CN111548319B - 1, 1-dicyanooxime ether compound and application thereof - Google Patents

1, 1-dicyanooxime ether compound and application thereof Download PDF

Info

Publication number
CN111548319B
CN111548319B CN202010078417.5A CN202010078417A CN111548319B CN 111548319 B CN111548319 B CN 111548319B CN 202010078417 A CN202010078417 A CN 202010078417A CN 111548319 B CN111548319 B CN 111548319B
Authority
CN
China
Prior art keywords
acid
compound
formula
general formula
hydrogen
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.)
Active
Application number
CN202010078417.5A
Other languages
Chinese (zh)
Other versions
CN111548319A (en
Inventor
张立新
张静
孙庚�
张力群
康卓
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.)
Shenyang University of Chemical Technology
Original Assignee
Shenyang University of Chemical Technology
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 Shenyang University of Chemical Technology filed Critical Shenyang University of Chemical Technology
Publication of CN111548319A publication Critical patent/CN111548319A/en
Application granted granted Critical
Publication of CN111548319B publication Critical patent/CN111548319B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/74—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 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • 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
    • A01N43/88—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 six-membered rings with three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D215/14—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/24—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles

Landscapes

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

Abstract

The invention discloses a 1, 1-dicyanooxime ether compound, the structure of which is shown as a general formula I, wherein the definition of each substituent group in the formula I is shown in the specification.

