CN114591262B - 一种含噁二唑取代基的间苯氨基酰胺类化合物、其制备方法及应用 - Google Patents
一种含噁二唑取代基的间苯氨基酰胺类化合物、其制备方法及应用 Download PDFInfo
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- CN114591262B CN114591262B CN202011408735.XA CN202011408735A CN114591262B CN 114591262 B CN114591262 B CN 114591262B CN 202011408735 A CN202011408735 A CN 202011408735A CN 114591262 B CN114591262 B CN 114591262B
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- pests
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- oxadiazole
- anilinamide
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- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000005557 antagonist Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- QSLZKWPYTWEWHC-UHFFFAOYSA-N broflanilide Chemical compound C=1C=CC(C(=O)NC=2C(=CC(=CC=2Br)C(F)(C(F)(F)F)C(F)(F)F)C(F)(F)F)=C(F)C=1N(C)C(=O)C1=CC=CC=C1 QSLZKWPYTWEWHC-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
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- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- QGVQVNIIRBPOAM-UHFFFAOYSA-N dodecyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCCCCCCCCCCCC)=CC=CC2=C1 QGVQVNIIRBPOAM-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- WQHQCQSAAOGHQP-UHFFFAOYSA-N formaldehyde;2-methylnaphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=CC2=C(S(O)(=O)=O)C(C)=CC=C21 WQHQCQSAAOGHQP-UHFFFAOYSA-N 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 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
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940083542 sodium Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 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
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
-
- 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
