Reaction Steps
To a solution of N,N-di[3-(4-nitrophenoxy)phenyl]-7-(benzothiazol-2-yl)-9,9-diethyl-fluoren-2-amine (Example 7; 13.68 g, 17.2 mmol) in 300 mL of 1/1 tetrahydrofuran/ethanol mixture under argon was added 10% palladium/carbon (500 mg). The mixture was heated to 60° C., and hydrazine hydrate (12.7 mL, ˜206 mmol) was added slowly over 40 min by addition funnel. The solution became dark, fluorescent green and, after 8 hr, was cooled to room temperature and poured into 1.5 L of distilled water. After a few hours of stirring to evaporate some THF, a fine yellow solid was filtered and purified by column chromatography eluting with ethyl acetate/toluene. The product was further slurried in 100 mL of hot EtOH, filtered at room temperature, and dried in vacuo at 70° C. overnight to give 8.4 g (65%). 1H NMR (400 MHz, CDCl3) δ ppm: 8.08 (m, 2H), 8.01 (dd, J1=8 Hz, J2=1.6 Hz, 1H), 7.91 (d, J=8 Hz, 1H), 7.70 (d, J=8 Hz, 1H), 7.48-7.55 (m, 1H), 7.35-7.42 (m, 1H), 7.05-7.18 (m, 4H), 6.52-6.59 (m, 2H), 3.5-3.6 (br. s, 4H), 1.95-2.15 (m, 4H), 0.34 (t, J=7 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ ppm: 168.97, 159.73, 154.38, 152.23, 150.91, 149.04, 148.61, 147.69, 144.56, 142.72, 135.98, 135.07, 131.71, 129.98, 127.39, 126.42, 125.11, 124.19, 123.08, 121.68, 121.59, 121.19, 121.00, 119.60, 119.54, 117.90, 116.31, 113.33, 111.70, 56.57, 32.77, 8.73; MS (m/z): 736 (M+); Anal. Calcd. for C48H40N4O2S: C, 78.23%; H, 5.47%; N, 7.60%; S, 4.35%%. Found: C, 78.01%%; H, 5.60%%; N, 7.62%%; S, 4.31%.