Description

1, 1-dicyanooxime ether compound and application thereof
Technical Field
The invention belongs to the field of agricultural bactericides, and particularly relates to a 1, 1-dicyanooxime ether compound and application thereof.
Background
Patent CN201611199611.9 discloses a compound of the following general formula, which has a certain bactericidal activity.
The bactericidal activity, in particular the bactericidal activity, of the compounds disclosed in the prior art is not satisfactory and needs to be continuously studied in order to satisfy the practical application.
In the prior art, the 1, 1-dicyanooxime ether compound shown in the invention has no reported bactericidal activity.
Disclosure of Invention
The invention aims to provide a 1, 1-dicyanooxime ether compound capable of controlling various plant bacterial diseases and fungal diseases, and a medicament for preparing the same in agriculture and other fields.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the 1, 1-dicyanooxime ether compound is characterized by being shown in a general formula I:
wherein:
w is selected from W 1 -W 4 One of the groups shown:
；
q is selected from Q 1 -Q 3 One of the groups shown, and, #1 is linked to W, #2 is linked to methylene,
X 1 、X 2 、X 3 、X 4 、X 5 、X 6 、X 7 、X 8 、X 9 、X 10 、X 11 、X 12 、X 13 、X 14 、X 15 、X 16 、X 17 each independently selected from hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, halo C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio, halo C 1 -C 6 Alkylthio, C 1 -C 6 Alkylamino, C 1 -C 6 Dialkylamino, C 1 -C 6 Alkylcarbonyl or C 1 -C 6 An alkoxycarbonyl group;
or salts of compounds of formula I.
The 1, 1-dicyanooxime ether compound of the invention can be further represented by the general formula I:
w is selected from W 1 -W 4 One of the groups shown;
q is selected from Q 1 -Q 3 One of the groups shown;
X 1 、X 2 、X 3 、X 4 、X 5 、X 6 、X 7 、X 8 、X 9 、X 10 、X 11 、X 12 、X 13 、X 14 、X 15 、X 16 、X 17 each independently selected from hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C 1 -C 4 Alkyl, C 3 -C 4 Cycloalkyl, halo C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, halo C 1 -C 4 Alkoxy, C 1 -C 4 Alkylthio, halo C 1 -C 4 Alkylthio, C 1 -C 4 Alkylamino, C 1 -C 4 Dialkylamino, C 1 -C 4 Alkylcarbonyl or C 1 -C 4 An alkoxycarbonyl group;
or salts of compounds of the general formula I with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
The 1, 1-dicyanooxime ether compound of the invention can be further represented by the general formula I:
w is selected from W 1 -W 4 One of the groups shown;
q is selected from Q 1 -Q 3 One of the groups shown;
X 1 、X 2 、X 3 、X 4 、X 5 、X 6 、X 7 、X 8 、X 9 、X 10 、X 11 、X 12 、X 13 、X 14 、X 15 、X 16 、X 17 each independently selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, hydroxy, mercapto, amino, carboxy, methyl, ethyl, N-propyl, isopropyl, cyclopropyl, N-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2, 2-trifluoroethyl, heptafluoroisopropyl, methoxy, ethoxy, N-propoxy, isopropoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, trifluoromethylthio, 2,2, 2-trifluoroethylthio, methylamino, ethylamino or N, N-dimethylamino;
or salts of compounds of the general formula I with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
In the definitions of the compounds of the general formula given above, the terms used in the collection generally represent the following substituents:
halogen: refers to fluorine, chlorine, bromine or iodine.
Alkyl: straight or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl or different butyl, pentyl or hexyl isomers, etc.
Cycloalkyl: a substituted or unsubstituted cyclic alkyl group such as cyclopropyl, cyclopentyl or cyclohexyl; substituents such as methyl, halogen, and the like.
Haloalkyl: straight or branched alkyl groups, the hydrogen atoms on these alkyl groups may be partially or fully substituted by halogen, such as monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2, 2-trifluoroethyl, heptafluoroisopropyl and the like.
An alkoxy group: a linear or branched alkyl group linked to the structure via an oxygen atom bond, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy and the like.
Haloalkoxy: straight-chain or branched alkoxy groups, the hydrogen atoms on these alkoxy groups may be partially or completely substituted by halogen, such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, 2,2, 2-trifluoroethoxy and the like.
Alkylthio: a linear or branched alkyl group linked to the structure via a sulfur atom bond, such as methylthio, ethylthio, and the like.
