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Diphenylamine (3.4 g, 20 mmol) potassium tert-butoxide(0.43 g, 4.5 mmol), Pd(dppf)Cl2 (0.15 mmol), dppf (1 mmol)and dried toluene (60 mL) were mixed in a three-necked flask.The mixture was heated at 70 Cfor10minwiththeaddition of 4-bromobenzophenone (5.2 g, 20 mmol). The resulting mixture was vigorously stirred for 24 h at 120 ??C. After the reaction finished, a certain amount of hydrochloric acid was slowly added. Subsequently, the residue was extracted with dichloromethane. The extraction solution was washed with brine, and then the organic layer was dried over MgSO4 and filtered. The crude product was purified by column chromatography using a dichloromethane?Chexane (1/50) mixture as eluent to obtain the desired compound in 44.2% yield (3.1 g);1HNMR(500MHz,CDCl3) d 7.79 (d, J = 7.0 Hz, 2H), 7.72 (dd,J =7.0 Hz, J = 1.5 Hz, 2H), 7.56 (t, J = 7.5 Hz, 1H), 7.48 (t, J =7.5 Hz, 2H), 7.35 (t, J = 9.0 Hz, 4H), 7.20 (d, J =7.5 Hz, 4H), 7.16 (t, J = 7.5 Hz, 2H), 7.03 (dd, J = 7.0 Hz, J = 2.0 Hz, 2H).13CNMR (500 MHz, CDCl3); d 195.2, 151.9, 146.5, 138.5, 131.9, 131.7, 129.6, 128.1, 126.0, 124.6, 119.6; crystallographic data for TPA-CO:C25H19NO, M = 349.41, orthorhombic, a =16.740(5) ˚ A, b = 12.432(5) ˚ A, c = 9.236(3) ˚ A; V = 1922.2(11) ˚ A3,T = 296(2) K, space group Pca2(1), DC = 1.207 g cmˆ??3, Z = 4,10 430 reflections collected, 3385 unique reflection (Rint =0.0308), the final R indices were R1=0.0384, wR2 = 0.0799 [I >2??(I)], CCDC=872836. |
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2楼2014-10-16 14:20:22
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3楼2014-10-16 23:29:40
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| 在三颈烧瓶中,加入二苯胺(3.4克,20 mmol)、叔丁醇钾(0.43克,4.5 mmol)、Pd(dppf)Cl2(0.15 mmol)、dppf(1 mmol)和干燥的甲苯(60 ml)。加入4-溴苯二酮(5.2克,20 mmol),在70℃加热混合液10分钟。在120℃用力搅拌得到的混合液24小时。反应结束后,缓慢加入一定量的盐酸。然后用二氯甲烷萃取残留物。用盐水冲洗萃取液,然后用硫酸镁干燥有机层,并过滤。使用二氯甲烷-己烷(1/50)作为洗脱剂通过柱色谱法纯化粗品得到目标化合物,收率为44.2%(3.1克);后面的是核磁数据和晶体数据了~~~就不一一译了~~~ |

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