CN114736168A - 一种含有氨甲环酸片段的异噁唑啉类衍生物及其制备和应用 - Google Patents
一种含有氨甲环酸片段的异噁唑啉类衍生物及其制备和应用 Download PDFInfo
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- CN114736168A CN114736168A CN202110016704.8A CN202110016704A CN114736168A CN 114736168 A CN114736168 A CN 114736168A CN 202110016704 A CN202110016704 A CN 202110016704A CN 114736168 A CN114736168 A CN 114736168A
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- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004775 chlorodifluoromethyl group Chemical group FC(F)(Cl)* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
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- 229910000514 dolomite Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JJOYCHKVKWDMEA-UHFFFAOYSA-N ethyl cyclohexanecarboxylate Chemical compound CCOC(=O)C1CCCCC1 JJOYCHKVKWDMEA-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
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- 239000000194 fatty acid Substances 0.000 description 1
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- 239000000417 fungicide Substances 0.000 description 1
- 150000002333 glycines Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000002439 hemostatic effect Effects 0.000 description 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 125000002950 monocyclic group Chemical group 0.000 description 1
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- NKCCODPFBDGPRJ-UHFFFAOYSA-N nitridocarbon(1+) Chemical group N#[C+] NKCCODPFBDGPRJ-UHFFFAOYSA-N 0.000 description 1
- 125000005246 nonafluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 102000004164 orphan nuclear receptors Human genes 0.000 description 1
- 108090000629 orphan nuclear receptors Proteins 0.000 description 1
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- 239000006072 paste Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
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- 125000003367 polycyclic group Chemical group 0.000 description 1
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- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229930002330 retinoic acid Natural products 0.000 description 1
- 235000009566 rice Nutrition 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
