CN110256404A - 具有杀虫活性的双烯化合物、其制备及用途 - Google Patents
具有杀虫活性的双烯化合物、其制备及用途 Download PDFInfo
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- CN110256404A CN110256404A CN201910364784.9A CN201910364784A CN110256404A CN 110256404 A CN110256404 A CN 110256404A CN 201910364784 A CN201910364784 A CN 201910364784A CN 110256404 A CN110256404 A CN 110256404A
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- 239000002728 pyrethroid Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 102000042094 ryanodine receptor (TC 1.A.3.1) family Human genes 0.000 description 1
- 108091052345 ryanodine receptor (TC 1.A.3.1) family Proteins 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000012873 virucide Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- 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
- 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
- A01N43/74—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 five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07—ORGANIC CHEMISTRY
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- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- 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
- C07D417/06—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 linked by a carbon chain containing only aliphatic carbon atoms
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- 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
- C07D417/14—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 three or more hetero rings
Abstract
本发明公开了一种具有杀虫活性的双烯化合物、其制备及用途。本发明的双烯化合物,具有通式Ⅰ所示结构,各取代基的定义如说明书和权利要求书所述。本发明的双烯化合物能够提高新烟碱类化合物的杀虫活性和/或扩大杀虫谱,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。
Description
技术领域
本发明涉及农药领域,涉及具有杀虫活性的双烯化合物、其制备及用途,更具体地涉及共轭双烯类新烟碱杀虫剂、其制备及用途。
技术背景
20世纪80年代中期拜耳公司(Bayer)开发出第一个新烟碱类杀虫剂吡虫啉,成为最成功的新型杀虫剂之一,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。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,已经成为农药创制的重要热点领域。
但是由于吡虫啉过量频繁使用造成的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;还有,近年的研究表明,新烟碱类杀虫剂具有一定的蜜蜂毒性;在一定程度上限制了该类化合物的应用,成为制约此类化合物发展的重要问题,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,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,使其应用于杀虫剂就成为本发明需要解决的技术问题。
发明内容
本发明目的就是提供一类更高效防治害虫的化合物及其制备方法。本发明的化合物能够提高新烟碱类化合物的杀虫活性和/或扩大杀虫谱。
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。
本发明的第一方面,提供一种具有通式Ⅰ所示结构的化合物,或其光学异构体、顺反异构体、在农药学上可接受的盐:
式中:R1为取代或未取代的含氮、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,所述取代为具有选自下组中的一个或多个取代基:卤素、C1-4卤代烷基或C1-4卤代烷氧基;
R2、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R2与R3、或R2与R4合并组成-CH2-CH2-、-CH2-CH2-CH2-、-CH2-CH2-CH2-CH2-或-CH2-XR-CH2-,其中X为选自N、O、S的杂原子,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、C2-3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C2-8不饱和烃基或C1-8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为取代或未取代的C1-8烷基、取代或未取代的C3-8环烷基、取代或未取代的C6-10芳基、取代或未取代的C1-4亚烷基-C6-10芳基、取代或未取代的含氮、氧和/或硫的五元或六元杂环基,所述取代是指具有选自下组的一个或多个取代基:C1-6烷基、硝基、氟、氯、溴、C1-6烷氧基、C1-6卤代烷基、羟基、氨基、甲胺基、二甲胺基,或者两取代基与连接的原子成环;
Z为硝基、氰基、酯基、三氟甲基、三氟乙酰基(-COCF3)、C1-6烷氧酰基、C1-6烷基-甲酰基、或三氟甲磺酰基(-SO2CF3)。
在另一优选例中,R1为取代或未取代的以下基团:苯基、吡啶基、噻唑基、嘧啶基、四氢呋喃和噁唑基,其中,所述取代为具有选自下组中的一个或多个取代基:卤素,C1-4卤代烷基。
在另一优选例中,R1选自取代或未取代的以下基团:苯基、吡啶基、噻唑基、嘧啶基、四氢呋喃,所述取代为具有选自下组中的一个或多个取代基:氟、氯、溴、C1-4氟代烷基(如-CF3)。
在另一优选例中,R2、R3、R4各自独立为氢、C1-4烷基、C2-4烷氧基烷基、C1-3烷氧基羰基、或苯氧羰基。
在另一优选例中,R2与R3、或者R2与R4合并组成-CH2-CH2-、-CH2-CH2-CH2-或-CH2-XR-CH2-,其中X为选自N,O,S的杂原子,R是杂原子上的C1-4烷基。
在另一优选例中,R4为氢。
在另一优选例中,R5为取代或未取代的C3-6环烷基、取代或未取代的C6-10芳基、取代或未取代的C1-4亚烷基-C6-10芳基、取代或未取代的含氮、氧和/或硫的五元或六元杂环基,所述含氮、氧和/或硫的五元或六元杂环基为吡啶基、噻唑基、嘧啶基、四氢呋喃或噁唑基;所述取代是指具有选自下组的一个或多个取代基:C1-6烷基、硝基、氟、氯、溴、C1-6烷氧基、C1-6卤代烷基、或者两取代基与连接的原子成环。
在另一优选例中,R5为取代或未取代的以下基团:苯基、苄基、环丙基、环丁基、环戊基、环己基、噻吩基、噻唑基、三氮唑基、吡咯基、吡啶基、萘基、呋喃基、或喹啉,所述取代是指具有选自下组的1、2或3个取代基:C1-6烷基、硝基、氟、氯、溴、C1-4烷氧基、C1-4卤代烷基(如-CF3、-CF(CF3)2)、或者两取代基与连接的原子成环。
在另一优选例中,Z为硝基、氰基、三氟甲基、三氟乙酰基、或三氟甲磺酰基。
在另一优选例中,Z为硝基。
在另一优选例中,所述化合物具有式(Ⅱ)所示结构:
式中,R1和R5如上述定义。
在另一优选例中,R1为
在另一优选例中,R5为说明书表格中列出的基团,如 (以下没有波浪线的基团,横线表示连接处) 等。
在另一优选例中,所述化合物为实施例中列出的任一化合物。
本发明的第二方面,提供一种农用组合物,其包含:
(a)第一方面所述的化合物或其在农药学上可接受的盐;以及
(b)农药学上可接受的载体和/或赋形剂。
在另一优选例中,所述农用组合物包含0.001-99.99重量%的第一方面所述的化合物或其在农药学上可接受的盐。
在另一优选例中,所述的具有通式Ⅰ所示结构的化合物或其农药学上可接受的盐的浓度为10-800ppm,较佳地100-500ppm。
在另一优选例中,所述的农药组合物的剂型为各种常规农药剂型,如饵剂等。
本发明的第三方面,提供第一方面所述的化合物或第二方面所述的农用组合物的用途,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害虫的杀虫剂组合物。
另一方面,本发明涉及上述化合物或其在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。
本发明的第四方面,提供一种杀虫和/或防虫方法,所述方法包括将第一方面所述的化合物或其在农药学上可接受的盐,或第二方面所述的杀虫剂组合物,施加于遭受或可能遭受虫害的植物体、动物体、其周围的土壤或环境中。
本发明还提供一种防治害虫的方法,在需要施用的植物种子或植物叶子和/或植物果实或植物正在生长或预期要生长的地方,施用杀虫有效量(如10-800ppm,更佳地100-500ppm)的本发明的具有通式Ⅰ所示结构的化合物。
