CN110627759B - 倍半萜类化合物及其制备方法和用途 - Google Patents
倍半萜类化合物及其制备方法和用途 Download PDFInfo
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- CN110627759B CN110627759B CN201910918693.5A CN201910918693A CN110627759B CN 110627759 B CN110627759 B CN 110627759B CN 201910918693 A CN201910918693 A CN 201910918693A CN 110627759 B CN110627759 B CN 110627759B
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Abstract
本发明涉及倍半萜类化合物及其制备方法和用于农药,尤其作为拒食剂和/或生长发育抑制剂的用途。所述化合物具有下述式1‑4所示结构:
Description
技术领域
本发明涉及倍半萜类化合物及其制备方法和用于农药,尤其作为昆虫拒食剂和/或昆虫生长发育抑制剂的用途。
背景技术
小菜蛾、甜菜夜蛾和斜纹夜蛾都是世界范围内分布十分广泛的杂食性农业害虫,对农业危害很大,而化学杀虫剂的滥用使得土地、空气和水资源的受污染,危害人类健康。此外,由于长期大量不合理使用化学药剂,导致这些农业害虫的抗药性不断增强,使得害虫防治更困难,一方面也导致了化学药剂的进一步大量使用,形成恶性循环。据估算,全球每年因为农药引起的损失高达千亿美元,随着科学理念的发展,科学界以及社会公众希望能在不危害环境和人类健康的前提下有效地防治害虫。害虫防治的目的是减少或者控制危害,目前使用的方法有灭杀、拒食趋避或者抑制发育繁殖,传统杀虫剂大多是直接杀死害虫,因此有高毒性且不易降解,但是如果通过拒食方式防止害虫侵扰或者抑制害虫生长发育繁殖来间接减少害虫数量,也可实现有效的保护。生产一款有效的、低毒性、低残留的产品对于农作物安全至关重要。因此从植物中筛选一种安全高效的昆虫拒食性化合物,对其加以开发利用,可以有效防治害虫侵扰。
植物是生物活性物质的天然宝库,不仅为人类对抗疾病提供有力武器,而且为我国植物源农药发展提供绿色低毒物质。毛莲蒿(Artemisia vestita Wall.ex Bess.)为菊科(Compositae)蒿属(Artemisia)植物,主要分布于的荒地和河滩,被广泛应用于藏药和中药中,是西藏姿势去藏药厂生产的结血蒿膏的主要药材,毛莲蒿地上部分入药,有清热、消炎、祛风、利湿之效。现代药理研究表明,毛莲蒿具有多种生物活性,包括抗炎作用[4 5],对LPS诱导的NO产生有抑制作用。此外,还发现A.vestita对Sitophilus zeamais和Haemonchus contortus具有较强的杀虫活性。毛莲蒿中含有黄酮类、有机酸、香豆素、生物碱、挥发油及油脂、甾体或三萜类等化学成分。从毛莲蒿中分离到大量倍半萜类化合物,具有一定的生物活性。倍半萜类化合物在植物防御害虫和植物病原真菌方面具有重要作用,可作为天然杀虫剂和抗真菌剂。
根据现有文献的报道,毛莲蒿的提取物的成分是非常复杂的,而且由于提取方法的不同而往往导致提取到不同的活性成分。
