CN110194742A - Replace (miscellaneous) aryl methylene pyrazole ether compounds and the preparation method and application thereof - Google Patents

Replace (miscellaneous) aryl methylene pyrazole ether compounds and the preparation method and application thereof Download PDF

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CN110194742A
CN110194742A CN201810160953.2A CN201810160953A CN110194742A CN 110194742 A CN110194742 A CN 110194742A CN 201810160953 A CN201810160953 A CN 201810160953A CN 110194742 A CN110194742 A CN 110194742A
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alkyl
halogenated
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alkoxy
carbonyl
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CN110194742B (en
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杜晓华
郝树林
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Zhejiang University of Technology ZJUT
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—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
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • 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
    • C07D231/14—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • 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
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D261/12—Oxygen atoms

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The invention discloses a kind of substitution (miscellaneous) aryl methylene pyrazole ether compounds and the preparation method and application thereof, and shown in structure such as formula (I), various substituent groups is defined in the specification in formula.Formula (I) compound all shows high insecticidal activity to adult, larva and the ovum of acarid harmful in agriculture, civilian and zoo technical field and insect.Such compound shows preferable bactericidal activity simultaneously.Therefore, formula (I) compound can be used as insecticide and/or fungicide is widely used in agricultural and other field.

Description

Replace (miscellaneous) aryl methylene pyrazole ether compounds and the preparation method and application thereof
Technical field
The invention belongs to agricultural insecticidal, mite killing, fungicide fields.More particularly to a kind of substitution (miscellaneous) aryl methylene pyrazoles ether Class compound and the preparation method and application thereof.
Background technique
Researcher finds that methoxy acrylic ester compounds have bioactivity a long time ago.Following document was once reported Such compound is crossed with desinsection brake mite activity in road: EP242081/EP299694/EP335519/US2006235075/ CN101311170 etc..
In addition, pyrimidine methoxy acrylic ester compounds also have been reported that crop desinsection, brake mite or fungicide:
Following general formula compound is as insecticide involved in patent US005106852:
Following general formula compound is as fungicide involved in patent US005378711:
Following general formula compound is as killing acarus and bacteria agent involved in patent US005935965:
Following general formula compound is as desinsection, fungicide involved in patent US006114342:
Following general formula compound is as desinsection, fungicide involved in patent CN101311170:
However, in many cases, the effect of compound on animals pest described in these documents is unsatisfactory 's.
Summary of the invention
The object of the present invention is to provide substitution (miscellaneous) aryl methylene pyrazole ether compounds, the compound is being prevented and treated In terms of harmful fungoid and animal pest, especially in terms of prevention and treatment fungi, insect, nematode and mite, especially in prevention and treatment insect and In terms of mite, there is improved performance.
We have now discovered that this purpose is realized by starting defined compound (I) herein.Furthermore we find that phase system Preparation Method and intermediate contain their compositions and application thereof.
Technical scheme is as follows:
The present invention provides substitution (miscellaneous) aryl methylene pyrazole ether compounds shown in a kind of formula (I):
In formula (I):
R1Selected from hydrogen, halogen, itrile group, nitro, C1-C12Alkyl, halogenated C1-C12Alkyl, C1-C12Alkoxy, halogenated C1-C12 Alkoxy, C1-C12Alkyl-carbonyl, C1-C12Alkoxy C1-C12Alkyl, halogenated C1-C12Alkoxy C1-C12Alkyl, C1-C12Alkyl One of amino, aryl, heteroaryl；
X is O or NR2；
R2Selected from hydrogen, C1-C12Alkyl, halogenated C1-C12Alkyl, C2-C12Alkenyl, halogenated C2-C12Alkenyl, C2-C12Alkynyl, halogen For C2-C12Alkynyl, C1-C12Alkyl-carbonyl, C1-C12Alkoxy carbonyl, C1-C12Alkoxy carbonyl C1-C12Alkyl, C1-C12Alkyl Sulfonyl, aryl, heteroaryl, aryl carbonyl or Heteroarylcarbonyl；
R3、R4Respectively stand alone as H, halogen, hydroxyl, C1-C12Alkyl, halogenated C1-C12Alkyl, C2-C12Alkenyl, halogenated C2-C12 Alkenyl, C2-C12Alkynyl, halogenated C2-C12Alkynyl, C1-C12Alkoxy, C1-C12Alkyl groups in the halogenalkoxy, aryl or heteroaryl；Or it is described R3And R4Carbon atom connected to them represents a C that is saturated or unsaturated, optionally replacing together3-C8Naphthenic base or C3- C8Heterocycle；
A is H by R5Substituted aryl or heteroaryl；
R5The different or identical following group below 1-5: hydrogen, halogen, hydroxyl, sulfydryl, amino, CN, NO2、 C1-C12Alkyl, halogenated C1-C12Alkyl, C3-C8Naphthenic base, C2-C12Alkenyl, halogenated C2-C12Alkenyl, C2-C12Alkynyl, halogenated C2- C12Alkynyl, C1-C12Alkyl amine group, two (C1-C12Alkyl) amido, halogenated C1-C12Alkyl amine group, C1-C12Alkoxy, halogenated C1- C12Alkoxy, C1-C12Alkylthio group, halogenated C1-C12Alkylthio group, C2-C12Alkenyloxy group, halogenated C2-C12Alkenyloxy group, C2-C12Alkynyloxy group, Halogenated C2-C12Alkynyloxy group, C1-C12Alkyl-carbonyl, halogenated C1-C12Alkyl-carbonyl, C1-C12Alkyl sulphinyl, halogenated C1-C12Alkane Base sulfinyl, C1-C12Alkyl sulphonyl, halogenated C1-C12Alkyl sulphonyl, C1-C12Alkyl carbonyl epoxide, C1-C12Alkyl oxycarbonyl Base amino, C1-C12Alkyl sulphonyl oxygroup, C1-C12Alkoxy carbonyl, C1-C12Alkoxy C1-C12Alkoxy, C1-C12Alkoxy Carbonyl C1-C12Alkyl, C1-C12Alkoxycarbonyl amino, C1-C12Alkoxy carbonyl C1-C12Alkoxy, aryl, heteroaryl, fragrant oxygen Base, heteroaryloxy, aralkyl oxy, heteroarylalkyl oxygroup, aryl amine or heteroaryl amido, the aryl, heteroaryl, fragrant oxygen Base, heteroaryloxy, aralkyl oxy, heteroarylalkyl oxygroup, aryl amine or heteroaryl amido respectively stand alone as it is being unsubstituted or its Hydrogen aryl replaced 1-4 following radicals, heteroaryl, aryloxy group, heteroaryloxy, aralkyl oxy, heteroarylalkyl oxygroup, Aryl amine or heteroaryl amido: halogen, CN, NO2、C1-C12Alkyl, C1-C12Halogenated alkyl, C1-C12Halogenated alkoxy, C1-C12Alkane Oxygroup, C1-C12Alkoxy carbonyl or C1-C12Alkyl sulphonyl；