另一优选例中,所述的害虫选自:蚜虫、粘虫。
本发明的第五方面,提供第一方面所述的化合物或其在农药学上可接受的盐的制备方法,包括步骤:
式a所示化合物和式b所示化合物反应从而得到具有通式Ⅰ所示结构的化合物,
式中,R1、R2、R3、R4、R5和Z的定义如前所述;
Y为O或S。
在另一优选例中,在反应溶剂中,使式a和式b所示化合物在催化剂作用下进行反应,从而得到具有通式Ⅰ所示结构的化合物。
在另一优选例中,所述溶剂选自下组中的一种或多种:乙腈、甲醇、四氢呋喃、乙醇、水、1,4-二氧六环、丙酮、二氯甲烷、或1,2-二氯乙烷。
在另一优选例中,所述催化剂为质子酸或路易斯酸,选自下组中的一种或多种:盐酸、醋酸、磷酸、对甲苯磺酸、三氟乙酸、三氯乙酸、三氟化硼、三氯化铝、三氯化铁、硼酸、硅酸、硝酸、氯化镁、氯化钴、氯化锶、氯化钯、或氯化镍(优选硼酸)。
在另一优选例中,所述反应在-20-80℃下进行;较佳地,在15-55℃下进行。
在另一优选例中,所述反应时间为2-96小时,较佳的为24-48小时。
本发明在现有的硝基亚甲基类新烟碱杀虫剂的硝基亚甲基上引入芳香(杂)环和/或烷烃取代的碳碳双键,合成了一种新型的共轭双烯新烟碱类化合物,该类化合物具有显著的杀虫活性,杀虫谱广,并且稳定性强。
应理解,在本发明范围内,本发明的上述各技术特征和在下文(如实施例)中具体描述的各技术特征可以互相组合,从而构成新的或优选的技术方案。限于篇幅,在此不再一一赘述。
具体实施方式
本发明的发明人通过长期而深入的研究,在现有的硝基亚甲基类新烟碱杀虫剂的结构基础上保留了活性药效团硝基亚甲基,引入了芳香(杂)环乙烯结构,合成了一种新型的共轭双烯新烟碱化合物。杀虫活性测试表明,本发明提供的化合物具有显著的杀虫活性,并具有扩大的杀虫谱。制备方法简单,有望开发成低毒、高效、环境友好的新型农药。
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”是指本发明化合物或其在农药学上可接受的盐,具有显著的杀虫活性,杀虫谱广,稳定性强。
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、由通式Ⅰ的化合物形成的酸加成盐包括无机酸形成的盐,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、贮藏谷类的害虫、危害动物健康的害虫以及公共卫生害虫等。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,如玉米象(Sitophilus zeamais),赤拟谷盗(Tribolium castaneum),马铃薯瓢虫(Henosepilachnavigintioctomaculata),二十八星瓢虫(Henosepilachna sparsa),细胸叩头虫(Agriotesfuscicollis),红脚绿金龟(Anomala cupripes),四纹丽金龟(Popillia quadriguttata),马铃薯叶甲(Monolepta hieroglyphica),松天牛(Monochamus alternatus),稻根象(Echinocnemus squameus),泡桐叶甲(Basiprionota bisignata),星天牛(Anoplophorachinensis),桑天牛(Apripona germari),脐腹小蠹(Scolytus schevy),或细胸金针虫(Agriotes fuscicollis);鳞翅目昆虫,如舞毒娥(Lymantria dispar),天幕毛虫(Malacosoma Neustria testacea),黄杨绢野螟(Diaphania perspectalis),大袋蛾(Clania variegata),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,如黑尾叶蝉(Nephotettix cincticeps),稻褐飞虱(Nilaparvatalugens),康氏粉蚧(Pseudococcus comstocki),矢尖蚧(Unaspis yanonensis),桃蚜(Myzus persicae),棉蚜(Aphis gossydii),萝卜蚜(Lipaphis erysimipseudobrassicae),梨班网蝽(Stephanitis nashi),或粉虱(Bemisia tabaci);直翅目昆虫,如德国小蠊(Blattella germanica),美国大蠊(Periplaneta american),非洲蝼蛄(Gryllotalpa africana),或亚洲飞蝗(Locus migratoria);等翅目昆虫,如入侵红火蚁(Solenopsis invicta),或家白蚁(Coptotermes formosanus);双翅目昆虫,如家蝇(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,如微小牛蜱(Boophilus microplus),长角血蜱(Haemaphysalis longicornis),小亚璃眼蜱(Hyalomma anatolicum),牛皮蝇(Hypoderma spp.),肝片吸虫(Fasciola hepatica),贝氏莫尼茨绦虫(Monieziablanchard),奥斯特线虫(Ostertagia spp.),原虫(Trypanosoma enansi,Babesiabigemina),兔球虫(Occidiosis),绦虫(tapeworm),球虫(Coccidium)等。
本发明涉及的化合物尤其对刺吸式、锉吸式、或咀嚼式口器害虫如:蚜虫、叶蝉、飞虱、粉虱、粘虫等农林害虫有特效。
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—块使用的制剂,例如烟熏药筒,烟熏罐和烟熏盘,以及ULV冷雾(Cold mist)和热雾(Warmmist)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,甲基异丁基酮或环已酮;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。
就液化气的稀释剂或载体说,指的是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。
固体载体可用研磨的天然矿物质,例如高岭土,粘土,滑石,石英,活性白土,蒙脱土,或硅藻土,和研磨合成的矿物质,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锆石,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,如偶氮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他活性化合物制成一种混合物存在于它们的商品制剂中或从这些制剂制备的使用剂型中,这些其他的活性化合物为杀虫剂,合饵,杀菌剂,杀螨剂,杀线虫剂,杀真菌剂,生长调节剂等。杀虫剂包括,例如有机磷类,氨基甲酸酯类,拟除虫菊酯类,氯化烃类,昆虫生长调节剂类,沙蚕毒素类、吡蚜酮、鱼尼丁受体抑制剂以及由微生物产生的物质,如阿维菌素。杀菌剂包括三唑类,甲氧基丙烯酸酯类,植物抗病激活剂或杀病毒剂类。
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。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。
本发明化合物的制备方法
本发明的目标化合物(如通式Ⅰ所示)可通过如下的方法制得,然而该方法的条件,例如反应物、溶剂、催化剂、碱、所用化合物的量、反应温度、反应所需时间等不限于下面的解释。本发明的目标化合物还可以通过将在本说明书中描述的或本领域已知的各种合成方法组合起来而方便地制得,这样的组合对本发明所属领域的技术人员而言是很容易进行的。
本发明的目标化合物的制备方法为:由式a和式b所示化合物在催化剂作用下反应得到目标化合物。
所述催化剂为质子酸或路易斯酸,选自下组中的一种或多种:盐酸、醋酸、磷酸、对甲苯磺酸、三氟乙酸、三氯乙酸、三氟化硼、三氯化铝、三氯化铁、硼酸、硅酸、硝酸、氯化镁、氯化钴、氯化锶、氯化钯、或氯化镍(优选硼酸)。
反应溶剂包括但不限于乙腈、甲醇、四氢呋喃、乙醇、水、1,4-二氧六环、丙酮、二氯甲烷、或1,2-二氯乙烷(优选乙腈)。
所述反应在-20-80℃下进行(优选15-55℃)。
所述反应时间为2-96小时(优选24-48小时)。
本发明的主要优点包括:
(1)本发明提供了一类结构新颖的化合物,且该类化合物具有显著的杀虫活性;
(2)本发明提供的化合物具有简单易得的合成方法。
(3)本发明化合物具有扩大的杀虫谱,尤其对桃蚜和粘虫都表现出了显著的杀虫活性。
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。
实施例1 2-氯-5-(((E)-2-((E)-1-硝基-3-苯基烯丙叉)咪唑烷-1-基)甲基)吡啶的合成
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.600g(5mmol)的苯乙醛。反应24小时后,除去溶剂,柱层析分离得到淡黄色粉末状纯品,产率为90%。mp=141.1-141.8℃;1HNMR(400MHz,DMSO)δ9.82(s,1H),8.38(d,J=2.4Hz,1H),7.83(dd,J=8.2,2.4Hz,1H),7.51(d,J=8.2Hz,1H),7.34–7.20(m,4H),7.14(d,J=16.4Hz,1H),7.11–7.07(m,1H),6.39(d,J=16.4Hz,1H),4.53(s,2H),3.96–3.73(m,4H).13C NMR(101MHz,DMSO)δ162.85,149.67,149.18,139.39,138.10,130.32,128.58,126.12,125.15,124.15,121.02,119.74,105.41,48.55,47.88,42.41.HRMS(ESI)C18H17N4O2Na35Cl(M+Na)+,计算值:379.0938,实测值:379.0937;C18H17N4O2Na37Cl(M+Na)+,计算值:381.0908,实测值:381.0905.
