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CN120136748A - 一种双酰胺类化合物及其应用 - Google Patents

一种双酰胺类化合物及其应用 Download PDF

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Publication number
CN120136748A
CN120136748A CN202411367766.3A CN202411367766A CN120136748A CN 120136748 A CN120136748 A CN 120136748A CN 202411367766 A CN202411367766 A CN 202411367766A CN 120136748 A CN120136748 A CN 120136748A
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CN
China
Prior art keywords
alkyl
halo
halogen
alkoxy
compound
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CN202411367766.3A
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English (en)
Inventor
连磊
彭学岗
华荣保
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Qingdao Kingagroot Chemical Compound Co Ltd
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Qingdao Kingagroot Chemical Compound Co Ltd
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Priority to PCT/CN2024/138293 priority Critical patent/WO2025124404A1/zh
Publication of CN120136748A publication Critical patent/CN120136748A/zh
Pending legal-status Critical Current

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    • C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
    • C07C317/38—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atom of at least one amino group being part of any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylaminosulfones
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Abstract

本发明属于农药技术领域，具体涉及一种双酰胺类化合物及其应用。所述化合物如通式I所示：

Description

一种双酰胺类化合物及其应用
技术领域
本发明属于农药技术领域，具体涉及一种双酰胺类化合物及其应用。
背景技术
在农业和园艺领域的作物生产中，由害虫引起的损害依然严重，并且由于对现有药剂具有抗性的害虫的产生等，因而期望开发出新颖的农业园艺用杀虫剂。
发明内容
为解决现有技术中存在的上述问题，本发明提供一种双酰胺类化合物，所述化合物对有害生物特别是农业园艺害虫具有优异防治作用，且对蜜蜂安全。
本发明采用的技术方案如下：
一种双酰胺类化合物，如式I所示：
其中，X是芳基或杂环基，其分别独立地是未取代的或被选自氧代，卤素，氰基，硝基，烷基，烯基，炔基，环烷基，卤代烷基，卤代烯基，卤代炔基，被烷基或卤素取代的环烷基，苯基，被选自卤素、氰基、硝基、烷基、卤代烷基、烷氧基羰基、烷硫基、烷基磺酰基、烷氧基或卤代烷氧基中的至少一个基团所取代的苯基，-OR，-SR，-(CO)OR，-S(O)nR，-N(R)2或-O-亚烷基-(CO)OR中的至少一个基团所取代的，或者环上相邻两个碳原子与未取代的或被卤素或烷基所取代的-OCH2CH2-或-OCH2O-形成稠环；
Y是卤素或烷氧基；
R分别独立地是氢，烷基，卤代烷基，苯基，或被选自卤素、氰基、硝基、烷基、卤代烷基、烷氧基羰基、烷硫基、烷基磺酰基、烷氧基或卤代烷氧基中的至少一个基团所取代的苯基；
n是0、1或2。
在一个具体实施方式中，X是芳基或杂环基，其分别独立地是未取代的或被选自氧代，卤素，氰基，硝基，C1-C8烷基，C2-C8烯基，C2-C8炔基，C3-C8环烷基，卤代C1-C8烷基，卤代C2-C8烯基，卤代C2-C8炔基，被C1-C8烷基或卤素取代的C3-C8环烷基，苯基，被选自卤素、氰基、硝基、C1-C8烷基、卤代C1-C8烷基、C1-C8烷氧基羰基、C1-C8烷硫基、C1-C8烷基磺酰基、C1-C8烷氧基或卤代C1-C8烷氧基中的至少一个基团所取代的苯基，-OR，-SR，-(CO)OR，-S(O)nR，-N(R)2或-O-(C1-C8)亚烷基-(CO)OR中的至少一个基团所取代的，或者环上相邻两个碳原子与未取代的或被卤素或C1-C8烷基所取代的-OCH2CH2-或-OCH2O-形成稠环；
Y是卤素或C1-C8烷氧基；
R分别独立地是氢，C1-C8烷基，卤代C1-C8烷基，苯基，或被选自卤素、氰基、硝基、C1-C8烷基、卤代C1-C8烷基、C1-C8烷氧基羰基、C1-C8烷硫基、C1-C8烷基磺酰基、C1-C8烷氧基或卤代C1-C8烷氧基中的至少一个基团所取代的苯基。
在另一个具体实施方式中，X是芳基或杂环基，其分别独立地是未取代的或被选自氧代，卤素，氰基，硝基，C1-C6烷基，C2-C6烯基，C2-C6炔基，C3-C6环烷基，卤代C1-C6烷基，卤代C2-C6烯基，卤代C2-C6炔基，被C1-C6烷基或卤素取代的C3-C6环烷基，苯基，被选自卤素、氰基、硝基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基羰基、C1-C6烷硫基、C1-C6烷基磺酰基、C1-C6烷氧基或卤代C1-C6烷氧基中的1～3个基团所取代的苯基，-OR，-SR，-(CO)OR，-S(O)nR，-N(R)2或-O-(C1-C6)亚烷基-(CO)OR中的1～3个基团所取代的，或者环上相邻两个碳原子与未取代的或被卤素或C1-C6烷基所取代的-OCH2CH2-或-OCH2O-形成稠环；
Y是卤素或C1-C6烷氧基；