Q is selected from Q1-Q14Shown in one of group (following group includes its stereoisomer):
The present invention more preferably formula (I) compound are as follows:
R1Selected from hydrogen, halogen, itrile group, nitro, C1-C6Alkyl, halogenated C1-C6Alkyl, C1-C6Alkoxy, halogenated C1-C6Alkane Oxygroup, C1-C6Alkyl-carbonyl, C1-C6Alkoxy C1-C6Alkyl, halogenated C1-C6Alkoxy C1-C6Alkyl, C1-C6Alkyl amino, virtue One of base, heteroaryl；
X is preferably O or NR2；
R2Selected from hydrogen, C1-C6Alkyl, halogenated C1-C6Alkyl, C2-C6Alkenyl, halogenated C2-C6Alkenyl, C2-C6It is alkynyl, halogenated C2-C6Alkynyl, C1-C6Alkyl-carbonyl, C1-C6Alkoxy carbonyl, C1-C6Alkoxy carbonyl C1-C6Alkyl, C1-C6Alkyl sulphonyl, Aryl, heteroaryl, aryl carbonyl or Heteroarylcarbonyl；
R3、R4Respectively stand alone as H, halogen, hydroxyl, C1-C6Alkyl, halogenated C1-C6Alkyl, C2-C6Alkenyl, halogenated C2-C6Alkene Base, C2-C6Alkynyl, halogenated C2-C6Alkynyl, C1-C6Alkoxy, C1-C6Alkyl groups in the halogenalkoxy, aryl or heteroaryl；Or the R3And R4 Carbon atom in connection represents a C that is saturated or unsaturated, optionally replacing together3-C6Naphthenic base or C3-C6Heterocycle Base；
A is H by R5Substituted aryl or heteroaryl；
R5The different or identical following group below 1-5: hydrogen, halogen, hydroxyl, sulfydryl, amino, CN, NO2、 C1-C6Alkyl, halogenated C1-C6Alkyl, C3-C6Naphthenic base, C2-C6Alkenyl, halogenated C2-C6Alkenyl, C2-C6Alkynyl, halogenated C2-C6Alkynes Base, C1-C6Alkyl amine group, two (C1-C6Alkyl) amido, halogenated C1-C6Alkyl amine group, C1-C6Alkoxy, halogenated C1-C6Alcoxyl Base, C1-C6Alkylthio group, halogenated C1-C6Alkylthio group, C2-C6Alkenyloxy group, halogenated C2-C6Alkenyloxy group, C2-C6Alkynyloxy group, halogenated C2-C6 Alkynyloxy group, C1-C6Alkyl-carbonyl, halogenated C1-C6Alkyl-carbonyl, C1-C6Alkyl sulphinyl, halogenated C1-C6Alkyl sulphinyl, C1-C6Alkyl sulphonyl, halogenated C1-C6Alkyl sulphonyl, C1-C6Alkyl carbonyl epoxide, C1-C6Alkyl-carbonyl-amino, C1-C6Alkane Base sulfonyl oxygroup, C1-C6Alkoxy carbonyl, C1-C6Alkoxy C1-C6Alkoxy, C1-C6Alkoxy carbonyl C1-C6Alkyl, C1- C6Alkoxycarbonyl amino, C1-C6Alkoxy carbonyl C1-C6Alkoxy, aryl, heteroaryl, aryloxy group, heteroaryloxy, aralkyl Oxygroup, heteroarylalkyl oxygroup, aryl amine or heteroaryl amido, the aryl, heteroaryl, aryloxy group, heteroaryloxy, aralkyl oxy Base, heteroarylalkyl oxygroup, aryl amine or heteroaryl amido respectively stand alone as be unsubstituted or its hydrogen and are taken by 1-4 following radicals Aryl, heteroaryl, aryloxy group, heteroaryloxy, aralkyl oxy, heteroarylalkyl oxygroup, aryl amine or the heteroaryl amido in generation: halogen Element, CN, NO2、C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Halogenated alkoxy, C1-C6Alkoxy, C1-C6Alkoxy carbonyl or C1-C6Alkyl sulphonyl；
Q is selected from Q1-Q14One of group.
Formula (I) compound advanced optimized are as follows:
R1Selected from hydrogen, halogen, itrile group, nitro, C1-C4Alkyl, halogenated C1-C4Alkyl, C1-C4Alkoxy, halogenated C1-C4Alkane Oxygroup, C1-C4Alkyl-carbonyl, C1-C4Alkoxy C1-C4Alkyl, halogenated C1-C4Alkoxy C1-C4Alkyl, C1-C4Alkyl amino, virtue Base, heteroaryl；
X is O or NR2；
R2Selected from hydrogen, C1-C4Alkyl, halogenated C1-C4Alkyl, C2-C4Alkenyl, halogenated C2-C4Alkenyl, C2-C4It is alkynyl, halogenated C2-C4Alkynyl, C1-C4Alkyl-carbonyl, C1-C4Alkoxy carbonyl, C1-C4Alkoxy carbonyl C1-C4Alkyl, C1-C4Alkyl sulphonyl, Aryl, heteroaryl, aryl carbonyl or Heteroarylcarbonyl；
R3、R4For H, halogen, hydroxyl, C1-C4Alkyl, halogenated C1-C4Alkyl, C2-C4Alkenyl, halogenated C2-C4Alkenyl, C2-C4 Alkynyl, halogenated C2-C4Alkynyl, C1-C4Alkoxy, C1-C4Alkyl groups in the halogenalkoxy, aryl, heteroaryl；Or the R3And R4With they institute The carbon atom of connection represents a C that is saturated or unsaturated, optionally replacing together3-C6Naphthenic base or C3-C6Heterocycle；
A is H by R5Substituted aryl or heteroaryl；
R5The different or identical following group below 1-5: hydrogen, halogen, hydroxyl, sulfydryl, amino, CN, NO2、 C1-C4Alkyl, halogenated C1-C4Alkyl, C3-C8Naphthenic base, C2-C4Alkenyl, halogenated C2-C4Alkenyl, C2-C4Alkynyl, halogenated C2-C4Alkynes Base, C1-C4Alkyl amine group, two (C1-C4Alkyl) amido, halogenated C1-C4Alkyl amine group, C1-C4Alkoxy, halogenated C1-C4Alcoxyl Base, C1-C4Alkylthio group, halogenated C1-C4Alkylthio group, C2-C4Alkenyloxy group, halogenated C2-C4Alkenyloxy group, C2-C4Alkynyloxy group, halogenated C2-C4 Alkynyloxy group, C1-C4Alkyl-carbonyl, halogenated C1-C4Alkyl-carbonyl, C1-C4Alkyl sulphinyl, halogenated C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, halogenated C1-C4Alkyl sulphonyl, C1-C4Alkyl carbonyl epoxide, C1-C4Alkyl-carbonyl-amino, C1-C4Alkane Base sulfonyl oxygroup, C1-C4Alkoxy carbonyl, C1-C4Alkoxy C1-C4Alkoxy, C1-C4Alkoxy carbonyl C1-C4Alkyl, C1- C4Alkoxycarbonyl amino, C1-C4Alkoxy carbonyl C1-C4Alkoxy, aryl, heteroaryl, aryloxy group, heteroaryloxy, aralkyl Oxygroup, heteroarylalkyl oxygroup, aryl amine or heteroaryl amido, the aryl, heteroaryl, aryloxy group, heteroaryloxy, aralkyl oxy Base, heteroarylalkyl oxygroup, aryl amine or heteroaryl amido respectively stand alone as be unsubstituted or its hydrogen and are taken by 1-4 following radicals Aryl, heteroaryl, aryloxy group, heteroaryloxy, aralkyl oxy, heteroarylalkyl oxygroup, aryl amine or the heteroaryl amido in generation: halogen Element, CN, NO2、C1-C4Alkyl, C1-C4Halogenated alkyl, C1-C4Halogenated alkoxy, C1-C4Alkoxy, C1-C4Alkoxy carbonyl or C1-C4Alkyl sulphonyl；
Q is selected from Q1-Q9One of group.
