| 29% |
With titanium tetrachloride; zinc In tetrahydrofuran at 78℃; for 12h; Inert atmosphere; |
[TPE-N2-Br2]
Michler's ketone (1 g, 3.726mmol), 4,4′-Dibromobenzophenone (1.2 g, 3.726mmol), and zinc powder (2.9 g, 44.71mmol) were mixed in freshly distilled cold tetrahydrofuran (THF, 20mL, 0°C), and titanium tetrachloride (TiCl4, 2.8mL) was added dropwise under an argon atmosphere with the rapid stirring of over 10min. The mixture was then slowly warmed up to 78°C with stirring, and the reaction was allowed to further proceed for 12h under reflux. After the reaction, the mixture was cooled to room temperature, and deionized water (DI H2O, 25mL) was added to quench the reaction. The resulting solution was filtered through a pad of celite to remove the remaining zinc powder. The filtrated solution was washed with ethyl acetate (EtOAc) and DI H2O. The collected organic extract was washed with brine and dried over anhydrous sodium sulfate (Na2SO4). The resulting residue was concentrated in vacuo and was purified by flash column chromatography (n-hex/EtOAc=9:1, v/v, TLC: Rf 0.5). TPE-N2-Br2 was collected with a 29% yield (bright yellow solid). 1H NMR (500MHz, CDCl3): δ 2.94 (s, 12H), 5.76 (s, 1H), 6.50 (d, J=9.2 Hz, 3H), 6.94-6.90 (m, 6H), 7.24 (s, 1H), 7.50 (d, J=8.6 Hz, 5H); 13C NMR (125MHz, CDCl3): δ 40.5, 75.1, 76.9, 77.2, 77.4, 111.5, 113,3, 119.7, 121.8, 128.3, 131.0, 131.8, 132.6, 133.3, 134.1, 142.4, 142.8, 144.0, 149.2. HRMS (m/z): calcd for C30H28Br2N2, 576.0598; found, 576.0599. Melting point: 210.0°C. |
|
With pyridine; titanium tetrachloride; zinc In tetrahydrofuran Inert atmosphere; Reflux; |
2.3. Synthesis
Under N2 atmosphere, a three-necked flask equipped with a magnetic stirrer was charged with zinc powder (4.2 g, 65 mmol)and 40 mL THF. The mixture was cooled to -5-0 °C, and TiCl4 (3.6 mL, 32.4 mmol) was slowly added by a syringe with the temperature kept under 10 °C. The suspending mixture was warmed to room temperature and stirred for 0.5 h, then heated at reflux for 2.5 h. The mixture was again cooled to -5-0 °C, charged with pyridine (0.24 mL, 3 mmol) and stirred for 10 min. The solution of two carbonyl compounds (in 6:6 mmol to 6:7.2 mmol mole ratios, in 15 mL THF) was added slowly. After addition, the reaction mixture was heated at reflux until the carbonyl compounds were consumed (monitored by TLC). The reaction was quenched with10% Na2CO3 aqueous solution and taken up with CH2Cl2. The organic layer was collected and concentrated. The crude material was purified by flash chromatography to give the desired products.The 1-(4-bromophenyl)-1,2,2-triphenylethylene was solved inTHF, the added n-BuLi at -78 °C for 2 h, followed by addition of dimethylformamide, the crude material was kept at room temperaturefor 2 h. The mixture was quenched by water and purified by flash chromatography, gave the expected aldehyde. Knoevenagel reaction was taking place between the aldehyde and the cyano derivative under alkaline conditions. The mixture was purified by flash chromatography, gave the target molecular. |
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