R分别独立地是氢，C1-C6烷基，卤代C1-C6烷基，苯基，或被选自卤素、氰基、硝基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基羰基、C1-C6烷硫基、C1-C6烷基磺酰基、C1-C6烷氧基或卤代C1-C6烷氧基中的1～3个基团所取代的苯基。
在上述通式所示化合物的定义和以下所有结构式中，所用专业术语不论单独使用或者使用在复合词中，代表如下取代基：具有多于两个碳原子的烷基基团可为直链或支链的。如复合词“-O-亚烷基-(CO)OR”中亚烷基可为-CH2-、-CH2CH2-、-CH(CH3)-、-C(CH3)2-等。烷基基团为，例如，C1烷基-甲基；C2烷基-乙基；C3烷基-丙基如正丙基或异丙基；C4烷基-丁基如正丁基、异丁基、叔丁基或2-丁基；C5烷基-戊基如正戊基；C6烷基-己基如正己基、异己基和1,3-二甲基丁基。类似地，烯基是例如乙烯基、烯丙基、1-甲基丙-2-烯-1-基、2-甲基丙-2-烯-1-基、丁-2-烯-1-基、丁-3-烯-1-基、1-甲基丁-3-烯-1-基和1-甲基丁-2-烯-1-基。炔基是例如乙炔基、炔丙基、丁-2-炔-1-基、丁-3-炔-1-基、1-甲基丁-3-炔-1-基。多重键可以在每个不饱和基团的任何位置。环烷基是具有例如三至六个碳原子的碳环饱和环体系，例如环丙基、环丁基、环戊基或环己基。类似地，环烯基是具有例如三至六个碳环成员的单环烯基，例如环丙烯基、环丁烯基、环戊烯基和环己烯基，其中双键可以在任何位置。卤素为氟、氯、溴或碘。
除非有特别说明的，本发明所述“芳基”包括但不限于苯基、萘基、 所述“杂环基”不仅包括但不限于饱和或不饱和的非芳族环状基团
还包括但不限于杂芳基，即含有例如3至6个环原子且还任选地有苯并环稠合的芳族环状基团，所述环原子中的1至4个(例如1、2、3或4个)杂原子选自氧、氮和硫，例如
如果一个基团被基团所取代，则这应理解为意指该基团被一个或多个相同或不同的选自所提及的那些基团的基团取代。另外，相同或不同取代基中含有的相同或不同的取代字符均独立地选择，可相同也可不同。这同样适用于由不同原子和单元形成的环体系。同时，权利要求的范围将排除那些为本领域技术人员知晓的在标准条件下化学不稳定的化合物。
另外，除非特别限定地，本发明所述“至少一个基团所取代的”是指被如1、2、3、4或5个基团所取代；未标注具体连接位置的基团(包括杂环基、芳基等)，可在任意位置连接，包括与C或N相连接的位置；如果其是被取代的，取代基同样可在任何位置取代，只要符合化合键连接规则。如被1个甲基所取代的杂芳基可代表
本发明的由式I表示的双酰胺类化合物在结构式中可以包含一个或复数个不对称中心，且在某些情况下，可以存在两种或更多种光学异构体和非对映异构体。本发明包括这样的光学异构体中的任一种和以任意比例含有它们的混合物。此外，本发明的由式I表示的双酰胺类化合物在结构式中可以具有衍生自碳-碳双键的两类几何异构体。本发明包括所有几何异构体和以任意比例含有它们的混合物。
本发明还提供所述双酰胺类化合物的制备方法，包括如下步骤：
(1)式II所示化合物与式III所示化合物或式V所示化合物与式VI所示化合物进行反应，得到式IV所示化合物；
(2)式IV所示化合物经氧化得到式I所示化合物；
其中，Hal代表卤素，优选Cl，取代基X和Y的定义如前所述。
在一个具体实施方式中，所述反应(1)在碱和溶剂的存在下进行。
在另一个具体实施方式中，所述碱选自无机碱(如K2CO3、Na2CO3、Cs2CO3、NaHCO3、KF、CsF、KI、NaI、K3PO4、NaOH、KOH、NaH、KH等)或有机碱(如MeONa、t-BuONa、EtONa、AcOK、AcONa、DMAP、吡啶、吡唑、三乙胺、DIEA等)中的至少一种。
在另一个具体实施方式中，所述溶剂选自THF、DMF、DMA、甲醇、乙醇、乙腈、二氯乙烷、DMSO、Dioxane、二氯甲烷(DCM)或乙酸乙酯中的至少一种。
在一个具体实施方式中，所述反应(2)在氧化剂和溶剂的存在下进行。
在另一个具体实施方式中，所述氧化剂选自间氯过氧苯甲酸、H2O2、H2O2/钨酸钠、NaClO或KMnO4中的至少一种。
在另一个具体实施方式中，所述溶剂选自THF、DMF、DMA、甲醇、乙醇、乙腈、二氯乙烷、DMSO、Dioxane、二氯甲烷(DCM)或乙酸乙酯中的至少一种。
本发明所述化合物的制备方法还可参照CN200810149162.6、CN200680022240.5、CN200680022139.X等制得。
本发明还提供一种杀虫组合物，其包含生物学有效量的所述的双酰胺类化合物中的至少一种；优选地，还包括制剂助剂；更优选地，还包括其他有效成分。
本发明还提供一种防治害虫的方法，其包括使所述害虫或其环境接触生物学有效量的所述的双酰胺类化合物或所述的组合物。
本发明还提供所述的双酰胺类化合物或所述的组合物在防治害虫中的用途。
术语“生物学有效量”是指当施用于(即接触)要防治的害虫或其环境、或植物、从中生长出植物的种子或植物的所在地(例如，生长培养基)时，足以产生所需生物学效应，从而保护植物免受害虫的伤害或达到其他所需效果(例如，提高植物活力)的生物学活性化合物(例如，式I的化合物)的量。本发明化合物还可以预防性地施用于预期出现害虫或寄生虫的地方。
含有本发明化合物作为有效成分的有害生物防除剂能够以低浓度有效地防除下述害虫：危害农园艺作物及树木等的各种农业害虫、对房屋等人们的生活环境带来不良影响的卫生害虫、危害仓库中储存的谷物等的储粮害虫、危害建筑物等木材的木材食害虫等的昆虫类、及在同样情况下发生、并进行危害的螨类、甲壳类、软体动物、线虫类中的任意的有害生物。
能够使用本发明化合物进行防除的昆虫类、螨类、甲壳类、软体动物及线虫类，具体而言例如可以举出下述物质，但并不限定于此：茶姬卷叶蛾(Adoxophyes honmai)、茶小卷叶蛾(Adoxophyes orana faciata)、梨黄卷蛾(Archips breviplicanus)、苹果小蛀蛾(Grapholita inopinata)、乱纹苹果卷叶蛾(Archips fuscocupreanus)、梨小食心虫(Grapholita molesta)、茶长卷叶蛾(Choristoneura magnanima)、大豆食心虫(Leguminivora glycinivorella)、桑树卷叶蛾(Olethreutes mori)、苹果卷叶细蛾(Caloptilia zachrysa)、桃白小卷蛾(Argyresthia conjugella)、梨细蛾(Spulerrinaastaurota)、豆小卷蛾(Matsumuraeses phaseoli)、苹果褐卷叶蛾(Pandemis heparana)、梨稜巢蛾(Bucculatrix pyrivorella)、桃潜蛾(Lyonetia clerkella)、桃蛀果蛾(Carposina niponensis)、银纹潜蛾(Lyonetia prunifoliella malinella)、茶细蛾(Caloptilia theivora)、金纹小潜细蛾(Phyllonorycter