CN109832277A - Nitrogenous hetero-aromatic ring formic acid imines ester derivant replaced and preparation method thereof, Herbicidal combinations and application - Google Patents

Nitrogenous hetero-aromatic ring formic acid imines ester derivant replaced and preparation method thereof, Herbicidal combinations and application Download PDF

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CN109832277A
CN109832277A CN201711260779.0A CN201711260779A CN109832277A CN 109832277 A CN109832277 A CN 109832277A CN 201711260779 A CN201711260779 A CN 201711260779A CN 109832277 A CN109832277 A CN 109832277A
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alkyl
halogen
alkoxy
substituted
alkenyl
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CN109832277B (en
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连磊
征玉荣
刘娜
刘鹏
崔琦
彭学岗
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Qingdao Qing Yuan Compound Co Ltd
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Qingdao Qing Yuan Compound Co Ltd
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Priority to PCT/CN2017/117865 priority patent/WO2019109401A1/en
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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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom

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

Abstract

The invention belongs to technical field of pesticide, and in particular to a kind of substituted nitrogenous hetero-aromatic ring formic acid imines ester derivant and preparation method thereof, Herbicidal combinations and application.The substituted nitrogenous hetero-aromatic ring formic acid imines ester derivant, as shown in general formula I:, wherein R1And R2Independently represent H, halogen etc.；Y represents H, halogen, NR3R4Deng；W represents H, halogen, alkoxy, alkyl, halogenated alkyl, alkenyl, alkynyl；X represents halogen, alkoxy etc.；Q is selected from halogen, contains or not contain alkyl, naphthenic base, the alkoxy of halogen, phenyl, 2,3- indanyl or the aryl of naphthalene etc..The activity of weeding of the compound is excellent, and has higher crop safety, establishes good selectivity especially for critical harvests such as wheat, corn, rice.