实施例2 2-氯-5-(((E)-2-((E)-1-硝基-3-(邻甲基苯基)烯丙叉)咪唑烷-1-基)甲基)吡啶
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.670g(5mmol)的2-甲基苯乙醛。反应24小时后,除去溶剂,柱层析分离得到淡黄色粉末状纯品,产率为85%。mp=148.6-149.2℃;1H NMR(400MHz,DMSO)δ9.77(s,1H),8.38(d,J=2.4Hz,1H),7.82(dd,J=8.2,2.4Hz,1H),7.50(d,J=8.2Hz,1H),7.29(d,J=7.6Hz,1H),7.13–7.00(m,3H),6.97(d,J=16.2Hz,1H),6.56(d,J=16.2Hz,1H),4.55(s,2H),3.96–3.75(m,4H),2.24(s,3H).13C NMR(101MHz,DMSO)δ163.37,149.60,149.21,139.26,137.19,133.98,130.74,130.11,125.97,125.75,124.10,123.62,122.42,116.80,105.68,48.72,48.31,42.45,19.53.HRMS(ESI)C19H19N4O2Na35Cl(M+Na)+,计算值:393.1094,实测值:393.1095;C19H19N4O2Na37Cl(M+Na)+,计算值:395.1065,实测值:395.1069.
实施例3 2-氯-5-(((E)-2-((E)-1-硝基-3-(间甲基苯基)烯丙叉)咪唑烷-1-基)甲基)吡啶
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.670g(5mmol)的3-甲基苯乙醛。反应24小时后,除去溶剂,柱层析分离得到淡黄色粉末状纯品,产率为88%。mp=135.2-135.7℃;1H NMR(400MHz,DMSO)δ9.79(s,1H),8.38(d,J=2.4Hz,1H),7.83(dd,J=8.2,2.4Hz,1H),7.51(d,J=8.2Hz,1H),7.14–7.01(m,4H),6.91(d,J=7.2Hz,1H),6.37(d,J=16.4Hz,1H),4.53(s,2H),3.92–3.76(m,4H),2.25(s,3H).13C NMR(101MHz,DMSO)δ167.80,163.23,149.63,149.20,139.30,138.36,137.48,133.79,133.52,133.21,132.63,128.41,124.15,121.12,105.27,48.61,45.14,42.50,20.96.HRMS(ESI)C19H19N4O2Na35Cl(M+Na)+,计算值:393.1094,实测值:393.1093;C19H19N4O2Na37Cl(M+Na)+,计算值:395.1065,实测值:395.1062.
实施例4 2-氯-5-(((E)-2-((E)-1-硝基-3-(对甲基苯基)烯丙叉)咪唑烷-1-基)甲基)吡啶
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.670g(5mmol)的4-甲基苯乙醛。反应24小时后,除去溶剂,柱层析分离得到淡黄色粉末状纯品,产率为91%。mp=145.4-145.8℃;1H NMR(400MHz,DMSO)δ9.78(s,1H),8.37(d,J=2.0Hz,1H),7.82(dd,J=8.2,2.4Hz,1H),7.50(d,J=8.2Hz,1H),7.19–7.03(m,5H),6.36(d,J=16.4Hz,1H),4.52(s,2H),3.95–3.72(m,4H),2.27(s,3H).13C NMR(101MHz,DMSO)δ163.27,149.62,149.26,139.33,135.69,134.98,130.67,129.13,125.00,124.12,120.56,119.28,105.21,48.60,48.25,42.45,20.68.HRMS(ESI)C19H19N4O2Na35Cl(M+Na)+,计算值:393.1094,实测值:393.1093;C19H19N4O2Na37Cl(M+Na)+,计算值:395.1065,实测值:395.1066.
实施例5 2-氯-5-(((E)-2-((E)-3-(3-甲氧基苯基)-1-硝基烯丙叉)咪唑烷-1-基)甲基)吡啶
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.750g(5mmol)的3-甲氧基苯乙醛。反应24小时后,除去溶剂,柱层析分离得到淡黄色粉末状纯品,产率为80%。mp=132.4-132.9℃;1H NMR(400MHz,DMSO)δ9.79(s,1H),8.35(d,J=2.2Hz,1H),7.83(dd,J=8.2,2.4Hz,1H),7.46(d,J=8.2Hz,1H),7.30–7.27(m,1H),7.11–7.03(m,2H),6.88(d,J=8.2Hz,1H),6.81(t,J=7.4Hz,1H),6.60(d,J=16.4Hz,1H),4.50(s,2H),3.86–3.69(m,4H),3.67(s,3H).13C NMR(101MHz,DMSO)δ163.28,155.64,149.60,149.19,139.23,130.33,127.21,126.63,125.01,124.23,121.51,120.48,114.79,111.10,105.93,55.29,48.61,48.11,42.58.HRMS(ESI)C19H19N4O3Na35Cl(M+Na)+,计算值:409.1043,实测值:409.1042;C19H19N4O3Na37Cl(M+Na)+,计算值:411.1014,实测值:411.1018.
实施例6 2-氯-5-(((E)-2-((E)-3-(2,6-二甲基苯基)-1-硝基烯丙叉)咪唑烷-1-基)甲基)吡啶
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.810g(5mmol)的2,4,6-三甲基苯乙醛。反应24小时后,除去溶剂,柱层析分离得到淡黄色粉末状纯品,产率为91%。mp=155.1-155.7℃;1H NMR(400MHz,DMSO)δ9.59(s,1H),8.32(d,J=2.4Hz,1H),7.81(dd,J=8.2,2.4Hz,1H),7.40(d,J=8.2Hz,1H),7.31(d,J=7.4Hz,1H),7.16–7.01(m,1H),6.90(d,J=16.4Hz,1H),6.52(d,J=16.4Hz,1H),4.53(s,2H),3.91–3.72(m,4H),2.38(s,3H),2.20(s,3H),2.03(s,3H).13C NMR(101MHz,DMSO)δ163.67,149.62,149.31,139.27,137.23,133.97,130.12,125.95,125.71,124.13,123.68,122.44,116.90,105.66,48.73,48.31,42.42,20.91,19.55,18.92.HRMS(ESI)C21H23N4O2Na35Cl(M+Na)+,计算值:421.1407,实测值:421.1408;C21H23N4O2Na37Cl(M+Na)+,计算值:423.1378,实测值:423.1379.
实施例7 2-氯-5-(((E)-2-((E)-1-硝基-3-(噻吩-2-基)烯丙叉)咪唑烷-1-基)甲基)吡啶
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.630g(5mmol)的噻吩-2-乙醛。反应24小时后,除去溶剂,柱层析分离得到黄绿色粉末状纯品,产率为84%。mp=141.2-141.6℃;1H NMR(400MHz,DMSO)δ9.79(s,1H),8.39(d,J=2.4Hz,1H),7.84(dd,J=8.2,2.4Hz,1H),7.52(d,J=8.2Hz,1H),7.24(d,J=5.0Hz,1H),6.96–6.92(m,1H),6.91–6.83(m,2H),6.65(d,J=16.0Hz,1H),4.52(s,2H),3.90–3.73(m,4H).13C NMR(101MHz,DMSO)δ163.08,149.65,149.30,144.31,139.38,130.55,127.76,124.13,123.43,122.70,121.09,112.84,104.77,48.58,48.25,42.46.HRMS(ESI)C16H15N4O2NaS35Cl(M+Na)+,计算值:385.0502,实测值:385.0504;C16H15N4O2NaS37Cl(M+Na)+,计算值:387.0472,实测值:387.0473.
实施例8 2-氯-5-(((E)-2-((E)-3-(5-甲基噻吩-2-基)-1-硝基烯丙叉)咪唑烷-1-基)甲基)吡啶
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.700g(5mmol)的5-甲基噻吩-2-乙醛。反应24小时后,除去溶剂,柱层析分离得到黄绿色粉末状纯品,产率为87%。mp=147.3-147.8℃;1H NMR(400MHz,DMSO)δ9.71(s,1H),8.33(d,J=2.4Hz,1H),7.82(dd,J=8.2,2.4Hz,1H),7.50(d,J=8.2Hz,1H),7.25(d,J=5.0Hz,1H),6.93–6.88(m,1H),6.91–6.83(m,1H),6.63(d,J=16.0Hz,1H),4.50(s,2H),3.91–3.72(m,4H),2.18(s,3H).13C NMR(101MHz,DMSO)δ163.15,149.66,149.39,144.38,139.32,130.45,124.16,123.41,122.77,121.06,112.83,105.27,48.48,48.23,42.41,20.15.HRMS(ESI)C17H17N4O2NaS35Cl(M+Na)+,计算值:399.0658,实测值:399.0659;C17H17N4O2NaS37Cl(M+Na)+,计算值:401.0629,实测值:401.0631.