ringoniella)、柑橘叶潜蛾(Phyllocnistis citrella)、葱菜蛾(Acrolepiopsis sapporensis)、山芋伪菜蛾(Acrolepiopsis suzukiella)、小菜蛾(Plutella xylostella)、柿举肢蛾(Stathmopodamasinissa)、甘薯阳麦蛾(Helcystogramma triannulella)、红铃麦蛾(Pectinophoragossypiella)、桃蛀果蛾(Carposina sasakii)、二化螟(Chilo suppressalis)、稻纵卷叶螟(Cnaphalocrocis medinalis)、烟草粉螟(Ephestia elutella)、桃蛀螟(Conogethespunctiferalis)、瓜绢野螟(Diaphania indica)、豆荚斑螟(Etiella zinckenella)、桑绢野螟(Glyphodes pyloalis)、一点螟(Scirpophaga incertulas)、菜螟(Hellulaundalis)、亚洲玉米螟(Ostrinia furnacalis)、豆秆野螟(Ostrinia scapulalis)、草螟(Parapediasia teterrella)、稻弄蝶(Parnara guttata)、大菜粉蝶(Pieris brassicae)、纹白蝶(Pieris rapae crucivora)、柑桔凤蝶(Papilio xuthus)、大造桥虫(Ascotisselenaria)、大豆夜蛾(Pseudoplusia includens)、茶黄毒蛾(Euproctispseudoconspersa)、舞毒蛾(Lymantria dispar)、旋古毒蛾(Orgyia thyellina)、秋幕蛾(Hyphantria cunea)、奇特望灯蛾(Lemyra imparilis)、枯叶夜蛾(Adris tyrannus)、白斑烦夜蛾(Aedia leucomelas)、球菜夜蛾(Agrotis ipsilon)、芜菁夜蛾(Agrotis segetum)、黑点银纹夜蛾(Autographa nigrisigna)、银纹夜蛾(Ctenoplusia agnata)、苹果小卷蛾(Cydla pomonella)、棉铃虫(Helicoverpa armigera)、烟夜蛾(Helicoverpa assulta)、谷实夜蛾(Helicoverpa zea)、烟芽夜蛾(Heliothis virescens)、玉米螟(Ostrinianubilalis)、甘蓝夜蛾(Mamestra brassicae)、粘虫(Mythimna separata)、稻蛀茎夜蛾(Sesamia inferens)、稻螟蛉(Naranga aenescens)、南方灰翅夜蛾(Spodopteraeridania)、甜菜夜蛾(Spodoptera exigua)、草地贪夜蛾(Spodoptera frugiperda)、海灰翅夜蛾(Spodoptera littoralis)、斜纹夜蛾(Spodoptera litura)、淡剑纹灰翅夜蛾(Spodoptera depravata)、粉纹夜蛾(Trichoplusia ni)、葡萄莓果飞蛾(Endopizaviteana)、番茄天蛾(Manduca quinquemaculata)、烟草天蛾(Manduca sexta)等鳞翅目昆虫；
葡萄阿小叶蝉(Arboridia apicalis)、黑胸二室叶蝉(Balclutha saltuella)、二点大叶蝉(Epiacanthus stramineus)、蚕豆微叶蝉(Empoasca fabae)、Empoascanipponica、大贯小绿叶蝉(Empoasca onukii)、板井小绿叶蝉(Empoasca sakaii)、Macrosteles striifrons、黑尾叶蝉(Nephotettix cinctinceps)、Psuedatomoscelisseriatus、灰飞虱(Laodelphax striatella)、褐飞虱(Nilaparvata lugens)、白背飞虱(Sogatella furcifera)、柑橘木虱(Diaphorina citri)、梨木虱(Psylla pyrisuga)、桔刺粉虱(Aleurocanthus spiniferus)、银叶粉虱(Bemisia argentifolii)、烟草粉虱(Bemisia tabaci)、柑橘粉虱(Dialeurodes citri)、温室白粉虱(Trialeurodesvaporariorum)、葡萄粉虱(Aleurolobus taonabae)、葡萄根瘤蚜(Viteus vitifolii)、萝卜蚜(Lipaphis erysimi)、棉蚜(Aphis gossypii)、绣线菊蚜(Aphis spiraecola)、桃蚜(Myzus persicae)、桔二叉蚜(Toxoptera aurantii)、草履蚧(Drosicha corpulenta)、吹绵蚧(Icerya purchasi)、石蒜绵粉蚧(Phenacoccus solani)、柑桔绵蚧(Pulvinariaaurantii)、桔臀纹粉蚧(Planococcus citri)、柑桔圆介壳虫(Pseudaonidia duplex)、藤臀纹粉蚧(Planococcus kuraunhiae)、康氏粉介壳虫(Pseudococcus comstocki)、梨圆介壳虫(Comstockaspis perniciosa)、角蜡蚧(Ceroplastes ceriferus)、红蜡蚧(Ceroplastes rubens)、红圆蚧(Aonidiella aurantii)、茶园盾介壳虫(Fioriniatheae)、牡丹网盾蚧(Pseudaonidia paeoniae)、桑白盾蚧(Pseudaulacaspis pentagona)、梅白蚧(Pseudaulacaspis prunicola)、卫矛蜕盾蚧(Unaspis euonymi)、箭头介壳虫(Unaspis yanonensis)、温带臭虫(Cimex lectularius)、斑须蝽(Dolycoris baccarum)、皱纹菜蝽(Eurydema rugosum)、北二星蝽(Eysarcoris aeneus)、日本二星蝽(Eysarcorislewisi)、黑腹蝽(Eysarcoris ventralis)、青蝽(Glaucias subpunctatus)、茶翅蝽(Halyomorpha halys)、黑须绿稻蝽(Nezara antennata)、稻绿蝽(Nezara viridula)、璧蝽(Piezodorus hybneri)、珀蝽(Plautia crossota)、稻黑蝽(Scotinophora lurida)、稻棘缘蝽(Cletus punctiger)、中华稻缘蝽(Leptocorisa chinensis)、棒蜂缘蝽(Riptortusclavatus)、胡萝卜缘蝽(Rhopalus msculatus)、甘蔗长蝽(Cavelerius saccharivorus)、葫芦长蝽(Togo hemipterus)、棉红蝽(Dysdercus cingulatus)、杜鹃冠网蝽(Stephanitispyrioides)、Halticus insularis、美洲牧草盲蝽(Lygus lineolaris)、西伯利亚狭盲蝽(Stenodema sibiricum)、赤条纤盲蝽(Stenotus rubrovittatus)、稻叶害虫(Trigonotylus caelestialium)等半翅目昆虫；
