CN112625035B - 5-chlorobenzoxazole derivative or salt acceptable as pesticide, composition and application thereof - Google Patents

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

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CN112625035B
CN112625035B CN201910902876.8A CN201910902876A CN112625035B CN 112625035 B CN112625035 B CN 112625035B CN 201910902876 A CN201910902876 A CN 201910902876A CN 112625035 B CN112625035 B CN 112625035B
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CN112625035A (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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  • General Health & Medical Sciences (AREA)
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Abstract

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

Description

5-chlorobenzoxazole derivative or salt 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 which are acceptable as pesticides, and application of the compounds or the salt and the composition thereof which are acceptable as pesticides as herbicides.
Background
After the eighties of the last century, the world pesticides enter a rapid development stage, and after 30 years of development, the pesticide has high efficiency, low toxicity and environmental friendliness and becomes a great direction. The existing herbicides on the market are various, but with the continuous expansion of the market, the problems of weed resistance, the service life of the medicines, the economy of the medicines and the like become particularly important, and meanwhile, as people pay more attention to the environmental protection problem, the research and development of new pesticides become particularly important. Among them, for the 5-chlorobenzoxazole structure, it is described in the patent of CN108084108A, but there is still a need for improvement in its bioactivity and safety to crops.
Technical problem
In order to solve the above-mentioned problems occurring in the prior art, the present invention provides a 5-chlorobenzoxazole derivative or a pesticidally acceptable salt thereof, a composition and use thereof, and the applicant has unexpectedly found that the above-mentioned 5-chlorobenzoxazole derivative or a pesticidally acceptable salt thereof has higher herbicidal activity than known compounds, and that it has 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 achieving the purpose is as follows: the 5-chlorobenzoxazole derivative or the salt thereof which is acceptable as pesticide can effectively control grassy weeds, has outstanding safety and selectivity to crops such as paddy, and the structural formula of the 5-chlorobenzoxazole derivative is shown as the formula (I):
in the formula (I) of the present invention,
R 1 selected from H, C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio, C 1 -C 6 Alkylamino, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl oxy, C 2 -C 6 Alkenyl, halo C 2 -C 6 Alkenyl, C 2 -C 6 Alkenyloxy, C 2 -C 6 Alkenylthio, C 2 -C 4 Alkynyl, C 1 -C 6 Alkylcarbonyl, halo C 1 -C 6 Alkylcarbonyl, C 1 -C 6 Alkoxycarbonyl, halo C 1 -C 6 Alkoxycarbonyl group, C 1 -C 6 Alkylaminocarbonyl, haloC 1 -C 6 Alkylaminocarbonyl, C 1 -C 6 Alkylsulfonyl, haloC 1 -C 6 Alkylsulfonyl, C 1 -C 6 Alkoxy substituted C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy substituted C 1 -C 6 Alkoxy, C 3 -C 6 Cycloalkyl-oxycarbonyl, C 3 -C 6 Cycloalkylaminocarbonyl, C 3 -C 6 Heterocyclyl, C 3 -C 6 Heterocyclyloxy, C 3 -C 6 Heterocyclyloxycarbonyl, C 3 -C 6 Heterocyclylaminocarbonyl, C 1 -C 6 Alkyl substituted C 3 -C 6 Heterocyclyl, aminocarbonyl substituted C 1 -C 6 Alkyl, CN, halogen, NO 2 Mercapto, carboxyl, aldehyde, hydroxyl or amino;
R 2 and R is 3 Identical or different, each independently selected from H, C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio or halogen C 1 -C 6 Alkylthio;
alternatively, R 2 And R is 3 Together form a group- (CH) 2 ) m M represents 1 to 7.
Further, in formula (I), R 2 And R is 3 Together form a group- (CH) 2 ) m M represents 1 to 6.
Or, further, in the formula (I),
R 1 selected from H, C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio, C 1 -C 6 Alkylamino, C 1 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl oxy, C 2 -C 6 Alkenyl, halo C 2 -C 6 Alkenyl, C 2 -C 6 Alkenyloxy, C 2 -C 6 Alkenylthio, C 2 -C 4 Alkynyl, C 1 -C 6 Alkylcarbonyl, halo C 1 -C 6 Alkylcarbonyl, C 1 -C 6 Alkoxycarbonyl, halo C 1 -C 6 Alkoxycarbonyl group, C 1 -C 6 Alkylaminocarbonyl, haloC 1 -C 6 Alkylaminocarbonyl, C 1 -C 6 Alkylsulfonyl, haloC 1 -C 6 Alkylsulfonyl, C 1 -C 6 Alkoxy substituted C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy substituted C 1 -C 6 Alkoxy, C 3 -C 6 Cycloalkyl-oxycarbonyl, C 3 -C 6 Cycloalkylaminocarbonyl, C 3 -C 6 Heterocyclyl, aminocarbonyl substituted C 1 -C 6 Alkyl, CN, halogen, NO 2 Mercapto, carboxyl, aldehyde, hydroxyl or amino;
R 2 and R is 3 Identical or different, each independently selected from H, C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, halo C 1 -C 6 An alkoxy group;
alternatively, R 2 And R is 3 Together form a group- (CH) 2 ) m M represents 1 to 6.
