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CN114106016A - Phenylpyrazoline derivative or salt thereof, composition and application thereof - Google Patents

Phenylpyrazoline derivative or salt thereof, composition and application thereof Download PDF

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Publication number
CN114106016A
CN114106016A CN202010890314.9A CN202010890314A CN114106016A CN 114106016 A CN114106016 A CN 114106016A CN 202010890314 A CN202010890314 A CN 202010890314A CN 114106016 A CN114106016 A CN 114106016A
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radical
alkyl
alkoxy
halo
substituted
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Inventor
葛尧伦
杨春河
邢阳阳
刘明东
马娥
李建国
杨庆亮
黄宝雷
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Hailir Pesticides and Chemicals Group Co Ltd
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Hailir Pesticides and Chemicals Group Co Ltd
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Priority to CN202010890314.9A priority Critical patent/CN114106016A/en
Priority to PCT/CN2020/140540 priority patent/WO2022041615A1/en
Publication of CN114106016A publication Critical patent/CN114106016A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems

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

Abstract

The invention belongs to the field of pesticides, and particularly relates to a substituted phenylpyrazoline derivative or a salt and a composition thereof acceptable as pesticides and application thereof, wherein the compound has a structure shown in a formula (I):

Description

Phenylpyrazoline derivative or salt thereof, composition and application thereof
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a phenylpyrazoline derivative or a salt and a composition thereof, and application of the compound or the salt and the composition thereof as a herbicide.
Background
With the improvement of agricultural production level, people increasingly recognize the important functions of herbicides, insecticides, bactericides and other medicaments, chemical weeding, insecticidal or bactericidal are generally adopted at present, and the herbicides, insecticides, bactericides and other medicaments are often used in the planting process of crops such as corn, soybean, cotton, wheat, rice and the like. Although the types of herbicides, insecticides, and fungicides used in agricultural production are now wide, there is still a need to continuously study the problems of high efficiency, cost, residue, and the like of the drugs such as insecticides, fungicides, and herbicides due to the continuous emergence of the problems of resistance to plant diseases, insect pests, and weeds, the efficiency of the drugs, the use cost, and the like. Among them, bioactive compounds having a phenylpyrazoline structure have been described in patents with publication numbers CN1292791A, CN1355806A, but the herbicidal activity of the plants after emergence may not be satisfactory and neither of them can have both bactericidal and herbicidal activities.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a substituted phenylpyrazoline derivative or a salt thereof, a composition and application thereof. Through a great deal of research on phenyl pyrazoline derivatives, the applicant develops a class of compounds which can be used as herbicides and/or bactericides and have very outstanding biological activity and crop safety by introducing substituted pyrazole groups based on the structure of the phenyl pyrazoline derivatives.
The technical scheme adopted by the invention for realizing the purpose is as follows: a phenylpyrazoline derivative or a salt thereof having the following structural formula:
in the formula (I), the compound is shown in the specification,
Figure BDA0002656714460000011
R1、R2、R3each independently selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radicalBase, C1-C6Alkylthio, halo C1-C6Alkylthio radical, C1-C6Alkylamino radical, halogeno C1-C6Alkylamino radical, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl radical, C2-C6Alkenyl radical, C2-C4Alkynyl, C1-C6Alkoxy-substituted C1-C6Alkyl radical, C1-C6Alkylthio substituted C1-C6Alkyl radical, C1-C6Alkoxy-substituted C1-C6Alkoxy radical, C1-C6Alkylcarbonyl group, C1-C6Alkoxycarbonyl group, C1-C6Alkylamino carbonyl, C1-C6Alkylsulfonyl, halogen, CN, NO2Hydroxyl, mercapto, carboxyl, aldehyde or amino;
R4and R5Same or different, each independently selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C1-C6Alkylthio or halogeno C1-C6An alkylthio group;
or, R4And R5Together form a radical- (CH)2)m-, m represents 1 to 6;
R6representation H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C1-C6Alkylamino radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl oxy, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C2-C6Alkenyloxy radical, C2-C6Alkenylthio radical, C2-C4Alkynyl, C1-C6Alkylcarbonyl, halo C1-C6Alkylcarbonyl group, C1-C6Alkoxycarbonyl, halo C1-C6Alkoxycarbonyl group, C1-C6Alkylaminocarbonyl, halogeno C1-C6Alkylamino carbonyl, C1-C6Alkylsulfonyl, halo C1-C6Alkylsulfonyl radical, C1-C6Alkoxy-substituted C1-C6Alkyl radical, C1-C6Alkoxy-substituted C1-C6Alkoxy radical, C3-C6Cycloalkanoyloxycarbonyl radical, C3-C6Cycloalkyl amine carbonyl, C3-C6Heterocyclic group, C3-C6Heterocyclyloxy, C3-C6Heterocyclic oxycarbonyl radical, C3-C6Heterocyclylaminocarbonyl group, C1-C6Alkyl substituted C3-C6Heterocyclyl aminocarbonyl-substituted C1-C6Alkyl, CN, halogen, NO2、COOR1、CONR1R2Mercapto, carboxyl, aldehyde, hydroxyl or amino;
further, in the formula (I), R1、R2Same or different, each independently selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C1-C6Alkylthio, halo C1-C6Alkylthio radical, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl radical, C2-C6Alkenyl radical, C2-C4Alkynyl, C1-C6Alkoxy-substituted C1-C6Alkyl radical, C1-C6Alkoxy-substituted C1-C6Alkoxy radical, C1-C6Alkylthio substituted C1-C6Alkyl, halogen, CN or amino;
R3selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C2-C6Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl, halogen, CN or amino;
R4and R5Same or different, each independently selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
or R4And R5Together form a radical- (CH)2)m-, m represents 2 to 6;
R6representation H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C1-C6Alkylamino radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl oxy, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C2-C6Alkenyloxy radical, C2-C6Alkenylthio radical, C2-C4Alkynyl, C1-C6Alkylcarbonyl, halo C1-C6Alkylcarbonyl group, C1-C6Alkoxycarbonyl, halo C1-C6Alkoxycarbonyl group, C1-C6Alkylaminocarbonyl, halogeno C1-C6Alkylamino carbonyl, C1-C6Alkylsulfonyl, halo C1-C6Alkylsulfonyl radical, C1-C6Alkoxy-substituted C1-C6Alkyl radical, C1-C6Alkoxy-substituted C1-C6Alkoxy radical, C3-C6Cycloalkanoyloxycarbonyl radical, C3-C6Cycloalkyl amine carbonyl, C3-C6Heterocyclyl aminocarbonyl-substituted C1-C6Alkyl, CN, halogen, NO2、COOR1、CONR1R2Mercapto, carboxyl, aldehyde, hydroxyl or amino;
