CN112625035A - 5-chlorobenzoxazole derivative or salt thereof acceptable as pesticide, composition and application thereof - Google Patents

5-chlorobenzoxazole derivative or salt thereof acceptable as pesticide, composition and application thereof Download PDF

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CN112625035A
CN112625035A CN201910902876.8A CN201910902876A CN112625035A CN 112625035 A CN112625035 A CN 112625035A CN 201910902876 A CN201910902876 A CN 201910902876A CN 112625035 A CN112625035 A CN 112625035A
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alkyl
alkoxy
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CN112625035B (en
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葛家成
杨春河
胡堂路
邢阳阳
李丽
刘明东
马娥
白光耀
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Hailir Pesticides and Chemicals Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems

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  • Agronomy & Crop Science (AREA)
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Abstract

The invention belongs to the field of pesticides, and particularly relates to a 5-chlorobenzoxazole derivative or a salt acceptable as a pesticide, a composition and an application thereof, wherein the compound has a structure shown in a formula (I):

Description

5-chlorobenzoxazole derivative or salt thereof acceptable as pesticide, composition and application thereof
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a 5-chlorobenzoxazole derivative or a salt and a composition thereof acceptable as pesticides, and application of the compounds or the salt and the composition thereof acceptable as pesticides as herbicides.
Background
After the eighties of the last century, the world pesticides enter a rapid development stage, and through the development of 30 years, the pesticide composition is high in efficiency, low in toxicity and friendly to the environment, and becomes a great direction. Although the types of herbicides are various in the market at present, with the continuous expansion of the market, the problems of weed resistance, the service life of the drugs, the economic efficiency of the drugs and the like become more important, and the research and development of new pesticides become more important because people pay more attention to the problem of environmental protection. Among them, 5-chlorobenzoxazole structure is described in patent CN108084108A, but there is still a need for improvement in its biological activity and safety to crops.
Technical problem
In order to solve the above problems in the prior art, the present invention provides a 5-chlorobenzoxazole derivative or a pesticidally acceptable salt thereof, a composition and use thereof, and applicants have unexpectedly found that the above 5-chlorobenzoxazole derivative or a pesticidally acceptable salt thereof has a higher herbicidal activity than known compounds, and that it has an outstanding biological activity against common weeds in paddy fields, particularly grassy weeds, and has relatively better selectivity and crop safety.
Technical solution
The technical scheme adopted by the invention for realizing the purpose is as follows: the 5-chlorobenzoxazole derivative or its salt acceptable as pesticide can prevent and kill gramineous weed effectively and has excellent safety and selectivity to rice and other crops, and its structural formula is shown as formula (I):
Figure BDA0002212357840000011
in the formula (I), the compound is shown in the specification,
R1selected from 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, NO2Mercapto, carboxyl, aldehyde, hydroxyl or amino;
R2and R3Same 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, R2And R3Together form a radical- (CH)2)m-, m represents 1 to 7.
Further, in the formula (I), R2And R3Together form a radical- (CH)2)m-, m represents 1 to 6.
Or, further, in the formula (I),
R1selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C1-C6Alkylamino radical, C1-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, NO2Mercapto, carboxyl, aldehyde, hydroxyl or amino;
R2and R3Same or different, each independently selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6An alkoxy group;
or, R2And R3Together form a radical- (CH)2)m-, m represents 1 to 6.
Further, in the formula (I),
R1representation 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 of alkyne, C1-C6Alkylcarbonyl group, C1-C6Alkoxycarbonyl group, C1-C6Alkylamino carbonyl, C1-C6Alkoxy-substituted C1-C6Alkyl radical, C1-C6Alkoxy-substituted C1-C6Alkoxy, aminocarbonyl substituted C1-C6Alkyl, CN, halogen, NO2Mercapto, carboxyl, aldehyde, hydroxyl or amino;
R2and R3Same or different, each independently selected from H, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4An alkoxy group;
or R2And R3Together form a radical- (CH)2)m-, m represents 1 to 5.
Further, in the formula (I),
R1representation 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, C1-C6Alkylcarbonyl group, C1-C6Alkoxycarbonyl group, C1-C6Alkylamino carbonyl, C1-C4Alkoxy-substituted C1-C4Alkyl radical, C1-C4Alkoxy-substituted C1-C4Alkoxy, aminocarbonylSubstituted C1-C4Alkyl, CN, halogen, NO2Mercapto, carboxyl, aldehyde, hydroxyl or amino;
R2and R3Same or different, each independently selected from H, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4An alkoxy group;
or R2And R3Together form a radical- (CH)2)m-, m represents 1 to 4.
