WO2010060379A1 - 具有含氮五元杂环的醚类化合物及其应用 - Google Patents

具有含氮五元杂环的醚类化合物及其应用 Download PDF

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WO2010060379A1
WO2010060379A1 PCT/CN2009/075131 CN2009075131W WO2010060379A1 WO 2010060379 A1 WO2010060379 A1 WO 2010060379A1 CN 2009075131 W CN2009075131 W CN 2009075131W WO 2010060379 A1 WO2010060379 A1 WO 2010060379A1
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alkyl
hydrogen
group
alkoxy
halogenated
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PCT/CN2009/075131
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English (en)
French (fr)
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刘长令
李淼
王军锋
张金波
张弘
郝树林
张静
杨吉春
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中国中化集团公司
沈阳化工研究院有限公司
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Priority to BRPI0922073A priority Critical patent/BRPI0922073B1/pt
Priority to US13/121,334 priority patent/US8222280B2/en
Priority to CN2009801381313A priority patent/CN102216294B/zh
Publication of WO2010060379A1 publication Critical patent/WO2010060379A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • 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
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-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
    • A01N43/72—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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07D401/04—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 directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07D409/04—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 directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07D417/02—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
    • C07D417/04—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 directly linked by a ring-member-to-ring-member bond

Definitions

  • the invention belongs to the field of agricultural insecticides and fungicides.
  • it relates to an ether compound having a nitrogen-containing five-membered heterocyclic ring, and the use thereof as an insecticidal or bactericidal agent in agriculture or other fields.
  • insects generally cause damage to crop growth not only in agriculture, but also damage to buildings and lawns, such as damage caused by soil insects such as termites and mites.
  • Insecticides and acaricides are useful in controlling insects and mites, but can cause significant damage to crops such as wheat, corn, soybeans, potatoes and cotton. From the protection of crops, humans need insecticides and acaricides that can control insects and mites without harming crops, while not being toxic to mammals and other living organisms.
  • Dihalogenated propylene compounds having insecticidal and acaricidal activity are reported in the following patents: CN1137265, CN1318535, CN168177K CN1780818, CN1780825, CN1860874, CN101208088, US5872137, US5922880, US6071861, US20060247283, US20050288186, US20040224994, US20070142229 WO2003074498, and the like. No reports have been reported on the bactericidal activity of such compounds. At the same time, people need to continuously develop novel insecticidal and fungicides to meet the needs of pests and diseases in agriculture or other fields.
  • the compound represented by this class, Pyridalyl is a patented product of Sumitomo Chemical Co., Ltd., which has excellent effects on a wide range of lepidopteran pests on vegetables and cotton.
  • the structural formula is as follows:
  • the object of the present invention is to provide an ether compound having a nitrogen-containing five-membered heterocyclic ring which can control various pests and diseases at a small dose, which can be applied to agriculture to control crop diseases and pests, or It is used as an insecticide and fungicide in his field.
  • the present invention provides an ether compound having a nitrogen-containing five-membered heterocyclic ring, as shown in the general formula (I):
  • R 2 is selected from the group consisting of hydrogen, halogen, CN, C0 2 R6, C r C 12 alkyl, halogenated C r C 12 alkyl, C r C 12 alkoxy, halo 12 alkoxy, 12 alkylthio, Halogenated 12 alkylthio, C 3 -C 6 cycloalkyl or R 7;
  • R 3 , R 4 and R 5 may be the same or different and are respectively selected from the group consisting of hydrogen, halogen, hydroxy, decyl, cyano, nitro, C r C 12 , and Ci-Ci2 3 ⁇ 43 ⁇ 4 ⁇ 4M4 ⁇ 4 C2-C 12 Hickey.
  • X is selected from NR 8 or 0;
  • Rg is selected as white hydrogen, Ci-Ci2 3 ⁇ 43 ⁇ 43 ⁇ 4 ⁇ ⁇ Ci-Ci2 3 ⁇ 43 ⁇ 43 ⁇ 4 C1-C12 Ci-Ci2 3 ⁇ 43 ⁇ 43 ⁇ 4 C1-C12 haloalkoxy C r C 12 alkyl, C 3 -C 6 cycloalkyl or R 7;
  • ⁇ ⁇ 2 may be the same or different and are respectively selected from hydrogen, fluorine, chlorine, bromine, CH 3 , CN or CF 3 ;
  • a 2 may be the same or different and are respectively selected from 0, S or ⁇ ;
  • R 7 is selected from aryl, heteroaryl, aryl dC 12 alkyl or heteroaryl C r C 12 alkyl, or the above groups further substituted by 1 to 5 groups independently selected from the group consisting of halogen, N0 2 , CN, C0 2 R6, CONHR 6 , CC 6 ⁇ ⁇ Ci-C 6 Ci-C 6 Ci-C 6 Ci-C 6 3 ⁇ 43 ⁇ 4 sulfonyl or R 7 ;
  • Q is selected from the group consisting of -CH 2 - , -CH 2 CH 2 , -CH 2 CH 2 CH 2 , -CH 2 CH 2 CH 2 CH 2 , -CH 2 CH 2 CH 2 CH 2 CH 2 , -CH(CH 3 )- , -CH(CH 3 )CH 2 - , -CH(CH 3 )CH 2 CH 2 - , -CH 2 CH 2 CH(CH 3 ) -, -CH(C 2 H 5 )-, -C(CH 3 ) 2 -, -CH(CH 3 )CH(CH 3 )-, -CH 2 C(CH 3 ) 2 CH 2 -, -CH2CH2OCH2CH2-, -CH2CH2NHCH2CH2-, -CH2CH2SCH2CH2-, -CH 2 CH 2 S0 2 CH 2 CH 2 -, -CH 2 COCH 2 -, -COCH 2 CO-, - CH 2 CH 2 CO-, -CO
  • the position of attachment of A 2 to the heterocyclic ring is selected from the 3, 4 or 5 position; when A 2 is bonded to the 5-position of the heterocyclic ring, it is in the 3 position, and R 2 is in the 4 position; when A 2 is bonded to the 3 position of the heterocyclic ring, Then in the 5 position, R 2 is in the 4 position; when A 2 is connected to the 4 position of the heterocyclic ring, it is in the 3 position and R 2 is in the 5 position.
  • Preferred compounds in the present invention are: in the formula (I)
  • R 2 is selected from the group consisting of hydrogen, halogen, CN, C0 2 R6, C r C 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy, halogenated C r C 6 alkoxy, C r C 6 alkylthio, halogenated C r C 6 alkylthio, C 3 -C 6 cycloalkyl or R 7 ;
  • R 3 , and R 5 may be the same or different and are respectively selected from hydrogen, halogen or C r C 6 alkyl;
  • X is selected from NR 8 or 0;
  • R 8 is selected from the group consisting of hydrogen, C r C 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy C r C 6 alkyl, dC 6 haloalkoxy C r C 6 alkyl, C 3 -C 6 cycloalkyl or R 7 ;
  • ⁇ ⁇ 2 may be the same or different and are respectively selected from hydrogen, fluorine, chlorine, bromine, CH 3 , CN or CF 3 ;
  • a 2 may be the same or different and are respectively selected from 0, S or ⁇ ;
  • R 7 is selected from the group consisting of phenyl, pyridyl, pyrimidinyl, triazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, furyl, thienyl, thiazolyl, benzyl, pyridylmethyl, thienylmethyl Or thiazolylmethyl, or the above groups further substituted by 1-3 independently selected from the group consisting of: halogen, N0 2 , CN, C0 2 R6, CONHR ⁇ CC 6 alkyl, halogenated C r C 6 alkyl , C r C 6 alkoxy, halogenated C r C 6 alkoxy, C r C 6 alkylthio, C r C 6 alkylsulfonyl, phenyl, p-chlorophenyl, phenoxy or p-chloro Phenoxy group;
  • Q is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -,
  • the position of attachment of A 2 to the heterocyclic ring is selected from the 3, 4 or 5 position; when A 2 is bonded to the 5-position of the heterocyclic ring, it is in the 3 position, and R 2 is in the 4 position; when A 2 is bonded to the 3 position of the heterocyclic ring, Then in the 5 position, R 2 is in the 4 position; when A 2 is connected to the 4 position of the heterocyclic ring, it is in the 3 position and R 2 is in the 5 position.
  • Further preferred compounds of the invention are: in formula (I)
  • R 2 is selected from the group consisting of hydrogen, halogen, CN, C0 2 R6, C r C 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy, halogenated C r C 6 alkoxy, C r C 6 alkylthio, halogenated C r C 6 alkylthio, C 3 -C 6 cycloalkyl or R 7 ;
  • R 3 is selected from chlorine
  • R 5 may be the same or different and are respectively selected from hydrogen or chlorine
  • X is selected from NR 8 or 0;
  • R 8 is selected from C r C 6 alkyl, halo C r C 6 alkyl or R 7;
  • ⁇ ⁇ 2 is selected from chlorine
  • ⁇ ⁇ 2 is selected from ⁇
  • R 7 is selected from phenyl, pyridyl, furyl, thienyl, thiazolyl or benzyl, or the above groups are further substituted by 1 to 3 groups independently selected from: halogen, N0 2 , CN, C0 2 R 6 , CONHR ⁇ C r C 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy, halogenated C r C 6 alkoxy, C r C 6 alkylthio, C r C 6 alkylsulfonyl, phenyl, p-chlorophenyl, phenoxy or p-chlorophenoxy;
  • Q is selected from -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or -CH 2 CH 2 CH 2 CH 2 -;
  • the position of A 2 is connected to the heterocycle is selected from 3, 4 or 5; when A 2 is connected to a heterocyclic 5, at 3, 4 in the structural formula shown in Figure 1-1; when the heterocycle 2 When 3-bit is connected, it is 5 digits, in 4 digits, and the structural formula is as shown in 1-2; when 2 is connected to the heterocyclic 4-position, it is in 3 digits, in 5 digits, and the structural formula is as shown in 1-3;
  • R 2 is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, CN, C0 2 R 6 or C r C 6 alkyl;
  • R 5 may be the same or different and are respectively selected from hydrogen or chlorine
  • X is selected from NR 8 ;
  • R8 is selected from the group of Ci-C4;
  • R 7 is selected from phenyl or phenyl which is further substituted by 1 to 3 groups independently selected from the group consisting of fluorine, chlorine, bromine, C r C 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy, halogenated C r C 6 alkoxy or C r C 6 alkylthio;
  • Q is selected from -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or -CH 2 CH 2 CH 2 CH 2 -;
  • R 2 is selected from the group consisting of hydrogen, fluorine, chlorine, bromine or C r C 6 alkyl
  • R 5 may be the same or different and are respectively selected from hydrogen or chlorine
  • X is selected from NR 8 ;
  • R 8 is selected from C r C 4 alkyl or R 7 ;
  • R 7 is selected from phenyl or phenyl which is further substituted by 1 to 3 groups independently selected from the group consisting of fluorine, chlorine, bromine, CN, dC 6 fluorenyl, halogenated dC 6 fluorenyl, dC 6 decyloxy And halogenated dC 6 decyloxy or dC 6 sulfonylthio;
  • Q is selected from -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or -CH 2 CH 2 CH 2 CH 2 - .
