几种雷公藤单碱的分离及其杀虫活性研究
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摘要
植物源农药具有低毒、低残留、对环境影响小，对人畜无害、害虫不易产生抗性等特点，是新型农药开发的方向之一。雷公藤（Tripterygium wilfordii Hook）是一种重要的中药资源，也是传统的杀虫植物。西北农林科技大学科技大学无公害农药研究服务中心研究发现雷公藤根皮中的主要杀虫活性物质是生物碱类。为了进一步明确雷公藤生物碱的杀虫活性及各单碱中的高活性成分。本研究对雷公藤根皮中的雷公藤单碱进行了分离并系统地测定了其杀虫活性。主要研究结果如下：
1.采用现代分离纯化手段对雷公藤总生物碱进行分离，得到了7个化合物并通过各种波谱数据和化合物的理化性质，鉴定了7个化合物的结构，分别为：雷公藤精碱（K0）、1-Desacetylwilforgine（K1）、雷公藤吉碱（K2）、1-Desacetylwilforine（K3）、雷公藤次碱（K4）、雷公藤春碱（K5）、Peritassines A（K6）；
2.采用小叶碟添加法、点滴法、载毒叶片法等方法测定了分离得到的7个单碱的杀虫活性。结果表明，7个化合物对小菜蛾（Plutella xylostella）、粘虫（Mythimna separatea(Walker)）、菜青虫(Pieris rapae L)、烟蚜(Myzus persicae(Sulzer))、桃蚜(Sitophilus zeamaisMotschulsky)以及玉米象（Sitophilus zeamais）均无触杀活性；对粘虫(M. separatea)、小菜蛾（P. xylostella）以及菜青虫(P. rapae)有一定的麻醉和拒食作用；其中雷公藤吉碱（K2）、1-Desacetylwilforine（K3）、雷公藤次碱（K4）对粘虫3龄幼虫24h的拒食中浓（AFC50）分别为17.24、33.52和4.10g/mL；48h麻醉中浓（KD50）分别为630.30、212.17和100.89g/mL；对小菜蛾3龄幼虫24h的拒食中浓分别为54.62、55.19和36.65g/mL；48h的麻醉中浓分别为164.43、337.66和96.42g/mL；对淡色库蚊（Culexpipiens pallenss Coquillett）4龄蚊虫有一定的毒杀作用；对家蝇（Musca domesticaLinnaeus）成虫有一定的击倒和毒杀作用；其中雷公藤精碱、1-Desacetylwilforgine、1-Desacetylwilforine、和Peritassines A的杀虫活性为首次报道。
3.雷公藤次碱和雷公藤吉碱是7种雷公藤单碱中主要的杀虫活性成分。
Botanical pesticides with low toxicity, low-residue, safe to the environment, harmless tohumans and animals, pests difficult to generate resistance, is one of the main developmentdirection of new pesticides. Tripterygium wilfordii Hook is an important traditional Chinesemedicine, and also a traditional botanical insecticides. A series of studies on Tripterygiumwilfordii Hook had proved that alkaloids from the root bark of Tripterygium wilfordii Hookare the main insecticidal compositions by Research&Development Center of BiorationalPesticide, Northwest A&F University. In this study, the insecticidal activities of severalalkaloids isolated from Tripterygium wilfordii Hook had been studied in order to verify themain insecticidal alkaloid which are the high-performance components. The main results weregiven as follows:
1. The chemical constituents of total alkaloid from the root bark of Tripterygium wilfordiiHook had been studied by means of modern separation and purification ways(~1H-NMR,~(13)C-NMR,IR,ESI-MS).7compounds were isolated from the total alkaloid and thestructures of7compounds were elucidated as Wilforjine (K0),1-Desacetylwilforgine(K1),Wilforgine(K2),1-Desacetylwilforine(K3), Wilforine(K4), Wilfotrine (K5) and PeritassinesA (K6)；
2. The insecticidal activities of7compounds were tested by leaf disk method, topicalapplication and the leaf sandwich method. The result showed that all tested compounds haveno contact toxicity against Plutella xylostella (L.)，Mythimna separatea (Walker),Pieris rapaeL.,Myzus persicae(Sulzer) and Sitophilus zeamais Motschulsky;1-Desacetylwilforgine(K1),Wilforgine(K2),1-Desacetylwilforine(K3) and Wilforine(K4) have antifeedant andnarcotization activity against Mythimna separatea (Walker),Pieris rapae L and Plutellaxylostella (L.); Wilforgine,1-Desacetylwilforine and Wilforine have antifeedant andarcotization activity against Plutella xylostella (L.) and Mythimna separatea (Walker). The24h post treatment AFC50of Wilforgine,1-Desacetylwilforine and Wilforine against3rd instarlarvae of Mythimna separatea (Walker) are17.24,33.52and4.10g/mL;48h post treatmentKD50are630,212.17and100.89g/mL respectively. The24h AFC50of Wilforgine,1-Desacetylwilforine and Wilforine against Plutella xylostella (L.) are54.62,55.19and36.65g/mL;48h post treatment KD50are164.43,337.66and96.42g/mL.1-Desacetylwilforgine, Wilforgine,1-Desacetylwilforine and Wilforine also have poisonousactivity against4th instar larvae of Culex pipiens pallenss Coquillett and know-down andpoisonous activity against Musca domestica Linnaeus. This is the first report on insecticidalactivity of Wilforjine,1-Desacetylwilforgine,1-Desacetylwilforine and Peritassines A;
3. Wilforgine and Wilforine are the the main insecticidal active ingredients of the7alkaloidsfrom Tripterygium wilfordii Hook.