古铜异丽金龟(Anomala cuprea)、姬金龟(Anomala rufocuprea)、小青花金龟(Gametis jucunda)、沥青七腮金龟(Heptophylla picea)、豆金龟(Popillia japonica)、马铃薯叶甲(Lepinotarsa decemlineata)、墨西哥豆瓢虫(Epilachna varivestis)、红薯梳爪叩甲(Melanotus fortnumi)、庶梳爪叩头虫(Melanotus tamsuyensis)、烟甲虫(Lasioderma serricorne)、褐粉蠹(Lyctusbrunneus)、松纵坑切梢小蠹(Tomicuspiniperda)、谷蠹(Rhizopertha dominica)、Epuraea domina、墨西哥豆瓢虫(Epilachnavarivestis)、二十八星瓢虫(Epilachna vigntioctopunctata)、黄粉虫(Tenebriomolitor)、赤拟谷盗(Tribolium castaneum)、星天牛(Anoplophora malasiaca)、松墨天牛(Monochamus alternatus)、黄星天牛(Psacothea hilaris)、葡萄虎天牛(Xylotrechuspyrrhoderus)、绿豆象(Callosobruchus chinensis)、黄守瓜(Aulacophora femoralis)、稻负泥虫(Oulema oryzae)、菾菜跳甲(Chaetocnema concinna)、黄瓜点叶甲(Diabroticaundecimpunctata)、玉米根叶甲(Diabrotica virgifera)、北方玉米根虫(Diabroticabarberi)、黄条叶蚤(Phyllotreta striolata)、茄窄胸跳甲(Psylliodesangusticollis)、桃实象(Rhynchites heros)、甘薯小象甲(Cylas formicarius)、墨西哥棉铃象(Anthonomus grandis)、稻象(Echinocnemus squameus)、西印度甘薯象(Euscepespostfasciatus)、紫苜蓿叶象(Hypera postica)、稻水象甲(Lissohoptrus oryzophilus)、葡萄黑耳喙象(Otiorhynchus sulcatus)、谷象(Sitophilus granarius)、玉米象(Sitophilus zeamais)、Sphenophorus venatus vestitus、青翅隐翅虫(Paederusfuscipes)等鞘翅目昆虫；
花蓟马(Frankliniella intonsa)、黄蓟马(Thrips flavus)、西方花蓟马(Frankliniella occidentalis)、温室蓟马(Heliothrips haemorrhoidalis)、茶黄蓟马(Scirtothrips dorsalis)、南黄蓟马(Thrips palmi)、葱蓟马(Thrips tabaci)、Ponticulothrips diospyrosi等总翅目昆虫；
Asphondylia yushimai、麦红吸浆虫(Sitodiplosis mosellana)、瓜实蝇(Bactrocera cucurbitae)、桔小实蝇(Bactrocera dorsalis)、地中海实蝇(Ceratitiscapitata)、大麦水蝇(Hydrellia griseola)、樱桃果蝇(Drosophila suzukii)、稻秆潜蝇(Agromyza oryzae)、豌豆彩潜蝇(Chromatomyia horticola)、番茄斑潜蝇(Liriomyzabryoniae)、葱斑潜蝇(Liriomyza chinensis)、蔬菜斑潜蝇(Liriomyza sativae)、非洲菊斑潜蝇(Liriomyza trifolii)、灰地种蝇(Delia platura)、葱蝇(Delia antique)、肖藜泉蝇(Pegomya cunicularia)、苹果实蝇(Rhagoletis pomonella)、麦瘿蚊(Mayetioladestructor)、家蝇(Musca domestica)、厩螫蝇(Stomoxys calcitrans)、绵羊虱蝇(Melophagus ovinus)、牛皮蝇(Hypoderma bovis)、纹皮蝇(Hypoderma lineatum)、羊狂蝇(Oestrus ovis)、刺舌蝇(Glossina palpalis，Glossina morsitans)、Prosimuliumyezoensis、虻(Tabanus trigonus)、白斑蛾蚋(Telmatoscopus albipunctatus)、Leptoconops nipponensis、淡色库蚊(Culex pipiens pallens)、埃及斑蚊(Aedesaegypti)、亚洲虎蚊(Aedes albopicutus)、Anopheles hyracanus sinesis等双翅目昆虫；
Apethymus kuri、新疆菜叶蜂(Athalia rosae)、玫瑰三节叶蜂(Arge pagana)、松柏锯角叶蜂(Neodiprion sertifer)、板栗瘿蜂(Dryocosmus kuriphilus)、行军蚁(Ecitonburchelli，Eciton schmitti)、日本弓背蚁(Camponotus japonicus)、大胡蜂(Vespamandarina)、公牛蚁(Myrmecia spp.)、红火蚁类(Solenopsis spp.)、法老蚁(Monomoriumpharaonis)等膜翅目昆虫；
黄脸油葫芦(Teleogryllus emma)、东方蝼蛄(Gryllotalpa orientalis)、飞蝗(Locusta migratoria)、小翅稻蝗(Oxya yezoensis)、沙漠蝗(Schistocerca gregaria)等直翅目昆虫；
菜白棘跳虫(Onychiurus folsomi)、北极棘跳虫(Onychiurus sibiricus)、黄星圆跳虫(Bourletiella hortensis)等粘管目昆虫；
黑胸大蠊(Periplaneta fuliginosa)、日本大蠊(Periplaneta japonica)、德国小蠊(Blattella germanica)、美洲非蠊(Periplaneta Americana)等网翅目昆虫；