实施例9 2-氯-5-(((E)-2-((E)-3-(呋喃-2-基)-1-硝基烯丙叉)咪唑烷-1-基)甲基)吡啶
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.550g(5mmol)的呋喃-2-乙醛。反应24小时后,除去溶剂,柱层析分离得到淡黄色粉末状纯品,产率为90%。mp=142.4-142.9℃;1H NMR(400MHz,DMSO)δ9.80(s,1H),8.41(d,J=2.2Hz,1H),7.82(dd,J=8.2,2.2Hz,1H),7.51(d,J=8.2Hz,1H),7.26(d,J=4.8Hz,1H),6.98–6.93(m,1H),6.90–6.82(m,2H),6.60(d,J=16.2Hz,1H),4.49(s,2H),3.95–3.74(m,4H).13C NMR(101MHz,DMSO)δ163.09,149.66,149.32,144.32,139.40,130.52,127.75,124.03,123.23,122.58,121.01,112.80,105.27,48.48,48.24,42.43.HRMS(ESI)C16H15N4O3Na35Cl(M+Na)+,计算值:369.0730,实测值:369.0731;C16H15N4O3Na37Cl(M+Na)+,计算值:371.0701,实测值:371.0703.
实施例10 2-氯-5-(((E)-2-((E)-1-硝基-3-(1H-吡咯-2-基)烯丙叉)咪唑烷-1-基)甲基)吡啶
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.545g(5mmol)的吡咯-2-乙醛。反应24小时后,除去溶剂,柱层析分离得到淡黄色粉末状纯品,产率为85%。mp=149.8-150.7℃;1H NMR(400MHz,DMSO)δ10.93(s,1H),9.76(s,1H),8.42(d,J=2.4Hz,1H),7.84(dd,J=8.4,2.4Hz,1H),7.52(d,J=8.4Hz,1H),7.25(d,J=4.8Hz,1H),6.96–6.91(m,1H),6.88–6.83(m,2H),6.65(d,J=16.4Hz,1H),4.56(s,2H),3.99–3.78(m,4H).13C NMR(101MHz,DMSO)δ163.19,149.62,149.36,144.35,139.41,130.51,127.69,124.07,123.23,122.59,121.02,112.81,104.99,48.45,48.22,42.42.HRMS(ESI)C16H16N5O2Na35Cl(M+Na)+,计算值:368.0890,实测值:368.0891;C16H16N5O2Na37Cl(M+Na)+,计算值:370.0861,实测值:370.0862.
实施例11 2-氯-5-(((E)-2-((E)-1-硝基-3-(噻吩-3-基)烯丙叉)咪唑烷-1-基)甲基)吡啶
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.630g(5mmol)的噻吩-3-乙醛。反应24小时后,除去溶剂,柱层析分离得到黄绿色粉末状纯品,产率为93%。mp=146.2-146.6℃;1H NMR(400MHz,DMSO)δ9.75(s,1H),8.37(d,J=2.4Hz,1H),7.83(dd,J=8.2,2.4Hz,1H),7.51(d,J=8.2Hz,1H),7.44(dd,J=5.0,3.0Hz,1H),7.22–7.12(m,2H),6.95(d,J=16.4Hz,1H),6.46(d,J=16.4Hz,1H),4.52(s,2H),3.92–3.72(m,4H).13C NMR(101MHz,DMSO)δ163.17,149.63,149.29,141.09,139.37,130.62,126.43,124.53,124.15,121.40,119.46,114.69,104.81,48.54,48.19,42.44.HRMS(ESI)C16H15N4O2NaS35Cl(M+Na)+,计算值:385.0502,实测值:385.0501;C16H15N4O2NaS37Cl(M+Na)+,计算值:387.0472,实测值:387.0474.
实施例12 4-((1E,3E)-3-(1-((6-氯吡啶-3-基)甲基)咪唑烷-2-烯丙叉)-3-硝基-1-基)噻唑
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.635g(5mmol)的噻唑-2-乙醛。反应24小时后,除去溶剂,柱层析分离得到淡黄色粉末状纯品,产率为78%。mp=161.2-161.8℃;1H NMR(400MHz,DMSO)δ9.79(s,1H),8.36(d,J=2.4Hz,1H),7.85(dd,J=8.2,2.4Hz,1H),7.53(d,J=8.2Hz,1H),7.48(dd,J=5.0,3.0Hz,1H),7.24–7.13(m,1H),6.99(d,J=16.2Hz,1H),6.47(d,J=16.2Hz,1H),4.51(s,2H),3.96–3.71(m,4H).13C NMR(101MHz,DMSO)δ163.09,149.62,149.27,141.19,139.39,130.61,126.44,124.18,121.41,119.56,114.73,104.85,48.50,48.22,42.34.HRMS(ESI)C15H14N5O2NaS35Cl(M+Na)+,计算值:386.0454,实测值:386.0455;C15H14N5O2NaS37Cl(M+Na)+,计算值:388.0425,实测值:388.0426.
实施例13 2-氯-5-(((E)-2-((E)-1-硝基-3-(4H-1,2,4-三氮唑-3-基)烯丙叉)咪唑烷-1-基)甲基)吡啶
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.555g(5mmol)的4H-1,2,4-三唑-3-乙醛。反应24小时后,除去溶剂,柱层析分离得到淡黄色粉末状纯品,产率为84%。mp=159.8-160.7℃;1H NMR(400MHz,DMSO)δ10.79(s,1H),9.77(s,1H),8.34(d,J=2.4Hz,1H),7.86(dd,J=8.2,2.4Hz,1H),7.53(d,J=8.2Hz,1H),7.27–7.14(m,1H),6.98(d,J=16.2Hz,1H),6.37(d,J=16.2Hz,1H),4.50(s,2H),3.97–3.72(m,4H).13C NMR(101MHz,DMSO)δ163.11,149.66,149.19,141.15,139.43,126.40,124.19,121.47,119.53,114.71,104.77,48.51,48.24,42.36.HRMS(ESI)C14H14N7O2Na35Cl(M+Na)+,计算值:370.0795,实测值:370.0796;C14H14N7O2Na37Cl(M+Na)+,计算值:372.0766,实测值:372.0767.
实施例14 2-氯-5-(((E)-2-((E)-1-硝基-3-(吡啶-2-基)烯丙叉)咪唑烷-1-基)甲基)吡啶
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.605g(5mmol)的吡啶-2-乙醛。反应24小时后,除去溶剂,柱层析分离得到黄色粉末状纯品,产率为81%。mp=156.3-156.9℃;1HNMR(400MHz,DMSO)δ9.85(s,1H),8.40(d,J=2.4Hz,1H),7.85(dd,J=8.2,2.4Hz,1H),7.50(d,J=8.2Hz,1H),7.35–7.21(m,2H),7.18(d,J=16.2Hz,1H),7.14–7.09(m,2H),6.34(d,J=16.2Hz,1H),4.51(s,2H),3.96–3.74(m,4H).13C NMR(101MHz,DMSO)δ163.25,149.77,149.17,139.36,138.11,136.40,130.36,128.58,126.13,125.19,124.14,121.03,119.77,105.42,48.54,47.82,42.44.HRMS(ESI)C17H16N5O2Na35Cl(M+Na)+,计算值:380.0890,实测值:380.0892;C17H16N5O2Na37Cl(M+Na)+,计算值:382.0861,实测值:382.0862.
