CN108084108B - 5-chlorobenzoxazole derivative and preparation method, herbicidal composition and application thereof - Google Patents

5-chlorobenzoxazole derivative and preparation method, herbicidal composition and application thereof Download PDF

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CN108084108B
CN108084108B CN201711452846.9A CN201711452846A CN108084108B CN 108084108 B CN108084108 B CN 108084108B CN 201711452846 A CN201711452846 A CN 201711452846A CN 108084108 B CN108084108 B CN 108084108B
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chlorobenzoxazole
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CN108084108A (en
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连磊
征玉荣
何彬
何永光
彭学岗
金涛
崔琦
刘娜
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Qingdao Kingagroot Chemical Compound Co Ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Chemical & Material Sciences (AREA)
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  • Plant Pathology (AREA)
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  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
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  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

The invention belongs to the technical field of pesticides, and particularly relates to a 5-chlorobenzoxazole derivative, a preparation method thereof, a weeding composition and application. The chemical structure of the 5-chlorobenzoxazole derivative is shown as a general formula I:
Figure DDA0001528739830000011
wherein, X represents halogen, cyano, trifluoromethyl, methyl; y represents NR1R2，R1Represents H, alkyl, alkylsulfonyl, haloalkyl, R2Represents unsubstituted or substituted aryl, heteroaryl; or R1And R2Linked to form an unsubstituted or substituted 5-or 6-membered unsaturated ring. The derivative and the weeding composition thereof have high drug effect on preventing and controlling gramineous weeds such as barnyard grass and the like, are very safe to crops such as rice and the like, and have good selectivity.

Description

5-chlorobenzoxazole derivative and preparation method, herbicidal composition and application thereof
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a 5-chlorobenzoxazole derivative, a preparation method thereof, a weeding composition and application.
Background
The control of weeds is a crucial link in the process of realizing high-efficiency agriculture, and the types of herbicides in the market are various, for example, patent CN1141876C discloses a series of herbicidal compounds with a general formula
Figure BDA0001528739820000011
Patent CN106172458A disclosesA herbicidal composition comprising the compound metamifop, having the english name metamifop and the chemical name: (R) -2- { (4-chloro-1, 3-benzoxazol-2-yloxy) phenoxy } -2' -fluoro-N-methyl-propionylaniline having the structure
Figure BDA0001528739820000012
The English and Chinese names are not consistent with the structural formula, and the structural formula of the metamifop is defined as
Figure BDA0001528739820000013
Namely, the structural formula disclosed in the patent is a wrong writing method of metamifop, and errors are marked on the Cl substitution positions; patent CN104277033A discloses an N- (aryl alkyl) aryloxy phenoxy carboxylic acid amide compound and an isomer thereof, and the general formula of the compound is
Figure BDA0001528739820000014
However, due to the expanding market, the resistance of weeds, the life span of drugs, and the economic nature of drugs, and the growing environmental importance, scientists are constantly researching and developing new classes of herbicides with high efficiency, safety, economy, and different modes of action.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a 5-chlorobenzoxazole derivative, a preparation method thereof, a weeding composition and application thereof.
The technical scheme adopted by the invention is as follows:
a5-chlorobenzoxazole derivative has a chemical structure shown in general formula I:
Figure BDA0001528739820000021
wherein,
x represents halogen, cyano, trifluoromethyl, methyl;
y represents NR1R2，R1Represents H, alkyl, alkylsulfonyl, haloalkyl, R2Represents unsubstituted or substituted aryl, heteroaryl; or R1And R2Linked to form an unsubstituted or substituted 5-or 6-membered unsaturated ring;
wherein "substituted" means substituted with one or more groups selected from halogen, cyano, nitro, carboxyl, hydroxyl, alkyl, alkenyl, cycloalkyl, alkoxy, alkenyloxy, alkylthio, aryl, aryloxy, benzyl, benzyloxy, alkoxycarbonyl, alkanoyl, acyloxy and amino which may be substituted with alkyl, aryl, aryloxy, alkanoyl, acyloxy and alkenyl.