Haloalkylthio: straight-chain or branched alkylthio groups, the hydrogen atoms on these alkylthio groups may be partially or wholly substituted with halogen, for example difluoromethylthio, trifluoromethylthio, 2,2, 2-trifluoroethylthio and the like.
Alkylamino: a linear or branched alkyl group linked to the structure via a nitrogen atom bond, such as methylamino, ethylamino, n-propylamino, isopropylamino or isomerised butylamine.
Dialkylamino group: two identical or different linear or branched alkyl groups are bonded to the structure via a nitrogen atom bond, such as N, N-dimethylamino, N-methyl-N-ethylamino, etc.
Alkylcarbonyl: the alkyl group is attached to the structure via a carbonyl group, such as acetyl (CH 3 CO-), n-propionyl (CH 3CH2 CO-), and the like.
Alkoxycarbonyl: alkyl-O-CO-, e.g. methoxycarbonyl (CH) 3 OCO-), ethoxycarbonyl (CH) 3 CH 2 OCO-), n-propoxycarbonyl (CH) 3 CH 2 CH 2 OCO-), n-butoxycarbonyl group (CH) 3 CH 2 CH 2 CH 2 OCO-) and the like.
Some of the compounds of the general formula I of the present invention are shown in tables 1 to 6, but the present invention is by no means limited to these compounds.
In formula I, when w=w 1 And q=q 1 In this case, the general formula I may be represented by the general formulae I to W 1 -Q 1 Representation (for convenience of description, W 1 Substituent X of (2) 1 、X 2 、X 3 、X 4 、X 5 Represented by R, supra).
Table 1: general formula I-W 1 -Q 1 Wherein R is different substituent groups shown in Table 1, and the number of the representative compounds is 1.1-1.354.
TABLE 1
In formula I, when w=w 1 And q=q 2 In this case, the formula I may be represented by the formula I-W 1 -Q 2 Representative compounds are shown in Table 2.
Table 2: general formula I-W 1 -Q 2 In which the substituents R correspond to Table 1 and represent the compound numbers 2.1 to 2.354, which correspond in turn to Table 1 from 1.1 to 1.354.
In formula I, when w=w 1 And q=q 3 In this case, the formula I may be represented by the formula I-W 1 -Q 3 Representative compounds are shown in Table 3.
Table 3: general formula I-W 1 -Q 3 In which the substituent R is the same as Table 1 and represents compound numbers 3.1 to 3.354, which correspond to 1.1 to 1.354 of Table 1 in order.
In formula I, when w=w 2 In this case, the formula I may be represented by the formula I-W 2 Representative compounds are shown in table 4:
TABLE 4 Table 4
/>
In formula I, when w=w 3 In this case, the formula I may be represented by the formula I-W 3 Representative compounds are shown in table 5:
TABLE 5
/>
/>
/>
In formula I, when w=w 4 In this case, the formula I may be represented by the formula I-W 4 Representative compounds are shown in table 6:
TABLE 6
/>
/>
/>
The physicochemical properties, nuclear magnetic data and mass spectrum data of a part of the compounds of the invention are shown in Table 7:
TABLE 7
/>
/>
/>
/>
/>
/>
/>
/>
/>
The compounds of the invention of the general formula I when Q is Q 1 When the compound of the general formula I is shown as the general formula I-1; when Q is Q 2 When the compound of the general formula I is shown as the general formula I-2; when Q is Q 3 When the compounds of the formula I are represented by the formula I-3, they can be prepared in accordance with the following method (in the formula, M represents a cation, e.g. Na, unless otherwise indicated + 、K + 、CS + 、Ag + Or NH 4 + Etc.):
the compound of the general formula II-1, the compound of the general formula II-2 and the compound of the general formula II-3 respectively react with the compound of the general formula III in a proper solvent at the temperature ranging from minus 10 ℃ to the boiling point of the solvent for 0.5 to 48 hours to respectively prepare the compound of the general formula I-1, the compound of the general formula I-2 and the compound of the general formula I-3. Suitable solvents may be the same or different and are selected from alcohols (e.g., methanol, ethanol, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), halogenated hydrocarbons (e.g., methylene chloride, etc., chloroform, carbon tetrachloride, etc.), esters (e.g., methyl acetate, ethyl acetate, etc.), ethers (e.g., tetrahydrofuran, dioxane, diethyl ether, 1, 2-dimethoxyethane, etc.), polar solvents (e.g., water, acetonitrile, dioxane, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, etc.), or mixtures of the above solvents.
Compounds of formula II-1 may be prepared according to known methods (e.g., european Journal of Medicinal Chemistry, 46 (4), 1367-1373; 2011, new Journal of Chemistry, 41 (13), 5875-5883; 2017, tetrahedron Letters, 58 (1), 87-91; 2017, bioorganic & Medicinal Chemistry Letters, 24 (22), 5154-5156; 2014 or CN103864769, etc. reported methods).