Further, in the formula (I),
R1representation H, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C1-C4Alkylamino radical, C3-C6Cycloalkyl radical, C2-C4Alkenyl radical, C1-C4Alkylcarbonyl group, C1-C4Alkoxycarbonyl group, C1-C4Alkylamino carbonyl, C1-C4Alkoxy-substituted C1-C4Alkyl, CN, halogen, NO2Mercapto, carboxyl, aldehyde, hydroxyl or amino;
R2and R3Same or different, each independently selected from H, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4An alkoxy group;
or R2And R3Together form a radical- (CH)2)m-, m represents 1, 3 or 4.
Further, in the formula (I), R1Represents H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH2Cl、CHF2、CH2F、CF3、CH2CF3MeO, EtO, n-PrO, i-PrO, n-BuO, i-BuO, s-BuO, t-BuO, MeS, EtS, methylamino, dimethylamino, cyclopropane, vinyl, methylcarbonyl, propylcarbonyl, methoxycarbonyl, ethoxycarbonylMethylaminocarbonyl, dimethylaminocarbonyl, methoxy-substituted ethyl, propoxy-substituted ethyl, CN, F, Cl, Br, NO2Mercapto, carboxyl, aldehyde, hydroxyl or amino;
R2and R3The same or different, are respectively and independently selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu and CH2Cl、CHF2、CH2F、CF3、CH2CF3、MeO、EtO、n-PrO、i-PrO、n-BuO、i-BuO、s-BuO、t-BuO；
Or R2And R3Together form a radical- (CH)2)m-, m represents 3 or 4.
Further, R2And R3Together form a radical- (CH)2)m-, m represents 3 or 4.
Further, the compound of formula (I) is selected from:
Figure BDA0002212357840000031
Figure BDA0002212357840000041
Figure BDA0002212357840000051
the agrochemically acceptable salt can be a salt prepared by reacting the 5-chlorobenzoxazole 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 agrochemically acceptable salt can also be a salt prepared by reacting the 5-chlorobenzoxazole derivative of the present invention 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, etc.).
Further, the salt acceptable as a pesticide may be a potassium salt, a sodium salt, an ammonium salt, a calcium salt, a pyridine salt or a choline salt.
The invention also discloses a weeding composition which comprises a herbicidally effective amount of at least one of the 5-chlorobenzoxazole derivatives or the salts thereof acceptable as pesticides.
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 to the unwanted vegetation a herbicidally effective amount of at least one of a 5-chlorobenzoxazole derivative or a salt thereof as described above or a herbicidal composition as described above.
The invention also discloses the use of the 5-chlorobenzoxazole derivative or at least one of the salts thereof acceptable as pesticides or the herbicidal composition as described above for controlling harmful plants.
In the definitions of the structural formulae of the compounds mentioned above, the terms used have the following meanings:
C1-C6alkyl groups: straight-chain or branched alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like.
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: a linear or branched alkyl group having 1 to 6 carbon atoms bonded to the structure via an oxygen atom bond.
Halogen substituted C1-C6Alkoxy groups: straight-chain or branched alkoxy groups having 1 to 6 carbon atoms in which the hydrogen atoms may be partially or wholly replaced by halogen, for exampleSuch as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy and the like.
C1-C6Alkylthio group: a linear or branched alkyl group having 1 to 6 carbon atoms bonded to the structure via a sulfur atom bond.
C1-C6Alkylamino group: a linear or branched alkyl group having 1 to 6 carbon atoms bonded to the structure via a nitrogen atom bond.
C3-C6Cycloalkyl groups: cycloalkyl groups having 3 to 6 carbon atoms such as a cyclopropane group, a cyclobutane group and a cyclopentane group.
C3-C6Cycloalkyloxy group: a cycloalkyl group having 3 to 6 carbon atoms bonded to the structure through an oxygen atom bond.
C2-C6Alkenyl: a linear or branched alkenyl group having 2 to 6 carbon atoms, such as an ethenyl group, a propenyl group and the like.
Halogen substituted C2-C6Alkenyl: a straight-chain or branched alkenyl group having 2 to 6 carbon atoms, wherein hydrogen atoms of the alkoxy groups may be partially or completely substituted with a halogen.
