β-二氢沉香呋喃倍半萜衍生物的合成及杀虫活性研究

发布时间：2018-10-24 07:58

【摘要】：我们以苦皮藤提取物的水解产物1β,2β,4α,6α,8β,9α,12-七羟基-β-二氢沉香呋喃为原料,设计合成了一系列β-二氢沉香呋喃倍半萜衍生物,采用了乙醚麻醉强制喂食法测定了它们对粘虫六龄幼虫的毒杀活性。主要研究结果如下:1.化合物的合成以及结构鉴定(1)以1β,2β,4α,6α,8β,9α,12-七羟基-β-二氢沉香呋喃(1)为主要原料,得到1β,4α,6α,9α-四羟基-β-二氢沉香呋喃(2),化合物2与多聚甲醛、乙醛、正丙醛、正丁醛、异丁醛生成1-位和9-位缩醛化合物2.1-2.5,然后在氢化钠的作用下与相应的卤代烃反应生成55个目标化合物2.1.1-2.1.11、2.2.1-2.2.11、2.3.1-2.3.11、2.4.1-2.4.11、2.5.1-2.5.11。(2)化合物2在三氯化铁催化下与丙酮反应生成1-位和9-位的缩酮化合物2.6,化合物2.6在氢化钠的作用下与相应的卤代烃生成化合物2.6.1-2.6.9,化合物2.6.1-2.6.9分别在0.8%H2SO4的催化作用下脱去丙酮生成中间体2.6.1.0-2.6.9.0,然后化合物2.6.1.0-2.6.9.0分别在氢化钠的作用下分别与邻氟溴苄、对氟溴苄反应生成18个目标化合物2.6.1.1-2.6.9.1、2.6.1.2-2.6.9.2。(3)所有的目标化合物的结构均通过1H NMR、13C NMR和DEPT-135°进行鉴定,通过NOESY谱和X-射线单晶衍射确定化合物2.3.7和2.5.11的立体构型。2.杀虫活性测定采用乙醚麻醉强制喂食法测定了73个目标化合物对粘虫六龄幼虫的毒杀活性,结果表明在20 mg/mL的浓度下,给药量为1μL时,化合物2.1.4、2.1.7、2.1.8、2.1.10、2.1.11、2.2.4、2.2.9、2.2.10、2.2.11、2.3.2、2.3.4、2.3.5、2.3.6、2.3.7、2.3.8、2.3.9、2.3.10、2.3.11、2.4.2、2.4.3、2.4.6、2.4.10、2.5.3、2.5.4、2.5.7显示良好的毒杀活性。LD50测定结果表明化合物2.1.10、2.2.9、2.2.10、2.2.11、2.3.4、2.3.6、2.3.7、2.5.4、2.5.7对六龄粘虫幼虫的LD50值均小于阳性对照苦皮藤素V,其中以化合物2.2.11的活性最佳,其LD50值为60.33μg/g。构效关系分析表明乙基、正丙基、正丁基、烯丙基、炔丙基、领氟苄基、对氟苄基等基团是活性基团。研究结果为开发高效、环境友好型农药提供了重要的理论与实验依据。
[Abstract]:A series of 尾 -dihydrofuran sesquiterpenoid derivatives were designed and synthesized from 1 尾, 2 尾, 4 伪, 6 伪, 8 尾, 9 伪, 12-heptahydro- 尾-dihydrofuran. The toxicity of ether anesthetic force-feeding method to sixth instar larvae of armyworm was determined. The main results are as follows: 1. Synthesis and structural characterization of the compounds (1) 1 尾, 4 尾, 4 伪, 6 伪, 8 尾, 9 伪, 12-heptahydroxy-尾-dihydrofuran (1) was used as the main raw material to obtain 1 尾, 4 伪, 6 伪, 9 伪-tetrahydroxy-尾-dihydrofuran (2), compound 2 and polyformaldehyde, acetaldehyde, n-propionaldehyde, n-butyraldehyde, Isobutyraldehyde produces 1-site and 9-site acetals 2.1-2.5, and then reacts with corresponding halogenated hydrocarbons in the presence of sodium hydride to form 55 target compounds, 2.1.1-2.1.112.2.2.2.112.3.1-2.3.112.4.1-2.4.112.2.5.1-2.5.11.The (2) compound 2 reacts with acetone catalyzed by ferric chloride to form 1- and 9- sites. Ketal compound 2.6, compound 2.6 reacted with corresponding halogenated hydrocarbon compounds 2.6.1-2.6.9. compounds 2.6.1-2.6.9 deacetone to form intermediate 2.6.1.0-2.6.9.0 under the catalysis of 0.8%H2SO4, and then compound 2.6.1.0-2.6.9.0 acted on sodium hydride, respectively. With o-fluorobenzyl bromide, 18 target compounds were synthesized by the reaction of fluorobenzyl bromide 2.6.1.1-2.6.9.1n 2.6.1.2-2.6.9.2. (3) the structures of all the target compounds were identified by 1H NMR,13C NMR and DEPT-135 掳, and the stereotypes of compounds 2.3.7 and 2.5.11 were determined by NOESY spectra and X-ray single crystal diffraction. The toxicity of 73 target compounds to the sixth instar larvae of armyworm was determined by using ether anesthesia force-feeding method. The results showed that at the concentration of 20 mg/mL, the dosage was 1 渭 L. Compound 2.1.42.2.1.7A 2.1.102.1.102.1.112.4.102.2.2.2.102.2.102.2.102.2.102.2.102.2.102.2.2.102.2.2.102.2.2.3.22.2.3.42.2.3.42.2.3.42.2.3.82.2.1.72.3.102.2.1.72.3.102.2.2.2.1.72.1.72.1.72.1.72.1.72.1.72.1.10 2.3.32.3.32.2.112.112.112.112.112.92.102.2.102.2.92.2.92.2.112.2.112.2.2.3.42.2.3.72.2.72.42.5.5.7 the LD50 value of compound 2.1.40.10 is lower than that of the control, with the best activity of LD50 being 60.33 g / r. Structure-activity relationship analysis showed that ethyl, n-propyl, normal Ding Ji, allyl, propargyl, fluorobenzyl, p-fluorobenzyl were active groups. The results provide an important theoretical and experimental basis for the development of efficient and environmentally friendly pesticides.
【学位授予单位】：西北农林科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ453

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