The compounds of formula II-2 may be prepared according to known methods (e.g., methods reported for Journal of Agricultural and Food Chemistry, 53 (8), 3120-3125; 2005, european Journal of Medicinal Chemistry, 113, 246-257; 2016, CN104844532 or CN105017242, etc.).
The compounds of formula II-3 may be prepared according to known methods (e.g., pharmaceutical Chemistry Journal, 50 (4), 234-238; 2016, new Journal of Chemistry, 41 (13), 5875-5883; 2017, journal of Medicinal Chemistry, 56 (10), 3783-3805; 2013 or WO2012129564, etc., as reported).
The compounds of formula III may be prepared according to known methods (e.g. as reported in CN103804321, WO2008139481, U.S. Pat. No. 3, 20130096098 or Journal of the Chemical Society of Pakistan, 33 (3), 324-332, 2011, etc.).
The compound shown in the general formula I can be used for controlling various plant bacterial diseases, such as fruit blotch (such as melon and fruit blotch and the like), leaf blotch (such as tomato bacterial leaf blotch and the like), bacterial wilt (such as tomato bacterial wilt and potato bacterial wilt and the like), bacterial blight, canker (such as citrus canker and kiwi canker and the like), soft rot (such as celery cabbage soft rot and the like), bacterial angular blotch (such as cucumber bacterial angular blotch and the like), bacterial leaf blotch (such as rice bacterial leaf blotch and the like), leaf blight, bacterial leaf blight (such as rice bacterial leaf blotch and the like), wild fire disease, bacterial scab and the like.
The compound can also be used for preventing and treating diseases caused by various fungi such as oomycetes, basidiomycetes, ascomycetes, fungi imperfecti and the like on various crops, for example, the compound has good prevention effect on diseases such as cucumber downy mildew, cucumber gray mold, cucumber anthracnose, cucumber powdery mildew, tomato early blight, tomato late blight, pepper blight, grape downy mildew, grape white rot, apple ring rot, apple alternaria leaf spot, rice sheath blight, rice blast, wheat rust, wheat leaf spot, wheat powdery mildew, rape sclerotinia, corn small spot and the like at a lower dosage.
The invention also provides a bactericidal composition, wherein the bactericidal composition is also provided with a compound shown in a general formula I and an agriculturally acceptable carrier, and the weight percentage of active components in the bactericidal composition is 0.1-99%.
The invention also provides a process for the preparation of a composition as defined above: the compound of formula I is admixed with a carrier. Such compositions may be comprised of a single compound of the invention or a mixture of compounds.
The carrier in the composition of the invention is a substance that satisfies the following conditions: it is formulated with the active ingredient and applied to the locus to be treated, for example, it may be a plant, seed or soil; or to facilitate storage, transport or handling. The carrier may be a solid or a liquid, including substances that are normally gaseous but which have been compressed into a liquid, and commonly used in formulating insecticidal and fungicidal compositions.
Suitable solid carriers include natural or synthetic clays or silicates, such as diatomaceous earth, talc, attapulgite, aluminum silicate (kaolin), montmorillonite, mica; calcium carbonate; calcium sulfate; ammonium sulfate; synthetic silica, synthetic calcium silicate or aluminum silicate; elements such as carbon and sulfur; natural or synthetic resins such as coumarone resins, polyvinyl chloride, styrene polymers or copolymers; solid polychlorinated phenol; asphalt; waxes such as beeswax, paraffin wax.
Suitable liquid carriers include water; alcohols such as isopropanol, ethanol; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexyl ketone; an ether; aromatic hydrocarbons such as benzene, toluene, xylene; petroleum fractions such as kerosene, mineral oil; chlorinated hydrocarbons such as carbon tetrachloride, perchloroethylene and trichloroethylene. In general, mixtures of these liquids are also suitable.
Detailed Description
The following specific examples serve to further illustrate the invention, but the invention is by no means limited to these examples. (the raw materials used are commercially available unless otherwise noted)
Synthetic examples
According to the synthetic route, the compounds shown in the general formula I of the invention can be prepared and obtained respectively by adopting different raw material compounds, and the following is further specifically described:
example 1: preparation of Compound 1.354
To a 50 ml reaction flask were added 2-chloromethyl-5-phenyl-1, 3, 4-oxadiazole (0.50 g, 2.58 mmol), malononitrile oxime ether sodium salt (0.34 g, 2.91 mmol) and 20 ml acetonitrile and the reaction was stirred at room temperature. After the reaction was completed, acetonitrile was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 0.44 g of a white solid.
Example 2: preparation of Compound 2.354
To a 50 ml reaction flask were added 2-chloromethyl-5-phenyl-1, 3, 4-thiadiazole (0.30 g, 1.43 mmol), malononitrile oxime ether sodium salt (0.20 g, 1.71 mmol) and 20 ml acetonitrile and the reaction was stirred at room temperature. After the reaction was completed, acetonitrile was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 0.27 g of a yellow solid.
Example 3: preparation of Compound 3.354
To a 50 ml reaction flask were added 5-chloromethyl-3-phenyl-1, 2, 4-oxadiazole (0.35 g, 1.80 mmol), malononitrile oxime ether sodium salt (0.25 g, 2.14 mmol) and 20 ml acetonitrile and the reaction was stirred at room temperature. After the reaction was completed, acetonitrile was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 0.31 g of a white solid.
Other compounds of formula I of the present invention may be prepared by reference to the methods described in the above specific examples and summary.
Biological Activity assay
Example 4: determination of biological Activity against Pyricularia oryzae or Gray mold
In vitro bactericidal activity assay: the high-throughput screening method is adopted, namely, a compound sample of the general formula I is dissolved by a proper solvent (the type of the solvent is such as acetone, methanol, DMF and the like, and is selected according to the dissolving capacity of the solvent to the sample) to prepare a solution with the required concentration to be tested. Under the ultra-clean working environment, the liquid to be detected is added into the micropores of the 96-hole culture plate, then the pathogenic bacteria propagule suspension is added into the micropores, and the treated culture plate is placed in a constant temperature incubator for culture. Investigation was performed 24 hours later, and the germination or growth of the pathogenic bacteria propagules was visually examined at the time of investigation, and the bacteriostatic activity of the compound was evaluated according to the germination or growth of the control treatment.
The test results were as follows:
25 In the case of mg/L of the solution, compounds 1.1, 1.2, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.12, 1.13, 1.15, 1.16, 1.17, 1.18, 1.19, 1.22, 1.25, 1.36, 1.39, 1.40, 1.43, 1.45, 1.88, 1.101, 1.104, 1.106, 1.107, 1.109, 1.110, 1.113, 1.167, 1.295, 1.354, 2.5, 2.6, 2.7, 2.8, 2.18, 2.19 2.22, 2.25, 2.43, 2.45, 2.53, 2.101, 2.104, 2.107, 2.110, 2.113, 2.167, 2.354, 3.1, 3.2, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 3.19, 3.22, 3.25, 3.36, 3.43, 3.45, 3.53, 3.101, 3.107, 3.110, 3.113, 3.354, 5.92 had 100% inhibition of rice blast spore germination.
25 In the case of mg/L of the solution, compounds 1.1, 1.2, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.12, 1.13, 1.15, 1.16, 1.17, 1.18, 1.19, 1.22, 1.25, 1.36, 1.39, 1.40, 1.43, 1.45, 1.88, 1.101, 1.104, 1.106, 1.107, 1.109, 1.110, 1.113, 1.167, 1.295, 1.354, 2.5, 2.6, 2.7, 2.8, 2.18, 2.19 2.22, 2.25, 2.43, 2.45, 2.53, 2.101, 2.104, 2.107, 2.110, 2.113, 2.167, 2.354, 3.1, 3.2, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 3.19, 3.22, 3.25, 3.36, 3.43, 3.45, 3.53, 3.101, 3.107, 3.110, 3.113, 3.354, 5.92 has 100% spore germination inhibition rate for vegetable botrytis.
Example 5: determination of control Effect on plant bacterial diseases
The compound of the invention is used for controlling and measuring various plant bacterial diseases, and the test procedures are as follows:
melon and fruit spot disease: the test compound is dissolved with a small amount of N, N dimethylformamide and diluted with water to the desired concentration. Uniformly mixing pathogenic bacteria cultured to a stationary growth period with a quantitative compound solution, putting melon seeds subjected to germination acceleration into a mixed solution of a bacterial solution and the compound, soaking for half an hour, sowing the seeds into an earthworm soil culture cup, putting the earthworm soil culture cup into a greenhouse for moisture preservation and culture, generally culturing for two weeks, and carrying out control effect investigation after the seeds are fully developed by contrast.
