CN102093389B - 双联和氧桥杂环新烟碱化合物及其制备方法 - Google Patents
双联和氧桥杂环新烟碱化合物及其制备方法 Download PDFInfo
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- CN102093389B CN102093389B CN200910258534.3A CN200910258534A CN102093389B CN 102093389 B CN102093389 B CN 102093389B CN 200910258534 A CN200910258534 A CN 200910258534A CN 102093389 B CN102093389 B CN 102093389B
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Classifications
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- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/86—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
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Abstract
本发明涉及吡虫啉硝基亚甲基类似物和二醛构建的双联和氧桥杂环新烟碱化合物及其制备方法和用途,提供了具有式(A)或(B)所示结构的化合物、或者所述化合物的光学异构体或农药学上可接受的盐:
Description
技术领域
本发明涉及新型新烟碱类的杀虫剂、及其制备方法和应用。具体而言,本发明涉及吡虫啉硝基亚甲基类似物和二醛构建的双联和氧桥杂环新烟碱化合物及其制备方法。
背景技术
以吡虫啉为代表的新烟碱类杀虫剂因杀虫活性高,杀虫谱广,对哺乳动物和水生动物毒性低,且有良好的系统物性及适当的田间稳定性和环境友好性,成为新农药创制的重要热点领域。后来又相继开发出噻虫啉、噻虫胺、噻虫嗪、啶虫脒、烯啶虫胺、呋虫胺等一系列烟碱类杀虫剂(参见欧洲专利247477、296453、685477、235725、235725、315826、192060、244777、0386565、580553和1031566,日本专利62292765、8259568、8291171和7242633)。
但是由于吡虫啉过量频繁使用造成较为严重的抗性问题以及由于结构相似性带来的新烟碱杀虫剂之间的交互抗性,在一定程度上限制了该类化合物的应用,制约了此类化合物发展,同时新烟碱类杀虫剂主要对同翅目和鞘翅目害虫高效,其相对较窄的杀虫谱也限制了虫害防治方面的用药选择性。
因此,如何对具有高活性的硝基亚甲基化合物进行结构改造,以产生新的、更有效的杀虫剂,解决新烟碱类杀虫剂的抗性问题,扩大杀虫谱,使其应用于杀虫剂组合物就成为本领域迫切需要解决的技术问题。
发明内容
本发明提供了新的、更有效的杀虫剂,解决了新烟碱类杀虫剂的抗性问题,扩大了杀虫谱,解决了现有技术中存在的问题。
本发明目的在于,提供一类高效防治害虫的化合物及其制备方法。
本发明的另一个目的是为生长中的和收获的作物不受昆虫攻击和侵扰而提供保护。
一方面,本发明提供了氧桥杂环新烟碱化合物,该化合物选自具有式(A)或(B)所示结构的化合物、或者所述化合物的光学异构体或农药学上可接受的盐:
式中:
R1为含氮、氧和/或硫的五元或六元杂环基,卤代的含氮、氧和/或硫的五元或六元杂环基,或者取代或未取代的苯基,其中,所述取代基为选自下组中的一个或多个:卤素,C1-4卤代烷基或C1-4氯代烷氧基;
R3和R4各自独立地为H,C1-6烷基,烯丙基,苄基,C1-4烷氧基-C1-4烷基,C1-4烷氧基-羰基,苯氧羰基,C2-6炔基-羰基,C2-3烯基-羰基,C3-6环烷基-羰基,苯甲酰基,或者被一个或多个选自卤原子、C1-4烷基、C1-4卤代烷基、C1-4烷氧基和C1-4烷基-羰基的取代基所取代的苯甲酰基,呋喃羰基或N,N-二甲基羰基,或者R3和R4共同构成-CH2-CH2-,-CH2-CH2-CH2-或-CH2-XR-CH2-,式中X为杂原子,R为杂原子上的取代基,选自H,C1-6烷基,烯丙基,苄基,苯基,C1-4烷氧基-C1-4烷基,C1-4烷氧基-羰基,苯氧羰基,C2-6炔基-羰基,C2-3烯基-羰基,C3-6环烷基-羰基,苯甲酰基,或者被一个或多个选自卤原子、C1-4卤代烷基、C1-8饱和或不饱和烷基或烷氧基和C1-4烷基-羰基的取代基所取代的苯甲酰基,呋喃羰基或N,N-二甲基羰基;
R5,R6,R7,R8和R9为H,饱和或不饱和C1-4烷基,卤素,C1-8饱和或不饱和烷氧基,卤代C1-4饱和或不饱和烷氧基,C1-4烷基-羰基,C1-8烷基-酯基,C1-4烷基-磺酸酯基,苯基或苄基;
Y为硝基,氰基,三氟甲基,三氟乙酰基或三氟甲磺酰基。
在一个优选的实施方式中,所述氧桥杂环新烟碱化合物选自下组:
以及
在另一个优选的实施方式中,所述氧桥杂环新烟碱化合物选自下组:
以及