台湾乳白蚁(Coptotermes formosanus)、栖北散白蚁(Reticulitermessperatus)、黑翅土白蚁(Odontotermes formosanus)等等翅目昆虫；
猫蚤(Ctenocephalidae felis)、狗蚤(Ctenocephalides canis)、鸡蚤(Echidnophaga gallinacea)、人蚤(Pulex irritans)、印鼠客蚤(Xenopsylla cheopis)等等翅目昆虫；
黄体羽虱(Menacanthus stramineus)、牛鸟虱(Bovicola bovis)等食毛目昆虫；
牛虱(Haematopinus eurysternus)、猪血虱(Haematopinus suis)、牛颚虱(Linognathus vituli)、水牛盲虱(Solenopotes capillatus)等虱目昆虫；
樱草植食螨(Phytonemus pallidus)、侧多食跗线螨(Polyphagotarsonemuslatus)、双叶跗线螨(Tarsonemus bilobatus)等埃螨类；
Penthaleus erythrocephalus、麦叶爪螨(Penthaleus major)等走螨类；
真梶小爪螨(Oligonychus shinkajii)、柑橘全爪螨(Panonychus citri)、桑全爪螨(Panonychus mori)、苹果全爪螨(Panonychus ulmi)、神泽叶螨(Tetranychuskanzawai)、二点叶螨(Tetranychus urticae)等叶螨类；
茶尖叶节蜱(Acaphylla theavagrans)、郁金香瘿螨(Aceria tulipae)、番茄刺皮瘿螨(Aculops lycopersici)、桔刺皮瘿螨(Aculops pelekassi)、斯氏刺瘿螨(Aculusschlechtendali)、Eriophyes chibaensis、桔皱叶刺瘿螨(Phyllocoptruta oleivora)等瘿螨类；
罗宾根螨(Rhizoglyphus robini)、腐蚀酪螨(Tyrophagus putrescentiae)、似食酪螨(Tyrophagus similis)等粉螨类；
雅氏瓦螨(Varroa jacobsoni)等瓦螨类；
微小牛蜱(Boophilus microplus)、血红扇头蜱(Rhipicephalus sanguineus)、长角血蜱(Haemaphysalis longicornis)、褐黄血蜱(Haemophysalis flava)、铃头血蜱(Haemophysalis campanulata)、卵形硬蜱(Ixodes ovatus)、全沟硬蜱(Ixodespersulcatus)、花蜱(Amblyomma spp.)、革蜱(Dermacentor spp.)等蜱类；
犬姬螯螨(Cheyletiella yasguri)、猫姬螯螨(Cheyletiella blakei)等肉食螨类；
犬蠕形螨(Demodex canis)、猫蠕形螨(Demodex cati)等蠕形螨类；
绵羊痒螨(Psoroptes ovis)等痒螨类；
疥螨(Sarcoptes scabiei)、猫背肛螨(Notoedres cati)、膝螨(Knemidocoptesspp.)等疥螨类；
平甲虫(Armadillidium vulgare)等甲壳类；
福寿螺(Pomacea canaliculata)、褐云玛瑙螺(Achatina fulica)、双线蛞蝓(Meghimatium bilineatum)、Limax Valentiana、蜗牛(Acusta despecta sieboldiana)、日本土地蜗牛(Euhadra peliomphala)等腹足类；
咖啡短体线虫(Prathylenchus coffeae)、穿刺短体线虫(Prathylenchuspenetrans)、伤残短体线虫(Prathylenchus vulnus)、马铃薯金线虫(Globoderarostochiensis)、大豆胞囊线虫(Heterodera glycines)、北方根结线虫(Meloidogynehapla)、南方根结线虫(Meloidogyne incognita)、水稻干尖线虫(Aphelenchoidesbesseyi)、松材线虫(Bursaphelenchus xylophilus)等线虫类等。
以本发明化合物作为有效成分的有害生物防除剂对侵害水田作物、旱田作物、果树、蔬菜、其他作物及花卉等的上述有害作物具有显著的防除效果，因此根据预测发生有害生物的时期，在有害生物发生前或确认到发生有害生物的时刻，对水田、旱田、果树、蔬菜、其他作物、花卉等的水田水、茎叶或土壤进行处理，由此能够得到作为本发明的有害生物防除剂的效果。
以本发明化合物作为有效成分的有害生物防除剂对在收割产物保存中产生的储粮害虫等具有显著的防除效果。即，用以本发明化合物作为有效成分的有害生物防除剂对收割产物、或收割产物的保存场所进行喷涂、涂抹、涂布、浸渍、粉衣、熏蒸·熏烟或加压注入等收获后(postharvest)处理即可。
另外，将以本发明化合物作为有效成分的有害生物防除剂适用于植物种子，由此能够预防由播种后的植物中产生的害虫所引起的侵害。即，将以本发明化合物作为有效成分的有害生物防除剂直接或用水等适当稀释或以使其悬浊的形态，以防除害虫的有效量对植物种子进行喷涂、涂抹、浸渍或粉衣等处理，由此使本发明化合物与植物种子接触即可。
所谓植物种子，是指储存植物幼苗发芽所需的营养成分、在农业上用于繁殖的物质。例如，可以举出玉米、大豆、小豆、棉花、水稻、制糖甜菜、小麦、大麦、向日葵、西红柿、黄瓜、茄子、菠菜、菜豆、南瓜、甘蔗、烟叶、甘椒及加拿大油菜等的种子或芋头、马铃薯、甘薯、蒟篛等的种芋、食用百合、郁金香等球根或薤等的种球等。
以本发明化合物作为有效成分的有害生物防除剂对双翅目害虫(淡色库蚊、地下家蚊、摇蚊、家蝇、蝶蝇、虻等)、纲翅目害虫(德国小蠊、黑胸大蠊、美洲非蠊等)等卫生害虫具有显著的防除效果。
以本发明化合物作为有效成分的有害生物防除剂对白蚁、褐粉蠹、谷蠹、窃蠹、天牛(Cerambycidae)等木材食害虫具有显著的防除效果，通过对土壤或建筑物等的木材进行处理，能够防除上述木材食害虫。
本发明化合物对各种有害生物显示防除效果，显示出保护有用作物的效果，同时以低药物量显示出作为杀虫剂或杀螨剂的优异的防除效果，因此具有对降低环境负荷做出巨大贡献的效果。并且，本发明化合物通过与其他农园艺用杀虫剂、杀螨剂、杀线虫剂、杀菌剂、除草剂、植物生长调节剂、生物农药等混合使用也可以显示优异的防除效果。
