CN114617125B - 2-甲氧基-3-甲基-1,4-苯醌在防治红火蚁和松墨天牛中的应用 - Google Patents
2-甲氧基-3-甲基-1,4-苯醌在防治红火蚁和松墨天牛中的应用 Download PDFInfo
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- CN114617125B CN114617125B CN202210240335.5A CN202210240335A CN114617125B CN 114617125 B CN114617125 B CN 114617125B CN 202210240335 A CN202210240335 A CN 202210240335A CN 114617125 B CN114617125 B CN 114617125B
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
本发明公开了2‑甲氧基‑3‑甲基‑1,4‑苯醌在防治红火蚁和松墨天牛中的应用。本发明从马陆的防御性化合物中筛选和开发的2‑甲氧基‑3‑甲基‑1,4‑苯醌对红火蚁和松墨天牛具有较强的驱避、触杀或熏蒸效果,可以用于红火蚁及其它蚂蚁的行为驱避、化学防治等方面,也可以用于松墨天牛的熏蒸毒杀方面,相比较于现阶段针对红火蚁和松墨天牛的化学防治方法,更加绿色环保、无毒安全,具有重要的市场应用和推广价值。
Description
技术领域
本发明属于利用昆虫的化学防御物质进行红火蚁和松墨天牛绿色防控的技术领域,具体涉及2-甲氧基-3-甲基-1,4-苯醌在防治红火蚁和松墨天牛中的应用。
背景技术
红火蚁(Solenopsis invicta)隶属于膜翅目蚁科,是一种重大外来入侵社会性昆虫,不仅影响农林业生产,而且还危害人畜健康、破坏公共设施和生态环境,因此被列为世界上最危险的100种入侵有害生物之一。我国于2003年在台湾的桃源及嘉义地区首次发现红火蚁,此后在广东、香港、澳门等地区相继出现红火蚁疫情,目前已扩散至全国12个省份,其中以广东省发生范围最广、面积最大、受害最为严重。化学防治是防治红火蚁的重要途径之一,目前主要包括饵剂法、药液灌巢法和粉剂灭巢法。其中饵剂法是最安全环保、持续性强的防治措施。药液灌巢法防治红火蚁虽然费时费工,但其是红火蚁快速应急防控中最有效的措施之一,且其施用受环境影响较小。然而,目前在药液灌巢法中使用的药剂大都毒性较高,且易污染生态环境。
松墨天牛(Monochamus alternatus)是我国松林一种最重要的蛀干害虫,主要危害马尾松Pinus massoniana、雪松Cedrus deodara、黑松P.thunbergii等松属植物。该害虫通过幼虫蛀食树干及枝条的韧皮部和木质部从而破坏和切断疏导组织的水分及养分的运输,严重影响林木生长。同时,松墨天牛是引起松类毁灭性病害松材线虫病的主要传播媒介。松树感染松材线虫病后2-3个月内即枯死,能在短时间内造成大面积松林毁灭,对我国松林构成严重威胁。
昆虫在面对自然天敌长期的协同进化过程中,形成了特有的防御机制来抵御天敌的捕食和侵扰。其中有些昆虫会分泌化学物质来进行抵御,如凤蝶幼虫的臭丫腺、屁步甲的臀腺、蝽类的臭腺、马陆的毒腺等等,其中部分化学防御物质对天敌具有重要的驱避作用和毒性。因此,这些昆虫自身合成的化学防御物质在开发害虫驱避剂及生物杀虫农药等方面具有重要的利用价值。
发明内容
本发明的目的是针对目前红火蚁和松材线虫病在我国快速扩散蔓延、危害日益猖獗,而现有技术中针对红火蚁和松材线虫的传播媒介昆虫松墨天牛的防治药剂种类不多,化学农药防治存在破坏生态环境等问题,提供一种对红火蚁和松墨天牛具有驱避、触杀或熏蒸作用的天然化合物药剂。
本发明通过GC-MS、GC-EAD、EthovisionXT行为选择等实验技术,获得一种基于雕马陆腺体分泌防御性化合物2-甲氧基-3-甲基-1,4-苯醌(其结构式如式I所示)的红火蚁和松墨天牛驱避、触杀和熏蒸药剂;
