CN108271786B - 一种ocotillol型化合物作为农业杀菌剂的新用途 - Google Patents

一种ocotillol型化合物作为农业杀菌剂的新用途 Download PDF

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CN108271786B
CN108271786B CN201810152570.0A CN201810152570A CN108271786B CN 108271786 B CN108271786 B CN 108271786B CN 201810152570 A CN201810152570 A CN 201810152570A CN 108271786 B CN108271786 B CN 108271786B
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孟庆国
宋萍萍
王文智
张建强
王朝明
刘智
邓建强
王嘉珍
翁卫钊
何萌
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Abstract

本发明公开了一种ocotillol型化合物作为农业杀菌剂的新用途。该化合物作为杀菌剂用于防治农业真菌性病害，可有效地防治水稻纹枯病、油菜菌核病、小麦赤霉病、葡萄炭疽病、玉米小斑病等农作物病害，尤其对于玉米小斑病菌的抑制活性较强。此化合物作为活性成分制成的农业杀菌剂对于玉米小斑病具有防治效果好以及低毒、无残留、无污染、无公害的特点。

Description

一种ocotillol型化合物作为农业杀菌剂的新用途
技术领域
本发明属于农业技术领域，具体涉及一种ocotillol型化合物作为活性成分制备农业杀菌剂的新用途。
背景技术
农作物的病害由于不像害虫和杂草那样容易被人们及时察觉，所以往往造成防治上的忽视和困难，因而其危害就更为严重。据报道，全世界单是由病原真菌引起的植物病害就多达一万种，所造成的损失占作物年度总损失的10％～30％。如果把病毒、细菌和线虫等引起的植物病害也算在内，其损失就更为可观。
为了满足人们对粮食和其它生活物质日益增长的需要，不得不采用化学品以保护作物不受有害生物的侵袭，其中杀菌剂起着重要作用。目前常用化学药剂苯并咪唑类、氨基甲酸酯类及对二甲酰亚胺类杀菌剂等已产生抗性，并且有些品种之间存在正交互抗性，导致药剂防效下降，因此亟需研发新型防治药剂进行交替使用，以减少产量损失、缓解抗药性问题。
Ocotillol型化合物是一种侧链含有呋喃环的四环三萜类化合物，其结构通式：
Figure BDA0001580257100000011
在前期研究中，我们分别以二醇组皂苷20(R/S)-PPD、20(S)-Rh2、20(S)-Rg3和三醇组皂苷20(S)-PPT、20(S)-Rh1、20(S)-Rg2为原料制备了ocotillol型衍生物，并通过NMR谱或单晶X-ray衍射对其立体构型进行了确证。该类化合物溶于甲醇、乙醇、丙酮、乙酸乙酯、氯仿等有机溶剂。对其活性作用研究较少，至今没有作为农业杀菌剂在农业上应用的相关文献或报道。
参考文献：
[1]Xu Y R,YangJ J,Liu J,et al.Synthesis and crystal structures ofC24-epimeric 20(R)-ocotillol-type saponins[J].Acta Crystallographica SectionC:Structural Chemistry,2016,72(6):498-503.
[2]Meng Q G,Tan W J,Hou G G,et al.Synthesis and structuralcharacterization of two epimers driven from 20(S)-protopanaxadiol[J].Journalof MolecularStructure,2013,1054:1-5.
[3]Bi Y,Wang T,Meng Q G,et al.Synthesis and myocardial ischemiaprotective effect of ocotillol-type derivatives[J].Records of NaturalProducts,2012,6(3):242-254.