further, in the formula (I), R1、R2Same or different, each independently selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C2-C6Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl or halo C3-C6A cycloalkyl group;
R3selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl radical, C2-C6Alkenyl radical, C2-C4Alkynyl, halogen or CN;
R4and R5Same or different, each independently selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
or R4And R5Together form a radical- (CH)2)m-, m represents 2 to 5;
R6representation H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C1-C6Alkylamino radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl radical, C2-C6Alkenyloxy radical, C2-C6Alkenylthio radical, C2-C4Alkynyl, C1-C6Alkyl carbonyl radical C1-C6Alkoxycarbonyl group, C1-C6Alkylamino carbonyl, C1-C6Alkoxy-substituted C1-C6Alkyl radical, C1-C6Alkoxy-substituted C1-C6Alkoxy, aminocarbonyl substituted C1-C6Alkyl, CN, halogen, NO2、COOR1Mercapto, carboxyl, aldehyde, hydroxyl or amino;
further, in the formula (I), R6Representation H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl radical, C1-C6Alkylcarbonyl group, C1-C6Alkoxycarbonyl group, C1-C6Alkoxy-substituted C1-C6Alkyl, aminocarbonyl substituted C1-C6Alkyl, CN, halogen, mercapto, carboxyl, hydroxyl or amino;
further, in the formula (I), R1、R2Are the same as and are each independently selected from H, C1-C6Alkyl radical, C1-C6Alkoxy or C2-C6An alkenyl group;
R3selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy radical, C2-C6Alkenyl, halogen or CN;
R4and R5Together form a radical- (CH)2)m-, m represents 3 to 5;
R6selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halogen, hydroxy or amino;
further, in the formula (I), R1、R2All are the same C1-C4An alkyl group;
R3is C1-C4An alkyl group;
R4and R5Together form a radical- (CH)2)3-or- (CH)2)4-；
R6Selected from H, C1-C4Alkyl radical, C1-C4Alkoxy, halogen, hydroxy or amino;
further, R1、R2All being the same methyl or ethyl radical, R3Is methyl or ethyl, R4And R5Together form a radical- (CH)2)3-or- (CH)2)4-，R6Selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, fluorine, chlorine, bromine, hydroxyl or amino;
further, R1、R2All being the same methyl or ethyl radical, R3Is methyl or ethyl, R4And R5Together form a radical- (CH)2)3-or- (CH)2)4-，R6Selected from H, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy, isopropoxy, fluoro, chloro, bromo, hydroxy or amino;
still further, the structure of formula (I) is any one of the following;
Figure BDA0002656714460000031
Figure BDA0002656714460000041
Figure BDA0002656714460000051
in the definitions of the structural formulae of the compounds mentioned above, the terms used have the following meanings:
C1-C6alkyl groups: a linear or branched alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, or the like.
Halogen or halogen: refers to fluorine, chlorine, bromine, iodine.
Halogen substituted C1-C6Alkyl groups: straight-chain or branched alkyl groups having 1 to 6 carbon atoms, wherein hydrogen atoms in the alkyl groups may be partially or completely substituted with halogen, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl and the like.
C1-C6Alkoxy groups: the straight chain or branched chain alkyl group having 1 to 6 carbon atoms is bonded to the structure via an oxygen atom, and examples thereof include methoxy group, ethoxy group and the like.
Halogen substituted C1-C6Alkoxy groups: straight or branched alkoxy having 1 to 6 carbon atoms, wherein hydrogen atoms in the alkoxy groups may be partially or wholly replaced by halogen, for example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, etc.
C1-C6Alkylthio group: a linear or branched alkyl group having 1 to 6 carbon atoms bonded to the structure via a sulfur atom, such as methylthio, ethylthio, etc.
Halogen substituted C1-C6Alkylthio group: straight or branched alkylthio groups having 1 to 6 carbon atoms in which hydrogen atoms are partially or wholly replaced by halogen atoms, for example, chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio and the like.
C2-C6Alkenyl: a linear or branched alkenyl group having 2 to 6 carbon atoms, for example, a vinyl group.
C2-C4Alkynyl: straight-chain or branched alkynyl having 2 to 4 carbon atoms, for example, ethynyl and the like.
C1-C6Alkylamino group: the straight chain or branched chain alkyl group having 1 to 6 carbon atoms is bonded to the structure via a nitrogen atom, for example, methylamino group, ethylamino group, etc.
Halogen substituted C1-C6Alkylamino group: straight-chain or branched alkylamino groups having 1 to 6 carbon atoms in which hydrogen atoms are partially or completely substituted with halogen, for example, chloromethylamino, dichloromethylamino, trichloromethylamino, fluoromethylamino, difluoromethylamino, trifluoromethylamino, chlorofluoromethylamino, trifluoroethylamino and the like.
C1-C6Alkoxy-substituted C1-C6Alkyl groups: by alkoxy having 1-6 carbon atoms as a substituent to carbon atomsAlkyl groups of 1 to 6 in number.
C1-C6Alkylthio substituted C1-C6Alkyl groups: a group in which an alkyl group having 1 to 6 carbon atoms is substituted with an alkylthio group having 1 to 6 carbon atoms as a substituent.
C1-C6Alkoxy-substituted C1-C6Alkoxy groups: a group in which an alkoxy group having 1 to 6 carbon atoms is substituted with an alkoxy group having 1 to 6 carbon atoms as a substituent.
C1-C6An alkylcarbonyl group: a group formed by connecting an alkyl group having 1 to 6 carbon atoms with a carbonyl group.
C1-C6Alkoxycarbonyl group: a group formed by connecting an alkoxy group having 1 to 6 carbon atoms with a carbonyl group.
C1-C6Alkylamino carbonyl group: a group formed by connecting an alkylamino group having 1 to 6 carbon atoms and a carbonyl group.
C1-C6An alkylsulfonyl group: a group formed by connecting an alkyl group having 1 to 6 carbon atoms with a sulfonyl group.
C3-C6Cycloalkyl groups: a cycloalkyl group having 3 to 6 carbon atoms.
Halogen substituted C3-C6Cycloalkyl groups: cycloalkyl groups having 3 to 6 carbon atoms, wherein hydrogen atoms in the cycloalkyl groups may be partially or completely substituted with halogen atoms.
Aminocarbonyl substituted C1-C6Alkyl groups: a group in which an alkyl group having 1 to 6 carbon atoms is substituted with a substituent group consisting of a group in which an amino group and a carbonyl group are sequentially bonded, for example, -CH2-CO-NH2。
C3-C6A cycloalkyloxycarbonyl group: a cycloalkyl group having 3 to 6 carbon atoms, an oxygen atom and a carbonyl group in this order.
C3-C6Heterocyclic group: a cycloalkyl group having 3 to 6 carbon atoms to which O, S or N is inserted.
C3-C6Heterocyclyloxy: a cycloalkyl group having 3 to 6 carbon atoms into which O is inserted,The group formed by S or N is attached to the structure via an oxygen atom bond.