论文“毛莲蒿化学成分研究”从毛莲蒿中提取并获取了18种化合物,用石油醚(60-90℃)-乙醚-甲醇(1:1:l)冷浸提3次,每次48h,获得浸膏后,用硅胶柱层析分段洗脱得到:石油醚部分、石油醚-乙醚(1:1)部分、乙酸乙酯类部分、甲醇部分部分,石油醚-乙醚部分经多次硅胶柱层析,分别以石油醚-苯,石油醚-乙醚,石油醚-乙酸乙酯,石油醚-丙酮适当极性比列分离纯化得到化合物taurin(1),1,11-Bis-epi-artesin(2),蒲公英赛醇乙酸醋(8),木栓酮(9),香树脂醇(10),麦角甾-5-烯-3,25-二醇(11),β-谷甾醇(12),二十八烷烃(18),乙酸乙酯部分分离获得化合物yomogin(3),achillin(4),胡萝卜甙(13),莨菪亭(14),7-羟基-6,8-二甲氧基香豆素(15),异阿魏酸(16),咖啡酸(17),氯仿-甲醇洗脱得到化合物5,7,3’,4’-四羟基-6,8-二甲氧基黄酮(5),nepetin(6),pealitin(7)。其中(1)(2)(3)(4)为倍半萜类,(5)(6)(7)为黄酮类,(8)(9)(10)为三萜类,(11)(12)(13)为甾体类,(14)(15)(16)(17)为香豆素及其衍生物。
论文“毛莲蒿挥发油成分研究”使用GC/MS(气相色谱/质谱联用)技术报道了毛莲蒿挥发油的化学组成,其中单萜类物质(通式C10H16)有3种,包括樟烯(莰烯)、β-松油烯和β-蒎烯;单萜类衍生物6种,包括1,8-桉叶素(1,8-桉树脑)、樟脑(莰酮)、冰片(龙脑)、β-侧柏酮(β-苧酮)、醋酸冰片酯和小茴香酮;倍半萜类3种,包括α-毕澄茄油烯、反丁香烯和γ-杜松烯。
论文“响应面法优化藏药毛莲蒿总香豆素的超声辅助提取工艺”(西南师范大学学报(自然科学版),杨正明等,2016年)中,优化了响应面法提取毛莲蒿中总香豆素的提取工艺,结果表明,毛莲蒿总香豆素的最佳提取工艺为乙醇体积分数72%,浸提时间71min,浸提温度68℃,料液比1:58(g/mL)及超声时间30min,在该条件下毛莲蒿总香豆素的平均得率为3.45%。
论文“Sesquiterpenes from the aerial parts of Artemisia vestita Wall.”研究蒿属植物毛莲蒿地上部分倍半萜类化学成分,通过硅胶柱色谱、反相硅胶柱色谱、制备高效液相色谱等色谱方法分离得到12个倍半萜类成分,经多种波谱方法鉴定其结构,分别为negunfurol(1),schensianol A(2),artemine(3),eudesm-4(14)-en-12-oic acid,erivanin(4),1,5-diepi-artemin(5),acetylartemin(6),naphtho[1,2-b]furan-2(3H)-one,6-(acetyloxy)-decahydro-9a-hydroxy-3,5a-dimethyl-9-methylene-(3S,3aS,5aS,6S,9aS,9bS)(7),naphtho[1,2-b]furan-2(3H)-one,6-(acetyloxy)-3a,4,5,5a,6,7,8,9b-octahydro-8-hydroxy-3,5a,9-trimethyl-(3S,3aS,5aR,6S,8S,9bS)(8),isoerivanin(9),barrelierin(10),(11S)-1-oxoeudesm-4(14)-eno-13,6α-lactone(11),1-epi-dehydroisoeranin(12)。其中化合物1和2为首次从蒿属植物中分离得到,其它化合物均为首次从毛莲蒿中分离得到。
论文“毛莲蒿化学成分研究”从毛莲蒿中提取并获取了18种化合物,用石油醚(60-90℃)-乙醚-甲醇(1:1:l)冷浸提3次,每次48h,获得浸膏后,用硅胶柱层析分段洗脱得到:石油醚部分、石油醚-乙醚(1:1)部分、乙酸乙酯类部分、甲醇部分部分,石油醚-乙醚部分经多次硅胶柱层析,分别以石油醚-苯,石油醚-乙醚,石油醚-乙酸乙酯,石油醚-丙酮适当极性比列分离纯化得到化合物taurin(1),1,11-Bis-epi-artesin(2),蒲公英赛醇乙酸醋(8),木栓酮(9),香树脂醇(10),麦角甾-5-烯-3,25-二醇(11),β-谷甾醇(12),二十八烷烃(18),乙酸乙酯部分分离获得化合物yomogin(3),achillin(4),胡萝卜甙(13),莨菪亭(14),7-羟基-6,8-二甲氧基香豆素(15),异阿魏酸(16),咖啡酸(17),氯仿-甲醇洗脱得到化合物5,7,3’,4’-四羟基-6,8-二甲氧基黄酮(5),nepetin(6),pealitin(7)。其中(1)(2)(3)(4)为倍半萜类,(5)(6)(7)为黄酮类,(8)(9)(10)为三萜类,(11)(12)(13)为甾体类,(14)(15)(16)(17)为香豆素及其衍生物。