实施例15 2-氯-5-(((E)-2-((E)-3-(5-氯吡啶-2-基)-1-硝基烯丙叉)咪唑烷-1-基)甲基)吡啶
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.775g(5mmol)的5-氯-2-吡啶乙醛。反应24小时后,除去溶剂,柱层析分离得到黄色粉末状纯品,产率为80%。mp=163.5-164.6℃;1H NMR(400MHz,DMSO)δ9.91(s,1H),8.45(d,J=2.2Hz,1H),7.84(dd,J=8.2,2.2Hz,1H),7.51(d,J=8.2Hz,1H),7.35–7.22(m,2H),7.17(d,J=16.4Hz,1H),7.13–7.08(m,1H),6.39(d,J=16.4Hz,1H),4.52(s,2H),3.95–3.73(m,4H).13C NMR(101MHz,DMSO)δ163.15,149.76,149.18,139.37,138.11,136.45,130.33,128.68,126.16,125.49,125.14,121.05,119.78,105.32,48.64,47.88,42.45.HRMS(ESI)C17H15N5O2Na35Cl2(M+Na)+,计算值:414.0500,实测值:414.0501;C17H15N5O2Na35Cl 37Cl(M+Na)+,计算值:416.0471,实测值:416.0472;C17H15N5O2Na37Cl2(M+Na)+,计算值:418.0508,实测值:418.0507.
实施例16 2-氯-5-(((E)-2-((E)-3-环己基-1-硝基烯丙叉)咪唑烷-1-基)甲基)吡啶
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.630g(5mmol)的环己烷乙醛。反应24小时后,除去溶剂,柱层析分离得到黄色粉末状纯品,产率为88%。mp=153.2-153.9℃;1HNMR(400MHz,DMSO)δ9.54(s,1H),8.34(d,J=2.4Hz,1H),7.77(dd,J=8.2,2.4Hz,1H),7.52(d,J=8.2Hz,1H),6.17(dd,J=16.2,1.0Hz,1H),5.41(dd,J=16.2,6.8Hz,1H),4.52(s,2H),3.83–3.63(m,4H),1.87–1.76(m,1H),1.64–1.53(m,4H),1.29–0.98(m,4H),0.96–0.84(m,2H).13C NMR(101MHz,DMSO)δ163.02,149.47,148.92,138.94,131.11,130.54,124.10,119.76,104.80,48.95,48.71,42.36,40.52,32.58,25.63,25.51.HRMS(ESI)C18H23N4O2Na35Cl(M+Na)+,计算值:385.1407,实测值:385.1408;C18H23N4O2Na37Cl(M+Na)+,计算值:387.1378,实测值:387.1378.
实施例17 2-氯-5-(((E)-2-((E)-3-环戊基-1-硝基烯丙叉)咪唑烷-1-基)甲基)吡啶
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.560g(5mmol)的环戊烷乙醛。反应24小时后,除去溶剂,柱层析分离得到黄色粉末状纯品,产率为84%。mp=139.9-140.6℃;1HNMR(400MHz,DMSO)δ9.59(s,1H),8.44(d,J=2.4Hz,1H),7.78(dd,J=8.2,2.4Hz,1H),7.55(d,J=8.2Hz,1H),6.18(d,J=16.4Hz,1H),5.81(d,J=16.4Hz,1H),4.51(s,2H),3.93–3.75(m,4H),1.88–1.76(m,1H),1.63–1.52(m,4H),1.27–0.96(m,4H).13C NMR(101MHz,DMSO)δ163.32,149.48,148.91,138.92,131.14,130.56,124.10,119.79,104.88,48.85,48.72,42.46,40.42,32.68,25.66.HRMS(ESI)C17H21N4O2Na35Cl(M+Na)+,计算值:371.1251,实测值:371.1252;C17H21N4O2Na37Cl(M+Na)+,计算值:373.1221,实测值:373.1222.
实施例18 2-氯-5-(((E)-2-((E)-3-(3-甲氧基苯基)-1-硝基烯丙叉)咪唑烷-1-基)甲基)噻唑
将0.520g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)噻唑加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.750g(5mmol)的3-甲氧基苯乙醛。反应24小时后,除去溶剂,柱层析分离得到黄色粉末状纯品,产率为82%。mp=127.6-128.1℃;1H NMR(400MHz,DMSO)δ9.64(s,1H),7.67(s,1H),7.40(dd,J=7.6,1.2Hz,1H),7.18–7.07(m,2H),6.95(d,J=8.0Hz,1H),6.88(t,J=7.4Hz,1H),6.75(d,J=16.6Hz,1H),4.66(s,2H),3.86–3.79(m,4H),3.79(s,3H).13C NMR(101MHz,DMSO)δ162.66,155.67,151.61,141.74,134.75,127.16,127.02,124.98,121.75,120.58,115.34,111.15,106.05,55.34,48.19,44.33,42.28.HRMS(ESI)C17H18N4O3S35Cl(M+H)+,计算值:393.0788,实测值:393.0787;C17H18N4O3S37Cl(M+H)+,计算值:395.0759,实测值:395.0756.
实施例19 2-氯-5-(((E)-2-((E)-3-环己基-1-硝基烯丙叉)咪唑烷-1-基)甲基)噻唑
将0.520g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)噻唑加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.630g(5mmol)的环己烷乙醛。反应24小时后,除去溶剂,柱层析分离得到黄色粉末状纯品,产率为87%。mp=128.3-128.7℃;1HNMR(400MHz,DMSO)δ9.39(s,1H),7.66(s,1H),6.25(dd,J=16.2,0.8Hz,1H),5.54(dd,J=16.2,6.8Hz,1H),4.64(s,2H),3.79–3.64(m,4H),2.01–1.90(m,1H),1.70–1.62(m,4H),1.27–0.99(m,6H).13C NMR(101MHz,DMSO)δ162.34,151.20,141.30,135.20,131.30,119.67,105.07,48.39,44.52,42.20,40.72,32.66,25.66,25.52.HRMS(ESI)C16H21N4O2NaS35Cl(M+Na)+,计算值:391.0971,实测值:391.0972;C16H21N4O2NaS37Cl(M+Na)+,计算值:393.0942,实测值:393.0947.
实施例20 2-氯-5-(((E)-2-((E)-1-硝基-3-(噻吩-2-基)烯丙叉)咪唑烷-1-基)甲基)噻唑
将0.520g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)噻唑加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.630g(5mmol)的噻唑-2-乙醛。反应24小时后,除去溶剂,柱层析分离得到墨绿色粉末状纯品,产率为80%。mp=133.3-133.9℃;1H NMR(400MHz,DMSO)δ9.68(s,1H),7.70(s,1H),7.27(d,J=5.0Hz,1H),6.99–6.94(m,1H),6.94–6.86(m,2H),6.76(d,J=16.0Hz,1H),4.64(s,2H),3.88–3.72(m,4H).13C NMR(101MHz,DMSO)δ162.43,151.69,144.30,141.82,134.66,127.81,123.61,122.88,121.07,113.72,105.02,48.19,44.32,42.30.HRMS(ESI)C14H13N4O2NaS2 35Cl(M+Na)+,计算值:391.0066,实测值:391.0067;C14H13N4O2NaS2 37Cl(M+Na)+,计算值:393.0037,实测值:393.0040.
实施例21 2-氯-5-(((E)-2-((E)-3-(5-甲基噻吩-2-基)-1-硝基烯丙叉)咪唑烷-1-基)甲基)噻唑
将0.520g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)噻唑加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.710g(5mmol)的4-甲基噻唑-2-乙醛。反应24小时后,除去溶剂,柱层析分离得到黄色粉末状纯品,产率为85%。mp=137.7-138.3℃;1H NMR(400MHz,DMSO)δ9.70(s,1H),7.71(s,1H),6.99–6.94(m,1H),6.94–6.86(m,2H),6.78(d,J=16.0Hz,1H),4.66(s,2H),3.89–3.71(m,4H),1.86(s,3H).13C NMR(101MHz,DMSO)δ162.49,152.19,144.50,141.92,134.65,127.82,123.65,122.93,121.01,113.81,105.13,48.30,44.22,42.31,15.32.HRMS(ESI)C15H15N4O2NaS2 35Cl(M+Na)+,计算值:405.0223,实测值:405.0224;C15H15N4O2NaS2 37Cl(M+Na)+,计算值:407.0193,实测值:407.0194.