因此,本发明的第一个目的是提供2-甲氧基-3-甲基-1,4-苯醌在防治农林业害虫中的应用。
优选,为2-甲氧基-3-甲基-1,4-苯醌在防治红火蚁和松墨天牛中的应用。
优选,所述的应用,2-甲氧基-3-甲基-1,4-苯醌作为红火蚁和松墨天牛的驱避剂、触杀剂和/或熏蒸剂。
一种防治农林业害虫的制剂,其包含有效量的2-甲氧基-3-甲基-1,4-苯醌作为害虫驱避剂、触杀剂和/或熏蒸剂。
优选,所述的防治农林业害虫的制剂为防治红火蚁和松墨天牛的制剂。
本发明还提供一种2-甲氧基-3-甲基-1,4-苯醌的制备方法,其制备反应式如下:
本发明从马陆的防御性化合物中筛选和开发的2-甲氧基-3-甲基-1,4-苯醌对红火蚁和松墨天牛具有较强的驱避、触杀或熏蒸效果。因此,本发明提供了一种防治重大入侵害虫红火蚁及松材线虫传播媒介-松墨天牛的驱避剂、触杀剂或熏蒸剂,相比较于现阶段针对红火蚁和松墨天牛的化学防治药剂,更加绿色环保、无毒安全,因此本发明具有重要的市场应用和推广价值。
附图说明
图1是近副雕马陆Glyphiulus proximus(上)及其躯干内红色毒腺提取化合物的GC-MS总离子流图(下)。
图2是红火蚁对雕马陆毒腺提取物的触角GC-EAD反应图。
图3是2-甲氧基-3-甲基-1,4-苯醌的化学合成路线图。
图4是毒腺内两种化合物对红火蚁的毒力测定,图中Chemical A为2-甲氧基-3-甲基-1,4-苯醌,p-Toluqionone为甲基苯醌。
图5是2-甲氧基-3-甲基-1,4-苯醌和甲基苯醌对红火蚁的驱避作用;(a)实验设计示意图;(b)驱避性结果,图中横轴上A代表2-甲氧基-3-甲基-1,4-苯醌,B代表甲基苯醌;(c)红火蚁在实验区域的行为轨迹图;(d)红火蚁在实验区域的行为轨迹热图。
图6是2-甲氧基-3-甲基-1,4-苯醌熏蒸处理后不同时间松墨天牛幼虫的死亡率结果。
具体实施方式
以下实施例是对本发明的进一步说明,而不是对本发明的限制。
实施例1:马陆毒腺化合物GC-MS分离鉴定
S1.溶液浸取法提取腺体化合物组分
利用解剖刀剖开雕马陆躯干,用手术剪剪下其中的毒腺腺体,置于含有色谱纯正己烷的2mL样品瓶中,置于室温下浸提15min。随后加入少量无水Na2SO4除去样品中的水分,用0.45μm孔径的有机滤膜对溶液进行过滤,随后用氮气浓缩至100μL。将浓缩好的样品贮存在-20℃冰箱内备用。
S2.毒腺化合物的鉴定
利用安捷伦气相色谱-质谱联用仪(8890-5977B GC-MS)对S1中制备的样品进行分析与鉴定,具体条件如下:
(1)色谱条件:进样口温度250℃,采用99.999%高纯氦气作为载气,载气流速1mL/min,采用恒流模式,不分流进样。
(2)质谱条件:离子源为EI 70eV,电压为350V,接口温度为280℃,扫描电压范围为50~550m/Z。
(3)升温程序:起始温度为50℃,保留3min,再以15℃/min升至300℃保持6min。每次取样1μL进行手动进样。
S3.结果表明正己烷浸泡提取得到5种有机化合物,化合物总离子流图如图1所示,其化合物列表见表1。其中含量最多的为2-甲氧基-3-甲基-1,4-苯醌,占比高达51.95%,其次为甲基苯醌,占22.02%。表中加星号的化合物表示经标准化合物比对鉴定,其它化合物则根据参考文献和NIST17谱库进行比对鉴定。
表1正己烷浸提马陆毒腺化合物列表
实施例2:触角电位(GC-EAD)实验筛选对红火蚁具有生理活性的化合物