Soft rot of chinese cabbage: cutting 2 cm square leaf of Chinese cabbage, and placing into glass culture dish with double layers of filter paper. Dissolving with N, N dimethylformamide, diluting with water to desired concentration, spraying on the surface of leaf of Chinese cabbage, air drying the liquid medicine on the surface of leaf in a fume hood, needling to form wound on the surface of leaf with inoculating needle, inoculating 5 microliter of soft rot fungus of Chinese cabbage cultured to stationary growth phase into the wound, and inoculating. Finally, the test materials are placed into an incubator for light-shielding cultivation for 48 hours, and the control effect investigation is carried out after the contrast is fully developed.
Bacterial leaf spot of cucumber, bacterial leaf spot of tomato, bacterial leaf streak of rice, bacterial leaf blight of rice: the test compound is dissolved with a small amount of N, N dimethylformamide and diluted with water to the desired concentration. Spraying the compound on the surface of a plant test material, air-drying the surface liquid medicine at a shade place, spraying and inoculating pathogenic bacteria bacterial liquid cultured to a stable growth period on the surface of the plant test material, and then placing the plant test material in a greenhouse for moisture preservation and culture. Usually, the culture is carried out for about ten days, and after the control is fully ill, the control effect investigation is carried out.
Potato scab: a certain amount of the compound to be measured is weighed and dissolved in acetone respectively according to the requirement of a solvent, and then added into water to prepare 100mL of liquid medicine containing 8mg of medicament. Placing potato blocks in a pot filled with bacteria-carrying soil, uniformly spraying 100mL of liquid medicine on the soil and the surfaces of the potato blocks, covering the soil, culturing in a greenhouse, harvesting the potato blocks after about 10 weeks, and carrying out experimental investigation.
The test results were as follows:
600 In the case of mg/L of the solution, compounds 1.1, 1.2, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.12, 1.13, 1.15, 1.16, 1.17, 1.18, 1.19, 1.22, 1.25, 1.36, 1.39, 1.40, 1.43, 1.45, 1.88, 1.101, 1.104, 1.106, 1.107, 1.109, 1.110, 1.113, 1.167, 1.295, 1.354, 2.5, 2.6, 2.7, 2.8, 2.18 2.19, 2.22, 2.25, 2.43, 2.45, 2.53, 2.101, 2.104, 2.107, 2.110, 2.113, 2.167, 2.354, 3.1, 3.2, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 3.19, 3.22, 3.25, 3.36, 3.43, 3.45, 3.53, 3.101, 3.107, 3.110, 3.113, 3.354, 5.92 had a 100% control of melon fruit blotch.
At the time of 400mg/L, the compounds 1.1, 1.2, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.12, 1.13, 1.15, 1.16, 1.17, 1.18, 1.19, 1.22, 1.25, 1.36, 1.39, 1.40, 1.43, 1.45, 1.88, 1.101, 1.104, 1.106, 1.107, 1.109, 1.110, 1.113, 1.167, 1.295, 1.354, 2.5, 2.6, 2.7, 2.8, 2.18, 2.19, 2.22, 2.25, 2.43, 2.45, 2.53, 2.101, 2.104, 2.107, 2.110, 2.113, 2.167, 2.354, 3.1, 3.2, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 3.19, 3.25, 3.35, 3.3.3.45, 3.37, 3.45, 3.37, 3.35, 3.36, 3.3.7, 3.45, 3.35, 3.37, 3.35, 3.7, 3.45, 3.3.35, 3.37, 3.35, 3.45, 3.3.3.7, 3.37, 3.35, 3.7, 3.17, 3.35, 3.101, 3.100% bacterial leaf-white, 3.100, 3.7, 3.100% of rice leaf spot.
At the time of 400mg/L, compounds 1.1, 1.2, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.12, 1.13, 1.15, 1.16, 1.17, 1.18, 1.19, 1.22, 1.25, 1.36, 1.39, 1.40, 1.43, 1.45, 1.88, 1.101, 1.104, 1.106, 1.107, 1.109, 1.110, 1.113, 1.167, 1.295, 1.354, 2.5, 2.6, 2.7, 2.8, 2.18, 2.19, 2.22 2.25, 2.43, 2.45, 2.53, 2.101, 2.104, 2.107, 2.110, 2.113, 2.167, 2.354, 3.1, 3.2, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 3.19, 3.22, 3.25, 3.36, 3.43, 3.45, 3.53, 3.101, 3.107, 3.110, 3.113, 3.354, 5.92 had a 100% control effect on chinese cabbage soft rot and tomato bacterial leaf spot.
At 8 mg/strain concentration, compounds 1.1, 1.2, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.12, 1.13, 1.15, 1.16, 1.17, 1.18, 1.19, 1.22, 1.25, 1.36, 1.39, 1.40, 1.43, 1.45, 1.88, 1.101, 1.104, 1.106, 1.107, 1.109, 1.110, 1.113, 1.167, 1.295, 1.354, 2.5, 2.6, 2.7, 2.8, 2.18, 2.19, 2.22, 2.25, 2.43, 2.45, 2.53, 2.101, 2.104, 2.107, 2.110, 2.113, 2.167, 2.354, 3.1, 3.2, 3.4, 3.5, 3.6, 3.7, 3.8, 3.19, 3.35, 3.36, 3.3.5, 3.45, 3.37, 3.3.37, 3.7, 3.35, 3.45, 3.3.3.3.35, 3.45, 3.37, 3.7, 3.35, 3.3.3.3.5, 3.3.35, 3.3.3.7, 3.35, 3.35.3.35, 3.3.3.5.3.3.7, 3.37, 3.7, 3.8, 3.9.9.17, 3.35.37.37.35.37.37, 3.3.3.5.5, 3.37, 3.3.3.3.3.3.3.3.3.3.3.3.3.3.3.3.37 mg.

