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Predicting Rate Constants for Nucleophilic Reactions of Amines with Diarylcarbenium Ions Using an ONIOM Method 下载免费PDF全文
The rate constants of the nucleophilic reactions between amines and benzhydrylium ions were calculated using first-principles theoretical methods. Solvation models including PCM, CPCM, and COSMORS, as well as different types of atomic radii including UA0, UAKS, UAHF, Bondi, and UFF, and several single-point energy calculation methods (B3LYP, B3P86, B3PW91, BHANDH, PBEPBE, BMK, M06, MP2, and ONIOM method) were exam-ined. By comparing the correlation between experimental rate constants and the calculated values, the ONIOM(CCSD(T)/6-311++G(2df,2p):B3LYP/6-311++G(2df,2p))// B3LYP/6-31G(d)/PCM/UFF) method was found to perform the best. This method was then employed to calculate the rate constants of the reactions between diverse amines and diarylcarbenium ions. The calculated rate constants for 65 reactions of amines with diarylcarbenium ions are in agreement with the experimental values, indicating that it is feasible to predict the rate constant of a reaction between an amine and a diarylcarbenium ion through ab initio calculation. 相似文献
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精确计算化学键解离能的ONIOM-G3B3方法及其在抗氧化剂研究中的应用 总被引:1,自引:0,他引:1
通过对179个有机化合物C—H, N—H, O—H键离解能的理论计算, 系统评估了高精度组合从头算方法(ONIOM-G3B3)和密度泛函理论方法(B3LYP)在预测键离解能上的可靠性. 研究发现ONIOM-G3B3方法可以准确预测各类有机化合物的键解离能, 精度达到5.9 kJ/mol. 运用ONIOM-G3B3方法成功预测了两类重要的天然抗氧化剂维生素E族和茶多酚族的键解离能, 并进一步讨论了抗氧化活性、自由基清除机理及其构效关系. 相似文献
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CBS-Q and G3 methods were used to generate a large number of reliable Si--H, P---H and S--H bond dissociation energies (BDEs) for the first time. It was found that the Si--H BDE displayed dramatically different substituent effects compared with the C--H BDE. On the other hand, the P---H and S--H BDE exhibited patterns of substituent effects similar to those of the N--H and O--H BDE. Further analysis indicated that increasing the positive charge on Si of XSiH3 would strengthen the Si--H bond whereas increasing the positive charge on P and S of XPH2 and XSH would weaken the P---H and S--H bonds. Meanwhile, increasing the positive charge on Si of XSiH2^+ stabilized the silyl radical whereas increasing the positive charge on P and S in XPH" and XS* destabilized P- and S-centered radicals. These behaviors could be reasonalized by the fact that Si is less electronegative than H while P and S are not. Finally, it was demonstrated that the spin-delocalization effect was valid for the Si-, P- and S-centered radicals. 相似文献
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本文利用UB3LYP/6-311++g(2df,2p)//UB3LYP/6-31+g(d)方法,首次就对位取代薁系列化合物(Y-C10H8X-H)的X-H(X=CH2, NH, O)键离解能进行了理论研究。结果发现,除了6-取代-2-甲基薁,取代基对薁X-H键离解能的效应与苯大致相同。然而,由于薁结构中固有偶极矩与不同取代基的电子效应相互作用,对位取代的羟基薁和氨基薁的反应常数( )变化非常显著。利用GE/RE和SIE理论方法,研究发现虽然基态效应在决定净取代基效应的大小中起了一定作用,但取代基效应主要来源于自由基效应的影响。 相似文献
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使用密度泛函方法在UB3LYP/6-311++G(3df, 2p)水平上对自由基环化合成β-内酰胺的四种反应途径进行理论研究. 结合Marcus理论对影响反应的热力学及动力学因素进行分析, 发现氨基甲酰基自由基4-exo环合反应是理想的动力学控制过程; 酰胺自由基的4-exo环合反应与5-endo环合反应相比是动力学有利的转化过程; 单取代的酰胺烷基自由基的4-exo环合反应是一类动力学和热力学都较为不利的反应; 羰基自由基加成亚胺N=C双键的4-exo环合反应与5-endo环合反应相比动力学不利而热力学有利. 相似文献
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偕二氟烯烃是一类重要的含氟有机化合物,在有机合成化学和药物化学研究领域展现出独特的结构优势.例如,偕二氟烯基可以便利地转化为单氟烯基、二氟烷基、三氟甲基以及其他多种含氟结构.偕二氟烯基结构作为羰基理想的电子等排体在药物设计研究中也有广泛的应用.报道了一种镍促进的电化学还原交叉偶联反应合成功能化的偕二氟烯烃.该反应在非分隔电解槽中进行,在温和的电化学还原条件下,实现了三氟甲基烯烃烯丙基脱氟、氧化还原活性羧酸酯脱羧或者烷基卤化物脱卤素的有机结合.反应可有效避免使用化学计量的金属粉末或有机还原剂.该反应为含偕二氟烯基功能结构的生物活性分子提供了有效的合成途径. 相似文献
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