1.采用现代分离纯化手段对雷公藤总生物碱进行分离，得到了7个化合物并通过各种波谱数据和化合物的理化性质，鉴定了7个化合物的结构，分别为：雷公藤精碱（K0）、1-Desacetylwilforgine（K1）、雷公藤吉碱（K2）、1-Desacetylwilforine（K3）、雷公藤次碱（K4）、雷公藤春碱（K5）、Peritassines A（K6）；
2.采用小叶碟添加法、点滴法、载毒叶片法等方法测定了分离得到的7个单碱的杀虫活性。结果表明，7个化合物对小菜蛾（Plutella xylostella）、粘虫（Mythimna separatea(Walker)）、菜青虫(Pieris rapae L)、烟蚜(Myzus persicae(Sulzer))、桃蚜(Sitophilus zeamaisMotschulsky)以及玉米象（Sitophilus zeamais）均无触杀活性；对粘虫(M. separatea)、小菜蛾（P. xylostella）以及菜青虫(P. rapae)有一定的麻醉和拒食作用；其中雷公藤吉碱（K2）、1-Desacetylwilforine（K3）、雷公藤次碱（K4）对粘虫3龄幼虫24h的拒食中浓（AFC50）分别为17.24、33.52和4.10g/mL；48h麻醉中浓（KD50）分别为630.30、212.17和100.89g/mL；对小菜蛾3龄幼虫24h的拒食中浓分别为54.62、55.19和36.65g/mL；48h的麻醉中浓分别为164.43、337.66和96.42g/mL；对淡色库蚊（Culexpipiens pallenss Coquillett）4龄蚊虫有一定的毒杀作用；对家蝇（Musca domesticaLinnaeus）成虫有一定的击倒和毒杀作用；其中雷公藤精碱、1-Desacetylwilforgine、1-Desacetylwilforine、和Peritassines A的杀虫活性为首次报道。
3.雷公藤次碱和雷公藤吉碱是7种雷公藤单碱中主要的杀虫活性成分。
Botanical pesticides with low toxicity, low-residue, safe to the environment, harmless tohumans and animals, pests difficult to generate resistance, is one of the main developmentdirection of new pesticides. Tripterygium wilfordii Hook is an important traditional Chinesemedicine, and also a traditional botanical insecticides. A series of studies on Tripterygiumwilfordii Hook had proved that alkaloids from the root bark of Tripterygium wilfordii Hookare the main insecticidal compositions by Research&Development Center of BiorationalPesticide, Northwest A&F University. In this study, the insecticidal activities of severalalkaloids isolated from Tripterygium wilfordii Hook had been studied in order to verify themain insecticidal alkaloid which are the high-performance components. The main results weregiven as follows:
1. The chemical constituents of total alkaloid from the root bark of Tripterygium wilfordiiHook had been studied by means of modern separation and purification ways(~1H-NMR,~(13)C-NMR,IR,ESI-MS).7compounds were isolated from the total alkaloid and thestructures of7compounds were elucidated as Wilforjine (K0),1-Desacetylwilforgine(K1),Wilforgine(K2),1-Desacetylwilforine(K3), Wilforine(K4), Wilfotrine (K5) and PeritassinesA (K6)；
2. The insecticidal activities of7compounds were tested by leaf disk method, topicalapplication and the leaf sandwich method. The result showed that all tested compounds haveno contact toxicity against Plutella xylostella (L.)，Mythimna separatea (Walker),Pieris rapaeL.,Myzus persicae(Sulzer) and Sitophilus zeamais Motschulsky;1-Desacetylwilforgine(K1),Wilforgine(K2),1-Desacetylwilforine(K3) and Wilforine(K4) have antifeedant andnarcotization activity against Mythimna separatea (Walker),Pieris rapae L and Plutellaxylostella (L.); Wilforgine,1-Desacetylwilforine and Wilforine have antifeedant andarcotization activity against Plutella xylostella (L.) and Mythimna separatea (Walker). The24h post treatment AFC50of Wilforgine,1-Desacetylwilforine and Wilforine against3rd instarlarvae of Mythimna separatea (Walker) are17.24,33.52and4.10g/mL;48h post treatmentKD50are630,212.17and100.89g/mL respectively. The24h AFC50of Wilforgine,1-Desacetylwilforine and Wilforine against Plutella xylostella (L.) are54.62,55.19and36.65g/mL;48h post treatment KD50are164.43,337.66and96.42g/mL.1-Desacetylwilforgine, Wilforgine,1-Desacetylwilforine and Wilforine also have poisonousactivity against4th instar larvae of Culex pipiens pallenss Coquillett and know-down andpoisonous activity against Musca domestica Linnaeus. This is the first report on insecticidalactivity of Wilforjine,1-Desacetylwilforgine,1-Desacetylwilforine and Peritassines A;
3. Wilforgine and Wilforine are the the main insecticidal active ingredients of the7alkaloidsfrom Tripterygium wilfordii Hook.
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