C3-C6Heterocyclic oxycarbonyl group: a heterocyclic group having 3 to 6 carbon atoms, an oxygen atom and a carbonyl group in this order.
The salt is a salt acceptable to pesticides, and specifically can be a salt prepared by reacting the phenylpyrazoline derivative of the present invention with a chemically acceptable acid, wherein the chemically acceptable acid can be an inorganic acid (such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid, etc.) or an organic acid (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzoic acid, etc.); the pesticide acceptable salt can also be a salt prepared by reacting the phenylpyrazoline derivative with a chemically acceptable base, wherein the chemically acceptable base can be an inorganic base (such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate) or an organic base (such as trimethylamine, triethylamine and the like);
further, the pesticidally acceptable salt may be a potassium, sodium, ammonium, calcium, pyridinium or choline salt.
The invention also discloses a weeding composition, which comprises at least one of the phenylpyrazoline derivative or the salt thereof; preferably, the composition also comprises a preparation carrier or a preparation auxiliary agent.
Also disclosed is a method of controlling undesired plant and/or crop diseases, which comprises applying an effective amount of at least one of the phenylpyrazoline derivatives or salts thereof as described above or the fungicidal and/or herbicidal composition as described above to the undesired plants and/or crops; preferably, the crop may be a crop with or without disease.
The invention also discloses the use of at least one of the phenylpyrazoline derivatives or salts thereof as described above or of a pesticidal and/or herbicidal composition as described above for controlling and/or preventing unwanted plant and/or crop diseases.
The invention also discloses a weeding composition, which comprises a herbicidally effective amount of at least one of the phenylpyrazoline derivatives or salts thereof; preferably, the composition also comprises a preparation carrier or a preparation auxiliary agent.
The invention also discloses a bactericidal composition which comprises at least one of the phenylpyrazoline derivatives or salts thereof with bactericidal effective dose; preferably, the composition also comprises a preparation carrier or a preparation auxiliary agent.
Also disclosed is a method for controlling unwanted vegetation, which comprises applying a herbicidally effective amount of at least one of the phenylpyrazoline derivatives or salts thereof as described above or the herbicidal composition as described above to the unwanted vegetation.
The invention also discloses a method for controlling crop diseases, which comprises the steps of applying an effective amount of at least one of the phenylpyrazoline derivatives or salts thereof or the bactericidal composition on crops; preferably, the crop may be a crop with or without disease.
The invention also discloses the use of at least one of the phenylpyrazoline derivatives or salts thereof as described above or of the herbicidal compositions as described above for controlling unwanted vegetation.
The invention also discloses the application of at least one of the phenylpyrazoline derivatives or the salts thereof or the bactericidal composition on controlling crop diseases.
The compounds of the formula I can be obtained by reacting an intermediate compound of the formula (II) with an intermediate compound of the formula (III) to give the product (in the formulae given below, the substituents and symbols have the same meanings as those defined in the formula I, unless otherwise specified):
Figure BDA0002656714460000071
in order to facilitate the reaction, an alkaline reagent can be used as an acid-binding agent in the reaction process shown above, and the preferred acid-binding agent is an organic alkaline reagent such as triethylamine and the like; the solvent can be one or more selected from acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, benzene, toluene, xylene, dichloroethane and ethyl acetate.
The compounds of the formula II are known or can be prepared analogously to known processes. The synthesis can be carried out, for example, according to the method provided in patent CN99803747.8, and the compound of formula III can be prepared from pyrazole acid having the corresponding structure. Pyrazole acids having corresponding structures can be prepared according to the methods provided in patents CN1161965A or CN102224149A, wherein the conversion of amino groups includes, but is not limited to, nucleophilic substitution reaction using concentrated hydrochloric acid, substitution of amino groups with chlorine groups, formation of grignard reagent using Mg/THF, carbon dioxide introduction, hydrolysis with acidic reagent, and SOCl2The amino group can be converted into acyl chloride group by reaction.
The compounds of the formula I according to the invention have outstanding herbicidal activity against a large number of annual, monocotyledonous and dicotyledonous unwanted plants. The active substances according to the invention are also effective against perennial weeds which grow from rhizomes, or other perennial organs. As regards the timing of use of the active substances according to the invention, it may be before sowing, before germination or after germination. With particular reference to representative examples of the monocotyledonous and dicotyledonous weed populations which can be controlled by the compounds of the invention, representative examples of weed species for which the active substances of the invention can act effectively include monocotyledonous plants: annual avena, lolium, alopecurus, barnyard grass, crab grass, setaria and sedge, and perennial agropyron, bermudagrass, festuca and sorghum, and perennial sedge.
With regard to dicotyledonous weed species, the action can be extended to species such as the annual cleavers, viola, veronica, picea, chickweed, amaranthus, sinapis, ipomoea, sida, matricaria and abutilon species, and the perennial weeds cyclocarya, thistle, sorrel and artemisia. The active substances according to the invention are still effective in controlling unwanted plants, such as barnyard grass, sagittaria, alisma, eleocharis, saccharum and cyperus, under the particular conditions of sowing in rice. If the compounds of the present invention are applied to the soil surface before germination, seedlings of weeds can be completely prevented before the weeds grow out, or the weeds stop growing when they grow out of cotyledons and finally die completely after three to four weeks. Although the compounds according to the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, they do not damage or damage only insignificantly to the important crop plants of the economic sector, such as wheat, barley, rye, rice, maize, sugar beet, cotton and soybean. The compounds according to the invention are therefore very suitable for selectively controlling unwanted vegetation in agricultural crops or ornamental plants. In addition, the compound of the invention can obviously regulate the growth of crop plants. These compounds are used to target the control of plant components and to promote harvesting, such as desiccation and stunting of plants, by regulating the metabolism of plants involved. They are also suitable for regulating and inhibiting undesirable vegetation without destroying the growth of the crop plants. Inhibiting plant growth plays a very important role in many monocotyledonous and dicotyledonous crop plants, since this reduces or completely prevents lodging.
The compound of the present invention can be applied using a general formulation, and wettable powder, soluble powder, emulsifiable concentrate, aqueous emulsion, suspension, dispersible oil suspension, powder, microcapsule suspension, water dispersible granule, water soluble granule, and the like can be used. Thus the present invention also provides herbicidal compositions comprising compounds of formula I. The compounds of formula I can be formulated in a variety of ways depending on the usual biological and/or chemical physical parameters. Examples of suitable formulation choices are: wettable Powders (WP), wettable liquids (SL), Soluble Powders (SP), dispersible liquids (DC), Aqueous Solutions (AS), Microemulsions (ME), Emulsifiable Concentrates (EC), aqueous Emulsions (EW), sprayable solutions, Suspensions (SC), dispersible oil suspensions (OD), powders (DP), microcapsule suspensions (CS), water dispersible granules (WG), water Soluble Granules (SG), macrogranules (GG), granules for spreading and soil application (GR), Aerosols (AE), ultra low volume agents (ULV) and wax products. Necessary formulation auxiliaries, such as inert substances, surfactants, solvents and other additives.
