Structural Modification of Turpentine with Natural Chiral Preservation and Low-Risk Application Prospects in Crop Protection
Structural Modification of Turpentine with Natural Chiral Preservation and Low-Risk Application Prospects in Crop Protection
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天然手性保护的松节油结构改性及其在作物保护中的低风险应用前景
DOI：
10.1021/acsomega.9b00241
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发表时间：
2019-04-01
期刊：
影响因子：
4.1
通讯作者：
Shang, Shibin
中科院分区：
文献类型：
--
作者：
Gao, Yanqing;Hao, Jin;Shang, Shibin
为了开发手性农药，应合理利用松节油的天然手性结构。制备了两个系列的酰胺衍生物来研究手性中心保留对杀菌活性的影响。对三种病原微生物的杀菌活性进行了广泛的研究。活动评价得到了一些令人满意的结论。最重要的是，衍生自顺式桃金娘酸(从β-蒎烯获得的手性化合物)的化合物(5'a-1)表现出比衍生自脱氢枯酸(从β-蒎烯获得的非手性化合物)更好的活性。总体效果良好，值得注意的是，化合物5'd（用N-（4-（三氟甲基）苯基）取代）、5'e（用N-（4-氟苯基）取代）和5'f（用N-（4-氯苯基）取代）表现出极其优异的活性，针对Valsa的EC50值分别为1.604、1.822和2.296μg/mL 马里。上述三种化合物在体外对苹果枝条上的苹果弧菌也表现出良好的防治效果。与未处理的对照相比，用 5'd、5'e 和 5'f 处理苹果酸杆菌会显着影响生理和生化指标，并且果胶酶活性显着降低。总结了初步的构效关系（SAR），表明通过手性获得的化合物 中心、卤素原子和小的空间位阻表现出更好的性能。同时，获得了定量构效关系（QSAR）模型（R-2 = 0.9288，F = 62.01，S-2 = 0.0138），两个最重要的结构特征是F原子的最大净原子电荷和阴影指数。以本研究为指导，高效、低毒、环境友好 通过对萜烯的合理改性可以制备杀菌剂。
For the purpose of chiral pesticide development, the natural chiral structure of turpentine should be applied rationally. Two series of amide derivatives were prepared to study the effect of chiral center retention on the fungicidal activity. The investigation of fungicidal activity against three pathogenic microbes was carried out extensively. Some satisfactory conclusions were obtained from the activity evaluation. Above all, compounds (5'a-l) derived from cis-myrtlecanic acid (a chiral compound obtained from beta-pinene) exhibited better activity than compounds (5a-l) derived from dehydrocumic acid (achiral compound obtained from beta-pinene). The overall effect was good, and it was remarkable that compounds 5'd (substitute with N-(4-(trifluoromethyl)phenyl), 5'e (substitute with N-(4-fluorophenyl)), and 5'f (substitute with N-(4-chlorophenyl)) demonstrated extremely excellent activity, with EC50 values of 1.604, 1.822, and 2.296 mu g/mL against Valsa mali. The above three compounds also showed a good control effect against V. mali in vitro on an apple branch. Treatment with 5'd, 5'e, and 5'f against V. mali resulted in significantly influenced physiological and biochemical indices, as well as markedly reduced pectinase activity in comparison with untreated controls. The preliminary structure-activity relationship (SAR) was summarized, showing that compounds obtained with chiral centers, a halogen atom, and small steric hindrance showed better performance. At the same time, the quantitative structure-activity relationship (QSAR) model (R-2 = 0.9288, F = 62.01, S-2 = 0.0138) was obtained, and two most important structural features were maximum net atomic charge for a F atom and shadow indices. Guided by this study, the highly efficient, low-toxicity, and environmentally friendly fungicide can be prepared through reasonable modification of terpene.