Claims (8)

1. The 1, 1-dicyanooxime ether compound is characterized by being shown in a general formula I:
wherein:
w is selected from W 1 、W 3 One of the groups shown:
q is selected from Q 1 -Q 3 One of the groups shown, and, #1 is linked to W, #2 is linked to methylene,
X 1 、X 2 、X 3 、X 4 、X 5 each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, halo C 1 -C 4 Alkoxy, C 1 -C 4 A dialkylamino group;
X 10 、X 11 、X 12 、X 13 each independently selected from hydrogen, halogen;
or salts of compounds of formula I.
2. A compound according to claim 1, wherein in formula I,
w is selected from W 1 、W 3 One of the groups shown;
q is selected from Q 1 -Q 3 One of the groups shown;
X 1 、X 2 、X 3 、X 4 、X 5 each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, halo C 1 -C 4 Alkoxy, C 1 -C 4 A dialkylamino group;
X 10 、X 11 、X 12 、X 13 each independently selected from hydrogen, fluorine, chlorine, bromine;
or salts of compounds of the general formula I with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
3. A compound according to claim 2, wherein in formula I,
w is selected from W 1 、W 3 One of the groups shown;
q is selected from Q 1 -Q 3 One of the groups shown;
X 1 、X 2 、X 3 、X 4 、X 5 each independently selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, N-propyl, isopropyl, N-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2-trifluoroethyl, heptafluoroisopropyl, methoxy, ethoxy, N-propoxy, isopropoxy, difluoromethoxy, trifluoromethoxy or N, N-dimethylamino;
X 10 、X 11 、X 12 、X 13 each independently selected from hydrogen, fluorine, chlorine;
or salts of compounds of the general formula I with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
4. The compound according to claim 1, wherein the compound of formula I is selected from the group consisting of:
5. use of a compound according to claim 1 as a bactericide for controlling bacterial diseases in the agricultural and forestry fields; the bacterial disease is selected from the group consisting of melon and fruit blotch, cucumber bacterial angular blotch, rice bacterial leaf spot, rice bacterial leaf blight and potato scab.
6. Use of a compound according to claim 1 as fungicide for controlling fungal diseases in the agricultural, forestry fields; the fungal disease is selected from rice blast.
7. A bactericidal composition characterized in that: the composition comprises the compound of the general formula I as defined in claim 1 and an agriculturally acceptable carrier, wherein the weight percentage of active components in the composition is 0.1-99%.
8. A method for controlling pathogens, characterized by: a fungicidal effective amount of the fungicidal composition of claim 7 applied to a crop or a growing medium or locus of a crop.
CN202010078417.5A 2019-02-11 2020-02-03 1, 1-dicyanooxime ether compound and application thereof Active CN111548319B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910110111 2019-02-11
CN2019101101110 2019-02-11