使用本发明化合物时，通常可以与适当的固体载体或液体载体混合，进而根据需要添加表面活性剂、浸透剂、展着剂(spreader)、增稠剂、防冻剂、粘合剂、防结块剂、崩解剂、消泡剂、防腐剂及分解防止剂等，制成下述任意的剂型用于实用，所述剂型为溶液剂(soluble concentrate)、乳剂(emulsifiable concentrate)、可湿性粉剂(wettablepowder)、水溶剂(water soluble powder)、水分散颗粒剂(water dispersible granule)、水溶性颗粒剂(water soluble granule)、悬浊剂(suspension concentrate)、浓乳剂(concentrated emulsion)、悬浮乳剂(suspoemulsion)、微乳(microemulsion)、粉剂(dustable powder)、颗粒剂(granule)片剂(tablet)及乳化性凝胶剂(emulsifiable gel)等。另外，从省力化及安全性提高的观点考虑，还可以将上述任意剂型的制剂封入水溶性胶囊及水溶性膜的袋等水溶性包装体中进行供应。
作为能够在本发明中使用的惰性载体可以为固体或液体中的任一种，作为能够形成固体惰性载体的材料，可以举出例如大豆粉、谷物粉、木粉、树皮粉、锯粉、烟叶茎粉、核桃壳粉、糠、纤维素粉末、植物提取物萃取后的残渣、粉碎合成树脂等合成聚合物、粘土类(例如高龄土、膨润土、酸性白土等)、滑石类(例如滑石、叶蜡石等)、二氧化硅类(例如硅藻土、硅砂、云母、白炭墨[也称为含水微粉硅、含水硅酸的合成高分散硅酸，根据产品的不同，有含硅酸钙作为主要成分的产品。])、活性碳、硫粉、浮石、烧结硅藻土、砖粉碎物、飞灰、砂、碳酸钙、磷酸钙等无机矿物性粉末、硫铵、磷铵、硝铵、尿素、氯化铵等化学肥料、堆肥等，上述载体可以单独使用，或者也可以以二种以上的混合物的形态进行使用。
作为能够成为液体惰性载体的材料，除其本身具有溶剂性能的材料之外，还可以选择不具有溶剂性能、但借助助剂的作用使有效成分化合物分散的材料，例如作为代表例可以举出下述列举的载体，下述载体可以单独使用或以2种以上的混合物的形态使用，例如水、醇类(例如，甲醇、乙醇、异丙醇、丁醇、乙二醇等)、酮类(例如丙酮、甲基乙基酮、甲基异丁基酮、二异丁基酮、环己酮等)、醚类(例如乙醚、二氧杂环己烷、溶纤剂、二异丙基醚、四氢呋喃等)、脂肪族烃类(例如煤油(kerosene)、矿物油等)、芳香族烃类(例如苯、甲苯、二甲苯、溶剂石脑油、烷基萘等)、卤代烃类(例如二氯甲烷、氯仿、四氯化碳、氯苯等)、酯类(例如乙酸乙酯、乙酸丁酯、丙酸乙酯、邻苯二甲酸二异丁酯、邻苯二甲酸二丁酯、邻苯二甲酸二辛酯等)、酰胺类(例如二甲基甲酰胺、二乙基甲酰胺、二甲基乙酰胺等)、腈类(例如乙腈等)。
上述固体及液体载体可以单独使用也可以同时使用2种以上。
作为表面活性剂，可以举出例如聚氧乙烯烷基醚、聚氧乙烯烷基(单或二)苯基醚、聚氧乙烯(单、二或三)苯乙烯基苯基醚、聚氧乙烯聚氧丙烯嵌段共聚物、聚氧乙烯脂肪酸(单或二)酯、失水山梨糖醇脂肪酸酯、聚氧乙烯失水山梨糖醇脂肪酸酯、蓖麻油环氧乙烷加成物、乙二醇(acetylene glycol)、炔属醇、乙二醇的环氧乙烷加成物、炔属醇的环氧乙烷加成物及烷基葡糖苷等非离子性表面活性剂、烷基硫酸酯盐、烷基苯磺酸盐、木素磺酸盐、烷基磺基琥珀酸盐、萘磺酸盐、烷基萘磺酸盐、萘磺酸的甲醛缩合物的盐、烷基萘磺酸的甲醛缩合物的盐、聚氧乙烯烷基醚硫酸或磷酸酯盐、聚氧乙烯(单或二)烷基苯基醚硫酸或磷酸酯盐、聚氧乙烯(单、二或三)苯乙烯基苯基醚硫酸或磷酸酯盐、聚羧酸盐(例如，聚丙烯酸盐、聚马来酸盐及马来酸与烯烃形成的共聚物等)及聚苯乙烯磺酸盐等阴离子性表面活性剂、烷基胺盐及烷基季铵盐等阳离子性表面活性剂、氨基酸型及内铵盐型等两性表面活性剂、聚硅氧烷类表面活性剂以及氟类表面活性剂。
上述表面活性剂的含量没有特别限定，相对于100重量份本发明的制剂，通常优选在0.05～20重量份的范围内。另外，上述表面活性剂可以单独使用或同时使用2种以上。
为了防除各种害虫，将其直接、或用水等适当稀释、或使其成悬浊的形态，以防除病害有效的量用于预测到产生该害虫的作物或在不希望发生的部位进行使用即可。其使用量根据各种因素例如目的、对象害虫、作物的生育状况、害虫的发生倾向、气候、环境条件、剂型、施用方法、施用场所、施用时期等而变动，通常期望有效成分以0.0001～5000ppm、优选为0.01～1000ppm的浓度使用。另外，每10a的施用量通常以有效成分计为1～300g。
本发明的化合物的有效成分量，通常情况下，粉剂时为0.1～20重量％、乳剂时为5～50重量％、可湿性粉剂时为3～90重量％、颗粒剂时为0.1～20重量％及混悬剂时为5～90重量％、水分散颗粒剂时为3～90重量％。另一方面，各剂型中的载体的量通常情况下，粉剂时为60～99.9重量％、乳剂时为40～95重量％、可湿性粉剂时为10～90重量％、颗粒剂时为80～99.9重量％、及混悬剂时为10～95重量％、水分散颗粒剂时为10～90重量％。另外，助剂的量通常情况下，粉剂时为0.1～20重量％、乳剂时为1～20重量％、可湿性粉剂时为0.1～20重量％、颗粒剂时为0.1～20重量％及混悬剂时为0.1～20重量％、水分散颗粒剂时为0.1～20重量％。
另外，使用本发明化合物作为农药时，根据需要在制剂时或散布时也可以与其他种类的除草剂、各种杀虫剂、杀螨剂、杀线虫剂、杀菌剂、植物生长调节剂、增效剂、肥料、土壤改良剂等混合施用。
本说明书中记载的全部文献、专利申请、及技术规格，与作为参考将各个文献、专利申请、及技术规章具体且分别引入的情况的程度相同地，作为参考引入本说明书中。
具体实施方式
以下实施例用于举例说明本发明，不应当视其为以任何方式限制本发明。本发明要求保护的权利范围通过权利要求书进行说明。
鉴于化合物的经济性与多样性，我们优选合成了一些化合物，在合成的诸多化合物中，选取部分列于下表1中。具体的化合物结构及相应的化合物信息如表1所示。表1中的化合物只是为了更好的说明本发明，但并不限定本发明，对于本领域的技术人员而言，不应将此理解为本发明上述主题的范围仅限于以下化合物。
表1化合物结构及其1H NMR
制备本发明化合物的数种方法详解说明于以下方案和实施例中。原料可以经市场购买到或者可以通过文献中已知的方法或者如详解所示进行制备。本领域技术人员应当理解，也可以利用其它合成路线合成本发明的化合物。尽管在下文中已经对合成路线中的具体原料和条件进行了说明，但是，可以很容易地将其替换为其它类似的原料及条件，这些对本发明制备方法的变型或者变体而产生的诸如化合物的各种异构等都包括在本发明范围内。另外，如下所述制备方法可以按照本发明公开内容、使用本领域技术人员熟知的常规化学方法进行进一步修饰。例如，在反应过程中对适当的基团进行保护等等。
以下提供的方法实施例用于促进对本发明的制备方法的进一步了解，使用的具体物质、种类和条件确定为是对本发明的进一步说明，并不是对其合理范围的限制。在下表中表明的合成化合物中使用的试剂或者可以市场购买到，或者可以由本领域普通技术人员轻易制备得到。
代表性化合物的实施例如下，其他化合物的合成方法类似，此处不再详细说明。
1、化合物1的合成