C2-C6Alkenyloxy: a linear or branched alkenyl group having 2 to 6 carbon atoms bonded to the structure via an oxygen atom bond.
C2-C6An alkenylthio group: a linear or branched alkenyl group having 2 to 6 carbon atoms bonded to the structure via a sulfur atom bond.
C2-C4Alkynyl: an alkynyl group having 2 to 4 carbon atoms.
C1-C6An alkylcarbonyl group: radicals formed by alkyl radicals having 1-6 carbon atoms attached to carbonyl groups, e.g.
Figure BDA0002212357840000061
Halogen substituted C1-C6An alkylcarbonyl group: radicals formed by linking alkyl radicals having 1-6 carbon atoms, the hydrogen atoms of which may be partially or wholly replaced by halogens, to carbonyl groups, e.g. chloromethylcarbonylDichloromethylcarbonyl, trichloromethylcarbonyl, fluoromethylcarbonyl, difluoromethylcarbonyl, trifluoromethylcarbonyl, chlorofluoromethylcarbonyl, trifluoroethylcarbonyl and the like.
C1-C6Alkoxycarbonyl group: examples of the group formed by linking an alkoxy group having 1 to 6 carbon atoms to a carbonyl group include methoxycarbonyl and ethoxycarbonyl.
Halogen substituted C1-C6Alkoxycarbonyl group: examples of the group formed by linking an alkoxy group having 1 to 6 carbon atoms and a carbonyl group, wherein hydrogen atoms in these alkoxy groups may be partially or entirely substituted by halogen include chloromethoxycarbonyl, dichloromethoxycarbonyl, trichloromethoxycarbonyl, fluoromethoxycarbonyl, difluoromethoxycarbonyl, trifluoromethoxy carbonyl, chlorofluoromethoxycarbonyl and trifluoroethoxycarbonyl.
C1-C6Alkylamino carbonyl group: a group formed by connecting an alkylamino group having 1 to 6 carbon atoms and a carbonyl group.
Halogen substituted C1-C6Alkylamino carbonyl group: examples of the group formed by linking an alkylamino group having 1 to 6 carbon atoms and a carbonyl group include a group in which hydrogen atoms in the alkylamino group are partially or completely substituted with a halogen, such as chloromethylaminocarbonyl, dichloromethylaminocarbonyl, trichloromethylaminocarbonyl, fluoromethylaminocarbonyl, difluoromethylaminocarbonyl, trifluoromethylaminocarbonyl, chlorofluoromethylaminocarbonyl, and trifluoroethylaminocarbonyl.
C1-C6An alkylsulfonyl group: radicals formed by linking alkyl radicals having 1-6 carbon atoms to sulphonyl radicals, e.g.
Figure BDA0002212357840000062
Halogen substituted C1-C6An alkylsulfonyl group: a group formed by linking an alkyl group having 1 to 6 carbon atoms with a sulfonyl group, wherein hydrogen atoms in these alkyl groups may be partially or entirely substituted with a halogen.
C1-C6Alkoxy-substituted C1-C6Alkyl groups: alkoxy having 1 to 6 carbon atoms is further substituted by alkoxy having 1 to 6 carbon atomsA group substituted by a row.
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, such as
Figure BDA0002212357840000063
C3-C6A cycloalkyloxycarbonyl group: a group formed by connecting a cycloalkyloxy group having 3 to 6 carbon atoms with a carbonyl group.
C3-C6Cycloalkylamine carbonyl group: a group formed by connecting a cycloalkylamino group having 3 to 6 carbon atoms with a carbonyl group.
C3-C6Heterocyclic group: a cyclic group having 3 to 6 carbon atoms containing 1 or more heteroatoms of N, O, S.
C3-C6Heterocyclyloxy: cyclic groups of 3 to 6 carbon atoms containing 1 or more N, O and/or S heteroatoms bonded to the structure via oxygen atom bonds.
C3-C6Heterocyclic oxycarbonyl group: a cyclic group having 3 to 6 carbon atoms containing 1 or more of N, O and/or S heteroatoms bonded to the structure in this order via an oxygen atom bond and a carbonyl group.
C3-C6Heterocyclylaminocarbonyl group: a cyclic group having 3 to 6 carbon atoms containing 1 or more heteroatoms of N, O and/or S is bonded to the structure via a nitrogen bond and a carbonyl group in that order.
