Methanol → N-Diphenylmethylene-4-bromoaniline

Participants

Reaction Steps

The method of Taguchi and Westheimer1 was modified as follows: benzophenone (455 g, 2.50 mol) and 4-bromoaniline (473 g, 2.75 mol) were dissolved in toluene (1.2 L) under argon in a 5 L flask containing activated molecular sieves (5 Å, 1.25 kg). The flask was fitted with a reflux condenser, rubber septum, and pressure outlet. The mixture was heated to gentle reflux and shaken occasionally; an intense yellow color soon developed. After 18 h, heating was discontinued and the solution was cooled to rt. The solution was decanted from the molecular sieves, and the sieves were washed with Et2O until the filtrate was colorless. The combined organic solutions were concentrated in vacuo to give an orange oil. MeOH (ca. 80 mL) and a seed crystal of 1 were added. The product was allowed to crystallize at 0° C. and the precipitate was collected by filtration. The mother liquor was further concentrated, and a second crop of crystals was collected from MeOH. Recrystallization of the combined material from MeOH afforded yellow crystals (760 g, 90%). 1: mp 82-83° C.; 1H NMR (300 Mz, CDCl3) δ 7.75 (dd, J=6.9, 1.6 Hz, 2H), 7.52-7.39 (m, 3H), 7.32-7.23 (m, 5H), 7.11 (dd, J=8.5, 2.0 Hz, 2H), 6.61 (dt, J=8.5, 2.0 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ 168.7, 150.4, 139.5, 136.1, 131.6, 131.0, 129.5, 128.8, 128.3, 128.2, 122.8, 116.3, 103.6;IR(CDCl3) 3058, 3024, 1615, 1478 cm−1; Anal. Calcd for C19H14BrN: C, 67.87; H, 4.20. Found: C, 68.08; H, 4.28.

Provenance & Evidence