CN107226812A - 一类哌啶噻唑肟醚甲氧基丙烯酸酯衍生物及其制备方法和用途 - Google Patents
一类哌啶噻唑肟醚甲氧基丙烯酸酯衍生物及其制备方法和用途 Download PDFInfo
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- CN107226812A CN107226812A CN201610186472.XA CN201610186472A CN107226812A CN 107226812 A CN107226812 A CN 107226812A CN 201610186472 A CN201610186472 A CN 201610186472A CN 107226812 A CN107226812 A CN 107226812A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明提供了一类哌啶噻唑肟醚甲氧基丙烯酸酯衍生物及其制备方法和用途,本发明涉及噻唑肟醚甲氧基丙烯酸酯类衍生物,它们具有如V所示的化学结构通式。
Description
技术领域
本发明的技术方案涉及含N含S的哌啶噻唑肟醚甲氧基丙烯酸酯类化合物,具体涉及哌啶噻唑酮、醛类肟醚化合物,即哌啶噻唑酮、醛类肟醚甲氧基丙烯酸酯衍生物。
背景技术
专利文献报道的生物活性化合物中,大部分具有杂环结构;五元杂环化合物具有植物激活剂、杀菌剂、植物生长调节剂和杀虫剂的活性(陈丹萍.现代农药,2014,14(2):5-10),其中,噻二唑是重要的五元含氮含硫杂环化合物,在农业领域有商品化的品种如棉花脱叶剂噻苯隆、植物激活剂本并噻二唑(简称BTH)和噻酰菌胺(简称TDL)。发明人所在的课题组发现了甲噻诱胺的诱导抗病活性并进行了产业化开发,创制出我国第一个具有自主知识产权的植物激活品种,该类化合物诱导抗病活性的研究已有一定的报道(Fan Z.J.,etal.J.Agric.Food Chem.,2009,57(10):4279-4286)。
噻唑类衍生物具有广泛的生物活性,噻唑类衍生物具有抗菌、镇痛、消炎、抗惊厥、强心、抗癌、抗结核和驱虫等活性(Sharshiral,E.M.,et al.J.Org.Chem.,2012,2(3):69-73.)。这类化合物的农药活性就包括杀虫、杀菌、除草、植物生长调节、抗病毒等(陈才俊,等.噻唑类杀虫剂的研究进展.农药,2005,44(2):53-55.)。哌啶类生物碱广泛分布于植物界,并显示多种生物活性(Richerson.G.B.,et al.,2003,90:1363-1374.)。哌啶类衍生物在农药方面也表现出广泛的生物活性,如杀菌剂苯锈啶、除草剂哌草丹、植物生长调节剂甲哌鎓等都具有较好的生物活性(Jiang Zhigan,et al.,Eur.J.Med.Chem,2014,82:490-497)。活性亚结构单元噻唑环和哌啶环结合的研究已有报道(Black,Janice.WO2007071900A1;Pasteris,et al.,WO2008091580 A2)。
肟醚衍生物是一类具有优良生物活性的化合物,不仅在医药上有着广泛的应用,在农药上也是一类重要的活性化合物。有关肟醚活性化合物,国内外已有大量报道(宋宝安,等.肟类衍生物的合成与农药生物活性的研究进展.有机化学,2005,25(5):507-525.),同时也有许多商品问世,比如对霜霉有效的霜脲氰(cymoxanil)、对尖音库蚊和家蝇具有较高活性的昆虫生长调节剂S-21149和S-21150、对梨红蜘蛛、柑橘红蜘蛛活性颇高的唑螨酯(fenpyroximate)、对许多主要的一年生和多年生禾本科杂草有较好防除效果的喔草酯(propa quizafop)等(范磊,等.现代农药,2008,7(2):6-11.)。肟醚结构常作为很好的药效团被引入到母体化合物分子中,以改善其生物活性。
甲氧基丙烯酸酯类杀菌剂具有广谱的杀菌活性,对几乎所有真菌类(子囊菌纲、担子菌纲、卵菌纲和半知菌类)病害都有很好的活性,如麦类的白粉病、叶枯病、赤斑病、网斑病、黑腥病、水稻的稻瘟病、纹枯病及霜霉病和疫病等(关爱莹.精细与专用化学品,2012,20(4):24-28)。该类药剂具备高效、广谱、低毒、内吸和易降解等多种优点,现已成为全球最主要的农用杀菌剂(袁小勇.2014,34:170-177)。已成功商品化的甲氧基丙烯酸酯类杀菌剂中重要的品种主要有:嘧菌酯(azoxystrobin)、醚菌酯(kresoxim-methyl)、吡唑醚菌酯(pyraclostrobin)、肟菌酯(trifloxystrobin)、氟嘧菌酯(fluoxastrobin)、啶氧菌酯(picoxystrobin)、苯氧菌胺(metaminostrobin)、醚菌胺(dimoxystrobin)、肟醚菌胺(orysastrobin)、烯肟菌酯(enestrobin)、唑菌酯(pyraoxystrobin)、烯肟菌胺(SYP-1620)等。由于Strobilurin类杀菌剂作用位点单一,大量高频高强度使用带来的抗性问题十分突出(Fisher,N.Pest.Manage.Sci.2005,61(10):973-978);植物激活剂具有光谱持久的系统获得抗病性,不直接作用于病原物而作用于植物本身,是21世纪植物保护的重要方向,该类药剂无抗药性的风险,因此,创制更多超过高效的药剂迫在眉睫。
为寻找和发现更加高效、广谱、低毒、低生态风险且无交互抗性的农药先导及侯选化合物,本发明将哌啶噻唑引入甲氧基丙烯酸酯的先导结构中,设计合成了一类哌啶噻唑肟醚甲氧基丙烯酸酯衍生物,并进行了系统的生物活性的筛选和评价。
发明内容
本发明所要解决的技术问题是:提供一类新的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物的合成方法,提供这类化合物调控农业、园艺和卫生以及林业植物害虫和植物病原物的生物活性及其测定方法,同时提供这些化合物在农业领域、园艺领域、林业领域以及卫生领域中的应用。
本发明解决该技术问题所采用的技术方案是:具有农业领域、园艺领域、林业领域杀虫、杀螨活性、杀菌活性、抗植物病毒活性、诱导植物产生抗病活性的哌啶噻唑肟醚甲氧基丙烯酸酯类化合物的化学结构通式见式V:
其中,R1选自:甲基、氢;R2选自:1,2-二氟乙基、炔丙基、环丙基、甲基、1-甲硫基-2-甲基丙-2-基、(R)-1-甲硫基丙-2-基;R3选自:氢、氯化氢;X选自:氧、氮,n=1,2;
本发明的1,2,3-哌啶噻唑肟醚甲氧基丙烯酸酯衍生物的合成方法如下:
其中,R1选自:甲基、氢;R2选自:1,2-二氟乙基、炔丙基、环丙基、甲基、1-甲硫基-2-甲基丙-2-基、(R)-1-甲硫基丙-2-基;R3选自:氢、氯化氢;X选自:氧、氮,n=1,2;
本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物的合成以及生物活性测定的具体方法分为以下步骤:
A.化合物II的制备:
在25毫升单口圆底烧瓶中加入1.10毫摩尔化合物I,用15毫升乙醇溶解,再加入1.00毫摩尔取代哌啶噻唑羰基化合物,所述哌啶噻唑羰基化合物选自:哌啶噻唑酮、哌啶噻唑醛,最后向反应体系中滴加两滴2摩尔/升的盐酸,室温搅拌12小时,反应完全后减压除去溶剂,残余物经200~300目硅胶柱层析纯化得化合物II,洗脱剂为60~90摄氏度的石油醚∶乙酸乙酯,根据产物的不同,体积比为9∶1-2∶1,收率40-50%;化合物II制备的量和反应容器的体积按相应比例扩大或缩小。
B.化合物III的制备:
在25毫升单口圆底烧瓶中加入0.24毫摩尔化合物II,用15毫升甲醇溶解,向反应中加入0.03克,即0.72毫摩尔氢氧化钠,然后加热回流30分钟,反应结束后将反应液浓缩,残余物用10毫升乙酸乙酯稀释,加入10毫升的水将固体全部溶解,分离出水层,水层用2摩尔/升的盐酸调节pH至3,然后用乙酸乙酯萃取,水层用乙酸乙酯反萃一遍,合并有机层,有机层用饱和氯化钠洗一遍,无水硫酸钠干燥,抽滤,减压除去溶剂,得化合物III;收率95-100%;化合物III制备的量和反应容器的体积按相应比例扩大或缩小。