C1-C6Alkyl substituted C3-C6Heterocyclic group: a cyclic group having 3 to 6 carbon atoms containing 1 or more N, O, S heteroatoms, whose hydrogen atoms may be partially or wholly substituted with an alkyl group having 1 to 6 carbon atoms.
Aminocarbonyl-substituted C1-C6Alkyl groups: straight or branched alkyl groups having 1 to 6 carbon atoms, wherein the hydrogen atoms of the alkyl groups may be partially or completely substituted with aminocarbonyl groups.
Halogen or halogen: refers to fluorine, chlorine, bromine, iodine.
A process for the synthesis of the compounds of formula I, in particular by acid halogenation of intermediate compounds of formula II with intermediate compounds of formula III in the presence of a base and a solvent (in the formulae given below, the substituents and symbols have the same meanings as those defined in formula I, provided they are not otherwise defined). The compounds represented by formula II can be synthesized by the method described in patent CN1036397C, and the compounds represented by formulas III and IV can be obtained commercially:
Figure BDA0002212357840000071
further, the solvent is selected from one or more of dichloromethane, toluene, DMF, DMSO, xylene, water, 1, 2-dichloroethane, tetrahydrofuran, ethanol, methanol and isopropanol.
Further, the reaction temperature is in the range of-50 to 150 ℃, preferably-10 to 100 ℃.
Further, the base is selected from triethylamine, DMF, anhydrous potassium carbonate, cesium carbonate, anhydrous sodium carbonate, potassium hydroxide, sodium hydroxide, lithium hydroxide, DBU, sodium hydrogen.
Further, the above reaction may be carried out in the presence of a dehydrating agent.
Further, the dehydrating agent is DCC, EDCI or CDI.
In particular, the compounds of formula I can be prepared according to the following synthetic routes:
Figure BDA0002212357840000081
further, AlCl as shown above3Other Lewis acids may be substituted;
further, introducing ammonia gas into the compound in the formula IX to obtain a compound shown as the general formula X;
further, the compound shown in the general formula X can be prepared into a compound shown in a general formula II in the presence of sodium hypobromite, alkali and a solvent;
further, the compound shown in the general formula II and the compound III react in the presence of a dehydrating agent to prepare the compound shown in the general formula I.
The compounds of the formula I according to the invention have outstanding herbicidal activity against a large number of annual monocotyledonous and dicotyledonous harmful 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 harmful 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 may be mixed with the mixtures of the formula I (remarks: name of the compound, either by common name according to the International organization for standardization (ISO), or by chemical name, where appropriate with a code number): 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, mefena, 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, 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, fluromet, 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, 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, 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, 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, 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, metolac, 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, thiofenapyrrhodin.
Advantageous effects
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
through chemical modification and molecular design of the 5-chlorobenzoxazole compound, a pyrazolo ring structure is introduced, and a series of compounds which are more efficient, have better selectivity and safety and have weeding activity and can be used for agriculture or forestry weeding are obtained, and the compounds have good activity and selectivity for common weeds in paddy fields, especially gramineous weeds, and have outstanding crop safety for paddy field crops, especially rice.
Modes for carrying out the invention
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 BDA0002212357840000111
TABLE 1 Structure of Compounds of formula I
Figure BDA0002212357840000112
Figure BDA0002212357840000121
Figure BDA0002212357840000131
TABLE 21H NMR data
Figure BDA0002212357840000141
Figure BDA0002212357840000151
Figure BDA0002212357840000161
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, biomaterials, etc. used in the following examples are commercially available unless otherwise specified. 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 I-1:
Figure BDA0002212357840000162
in a dry 500mL single neck flask, intermediate II (3.33g, 0.01mol) was dissolved in 100mL of dichloromethane, oxalyl chloride (1.26g, 0.01mol) and DMF (0.078g, 0.001mol) were added under ice water bath and stirred for 30min, then intermediate III-1(1.51g, 0.01mol) and triethylamine (1.01g, 0.01mol) were added and reacted for 2h, LC-MS monitored the reaction, after the reaction was completed, 100mL of water was added, extraction was carried out three times with 150mL of dichloromethane, the organic phases were combined, dried, desolventizing gave 3.86g of I-1,1H NMR(500MHz,CDCl3-d6)δ:1.79-1.88(d,3H),2.02(s,3H),2.01-2.12(t,2H),2.48-2.62(m,4H),4.01-4.10(t,2H),4.85-4.90(q,1H),7.01-7.10(s,3H),7.21-7.32(s,3H),7.52-7.61(s,1H)。
example 2
Synthesis of Compound I-3:
Figure BDA0002212357840000171
in a dry 500mL single neck flask, intermediate II (3.33g, 0.01mol) was added and dissolved in 100mL of dichloromethane, oxalyl chloride (1.26g, 0.01mol) and DMF (0.078g, 0.001mol) were added under ice water bath and stirred for 30min, after which intermediate III-3(1.65g, 0.01mol) and triethylamine (1.01g, 0.01mol) were added and reacted for 2h, LC-MS monitored the reaction, after the reaction was complete, 100mL of water was added, extracted three times with 150mL of dichloromethane, and combinedThe organic phase was dried and desolventized to give 3.86g of I-3,1H NMR(500MHz,CDCl3-d6)δ:1.31-1.42(t,3H),1.68(s,3H),2.01-2.12(t,2H),2.48-2.62(m,4H),3.02-3.14(q,2H),4.01-4.10(t,2H),4.75-4.83(q,1H),7.10-7.12(s,2H),7.25-7.31(s,1H),7.35-7.49(m,5H)。
example 3
Synthesis of Compound I-4:
Figure BDA0002212357840000172
in a dry 500mL single neck flask, intermediate II (3.33g, 0.01mol) was dissolved in 100mL of dichloromethane, oxalyl chloride (1.26g, 0.01mol) and DMF (0.078g, 0.001mol) were added under ice water bath and stirred for 30min, then intermediate III-4(1.79g, 0.01mol) and triethylamine (1.01g, 0.01mol) were added and reacted for 2h, LC-MS monitored the reaction, after the reaction was completed, 100mL of water was added, extraction was carried out three times with 150mL of dichloromethane, the organic phases were combined, dried, desolventization yielded 3.86g of I-4,1H NMR(500MHz,CDCl3-d6)δ1.25-1.35(d,6H),1.68(s,3H),1.72-1.81(m,1H),2.01-2.12(t,2H),2.48-2.62(m,4H),4.01-4.10(t,2H),4.75-4.83(q,1H),7.10-7.12(s,2H),7.25-7.31(s,1H),7.35-7.49(m,5H)。
example 4
Synthesis of Compound I-6:
Figure BDA0002212357840000181
in a dry 500mL single neck flask, intermediate II (3.33g, 0.01mol) was dissolved in 100mL of dichloromethane, oxalyl chloride (1.26g, 0.01mol) and DMF (0.078g, 0.001mol) were added under ice water bath and stirred for 30min, then intermediate III-6(1.93g, 0.01mol) and triethylamine (1.01g, 0.01mol) were added and reacted for 2h, LC-MS monitored the reaction, after the reaction was completed, 100mL of water was added, extraction was carried out three times with 150mL of dichloromethane, the organic phases were combined, dried, desolventization yielded 3.86g of I-6,1H NMR(500MHz,CDCl3-d6)δ1.35-1.45(d,9H),1.68(s,3H),2.01-2.12(t,2H),2.48-2.62(m,4H),4.01-4.10(t,2H),4.75-4.83(q,1H),7.10-7.12(s,2H),7.25-7.31(s,1H),7.35-7.49(m,5H)。
example 5
Preparation of the preparation:
1. powder preparation: weighing 20% of the compound of the formula (I) and 80% of kaolin, uniformly mixing, and crushing to obtain the product.
2. Wettable powder: weighing 20% of the compound of formula (I), 8% of calcium lignosulfonate, 2% of sodium lauryl sulfate, 3% of white carbon black and kaolin to 100%. Mixing uniformly, and performing jet milling to obtain the product.
3. Water dispersible granules: 60% of the compound of formula (I), 6% of sodium lignosulfonate, 4% of NNO (alkyl naphthalene sulfonate formaldehyde condensate), 2% of nekal BX (sodium dibutylnaphthalene sulfonate), 3% of K-12 (sodium dodecyl sulfate), 5% of carboxymethyl (ethyl) cellulose, 5% of diatomaceous earth, 5% of glucose and kaolin are weighed to 100%. Uniformly mixing, after jet milling, weighing the powder, adding water for mixing, granulating in a granulator, and then drying and screening to obtain granular products.
4. And (3) missible oil: weighing 15% of the compound of the formula (I), 5% of Nongru 700#, 5% of Nongru 500#, 6% of Nongru 1601#, 10% of cyclohexanone, 3% of N-methylpyrrolidone and solvent oil 150, adding to 100%, dissolving completely and mixing uniformly to obtain the product.