In the definitions of the compounds of the general formula given above, the terms used are collectively defined as follows:
the aryl group includes phenyl, 2, 3-indanyl or naphthyl, etc.; the heteroaryl group includes a 5-to 10-membered heteroaryl group containing 1 to 3O, S, N heteroatoms, such as pyridyl, pyrimidinyl, pyrazinyl, furyl, thienyl, pyrrolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, imidazolyl, triazolyl, oxadiazolyl, thiadiazolyl, pyridazinyl, triazinyl, quinolyl, quinoxalyl, indolyl, benzotriazolyl, benzothienyl, benzofuryl, isoquinolyl, tetrahydroquinolyl,
Figure BDA0001528739820000022
And the like.
Preferably, X represents F, Cl, Br, cyano, trifluoromethyl, methyl;
y represents NR1R2，R1Represents H, C1-C8 alkyl, C1-C8 alkylsulfonyl, halogenated C1-C8 alkyl, R2Represents unsubstituted or substituted phenyl, pyridyl, pyrazolyl, isoxazolyl, thienyl, thiazolyl, thiadiazolyl,
Figure BDA0001528739820000023
Figure BDA0001528739820000024
Or R1And R2Linked to form unsubstituted or substituted
Figure BDA0001528739820000025
Wherein, the substituted refers to the substitution by one or more groups selected from halogen, cyano, nitro, C1-C8 alkoxycarbonyl, amino, C1-C8 alkylamino, C1-C8 alkyl with or without halogen, C1-C8 alkoxy, C3-C8 cycloalkyl, C2-C8 alkenyl, C2-C8 alkynyl and phenyl.
More preferably, X represents Cl, cyano, trifluoromethyl, methyl;
y represents NR1R2，R1Represents H, C1-C6 alkyl, C1-C6 alkylsulfonyl, halogenated C1-C6 alkyl, R2Represents unsubstituted or substituted by one or more substituents selected from C1-C6 alkyl, cyano, nitro, halogen, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, phenyl, halogen-substituted phenyl, C1-C6 alkoxycarbonyl, amino
Figure BDA0001528739820000031
Figure BDA0001528739820000032
Further preferably, X represents Cl;
y represents NR1R2，R1Represents H, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, SO2Et、CH2CHF2，R2Represents unsubstituted or selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyano, nitro, F, Cl, Br, CF3、OCF3One or more substituents selected from methoxy, ethoxy, phenyl, halogen substituted phenyl, methoxycarbonyl, ethoxycarbonyl and amino
Figure BDA0001528739820000033
Figure BDA0001528739820000034
Even more preferably, NR is when X is Cl1R2Is not that
Figure BDA0001528739820000035
Wherein, the compound of the general formula I is preferably in an R configuration (shown as a general formula I-1):
Figure BDA0001528739820000036
the preparation method of the 5-chlorobenzoxazole derivative comprises the following steps:
(1) reacting a compound IV with a compound V in the presence of alkali and a solvent to prepare a compound shown as a general formula III;
(2) carrying out acyl halogenation on the compound shown in the general formula III to obtain a compound shown in a general formula II;
(3) reacting a compound shown as a general formula II with a compound HY in the presence of alkali and a solvent to obtain a compound shown as a general formula I;
the chemical reaction equation is as follows:
Figure BDA0001528739820000041
wherein L is Cl or Br;
or reacting the compound shown as the general formula III with a compound HY in the presence of a dehydrating agent to obtain the compound shown as the general formula I, wherein the chemical reaction formula is as follows:
Figure BDA0001528739820000042
the reaction temperature is within the range of-50 to 180 ℃, and preferably-10 to 80 ℃.
The solvent is selected from one or more of acetonitrile, ethyl acetate, toluene, xylene, DMF, DMSO, NMP and the like.