Suitable active substances which can be mixed with the active substances according to the invention in a mixed or tank-mixed formulation are, for example, the substances known from the "national institute of New agricultural chemical technology" (national agricultural science and technology, published under the name 2010.9). For example, the herbicidal active substances mentioned below can be mixed with compounds of the formula I: acetochlor, butachlor, alachlor, propisochlor, metolachlor, s-metolachlor, pretilachlor, propyzamide, pretilachlor, napropamide, R-levulinyl-propyzamide, propanil, mefenacet, dibenzamide, diflufenican, flumetsulam, bromobutyrolac, dimethenamid, ethofenoxate, flufenacet, methoxyfenacet, metazachlor, isoxaben, haloxynil, flumethan-butyl, dinafop-propargyl, butachlor, propisochlor, dimethenamid, metamifop, trinitron, chloroformamid, propyzamide, pencycuramide, carprofessin, difloram, diclofenacet, butafenacet, benfluramine, mefenacet, and the, Grazing amine, bensulfuron, quinoxalamine, bensulfuron-methyl, naproxen, acetochlor, naproxen, thiachlor, metazachlor, bensulam, bensulfuron-methyl, prochloraz, chlorophthalimide, butanamide, fluazinam, atrazine, simazine, prometryn, cyanazine, simetryn, ametryn, prometryn, ipratron, flurazin, terbutryn, terbuthylazine, triazineaf-flurazon, ciprofloxacin, cyanazine, prometryn, simatong, azidezin, diuron, isopentetryn, metribuzin, terbuton, metocloprid, cyanazine, bentazon, clonazine, clonorcetryn, atrazine, omethoate, rimsulfuron, thiocyanoton, indoziflam, chlorsulfuron, meturon, bensulfuron, tribenuron, thifensulfuron-methyl, pyrazosulfuron-methyl, sulfosulfuron-methyl ether, sulfometuron, bensulfuron-methyl, Sulfometuron-methyl, nicosulfuron, ethametsulfuron, amidosulfuron, ethoxysulfuron, cyclosulfamuron, rimsulfuron, tetrazolsulfuron, flazasulfuron, monosulfuron-methyl, monosulfuron-ester, flucarbazone-methyl, flupyrsulfuron-methyl, halosulfuron-methyl, imazosulfuron, primisulfuron-methyl, prosulfuron, sulfosulfuron, trifloxysulfuron, triflusulfuron, prosulfuron, triflusulfuron-methyl, metsulfuron-methyl, primisulfuron-methyl, Propyrisulfuron, acifluorfen-methyl, acifluorfen-ethyl, fluoroglycofen-ethyl, oxyfluorfen-ethyl, cumylether, aclonifen, clofenfluroether, fluroxypyr, benfluroxypyr-methyl, trifluoromethoxyfen-methyl, metofen-ethyl, trifluoromethoxyfen-ethyl, trifluofen-ethyl, fluoroglycofen-ethyl, fluromethoxyfen, metofen-ethyl, trifluofen-ethyl, fluromethoxyfen, trifluofen-ethyl, flurometfen, fluromethoxyfen, flurometfen, benfen, flurometfen, benflurometfen, benfluridone, Fluoroglycofen-ester, Halosafen, chlortoluron, isoproturon, linuron, diuron, lufenuron, fluometuron, mefenthiuron, benzuron, sulfosulfuron, isosulfuron, tebuthiuron, clodinuron, chlorsulfuron, metsulfuron, metoxuron, bromuron, metoxuron, chlorsulfuron, mesosulfuron, cyclouron, fensulfuron, meturon, sulfosulfuron, meturon, metoxuron, cyclouron, thifensulfuron-methyl, buthiuron, kuron, cymarone, metoxuron, Chloreturon, tefluron, benuron, phenmedipham, metoron, chlon, tebuthiuron, teflubenzuron, phenmedipham, buthiuron, bensulfuron-ethyl, desmetryn, benazol, benazolin, buthan, benoxa, buthan, bencarb, buthan, benazol, buthan, benazol, buthan, p, buthan, p, buthan, benazol, p, buthan, benazol, p-methyl, p-methyl, benazol, p-methyl, p-methyl, p-methyl, p, Triallate, paraquat, diclofop, pyributicarb, dichlormate, chlometrine, ethiofen, prosulfocarb, clomazone, prosulfocarb, dichlorvos, thiobencarb, promethazine, Isopolinate, Methiobencarb, 2, 4-d butyl ester, 2 methyl 4-sodium chloride, 2, 4-d isooctyl ester, 2 methyl 4-chloroisooctyl ester, 2, 4-d sodium salt, 2, 4-d dimethylamine salt, 2 methyl 4-chloroethyl thioester, 2 methyl 4 chloride, 2, 4-d propionic acid, high 2, 4-d propionate, 2, 4-d butyric acid, 2 methyl 4 chloropropionic acid, 2 methyl 4 chloropropionate, 2 methyl 4 chlorobutyric acid, 2,4, 5-d nasal discharge propionic acid, 2,4, 5-d aldicarb acid, 2 methyl 4-chlomethionate, dicamba, norbenoxanone, valacic acid, triclosanoic acid, triclosan, metoclopramide, triclosan, mechlorvinphos, mechlorvina, dicamba, benoxanil, benazol, benazolin, and so, Diclofop-methyl, fluazifop-p-butyl, haloxyfop-methyl, haloxyfop-ethyl, quizalofop-p-ethyl, fenoxaprop-p-ethyl, propaquizafop-ethyl, fenoxaprop-p-ethyl, clodinafop-ethyl, benfop-p-butyl, benazolin-ethyl, benazolin-p-ethyl, benazolin-ethyl, benfluralin-ethyl, chloroethafloxacin, aminofluanid, benazolin-ethyl, Methalpropalin, propamol, glyphosate, anilofol, glufosinate-ethyl, thiophosphine, piproline, bialaphos, benfop-methyl, bensulide, bialaphos-ethyl, bensulide, dichlorphos, bensulin, fenphos-ethyl, mefenofos, mefenamic acid, me, Mebendazole, imazamethabenz-methyl, fluroxypyr-meptyl, clopyralid, picloram, triclopyr, dithiopyr, haloxydine, triclopyr, thiazopyr, fluridone, aminopyralid, diflufenzopyr, butoxyethyl triclopyr, Clodinate, sethoxydim, clethodim, cycloxydim, dicentrazone, clethodim, tralkoxydim, topramezone, pyroxene, Buthidazole, metribuzin, metamitron, bromoxynil, octanoyl ioxynil, dichlobenil, diphenylacetonitrile, pyraclonil, oxypyr, iobonil, Iodobonil, flumetsulam, florasulam, penoxsulam, flumetsulam, clofenapyr, diclosulam, pyriminobac, pyriftalid, pyriminobac, pyriben, pyribensulbensulbensulben, pyriben, pyribensulam, pyribensulbensulam, pyriben, pyribensulben, clomeben, pyribensulben, pyribensulbensulben, pyriben, clomeben, clomebensulben, clomeben, clofenthi, clomeben, clofenpyr, clofenthi, clofenpyr, clofenthi, clofen, Pyrithiobac-methyl, benzobicyclon, mesotrione, sulcotrione, Tembotrione, Tefuryltrione, Bicyclopyrone, ketodradox, isoxaflutole, fenoxasulfofone, Methiozolin, isopyrafen, pyraflufen, pyraflutole, difenzoquat, pyraflutole, pyroxaflutole, pyroxasulfofone, flumetsul, flumetsulam, metamitron, amicarbazone, oxadiazon, flumetsul, sulfentrazone, Bencarbazone, bisphenoxydim, butafenacil, herbicidal