- 125000003548 sec-pentyl group Chemical group [H]C([H])([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
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
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- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 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
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229960001727 tretinoin Drugs 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
- C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
- C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
-
- 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
- A01N43/80—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 1,2
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
本发明属于杀螨剂、杀虫剂领域,具体涉及一种含有氨甲环酸片段的异噁唑啉类衍生物及其制备和应用。含有氨甲环酸片段的异噁唑啉类化合物,如通式I所示,式中各取代基团定义见说明书。通式化合物I具有优异的杀螨、杀虫活性,可用于防治螨害、虫害。式中各取代基团的定义见说明书。
Description
技术领域
本发明属于杀螨剂、杀虫剂领域,具体涉及一种含有氨甲环酸片段的异噁唑啉类衍生物及其制备和应用。
背景技术
杀螨剂、杀虫剂在使用一段时间后,对应的防治对象会对其产生抗性,所以需要不断研发新型或改进的杀螨剂、杀虫剂及其组合物。
氨甲环酸(II)是赖氨酸合成衍生物,属于抗纤溶药,具有止血特性,含有氨甲环酸片段的化合物在医药合成领域中可见报道,例如用于治疗维甲酸相关孤核受体γ引起的新陈代谢类疾病及自身免疫力疾病(专利WO2019063748A1)。但含有氨甲环酸片段的具有杀螨杀虫活性的化合物的研究暂无报道。
专利WO2016002790A和US20110144334A公等开了某些异噁唑啉类化合物及其应用。专利JP2008239611A中的化合物KC1在500ppm具有较高杀虫、杀螨活性,其通用名为Fluxametamide。
在现有技术中,含有氨甲环酸衍生物片段的异噁唑啉类化合物,其制备及其杀螨、杀虫活性未见报道。
发明内容
本发明的目的在于提供一种含有氨甲环酸片段的异噁唑啉类衍生物及其制备和应用。
为实现上述目的,本发明采用技术方案为:
一种含有氨甲环酸片段的异噁唑啉类衍生物,含有氨甲环酸片段的异噁唑啉类化合物,如通式I所示:
式中,
X1、X3选自卤素;
X2选自H或卤素;
A1选自NH、O或S;
R1选自H、C1-C6烷基、C3-C8环烷基、C2-C6烯烃、C2-C6炔烃、C1-C6卤代烷基、-CH2C(O)R2或被氰基取代的C1-C6烷基,其中R2表示C1-C6烷基。
进一步所述通式I中,
X1、X3选自F、Cl或Br;
X2选自H、F、Cl或Br;
R1选自H、C1-C6烷基、C3-C8环烷基、C2-C6烯烃、C2-C6炔烃、被F、Cl或Br取代的C1-C6烷基、-CH2C(O)R2或被氰基取代的C1-C3烷基,其中R2表示C1-C3烷基。
更进一步所述通式I中,
X1、X3选自Cl;
X2选自H、F或Cl;
R1选自H、C1-C6烷基、C3-C8环烷基、C2-C6烯烃、C2-C6炔烃、被F或Cl取代的C1-C6烷基、亚甲基氰基、1,2-亚乙基氰基、1,1-亚乙基氰基、亚异丙基氰基或-CH2C(O)R2,其中R2表示甲基、乙基或正丙基。
一种制备含有氨甲环酸片段的异噁唑啉类衍生物的中间体化合物,中间体化合物,如通式III所示,
A1选自NH、O或S;
R1选自H、C1-C6烷基、C3-C8环烷基、C2-C6烯烃、C2-C6炔烃、C1-C6卤代烷基、-CH2C(O)R2或被氰基取代的C1-C6烷基,其中R2表示C1-C6烷基;
或,式III所示化合物的盐。
进一步上述式中,
A1选自NH、O或S;
R1选自H、C1-C6烷基、C3-C8环烷基、C2-C6烯烃、C2-C6炔烃、被F、Cl或Br取代C1-C6烷基、-CH2C(O)R2或被氰基取代的C1-C3链烷基,其中R2表示C1-C3烷基;
或,式III所示化合物的盐酸盐或三氟乙酸盐,其通式分别为III·HCl或III·CF3COOH。
更进一步上述式中,
A1选自NH、O或S;
R1选自H、C1-C6烷基、C3-C8环烷基、C2-C6烯烃、C2-C6炔烃、被F或Cl取代的C1-C6链烷基、亚甲基氰基、1,2-亚乙基氰基、1,1-亚乙基氰基、亚异丙基氰基或-CH2C(O)R2,其中R2表示甲基、乙基或正丙基;或,式III所示化合物的盐酸盐或三氟乙酸盐。