Further, in the formula (I),
R 1 representation H, C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio, C 1 -C 6 Alkylamino, C 3 -C 6 Cycloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkenyloxy, C 2 -C 6 Alkenylthio, C 2 -C 4 Alkynyl, C 1 -C 6 Alkylcarbonyl, C 1 -C 6 Alkoxycarbonyl group, C 1 -C 6 Alkylaminocarbonyl, C 1 -C 6 Alkoxy substituted C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy substituted C 1 -C 6 Alkoxy, aminocarbonyl substituted C 1 -C 6 Alkyl, CN, halogen, NO 2 Mercapto, carboxyl, aldehyde, hydroxy orAn amino group;
R 2 and R is 3 Identical or different, each independently selected from H, C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, halo C 1 -C 4 An alkoxy group;
or R is 2 And R is 3 Together form a group- (CH) 2 ) m M represents 1 to 5.
Further, in the formula (I),
R 1 representation H, C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio, C 1 -C 6 Alkylamino, C 3 -C 6 Cycloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkenyloxy, C 1 -C 6 Alkylcarbonyl, C 1 -C 6 Alkoxycarbonyl group, C 1 -C 6 Alkylaminocarbonyl, C 1 -C 4 Alkoxy substituted C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy substituted C 1 -C 4 Alkoxy, aminocarbonyl substituted C 1 -C 4 Alkyl, CN, halogen, NO 2 Mercapto, carboxyl, aldehyde, hydroxyl or amino;
R 2 and R is 3 Identical or different, each independently selected from H, C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, halo C 1 -C 4 An alkoxy group;
or R is 2 And R is 3 Together form a group- (CH) 2 ) m M represents 1 to 4.
Further, in the formula (I),
R 1 representation H, C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, C 1 -C 4 Alkylthio, C 1 -C 4 Alkylamino, C 3 -C 6 Cycloalkyl, C 2 -C 4 Alkenyl, C 1 -C 4 Alkylcarbonyl, C 1 -C 4 Alkoxycarbonyl group, C 1 -C 4 Alkylaminocarbonyl, C 1 -C 4 Alkoxy substituted C 1 -C 4 Alkyl, CN, halogen, NO 2 Mercapto, carboxyl, aldehyde, hydroxyl or amino;
R 2 and R is 3 Identical or different, each independently selected from H, C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, halo C 1 -C 4 An alkoxy group;
or R is 2 And R is 3 Together form a group- (CH) 2 ) m M represents 1, 3 or 4.
Further, in formula (I), R 1 Represent H, me, et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH 2 Cl、CHF 2 、CH 2 F、CF 3 、CH 2 CF 3 MeO, etO, n-PrO, i-PrO, n-BuO, i-BuO, s-BuO, t-BuO, meS, etS, methylamino, dimethylamino, cyclopropanyl, vinyl, methylcarbonyl, propylcarbonyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, methoxy-substituted ethyl, propoxy-substituted ethyl, CN, F, cl, br, NO 2 Mercapto, carboxyl, aldehyde, hydroxyl or amino;
R 2 and R is 3 Identical or different, each independently selected from H, me, et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH 2 Cl、CHF 2 、CH 2 F、CF 3 、CH 2 CF 3 、MeO、EtO、n-PrO、i-PrO、n-BuO、i-BuO、s-BuO、t-BuO；
Or R is 2 And R is 3 Together form a group- (CH) 2 ) m M represents 3 or 4.
Further, R 2 And R is 3 Together form a group- (CH) 2 ) m M represents 3 or 4.
Further, the structural compound of formula (I) is selected from:
the salt which is acceptable as pesticide can be a salt prepared by reacting the 5-chlorobenzoxazole derivative with a chemically acceptable acid, wherein the chemically acceptable acid can be inorganic acid (such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid and the like) or organic acid (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzoic acid and the like); the pesticidally acceptable salt may also be a salt obtained by reacting the 5-chlorobenzoxazole derivative of the present invention with a chemically acceptable base, wherein the chemically acceptable base may be an inorganic base (e.g., sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate) or an organic base (e.g., trimethylamine, triethylamine, etc.).
Further, the salt acceptable as a pesticide may be potassium salt, sodium salt, ammonium salt, calcium salt, pyridine salt or choline salt.
The invention also discloses a weeding composition, which comprises an effective weeding amount of at least one of the 5-chlorobenzoxazole derivative or the salt thereof which can be accepted as pesticide.
Preferably, a formulation carrier or formulation aid is also included.
Also disclosed is a method of controlling unwanted vegetation which comprises applying a herbicidally effective amount of at least one of the 5-chlorobenzooxazole derivatives as described above or as a pesticidally acceptable salt thereof or a herbicidal composition as described above to the unwanted vegetation.
The invention also discloses the use of at least one of the 5-chlorobenzoxazole derivatives or the salts thereof as described above as an agrochemical acceptable or the herbicidal composition as described above for controlling harmful plants.
In the definition of the structural formula of the above compounds, the terms used have the following meanings:
C 1 -C 6 alkyl: straight or branched alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl or n-butyl, isobutyl, sec-butyl, tert-butyl and the like.
Halogenated C 1 -C 6 Alkyl: straight-chain or branched alkyl groups having 1 to 6 carbon atoms, and hydrogen atoms on these alkyl groups may be partially or entirely substituted with halogen, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl and the like.
C 1 -C 6 An alkoxy group: a straight or branched alkyl group having 1 to 6 carbon atoms is bonded to the structure through an oxygen atom bond.
Halogenated C 1 -C 6 An alkoxy group: straight-chain or branched alkoxy groups having 1 to 6 carbon atoms, and hydrogen atoms on these alkoxy groups may be partially or entirely substituted with halogen, for example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy and the like.
C 1 -C 6 Alkylthio: a straight or branched alkyl group having 1 to 6 carbon atoms is bonded to the structure via a sulfur atom bond.