isoxadine, cyclanilazine, terfenadine, flupropyzamide, flupropazabicolol, indoxacarb-ethyl, flumethrin, flumethron, propyzamide, flumethazine, flumethol, carfentrazone, metolachlor, metolachlorfen, metolachlor, Bromopicloram, dimethenamid, pyridaben, Pyridafol, quinclorac, chloroquinate, bentazon, pyridate, oxaziclomefone, benazolin, isoxaflutole, cinmethylin, isopropyl pyriproxyfen, indanthrone, sodium chlorate, dalapon, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, mequat, bromophenol oxime, triazasulam, imazazole, flurtamone, ethofumesate, pyrimethanil, clohalon, fluroxypyr, pyrimethanil, acraldehyde, phenmedil, imazachlor, triazophos, aloac, diethamnaztre, ethonium, iprididamide, Ipfencarbazone, thiencazol, thifenpyrazone, pyroxim, pyrazachlor, triclopyr, pyraflufen, triclopyr, chlorpyrifos, clofenapyr, chlorpyrifos, thiofenapyrrhodinafol, thiofenapyrrhodinium, thiofenapyr-methyl, thiofenapyrrhodinil, thiofenapyr-methyl, thiofenapyrrhodinafur, thiofenapyr-methyl, thiofenapyr-methyl, thiofenapyr-methyl, thiofenapyr-p-methyl, thiopyrazachlor, thiofenapyr-methyl, thiofenapyr-p-methyl, thiofenapyr, thiopyraclostridid, thiofenapyr-methyl, thiofenapyr-p-methyl-p-methyl, chlorpyrifos-p-methyl, chlorpyrifos-methyl, chlorpyrifos-p, chlorpyrifos-methyl, chlorpyrifos-p-methyl, chlorpyrifos-methyl, chlorpyrifos.
For example, the substances mentioned below with fungicidal activity can be mixed with the compounds of the formula I: benalaxyl, benalaxyl-M, bupirimate, chiralaxyl, clozylacon, dimetrimol, ethirimol, furalaxyl, hymexazol, metalaxyl, mefenoxam, furoamide (ofaracane), oxadixyl, quinconazole, benomyl, carbendazim, diethofencarb, fuberidazole, pencycuron, probenazole, thiophanate-methyl, zoxamide, fluopyram, bixafen, boscalid, carboxin, methylfuroamide, fluopyram, flutolanil, furametryn, fenazamide, pyraoxystrobin, penthiopyrad, flufenpyrazoxazole, N- [2- (1, 3-dimethylbutyl) phenyl ] -5-fluoro-1, 3-dimethyl-1H-pyrazole-4-carboxamide, sulfindamide, azoxystrobin, cyazofamid, dimoxystrobin, trifloxystrobin, famoxadone, kresoximidazolirtisone, kresoxim-methyl, Metominostrobin, orysastrobin, pyraclostrobin, pyribencarb, picoxystrobin, trifloxystrobin, dinocap, fluazinam, fentin acetate, triphenyl tin chloride, fentin chloride, silthiopham, ethametil, blasticidin, cyprodinil, kasugamycin-hydrate hydrochloride, mepanipyrim, pyrimethanil, fenpiclonil, fludioxonil, phenoxyquinoline, ethiprole, iprodione, procymidone, vinclozolin, aminopropyl phosphonic acid, potassium aminopropyl phosphonate, edifenphos, iprobenfos, isoprothiolane, pirimiphos, methiophos-methyl, propamocarb hydrochloride, fenhexamid, epoxiconazole, bitertanol, bromuconazole, chlorotriazole, difenoconazole, diniconazole, R-diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furconazole, furazolidone, furazol, furazolidone, metconazole, pyraclostrobin, pyrimethanil, clotrimazole, pyrimethanil, fenpyr-il, fenpyr-a, fenpyr-il, fenpyr-il, fenpyr-il, fenpyr-il, fenpyr, paclobutrazol, penconazole, propiconazole, simeconazole, spiroxamine, tebuconazole, triadimefon, triadimenol, triticonazole, uniconazole, voriconazole, imazalil, oxpoconazole, fenarimol, flurprimidol, pyribenzoxim, triforine, pefurazoate, prochloraz, triflumizole, dimethomozole, aldimorph, dodecamorph acetate, fenpropimorph, tridemorph, fenpropidin, spiroxamine, naftifine, barnyard grass, terbinafine, benthiavalicarb, bialaphos, dimethomorph, flumorph, iprovalicarb, polyoxin, validamycin a, cyclopropanamide, diclocyanide (diclocymet), cyhalodiamide, tetrachlorophthalide, pyroquilon, tricyclazole, benzothiadiazole, thiabendazole, tiadinil, captan, captopril, captan, chlorothalonil, a, copper salts such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and bordeaux mixture, benfluanid, dithianon, dodine free base, ferbam, folpet, flutriafol, iminoctadine acetate, mancopper, mancozeb, maneb, metiram, zineb, propineb, sulfur and sulfur formulations including calcium polysulfide, thiram, tolylfluanid, zineb, ziram, foscarnet, amibrodol, thiocyanogen, pyridaben, carbachomycin, carvone, imazamox, chloropicrin, cyflufenamid, dazole, fenaminosulfenamide, prochloraz, imicarb, pyridaben, dichlorophen, clonidine, fenfluramine, thizamide, cyprodinil, sulfentrazone, fluometuron, fluometrazil, fluopicolide, fluopicolinafil, fluopicolinafion, fluopicolinaf, Fosetyl-aluminum, hexachlorobenzene, 8-hydroxyquinoline, iprodione, isotianil, sulbencarb, metrafenone, cyhalonil, milomycin, polymyxin, foscarnet, phthalidyl, octreone, oxamocarb, oxyfenthiin, pentachlorophenol and salts thereof, 2-phenylphenol and salts thereof, procymidone, propanamine-sodium, proquinazid, nitropyrrolidine, pentachloronitrobenzene, phyllophthalein, tetrachloronitrobenzene, imidazozine, salicylamid, cyanamide.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
through chemical modification and molecular design of phenyl pyrazoline derivatives, substituted pyrazolyl structures are introduced, a series of compounds which are more efficient, have better selectivity and safety, can be used for weeding in agriculture or forestry and/or preventing and treating crop diseases and have herbicidal activity and/or bactericidal activity are obtained, and the compounds have good activity and selectivity especially for common weeds in paddy fields and simultaneously have excellent control effect on cucumber downy mildew.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
By taking into account the economics, diversity and biological activity of the synthesized compounds, it is preferred that some of the compounds are listed in the following table. Specific compound structures are shown in table 1, and specific compound physical property data are shown in table 2. The compounds in tables 1-2 are only for better illustration of the invention and are not intended to be limiting, and those skilled in the art will not understand that the scope of the above subject matter of the invention is limited to the following compounds.
