CN110452220A - 9 oxime derivate and its application in agricultural - Google Patents

9 oxime derivate and its application in agricultural Download PDF

Info

Publication number
CN110452220A
CN110452220A CN201810382505.7A CN201810382505A CN110452220A CN 110452220 A CN110452220 A CN 110452220A CN 201810382505 A CN201810382505 A CN 201810382505A CN 110452220 A CN110452220 A CN 110452220A
Authority
CN
China
Prior art keywords
alkyl
halogenated
alkoxy
compound
aryl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810382505.7A
Other languages
Chinese (zh)
Other versions
CN110452220B (en
Inventor
李义涛
林健
熊力
李艳芳
卢辉
田宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongguan Dongyangguang Pesticide R & D Co Ltd
Original Assignee
Dongguan Dongyangguang Pesticide R & D Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongguan Dongyangguang Pesticide R & D Co Ltd filed Critical Dongguan Dongyangguang Pesticide R & D Co Ltd
Priority to CN201810382505.7A priority Critical patent/CN110452220B/en
Publication of CN110452220A publication Critical patent/CN110452220A/en
Application granted granted Critical
Publication of CN110452220B publication Critical patent/CN110452220B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • 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
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention provides a kind of fungicide 9 oxime derivate；In particular it relates to 9 oxime derivate, their preparation method and they as the purposes of fungicide and its form of Fungicidal composition, and the method for controlling with these compound or compositions plant pathogenic fungi.

