirring over about 20 min. The reaction mixture was stirred for an additional 20 min while salicylic acid (3.68 g, 26.6 mmol) was dissolved in an aqueous NaOH solution (8.0 g NaOH in 100 mL H2O). This basic salicylic acid solution was vigorously stirred at 0° C. and the solution of the diazonium salt added dropwise. The pH was maintained at 12-14 by adding 8M NaOH solution. After the addition was complete, the solution was allowed to warm to room temperature and was stirred for an additional 30 min. The mixture was diluted with EtOAc (100 mL), washed with water (3×20 mL), 5% NaHCO3 (2×20 mL), brine, dried over Na2SO4, and filtered. Volatiles were removed in vacuo and the residue subjected to column chromatography on silica gel 60 (230-400 mesh) using EtOAc and methanol (98:2) as elutant. The product (1.40 g, 3.1 mmol, 40%) was obtained as a red-brown solid, mp 180-182° C. 1H NMR (500 MHz, CDCl3) δ 1.25-1.44 (m, 8H), 1.72-1.85 (m, 4H), 3.38 (t, J=Hz, 2H), 3.93 (t, J=6.5 Hz, 2H), 6.86-6.91 (m, 3H), 7.69 (d, J=Hz, 2H), 7.84 (dd, J=10 Hz, Hz, 1H), 8.42 (s, 1H); 13C NMR (125 MHz, CDCl3) δ 25.8, 25.9, 28.0, 28.5, 29.0, 29.1, 29.2, 31.7, 32.7, 33.9, 35.2, 68.1, 113.3, 118.4, 123.1, 124.0, 126.1, 127.5, 144.9, 146.5, 161.0; HRMS (ESI) calculated for C21H26BrN2O4 (M+H)+449.1070, observed 449.1063.

Provenance & Evidence