实施例22 2-氯-5-(((E)-2-((E)-3-(呋喃-2-基)-1-硝基烯丙叉)咪唑烷-1-基)甲基)噻唑
将0.520g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)噻唑加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.550g(5mmol)的呋喃-2-乙醛。反应24小时后,除去溶剂,柱层析分离得到黄色粉末状纯品,产率为82%。mp=140.3-140.9℃;1HNMR(400MHz,DMSO)δ9.65(s,1H),7.71(s,1H),7.26(d,J=5.2Hz,1H),6.98–6.92(m,1H),6.91–6.82(m,2H),6.74(d,J=16.0Hz,1H),4.60(s,2H),3.87–3.73(m,4H).13C NMR(101MHz,DMSO)δ162.44,151.79,144.35,141.85,134.64,127.80,123.63,122.88,121.12,113.76,105.01,48.22,44.35,42.28.HRMS(ESI)C14H13N4O3NaS35Cl(M+Na)+,计算值:375.0295,实测值:375.0296;C14H13N4O3NaS37Cl(M+Na)+,计算值:377.0265,实测值:377.0267.
实施例23 2-氯-5-(((E)-2-((E)-3-2,4,6-三甲基苯基-1-硝基烯丙叉)咪唑烷-1-基)甲基)噻唑
将0.520g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)噻唑加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.810g(5mmol)的2,4,6-三甲基苯基乙醛。反应24小时后,除去溶剂,柱层析分离得到黄色粉末状纯品,产率为89%。mp=147.0-147.6℃;1H NMR(400MHz,DMSO)δ9.66(s,1H),7.74(s,1H),7.26(d,J=5.0Hz,1H),7.18–7.02(m,2H),6.75(d,J=16.0Hz,1H),4.59(s,2H),3.88–3.72(m,4H),2.60(s,9H).13C NMR(101MHz,DMSO)δ163.04,151.89,144.32,141.83,134.67,133.10,132.88,127.80,123.63,122.88,121.12,113.76,105.11,48.24,44.34,42.26,22.11,21.28,20.11.HRMS(ESI)C19H21N4O2NaS35Cl(M+Na)+,计算值:427.0971,实测值:427.0972;C19H21N4O2NaS37Cl(M+Na)+,计算值:429.0942,实测值:429.0944.
实施例24(E)-2-((E)-1-硝基-3-(噻吩-2-基)烯丙叉)-1-((四氢呋喃-3-基)甲基)咪唑烷
将0.426g(2mmol)的(2-(硝基亚甲基)-1-(四氢呋喃-3-基)甲基)咪唑烷加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.630g(5mmol)的噻唑-2-乙醛。反应24小时后,除去溶剂,柱层析分离得到黄色粉末状纯品,产率为80%。mp=131.1-131.9℃;1HNMR(400MHz,DMSO)δ9.58(s,1H),7.26(d,J=5.0Hz,1H),7.18–7.02(m,3H),6.76(d,J=16.0Hz,1H),4.59(s,2H),4.26–4.05(m,4H),3.88–3.72(m,4H),2.31(m,1H),1.63(m,2H).13C NMR(101MHz,DMSO)δ151.69,144.31,141.86,134.68,132.84,127.85,113.73,105.21,80.16,78.55,48.24,44.32,42.26,33.11,20.28.HRMS(ESI)C15H19N3O3NaS(M+Na)+,计算值:344.1045,实测值:344.1046.
实施例25(E)-2-((E)-1-硝基-3-(间甲基苯基)烯丙叉)-1-((四氢呋喃-3-基)甲基)咪唑烷
将0.426g(2mmol)的(2-(硝基亚甲基)-1-(四氢呋喃-3-基)甲基)咪唑烷加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.670g(5mmol)的3-甲基苯乙醛。反应24小时后,除去溶剂,柱层析分离得到黄色粉末状纯品,产率为92%。mp=134.4-135.3℃;1HNMR(400MHz,DMSO)δ9.61(s,1H),7.35(d,J=5.0Hz,1H),7.22(d,J=4.8Hz,1H),7.19–7.01(m,3H),6.68(d,J=16.0Hz,1H),4.53(s,2H),4.21–4.02(m,4H),3.86–3.71(m,4H),2.31(m,1H),2.11(s,3H),1.62(m,2H).13CNMR(101MHz,DMSO)δ152.65,144.30,141.76,134.63,134.26,133.66,132.84,127.82,113.71,105.11,80.12,78.59,48.34,44.36,42.29,33.18,20.33,15.81.HRMS(ESI)C18H23N3O3Na(M+Na)+,计算值:352.1637,实测值:352.1638.
实施例26 5-(((E)-2-((E)-1-硝基-3-(噻吩-2-基)烯丙叉)咪唑烷-1-基)甲基)-2-(三氟甲基)吡啶
将0.576g(2mmol)的2-三氟甲基-5-((2-(硝基亚甲基)咪唑啉-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.630g(5mmol)的噻唑-2-乙醛。反应24小时后,除去溶剂,柱层析分离得到黄色粉末状纯品,产率为82%。mp=145.2-145.8℃;1H NMR(400MHz,DMSO)δ9.61(s,1H),7.88(m,2H),7.25(d,J=5.0Hz,1H),7.19–7.02(m,4H),6.72(d,J=16.0Hz,1H),4.49(s,2H),3.86–3.68(m,4H).13C NMR(101MHz,DMSO)δ160.25,151.69,144.31,143.28,143.01,141.86,134.68,134.54,134.21,132.84,127.85,113.73,105.21,80.16,48.24,44.32,42.26.HRMS(ESI)C17H15N4O2NaSF3(M+Na)+,计算值:419.0766,实测值:419.0767.
实施例27 5-(((E)-2-((E)-1-硝基-3-(间甲基苯基)烯丙叉)咪唑烷-1-基)甲基)-2-(三氟甲基)吡啶
将0.576g(2mmol)的2-三氟甲基-5-((2-(硝基亚甲基)咪唑啉-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.670g(5mmol)的3-甲基苯乙醛。反应24小时后,除去溶剂,柱层析分离得到黄色粉末状纯品,产率为85%。mp=149.1-150.1℃;1HNMR(400MHz,DMSO)δ9.67(s,1H),7.79(m,2H),7.26(d,J=5.0Hz,1H),7.19–7.02(m,5H),6.74(d,J=16.0Hz,1H),4.51(s,2H),3.91–3.78(m,4H),2.79(s,3H).13C NMR(101MHz,DMSO)δ160.25,151.72,144.33,143.27,143.01,141.86,134.68,134.54,134.21,133.95,133.64,132.84,127.85,113.73,105.21,80.16,48.24,44.32,42.26,20.15.HRMS(ESI)C20H19N4O2NaF3(M+Na)+,计算值:427.1358,实测值:427.1359.
实施例28(E)-1-((6-氯吡啶-3-基)甲基)-2-((E)-1-硝基-3-(间甲基苯基)烯丙叉)六氢嘧啶
将0.536g(2mmol)的1-(6-氯-3-甲基吡啶基)-2-硝基亚甲基六氢嘧啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.670g(5mmol)的3-甲基苯乙醛。反应24小时后,除去溶剂,柱层析分离得到黄色粉末状纯品,产率为86%。mp=144.2-144.9℃;1HNMR(400MHz,DMSO)δ9.77(s,1H),8.36(d,J=2.2Hz,1H),7.86(dd,J=8.2,2.2Hz,1H),7.51(d,J=8.2Hz,1H),7.16–7.05(m,4H),6.91(d,J=7.2Hz,1H),6.44(d,J=16.4Hz,1H),4.52(s,2H),3.91–3.78(m,4H),2.35(s,3H),1.99–1.89(m,2H).13C NMR(101MHz,DMSO)δ167.80,163.23,149.63,149.20,139.30,138.36,137.48,133.79,133.52,133.21,132.63,128.41,124.15,121.12,105.27,48.61,45.45,45.14,42.50,20.96.HRMS(ESI)C20H21N4O2Na35Cl(M+Na)+,计算值:407.1251,实测值:407.1252;C20H21N4O2Na37Cl(M+Na)+,计算值:409.1221,实测值:409.1222.