Description

9 oxime derivate and its application in agricultural
Technical field
The present invention relates to new 9 oxime derivate and contain their pesticides as effective component, especially plant disease control agent.
Background technique
Now agriculture since the long-time of pesticide frequently uses, the disease on crop makes existing to which create drug resistances Pesticide control effect be substantially reduced, in order to solve this problem, need to continually develop that have provided controlling plant diseases active new Type compound.
Summary of the invention
The present invention provides a new class of 9 oxime derivate, and the composition comprising this analog derivative, the 9 oxime derivate and its Composition is for preventing and treating plant pathogenic fungi.
Specifically:
On the one hand, the present invention provides salt, N- oxide, (E) of compound shown in formula (I) compound represented or formula (I) Or (Z) isomers and their mixture:
Wherein:
R1For halogen, cyano, nitro, hydroxyl, carboxyl, amino, C1-6Alkyl, halogenated C1-6Alkyl, C1-6Alkoxy, C1-6Alkane Sulfenyl, halogenated C1-6Alkoxy, halogenated C1-6Alkylthio group, C1-6Alkoxy -C1-6Alkyl-, C1-6Alkoxy-(C=O), C1-6Alkyl- SO2-、C1-6Alkyl-substituted amino, C2-8Alkenyl, C2-8Alkynyl, C6-14Aryl, halogenated C6-14Aryl, C1-6Alkyl-substituted C6-14 Aryl, halogenated C1-6Alkyl-substituted C6-14Aryl, C1-6The C that alkoxy replaces6-14Aryl, halogenated C1-6The C that alkoxy replaces6-14 Aryl, C6-14Aryloxy group or halogenated C6-14Aryloxy group；
R2For halogen, cyano, nitro, C1-6Alkyl, halogenated C1-6Alkyl, C1-6Alkoxy, halogenated C1-6Alkoxy, C2-8Alkene Base, C2-8Alkenyloxy group, C2-8Alkynyl, C2-8Alkynyloxy group, C1-6Alkyl-SO2-、NRaRb-SO2-、C3-8Naphthenic base, C6-14Aryl, C6-14 Aryloxy group or 5-10 unit's heteroaryl；Wherein, R2Optionally replaced by 1,2,3 or 4 substituent group selected from A1；
Wherein, A1 is halogen, C1-6Alkyl, halogenated C1-6Alkyl, C1-6Alkoxy or halogenated C1-6Alkoxy；
RaAnd RbIt is each independently hydrogen or C1-6Alkyl；
N is 0,1,2,3,4 or 5；
M is 0,1,2,3,4 or 5.
In some embodiments, R1For halogen, cyano, nitro, hydroxyl, carboxyl, amino, C1-4Alkyl, halogenated C1-4Alkane Base, C1-4Alkoxy, C1-4Alkylthio group, halogenated C1-4Alkoxy, halogenated C1-4Alkylthio group, C1-4Alkoxy -C1-4Alkyl-, C1-4Alcoxyl Base-(C=O), C1-4Alkyl-SO2-、C1-4Alkyl-substituted amino, C2-6Alkenyl, C2-6Alkynyl, C6-10Aryl, halogenated C6-10Virtue Base, C1-4Alkyl-substituted C6-10Aryl, halogenated C1-4Alkyl-substituted C6-10Aryl, C1-4The C that alkoxy replaces6-10Aryl, halogen For C1-4The C that alkoxy replaces6-10Aryl, C6-10Aryloxy group or halogenated C6-10Aryloxy group.
In other embodiments, R1For halogen, cyano, nitro, hydroxyl, carboxyl, amino, C1-4Alkyl, halogenated C1-4 Alkyl, C1-4Alkoxy, C1-4Alkylthio group, halogenated C1-4Alkoxy, halogenated C1-4Alkylthio group, C1-4Alkoxy -C1-4Alkyl-, C1-4Alkane Base-SO2-、C1-4Alkyl-substituted amino or C6-10Aryl.
Also in other embodiments, R1For fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxyl, carboxyl, amino ,-CH3、- CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)CH3、-CH(CH3)CH2CH3、-C(CH3)3、-CHF2、- CF3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OC(CH3)3、-SCH3、-OCHF2、- OCF3、-CH2-OCH3、CH3-SO2-、-NHCH3、-N(CH3)2、-NHCH2CH3、-N(CH2CH3)2、-N(CH2CH3)CH3Or phenyl.
In some embodiments, R2For halogen, cyano, nitro, C1-4Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy, halogen For C1-4Alkoxy, C2-6Alkenyl, C2-6Alkenyloxy group, C2-6Alkynyl, C2-6Alkynyloxy group, C1-4Alkyl-SO2-、NRaRb-SO2-、C3-6Cycloalkanes Base, C6-10Aryl, C6-10Aryloxy group or 5-6 unit's heteroaryl；Wherein, R2Optionally replaced by 1,2,3 or 4 substituent group selected from A1；
Wherein, A1 is halogen, C1-4Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy or halogenated C1-4Alkoxy；
RaAnd RbIt is each independently hydrogen or C1-4Alkyl.
In other embodiments, R2For halogen, cyano, nitro, C1-4Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy, Halogenated C1-4Alkoxy, C1-4Alkyl-SO2-、NRaRb-SO2-、C3-6Naphthenic base, C6-10Aryl, C6-10Aryloxy group or 5-6 member heteroaryl Base；Wherein, R2Optionally replaced by 1,2,3 or 4 substituent group selected from A1；
Wherein, A1 is halogen, C1-4Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy or halogenated C1-4Alkoxy；
RaAnd RbIt is each independently hydrogen or C1-4Alkyl.
Also in other embodiments, R2For fluorine, chlorine, bromine, iodine, cyano, nitro ,-CH3、-CH2CH3、- CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)CH3、-CH(CH3)CH2CH3、-C(CH3)3、-CHF2、- CF3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OC(CH3)3、-OCHF2、-OCF3、 CH3-SO2-、NH2-SO2-、NH(CH3)-SO2Or N (CH3)2-SO2-。
Also in other embodiments, R2For following subformula:
In some embodiments, the present invention provides the compound with one of following structure or has one of following structure The salt of compound, N- oxide, (E) or (Z) isomers and their mixture:
On the other hand, the present invention provides a kind of composition, includes compound of the present invention.
In some embodiments, composition of the present invention further includes acceptable surface-active in Pesticide Science Agent and carrier.
On the other hand, the present invention provides compound of the present invention or composition of the present invention in control of plant disease Application.
In some embodiments, compound of the present invention or composition of the present invention are in therapeutic or preventative control Application in the plant pathogenic fungi of plant or crop processed.
Also in other embodiments, compound of the present invention or composition of the present invention are in prevention and treatment cucumber downy mildew Application in germ or/and botrytis cinerea pers.
On the other hand, the present invention provides the side of the plant pathogenic fungi of the therapeutic or preventive control plant of one kind or crop Compound of the present invention or composition of the present invention are administered to seed, plant or fruit or are administered to just by method In the soil for growing or needing growing plant.
Formula (I) compound represented may be deposited with different stereoisomer or optical isomer or tautomeric form In.The present invention includes the mixture and isotope form example of all such isomers and tautomer and its various ratios Such as deuterated compound.
It is worth noting that, the stereochemical structure of oxime part present in oximido derivant of the present invention includes (E) or (Z) isomery Body, and these stereoisomers constitute a part of the invention.
In the presence of the compound of the present invention can be in the form of tautomer, in where applicable, institute above and below It states compound and is interpreted as also including corresponding tautomeric form, even if these tautomeric forms are not bright in each case Really refer to.
The structure that the general formula that there is the compound of isotope enrichment the present invention to provide is described, in addition to one or more atom quilts It is replaced with selected atomic weight or the atom of mass number.The Exemplary isotopes that can be introduced into the compounds of this invention include hydrogen, Carbon, nitrogen, oxygen, phosphorus, sulphur, fluorine and chlorine isotope, such as2H,3H,11C,13C,14C,15N,17O,18O,18F,31P,32P,35S,36Cl With125I。
Any asymmetric atom (for example, carbon etc.) of disclosed compound of present invention can be enriched with racemic or enantiomer Form exist, such as (R)-, (S)-or (R, S)-configuration exist.
Content noted earlier only outlines certain aspects of the invention, but be not limited to these aspect and it is otherwise in Appearance will make more specific complete description below.
Detailed description of the invention
Definition and general terms
It will now be described in more detail certain embodiments of the present invention, the example is by the structural formula and chemical formula explanation that are appended.This Invention is intended to cover all replacement, modification and equivalent technical solutions, they are included in the present invention defined such as claim In range.Those skilled in the art will appreciate that many can be used in similar or equivalent method and material of the present invention The practice present invention.The present invention is not limited to method of the present invention and material.In document, patent and the similar material combined One or more or contradict in the case where (including but not limited to defined in term, term application, institutes different from the application Technology of description, etc.), it is subject to the application.
It will further be appreciated that certain features of the invention, be it is clearly visible, carry out in a number of independent embodiments Description, but can also provide in combination in a single embodiment.Conversely, various features of the invention, for brevity, It is described in a single embodiment, but can also be individually or with the offer of any suitable sub-portfolio.
Unless otherwise stated, all scientific and technical terminologies used in the present invention have with those skilled in the art of the invention's It is generally understood identical meaning.All patents of the present invention and public publication are integrally incorporated this hair by reference It is bright.
Unless otherwise stated, following definition used in the present invention should be applied.For purposes of the present invention, chemical element With the periodic table of elements CAS editions, and " Handbook of Chemistry and Physics ", the 75th edition, 1994 is consistent.In addition, organic chemistry General Principle can With reference to " Organic Chemistry ", Thomas Sorrell, University Science Books, Sausalito: 1999, and " March's Advanced Organic Chemistry " by Michael B.Smith and Jerry Description in March, John Wiley&Sons, New York:2007, entire contents are incorporated by reference into the present invention.
There is apparent conflict unless otherwise indicated or in context, the article " one " used herein, " one (kind) " " described " is intended to include "at least one" or " one or more ".Therefore, these articles used herein refer to one or The article of more than one (i.e. at least one) object.For example, " component " refers to one or more components, it is possible to have more than one Component be taken into account in the embodiment of the embodiment and use or use.
Term "comprising" is open language, that is, includes content specified by the present invention, but be not precluded otherwise Content.
" stereoisomer " refers to identical chemical constitution, but the spatially different change of arrangement mode of atom or group Close object.Stereoisomer includes enantiomter, diastereoisomer, conformer (rotational isomer), geometric isomer (cis/trans) isomers, atropisomer, etc..
" enantiomter " refers to two isomers that cannot be overlapped but be mutually mirror of a compound.
" diastereoisomer " refer to there are two or multiple chiral centres and its molecule not alloisomerism of mirror image each other Body.Diastereoisomer has different physical properties, such as fusing point, boiling point, spectral property and reactivity.Diastereoisomer is mixed Such as electrophoresis and chromatography, such as HPLC can be operated by high resolution analysis to separate by closing object.
Stereochemical definitions used in the present invention and rule generally follow S.P.Parker, Ed., McGraw-Hill Dictionary of Chemical Terms(1984)McGraw-Hill Book Company,New York；and Eliel,E.and Wilen,S.,“Stereochemistry of Organic Compounds”,John Wiley&Sons, Inc., New York, Stereochemical definitions described in 1994 and rule.