[4]Meng Q G,Liu L D,Guo H M,et al.(3R,6R,12R,20S,24S)-20,24-Epoxydammarane-3,6,12,25-tetraol dihydrate[J].Acta Crystallographica SectionE:Structure Reports Online,2010,66(12):o3210-o3210.
[5]Zhang L,Guo H M,Li W J,et al.(3R,6R,12R,20S,24R)-20,24-Epoxydammarane-3,6,12,25-tetraol[J].Acta Crystallographica Section E:Structure Reports Online,2011,67(4):o846-o846.
[6]Yi Bi,Tian J W,Ji C M,et al.Ocotillol-type derivatives(II)synthesis and protective effects on cultured anoxia/reoxygen injurymyocardiocytes[J].Journal of Medicinal Plants Research,2011,5(31):6731-6737.
发明内容
本发明的目的是提供ocotillol型化合物作为活性成分在制备农业杀菌剂的新应用。一种ocotillol型化合物作为农业杀菌剂的用途，所述ocotillol型化合物结构如通式(Ⅰ)所示：
Figure BDA0001580257100000031
其中：C-20构型为R或S，C-24构型为R或S，R2为-H时，R1选自基团-OH或
Figure BDA0001580257100000032
R1为-OH时，R2选自基团-OH或
Figure BDA0001580257100000033
所述ocotillol型化合物结构如下化合物1-24所示：
Figure BDA0001580257100000041
本发明所合成的上述ocotillol型化合物作为活性成分制备得到的农业杀菌剂具有优异的杀菌活性，可应用在防治各种农作物上的真菌性病害，如：玉米小斑病、葡萄炭疽病、油菜菌核病、水稻纹枯病、小麦赤霉病等，尤其对于玉米小斑病菌的抑制活性较强。
所合成的上述ocotillol型化合物作为活性成分和农药助剂、赋型剂配制成农药上允许的任意一种剂型。其还可以和其它农药复配，与农药助剂、赋型剂混合制成农药上允许的任意一种剂型。所述的剂型可以是乳油、悬浮剂、水乳剂、可湿性粉剂、微乳剂或水分散颗粒剂等。所述农药助剂可以采用十二烷基苯磺酸钙、吡咯烷酮、聚氧乙烯聚氧丙稀嵌段化合物、壬基酚聚氧乙烯醚等，所述赋形剂可为环己酮、溶剂油、水、丙二醇、去离子水等。复配所用的其他农药可为有机杀菌剂类，如三唑类杀菌剂三唑醇等。
与现有技术比较本发明的有益效果：所合成的ocotillol型化合物作为杀菌剂，抑菌谱广，持效期长，是农业上理想的杀菌剂。ocotillol型化合物为天然化学成分的结构优化产物，与一般化学农药相比，对于各种粮食、瓜果、蔬菜等经济作物具有低毒、无残留、无污染、无公害的特点，更有利环境保护。
具体实施方式
以下通过具体实施方式对本发明效果做进一步说明：
表1本发明中部分化合物的NMR和HR-MS数据
Figure BDA0001580257100000051
Figure BDA0001580257100000061
表2化合物13和14的晶体数据
Figure BDA0001580257100000062
Figure BDA0001580257100000071
R1＝Σ||Fo|-|Fc||/Σ|Fo|.wR2＝{Σ[w(Fo 2–Fc 2)2]/Σ[w(Fo 2)2]}1/2
实施例1：Ocotillol型化合物对农业病害的防治