- A01N43/82—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 three ring hetero atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
本发明公开了一种通式(I)表示的含噁二唑取代基的间苯氨基酰胺类化合物：
Description
技术领域
本发明属于杀虫剂领域，具体涉及一种含噁二唑取代基的间苯氨基酰胺类化合物及其制备方法，以及所述间苯氨基酰胺类化合物在防治害虫上的应用。
背景技术
害虫数量过多会造成农作物减产，故有效管理害虫数量是农业上重要的课题。农业上，长期使用同一杀虫剂容易使得害虫产生抗药性，因此，需要经常使用不同的杀虫剂来防治害虫。
近年来，含噁二唑结构的化合物在虫类防治上表现出了较好的效果，引起了大家的关注。如中国专利CN108299409A公开了含二苯醚的噁二唑类化合物，可用于防治甜菜夜蛾。
而同时包含噁二唑结构和酰胺结构的杀虫类化合物却鲜有报道。PestManagement Science(Volume 73,Issue 5,Pages 917-924)公开了一种含噁二唑的酰胺类化合物，可用作有害节肢动物防除剂，其认为该类化合物的作用机制类似于鱼尼汀受体类杀虫剂氯虫酰胺。
专利CN102119144A和Bioorganic&Medicinal Chemistry(2016,Pages 372-377)等公开了一类具有较高杀虫活性的间酰胺类化合物，如Broflanilide，可用于防治日益发展的双酰胺类杀虫剂(如氯虫酰胺)抗性害虫，而被认为是具有全新作用机制的GABA-R类拮抗剂。
截至目前，关于具有杀虫活性的含噁二唑取代基的间苯氨基酰胺类化合物却未见任何报道。然而，伴随着邻双酰胺类杀虫剂的大量使用，病害抗性风险逐渐加大(植物保护学报，2015，42：481-487)，有必要对间苯氨基酰胺类化合物进行研究，尤其是对同时具备噁二唑类结构取代基的间苯氨基酰胺类化合物进行探索和开发，实现对害虫的综合治理。
发明内容
为了解决上述技术问题，本发明提出了下式(I)所示的含噁二唑取代基的间苯氨基酰胺类化合物：
其中：
R1、R2独立选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基；
Z选自直链键、羰基、砜基、亚砜基、氮、氧、硫、酰胺基或-(CH2)n-，n为1～8的整数；
R3选自氢、卤素、C1-C6烷基、C1-C6烷氧基、C3-C6环烷基、C2-C6烯基、C2-C6炔基、C1-C6卤代烷基、C1-C6卤代烷氧基、C3-C6卤代环烷基、C2-C6卤代烯基、C3-C6卤代炔基、硝基、氰基、苯基、取代苯基、芳基、取代芳基，以及五元芳杂环、取代五元芳杂环、六元芳杂环、取代六元芳杂环、含双键的五元杂环或六元杂环、含双键的取代五元杂环或六元杂环；其中，杂环中的杂原子选自N、O或S，且杂原子的个数为1～4；取代苯基、取代芳基、取代五元芳杂环、取代六元芳杂环、含双键的取代五元杂环或六元杂环中的取代基选自卤素、C1-C6烷基、C1-C6烷氧基、C2-C6烯基、C2-C6炔基、C1-C6卤代烷基、C1-C6卤代烷氧基、C2-C6卤代烯基、C3-C6卤代炔基、硝基；
A1、A2、A3、A4、A5选自N或CR4，式中，R4选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基；且N的数量为1～3。
进一步地，
R1、R2独立选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基；
Z选自直链键、羰基、氮、氧、酰胺基或-(CH2)n-，n为1～8的整数；
R3选自氢、卤素、C1-C6烷基、C1-C6烷氧基、C3-C6环烷基、C2-C6烯基、C2-C6炔基、C1-C6卤代烷基、C1-C6卤代烷氧基、C3-C6卤代环烷基、C2-C6卤代烯基、C3-C6卤代炔基、苯基、取代苯基、芳基、取代芳基，以及五元芳杂环、取代五元芳杂环、六元芳杂环、取代六元芳杂环；其中，杂环中的杂原子选自N、O或S，且杂原子的个数为1～4；取代苯基、取代芳基、取代五元芳杂环、取代六元芳杂环中的取代基选自卤素、C1-C6烷基、C1-C6烷氧基、C2-C6烯基、C2-C6炔基、C1-C6卤代烷基、C1-C6卤代烷氧基、C2-C6卤代烯基、C3-C6卤代炔基、硝基；