在另一个优选的实施方式中,所述氧桥杂环新烟碱化合物是昆虫烟碱乙酰胆碱受体的拮抗剂。
在另一个优选的实施方式中,所述氧桥杂环新烟碱化合物(1a)和(1b)对吡虫啉抗性褐飞虱和烟粉虱的活性是吡虫啉的2-30倍。
另一方面,本发明提供了一种农用组合物,它包含:
(a)0.001-99.99重量%的上述氧桥杂环新烟碱化合物、其光学异构体或农药学上可接受的盐、或者它们的组合;以及
(b)农药学上可接受的载体和/或赋形剂。
另一方面,本发明涉及所述农用组合物的用途,用于杀灭或预防农业害虫、卫生害虫和危害动物健康的害虫;或用作用于杀灭或预防农业害虫、卫生害虫和危害动物健康的杀虫剂组合物。
另一方面,本发明提供了一种杀虫和/或防虫方法,所述方法包括将上述农用组合物施加于遭受或可能遭受虫害的植物体、其周围的土壤或环境中。
另一方面,本发明涉及上述化合物、其光学异构体或农药学上可接受的盐、或它们的组合在制备杀虫剂组合物中的用途。
再一方面,本发明提供了上述化合物、基光学异构体或农药学上可接受的盐的制备方法,所述方法包括步骤:
在催化量酸的存在下,于室温下,使式(a)化合物与式(b)或(c)化合物反应,从而制得具有式(A)或(B)的化合物,
式中,R1、R3、R4、R5、R6,R7,R8,R9和Y如上述定义。
在一个优选的实施方式中,所述方法包括步骤:
在乙腈中,于催化量的酸存在下,于室温下,进行如下反应2-24小时,从而获得式(1a)的化合物:
在乙腈中,于催化量的酸存在下,于室温下,进行如下反应2-24小时,从而获得式(1b)的化合物:
在乙腈中,于催化量的酸存在下,于室温下,进行如下反应2-24小时,从而获得式(1c)的化合物:
在乙腈中,于催化量的酸存在下,于室温下,进行如下反应2-24小时,从而获得式(1d)的化合物:
在乙腈中,于催化量的酸存在下,于室温下,进行如下反应2-24小时,从而获得式(2a)的化合物:
在乙腈中,于催化量的酸存在下,于室温下,进行如下反应2-24小时,从而获得式(2b)的化合物:
在乙腈中,于催化量的酸存在下,于室温下,进行如下反应2-24小时,从而获得式(2c)的化合物:
在乙腈中,于催化量的酸存在下,于室温下,进行如下反应2-24小时,从而获得式(2d)的化合物:
在乙腈中,于催化量的酸存在下,于室温下,进行如下反应2-24小时,从而获得式(1e)的化合物:
在乙腈中,于催化量的酸存在下,于室温下,进行如下反应2-24小时,从而获得式(2e)的化合物:
具体实施方式
本发明的发明人通过长期而深入的研究,基于现有的吡虫啉硝基亚甲基类新烟碱杀虫剂的吡虫啉硝基亚甲基结构,通过二醛与吡虫啉硝基亚甲基类化合物反应,合成了一种新型的新烟碱化合物,该化合物的杀虫活性显著提高,并具有扩大的杀虫谱。在此基础上,发明人完成了本发明。
基团定义
如本文所用,术语“C1-6烷基”指具有1-6个碳原子的直链或支链烷基,例如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、或类似基团。
术语“C1-4烷氧基”指具有1-4个碳原子的直链或支链烷氧基,例如甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基、仲丁氧基、叔丁氧基、或类似基团。
术语“卤素”指氟、氯、溴、或碘。术语“卤代的”指被相同或不同的一个或多个上述卤原子取代的基团,例如三氟甲基、五氟乙基、或类似基团。
术语“五元或六元杂环基”指含一个或多个选自氮、氧或硫的杂原子的五元或六元环,例如吡啶基、噻唑基、嘧啶基、四氢呋喃基、或噁唑基等。
本发明化合物的制备方法
本发明化合物可通过上文所描述的反应步骤合成。
在本发明的一个具体实施方式中,式(1a)化合物的合成方法如下:
在本发明的一个具体实施方式中,式(1b)化合物的合成方法如下:
在本发明的一个具体实施方式中,式(1c)化合物的合成方法如下:
在本发明的一个具体实施方式中,式(1d)化合物的合成方法如下:
在本发明的一个具体实施方式中,式(2a)化合物的合成方法如下:
在本发明的一个具体实施方式中,式(2b)化合物的合成方法如下:
在本发明的一个具体实施方式中,式(2c)化合物的合成方法如下:
在本发明的一个具体实施方式中,式(2d)化合物的合成方法如下:
在本发明的一个具体实施方式中,式(1e)化合物的合成方法如下:
在本发明的一个具体实施方式中,式(2e)化合物的合成方法如下:
在本发明的一个实施方式中,式(1a)-(1e)的化合物可通过下列反应制备:
将2,5-二乙氧基四氢呋喃(2g,12.5mmol)和盐酸水溶液(0.1M,10mL)的混合液加热到90℃反应一个小时,然后冷却到室温。然后以此加入乙腈(40mL),吡虫啉硝基亚甲基类似物(10mmol),常温搅拌反应,TLC跟踪反应,反应完毕后,饱和碳酸氢钠水溶液中和至中性,萃取,减压蒸除溶剂,柱层析分离(洗脱剂:二氯甲烷/丙酮=3/1(v/v)得到淡黄色粉末,即产品。
在另一个实施方式中,式(2a)-(2e)的化合物可通过下列反应制备:
将吡虫啉硝基亚甲基类似物(5mmol),30ml的无水乙腈,3ml 25%戊二醛水溶液,催化量的HCl置于50ml的圆底烧瓶中。常温下搅拌,TLC跟踪反应。反应结束后,饱和碳酸氢钠水溶液中和至中性,萃取,减压蒸除溶剂,柱层析分离(洗脱剂:二氯甲烷/丙酮=3/1(v/v)得到淡黄色粉末,即产品。
本发明活性物质的杀虫活性
术语“本发明的活性物质”或“本发明的活性化合物”是指本发明化合物、其光学异构体或农药学上可接受的盐,其具有显著提高的虫活性,以及扩大的杀虫谱。
术语“农药学上可接受的盐”意指该盐的阴离子在形成杀虫剂药学上可接受的盐时为已了解的和可接受的。该盐较好的为水溶性的。合适的、由式(A)和(B)化合物形成的酸加成盐包括有无机酸形成的盐,例如盐酸盐、磷酸盐、硫酸盐、硝酸盐;及包括有机酸形成的盐,如醋酸盐,苯甲酸盐。
本发明的活性物质能用作控制和消灭广泛的农林植物害虫、贮臧谷类的害虫、公共卫生害虫以及危害动物健康的害虫等。在本说明书中,“杀虫剂”是具有防治上述提到的所有害虫的作用的物质的统称。害虫的例子包括但不限于:鞘翅目昆虫:玉米象(Sitophilus zeamais),赤拟谷盗(Tribolium castaneum),马铃薯瓢虫(Henosepilachna vigintioctomaculata),二十八星瓢虫(Henosepilachna sparsa),细胸叩头虫(Agriotes fuscicollis),红脚绿金龟(Anomalacupripes),四纹丽金龟(Popillia quadriguttata),马铃薯叶甲(Monoleptahieroglyphica),松天牛(Monochamus alternatus),稻根象(Echinocnemussquameus),泡桐叶甲(Basiprionota bisignata),星天牛(Anoplophora chinensis),桑天牛(Apripona germari),脐腹小蠹(Scolytus schevy),或细胸金针虫(Agriotesfuscicollis);鳞翅目昆虫:舞毒娥(Lymantria dispar),天幕毛虫(Malacosomaneustria testacea),黄杨绢野螟(Diaphaniaperspectalis),大袋蛾(Claniavariegata),黄刺蛾(Cnidocampa flauescens),马尾松毛虫(Dendrolimuspunctatus),古毒蛾(Orgyia gonostigma),白杨透翅蛾(Paranthrene tabaniformis),斜纹夜蛾(Spodoptera litura),二化螟(Chilo suppressalis),玉米螟(Ostrinianubilalis),粉斑螟(Ephestia cautella),棉卷蛾(Adoxophyes orana),栗子小卷蛾(laspyresia splendana),小地老虎(Agrotis fucosa),大蜡螟(Galleria mellonella),菜蛾(Plutella xylostella),桔潜蛾(Phyllocnistis citrella),或东方粘虫(Mythimnaseparata);同翅目昆虫:黑尾叶蝉(Nephotettix cincticeps),稻褐飞虱(Nilaparvatalugens),康氏粉蚧(Pseudococcus comstocki),矢尖蚧(Unaspis yanonensis),桃蚜(Myzus persicae),棉蚜(Aphisgossydii),萝卜蚜(Lipaphis erysimipseudobrassicae),梨班网蝽(Stephanitis nashi),或粉虱(Bemisia tabaci);直翅目昆虫:德国小蠊(Blattella germanica),美国大蠊(Periplaneta american),非洲蝼蛄(Gryllotalpa africana),或亚洲飞蝗(Locu smigra toria);等翅目昆虫:入侵红火蚁(Solenopsis invicta),或家白蚁(Coptotermes formosanus);双翅目昆虫:家蝇(Muscadomestica),埃及伊蚊(Aedes aegypti),种蝇(Delia platura),库蚊(Culex sp.),或中华按蚊(Anopheles sinensis)。危害动物健康的害虫包括微小牛蜱(Boophilus microplus),长角血蜱(Haemaphysalis longicornis),小亚璃眼蜱(Hyalomma anatolicum),牛皮蝇(Hypoderma spp.),肝片吸虫(Fasciolahepatica ),贝氏莫尼茨绦虫(Moniezia blanchard),奥斯特线虫(Ostertagiaspp.),原虫Trypanosoma enansi,Babesia bigemina等。
本发明涉及的化合物尤其对刺吸式、锉吸式口器害虫,如蚜虫、叶蝉、飞虱、蓟马、粉虱等农林害虫有特效。
含本发明活性物质的杀虫剂组合物
可将本发明的活性物质以常规的方法制备成杀虫剂组合物。这些活性化合物可做成常规的制剂,例如溶液剂,乳剂,混悬剂,粉剂,泡沫剂,糊剂,颗粒剂;气雾剂,用活性物质浸渍的天然的和合成的材料,在多聚物中的微胶囊,用于种子的包衣复方,和与燃烧装置一起使用的制剂,例如烟熏药筒,烟熏罐和烟熏盘,以及ULV冷雾(Cold mist)和热雾(Warm mist)制剂。