Formula (I) compound still more preferably is preferably compound shown in formula (IA), (IB), (IC) or (ID):
Formula (IA), (IB), (IC), in (ID),
R1A、R1B、R1C、R1DIt is each independently selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl Base, normal-butyl, isobutyl group, methoxyl group, ethyoxyl or trifluoro ethoxy；
XAFor O or NR2A；XBFor O or NR2B；XCFor O or NR2C；XDFor O or NR2D；
R2A、R2B、R2C、R2DIt is each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary fourth Base, a methyl fluoride, difluoromethyl, trifluoromethyl, trifluoroethyl, acetyl group, trifluoroacetyl group, methyl sulphonyl or ethyl sulphonyl Base；
R3A、R3B、R3C、R3D、R4A、R4B、R4C、R4DRespectively stand alone as hydrogen, fluorine, chlorine, bromine, methyl, ethyl, ethyl, positive third Base, isopropyl, normal-butyl, methoxyl group, ethyoxyl, methyl mercapto, ethylmercapto group or trifluoro ethoxy；Alternatively, the R3AAnd R4AWith it The carbon atom that is connected form cyclopropyl, cyclobutyl or cyclopenta, the R3BAnd R4BCarbon atom connected to them is formed Cyclopropyl, cyclobutyl or cyclopenta, the R3CAnd R4CCarbon atom connected to them forms cyclopropyl, cyclobutyl or ring penta Base, the R3DAnd R4DCarbon atom connected to them forms cyclopropyl, cyclobutyl or cyclopenta；
R5A、R5B、R5C、R5DBe each independently selected from one of following group or a variety of: fluorine, chlorine, bromine, iodine, cyano, amino, Nitro, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, trifluoromethyl, trichloromethyl, two It is fluorine chloromethyl, one methyl fluoride of dichloro, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, different Butoxy, tert-butoxy, trifluoromethoxy, trifluoro ethoxy, methyl mercapto, trifluoromethylthio, methoxycarbonyl, ethyoxyl carbonyl Base, dimethylamino, amino carbonyl, methylaminocarbonyl, ethyl aminocarbonyl or dimethylamino carbonyl；
nA、nB、nC、nDIt is each independently selected from 0 to 5 integer, when for 0, unsubstituted on phenyl ring or pyridine ring；When big When 1, R5AIt may be the same or different (R5B、R5C、R5DSimilarly)；
QA、QB、QC、QDIt is each independently selected from Q1-Q6One of group.
Further formula (I) is preferably in formula (IA) compound:
In formula (IA) compound,
R1ASelected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, normal-butyl or isobutyl group；
XAFor O or NR2A；
R2ASelect hydrogen, methyl, ethyl, isopropyl, tert-butyl or trifluoroethyl；
R3A、R4ARespectively stand alone as hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxyl group, ethyoxyl, methyl mercapto, ethylmercapto group or three Fluorine ethyoxyl；
R5ASelected from one of following group or a variety of: fluorine, chlorine, bromine, iodine, cyano, amino, nitro, methyl, ethyl, different Propyl, tert-butyl, trifluoromethyl, trichloromethyl, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, trifluoromethoxy, trifluoro Ethyoxyl, methyl mercapto, trifluoromethylthio, methoxycarbonyl or dimethylamino；
nASelected from 0 to 5 integer, work as nAWhen being 0, unsubstituted on phenyl ring；Work as nAWhen greater than 1, R5AIt may be the same or different；
QASelected from Q1-Q4One of group.
Formula (IA) compound still more preferably are as follows:
R1ASelected from hydrogen or chlorine；
XAFor O or NR2A；
R2ASelected from hydrogen, methyl, ethyl or tert-butyl；
R3A、R4ARespectively stand alone as hydrogen, fluorine；
R5ASelected from one of following group or a variety of: fluorine, chlorine, cyano, nitro, methyl, trifluoromethyl, trichloromethyl, Methoxyl group, trifluoromethoxy, dimethylamino；
nASelected from 0 to 5 integer, work as nAWhen being 0, unsubstituted on phenyl ring；Work as nAWhen greater than 1, R5AIt may be the same or different；
QASelected from Q1-Q4One of group.
In the definition of formula (I) compound given above, collects term used and is generally defined as follows:
Halogen: refer to fluorine, chlorine, bromine or iodine.
Alkyl: linear or branched alkyl group, such as methyl, ethyl, propyl, isopropyl, normal-butyl or tert-butyl.
Naphthenic base: substituted or unsubstituted cyclic alkyl, such as cyclopropyl, cyclopenta or cyclohexyl.Substituent group such as methyl, Halogen etc..
Halogenated alkyl: linear or branched alkyl group, the hydrogen atom on these alkyl can partly or entirely be taken by halogen atom Generation, for example, chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl etc..
Cyanoalkyl: linear or branched alkyl group, hydrogen atom on these alkyl can part replaced cyano, for example,- CH2CN、-CH2CH2CN、-CH2C(CH3)2CN、-CH2CH(CN)2Deng.
Alkoxy: linear or branched alkyl group is keyed in structure through oxygen atom.
Cyano alkoxy: cyanoalkyl is keyed in structure through oxygen atom.Such as CNCH2O-。
Alkoxyalkyl: alkoxy is connected in structure through alkyl.Such as CH3OCH2, CH3CH2OCH2-。
Halogenated alkoxy alkyl: the hydrogen atom on the alkyl of alkoxyalkyl can be partly or entirely replaced halogen atom. Such as ClCH2CH2OCH2-。
Alkoxy carbonyl: alkoxy is connected in structure through carbonyl.Such as CH3OCO-, CH3CH2OCO-.Alkoxy carbonyl alkane Base: alkoxy carbonyl is connected in structure using alkyl.
Halogenated alkoxy: straight or branched alkoxyl, the hydrogen atom on these alkoxies can be partly or entirely by halogen original Replaced son.For example, chloromethane epoxide, dichloro methoxyl group, trichloromethoxy, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, Chlorine fluorine methoxyl group, trifluoro ethoxy etc..
Alkylthio group: linear or branched alkyl group is keyed in structure through sulphur atom.
Alkylthio alkyl: alkylthio group is connected in structure through alkyl.Such as CH3SCH2-。
Halogenated alkylthio: linear chain or branched chain alkylthio group, the hydrogen atom on these alkyl can be partly or entirely by halogen atom It is replaced.For example, chloromethane sulfenyl, dichloro methyl mercapto, trichloro-methylthio, fluorine methyl mercapto, difluoro methyl mercapto, trifluoromethylthio, chlorine Fluorine methyl mercapto etc..
Haloalkylthioalkyl: halogenated alkylthio is connected in structure through alkyl.Alkyl amino: linear or branched alkyl group, It is keyed in structure through nitrogen-atoms.
Alkyl amino-carbonyl: such as CH3NHCO-, CH3CH2NHCO-。
Haloalkylamino carbonyl: the hydrogen atom on the alkyl of alkyl amino-carbonyl can partly or entirely be taken by halogen atom Generation.Such as CF3NHCO-。
Haloalkylamino: linear or branched alkyl group amino, the hydrogen atom on these alkyl can be partly or entirely by halogen Replaced atom.
Alkenyl: linear chain or branched chain alkenes, such as vinyl, 1- acrylic, 2- acrylic and different cyclobutenyls, pentenyl And hexenyl isomers.