A1、A2、A3、A4、A5选自N或CR4，式中，R4选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基；且N的数量为1～3。
优选地，
R1、R2独立选自氢、卤素、硝基、氰基、C1-C4烷基、C1-C4卤代烷基、C3-C4环烷基、C3-C4卤代环烷基、C1-C4烷氧基、C1-C4卤代烷氧基、C1-C4烷硫基、C1-C4卤代烷硫基；
Z选自直链键、羰基、氮、氧、酰胺基或-(CH2)n-，n为1～4的整数；
R3选自氢、卤素、C1-C4烷基、C1-C4烷氧基、C3-C4环烷基、C2-C4烯基、C2-C4炔基、C1-C4卤代烷基、C1-C4卤代烷氧基、C3-C4卤代环烷基、C2-C4卤代烯基、C3-C4卤代炔基、苯基、取代苯基、芳基、取代芳基，以及五元芳杂环、取代五元芳杂环、六元芳杂环、取代六元芳杂环；其中，杂环中的杂原子选自N、O或S，且杂原子的个数为1～2；取代苯基、取代芳基、取代五元芳杂环、取代六元芳杂环中的取代基选自卤素、C1-C4烷基、C1-C4烷氧基、C2-C4烯基、C2-C4炔基、C1-C4卤代烷基、C1-C4卤代烷氧基、C2-C4卤代烯基、C3-C4卤代炔基、硝基；
A1、A2、A3、A4、A5选自N或CR4，式中，R4选自氢、卤素、硝基、氰基、C1-C4烷基、C1-C4卤代烷基、C3-C4环烷基、C3-C4卤代环烷基、C1-C4烷氧基、C1-C4卤代烷氧基、C1-C4烷硫基、C1-C4卤代烷硫基；且N的数量为1～2。
更为优选地，
R1、R2独立选自氢、卤素、甲基、乙基；
Z选自直链键、氮或氧；
R3选自甲基、乙基、丙基、环丙基、叔丁基、三氟甲基、五氟乙基、七氟丙基、取代苯基，所述取代苯基上的取代基选自三氟甲基、三氟甲氧基、全氟异丙基；
A1、A2、A3、A4、A5选自N或CR4，式中，R4选自氢、卤素、甲基、三氟甲基、全氟异丙基；且N的数量为1。
在一种具体的实施方式中，本发明含噁二唑取代基的间苯氨基酰胺类化合物选自以下结构中的至少一种：
最为优选地，本发明含噁二唑取代基的间苯氨基酰胺类化合物选自以下结构中的至少一种：
本发明提供的含噁二唑取代基的间苯氨基酰胺类化合物，作为示例，将部分代表性化合物列于表1和表2。需要说明的是，本发明的间苯氨基酰胺类化合物并不限于表中所列举的化合物。
以下式F-1为例，R1＝2-F，R2＝H，间苯氨基酰胺类化合物结构式如下：
表1部分化合物结构
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以下式F-1为例，R1＝2-CH3，R2＝H，间苯氨基酰胺类化合物结构式如下：
表2部分化合物结构
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本发明还提供一种通式(I)所示的含噁二唑取代基的间苯氨基酰胺类化合物的制备方法，所述制备方法包括：
其中，R1、R2、Z、R3、A1、A2、A3、A4、A5和R4的定义同上所述。
具体地，所述制备方法进一步包括以下步骤：
A1.氰基取代物在盐酸羟胺的作用下生成偕胺肟中间体；
A2.偕胺肟中间体与硝基原料进行环化反应，生成含噁二唑的硝基中间体；
A3.含噁二唑的硝基中间体在还原剂的作用下还原生成芳胺化合物；
A4.芳胺化合物与原料反应获得所述含噁二唑取代基的间苯氨基酰胺类化合物。
A1步骤可视情况加入碱，所述碱选自碳酸锂、碳酸氢钠、碳酸钠、碳酸氢钾、碳酸钾、碳酸铯、碳酸镁、氢氧化锂、氢氧化钠、氢氧化钾、氢氧化镁、氢氧化钙、氢氧化钡、氢氧化锶中的至少一种；
A2步骤可视情况加入碱，所述碱选自碳酸锂、碳酸氢钠、碳酸钠、碳酸氢钾、碳酸钾、碳酸铯、碳酸镁、三甲胺、三乙胺、三丙胺、三丁胺、N,N-二甲基苯胺、N,N-二甲基苯甲胺、吡啶、N,N-二甲基氨基吡啶、甲基吡啶、二甲基吡啶和喹啉中的至少一种；
A3步骤还原试剂选自Ni、Rh、SnCl2、Fe、Pd/C、Zn、TiCl3中的至少一种；
A4步骤可视情况加入碱，所述碱为碳酸锂、碳酸氢钠、碳酸钠、碳酸氢钾、碳酸钾、碳酸铯、碳酸镁、三甲胺、三乙胺、三丙胺、三丁胺、N,N-二甲基苯胺、N,N-二甲基苯甲胺、吡啶、N,N-二甲基氨基吡啶、甲基吡啶、二甲基吡啶和喹啉中的至少一种。