目前对于毛莲蒿提取物的活性成分和活性进行较多的研究,而且对于毛莲蒿的认识仅仅是其医用及医用卫生活性,未见本专利涉及倍半萜类新化合物及其在拒食剂方面的应用,更未见对小菜蛾、甜菜夜蛾和斜纹夜蛾生长发育抑制方面的研究报道。
发明内容
本发明的目的之一在于提供新型倍半萜类化合物,其选自下述式1-4所示化合物或者其晶型、或其立体异构体、或其农药学上可接受的盐、或其溶剂合物、或其前体药物、或其代谢产物、或其衍生物中的一种或多种:
发明人在研究中发现,上述新型化合物具有较好的脂溶性、通透性和渗透性等优点。
本发明的第二个目的在于提供上述倍半萜类化合物的制备方法,包括以下步骤:
1)室温萃取毛莲蒿,获得毛莲蒿萃取物;
2)将萃取物减压浓缩,得到渣油,分散水中,依次用石油醚、氯仿、乙酸乙酯、正丁醇分馏,得到石油醚浸膏、氯仿浸膏、乙酸乙酯浸膏、正丁醇浸膏、和水相浸膏;
3)取2)中氯仿浸膏,采用硅胶柱色谱依次以石油醚-氯仿体积比15:1、10:1、5:1、3:1、1:1为洗脱剂进行梯度洗脱,分别得到5个组分A-E;
4)取3)中A部分,采用硅胶柱色谱,以石油醚-乙酸乙酯体积比12:1为洗脱剂洗脱,薄层色谱检测,显色,经Sephadex LH-20(羟丙基葡聚糖凝胶)层析,以氯仿-甲醇体积比1:1洗脱,得到化合物经过薄层检测、显色,根据Rf值确定为化合物1(Rf=0.46)和化合物2(Rf=0.39);
5)取3)中B部分,采用硅胶柱色谱,以石油醚-乙酸乙酯体积比8:1为洗脱剂洗脱,薄层色谱检测,显色,合并相同Rf值的洗脱部分,得到化合物3(Rf=0.51);
6)取3)中C部分,采用硅胶柱色谱,以石油醚-氯仿体积比3:1为洗脱剂洗脱,薄层色谱检测,显色,合并相同Rf值的洗脱部分,得到化合物4(Rf=0.43)。
进一步的,本发明进行薄层色谱显色条件:紫外灯(254nm)下观察暗斑,喷洒10%硫酸乙醇后,105℃烘烤至显色。
进一步的,步骤1)中,萃取所用溶剂优选是甲醇。
进一步地,步骤1)包括将毛莲蒿干燥并粉碎至10-100目(例如20目),室温下萃取3次,每次7天,得到萃取物。
本发明的第三个目的在于提供上述倍半萜类化合物作为昆虫拒食剂和/或昆虫生长发育抑制剂在农药中的应用。进一步的,所述的昆虫为鳞翅目昆虫中的至少一种。进一步地,所述的昆虫为菜蛾科、夜蛾科昆虫中的至少一种。
本发明的化合物对小菜蛾、甜菜夜蛾和斜纹夜蛾有拒食活性和抑制生长发育活性,从而对小菜蛾、甜菜夜蛾和斜纹夜蛾具有较好综合防治效果,可减少现有化学农药杀虫剂使用的次数和用量。
本发明的第四个目的是提供一种农药制剂,其包括(A)上述式1-4所示倍半萜类化合物或其药学上可接受的盐、或其溶剂合物、或其前体药物、或其代谢产物中的一种或多种,以及(B)农药学上可接受的辅料。本发明的药物制剂中,组分(A)的质量百分数为10~25%,组分(B)的质量百分数为75~90%。
本发明的倍半萜类新化合物包括任何其晶型或其立体异构体。
在具体应用过程中,可以将本发明的所述的倍半萜类新化合物与无机酸或有机酸形成生理上可接受的盐,使化合物结构更加稳定,有利于保存和制备拒食剂和昆虫生长发育抑制剂,发挥拒食和抑制昆虫生长活性。
上述倍半萜类新化合物或其盐类化合物用做农用拒食剂、昆虫生长发育抑制剂时,可以直接使用,或者以农药组合物的形式使用。使用方式可以为灌根或喷洒植物。