Publications (2)

Publication Number Publication Date
CN111548319A CN111548319A (en) 2020-08-18
CN111548319B true CN111548319B (en) 2024-03-08

Family

ID=72002804

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010078417.5A Active CN111548319B (en) 2019-02-11 2020-02-03 1, 1-dicyanooxime ether compound and application thereof

Country Status (2)

Country Link
CN (1) CN111548319B (en)
WO (1) WO2020164403A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115124481B (en) * 2022-07-08 2024-09-17 中国农业大学 Malononitrile oxime ether compound, and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101875639A (en) * 2009-04-29 2010-11-03 中国中化股份有限公司 Substituted pyrimidinyl ether compound and application thereof
WO2017107939A1 (en) * 2015-12-25 2017-06-29 沈阳中化农药化工研发有限公司 Malononitrile oxime ether compound and use thereof
CN110713443A (en) * 2018-07-13 2020-01-21 沈阳中化农药化工研发有限公司 Process for preparing malononitrile oxime ether compounds and intermediate compounds

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020158391A (en) * 2017-06-13 2020-10-01 株式会社富士薬品 Novel nitrocatechol derivative

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101875639A (en) * 2009-04-29 2010-11-03 中国中化股份有限公司 Substituted pyrimidinyl ether compound and application thereof
WO2017107939A1 (en) * 2015-12-25 2017-06-29 沈阳中化农药化工研发有限公司 Malononitrile oxime ether compound and use thereof
CN106916084A (en) * 2015-12-25 2017-07-04 沈阳中化农药化工研发有限公司 A kind of malononitrile oximido ether compound and application thereof
CN106916774A (en) * 2015-12-25 2017-07-04 沈阳中化农药化工研发有限公司 A kind of reporting system for being applied to the type excretory system of plant pathogenetic bacteria III and its application
CN109942461A (en) * 2015-12-25 2019-06-28 沈阳中化农药化工研发有限公司 Malononitrile oximido ether compound and application thereof
CN110015977A (en) * 2015-12-25 2019-07-16 沈阳中化农药化工研发有限公司 A kind of malononitrile oximido ether compound and application thereof
CN110713443A (en) * 2018-07-13 2020-01-21 沈阳中化农药化工研发有限公司 Process for preparing malononitrile oxime ether compounds and intermediate compounds

Also Published As

Publication number Publication date
WO2020164403A1 (en) 2020-08-20
CN111548319A (en) 2020-08-18

Similar Documents

Publication Publication Date Title
CN109942461B (en) Malononitrile oxime ether compound and its use
KR100281248B1 (en) Substituted Carboxylic Acid Derivatives and Plant Disease Control Agents Using the Same
KR100482919B1 (en) Pyrimidine-4-one derivatives as insecticides
KR100956277B1 (en) Aromatic ether compounds, preparation and usage thereof
UA127652C2 (en) Quinoline carboxylic acid ester compound and preparation method and use thereof
CN110563645A (en) Novel quinolone compound and preparation method and application thereof
WO2021094904A2 (en) Novel sulfilimines or sulfoximines containing fungicidal heterocyclic compounds
TW201208568A (en) Novel heterocyclic alkanol derivatives
CN111548319B (en) 1, 1-dicyanooxime ether compound and application thereof
JP6975184B2 (en) Benzosultams and analogs, as well as their use as fungicides
CN113968799B (en) Malononitrile compound and application thereof
TW201206351A (en) Novel heterocyclic alkanol derivatives
CN102695699B (en) As the amino acrylates of sterilant
CN113754607B (en) Oxadiazole compound and application thereof
CN112741095B (en) Application of pyridazinone isoxazole methyl sulfide compound as bactericide
CN112745312B (en) Pyridazinone isoxazole methyl ether compound and application thereof
CN113549053B (en) Pyrazoloquine (azolyl) ether compound and application thereof
CN111484429B (en) Malononitrile compound and application thereof
CN111606825B (en) 1, 1-dicyanohydrazone compound and application thereof
CN112778232B (en) Oxime ether compound and application thereof
CN105777640B (en) Pyrazole cyclohexanediol ether compound and application thereof
CN111602661B (en) Application of 1, 1-dicyan hydrazone compound as agricultural bactericide
CN110724136B (en) Amide compound and preparation method and application thereof
CN113651718B (en) 1, 1-dicyanooxime ether compound and application thereof
CN111303048B (en) Pyrimidine guanidine compound, and preparation method and application thereof

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