本发明还提供一种通式(I)所示的含噁二唑取代基的间苯氨基酰胺类化合物的应用，所述间苯氨基酰胺类化合物用于防治害虫。
进一步地，所述含噁二唑取代基的间苯氨基酰胺类化合物用于防治鳞翅目害虫、鞘翅目害虫、半翅目害虫、缨翅目害虫、双翅目害虫、直翅目害虫、同翅目害虫、等翅目害虫、膜翅目害虫、叶螨害虫中的至少一种。
优选地，所述含噁二唑取代基的间苯氨基酰胺类化合物用于防治玉米粘虫、铃虫、小菜蛾、甜菜夜蛾、斜纹夜蛾、菜青虫、二化螟、三化螟、大螟、草地夜蛾、稻纵卷叶螟、稻蓟马、西花蓟马、瓜蓟马、葱蓟马、大姜蓟马、芒果蓟马、桃蚜、棉蚜、苜蓿蚜、苹果黄蚜、麦蚜、跳甲、椿象、灰飞虱、褐飞虱、白背飞虱、白蚁、蚊蝇、朱砂叶螨、柑橘全爪螨中的至少一种。
本发明还提供一种杀虫剂，所述杀虫剂含有1～99％质量百分含量的前述任一所述通式(I)所示的含噁二唑取代基的间苯氨基酰胺类化合物，其余为农业上可接受的载体。
所述杀虫剂，可以被配制成乳油、悬浮剂、水悬剂、微乳剂、(水)乳剂、粉剂、可湿性粉剂、可溶性粉剂、(水分散性)颗粒剂或胶囊剂等。
在配制杀虫剂时，载体可以是固体或液体。合适的固体载体包括天然的或合成的粘土和硅酸盐，例如天然硅石和硅藻土；硅酸镁例如滑石；硅酸铝镁例如高岭石、高岭土、蒙脱土和云母；白碳黑、碳酸钙、轻质碳酸钙；硫酸钙；石灰石；硫酸钠；胺盐如硫酸铵、六甲撑二胺。液体载体包括水和有机溶剂，当用水做溶剂或稀释剂时，有机溶剂也能用做辅助剂或防冻添加剂。合适的有机溶剂包括芳烃例如苯、二甲苯、甲苯等；氯代烃，例如氯代苯、氯乙烯、三氯甲烷、二氯甲烷等；脂肪烃，例如石油馏分、环己烷、轻质矿物油；醇类，例如异丙醇、丁醇、乙二醇、丙三醇和环己醇等；以及它们的醚和酯；还有酮类，例如丙酮、环己酮以及二甲基甲酰胺和N-甲基-吡咯烷酮。
载体也可以是表面活性剂。合适的表面活性剂可以是乳化剂、分散剂或湿润剂；可以是离子型的或非离子型的。非离子型乳化剂例如聚氧乙烯脂肪酸脂、聚氧乙烯脂肪醇醚、聚氧乙烯脂肪氨，以及市售的乳化剂：农乳2201B、农乳0203B、农乳100#、农乳500#、农乳600#、农乳600-2#、农乳1601、农乳2201、农乳NP-10、农乳NP-15、农乳507#、农乳OX-635、农乳OX-622、农乳OX-653、农乳OX-667、宁乳36#。分散剂包括木质素磺酸钠、拉开粉、木质素磺酸钙、甲基萘磺酸甲醛缩合物等。湿润剂为：月桂醇硫酸钠、十二烷基苯磺酸钠、烷基萘磺酸钠等。
上述杀虫剂可由通用的方法制备。例如，将活性物质与液体溶剂和/或固体载体混合，同时加入表面活性剂如乳化剂、分散剂、稳定剂、湿润剂，还可以加入其它助剂如：粘合剂、消泡剂、氧化剂等。
本发明所述的含噁二唑取代基的间苯氨基酰胺类化合物还可以与除草剂、杀菌剂、杀线虫剂、植物生长调节剂、肥料，以及其它杀虫剂或其他农用化学品混配使用。
在防治害虫时，应当将本发明所述杀虫剂施于需要控制的有害生物或其生长的介质上，其中活性组分，即式(I)所示的含噁二唑取代基的间苯氨基酰胺类化合物的有效量施用量为每公顷10克至1000克。
本发明的含噁二唑取代基的间苯氨基酰胺类化合物，相比现有技术，具有如下优势：
1.本发明创造性地提出了含噁二唑取代基的间苯氨基酰胺类化合物，害虫防治效果好。
2.本发明的含噁二唑取代基的间苯氨基酰胺类化合物制备简单，易于合成。
具体实施方式
下面结合具体实施例来对本发明进行进一步说明，但并不将本发明局限于这些具体实施方式。本领域技术人员应该认识到，本发明涵盖了权利要求书范围内所可能包括的所有备选方案、改进方案和等效方案。
一、化合物制备
实施例1：化合物331合成
合成路线：
中间体A1的制备：
将17g(0.1mol)的2,4-二氯苯甲腈加入到250mL烧瓶中，加入100mL无水乙醇溶解，加入10.5g(0.15mol)盐酸羟胺，升温至回流，TLC跟踪监测至反应完毕。冷却，将反应液倒入冰水中，搅拌，析出固体，过滤，得到16g 2,4-二氯-N'-羟基苯甲酰胺肟，灰白色固体，ESI-MS：204[M+H]+
中间体A3的制备：