C 1 -C 6 Alkylamino: a straight or branched alkyl group having 1 to 6 carbon atoms is bonded to the structure through a nitrogen atom bond.
C 3 -C 6 Cycloalkyl: cycloalkyl having 3 to 6 carbon atoms, such as cyclopropane group, cyclobutane group, cyclopentane group and the like.
C 3 -C 6 Cycloalkyloxy: cycloalkyl groups having 3 to 6 carbon atoms are bonded to the structure through an oxygen atom bond.
C 2 -C 6 Alkenyl: straight or branched alkenyl groups having 2 to 6 carbon atoms, such as vinyl, propenyl, and the like.
Halogenated C 2 -C 6 Alkenyl: straight-chain or branched alkenyl groups having 2 to 6 carbon atoms, and hydrogen atoms on these alkoxy groups may be partially or entirely substituted with halogen.
C 2 -C 6 Alkenyloxy: a straight or branched alkenyl group having 2 to 6 carbon atoms is bonded to the structure via an oxygen atom bond.
C 2 -C 6 An alkenylthio group: a straight or branched alkenyl group having 2 to 6 carbon atoms is bonded to the structure via a sulfur atom bond.
C 2 -C 4 Alkynyl: alkynyl with 2-4 carbon atoms.
C 1 -C 6 Alkylcarbonyl: groups formed by linking alkyl groups having 1-6 carbon atoms to carbonyl groups, e.g.
Halogenated C 1 -C 6 Alkylcarbonyl: the group formed by linking an alkyl group having 1 to 6 carbon atoms to a carbonyl group may have a part or all of hydrogen atoms on the alkyl group substituted with halogen, for example, chloromethylcarbonyl, dichloromethylcarbonyl, trichloromethylcarbonyl, fluoromethylcarbonyl, difluoromethylcarbonyl, trifluoromethylcarbonyl, chlorofluoromethylcarbonyl, trifluoroethylcarbonyl and the like.
C 1 -C 6 Alkoxycarbonyl: and a group formed by linking an alkoxy group having 1 to 6 carbon atoms to a carbonyl group, for example, a methoxycarbonyl group, an ethoxycarbonyl group, or the like.
Halogenated C 1 -C 6 Alkoxycarbonyl: the group formed by linking an alkoxy group having 1 to 6 carbon atoms to a carbonyl group may have a part or all of hydrogen atoms in the alkoxy group substituted by halogen, for example, chloromethoxycarbonyl, dichloromethoxycarbonyl, trichloromethoxycarbonyl, fluoromethoxycarbonyl, difluoromethoxycarbonyl, trifluoromethoxycarbonyl, chlorofluoromethoxycarbonyl, trifluoroethoxycarbonyl and the like.
C 1 -C 6 Alkylaminocarbonyl group: a group formed by linking an alkylamino group having 1 to 6 carbon atoms to a carbonyl group.
Halogenated C 1 -C 6 Alkylaminocarbonyl group: the group formed by linking an alkylamino group having 1 to 6 carbon atoms to a carbonyl group may have a part or all of the hydrogen atoms on the alkylamino group substituted with halogen, for example, chloromethyl aminocarbonyl group, dichloromethylaminocarbonyl group, trichloromethylaminocarbonyl group, fluoromethylaminocarbonyl group, difluoromethylaminocarbonyl group, trifluoromethylaminocarbonyl group, chlorofluoromethylaminocarbonyl group, trifluoroethylaminocarbonyl group and the like.
C 1 -C 6 Alkylsulfonyl: groups formed by linking alkyl groups having 1 to 6 carbon atoms to sulfonyl groups, e.g.
Halogenated C 1 -C 6 Alkylsulfonyl: the group formed by linking an alkyl group having 1 to 6 carbon atoms with a sulfonyl group may have a part or all of hydrogen atoms in the alkyl group substituted with halogen.
C 1 -C 6 Alkoxy substituted C 1 -C 6 Alkyl: and 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.
C 1 -C 6 Alkoxy substituted C 1 -C 6 An alkoxy group: groups 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, e.g.
C 3 -C 6 Cycloalkyl-oxycarbonyl: a group formed by linking a cycloalkyloxy group having 3 to 6 carbon atoms to a carbonyl group.
C 3 -C 6 Cycloalkylamine carbonyl: a group formed by linking a cycloalkylamino group having 3 to 6 carbon atoms to a carbonyl group.
C 3 -C 6 A heterocyclic group: a cyclic group having 3 to 6 carbon atoms and containing 1 or more N, O, S hetero atoms.
C 3 -C 6 Heterocyclyloxy: containing 1 or moreA cyclic group of 3 to 6 carbon atoms of N, O and/or S heteroatoms, linked to the structure via an oxygen atom bond.
C 3 -C 6 Heterocyclyloxycarbonyl group: a cyclic group having 3 to 6 carbon atoms and containing 1 or more hetero atoms of N, O and/or S is sequentially connected to the structure via an oxygen atom bond and a carbonyl group.
C 3 -C 6 Heterocyclylaminocarbonyl group: a cyclic group containing 1 or more N, O and/or S heteroatoms and having 3 to 6 carbon atoms, which is linked to the structure via a nitrogen atom bond and a carbonyl group.
C 1 -C 6 Alkyl substituted C 3 -C 6 A heterocyclic group: a cyclic group having 3 to 6 carbon atoms containing 1 or more hetero atoms of N, O, S, and the hydrogen atom of the cyclic group may be partially or wholly substituted with an alkyl group having 1 to 6 carbon atoms.