供试菌株长蠕孢菌(Helminthosporium maydis Nisik&Miy)从玉米病叶上分离；立枯丝核菌(Thanatephorus cucumeris)从水稻纹枯病病叶上分离；核盘菌(Sclerotioiaselerotiorum)从油菜菌核病菌株上分离得到；胶孢炭疽菌(Colletotrichumgloeosporioides)从葡萄病果上分离得到；禾谷镰孢菌(Fusarium.graminearm)从小麦赤霉病穗上分离得到。
分别将供试化合物溶于甲醇，制成1000μg/mL母液，4℃保存备用。PDA培养基:200g去皮马铃薯切成块，煮沸10min后，取汁，加入20g琼脂，加热至熔化，再加入20g葡萄糖，用水定容至1000mL。
采用菌丝生长速率测定法对菌丝生长的抑制测定，从PDA平板上预培养的供试菌边缘打取菌碟(直径5mm)，将供试药剂母液与培养基均匀混合，使供试药剂最终浓度为10ppm，混合液倾入直径为9cm的灭菌培养皿中制成平板，每皿接种一菌碟，菌丝面朝上，每处理重复3次。25℃培养至对照菌落布满培养皿三分之二以上时，十字交叉法测量菌落增长直径。由菌落直径平均值(mm)计算生长抑制率。
从结果中可以看出供试化合物有效地防治玉米小斑病、葡萄炭疽病、油菜菌核病、水稻纹枯病、小麦赤霉病等，具体实验结果见表3；通过实验充分体现了本发明提供供试化合物的农药用途的显著效果，尤其对真菌性病害玉米小斑病防治效果明显。
表3部分化合物对农业病害的抑菌率％
Figure BDA0001580257100000081
实施例2：
由于化合物对真菌性病害玉米小斑病防治效果较好，采用菌丝生长速率测定法测定化合物对菌丝生长的抑制。从PDA平板上预培养的供试菌边缘打取菌碟(直径5mm)，将供试药剂母液与培养基均匀混合，使供试药剂最终浓度为30、20、10、5、2.5ppm，混合液倾入直径为9cm的灭菌培养皿中制成平板，每皿接种一菌碟，菌丝面朝上，每处理重复3次。25℃培养至对照菌落布满培养皿三分之二以上时，十字交叉法测量菌落增长直径。根据下列公式，计算出不同浓度下的抑制率(％)。抑制率(％)＝[(对照菌落直径(mm)-处理菌落直径(mm))/(对照菌落直径(mm)-5)]×100，式中：5为打孔器直径。通过DPS数据处理软件，根据药剂浓度的对数(X)与抑制率对应的几率值(Y)，求出毒力回归曲线方程Y＝a+bX及EC50。每组数据均采用means±SEM进行表示，用Student’s t-test和One-way ANOVA进行组间比较，P<0.05提示有显著差异，P<0.01提示有极显著差异。
表4部分化合物对玉米小斑病菌的EC50
Figure BDA0001580257100000082
Figure BDA0001580257100000091
实施例3：
称取化合物1(或化合物2、或化合物13、或化合物14)，与木质素、硅藻土等常规辅料按照常规工艺，制成有效成分浓度为2％的可湿性粉剂。
实施例4：
称取化合物1(或化合物2、或化合物13、或化合物14)，与十二烷基苯磺酸钙、苯乙基酚聚氧乙烯醚、溶剂油等常规辅料按照常规工艺，制成有效成分浓度为2％的乳油。
实施例5：
称取化合物1(或化合物2、或化合物13、或化合物14)，与木质磺酸钠、高岭土等常规辅料按照常规工艺，制成有效成分浓度为2％的水分散粒剂。
实施例6：
称取化合物1(或化合物2、或化合物13、或化合物14)，与溶剂油、吡咯烷酮，黄原胶等常规辅料按照常规工艺，制成有效成分浓度为1％的水乳剂。
实施例7：
称取化合物1(或化合物2、或化合物13、或化合物14)，与十二烷基苯磺酸钙、吡咯烷酮等常规辅料按照常规工艺，制成有效成分浓度为1％的微乳剂。
实施例8：
按照重量比1：5的比例称取化合物1(或化合物2、或化合物13、或化合物14)和三唑醇，与溶剂油、吡咯烷酮，黄原胶等常规辅料按照常规工艺，制成有效成分浓度为5％的水乳剂。

Claims (1)

1.一种ocotillol型化合物作为农业杀菌剂的用途，其特征在于所述ocotillol型化合物为化合物1-2、化合物13-14，
Figure FDA0002504209760000011
并且，所述化合物1-2、化合物13-14作为玉米小斑病、葡萄炭疽病、油菜菌核病、水稻纹枯病、小麦赤霉病的农业杀菌剂的用途。
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