将A2 20g(0.1mol)溶于THF中，冰水浴下缓慢滴加至A1 20.3g(0.1mol)的THF溶液中，滴加完毕后，滴加三乙胺，保持温度在10-20℃左右。滴加完毕后继续搅拌1h。TLC检测反应完毕后蒸出THF，加入90mL DMF溶解，并在油浴锅下加热至100℃左右，TLC跟踪至反应完毕。冷却，将反应液倒入冰水中，搅拌下缓慢析出固体，过滤，得到27g灰色固体3-(2,4-二氯苯基)-5-(2-甲基-3-硝基苯基)-1,2,4-恶二唑，收率77.1％。经测试，制备得到的化合物为A3，其性能数据如下：
1H NMR(600MHz,CDCl3)δ:2.84(s,3H,CH3),7.42-7.44(dd,J＝8.4,2.0Hz,1H,Ar-H),7.54-7.56(t,J＝8.0Hz,1H,Ar-H),7.61(d,J＝2.0Hz,1H,Ar-H),7.95-7.97(d,J＝8.0Hz,1H,Ar-H),8.01-8.02(d,J＝8.4Hz,1H,Ar-H),8.31-8.32(d,J＝7.9Hz,1H,Ar-H)；13CNMR(150MHz,CDCl3)δ:174.21,167.05,152.39,137.68,134.46,133.96,133.11,132.55,131.08,127.51,127.40,127.14,126.06,124.30,16.72；ESI-MS:350[M+H]+
中间体A4的制备：
将A3 3.5g(0.01mol)溶于50mL无水乙醇中，加入7.6g(0.04mol)氯化亚锡和10mL浓盐酸，加热至回流温度，TLC跟踪监测至反应完毕。蒸出部分溶剂，冷却，将剩余物倒入冰水中，用10％的NaOH溶液调节至碱性，加入适量EA萃取，水洗，干燥，浓缩，得到2.6g 3-(2,4-二氯苯基)-5-(2-甲基-3-氨基苯基)-1,2,4-恶二唑，收率81.5％。经测试，制备得到的化合物为A4，其性能数据如下：
1H NMR(600MHz,CDCl3)δ:2.54(s,3H,CH3),3.84(s,2H,NH2),6.90-6.92(d,J＝7.9Hz,1H,Ar-H),7.17-7.20(t,J＝7.8Hz,1H,Ar-H),7.39-7.41(dd,J＝8.4,2.0Hz,1H,Ar-H),7.49-7.50(d,J＝7.7Hz,1H,Ar-H),7.59(d,J＝2.0Hz,1H,Ar-H),8.01-8.03(d,J＝8.4Hz,1H,Ar-H)；13C NMR(150MHz,CDCl3)δ:176.57,166.61,145.90,137.18,134.36,132.58,130.89,127.35,126.84,124.96,124.03,122.75,120.85,118.81,14.21；ESI-MS:320[M+H]+
目标产物331的制备：
将0.32g(0.001mol)溶于20mL干燥的THF中，冰水浴下滴加0.08g(0.0011mol)乙酰氯，再滴加0.15g(0.0014mol)TEA，TLC跟踪至反应完毕。蒸出溶剂，剩余物经薄层层析法提纯得到目标产物为331，其性能数据如下：
1H NMR(600MHz,CDCl3)δ:2.27(s,3H,CH3),2.64(s,3H,CH3),7.20(s,1H,NH),7.37-7.39(d,1H,Ar-H),7.40-7.41(dd,1H,Ar-H),7.59(d,1H,Ar-H),7.94-7.95(d,2H,Ar-H,NH),8.00-8.01(d,1H,Ar-H):362[M+H]+
实施例2：化合物335合成
使用与实施例1同样方法制备化合物335。得到的化合物335的性能数据如下：
1H NMR(600MHz,CDCl3)δ:0.88-0.92(m,2H,Cyclopropyl-H),1.12-1.15(m,2H,Cyclopropyl-H),3.73-3.76(m,1H,Cyclopropyl-H),2.68(s,3H,CH3),7.36-7.39(m,2H,Ar-H),7.40-7.42(dd,1H,Ar-H),7.59-7.60(d,1H,Ar-H),7.92(s,1H,NH),8.01-8.02(m,2H,Ar-H),8.08-8.09(d,1H,Ar-H)；ESI-MS:388[M+H]+
实施例3：化合物337合成
使用与实施例1同样方法制备化合物337。得到的化合物337的性能数据如下：