这些制剂可用已知的方法生产,例如,将活性化合物与扩充剂混合,这些扩充剂就是液体的或液化气的或固体的稀释剂或载体,并可任意选用表面活性剂即乳化剂和/或分散剂和/或泡沫形成剂。例如在用水作扩充剂时,有机溶剂也可用作助剂。
用液体溶剂作稀释剂或载体时基本上是合适的,如:芳香烃类,例如二甲苯,甲苯或烷基萘;氯化的芳香或氯化的脂肪烃类,例如氯苯,氯乙烯或二氯甲烷;脂肪烃类,例如环己烷或石蜡,例如矿物油馏分;醇类,例如乙醇或乙二醇以及它们的醚和脂类;酮类,例如丙酮,甲乙酮,甲基异丁基酮或环己酮;或不常用的极性溶剂,例如二甲基甲酰胺和二甲基亚砜,以及水。液化气的稀释剂或载体是指在常温常压下将成为气体的液体,例如气溶胶推进剂,如卤化的烃类以及丁烷,丙烷,氮气和二氧化碳。
固体载体可用地面天然的矿物质,例如高岭土,粘土,滑石,石英,活性白土,蒙脱土,或硅藻土,和地面合成的矿物质,例如高度分散的硅酸,氧化铝和硅酸盐。供颗粒用的固体载体是碾碎的和分级的天然告石,例如方解石,大理石,浮石,海泡石和白云石,以及无机和有机粗粉合成的颗粒,和有机材料例如锯木屑,椰子壳,玉米棒子和烟草梗的颗粒等。
非离子的和阴离子的乳化列可用作乳化剂和/或泡沫形成剂。例如聚氧乙烯-脂肪酸酯类,聚氧乙烯-脂肪醇醚类,例如烷芳基聚乙二醇醚类,烷基磺酸酯类,烷基硫酸酯类,芳基磺酸酯类以及白蛋白水解产物。分散剂包括,例如木质素亚硫酸盐废液和甲基纤维素。
在制剂中可以用粘合剂,例如羧甲基纤维素和以粉末,颗粒或乳液形式的天然和合成的多聚物,例如阿拉伯胶,聚乙烯基醇和聚乙烯醋酸酯。可以用着色剂例如无机染料,如氧化铁,氧化钻和普鲁士蓝;有机染料,如有机染料,如偶氯染料或金属钛菁染料;和用痕量营养剂,如铁,猛,硼,铜,钴,铝和锌的盐等。
本发明的这些活性化合物可与其它活性化合物制成混合物存在于商品制剂中或从这些制剂制备的使用剂型中,所述其它的活性化合物包括但不限于:杀虫剂,合饵,杀菌剂,杀螨剂,杀线,杀真菌剂,生长控制剂等。杀虫剂包括,例如磷酸酯类,氨基甲酸酯类,除虫菊酯类,氯化烃类,苯甲酰脲类,沙蚕毒素类以及由微生物产生的物质,如阿维菌素。
此外,本发明的这些活性化合物也可与增效剂制成一种混合物存在于它们的商品制剂中成从这些制剂制备的使用剂型中。增效剂是提高活性化合物作用的化合物,由于活性化合物本身有活性,也可不必加增效剂。
这些制剂通常含有占所述杀虫剂组合物0.001-99.99重量%,优选0.01-99.9重量%,更优选0.05-90重量%的本发明的活性化合物。从商品制剂制成使用剂型中的活性化合物的浓度可在广阔的范围内变动。使用剂型中的活性化合物的浓度可从0.0000001-100%(g/v),最好在0.0001与1%之间。
实施例
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法,通常按照常规条件,或按照制造厂商所建议的条件。除非另外说明,否则百分比和份数按重量计算。其中,r.t.代表室温。
实施例1:9-((6-氯吡啶-3-基)甲基)-4-硝基-8-氧杂-10,11-二氢咪唑并[2,3-a]双环[3,2,1]辛-3-烯(化合物1a)的合成
2,5-二乙氧基四氢呋喃(2g,12.5mmol)和盐酸水溶液(0.1M,10mL)的混合液加热到90℃反应一个小时,然后冷却到室温。然后以此加入乙腈(40mL),2-氯-5-(2-硝基亚甲基-咪唑烷-1-基甲基)-吡啶(2.54g 10mmol),常温搅拌反应,TLC跟踪反应,反应完毕后,饱和碳酸氢钠水溶液中和至中性,萃取,减压蒸除溶剂,柱层析分离(洗脱剂:二氯甲烷/丙酮=3/1(v/v)得到淡黄色粉末。产率,53%;mp=149.0-150.0℃;1H NMR(400Mz,DMSO-d6):δ8.35(d,J=2.4H z,1H ),7.81(dd,J1=2.4Hz,J2=8.4Hz,1H),7.51(d,J=8.4Hz,1H),5.36-5.39(s,2H),5.00(d,J=15.6Hz,1H),4.68(d,J=15.6Hz,1H),3.57-3.73(m,4H),1.942.04(m,4H)ppm;13C NMR(100Mz,DMSO-d6):δ155.6,149.7,149.6,139.7,132.6,124.5,109.6,87.0,75.1,51.2,50.3,46.6,31.9,31.7ppm;HRMS(ES+)计算值:C14H16N4O3 35Cl(M+H)+,323.0911;实测值:323.0912.计算值:C14H16N4O3 37Cl(M+H)+,325.0811;实测值:325.0895.计算值:C14H15N4O3 35ClNa(M+Na)+,345.0730;计算值:345.0722.计算值:C14H15N4O3 37ClNa(M+Na)+,347.0701;计算值:347.0692。
实施例2:9-((2-氯噻唑-5-基)甲基)-4-硝基-8-氧杂-10,11-二氢咪唑并[2,3-a]双环[3,2,1]辛-3-烯(化合物1b)的合成