  • Still further preferred compounds of the present invention are: in the formula (1-1) or in the formula (1-2)
  • a phenyl group selected from phenyl or further substituted with 1-3 independently selected from the group consisting of fluorine, chlorine, bromine,
  • R 2 is selected from the group consisting of hydrogen, chlorine or c r c 4 alkyl
  • R 5 may be the same or different and are respectively selected from hydrogen or chlorine
  • X is selected from NR 8 ;
  • R8 is selected from the group of C r C4;
  • Q is selected from -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or -CH 2 CH 2 CH 2 CH 2 -;
  • R 2 is selected from the group consisting of hydrogen, fluorine, chlorine, bromine or C r C 4 alkyl
  • R 5 may be the same or different and are respectively selected from hydrogen or chlorine
  • X is selected from NR 8 ;
  • R 8 is selected from C r C 4 alkyl, phenyl, or phenyl which is further substituted by 1 to 3 groups independently selected from the group consisting of fluorine, chlorine, bromine, C r C 4 alkyl, halogenated C r C a 4- alkyl, C r C 4 alkoxy or halogenated C r C 4 alkoxy group; selected from hydrogen or C r C 4 alkyl;
  • Q is selected from -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or -CH 2 CH 2 CH 2 CH 2 - .
  • Unsubstituted means that all substituents are hydrogen.
  • Halogen refers to fluorine, chlorine, bromine or iodine.
  • Alkyl a linear or branched alkane such as methyl, ethyl, propyl, isopropyl or t-butyl.
  • Haloalkyl a straight or branched alkyl group in which a hydrogen atom may be partially or completely substituted by a halogen atom, for example, a haloalkyl group such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl Base, difluoromethyl or trifluoromethyl.
  • Alkenyl straight or branched and may have a double bond at any position, such as a vinyl or allyl group.
  • Block base Straight or branched and may have a triple bond at any position, such as an ethyl group or a block propyl group.
  • the aryl group in the aryl group and the aralkyl group includes a phenyl group or a naphthyl group and the like.
  • the heteroaryl group referred to in the present invention is a five-membered or six-membered ring containing one or more N, 0, S hetero atoms.
  • pyridine furan, pyrimidine, pyrazine, pyridazine, triazine, quinoline, thiazolyl, benzothiazolyl, benzofuran and the like.
  • preferred partial groups of R and R 2 and substituents thereof are shown in Tables 1 to 9.
  • Q -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 - R 4 , may be the same or different, respectively, select H, CI Is/D/ Osz-osId 6/-iosoiAV
  • the compound represented by the formula (I) of the present invention may be alkaline with a hydroxyl group-containing pyrazole or isoxazole compound represented by the formula (II) and a halogenated propylene compound represented by the formula (IV).
  • the condensation is obtained under the conditions, or the pyrazole or isoxazole compound represented by the formula (III) and the hydroxyl group-containing halogenated propylene compound represented by the formula (V) can be condensed under alkaline conditions.
  • L is a leaving group selected from chlorine or bromine; and the other groups are as defined above.
  • the compounds of the formulae (IV) and (V) can be produced by known methods, as described in more detail in CN1860874, US20030073847 and W09727173.
  • a suitable solvent may be selected from, for example, tetrahydrofuran, acetonitrile, toluene, xylene, benzene, N,N-dimethylformamide, dimethyl sulfoxide, acetone or methyl ethyl ketone.
  • Suitable bases may be selected from, for example, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium t-butoxide or sodium t-butoxide.
  • the reaction temperature may be between room temperature and the boiling point of the solvent, and is usually from 20 to 100 °C.
  • the reaction time is from 30 minutes to 20 hours, usually from 1 to 10 hours.
  • the intermediate (II) is commercially available or can be prepared according to known methods. Wherein: when the 3- or 5-position of the 5-membered heterocyclic ring is a hydroxyl group, it is prepared by condensation of an intermediate (VI) with a (substituted) anthracene or hydroxylamine, see: WO2005080344A1, Synlett 2004, 5, 795-798, J. Chem. Soc, Perkin Trans. 2, 1987, 969-975, and the like. When the 4-position of the five-membered heterocyclic ring is a hydroxyl group, it can be obtained by esterification of the intermediate (VI) and ring-forming with an amine compound, see Organic Preparation and Procedures International, 2002, 34(1): 98-102.
  • the general formula (III) can be obtained by halogenation of the general formula (II).
  • the compound of the formula (I) of the present invention exhibits high insecticidal activity against adults, larvae and eggs of harmful insects in the fields of agriculture, civil and animal technology. Some of the compounds showed better bactericidal activity. Accordingly, the present invention also encompasses the use of the compound of formula (I) as an insecticide and/or bactericide in agriculture and other fields.
  • the compounds of the general formula (I) are active against important pests of the following families and purposes: Lepidopteran pests such as Chilo suppressalis, Rice leaf roller, Corn borer, Tobacco moth, Small heartworm, Plutella xylostella, Beet armyworm , Spodoptera litura, etc.
  • Lepidopteran pests such as Chilo suppressalis, Rice leaf roller, Corn borer, Tobacco moth, Small heartworm, Plutella xylostella, Beet armyworm , Spodoptera litura, etc.
  • Plutella xylostella and Spodoptera exigua are more active, and good results can be obtained at very low doses.
  • the present invention also has high activity against pests of the same wing, such as aphids. Therefore, the compound of the formula (I) of the present invention is preferably used for the control of lepidopteran and homopteran pests in agriculture and other fields.
  • some of the compounds of the invention have good bactericidal activity and can be used for controlling rice blast, tomato late blight, vegetable gray mold, wheat powdery mildew, cucumber downy mildew, anthracnose, etc., especially for rice blast Cucumber downy mildew and anthrax have good activity.
  • the compounds of formula (I) are less toxic to many beneficial insects and aphids, mammals, fish, birds, and are not phytotoxic.
  • the above compounds are advantageously used to protect crops, livestock and stocks important in agriculture and horticulture, as well as the environment frequented by humans from harmful insects and fungi.
  • the amount of the compound varies depending on various factors such as the compound used, the crop to be protected, the type of the pest, the degree of infection, the climatic conditions, the method of application, and the dosage form employed.
  • a dose of 10 grams to 1000 grams of compound per hectare provides adequate control.
  • a further object of the invention relates to the control of insect and/or phytopathogenic fungi in an environment which is important for agriculture and horticulture, and/or livestock and livestock and/or humans, by administering a compound of the general formula (I). Methods.
  • the amount of the compound varies from 10 g to 1000 g per hectare.
  • composition comprising one or more compounds of formula (I).
  • another object of the present invention relates to an insecticidal and/or bactericidal composition containing one or more compounds of the formula (I) as an active ingredient, the active ingredient being present in an amount of from 0.1 to 99% by weight.
  • compositions may be used in the form of dry powders, wettable powders, emulsifiable concentrates, microemulsions, pastes, granules, solutions, suspensions and the like: The choice of the type of composition depends on the particular application.
  • composition is prepared by known methods, for example by diluting or dissolving the active substance with a solvent medium and/or a solid diluent, optionally in the presence of a surfactant.
  • Useful solid diluents or carriers are, for example: silica, kaolin, bentonite, talc, diatomaceous earth, dolomite, calcium carbonate, magnesium oxide, chalk, clay, synthetic silicate, attapulgite, sepiolite, etc. .
  • useful liquid diluents include, for example, aromatic organic solvents (mixtures of xylene or alkylbenzenes, chlorobenzene, etc.), paraffin (petroleum fractions), alcohols (methanol, propanol, butanol, octanol). , glycerol), esters (ethyl acetate, isobutyl acetate, etc.), ketones (cyclohexanone, acetone, acetophenone, isophorone, ethyl amyl ketone, etc.), amides (N, N) - dimethylformamide, N-methylpyrrolidone, etc.).
  • Usable surfactants are sodium, calcium, triethylamine, such as alkyl sulfonates, alkyl aryl sulfonates, polyoxyethylene alkyl phenols, polyoxyethylene esters of sorbitol, lignosulfonates, and the like. Or triethanolamine salt.
  • composition may also contain specific additives for specific purposes, such as containing a binder such as acacia, polyvinyl alcohol, polyvinylpyrrolidone or the like.
  • a binder such as acacia, polyvinyl alcohol, polyvinylpyrrolidone or the like.
  • the concentration of the active ingredient in the above composition may vary widely depending on the active ingredient, the purpose of use, the environmental conditions, and the type of preparation employed.
  • the concentration of the active ingredient is usually in the range of 0.5 to 90%, preferably 5 to 60%.
  • compositions may be added to the composition, such as other acaricides/insecticides, fungicides, plant growth regulators, antibiotics, herbicides, fertilizers.
  • active ingredients compatible with the compound of formula (I) may be added to the composition, such as other acaricides/insecticides, fungicides, plant growth regulators, antibiotics, herbicides, fertilizers.
  • suspending agent The active ingredient content in the commonly used formulation is 5-35%.
  • the water is used as a medium, and the original drug, the dispersing agent, the suspending agent and the antifreezing agent are added to a sand mill to be ground to prepare a suspension.
  • Preparation of water emulsion The original drug, solvent and emulsifier are added together to dissolve into a uniform oil phase. Water, antifreeze, and the like are mixed together to form a uniform aqueous phase. The aqueous phase is added to the oil phase or the oil phase is added to the aqueous phase under high-speed agitation to form a water emulsion having good dispersibility.
  • the aqueous emulsion active ingredient of the present invention is generally present in an amount of from 5% to 15%.
  • the compound of the present invention can be dissolved in one or several mixed solvents, and an emulsifier is added to enhance the dispersion of the compound in water.
  • Preparation of wettable powder According to the formulation requirements, the original drug, various surfactants and solid diluents are thoroughly mixed, and after being pulverized by an ultrafine pulverizer, a predetermined content (for example, 10-60%) of wettable powder is obtained. product.
  • the compounds of the invention may be admixed with finely divided solid powders such as clays, inorganic silicates, carbonates, and wetting agents, binders and/or dispersing agents.
  • Preparation of water-dispersible granules Mix and pulverize the original drug with powdered solid diluent, wetting spreader and binder, add water and knead, and then add it to a granulator equipped with a certain size sieve. Granulation, then drying and sieving (by screen area).
  • the original drug, dispersing agent, disintegrating agent and wetting agent and solid diluent may also be added to a sand mill, ground with water as a suspending agent, and then spray-dried and granulated, usually in a content of 20- 30% granular product.
  • Compound 8 an oily substance. Sppm 7.67(m, 2H), 7.27(m, 2H), 6.84(s, 2H), 6.12(t, 1H), 5.84(s, 1H), 4.59(d, 2H), 4.40(t, 2H), 4.14(t, 2H), 3.69(s, 3H), 2.50(s, 3H), 2.32(m, 2H).
  • Compound 21 an oil. 5ppm 7.78(m, 1H), 7.42(m, 1H), 7.23(m, 2H), 6.84(s, 2H), 6.11(m, 2H), 4.58(d, 2H), 4.42(t, 2H), 4.16(t, 2H), 3.72(s, 3H), 2.33(m, 2H).
  • Compound 76 an oil. ⁇ 7.63(d, 2 ⁇ ), 7.4 l(t, 2H), 7.32(t, 1H), 6.83(s, 2H), 6.10(t, 1H), 4.58(d, 2H), 4.40(t, 2H) , 4.18(t, 2H), 3.76(s, 3H), 2.3 l(m, 2H), 2.17(s, 3H).