Many organic compounds exist with optical active forms, i.e., they, which have, rotates the plane of linearly polarized light Ability.When describing optically active compound, indicate molecule about one or more hand using prefix D and L or R and S The absolute configuration at property center.Prefix d and l or (+) and (-) are the symbols for the rotation of linearly polarized light caused by appointed compound, Wherein (-) or l indicate that compound is left-handed.Prefix is (+) or the compound of d is dextrorotation.A kind of specific alloisomerism Body is enantiomter, and the mixture of this isomers is referred to as enantiomeric mixture.The 50:50 mixture of enantiomter Referred to as racemic mixture or racemic modification, when chemical reaction or in the process without stereoselectivity or stereospecificity when, It may occur in which such case.
As described in the invention, the compound of the present invention can be optionally replaced one or more substituent groups, such as General formula compound above, or as example special inside embodiment, subclass, and a kind of compound that the present invention is included. It should be appreciated that this term can be used interchangeably " optionally replacing " this term with " substituted or non-substituted ".In general, art " substituted " the one or more hydrogen atoms indicated in given structure of language are replaced specific substituent group.Unless other aspect tables Bright, an optional substituent group can be replaced at various substitutable position of that group.When in given structural formula not Only a position can be replaced one or more substituent groups selected from specific group, then substituent group can identical or differently Replace at various locations.Wherein the substituent group can be, but be not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitre Base, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkyloxy-alkoxy, alkoxy alkylamino, aryloxy group, heteroaryl oxygen Base, heterocycle oxygroup, alkoxy aryl, heteroarylalkoxy, heterocyclylalkoxy, cycloalkyl alkoxy, alkylamino, alkylamino Alkyl, alkylamino alkylamino, cycloalkyl amino, amino-n-cycloalkyl, alkylthio group, halogenated alkyl, halogenated alkoxy, hydroxyl replace Alkyl, hydroxyl replace alkylamino, cyano replace alkyl, cyano replace alkoxy, cyano replace alkylamino, amino Substituted alkyl, alkyl acyl, miscellaneous alkyl, naphthenic base, cycloalkenyl, cycloalkyl-alkyl, heterocycle, heterocyclylalkyl group, heterocycle Acyl group, aryl, aryl alkyl, fragrant amino, heteroaryl, heteroaryl alkyl, heteroaryl amino, amide groups, sulfonyl, aminosulfonyl Base etc..
In addition, it is necessary to explanation, unless otherwise explicitly point out, in the present invention used by describing mode " each ... independently be " and " ... be each independently " and " ... independently be " can be interchanged, and shall be understood in a broad sense, both may be used To refer among the different groups, does not influence mutually, can also indicate in phase between expressed specific option between the same symbol In same group, do not influenced mutually between expressed specific option between the same symbol.
It is disclosed in the substituent group of each section of this specification, disclosed compound of present invention according to radical species or range.It is special It does not point out, the present invention includes each independent sub-combinations thereof of each member of these radical species and range.For example, term “C1-C6Alkyl " or " C1-6Alkyl " refers in particular to the methyl being individually disclosed, ethyl, C3Alkyl, C4Alkyl, C5Alkyl and C6Alkyl.
Terminology used in the present invention " alkyl " or " alkyl group ", indicate contain 1 to 20 carbon atom, the straight chain of saturation or Branch univalent hydrocarbyl group；Replaced the substituent group that wherein alkyl group is optionally described by one or more present invention. Unless otherwise detailed instructions, alkyl group contains 1-20 carbon atom.In one embodiment, alkyl group contains 1-12 carbon Atom；In one embodiment, alkyl group contains 1-8 carbon atom；In another embodiment, alkyl group contains 1-6 A carbon atom；In yet another embodiment, alkyl group contains 1-4 carbon atom；Also in one embodiment, alkyl group contains There is 1-3 carbon atom.
The example of alkyl group includes, but is not limited to, methyl (Me ,-CH3), ethyl (Et ,-CH2CH3), n-propyl (n- Pr、-CH2CH2CH3), isopropyl (i-Pr ,-CH (CH3)2), normal-butyl (n-Bu ,-CH2CH2CH2CH3), isobutyl group (i-Bu ,- CH2CH(CH3)2), sec-butyl (s-Bu ,-CH (CH3)CH2CH3), tert-butyl (t-Bu ,-C (CH3)3), n-pentyl (- CH2CH2CH2CH2CH3), 2- amyl (- CH (CH3)CH2CH2CH3), 3- amyl (- CH (CH2CH3)2), 2- methyl -2- butyl (- C (CH3)2CH2CH3), 3- methyl -2- butyl (- CH (CH3)CH(CH3)2), 3- methyl-1-butyl (- CH2CH2CH(CH3)2), 2- first Base -1- butyl (- CH2CH(CH3)CH2CH3), n-hexyl (- CH2CH2CH2CH2CH2CH3), 2- hexyl (- CH (CH3) CH2CH2CH2CH3), 3- hexyl (- CH (CH2CH3)(CH2CH2CH3)), 2- methyl -2- amyl (- C (CH3)2CH2CH2CH3), 3- first Base -2- amyl (- CH (CH3)CH(CH3)CH2CH3), 4- methyl -2- amyl (- CH (CH3)CH2CH(CH3)2), 3- methyl -3- penta Base (- C (CH3)(CH2CH3)2), 2- methyl -3- amyl (- CH (CH2CH3)CH(CH3)2), 2,3- dimethyl -2- butyl (- C (CH3)2CH(CH3)2), 3,3- dimethyl -2- butyl (- CH (CH3)C(CH3)3), etc..
Term " alkenyl " indicates the linear chain or branched chain monovalent hydrocarbon containing 2-12 carbon atom, wherein at least one insatiable hunger And site, that is, there is a carbon-to-carbon sp2Double bond, wherein the alkenyl group can be retouched optionally by one or more present invention Replaced the substituent group stated comprising the positioning of " cis " and " tans ", or the positioning of " E " and " Z ".In one embodiment, Alkenyl group includes 2-8 carbon atom；In another embodiment, alkenyl group includes 2-6 carbon atom；In another embodiment party In case, alkenyl group includes 2-4 carbon atom.The example of alkenyl group includes, but is not limited to, vinyl (- CH=CH2), Allyl (- CH2CH=CH2), acrylic (CH3- CH=CH-), the cyclobutenyl (CH of oxo3- C (=O)-CH=CH-) etc..
Term " alkynyl " indicates the linear chain or branched chain monovalent hydrocarbon containing 2-12 carbon atom, wherein at least one carbon- Tri- key of carbon sp.In one embodiment, alkynyl group includes 2-8 carbon atom；In another embodiment, alkynyl group includes 2-6 carbon atom；In yet another embodiment, alkynyl group includes 2-4 carbon atom.The example of alkynyl group includes, but simultaneously It is not limited to ,-C ≡ CH ,-CH2-C≡CH、-CH2-C≡CCH3、-CH2CH2-C≡CH、-CH2-C≡CCH2CH3Etc..
Term " alkoxy " indicates that alkyl group is connected by oxygen atom with molecule rest part, and wherein alkyl group has Meaning as described in the present invention.The example of alkoxy base includes, but is not limited to, methoxyl group (MeO ,-OCH3), ethyoxyl (EtO、-OCH2CH3), 1- propoxyl group (n-PrO, n- propoxyl group ,-OCH2CH2CH3), 2- propoxyl group (i-PrO, i- propoxyl group ,- OCH(CH3)2) etc..
Term " alkoxy-alkyl " refers to that alkoxy base is connected by alkyl group with molecule rest part, wherein alkane Oxygroup or alkyl group have meaning of the present invention.
Term " alkylthio group " refers to that the alkyl of linear chain or branched chain is connected on the sulphur atom of divalent, and wherein alkyl group has such as Meaning of the present invention.The example of alkylthio radicals includes, but is not limited to ,-SCH3、-SCH2CH3、-SCH2CH2CH3Deng Deng.
Term " halogen " refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
Term " halogenated alkyl " indicates alkyl group replaced one or more halogen atoms, and such example includes, But it is not limited to ,-CF3,-CHF2,-CH2Cl ,-CH2CF3,-CH2CHF2,-CH2CH2CF3Deng.
Term " halogenated alkoxy " expression alkoxy base is replaced one or more halogen atoms, such example packet Contain, but is not limited to ,-OCF3,-OCHF2,-OCHCl2,-OCH2CHF2,-OCH2CHCl2,-OCH (CH3)CHF2Deng.
Term " halogenated alkylthio " expression alkylthio radicals are replaced one or more halogen atoms, such example packet Contain, but is not limited to ,-SCF3,-SCHF2,-SCHCl2,-SCH2CHF2,-SCH2CHCl2,-SCH (CH3)CHF2Deng.
Term " naphthenic base " indicates containing 3-12 carbon atom, monovalent or multivalence saturation monocyclic, bicyclic or tricyclic body System.In one embodiment, naphthenic base includes 3-10 carbon atom；In another embodiment, naphthenic base includes that 3-8 carbon is former Son；In yet another embodiment, naphthenic base includes 3-6 carbon atom.The group of naphthene base is optionally by one or more sheets It invents replaced described substituent group.Such example includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopenta, hexamethylene Base, suberyl, cyclooctyl, cyclononyl, cyclodecyl, ring undecyl, cyclo-dodecyl, etc.；Or naphthenic base includes, but simultaneously It is not limited to having structure:
Deng.
Term " aryl " indicates the monocycle containing 6-14 annular atom or 6-12 annular atom or 6-10 annular atom, double The carbocyclic ring system of ring and tricyclic, wherein at least one ring system be it is aromatic, wherein each ring system include 3-7 original Molecular ring, and there are one or more attachment points to be connected with the rest part of molecule.Term " aryl " can be with term " fragrance Ring " is used interchangeably.The example of aryl group may include phenyl, indenyl, naphthalene and anthryl.
Term " aryloxy group " indicates that aryl group is connected by oxygen atom with molecule rest part, and wherein aryl group has Meaning as described in the present invention.
Monocycle of term " heteroaryl " expression containing 5-12 annular atom or 5-10 annular atom or 5-6 annular atom, Bicyclic and three-ring system, wherein at least one ring system are aromatic, and at least one ring system includes one or more miscellaneous Atom, wherein each ring system includes 5-7 former molecular ring, and has one or more attachment points and molecule rest part It is connected.Term " heteroaryl " can be used interchangeably with term " hetero-aromatic ring " or " heteroaromatics ".The heteroaryl groups are appointed Selection of land is replaced one or more substituent groups described in the invention.In one embodiment, 5-10 original is molecular miscellaneous Aryl includes 1,2,3 or 4 hetero atom for being independently selected from O, S and N.
In one embodiment, heteroaryl basis representation contains 1-9 carbon atom and at least one is selected from nitrogen, sulphur and oxygen atom Hetero atom；In one embodiment, heteroaryl basis representation contains 1-6 carbon atom and at least one is selected from nitrogen, sulphur and oxygen atom Hetero atom；In one embodiment, heteroaryl basis representation contains 1-5 carbon atom and at least one is selected from nitrogen, sulphur and oxygen atom Hetero atom；In one embodiment, heteroaryl basis representation contains 1-4 carbon atom and at least one is selected from nitrogen, sulphur and oxygen atom Hetero atom；In one embodiment, heteroaryl basis representation contains 2-4 carbon atom and at least one is selected from nitrogen, sulphur and oxygen atom Hetero atom.