The alkali is selected from one or more of anhydrous sodium carbonate, anhydrous potassium carbonate, sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, sodium ethoxide, triethylamine, N-diisopropylethylamine, DBU and the like.
The halogenating reagent adopted in the step (2) is oxalyl chloride, thionyl chloride, phosphorus oxychloride, phosphorus trichloride, oxalyl bromide, thionyl bromide, phosphorus oxybromide or phosphorus tribromide and the like.
The dehydrating agents include, but are not limited to DCC, HOBt, EDCI, CDI, and the like.
When the compound of the general formula I is in an R configuration (shown as a general formula I-1), the compound IV-1 is used as a raw material to carry out the reaction.
Figure BDA0001528739820000043
A herbicidal composition comprising a herbicidally effective amount of at least one of said 5-chlorobenzoxazole derivatives.
The herbicide composition of the 5-chlorobenzoxazole derivative also includes preparation assistants.
A method for controlling harmful plants, which comprises applying a herbicidally effective amount of at least one of said 5-chlorobenzoxazole derivatives or said herbicidal composition on plants or in the area of harmful plants.
The use of at least one of said 5-chlorobenzoxazole derivatives or said herbicidal compositions for controlling undesirable vegetation.
Preferably, at least one of said 5-chlorobenzoxazole derivatives or said herbicidal composition is used for controlling harmful plants in crops of useful plants.
More preferably, the useful crop is a transgenic crop or a crop treated with genome editing techniques.
Further preferably, the useful crop is a paddy field.
The compounds of the formula I according to the invention have outstanding herbicidal activity against a large number of economically important monocotyledonous harmful plants. The active substances according to the invention are also effective against perennial weeds which grow from rhizomes, or other perennial organs and are difficult to control. In this connection, it is generally immaterial whether the substance is used before sowing, before germination or after germination. Mention is made in particular of representative examples of the monocotyledonous weed populations which the compounds of the invention can control, without limitation to a defined species. Examples of weed species for which the active substance acts effectively include monocotyledons: annual avena, rye, grass, alopecurus, farris, barnyard grass, digitaria, setaria and sedge, and perennial agropyron, bermudagrass, cogongrass and sorghum, and perennial sedge.
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 of the present invention have excellent herbicidal activity against monocotyledonous weeds, they are not at all harmful or are only insignificantly harmful to important economic crop plants, such as wheat, barley, rye, rice, maize, sugar beet, cotton and soybean. In particular, it is well compatible with cereal crops such as wheat, barley and maize, and in particular rice, and therefore the compounds of the invention are very suitable for selectively controlling unwanted vegetation in agricultural crops or ornamental plants.
Due to their herbicidal properties, these active substances can be used for controlling harmful plants in the cultivation of genetically engineered plants which are known or are to occur. Transgenic plants often have advantageous traits, such as resistance to specific insecticides, particularly to specific herbicides, resistance to plant diseases or to microorganisms pathogenic to plant diseases, such as specific insects or microorganisms of fungi, bacteria or viruses. Other specific traits are related to the conditions of the product, such as quantity, quality, storage stability, composition and specific ingredients. Thus, it is known that the resulting transgenic plant products have an increased starch content or an improved starch quality or a different fatty acid composition.
The compounds of the formula I according to the invention or their salts are preferably used for economically important transgenic crops and ornamentals, for example cereals, such as wheat, barley, rye, oats, millet, rice, cassava and maize, or for the cultivation of sugar beet, cotton, soybean, rapeseed, potato, tomato, pea and other vegetable plants. The compounds of the formula I are preferably used as herbicides for cultivating useful plants which are resistant to the action of the herbicide or which are resistant to the toxic action of the herbicide by genetic engineering.
Conventional methods for breeding plants having improved shape over known plants include, for example, conventional mating methods and mutant breeding. In other words, new plants with improved traits may be obtained by means of methods of genetic engineering (see, for example, EP-0221044A, EP-0131624A). For example, several methods have been described:
to improve starch synthesis in plants, crop plants are altered by genetic engineering (e.g. WO 92/11376, WO 92/14827, WO 91/19806);
transgenic crop plants which are resistant to particular herbicides, to glufosinate herbicides (e.g. EP-0242236A, EP-0242246A) or to glyphosate-type herbicides (WO 92/00377), or to sulfonylurea-type herbicides (EP-0257993A, US-5013659A);
transgenic crop plants, such as cotton, which produce Bacillus thuringiensis toxins (Bt toxins) which protect against attack on plants by specific pests (EP-0142924A, EP-0193259A);
-transgenic crop plants with improved fatty acid composition (WO 91/13972).
A number of molecular biotechnologies are known which enable the production of transgenic plants with improved traits (see, for example, Sambrook et al, 1989, molecular amplification, second edition of the laboratory Manual, Cold spring harbor laboratory publications in USA, Cold spring harbor, New York; or Winnacker "Gene und Klone" [ genes and clones ], VCH Weinheim, second edition 1996 or Christou, "trends in plant science" 1(1996)423- "431)). In order to carry out the manipulation of genetic engineering, it is possible to introduce nucleic acid molecules into plasmids, which undergo mutations or sequence changes by recombination of DNA sequences. Using standard methods as described above, it is possible, for example, to exchange substrates, remove partial sequences or add natural or synthetic sequences. In order to ligate the DNA fragments to each other, it is possible to attach a binder or a linker to the fragments.
Plant cells of reduced activity gene products can be prepared, for example, by expressing at least one suitable antisense-RNA, sense-RNA to achieve a cosuppression effect, or by expressing at least one suitably configured ribozyme which specifically cleaves transcripts of the gene products.
For this purpose, it is possible to use DNA molecules which contain the entire coding sequence of the gene product, including any flanking sequences which may be present, and to use DNA molecules which contain only a part of the coding sequence which has to be long enough to achieve an antisense effect in the cell. Sequences that are highly homologous but not identical to the coding sequence of the gene product may also be used.
When expressing the nucleic acid molecule in a plant, the synthetic protein can be localized in any desired plant cell compartment. However, for localization in a specific chamber, it is possible, for example, to link the coding region to a DNA sequence in order to ensure localization in a specific location. These sequences are known to those skilled in the art (see, for example, Braun et al, EMBO J.11(1992) 3219-3227; Wolter et al, Proc. Natl. Acad. Sci. USA 85(1988), 846-850; Sonnewald et al Plant J.1(1991), 95-106).
Transgenic plant cells can be recombined into whole plants using known techniques. The transgenic plant may be of any desired plant variety, i.e., monocotyledonous and dicotyledonous plants. In this way, it is possible to obtain transgenic plants with improved traits by overexpressing, inhibiting or suppressing homologous (═ natural) genes or gene sequences, or by expressing heterologous (═ external) genes or gene sequences.
When the active substances according to the invention are used on transgenic crops, in addition to the harmful-plant-inhibiting effects observed on other crops, special effects are often observed on the corresponding transgenic crops, for example an improved or enlarged spectrum of weed control, improved application rates in the application, preferably a good combination of resistance of the transgenic crop and herbicide performance, and an influence on the growth and yield of the transgenic crop plants. The invention therefore also provides for the use of the compounds as herbicides for controlling harmful plants in transgenic crop 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 compounds of the present invention can be applied using general formulations, and wettable powders, concentrated emulsions, sprayable solutions, powders or granules 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), water Soluble Powders (SP), water soluble concentrates, Emulsion Concentrates (EC), emulsions dispersed in water (EW), for example, oil-in-water and water-in-oil (EW), sprayable solutions, Suspension Concentrates (SC), dispersible oil suspensions (OD), suspensions with oil or water as diluent, solutions of miscible oils, powders (DP), Capsule Suspensions (CS), core (cutting) compositions, granules for spreading and soil application, spray granules, coated granules and absorbent granules, water dispersible granules (WG), water Soluble Granules (SG), ULV (ultra low volume) formulations, microcapsules and wax preparations. These individual formulation types are known and described in, for example, Winnacker-Kuchler, "Chemische Techologie" [ Chemicals Process ], Vol.7, C.Hauser Verlag Munich, 4 th edition 1986; wade van Valkenburg, "Pesticide Formulations," Marcel Dekker, n.y., 1973; martens, "Spray Drying" handbook, 3 rd edition 1979, g.
The necessary formulation auxiliaries, such as inerts, surfactants, solvents and other additives, are likewise known and are described in the documents mentioned below, for example in Watkins, "handbook of powdered diluents pesticides and carriers", second edition, Darland book Caldwell n.j.; h.v.01phen, "entry to clay colloid chemistry," second edition, j.wiley and Sons, n.y.; marsden, second edition "solvent guide", Interscience, n.y.1963; "annual report of detergents and emulsifiers" by McCutcheon, MC issues, Ridgewood n.j.; sisley and Wood, "surfactant encyclopedia", chemical publishing company, n.y.1964;
Figure BDA0001528739820000072
is/are as follows
Figure BDA0001528739820000073
[ ethylene oxide adduct surfactant]Uss.verlagageell.stuttgart 1976; "Chemische technology" by Winnacker-Kuchler [ chemical Process]Volume 7, c.hauser Verlag Munich, 4 th edition 1986.
Wettable powders can be uniformly dispersed in water and, in addition to the active substance, include diluents or inert substances, ionic and nonionic surfactants (wetting agents, dispersants), such as polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkylsulfonates, alkylphenylsulfonates, sodium lignosulfonates, sodium 2,2 '-dinaphthylmethane-6, 6' -disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurate. To prepare wettable powders, the active substances of the herbicides are finely ground, for example using customary instruments, such as hammer mills, fan mills and jet mills, with simultaneous or sequential incorporation of the adjuvants.
Emulsions are prepared by dissolving the active substance in an organic solvent, such as butanol, cyclohexanone, dimethylformamide, xylene or higher boiling aromatics or hydrocarbons or mixtures of solvents, and adding one or more ionic and/or nonionic surfactants (emulsifiers). Examples of emulsifiers which may be used are calcium alkylarylsulfonates, for example calcium dodecylbenzenesulfonate, or nonionic emulsifiers, for example polyglycol esters of fatty acids, alkylarylpolyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, for example polyoxyethylene sorbitan fatty acid esters.
The active substance and finely divided solid substances, for example talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth, are ground to give a powder. Water or oil based suspensions may be prepared, for example, by wet milling using a commercially available bead mill, with or without the addition of a surfactant of the other formulation type described above.
For preparing emulsions, for example oil-in-water Emulsions (EW), it is possible to use aqueous organic solvents, using stirrers, colloid mills and/or static mixers, and, if desired, to add surfactants of another formulation type as described above.
Granules are prepared by spraying the active substance onto the adsorbate, granulating with inert material, or concentrating the active substance onto the surface of a carrier, for example sand, kaolinite, and granulating the inert material with a binder, for example polyvinyl alcohol, sodium polyacrylate or mineral oil. Suitable active substances can be granulated by the process for preparing fertilizer granules, if desired mixed with fertilizers. The preparation of water-suspendable granules is carried out by customary methods, for example spray-drying, fluidized-bed granulation, millstone granulation, mixing using high-speed mixers and extrusion without solid inert materials.
For the preparation of granules using a millstone, a fluidized bed, an extruder and Spray coating, see the following processes, for example "Spray Drying handbook", third edition 1979, g.goodwin ltd, london; browning, "Agglomeration", chemical and engineering 1967, page 147 ff; "Perry's handbook of Engineers of chemistry", fifth edition, McGraw-Hill, New York 1973, pages 8-57. If preparations for crop protection products are to be known, see, for example, G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, New York, pages 196181-96 and J.D. Freyer, S.A. Evans, "Weed Control Manual", fifth edition, Blackwell Scientific rules, Oxford university 1968, page 101-.
Agrochemical formulations generally comprise from 0.1 to 99%, in particular from 0.1 to 95% by weight of active substance of formula I. The concentration of active substance in wettable powders is, for example, from about 10 to 99% by weight, with usual formulation components making up the remainder to 100% by weight. The concentration of the active substance in the emulsion concentrate may be about 1 to 90%, preferably 5 to 80% by weight. Powder formulations contain from 1 to 30% by weight of active, usually preferably from 5 to 20% by weight of active, whereas sprayable solutions contain from about 0.05 to 80%, preferably from 2 to 50% by weight of active. The content of active substance in the aqueous suspension granules depends primarily on whether the active substance is liquid or solid, and the auxiliaries, fillers and the like used in granulation. The content of active substance in the water-suspendable granule formulation is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
The active substance formulations mentioned may additionally comprise tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreezes, solvents, fillers, carriers, colorants, antifoams, evaporation inhibitors and generally customary pH and viscosity regulators in all cases.
On the basis of these formulations, it is also possible to mix them with other insecticide active substances, such as insecticides, acaricides, herbicides and fungicides, and also with safeners, fertilizers and/or plant growth regulators, either premixed or mixed in containers.
When used, the commercially available formulations are diluted in the usual manner, if desired, for example in wettable powders, concentrated emulsions, suspensions and granules suspended in water, using water. Powders, granules for soil application or solutions for spreading and spraying generally do not require further dilution with inert substances before use. The required amount of the compound of formula I to be used varies with the external conditions, such as temperature, humidity, the nature of the herbicide used, etc. It may vary widely, for example between 0.001 and 1.0kg/ha, or more of active substance, but preferably between 0.005 and 750g/ha, in particular between 0.005 and 250 g/ha.
Detailed Description
The following examples are intended to illustrate the invention and should not be construed as limiting it in any way. The scope of the invention is indicated by the appended claims.
In view of the economic and diversity of the compounds, we prefer to synthesize some of the compounds, a selection of which are listed in table 1 below. Specific compound structures and corresponding compound information are shown in table 1. The compounds in table 1 are only for better illustrating the present invention, but not for limiting the present invention, and it should not be understood to limit the scope of the above-mentioned subject matter of the present invention to the following compounds for those skilled in the art.
Table 1 Structure of Compounds and methods of use thereof1HNMR data
Figure BDA0001528739820000091
Figure BDA0001528739820000092
Figure BDA0001528739820000101
Figure BDA0001528739820000111
Figure BDA0001528739820000121
Figure BDA0001528739820000131
Figure BDA0001528739820000141
Several methods for preparing the compounds of the present invention are illustrated in the schemes and examples below. The starting materials are commercially available or can be prepared by methods known in the literature or as shown in detail. It will be appreciated by those skilled in the art that other synthetic routes may also be utilized to synthesize the compounds of the present invention. Although specific starting materials and conditions for the synthetic route 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.
The following process examples are provided to facilitate a further understanding of the methods of preparation of the invention, and the particular materials, species and conditions used are intended to be further illustrative of the invention and are not intended to limit the reasonable scope thereof. The reagents used in the synthesis of the compounds indicated in the following table are either commercially available or can be readily prepared by one of ordinary skill in the art.
Examples of representative compounds are as follows:
preparation of Compound 01
Figure BDA0001528739820000142
Dissolving 18.2g of the compound A1 in 100mL of DMF, adding 40g of anhydrous potassium carbonate while stirring, heating to 80 ℃, stirring for reaction for 1 hour, cooling to room temperature, then adding 18.8g of the compound A2 in batches, heating the reaction mixture to 80 ℃, stirring for reaction for 1 hour, cooling to room temperature, adding 500mL of water for dilution, adjusting the pH value to about 3 with hydrochloric acid, precipitating a large amount of white solid, and filtering. The filter cake was dried to give 30.1g of a white solid, compound A3. The yield is 90.4%, and the HPLC purity is more than 95%.
10g of Compound A3 was mixed with 15mL of thionyl chloride, and the mixture was refluxed for 30min, and excess thionyl chloride was evaporated under reduced pressure to give 11.2g of a colorless transparent syrup-like Compound A4. It was diluted with 20mL of dichloroethane and used for the next reaction.
3.3g of aniline and 5mL of triethylamine are dissolved in 30mL of dichloroethane, the temperature is reduced to 0 ℃ by stirring, the dichloroethane solution of the compound A4 prepared in the previous step is slowly dropped into the dichloroethane solution, and the reaction temperature is controlled to be not higher than 10 ℃. After the dropping, the temperature was raised to room temperature and stirred overnight. 30mL of water was added to the reaction mixture, and the mixture was separated. The organic phase was washed successively with dilute hydrochloric acid, a saturated sodium bicarbonate solution, water and a saturated sodium chloride solution, dried over anhydrous sodium sulfate and concentrated. The crude product obtained was purified by silica gel column chromatography to give 9.9g of a white solid in 80.9% yield with an HPLC purity of 98.5%.
Preparation of Compound 02
Figure BDA0001528739820000151
10g of Compound A3 and 3.6g of 3-amino-4-cyanopyrazole (A2) were added to 20mL of DMF, and 7.0 of 7.0g N, N' -Dicyclohexylcarbodiimide (DCC) was slowly added thereto with stirring at room temperature, and the mixture was stirred at room temperature overnight. 30mL of water was added to the reaction mixture, and the mixture was separated. The organic phase was washed successively with dilute hydrochloric acid, a saturated sodium bicarbonate solution, water and a saturated sodium chloride solution, dried over anhydrous sodium sulfate and concentrated. The crude product obtained was purified by silica gel column chromatography to give 8.6g of a white solid in 61.0% yield with an HPLC purity of 98.0%.
Evaluation of biological Activity:
the activity level criteria for harmful plant destruction (i.e. growth control rate) are as follows:
10 level: death is complete;
and 9, stage: the growth control rate is more than 95 percent;
and 8, stage: the growth control rate is more than 90%;
and 7, stage: the growth control rate is more than 80 percent;
and 6, level: the growth control rate is more than 70%;
and 5, stage: the growth control rate is more than 60 percent;
4, level: the growth control rate is more than 50%;
and 3, level: the growth control rate is more than 20 percent;
and 2, stage: the growth control rate is 5-20%;
level 1: the growth control rate is below 5%;
level 0: no effect is produced.
The growth control rate is the fresh weight control rate.
Post-emergence test experiments: placing single-leaf seeds and main crop seeds (rice, wheat and soybean) in a plastic pot filled with soil, then covering 0.5-2 cm of soil to enable the single-leaf seeds and the main crop seeds to grow in a good greenhouse environment, treating test plants in a weed 2-3 leaf period and a crop 3-4 leaf period after sowing for 2-3 weeks, respectively dissolving a compound of the invention to be tested by acetone, then adding Tween 80, diluting the solution into a solution with a certain concentration by using a certain amount of water, and spraying the solution onto the plants by using a spray tower. The weeds were cultured in the greenhouse for 3 weeks after application, and the experimental effects of the weeds after 3 weeks are shown in Table 2.
TABLE 2 post emergence weed test (150 g/hectare)
Figure BDA0001528739820000161
Figure BDA0001528739820000171
Figure BDA0001528739820000181
Comparative experiment: the conditions for the postemergence test were the same as above, and the results are shown in table 3.
Control compound 1:
Figure BDA0001528739820000182
control compound 2:
Figure BDA0001528739820000183
control compound 3:
Figure BDA0001528739820000184
(selected from patents CN106172458A and CN1141876C)
Control compound 4:
Figure BDA0001528739820000185
control compound 5:
Figure BDA0001528739820000186
(selected from the patent CN104277033A)
TABLE 3 comparative experimental results
Figure BDA0001528739820000187
Figure BDA0001528739820000191
Note: rice (direct seeding indica rice at 2 leaf stage), barnyard grass (4 leaf stage); n represents no data.
As can be seen from the above table, the compounds of the present invention are superior in the control activity against barnyard grass and have higher crop safety, especially establish good selectivity for rice, as compared with the control compounds 1 to 5.
Meanwhile, a plurality of tests show that the compound has good selectivity on gramineous lawns such as zoysia japonica, bermuda grass, tall fescue, blue grass, ryegrass, seashore paspalum and the like, and can prevent and kill a plurality of key gramineous weeds. Tests on soybeans, cotton, sunflower, potatoes, fruit trees, vegetables and the like under different application modes also show excellent selectivity and commercial value.

Claims (10)

1. A5-chlorobenzoxazole derivative characterized by being selected from any one of the following compounds:
Figure FDF0000007311310000011
Figure FDF0000007311310000012
Figure FDF0000007311310000021
Figure FDF0000007311310000031
Figure FDF0000007311310000041
Figure FDF0000007311310000051
。
2. a process for the preparation of a 5-chlorobenzoxazole derivative as set forth in claim 1 comprising the steps of:
(1) reacting a compound IV with a compound V in the presence of alkali and a solvent to prepare a compound shown as a general formula III;
(2) carrying out acyl halogenation on the compound shown in the general formula III to obtain a compound shown in a general formula II;
(3) reacting a compound shown as a general formula II with a compound HY in the presence of alkali and a solvent to obtain a compound shown as a general formula I;
the chemical reaction equation is as follows:
Figure FDF0000007311310000052
wherein L is Cl or Br;
or reacting the compound shown as the general formula III with a compound HY in the presence of a dehydrating agent to obtain the compound shown as the general formula I, wherein the chemical reaction formula is as follows:
Figure FDF0000007311310000053
wherein, the compound is
Figure FDF0000007311310000061
The raw materials are subjected to the reaction to prepare the compound shown as the general formula I-1
Figure FDF0000007311310000062
And group X, Y is as defined in claim 1.
3. The preparation method of the 5-chlorobenzoxazole derivative as claimed in claim 2, wherein the reaction temperature is in the range of-50 to 180 ℃; the solvent is selected from one or more of acetonitrile, ethyl acetate, toluene, xylene, DMF, DMSO and NMP; the alkali is selected from one or more of anhydrous sodium carbonate, anhydrous potassium carbonate, sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, sodium ethoxide, triethylamine, N-diisopropylethylamine and DBU; the halogenating reagent adopted in the step (2) is oxalyl chloride, thionyl chloride, phosphorus oxychloride, phosphorus trichloride, oxalyl bromide, thionyl bromide, phosphorus oxybromide or phosphorus tribromide; the dehydrating agent is DCC, HOBt, EDCI or CDI.
4. The preparation method of the 5-chlorobenzoxazole derivative as claimed in claim 3, wherein the reaction temperature is in the range of-10 to 80 ℃.
5. A herbicidal composition comprising a herbicidally effective amount of at least one of the 5-chlorobenzoxazole derivatives as set forth in claim 1.
6. A herbicidal composition according to claim 5, further comprising formulation adjuvants.
7. A method for controlling harmful plants, which comprises applying a herbicidally effective amount of at least one of the substituted 5-chlorobenzoxazole derivatives as claimed in claim 1 or a herbicidal composition as claimed in any one of claims 5 to 6 to the plants or to the area of the harmful plants.
8. Use of at least one of the substituted 5-chlorobenzoxazole derivatives as claimed in claim 1 or the herbicidal composition as claimed in any one of claims 5 to 6 for controlling harmful plants.
9. Use according to claim 8, characterized in that the substituted 5-chlorobenzoxazole derivatives are used for combating harmful plants in crops of useful plants, which are transgenic or genome editing technology treated crops.
10. The use according to claim 9, wherein the useful crop is a paddy field.
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