5. Suspending agent: weighing 15% of a compound shown in the formula (I), 4% of FS3000 (phosphate type anionic surfactant), 2% of NS-500LQ (nonionic hydroxy polyethylene oxide block copolymer), 0.2% of xanthan gum, 1% of magnesium aluminum silicate, 5% of ethylene glycol, 0.1% of BIT (1, 2-benzisothiazolin-3-one), 0.3% of organic modified siloxane defoamer and adding deionized water to 100%, preparing slurry, and sanding to obtain the product.
The above are all weight percentages.
Example 6
Evaluation of biological activity (post-emergence):
the compound to be tested is dissolved in DMF to prepare 2.5% mother liquor, and then diluted with 0.1% Tween-80 water for later use. Preparing nutrient soil, placing into a plastic basin with a basin mouth diameter of 10cm and a height of 9cm, scattering target seeds (barnyard grass and moleplant seed) into the plastic basin, covering soil of 0.5-1cm after sowing, placing the plastic basin in a greenhouse for culturing after absorbing water at the bottom, carrying out stem leaf spraying treatment by using a spraying tower according to the design dosage of the test when the barnyard grass grows to the 2-3 leaf stage and the 2-3 leaf stage of the moleplant seed, and repeating the test for 3 times. After the liquid medicine is naturally dried, the liquid medicine is placed in a greenhouse to be managed according to a conventional method, the growth and development conditions of the test material are regularly observed, and the weed control effect of the test agent on the weeds is regularly investigated through a visual method according to the part 4 of the bioassay test criteria in the pesticide chamber and the actual conditions after treatment. 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.
According to the above method, a part of compounds (compound numbers are shown in table 3) were selected and respectively subjected to the parallel determination of herbicidal activity with the following compounds:
metamifop (with a specific structure of
Figure BDA0002212357840000191
)、
Comparative Compound 1 (described in CN108084108A, having a specific Structure
Figure BDA0002212357840000192
)、
Control Compound 28(CN108084108A Note)The carrier has the structure that
Figure BDA0002212357840000193
)、
Control Compound 47 (described in CN108084108A, having the specific Structure
Figure BDA0002212357840000194
)、
Control Compound 49 (described in CN108084108A, having the specific Structure
Figure BDA0002212357840000195
)、
Control Compound 53 (described in CN108084108A, having a specific Structure
Figure BDA0002212357840000196
)。
The results of the herbicidal activity test after application are shown in the following table:
TABLE 3 control Effect grades
Figure BDA0002212357840000197
Figure BDA0002212357840000201
Figure BDA0002212357840000211
Figure BDA0002212357840000221
Through the experiment, the protected compound has outstanding biological activity and better commercial application prospect.
Example 7
Evaluation of biological activity in paddy field (post-emergence):
the test compound was dissolved in DMF and diluted to the desired concentration with water containing 0.1% tween 80. Preparing water, sieving, air drying, filling sandy loam into the 3/4 position (opaque flowerpot made of plastic with diameter of 11cm, bottom diameter of 7cm and height of 11 cm), adding water into each flowerpot, mixing the soil and water uniformly, and keeping the soil completely wet and smooth. The weed seeds and the rice seeds are scattered in a flowerpot and pressed into soil, the mixture is placed in a greenhouse to be managed according to a conventional method (a water layer is always kept about 1 cm), the mixture is sprayed according to an experimental design dosage when barnyard grass and moleplant seeds grow to 3-4 leaves, monochoria vaginalis grows to 3-4 leaves and rice grows to 2-3 leaves, the mixture is continuously placed in the greenhouse to be observed regularly for the growth and development conditions of the test material after application, and the weed control effect and the safety of the test agent to crops are investigated regularly through a visual inspection method after treatment according to actual conditions. According to the 8 th part and the 9 th part of the indoor bioassay test criteria of the pesticide, the weeding activity and the crop safety of the pesticide are evaluated according to the damage symptoms and severity of the tested target weeds and crops, and the unified level is adopted for investigation:
effect grading standard:
and 9, stage: 67.6-100% of weeds in a blank control area (the level is no phytotoxicity, no obvious phytotoxicity or slight phytotoxicity for crops);
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;
the main symptoms of phytotoxicity are:
1) color change (yellowing, whitening, purplish, etc.);
2) morphological changes (new leaf malformation, distortion, etc.);
3) growth changes (dehydration, wilting, dwarfing, clumping, etc.).