The example of heteroaryl groups includes, but is not limited to, 2- furyl, 3- furyl, TMSIM N imidazole base, 2- imidazole radicals, 4- imidazole radicals, 5- imidazole radicals, 3- isoxazolyl, 4- isoxazolyl, 5- isoxazolyl, 2- oxazolyl, 4- oxazolyl, 5- oxazole Base, N- pyrrole radicals, 2- pyrrole radicals, 3- pyrrole radicals, 2- pyridyl group, 3- pyridyl group, 4- pyridyl group, 2- pyrimidine radicals, 4- pyrimidine radicals, 5- Pyrimidine radicals, pyridazinyl (such as 3- pyridazinyl), 2- thiazolyl, 4- thiazolyl, 5- thiazolyl, tetrazole radical (such as 5- tetrazole radical), triazole Base (such as 2- triazolyl and 5- triazolyl), 2- thienyl, 3- thienyl, pyrazolyl, isothiazolyl, 1,2,3-oxadiazoles base, 1, 2,5- oxadiazoles bases, 1,2,4- oxadiazoles base, 1,2,3-triazoles base, 1,2,3- thio biphosphole base, 1,3,4- thio biphosphole base, 1, 2,5- thio biphosphole bases, pyrazinyl, 1,3,5-triazines base, pyrimidine ketone group, pyriconyl；It also include below bicyclic, but never It is bicyclic to be limited to these: benzimidazolyl, benzofuranyl, benzo tetrahydrofuran base, benzothienyl, indyl (such as 2- indoles Base), etc..
In one embodiment, heteroaryl groups are following subformula:
Deng.
As described herein,It indicates that the compound comprising carbon-to-nitrogen double bon can be Z configuration, is also possible to E configuration, Or indicate the mixture of Z configuration and E configuration.
The composition of the compounds of this invention, preparation and application thereof
The present invention provides a kind of fungicide composite, the composition includes: it is a effective amount of as defined herein Logical formula (I) compound acceptable carrier (support), carrier or filler (filler) as active constituent and agriculturally.
According to the present invention, term " carrier " indicates a kind of natural or synthesis organic or inorganic compound, with formula (I) Active compound or joint so that reactive compound is easier to be applied to plant, especially to the part of plant. Therefore, this carrier is usually inert, and should be agriculturally acceptable.Carrier can be solid or liquid.Suitable load The example of body include clay, natural or synthetic silicate, silica, resin, wax, solid fertilizer, water, alcohols (especially Butanol), organic solvent, mineral oil and vegetable oil and its derivative.Also the mixture of such carrier can be used.
Composition of the invention can also include other components.Specifically, the composition also may include surfactant. The surfactant can be ionic or non-ionic emulsifier, dispersing agent or wetting agent or these surfactants Mixture.Such as, it may include polyacrylate, lignosulphonates, sulfocarbolate or naphthalene sulfonate, ethylene oxide and fatty alcohol or With fatty acid or with the condensation polymer of fatty amine, substituted phenol (especially alkyl phenol or aryl phenol), the salt of sulfosuccinate, ox Sulfonic acid (especially taurine Arrcostab), the phosphate of oxyethylated alcohol or phenol, polyalcohol aliphatic ester and The derivative of above compound comprising sulfate radical, sulfonate radical or phosphonate functional group.In general, when reactive compound and/or lazy When medium reagent that is that property carrier is insoluble in water and being applied is water, it is necessary to which there are at least one surfactants.Preferably, With the poidometer of composition, the content of surfactant is 5-40 weight %.
Optionally, may also include other components, for example, protective colloid, adhesive, thickener, thixotropic agent, bleeding agent, Stabilizer, chelating agent.It more generally, can be by the reactive compound and any solid or liquid that meet common preparation technique Additive is combined.
In general, composition of the invention may include the reactive compound of 0.05-99 weight %, preferably 10-70 weight %.
Composition of the invention can in a variety of manners using and can be used for various preparations, such as aerosol dispersing agent, glue Capsule suspending agent (capsule suspension), harl concentrating agents, can dusting powder, emulsifiable concentrating agents, oil-in-water emulsion, oil Packet aqueous emulsion, encapsulated granula, fine grained agent, the flowable concentrating agents for seed treatment, gas (under pressure) preparation, gas hair Raw agent, granule, hot mist concentrating agents, big granula, fine granule, oily dispersible powder, the flowable concentrating agents of oily compatibility, oil are mixed Insoluble liquid, paste, plant spillikin, the seed for doing kind of a pulvis for processing, coated pesticidal, soluble concentrating agents, solubility Pulvis, the solution for seed treatment, suspension concentrating agents (flowable concentrating agents), ultra-low volume (ULV) liquid, ultra-low volume (ULV) granula or tablet, water dispersible pulvis, water-soluble granule or tablet for slurries processing, use can be dispersed in suspending agent, water In the water solube powder and wettability pulvis of seed treatment.These compositions not only include that will use suitable equipment (example Such as sprayer or dusting equipment) it is applied to the composition on processed plant or seed, and be included in and be applied to crops The commercial composite for the concentration that must be diluted before.
Preparation can be prepared by mode known to script, such as by the way that active constituent and at least one is following conventional It is prepared by material mixing: expanding material, surfactant, solvent or diluent, adjuvant, emulsifier, dispersing agent and/or binder or Fixative, wetting agent, waterproofing agent, (if applicable) desiccant and UV stabilizer, and (if applicable) dyestuff With pigment, defoaming agent, preservative, inorganic and organic thickening agent, adhesive, gibberellin and other processing aids and water.According to Preparation type to be prepared needs other procedure of processings, such as wet grinding, dry grinding and granulation.
In solid pharmaceutical preparation, the vegetalitas such as soy meal, wheat flour powder, diatomite, apatite, gypsum, cunning can be used Organic and inorganic compounds such as the minerals such as stone, bentonite, pyrophillite, clay micropowder, sodium benzoate, urea, sodium sulphate etc. Additive and/or carrier.
In liquid preparation, can be used the petroleum distillates such as kerosene, dimethylbenzene and solvent naphtha, hexamethylene, cyclohexanone, Dimethylformamide, dimethyl sulfoxide, alcohol, acetone, trichloro ethylene, methyl iso-butyl ketone (MIBK), mineral oil, vegetable oil, water equal solvent.
It is a further object of the invention to provide a kind of method of control plant, the plant pathogenic fungi of crop or seed, It is characterized in that, by agriculturally effectively and substantially non-phytotoxic amount microbicide compositions of the invention with seed treatment, Leaf portion applies, stem applies, be impregnated with or the mode of trickle irrigation application (chemistry applies) is applied to following part: seed, plant or plant Object fruit, or planted or intended the soil or inert base (such as inorganic matrix, such as sand, asbestos, mineral wool of planting plants； Expand minerals, such as perlite, vermiculite, zeolite or expanded clay), float stone, pyroclast substance or material, synthesis it is organic Matrix (such as polyurethane), organic substrate (such as peat, compost, trees waste product (such as coconut husk, wood-fibred or sawdust, tree Skin)) or fluid matrix (such as floating hydroponic system, nutrient film techinique, gas carrying agent system).
The amount of application of fungicide of the present invention according to meteorological condition, dosage form, Dressing date, method of administration, application place, Control object disease, object crop etc. are different and different, but usually every 1 hectare of effective component chemical combination object amount is 0.01~1000g, excellent It is selected as 10~100g.
Term administering is in plant to be processed " it is understood to refer to for purposes of the present invention, it can be by following various Processing method applies the composition pesticide as present subject matter:
One, liquid of the aerial part spraying comprising one of the composition of Xiang Suoshu plant；
Two, it dusts in the surrounding plants, particle or powder is incorporated into soil, is spraying and when the plant is It is injected or is smeared in the case where trees；
Three, by the plant protection mixture comprising one of the composition, to the seed of the plant carry out coating or Film coating.
Method of the invention can be healing, prevention or the method eradicated.
It is such as but not limited to the crop of composition pesticide or combined treatment of the invention, such as vine, can also be Cereal, vegetables, clover, soybean, commercially available garden crop, turf, trees or gardening plant.
Processing method of the invention can also be used to handling propagation material (such as stem tuber or rhizome) and seed, seedling or Transplant seedling and plant or transplanting plant.The processing method can also be used for processing root.Processing method of the invention can also be used for Handle the aerial part of plant, such as the trunk in relation to plant, stem or stalk, leaf, flower and fruit.
Can with or can have cotton, flax, liana, fruit or vegetables with the plant that method of the invention is protected Crop, as (for example, pip fruit, such as apple and pears, there are also drupe, such as apricot, almond for rosaceae (Rosaceae sp.) (almond) and peach), tea sugarcane scarabaeidae (Ribesioidae sp.), Juglandaceae (Juglandaceae sp.), Betulaceae (Betulaceae sp.), Anacardiaceae (Anacardiaceae sp.), Fagaceae (Fagaceae sp.), Moraceae (Moraceae sp.), Oleaceae (Oleaceae sp.), Actinidiaceae (Actinidaceaesp.), Lauraceae (Lauraceae Sp.), Musaceae (Musaceae sp.) (such as Banana tree and powder bajiao banana (plantins)), Rubiaceae (Rubiaceae Sp.), Theaceae (Theaceae sp.), Sterculiaceae (Sterculiceae sp.), Rutaceae (Rutaceae sp.) (such as Lemon, orange and grape fruit)；Solanaceae (Solanaceae sp.) (such as tomato), Liliaceae (Liliaceae sp.) are purple Aster section (Asteraceae sp.) (such as lettuce), Umbelliferae (Umbelliferae sp.), Cruciferae (Cruciferae Sp.), Chenopodiaceae (Chenopodiaceae sp.), Curcurbitaceae (Cucurbitaceae sp.), Papilionaceae (Papilionaceae sp.) (such as pea), rosaceae (Rosaceae sp.) (such as strawberry)；Chief crop, such as grass Section (Graminae sp.) (such as corn, lawn or cereal such as wheat, rice, barley and triticale), aster section (Asteraceae Sp.) (such as sunflower), crucifer (such as rape), pulse family (Fabacae sp.) (such as peanut), Papilionaceae (Papilionaceae sp.) (such as soybean), Solanaceae (Solanaceae sp.) (such as potato), Chenopodiaceae (Chenopodiaceae sp.) (such as beet root)；Garden crop and forestry crop；And the genetic changec of these crops Homologue.
In the disease of controllable plant or crop by the method for the invention, it can be mentioned that:
Powdery mildew, such as:
Powdery mildew (Blumeria diseases) is caused by such as wheat powdery mildew (Blumeria graminis)；
Podosphaera disease (Podosphaera diseases), by for example white cross hair list softgel shell (Podosphaera Leuco-tricha) cause；
Sphaerotheca disease (Sphaerotheca diseases), by such as Siberian cocklebur monofilament shell (Sphaerotheca Fuliginea caused by)；
Uncinula disease (Uncinula diseases), such as caused by grape fishing line shell (Uncinula necator)；
Rust, such as:
Glue Rust is sick (Gymnosporangium diseases), by such as absorption unit rest fungus (Gymnosporangium Sabinae) cause；
Hunchbacked spore rust (Hemileia diseases), is drawn by such as coffee rust (Hemileia vastatrix) It rises；
Phakopsora disease (Phakopsora diseases), by such as Phakopsora pachyrhizi (Phakopsora Pachyrhizi) or mountain horseleech layer rest fungus (Phakopsora meibomiae) causes；