一种所述的含有氨甲环酸片段的异噁唑啉类衍生物的制备方法,通式IV化合物与通式III化合物反应制备通式I化合物,反应式为:
通式IV中的LG选自OH或卤素。
其中,
当LG为羟基时,其通式为IV-a,当LG为氯原子时,其通式为IV-b。
当LG为羟基时,通式IV-a在适宜的缩合试剂(如EDCI和HOBT的组合或者HATU等)条件下与通式III反应制备通式I化合物。其中通式III化合物的制备方法为:通式V与三氟乙酸/二氯甲烷混合溶剂或盐酸的1,4-二氧六环的溶剂中反应生成相应的三氟乙酸盐化合物III·CF3COOH或盐酸盐化合物III·HCl,再与适宜的碱反应得到化合物III。
当LG为卤素时,,通式IV-a化合物与适宜的卤化试剂(如草酰氯、氯化亚砜、N-溴代丁二酰亚胺、4-叔丁基-2,6-二甲基苯基三氟化硫等)反应制备酰卤IV-b,再与通式III化合物反应制备通式I化合物。
上述中间体通式IV可以按照专利US20110144334A1、US20150119576A1、WO2012007426A1中提供的方法制备。
一种所述的通式I化合物在控制害虫、害螨中的应用。
一种杀虫、杀螨组合物,组合物含有活性成分和农业、林业或卫生上可接受的载体;其中,活性成分的重量百分含量为1-99%,活性成分含权利要求1所述的通式I所示化合物。
一种控制螨害、虫害的方法,将所述的组合物以每公顷10克到1000克的有效剂量施于需要控制的害虫、害螨或其生长的介质上。
上面给出的通式化合物的定义中,汇集所用术语一般代表如下取代基:
卤素:指F、Cl、Br或I。
Ca~Cb链烷基:碳原子数为a~b直链状、支链状烃基,例如甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、1-乙基丙基、1,1-二甲基丙基、1,2-二甲基丙基、新戊基等。
Ca~Cb环烷基:碳原子数为a~b的环状烃基,并且可以形成3元环~6元环的单环或多环结构。另外,各个环可以在指定的碳原子数范围内被烷基任意取代,例如环丙基、1-甲基环丙基、2-甲基环丙基、环戊基、2-甲基环戊基、环己基、2-甲基环己基等。
Ca~Cb链烯烃:碳原子数为a~b的直链状或支链状的、且在分子内具有1个或两个以上双肩的不饱和烃基。例如乙烯基、1-丙烯基、1-甲基乙烯基、2-丙烯基、2-丁烯基、1-甲基-2-丙烯基、2-甲基-2-丙烯基、2-甲基-2-丁烯基、3-甲基-2-丁烯基、2-己烯基、2-甲基-2-戊烯基等。
Ca~Cb链炔烃:碳原子数为a~b的直链状的、且分子内具有1个或2个以上三键的不饱和烃基。例如乙炔基、1-丙炔基、2-丙炔基、1-甲基-2-丙炔基、2-丁炔基、2-戊炔基、1-甲基-2-丁炔基、2-己炔基。
卤代Ca~Cb烷基:在碳原子上的氢原子被卤素原子任意取代的、碳原子数为a~b的直链状或支链状的烃基。当被2个以上卤素原子取代时,这些卤素原子可以是相同的,也可以使互不相同的。比如氟甲基、氯甲基、溴甲基、二氟甲基、二氯甲基、、三氟甲基、氯二氟甲基、三氯甲基、溴二氟甲基、2-氟乙基、2-氯乙基、2-溴乙基、2,2-二氟乙基、2-氯-2-氟乙基、2,2-二氯乙基、2-溴-2-氟乙基、2-溴-2-氯乙基、2,2,2-三氟乙基、2-氯-2,2-二氟乙基、2,2-二氯-2-氟乙基、2,2,2-三氯乙基、2-溴-2,2-二氟乙基、2-溴-2-氯-2-氟乙基、2-溴-2,2-二氯乙基、五氟乙基、2-氟丙基、2-氯丙基、2-溴丙基、2,3-二氯丙基、2,3-二溴丙基、3,3,3-三氟丙基、3-溴-3,3-二氟丙基、2,2,3,3-四氟丙基、2-氯-3,3,3-三氟丙基、2,2,3,3,3-五氟丙基、2,2,2-三氟-1-1-三氟甲基乙基、七氟丙基、1,2,2,2-四氟-1-三氟甲基乙基、2,2,3,3,4,4-六氟丁基、2,2,3,4,4,4-六氟丁基、2,2,3,3,4,4,4,-七氟丁基、九氟丁基、5-氯-2,2,3,4,4,5,5-七氟戊基等。
表1中列出的通式I的具体化合物可以用来说明本发明,但并不限定本发明。
表1
部分化合物的1H NMR及物化性质如下:
表2中列出的通式III的具体化合物可以用来说明本发明,但并不限定本发明。
表2
部分化合物的1H NMR及物化性质如下:
同已知化合物KC1相比较,本发明的异噁唑啉类衍生物(通式I化合物)具有较高杀虫、杀螨活性,可以防治如下害虫:鳞翅目害虫,如粘虫、甜菜夜蛾和小菜蛾等;同翅目害虫,如桃蚜、叶婵和飞虱等;半翅目害虫,如玉米长蝽、番茄盲蝽和稻臭椿等;缨翅目害虫,如棉蓟马、苜蓿蓟马和黄豆蓟马等;鞘翅目害虫,如跳甲、马铃薯甲虫和叩甲等;双翅目害虫,如蝇和蚊等;膜翅目害虫,如蜂和蚁等。可以防治如下害螨:叶螨科(二斑叶螨、朱砂叶螨、苹果全爪螨、柑橘全爪螨等)、瘿螨科、跗线螨科等。因此,本发明还包括通式I化合物用于农业、林业及卫生领域中控制螨害和虫害的用途。
本发明还包括一种杀螨、杀虫组合物,所述组合物中含上述通式I所示化合物和农业、林业或卫生邻域上可接受的载体;以所述通式I所示化合物为活性组分,所述组合物中活性组分的重量百分含量为0.1-99%。所述组合物可包括各异体结构存在形式的上述通式I所示的化合物。