According to the method, part of the compounds, the metamifop and the control compounds 1, 28, 47, 49 and 53 (the specific structures are shown as the above) are selected to carry out parallel determination on the herbicidal activity and the crop safety. The experimental effects of weed control activity and crop safety 3 weeks after application are shown in the following table:
TABLE 4 Paddy field control level
Figure BDA0002212357840000231
Figure BDA0002212357840000241
Through the experiment, the protected compound has outstanding biological activity of paddy field weeds, has good effect on common weeds in the paddy field, and has good commercial application prospect; in addition, the compound protected by the invention has basically no phytotoxicity (the phytotoxicity degree is 0) or no obvious phytotoxicity (the phytotoxicity degree is 1-10%) observed by a rice visual inspection method under the current dosage, so the compound has good safety to crops, especially rice, under the proper dosage.
Example 8
Evaluation of crop safety:
the compound to be tested is dissolved in DMF to prepare 2.5% mother liquor, and then diluted with 0.1% Tween-80 water for later use. Preparing nutrient soil, placing into a plastic pot with pot mouth diameter of 10cm and height of 9cm, spreading wheat and corn seeds, covering soil of 0.5-1cm after sowing, placing in a greenhouse for culturing after bottom water absorption, performing stem and leaf spraying treatment with a spray tower according to experimental design dosage when wheat is in 3-4 leaf stage and corn is in 3-4 leaf stage, and repeating the experiment for 3 times. After the liquid medicine is naturally air-dried, the liquid medicine is placed in a greenhouse and managed according to a conventional method, the growth and development conditions of the test material are regularly observed, the influence of the tested liquid medicine on crops is regularly investigated by a visual method after treatment according to the 8 th part of the biological determination test criterion in the pesticide room and the actual condition, and the symptoms of phytotoxicity are described 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 the compounds, the metamifop and the control compounds 1, 28, 47, 49 and 53 (the specific structures are shown as the above) are selected for carrying out parallel determination on the crop safety. The effect of the crop safety test 3 weeks after application is shown in the following table:
TABLE 5 crop safety test
Compound numbering Application rate (g ai/ha) Wheat (Triticum aestivum L.) Corn (corn)
3 300 a a
12 300 a a
14 300 a a
21 300 a a
40 300 a a
45 300 a a
70 300 a a
Metamifop 300 a b
Control Compound 1 300 a b
Control Compound 28 300 a b
Control Compound 47 300 b b
Control Compound 49 300 a b
Control Compound 53 300 a b
It can be seen that the compounds protected by the present invention have substantially no phytotoxicity or no obvious phytotoxicity to wheat or corn under visual inspection at the current dosage, and therefore, have good safety to crops, especially wheat or corn, at the proper dosage.
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.
Industrial applicability
The compound of the invention can be used as a selective herbicide for paddy fields.

Claims (10)

1. A5-chlorobenzoxazole derivative or a salt thereof which is acceptable as a pesticide has a structural formula shown in formula (I):
Figure FDA0002212357830000011
in the formula (I), the compound is shown in the specification,
R1selected from 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, NO2Mercapto, carboxyl, aldehyde, hydroxyl or amino;
R2and R3Same 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, R2And R3Together form a radical- (CH)2)m-, m represents 1 to 7.
2. A5-chlorobenzoxazole derivative or a pesticidally acceptable salt thereof as claimed in claim 1 wherein R in the formula (I)2And R3Together form a radical- (CH)2)m-, m represents 1 to 6.
3. A5-chlorobenzoxazole derivative or a pesticidally acceptable salt thereof as claimed in claim 1 wherein, in the formula (I),
R1representation 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 of alkyne, C1-C6Alkylcarbonyl group, C1-C6Alkoxycarbonyl group, C1-C6Alkylamino carbonyl, C1-C6Alkoxy-substituted C1-C6Alkyl radical, C1-C6Alkoxy-substituted C1-C6Alkoxy, aminocarbonyl substituted C1-C6Alkyl, CN, halogen, NO2Mercapto, carboxyl, aldehyde, hydroxyl or amino;
R2and R3Same or different, each independently selected from H, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4An alkoxy group;
or R2And R3Together form a radical- (CH)2)m-, m represents 1 to 5.