1H NMR(600MHz,CDCl3)δ:2.70(s,3H,CH3),7.41-7.43(dd,1H,Ar-H),7.46-7.49(t,1H,Ar-H),7.60(d,1H,Ar-H),7.94(s,1H,NH),7.95-7.97(d,1H,Ar-H),8.00-8.01(d,1H,Ar-H),8.08-8.09(d,1H,Ar-H)；ESI-MS:416[M+H]+
二、制剂配制
以下实施例按照质量配比配制。
实施例4、30％悬浮剂
将化合物331及其它组分充分混合，由此得到的30％悬浮剂。用水稀释所得悬浮剂可得到任何所需浓度的稀释液。
实施例5、30％含水悬浮液
将化合物335与应加水量的80％及十二烷基磺酸钠在球磨机中一起粉碎，半纤维素和环氧丙烷溶解在其余20％的水中，然后搅拌加入上述组分，得到30％含水悬浮液。
实施例6、30％乳油
将亚磷酸溶解在甲苯中，加入化合物337和乙氧基化甘油三酸酯，得到透明的溶液，即为30％乳油。
实施例7、60％可湿粉剂
将化合物335、十二烷基萘磺酸钠、木质素磺酸钠何硅澡土混合在一起，在粉碎机中粉碎，直到颗粒达到标准后得到60％可湿粉剂。
三、性能测试
杀虫活性评价试验根据下列方法进行：
用分析天平(0.0001g)称取一定质量的原药，用含1％吐温-80乳化剂的DMF溶解配制成1～2.5％母液，然后用蒸馏水稀释备用。
浸叶法：供试靶标为玉米粘虫，即将适量玉米叶在配好的药液中充分浸润后自然阴干，放入垫有滤纸的培养皿中，接玉米粘虫3龄中期幼虫10头/皿，置于24～27℃观察室内培养，3d后调查结果。以毛笔触动虫体，无反应视为死虫。
喷雾法：供试靶标为朱砂叶螨、苜蓿蚜，即分别将接有朱砂叶螨和苜蓿蚜的蚕豆叶片置于Potter喷雾塔下喷雾处理，处理后朱砂叶螨置于24～27℃观察室内培养，苜蓿蚜置于20～22℃观察室内培养，48h后调查结果。以毛笔触动虫体，无反应视为死虫。
试验统计：统计各个处理的死虫数和活虫数，计算死亡率。死亡率计算公式如下：
CK对照死亡率<20％，试验结果可信，试验结果进行校正，CK对照死亡率<5％时可不校正。生测试验结果表明：
在500mg/L浓度时，化合物5、8、9、10、12、26、27、106、107、109、112、134、135、136、137、138、140、142、143、182、183、186、187、240、241、243、246、331、332、335、337、338处理的玉米粘虫死亡率均高于90％或为100％，且普遍取食较少。
在250mg/L浓度时，化合物8、9、26、27、106、107、134、135、137、138、140、142、182、183、187、240、243、331、335、337处理的玉米粘虫死亡率均高于80％，且普遍取食较少。
Claims (6)
1.一种通式(I)所示的含噁二唑取代基的间苯氨基酰胺类化合物：
所述化合物选自以下结构中的至少一种：
2.根据权利要求1所述的通式(I)所示的含噁二唑取代基的间苯氨基酰胺类化合物的制备方法，其特征在于：所述制备方法包括：
其中，
取代基R1、R2、R3、Z、A1、A2、A3、A4、A5的定义如同权利要求1。
3.权利要求1所述通式(I)所示的含噁二唑取代基的间苯氨基酰胺类化合物的应用，其特征在于：所述间苯氨基酰胺类化合物用于防治害虫。
4.根据权利要求3所述的应用，其特征在于：所述间苯氨基酰胺类化合物用于防治鳞翅目害虫、鞘翅目害虫、半翅目害虫、缨翅目害虫、双翅目害虫、直翅目害虫、同翅目害虫、等翅目害虫、膜翅目害虫、叶螨害虫中的至少一种。
5.根据权利要求3所述的应用，其特征在于：所述间苯氨基酰胺类化合物用于防治玉米粘虫、铃虫、小菜蛾、甜菜夜蛾、斜纹夜蛾、菜青虫、二化螟、三化螟、大螟、草地夜蛾、稻纵卷叶螟、稻蓟马、西花蓟马、瓜蓟马、葱蓟马、大姜蓟马、芒果蓟马、桃蚜、棉蚜、苜蓿蚜、苹果黄蚜、麦蚜、跳甲、椿象、灰飞虱、褐飞虱、白背飞虱、白蚁、蚊蝇、朱砂叶螨、柑橘全爪螨中的至少一种。
6.一种杀虫剂，其特征在于：所述杀虫剂含有1～99％质量百分含量的权利要求1所述通式(I)所示的含噁二唑取代基的间苯氨基酰胺类化合物。
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