实施例29(E)-1-((6-氯吡啶-3-基)甲基)-2-((E)-1-硝基-3-(噻吩-2-基)烯丙叉)六氢嘧啶
将0.536g(2mmol)的1-(6-氯-3-甲基吡啶基)-2-硝基亚甲基六氢嘧啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.630g(5mmol)的噻吩-2-乙醛。反应24小时后,除去溶剂,柱层析分离得到黄绿色粉末状纯品,产率为90%。mp=132.2-133.1℃;1HNMR(400MHz,DMSO)δ9.76(s,1H),8.39(d,J=2.4Hz,1H),7.84(dd,J=8.2,2.4Hz,1H),7.51(d,J=8.2Hz,1H),7.45(dd,J=5.0,3.0Hz,1H),7.22–7.12(m,2H),6.85(d,J=16.4Hz,1H),6.46(d,J=16.4Hz,1H),4.50(s,2H),3.92–3.72(m,4H),1.97–1.87(m,2H).13C NMR(101MHz,DMSO)δ163.17,149.63,149.29,141.09,139.37,130.62,126.43,124.53,124.15,121.40,119.46,114.69,104.81,48.54,48.19,48.01,42.44.HRMS(ESI)C17H17N4O2NaS35Cl(M+Na)+,计算值:399.0658,实测值:399.0659;C17H17N4O2NaS37Cl(M+Na)+,计算值:401.0629,实测值:401.0630.
实施例30(1E,3E)-N-((6-氯吡啶-3-基)甲基)-N-乙基-N'-甲基-2-硝基-4-(噻吩-2-基)丁-1,3-二烯-1,1-二胺
将0.540g(2mmol)的N-((6-氯吡啶-3-基)甲基)-N-乙基-N-甲基-2-硝基乙烯-1,1-二胺加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.630g(5mmol)的噻吩-2-乙醛。反应24小时后,除去溶剂,柱层析分离得到黄绿色粉末状纯品,产率为78%。mp=121.2-121.9℃;1H NMR(400MHz,DMSO)δ9.78(s,1H),8.32(d,J=2.4Hz,1H),7.80(dd,J=8.2,2.4Hz,1H),7.54(d,J=8.2Hz,1H),7.24(d,J=5.0Hz,1H),6.96–6.92(m,1H),6.91–6.83(m,2H),6.62(d,J=16.0Hz,1H),4.53(s,2H),3.24(m,2H),2.10(m,3H),1.45(s,3H).13C NMR(101MHz,DMSO)δ163.18,149.67,149.32,144.30,139.35,130.56,127.76,124.15,123.44,122.71,121.04,112.82,104.97,48.48,28.25,24.46,15.26.HRMS(ESI)C17H19N4O2NaS35Cl(M+Na)+,计算值:401.0815,实测值:401.0816;C17H19N4O2NaS37Cl(M+Na)+,计算值:403.0785,实测值:403.0786.
实施例31(1E,3E)-N-((6-氯吡啶-3-基)甲基)-N-乙基-N'-甲基-2-硝基-4-(间甲基苯基)丁-1,3-二烯-1,1-二胺
将0.540g(2mmol)的N-((6-氯吡啶-3-基)甲基)-N-乙基-N-甲基-2-硝基乙烯-1,1-二胺加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.670g(5mmol)的3-甲基苯乙醛。反应24小时后,除去溶剂,柱层析分离得到黄色粉末状纯品,产率为81%。mp=124.2-124.9℃;1H NMR(400MHz,DMSO)δ9.74(s,1H),8.38(d,J=2.4Hz,1H),7.86(dd,J=8.2,2.4Hz,1H),7.51(d,J=8.2Hz,1H),7.14–7.02(m,4H),6.88(d,J=7.2Hz,1H),6.49(d,J=16.4Hz,1H),4.53(s,2H),3.25(m,2H),2.14(m,3H),2.35(s,3H),1.46(s,3H).13C NMR(101MHz,DMSO)δ167.83,163.26,149.64,149.21,139.34,138.37,137.48,133.79,133.53,133.21,132.63,128.41,124.15,121.12,105.19,48.61,25.45,22.14,20.50,15.96.HRMS(ESI)C20H23N4O2Na35Cl(M+Na)+,计算值:409.1407,实测值:409.1408;C20H23N4O2Na37Cl(M+Na)+,计算值:411.1378,实测值:411.1379.
实施例32 2-氯-5-(((E)-2-((E)-1-硝基-3-(4-硝基苯基)烯丙叉)咪唑烷酮-1-基)甲基)吡啶
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.825g(5mmol)的4-硝基苯乙醛。反应24小时后,除去溶剂,柱层析分离得到淡黄色粉末状纯品,产率为82%。mp=139.8-140.6℃;1H NMR(400MHz,DMSO)δ9.77(s,1H),8.35(d,J=2.0Hz,1H),7.81(dd,J=8.2,2.4Hz,1H),7.51(d,J=8.2Hz,1H),7.18–7.01(m,5H),6.35(d,J=16.4Hz,1H),4.50(s,2H),3.94–3.73(m,4H).13C NMR(101MHz,DMSO)δ163.29,149.58,149.25,139.34,135.66,134.88,130.61,129.17,125.04,124.22,120.46,119.23,105.20,48.61,48.35,42.49.HRMS(ESI)C18H16N5O4Na35Cl(M+Na)+,计算值:424.0789,实测值:424.0790;C18H16N5O4Na37Cl(M+Na)+,计算值:426.0759,实测值:426.0761.
实施例33 2-氯-5-(((E)-2-((E)-3-(4-氟苯基)-1-硝基烯丙叉)咪唑烷酮-1-基)甲基)吡啶
将0.508g(2mmol)的2-氯-5-((2-(硝基亚甲基)咪唑烷-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.690g(5mmol)的4-氟苯乙醛。反应24小时后,除去溶剂,柱层析分离得到黄色粉末状纯品,产率为88%。mp=122.5-123.2℃;1HNMR(400MHz,DMSO)δ9.75(s,1H),8.32(d,J=2.2Hz,1H),7.82(dd,J=8.4,2.2Hz,1H),7.52(d,J=8.4Hz,1H),7.17–7.01(m,5H),6.32(d,J=16.4Hz,1H),4.51(s,2H),3.97–3.75(m,4H).13C NMR(101MHz,DMSO)δ163.31,149.54,149.29,139.35,135.68,134.85,130.61,129.14,125.14,124.18,120.44,119.33,105.21,48.62,48.32,42.44.HRMS(ESI)C18H16N4O2Na35ClF(M+Na)+,计算值:397.0844,实测值:397.0845;C18H16N4O2Na37ClF(M+Na)+,计算值:399.0814,实测值:399.0815.
实施例34(2E,3E)-2-(1-((6-氯吡啶-3-基)甲基)咪唑烷-2-叉)-4-(噻吩-2-基)烯基-3-乙腈
将0.468g(2mmol)的(E)-2-(1-((6-氯吡啶-3-基)甲基)咪唑啉-2-基亚乙烯基)乙腈加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.630g(5mmol)的噻吩-2-乙醛。反应24小时后,除去溶剂,柱层析分离得到黄绿色粉末状纯品,产率为85%。mp=137.2-137.9℃;1H NMR(400MHz,DMSO)δ9.81(s,1H),8.38(d,J=2.2Hz,1H),7.85(dd,J=8.2,2.2Hz,1H),7.50(d,J=8.2Hz,1H),7.22(d,J=5.0Hz,1H),6.97–6.93(m,1H),6.90–6.83(m,2H),6.64(d,J=16.0Hz,1H),4.51(s,2H),3.89–3.72(m,4H).13C NMR(101MHz,DMSO)δ163.18,149.64,149.31,144.32,139.35,130.45,128.55,127.76,124.14,123.42,122.71,121.03,112.80,104.75,48.49,48.20,42.41.HRMS(ESI)C17H15N4NaS35Cl(M+Na)+,计算值:365.0604,实测值:365.0605;C17H15N4NaS37Cl(M+Na)+,计算值:367.0574,实测值:367.0575.
