论文部分内容阅读
2-锗萘由于其芳香性和高反应性,而引起化学家们的浓厚兴趣。本文采用密度泛函理论(DFT)在B3LYP/6-311G(d,p)水平,研究2-锗萘与甲醛、二苯甲酮的[2+2]和[4+2]杂环加成反应的微观机理、势能剖面,考察取代基和四氢呋喃溶剂对反应势能剖面的影响。计算结果表明,所研究的反应均为协同但非同步的方式,且Ge-O键总是先于C-C键形成。羰基碳原子上的苯取代基不利于反应,而2-锗萘分子中锗原子上的C(CH_3)_3与CCl_3取代基却有利于反应。四氢呋喃溶剂对加成反应的势能剖面影响不大。[2+2]比[4+2]反应容易,与实验一致。
2-Germanium naphthalene has attracted a great deal of chemists’ interest due to its aromaticity and high reactivity. In this paper, the density functional theory (DFT) at B3LYP / 6-311G (d, p) levels, 2-germanium naphthalene and formaldehyde, benzophenone [2 +2] and [4 +2] The micro-mechanism of reaction, potential energy profile, the effect of substituent and tetrahydrofuran solvent on the potential energy profile of the reaction were investigated. The calculated results show that all the reactions studied are in a synergistic but non-synchronous manner, and the Ge-O bond always precedes the C-C bond. Benzene substituents on the carbonyl carbon atoms are not conducive to the reaction, while the C (CH_3) _3 and CCl_3 substituents on the germanium atom in 2-germanium naphthalene are favorable for the reaction. Tetrahydrofuran solvent has little effect on the energy profile of the addition reaction. [2 + 2] than [4 + 2] reaction easy, consistent with the experiment.