Alkenyl further includes polyenoid class, such as 1,2- allene base and 2,4- hexadienyl.
Halogenated alkenyl: linear chain or branched chain alkenes, the hydrogen atom on these alkenyls can partly or entirely be taken by halogen atom Generation.
Alkynyl: linear chain or branched chain acetylenic, such as acetenyl, 1- propinyl, 2-propynyl and different butynyls, pentynyl And hexynyl isomers.Alkynyl further includes the group being made of multiple three keys, such as 2,5- adipic alkynyl.
Halo alkynyl: linear chain or branched chain acetylenic, the hydrogen atom on these alkynyls can partly or entirely be taken by halogen atom Generation.
Alkenyloxy group: linear chain or branched chain alkenes are keyed in structure through oxygen atom.
Haloalkenyloxy: linear chain or branched chain alkenyloxy group, the hydrogen atom in these alkenyloxy groups can be partly or entirely by halogen original Replaced son.
Alkynyloxy group: linear chain or branched chain acetylenic is keyed in structure through oxygen atom.
Halogenated alkynyloxy group: linear chain or branched chain alkynyloxy group, the hydrogen atom on these alkynyloxy groups can be partly or entirely by halogen original Replaced son.
Alkenylthio group: linear chain or branched chain alkenes are keyed in structure through sulphur atom.
Halogenated alkenylthio group: linear chain or branched chain alkenylthio group, the hydrogen atom on these alkenylthio groups can be partly or entirely by halogen original Replaced son.
Alkynes sulfenyl: linear chain or branched chain acetylenic is keyed in structure through sulphur atom.
Acetylenic halide sulfenyl: linear chain or branched chain alkynes sulfenyl, the hydrogen atom on these alkynes sulfenyls can be partly or entirely by halogen original Replaced son.
Alkyl-carbonyl: alkyl is connected in structure through carbonyl, such as CH3CO-, CH3CH2O-。
Halogenated alkyl carbonyl: the hydrogen atom on the alkyl of alkyl-carbonyl can be partly or entirely replaced halogen atom, such as CF3CO-。
Alkyl sulphinyl: linear or branched alkyl group is connected in structure through sulfinyl (- SO-), such as methylsulfinyl Base.
Alkylsulfinyl: linear or branched alkyl group sulfinyl, the hydrogen atom on alkyl can be part or all of Replaced halogen atom.
Alkyl sulphonyl: linear or branched alkyl group is through sulfonyl (- SO2) be connected in structure, such as methyl sulphonyl.
Halogenated alkyl sulfonyl: linear or branched alkyl group sulfonyl, the hydrogen atom on alkyl can be partly or entirely by halogen Replaced atom.
Phenyloxycarbonyl: phenoxy group is connected in structure through carbonyl, such as PhOCO-.
Phenyl amino carbonyl: phenyl amino is connected in structure through carbonyl, such as PhNHCO-.
Phenylalkyl: phenyl is connected in structure through alkyl, such as benzyl, phenethyl etc..
Naphthylalkyl: naphthalene is connected in structure through alkyl, such as menaphthyl, naphthylethyl etc..
Heteroaryl: signified heteroaryl is containing the heteroatomic five-membered ring of one or more N, O, S or hexa-atomic cyclophane in the present invention Base.Such as pyridyl group, pyrimidine radicals, pyrazinyl, pyridazinyl, furyl, thiazolyl, quinolyl, isothiazolyl, oxazolyl, different evil Oxazolyl, pyrazolyl, benzothiazolyl, benzofuranyl etc..
Heteroarylcarbonyl: heteroaryl is connected in structure through carbonyl, such as picolinoyl, pyrimidine formoxyl, pyrazoles formyl Base.
Heteroaryloxycarbonyl: heteroaryl oxygroup is connected in structure through carbonyl.
Heteroarylaminocarbonyl: heteroaryl amino is connected in structure through carbonyl.
Heteroaryl alkyl: heteroaryl is connected in structure through alkyl, such as furfuryl, pyridine ethyl etc..
In the compound of the present invention, since carbon-to-carbon double bond or carbon-to-nitrogen double bond connect different substituent groups and it can be formed Stereoisomer (respectively with z and E to indicate different configurations).The present invention includes Z-type isomers and E-isomer and its any The mixture of ratio.
When A is phenyl in formula (I) of the invention, shown in general formula such as formula (IA), part of compounds can be in table 1- table 2 The particular compound and physics temper listed are to illustrate, but restriction is of the invention.
Work as X in general formula IAA=NR2, list compound is shown in Table 1
Table 1
Work as X in formula (IA)A=O, list compound are shown in Table 2
Table 2
Specifically, compound shown in formula (I) is preferred are as follows:
Compound 37,40,43,49,51,52,53,54,55,61,63,64,65,61,65,112.
Logical formula (I) compound of the invention can be prepared in accordance with the following methods:
Q is selected from Q in the compound shown in formula (I)1、Q2、Q3、Q6-Q13In any group when, hydroxyl shown in formula (III) Pyrimidines and formula (IV) shown in benzyl halogen under alkaline matter existence condition in organic solvent, it is anti-at 20-100 DEG C It answers 0.5 hour to 20 hours, post-treated obtained formula (I) compound of reaction solution:
In formula (III), (IV), X is leaving group, is selected from chlorine or bromine；The same formula of the definition of other each groups (I).
In the above method, the mass ratio of the material of compound shown in formula (III) and compound shown in formula (IV) is 1:1~1.1.
It reacts and is carried out in suitable organic solvent, the optional tetrahydrofuran freely of suitable organic solvent, acetonitrile, diformazan Benzene, benzene, DMF, DMSO, acetone, butanone or methyl tertiary butyl ether(MTBE) etc..
Suitable alkaline matter is selected from potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyrrole Pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide or sodium tert-butoxide etc.
Reaction temperature can be in room temperature between solvent boiling point temperature, and usually 20-100 DEG C.
Reaction time is 30 minutes to 20 hours, usually 1-12 hours.
The post-processing are as follows: reaction solution is poured into saturated salt solution, is extracted with ethyl acetate for several times, it is dry, after precipitation, With petroleum ether: ethyl acetate 1000:1~500 are eluant, eluent, obtain target product through column chromatographic purifying.
Q is selected from Q in the compound shown in formula (I)4、Q5Or Q14When, the method is that each free Q is Q3、Q2、Q13Formula (I) It is Q that corresponding Q, which is made, with methylamine water solution reaction in shown compound4、Q5Or Q14Formula (I) shown in compound；The methylamine water The mass concentration of solution is 20~60%；The Q is Q3、Q2、Q13Formula (I) shown in carbinolamine in compound and methylamine water solution The mass ratio of the material be 1:5~10.
Intermediate III can refer to WO 9307138, A1, Synthetic Communications, 2002,32 (5), 785- 791 prepare.
Formula (IV) compound represented can be made by known method, referring specifically to US4723034 and US5554578 etc..
Formula (I) compound to adult, larva and the ovum of acarid harmful in agriculture, civilian and zoo technical field and insect all Show high insecticidal activity.Such compound shows preferable bactericidal activity simultaneously.