C.化合物IV的制备:
在25毫升单口圆底烧瓶中加入0.30毫摩尔化合物III,用15毫升干燥的二氯甲烷溶解,向反应中加入0.69克,即0.36毫摩尔的EDCI,即1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐和0.43克,即0.32毫摩尔的HOBT,即1-羟基苯并三氮唑,加完之后室温搅拌30分钟,然后向反应体系中加入0.32毫摩尔的R2-XHn,n=1,2;室温搅拌2小时,反应结束后,反应液用15毫升的水洗两遍,分离出有机层,有机层分别用饱和碳酸氢钠和饱和氯化钠各洗一遍,无水硫酸钠干燥,抽滤,减压除去溶剂,残余物经200~300目硅胶柱层析纯化得到白色固体,洗脱剂为60~90摄氏度的石油醚∶乙酸乙酯,体积比为4∶1,收率60%-95%;化合物IV制备的量和反应容器的体积按相应比例扩大或缩小。
D.化合物V的制备:
在25毫升单口圆底烧瓶中加入0.30毫摩尔化合物IV,用15毫升干燥的二氯甲烷中,冰浴条件下滴1.5毫升的三氟乙酸,加入完毕,室温搅拌过夜,反应结束,用1摩尔每升的氢氧化钠中和至PH=7-8,分离出有机层,有机层分别用饱和碳酸氢钠和饱和氯化钠各洗一遍,无水硫酸钠干燥,抽滤,减压除去溶剂,残余物经200~300目硅胶柱层析纯化得到白色固体,洗脱剂为二氯甲烷∶甲醇,体积比为8∶1,收率96.26%;化合物V制备的量和反应容器的体积按相应比例扩大或缩小。
E.本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V的杀菌活性测定:
本发明的哌啶噻唑肟醚甲氧基丙烯酸酯V的杀菌或抑菌活性采用菌体生长率测定法,具体步骤为:取1.8毫克样品溶解在2滴N,N-二甲基甲酰胺中,然后用含有一定量吐温20乳化剂的水溶液稀释至500微克/毫升的药剂,将供试药剂在无菌条件下各吸取1毫升于培养皿内,再分别加入9毫升PDA培养基,摇匀后制成50微克/毫升含药平板,以添加1毫升灭菌水的平板做空白对照,用直径4毫米的打孔器沿菌丝外缘切取菌盘,移至含药平板上,呈等边三角形摆放,每处理重复3次,将培养皿放在24±1摄氏度恒温培养箱内培养,待对照菌落直径扩展到2-3厘米后调查各处理菌盘扩展直径,求平均值,与空白对照比较计算相对抑菌率,供试菌种为我国农业生产中田间实际发生的大部分典型植物病原菌的种属,其代号和名称如下:AS:番茄早疫病菌,其拉丁名为:Alternaria solani、BC:黄瓜灰霉病菌,其拉丁名为:Botrytis cinerea、CA:花生褐斑病菌,其拉丁名为:Cercospora arachidicola、GZ:小麦赤霉病菌,其拉丁名为:Gibberella zeae、PI:马铃薯晚疫病菌,其拉丁名为:Phytophthora infestans(Mont.)de Bary、PP:苹果轮纹病菌,其拉丁名为:Physalosporapiricola、PS:水稻纹枯病菌,其拉丁名为:Pellicularia sasakii、RC:禾谷丝核菌,其拉丁名为:Rhizoctonia cerealis、SS:油菜菌核病菌,其拉丁名为:Sclerotiniasclerotiorum。
F.本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V诱导抗病活性的测定:
哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V的活性筛选方法如下,烟草花叶病毒简写为TMV:
(1).阳性对照植物激活剂:选择质量纯度纯度大于99.5%的噻酰菌胺为阳性对照的植物激活剂;噻酰菌胺简写为TDL;
(2).哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V的诱导烟草抗TMV活性的筛选方法:离体直接抗病毒活性的测定采用半叶法进行;活体诱导是将苗龄一致的普通烟,3盆为一组,分别于接种前7天前处理过的烟苗,处理方式包括:喷施供试化合物溶液2到3次,每次10毫升,或土壤处理,每次10毫升,测定浓度为100微克/毫升,第7天于新长出的烟叶上摩擦接种TMV,将烟苗置于其生长适宜温度及光照下培养3天后,检查发病情况,综合病斑数目按下式计算出供试化合物对TMV的诱导抗病毒效果,每一处理设3次重复,空白对照和标准药剂对照分别选择水和TDL:
其中,R为供试化合物对烟草抗TMV的诱导效果,单位:%;CK为清水对照叶片的平均枯斑数,单位:个;I为经供试化合物诱导处理后叶片的平均枯斑数,单位:个。
本发明的有益效果是:对哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V进行了先导优化,并对哌啶噻唑肟醚甲氧基丙烯酸酯衍生物进行了抑菌活性的筛选。
本发明通过特定制备和生物活性测定实施例更加具体说明哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V的合成与生物活性及应用,所述实施例仅用于具体说明本发明而非限制本发明,尤其是生物活性仅是举例说明,而非限制本专利,具体实施方式如下:
实施例1:化合物II的制备:
在25毫升单口圆底烧瓶中加入1.10毫摩尔化合物I,用15毫升乙醇溶解,再加入1.00毫摩尔取代哌啶噻唑羰基化合物,所述哌啶噻唑羰基化合物选自:哌啶噻唑酮、哌啶噻唑醛,最后反应体系中滴加两滴2摩尔/升的盐酸,室温搅拌12小时,反应完全后减压除去溶剂,残余物经200~300目硅胶柱层析纯化得化合物II,洗脱剂为60~90摄氏度的石油醚∶乙酸乙酯,体积比为9∶1,收率40-50%;当R1为甲基,该化合物的核磁数据如下:δ7.49(s,1H,ArH),7.45-7.35(m,3H,ArH),7.19(d,J=7.2Hz,1H,ArH),5.13(s,2H,Ph-CH2),4.26-4.12(m,2H,N-CH2),4.03(s,3H,O-CH3),3.83(s,3H,N-CH3),3.19(ddd,J=11.6,8.0,3.7Hz,1H,Piperidine-H),2.88(d,J=11.7Hz,2H,Piperidine-H),2.26(s,3H,thiadiazole-CH3),2.09(d,J=11.5Hz,2H,Piperidine-H),1.73-1.67(m,2H,Piperidine-H),1.47(s,9H,Boc-H)。化合物II制备的量和反应容器的体积按相应比例扩大或缩小。化合物II的理化参数和结构参数见表1。
实施例2:化合物III的制备:
在25毫升单口圆底烧瓶中加入0.24毫摩尔化合物II,用15毫升甲醇溶解,向反应中加入0.03克,即0.72毫摩尔氢氧化钠,然后加热回流30分钟,反应结束后将反应液浓缩,残余物用10毫升乙酸乙酯稀释,加入10毫升的水将固体全部溶解,分离出水层,水层用2摩尔/升的盐酸调节pH至3,然后用乙酸乙酯萃取,水层用乙酸乙酯反萃一遍,合并有机层,有机层用饱和氯化钠洗一遍,无水硫酸钠干燥,抽滤,减压除去溶剂,得化合物III;收率95-100%;化合物III制备的量和反应容器的体积按相应比例扩大或缩小。化合物III的理化参数和结构参数见表1。
实施例3:化合物IV的制备:
在25毫升单口圆底烧瓶中加入0.30毫摩尔化合物III,用15毫升干燥的二氯甲烷溶解,向反应中加入0.69克,即0.36毫摩尔的EDCI,即1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐和0.43克,即0.32毫摩尔的HOBT,即1-羟基苯并三氮唑,加完之后室温搅拌30分钟,然后向反应体系中加入0.32毫摩尔的R2-XHn,n=1,2;室温搅拌2小时,反应结束后,反应液用15毫升的水洗两遍,分离出有机层,有机层分别用饱和碳酸氢钠和饱和氯化钠各洗一遍,无水硫酸钠干燥,抽滤,减压除去溶剂,残余物经200~300目硅胶柱层析纯化得白色固体IV,洗脱剂为60~90摄氏度的石油醚∶乙酸乙酯,体积比为4∶1,收率60%-90%;当R1为甲基,R2为环丙基,该化合物的核磁数据如下:δ7.47(d,J=7.2Hz,1H),7.43(s,1H),7.39-7.33(m,2H),7.19(d,J=7.3Hz,1H),6.90(d,J=2.5Hz,1H),5.12(s,2H),4.18(s,2H),3.91(s,3H),3.19(t,J=11.5Hz,1H),2.86(s,2H),2.81-2.72(m,1H),2.26(s,3H),2.09(d,J=12.1Hz,2H),1.70(d,J=12.0Hz,2H),1.47(s,9H),0.76(d,J=6.9Hz,2H),0.56(s,2H)。化合物IV制备的量和反应容器的体积按相应比例扩大或缩小。化合物IV的理化参数和结构参数见表1。
实施例4:化合物V的制备:
在25毫升单口圆底烧瓶中加入0.30毫摩尔化合物IV,用15毫升干燥的二氯甲烷中,冰浴条件下滴1.5毫升的三氟乙酸,加入完毕,室温搅拌过夜,反应结束,用1摩尔每升的氢氧化钠中和至PH=7-8,分离出有机层,有机层分别用饱和碳酸氢钠和饱和氯化钠各洗一遍,无水硫酸钠干燥,抽滤,减压除去溶剂,残余物经200~300目硅胶柱层析纯化得到白色固体,洗脱剂为二氯甲烷∶甲醇,体积比为8∶1,收率96.26%;化合物V制备的量和反应容器的体积按相应比例扩大或缩小。化合物V的理化参数和结构参数见表1。
实施例5:化合物CL05-00的制备方法:
在25毫升单口圆底烧瓶中加入1.10毫摩尔化合物b,用15毫升乙醇溶解,再加入1.00毫摩尔a,最后反应体系中滴加两滴2摩尔/升的盐酸,室温搅拌12小时,反应完全后减压除去溶剂,残余物经200~300目硅胶柱层析纯化得化合物CL05-00,洗脱剂为60~90摄氏度的石油醚∶乙酸乙酯,体积比为4∶1,收率63.12%。
实施例6:本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V的抑菌活性测定结果:
本发明测试的常见植物病原真菌的代号和名称如下:AS:番茄早疫病菌,其拉丁名为:Alternaria solani、BC:黄瓜灰霉病菌,其拉丁名为:Botrytis cinerea、CA:花生褐斑病菌,其拉丁名为:Cercospora arachidicola、GZ:小麦赤霉病菌,其拉丁名为:Gibberellazeae、PI:马铃薯晚疫病菌,其拉丁名为:Phytophthora infestans(Mont.)de Bary、PP:苹果轮纹病菌,其拉丁名为:Physalospora piricola、PS:水稻纹枯病菌,其拉丁名为:Pellicularia sasakii、RC:禾谷丝核菌,其拉丁名为:Rhizoctonia cerealis、SS:油菜菌核病菌,其拉丁名为:Sclerotinia sclerotiorum,这些菌种具有很好的代表性,能够代表农业生产中田间发生的大部分病原菌的种属。
值得注意的是本发明中化合物CL05-00为专利WO 2000003974 A1中报道过的化学结构与本发明目标化合物最接近的已知化合物,为了比较本发明合成的新化合物的生物活性,本发明合成了结构最接近本发明目标化合物的已知化合物CL05-00作为对照化合物,并与本发明目标化合物进行活性比较。
菌体生长率法测定结果见表2,表2表明,在50微克/毫升时,本发明合成的所有化合物均有不同程度的杀菌活性。对于番茄早疫病菌而言,本发明的化合物CL04-43A、CL04-43B、CL04-45D、CL05-15的抑制率达到40%以上,上述化合物的杀菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 20%以上,其中化合物CL04-43B的杀菌活性达到45.45%;对于花生褐斑病菌而言,化合物CL04-43A、CL04-43B、CL04-45A、CL04-45B、CL04-45C、CL04-45D、CL05-15的杀菌活性均在30%以上,上述化合物的杀菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 10%以上,其中化合物CL04-43A、CL04-43B、CL04-45D、CL05-15的杀菌活性均在50%以上,均与对照药嘧菌酯相当,其中化合物CL04-45D抑制率最高,达58.33%;对于小麦赤霉病菌的活性表明,化合物CL04-43A、CL04-45B、CL04-45C、CL04-45D和CL05-15的抑制率均在40%以上,上述化合物的杀菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-0030%以上,其中化合物CL04-45B的杀菌活性最高,达57.58%;对苹果轮纹病菌而言,化合物CL04-43A、CL04-45B、CL04-45C、CL04-45D和CL05-15的抑制率均在50%以上,上述化合物的杀菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 30%以上,且化合物CL04-45C的抑制率最高,达56.30%;对于黄瓜灰霉病菌而言,化合物CL04-43A、CL04-43B、CL04-45A、CL04-45B、CL04-45C、CL04-45D、CL04-45E和CL05-15的抑制率均在40%以上,上述化合物的杀菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 10%以上,且化合物CL04-43A、CL04-43B和CL05-15的抑制率均在70%以上,其中化合物CL04-43A和CL05-15的杀菌活性最高,达75.00%;对于油菜菌核病菌而言,化合物CL04-43A、CL04-43B、CL04-45A、CL04-45B、CL04-45D和CL05-15的杀菌活性均在40%以上,上述化合物的杀菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 10%以上,其中化合物CL04-45B和CL04-45D的抑制率最高,达64.71%;对于禾谷丝核菌而言,化合物CL04-43A、CL04-43B、CL04-45A、CL04-45B、CL04-45C、CL04-45D、CL04-45E和CL05-15的杀菌活性均在30%以上,上述化合物的杀菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 30%以上,其中化合物CL04-43A、CL04-43B、CL04-45B、CL04-45D和CL05-15的杀菌活性均在70%以上,且化合物CL04-43A、CL04-43B、CL04-45B和CL05-15的杀菌活性最高,达78.00%;对水稻纹枯病菌的活性表明,化合物CL04-43A、CL04-43B、CL04-45A、CL04-45B、CL04-45C、CL04-45D和CL05-15的杀菌活性均在30%以上,上述化合物的杀菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 10%以上,其中化合物CL04-43A、CL04-45D和CL05-15的杀菌活性均在50%以上,且杀菌活性最高,达54.55%;对于马铃薯晚疫病菌而言,化合物CL04-43A、CL04-43B、CL04-45B、CL04-45D和CL05-15的杀菌活性均在40%以上,上述化合物的杀菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 20%以上,其中化合物CL04-43A、CL04-43B、CL04-45D和CL05-15的杀菌活性均高于对照药嘧菌酯,且化合物CL04-43A的杀菌活性最高,达62.86%;综上可得,上述的大部分化合物均具有广谱的杀菌活性。