(1)将1-1(500mg，1.15mmol，1eq)溶解在乙腈(10ml)中，加入到50ml单口瓶，加入碘化钾(47mg，0.28mmol，0.25eq)，1-2(628mg，2.3mmol，2eq)，85℃反应12h。监测反应完成，浓缩乙腈，加入乙酸乙酯萃取，有机相用饱和食盐水洗涤二次，用无水硫酸钠干燥，拌样，正相分离(EA/PE＝2/3)，得到1-3为300mg，收率：37.5％。
(2)将1-3(300mg，0.44mmol，1eq)溶解在二氯甲烷(10ml)中，加入到50ml单口瓶，加入间氯过氧苯甲酸(151mg，0.88mmol，2eq)，室温反应2h。监测反应完成，加入水萃取，有机相用饱和食盐水洗涤二次，用无水硫酸钠干燥，拌样，正相分离(EA/PE＝1/2)，得到化合物1为80mg，收率：26％。
2、化合物2的合成
(1)在50ml单口瓶中，将1-1(1g，2.3mmol)溶解在乙腈(20ml)中，加入碘化钾(94mg，0.57mmol，0.25eq)和2-1(1.1g，4.6mmol，2eq)，80℃反应12h。监测反应完成，浓缩除去乙腈，加入乙酸乙酯萃取，有机相用饱和食盐水洗涤二次，用无水硫酸钠干燥，拌样，正相分离(EA/PE＝2/3)，得到2-2(912mg，收率78.1％，白色固体)。
(2)在100ml单口瓶中，将2-2(912mg，1.5mmol)溶解在乙醇(50ml)中，加入氯化铵(0.16g，3mmol)的水溶液，然后加入铁粉(0.17g，3mmol)，60℃反应1h。监测反应完成，趁热抽滤，滤液浓缩，加水萃取，有机相旋干得到粗品2-3(549mg，收率63.3％，白色固体)。
(3)将2-3(549mg，0.93mmol)溶解在5ml浓硫酸中，冰浴下缓慢滴加2ml甲醛水溶液，缓慢升到50℃，反应1h，监测反应直到起始原料消失。反应液加水，用乙酸乙酯萃取三次，饱和食盐水洗涤三次。无水硫酸钠干燥后拌样过柱，馏分旋干得到2-4(146mg，收率25.9％，白色固体)。
(4)将2-4(146mg，0.24mmol)溶解在10ml THF中，加入吡啶(37.9mg，0.48mmol)，冰浴下缓慢滴加苯甲酰氯(33.6mg，0.24mmol)，室温反应1h，监测反应直到起始原料消失。反应液加水，用乙酸乙酯萃取三次，饱和食盐水洗涤三次。无水硫酸钠干燥后拌样过柱，馏分旋干得到2-5(102mg，收率59.6％，白色固体)。
(5)将2-5(102mg，0.14mmol)溶解在10ml DCM中，加入间氯过氧苯甲酸(48.2mg，0.28mmol)，室温反应5h，监测反应直到起始原料消失。反应液加水，用DCM萃取三次，饱和食盐水洗涤三次。无水硫酸钠干燥后拌样过柱，馏分旋干得到化合物2(61mg，收率57.5％，白色固体)。
3、化合物46的合成
(1)在250mL单口瓶中，将1-1(10g，1.0eq，23.09mmol)加入到100mL乙腈中，依次加入碘化钾(766.5mg，0.2eq，4.62mmol)和46-1(5.0g，1.0eq，23.09mmol)，氮气置换三次，升温至80℃反应过夜。监测反应直到起始原料消失。反应液浓缩，残留物加水(50mL)稀释后用乙酸乙酯(50mL x 3)萃取，有机相用饱和食盐水洗涤(50mL x 3)，无水硫酸钠干燥浓缩后拌样过柱，得到产物46-2(12.5g，产率88％，黄色油状物)。
(2)在250mL单口瓶中，将46-2(12.5g，1.0eq，20.42mmol)加入到90mL乙醇和30mL水中，加氯化铵(3.3g，3.0eq，61.25mmol)和铁粉(3.42g，3.0eq，61.25mmol)，升温至80℃反应2h。监测反应直到起始原料消失。反应液浓缩，残留物加水(50mL)稀释后用乙酸乙酯(50mL x 3)萃取，有机相用饱和食盐水洗涤(50mL x 3)，无水硫酸钠干燥浓缩后拌样过柱，得到产物46-3(6.3g，产率53％，棕色固体)。
(3)在100mL单口瓶中，将46-3(6.3g，1.0eq，10.8mmol)加入到50mL浓硫酸中，加入多聚甲醛(1.3g，4.0eq，43.3mmol)，升温至40℃，反应2h。监测反应直到起始原料消失。反应完毕，将反应液倒入100mL水中，调pH至中性，用乙酸乙酯(50mL x 3)萃取，有机相用饱和食盐水洗涤(50mL x 3)，无水硫酸钠干燥浓缩后拌样过柱，得到产物46-4(3.2g，产率49％，白色固体)。
(4)在50mL单口瓶中，将46-4(0.1g，1.0eq，167.7μmol)加入到5mL二氯甲烷中，依次加入46-5(0.04g，1.5eq，251.55μmol)和三乙胺(0.02g，1.0eq，167.7μmol)，室温反应过夜。监测反应直到起始原料消失。反应完毕，将反应液倒入10mL水中，用乙酸乙酯(10mL x3)萃取，有机相用饱和食盐水洗涤(10mL x 3)，无水硫酸钠干燥浓缩后拌样过柱，得到产物46-6(0.1g，产率80％，白色固体)。
(5)在50mL单口瓶中，将46-6(0.1g，1.0eq，135.80μmol)加入到5mL二氯甲烷中，加入间氯过氧苯甲酸(0.06g，2.0eq，271.59μmol)，室温反应2h。监测反应直到起始原料消失。反应完毕，将反应液倒入20mL饱和硫代硫酸钠溶液中，用乙酸乙酯(10mLx 3)萃取，有机相用饱和碳酸氢钠溶液洗涤(10mL x 3)，无水硫酸钠干燥浓缩后拌样过柱，得到产物化合物46(0.05g，产率48％，白色固体)。
4、化合物76的合成
(1)在50mL单口瓶中，将46-4(0.1g，1.0eq，167.7μmol)加入到5mL二氯甲烷中，依次加入76-1(0.04g，1.5eq，251.55μmol)和三乙胺(0.02g，1.0eq，167.7μmol)，室温反应过夜。监测反应直到起始原料消失。反应完毕，将反应液倒入10mL水中，用乙酸乙酯(10mL x3)萃取，有机相用饱和食盐水洗涤(10mL x 3)，无水硫酸钠干燥浓缩后拌样过柱，得到产物76-2(0.1g，产率85％，白色固体)。
(2)在50mL单口瓶中，将76-2(0.1g，1.0eq，142.57μmol)加入到5mL乙腈中，加入双氧水(0.02g，3.0eq，427.72μmol)，再加入钨酸钠(0.004g，0.1eq，14.26μmol)，升温至50℃反应2h。监测反应直到起始原料消失。反应完毕，反应液浓缩，残留物加水(10mL)稀释后用乙酸乙酯(10mL x 3)萃取，有机相用氯化钠溶液洗涤(10mL x 3)，无水硫酸钠干燥浓缩后拌样过柱，得到化合物76(0.07g，产率48％，白色固体)。
生物活性评价：
(1)杀虫活性测试：
药剂配制：原药用丙酮溶解后，用蒸馏水将药液稀释至梯度剂量。
施药方法：
草地贪夜蛾(浸叶法)：采摘未用药且不含抗虫基因的玉米叶片，剪成3-4cm长度的叶段，分别在药液中浸泡20s，取出后在吸水纸上晾干，然后取3片施药后的叶片放入塑料盒中，接入10头经饥饿处理2h的3龄试虫。每盒为1个重复，每个处理重复3次，以最高剂量所含丙酮为对照。施药后转移至饲养条件下饲养。48h后调查死亡虫数，统计死亡率。