Aminocarbonyl-substituted C 1 -C 6 Alkyl: straight-chain or branched alkyl groups having 1 to 6 carbon atoms, and hydrogen atoms on these alkyl groups may be partially or entirely substituted with an aminocarbonyl group.
Halogen or halogen: refers to fluorine, chlorine, bromine and iodine.
The synthesis method of the compound shown in the formula I comprises the steps of carrying out acyl halogenation on an intermediate compound shown in the formula II and then reacting with an intermediate compound shown in the formula III in the presence of alkali and a solvent (in the chemical formulas listed below, substituents and symbols have the same meanings as the substituents and symbols defined in the formula I as long as the substituents and symbols are not defined otherwise). The compounds of formula II can be synthesized by the method described in patent CN1036397C, and the compounds of formula III and IV can be obtained commercially:
further, the solvent is selected from one or more solvents selected from dichloromethane, toluene, DMF, DMSO, xylene, water, 1, 2-dichloroethane, tetrahydrofuran, ethanol, methanol, isopropanol.
Further, the reaction temperatures are in the range of-50 to 150℃and 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.
Specifically, the compounds of formula I may be prepared according to the following synthetic route:
further, alCl as shown above 3 Other lewis acids may be substituted;
further, introducing ammonia gas into the compound shown in the formula IX to obtain a compound shown in the formula X;
further, the compound shown in the general formula X can be obtained in the presence of sodium hypobromite, alkali and solvent to obtain the compound shown in the general formula II;
further, the compound shown in the general formula II reacts with the compound III in the presence of a dehydrating agent to prepare the compound shown in the general formula I.
The compounds of formula I of the present invention have outstanding herbicidal activity against many annual monocotyledonous and dicotyledonous harmful plants. The actives of the present invention are also effective against perennial weeds that grow from rhizomes, or other perennial organs. As regards the use of the active substances according to the invention, this may be before sowing, before germination or after germination. In particular, mention is made of representative examples of monocotyledonous and dicotyledonous weed populations which can be controlled by the compounds according to the invention, representative examples of weed species which can be effective for the active substances according to the invention include monocotyledonous plants: annual oat, lolium, myrtle, barnyard grass, crabgrass, green bristlegrass and sedge, and perennial agrocybe, bermuda, cogongrass and sorghum, and perennial sedge.
Regarding dicotyledonous weed species, the effects of which can be extended to species such as the annual galium, viola, veronica, sesamum, chickweed, amaranthus, sinapis, sweet potato, sida, chamomile and abutilon, and perennial weeds inula, thistle, sorangium and mugwort. The active substances of the invention can still effectively control harmful plants under the specific condition of rice sowing, such as barnyard grass, arrowhead, alisma, chufa, kefir and sedge. If the compounds according to the invention are applied to the soil surface before germination, seedlings of the weeds can be completely prevented before the weeds grow or the growth can be stopped when the weeds grow out of the cotyledons and finally die completely after three to four weeks. Although the compounds of the invention have good herbicidal activity against monocotyledonous and dicotyledonous weeds, there is no, or very little, damage to important commercial crop plants, such as wheat, barley, rye, rice, maize, sugar beet, cotton and soybean. The compounds of the invention are therefore very suitable for the selective control of unwanted plants in agricultural crops or ornamental plants. In addition, the compounds of the invention can obviously regulate the growth of crop plants. These compounds are used to direct control of plant components and to promote harvest, such as desiccation and dwarf growth, by modulating plant metabolism. But they are also suitable for regulating and inhibiting unwanted plant growth without damaging the growth of the crop. Inhibition of plant growth plays a very important role in many monocot and dicot crops, as lodging can be reduced or prevented entirely.
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 herbicide compositions comprising the compounds of formula I. The compounds of formula I may 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 Solutions (SL), soluble Powders (SP), dispersible solutions (DC), aqueous Solutions (AS), microemulsions (ME), emulsifiable Concentrates (EC), aqueous Emulsions (EW), sprayable solutions, suspensions (SC), dispersible oil suspensions (OD), powders (DP), microencapsulated suspensions (CS), water dispersible granules (WG), water Soluble Granules (SG), macrogranules (GG), granules (GR) for broadcasting and soil application, 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 admixed with the active substances according to the invention in the formulation or tank mix are, for example, the substances known from the world technical university of new agricultural chemicals (national agricultural science and technology Press, 2010.9). For example, the herbicide active substances mentioned below can be mixed with mixtures of the formula I, (remark: the name of the compound, either the usual name