Puccinia disease (Puccinia diseases), such as drawn by Puccinia recondita (Puccinia recondite) It rises；
Uromyces disease (Uromyces diseases), by such as wart top uromyce (Uromyces Appendiculatus) cause；
Oomycetes disease (Oomycete diseases), such as:
Bremia disease (Bremia diseases) is obstructed mould (Bremia lactucae) by such as lettuce disk and is caused；
Peronospora disease (Peronospora diseases), by such as pea downy mildew (Peronospora pisi) or rape Downy mildew (P.brassicae) causes；
Phytophthora disease (Phytophthora diseases), by such as phytophthora infestans (Phytophthora Infestans) cause；
Plasmopara disease (Plasmopara diseases), by the raw uniaxial mould (Plasmopara of such as grape Viticola) cause；
Pseudoperonospora disease (Pseudoperonospora diseases), by such as humulus grass downy mildew Caused by (Pseudoperonospora humuli) or cucumber downy mildew (Pseudoperonospora cubensis)；
Pythium disease (Pythium diseases), is caused by such as Pythium ultimum (Pythium ultimum)；
Leaf spot, leaf blotch and leaf blight, such as:
Alternaria disease (Alternaria diseases), such as drawn by alternaria solani sorauer (Alternaria solani) It rises；
Cercospora disease (Cercospora diseases), it is raw tail spore (Cercospora beticola) by such as beet Cause；
Chrysosporium disease (Cladiosporum diseases), such as by melon fruit fly (Cladiosporium Cucumerinum) cause；
Cochliobolus disease (Cochliobolus diseases), such as by standing grain cochliobolus (Cochliobolus Sativus) cause；
Colletotrichum disease (Colletotrichum diseases) pierces disk spore (Colletotrichum by such as beans Lindemuthianum) cause；
Olive peacock's eye disease disease (Cycloconium diseases), by such as olive peacock plaque (Cycloconium oleaginum) causes；
Beancurd sheet shell bacterium layer is sick (Diaporthe diseases), is drawn by seat shell between such as citrus (Diaporthe citri) It rises；
Elsinoe disease (Elsinoe diseases), by such as citrus Elsinochrome (Elsinoe fawcettii) Cause；
Long spore belongs to sick (Gloeosporium diseases), by for example happy long spore (Gloeosporium of colour disk Laeticolor) cause；
Small cluster shell belongs to sick (Glomerella diseases), by such as GLOMERFLLA CINGULATA (Glomerella cingulate) Cause；
Ball seat Pseudomonas is sick (Guignardia diseases), by such as grape Guignardia (Guignardia Bidwellii) cause；
Leptosphaeria disease (Leptosphaeria diseases), by such as Cruciferae ball cavity bacteria (Leptosphaeria maculans), the withered ball cavity bacteria (Leptosphaeria nodorum) of grain husk cause；
Rice blast (Magnaporthe diseases) is caused by such as rice blast fungus (Magnaporthe grisea)；
Mycosphaerella disease (Mycosphaerella diseases), by such as standing grain green-ball chamber bacterium (Mycosphaerella Graminicola), peanut spherical cavity bacterium (Mycosphaerella arachidicola), banana secret note tikka bacterium Caused by (Mycosphaerella fijiensis)；
Septoria disease (Phaeosphaeria diseases), by such as phaeosphaeria nodorum (Phaeosphaeria Nodorum) cause；
Pyrenophora disease (Pyrenophora diseases), such as drawn by circle nuclear cavity bacteria (Pyrenophora teres) It rises；
Ramularia disease (Ramularia diseases), by for example pungent strutting every spore (Ramularia collo- Cygni) cause；
Beak genuss disease (Rhynchosporium diseases), by such as rye beak spore (Rhynchosporium Secalis) cause；
Septoria disease (Septoria diseases), by such as Septoria apii (Septoria apii) or tomato Septoria musiva (Septoria lycopersici) causes；
Core coral bacterium is sick (Typhula diseases), is caused by for example yellowish pink core coral bacterium (Typhula incarnata)；
Venturia disease (Venturia diseases), such as drawn by venturia inaequalis (Venturia inaequalis) It rises；
Root disease and stem disease, such as:
Photovoltaicing leather bacteria disease (Corticium diseases), is drawn by such as standing grain photovoltaicing leather bacteria (Corticium graminearum) It rises；
(mould) category of Fusariumsp is sick (Fusarium diseases), is drawn by for example sharp fusarium (Fusarium oxysporum) It rises；
Sturgeon shape belongs to sick (Gaeumannomyces diseases), by such as gaeumannomyce (Gaeumannomyces Graminis) cause；
Rhizoctonia disease (Rhizoctonia diseases), by such as Rhizoctonia solani Kuhn (Rhizoctonia solani) Cause；
Ta Pusi (Tapesia diseases), by such as Ta Pusi clostruidium (Tapesia acuformis) Cause；
Thiclaviopsis disease (Thielaviopsis diseases), by such as thielaviopsis sp (Thielaviopsis Basicola) cause；
Ear fringe and panicle disease, such as:
Alternaria disease (Alternaria diseases), is caused by such as rod method (Alternaria spp.)；
Aspergillosis (Aspergillus diseases) is caused by such as aspergillus flavus (Aspergillus flavus)；
Branch spore is sick (Cladosporium diseases), is caused by such as branch spore (Cladosporium spp.)；
Claviceps disease (Claviceps diseases), is caused by such as ergot (Claviceps purpurea)；
(mould) category of Fusariumsp is sick (Fusarium diseases), is drawn by such as machete fusarium (Fusarium culmorum) It rises；
Head blight (Gibberella diseases) is caused by such as Gibberella zeae (Gibberella zeae)；
Rice Gerlachia oryaae (Monographella diseases), by such as rice cloud shape bacterium (Monographella Nivalis) cause；
Smut and bunt, such as:
Axis Ustilago is sick (Sphacelotheca diseases), by such as silk axis smut (Sphacelotheca Reilinana) cause；
Tilletia disease (Tilletia diseases), by such as Tilletia caries (Tilletia caries) Cause；
Urocystis disease (Urocystis diseases), by such as hidden smut (Urocystis occulta) Cause；
Ustilago disease (Ustilago diseases), is caused by such as naked smut (Ustilago nuda)；
Fruit rot and mycosis, such as:
Aspergillosis (Aspergillus diseases) is caused by such as aspergillus flavus (Aspergillus flavus)；
Botrytis belongs to sick (Botrytis diseases), is caused by such as botrytis (Botrytis cinerea) 's；
Penicilliosis (Penicillium diseases) is drawn by such as sweet potato mould (Penicillium expansum) It rises；
Sclerotinia disease (Sclerotinia diseases), by such as sclerotinite (Sclerotinia Sclerotiorum) cause；
Verticillium disease (Verticilium diseases), by such as black and white wheel branch spore (Verticillium Alboatrum) cause；
Rotten, mouldy, withered, corrupt and samping off in seed and soil:
Alternariosis (Alternaria diseases), by such as mustard rod method (Alternaria brassicicola) Cause；
Aphanomyces disease (Aphanomyces diseases), by such as mould (Aphanomyces of pea silk capsule Euteiches) cause；
Ascochyta disease (Ascochyta diseases), is drawn by such as two born of the same parents bacterium of crystalline lens (Ascochyta lentis) It rises；
Aspergillosis (Aspergillus diseases) is caused by such as aspergillus flavus (Aspergillus flavus)；
Branch spore is sick (Cladosporium diseases), is drawn by such as multi-trunk natalensis (Cladosporium herbarum) It rises；
Cochliobolus disease (Cochliobolus diseases), such as by standing grain cochliobolus (Cochliobolus Sativus) (Conidiaform:Drechslera, Bipolaris Syn:Helminthosporium) causes；
It is sick (Colletotrichum diseases) to pierce disk spore, disk spore (Colletotrichum is pierced by such as coccoid Coccodes) cause；
(mould) category of Fusariumsp is sick (Fusarium diseases), is drawn by such as machete fusarium (Fusarium culmorum) It rises；
Head blight (Gibberella diseases) is caused by such as Gibberella zeae (Gibberella zeae)；
Shell ball spore is sick (Macrophomina diseases), by such as beans shell ball spore (Macrophomina Phaseolina) cause；
Rice Gerlachia oryaae (Monographella diseases), by such as rice cloud shape bacterium (Monographella Nivalis) cause；
Penicilliosis (Penicillium diseases) is drawn by such as sweet potato mould (Penicillium expansum) It rises；
Phoma sp disease (Phoma diseases), is caused by such as balck shank (Phoma lingam)；
Fungi point mold (Phomopsis diseases) is caused by such as soybean Phoma sp (Phomopsis sojae)；
Phytophthora disease (Phytophthora diseases), is caused by such as Phytophthora cactorum (Phytophthora cactorum)；
Nuclear cavity bacteria disease (Pyrenophora diseases), by such as wheat nuclear cavity bacteria (Pyrenophora graminea) Cause；
Pyricularia Sacc. disease (Pyricularia diseases), caused by such as Magnaporthe grisea (Pyricularia oryzae)；
Pythium disease (Pythium diseases), is caused by such as Pythium ultimum (Pythium ultimum)；
Rhizoctonia disease (Rhizoctonia diseases), by such as Rhizoctonia solani Kuhn (Rhizoctonia solani) Cause；
Head mold disease (Rhizopus diseases) is caused by such as Rhizopus oryzae (Rhizopus oryzae)；
Pyrenomycetes disease (Sclerotium diseases), is drawn by such as Sclerotium rolfsii (Sclerotium rolfsii) It rises；
Septoria musiva disease (Septoria diseases), such as caused by phaeosphaeria nodorum (Septoria nodorum)；
Core coral bacterium is sick (Typhula diseases), is caused by for example yellowish pink core coral bacterium (Typhula incarnata)；
It is sick (Verticillium diseases) to take turns branch spore, by such as Verticilliumdahliae (Verticillium Dahliae) cause；
Ulcer, cracking and top dry, such as:
Nectria disease (Nectria diseases), is caused by for example dry red shell bacterium of cancer clump (Nectria galligena)；
Wilt disease, such as:
Chain sclerotinia sclerotiorum belong disease (Monilinia diseases), is caused by such as drupe chain sclerotinia sclerotiorum (Monilinia laxa)；
Leaf bubble or leaf curl, such as:
Exoascus disease (Taphrina diseases) is caused by for example lopsided external capsule bacterium (Taphrina deformans)；
Wood plant decline disease, such as:
It is sick (Esca diseases) according to section, caused by such as head mold lattice spore bacterium (Phaeomoniella clamydospora)；
Eutypa dieback (Eutypa dyeback) is caused by such as grapevine da mping-off fungi (Eutypa lata)；
Dutch elm disease (Dutch elm disease), is caused by such as silique category mite (Ceratocystsc ulmi)；
Colored and seed disease, such as:
Botrytis belongs to sick (Botrytis diseases), caused by such as botrytis (Botrytis cinerea)；
Tubers disease, such as:
Rhizoctonia disease (Rhizoctonia diseases), by such as Rhizoctonia solani Kuhn (Rhizoctonia solani) Cause；
Helminthosporium disease (Helminthosporium diseases), by for example founding the compacted spore of withered length (Helminthosporium solani) causes.
The compound of the present invention can also be with one or more insecticides, fungicide, bactericide, attractant, acaricide Or pheromonal activity substance or other biologically active compounds mix.Thus obtained mixture has broad spectrum of activity. It is particularly advantageous with the mixture of other Fungicidal compounds.The mixture of compound comprising formula (I) and bactericidal compound It is also particularly advantageous with composition of the invention.