本发明所述农药学上可接受的辅料,是指除活性成分以外包含在剂型中的物质,例如在可湿性粉剂的情况下,其可以选自十二烷基硫酸钠、CMC十二烷基硫酸钠、高岭土、凹凸棒粘土、分散剂等中的一种或多种。
在一个具体实施方案中,作为可湿性粉剂,其包括:本发明的化合物的粉末15-25wt%,白炭黑15-25wt%,十二烷基硫酸钠2-8wt%,CMC十二烷基硫酸钠0.5-2wt%和拉开粉1-6wt%,凹凸棒土46-56wt%。
本发明的化合物还可以根据常规方法制成其他任何适当的农药剂型,包括但不限于溶液、悬浮液、乳液等中的任何一种,例如剂型可以为为水乳剂、微乳剂和干悬浮剂的任何一种。
本发明的有益效果:本发明提供的式(1)所示的化合物可由可食用药用植物毛莲蒿提取分离而获得,证明其对人体比较安全;式(1)所示的化合物来源于天然植物,在环境中易于降解,具有低毒低残留特性,对非靶标生物安全、环境相容性好,符合绿色植保和可持续农业生产和发展的需要;式(1)所示的化合物对小菜蛾、甜菜夜蛾和斜纹夜蛾有拒食活性和抑制生长发育活性;式(1)所示的化合物对小菜蛾、甜菜夜蛾和斜纹夜蛾具有较好综合防治效果,通过减少现有化学农药杀虫剂使用的次数和用量,有助于我国保护地的绿色发展和高附加值作物的可持续性栽培。
附图说明
图1为实施例1中制备的化合物1的1H NMR谱图。
图2为实施例1中制备的化合物1的13C NMR谱图。
图3为实施例1中制备的化合物1的1H–1H COSY谱图。
图4为实施例1中制备的化合物1的HSQC谱图。
图5为实施例1中制备的化合物1的HMBC图。
图6为实施例1中制备的化合物1的NOESY谱图。
图7为实施例1中制备的化合物1的HRESIMS谱图。
图8为实施例1中制备的化合物2的1H NMR谱图。
图9为实施例1中制备的化合物2的13C NMR谱图。
图10为实施例1中制备的化合物2的1H–1H COSY谱图。
图11为实施例1中制备的化合物2的HSQC谱图。
图12为实施例1中制备的化合物2的HMBC图。
图13为实施例1中制备的化合物2的NOESY谱图。
图14为实施例1中制备的化合物2的HRESIMS谱图。
图15为实施例1中制备的化合物3的1H NMR谱图。
图16为实施例1中制备的化合物3的13C NMR谱图。
图17为实施例1中制备的化合物3的1H–1H COSY谱图。
图18为实施例1中制备的化合物3的HSQC谱图。
图19为实施例1中制备的化合物3的HMBC图。
图20为实施例1中制备的化合物3的NOESY谱图。
图21为实施例1中制备的化合物3的HRESIMS谱图。
图22为实施例1中制备的化合物4的1H NMR谱图。
图23为实施例1中制备的化合物4的13C NMR谱图。
图24为实施例1中制备的化合物4的1H–1H COSY谱图。
图25为实施例1中制备的化合物4的HSQC谱图。
图26为实施例1中制备的化合物4的HMBC图。
图27为实施例1中制备的化合物4的NOESY谱图。
图28为实施例1中制备的化合物4的HRESIMS谱图。
图29(a)为化合物1的ECD数据图,(b)为化合物3的ECD数据图,(c)为化合物4的ECD数据图。
具体实施方式
实施例1:倍半萜类新化合物的制备
1、实验材料:
1)药材
毛莲蒿植株于2017年8月采自内蒙古自治区阿拉善盟阿拉善左旗,经本申请发明人武海波博士鉴定为菊科蒿属植物毛莲蒿(学名:Artemisia vestita Wall.ex Bess.)。
2)试剂和填料
薄层层析硅胶GF254(化学纯),购于青岛海洋硅胶干燥剂厂;柱层析硅胶,200~300目(试剂级),购于青岛海洋硅胶干燥剂厂;GF254硅胶制备薄层,购于烟台江友硅胶开发有限公司;Sephadex LH-20葡聚糖凝胶,购于瑞典Amersham公司;石油醚、正己烷、氯仿、乙酸乙酯、丙酮、甲醇等分析纯试剂,购于北京化工厂。
3)实验仪器