方法同上,减压蒸除溶剂,柱层析分离(洗脱剂:二氯甲烷/丙酮=3/1(v/v)得到淡黄色粉末状固体。产率,56%;mp=136.5-138.0℃;1H NMR(400Mz,DMSO-d6):δ7.47(s,1H),5.61(d,J=5.2Hz,1H),5.28(d,J=15.4Hz,lH),5.16(d,J=5.00H z,lH),4.70(d,J=15.4Hz,1H),3.66-3.82(m,3H),3.54-3.61(m,1H),2.22-2.29(m,1H),2.12-2.21(m,2H),1.99-2.07(m,1H)ppm;13C NMR(100Mz,DMSO-d6):δ154.6,154.3,140.6,135.1,110.4,87.4,75.4,49.6,47.9,46.5,31.8,31.8ppm;HRMS(ES+)计算值:C12H14N4O3S35Cl(M+H)+,329.0475;计算值:329.0475.计算值:C12H14N4O3S37Cl(M+H)+,331.0446;计算值:331.0461。
实施例3:9-苄基-4-硝基-8-氧杂-10,11-二氢咪唑并[2,3-a]双环[3,2,1]辛-3-烯(化合物1c)的合成
方法同上,减压蒸除溶剂,柱层析分离(洗脱剂:二氯甲烷/丙酮=3/1(v/v)得到淡黄色粉末状固体。产率,58%;mp=149.0-149.8℃;1H NMR(400Mz,DMSO-d6):δ7.28-7.39(m,5H),5.66(d,J=4.3H z,1H),5.14(d,J=4.5Hz,1H),4.92-5.01(m,2H),3.57-3.74(m,3H),3.47-3.53(m,1H),2.30-2.34(m,1H),2.13-2.22(m,2H),2.00-2.07(m,1H )ppm;13NMR(100Mz,DMSO-d6):δ155.5,135.9,128.9,128.2,128.1,87.7,75.6,54.4,48.9,47.2,31.8,31.6ppm;HRMS(ES+)计算值:C15H17N3O3(M+H)+,287.1270;计算值:287.1272。
实施例4:9-(4-氯-苄基)-4-硝基-8-氧杂-10,11-二氢咪唑并[2,3-a]双环[3,2,1]辛-3-烯(化合物1d)的合成
方法同上,减压蒸除溶剂,柱层析分离(洗脱剂:二氯甲烷/丙酮=3/1(v/v)得到淡黄色粉末状固体。产率,38%;mp=140.0-140.9℃;1H NMR(400Mz,DMSO-d6):δ7.27-7.34(m,4H),5.63(d,J=5.4Hz,1H),5.14(d,J=5.2Hz,1H),5.04(d,J=15.1Hz,1H),4.78(d,J=15.1Hz,1H),3.62-3.73(m,3H),3.45-3.51(m,1H),2.26-2.31(m,1H),2.11-2.21(m,2H),1.98-2.07(m,1H)ppm;13C NMR(100Mz,DM SO-d6):δ155.3,134.4,133.9,129.6,129.0,110.2,87.6,75.5,53.9,49.2,47.0,31.8,31.7ppm;HRMS(ES+)计算值:C15H17N3O3 35Cl(M+H)+,322.0958;计算值:322.0972.计算值:C15H17N3O3 37Cl(M+H)+,324.0929;计算值:324.0938。
实施例5:9-((四氢呋喃-3-基)甲基)-4-硝基-8-氧杂-10,11-二氢咪唑并[2,3-a]双环[3,2,1]辛-3-烯(化合物1e)的合成
方法同上,减压蒸除溶剂,柱层析分离(洗脱剂:二氯甲烷/丙酮=3/1(v/v)得到淡黄色粉末状固体。收率:57%。mp=126.3-127.9℃;1H NMR(400Mz,DMSO-d6):δ5.11(s,1H),5.00-5.03(m,1H),4.18(d,J=3.2Hz,2H),4.05-4.25(m,2H),3.85-3.96(m,4H ),2.25(m,1H),1.66-1.81(m,4H),2.35-2.40(m,1H),2.17-2.21(m,2H ),1.93-2.01(m,1H)ppm;ppm;13C NMR(100Mz,DMSO-d6):δ81.9,81.6,77.9,68.2,53.1,49.9,48.0,44.1,36.4,33.9,29.5,23.2,19.8,ppm;HRMS(E1+)计算值:C13H19N3O4(M+),281.1376;实测值:281.1365。
实施例6:10-((6-氯吡啶-3-基)甲基)-4-硝基-9-氧杂-11,12-二氢咪唑并[2,3-a]双环[3,3,1]壬-3-烯(化合物2a)的合成