The example for the fungicide that can be suitably mixed is selected from following: benzimidazole methyl carbamate class is antifungal The compound of agent, the compound of dicarboximide class fungicide, demethylation inhibin class fungicide compound, benzamide Compound, the amine/morpholine of class fungicide kill the change of the compound of class epiphyte pharmaceutical, phosphatide biosynthesis inhibin class fungicide Close object, the compound of carboxyl acylamide fungicide, the compound of hydroxyl (2- amino -) pyrimidine fungicide, aniline pyrimidine class The compound of fungicide, the compound of N- carbanilate class fungicide, inhibin class fungicide outside quinone Compound, the compound of phenylpyrrole class fungicide, the compound of quinolines fungicide, lipid peroxidized inhibin class are killed The compound of epiphyte pharmaceutical, melanocyte biosynthesis inhibin-reduction enzyme fungicide compound, melanocyte biosynthesis inhibit Element-the compound of dehydration enzyme fungicide, the compound of hydroxy benzenes amine fungicide, squalene-epoxidase inhibin class The compound of fungicide, the compound of polyoxin class fungicide, the compound of phenyl ureas fungicide, the suppression of quinone inside Compound, the enol pyrans uronic acid antibiotics of the compound, benzamides fungicide of making plain class fungicide kill very The compound of microbial inoculum, the compound of own pyrans sugar-antibiotics fungicide, glucopyranosyl antibiotic: protein synthesizes class Compound, the glucopyranosyl antibiotic of fungicide: the compound of trehalase and inose biosynthesis class fungicide, The compound of cyanoacetamide oximes fungicide, the compound of Carbamates fungicide, oxidative phosphorylation uncoupling The compound of class fungicide, the compound of organic tin fungicide, the compound of carboxylic acids fungicide, the heteroaryl same clan kill The compound of epiphyte pharmaceutical, the compound of phosphonic acid ester fungicide, the compound of phthalamidic acid class fungicide, phentriazine class are killed The compound of epiphyte pharmaceutical, the compound of benzene sulfonamide fungicide, pyridazinone fungicide compound, thiophenecarboxamides The compound of class fungicide, the compound of pyrimidine amides fungicide, carboxyl acylamide fungicide compound, tetracycline The compound of antibiotics fungicide, the compound of thiocarbamates fungicide, benzamides fungicide Compound, the host plant defence compound of induction type fungicide, multidigit point contact activity class fungicide compound And the compound of other fungicides.
Further, the example of fungicide compound is selected from following: benomyl, carbendazim, thiophanate-methyl, corruption are mould Benefit, iprodione, vinclozolin, epoxiconazole, Fluquinconazole, Triadimenol, simeconazoles, kind bacterium azoles, triforine, cyproconazole, Difenoconazole, Flusilazole, Flutriafol, metconazole, nitrile bacterium azoles, prochloraz, propiconazole, prothioconazoles, Tebuconazole, fluorine ether azoles, Metalaxyl-M, first White spirit, mefenoxam, M 9834, benalaxyl-M, furalaxyl, ofurace, Wakil, cartap, dodemorph, butylbenzene Morpholine, tridemorph, Trimorfamid Fademorf, fenpropidin, pipron, volution bacterium amine, edifenphos, Isoprothiolane, Boscalid, pyrrole thiophene bacterium Amine, bixafen, carboxin, oxycarboxin, ethirimol, cyprodinil, diethofencarb, Fluoxastrobin, pyraclostrobin, gram glad, oxime of receipts Bacterium ester, ZEN 90160, pyribencarb, Famoxate, Fenamidone, discostrobin, enestrobin, dimoxystrobin, benzene Oxygen bacterium amine, orysastrobin, fluoxastrobin, fenpiclonil, fludioxonil, fast promise sweet smell, chloroneb, pyroquilon, tricyclazole, cyclopropyl acyl bacterium Amine, fenhexamid, pyributicarb, polyoxin, Pencycuron, match seat go out, amisulbrom, oxamides, blasticidin S-S, spring thunder Mycin, streptomysin, jinggangmeisu, cymoxanil, Propamocarb, prothiocarb, iodo propinyl butyl carbamate, fluazinam, pleasure are killed Mite, ferimzone, dinocap, dinocap, fentin acetate, oxolinic acid, hymexazol, phosphorous acid and its various salt, triethylphosphine acid Aluminium, tecloftalam, azoles bacterium piperazine, flusulfamide, diclomezine, Silthiopham, difluoro woods, dimethomorph, benzene metsulfovax, benzene metsulfovax-are different Propyl, Propineb, downy mildew go out, mandipropamid, flumorph, oxytetracycline, methasulfocarb, fluopicolide, fluopyram, I Acid benzene-S-methyl, Cupravit, copper sulphate, Kocide SD, Bordeaux mixture composition (ternary copper sulphate), elementary sulfur, maneb Zinc, Carbatene, Propineb, fervam, maneb, arasan, zineb, ziram, folpet, captan, enemy Bacterium pellet, Bravo, Guardian, cyflufenamid, the third oxygen quinoline, metrafenone, the chloro- 6- of 5- (2,4,6- trifluorophenyl) -7- (4- first Phenylpiperidines -1- base) [1,2,4] triazol [1,5-a] pyrimidine, the iodo- 3- propyl -4H-1- benzopyran-4-one of 2- butoxy -6-, 3- [5- (4- chlorphenyl) -2,3- dimethyl -3- isoxazolidinyl] pyridine, N- [1- [[[1- (4- cyano-phenyl) ethyl] sulphonyl Base] methyl] propyl] carbamic acid 4- fluorobenzene ester, N- [[(cyclo propyl methoxy) amino] [6- (difluoro-methoxy) -2,3- difluoro Phenyl] methylene] phenyl acetamide, N '-[4- [4- chloro- 3- (trifluoromethyl) phenoxy group] -2,5- 3,5-dimethylphenyl]-N- ethyl - N- methyl carboximidamide, 2- [[2- fluoro- 5- (trifluoromethyl) phenyl] sulfenyl] -2- [3- (2- methoxyphenyl) Asia -2- thiazole Alkyl] acetonitrile and N- (the chloro- 2- nitrobenzophenone of 4-)-N- ethyl -4- methyl benzenesulfonamide.
The example for the bactericide that can be suitably mixed can be selected from following: bronopol, double fluorine phenol, N-Serve, dimethyl Aminodithioformic acid nickel, kasugarnycin, octhilinone, furancarboxylic acid, terramycin, probenazole, streptomysin, tecloftalam, copper sulphate With other copper agents.
General synthesis process
Those skilled in the art will realize that: chemical reaction described in the invention can be used to suitably prepare perhaps Other compounds mostly of the invention, and other methods for the preparation of the compounds of the present invention are considered as in model of the invention Within enclosing.For example, the synthesis of the compound of those non-illustrations can be successfully by those skilled in the art according to the present invention It is completed by method of modifying, such as protection interference group appropriate, by utilizing other known reagent (in addition to described in the invention ), or reaction condition is made into some conventional modifications.In addition, reaction disclosed in this invention or known reaction condition are also public It is suitable for the preparation of other compounds of the invention with recognizing.
Following synthetic schemes describes the step of preparation disclosed compound of present invention.Wherein, R1、R2, n and m there is the present invention Described meaning.
Synthetic schemes
Synthetic schemes one
Target compound I-1 can be prepared by synthetic schemes one.Compound a and reaction of sodium azide obtain chemical combination Object b；The compound d that compound b reacts in a heated condition with compound c；Compound d is reacted with hydroxylamine hydrochloride, is obtained Compound e；Compound e reacts to obtain target compound I-1 with compound f.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment
In the examples below, the compounds of this invention is described in detail by taking part of compounds of the invention as an example in inventor Preparation process.
Embodiment 1:(Z)-tert-butyl (6- (((((1- (4- luorobenzyl) -1H-TETRAZOLE -5- base) (phenyl) methylene) ammonia Base) oxygroup) methyl) pyridine -2- base) carbamate synthesis
The synthesis of step 1:1- (azido methyl) -4- fluorophenyl
Be added in 100mL round-bottomed flask 4- fluorobenzyl bromide (3.00g, 15.87mmol) and sodium azide (1.55g, 23.81mmol), it adds n,N-Dimethylformamide (50mL), is reacted 8 hours at 60 DEG C.It is added ethyl acetate (50mL), uses Saturated common salt water washing (50mL x 3), anhydrous sodium sulfate dries, filters, and filtrate is concentrated under reduced pressure, obtains pale yellow oily liquid 2.21g, yield: 92%.
Step 2:(Z)-(1- (4- luorobenzyl) -1H-TETRAZOLE -5- base) (phenyl) ketoxime synthesis
1- (azido methyl) -4- fluorophenyl (1.00g, 6.62mmol) and benzoyl nitrile are added in 120mL tube sealing (1.50g, 10.38mmol) reacts 8 hours at 120 DEG C, obtains intermediate (1- (4- luorobenzyl) -1H-TETRAZOLE -5- base) (benzene Base) ketone, hydroxylamine hydrochloride (1.75g, 26.48mmol) is added in the reaction system, adds pyridine (10mL), is reacted at 60 DEG C 24 hours.Solvent is removed under reduced pressure, column chromatography for separation [PE/EtOAc (v/v)=4/1] obtains white solid 0.78g, yield: 40%.
LC-MS:m/z 298.29[M+H]+。
Step 3:(Z)-tert-butyl (6- (((((1- (4- luorobenzyl) -1H-TETRAZOLE -5- base) (phenyl) methylene) amino) Oxygroup) methyl) pyridine -2- base) and carbamate synthesis
In 100mL round-bottomed flask be added (Z)-(1- (4- luorobenzyl) -1H-TETRAZOLE -5- base) (phenyl) ketoxime (300mg, 1.01mmol), tert-butyl (6- (bromomethyl) pyridine -2- base) carbamate (347.73mg, 1.21mmol) and potassium carbonate (139.47mg, 1.01mmol) adds n,N-Dimethylformamide (20mL), reacts 24 hours at room temperature.Acetic acid second is added Ester (50mL) extracts (50mL x 5) with saturated salt solution, retains upper organic phase, after solvent is removed under reduced pressure, chromatograph through column pure Change [PE/EtOAc (v/v)=3/1], obtains white solid 198mg, yield: 40%.
LC-MS:m/z 504.39[M+H]+；
1H NMR(400MHz,CDCl3) δ (ppm): 7.86 (d, J=8.3Hz, 1H), 7.66 (t, J=7.9Hz, 1H), 7.42-7.31 (m, 1H), 7.28-7.20 (m, 4H), 7.17 (s, 1H), 7.06 (dd, J=8.6,5.2Hz, 2H), 6.91 (d, J =7.4Hz, 1H), 6.83 (t, J=8.6Hz, 2H), 5.47 (s, 2H), 5.20 (s, 2H), 1.50 (s, 9H).
The target compound in table 1 can be obtained by the similar synthetic method of embodiment 1 using corresponding raw material.
Table 1
Active testing
In following test case, inventor has detected the compounds of this invention to having by taking part of compounds of the invention as an example The prophylactic-therapeutic effect of evil fungi.
Biological test example
This test case is used to measure the bactericidal activity of compound obtained in embodiment.
Experiment target in this test case is designated as botrytis cinerea pers and bacterium of downy mildew of cucumber.
It is spare that 1%EC is dissolved into DMF.Using living body pot-culture method, these compounds are evaluated under 500mg/L dosage to 2 A experiment target target bactericidal activity.Test method is using initiative pesticide bioactivity evaluation SOP (fungicide volume).
1) bacterium of downy mildew of cucumber test (Pseudoperonospora cubensis)
Select 1 consistent potting cucumber seedling of leaf period (plucking growing point) growing way, naturally dry after spraying treatment, processing It is inoculated with after 24 hours afterwards, takes fresh cucumber downy mildew disease leaf, dipped the lower sick leaf back sporangium of distillation washing with writing brush, match At sporangia suspension (2-3x 105A/mL).With inoculation sprayer (pressure 0.1MPa), even spraying is inoculated on cucumber seedling, Test material after inoculation moves to phjytotron, holding relative humidity 100%, and temperature keeps temperature after being 21 DEG C or so, 24 hours 21 DEG C or so, 95% or so moisturizing of relative humidity induces, and backsight blank control incidence carries out classification investigation within 5 days, refers to by disease Calculate preventive effect.
2) botrytis cinerea pers test (Botrytis cinerea)
Using blade bacterination process.The consistent potting cucumber seedling of two leaf period growing ways is selected to connect bacterium after reagent spray dries Cake is on blade.24-26 DEG C after half-light moisturizing 24 hours, is restored natural lighting moisturizing culture about 3 days.After the onset of compareing sufficiently Each vaccination lesion diameter is measured with slide calliper rule, calculates preventive effect.
Test result: embodiment 2, embodiment 3, embodiment 5, embodiment 11, embodiment 13 and embodiment 16 are to cucumber cream Mildew preventive effect reaches 100%；Embodiment 4, embodiment 9, embodiment 14, embodiment 15 and embodiment 17 prevent gray mold of cucumber Effect reaches 100%.
The compounds of this invention is to plant pathogenic fungi, especially bacterium of downy mildew of cucumber and cucumber grey mold from the above results Germ has good control efficiency, provides thinking for the exploitation of new type bactericide.