Figure BDA0002656714460000111
TABLE 1 Structure of Compounds of formula I
Figure BDA0002656714460000112
Figure BDA0002656714460000121
Figure BDA0002656714460000131
Figure BDA0002656714460000141
Figure BDA0002656714460000151
TABLE 21H NMR data
Figure BDA0002656714460000152
Figure BDA0002656714460000161
Figure BDA0002656714460000171
Figure BDA0002656714460000181
The methods for preparing the compounds of the present invention are illustrated in the following schemes and examples. The starting materials are commercially available or can be prepared by methods known in the literature or as shown in detail. It will be appreciated by those skilled in the art that other synthetic routes may also be utilized to synthesize the compounds of the present invention. Although specific starting materials and conditions for the synthetic routes are described below, they can be readily substituted with other similar starting materials and conditions, and variations or modifications of the preparation process of the present invention, such as various isomers of the compounds, are included in the scope of the present invention. In addition, the preparation methods described below may be further modified in accordance with the present disclosure using conventional chemical methods well known to those skilled in the art. For example, protecting the appropriate groups during the reaction, and the like.
Example 1
Synthesis of compound 10:
Figure BDA0002656714460000182
Figure BDA0002656714460000191
adding the intermediate 1(3.16g, 10mmol) and acetonitrile (30ml) into a reaction flask, adding the intermediate 2(1.98g, 10mmol) at 10 ℃ under stirring, adding triethylamine (2eq) under 10 ℃ under stirring for reaction, tracking the reaction by TLC (ethyl acetate: petroleum ether ═ 1:1, GF254, UV color development), after the reaction is completed, removing the solvent by spinning, and purifying the compound by column chromatography to obtain the target compound 10, which is white solid powder and has a melting point: 126 ℃ and 128 ℃;1H-NMR(CDCl3-d6,500MHz)δ:6.88(s,2H),4.31-4.28(m,2H),4.05-4.00(t,2H),3.96-3.93(t,2H),3.92-3.89(m,4H),2.78-2.73(t,2H),2.59-2.52(m,2H),2.48-2.43(m,2H),2.29-2.25(s,6H),1.99-1.93(s,2H),1.79-1.74(s,2H),1.13-1.08(m,6H)。
example 2
Synthesis of compound 11:
Figure BDA0002656714460000192
adding the intermediate 1(3.16g, 10mmol) and acetonitrile (30ml) into a reaction flask, adding the intermediate 3(2.52g, 10mmol) at 10 ℃ under stirring, adding triethylamine (2eq) under 10 ℃ under stirring for reaction, tracking the reaction by TLC (ethyl acetate: petroleum ether ═ 1:1, GF254, UV color development), after the reaction is completed, removing the solvent by spinning, and purifying the compound by column chromatography to obtain the target compound 11, which is white solid powder and has a melting point: 138 ℃ and 141 ℃;1H-NMR(CDCl3-d6,500MHz)δ:6.87(s,2H),4.33-4.30(t,2H),4.06-4.02(t,2H),3.95-3.92(t,2H),3.67-3.63(m,4H),2.72-2.68(t,2H),2.67-2.63(m,4H),2.53-2.49(s,3H),1.97-1.93(m,2H),1.77-1.74(m,2H),1.15-1.11(m,6H)。
example 3
Synthesis of compound 12:
Figure BDA0002656714460000193
adding the intermediate 1(3.16g, 10mmol) and acetonitrile (30ml) into a reaction flask, adding the intermediate 4(2.40g, 10mmol) at 10 ℃ under stirring, adding triethylamine (2eq) under 10 ℃ under stirring for reaction, tracking the reaction by TLC (ethyl acetate: petroleum ether ═ 1:1, GF254, UV color development), after the reaction is completed, removing the solvent by spinning, and purifying the compound by column chromatography to obtain the target compound 12, a light yellow solid powder, a melting point: 133-136 ℃;1H-NMR(CDCl3-d6,500MHz)δ:6.88(s,2H),4.35-4.31(t,2H),4.05-4.01(t,2H),3.93-3.90(t,2H),3.68-3.64(m,4H),2.73-2.69(t,2H),2.67-2.63(m,4H),2.54-2.50(s,3H),1.98-1.93(m,2H),1.78-1.74(m,2H),1.26-1.22(s,9H),1.16-1.11(m,6H)。
example 4
Synthesis of compound 66:
Figure BDA0002656714460000201
intermediate 1(3.16g, 10mmol), acetonitrile (30ml) were added to the reactionAdding the intermediate 5(1.84g, 10mmol) into a flask, stirring at 10 ℃, adding triethylamine (2eq) into the flask, stirring at 10 ℃, performing TLC (ethyl acetate: petroleum ether ═ 1:1, GF254, performing UV color development), after the reaction is completed, spinning out the solvent, and purifying the compound by column chromatography to obtain the target compound 66, yellow solid powder, melting point: 128-131 ℃;1H-NMR(CDCl3-d6,500MHz)δ:6.88(s,2H),4.38-4.31(t,2H),4.09-4.04(t,2H),3.97-3.95(t,2H),3.96-3.90(m,4H),2.83-2.79(m,2H),2.59-2.52(m,4H),2.49-2.43(m,2H),2.35-2.32(s,3H),2.30-2.27(s,3H),1.13-1.08(m,6H)。
example 5
Synthesis of compound 120:
Figure BDA0002656714460000202
adding the intermediate 1(3.16g, 10mmol) and acetonitrile (30ml) into a reaction flask, adding the intermediate 120(2.15g, 10mmol) at 10 ℃ under stirring, adding triethylamine (2eq) under 10 ℃ under stirring for reaction, tracking the reaction by TLC (ethyl acetate: petroleum ether ═ 1:1, GF254, UV color development), after the reaction is completed, removing the solvent, and purifying the compound by column chromatography to obtain the target compound 120, namely light yellow solid powder with a melting point: 121-123 ℃;1H-NMR(CDCl3-d6,500MHz)δ:6.86(s,2H),4.26(s,3H),4.14-4.10(m,4H),3.75-3.72(m,4H),2.66(m,2H),2.66-2.60(m,4H),2.42-2.38(s,3H),1.17-1.10(m,9H),2.13(m,2H),1.05-1.02(m,3H)。
example 6
Evaluation of herbicidal biological activity (post-emergence):
the compound to be tested is dissolved in DMF to prepare 2.5% mother liquor, and then diluted with water containing 0.1% Tween-80 for use. Sowing the target seeds in a plastic pot with the height of 9cm and the diameter of the pot mouth of 10cm, covering soil of 0.5-1cm after sowing, placing the sowed seed in a greenhouse for culture after the bottom absorbs water, performing stem and leaf spraying treatment by using a spraying tower according to the experimental design dosage when the seed grows to the two-leaf stage, and repeating the experiment for 3 times. After the soil surface liquid medicine is naturally air-dried, the soil is treated and absorbs water to 60% at the bottom, then the soil is moved into a greenhouse for culture according to a conventional method, the growth and development conditions of the test material are regularly observed, the 4 th part NY/T1155.4-2006 of the indoor bioassay test rule of the pesticide is adopted, and the weed control effect of the test agent is regularly investigated by a visual method after the treatment according to the actual conditions. Grading standard of control effect:
and 9, stage: corresponding to 67.6-100% of weeds in a blank control area;
and 8, stage: 35.1-67.5% of weeds in a blank control area;
and 7, stage: equivalent to 25.1-35% of weeds in a blank control area;
and 6, level: corresponding to 15.1-25% of weeds in a blank control area;
and 5, stage: equivalent to 10.1-15% of weeds in a blank control area;
4, level: 5.1-10% of weeds in a blank control area;
and 3, level: 2.6-5% of weeds in a blank control area;
and 2, stage: equivalent to 0-2.5% of weeds in a blank control zone;
level 1: all died.