  • Compound 130 an oil. ⁇ 7.70(m, 2 ⁇ ), 7.34(m, 2H), 6.84(s, 2H), 6.12(t, 1H), 4.58(d, 2H), 4.42(t, 2H), 4.15(t, 2H), 4.04 (m, 2H), 2.32 (m, 2H), 1.37 (m, 3H).
  • Compound 148 Oil. ⁇ 7.68(d, 2 ⁇ ), 7.33(d, 2H), 7.08(s, 1H), 6.39(t, 1H), 6.10(s, 1H), 4.77(d, 2H), 4.39(t, 2H), 4.24(t, 2H), 3.64(s, 3H), 2.34(m, 2H).
  • Compound 235 Oil. ⁇ 7.58(d, 2 ⁇ ), 7.39(t, 2H), 7.28(t, 1H), 7.11(s, 2H), 6.38(t, 1H), 4.66(d, 2H), 4.44(t, 2H), 4.23(t, 2H), 3.71(s, 3H), 2.14(s, 3H).
  • Compound 247 Oil. ⁇ 7.67(d, 2 ⁇ ), 7.3 l(d, 2H), 6.96(s, 2H), 6.27(t, 1H), 5.96(s, 1H), 4.63(d, 2H), 4.20(t, 2H) , 3.99(t, 2H), 3.63(s, 3H), 2.02(m, 4H).
  • Compound 248 Oil. ⁇ 7.68(d, 2 ⁇ ), 7.45(d, 2H), 7.33(d, 2H), 7.01(s,lH), 6.33(t, 1H), 5.71(s, 1H), 4.64(d, 2H), 3.97(t, 2H), 3.68(t, 2H), 3.56(s, 3H), 1.94 (m, 4H).
  • Compound 268 Oily. ⁇ 7.43(m, 5 ⁇ ), 6.84(s, 2 ⁇ ), 6.15(t, 1H), 5.68(s, 1H), 4.60(d, 2H), 4.43(t, 2H), 4.18(t, 2H), 3.77(s, 3H), 2.32(m, 2H).
  • Compound 350 Oily. 5ppm 7.49(m, 3H), 7.45(m, 2H), 6.96(s, 1H), 6.92(s, 1H), 4.48(m, 2H), 4.17(m, 2H), 3.64(s, 3H), 2.3 l(m, 2H), 1.88(s, 3H), 1.25(s, 3H).
  • Compound 352 Oil. 5ppm 7.30(m, 2H), 7.18(m, 2H), 6.84(s, 2H), 6.12(t, 1H), 4.58(d, 2H), 4.49(t, 2H), 4.17(t, 2H), 3.60(s, 3H), 2.32(m, 2H), 1.85(s, 3H).
  • Compound 356 Oil. 5ppm 7.22(m, 2H), 6.98(m, 2H), 6.84(s, 2H), 6.11(t, 1H),
  • Compound 360 oily. 5ppm 7.52(m, 1H), 7.33(m, 1H), 7.18(m, 1H), 6.82(s, 2H), 6.10(t, 1H), 4.56(d, 2H), 4.45(t, 2H), 4.15(t, 2H), 3.47(s, 3H), 2.3 l(m, 2H), 1.74(s, 3H).
  • Compound 361 an oil.
  • Compound 363 Oil. 5ppm 7.25(m, 2H), 6.98(m, 2H), 6.84(s, 2H), 6.12(t, 1H), 4.58(d, 2H), 4.47(t, 2H), 4.17(t, 2H), 3.86(s, 3H), 3.61(s, 3H), 2.32(m, 2H), 1.86(s, 3H).
  • Compound 367 Oil. Sppm 7.28(d, 2H), 7.2 l(d, 2H), 6.84(s, 2H), 6.12(t, 1H), 4.60(d, 2H), 4.47(t, 2H), 4.17(m, 2H) , 3.61(s, 3H), 2.42(s, 3H), 2.32(t, 2H), 1.86(s, 3H).
  • Compound 368 oil. 5ppm 7.21-7.31(m, 4H), 6.84(s, 2H), 6.12(t, 1H), 4.58(d, 2H), 4.47(t, 2H), 4.17(t, 2H), 3.62(s, 3H ), 2.7 l(m, 2H), 2.32(m, 2H), 1.87(s, 3H), 1.28(t, 3H).
  • Compound 376 an oil. Sppm 7.12(s, 1H), 7.06(m, 2H), 6.84(s, 2H), 6.12(t, 1H), 4.57(d,
  • Compound 377 Oil. 5ppm 7.24(m, 1H), 7.07(m, 2H), 6.84(s, 2H), 6.11(t, 1H), 4.58(d, 2H), 4.49(t, 2H), 4.17(t, 2H), 3.62(s, 3H), 2.34(s, 6H), 2.32(m, 2H), 1.86(s, 3H).
  • Compound 378 Oil. 5ppm 7.17(m, 2H), 6.96(s, 1H), 6.84(s, 2H), 6.10(t, 1H),
  • Compound 423 Oil. ⁇ 7.42(d, 2 ⁇ ), 7.34(d, 2H), 6.88(s, 1H), 6.19(t, 1H), 5.73(s, 1H), 4.68(d, 2H), 4.39(t, 2H), 4.15(t, 2H), 3.71(s, 3H), 2.3 l(m, 2H).
  • Compound 516 Oil. 5ppm 7.27(m, 2H), 7.18(m, 2H), 6.85(s, 2H), 6.12(t, 1H), 4.59(m, 4H), 4.36(m, 2H), 3.60(s, 3H), 2.41(s, 3H), 1.87(s, 3H).
  • Compound 522 Oil. ⁇ 7.43(s, 4 ⁇ ), 6.94(s, 2 ⁇ ), 6.24(t, 1H), 5.65(s, 1H), 4.63(d, 2H), 4.17(t, 2H), 3.98(t, 2H), 3.69 (s, 3H), 1.96 (s, 4H).
  • Compound 532 Oil. ⁇ 7.45(m, 3 ⁇ ), 7.3 l(d, 2H), 6.95(s, 2H), 6.27(t, 1H), 4.63(d, 2H), 4.19(t, 2H), 3.99(t, 2H) , 3.56(s, 3H), 1.96(s, 4H), 1.82(s, 3H).
  • Compound 540 Oil. 5ppm 7.27(m, 4H), 6.85(s, 2H), 6.13(t, 1H), 4.58(m, 2H), 4.29(m, 2H), 4.04(m, 2H), 3.62(s, 3H), 2.7 l(m, 2H), 2.03(m, 2H), 1.87(s, 3H), 1.29(t, 3H).
  • Compound 547 Oil. S ppm 7.64(d, 2H), 7.58(s, 1H), 7.50(s, 1H), 7.27(d, 2H), 6.84(s, 2H), 6.10 (t, 1H), 4.59(d, 2H) , 4.24 (t, 2H), 4.14(t, 2H), 2.28(q, 2H).
  • Compound 550 Oil. 5ppm 7.76(d, 2H), 7.65(s, 1H), 7.29(d, 2H), 6.38(s, 2H), 6.10 (t, 1H), 4.56(d, 2H), 4.44 (q, 2H), 4.33(t, 2H), 4.19(t, 2H), 2.35(q, 2H), 1.41 (t, 3H).
  • Compound 551 Oil. 5ppm 7.32(s, 1H), 7.29(d, 2H), 7.28(s, 1H), 7.26(d, 2H), 6.83(s, 2H), 6.11 (t, 1H), 4.59(d, 2H), 4.42 (q, 2H), 4.29(t, 2H), 4.18(t, 2H), 2.35(q, 2H), 2.22 (s, 3H), 1.41 (t, 3H).
  • Formulation examples (The components are added in a percentage by weight, and the active compound is metered in.)
  • Example 7 30% wettable powder
  • Compound 2 and other components were thoroughly mixed and pulverized by an ultrafine pulverizer to obtain a 30% wettable powder product.
  • Example 9 60% water dispersible granules
  • Kaolin is made up to 100% Compound 367 and other components were mixed and pulverized, kneaded by water, and then granulated by adding a 10-100 mesh sieve granulator, followed by drying and sieving (by sieve range).
  • Biological activity assay example
  • Example 10 Determination of insecticidal and acaricidal activity
  • test compound was dissolved in a mixed solvent of acetone/methanol (1:1) and diluted to the desired concentration with water containing 0.1% (wt) Tween 80.
  • the insecticidal activity was determined by the airbrush spray method with the target of Plutella xylostella.
  • Plutella xylostella The cabbage leaves were punched into a disc with a diameter of 1 cm.
  • the airbrush spray treatment pressure was 10 psi (about 0.7 kg/cm 2 ), and the spray was sprayed on the front and back of each leaf. It is 0.5 ml.
  • 10 heads of 2nd intestines were connected to each treatment, and each treatment was repeated 3 times.
  • the cells were cultured at 25 ° C and relative humidity of 60 to 70%, and the number of viable insects was investigated after 72 hours, and the mortality was calculated.
  • the compounds with a mortality rate of 100% for the second instar larvae of Plutella xylostella are 1, 2, 8, 11, 13, 16, 17, 18, 24, 26, 38, 76, 77, 86, 92, 225, 247, 248, 257, 268, 269, 278, 280, 283, 284, 293, 306, 352, 356, 360, 361, 363, 367, 368, 377, 387, 389, 500, 522, 532, 538, 546.
  • the lethal rate of the control drug pyridalyl was also 100%.
  • the concentration of the drug solution is 25 mg/L
  • the compounds with a mortality rate of 100% for the second instar larvae of Plutella xylostella are 2, 225, 247, 248, 268, 269, 352, 367, 377, 387.
  • the mortality rate of the control drug Upyridalyl was also 100%.
  • test method is as follows: Determination of the activity of the living body protection: The method of measuring the living body pot. The test compound was dissolved in a small amount of acetone, and diluted to the desired concentration with water containing 0.1% (wt) Tween 80. The spray was applied to the plant test material, and the disease was inoculated 24 hours later. After inoculation, the plants are placed in a constant temperature and humidity incubator to continue the infection, and the evaluation is conducted after the control is fully ill (usually one week).