according to the International organization for standardization (ISO), or the chemical name, where appropriate with code): acetochlor, butachlor, alachlor, metolachlor, pretilachlor, naproxen, R-naproxen, propanil, mefenacet, bispyribac-sodium, diflufenican, oxadiazon, fluobutachlor, bromobutachlor, dimethenamid, mefenacet, acetochlor, flufenacet, mefenacet, metazachlor, diflufenican clomazone, high-efficiency wheat straw fluoromethyl ester, high-efficiency wheat straw fluoropropyl ester, dipropamid, clethodim, butyramide, cyproconazole, fluorosulfonamide, heptanamide, ibudimide, propyne, terbutamide, xylylenediamine, dimethenamine, larchlor, tricyclooxamide, chloroformyl amine, propyne, penoxsulam, carpronium, neo-Yan, tricyclothiabendazole, butachlor the composition comprises the following components of forage grass, benoxamine, quinolizine, benoxamide, napropylamine, acetochlor, naproxen, thiabendazole, pyrifenacet, benoxaden, oxaden, chlorthalimide, dingan, fluopicolide, atrazine, simazine, prometryn, cyanogen, simetryn, amethodim, chlorphenamine, isoproturon, flubenoxazine, terbutryn, terbutazine, triazachlor, ciprofen, asphanate, indac, amitrazine, tembot, azido, diquat, isofioxazine, atrazine, terbutryn, zhong Dingtong, terbutamid, methoprene, chlorphenamine, imazamox, colazine, atrazine, imazamox, liquorice, cyanuric acid, azazin, chlorsulfuron, mesosulfuron, bensulfuron, chlorsulfuron, bensulfuron, sulfosulfuron, thiosulfuron, mesosulfuron, methyl sodium, iodosulfuron, sulfamethoxide, and pyriminomethyl, ether-sulfuron, methyl-sulfuron, nicosulfuron, amisulfuron, acyl-sulfuron, ethoxysulfuron, cyclosulfamuron, rimsulfuron, tetrazole-sulfuron, flazasulfuron, monosulfuron, pyriminosulf-ethyl flucarbazone, fluflazasulfuron, flupyrazosulfuron, cycloxaprid, pyrazosulfuron, fluazosulfuron, propylbenzene, trifloxysulfuron, sulfonylsulfuron, trifloxysulfuron, flusulfamuron trifloxysulfuron, sodium salt of methylsulfuron, flupyrsulfuron, methylsulfuron-methyl, pyriminosulf-methyl, propyrithiosulfuron, oxaziclomefone, acifluorfen, fomesafen, lactofen, fluoroglycofen-ethyl, oxyfluorfen, cumyl ether, benfen, clofluroxypyr-meptyl, carbobenzoxim, trifluoperal, methoxyben-m-ethyl, trinitrofen, fluorobenfen Flurofen, herbicidal ethers, methofen, dimethachlor, fluoroester oxime ether, fluoroxyfen, haloafen, chlormeuron, isoproturon, linuron, diuron, sepouron, flubenuron, thidiazuron, methabenzthiazuron, benzbenuron, sulfometuron, isoxaben, tebuthiuron, clodinafop-propargyl, tribenuron-methyl, meturon, acyl-sodium, methoxyfenoxaprop, bromuron, methoxymethyl, chlormeuron, meturon, cyclouron, fecaluron, dithiouron, diuron, cumuron, diuron, isodiuron, cyclouron, thifluuron, buthiuron, diuron, p-fluuron, methamidothiazuron, long Caote, triisourea, oxazomet, monisouron, anisuron, methiuron, chloreturon, tetrafluoro-ron, benazolin-ethyl, benazolin, sulbenazolin, terbenazolin, avenanthramide, anil, chlorpropham, clomazone, clodinafop-propargyl, carboxazole, chlorprocarb, fenasulam, BCPC, CPPC, carbasulam, butoxide, prosulfocarb, imago, graminetin, imago, pyribenzoxim, imazamox, barnyard, cyclobenfop, avenanthramide, thiofida, ethionamide, prosulfocarb, captan, prosulfocarb, secondary prosulfocarb, thioprosulfocarb, oxadiazon, isopolinate, methiobencarb, 2, 4-d-butyl, 2-methyl 4-sodium chloride, 2, 4-d-isooctyl, 2, 4-d-sodium salt, 2, 4-d-dimethylamine salt, 2-methyl 4-thiomethyl, 2-methyl 4-chloro, 2, 4-d-propionic acid, homo2, 4-d-propionic acid, 2, 4-d-butyric acid, 2-methyl 4-chloropropionate, 2-methyl 4-chlorobutanoic acid, 2,4, 5-aldicarb-5-aldicarb, 2, mevalicarb, fluazifop, trifluram, fluazifop-p-butyl, benfop-butyl, fluben, benfop-butyl, flubenon-butyl, flubenfop-butyl, flubenon-methyl high-efficiency fluazifop-p-butyl, quizalofop-p-ethyl, fenoxaprop-p-ethyl, oxadiazon, cyhalofop-butyl, oxazomet, clodinafop-propargyl, ethaboxam, hydroxyvalerate, trifluoperazone oxime, clomazone, diquat, ambrox, ethambutol, isoproturon, mefone, ciprofloxacin, aminoprofloxacin, benfot-butyl, halofop-butyl, haloxyfop-butyl Aminoethyl, diltiazem, clodinafop-propargyl, methalproplin, prochloraz, glyphosate, anilofos, glufosinate, methamidophos, glufosinate, pipradophos, bialaphos, triazophos, imazalil, prazophos, validronate, dimefon, glufosinate, imazethapyr, imazamox, imazethapyr-ammonium salt, imazethapyr, prochloraz, fluroxypyr, isooctyl fluroxypyr, clopyralid, picloram, triclopyr, dithiopyr, haloxyfop-butyl, triclopyr, thiotepa, fluazinone, clopyralid, diflufenzopyr, butoxyethyl triclopyr, cliodinate, sethoxydim, clethodim, thiotepa, graminezil, fenpropion, oxime, pyrone, buthidazole, oxaziclomefone, fenpropion Cyclozinone, benzozinone, buprofezin, ametridione, amibuzin, bromoxynil octanoate, xin Xiandian-benzonitrile, ioxynil, dixynil, diphenylacetonitrile, biscarfentrazone-ethyl, hydroxydixynil, iodobonil, flumetsulam, florasulam, penoxsulam, sulfentrazone, clofenacet, diclosulam, pyroxsulam, furben, bispyribac-sodium, pyribenzoxim, pyriminobac-methyl, pyrithiobac-sodium, pyriminobac-methyl bicyclosultone, mesotrione, sulcotrione, tembotrione, tefuryltrione, bicyclopyrone, ketodpiradox, isoxaflutole, clomazone, fenoxasulfone, methiozolin, propisochlor, pyriproxyfen, topramezone, difenoconazole, benazolin, pyriftalid, pyrasulfotole, topramezone, pyroxasulfone, flumetsulam, carfentrazone-ethyl, flumetsulam, sulfentrazone, bencarbazone, pyriftalid, flumetsulam herbicidal, isoxadifen, cycloxaprid, terfenadine, fluaroxazole, flumetofen, flumioxazin, clodinafop-propargyl, phtalol, flumezin, pentachlorophenol (sodium), dinol, terfenacil, terbutryn Le