A portion of the compound was selected and tested in parallel with a control (95% pinoxaden TC, commercially available) for herbicidal activity according to the above method. The results of the herbicidal activity experiments are shown in the following table:
TABLE 3 control Effect grades
Figure BDA0002656714460000211
Figure BDA0002656714460000221
Through the experiments, the compound protected by the invention has excellent bioactivity, particularly has good weeding effect on ryegrass and bluegrass, and has good commercial application prospect.
Example 7
Evaluation of crop safety:
preparing nutrient soil, filling the nutrient soil into a paper cup with the diameter of 10cm and the height of 9cm, scattering quantitative crop seeds into the paper cup, covering soil for 1.5cm after sowing, compacting, spraying water, culturing in a greenhouse for 2 weeks, diluting an acetone solution in which a raw pesticide of a compound to be detected is dissolved by using water containing 0.1% Tween 80 to a required concentration, carrying out stem and leaf spraying treatment by using a spraying tower according to a test design dosage (3 times of repeated treatment is set for each treatment), then placing the stem and leaf spraying treatment in the greenhouse for management according to a conventional method, regularly observing the growth and development conditions of a test material, regularly investigating the influence of a test reagent on crops by a visual method after treatment according to the actual conditions according to the part 8 of a biological assay test criterion in the pesticide chamber, and describing phytotoxicity symptoms at the same time, wherein the main symptoms comprise:
1) color change (yellowing, whitening, purplish, etc.);
2) morphological changes (new leaf malformation, distortion, etc.);
3) growth changes (dehydration, wilting, dwarfing, clumping, etc.).
And (3) evaluating and grading phytotoxicity:
a stage: no chemical injury;
b, stage: the degree of the phytotoxicity is 1-10%, and no obvious phytotoxicity exists;
c, stage: the degree of phytotoxicity is 11-30%, and slight phytotoxicity is caused;
d stage: the degree of phytotoxicity is 31-50%, moderate phytotoxicity;
e, level: the degree of phytotoxicity is 51-100%, and serious phytotoxicity is caused.
According to the method, part of compounds (compound numbers 10-13, compound numbers 16, compound numbers 19, compound numbers 66, compound numbers 69-70 and compound numbers 73) and pinoxaden are selected for carrying out parallel determination on the safety of crops. The effect of the crop safety test 3 weeks after application is shown in the following table:
TABLE 4 crop safety test
Figure BDA0002656714460000231
Figure BDA0002656714460000241
It can be seen that the compounds protected by the present invention are essentially non-phytotoxic or significantly non-phytotoxic to wheat or barley under visual inspection at the current dosage levels, and therefore, have good safety to crops, especially wheat or barley, at the appropriate dosage levels.
Example 8
And (3) evaluation of bactericidal biological activity:
weighing a certain mass of compound sample, dissolving in acetone, and preparing into mother liquor for later use. In the test, compound samples and control agents (95% Fluopyram TC, 10% Fluthiazolepyrithylone OD and 95% pinoxaden TC, which are all commercially available) were prepared into serial concentration gradient solutions (test compound and control agent concentration: 400mg/L) with 0.1% Tween 80 in water for in vivo screening. 1-leaf 1-heart pot cucumber seedlings (Sintami thorns) which grow neatly and consistently were selected as test host plants for cucumber downy mildew (Pseudoperonospora cubensis). The sprayer is a measuring spray tower, 30ml of liquid medicine is sprayed for each treatment, and the liquid medicine is naturally dried. After 24h, the pathogenic bacteria are inoculated, and a blank control is set. Spraying the cucumber downy mildew spore suspension on cucumber seedlings by using an inoculator, bagging the inoculated cucumber seedlings by using a black plastic bag for preserving moisture for 12h, picking the bags, and culturing in a greenhouse (22 ℃, RH is 50 and no light). After 4d-10d, the bactericidal activity of the compound was investigated when the seedlings grew to 4-6 true leaves. The results were examined with reference to the American society for Plant Diseases, A Manual of Association, expressed as 100-0, with "100" representing no disease and "0" representing the most severe degree of disease.
TABLE 5 results of the test on cucumber downy mildew
Figure BDA0002656714460000242
Figure BDA0002656714460000251
Figure BDA0002656714460000261
Through the experiments, the compound has excellent bactericidal bioactivity, especially has excellent control effect on cucumber downy mildew, and has good commercial application prospect.
The above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention accordingly, and not to limit the protection scope of the present invention accordingly. All equivalent changes or modifications made in accordance with the spirit of the present disclosure are intended to be covered by the scope of the present disclosure.