组合物的使用形式可以是干粉、可湿性粉剂、乳油、微乳剂、糊剂、颗粒剂、溶液、悬浮剂等,组合物类型的选择取决于具体的应用。
组合物是以已知方式制备的,例如任选在表面活性剂的存在下,通过用溶剂介质和/或固体稀释剂稀释或溶解活性物质。
可用的固体稀释剂或载体可以是二氧化硅、高岭土、膨润土、滑石、硅藻土、白云石、碳酸钙、氧化镁、白垩、粘土、合成硅酸盐、硅镁土、海泡石等。
除水以外,可用的液体稀释剂是芳族有机溶剂(二甲苯或烷基苯的混合物、氯苯等)、石蜡(石油馏分)、醇类(甲醇、丙醇、丁醇、辛醇、甘油)、酯类(乙酸乙酯、乙酸异丁酯等)、酮类(环己酮、丙酮、苯乙酮、异佛尔酮、乙基戊基酮等)、酰胺类(N,N-二甲基甲酰胺、N-甲基吡咯烷酮等)。
可用的表面活性剂是烷基磺酸盐、烷基芳基磺酸盐、烷基酚聚氧乙烯醚、聚氧乙烯山梨醇脂肪酸酯、木质素磺酸盐等。
组合物还可含特殊的添加剂用于特定的目的,例如粘合剂如***胶、聚乙烯醇、聚乙烯吡咯烷酮等。
上述组合物中活性成分的浓度可根据活性成分、其使用目的、环境条件和采用的制剂类型而在较宽范围内改变。通常,活性成分的浓度范围是1-90%,优选5-50%。
本发明的技术方案还包括防治害螨的方法:将本发明的化合物以及杀虫组合物施于所述的害螨或其生长介质上。通常选择的较为适宜有效量为每公顷10克到1000克,优选有效量为每公顷20克到500克。
本发明的技术方案还包括防治害虫的方法:将本发明的化合物以及杀虫组合物施于所述的害虫或其生长介质上。通常选择的较为适宜有效量为每公顷10克到1000克,优选有效量为每公顷20克到500克。
本发明的技术方案还包括防治病害的方法:将本发明的化合物以及杀虫组合物施于所述的病害或其生长介质上。通常选择的较为适宜有效量为每公顷10克到1000克,优选有效量为每公顷20克到500克。
对于某些应用,如在农业上,在本发明的化合物以及杀虫、杀螨组合物中加入一种或多种其它的杀菌剂、杀虫剂、杀螨剂、除草剂、植物生长调节剂或肥料等,可产生附加的优点和效果。
应该明确的是,在本发明的权利要求所限定的范围内,可以进行各种变换和改动。
本发明所具有的优点:
在有机分子中,由于取代基的电负性、体积大小或空间构型的不同,整个分子在昆虫和植物等生物体内的输导性能或与受体结合差异性会很大,表现出的生物活性差异也会有很大,而分子的输导性能和与受体结合的合适性是不可预测的;而本申请化合物以异噁唑啉类化合物为先导,通过引入适当的氨甲环酸衍生物活性结构得到通式I化合物。由于引入新的活性结构片段,提高了分子与受体相互作用和结合的机会,获得了在杀螨、杀虫方面较好的生物活性结果,使得本发明获得的氨甲环酸衍生物具有更全面的生物学特性。
具体实施方式
以下具体实施例用来进一步说明本发明,但本发明绝非限于这些例子。
合成实施例
化合物2-甲基-4-{[5-(3,5)-二氯苯基]-4,5-二氢-5-三氟甲基-3-异噁唑基}-1-苯甲酸的合成方法参见专利为US20110144334A1和US20150119576A1中记载合成。
实施例1:化合物A-2的制备
(1)4-氨甲基环己羧酸乙酯盐酸盐(J-2)的制备
0℃下,将氨甲环酸(2.0g,12.7mmol)溶于25mL乙醇中,再缓慢滴加氯化亚砜(4.54g,38.1mmol),升温至回流,反应12h。反应结束后待温度降至室温,减压蒸馏除去多余的溶剂得到白色固体。向固体中加入冰冷的***并剧烈搅拌,过滤得到的滤饼在真空条件下干燥,得到4-氨甲基环己羧酸乙酯盐酸盐。1H NMR(600MHz,DMSO-d6)δ(ppm):8.06(s,3H),4.04(q,2H),2.62(s,2H),2.22(t,1H),1.91(d,2H),1.82(d,J=10.8Hz,2H),1.55(s,1H),1.28(qd,2H),1.17(t,3H),0.98(qd,2H).
(2)4-N-{2-甲基-4-[5-(3,5-二氯-苯基)-5-三氟甲基-4,5-二氢-异噁唑-3-基]苯甲酰基}亚甲基环己基甲酸乙酯(化合物A-2)的合成
将2-甲基-4-{[5-(3,5)-二氯苯基]-4,5-二氢-5-三氟甲基-3-异噁唑基}-1-苯甲酸(418.2mg,1.0mmol),1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(280.9mg,1.2mmol),1-羟基苯并***(162.2mg,1.2mmol),N,N-二异丙基乙胺(387.9mg,3.0mmol)溶于10mL二氯甲烷,搅拌10min后加入4-氨甲基环己羧酸乙酯盐酸盐(213.1mg,1.1mmol),室温下反应12h。反应结束后分别用水30mL洗涤有机层2次,饱和食盐水洗涤1次。有机层用无水硫酸钠干燥,过滤、浓缩,再经柱层析分离得到白色固体。1H NMR(600MHz,CDCl3)δ(ppm):7.53–7.47(m,4H),7.43(s,1H),7.38(d,1H),5.90(s,1H),4.14–4.05(m,3H),3.70(d,1H),3.31(t,2H),2.45(s,3H),2.24(s,1H),2.03(d,2H),1.89(d,2H),1.62–1.53(m,1H),1.49–1.38(m,2H),1.25(t,3H),1.11–0.99(m,2H).