Claims (8)

1. a kind of compound, be the salt of the compound as shown in formula (I) compound represented or formula (I), N- oxide, (E) or (Z) isomers and their mixture:
Wherein:
R1For halogen, cyano, nitro, hydroxyl, carboxyl, amino, C1-6Alkyl, halogenated C1-6Alkyl, C1-6Alkoxy, C1-6Alkylthio group, Halogenated C1-6Alkoxy, halogenated C1-6Alkylthio group, C1-6Alkoxy -C1-6Alkyl-, C1-6Alkoxy-(C=O)-, C1-6Alkyl- SO2-、C1-6Alkyl-substituted amino, C2-8Alkenyl, C2-8Alkynyl, C6-14Aryl, halogenated C6-14Aryl, C1-6Alkyl-substituted C6-14 Aryl, halogenated C1-6Alkyl-substituted C6-14Aryl, C1-6The C that alkoxy replaces6-14Aryl, halogenated C1-6The C that alkoxy replaces6-14 Aryl, C6-14Aryloxy group or halogenated C6-14Aryloxy group；
R2For halogen, cyano, nitro, C1-6Alkyl, halogenated C1-6Alkyl, C1-6Alkoxy, halogenated C1-6Alkoxy, C2-8Alkenyl, C2-8 Alkenyloxy group, C2-8Alkynyl, C2-8Alkynyloxy group, C1-6Alkyl-SO2-、NRaRb-SO2-、C3-8Naphthenic base, C6-14Aryl, C6-14Aryloxy group Or 5-10 unit's heteroaryl；Wherein, R2Optionally replaced by 1,2,3 or 4 substituent group selected from A1；
Wherein, A1 is halogen, C1-6Alkyl, halogenated C1-6Alkyl, C1-6Alkoxy or halogenated C1-6Alkoxy；
RaAnd RbIt is each independently hydrogen or C1-6Alkyl；
N is 0,1,2,3,4 or 5；
M is 0,1,2,3,4 or 5.
2. compound according to claim 1, in which:
R1For halogen, cyano, nitro, hydroxyl, carboxyl, amino, C1-4Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy, C1-4Alkylthio group, Halogenated C1-4Alkoxy, halogenated C1-4Alkylthio group, C1-4Alkoxy -C1-4Alkyl-, C1-4Alkoxy-(C=O), C1-4Alkyl-SO2-、 C1-4Alkyl-substituted amino, C2-6Alkenyl, C2-6Alkynyl, C6-10Aryl, halogenated C6-10Aryl, C1-4Alkyl-substituted C6-10Aryl, Halogenated C1-4Alkyl-substituted C6-10Aryl, C1-4The C that alkoxy replaces6-10Aryl, halogenated C1-4The C that alkoxy replaces6-10Aryl, C6-10Aryloxy group or halogenated C6-10Aryloxy group.
3. compound according to claim 2, in which:
R1For fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxyl, carboxyl, amino ,-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、- CH2CH2CH2CH3、-CH2CH(CH3)CH3、-CH(CH3)CH2CH3、-C(CH3)3、-CHF2、-CF3、-OCH3、-OCH2CH3、- OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OC(CH3)3、-SCH3、-OCHF2、-OCF3、-CH2-OCH3、CH3- SO2-、-NHCH3、-N(CH3)2、-NHCH2CH3、-N(CH2CH3)2、-N(CH2CH3)CH3Or phenyl.
4. compound according to claim 1, in which:
R2For halogen, cyano, nitro, C1-4Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy, halogenated C1-4Alkoxy, C2-6Alkenyl, C2-6 Alkenyloxy group, C2-6Alkynyl, C2-6Alkynyloxy group, C1-4Alkyl-SO2-、NRaRb-SO2-、C3-6Naphthenic base, C6-10Aryl, C6-10Aryloxy group Or 5-6 unit's heteroaryl；Wherein, R2Optionally replaced by 1,2,3 or 4 substituent group selected from A1；
Wherein, A1 is halogen, C1-4Alkyl, halogenated C1-4Alkyl, C1-4Alkoxy or halogenated C1-4Alkoxy；
RaAnd RbIt is each independently hydrogen or C1-4Alkyl.
5. compound according to claim 4, in which:
R2For fluorine, chlorine, bromine, iodine, cyano, nitro ,-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、- CH2CH(CH3)CH3、-CH(CH3)CH2CH3、-C(CH3)3、-CHF2、-CF3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH (CH3)2、-OCH2CH2CH2CH3、-OC(CH3)3、-OCHF2、-OCF3、CH3-SO2-、NH2-SO2-、NH(CH3)-SO2Or N (CH3)2-SO2-；
Or R2For following subformula:
6. compound described in -5 any one according to claim 1 for the compound with one of following structure or has The salt of one of following structural compounds, N- oxide, (E) or (Z) isomers and their mixture:
7. a kind of composition, living comprising acceptable surface on compound as claimed in any one of claims 1 to 6 and Pesticide Science Property agent and/or carrier.
8. compound as claimed in any one of claims 1 to 6 or composition as claimed in claim 7 are in prevention and treatment plant-pathogenic Application in fungi.
CN201810382505.7A 2018-04-26 2018-04-26 Oxime derivatives and their use in agriculture Active CN110452220B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810382505.7A CN110452220B (en) 2018-04-26 2018-04-26 Oxime derivatives and their use in agriculture