将1.27g(0.005mol)的2-氯-5-(2-硝基亚甲基-咪唑烷-1-基甲基)-吡啶,30ml的无水乙腈,3ml 25%戊二醛水溶液,催化量的HCl置于50ml的圆底烧瓶中。常温下搅拌,TLC 跟踪反应。反应结束后,饱和碳酸氢钠水溶液中和至中性,萃取,减压蒸除溶剂,柱层析分离(洗脱剂:二氯甲烷/丙酮=3/1(v/v)得到淡黄色粉末。产率,76%;mp=174.7-175.4℃;1H NMR(400Mz,DMSO-d6):δ8.38(dd,J1=0.6Hz,J2=2.4Hz,1H),7.84(dd,J1=2.4Hz,J2=8.4Hz,1H),7.52(dd,J1=0.6Hz,J2=8.4Hz,1H),5.12(s,1H),5.04-5.05(m,1H),4.97(d,J=15.6Hz,1H),4.71(d,J=15.6Hz,1H),3.62-3.74(m,4H),1.66-1.81(m,4H),1.51-1.55(m,1H),1.32-1.44(m,1H)ppm;13C NMR(100Mz,DMSO-d6):δ156.6,149.7,149.6,139.7,132.9,124.5,105.8,81.7,68.9,51.7,50.0,46.3,28.8,27.2,14.8ppm;HRMS(EI+)计算值:C15H17N4O3 35Cl(M+),336.0989;计算值:336.0988.计算值:C15H17N4O3 37Cl(M+),338.0960;计算值:338.0968。
实施例7:10-((2-氯噻唑-5-基)甲基)-4-硝基-9-氧杂-11,12-二氢咪唑并[2,3-a]双环[3,3,1]壬-3-烯(化合物2b)的合成
方法同上,减压蒸除溶剂,柱层析分离(洗脱剂:二氯甲烷/丙酮=3/1(v/v)得到白色粉末状固体。产率,62%;mp=159.1-160.5℃;1H NMR(400Mz,DMSO-d6):δ7.48(s,1H ),5.30(d,J=3.2Hz,1H),5.24(d,J=15.4Hz,1H),4.98(s,1H),4.78(d,J=15.4Hz,1H),3.76-3.87(m,1H),3.60-3.71(m,3H),2.12(d,J=14.0Hz,1H),1.82-1.96(m,2H ),1.64-1.77(m,2H),1.48-1.60(m,1H)ppm;13C NMR(100Mz,DM SO-d6):δ155.7,154.1,140.5,135.6,107.0,82.7,69.4,49.4,48.3,46.2,29.4,26.5,14.9ppm;HRMS(EI+)计算值:C13H15N4O3S35Cl(M+),342.0553;计算值:342.0548.计算值:C13H15N4O3S37Cl(M+),344.0524;计算值:344.0564。
实施例8:10-苄基-4-硝基-9-氧杂-11,12-二氢咪唑并[2,3-a ]双环[3,3,1]壬-3-烯(化合物2c)的合成
方法同上,减压蒸除溶剂,柱层析分离(洗脱剂:二氯甲烷/丙酮=3/1(v/v)得到淡黄色粉末状固体。产率,77%;mp=180.5-181.2℃;1H NMR(400Mz,DMSO-d6):δ7.29-7.37(m,5H),5.33(d,J=3.1Hz,1H),5.02(d,J=15.0Hz,1H),4.95(s,1H),4.85(d,J=15.0Hz,1H),3.68-3.75(m,1H),3.48-3.64(m,3H),2.14(d,J=13.1Hz,1H),1.81-1.93(m,2H),1.51-1.70(m,3H)ppm;13C NMR(100Mz,DMSO-d6):δ156.6,136.4,128.8,128.3,128.0,106.7,83.0,69.7,54.8,48.6,46.7,29.5,26.5,15.0ppm;HRMS(EI+)计算值:C16H19N3O3(M+),301.1426;计算值:301.1429。
实施例9:10-(4-氯苄基)-4-硝基-9-氧杂-11,12-二氢咪唑并[2,3-a]双环[3,3,1]壬-3-烯(化合物2d)的合成
方法同上,减压蒸除溶剂,柱层析分离(洗脱剂:二氯甲烷/丙酮=3/1(v/v)得到淡黄色粉末状固体。产率,70%;mp=156.9-158.3℃;1H NMR(400Mz,DMSO-d6):δ7.29-7.34(m,4H),5.33(d,J=4.0Hz,1H),5.05(d,J=15.1Hz,1H),4.96(s,1H),4.75(d,J=15.1Hz,1H),3.66-3.73(m,1H),3.55-3.60(m,3H),2.14(d,J=13.6Hz,1H ),1.82-1.95(m,2H),1.51-1.71(m,3H)ppm;13C NMR(100Mz,DM SO-d6):δ156.5,134.9,133.8,129.7,129.0,106.8,83.0,69.6,54.4,48.9,46.6,29.6,26.5,15.0ppm;HRMS(EI+)计算值:C16H18N3O3 35Cl(M+),335.1037;计算值:335.1044.计算值:C16H18N3O3 37Cl(M+),337.1007;计算值:337.1036。
实施例10:10-((四氢呋喃-3-基)甲基)-4-硝基-9-氧杂-11,12-二氢咪唑并[2,3-a]双环[3,3,1]壬-3-烯(化合物2e)的合成
将1.065g(0.005mol)的1-((四氢呋喃-3-基)甲基)-2-(-硝基亚甲基)-1-咪唑啉,3ml 25%戊二醛水溶液,催化量的HCl置于50ml的圆底烧瓶中。常温下搅拌,TLC跟踪反应。待反应结束后,除去溶剂,柱层析分离得到淡黄色粉末状纯品,产率为36%。