Zhi, pentanitol, dinitrate, chloronitol, dinotefuran, oxadiazon, cyclopentaoxadiazon, flumetsulam, oxaziclomefone, tebufenoxam, fluidazin, chlorpyrifos, bromoamesine, dimethomorph, pyridate, grass pyridazinone, grass pyridate, grass pine, grass volts, pyridasol, quinclorac, chloroquine, bendasone, pyridate, oxazinone, benazolin, isoxabenone, cycloheptane, isopropyl ether, propyl ether, indenone, sodium chlorate, thaumatin, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, forage grass, bromophenoxime, triazolesulfone, mefenamic acid, furben, ethofumesate, pyriminox, chlorophthalic acid, fludioxonil, barnacle, acrolein, benomyl, avenanthramide, thiodicarb, raffinne, hydroxyzinone, metrafenone, bensulfuron, chloracyl phosphine, trichloropropionic acid, alorac, diethamquat, etnipromid, iprymidam, ipfencarbazone, thiencarbazonemethyl, pyrimisulfan, chlorflurazole, tripropindan, sulglycapin, trifluralin, cambendior, cycloproprimac, flurbipyridyl, flurbiprofloxacin.
Advantageous effects
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
through chemical modification and molecular design of the 5-chlorobenzoxazole compound, pyrazolo ring 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, have good activity and selectivity especially for common weeds in paddy fields, especially grassy weeds, and have outstanding crop safety for paddy field crops, especially paddy rice.
Embodiments of the invention
The technical solutions in the embodiments of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
By comprehensively considering the economy, diversity and bioactivity 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 of tables 1-2 are only for better illustration of the present invention and are not meant to limit the present invention, and those skilled in the art should not understand that the scope of the above subject matter of the present invention is limited to the following compounds.
TABLE 1 Structure of Compounds of formula I
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TABLE 2 1 H NMR data
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The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, biological materials, etc. used in the examples described below are commercially available unless otherwise specified. Those skilled in the art will appreciate that other synthetic routes may also be used to synthesize the compounds of the present invention. Although specific starting materials and conditions in the synthetic routes have been described below, they may be readily replaced with other similar starting materials and conditions, and modifications or variations of the preparation methods of the present invention, such as various isomers of the compounds, are included within 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, protection of the appropriate groups during the reaction, and the like.
Example 1
Synthesis of Compound I-1:
in a dry 500mL single-neck flask, adding intermediate II (3.33 g,0.01 mol) to dissolve with 100mL dichloromethane, adding oxalyl chloride (1.26 g,0.01 mol) under ice-water bath, adding DMF (0.078 g,0.001 mol) after stirring for 30min, adding intermediate III-1 (1.51 g,0.01 mol) and triethylamine (1.01 g,0.01 mol) to react for 2h, monitoring the reaction by LC-MS, after the reaction is finished,100mL of water was added, the mixture was extracted three times with 150mL of methylene chloride, the organic phases were combined, dried, desolventized to give 3.86g of I-1, 1 H NMR(500MHz,CDCl 3 -d 6 )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:
a dry 500mL single-neck flask was charged with intermediate II (3.33 g,0.01 mol) and dissolved in 100mL dichloromethane, oxalyl chloride (1.26 g,0.01 mol) was added under ice-water bath, DMF (0.078 g,0.001 mol) was stirred for 30min, then intermediate III-3 (1.65 g,0.01 mol) and triethylamine (1.01 g,0.01 mol) were added to react for 2h, after the reaction was completed, LC-MS was monitored for reaction, 100mL of water was added, 150mL dichloromethane was used to extract three times, the organic phases were combined, dried, desolventized to give 3.86g of I-3, 1 H NMR(500MHz,CDCl 3 -d 6 )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:
a dry 500mL single-neck flask was charged with intermediate II (3.33 g,0.01 mol) and dissolved in 100mL dichloromethane, oxalyl chloride (1.26 g,0.01 mol) was added in an ice-water bath, DMF (0.078 g,0.001 mol) was stirred for 30min, then intermediate III-4 (1.79 g,0.01 mol) and triethylamine (1.01 g,0.01 mol) were added to react for 2h, after the reaction was completed, LC-MS was monitored for reaction, 100mL of water was added, extracted three times with 150mL dichloromethane, the organic phases were combined, dried, desolventized to give 3.86g of I-4, 1 H NMR(500MHz,CDCl 3 -d 6 )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:
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a dry 500mL single-neck flask was charged with intermediate II (3.33 g,0.01 mol) and dissolved in 100mL dichloromethane, oxalyl chloride (1.26 g,0.01 mol) was added under ice-water bath, DMF (0.078 g,0.001 mol) was stirred for 30min, then intermediate III-6 (1.93 g,0.01 mol) and triethylamine (1.01 g,0.01 mol) were added to react for 2h, after the reaction was completed, LC-MS was monitored for reaction, 100mL of water was added, 150mL dichloromethane was used to extract three times, the organic phases were combined, dried, desolventized to give 3.86g of I-6, 1 H NMR(500MHz,CDCl 3 -d 6 )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 formula (I) and 80% of kaolin, uniformly mixing, and crushing to obtain the product.
2. Wettable powder: 20% of the compound of formula (I), 8% of calcium lignosulfonate, 2% of sodium dodecyl sulfate, 3% of white carbon black and kaolin are weighed to 100%. Mixing uniformly, and obtaining the product after jet milling.
3. Water dispersible granule: 60% of the compound of formula (I), 6% of sodium lignin sulfonate, 4% of NNO (alkyl naphthalene sulfonate formaldehyde condensate), 2% of nekal BX (dibutyl sodium naphthalene sulfonate), 3%K-12 (sodium dodecyl sulfate), 5% of carboxymethyl (ethyl) cellulose, 5% of diatomite, 5% of glucose and kaolin are weighed up to 100%. Mixing uniformly, pulverizing by air flow, weighing powder, adding water, mixing, granulating in a granulator, drying, and sieving to obtain granular product.
4. Emulsifiable concentrate: 15% of a compound of formula (I), 5% of agricultural emulsion 700#, 5% of agricultural emulsion 500#, 6% of agricultural emulsion 1601#, 10% of cyclohexanone, 3% of N-methyl pyrrolidone and 150% of solvent oil are weighed to be 100%, and the product is obtained after complete dissolution and uniform mixing.
5. Suspending agent: 15% of a compound of formula (I), 4% of FS3000 (phosphate type anionic surfactant), 2% of NS-500LQ (nonionic hydroxyl 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 deionized water are weighed, 100% of the mixture is added to prepare slurry, and sanding is carried out to obtain the product.
All the above are weight percentages.
Example 6
Biological Activity evaluation (post-emergence):
the original medicine DMF of the compound to be tested is dissolved and prepared into 2.5% mother liquor, and then diluted with 0.1% Tween-80 water for standby. Preparing nutrient soil, putting the nutrient soil into a plastic basin with the basin mouth diameter of 10cm and the height of 9cm, scattering target seeds (barnyard grass and euphorbia lathyris) into the plastic basin, covering the soil by 0.5-1cm after sowing, placing the seeds in a greenhouse for cultivation after the bottom absorbs water, and carrying out stem and leaf spraying treatment by a spray tower according to the test design dose when the barnyard grass grows to 2-3 leaf stages and the euphorbia lathyris 2-3 leaf stages, wherein the test is repeated for 3 times. After the liquid medicine is naturally air-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 materials are observed regularly, and according to the 4 th part of the biological assay test rule in the pesticide room, the control effect of the test agent on weeds is investigated by a visual inspection method regularly after the treatment according to the actual conditions. Grading standard of control effect:
stage 9: 67.6-100% of weeds in the blank control area;
8 stages: 35.1-67.5% of weeds in the blank control area;
7 stages: 25.1-35% of weeds in the blank control area;
stage 6: 15.1-25% of weeds in the blank control area;
5 stages: corresponding to 10.1-15% of weeds in a blank control area;
4 stages: 5.1-10% of weeds in the blank control area;
3 stages: 2.6-5% of weeds in the blank control area;
2 stages: 0-2.5% of weeds corresponding to the blank control area;
stage 1: all die.
According to the above method, a portion of the compounds (compound numbers are shown in table 3) were selected and subjected to parallel measurement of herbicidal activity with the following compounds, respectively:
oxazoxamide (with specific structure)、
Control Compound 1 (CN 108084108A, specific structure is)、
Control Compound 28 (CN 108084108A, specific Structure is)、
Control Compound 47 (CN 108084108A, specific Structure is)、
Control Compound 49 (CN 108084108A, specific Structure is)、
Control Compound 53 (CN 108084108A, specific Structure is)。
The herbicidal activity test effect after application is shown in the following table:
TABLE 3 level of control effect
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Through the experiment, the compound protected by the invention has outstanding biological activity and good commercial application prospect.
Example 7
Evaluation of biological Activity in Paddy field (post-emergence):
the original DMF of the compound to be tested is dissolved and then diluted to the required concentration by water containing 0.1% Tween 80. Preparing water, sieving, air drying, and loading sand soil to 3/4 of flowerpot (plastic opaque flowerpot with aperture of 11cm, bottom diameter of 7cm, and height of 11 cm), adding water into each flowerpot, mixing soil and water uniformly, and keeping soil completely moist and surface flat. The weed seeds and the rice seeds are scattered into a flowerpot and pressed into soil, the flowerpot and the rice seeds are placed into a greenhouse to be managed according to a conventional method (a water layer is always kept to be about 1 cm), spraying treatment is carried out according to experimental design doses when barnyard grass and stephania japonica are grown to 3-4 leaf periods, the glossodes are grown to 3-4 leaf periods and the rice is grown to 2-3 leaf periods, the pot is continuously placed into the greenhouse after pesticide application, the growth and development conditions of test materials are observed regularly, and according to actual conditions, the weed prevention and removal effect of test agents on weeds and the safety of crops are investigated by a visual inspection method regularly after the treatment. According to the 8 th and 9 th parts of the indoor biological measurement test criteria of pesticides, according to the victim symptoms and severity of the target weeds and crops, the weeding activity and the crop safety of the pesticides are evaluated, and the unified level is adopted for investigation:
effect grading standard:
stage 9: 67.6-100% of weeds in the blank area (the grade is no phytotoxicity or no obvious phytotoxicity or slight phytotoxicity for crops);
8 stages: 35.1-67.5% of weeds in the blank control area;
7 stages: 25.1-35% of weeds in the blank control area;
stage 6: 15.1-25% of weeds in the blank control area;
5 stages: corresponding to 10.1-15% of weeds in a blank control area;
4 stages: 5.1-10% of weeds in the blank control area;
3 stages: 2.6-5% of weeds in the blank control area;
2 stages: 0-2.5% of weeds corresponding to the blank control area;
stage 1: all die;
the main symptoms of the phytotoxicity are as follows:
1) Color change (yellowing, whitening, purple-turning, etc.);
2) Morphological changes (new leaf deformity, distortion, etc.);
3) Growth changes (dehydration, wilting, dwarfing, tufting, etc.).
