Reaction Steps
A mixture of N,N-di(4-methoxyphenyl)-7-(benzothiazol-2-yl)-9,9-diethyl-fluoren-2-amine, (Example 9; 11.0 g, 18.9 mmol), 2-aminothiophenol (9.0 mL, 10.53 g, 84.0 mmol), potassium carbonate (0.58 g, 4.2 mmol) and 1-methylpyrrolidine-2-one (NMP, 50 mL) was heated to 195° C., and held at this temperature for 6 hours. After cooling, the mixture was poured into a mixture of acetic acid (100 mL) and water (750 mL). The separated solids were collected and reslurried in a mixture of ethanol (100 mL) and toluene (50 mL), and the insoluble solids, 7.44 g, m.p. 294-297° C. were collected. Additional 2.71 g, with the same melting point was obtained by concentration of the filtrate, and slurrying the crude product in toluene. Total product recovered was 10.15 g (97% yield). A sample for analysis was prepared by heating 1 g of the sample with 2:1 acetic-acid-water mixture (75 mL), 0.98 g, m.p. 294.2-294.5° C. Mass spec: m/z 554 (M+). Anal. Calcd for C36H30N2O2S: C, 77.95%; H, 5.45%; N, 5.05%; S, 5.78%. Found; C, 77.95%; H, 5.53%; N, 5.18%; S, 5.90%. 1H NMR (DMSO-d6) δ ppm: 0.30 (t, 6H, 7.3 Hz), 1.80-1.84 (m, 2H), 1.99-2.04 (m, 2H), 6.70-6.81 (m, 6H), 6.94-6.97 (m, 4H), 7.42-7.46 (m, 1H), 7.52-7.56 (m, 1H), 7.65 (d, 1H, 8.4 Hz), 7.78 (d, 1H, 7.92 Hz), 7.97-8.13 (m, 4H), 9.38 (s, 2H). 13C NMR (DMSO-d6) δ ppm: 8.96, 32.23, 56.01 (3 sp3C), 113.42, 116.71, 118.47, 119.66, 121.28, 121.77, 122.68, 123.02, 125.69, 127.06, 127.42, 127.59, 130.52, 131.90, 134.77, 139.22, 145.09, 150.09, 150.34, 151.87, 154.15, 154.50, and 169.38 (23 sp2C).