Description

具有含氮五元杂环的醚类化合物及其应用 技术领域
本发明属农用杀虫、 杀菌剂领域。 具体地涉及一种具有含氮五元杂环的醚类化 合物， 以及使用它们在农业或其他领域中作为杀虫、 杀菌剂的应用。
背景技术
众所周知， 昆虫一般不仅在农业上造成农作物生长受损，也破坏建筑物和草坪， 例如由土壤昆虫 （例如白蚁和蛴螬） 造成的损害。
这种损害可导致相关的农作物、 草坪或建筑物的数百万美元的损失。 杀虫剂和 杀螨剂在防治昆虫和螨虫中是有用的， 但可能会对农作物例如小麦、 玉米、 大豆、 土豆和棉花等造成显著的损害。 从保护农作物出发人类需要既能防治昆虫和螨虫而 且不损害农作物， 同时对哺乳动物和其它活的生物无毒害作用的杀虫剂和杀螨剂。
如下专利报道了具有杀虫和杀螨活性的二卤丙烯化合物： CN1137265、 CN1318535、 CN168177K CN1780818、 CN1780825、 CN1860874、 CN101208088、 US5872137、 US5922880、 US6071861 、 US20060247283、 US20050288186、 US20040224994、 US20070142229 WO2003074498等。未见该类化合物具有杀菌活 性的报道。 同时人们需要不断开发结构新颖的杀虫、 杀菌剂， 以满足农业或其他领 域中用于防治病虫害的需要。该类化合物代表品种 Pyridalyl是日本住友化学株式会 社的一个专利产品， 对蔬菜和棉花上广泛的鳞翅目害虫具有卓效， 结构式如下：
Figure imgf000003_0001
发明内容
本发明的目的在于提供一种在很小的剂量下就可以控制各种病虫害的具有含氮 五元杂环的醚类化合物， 它可应用于农业上以防治作物的病害和虫害， 或其在他领 域中作为杀虫、 杀菌剂的应用。
本发明的技术方案如下：
本发明提供一种具有含氮五元杂环的醚类化合物， 如通式 （I ) 所示：
Figure imgf000003_0002
( I )
式中：
选自氢、 C02R6、 CrC12烷基、 卤代 CrC12烷基、 CrC12烷氧基 CrC12烷基、 C C12卤代烷氧基 CrC12烷基、 C3-C6环烷基或 R7 ;
R2选自氢、 卤素、 CN、 C02R6、 CrC12烷基、 卤代 CrC12烷基、 CrC12烷氧基、 卤代 12烷氧基、 12烷硫基、 卤代 12烷硫基、 C3-C6环烷基或 R7;
R3、 R4、 R5可相同或不同，分别选自氢、 卤素、羟基、巯基、氰基、硝基、 CrC12 院基、 Ci-Ci2 ¾¾¾ Ci-Ci2¾¾¾M¾ C2-C12希基、 l¾代 C2-C12希基、 C2-Ci2 块基、 12烷氧基、 ^代 12烷氧基、 C2-C12烯氧基、 ^代 C2-C12烯氧基、 C3-C12 块氧基、 卤代 C3-C12块氧基、 12烷硫基、 卤代 12烷硫基、 12烷基磺酰 、 Ci-Ci2 ¾¾¾M¾Ri¾ C1-C12 C1-C12 C1-C12 Ci-Ci2 ¾¾¾, 基羰基 CrC12烷基或 CrC12卤代烷氧基 CrC12烷基；
X选自 NR8或0;
Rg选白氢、 Ci-Ci2 ¾¾¾ \ ί Ci-Ci2 ¾¾¾ C1-C12 Ci-Ci2 ¾¾¾ C1-C12 卤代烷氧基 CrC12烷基、 C3-C6环烷基或 R7;
Υι Υ2可相同或不同， 分别选自氢、 氟、 氯、 溴、 CH3、 CN或 CF3 ;
A2可相同或不同， 分别选自 0、 S或 Ν ;
选自氢或 CrC12烷基；
R7选自芳基、 杂芳基、 芳基 d-C12烷基或杂芳基 CrC12烷基， 或者被 1-5个独 立选自以下基团进一步取代的上述基团： 卤素、 N02、 CN、 C02R6、 CONHR6、 C C6 \ ί Ci-C6 Ci-C6 Ci-C6 Ci-C6 Ci-C6 ¾¾ 基磺酰基或 R7 ;
Q 选 自 -CH2- 、 -CH2CH2- 、 -CH2CH2CH2- 、 -CH2CH2CH2CH2- 、 -CH2CH2CH2CH2CH2- 、 -CH(CH3)- 、 -CH(CH3)CH2- 、 -CH(CH3)CH2CH2- 、 -CH2CH2CH(CH3) -、 -CH(C2H5)-、 -C(CH3)2-、 -CH(CH3)CH(CH3)-、 -CH2C(CH3)2CH2-、 -CH2CH2OCH2CH2- 、 -CH2CH2NHCH2CH2- 、 -CH2CH2SCH2CH2- 、 -CH2CH2S02CH2CH2-、 -CH2COCH2-、 -COCH2CO-、 -CH2CH2CO-、 -COCH2CH2-、 -CH2CO- 、 -COCH2- 、 -CH2C(=NOCH3)CH2- 、 -CH2C(=NN(CH3)2)CH2- 、 -CH2CH(OH)CH2-、 -CH2CH(OCH3)CH2-、
Figure imgf000004_0001
A2与杂环的连接位置选自 3、 4或 5位； 当 A2与杂环 5位连接时， 则 在 3 位， R2在 4位； 当 A2与杂环 3位连接时， 则 在5位， R2在 4位； 当 A2与杂环 4 位连接时， 则 在3位， R2在 5位。 本发明中较为优选的化合物为： 通式 （I ) 中
选自氢、 C02R6、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基 CrC6烷基、 C C6卤代烷氧基 CrC6烷基、 C3-C6环烷基或 R7 ;
R2选自氢、 卤素、 CN、 C02R6、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6烷氧基、 CrC6烷硫基、 卤代 CrC6烷硫基、 C3-C6环烷基或 R7 ;
R3、 、 R5可相同或不同， 分别选自氢、 卤素或 CrC6烷基；
X选自 NR8或0;
R8选自氢、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基 CrC6烷基、 d-C6卤代 烷氧基 CrC6烷基、 C3-C6环烷基或 R7 ;
Υι Υ2可相同或不同， 分别选自氢、 氟、 氯、 溴、 CH3、 CN或 CF3 ;
A2可相同或不同， 分别选自 0、 S或 Ν ;
选自氢或 CrC6烷基；
R7选自苯基、 吡啶基、 嘧啶基、 ***基、 恶唑基、 噻二唑基、 恶二唑基、 呋喃 基、 噻吩基、 噻唑基、 苄基、 吡啶甲基、 噻吩甲基或噻唑甲基， 或者被 1-3个独立 选自以下基团进一步取代的上述基团： 卤素、 N02、 CN、 C02R6、 CONHR^ C C6 烷基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6烷氧基、 CrC6烷硫基、 CrC6烷 基磺酰基、 苯基、 对氯苯基、 苯氧基或对氯苯氧基；
Q选自 -CH2CH2-、 -CH2CH2CH2-、 -CH2CH2CH2CH2-、
Figure imgf000004_0002
A2与杂环的连接位置选自 3、 4或 5位； 当 A2与杂环 5位连接时， 则 在 3 位， R2在 4位； 当 A2与杂环 3位连接时， 则 在5位， R2在 4位； 当 A2与杂环 4 位连接时， 则 在3位， R2在 5位。 本发明进一步优选的化合物为： 通式 （I ) 中
选自氢、 C02R6、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基 CrC6烷基、 C C6卤代烷氧基 CrC6烷基、 C3-C6环烷基或 R7 ;
R2选自氢、 卤素、 CN、 C02R6、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6烷氧基、 CrC6烷硫基、 卤代 CrC6烷硫基、 C3-C6环烷基或 R7 ;
R3选自氯；
、 R5可相同或不同， 分别选自氢或氯；
X选自 NR8或0;
R8选自 CrC6烷基、 卤代 CrC6烷基或 R7;
Υι Υ2选自氯；
Αι Α2选自 Ο;
选自氢或 CrC6烷基；
R7选自苯基、 吡啶基、 呋喃基、 噻吩基、 噻唑基或苄基， 或者被 1-3个独立选 自以下基团进一步取代的上述基团： 卤素、 N02、 CN、 C02R6、 CONHR^ CrC6烷 基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6烷氧基、 CrC6烷硫基、 CrC6烷基 磺酰基、 苯基、 对氯苯基、 苯氧基或对氯苯氧基；
Q选自 -CH2CH2-、 -CH2CH2CH2-或 -CH2CH2CH2CH2-；
A2与杂环的连接位置选自 3、 4或 5位； 当 A2与杂环 5位连接时， 则 在 3 位， 在4位， 结构式如 1-1所示； 当 2与杂环 3位连接时， 则 在5位， 在 4位， 结构式如 1-2所示； 当 2与杂环 4位连接时， 则 在3位， 在5位， 结 构式如 1-3所示；
Figure imgf000005_0001
本发明更进一步优选的化合物为： 通式 （1-1 ) 或通式 （1-2) 中
选自氢、 C02R6、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基 CrC6烷基、 C C6卤代烷氧基 CrC6烷基、 C3-C6环烷基或 R7 ;
R2选自氢、 氟、 氯、 溴、 CN、 C02R6或 CrC6烷基；
、 R5可相同或不同， 分别选自氢或氯；
X选自 NR8;
R8选自 Ci-C4院基；
选自氢或 CrC4烷基；
R7选自苯基， 或者被 1-3个独立选自以下基团进一步取代的苯基： 氟、 氯、 溴、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6烷氧基或 CrC6烷硫基；
Q选自 -CH2CH2-、 -CH2CH2CH2-或 -CH2CH2CH2CH2-；
或者， 通式 （1-3) 中
选自氢、 C02R6或 CrC6烷基；
R2选自氢、 氟、 氯、 溴或 CrC6烷基；
、 R5可相同或不同， 分别选自氢或氯；
X选自 NR8;
R8选自 CrC4烷基或 R7 ;
选自氢或 CrC4烷基；
R7选自苯基， 或者被 1-3个独立选自以下基团进一步取代的苯基： 氟、 氯、 溴、 CN、 d-C6浣基、 卤代 d-C6浣基、 d-C6浣氧基、 卤代 d-C6浣氧基或 d-C6浣硫基； Q选自 -CH2CH2-、 -CH2CH2CH2-或 -CH2CH2CH2CH2- 。 本发明再进一步优选的化合物为： 通式 （1-1 ) 或通式 （1-2) 中
选自苯基， 或者被 1-3个独立选自以下基团进一步取代的苯基： 氟、 氯、 溴、
Ci-C4 Ci-C4 C1-C4 C1-C4 C1-C4
R2选自氢、 氯或 crc4烷基；
、 R5可相同或不同， 分别选自氢或氯；
X选自 NR8;
R8选自 CrC4院基；
选自氢或 CrC4烷基；
Q选自 -CH2CH2-、 -CH2CH2CH2-或 -CH2CH2CH2CH2-；
或者， 通式 （1-3) 中
选自氢、 C02R6或 CrC4烷基；
R2选自氢、 氟、 氯、 溴或 CrC4烷基；
、 R5可相同或不同， 分别选自氢或氯；
X选自 NR8;
R8选自 CrC4烷基、 苯基、 或者被 1-3个独立选自以下基团进一步取代的苯基: 氟、 氯、 溴、 CrC4烷基、 卤代 CrC4烷基、 CrC4烷氧基或卤代 CrC4烷氧基； 选自氢或 CrC4烷基；
Q选自 -CH2CH2-、 -CH2CH2CH2-或 -CH2CH2CH2CH2- 。 上面给出的通式 （I ) 化合物的定义中， 汇集所用术语一般定义如下： 未取代表示所有取代基都为氢。