Therefore, another object of the present invention be related to formula (I) compound agricultural or other field in be used as insecticide and/or The application of fungicide.Especially, formula (I) compound is active to following important species: Tetranychidae (Tetranychus urticae, linden two o'clock Tetranychid, Tetranychus cinnabarinus, Eotetranychus carpini, panonychus ulmi, panonychus citri etc.), (hazel plants plumage fistula mite, grape fistula to Eriophyidae Mite, pears fistula mite etc.), Tarsonemidae (narrow tarsonemid of primrose etc.).Meanwhile part of compounds of the invention also has good sterilization It is white to can be used for preventing and treating rice sheath blight disease, rice blast, tomato late blight, cucumber downy mildew, gray mold of cucumber, cucumber for activity Powder disease, wheat powdery mildew, wheat gray mold, anthracnose, head blight, soybean rust etc..
Meanwhile formula (I) compound has hypotoxicity to many beneficial insects and acarid, mammal, fish, bird, and There is no phytotoxicity.
Due to its positive characteristic, above compound is advantageously used for protection agricultural and the important crop of horticulture, family The environment that poultry and breeding stock and the mankind often go is from harmful acarid, the injury of insect.
To obtain ideal effect, the dosage of compound changes because of various factors.Such as it compound used therefor, in advance protects Crop, the type of harmful organism, gradient of infection, weather conditions, application method, the dosage form of use.
10 grams of -5 kilograms of compound dosage of per hectare can provide sufficient prevention and treatment.
Another object of the present invention is further related to through application formula (I) compound, prevention and treatment agricultural and the important crop of horticulture And/or the method for the pest and/or plant pathogenic fungi in the environment that often goes of poultry and breeding stock and/or the mankind.Especially, change The dosage of conjunction object variation effect in 10 grams -5 kilograms of per hectare is preferable.
It the use of the composition containing one or more formulas (I) compound is usually beneficial to be applied to agricultural.
Therefore, another object of the present invention be related to containing one or more formulas (I) compound as active constituent desinsection with/ Or bactericidal composition.The composition include formula (I) compound and dissolving medium as active constituent, surfactant and/ Or diluent.
Composition is prepared in a known way, such as optionally in the presence of surfactant, by with solvent medium And/or dilute dilution agent or dissolution active material.
Available diluent includes solid diluent and liquid diluent, and solid diluent or carrier are for example: titanium dioxide Silicon, kaolin, bentonite, magnificent scholar, dolomite, calcium carbonate, magnesia, chalk, clay, synthetic silicate, Attagel, Hai Pao Stone, sulfate etc..
Than water, available liquid diluent is such as aromatic organic solvent (mixture of dimethylbenzene or alkylbenzene, chlorine Benzene etc.).Paraffin (petroleum distillate), alcohols (methanol, propyl alcohol, butanol, propylene glycol, ethylene glycol, glycerol, octanol), esters (acetic acid second Ester, isobutyl acetate etc.), ketone (electrodeless ketone of cyclohexanone, acetone, acetophenone, isophorone, ethyl etc.), amides (N, N- bis- Methylformamide, methyl pyrrolidone etc.).
Available surfactant is the polyoxy of alkylsulfonate, alkylaryl sulfonates, polyoxyethylene groups phenol, sorbierite Sodium, calcium, triethylamine or the triethanolamine salt of vinyl acetate, lignosulfonates etc..
Composition can also contain special additive for specific purpose, for example, adhesive for example Arabic gum, polyvinyl alcohol, Polyvinylpyrrolidone etc..
In above-mentioned composition the concentration of active constituent can according to active constituent, its use purpose, environmental condition and use Preparation type and change in a wide range.In general, the concentration range of active constituent is 1-90%, preferably 5-50%.
If desired, other active components that can be compatible with compound of Formula I can be added into composition, such as other Acaricide/insecticide, fungicide, plant growth regulator, antibiotic, herbicide, fertilizer.
Specific embodiment
Next combined with specific embodiments below the present invention is further described, but it is specific real not limit the invention to these Apply mode.Benzene field technical staff is it should be appreciated that all present invention encompasses what be may include in Claims scope Alternative, improvement project and equivalent scheme.
Embodiment 1: the synthesis of compound 111
1.3g (0.005mol) 1a is dissolved in 10 milliliters of n,N-Dimethylformamide, potassium carbonate 0.83g, stirring is added 0.5h is added portionwise 2a (1.26g), finishes and be warming up to 80 DEG C, be stirred to react 8h.TLC is detected after completion of the reaction, and reaction solution is fallen Enter in 50ml saturated salt solution, is extracted in three times with 100ml ethyl acetate, it is dry.After precipitation, with petroleum ether: ethyl acetate 1000:1~500 are that eluant, eluent column chromatographic purifying obtains oily product 1.86g.
Embodiment 2: the synthesis of compound 87
1.1g (0.005mol) 1b is dissolved in 10 milliliters of n,N-Dimethylformamide, potassium carbonate 0.83g, stirring is added 0.5h is added dropwise to the DMF solution of 2b (1.4g), finishes and is warming up to 80 DEG C, is stirred to react 8h.TLC is detected after completion of the reaction, will be anti- It answers liquid to pour into 50ml saturated salt solution, is extracted in three times with 100ml ethyl acetate, it is dry.After precipitation, with petroleum ether: acetic acid Ethyl ester 1000:1~200 are that eluant, eluent column chromatographic purifying obtains oily product 1.68g.
Other compounds of the invention are referred to above embodiments preparation.
The nuclear magnetic data of part of compounds:
Compound 37:1HNMR(400MHz,DMSO)δ(ppm):3.51(s,3H,CH3),3.60(s,3H,CH3),3.80 (s,3H,CH3),5.01(s,2H,CH2), 5.94 (s, 1H, pyrazolyl1-H), 7.13-7.53 (m, 9H, Ar-H), 7.67 (s, 1H,CH)
Compound 39:1HNMR(400MHz,DMSO)δ(ppm):3.58(s,3H,CH3),3.59(s,3H,CH3),3.79 (s,3H,CH3),5.08(s,2H,CH2),6.04(s,1H,pyrazolyl1-H),7.41-7.68(m,4H,Ar-H),7.65(s, 1H,CH)
Compound 52:1HNMR(400MHz,DMSO)δ(ppm):3.49(s,3H,CH3),3.73(s,3H,CH3),3.74 (s,3H,CH3),3.94(s,3H,CH3),5.05(s,2H,CH2),6.10(s,1H,pyrazolyl1-H),7.28-7.89(m, 8H, Ar-H),
Compound 63:1HNMR(400MHz,DMSO)δ(ppm):3.56(s,3H,CH3),3.66(s,3H,CH3),3.69 (s,3H,CH3),5.19(s,2H,CH2), 6.06 (s, 1H, pyrazolyl1-H), 7.42-7.66 (m, 8H, Ar-H),
Compound 64:1HNMR(400MHz,DMSO)δ(ppm):3.66(s,3H,CH3),3.69(s,3H,CH3),3.73 (s,3H,CH3),3.83(s,3H,CH3),5.30(s,2H,CH2),6.05(s,1H,pyrazolyl1-H),7.13-7.58(m, 8H, Ar-H),
Example of formulations
Each component additional amount is weight percentage.Active component can appoint in formula (I) of the present invention in preparation Meaning compound, it is post-dised through folding hundred.
Embodiment 3:30% wettable powder
Compound and other components are sufficiently mixed, to get to 30% wettable powder after ultra-fine pulverizer disintegrating Product.
Embodiment 4:40% suspension concentrates
Compound and other components are sufficiently mixed, thus obtained suspension concentrates, and it is available that gained suspending agent is diluted with water The dilution of concentration needed for any.
Embodiment 5:60% water-dispersible granules
By compound and other components co-grinding, after adding water kneading, be added 10-100 mesh screen pelletizer in into Row is granulated, then again through drying, screening (pressing screen cloth scope).