Bruker-AVIIIHD-600核磁共振仪(瑞士Bruker);BP211D十万分之一电子天平(瑞士Sartorius);Nicolet 5700红外光谱仪(美国Thermo公司);DZG-6050型真空干燥箱(上海森信);R-210旋转蒸发器(瑞士BUCHI)。
2、成分的分离纯化:
1)将毛莲蒿植株5kg粉碎至20目,加入分液漏斗,使用甲醇萃取3次,每次7天;
2)将萃取物减压浓缩,得到渣油225.0g,分散水中,依次用石油醚、氯仿、乙酸乙酯、正丁醇分馏,得到石油醚浸膏、氯仿浸膏、乙酸乙酯浸膏、正丁醇浸膏、和水相浸膏;
3)取2)中氯仿浸膏(45.5g),采用硅胶柱色谱依次以石油醚-氯仿体积比15:1、10:1、5:1、3:1、1:1为洗脱剂进行梯度洗脱,经薄层色谱进行检测,显色,合并相同洗脱部分,得到得到5个馏分A-E;其中,A为石油醚-氯仿体积比15:1馏分,B为石油醚-氯仿体积比10:1馏分;C为石油醚-氯仿体积比8:1馏分;D为石油醚-氯仿体积比5:1馏分;E为石油醚-氯仿体积比3:1馏分,共5个馏分;
4)取3)中A(4.2g),采用硅胶柱色谱,以石油醚-乙酸乙酯体积比12:1为洗脱剂洗脱,薄层色谱检测,显色,经Sephadex LH-20(羟丙基葡聚糖凝胶)层析,以氯仿-甲醇体积比1:1洗脱,得到化合物经过薄层检测、显色,根据Rf值确定为化合物1(Rf=0.46)(6.1mg)和化合物2(Rf=0.39)(4.1mg);
5)取3)中B(1.6g),采用硅胶柱色谱,以石油醚-乙酸乙酯体积比8:1为洗脱剂洗脱,薄层色谱检测,显色,得到化合物3(Rf=0.51)(3.3mg);
6)取3)中C(1.9g),采用硅胶柱色谱,以石油醚-氯仿体积比3:1为洗脱剂洗脱,薄层色谱检测,显色,得到化合物4(Rf=0.43)(1.6mg)。
进一步的,本发明进行薄层色谱显色条件:紫外灯(254nm)下观察暗斑,喷洒10%硫酸乙醇后,105℃烘烤至显色。
3、化合物鉴定:
在分离得到各化合物后,对其理化性质和分子结构进行了鉴定,得到化合物1、化合物2、化合物3和化合物4为新化合物,化合物1-4的分子结构如下所示,其具体理化性质和波谱数据如下表1:
表1化合物1-4的核磁数据
化合物1:无色胶质;UV(CH3CN)λmax(logε)200(2.42)nm;ECD(CH3CN)λmax(Δε)212(–5.1),227(+5.37)nm;IR(KBr)νmax 1782,1729,1625,1157cm-1;1H and 13C NMR数据(见表1);HR-ESI-MS m/z 343.1881(calcd for C19H28NaO4,343.1880).相关数据图见图1-7。
化合物2:无色胶质;UV(CH3CN)λmax(logε)231(3.39)nm;ECD(CH3CN)λmax(Δε)211(–34.4),233(+2.94)nm;IR(KBr)νmax 1781,1716,1634,1166cm-1;1H and 13C NMR数据(见表1);HR-ESI-MS m/z 341.1721(calcd for C19H26NaO4,341.1723).相关数据图见图8-14。
化合物3:无色胶质;UV(CH3CN)λmax(logε)200(1.22)nm;ECD(CH3CN)λmax(Δε)200(+45.7)nm;IR(KBr)νmax 1773,1726,1613,1157cm-1;1H and 13CNMR数据(见表1);HR-ESI-MS m/z 354.2280(calcd for C19H32NO5,354.2275).相关数据图见图15-21。