卤： 指氟、 氯、 溴或碘。
烷基： 直链或支链烷 ， 例如甲基、 乙基、 丙基、 异丙基或叔丁基。 卤代烷基： 直链或支链烷基， 在这些烷基上的氢原子可部分或全部被卤原子所 取代， 例如， 卤代烷基诸如氯甲基、 二氯甲基、 三氯甲基、 氟甲基、 二氟甲基或三 氟甲基。
烯基： 直链或支链并可在任何位置上存在有双键， 例如乙烯基或烯丙基。
块基： 直链或支链并可在任何位置上存在有三键， 例如乙块基或块丙基。
芳基以及芳烷基中的芳基部分包括苯基或萘基等。
本发明中所指杂芳基是含 1个或多个N、 0、 S杂原子的五元环或六元环。 例如吡 啶、 呋喃、 嘧啶、 吡嗪、 哒嗪、 三嗪、 喹啉、 噻唑基、 苯并噻唑基、 苯并呋喃等。 在本发明优选的通式 （1-1 )、 （1-2)、 ( 1-3 ) 化合物中， R 、 R2优选的部分基 团及其取代基见表 1-表 9。
Figure imgf000007_0001
Q=-CH2CH2-、 -CH2CH2CH2-、 -CH2CH2CH2CH2- 、 1 5可相同或不同， 分别选自11、 C1
通式 （1-1 ) 中： 当 为苯基时， 苯环上的取代基见表 1 ; 当 为吡啶基时， 吡啶环上的取代基见表 2-表 4; 当 为噻唑基时， 噻唑环上的取代基见表 5 ; 当^ 为噻吩或呋喃时， 噻吩或呋喃环上的取代基见表 6-表 7; 当 ^为其他取基时， 取代 基见表 8。
通式 （1-1 ) 中： 当 R2为苯基时， 苯环上的取代基见表 1 ; 当 R2为吡啶基时， 吡啶环上的取代基见表 2-表 4; 当 R2为噻唑基时， 噻唑环上的取代基见表 5 ; 当 R2 为噻吩或呋喃时， 噻吩或呋喃环上的取代基见表 6-表 7; 当 R2为其他取基时， 取代 基见表 9。 通式 （1-2)、 ( 1-3 ) 中 、 R2的具体定义同通式 （1-1 )。
Figure imgf000007_0002
Q=-CH2CH2\ -CH2CH2CH2-、 -CH2CH2CH2CH:
、 可相同或不同， 分别选 § Η、 C1
Figure imgf000007_0003
Q=-CH2CH2-、 -CH2CH2CH2-、 -CH2CH2CH2CH2- R4、 可相同或不同， 分别选 H、 CI is/D/ Osz-osId 6/-iosoiAV
Figure imgf000008_0001
Figure imgf000008_0002
续表 1
Figure imgf000009_0001
is/D/ Osz-osId 6/-iosoiAV
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000010_0003
is/D/ Osz-osId 6/-iosoiAV
Figure imgf000011_0003
Figure imgf000011_0001
Figure imgf000011_0002
is/D/ Osz-osId 6/-iosoiAV
Figure imgf000012_0001
Figure imgf000012_0003
Figure imgf000012_0002
Figure imgf000013_0001
Figure imgf000013_0003
部分化合物可以用表 10、 表 11、 表 12中列出的具体化合物来说明本发明， 但 并不限定本发明。
表 10
1-1
Figure imgf000013_0002
Figure imgf000013_0004
Figure imgf000014_0001
/〇 l2s600si/-S90M
Figure imgf000015_0001
Figure imgf000016_0001
is/D/ Osz-osId 6/-iosoiAV
Figure imgf000017_0001
is/D/ Osz-osId 6/-iosoiAV
Figure imgf000018_0001
is/D/ Osz-osId 6/-iosoiAV
Figure imgf000019_0001
is/D/ Osz-osId 6/-iosoiAV
Figure imgf000020_0001
Figure imgf000020_0002
Figure imgf000020_0003
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
is/D/ Osz-osId 6/-iosoiAV
Figure imgf000024_0001
is/D/ Osz-osId 6/-iosoiAV
Figure imgf000025_0001
is/D/ Osz-osId 6/-iosoiAV
Figure imgf000026_0001
表 12
Figure imgf000027_0001
Figure imgf000027_0003
本发明的通式 （I)所代表的化合物可以由通式 （II)所示的含羟基的吡唑或异 恶唑类化合物与通式 （IV) 所示的卤代丙烯类化合物在碱性条件下縮合制得， 或者 可以由通式 （III) 所示的吡唑或异恶唑类化合物与通式 （V) 所示的含羟基的卤代 丙烯类化合物在碱性条件下縮合制得：
Figure imgf000027_0002
II IV
Figure imgf000028_0001
通式 （111 )、 (IV) 中， L是离去基团， 选自氯或溴； 其他各基团的定义同上。
通式 （IV)、 (V) 所示的化合物可以由已知方法制得， 具体参见 CN1860874、 US20030073847和 W09727173等。
反应在适宜的溶剂中进行， 适宜的溶剂可选自如四氢呋喃、 乙腈、 甲苯、 二甲 苯、 苯、 N，N-二甲基甲酰胺、 二甲亚砜、 丙酮或丁酮等。
适宜的碱可选自如氢氧化钾、 氢氧化钠、 碳酸钠、 碳酸钾、 碳酸氢钠、 三乙胺、 吡啶、 甲醇钠、 乙醇钠、 氢化钠、 叔丁醇钾或叔丁醇钠等。
反应温度可在室温至溶剂沸点温度之间， 通常为 20〜100°C。
反应时间为 30分钟至 20小时， 通常 1〜10小时。
中间体 （II ) 可购得， 或者按照已知方法制备。 其中： 当五元杂环的 3-位或 5- 位为羟基时，由中间体（VI )与（取代的）肼、羟胺縮合制得，参见： WO2005080344A1 , Synlett 2004, 5， 795-798, J. Chem. Soc, Perkin Trans. 2, 1987, 969-975等。 当五元杂环 的 4-位为羟基时， 可由中间体 （VI ) 酯解后与胺类化合物合环制得， 参见 Organic Preparation and Procedures International, 2002, 34(1): 98-102。通式（III )可由通式（II ) 卤化得到。
Figure imgf000028_0002
本发明的通式 （I )化合物对农业、 民用和动物技术领域中有害昆虫的成虫、 幼 虫和卵都显示出高杀虫活性。 部分化合物表现出较好的杀菌活性。 因此， 本发明还 包括通式 （I ) 化合物在农业和其他领域中用作杀虫剂和 /或杀菌剂的应用。
尤其是， 通式 （I )化合物对下列科和目的重要害虫有活性： 鳞翅目害虫， 如二 化螟、 稻纵卷叶螟、 玉米螟、 烟叶蛾、 小食心虫、 小菜蛾、 甜菜夜蛾、 斜纹夜蛾等。 特别是对小菜蛾、 甜菜夜蛾活性更好， 在很低的剂量下就可以获得很好的效果。 本 发明对同翅目的害虫如蚜虫等也具有很高的活性。 因此本发明的通式 （I ) 化合物 优选在农业和其他领域中用于防治鳞翅目和同翅目害虫的应用。 同时， 本发明的部 分化合物还具有很好的杀菌活性， 可用于防治水稻稻瘟病、 番茄晚疫病、 蔬菜灰霉 病、 小麦白粉病、 黄瓜霜霉病、 炭疽病等， 特别是对水稻稻瘟病、 黄瓜霜霉病、 炭 疽病有很好的活性。
同时， 通式 （I )化合物对许多有益的昆虫和螨虫、 哺乳动物、 鱼、 鸟具有低毒 性， 而且没有植物毒性。
由于良好的性能， 上述化合物可有利地用于保护农业和园艺业重要的作物、 家 畜和种畜， 以及人类常去的环境免于有害昆虫和真菌的伤害。
为获得理想效果， 化合物的用量因各种因素而改变， 例如所用化合物、 被保护 的作物、 有害生物的类型、 感染程度、 气候条件、 施药方法、 采用的剂型。 每公顷 10克一 1000克的化合物剂量能提供充分的防治。
本发明的另一目的还涉及通过施用通式（I )化合物， 防治农业和园艺业重要的 作物和 /或家畜和种畜和 /或人类常去的环境中的昆虫和 /或植物致病性真菌的方法。 尤其是， 化合物的用量在每公顷 10克一 1000克内变化。
为了实际应用于农业， 使用含一种或多种通式（I )化合物的组合物通常是有益 的。
因此， 本发明的另一目的涉及含一种或多种通式（I )化合物作为活性成分的杀 虫和 /或杀菌组合物， 组合物中活性成分的重量百分含量为 0.1-99%。
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。
组合物是以已知方法制备的， 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是例如： 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， 可用的液体稀释剂还包括如芳族有机溶剂 （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、 聚氧乙烯烷基酚、 山梨醇 的聚氧乙烯酯、 木质素磺酸盐等的钠、 钙、 三乙基胺或三乙醇胺盐。
组合物还可含特殊的添加剂用于特定的目的， 例如含有粘合剂如***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、 使用目的、 环境条件和采用的 制剂类型而在宽范围内改变。 活性成分的浓度范围通常为 0.5-90%， 优选 5-60 %。
如果需要， 可以向组合物中添加能与通式 （I )化合物兼容的其他活性成分， 例 如其他杀螨剂 /杀虫剂、 杀真菌剂、 植物生长调节剂、 抗生素、 除草剂、 肥料。
几种常见剂型的配制方法举例如下：
悬浮剂的配制： 常用配方中活性组分含量为 5-35%。 以水为介质， 将原药、 分 散剂、 助悬剂和抗冻剂等加入砂磨机中， 进行研磨， 制成悬浮剂。
水乳剂的配制： 将原药、 溶剂和乳化剂加在一起， 使溶解成均匀油相。 将水、 抗冻剂等混合一起， 成为均一水相。 在高速搅拌下， 将水相加入到油相或将油相加 入到水相，形成分散性良好的水乳剂。本发明的水乳剂活性组分含量一般为 5%-15%。 为制备浓乳剂， 本发明的化合物可溶解于一种或数种混合溶剂， 再加入乳化剂来增 强化合物在水中的分散效果。
可湿性粉剂的配制： 按配方要求， 将原药、 各种表面活性剂及固体稀释剂等充 分混合， 经超细粉碎机粉碎后， 即得到预定含量（例如 10-60%)的可湿性粉剂产品。 为制备适于喷洒用的可湿性粉剂， 本发明的化合物可以和研细的固体粉末如粘土、 无机硅酸盐、 碳酸盐以及润湿剂、 粘合剂和 /或分散剂组成混合物。
水分散性粒剂的配制： 将原药和粉状固体稀释剂、润湿展着剂及粘合剂等进行 混合粉碎， 再加水捏合后， 加入装有一定规格筛网的造粒机中进行造粒， 然后再经 干燥、 筛分 (按筛网范围）。 也可将原药、 分散剂、 崩解剂和润湿剂及固体稀释剂加 入砂磨机中， 以水为介质研磨， 制成悬浮剂， 然后进行喷雾干燥造粒， 通常配制含 量为 20-30%颗粒状产品。 具体实施方式
以下具体实施例用来进一步说明本发明， 但本发明绝非仅限于这些例子。 合成实施例
实例 1 : 中间体的制备
Figure imgf000030_0001
