将α-蒎烯选择性氧化制备马鞭草烯酮,对羰基进行肟化和分离,再发生亲核取代反应,合成得到40个新型( Z )-/( E )-马鞭草烯酮肟醚(4a ~4t ,包括20对 Z / E 异构体),采用 1 H NMR、 13 C NMR 、FT-IR、UV-vis和ESI-MS对目标化合物进行了结...将α-蒎烯选择性氧化制备马鞭草烯酮,对羰基进行肟化和分离,再发生亲核取代反应,合成得到40个新型( Z )-/( E )-马鞭草烯酮肟醚(4a ~4t ,包括20对 Z / E 异构体),采用 1 H NMR、 13 C NMR 、FT-IR、UV-vis和ESI-MS对目标化合物进行了结构表征,并测试其抑菌活性。研究结果表明:在质量浓度50 mg/L下,目标化合物对8种植物病原菌均显示出不同程度的抑菌活性,其中化合物( E )- 4r (R=2,6-Cl)对苹果轮纹病菌的抑制率为77.8%,化合物( E )- 4s (R=2,6-F)对水稻纹枯病菌的抑制率为72.7%,化合物( E )- 4n (R= p -CN)对玉米小斑病菌的抑制率为70.8%,( Z )-/( E )-异构体对一些植物病原菌的抑制活性显示一定差异。建立了( E )-马鞭草烯酮肟醚化合物对水稻纹枯病菌抑制活性的CoMFA模型( r 2 =0.992, q 2 =0.507),进行3D-QSAR研究,结果表明建立的模型可用于设计具有潜在高活性的先导化合物。展开更多
The isomerization reaction of pinene is one of the most important chemical reactions in the deep processing of pinene. The purpose of this study is to improve the performance of the metatitanic acid by composite. The ...The isomerization reaction of pinene is one of the most important chemical reactions in the deep processing of pinene. The purpose of this study is to improve the performance of the metatitanic acid by composite. The composite metatitanic acid catalyst TiM was prepared by adding Mn elements in the preparation process. The catalytic performance of TiM was evaluated. Comparison of TiM and metatitanic acid catalyst(Ti-FGP), the reaction rate of TiM catalyst was faster, and after the reaction, the yield of camphene and tricyclene increased about 1%. The catalysts were characterized by an SEM, FT-IR and laser particle size analyzer. The results show that the pinene isomerization reaction requires the synergistic action of the Br?nsted acid and Lewis acid.Br?nsted acid has great influence on the activity of catalyst, and Lewis acid has a great influence on the selectivity of the catalyst. The structure and morphology of the catalyst have a certain effect on the selectivity of pinene isomerization reaction.展开更多
为研究α-蒎稀的光电离解离机制,采用同步辐射光电离质谱,在7.9-15.5 e V能量范围内研究了α-蒎稀的紫外光电离解离,对α-蒎稀的电离解离能及其碎片离子的出现势进行了理论分析.实验测得光电离效率曲线,从光电离效率曲线中获得α-蒎稀C1...为研究α-蒎稀的光电离解离机制,采用同步辐射光电离质谱,在7.9-15.5 e V能量范围内研究了α-蒎稀的紫外光电离解离,对α-蒎稀的电离解离能及其碎片离子的出现势进行了理论分析.实验测得光电离效率曲线,从光电离效率曲线中获得α-蒎稀C10H16的电离能和碎片离子C9H+13,C7H+10,C3H6+及CHH3+的出现势.用Gaussian 03理论方法计算了C10H16和主要的光解离碎片的总能量,用高级能量计算方法计算了C10H16的电离能和部分碎片离子的出现势及主要的解离通道的离解能.根据实验和理论计算结果,分析了产生碎片离子的主要的解离通道.分析表明实验测得的结果与理论计算提出的C10H16的光解离通道获得的解离能符合得较好.展开更多
文摘将α-蒎烯选择性氧化制备马鞭草烯酮,对羰基进行肟化和分离,再发生亲核取代反应,合成得到40个新型( Z )-/( E )-马鞭草烯酮肟醚(4a ~4t ,包括20对 Z / E 异构体),采用 1 H NMR、 13 C NMR 、FT-IR、UV-vis和ESI-MS对目标化合物进行了结构表征,并测试其抑菌活性。研究结果表明:在质量浓度50 mg/L下,目标化合物对8种植物病原菌均显示出不同程度的抑菌活性,其中化合物( E )- 4r (R=2,6-Cl)对苹果轮纹病菌的抑制率为77.8%,化合物( E )- 4s (R=2,6-F)对水稻纹枯病菌的抑制率为72.7%,化合物( E )- 4n (R= p -CN)对玉米小斑病菌的抑制率为70.8%,( Z )-/( E )-异构体对一些植物病原菌的抑制活性显示一定差异。建立了( E )-马鞭草烯酮肟醚化合物对水稻纹枯病菌抑制活性的CoMFA模型( r 2 =0.992, q 2 =0.507),进行3D-QSAR研究,结果表明建立的模型可用于设计具有潜在高活性的先导化合物。
基金This work was supported by the Ministry of Science and Technology of China (Nos. 2016YFC0202700, 2016YFE0112200, 2014BAC22B01), the National Natural Science Foundation of China (Nos. 21527814, 2107702S) and the Marie Sktodowska- Curie Actions (Nos. 690958-MARSU-RISE-2015).
文摘The isomerization reaction of pinene is one of the most important chemical reactions in the deep processing of pinene. The purpose of this study is to improve the performance of the metatitanic acid by composite. The composite metatitanic acid catalyst TiM was prepared by adding Mn elements in the preparation process. The catalytic performance of TiM was evaluated. Comparison of TiM and metatitanic acid catalyst(Ti-FGP), the reaction rate of TiM catalyst was faster, and after the reaction, the yield of camphene and tricyclene increased about 1%. The catalysts were characterized by an SEM, FT-IR and laser particle size analyzer. The results show that the pinene isomerization reaction requires the synergistic action of the Br?nsted acid and Lewis acid.Br?nsted acid has great influence on the activity of catalyst, and Lewis acid has a great influence on the selectivity of the catalyst. The structure and morphology of the catalyst have a certain effect on the selectivity of pinene isomerization reaction.
基金The Scientific Research Foundation of the Education Ministry for Returned Chinese Scholars,China(No.[2013]693) the National Natural Science Foundation of China(No.11404039)
文摘为研究α-蒎稀的光电离解离机制,采用同步辐射光电离质谱,在7.9-15.5 e V能量范围内研究了α-蒎稀的紫外光电离解离,对α-蒎稀的电离解离能及其碎片离子的出现势进行了理论分析.实验测得光电离效率曲线,从光电离效率曲线中获得α-蒎稀C10H16的电离能和碎片离子C9H+13,C7H+10,C3H6+及CHH3+的出现势.用Gaussian 03理论方法计算了C10H16和主要的光解离碎片的总能量,用高级能量计算方法计算了C10H16的电离能和部分碎片离子的出现势及主要的解离通道的离解能.根据实验和理论计算结果,分析了产生碎片离子的主要的解离通道.分析表明实验测得的结果与理论计算提出的C10H16的光解离通道获得的解离能符合得较好.