According to the method, part of compounds are selected to carry out parallel measurement of herbicidal activity and crop safety with the metamifop and the control compounds 1, 28, 47, 49 and 53 (specific structures are shown as before). The weed control activity and crop safety test effect after 3 weeks of application are shown in the following table:
TABLE 4 field control level
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Through the experiment, the compound disclosed by the invention has outstanding biological activity of paddy field weeds, has good effects on common weeds in paddy fields, 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%) on the visual inspection of rice at the current dosage, so the compound has good safety on crops, especially rice at a proper dosage.
Example 8
Crop safety evaluation:
the original medicine DMF of the compound to be tested is dissolved and prepared into 2.5% mother liquor, and then diluted with 0.1% Tween-80 water for standby. Preparing nutrient soil, putting the nutrient soil into a plastic basin with the basin mouth diameter of 10cm and the height of 9cm, scattering wheat and corn seeds into the plastic basin, covering soil by 0.5-1cm after sowing, placing the plastic basin in a greenhouse for cultivation after water absorption at the bottom, and carrying out stem and leaf spraying treatment by a spray tower according to the test design dose when the wheat grows to 3-4 leaf stages and the corn grows to 3-4 leaf stages, wherein the test is repeated for 3 times. After the liquid medicine is naturally air-dried, the liquid medicine is placed in a greenhouse and is managed according to a conventional method, the growth and development conditions of test materials are regularly observed, according to the 8 th part of the biological assay test rule in the pesticide room, and according to the actual conditions, the influence of the test agent on crops is regularly investigated by a visual inspection method after the treatment, and meanwhile, the phytotoxicity symptoms are described, wherein the main symptoms are as follows:
1) Color change (yellowing, whitening, purple-turning, etc.);
2) Morphological changes (new leaf deformity, distortion, etc.);
3) Growth changes (dehydration, wilting, dwarfing, tufting, etc.).
Grading the phytotoxicity evaluation:
a level: no chemical injury exists;
b stage: the phytotoxicity degree is 1-10%, and obvious phytotoxicity is avoided;
c stage: the phytotoxicity degree is 11-30%, and the phytotoxicity is slight;
d stage: the phytotoxicity degree is 31-50%, and the moderate phytotoxicity is achieved;
stage e: the phytotoxicity degree is 51-100%, and serious phytotoxicity is caused.
According to the method, a part of compounds are selected to carry out parallel measurement of crop safety with the metamifop and the control compounds 1, 28, 47, 49 and 53 (the specific structures are shown as before). The effect of the crop safety test after 3 weeks of application is shown in the following table:
table 5 crop safety test
Numbering of compounds Dosage (g ai/ha) Wheat 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
Oxazoxamide 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 are substantially harmless or free of obvious phytotoxicity to wheat or corn by visual inspection at the current dosage, and therefore have good safety to crops, especially wheat or corn, at the appropriate dosages.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention are intended to be included within the scope of the present invention.
Industrial applicability
The compound of the invention can be used as a selective herbicide for paddy fields.

Claims (6)

1. A5-chlorobenzoxazole derivative or a salt thereof which is acceptable as pesticide has the structural formula shown in the formula (I):
in the formula (I) of the present invention,
R 1 represent H, me, et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH 2 Cl、CHF 2 、CH 2 F、CF 3 、CH 2 CF 3 MeO, etO, n-PrO, i-PrO, n-BuO, i-BuO, s-BuO, t-BuO, meS, etS, methylamino, dimethylamino, cyclopropanyl, vinyl, methylcarbonyl, propylcarbonyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, methoxy-substituted ethyl, propoxy-substituted ethyl, CN, F, cl, br, NO 2 Mercapto, carboxyl, aldehyde, hydroxyl or amino;
R 2 and R is 3 Together form a group- (CH) 2 ) m M represents 3 or 4.
2. A 5-chlorobenzooxazole derivative or a pesticidally acceptable salt thereof as claimed in claim 1 wherein the structural compound of formula (I) is selected from:
3. a herbicidal composition comprising a herbicidally effective amount of at least one of the 5-chlorobenzooxazole derivatives or as pesticidally acceptable salts thereof of claim 1.
4. A herbicidal composition as claimed in claim 3, further comprising a formulation carrier or formulation adjuvant.
5. A method of controlling unwanted vegetation which comprises applying a herbicidally effective amount of at least one of the 5-chlorobenzooxazole derivatives or as pesticidally acceptable salts thereof of any of claims 1 to 2 or of a herbicidal composition of any of claims 3 to 4 to unwanted vegetation.
6. Use of a 5-chlorobenzooxazole derivative according to any of claims 1 to 2 or as at least one of the pesticidally acceptable salts thereof or a herbicidal composition according to any of claims 3 to 4 for controlling unwanted plants.
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