实施例2:化合物A-9的制备
(1)4-[(叔丁氧羰基)甲基]环己烷羧酸的制备
0℃冰水浴下,将氨甲环酸(8.35g,53.1mmol)溶于100mL 1,4-二氧六环和60mL水中,再加入氢氧化钠(4.25g,106.2mmol)。之后向瓶中滴加二碳酸二叔丁酯(13.9g,63.7mmol),室温下反应16h。反应结束后浓缩,加入乙酸乙酯稀释,加入柠檬酸的水溶液调至pH≈3。用乙酸乙酯萃取水层。合并有机层,饱和氯化钠溶液洗涤有机层1次,无水硫酸钠干燥,过滤并浓缩得到白色固体。向白色固体中加入正己烷并剧烈搅拌,过滤得到白色滤饼为目标产物4-[(叔丁氧羰基)甲基]环己烷羧酸,直接用于下一步。1H NMR(600MHz,d6-DMSO)δ(ppm):6.78(1H,m),2.73(2H,t),2.07(1H,m),1.85(2H,m),1.67(2H,m),1.35(9H,s),1.22(2H,m),0.84(2H,m).
(2)4-[(叔丁氧羰基)甲基]环己烷甲酸2-丙炔-1-基酯的合成
0℃下,将4-[(叔丁氧羰基)甲基]环己烷羧酸(514.7mg,2.0mmol),3-溴丙炔(357.0mg,3.0mmol),碳酸钾(414.7mg,3.0mmol)溶于DMF中,升至室温反应16h。反应结束后加水稀释,用乙酸乙酯萃取混合液,有机层用饱和食盐水洗涤1次,无水硫酸钠干燥后过滤并浓缩,再通过柱层析分离得到4-[(叔丁氧羰基)甲基]环己烷甲酸2-丙炔-1-基酯。1H NMR(600MHz,CDCl3)δ(ppm):4.67(t,3H),3.05–2.88(m,2H),2.51–2.40(m,1H),2.34–2.23(m,1H),2.03(d,2H),1.84(d,2H),1.44(s,12H),1.03–0.91(m,2H).
(3)4-N-{2-甲基-4-[5-(3,5-二氯-苯基)-5-三氟甲基-4,5-二氢-异噁唑-3-基]苯甲酰基}亚甲基环己基甲酸丙炔酯(化合物A-9)的合成
向装有4-[(叔丁氧羰基)甲基]环己烷甲酸2-丙炔-1-基酯(355.0mg,1.2mmol)的圆底烧瓶中加入4mL三氟乙酸/二氯甲烷(V/V=1:1),室温反应2h。浓缩得到黄色油状物。将2-甲基-4-{[5-(3,5)-二氯苯基]-4,5-二氢-5-三氟甲基-3-异噁唑基}-1-苯甲酸(418.2mg,1.0mmol),1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(280.9mg,1.2mmol),1-羟基苯并***(162.2mg,1.2mmol)溶于10mL二氯甲烷中得到混合液。将上述黄色油状物溶于5mL二氯甲烷中,加入N,N-二异丙基乙胺(387.9mg,3.0mmol)搅拌10min后将其滴加到上述混合液中,室温反应12h。反应结束后分别用水30mL洗涤有机层2次,饱和食盐水洗涤1次。有机层用无水硫酸钠干燥,过滤、浓缩,再经柱层析分离得到白色固体。1H NMR(600MHz,CDCl3)δ(ppm):7.50(dd,4H),7.43(t,1H),7.39(d,1H),5.86(t,1H),4.67(d,2H),4.08(d,1H),3.70(d,1H),3.31(t,2H),2.46(d,3H),2.37–2.26(m,1H),2.14–1.97(m,2H),1.93–1.85(m,2H),1.69–1.55(m,2H),1.46(qd,2H),1.07(tt,2H).
实施例3:化合物C-2的制备
(1)4-[(叔丁氧羰基)甲基]环己烷甲酸硫代乙酯的合成
依次将4-[(叔丁氧羰基)甲基]环己烷羧酸(514.7mg,2mmol),乙硫醇(149.3mg,2.4mmol),2-(1H-苯并三偶氮L-1-基)-1,1,3,3-四甲基脲四氟硼酸酯(771mg,2.4mmol),N,N-二异丙基乙胺(775.9mg,6.0mmol)溶于15mL乙腈中,室温反应2h,经硅藻土过滤得到的滤液再用水洗1次,饱和食盐水洗1次,无水硫酸钠干燥,过滤、浓缩,经柱层析分离得到4-[(叔丁氧羰基)甲基]环己烷甲酸硫代乙酯。1H NMR(600MHz,CDCl3)δ(ppm):4.51(s,1H),2.91(t,2H),2.78(q,2H),2.35(tt,1H),1.92(d,2H),1.77(d,2H),1.46–1.30(m,12H),1.17(dd,3H),0.89(td,2H).