向 4.10克 （18.5毫摩尔） 4-C3，3-二氯烯丙氧基)苯酚的 30毫升甲苯溶液中加入 4滴 （0.1毫升）二丁胺， 于 65-70°C下缓慢滴入 0. 95-3倍（摩尔） 的磺酰氯的甲苯 溶液， 约 2小时滴完， 继续反应 1-2小时， TLC监测反应完毕后， 加入饱和碳酸氢 钠溶液， 分出甲苯层， 水层用甲苯萃取， 有机层合并， 干燥， 脱溶， 柱层析得中间 体。
Figure imgf000030_0004
实例 2: 中间体 IV-1的制备
Figure imgf000030_0002
IV-1
向 20毫升 N，N-二甲基甲酰胺 （DMF) 中加入 4.2克 1，3-二溴丙烷、 2.9克无水 碳酸钾， 向其中滴加溶有 3.8克 2，6-二氯 -4- 3 ' ,3 ' -二氯)烯丙氧基苯酚的 10毫升 DMF溶液， 控制温度在 15 °C左右， 在此温度下反应 1小时， TLC监测反应完毕后， 向反应瓶中倒入 50毫升饱和食盐水， 用 60毫升乙酸乙酯分三次进行萃取， 干燥， 脱溶， 柱层析得 4.35克中间体 IV-1。 实例 3 : 化合物 2的制备
Figure imgf000030_0003
II-1 IV- 1
取 0.22克 II-1 (自制， 按照 WO2005080344A1提供的方法制备）、 0.23克无水 碳酸钾于 100毫升反应瓶中， 加入 40毫升 N，N-二甲基甲酰胺（DMF)， 搅拌下加入 0.45克 IV-1 , 升温至 35 °C搅拌反应 3小时。 TLC监测反应完毕后， 减压脱溶后， 向反应瓶中倒入 50毫升饱和食盐水， 用 60毫升乙酸乙酯分三次进行萃取， 干燥， 脱溶， 柱层析得产品 0.37克， 即化合物 2。 实例 4: 化合物 269的制备
Figure imgf000031_0001
取 0.18克 II-2 (自制， 按照 J. Chem. Soc, Perkin Trans. 2, 1987, 969-975提供 的方法制备）、 0.20克无水碳酸钾于 100毫升反应瓶中， 加入 40毫升 N，N-二甲基甲 酰胺（DMF)， 搅拌下加入 0.40克 IV-1 , 升温至 35 °C搅拌反应 3小时。 TLC监测反 应完毕后， 减压脱溶后， 向反应瓶中倒入 50毫升饱和食盐水， 用 60毫升乙酸乙酯 分三次进行萃取， 干燥， 脱溶， 柱层析得产品 0.33克， 即化合物 269。 实例 5 : 化合物 367的制备
Figure imgf000031_0002
取 0.24克 II-3 (自制，按照 J. Chem. Soc, Perkin Trans. 2, 1987, 969-975提供的 方法制备）、 0.27克无水碳酸钾于 100毫升反应瓶中， 加入 40毫升 N，N-二甲基甲酰 胺（DMF), 搅拌下加入 0.49克 IV-1 , 升温至 35 °C搅拌反应 3小时。 TLC监测反应 完毕后， 减压脱溶后， 向反应瓶中倒入 50毫升饱和食盐水， 用 60毫升乙酸乙酯分 三次进行萃取， 干燥， 脱溶， 柱层析得产品 0.30克， 即化合物 367。
Figure imgf000031_0003
取 0.25克 11-4(自制，按照 Organic Preparation and Procedures International, 2002, 34(1): 98-102提供的方法制备）、 0.28克无水碳酸钾于 100毫升反应瓶中， 加入 40 毫升 N，N-二甲基甲酰胺（DMF)， 搅拌下加入 0.52克 IV-1 , 升温至 35 °C搅拌反应 3 小时。 TLC监测反应完毕后， 减压脱溶后， 向反应瓶中倒入 50毫升饱和食盐水， 用 60毫升乙酸乙酯分三次进行萃取， 干燥， 脱溶， 柱层析得产品 0.35克， 即化合 物 546。 通式 （I ) 的其他化合物可以用本发明提供的制备方法制得。 部分化合物熔点和核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： 化合物 1 :油状物。 Sppm 7.75(m, 2H), 7.38(m, 2H), 7.28(m, 1H), 6.85(s, 2H), 6.11(t, 1H), 5.89(s， 1H), 4.58(d， 2H), 4.42(t, 2H), 4.15(t， 2H), 3.71(s, 3H), 2.32(m, 2H)。
化合物 2： 熔点 68-70 °C。 5ppm 7.68(m, 2H), 7.33(m, 2H), 6.85(s， 2H), 6.11(t， 1H)， 5.85(s, 1H), 4.58(d， 2H), 4.4 l(t, 2H), 4.15(t， 2H), 3.70(s, 3H), 2.32(m, 2H)。
化合物 8:油状物。 Sppm 7.67(m, 2H), 7.27(m, 2H), 6.84(s, 2H), 6.12(t, 1H), 5.84(s, 1H), 4.59(d， 2H), 4.40(t， 2H), 4.14(t， 2H), 3.69(s, 3H), 2.50(s, 3H), 2.32(m, 2H)。
化合物 13：熔点 78-80°C o 5ppm 7.67(m, 2H), 6.9 l(m, 4H)， 6.1 l(t, 1H), 5.81(s, 1H)， 4.58(d， 2H), 4.40(t， 2H), 4.15(t， 2H), 3.83(s, 3H), 3.69(s, 3H), 2.32(m, 2H)。
化合物 16:油状物。 Sppm 7.64(m, 2H), 7.50(m, 2H), 6.85(s, 2H), 6.11(t, 1H), 5.86(s:
1H), 4.58(d， 2H), 4.4 l(t, 2H), 4.14(t， 2H), 3.70(s, 3H), 2.32(m, 2H)。
化合物 21 : 油状物。 5ppm 7.78(m, 1H), 7.42(m, 1H), 7.23(m, 2H), 6.84(s， 2H), 6.11(m, 2H), 4.58(d， 2H), 4.42(t, 2H), 4.16(t， 2H), 3.72(s, 3H), 2.33(m, 2H)。
化合物 76:油状物。 δ 7.63(d, 2Η), 7.4 l(t, 2H), 7.32(t, 1H), 6.83(s, 2H), 6.10(t， 1H)， 4.58(d， 2H), 4.40(t， 2H), 4.18(t, 2H), 3.76(s, 3H), 2.3 l(m, 2H), 2.17(s, 3H)。
化合物 130： 油状物。 δ 7.70(m, 2Η), 7.34(m, 2H), 6.84(s， 2H), 6.12(t, 1H), 4.58(d， 2H), 4.42(t, 2H), 4.15(t, 2H), 4.04(m， 2H), 2.32(m, 2H), 1.37(m, 3H)。
化合物 148： 油状物。 δ 7.68(d, 2Η), 7.33(d, 2H), 7.08(s, 1H), 6.39(t, 1H), 6.10(s， 1H), 4.77(d, 2H), 4.39(t, 2H), 4.24(t, 2H), 3.64(s, 3H), 2.34(m, 2H)。
化合物 166:油状物。 δ 7.55(m, 2Η), 7.35(m, 2H), 7.25(m, 1H), 7.02(s, 1H), 6.35(t,
1H), 4.76(d, 2H), 4.35(t, 2H), 4.18(t， 2H), 3.69(s, 3H), 2.30(m, 2H), 2.14(s, 3H)。
化合物 225: 熔点 117-119°C。 δ 7.72(d, 2H), 7.39(d, 2H), 7.10(s, 2H), 6.4 l(t, 1H), 6.17(s, 1H), 4.66(d， 2H), 4.44(t， 2H), 4.3 l(t, 2H), 3.59(s, 3H)。
化合物 235: 油状物。 δ 7.58(d, 2Η), 7.39(t, 2H), 7.28(t, 1H), 7.11(s, 2H), 6.38(t, 1H)， 4.66(d， 2H), 4.44(t， 2H), 4.23(t, 2H), 3.71(s, 3H), 2.14(s, 3H)。
化合物 247: 油状物。 δ 7.67(d, 2Η), 7.3 l(d, 2H), 6.96(s, 2H), 6.27(t, 1H), 5.96(s， 1H), 4.63(d, 2H), 4.20(t, 2H), 3.99(t, 2H), 3.63(s, 3H), 2.02(m, 4H)。
化合物 248： 油状物。 δ 7.68(d, 2Η), 7.45(d, 2H), 7.33(d, 2H), 7.01(s,lH), 6.33(t, 1H), 5.71(s, 1H), 4.64(d， 2H), 3.97(t, 2H), 3.68(t, 2H), 3.56(s, 3H), 1.94(m, 4H)。
化合物 257: 油状物。 δ 7.56(d, 2Η), 7.34(t, 2H), 7.22(t, 1H), 6.93(s, 2H), 6.22(t,
1H), 4.62(d, 2H), 4.16(t， 2H), 4.0 l(t, 2H), 3.69(s, 3H), 2.13(s, 3H), 2.04(s, 4H)。
化合物 268： 油状物。 δ 7.43(m, 5Η)， 6.84(s， 2Η), 6.15(t， 1H), 5.68(s， 1H), 4.60(d， 2H), 4.43(t, 2H), 4.18(t， 2H), 3.77(s, 3H), 2.32(m, 2H)。
化合物 269: 熔点 63-64°C。 δ 7.46(d，2H)， 7.35(d, 2H), 6.84(s, 2H), 6.1 l(t, 1H)， 5.77(s, 1H), 4.58(d， 2H), 4.50(t， 2H), 4.15(t， 2H), 3.81(s, 3H), 2.32(m, 2H)。
化合物 350: 油状物。 5ppm 7.49(m, 3H), 7.45(m, 2H), 6.96(s， 1H), 6.92(s, 1H)， 4.48(m， 2H), 4.17(m, 2H), 3.64(s, 3H), 2.3 l(m, 2H), 1.88(s, 3H), 1.25(s, 3H)。
化合物 352: 油状物。 5ppm 7.30(m, 2H), 7.18(m, 2H), 6.84(s， 2H), 6.12(t, 1H)， 4.58(d， 2H), 4.49(t， 2H), 4.17(t, 2H), 3.60(s, 3H), 2.32(m, 2H), 1.85(s, 3H)。
化合物 356: 油状物。 5ppm 7.22(m, 2H), 6.98(m， 2H), 6.84(s， 2H), 6.11(t, 1H)，
4.58(d， 2H), 4.46(t， 2H), 4.17(t, 2H), 4.06(m， 2H), 3.42(s, 3H), 2.32(m, 2H), 1.86(s, 3H),
Figure imgf000032_0001
化合物 360： 油状物。 5ppm 7.52(m, 1H), 7.33(m, 1H), 7.18(m, 1H), 6.82(s, 2H), 6.10(t, 1H), 4.56(d， 2H), 4.45(t， 2H), 4.15(t， 2H), 3.47(s, 3H), 2.3 l(m, 2H), 1.74(s, 3H)。 化合物 361： 油状物。 5ppm 7.55(m, 1H)， 7.4 l(m, 1H)， 7.16(m, 1H)， 6.84(s， 2H), 6.11(t, 1H), 4.58(d， 2H), 4.49(t， 2H), 4.17(t, 2H), 3.62(s, 3H), 2.32(m, 2H), 1.86(s, 3H)。