Biological activity determination embodiment
Active determination test has been carried out with adult of the compounds of this invention to Tetranychus cinnabarinus.Method for measuring is as follows:
Embodiment 6: mythimna separata insecticidal activity assay
The raw medicine that certain mass is weighed with assay balance (0.0001g) is matched with the DMF dissolution containing 1% Tween-80 emulsifier 1% mother liquor is made, is then diluted with distilled water spare.
Leaf dipping method is used by target of mythimna separata, insecticidal activity assay is carried out using spray-on process with alfalfa bud.
The determination of activity of mythimna separata
Leaf dipping method: being mythimna separata for examination target, i.e., naturally negative after sufficiently infiltrating appropriate maize leaf in the medical fluid prepared It is dry, it is put into the culture dish for being lined with filter paper, connects mythimna separata 3 age mid-term larva, 10/ware, be placed in 24~27 DEG C of observation ward and cultivate, Investigation result after 3d.Polypide is touched with writing brush, it is reactionless to be considered as dead worm.
Partial test result is as follows:
Under experimental concentration 500mg/L, 40,51,55 pairs of aphid lethalities of compound are 80% or more, compound 37,43, 49,52,53,54,61,63,64,65 pairs of aphid lethalities are 100%.
Embodiment 7: the determination of activity of aphis craccivora:
Spray-on process: it is aphis craccivora for examination target, i.e., will be connected to the Broad Bean Leaves of aphis craccivora respectively under Potter spray tower Spraying treatment, Tetranychus cinnabarinus is placed in 24~27 DEG C of observation ward and cultivates after processing, and aphis craccivora is placed in 20~22 DEG C of observation ward and trains It supports, investigation result after 2d.Polypide is touched with writing brush, it is reactionless to be considered as dead worm.
When experimental concentration 500mg/L, compound 65 is 100% or more to the lethality of aphis craccivora
(2) living body protection activity measures
Embodiment 8: powdery mildew of cucumber prophylactic tria
Measuring method is as follows:
Using living body potting measuring method, i.e., by test compound sample a small amount of DMF solvent (type of solvent such as third Ketone, methanol, DMF etc., and select according to its solvability to sample, the volume ratio of quantity of solvent and spouting liquid are equal to or small In 0.05) dissolving, is diluted with the water containing 0.1% Tween 80, be configured to required concentration prepare liquid.Prepared medicament is sprayed Rifle is uniformly sprayed for trying a leaf period, on the consistent cucumber seedling of growing way, and is air-dried, and every concentration is a processing, every processing 3 Secondary repetition separately sets comparison medicament and clear water blank control.The fresh Powdery Mildew spore taken on cucumber leaves is washed, double gauze is used The suspension that spore concentration is 100,000/mL or so, spray inoculation is made in filtering, and the test material after inoculation moves into artificial climate, Relative humidity is maintained between 60-70%, and temperature is kept for 23 degree, and 10d or so carries out classification investigation depending on blank control incidence, Amine disease, which refers to, calculates preventive effect %.
Test result is as follows for the living body protection activity of part of compounds:
Under 200ppm concentration, 61,65,112 pairs of prevention powdery mildew effects of compound reach 80% or more.

Claims (10)

1. replacing (miscellaneous) aryl methylene pyrazole ether compounds shown in a kind of formula (I):
In formula (I):
R1Selected from hydrogen, halogen, itrile group, nitro, C1-C12Alkyl, halogenated C1-C12Alkyl, C1-C12Alkoxy, halogenated C1-C12Alcoxyl Base, C1-C12Alkyl-carbonyl, C1-C12Alkoxy C1-C12Alkyl, halogenated C1-C12Alkoxy C1-C12Alkyl, C1-C12Alkyl amino, One of aryl, heteroaryl；
X is O or NR2；
R2Selected from hydrogen, C1-C12Alkyl, halogenated C1-C12Alkyl, C2-C12Alkenyl, halogenated C2-C12Alkenyl, C2-C12Alkynyl, halogenated C2- C12Alkynyl, C1-C12Alkyl-carbonyl, C1-C12Alkoxy carbonyl, C1-C12Alkoxy carbonyl C1-C12Alkyl, C1-C12Alkyl sulfonyl Base, aryl, heteroaryl, aryl carbonyl or Heteroarylcarbonyl；
R3、R4Respectively stand alone as H, halogen, hydroxyl, C1-C12Alkyl, halogenated C1-C12Alkyl, C2-C12Alkenyl, halogenated C2-C12Alkene Base, C2-C12Alkynyl, halogenated C2-C12Alkynyl, C1-C12Alkoxy, C1-C12Alkyl groups in the halogenalkoxy, aryl or heteroaryl；Or the R3 And R4Carbon atom connected to them represents a C that is saturated or unsaturated, optionally replacing together3-C8Naphthenic base or C3-C8 Heterocycle；
A is H by R5Substituted aryl or heteroaryl；
R5The different or identical following group below 1-5: hydrogen, halogen, hydroxyl, sulfydryl, amino, CN, NO2、C1-C12 Alkyl, halogenated C1-C12Alkyl, C3-C8Naphthenic base, C2-C12Alkenyl, halogenated C2-C12Alkenyl, C2-C12Alkynyl, halogenated C2-C12Alkynes Base, C1-C12Alkyl amine group, two (C1-C12Alkyl) amido, halogenated C1-C12Alkyl amine group, C1-C12Alkoxy, halogenated C1-C12Alkane Oxygroup, C1-C12Alkylthio group, halogenated C1-C12Alkylthio group, C2-C12Alkenyloxy group, halogenated C2-C12Alkenyloxy group, C2-C12It is alkynyloxy group, halogenated C2-C12Alkynyloxy group, C1-C12Alkyl-carbonyl, halogenated C1-C12Alkyl-carbonyl, C1-C12Alkyl sulphinyl, halogenated C1-C12Alkyl is sub- Sulfonyl, C1-C12Alkyl sulphonyl, halogenated C1-C12Alkyl sulphonyl, C1-C12Alkyl carbonyl epoxide, C1-C12Alkyl-carbonyl ammonia Base, C1-C12Alkyl sulphonyl oxygroup, C1-C12Alkoxy carbonyl, C1-C12Alkoxy C1-C12Alkoxy, C1-C12Alkoxy carbonyl C1-C12Alkyl, C1-C12Alkoxycarbonyl amino, C1-C12Alkoxy carbonyl C1-C12Alkoxy, aryl, heteroaryl, aryloxy group, Heteroaryloxy, aralkyl oxy, heteroarylalkyl oxygroup, aryl amine or heteroaryl amido, it is the aryl, heteroaryl, aryloxy group, miscellaneous Aryloxy group, aralkyl oxy, heteroarylalkyl oxygroup, aryl amine or heteroaryl amido respectively stand alone as be unsubstituted or its hydrogen by 1- Aryl replaced 4 following radicals, heteroaryl, aryloxy group, heteroaryloxy, aralkyl oxy, heteroarylalkyl oxygroup, aryl amine Or heteroaryl amido: halogen, CN, NO2、C1-C12Alkyl, C1-C12Halogenated alkyl, C1-C12Halogenated alkoxy, C1-C12Alkoxy, C1- C12Alkoxy carbonyl or C1-C12Alkyl sulphonyl；