mp=115.3-116.9℃;1H NMR(400Mz,DMSO-d6):δ5.11(s,1H),5.00-5.03(m,1H),4.18(d,J=3.2Hz,2H),4.05-4.25(m,2H),3.85-3.96(m,4H),2.25(m,1H),1.66-1.81(m,4H),1.63-1.64(m,2H),1.57-1.59(m,2H),1.51-1.55(m,1H),1.32-1.44(m,1H)ppm;13C NMR(100Mz,DMSO-d6):δ81.7,80.6,78.5,68.9,50.0,49.7,46.9,44.6,36.8,33.9,28.8,27.2,17.8,14.8ppm;HRMS(EI+)计算值:C14H21N3O4(M+),295.1532;实测值:295.1598。
实施例11:本发明化合物的杀虫活性测试
(1)对蚜虫的杀虫活性
蚜虫属于同翅目害虫,具有刺吸口器,是一种常见的农作物害虫。以豆蚜(Aphis craccivora)为测试对象,采用浸渍法测试。
测试方法:准确称量各样品,分别加入DM SO 2mL及18mL清水,再加入三滴乳化剂2201配成药液,空白用DMSO 2mL及18mL清水,加入三滴乳化剂220I配成。将附有一定数量的待测昆虫蚕豆叶在药液中浸泡3-5秒,取出晾干,将试虫和食料移入干净的器皿内,放置于干恒温恢复室内,24小时后检查试虫中毒死亡情况。结果见下表1。
(2)对稻褐飞虱的杀虫活性
稻褐飞虱属于同翅目害虫,具有刺吸口器,是一种常见的农作物害虫。以稻褐飞虱(Nilaparvata lugens)为测试对象,采用Nagata报道的微量点滴测定法。
操作过程:选取羽化2-3天的未交配有翅雌虫作为测试对象,将化合物用丙酮稀释成系列浓度,用二氧化碳将测试昆虫麻痹后,用手动微量点滴器(Burkard Manufacturing Co.Ltd,Rickmansworth,UK)将药滴(0.08μL)点滴于测试昆虫的前胸背板上。每个浓度处理大约30头成虫,每个处理重复3次。以丙酮作对照。处理后的成虫饲养于培养箱(20×20×10cm)内的无土栽培稻苗上,温度控制在25±1℃,光照16(L)/8(D)小时。48小时后检查结果,用标准的概率值分析法计算LD50值。结果见下表2。
(3)对粘虫的杀虫活性
以粘虫(Pseudaletia separate Walker)二龄的幼虫为测试对象,采取浸叶法测试。
粘虫是一种很重要的杂谷类鳞翅目害虫,其应用面较广,适应于作为杀虫剂的胃毒,触杀,综合和残效等毒力测定以及昆虫毒理学方面的研究,也适应于新化合物的筛选试验,按照文献报道的方法进行粘虫杀灭活性的测试。
浸叶法的操作过程:准确称量各样品,分别加入DMSO(2mL)及18mL清水,再加入三滴乳化剂220I(上海农药厂提供)配成药液,空白用DMSO(2mL)及28mL清水,加入三滴乳化剂220I配成。将新鲜的玉米叶片撕成小块,在药液中浸泡5秒钟左右,取出晾干,放入100mL的广口瓶中,再放入二龄幼虫约20头,广口瓶用白纱布及橡皮筋扎紧,连续喂浸过药液的玉米,5天后检查幼虫的死亡率。要求温度22-27℃,湿度70-80%。若空白死亡率在5%以下,各处理死亡率不必校正;若对照死亡率在5-20%,用Abbott公式校正各处理死亡率。Abbott公式为:
校正死亡率=[(死亡处理率-对照死亡率)/(100-对照死亡率)]×100。
结果见表1。
表1目标化合物对蚜虫和粘虫的活性
表2化合物D4和D8对敏感和抗性褐飞虱的活性
测试了目标化合物对蚜虫,粘虫和褐飞虱的活性,其结果如表1和2。由表1-2可见,氧桥杂环化合物1a具有很高的活性,对蚜虫的LC50为1.52mg L-1,对粘虫的LC50为12.5mg L-1,其活性显著超过吡虫啉。更为重要的是,化合物1a对敏感的褐飞虱活性和吡虫啉差不多,而对吡虫啉抗性褐飞虱的活性是吡虫啉的50倍。化合物1a性则较弱。有趣的是,由戊二醛构建的氧桥杂环化合物2a-2c的活性则弱很多,部分化合物只对蚜虫有活性。分析化合物化合物1a与2a的晶体结构,可以看出化合物1a与2a的氧桥构型不同,氧桥的指向相反,将二者分子叠合可以很明显的看出这种差异。这种氧桥的构型的差异可能导致化合物1a与2a 活性显著的不同。
实施例12:化合物(1a)作用机制的研究
对化合物(1a)分别进行了电生理实验和同位素标记物取代实验,化合物(1a)可以抑制激动剂的反应;化合物(1a)对美国蜚蠊烟碱乙酰胆碱受体和卵母细胞表达的Nl α1/β2受体没有激动作用;化合物(1a)可以抑制激动剂乙酰胆碱的反应,这些实验表明化合物是烟碱乙酰胆碱受体(nAChRs)的拮抗剂。
实施例13:含有本发明化合物的杀虫剂组合物的制备
(a)油状悬浮液
按比例准备以下组分:25%(重量百分比,下同)化合物1a-1e和2a-2e中任一种化合物;5%聚氧乙烯山梨醇六油酸酯;70%高级脂肪族烃油。将各组分在沙磨中一起研磨,直到固体颗粒降至约5微米以下为止。所得的粘稠悬浮液可直接使用,但也可在水中乳化后使用。
(b)水悬浮液