(2)4-N-{2-甲基-4-[5-(3,5-二氯-苯基)-5-三氟甲基-4,5-二氢-异噁唑-3-基]苯甲酰基}亚甲基环己基甲酸硫代乙酯(化合物C-2)的合成
向装有4-[(叔丁氧羰基)甲基]环己烷甲酸乙硫酯(361.7mg,1.2mmol)的圆底烧瓶中加入4mL三氟乙酸/二氯甲烷(V/V=1:1),室温反应2h,浓缩得到黄色油状物。向装有2-甲基-4-{[5-(3,5)-二氯苯基]-4,5-二氢-5-三氟甲基-3-异噁唑基}-1-苯甲酸(418.2mg,1.0mmol)圆底烧瓶中加入氯化亚砜3mL,甲苯5mL,N,N-二甲基甲酰胺1滴,80℃反应2h后浓缩得到酰氯化合物。酰氯化合物溶于5mL二氯甲烷溶液备用。将上述黄色油状物溶于5mL二氯甲烷中,向其加入N,N-二异丙基乙胺(387.9mg,3.0mmol)并搅拌10min后将其滴加到溶于二氯甲烷的酰氯混合液中,室温下反应12h。反应结束后分别用水30mL洗涤有机层2次,饱和食盐水洗涤1次。有机层用无水硫酸钠干燥,过滤、浓缩,经柱层析分离得到白色固体。1HNMR(600MHz,CDCl3)δ(ppm):7.51(s,4H),7.42(d,2H),5.83(s,1H),4.09(dd,1H),3.70(dd,1H),3.37–3.27(m,2H),2.86(dt,2H),2.46(t,4H),2.08–1.98(m,2H),1.91(d,2H),1.64–1.58(m,1H),1.49(d,2H),1.25(dt,3H),1.07(d,2H).
实施例4:化合物B-2的制备
(1)4-[(叔丁氧羰基)甲基]-N-乙基-1-环己酰胺
0℃的冰水浴下,将4-[(叔丁氧羰基)甲基]环己烷羧酸(514.7mg,2.0mmol),二环己基碳二亚胺(619.0mg,3.0mmol)溶于6mL DMF中并搅拌30min。加入2mL乙胺的四氢呋喃溶液(2M)并保持0℃下搅拌1h,升至室温继续反应24h。反应结束后加水稀释,用乙酸乙酯萃取3次,并用饱和碳酸氢钠水溶液洗涤1次,再用柠檬酸水溶液洗涤1次。无水硫酸钠干燥,过滤、浓缩,经柱层析分离得到4-[(叔丁氧羰基)甲基]-N-乙基-1-环己酰胺。1H NMR(600MHz,CDCl3)δ(ppm):5.53(t,1H),4.69–4.56(m,1H),3.36–3.20(m,2H),2.98(t,2H),2.04–1.96(m,1H),1.94–1.89(m,2H),1.84(dd,,2H),1.55–1.34(m,12H),1.13(t,3H),0.95(qd,2H).
(2)4-N-{2-甲基-4-[5-(3,5-二氯-苯基)-5-三氟甲基-4,5-二氢-异噁唑-3-基]苯甲酰基}亚甲基环己基甲酸-N-乙酰胺(化合物B-2)的合成
向装有4-[(叔丁氧羰基)甲基]环己烷甲酸乙酰胺(341.3mg,1.2mmol)的圆底烧瓶中加入4mL三氟乙酸/二氯甲烷(V/V=1:1),室温反应2h,浓缩得到黄色油状物。将2-甲基-4-{[5-(3,5)-二氯苯基]-4,5-二氢-5-三氟甲基-3-异噁唑基}-1-苯甲酸(418.2mg,1.0mmol),1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(280.9mg,1.2mmol),1-羟基苯并***(162.2mg,1.2mmol)溶于10mL二氯甲烷中得到混合液。将上述黄色油状物溶于5mL二氯甲烷中,向其加入N,N-二异丙基乙胺(387.9mg,3.0mmol)搅拌10min后将其滴加到上述混合液中,室温下反应12h。反应结束后分别用水30mL洗涤有机层2次,饱和食盐水洗涤1次。有机层用无水硫酸钠干燥,过滤、浓缩,再经柱层析分离得到白色固体。1H NMR(600MHz,CDCl3)δ(ppm):7.11(dd,2H),7.04(d,2H),6.93(d,1H),5.41(s,1H),5.03(s,1H),3.66–3.57(m,1H),3.51–3.43(m,1H),3.23(d,1H),2.85(t,2H),2.33(t,3H),1.99(d,3H),1.62–1.52(m,1H),1.51–1.39(m,4H),1.13(s,2H),1.03(dd,2H),0.84–0.75(m,1H),0.59(dd,2H).
