Preparation of symmetrical and unsymmetrical monomers towards bridge trifluoromethylated poly(p-phenylenevinylene)

Oxidation of α-Trifluoromethyl Alcohols Using a Recyclable Oxoammonium Salt

“…The title compound (3.790 g, 92%) was prepared according to the representative procedure for trifluoromethylation from 4-(hydroxymethyl)benzaldehyde (2.720 g, 0.020 mol, 1 equiv) and an excess of TMS-CF 3 (6.25 g, 0.044 mol, 2.2 equiv) and obtained as an light yellow solid (mp 86–88 °C, lit . mp 92–94 °C); no further purification was necessary: 1 H NMR (MeOD, 400 MHz; δ, ppm) 4.80 (s, 2 H), 5.13 (br s, 1 H), 5.23 (q, J = 7.09 Hz, 1 H), 7.57 (d, J = 8.31 Hz, 2 H), 7.69 (d, J = 8.07 Hz, 2 H); 13 C NMR (MeOD, 101 MHz; δ, ppm) 66.1 (CH 2 ), 74.3 (q, J C–C–F = 32.3 Hz, CH), 123.3–131.7 (q, J C–F = 281.7 Hz, CF 3 ), 129.2 (CH), 130.1 (CH), 137.0 (d, J C–C–C–F = 1.5 Hz, C), 144.8 (C); 19 F NMR (MeOD, 400 MHz; δ, ppm) −79.11 (d, J = 6.81 Hz); GC-MS (EI) 206 ([M] + , 31%), 138 (10%), 137 (100%), 135 (34%), 133 (10%), 109 (15%), 107 (34%), 105 (13%), 91 (31%), 79 (87%), 77 (44%), 69 (7%), 51 (13%), 40 (14%); HRMS (ESI+) calcd for C 9 H 9 F 3 O 2 [M + H – H 2 O] + 189.0527, found 189.0521.…”

Complete assignment of 19F, 1H and 13C NMR spectra of monomers and precursors towards bridge trifluoromethylated poly(p‐phenylenevinylene)

“…Towards this end, a series of trifluoromethylated and bistrifluoromethylated precursors and monomers were prepared with a selection of different leaving groups and polarizers 24 (see Table 1). Compounds 1a-o were characterized prior to their polymerization and subsequent thermal elimination to introduce conjugation.…”