Q is selected from Q1-Q14Shown in one of group:
2. compound as described in claim 1, it is characterised in that:
In formula (I), R1Selected from hydrogen, halogen, itrile group, nitro, C1-C6Alkyl, halogenated C1-C6Alkyl, C1-C6Alkoxy, halogenated C1- C6Alkoxy, C1-C6Alkyl-carbonyl, C1-C6Alkoxy C1-C6Alkyl, halogenated C1-C6Alkoxy C1-C6Alkyl, C1-C6Alkyl ammonia One of base, aryl, heteroaryl；
X is preferably O or NR2；
R2Selected from hydrogen, C1-C6Alkyl, halogenated C1-C6Alkyl, C2-C6Alkenyl, halogenated C2-C6Alkenyl, C2-C6Alkynyl, halogenated C2-C6Alkynes Base, C1-C6Alkyl-carbonyl, C1-C6Alkoxy carbonyl, C1-C6Alkoxy carbonyl C1-C6Alkyl, C1-C6Alkyl sulphonyl, aryl, Heteroaryl, aryl carbonyl or Heteroarylcarbonyl；
R3、R4Respectively stand alone as H, halogen, hydroxyl, C1-C6Alkyl, halogenated C1-C6Alkyl, C2-C6Alkenyl, halogenated C2-C6Alkenyl, C2-C6Alkynyl, halogenated C2-C6Alkynyl, C1-C6Alkoxy, C1-C6Alkyl groups in the halogenalkoxy, aryl or heteroaryl；Or the R3And R4With The carbon atom that they are connected represents a C that is saturated or unsaturated, optionally replacing together3-C6Naphthenic base or C3-C6Heterocycle；
A is H by R5Substituted aryl or heteroaryl；
R5The different or identical following group below 1-5: hydrogen, halogen, hydroxyl, sulfydryl, amino, CN, NO2、C1-C6Alkane Base, halogenated C1-C6Alkyl, C3-C6Naphthenic base, C2-C6Alkenyl, halogenated C2-C6Alkenyl, C2-C6Alkynyl, halogenated C2-C6Alkynyl, C1-C6 Alkyl amine group, two (C1-C6Alkyl) amido, halogenated C1-C6Alkyl amine group, C1-C6Alkoxy, halogenated C1-C6Alkoxy, C1-C6Alkane Sulfenyl, halogenated C1-C6Alkylthio group, C2-C6Alkenyloxy group, halogenated C2-C6Alkenyloxy group, C2-C6Alkynyloxy group, halogenated C2-C6Alkynyloxy group, C1- C6Alkyl-carbonyl, halogenated C1-C6Alkyl-carbonyl, C1-C6Alkyl sulphinyl, halogenated C1-C6Alkyl sulphinyl, C1-C6Alkyl sulphur Acyl group, halogenated C1-C6Alkyl sulphonyl, C1-C6Alkyl carbonyl epoxide, C1-C6Alkyl-carbonyl-amino, C1-C6Alkyl sulphonyl oxygen Base, C1-C6Alkoxy carbonyl, C1-C6Alkoxy C1-C6Alkoxy, C1-C6Alkoxy carbonyl C1-C6Alkyl, C1-C6Alkoxy carbonyl Base amino, C1-C6Alkoxy carbonyl C1-C6Alkoxy, aryl, heteroaryl, aryloxy group, heteroaryloxy, aralkyl oxy, heteroaryl Alkyl oxy, aryl amine or heteroaryl amido, the aryl, heteroaryl, aryloxy group, heteroaryloxy, aralkyl oxy, heteroaryl alkane Base oxygroup, aryl amine or heteroaryl amido respectively stand alone as be unsubstituted or its hydrogen aryl replaced 1-4 following radicals, Heteroaryl, aryloxy group, heteroaryloxy, aralkyl oxy, heteroarylalkyl oxygroup, aryl amine or heteroaryl amido: halogen, CN, NO2、 C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Halogenated alkoxy, C1-C6Alkoxy, C1-C6Alkoxy carbonyl or C1-C6Alkyl sulphur Acyl group；
Q is selected from Q1-Q14One of group.
3. compound as claimed in claim 2, it is characterised in that:
In formula (I), R1Selected from hydrogen, halogen, itrile group, nitro, C1-C4Alkyl, halogenated C1-C4Alkyl, C1-C4Alkoxy, halogenated C1- C4Alkoxy, C1-C4Alkyl-carbonyl, C1-C4Alkoxy C1-C4Alkyl, halogenated C1-C4Alkoxy C1-C4Alkyl, C1-C4Alkyl ammonia Base, aryl, heteroaryl；
X is O or NR2；
R2Selected from hydrogen, C1-C4Alkyl, halogenated C1-C4Alkyl, C2-C4Alkenyl, halogenated C2-C4Alkenyl, C2-C4Alkynyl, halogenated C2-C4 Alkynyl, C1-C4Alkyl-carbonyl, C1-C4Alkoxy carbonyl, C1-C4Alkoxy carbonyl C1-C4Alkyl, C1-C4Alkyl sulphonyl, virtue Base, heteroaryl, aryl carbonyl or (miscellaneous) aryl carbonyl；
R3、R4For H, halogen, hydroxyl, C1-C4Alkyl, halogenated C1-C4Alkyl, C2-C4Alkenyl, halogenated C2-C4Alkenyl, C2-C4Alkynyl, Halogenated C2-C4Alkynyl, C1-C4Alkoxy, C1-C4Alkyl groups in the halogenalkoxy, aryl, heteroaryl；Or the R3And R4It is connected to them Carbon atom represents a C that is saturated or unsaturated, optionally replacing together3-C6Naphthenic base or C3-C6Heterocycle；
A is H by R5Substituted aryl or heteroaryl；
R5The different or identical following group below 1-5: hydrogen, halogen, hydroxyl, sulfydryl, amino, CN, NO2、C1-C4Alkane Base, halogenated C1-C4Alkyl, C3-C8Naphthenic base, C2-C4Alkenyl, halogenated C2-C4Alkenyl, C2-C4Alkynyl, halogenated C2-C4Alkynyl, C1-C4 Alkyl amine group, two (C1-C4Alkyl) amido, halogenated C1-C4Alkyl amine group, C1-C4Alkoxy, halogenated C1-C4Alkoxy, C1-C4Alkane Sulfenyl, halogenated C1-C4Alkylthio group, C2-C4Alkenyloxy group, halogenated C2-C4Alkenyloxy group, C2-C4Alkynyloxy group, halogenated C2-C4Alkynyloxy group, C1- C4Alkyl-carbonyl, halogenated C1-C4Alkyl-carbonyl, C1-C4Alkyl sulphinyl, halogenated C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphur Acyl group, halogenated C1-C4Alkyl sulphonyl, C1-C4Alkyl carbonyl epoxide, C1-C4Alkyl-carbonyl-amino, C1-C4Alkyl sulphonyl oxygen Base, C1-C4Alkoxy carbonyl, C1-C4Alkoxy C1-C4Alkoxy, C1-C4Alkoxy carbonyl C1-C4Alkyl, C1-C4Alkoxy carbonyl Base amino, C1-C4Alkoxy carbonyl C1-C4Alkoxy, aryl, heteroaryl, aryloxy group, heteroaryloxy, aralkyl oxy, heteroaryl Alkyl oxy, aryl amine or heteroaryl amido, the aryl, heteroaryl, aryloxy group, heteroaryloxy, aralkyl oxy, heteroaryl alkane Base oxygroup, aryl amine or heteroaryl amido respectively stand alone as be unsubstituted or its hydrogen aryl replaced 1-4 following radicals, Heteroaryl, aryloxy group, heteroaryloxy, aralkyl oxy, heteroarylalkyl oxygroup, aryl amine or heteroaryl amido: halogen, CN, NO2、 C1-C4Alkyl, C1-C4Halogenated alkyl, C1-C4Halogenated alkoxy, C1-C4Alkoxy, C1-C4Alkoxy carbonyl or C1-C4Alkyl sulphur Acyl group；
Q is selected from Q1-Q9One of group.