见表3,表3表明,本发明合成的所有化合物均有不同程度的杀菌活性,在400微克/毫升时,对于黄瓜霜霉病而言,化合物CL04-43A、CL04-43B、CL04-45A、CL04-45B和CL04-45D的抑制率均在70%以上,上述的化合物的杀菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 40%以上,其中化合物CL04-45B的杀菌活性与对照药嘧菌酯的活性一样,达85%;对于小麦白粉病而言,化合物CL04-43A、CL04-45D和CL05-15的杀菌活性均为100%,上述的化合物的杀菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 70%以上,与对照药嘧菌酯的杀菌活性一样;对于玉米锈病而言,化合物CL04-43A、CL04-43B、CL04-45D和CL05-15的抑制率均在70%以上,上述的化合物的杀菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-0040%以上,均高于对照药嘧菌酯,且化合物CL05-15的杀菌活性最高,达100%;对于西瓜炭疽病而言,化合物CL04-43A、CL04-43B、CL04-45C和CL04-45D的杀菌活性均在70%以上,上述的化合物的杀菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 50%以上,且化合物CL04-43B、CL04-45C的杀菌活性与对照药嘧菌酯相当;在25微克/毫升时,对于水稻稻瘟病而言,化合物CL04-43A、CL04-43B、CL04-45A、CL04-45B、CL04-45C、CL04-45D和CL05-15的杀菌活性均在80%以上,上述的化合物的杀菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 40%以上,其中化合物CL04-43A、CL04-45B和CL04-45D的杀菌活性均在90%以上,均高于对照药嘧菌酯10%以上,且化合物CL04-43A和CL04-45B的杀菌活性最高,达100%;对于黄瓜灰霉病而言,化合物CL05-15的抑制率达到100%,上述的化合物的杀菌活性高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 90%和对照药嘧菌酯50%以上,综上所述,化合物CL04-43A和CL05-15具有广谱的杀菌活性。
实施例7:本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物IV的抗烟草花叶病毒(TMV)活性:
TMV活性的测定结果见表4,表4表明,本发明的大部分化合物具有较好的抗TMV的活性;在100微克/毫升时,本发明合成的所有化合物均有不同程度的抗TMV活性。在治疗模式下,化合物CL04-43B、CL04-45D和CL04-45F的治疗活性高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 30%以上,虽然低于对照药宁南霉素,但是仍然具有较好的治疗效果;在钝化模式下,化合物CL04-43A、CL04-45F和CL05-15的钝化抑制率在20%以上,上述化合物的钝化活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 10%以上,虽然低于对照药病毒唑,但还是表现了较好的钝化活性;在保护模式下,化合物CL04-43A、CL04-43B、CL04-45A、CL04-45B、CL04-45C、CL04-45D、CL04-45E、CL04-45F和CL05-15的保护活性均在30%以上,上述化合物的保护活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 10%以上,其中CL04-43B的保护活性最高,达53.79%,虽然低于对照药BTH,但还是表现了较好的钝化活性;在诱导模式下,化合物CL04-43A、CL04-43B、CL04-45A、CL04-45C、CL04-45D、CL04-45E和CL04-45F的诱导活性均在40%以上,上述化合物的诱导活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 30%以上,其中化合物CL04-45C的诱导活性最高,达到了74.89%,与对照药TDL、BTH、SZG-7相当;可见,本发明的大部分化合物具有很好的抗TMV活性。
本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物IV还对水稻矮缩病、黄矮病、条纹叶枯病、番茄蕨叶病毒病、辣椒花叶病毒病、烟草脉坏死病毒病、玉米矮花叶病、花椰菜花叶病毒、柑橘病毒病、建兰花叶病毒病、建兰环斑病毒的农业和林业以及园艺植物病毒病害具有很好的抗病毒活性。
实施例8:本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与杀虫剂组合在防治农业和林业以及园艺植物虫害中的应用:
本发明的所有哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与商品杀虫剂中的任意一种或两种组合形成杀虫组合物用于防治农业和林业以及园艺植物虫害,所述商品杀虫剂选自:毒死蜱、地亚哝、啶虫脒、甲氨基阿维菌素、弥拜菌素、阿维菌素、多杀菌素、氰戊菊酯、高效氰戊菊酯、氯氰菊酯、高效氯氰菊酯、三氟氯氰菊酯、溴氰菊酯、甲氰菊酯、Beta-氟氯氰菊酯、Lambda-三氟氯氰菊酯、二氯苯醚菊酯、苄氯菊酯、丙烯菊酯、联苯菊酯、氯菊酯、醚菊酯、氟氯苯菊酯、氯氟胺氰戊菊酯、吡虫啉、烯啶虫胺、氯噻啉、噻虫啉、噻虫嗪、噻虫胺、呋虫胺、可尼丁、达特南、除虫脲、灭幼脲、伏虫隆、除虫隆、氟铃脲、氟虫脲、啶虫隆、虱螨脲、毒虫脲、氟幼脲、Noviflumuron即多氟脲,其CAS号为121451-02-3、氟螨脲、Novaluron即双苯氟脲、氟啶脲、Bay sir 6874即1-[(3.5-二氯-4)4-硝基苯氧基苯基3-3-(2-氯苯)-脲、Bay SIR-8514即1-(4-三氟甲氧基苯基)-3-(2-氯苯)-脲、嗪虫脲、Bistrifluron即双三氟虫脲、呋喃虫酰肼、虫酰肼、氯虫酰肼、甲氧虫酰肼、环虫酰肼、乐果、氧化乐果、敌敌畏、乙酰甲胺磷、三唑磷、喹硫磷、哒嗪硫磷、氯唑磷、叶蝉散、西维因、抗蚜威、速灭威、异丙威、杀螟丹、仲丁威、叶飞散、甲萘威、丙硫克百威、丁硫克百威、杀螟丹、溴螨酯、噻螨酮、唑螨酯、哒螨酮、四螨嗪、炔螨特、丁醚脲、吡蚜酮、螺螨酯、螺虫酯、螺虫乙酯、丁烯氟虫腈、三唑锡、噻嗪酮、灭线磷、氟虫腈、杀虫单、杀虫双、氯虫酰胺、氟虫酰胺、氟氰虫酰胺、氰虫酰胺、唑虫酰胺、溴虫腈、吡嗪酮、乙螨唑、吡螨胺、哒幼酮、吡丙醚、埃玛菌素;本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V在所述杀虫组合物中的质量百分含量是1%-90%,本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与前述商品杀虫剂的比例为质量百分比1%∶99%到99%∶1%;所述杀虫组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;所述杀虫组合物防治的植物虫害选自:红蜘蛛、东亚飞蝗、云斑车蝗、中华稻蝗、日本黄脊蝗、