按照上述实施例的记载,将原料进行替换即可制备获得通式I所示的其他化合物。
生物活性测定
实施例5:杀虫活性测定
根据待测化合物的溶解性,用丙酮或二甲基亚砜溶解,然后用0.1%的吐温80溶液配制成所需浓度的待测液50毫升,丙酮或二甲基亚砜在总溶液中的含量不超过10%,待用。
实施例5.1:对粘虫活性的测定
选新鲜玉米中部叶片剪成3厘米小段,放入至上述配制好的药液中浸渍10秒,阴干后置于放有滤纸的直径为9厘米的培养皿中,接入整齐的健康试虫(3龄),每处理14头,试验设4次重复,设清水处理为空白对照。处理后放入24℃,相对湿度60%-70%,自然光照的室内培养,72h后调查存活虫数,计算死亡率。
部分供试的化合物中,化合物A-1、A-2、A-3、A-4、A-6、A-7、A-8、A-9、A-10、A-11、A-12、A-16、A-17、A-18、A-20、B-1、B-2、B-3、C-1、C-2、D-1、D-2、D-11、E-1、E-2、G-1、G-2、G-3、H-1、H-2在浓度为600mg/L时对粘虫的防效较好,死亡率在80%以上。
实施例5.2:对小菜蛾活性的测定
选室温培养的甘蓝叶片,除去表面蜡质层,用打孔器打成直径为2厘米的圆形叶碟,放入至配制好的药液中浸渍10秒,阴干后置于放有滤纸的直径为9厘米的培养皿中,接入整齐的健康试虫(2龄),每处理10头,试验设4次重复,设清水处理为空白对照。处理后放入24℃,相对湿度60%-70%,自然光照的室内培养,72h后调查存活虫数,计算死亡率。
部分供试的化合物中,化合物A-1、A-2、A-3、A-4、A-6、A-7、A-8、A-9、A-10、A-11、A-12、A-17、A-18、A-20、B-1、B-2、B-3、C-1、C-2、D-1、D-2、D-11、E-1、E-2、G-1、G-2、H-1、H-2在浓度为600mg/L时对小菜蛾的防效较好,死亡率在80%以上。
实施例5.3:对桃蚜活性的测定
取直径6厘米培养皿,皿底覆一层滤纸,并滴加适量自来水保湿。从培养桃蚜的甘蓝植株上剪取大小适宜(直径约3厘米)且长有15-30头蚜虫的甘蓝叶片,去除有翅蚜和叶片正面的蚜虫,调查结束后,叶背向置于培养皿内,用手持式Airbrush喷雾器进行喷雾处理,喷液量为0.5毫升,试验设3次重复,处理后置于标准观察室内,48h后调查存活数,计算死亡率。
部分供试的化合物中,化合物A-1、A-2和A-11在浓度为600mg/L时对桃蚜的防效较好,死亡率在80%以上。
实施例5.4:杀螨活性测定
根据待测化合物的溶解性,用丙酮或二甲基亚砜溶解,然后用0.1%的吐温80溶液配制成所需浓度的待测液50毫升,丙酮或二甲基亚砜在总溶液中的含量不超过10%。
在处理前一天选择具有两片真叶的菜豆苗,移栽于培养纸杯中,每杯一株。待移栽苗恢复正常生长后,于处理前3h剪去心叶及一片真叶,在上面接上适量的雌成螨,并记录基数。用Airbrush喷雾机在叶片正反面均匀喷雾。待叶片自然阴干后移入标准观察室内,定期观察,72h后进行调查,记录整株菜豆苗上的活虫数,计算死亡率。
部分供试的化合物中,化合物A-2、A-4、A-6、A-7、A-8、A-11、A-15、B-1、B-2、C-1、C-2在浓度为100mg/L时对螨虫的防效较好,死亡率在80%以上。
进一步的采用本发明化合物A-2与对照化合物KC1对朱砂叶螨成螨活性的平行测定结果见下表3。
表3:化合物A-2和KC1对朱砂叶螨活性的平行测定结果(死亡率,%)
实施例5.5:跳甲成虫测定
选择温室栽培的新鲜甘蓝叶片,用打孔器打成大小一致的甘蓝叶碟,然后按试验设计从低剂量到高剂量的顺序进行均匀喷雾,每叶蝶1.5mL,自然阴干后置于50mL聚乙烯离心管中,接入整齐、健康的跳甲成虫,每处理20头,3次重复,另设空白对照。处理后将试材置于一定条件的观察室中,72h后调查死、活虫数。
部分供试的化合物中,化合物A-2、A-4、A-6、A-7、A-8、A-11、A-15、B-1、B-2、C-1、C-2在浓度为600mg/L时对跳甲的防效较好,死亡率在80%以上。