用GC-EAD方法测试红火蚁触角对马陆毒腺化合物的触角电生理反应,以筛选潜在的驱避剂活性物质。气相色谱型号为安捷伦7890B,色谱条件为:HP-5(30m,0.25mm内径,0.25μm膜厚)毛细管色谱柱,载气为高纯氮气,进样口温度250℃,FID检测器温度320℃,柱箱升温程序为50℃,保留时间为3min、然后以15℃/min升至300℃并保持6min。利用EAG昆虫触角电位记录仪(荷兰Syntech公司)测定马陆毒腺对红火蚁的触角电生理反应大小。沿昆虫触角基部剪下触角,将触角两端分别连接到EAG的两个玻璃毛细管电极上。采用手动模式不分流进样,进样量为1μL,GC和EAG的样品分流比为1:1。每次实验重复6根触角以上。
结果表明,在GC-MS出峰时间为7.167min和9.158min处的2个物质能够重复引起红火蚁强烈的电生理反应(图2),说明这些物质是潜在的对红火蚁具有生理行为活性物质。经过正构烷烃出峰时间计算保留指数,合成或购买标准品以及和GC-MS数据和峰形比对,确定这两种物质分别为甲基苯醌和2-甲氧基-3-甲基-1,4-苯醌。
实施例3:2-甲氧基-3-甲基-1,4-苯醌的化学合成和结构鉴定
实验方法:总合成路线如图3所示。具体详细步骤为:
(1)将3.0g 2,6-二甲氧基甲苯(式III)与12mL冰醋酸以及373mg对甲基苯磺酸(TsOH)混合搅拌均匀。随后加入4.3mL质量分数30%双氧水。混合均匀1h后在室温下进行薄层色谱。12h后加入正己烷:EA(丙烯酸乙酯)=10:1作为展开剂,升温到75℃,保温反应1h。将反应液倾入50mL的质量分数40%氢氧化钾水溶液中,将pH调至大于11。加50mL的EA溶液进行萃取两次。萃取液中加入70%浓硫酸综合酸化至pH<1,随后继续用50mL的EA溶液萃取3次,干燥浓缩得到式II所示化合物II。
(2)取3.5g式II所示化合物II,加入1.19g乙酸、2.0g质量分数65%的浓硝酸、92mLACN(乙腈)溶液、138mL水,在室温下持续搅拌12h,直至TLC检测原料消失。过滤溶液,用乙腈淋洗滤饼,随后将滤液浓缩。浓缩后加入400mL DCM(二氯甲烷)溶液和100m水,测试水相pH值偏中性(pH=7)。使用50mL饱和碳酸氢钠淋洗。水相用100mLDCM溶液进行反洗,将有机层合并混合浓缩。过柱纯化即得褐色油状的目标化合物I(2-甲氧基-3-甲基-1,4-苯醌,如式I所示),重量约2.1g。
实验结果:目标化合物I经过核磁共振氢谱(1HNMR)及高分辨质谱进行结构鉴定,鉴定数据见表2。
表2化合物2-甲氧基-3-甲基-1,4-苯醌结构鉴定数据
由此,确定了目标化合物为2-甲氧基-3-甲基-1,4-苯醌。
实施例4:活性物质对红火蚁的触杀毒力测试
用丙酮溶液将甲基苯醌和2-甲氧基-3-甲基-1,4-苯醌两种物质纯品稀释成不同供试浓度。采用点滴法在每只红火蚁中型工蚁的胸部背面滴2μL的药剂,丙酮溶剂作为对照。每个浓度处理60头工蚁。处理过的蚂蚁放置于人工气候箱中(温度25±1℃,相对湿度70%~80%,光周期14L∶10D,下同)。处理后每隔12h观察并记录蚂蚁的死亡数,连续观察48h。采用SPSS的Probit模块计算不同药剂对红火蚁的致死中浓度LC50和致死中时间LT50。
两种药剂处理后红火蚁的死亡率结果如图4所示。结果表明2-甲氧基-3-甲基-1,4-苯醌对红火蚁具有较强的触杀作用,而甲基苯醌即使在最高浓度,红火蚁的死亡率也非常低,说明甲基苯醌对红火蚁没有触杀作用。2-甲氧基-3-甲基-1,4-苯醌处理后不同时间对红火蚁的致死中浓度(LC50)结果如表3所示。处理48h后LC50最小,仅为0.02g/mL。2-甲氧基-3-甲基-1,4-苯醌处理后不同时间对红火蚁的致死中时间(LT50)结果如表4所示。在浓度为0.2g/mL条件下,红火蚁的LT50为10.17h,在0.01g/mL浓度下,LT50为50.25h。这些结果均表明2-甲氧基-3-甲基-1,4-苯醌具有较强的触杀作用,而且致死速度较快,是一种具有开发潜力的红火蚁防治药剂。
表3 2-甲氧基-3-甲基-1,4-苯醌处理后不同时间腺体化合物对红火蚁工蚁的致死中浓度(LC50)
am表示经Probit转换的死亡率,c表示处理药剂的浓度.