化合物4:淡黄色油状物UV(CH3CN)λmax(logε)210(0.35)nm;ECD(CH3CN)λmax(Δε)205(+27.6),223(–20.6),253(+3.5)nm;IR(KBr)νmax 3431,1738,1634,1385,1120cm-1;1H and 13C NMR数据(见表1);HR-ESI-MS m/z 307.1540(calcdfor C17H23O5,307.1546).相关数据图见图22-28。
根据图29(a),化合物1的绝对构型为(1R,6S,7S,10R,11S),通过与化合物1的ECD数据比较,得出化合物2的绝对构型为(1R,6S,7S,10R,11S),根据图29(b),化合物3的绝对构型为(1R,5R,6S,7S,10S,11S);根据图29(c),化合物4的绝对构型为(1R,4R,5R,6R,7R,8S)。
实施例2:农药制剂的制备
实施例1所得化合物1的粉末20%,白炭黑20%,十二烷基硫酸钠5%,CMC十二烷基硫酸钠1%和拉开粉3%,凹凸棒土余量,所述%以农药制剂的总重量为基准。将上述原料混合均匀,控制加工温度0-50℃,在气流粉碎机或其它高目粉碎机中,粉碎到150目以上,水分控制在6-8%(质量百分含量),pH控制在7-7.5。即可制得20%式(1)所示化合物的可湿性粉剂。经制剂的水中分散性、稀释液稳定性、冷热贮稳定性符合商品农药制剂的要求。
实施例3:农药制剂的制备
实施例1所得化合物2的粉末20%,白炭黑20%,十二烷基硫酸钠5%,CMC十二烷基硫酸钠1%和拉开粉3%,凹凸棒土余量,所述%以农药制剂的总重量为基准。将上述原料混合均匀,控制加工温度0-50℃,在气流粉碎机或其它高目粉碎机中,粉碎到150目以上,水分控制在6-8%(质量百分含量),pH控制在7-7.5。即可制得20%式(1)所示化合物的可湿性粉剂。经制剂的水中分散性、稀释液稳定性、冷热贮稳定性符合商品农药制剂的要求。
实施例4:农药制剂的制备
实施例1所得化合物3的粉末20%,白炭黑20%,十二烷基硫酸钠5%,CMC十二烷基硫酸钠1%和拉开粉3%,凹凸棒土余量,所述%以农药制剂的总重量为基准。将上述原料混合均匀,控制加工温度0-50℃,在气流粉碎机或其它高目粉碎机中,粉碎到150目以上,水分控制在6-8%(质量百分含量),pH控制在7-7.5。即可制得20%式(1)所示化合物的可湿性粉剂。经制剂的水中分散性、稀释液稳定性、冷热贮稳定性符合商品农药制剂的要求。
实施例5:农药制剂的制备
实施例1所得化合物4的粉末20%,白炭黑20%,十二烷基硫酸钠5%,CMC十二烷基硫酸钠1%和拉开粉3%,凹凸棒土余量,所述%以农药制剂的总重量为基准。将上述原料混合均匀,控制加工温度0-50℃,在气流粉碎机或其它高目粉碎机中,粉碎到150目以上,水分控制在6-8%(质量百分含量),pH控制在7-7.5。即可制得20%式(1)所示化合物的可湿性粉剂。经制剂的水中分散性、稀释液稳定性、冷热贮稳定性符合商品农药制剂的要求。
实施例6:四种化合物对昆虫的拒食活性测定
1)方法:
待测化合物1-4及苦楝油(Neem Oil)分别用丙酮溶解制备成浓度为104mg/L的母液。用0.1%(V/V)吐温-80水溶液稀释待测化合物,保证最终待测化合物中有机溶剂含量不超过1%(V/V)。将卷心菜切成1cm×1cm的叶盘,浸于含化合物的丙酮溶液中10s,室温风干。将5个处理过的叶盘和10只小菜蛾(Plutella xylostella)三龄幼虫放在一个直径90mm的培养皿中,每个处理重复4次并设置空白对照组。室温培养24h后,使用坐标纸测量残叶面积的,记录残叶面积。将小菜蛾幼虫更换为甜菜夜蛾(Spodoptera exigua)三龄幼虫和斜纹夜蛾(Spodoptera litura)三龄幼虫进行同样的操作。拒食率计算公式如下:
拒食率(%)=((CK-T)/CK)×100
(CK——空白对照组被取食的叶面积,T——实验组被取食的叶面积)
计算四种化合物对小菜蛾、甜菜夜蛾、斜纹夜蛾三龄幼虫的拒食的半最大效应浓度(EC50,μg/cm2)
2)生测结果:
表2四种化合物对小菜蛾、甜菜夜蛾、斜纹夜蛾三龄幼虫的拒食的半最大效应浓度(EC50,μg/cm2)
从以上实验数据可以看出,本发明获得的倍半萜类新化合物具有较强的拒食活性。
实施例7:四种化合物对昆虫生长发育的抑制活性
1)方法:
将浓度为5μg/g的化合物添加到饲料中,给昆虫喂食72h,其中小菜蛾为3龄中期幼虫,甜菜夜蛾为2龄末期幼虫;对照组喂食正常饲料;进食72h后取样检测昆虫体重;3龄中期小菜蛾幼虫进食7天,2龄末期甜菜夜蛾幼虫进食10天后计算化蛹率。
2)生测结果:
表3对昆虫生长发育影响
化合物 | 1 | 2 | 3 | 4 | 对照组 |
小菜蛾 | 0.016 | 0.017 | 0.014 | 0.015 | 0.030 |
甜菜夜蛾 | 0.020 | 0.021 | 0.019 | 0.023 | 0.037 |
表4对昆虫化蛹率影响
化合物 | 1 | 2 | 3 | 4 | 对照组 |
小菜蛾 | 21.1% | 26.8% | 28.2% | 30.5% | 93.2% |
甜菜夜蛾 | 20.9% | 25.5% | 22.3% | 18.9% | 94.9% |
从以上实验数据可以看出,本发明获得的倍半萜类新化合物具有很强的抑制昆虫生长发育繁殖的活性。
由于本发明分离获得的式(1)化合物是从药食两用植物了毛莲蒿中提取,在自然条件下易分解,不会引起生物富集现象,对人畜安全,可以作为天然农药长期使用。使用本发明获得的式(1)化合物可以减少小菜蛾、甜菜夜蛾、斜纹夜蛾对蔬菜的取食,也可以抑制上述昆虫的生长发育繁殖,不仅能够达到化学农药减量减施,而且能够避免化学农药施用带来的负面影响,有益于我国可持续农业发展。
Claims (7)
2.权利要求1所述的化合物的制备方法,包括以下步骤:
1)室温甲醇提取毛莲蒿,获得毛莲蒿提取物;
2)将毛莲蒿提取物减压浓缩,得到渣油,分散水中,依次用石油醚、氯仿、乙酸乙酯、正丁醇萃取,得到石油醚浸膏、氯仿浸膏、乙酸乙酯浸膏、正丁醇浸膏、和水相浸膏;
3)取2)中氯仿浸膏,采用硅胶柱色谱依次以石油醚-氯仿体积比15:1、10:1、5:1、3:1、1:1为洗脱剂进行梯度洗脱,得到5个组分A-E;
4)取3)中A部分,采用硅胶柱色谱,以石油醚-乙酸乙酯体积比12:1为洗脱剂洗脱,薄层色谱检测,显色,经 Sephadex LH-20层析,以氯仿-甲醇体积比1:1洗脱,得到化合物经过薄层色谱检测、显色,根据Rf值确定为Rf=0.46的化合物1和Rf=0.39的化合物2;
5)取3)中B部分,采用硅胶柱色谱,以石油醚-乙酸乙酯体积比8:1为洗脱剂洗脱,薄层色谱检测,显色,合并相同Rf值的洗脱部分,得到Rf=0.51的化合物3;
6)取3)中C部分,采用硅胶柱色谱,以石油醚-氯仿体积比3:1为洗脱剂洗脱,薄层色谱检测,显色,合并相同Rf值的洗脱部分,得到Rf=0.43的化合物4。
3.权利要求1所述的倍半萜类化合物作为昆虫拒食剂和/或昆虫生长发育抑制剂在农药中的应用,所述的昆虫为夜蛾科、菜蛾科昆虫中的至少一种。
4.一种农药制剂,其包括(A)权利要求1所述的倍半萜类化合物以及(B)农药学上可接受的辅料。
5.根据权利要求4所述的农药制剂,其中,组分(A)的质量百分数为10~25%,组分(B)的质量百分数为75~90%,以农药的总质量为基准计。
6.根据权利要求4或5所述的农药制剂,其特征在于,所述的农药制剂的剂型为水乳剂、微乳剂和干悬浮剂中的一种。
7.根据权利要求4或5所述的农药制剂,其特征在于,所述的农药制剂的剂型为可湿性粉剂,其包括:权利要求1所述的倍半萜类化合物中的一种或多种15-25wt %、白炭黑15-25wt%、十二烷基硫酸钠2-8wt%、拉开粉1-6wt%和凹凸棒土46-56wt%。
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