4. A5-chlorobenzoxazole derivative or a pesticidally acceptable salt thereof as claimed in claim 1 wherein, in the formula (I),
R1representation 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, C1-C6Alkylcarbonyl group, C1-C6Alkoxycarbonyl group, C1-C6Alkylamino carbonyl, C1-C4Alkoxy-substituted C1-C4Alkyl radical, C1-C4Alkoxy-substituted C1-C4Alkoxy, aminocarbonyl substituted C1-C4Alkyl, CN, halogen, NO2Mercapto, carboxyl, aldehyde, hydroxyl or amino;
R2and R3Same or different, each independently selected from H, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4An alkoxy group;
or R2And R3Together form a radical- (CH)2)m-, m represents 1 to 4.
5. A5-chlorobenzoxazole derivative or a pesticidally acceptable salt thereof as claimed in claim 1 wherein, in the formula (I),
R1representation H, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C1-C4Alkylamino radical, C3-C6Cycloalkyl radical, C2-C4Alkenyl radical, C1-C4Alkylcarbonyl group, C1-C4Alkoxycarbonyl group, C1-C4Alkylamino carbonyl, C1-C4Alkoxy-substituted C1-C4Alkyl, CN, halogen, NO2Mercapto, carboxyl, aldehyde, hydroxyl or amino;
R2and R3Same or different, each independently selected from H, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4An alkoxy group;
or R2And R3Together form a radical- (CH)2)m-, m represents 1, 3 or 4.
6. A5-chlorobenzoxazole derivative or a pesticidally acceptable salt thereof as claimed in claim 1 wherein R in the formula (I)1Represents H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH2Cl、CHF2、CH2F、CF3、CH2CF3MeO, EtO, n-PrO, i-PrO, n-BuO, i-BuO, s-BuO, t-BuO, MeS, EtS, methylamino, dimethylamino, cyclopropane, vinyl, methylcarbonyl, propylcarbonyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, methoxy-substituted ethyl, propoxy-substituted ethyl, CN, F, Cl, Br, NO2Mercapto, carboxyl, aldehyde, hydroxyl or amino;
R2and R3The same or different, are respectively and independently selected from H, Me, Et, n-Pr, i-Pr and n-Bu、i-Bu、s-Bu、t-Bu、CH2Cl、CHF2、CH2F、CF3、CH2CF3、MeO、EtO、n-PrO、i-PrO、n-BuO、i-BuO、s-BuO、t-BuO；
Or R2And R3Together form a radical- (CH)2)m-, m represents 3 or 4.
7. A5-chlorobenzoxazole derivative or a pesticidally acceptable salt thereof as claimed in any one of claims 1 to 6 wherein the compound of formula (I) is selected from:
Figure FDA0002212357830000021
Figure FDA0002212357830000031
Figure FDA0002212357830000041
8. a herbicidal composition, characterized by comprising a herbicidally effective amount of at least one of 5-chlorobenzoxazole derivatives or salts thereof as pesticidally acceptable as claimed in 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 unwanted vegetation which comprises applying a herbicidally effective amount of at least one of a 5-chlorobenzoxazole derivative or a salt thereof as a pesticidally acceptable salt thereof as claimed in any one of claims 1 to 7 or a herbicidal composition as claimed in claim 8 to the unwanted vegetation.
10. Use of a 5-chlorobenzoxazole derivative or at least one of its salts as a pesticidally acceptable salt as claimed in any one of claims 1 to 7 or a herbicidal composition as claimed in claim 8 for controlling unwanted vegetation.
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CN1195753C (en) * 1998-09-09 2005-04-06 石原产业株式会社 Fused-benzene derivatives useful as herbicides
CN104277033A (en) * 2013-07-02 2015-01-14 湖南化工研究院 N-(arylalkyl)aryloxy phenoxy carboxylic acid amide compounds, and preparation method and application thereof
CN106172458A (en) * 2015-06-01 2016-12-07 四川利尔作物科学有限公司 Herbicidal combinations and application thereof
CN108084108A (en) * 2017-12-28 2018-05-29 青岛清原化合物有限公司 A kind of 5- Lv benzoxazole derivatives and preparation method thereof, Herbicidal combinations and application
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CN1141876C (en) * 1998-07-25 2004-03-17 东部韩农化学株式会社 Herbicidal phenoxypropionic acid N-alkyl-N-2-fluorophenyl amide compounds
CN1195753C (en) * 1998-09-09 2005-04-06 石原产业株式会社 Fused-benzene derivatives useful as herbicides
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