4. compound as described in claim 1, it is characterised in that replace (miscellaneous) aryl methylene pyrazole ether shown in formula (I) Compound is compound shown in formula (IA), (IB), (IC) or (ID):
Formula (IA), (IB), (IC), in (ID),
R1A、R1B、R1C、R1DIt is each independently selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, just Butyl, isobutyl group, methoxyl group, ethyoxyl or trifluoro ethoxy；
XAFor O or NR2A；XBFor O or NR2B；XCFor O or NR2C；XDFor O or NR2D；
R2A、R2B、R2C、R2DBe each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, One methyl fluoride, difluoromethyl, trifluoromethyl, trifluoroethyl, acetyl group, trifluoroacetyl group, methyl sulphonyl or ethylsulfonyl；
R3A、R3B、R3C、R3D、R4A、R4B、R4C、R4DRespectively stand alone as hydrogen, fluorine, chlorine, bromine, methyl, ethyl, ethyl, n-propyl, isopropyl Base, normal-butyl, methoxyl group, ethyoxyl, methyl mercapto, ethylmercapto group or trifluoro ethoxy；Alternatively, the R3AAnd R4AWith their companies, institute The carbon atom connect forms cyclopropyl, cyclobutyl or cyclopenta, the R3BAnd R4BCarbon atom connected to them forms cyclopropyl Base, cyclobutyl or cyclopenta, the R3CAnd R4CCarbon atom connected to them forms cyclopropyl, cyclobutyl or cyclopenta, institute State R3DAnd R4DCarbon atom connected to them forms cyclopropyl, cyclobutyl or cyclopenta；
R5A、R5B、R5C、R5DIt is each independently selected from one of following group or a variety of: fluorine, chlorine, bromine, iodine, cyano, amino, nitre Base, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, trifluoromethyl, trichloromethyl, difluoro Chloromethyl, one methyl fluoride of dichloro, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutyl Oxygroup, tert-butoxy, trifluoromethoxy, trifluoro ethoxy, methyl mercapto, trifluoromethylthio, methoxycarbonyl, ethoxy carbonyl, Dimethylamino, amino carbonyl, methylaminocarbonyl, ethyl aminocarbonyl or dimethylamino carbonyl；
nA、nB、nC、nDIt is each independently selected from 0 to 5 integer；
QA、QB、QC、QDIt is each independently selected from Q1-Q6One of group.
5. compound as claimed in claim 4, it is characterised in that: replace (miscellaneous) aryl methylene pyrrole shown in the formula (I) Azoles ether compound is compound shown in formula (IA), in formula (IA), R1ASelected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, second Base, n-propyl, isopropyl, normal-butyl or isobutyl group；
XAFor O or NR2A；
R2ASelect hydrogen, methyl, ethyl, isopropyl, tert-butyl or trifluoroethyl；
R3A、R4ARespectively stand alone as hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxyl group, ethyoxyl, methyl mercapto, ethylmercapto group or trifluoro second Oxygroup；
R5ASelected from one of following group or a variety of: fluorine, chlorine, bromine, iodine, cyano, amino, nitro, methyl, ethyl, isopropyl, Tert-butyl, trifluoromethyl, trichloromethyl, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, trifluoromethoxy, trifluoroethoxy Base, methyl mercapto, trifluoromethylthio, methoxycarbonyl or dimethylamino；
nASelected from 0 to 5 integer, work as nAWhen being 0, unsubstituted on phenyl ring；Work as nAWhen greater than 1, R5AIt may be the same or different；
QASelected from Q1-Q4One of group.
6. compound as claimed in claim 4, it is characterised in that: replace (miscellaneous) aryl methylene pyrrole shown in the formula (I) Azoles ether compound is compound shown in formula (IA), in formula (IA),
R1ASelected from hydrogen or chlorine；
XAFor O or NR2A；
R2ASelected from hydrogen, methyl, ethyl or tert-butyl；
R3A、R4ARespectively stand alone as hydrogen, fluorine；
R5ASelected from one of following group or a variety of: fluorine, chlorine, cyano, nitro, methyl, trifluoromethyl, trichloromethyl, methoxy Base, trifluoromethoxy, dimethylamino；
nASelected from 0 to 5 integer, work as nAWhen being 0, unsubstituted on phenyl ring；Work as nAWhen greater than 1, R5AIt may be the same or different；
QASelected from Q1-Q4One of group.
7. the preparation method of compound as described in claim 1, it is characterised in that the method are as follows:
Q in formula (I) compound is selected from Q1、Q2、Q3、Q6-Q13In any group when, the miazines of hydroxyl shown in formula (III) It is small that compound reacts 0.5 with benzyl halogen shown in formula (IV) under alkaline matter existence condition in organic solvent, at 20-100 DEG C Up to 20 hours, post-treated corresponding formula (I) compound that is made of reaction solution: compound shown in formula (III) and formula (IV) shownization The mass ratio of the material for closing object is 1:1~1.1；The alkaline matter is selected from potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, carbon Sour hydrogen sodium, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide or sodium tert-butoxide；
In formula (III), (IV), X is leaving group, is selected from chlorine or bromine；The same formula of the definition of other each groups (I)；
Q in formula (I) compound is selected from Q4、Q5Or Q14When, the method is that each free Q is Q3、Q2、Q13Formula (I) shown in chemical combination It is Q that corresponding Q, which is made, with methylamine water solution reaction in object4、Q5Or Q14Formula (I) shown in compound；The matter of the methylamine water solution Measuring concentration is 20~60%；The Q is Q3、Q2、Q13Formula (I) shown in the substance of carbinolamine in compound and methylamine water solution Amount is than being 1:5~10.
8. the method for claim 7, it is characterised in that: the organic solvent be tetrahydrofuran, acetonitrile, dimethylbenzene, benzene, DMF, DMSO, acetone, butanone or methyl tertiary butyl ether(MTBE).
9. substitution (miscellaneous) aryl methylene pyrazole ether compounds shown in formula (I) as described in claim 1 are used as insecticide And/or the application of fungicide.
10. a kind of desinsection and/or bactericidal composition, it is characterised in that the composition is by formula as described in claim 1 (I) institute Substitution (miscellaneous) aryl methylene pyrazole ether compounds and dissolving medium, surfactant and/or the diluent composition shown, it is described The mass fraction of formula described in composition (I) compound represented is 1-90%.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2773155A1 (en) * 1997-12-29 1999-07-02 Rhone Poulenc Agrochimie NEW FUNGICIDE COMPOUNDS
WO2005080344A1 (en) * 2004-02-20 2005-09-01 Shenyang Research Institute Of Chemical Industry Substituted azole compounds and thereof preparation and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2773155A1 (en) * 1997-12-29 1999-07-02 Rhone Poulenc Agrochimie NEW FUNGICIDE COMPOUNDS
WO2005080344A1 (en) * 2004-02-20 2005-09-01 Shenyang Research Institute Of Chemical Industry Substituted azole compounds and thereof preparation and application

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