单刺蝼蛄、东方蝼蛄、稻蓟马、烟蓟马、温室蓟马、稻管蓟马、麦简管蓟马、温室白粉虱、烟粉虱、黑尾叶蝉、大青叶蝉、棉叶蝉、斑衣蜡蝉、褐飞虱、白背飞虱、灰飞虱、甘蔗扁角飞虱、棉蚜、麦二叉蚜、麦长管蚜、桃蚜、高粱蚜、萝卜蚜、吹绵蚧、桑盾蚧、矢尖盾蚧、梨圆蚧、白蜡虫、红蜡蚧、朝鲜球坚蚧、梨网蝽、香蕉网蝽、细角花蝽、微小花蝽、针缘蝽、稻蛛缘蝽、稻褐蝽、稻黑蝽、稻绿蝽、绿盲蝽、苜蓿盲蝽、中黑盲蝽、大草蛉、丽草蛉、中华草蛉、谷蛾、衣蛾、黄刺蛾、褐刺蛾、扁刺蛾、麦蛾、棉红铃虫、甘薯麦蛾、小菜蛾、桃小食心虫、大豆食心虫、桃小食心虫、苹果顶梢卷叶蛾、褐带长卷叶蛾、拟小黄卷叶蛾、二化螟、豆荚螟、玉米螟、三化螟、菜螟、稻纵卷叶螟、条螟、棉卷叶野螟、桃蛀螟、黏虫、斜纹夜蛾、稻螟蛉、棉小造桥虫、甜菜夜蛾、大螟、棉铃虫、鼎点金刚钻、小地老虎、大地老虎、黄地老虎、盗毒蛾、舞毒蛾、甘薯天蛾、豆天蛾、直纹稻弄蝶、隐纹谷弄蝶、柑橘凤蝶、玉带凤蝶、菜粉蝶、苎麻赤蛱蝶、苎麻黄蛱蝶、豆芫菁、金星步甲、皱鞘步甲、麦穗步甲、沟金针虫、细胸金针虫、谷斑皮蠹、黑皮蠹、柑橘小吉丁虫、金缘吉丁虫、黄粉虫、黑粉虫、赤拟谷盗、杂拟谷盗、铜绿异丽金龟、暗黑金龟、华北大黑鳃金龟、桑天牛、星天牛、橘褐天牛、桃红颈天牛、大猿叶虫、小猿叶虫、黄守瓜、黄曲条跳甲、绿豆象、豌豆象、蚕豆象、玉米象、米象、小麦叶蜂、梨实蜂、黄带姬蜂、黏虫白星姬蜂、螟蛉悬茧姬蜂、棉铃虫齿唇姬蜂、螟黑点疣姬蜂、蚊、蝇、虻、麦红吸浆虫、麦黄吸浆虫、稻瘿蚊、柑橘大实蝇、瓜实蝇、麦叶灰潜蝇、美洲斑潜蝇、豆秆黑潜蝇、麦秆蝇、种蝇、葱蝇、萝卜蝇、伞裙追寄蝇、玉米螟厉寄蝇、黏虫;所述杀虫组合物防治的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景
实施例9:本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与杀菌剂组合在防治农业和林业以及园艺植物病害中的应用:
本发明的所有哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与商品杀菌剂中的任意一种或两种组合形成杀菌组合物用于防治农业和林业以及园艺植物病害,所述商品杀菌剂选自:苯并噻二唑、噻酰菌胺,简写为TDL、噻酰胺、甲噻诱胺、4-甲基-1,2,3-噻二唑-5-甲酸、4-甲基-1,2,3-噻二唑-5-甲酸钠、4-甲基-1,2,3-噻二唑-5-甲酸乙酯、DL-β-氨基丁酸、异噻菌胺,其英文通用名为:isotianil、3,4-二氯并噻唑-5-甲酸、3,4-二氯异噻唑-5-甲酸钠、3,4-二氯异噻唑-5-甲酸乙酯、病毒唑、安托芬、宁南霉素或水杨酸、霜脲氰、福美双、福美锌、代森锰锌、乙磷铝、甲基硫菌灵、百菌清、敌可松、腐霉利、苯锈啶、甲基托布津、托布津、精甲霜灵、氟吗啉、烯酰吗啉、高效甲霜灵、高效苯霜灵、双氯氰菌胺、磺菌胺、甲磺菌胺、噻氟菌胺、氟酰胺、叶枯酞、环丙酰菌胺、环氟菌胺、环酰菌胺、氰菌胺、硅噻菌胺、呋吡菌胺、吡噻菌胺、双炔酰菌胺、苯酰菌胺、甲呋酰胺、萎锈灵、乙菌利、异菌脲、嘧菌酯、醚菌胺、氟嘧菌酯、醚菌酯、苯氧菌胺、肟醚菌胺、啶氧菌酯、唑菌胺酯、肟菌酯、烯肟菌酯、烯肟菌胺、氧环唑、糠菌唑、环丙唑醇、苯醚甲环唑、烯唑醇、高效烯唑醇、氟环唑、腈苯唑、氟喹唑、氟硅唑、粉唑醇、己唑醇、亚胺唑、种菌唑、叶菌唑、腈菌唑、戊菌唑、丙环唑、丙硫菌唑、硅氟唑、戊唑醇、四氟醚唑、三唑醇、灭菌唑、联苯三唑醇、噻菌灵、麦穗宁、抑霉唑、高效抑霉唑、咪鲜胺、氟菌唑、氰霜唑、咪唑菌酮、噁咪唑、稻瘟酯、噁唑菌酮、啶菌噁唑、噁霉灵、噁霜灵、噻唑菌胺、土菌灵、辛噻酮、苯噻硫氰、十二环吗啉、丁苯吗啉、十三吗啉、拌种咯、咯菌腈、氟啶胺、啶斑肟、环啶菌胺、啶酰菌胺、氟啶酰菌胺、啶菌胺、嘧菌环胺、氟嘧菌胺、嘧菌腙、嘧菌胺、嘧霉胺、氯苯嘧啶醇、氟苯嘧啶醇、灭螨猛、二氰蒽醌、乙氧喹啉、羟基喹啉、丙氧喹啉、苯氧喹啉、乙霉威、异丙菌胺、苯噻菌胺、霜霉威、磺菌威、敌瘟磷、异稻瘟净、吡菌磷、甲基立枯磷、灭瘟素、春雷霉素、多抗霉素、多氧霉素、有效霉素、井冈霉素、链霉素、甲霜灵、呋霜灵、苯霜灵、呋酰胺、灭锈胺、多菌灵、苯菌灵、甲基硫菌灵、三唑酮、乙嘧酚磺酸酯、二甲嘧酚、乙嘧酚、敌菌丹、克菌丹、灭菌丹、乙烯菌核利、氟氯菌核利、菌核净、百菌清、稻瘟灵、稻瘟净、叶枯唑、五氯硝基苯、丙森锌、三乙膦酸铝、硫磺、波尔多液、硫酸铜、氧氯化铜、氧化亚铜、氢氧化铜、苯菌酮、戊菌隆、哒菌酮、四氯苯酞、咯喹酮、螺环菌胺、三环唑、嗪胺灵、多果啶、双胍辛盐、双胍辛胺、氯硝胺、苯磺菌胺、甲苯磺菌胺、吲哚酯、敌磺钠、喹菌酮、烯丙苯噻唑、溴硝醇、碘甲烷、威百亩、敌线酯、棉隆、二氯异丙醚、噻唑磷、硫线磷、丰索磷、虫线磷、苯线磷、灭线磷、除线磷、氯唑磷、丁硫环磷、杀线威、涕灭威、克百威、硫酰氟、二氯丙烯、二氯异烟酸、烯丙异噻唑;本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V在所述杀菌组合物中的总的质量百分含量是1%-90%,本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与前述商品杀菌剂的比例为质量百分比1%∶99%到99%∶1%;所述杀菌组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;所述杀菌组合物防治的植物病害选自:稻苗绵腐病、番茄根腐病、马铃薯晚疫病、烟草黑胫病、谷子白粉病、葡萄霜霉病、莴苣霜霉病、黄瓜霜霉病、黄瓜炭疽病;所述杀菌组合物适用的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。
实施例10:本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与抗植物病毒剂组合在防治农业和林业以及园艺植物病毒病害中的应用:
本发明的所有哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与商品抗病毒药剂中的任意一种或两种组合形成抗病毒组合物用于防治农业和林业以及园艺植物病毒病害,所述商品抗病毒药剂选自:苯并噻二唑、噻酰菌胺,简写为TDL、异噻菌胺,其英文通用名为:isotianil、4-甲基-1,2,3-噻二唑-5-甲酸、4-甲基-1,2,3-噻二唑-5-甲酸钠、4-甲基-1,2,3-噻二唑-5-甲酸乙酯、3,4-二氯异噻唑-5-甲酸、3,4-二氯异噻唑-5-甲酸钠、3,4-二氯异噻唑-5-甲酸乙酯、DL-β-氨基丁酸、病毒唑、安托芬、宁南霉素、噻酰胺、甲噻诱胺或水杨酸、嘧肽霉素、二氯异烟酸、烯丙异噻唑、井冈羟胺、井冈霉素;本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V在所述抗病毒组合物中的总的质量百分含量是1%-90%,本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与前述商品抗植物病毒剂的比例为质量百分比1%∶99%到99%∶1%;所述抗病毒组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;所述抗病毒组合物防治的病毒病害选自:水稻矮缩病、黄矮病、条纹叶枯病、番茄蕨叶病毒病、辣椒花叶病毒病、烟草脉坏死病毒病、玉米矮花叶病、花椰菜花叶病毒、柑橘病毒病、建兰花叶病毒、建兰环斑病毒;所述抗病毒组合物用于防治的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。
实施例11:本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与杀螨剂组合在防治农业和林业以及园艺植物螨害中的应用:
