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采用量子化学密度泛函理论在B3LYP/6-311++G**水平上对精甲霜灵分子几何构型进行优化;在优化的基础上进行圆二色谱究。计算结果表明:(1)C(8)=O(9)与N(1)、C(3)=O(4)与O(5)之间均存在p—π共轭,N原子上另外2个取代基分别位于苯环上下方为最稳定构型。(2)VCD谱中,C(10)—H沿C(8)—C(10)—O(11)平面的摇摆振动在1020cm-1处存在正性康登效应;垂直于该平面的摇摆振动在1273cm-1处出现负性康登效应。C(2)原子上的C—H摇摆振动在的1334cm-1处存在强的康登效应。C(3)=O(4)在的1788cm-1处出现较强的吸收峰;C(8)=O(9)由于与手性中心的间隔一个N原子,其在VCD谱中未出现康登效应。(3)甲醇溶液中的理论ECD谱,228nm处存在正性康登效应,与实验值符合较好;同时,理论计算还预测标题化合物在201nm处存在负性康登效应。
Quantum chemical density functional theory was used to optimize the molecular configuration of metalaxylmetry at B3LYP / 6-311 ++ G ** level. Circular dichroism was performed on the basis of optimization. The calculated results show that there exists p-π conjugation between (1) C (8) = O (9) and N (1) and C (3) = O (4) Two substituents are located in the upper and lower benzene ring for the most stable configuration. (2) In VCD spectrum, the oscillating vibration of C (10) -H along the C (8) -C (10) -O (11) plane has a positive Corning effect at 1020 cm -1; Vibration at 1273cm-1 at the Department of Negative Condon effect. The C-H oscillation on the C (2) atom has a strong Condon effect at 1334 cm-1. C (3) = O (4) showed a strong absorption peak at 1788 cm-1; C (8) = O (9) due to the separation of one N atom from the chiral center, Effect. (3) The theoretical ECD spectrum in methanol solution shows a positive Condon effect at 228 nm, which is in good agreement with the experimental data. Meanwhile, theoretical calculations also predict that the title compound has a negative Condon effect at 201 nm.