进一步的采用本发明化合物A-2与对照化合物KC1对跳甲成虫活性的平行测定结果见下表4。
表4:化合物A-2和KC1对跳甲活性的平行测定结果(死亡率,%)
Claims (10)
2.按权利要求1所述的异噁唑啉类衍生物,其特征在于:所述通式I中,
X1、X3选自F、Cl或Br;
X2选自H、F、Cl或Br;
R1选自H、C1-C6烷基、C3-C8环烷基、C2-C6烯烃、C2-C6炔烃、被F、Cl或Br取代的C1-C6烷基、-CH2C(O)R2或被氰基取代的C1-C3烷基,其中R2表示C1-C3烷基。
3.按权利要求2所述的异噁唑啉类衍生物,其特征在于:所述通式I中,
X1、X3选自Cl;
X2选自H、F或Cl;
R1选自H、C1-C6烷基、C3-C8环烷基、C2-C6烯烃、C2-C6炔烃、被F或Cl取代的C1-C6烷基、亚甲基氰基、1,2-亚乙基氰基、1,1-亚乙基氰基、亚异丙基氰基或-CH2C(O)R2,其中R2表示甲基、乙基或正丙基。
5.按权利要求4所述的中间体化合物,其特征在于:式中,
A1选自NH、O或S;
R1选自H、C1-C6烷基、C3-C8环烷基、C2-C6烯烃、C2-C6炔烃、被F、Cl或Br取代C1-C6烷基、-CH2C(O)R2或被氰基取代的C1-C3链烷基,其中R2表示C1-C3烷基;
或,式III所示化合物的盐酸盐或三氟乙酸盐。
6.按权利要求5所述的中间体化合物,其特征在于:式中,
A1选自NH、O或S;
R1选自H、C1-C6烷基、C3-C8环烷基、C2-C6烯烃、C2-C6炔烃、被F或Cl取代的C1-C6链烷基、亚甲基氰基、1,2-亚乙基氰基、1,1-亚乙基氰基、亚异丙基氰基或-CH2C(O)R2,其中R2表示甲基、乙基或正丙基;
或,式III所示化合物的盐酸盐或三氟乙酸盐。
8.一种按照权利要求1所述的通式I化合物在控制害虫、害螨中的应用。
9.一种杀虫、杀螨组合物,其特征在于:组合物含有活性成分和农业、林业或卫生上可接受的载体;其中,活性成分的重量百分含量为1-99%,活性成分含权利要求1所述的通式I所示化合物。
10.一种控制螨害、虫害的方法,其特征在于:将权利要求1所述的组合物以每公顷10克到1000克的有效剂量施于需要控制的害虫、害螨或其生长的介质上。
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JP2008239611A (ja) * | 2007-02-27 | 2008-10-09 | Nissan Chem Ind Ltd | イソキサゾリン置換ベンズアミド化合物及び有害生物防除剤 |
CN102911066A (zh) * | 2012-10-18 | 2013-02-06 | 白银朗佑生物医药科技有限公司 | 反式-4-氨基环己基甲酸衍生物的合成方法 |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1930136A (zh) * | 2004-03-05 | 2007-03-14 | 日产化学工业株式会社 | 异噁唑啉取代苯甲酰胺化合物及有害生物防除剂 |
CN102532048A (zh) * | 2004-03-05 | 2012-07-04 | 日产化学工业株式会社 | 异噁唑啉取代苯甲酰胺化合物的制备中间体 |
JP2008239611A (ja) * | 2007-02-27 | 2008-10-09 | Nissan Chem Ind Ltd | イソキサゾリン置換ベンズアミド化合物及び有害生物防除剤 |
CN102911066A (zh) * | 2012-10-18 | 2013-02-06 | 白银朗佑生物医药科技有限公司 | 反式-4-氨基环己基甲酸衍生物的合成方法 |
Non-Patent Citations (1)
Title |
---|
靳贝贝: "具体化合物", STN 检索报告, pages 1 - 3 * |
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