按比例准备以下组分:25%化合物1a-1e和2a-2e中任一种化合物;3%水合硅镁土(hydrate attapulgit);10%木质素磺酸钙;0.5%磷酸二氢钠;61.5%水。将各组分在球磨机中一起研磨,直到固体颗粒降至约10微米以下为止。该水悬浮液可直接使用。
(c)饵剂
按比例准备以下组分:0.1-10%化合物1a-1e和2a-2e 中任一种化合物;80%小麦面粉;19.9-10%糖蜜。将这些组分完全混合,按需要形成饵形状。可食用饵可以分散到卫生害虫所侵染的场所,例如家居或工业场所,诸如厨房、医院或商店或户外区域,以通过口服摄入来防治害虫。
本发明提及的所有文献都在本申请中引用作为参考,就如同每一篇文献被单独引用作为参考那样。此外应理解,在阅读了本发明的上述讲授内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
Claims (4)
1.氧桥杂环新烟碱化合物,其特征在于,所述氧桥杂环新烟碱化合物选自下组:
以及
2.一种农用组合物,它包含:
(a)0.001-99.99重量%的权利要求1所述的氧桥杂环新烟碱化合物、或其农药学上可接受的盐、或者它们的组合;以及
(b)农药学上可接受的载体和/或赋形剂。
3.权利要求2所述的农用组合物的用途,其特征在于,用作用于杀灭或预防农业害虫、卫生害虫和危害动物健康的杀虫剂组合物。
4.权利要求1所述的氧桥杂环新烟碱化合物、或其农药学上可接受的盐的制备方法,所述方法包括步骤:
在乙腈中,于催化量的酸存在下,于室温下,进行如下反应2-24小时,从而获得式(1c)的化合物:
在乙腈中,于催化量的酸存在下,于室温下,进行如下反应2-24小时,从而获得式(1d)的化合物:
在乙腈中,于催化量的酸存在下,于室温下,进行如下反应2-24小时,从而获得式(2c)的化合物:
在乙腈中,于催化量的酸存在下,于室温下,进行如下反应2-24小时,从而获得式(2d)的化合物:
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WO2007101369A1 (fr) * | 2006-03-09 | 2007-09-13 | East China University Of Science And Technology | Méthode de préparation et utilisation de composés présentant une action biocide |
CN101045728B (zh) * | 2006-03-28 | 2012-03-21 | 华东理工大学 | 一类具有高杀虫活性化合物的制备方法及用途 |
CN101747320B (zh) * | 2008-12-19 | 2013-10-16 | 华东理工大学 | 二醛构建的具有杀虫活性的含氮或氧杂环化合物及其制备方法 |
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MX2012006663A (es) | 2012-10-15 |
UA106256C2 (ru) | 2014-08-11 |
AU2010330474A1 (en) | 2012-07-26 |
CO6561790A2 (es) | 2012-11-15 |
WO2011069456A1 (zh) | 2011-06-16 |
AU2010330474B2 (en) | 2015-01-29 |
KR101504575B1 (ko) | 2015-03-30 |
CN102093389A (zh) | 2011-06-15 |
US8809319B2 (en) | 2014-08-19 |
JP5600750B2 (ja) | 2014-10-01 |
IL220237A0 (en) | 2012-07-31 |
JP2013513553A (ja) | 2013-04-22 |
RU2531920C2 (ru) | 2014-10-27 |
IL220237A (en) | 2017-08-31 |
EP2511279A1 (en) | 2012-10-17 |
CL2012001517A1 (es) | 2013-01-11 |
EP2511279B1 (en) | 2015-11-11 |
EP2511279A4 (en) | 2013-05-01 |
CA2783504C (en) | 2013-07-09 |
ZA201205074B (en) | 2013-03-27 |
KR20120094111A (ko) | 2012-08-23 |
CR20120361A (es) | 2012-12-18 |
RU2012127868A (ru) | 2014-01-20 |
US20120245126A1 (en) | 2012-09-27 |
BR112012013846A2 (pt) | 2015-09-15 |
CA2783504A1 (en) | 2011-06-16 |
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