【摘要】 采用密度泛函理论方法优化计算了乙酰乙酸乙酯、间硝基苯甲醛和2-(3-硝基亚苄基)乙酰乙酸乙酯分子结构,分析了电荷布局分布和前线分子轨道,探讨了各物质的分子热力学性质和反应平衡常数。在此基础上用含时密度泛函方法(TD-DFT)计算了分子吸收光谱。计算结果表明,在298～1 000 K温度范围内,用乙酰乙酸乙酯和间硝基苯甲醛合成医药中间体2-(3-硝基亚苄基)乙酰乙酸乙酯是一个放热反应,且吉布斯自由能为负,反应在温和的条件(298～400 K)下就易自发进行,反应平衡常数较大,还可用紫外光谱来监测反应进程。更多还原

【Abstract】 Geometric configurations of acetylacetic ether and 3-Nitrobenzaldehyde and 2-(3-Nitrobenzylidene) acetoacetate were optimized by using density functional theory(DFT) method at the B3LYP/6-31G level.The charge distribution and the energies of their frontier molecular orbital were investigated theoretically.The thermodynamic properties of the molecules of each substance and reaction equilibrium constant were discussed.The molecular absorption spectrometry was calculated with TD-DFT.The calculation results showed that the reaction occurred in the 298~1 000 K were exothermic and changes of Gibbs free energies of the reaction were all negative.The reaction could occur spontaneously under mild conditions at 298~400 K with high values of equilibrium constants.UV spectrum can be used to monitor the reaction process.更多还原