67% |
With phosphorous (V) sulfide; sodium hydrogencarbonate; In tetrahydrofuran; at 0 - 50℃; for 3h;Heating / reflux; |
A solution of 3 (327 mg, 1 mmol) was stirred in THF (30 ml) at 50 C. under a nitrogen protective gas atmosphere. Phosphorus pentasulphide (250 mg, 1.12 mmol) and sodium hydrogencarbonate (370 mg, 4.4 mmol) were added consecutively. After three hours of heating under reflux in a nitrogen protective gas atmosphere, the reaction mixture was allowed to cool to room temperature and the reaction mixture was then placed on ice (50 g). Stirring took place until the ice had completely melted. Then the precipitate formed was drawn off, washed with water and recrystallised out of ethanol/toluol. Yield: 67% of slightly yellow crystals: Mp.: >330 C.; IR: 3430, 3140 cm-1 (NH); 1H NMR (400 MHz) 3.91 (s, 2H, CH2), 7.30 (dd, 1H, 1.5/8.6 Hz), 7.39-7.45 (m, 4H), 7.79 (d, 1H, 7.1 Hz), 7.86 (d, 1H, 1.5 Hz), 11.92 (s, 1H, NH), 12.07 (s, 1H, NH). |
67% |
With diphosphorus pentasulfide; sodium hydrogencarbonate; In tetrahydrofuran; |
Example 18 This example describes the synthesis of 9-bromo-7,12-dihydro-indolo[3,2-d][1]benzazepine-6(5H) -thione. A solution of 9-bromo-7,12-dihydroindolo[3,2-d]-1-benzazepin-6(5H)-one (327 mg, 1 mmol) in THF (30 mL) was stirred under nitrogen at 50 C. Phosphorus pentasulfide (250 mg, 1,12 mmol) and sodium hydrogencarbonate (370 mg, 4.4 mmol) were added successively. After refluxing for 3 hours under nitrogen, the mixture is allowed to cool to room temperature and then poured onto crushed ice (50 g). The mixture was then stirred until the ice is molten, and the precipitate which formed was filtered off with suction, washed with water and recrystallized from ethanol/toluene yielding 67% pale yellow crystals, m. p. >330, ir (KBr): 3430, 3140 cm-1 (NH); 1H-nmr (DMSO-d6, 400 MHz): delta (ppm)=3.91 (s, 2H, CH2), 7.30 (dd, 1H, 1.5/8.6 Hz), 7.39-7.45 (m, 4H), 7.79 (d, 1H, 7.1 Hz), 7.86 (d, 1H, 1.5 Hz), 11.92 (s, 1H, NH), 12.07(s, 1H, NH); 13C-nmr (DMSO-d6, 100.6 MHz): delta (ppm)=39.6, 109.3, 111.8, 113.5, 120.3, 123.1, 123.7,124.8, 125.5, 126.9, 127.8, 128.1, 133.3, 136.2, 136.2, 200.2; C16H11BrN2S (343.24); Calcd. C 55.99, H 3.23, N 8.16, Br 23.28, S 9.34; Found C 55.81, H 3.28, N 8.00, Br 22.42, S 9.51. |