本发明的所有哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与商品杀螨剂中的任意一种或两种组合形成杀螨组合物用于防治农业和林业以及园艺植物螨害,所述商品杀螨剂选自:三唑锡、三环锡、苯丁锡、三磷锡、毒虫畏、甲基毒虫畏、巴毒磷、敌敌畏、庚烯磷、速灭磷、久效磷、二溴磷、毒死蜱、嘧啶磷、氯甲亚胺硫磷、氧乐果、敌杀磷、乙硫磷、马拉硫磷、虫螨畏、伏杀硫磷、辛硫磷、甲基嘧啶硫磷、喹硫磷、治螟磷、三唑磷、蚜灭多、水胺硫磷、甲胺磷、胺丙畏、氯亚胺硫磷、亚胺硫磷、氟丙菊酯、联苯菊酯、氯氟氰菊酯、精高效氯氟氰菊酯、甲氰菊酯、氟氰戊菊酯、氟氯苯菊酯、氟胺氰菊酯、溴氟菊酯、联苯肼酯、苯硫威、涕灭威、丁酮威、杀线威、抗虫威、久效威、苯菌灵、氯灭杀威、克百威、丁硫克百威、速灭威、蜱虱威、伐虫脒、单甲脒、杀螨脒、双甲脒、杀虫脒、苯甲酸苄酯、溴螨酯、丁氟螨酯、灭螨醌、氟蚜螨、氟虫脲、浏阳霉素、虫螨霉素、苏云金素、杀螨素、浏阳霉素、阿维菌素、多拉菌素、埃普利诺菌素、伊维菌素、赛拉菌素、莫西菌素、除虫菊素、烟碱、苦参碱、印楝素、鱼藤酮、吡螨胺、哒螨酮、唑螨酯、四螨嗪、炔螨特、噻螨酮、螺螨酯、嘧螨酯、杀螨酯、克螨特、哒螨灵;本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V在所述杀螨组合物中的总的质量百分含量是1%-90%,本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与所述商品杀螨剂的比例为质量百分比1%∶99%到99%∶1%;所述杀螨组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;所述杀螨组合物防治的螨害选自:螨害选自叶螨科、细须螨科、呋线螨、瘿螨科、红叶螨属、瘿螨科的害螨,这些害螨是世界性农业害螨、林业害螨、园艺害螨和卫生害螨;所述杀螨组合物用于防治的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。
表2本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V的抑菌活性(50微克/毫升的抑制率/%)
| 序号 | 化合物 | AS | CA | GZ | PP | BC | SS | RC | PS | PI |
| 1 | CL04-43A | 41.82 | 54.17 | 51.52 | 52.94 | 75.00 | 52.94 | 78.00 | 54.55 | 62.86 |
| 2 | CL04-43B | 45.45 | 54.17 | 39.39 | 52.94 | 73.21 | 41.18 | 78.00 | 42.42 | 54.29 |
| 3 | CL04-45A | 9.09 | 12.50 | 21.21 | 36.13 | 55.36 | 52.94 | 50.00 | 30.30 | 17.14 |
| 4 | CL04-45B | 27.27 | 33.33 | 57.58 | 36.13 | 46.43 | 64.71 | 74.00 | 45.45 | 45.71 |
| 5 | CL04-45C | 27.27 | 33.33 | 51.52 | 56.30 | 42.86 | 29.41 | 68.00 | 30.30 | 28.57 |
| 6 | CL04-45D | 41.82 | 58.33 | 48.48 | 52.10 | 76.79 | 64.71 | 70.00 | 54.55 | 54.29 |
| 7 | CL04-45E | 5.45 | 12.50 | 21.21 | 21.01 | 41.07 | 5.88 | 38.00 | 15.15 | 17.14 |
| 8 | CL04-45F | 12.73 | 16.67 | 27.27 | 24.37 | 25.00 | 64.71 | 46.00 | 24.24 | 14.29 |
| 9 | CL05-15 | 41.82 | 54.17 | 51.52 | 52.94 | 75.00 | 52.94 | 78.00 | 54.55 | 62.85 |
| 10 | CL05-00 | 21.56 | 13.42 | 20.11 | 20.43 | 30.87 | 30.10 | 15.08 | 20.76 | 21.61 |
| 11 | 嘧菌酯 | 75.00 | 55.56 | 71.43 | 100 | 91.18 | 88.10 | 84.06 | 80.77 | 46.88 |
表3本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V的抑菌活性(抑制率/%)
表4本发明的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V的抗烟草花叶病毒活性(100微克/毫升的抑制率/%)
| 序号 | 化合物 | 治疗模式 | 钝化模式 | 保护模式 | 诱导模式 |
| 1 | CL04-43A | 1.52±0.62 | 25.24±6.60 | 40.21±1.21 | 50.81±0.21 |
| 2 | CL04-43B | 85.00±3.55 | 0.89±0.21 | 53.79±2.83 | 63.79±8.83 |
| 3 | CL04-45A | 49.98±0.49 | 0.44±0.11 | 34.92±3.17 | 44.92±4.17 |
| 4 | CL04-45B | 1.52±0.62 | 0.44±0.21 | 39.64±0.87 | 39.64±0.87 |
| 5 | CL04-45C | 29.52±3.92 | 4.60±0.99 | 44.89±0.46 | 74.89±7.46 |
| 6 | CL04-45D | 70.76±2.70 | 2.22±0.85 | 46.30±1.16 | 66.30±2.16 |
| 7 | CL04-45E | 42.79±0.93 | 2.22±0.85 | 36.47±0.08 | 56.47±3.08 |
| 8 | CL04-45F | 62.91±2.62 | 41.79±0.92 | 32.53±1.50 | 52.53±6.70 |
| 9 | CL05-15 | 34.92±1.17 | 23.10±1.04 | 30.21±1.62 | 30.20±1.24 |
| 10 | CL05-00 | 30.32±1.12 | 11.42±1.10 | 23.43±1.50 | 12.44±2.16 |
| 11 | 宁南霉素 | 74.10±2.04 | - | - | - |
| 12 | TDL | - | - | - | 65.00±2.00 |
| 13 | BTH | - | - | 78.10±0.54 | 78.00±1.34 |
| 14 | SZG-7 | - | - | - | 79.00±2.27 |
| 15 | 病毒唑 | - | 78.00±1.00 | - | - |
Claims (9)
1.一类哌啶噻唑肟醚甲氧基丙烯酸酯衍生物,其特征在于具有式V所示的化学结构通式:
其中,R1选自:甲基、氢;R2选自:1,2-二氟乙基、炔丙基、环丙基、甲基、1-甲硫基-2-甲基丙-2-基、(R)-1-甲硫基丙-2-基;R3选自:氢、氯化氢;X选自:氧、氮,n=1,2。
2.权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V的合成方法,具体合成路线为:
其中,R1选自:甲基、氢;R2选自:1,2-二氟乙基、炔丙基、环丙基、甲基、1-甲硫基-2-甲基丙-2-基、(R)-1-甲硫基丙-2-基;R3选自:氢、氯化氢;X选自:氧、氮,n=1,2;
