Theoretical Study on the Reaction Mechanism of 2-Methoxybenzaldehyde,4-Bromo-indanone,Malononitrile and Ammonium Acetate One-pot to Form 6-(2-Methoxyphenyl)-2-amino-6-bromo-5H-indeno[1,2-b]pyridine-3-carbonitrile

The reaction mechanism of 2-methoxybenzaldehyde, 4-bromo-indanone, malononitrile and ammonium acetate one-pot to form 6-（2-methoxyphenyl）-2-amino-6-bromo-5 Hindeno[1,2-b]pyridine-3-carbonitrile was studied by density functional theory. The geometries of the reactants, transition states, intermediates and products were optimized at the PW91/DNP level. Vibration analysis was carried out to confirm the transition state structure. Reaction pathways were investigated in this study. The result indicates that the reaction Re→ TSB1→IMB1→ TSB2→ IMB2→TSB3→IMB3→TSB4→IMB4→TSB5→IMB5→TSB6→IMB6→TSB7→IMB7→ TSB8→IMB8→TSB9→IMB9→P2 is the main pathway, the activation energy of which is the lowest. The dominant product predicted theoretically is in agreement with the experiment results.

4-溴-2-(溴甲基)苯甲醛的合成研究

4-溴-2-(溴甲基)苯甲醛是合成1,2-二氢酞嗪化合物的重要中间体。以4-溴-2-甲基苯腈为原料,通过溴代、还原得两步反应得到目标化合物4-溴-2-(溴甲基)苯甲醛。确定了溴代反应最佳条件:N-溴代丁二酰亚胺(24.0mmol)、过氧苯甲酰(4.0mmol),反应体系在CCl4中回流反应8h。还原反应最佳条件:二异丁基氢化铝(DIBAL-H)(12.0mmol),反应溶剂二氯甲烷,室温反应3h。两步反应总收率85.4%,产物及中间体结构通过1 H NMR、13 C NMR和电喷雾电离质谱(ESI-MS)进行了表征。

4-溴邻苯二胺的合成

采用两条路线合成４溴邻苯二胺，并对路线（Ⅱ）中水解一步作了探讨这两条路线是：１．用漆原镍催化氢化 ４溴２硝基苯胺；２．邻苯二胺溴化后，碱水解中间体 Ｎ， Ｎ（４溴１。

微波辐射下一锅法合成2-氨基-6-溴-4-芳基-5H-茚并[1,2-b]吡啶-3-腈衍生物

以芳香醛、4-溴茚酮、丙二腈和醋酸铵为原料,分别用微波辐射和传统加热法,一步法合成7种未见文献报道的2-氨基-6-溴基-4-芳基-5H-茚并[1,2-b]吡啶-3-腈衍生物.对比两种方法,在常压下微波具有反应时间短、产率较高等特点.所有化合物均经IR,1HNMR和元素分析确定.

对溴联苯合成工艺研究

采用定向催化技术催化联苯的溴化反应,并使用氯气替代一部分液溴,可以自由控制反应的发生和停止,有效地抑制邻位溴代和二溴取代副产物的产生。粗产品经减压精馏和重结晶,产品含量≥98%。