化合物 363: 油状物。 5ppm 7.25(m, 2H), 6.98(m， 2H), 6.84(s， 2H), 6.12(t, 1H)， 4.58(d， 2H), 4.47(t, 2H), 4.17(t, 2H), 3.86(s, 3H), 3.61(s, 3H), 2.32(m, 2H), 1.86(s, 3H)。
化合物 367：油状物。 Sppm 7.28(d, 2H), 7.2 l(d, 2H), 6.84(s， 2H), 6.12(t, 1H), 4.60(d， 2H), 4.47(t, 2H), 4.17(m, 2H), 3.61(s, 3H), 2.42(s, 3H), 2.32(t, 2H), 1.86(s, 3H)。
化合物 368：油状物。 5ppm 7.21-7.31(m, 4H)， 6.84(s， 2H), 6.12(t, 1H)， 4.58(d， 2H), 4.47(t, 2H), 4.17(t, 2H), 3.62(s, 3H), 2.7 l(m, 2H), 2.32(m, 2H), 1.87(s, 3H), 1.28(t, 3H)。
化合物 376:油状物。 Sppm 7.12(s, 1H), 7.06(m, 2H), 6.84(s, 2H), 6.12(t, 1H), 4.57(d，
2H), 4.47(t, 2H), 4.19(t， 2H), 3.43(s, 3H), 2.38(s, 3H), 2.30(t, 2H), 2.10(s, 3H), 1.73(s, 3H)。
化合物 377: 油状物。 5ppm 7.24(m, 1H), 7.07(m, 2H), 6.84(s， 2H), 6.11(t, 1H)， 4.58(d， 2H), 4.49(t， 2H), 4.17(t, 2H), 3.62(s, 3H), 2.34(s, 6H)， 2.32(m, 2H), 1.86(s, 3H)。
化合物 378: 油状物。 5ppm 7.17(m, 2H), 6.96(s， 1H), 6.84(s， 2H), 6.10(t， 1H)，
4.57(d, 2H), 4.48(t， 2H), 4.18(t， 2H), 3.43(s, 3H), 2.34(s, 3H), 2.32(m, 2H), 2.08(s, 3H), 1.73(s, 3H) o
化合物 387:油状物。 Sppm 7.3 l(d, 2H), 7.23(d, 2H), 6.84(s, 2H), 6.12(t, 1H), 4.58(d 2H), 4.48(t, 2H), 4.17(t, 2H), 3.63(s, 3H), 2.93(m, 1H), 2.32(m, 2H), 1.87(s, 3H), 1.31(s, 3H)， 1.28(s，3H)。
化合物 389: 油状物。 5ppm 7.46(m, 2H), 7.25(m, 2H), 6.84(s， 2H), 6.12(t, 1H)， 4.58(d， 2H), 4.46(t， 2H), 4.18(t， 2H), 3.62(s, 3H), 2.3 l(m, 2H), 1.88(s， 3H), 1.36(s, 9H)。
化合物 423: 油状物。 δ 7.42(d, 2Η), 7.34(d, 2H), 6.88(s, 1H), 6.19(t， 1H), 5.73(s, 1H), 4.68(d， 2H), 4.39(t, 2H), 4.15(t， 2H), 3.71(s, 3H), 2.3 l(m, 2H)。
化合物 443:油状物。 δ 7.30(m, 3Η), 7.2 l(d, 2H), 6.3 l(t, 1H), 4.76(d, 2H), 4.35(t,
2H), 4.11(t， 2H), 3.55(s, 3H), 2.40(s, 3H), 1.80(s, 3H)。
化合物 444:油状物。 δ 7.31(d,2H), 7.24(d, 2H), 7.16(s, 1H), 6.29(t, 1H), 4.76(d, 2H), 4.34(t, 2H), 4.1 l(t, 2H), 3.55(s, 3H), 2.68(m, 2H), 2.23(q, 2H), 1.80(s， 3H), 1.26(t,3 H)。
化合物 499: 油状物。 δ 7.44(m, 3Η), 7.32(d, 2H), 6.96(s, 2H), 6.27(t, 1H), 4.63(d,
2H), 4.45(t， 2H), 4.28(t, 2H), 3.57(s, 3H), 1.82(s, 3H)。
化合物 500: 熔点 82-83°C。 δ 7.48(s, 4H)， 7.03(s, 2H), 6.35(t, 1H), 5.78(s, 1H)， 4.65(d, 2H), 4.40(t, 2H), 4.24(t, 2H), 3.69(s, 3H)。
化合物 516: 油状物。 5ppm 7.27(m, 2H), 7.18(m, 2H), 6.85(s， 2H), 6.12(t, 1H)， 4.59(m， 4H)， 4.36(m, 2H), 3.60(s, 3H), 2.41(s, 3H), 1.87(s, 3H)。
化合物 518 (DMSO):油状物。 Sppm 7.30(m, 2H), 7.23(m, 2H), 7.05(s, 2H), 6.38 (m， 1H), 4.65(m， 2H), 4.45(m， 2H), 4.27(m, 2H), 3.55(s, 3H), 2.68(m, 2H), 1.80(s, 3H), 1.27(m, 3H)。
化合物 522： 油状物。 δ 7.43(s, 4Η)， 6.94(s， 2Η), 6.24(t, 1H), 5.65(s， 1H), 4.63(d, 2H), 4.17(t, 2H), 3.98(t, 2H), 3.69(s, 3H), 1.96(s, 4H)。
化合物 532： 油状物。 δ 7.45(m, 3Η), 7.3 l(d, 2H), 6.95(s， 2H), 6.27(t, 1H), 4.63(d, 2H), 4.19(t， 2H), 3.99(t, 2H), 3.56(s, 3H), 1.96(s, 4H)， 1.82(s, 3H)。
化合物 538 (DMSO):油状物。 Sppm 7.26(m, 2H), 7.19(m, 2H), 7.03(s, 2H), 6.36(m, 1H), 4.64(m， 2H), 4.17(m, 2H), 3.98(m, 2H), 3.53(s, 3H), 2.38(s, 3H), 1.94(m， 4H)， 1.79(s, 3H) o
化合物 540: 油状物。 5ppm 7.27(m, 4H)， 6.85(s， 2H), 6.13(t, 1H), 4.58(m， 2H), 4.29(m, 2H), 4.04(m， 2H), 3.62(s, 3H), 2.7 l(m, 2H), 2.03(m, 2H), 1.87(s, 3H), 1.29(t, 3H)。
化合物 546:油状物。 Sppm 7.58(s, 1H), 7.56(d, 2H), 7.50(s, 1H), 7.38(d, 2H), 6.84(s:
2H), 6.10 (t， 1H)， 4.59(d， 2H), 4.24 (t， 2H), 4.14(t， 2H), 2.27(q, 2H)。
化合物 547: 油状物。 S ppm 7.64(d, 2H), 7.58(s, 1H), 7.50(s, 1H), 7.27(d, 2H), 6.84(s， 2H), 6.10 (t， 1H)， 4.59(d， 2H), 4.24 (t， 2H), 4.14(t， 2H), 2.28(q, 2H).
化合物 550： 油状物。 5ppm 7.76(d, 2H),7.65(s, 1H), 7.29(d, 2H), 6.38(s, 2H), 6.10 (t， 1H), 4.56(d， 2H), 4.44 (q， 2H), 4.33(t, 2H), 4.19(t, 2H)， 2.35(q, 2H), 1.41 (t， 3H)。
化合物 551 : 油状物。 5ppm 7.32(s, 1H), 7.29(d, 2H), 7.28(s, 1H), 7.26(d, 2H)， 6.83(s, 2H), 6.11 (t， 1H), 4.59(d， 2H), 4.42 (q， 2H), 4.29(t, 2H), 4.18(t， 2H)， 2.35(q, 2H), 2.22 (s， 3H), 1.41 (t， 3H)。 制剂实施例 （各组分加入量均为重量百分含量， 活性化合物折百后计量加入） 实例 7: 30%可湿性粉剂
化合物 2 30%
十二烷基硫酸钠 2%
木质素磺酸钠 3%
萘磺酸甲醛縮合物 5 %
轻质碳酸钙 补足至 100%
将化合物 2及其他组分充分混合 ， 经超细粉碎机粉碎后， 即得到 30%的可湿性 粉剂产品。
实例 8: 40%浓悬浮剂
化合物 367 40 %
乙二醇 10%
壬基苯酚聚乙二醇醚 6%
木质素磺酸钠 10%
羧甲基纤维素 1 %
37%甲醛水溶液 0.2%
75 %硅油水乳液 0.8 %
水 补足至 100%
将化合物 367及其他组分充分混合， 由此得到的浓悬浮剂， 用水稀释所得悬浮 剂可得到任何所需浓度的稀释液。
实例 9: 60%水分散性粒剂
化合物 367 60%
萘磺酸钠甲醛縮合物 12%
N-甲基 - N-油酰基-牛磺酸钠 8%
聚乙烯吡咯烷酮 2%
羧甲基纤维素 2%
高岭土 补足至 100% 将化合物 367及其他组分混合粉碎， 再加水捏合后， 加入 10-100目筛网的 造粒机中进行造粒， 然后再经干燥、 筛分 (按筛网范围)。 生物活性测定实施例
实例 10: 杀虫杀螨活性测定
用本发明化合物对几种昆虫和螨类进行了杀虫活性测定试验。 测定的方法如 下：
待测化合物用丙酮 /甲醇 （1 : 1 ) 的混合溶剂溶解后， 用含有 0.1% (wt) 吐温 80的水稀释至所需的浓度。
以小菜蛾为靶标， 采用 airbrush喷雾法进行杀虫活性测定。
对于小菜蛾的测定： 将甘蓝叶片用打孔器打成直径 l cm的叶碟， airbrush 喷雾 处理的压力为 10 psi (约合 0.7 kg/cm2), 每叶碟正反面喷雾， 喷液量为 0.5 ml。 阴干 后每处理接入 10头 2龄试虫， 每处理 3次重复。 处理后放入 25 °C、 相对湿度 60〜 70%观察室内培养， 72小时后调查存活虫数， 计算死亡率。
部分测试结果如下：
药液浓度为 100 mg/L时，对小菜蛾 2龄幼虫致死率达到 100%的化合物有 1、 2、 8、 11、 13、 16、 17、 18、 24、 26、 38、 76、 77、 86、 92、 225、 247、 248、 257、 268、 269、 278、 280、 283、 284、 293、 306、 352、 356、 360、 361、 363、 367、 368、 377、 387、 389、 500、 522、 532、 538、 546。 在此浓度下， 对照药剂 pyridalyl 的致死率 亦为 100%。
药液浓度为 25 mg/L时， 对小菜蛾 2龄幼虫致死率达到 100%的化合物有 2、 225、 247、 248、 268、 269、 352、 367、 377、 387。 在此浓度下， 对照药齐 Upyridalyl的致 死率亦为 100%。