权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物的合成方法分为以下步骤:
A.化合物II的制备:
在25毫升单口圆底烧瓶中加入1.10毫摩尔化合物I,用15毫升乙醇溶解,再加入1.00毫摩尔取代哌啶噻唑羰基化合物,所述哌啶噻唑羰基化合物选自:哌啶噻唑酮、哌啶噻唑醛,最后向反应体系中滴加两滴2摩尔/升的盐酸,室温搅拌12小时,反应完全后减压除去溶剂,残余物经200~300目硅胶柱层析纯化得化合物II,洗脱剂为60~90摄氏度的石油醚∶乙酸乙酯,根据产物的不同,体积比为9∶1-2∶1,收率40-50%;化合物II制备的量和反应容器的体积按相应比例扩大或缩小;
B.化合物III的制备:
在25毫升单口圆底烧瓶中加入0.24毫摩尔化合物II,用15毫升甲醇溶解,向反应中加入0.03克,即0.72毫摩尔氢氧化钠,然后加热回流30分钟,反应结束后将反应液浓缩,残余物用10毫升乙酸乙酯稀释,加入10毫升的水将固体全部溶解,分离出水层,水层用2摩尔/升的盐酸调节pH至3,然后用乙酸乙酯萃取,水层用乙酸乙酯反萃一遍,合并有机层,有机层用饱和氯化钠洗一遍,无水硫酸钠干燥,抽滤,减压除去溶剂,得化合物III;收率95-100%;化合物III制备的量和反应容器的体积按相应比例扩大或缩小;
C.化合物IV的制备:
在25毫升单口圆底烧瓶中加入0.30毫摩尔化合物III,用15毫升干燥的二氯甲烷溶解,向反应中加入0.69克,即0.36毫摩尔的EDCI,即1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐和0.43克,即0.32毫摩尔的HOBT,即1-羟基苯并三氮唑,加完之后室温搅拌30分钟,然后向反应体系中加入0.32毫摩尔的R2-XHn,n=1,2;室温搅拌2小时,反应结束后,反应液用15毫升的水洗两遍,分离出有机层,有机层分别用饱和碳酸氢钠和饱和氯化钠各洗一遍,无水硫酸钠干燥,抽滤,减压除去溶剂,残余物经200~300目硅胶柱层析纯化得到白色固体,洗脱剂为60~90摄氏度的石油醚∶乙酸乙酯,体积比为4∶1,收率60%-95%;化合物IV制备的量和反应容器的体积按相应比例扩大或缩小;
D.化合物V的制备:
在25毫升单口圆底烧瓶中加入0.30毫摩尔化合物IV,用15毫升干燥的二氯甲烷中,冰浴条件下滴1.5毫升的三氟乙酸,加入完毕,室温搅拌过夜,反应结束,用1摩尔每升的氢氧化钠中和至pH=7-8,分离出有机层,有机层分别用饱和碳酸氢钠和饱和氯化钠各洗一遍,无水硫酸钠干燥,抽滤,减压除去溶剂,残余物经200~300目硅胶柱层析纯化得到白色固体,洗脱剂为二氯甲烷∶甲醇,体积比为8∶1,收率96.26%;化合物V制备的量和反应容器的体积按相应比例扩大或缩小。
3.权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与农业上可接受的助剂在制备杀菌剂中的用途。
4.权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与农业上可接受的助剂在制备抗烟草花叶病毒剂中的用途。
5.权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与农业上可接受的助剂在制备植物激活剂用于诱导烟草抗烟草花叶病毒中的用途。
6.权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与杀虫剂组合在防治农业和林业以及园艺植物虫害中的用途:
权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与商品杀虫剂中的任意一种或两种组合形成杀虫组合物用于防治农业和林业以及园艺植物虫害,所述商品杀虫剂选自:毒死蜱、地亚哝、啶虫脒、甲氨基阿维菌素、弥拜菌素、阿维菌素、多杀菌素、氰戊菊酯、高效氰戊菊酯、氯氰菊酯、高效氯氰菊酯、三氟氯氰菊酯、溴氰菊酯、甲氰菊酯、Beta-氟氯氰菊酯、Lambda-三氟氯氰菊酯、二氯苯醚菊酯、苄氯菊酯、丙烯菊酯、联苯菊酯、氯菊酯、醚菊酯、氟氯苯菊酯、氯氟胺氰戊菊酯、吡虫啉、烯啶虫胺、氯噻啉、噻虫啉、噻虫嗪、噻虫胺、呋虫胺、可尼丁、达特南、除虫脲、灭幼脲、伏虫隆、除虫隆、氟铃脲、氟虫脲、啶虫隆、虱螨脲、毒虫脲、氟幼脲、Noviflumuron即多氟脲,其CAS号为121451-02-3、氟螨脲、Novaluron即双苯氟脲、氟啶脲、Bay sir 6874即1-[(3.5-二氯-4)4-硝基苯氧基苯基3-3-(2-氯苯)-脲、Bay SIR-8514即1-(4-三氟甲氧基苯基)-3-(2-氯苯)-脲、嗪虫脲、Bistrifluron即双三氟虫脲、呋喃虫酰肼、虫酰肼、氯虫酰肼、甲氧虫酰肼、环虫酰肼、乐果、氧化乐果、敌敌畏、乙酰甲胺磷、三唑磷、喹硫磷、哒嗪硫磷、氯唑磷、叶蝉散、西维因、抗蚜威、速灭威、异丙威、杀螟丹、仲丁威、叶飞散、甲萘威、丙硫克百威、丁硫克百威、杀螟丹、溴螨酯、噻螨酮、唑螨酯、哒螨酮、四螨嗪、炔螨特、丁醚脲、吡蚜酮、螺螨酯、螺虫酯、螺虫乙酯、丁烯氟虫腈、三唑锡、噻嗪酮、灭线磷、氟虫腈、杀虫单、杀虫双、氯虫酰胺、氟虫酰胺、氟氰虫酰胺、氰虫酰胺、唑虫酰胺、溴虫腈、吡嗪酮、乙螨唑、吡螨胺、哒幼酮、吡丙醚、埃玛菌素;权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V在所述杀虫组合物中的质量百分含量是1%-90%,权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与前述商品杀虫剂的比例为质量百分比1%∶99%到99%∶1%;所述杀虫组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;所述杀虫组合物防治的植物虫害选自:红蜘蛛、东亚飞蝗、云斑车蝗、中华稻蝗、日本黄脊蝗、单刺蝼蛄、东方蝼蛄、稻蓟马、烟蓟马、温室蓟马、稻管蓟马、麦简管蓟马、温室白粉虱、烟粉虱、黑尾叶蝉、大青叶蝉、棉叶蝉、斑衣蜡蝉、褐飞虱、白背飞虱、灰飞虱、甘蔗扁角飞虱、棉蚜、麦二叉蚜、麦长管蚜、桃蚜、高粱蚜、萝卜蚜、吹绵蚧、桑盾蚧、矢尖盾蚧、梨圆蚧、白蜡虫、红蜡蚧、朝鲜球坚蚧、梨网蝽、香蕉网蝽、细角花蝽、微小花蝽、针缘蝽、稻蛛缘蝽、稻褐蝽、稻黑蝽、稻绿蝽、绿盲蝽、苜蓿盲蝽、中黑盲蝽、大草蛉、丽草蛉、中华草蛉、谷蛾、衣蛾、黄刺蛾、褐刺蛾、扁剌蛾、麦蛾、棉红铃虫、甘薯麦蛾、小菜蛾、桃小食心虫、大豆食心虫、桃小食心虫、苹果顶梢卷叶蛾、褐带长卷叶蛾、拟小黄卷叶蛾、二化螟、豆荚螟、玉米螟、三化螟、菜螟、稻纵卷叶螟、条螟、棉卷叶野螟、桃蛀螟、黏虫、斜纹夜蛾、稻螟蛉、棉小造桥虫、甜菜夜蛾、大螟、棉铃虫、鼎点金刚钻、小地老虎、大地老虎、黄地老虎、盗毒蛾、舞毒蛾、甘薯天蛾、豆天蛾、直纹稻弄蝶、隐纹谷弄蝶、柑橘凤蝶、玉带凤蝶、菜粉蝶、苎麻赤蛱蝶、苎麻黄蛱蝶、豆芫菁、金星步甲、皱鞘步甲、麦穗步甲、沟金针虫、细胸金针虫、谷斑皮蠹、黑皮蠹、柑橘小吉丁虫、金缘吉丁虫、黄粉虫、黑粉虫、赤拟谷盗、杂拟谷盗、铜绿异丽金龟、暗黑金龟、华北大黑鳃金龟、桑天牛、星天牛、橘褐天牛、桃红颈天牛、大猿叶虫、小猿叶虫、黄守瓜、黄曲条跳甲、绿豆象、豌豆象、蚕豆象、玉米象、米象、小麦叶蜂、梨实蜂、黄带姬蜂、黏虫白星姬蜂、螟蛉悬茧姬蜂、棉铃虫齿唇姬蜂、螟黑点疣姬蜂、蚊、蝇、虻、麦红吸浆虫、麦黄吸浆虫、稻瘿蚊、柑橘大实蝇、瓜实蝇、麦叶灰潜蝇、美洲斑潜蝇、豆秆黑潜蝇、麦秆蝇、种蝇、葱蝇、萝卜蝇、伞裙追寄蝇、玉米螟厉寄蝇、黏虫;所述杀虫组合物防治的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。
7.权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与杀菌剂组合在防治农业和林业以及园艺植物病害中的用途:
权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与商品杀菌剂中的任意一种或两种组合形成杀菌组合物用于防治农业和林业以及园艺植物病害,所述商品杀菌剂选自:苯并噻二唑、噻酰菌胺,简写为TDL、噻酰胺、甲噻诱胺、4-甲基-1,2,3-噻二唑-5-甲酸、4-甲基-1,2,3-噻二唑-5-甲酸钠、4-甲基-1,2,3-噻二唑-5-甲酸乙酯、DL-β-氨基丁酸、异噻菌胺,其英文通用名为:isotianil、3,4-二氯异噻唑-5-甲酸、3,4-二氯异噻唑-5-甲酸钠、3,4-二氯异噻唑-5-甲酸乙酯、病毒唑、安托芬、宁南霉素或水杨酸、霜脲氰、福美双、福美锌、代森锰锌、乙磷铝、甲基硫菌灵、百菌清、敌可松、腐霉利、苯锈啶、甲基托布津、托布津、精甲霜灵、氟吗啉、烯酰吗啉、高效甲霜灵、高效苯霜灵、双氯氰菌胺、磺菌胺、甲磺菌胺、噻氟菌胺、氟酰胺、叶枯酞、环丙酰菌胺、环氟菌胺、环酰菌胺、氰菌胺、硅噻菌胺、呋吡菌胺、吡噻菌胺、双炔酰菌胺、苯酰菌胺、甲呋酰胺、萎锈灵、乙菌利、异菌脲、嘧菌酯、醚菌胺、氟嘧菌酯、醚菌酯、苯氧菌胺、肟醚菌胺、啶氧菌酯、唑菌胺酯、肟菌酯、烯肟菌酯、烯肟菌胺、氧环唑、糠菌唑、环丙唑醇、苯醚甲环唑、烯唑醇、高效烯唑醇、氟环唑、腈苯唑、氟喹唑、氟硅唑、粉唑醇、己唑醇、亚胺唑、种菌唑、叶菌唑、腈菌唑、戊菌唑、丙环唑、丙硫菌唑、硅氟唑、戊唑醇、四氟醚唑、三唑醇、灭菌唑、联苯三唑醇、噻菌灵、麦穗宁、抑霉唑、高效抑霉唑、咪鲜胺、氟菌唑、氰霜唑、咪唑菌酮、噁咪唑、稻瘟酯、噁唑菌酮、啶菌噁唑、噁霉灵、噁霜灵、噻唑菌胺、土菌灵、辛噻酮、苯噻硫氰、十二环吗啉、丁苯吗啉、十三吗啉、拌种咯、咯菌腈、氟啶胺、啶斑肟、环啶菌胺、啶酰菌胺、氟啶酰菌胺、啶菌胺、嘧菌环胺、氟嘧菌胺、嘧菌腙、嘧菌胺、嘧霉胺、氯苯嘧啶醇、氟苯嘧啶醇、灭螨猛、二氰蒽醌、乙氧喹啉、羟基喹啉、丙氧喹啉、苯氧喹啉、乙霉威、异丙菌胺、苯噻菌胺、霜霉威、磺菌威、敌瘟磷、异稻瘟净、吡菌磷、甲基立枯磷、灭瘟素、春雷霉素、多抗霉素、多氧霉素、有效霉素、井冈霉素、链霉素、甲霜灵、呋霜灵、苯霜灵、呋酰胺、灭锈胺、多菌灵、苯菌灵、甲基硫菌灵、三唑酮、乙嘧酚磺酸酯、二甲嘧酚、乙嘧酚、敌菌丹、克菌丹、灭菌丹、乙烯菌核利、氟氯菌核利、菌核净、百菌清、稻瘟灵、稻瘟净、叶枯唑、五氯硝基苯、丙森锌、三乙膦酸铝、硫磺、波尔多液、硫酸铜、氧氯化铜、氧化亚铜、氢氧化铜、苯菌酮、戊菌隆、哒菌酮、四氯苯酞、咯喹酮、螺环菌胺、三环唑、嗪胺灵、多果啶、双胍辛盐、双胍辛胺、氯硝胺、苯磺菌胺、甲苯磺菌胺、吲哚酯、敌磺钠、喹菌酮、烯丙苯噻唑、溴硝醇、碘甲烷、威百亩、敌线酯、棉隆、二氯异丙醚、噻唑磷、硫线磷、丰索磷、虫线磷、苯线磷、灭线磷、除线磷、氯唑磷、丁硫环磷、杀线威、涕灭威、克百威、硫酰氟、二氯丙烯、二氯异烟酸、烯丙异噻唑;权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V在所述杀菌组合物中的总的质量百分含量是1%-90%,权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与前述商品杀菌剂的比例为质量百分比1%∶99%到99%∶1%;所述杀菌组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;所述杀菌组合物防治的植物病害选自:稻苗绵腐病、番茄根腐病、马铃薯晚疫病、烟草黑胫病、谷子白粉病、葡萄霜霉病、莴苣霜霉病、黄瓜霜霉病、黄瓜炭疽病;所述杀菌组合物适用的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。
8.权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与抗植物病毒剂组合防治农业和林业以及园艺植物病毒病害中的用途:
权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与商品抗病毒药剂中的任意一种或两种组合形成抗病毒组合物用于防治农业和林业以及园艺植物病毒病害,所述商品抗病毒药剂选自:苯并噻二唑、噻酰菌胺,简写为TDL、异噻菌胺,其英文通用名为:isotianil、4-甲基-1,2,3-噻二唑-5-甲酸、4-甲基-1,2,3-噻二唑-5-甲酸钠、4-甲基-1,2,3-噻二唑-5-甲酸乙酯、3,4-二氯异噻唑-5-甲酸、3,4-二氯异噻唑-5-甲酸钠、3,4-二氯异噻唑-5-甲酸乙酯、DL-β-氨基丁酸、病毒唑、安托芬、宁南霉素、噻酰胺、甲噻诱胺或水杨酸、嘧肽霉素、二氯异烟酸、烯丙异噻唑、井冈羟胺、井冈霉素;权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V在所述抗病毒组合物中的总的质量百分含量是1%-90%,权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与前述商品抗植物病毒剂的比例为质量百分比1%∶99%到99%∶1%;所述抗病毒组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;所述抗病毒组合物防治的病毒病害选自:水稻矮缩病、黄矮病、条纹叶枯病、番茄蕨叶病毒病、辣椒花叶病毒病、烟草脉坏死病毒病、玉米矮花叶病、花椰菜花叶病毒、柑橘病毒病、建兰花叶病毒、建兰环斑病毒;所述抗病毒组合物用于防治的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。
9.权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与杀螨剂组合在防治农业和林业以及园艺植物螨害中的应用:
权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与商品杀螨剂中的任意一种或两种组合形成杀螨组合物用于防治农业和林业以及园艺植物螨害,所述商品杀螨剂选自:三唑锡、三环锡、苯丁锡、三磷锡、毒虫畏、甲基毒虫畏、巴毒磷、敌敌畏、庚烯磷、速灭磷、久效磷、二溴磷、毒死蜱、嘧啶磷、氯甲亚胺硫磷、氧乐果、敌杀磷、乙硫磷、马拉硫磷、虫螨畏、伏杀硫磷、辛硫磷、甲基嘧啶硫磷、喹硫磷、治螟磷、三唑磷、蚜灭多、水胺硫磷、甲胺磷、胺丙畏、氯亚胺硫磷、亚胺硫磷、氟丙菊酯、联苯菊酯、氯氟氰菊酯、精高效氯氟氰菊酯、甲氰菊酯、氟氰戊菊酯、氟氯苯菊酯、氟胺氰菊酯、溴氟菊酯、联苯肼酯、苯硫威、涕灭威、丁酮威、杀线威、抗虫威、久效威、苯菌灵、氯灭杀威、克百威、丁硫克百威、速灭威、蜱虱威、伐虫脒、单甲脒、杀螨脒、双甲脒、杀虫脒、苯甲酸苄酯、溴螨酯、丁氟螨酯、灭螨醌、氟蚜螨、氟虫脲、浏阳霉素、虫螨霉素、苏云金素、杀螨素、浏阳霉素、阿维菌素、多拉菌素、埃普利诺菌素、伊维菌素、赛拉菌素、莫西菌素、除虫菊素、烟碱、苦参碱、印楝素、鱼藤酮、吡螨胺、哒螨酮、唑螨酯、四螨嗪、炔螨特、噻螨酮、螺螨酯、嘧螨酯、杀螨酯、克螨特、哒螨灵;权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V在所述杀螨组合物中的总的质量百分含量是1%-90%,权利要求1所述的哌啶噻唑肟醚甲氧基丙烯酸酯衍生物V与所述商品杀螨剂的比例为质量百分比1%∶99%到99%∶1%;所述杀螨组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;所述杀螨组合物防治的螨害选自:螨害选自叶螨科、细须螨科、呋线螨、瘿螨科、红叶螨属、瘿螨科的害螨,这些害螨是世界性农业害螨、林业害螨、园艺害螨和卫生害螨;所述杀螨组合物用于防治的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。
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