表4 2-甲氧基-3-甲基-1,4-苯醌处理后不同时间腺体化合物对红火蚁工蚁的致死中时间(LT50)
am表示经Probit转换的死亡率,t表示药剂处理后时间
实施例5:活性物质对红火蚁的驱避性测试
采用Ethovision XT11.5软件记录红火蚁对活性物质的行为特性。在直径9cm的培养皿的两处对角处分别放置表面涂有药剂和对照溶剂的干黄粉虫食物,利用两只黄粉虫相交的垂直线将培养皿划分成对照区和处理区两个区域(图5a),然后将红火蚁工蚁在培养皿的正中间放置进入培养皿,利用Ethovision XT自带的视频软件拍摄记录红火蚁在培养皿内的活动轨迹,并自动统计红火蚁在不同区域的活动时间。利用SPSS t检验对红火蚁在不同区域的活动时间进行差异显著性比较(P=0.05)。
结果如图5和下表5所示。结果表明2-甲氧基-3-甲基-1,4-苯醌在浓度为1g/mL和0.2g/mL时,对红火蚁具有较强的驱避作用,红火蚁停留在对照区域的时间显著高于停留在化合物处理的区域。在浓度为0.2g/mL和0.1g/mL时,2-甲氧基-3-甲基-1,4-苯醌对红火蚁具有驱避作用的趋势(p<0.1)(图5b);从红火蚁的行为轨迹中也可看出,高浓度时2-甲氧基-3-甲基-1,4-苯醌对红火蚁具有明显的行为驱避性(图5c,d)。浓度为0.02g/mL和0.01g/mL时,对红火蚁没有驱避性(图5b)。甲基苯醌即使在最高浓度时,对红火蚁也无任何驱避效果。
表5不同浓度马陆毒腺化合物对红火蚁驱避性统计结果
实施例6:活性物质对红火蚁的熏蒸毒性测试
用丙酮溶液将2-甲氧基-3-甲基-1,4-苯醌纯品稀释成不同供试浓度。往每个15mL的样品瓶内放入30头红火蚁工蚁,将2μL不同浓度药液分别点滴在5*1cm的长条形试纸上,将试纸悬挂在样品瓶的正中央,盖上瓶盖,丙酮溶剂作为对照。每个浓度处理60头工蚁。将熏蒸实验的样品瓶放置于人工气候箱中(温度25±1℃,相对湿度20%~40%)。处理后每隔2h观察并记录工蚁的死亡数,连续观察12h。采用SPSS的Probit模块计算不同浓度药剂熏蒸对红火蚁的致死中浓度LC50和致死中时间LT50。
2-甲氧基-3-甲基-1,4-苯醌熏蒸处理后不同时间对红火蚁的致死中浓度(LC50)结果如表6所示。处理12h后LC50最小,仅为0.007g/mL,表明2-甲氧基-3-甲基-1,4-苯醌对红火蚁具有较强的熏蒸效果。2-甲氧基-3-甲基-1,4-苯醌熏蒸处理后不同时间对红火蚁的致死中时间(LT50)结果如表7所示。在浓度为0.2g/mL条件下,红火蚁的LT50为2.78h,在0.01g/mL浓度下,LT50为13.95h。这些结果均表明2-甲氧基-3-甲基-1,4-苯醌具有较强的熏蒸效果,而且熏蒸致死速度较快。
表6 2-甲氧基-3-甲基-1,4-苯醌处理后不同时间对红火蚁工蚁的熏蒸致死中浓度(LC50)
am表示经Probit转换的死亡率,c表示处理药剂的浓度.
表7 2-甲氧基-3-甲基-1,4-苯醌处理后不同时间对红火蚁工蚁的熏蒸致死中时间(LT50)
am表示经Probit转换的死亡率,t表示药剂熏蒸处理后时间。
实施例7:活性物质对松墨天牛幼虫的熏蒸毒性测试
用浓度为0.2g/mL的2-甲氧基-3-甲基-1,4-苯醌溶液对松墨天牛进行熏蒸毒力测试。往每个50mL的玻璃瓶内放入5头松墨天牛幼虫,同时放入少量松木屑作为食物。将5μL浓度为0.2g/mL的2-甲氧基-3-甲基-1,4-苯醌溶液药液点滴在5*1cm的长条形试纸上,将试纸悬挂在样品瓶的正中央,盖上瓶盖(为药剂熏蒸组);丙酮溶剂作为对照。每个浓度处理30头松墨天牛3-5齡幼虫。将熏蒸实验的样品瓶放置于人工气候箱中(温度25±1℃,相对湿度20%~40%)。处理后每隔12h观察并记录松墨天牛幼虫的死亡数,连续观察72h。采用SPSS生存分析中的Breslow statistic(Kaplan-Meier survival test)和Cox回归分析(CoxProportional Regression analysis)对不同组间松墨天牛幼虫的存活率以及死亡风险比率进行比较。
2-甲氧基-3-甲基-1,4-苯醌熏蒸处理后不同时间松墨天牛的死亡率结果如图6所示。药剂熏蒸和溶剂对照条件下松墨天牛幼虫死亡率差异显著(Wald Statistic=19.398,df=1,P<0.001)。同时,溶剂对照下松墨天牛的生存时间显著高于药剂熏蒸条件下的生存时间(Breslow Statistic=39.585,df=1,P<0.001)。
Claims (2)
1.2-甲氧基-3-甲基-1,4-苯醌在防治红火蚁和松墨天牛中的应用。
2.根据权利要求1所述的应用,其特征在于,2-甲氧基-3-甲基-1,4-苯醌作为红火蚁和松墨天牛的驱避剂、触杀剂和/或熏蒸剂。
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