Claims (10)

1. A phenylpyrazoline derivative or a salt thereof having the following structural formula:
in the formula (I), the compound is shown in the specification,
Figure FDA0002656714450000011
R1、R2、R3each independently selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C1-C6Alkylthio, halo C1-C6Alkylthio radical, C1-C6Alkylamino radical, halogeno C1-C6Alkylamino radical, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl radical, C2-C6Alkenyl radical, C2-C4Alkynyl, C1-C6Alkoxy-substituted C1-C6Alkyl radical, C1-C6Alkylthio substituted C1-C6Alkyl radical, C1-C6Alkoxy-substituted C1-C6Alkoxy radical, C1-C6Alkylcarbonyl group, C1-C6Alkoxycarbonyl group, C1-C6Alkylamino carbonyl, C1-C6Alkylsulfonyl, halogen, CN, NO2Hydroxyl, mercapto, carboxyl, aldehyde or amino;
R4and R5Same or different, each independently selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C1-C6Alkylthio or halogeno C1-C6An alkylthio group;
or, R4And R5Together form a radical- (CH)2)m-, m represents 1 to 6;
R6representation H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C1-C6Alkylamino radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl oxy, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C2-C6Alkenyloxy radical, C2-C6Alkenylthio radical, C2-C4Alkynyl, C1-C6Alkylcarbonyl, halo C1-C6Alkylcarbonyl group, C1-C6Alkoxycarbonyl, halo C1-C6Alkoxycarbonyl group, C1-C6Alkylaminocarbonyl, halogeno C1-C6Alkylamino carbonyl, C1-C6Alkylsulfonyl, halo C1-C6Alkylsulfonyl radical, C1-C6Alkoxy-substituted C1-C6Alkyl radical, C1-C6Alkoxy-substituted C1-C6Alkoxy radical, C3-C6Cycloalkanoyloxycarbonyl radical, C3-C6Cycloalkyl amine carbonyl, C3-C6Heterocyclic group, C3-C6Heterocyclyloxy, C3-C6Heterocyclic oxycarbonyl radical, C3-C6Heterocyclylaminocarbonyl group, C1-C6Alkyl substituted C3-C6Heterocyclyl aminocarbonyl-substituted C1-C6Alkyl, CN, halogen, NO2、COOR1、CONR1R2Mercapto, carboxyl, aldehyde, hydroxyl or amino.
2. The phenylpyrazoline derivative or a salt thereof according to claim 1, wherein in the formula (I), R is1、R2Same or different, each independently selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C1-C6Alkylthio, halo C1-C6Alkylthio radical, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl radical, C2-C6Alkenyl radical, C2-C4Alkynyl, C1-C6Alkoxy-substituted C1-C6Alkyl radical, C1-C6Alkoxy-substituted C1-C6Alkoxy radical, C1-C6Alkylthio substituted C1-C6Alkyl, halogen, CN or amino;
R3selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C2-C6Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl, halogen, CN or amino;
R4and R5Same or different, each independently selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
or R4And R5Together form a radical- (CH)2)m-, m represents 2 to 6;
R6representation H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C1-C6Alkylamino radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl oxy, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C2-C6Alkenyloxy radical, C2-C6Alkenylthio radical, C2-C4Alkynyl, C1-C6Alkylcarbonyl, halo C1-C6Alkylcarbonyl group, C1-C6Alkoxycarbonyl, halo C1-C6Alkoxycarbonyl group, C1-C6Alkylaminocarbonyl, halogeno C1-C6Alkylamino carbonyl, C1-C6Alkylsulfonyl, halo C1-C6Alkylsulfonyl radical, C1-C6Alkoxy-substituted C1-C6Alkyl radical, C1-C6Alkoxy-substituted C1-C6Alkoxy radical, C3-C6Cycloalkanoyloxycarbonyl radical, C3-C6Cycloalkyl amine carbonyl, C3-C6Heterocyclyl aminocarbonyl-substituted C1-C6Alkyl, CN, halogen, NO2、COOR1、CONR1R2Mercapto, carboxyl, aldehyde, hydroxyl or amino.
3. The phenylpyrazoline derivative or a salt thereof according to claim 2, wherein in the formula (I), R is1、R2Same or different, each independently selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C2-C6Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl or halo C3-C6A cycloalkyl group;
R3selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl radicals、C2-C6Alkenyl radical, C2-C4Alkynyl, halogen or CN;
R4and R5Same or different, each independently selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
or R4And R5Together form a radical- (CH)2)m-, m represents 2 to 5;
R6representation H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C1-C6Alkylamino radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl radical, C2-C6Alkenyloxy radical, C2-C6Alkenylthio radical, C2-C4Alkynyl, C1-C6Alkyl carbonyl radical C1-C6Alkoxycarbonyl group, C1-C6Alkylamino carbonyl, C1-C6Alkoxy-substituted C1-C6Alkyl radical, C1-C6Alkoxy-substituted C1-C6Alkoxy, aminocarbonyl substituted C1-C6Alkyl, CN, halogen, NO2、COOR1Mercapto, carboxyl, aldehyde, hydroxyl or amino.
4. The phenylpyrazoline derivative or a salt thereof according to claim 3, wherein R is6Representation H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl radical, C1-C6Alkylcarbonyl group, C1-C6Alkoxycarbonyl group, C1-C6Alkoxy-substituted C1-C6Alkyl, aminocarbonyl substituted C1-C6Alkyl, CN, halogen, mercaptoCarboxyl, hydroxyl or amino.
5. The phenylpyrazoline derivative or a salt thereof according to any one of claims 1 to 4, wherein in the formula (I), R is1、R2Are the same as and are each independently selected from H, C1-C6Alkyl radical, C1-C6Alkoxy or C2-C6An alkenyl group;
R3selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy radical, C2-C6Alkenyl, halogen or CN;
R4and R5Together form a radical- (CH)2)m-, m represents 3 to 5;
R6selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halogen, hydroxy or amino.
6. The phenylpyrazoline derivative or a salt thereof according to claim 5, wherein in the formula (I), R is1、R2All are the same C1-C4An alkyl group;
R3is C1-C4An alkyl group;
R4and R5Together form a radical- (CH)2)3-or- (CH)2)4-；
R6Selected from H, C1-C4Alkyl radical, C1-C4Alkoxy, halogen, hydroxy or amino.
7. The phenylpyrazoline derivative or a salt thereof according to claim 1 or 6, wherein the formula (I) has any one of the following structures:
Figure FDA0002656714450000031
Figure FDA0002656714450000041
8. a fungicidal and/or herbicidal composition, characterized by comprising at least one of the phenylpyrazoline derivatives or salts thereof according to any one of claims 1 to 7; preferably, the composition also comprises a preparation carrier or a preparation auxiliary agent.
9. A method for controlling undesired plant and/or crop diseases, characterized in that it comprises applying an effective amount of at least one of the phenylpyrazoline derivatives or salts thereof according to any one of claims 1 to 7 or the fungicidal and/or herbicidal composition according to claim 8 to undesired plants and/or crops; preferably, the crop may be a crop with or without disease.
10. Use of at least one of the phenylpyrazoline derivatives or salts thereof according to any one of claims 1 to 8 or the fungicidal and/or herbicidal compositions according to claim 8 for the control and/or prevention of undesired plant and/or crop diseases.
CN202010890314.9A 2020-08-29 2020-08-29 Phenylpyrazoline derivative or salt thereof, composition and application thereof Pending CN114106016A (en)

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