药液浓度为 6.25mg/L时， 对小菜蛾 2龄幼虫致死率达到 80%以上的化合物有 2、 248、 367、 377、 387， 致死率达到 90%以上的化合物有 2、 367。 在此浓度下， 对照 药剂 pyridalyl的致死率为 65%。 实例 11 杀菌活性测定
用本发明化合物对植物的各种菌病害进行了试验。 试验的方法如下： 活体保护活性测定： 采用活体盆栽测定方法。 待测化合物原药用少量丙酮溶解， 用含有 0.1% (wt) 吐温 80的水稀释至所需的浓度。 喷雾施药到植物试材上， 24小时 后进行病害接种。 接种后， 将植物放在恒温恒湿培养箱中， 使感染继续， 待对照充分 发病后 （通常为一周时间） 进行评估调查。
部分测试结果如下：
活体保护活性测定： 药液浓度为 400ppm时， 化合物 2等对小麦白粉病防效在 70% 以上。

Claims

权 利 要 求 书
1、 一种具有含氮五元杂环的醚类化合物， 如通式 （ I ) 所示:
Figure imgf000036_0001
式中：
选自氢、 C02R6、 CrC12烷基、 卤代 CrC12烷基、 CrC12烷氧基 CrC12烷基、 C C12卤代烷氧基 CrC12烷基、 C3-C6环烷基或 R7 ;
R2选自氢、 卤素、 CN、 C02R6、 CrC12烷基、 卤代 CrC12烷基、 CrC12烷氧基、 卤代 12烷氧基、 12烷硫基、 卤代 12烷硫基、 C3-C6环烷基或 R7;
R3、 R4、 R5可相同或不同，分别选自氢、 卤素、羟基、巯基、氰基、硝基、 d-C12 院基、 Ci-Ci2 ¾¾¾ Ci-Ci2¾¾¾M¾ C2-C12希基、 l¾代 C2-C12希基、 C2-Ci2 块基、 12烷氧基、 ^代 12烷氧基、 C2-C12烯氧基、 ^代 C2-C12烯氧基、 C3-C12 块氧基、 卤代 C3-C12块氧基、 12烷硫基、 卤代 12烷硫基、 12烷基磺酰 、 Ci-Ci2 ¾¾¾M¾Ri¾ C1-C12 C1-C12 C1-C12 Ci-Ci2 ¾¾¾, 基羰基 CrC12烷基或 CrC12卤代烷氧基 CrC12烷基；
X选自 NR8或0;
R8选白氢、 Ci-Ci2 ¾¾¾ \ ί Ci-Ci2 ¾¾¾ C1-C12 Ci-Ci2 ¾¾¾ C1-C12 卤代烷氧基 CrC12烷基、 C3-C6环烷基或 R7;
Υι Υ2可相同或不同， 分别选自氢、 氟、 氯、 溴、 CH3、 CN或 CF3 ;
A2可相同或不同， 分别选自 0、 S或 Ν ;
选自氢或 CrC12烷基；
R7选自芳基、 杂芳基、 芳基 CrC12烷基或杂芳基 CrC12烷基， 或者被 1-5个独 立选自以下基团进一步取代的上述基团： 卤素、 N02、 CN、 C02R6、 CONHR6、 C C6 \ ί Ci-C6 Ci-C6 Ci-C6 Ci-C6 Ci-C6 ¾¾ 基磺酰基或 R7;
Q 选 自 -CH2- 、 -CH2CH2- 、 -CH2CH2CH2- 、 -CH2CH2CH2CH2- 、 -CH2CH2CH2CH2CH2- 、 -CH(CH3)- 、 -CH(CH3)CH2- 、 -CH(CH3)CH2CH2- 、 -CH2CH2CH(CH3) -、 -CH(C2H5)-， -C(CH3)2-、 -CH(CH3)CH(CH3)-、 -CH2C(CH3)2CH2-、 -CH2CH2OCH2CH2- 、 -CH2CH2NHCH2CH2- 、 -CH2CH2SCH2CH2- 、 -CH2CH2S02CH2CH2-、 -CH2COCH2-、 -COCH2CO-、 -CH2CH2CO-、 -COCH2CH2-、 -CH2CO- 、 -COCH2- 、 -CH2C(=NOCH3)CH2- 、 -CH2C(=NN(CH3)2)CH2- 、
-CH2CH(OH)CH2-、 -CH2CH(OCH3)CH2-、
Figure imgf000036_0002
A2与杂环的连接位置选自 3、 4或 5位； 当 A2与杂环 5位连接时， 则 在 3 位， R2在 4位； 当 A2与杂环 3位连接时， 则 在5位， R2在 4位； 当 A2与杂环 4 位连接时， 则 在3位， R2在 5位。
2、 根据权利要求 1所述的化合物， 其特征在于： 通式 （ I ) 中
选自氢、 C02R6、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基 CrC6烷基、 C C6卤代烷氧基 CrC6烷基、 C3-C6环烷基或 R7 ;
R2选自氢、 卤素、 CN、 C02R6、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6烷氧基、 CrC6烷硫基、 卤代 CrC6烷硫基、 C3-C6环烷基或 R7 ;
R3、 、 R5可相同或不同， 分别选自氢、 卤素或 CrC6烷基；
X选自 NR8或0;
R8选自氢、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基 CrC6烷基、 d-C6卤代 烷氧基 CrC6烷基、 C3-C6环烷基或 R7 ;
Υι Υ2可相同或不同， 分别选自氢、 氟、 氯、 溴、 CH3、 CN或 CF3 ;
A2可相同或不同， 分别选自 0、 S或 Ν ;
选自氢或 CrC6烷基；
R7选自苯基、 吡啶基、 嘧啶基、 ***基、 恶唑基、 噻二唑基、 恶二唑基、 呋喃 基、 噻吩基、 噻唑基、 苄基、 吡啶甲基、 噻吩甲基或噻唑甲基， 或者被 1-3个独立 选自以下基团进一步取代的上述基团： 卤素、 N02、 CN、 C02R6、 CONHR^ C C6 \ ί Ci-C6 Ci-C6 Ci-C6 Ci-C6 Ci-C6 ¾¾ 基磺酰基、 苯基、 对氯苯基、 苯氧基或对氯苯氧基；
Q选自 -CH2CH2-、 -CH2CH2CH2-、 -CH2CH2CH2CH2-、
Figure imgf000037_0001
A2与杂环的连接位置选自 3、 4或 5位； 当 A2与杂环 5位连接时， 则 在 3 位， R2在 4位； 当 A2与杂环 3位连接时， 则 在5位， R2在 4位； 当 A2与杂环 4 位连接时， 则 在3位， R2在 5位。
3、 根据权利要求 2所述的化合物， 其特征在于： 通式 （ I ) 中
选自氢、 C02R6、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基 CrC6烷基、 CrC6卤代烷氧基 CrC6烷基、 C3-C6环烷基或 R7 ;
R2选自氢、 卤素、 CN、 C02R6、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6烷氧基、 CrC6烷硫基、 卤代 CrC6烷硫基、 C3-C6环烷基或 R7 ;
R3选自氯；
、 R5可相同或不同， 分别选自氢或氯；
X选自 NR8或 0;
R8选自 CrC6烷基、 卤代 CrC6烷基或 R7;
Υι Υ2选自氯；
Ai A2选自 O;
选自氢或 CrC6烷基；
R7选自苯基、 吡啶基、 呋喃基、 噻吩基、 噻唑基或苄基， 或者被 1-3个独立选 自以下基团进一步取代的上述基团： 卤素、 N02、 CN、 C02R6、 CONHR^ CrC6烷 基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6烷氧基、 CrC6烷硫基、 CrC6烷基 磺酰基、 苯基、 对氯苯基、 苯氧基或对氯苯氧基；
Q选自 -CH2CH2-、 -CH2CH2CH2-或 -CH2CH2CH2CH2-；
A2与杂环的连接位置选自 3、 4或 5位； 当 A2与杂环 5位连接时， 则 在 3 位， 在4位， 结构式如 1-1所示； 当 2与杂环 3位连接时， 则 在5位， 在 4位， 结构式如 1-2所示； 当 2与杂环 4位连接时， 则 在3位， 在5位， 结 构式如 1-3所示;
Figure imgf000038_0001
4、 根据权利要求 3所述的化合物， 其特征在于： 通式 （1-1 ) 或通式 （1-2) 中 选自氢、 C02R6、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基 CrC6烷基、
C C6卤代烷氧基 CrC6烷基、 C3-C6环烷基或 R7 ;
R2选自氢、 氟、 氯、 溴、 CN、 C02R6或 CrC6烷基；
、 R5可相同或不同， 分别选自氢或氯；
X选自 NR8;
R8选自 CrC4院基；
选自氢或 CrC4烷基；
R7选自苯基， 或者被 1-3个独立选自以下基团进一步取代的苯基： 氟、 氯、 溴、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6烷氧基或 CrC6烷硫基； Q选自 -CH2CH2-、 -CH2CH2CH2-或 -CH2CH2CH2CH2- 。
5、 根据权利要求 3所述的化合物， 其特征在于： 通式 （1-3) 中
选自氢、 C02R6或 CrC6烷基；
R2选自氢、 氟、 氯、 溴或 CrC6烷基；
、 R5可相同或不同， 分别选自氢或氯；
X选自 NR8;
R8选自 CrC4烷基或 R7 ;
选自氢或 CrC4烷基；
R7选自苯基， 或者被 1-3个独立选自以下基团进一步取代的苯基： 氟、 氯、 溴、
CN、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6烷氧基或 CrC6烷硫 基；
Q选自 -CH2CH2-、 -CH2CH2CH2-或 -CH2CH2CH2CH2- 。
6、 根据权利要求 4所述的化合物， 其特征在于： 通式 （1-1 ) 或通式 （1-2) 中 选自苯基， 或者被 1-3个独立选自以下基团进一步取代的苯基： 氟、 氯、 溴、 CrC4烷基、 卤代 CrC4烷基、 ^ 4烷氧基、 卤代 4烷氧基或 ^ 4烷硫基； R2选自氢、 氯或 CrC4烷基；
、 R5可相同或不同， 分别选自氢或氯；
X选自 NR8;
R8选自 Ci-C4院基；
选自氢或 CrC4烷基；
Q选自 -CH2CH2-、 -CH2CH2CH2-或 -CH2CH2CH2CH2-；
7、 根据权利要求 5所述的化合物， 其特征在于： 通式 （1-3) 中
选自氢、 C02R6或 CrC4烷基；
R2选自氢、 氟、 氯、 溴或 CrC4烷基；
、 R5可相同或不同， 分别选自氢或氯；
X选自 NR8;
R8选自 CrC4烷基、 苯基、 或者被 1-3个独立选自以下基团进一步取代的苯基: 氟、 氯、 溴、 CrC4烷基、 卤代 CrC4烷基、 CrC4烷氧基或卤代 CrC4烷氧基； 选自氢或 CrC4烷基；
Q选自 -CH2CH2-、 -CH2CH2CH2-或 -CH2CH2CH2CH2- 。
8、 一种按照权利要求 1所述的通式（I )化合物在农业或其他领域中防治害虫 的应用。
9、 一种按照权利要求 1所述的通式（I )化合物在农业或其他领域中防治病菌 的应用。
10、 一种杀虫杀菌组合物， 其特征在于： 含有如权利要求 1所述的通式 （I ) 化合物作为活性组分， 组合物中活性组分的重量百分含量为 0.1-99%。
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BRPI0922073B1 (pt) 2018-09-25
US20110178149A1 (en) 2011-07-21
CN101747276A (zh) 2010-06-23
BRPI0922073A2 (pt) 2015-08-11
CN102216294A (zh) 2011-10-12

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