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810382505.7A CN110452220B (en) 2018-04-26 2018-04-26 Oxime derivatives and their use in agriculture

Publications (2)

Publication Number Publication Date
CN110452220A true CN110452220A (en) 2019-11-15
CN110452220B CN110452220B (en) 2020-08-14

Family

ID=68471566

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810382505.7A Active CN110452220B (en) 2018-04-26 2018-04-26 Oxime derivatives and their use in agriculture

Country Status (1)

Country Link
CN (1) CN110452220B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1553907A (en) * 2001-08-20 2004-12-08 ���ձ���ī��ѧ��ҵ��ʽ���� Tetrazoyl oxime derivative and agrochemical containing the same as active ingredient
CN102791691A (en) * 2010-03-12 2012-11-21 日本曹达株式会社 Compound containing pyridine ring and method for producing halogenated picoline derivative and tetrazolyloxime derivative
CN102946734A (en) * 2010-04-20 2013-02-27 巴斯夫欧洲公司 Fungicidal mixtures comprising ametoctradin and a tetrazoloxime derivative

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1553907A (en) * 2001-08-20 2004-12-08 ���ձ���ī��ѧ��ҵ��ʽ���� Tetrazoyl oxime derivative and agrochemical containing the same as active ingredient
CN102791691A (en) * 2010-03-12 2012-11-21 日本曹达株式会社 Compound containing pyridine ring and method for producing halogenated picoline derivative and tetrazolyloxime derivative
CN102946734A (en) * 2010-04-20 2013-02-27 巴斯夫欧洲公司 Fungicidal mixtures comprising ametoctradin and a tetrazoloxime derivative

Also Published As

Publication number Publication date
CN110452220B (en) 2020-08-14

Similar Documents

Publication Publication Date Title
ES2359877T3 (en) FUNGICIDE DERIVATIVES OF N-CICLOALQUIL-BENCIL-THIOCARBOXAMIDS OR N-CICLOALQUIL-BENCIL-AMIDINA-N&#39;-SUBSTITUTED.
KR101280112B1 (en) Fungicide 2-pyridyl-methylene-carboxamide derivatives
JP5133985B2 (en) Tetrazoyl oxime derivatives and plant disease control agents
RU2427577C2 (en) Fungicide hydroximoyl-tetrazole derivatives
ES2502840T3 (en) Heterocyclythylheterocyclylcarboxamide derivatives as fungicides
KR20100029843A (en) Tetrazoyloxime derivative and plant disease control agent
JP2008507494A (en) 3-pyridinylethylcarboxamide derivatives as fungicides
JP2008545638A (en) Novel 2-pyridinylcycloalkylcarboxamide derivatives as fungicides
KR20100020454A (en) Fungicide heterocyclyl-pyrimidinyl-amino derivatives
CN105829306B (en) The crystalline form of compound, includes its composition and application thereof at preparation method
BRPI0813022B1 (en) compost, fungicidal composition and method for the control of plant pathogenic fungus
BRPI0811354B1 (en) compost, fungicidal composition and method for controlling pathogenic fungi in crops
CN109983010A (en) 1- [2- (1- chlorine cyclopropyl) -2- hydroxyl -3- (3- phenyl -1,2- oxazole -5- base) propyl] -1H- imidazoles -5- 6-carbonitrile derivatives and related compound as the fungicide for crop protection
CN102791132A (en) Plant disease control agent
KR20080033298A (en) Benzoheterocyclylethylcarboxamide derivatives
CN101765598B (en) Fungicide N-5-membered fused heteroaryl-methylene-N-cycloalkyl-carboxamide derivatives
ES2410879T3 (en) New N-alkyl-heterocyclylcarboxamide derivatives
JP2008507492A (en) N- [2- (4-pyridinyl) ethyl] benzamide derivatives as fungicides
JP2009542601A (en) N- (4-pyridin-2-ylbutyl) benzamide derivatives and their use as fungicides
CN109305964B (en) Fungicide hydroximoyl-tetrazole derivatives
CN108947964B (en) Fungicide hydroximoyl-tetrazole derivatives
CN109320452B (en) Quinoline derivatives and its preparation method and application
CN109574990A (en) Fungicide hydroximoyl-tetrazole derivatives
CN110452220A (en) 9 oxime derivate and its application in agricultural
JP5322296B2 (en) Method for using plant disease control agent containing tetrazoyloxime derivative

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant