反应详情

To cold (ice bath) anhydrous methanol (13.2 mL) was added sodium hydride (80% by weight suspension in mineral oil, 1.70 g, 56.6 mmol) in three portions. After stirring in the cold for 0.5 hours and at ambient temperature for 50 minutes copper II chloride (0.251 g, 1.87 mmol) and solution of methanesulfonic acid 4-(6-iodo-benzo[b]naphtho[2,3-d]thiophen-11-yl)-phenyl ester (3.00 g, 5.66 mmol) in dry N,N-dimethylformamide (24 mL) were added. The reaction mixture was heated at reflux for approximately 3 hours, cooled to room temperature, diluted with water (400 mL), acidified with 10% hydrochloric acid and extracted with diethyl ether. The extracts were combined, silica gel was added and the solvent removed. The adsorbate was flash chromatographed (40/60 petroleum ether/methylene chloride) to provide the title compound as a white solid (1.82 g, 90%): mp 218-223° C. (dec); NMR (CDCl3); δ 8.27 (ddd, J=8, 1, 1 Hz, 1H), 7.80 (ddd, J=8, 1, 1 Hz, 1H), 7.65 (ddd, J=8, 1, 1 Hz, 1H), 7.57 (ddd, J=8, 7, 1 Hz, 1H), 7.40 (ddd, J=8, 7, 1 Hz, 1H), 7.36 (ddd, J=8, 7, 1 Hz, 1H), 7.30-7.26 (m, 2H), 7.13-7.07 (m, 3H), 6.85 (ddd, J=8, 1, 1 Hz, 1H), 4.98 (s, 1H), 4.21 (S, 3H); MS (EI): [M+], 356 (100%); Anal. Calc. for C23H16O2S: C, 77.50, H, 4.52, N, 0.00; Found C, 76.79, H, 4.61, N, 0.11.

1. temperatureThe reaction mixture was heated
2. temperatureat reflux for approximately 3 hours
3. extractionextracted with diethyl ether
4. additionsilica gel was added
5. customthe solvent removed
6. customchromatographed (40/60 petroleum ether/methylene chloride)