韭菜迟眼蕈蚊(点滴法+浸叶法)：于培养皿中垫2层滤纸，用水湿润滤纸后，每皿接入15头经饥饿处理2h的3龄试虫，然后使用移液枪吸取400uL药液均匀点滴在韭菜迟眼蕈蚊幼虫身上。然后取2cm长度的韭菜假茎，洗净晾干后，分别在药液中浸泡20s，取出后在吸水纸上晾干，放入到培养皿中韭菜迟眼蕈蚊幼虫的旁边。每个培养皿为1个重复，每处理重复3次，以最高剂量所含丙酮为对照。施药后转移至饲养条件下饲养。48h后调查结果，分别统计各处理的死亡情况，计算死亡率。
黄粉虫(浸叶法)：采摘未用药且不含抗虫基因的甘蓝叶片，剪成2*2cm的正方形，分别在药液中浸泡20s，取出后在吸水纸上晾干，然后取2片施药后的叶片放入塑料盒中，接入10头经饥饿处理2h的试虫。每盒为1个重复，每个处理重复3次，以最高剂量所含丙酮为对照。施药后转移至饲养条件下饲养。48h后调查死亡虫数，统计死亡率。
桃蚜(浸虫法)：剪取带虫叶片，分别在药液中浸泡5s，取出后在吸水纸上晾干，然后放入外径9cm塑料小盒中，48h后调查死亡虫数，统计死亡率。
粘虫、斜纹夜蛾(喷雾法)：选取室内饲养生理状态一致的试虫，放入一次性酱料盒杯中，每个盒中接入10头生长一致的试虫，并放入寄主植物叶片或茎秆，然后使用喷雾塔进行喷雾，喷雾结束后盖紧盖子，重复3次，以最高剂量所含丙酮为对照，施药后转移至饲养条件下饲养。
死亡率＝(死虫数/供试虫数)×100％
表2代表性化合物杀虫活性测试结果
注：N代表无数据；对照化合物A：对照化合物B：对照化合物C：
(2)蜜蜂急性毒性试验：
按照GB/T 31270.10-2014所述方法进行蜜蜂急性毒性试验，观察记录处理96h后的中毒症状和死亡数，测试结果表明本发明化合物1对蜜蜂的急性经口毒性和急性接触毒性的半致死剂量LD50均大于2μg a.i./蜂，而对照化合物B(溴虫氟苯双酰胺)的急性经口毒性的半致死剂量LD50为0.0008μg a.i./蜂，急性接触毒性的半致死剂量LD50为0.005μga.i./蜂，可见本申请所述化合物对蜜蜂的毒性明显降低、安全性更好。
同时经过很多测试发现，本发明所述化合物作为有害生物防除剂特别是农业园艺用杀虫剂具有优良的作用，具有一定的商业价值。

Claims (7)

1.一种如式I所示的双酰胺类化合物，
其中，X是芳基或杂环基，其分别独立地是未取代的或被选自氧代，卤素，氰基，硝基，烷基，烯基，炔基，环烷基，卤代烷基，卤代烯基，卤代炔基，被烷基或卤素取代的环烷基，苯基，被选自卤素、氰基、硝基、烷基、卤代烷基、烷氧基羰基、烷硫基、烷基磺酰基、烷氧基或卤代烷氧基中的至少一个基团所取代的苯基，-OR，-SR，-(CO)OR，-S(O)nR，-N(R)2或-O-亚烷基-(CO)OR中的至少一个基团所取代的，或者环上相邻两个碳原子与未取代的或被卤素或烷基所取代的-OCH2CH2-或-OCH2O-形成稠环；
Y是卤素或烷氧基；
R分别独立地是氢，烷基，卤代烷基，苯基，或被选自卤素、氰基、硝基、烷基、卤代烷基、烷氧基羰基、烷硫基、烷基磺酰基、烷氧基或卤代烷氧基中的至少一个基团所取代的苯基；
n是0、1或2。
2.根据权利要求1所述的一种双酰胺类化合物，其特征在于，
X是芳基或杂环基，其分别独立地是未取代的或被选自氧代，卤素，氰基，硝基，C1-C8烷基，C2-C8烯基，C2-C8炔基，C3-C8环烷基，卤代C1-C8烷基，卤代C2-C8烯基，卤代C2-C8炔基，被C1-C8烷基或卤素取代的C3-C8环烷基，苯基，被选自卤素、氰基、硝基、C1-C8烷基、卤代C1-C8烷基、C1-C8烷氧基羰基、C1-C8烷硫基、C1-C8烷基磺酰基、C1-C8烷氧基或卤代C1-C8烷氧基中的至少一个基团所取代的苯基，-OR，-SR，-(CO)OR，-S(O)nR，-N(R)2或-O-(C1-C8)亚烷基-(CO)OR中的至少一个基团所取代的，或者环上相邻两个碳原子与未取代的或被卤素或C1-C8烷基所取代的-OCH2CH2-或-OCH2O-形成稠环；
Y是卤素或C1-C8烷氧基；
R分别独立地是氢，C1-C8烷基，卤代C1-C8烷基，苯基，或被选自卤素、氰基、硝基、C1-C8烷基、卤代C1-C8烷基、C1-C8烷氧基羰基、C1-C8烷硫基、C1-C8烷基磺酰基、C1-C8烷氧基或卤代C1-C8烷氧基中的至少一个基团所取代的苯基。
3.根据权利要求1或2所述的一种双酰胺类化合物，其特征在于，
X是芳基或杂环基，其分别独立地是未取代的或被选自氧代，卤素，氰基，硝基，C1-C6烷基，C2-C6烯基，C2-C6炔基，C3-C6环烷基，卤代C1-C6烷基，卤代C2-C6烯基，卤代C2-C6炔基，被C1-C6烷基或卤素取代的C3-C6环烷基，苯基，被选自卤素、氰基、硝基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基羰基、C1-C6烷硫基、C1-C6烷基磺酰基、C1-C6烷氧基或卤代C1-C6烷氧基中的1～3个基团所取代的苯基，-OR，-SR，-(CO)OR，-S(O)nR，-N(R)2或-O-(C1-C6)亚烷基-(CO)OR中的1～3个基团所取代的，或者环上相邻两个碳原子与未取代的或被卤素或C1-C6烷基所取代的-OCH2CH2-或-OCH2O-形成稠环；
Y是卤素或C1-C6烷氧基；
R分别独立地是氢，C1-C6烷基，卤代C1-C6烷基，苯基，或被选自卤素、氰基、硝基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基羰基、C1-C6烷硫基、C1-C6烷基磺酰基、C1-C6烷氧基或卤代C1-C6烷氧基中的1～3个基团所取代的苯基。
4.一种如权利要求1-3任意一项所述的双酰胺类化合物的制备方法，其特征在于，包括以下步骤：
(1)式II所示化合物与式III所示化合物或式V所示化合物与式VI所示化合物进行反应，得到式IV所示化合物；
(2)式IV所示化合物经氧化得到式I所示化合物；
其中，Hal代表卤素，优选Cl，取代基X和Y的定义如权利要求1-3任意一项所述；
优选地，所述反应(1)在碱和溶剂的存在下进行；更优选地，所述碱选自无机碱或有机碱中的至少一种；更优选地，所述溶剂选自THF、DMF、DMA、甲醇、乙醇、乙腈、二氯乙烷、DMSO、Dioxane、二氯甲烷或乙酸乙酯中的至少一种；
优选地，所述反应(2)在氧化剂和溶剂的存在下进行；更优选地，所述氧化剂选自间氯过氧苯甲酸、H2O2、H2O2/钨酸钠、NaClO或KMnO4中的至少一种；更优选地，所述溶剂选自THF、DMF、DMA、甲醇、乙醇、乙腈、二氯乙烷、DMSO、Dioxane、二氯甲烷或乙酸乙酯中的至少一种。
5.一种杀虫组合物，其特征在于，包含生物学有效量的权利要求1-3任意一项所述的双酰胺类化合物中的至少一种；优选地，还包括制剂助剂；更优选地，还包括其他有效成分。
6.一种防治害虫的方法，其特征在于，包括使所述害虫或其环境接触生物学有效量的权利要求1-3任意一项所述的双酰胺类化合物或权利要求5所述的组合物。
7.如权利要求1-3任意一项所述的双酰胺类化合物或权利要求5所述的组合物在防治害虫中的用途。
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