实施例35(3E,4E)-3-(1-((6-氯吡啶-3-基)甲基)咪唑烷-2-叉)-1,1,1-三氟-5-(噻吩-2-基)丙烷-4-E-2-酮
将0.610g(2mmol)的(E)-3-(1-((6-吡啶-3-基)甲基)咪唑啉-2-基亚乙烯基)-1,1,1-三氟丙烷-2-酮加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.630g(5mmol)的噻吩-2-乙醛。反应24小时后,除去溶剂,柱层析分离得到浅黄色粉末状纯品,产率为90%。mp=144.9-145.5℃;1H NMR(400MHz,DMSO)δ9.80(s,1H),8.36(d,J=2.2Hz,1H),7.84(dd,J=8.2,2.2Hz,1H),7.51(d,J=8.2Hz,1H),7.21(d,J=5.0Hz,1H),6.98–6.92(m,1H),6.88–6.83(m,2H),6.62(d,J=16.0Hz,1H),4.50(s,2H),3.88–3.73(m,4H).13CNMR(101MHz,DMSO)δ163.28,149.61,149.32,144.30,139.33,130.44,128.56,127.66,125.75,124.16,123.41,122.73,121.13,112.76,104.73,48.44,48.16,42.39.HRMS(ESI)C18H15N3OF3NaS35Cl(M+Na)+,计算值:436.0474,实测值:436.0475;C18H15N3OF3NaS37Cl(M+Na)+,计算值:438.0445,实测值:438.0446.
实施例36 2-氯-5-(((E)-2-((E)-3-(噻吩-2-基)-1-((三氟甲基)磺酰基)烯丙叉)咪唑烷酮-1-基)甲基)吡啶
将0.682g(2mmol)的(E)-2-氯-5-((2-(((三氟甲基)磺酰基)亚甲基)咪唑啉-1-基)甲基)吡啶加入20ml乙腈中,室温条件下搅拌溶解。10分钟后,慢慢滴加0.630g(5mmol)的噻吩-2-乙醛。反应24小时后,除去溶剂,柱层析分离得到黄绿色粉末状纯品,产率为88%。mp=142.6-143.3℃;1H NMR(400MHz,DMSO)δ9.83(s,1H),8.37(d,J=2.4Hz,1H),7.84(dd,J=8.2,2.4Hz,1H),7.49(d,J=8.2Hz,1H),7.20(d,J=5.0Hz,1H),6.96–6.92(m,1H),6.88–6.83(m,2H),6.64(d,J=16.0Hz,1H),4.50(s,2H),3.89–3.71(m,4H).13C NMR(101MHz,DMSO)δ163.28,149.65,149.30,144.31,139.34,130.46,128.53,127.74,124.15,123.41,122.72,121.04,112.79,104.78,48.46,48.21,42.42.HRMS(ESI)C17H15N3O2F3NaS2 35Cl(M+Na)+,计算值:472.0144,实测值:472.0145;C17H15N3O2F3NaS2 37Cl(M+Na)+,计算值:474.0114,实测值:474.0115.
参考以上实施例的制备方法获得表1中所示的其他化合物。
实施例37: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(Aphiscraccivora)为测试对象,采用浸渍法测试。
操作过程:准确称量各种样品,分别加入N,N-二甲基甲酰胺配制成10g/L母液,实验时用含0.2mL/L Triton X-100的水溶液将其稀释至100mg/L的浓度。待无翅成蚜在豆芽上稳定吸食后,连同豆芽一起浸入浓度为100mg/L的药液中,5s后取出,用吸水纸吸去多余药液,移入干净器皿中于23℃恒温饲养。每浓度设3次重复,对照组为含0.2mL/L Triton X-100的水溶液。处理24小时后,统计试蚜的死亡虫数,并计算死亡率(%):死亡率(%)=(对照活虫数-处理活虫数)/对照活虫数×100%。结果见下表。
(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,采用喷雾法测试。
操作过程:将待测化合物以丙酮为溶剂准确配制成100mg/L的溶液,并以丙酮水溶液处理作空白对照。每个处理重复3杯(即重复3次)。用小型手动喷雾器每杯均匀喷雾2mL。施药前6小时每盆接稻褐飞虱10头。先后共进行了3批次试验。处理24小时后,统计试虫的死亡虫数,并计算死亡率(%):
死亡率(%)=(对照活虫数-处理活虫数)/对照活虫数×100%。
结果见下表1。
表1 通式Ⅰ所示的化合物的活性
实施例38
(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1-187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,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1-187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1-187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。
在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 (10)
1.一种具有通式Ⅰ所示结构的化合物,或其光学异构体、顺反异构体、在农药学上可接受的盐:
式中:
R1为取代或未取代的含氮、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,所述取代为具有选自下组中的一个或多个取代基:卤素、C1-4卤代烷基或C1-4卤代烷氧基;
R2、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R2与R3、或R2与R4合并组成-CH2-CH2-、-CH2-CH2-CH2-、-CH2-CH2-CH2-CH2-或-CH2-XR-CH2-,其中X为选自N、O、S的杂原子,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、C2-3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C2-8不饱和烃基或C1-8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为取代或未取代的C1-8烷基、取代或未取代的C3-8环烷基、取代或未取代的C6-10芳基、取代或未取代的C1-4亚烷基-C6-10芳基、取代或未取代的含氮、氧和/或硫的五元或六元杂环基,所述取代是指具有选自下组的一个或多个取代基:C1-6烷基、硝基、氟、氯、溴、C1-6烷氧基、C1-6卤代烷基、羟基、氨基、甲胺基、二甲胺基,或者两取代基与连接的原子成环;
Z为硝基、氰基、酯基、三氟甲基、三氟乙酰基(-COCF3)、C1-6烷氧酰基、C1-6烷基-甲酰基、或三氟甲磺酰基(-SO2CF3)。
2.如权利要求1所述的化合物或其在农药学上可接受的盐,其特征在于,R1为取代或未取代的以下基团:苯基、吡啶基、噻唑基、嘧啶基、四氢呋喃和噁唑基,其中,所述取代为具有选自下组中的一个或多个取代基:卤素,C1-4卤代烷基。
3.如权利要求1所述的化合物或其在农药学上可接受的盐,其特征在于,R2、R3、R4各自独立为氢、C1-4烷基、C2-4烷氧基烷基、C1-3烷氧基羰基、或苯氧羰基。
4.如权利要求1所述的化合物或其在农药学上可接受的盐,其特征在于,R2与R3、或者R2与R4合并组成-CH2-CH2-、-CH2-CH2-CH2-或-CH2-XR-CH2-,其中X为选自N,O,S的杂原子,R是杂原子上的C1-4烷基。
5.如权利要求1所述的化合物或其在农药学上可接受的盐,其特征在于,R5为取代或未取代的C3-6环烷基、取代或未取代的C6-10芳基、取代或未取代的C1-4亚烷基-C6-10芳基、取代或未取代的含氮、氧和/或硫的五元或六元杂环基,所述含氮、氧和/或硫的五元或六元杂环基为吡啶基、噻唑基、嘧啶基、四氢呋喃或噁唑基;所述取代是指具有选自下组的一个或多个取代基:C1-6烷基、硝基、氟、氯、溴、C1-6烷氧基、C1-6卤代烷基、或者两取代基与连接的原子成环。
6.如权利要求1所述的化合物或其在农药学上可接受的盐,其特征在于,具有式(Ⅱ)所示结构:
式中,R1和R5如上述定义。
7.一种农用组合物,其包含:
(a)权利要求1-6中任一项所述的化合物或其在农药学上可接受的盐;以及
(b)农药学上可接受的载体和/或赋形剂。
8.如权利要求1-5任一项所述的化合物或权利要求6所述的农用组合物的用途,其特征在于,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害虫的杀虫剂组合物。
9.一种杀虫和/或防虫方法,所述方法包括将权利要求1-5中任一项所述的化合物或其在农药学上可接受的盐,或权利要求6所述的杀虫剂组合物,施加于遭受或可能遭受虫害的植物体、动物体、其周围的土壤或环境中。
10.如权利要求1-5所述的化合物或其在农药学上可接受的盐的制备方法,其特征在于,所述方法包括步骤:式a所示化合物和式b所示化合物反应从而得到具有通式Ⅰ所示结构的化合物,
式中,R1、R2、R3、R4、R5和Z的定义如权利要求1-5中所述;
Y为O或S。
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CN103450175A (zh) * | 2013-08-12 | 2013-12-18 | 湖北省生物农药工程研究中心 | 共轭双烯衍生物及其制备方法和作为抗癌药物的用途 |
CN104557912A (zh) * | 2013-10-25 | 2015-04-29 | 济南大学 | 具有杀虫活性的含氟二氢吡啶化合物的制备方法及其应用 |
CN105669660A (zh) * | 2014-11-20 | 2016-06-15 | 华东理工大学 | 含氮杂环化合物及其用途 |
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