Description

Substituted nitrogen-containing heteroaromatic imine formate derivative, preparation method thereof, herbicidal composition and application
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a substituted nitrogen-containing heteroaromatic imine formate derivative, a preparation method thereof, a weeding composition and application thereof.
Background
The control of weeds is a crucial step in the realization of efficient agricultural processes, and although there are various kinds of herbicides on the market, for example, patent WO2003/011853 discloses the use of 6-aryl-4-picolinates and derivatives thereof represented by the following general formula i as herbicides:however, due to the expanding market, the resistance of weeds, the life span of the drugs, and the economic nature of the drugs, and the growing environmental importance, scientists are required to research and develop new herbicide varieties with high efficiency, safety, economy, and different modes of action.
Disclosure of Invention
The invention provides a substituted nitrogen-containing heteroaromatic imine formate derivative, a preparation method thereof, a weeding composition and application thereof.
The technical scheme adopted by the invention is as follows:
a substituted nitrogen-containing heteroaromatic imine formate derivative is shown as a general formula I:
wherein,
R1and R2Independently represent H, halogen, cyano, nitro, alkyl, haloalkyl, alkenyl, cycloalkyl, alkoxy, acyloxy, alkylthio, substituted or unsubstituted aryl, benzyl, heteroaryl, aryloxy, arylthio, heteroaryloxy and heteroarylthio; and formula-COR5A group shown in the formula, wherein R5Represents alkyl, haloalkyl, alkenyl, cycloalkyl, alkoxy, alkenyloxy, cycloalkoxy, alkylthio, alkenylthio, cycloalkylthio, substituted or unsubstituted benzyl, aryl, heteroaryl, aryloxy, heteroaryloxy, arylmethoxy, heteroarylmethoxy, benzylthio, arylthio, heteroarylthio and amino which may be substituted by alkyl, acyl, acyloxy, substituted or unsubstituted aryl, heteroaryl, arylalkyl, heteroarylalkyl; or R1And R2Are linked to form a 5-or 6-membered saturated or unsaturated ring;
y represents H, halogen, cyano, nitro, alkyl, haloalkyl, alkenyl, cycloalkyl, alkoxy, acyloxy, alkylthio, NR3R4Wherein R is3And R4Independently represents H, alkyl, alkenyl, alkynyl, hydroxy, haloalkyl, alkoxy, amino, acyl, alkoxycarbonyl, alkylcarbamoyl, alkylsulfonyl, trialkylsilyl or dialkylphosphono, or NR3R4Represents a 5-or 6-membered saturated ring or a 5-membered unsaturated ring;
w represents H, halogen, alkoxy, alkyl, haloalkyl, alkenyl, alkynyl;
x represents halogen, alkoxy, alkyl, haloalkyl, alkenyl, alkynyl or cyano;
q is selected from halogen, alkyl, cycloalkyl, alkoxy, phenyl, 2, 3-indanyl or naphthyl, with or without halogen, orIs unsubstituted or substituted, wherein one or more substituents are selected from the group consisting of: halogen, cyano, aryloxy, alkyl, alkoxy, haloalkyl, haloalkoxy, acyl, alkylthio, phenyl, -OCH2CH2-、-OCH2O-or-OCH2CH2O-。
Preferably, R1And R2Independently represent H, cyano, C1-C8 alkyl, halo C1-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1-C8 acyloxy, C1-C8 alkylthio, substituted or unsubstituted aryl, benzyl, heteroaryl, aryloxy, arylthio, heteroaryloxy and heteroarylthio; and formula-COR5A group shown in the formula, wherein R5Represents C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C2-C8 alkenyloxy, C3-C8 cycloalkoxy, C1-C8 alkylthio, C2-C8 alkenylthio, C3-C8 cycloalkylthio, substituted or unsubstituted benzyl, aryl, heteroaryl, aryloxy, heteroaryloxy, arylmethoxy, heteroarylmethoxy, benzylthio, arylthio, heteroarylthio and amino which may be substituted by C1-C8 alkyl, C1-C8 acyl, C1-C8 acyloxy, substituted or unsubstituted aryl, heteroaryl, arylC 1-C8 alkyl, heteroarylC 1-C8 alkyl; wherein "substituted" means substituted with one or more groups selected from the group consisting of halogen, cyano, nitro, C1-C8 alkyl, halo C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C2-C8 alkenyloxy, C1-C8 alkylthio, aryl, aryloxy, benzyl, benzyloxy, C1-C8 acyl, C1-C8 acyloxy, C2-C8 alkenyl, and amino which may be substituted with C1-C8 alkyl, aryl, aryloxy, C1-C8 acyl, C1-C8 acyloxy, and C2-C8 alkenyl;
y represents H, halogen, cyano, nitro, C1-C8 alkyl, halo C1-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1-C8 acyloxy, C1-C8 alkylthio, NR3R4Wherein R is3And R4Independently represent H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, hydroxy, haloC 1-C8 alkyl, C1-C8 alkoxy, amino, C1-C8 acyl, C1-C8 alkoxycarbonyl, C1-C8 alkylcarbamoyl, C1-C8 alkylsulfonyl, tri C1-C8 alkylsilyl or di C1-C8 alkylphosphonyl, or R3R4N represents a 5-or 6-membered saturated ring or a 5-membered unsaturated ring;
w represents H, halogen, C1-C8 alkoxy, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl;
x represents halogen, C1-C8 alkoxy, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl or cyano;
q is selected from halogen, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, phenyl, 2, 3-indanyl or naphthyl, or aryl, which may or may not contain halogenIs unsubstituted or substituted, wherein one or more substituents are selected from the group consisting of: halogen, cyano, aryloxy, C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkyl, halogenated C1-C8 alkoxy, C1-C8 acyl, C1-C8 alkylthio, phenyl, -OCH2CH2-、-OCH2O-or-OCH2CH2O-。
More preferably, R1And R2Independently represent hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, cyano, C1-C6 alkoxycarbonyl, and phenyl which is unsubstituted or substituted by one or more groups selected from halogen, halogeno C1-C6 alkyl, C1-C6 alkyl, C1-C6 alkoxy and C2-C6 alkenyl;
y represents H, NR3R4Wherein R is3And R4Independently represent H, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 acyl;
w represents H, halogen;
x represents halogen, C1-C6 alkyl, C1-C6 alkoxy, cyano;
q is selected from halogen, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, phenyl unsubstituted or substituted by one or more groups selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkyl.
Further preferably, R1And R2Independently represent hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, methylthio, ethylthio, cyano, methoxycarbonyl, ethoxycarbonyl, and optionally are selected from halogen, CF3Phenyl substituted with one or more of methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, methoxy and ethoxy;
x represents chlorine, bromine, methoxy, ethoxy, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyano;
y represents H, NH2、
W represents H, chlorine, fluorine;
q represents cyclopropyl, trifluoromethyl, chlorine, fluorine,
In the definitions of the compounds of the general formula given above, the terms used are collectively defined as follows:
the R is1And R2The aryl group in the group preferably includes phenyl, 2, 3-indanyl, naphthyl or the like; 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, quinolinylA quinoxalinyl, indolyl, benzotriazolyl, benzothienyl, benzofuranyl, isoquinolyl, tetrahydroquinolyl, and the like.
The preparation method of the substituted nitrogen-containing heteroaromatic imine formate derivative comprises the following steps:
the compound shown in the general formula I is prepared by reacting the compound shown in the general formula II with the compound shown in the general formula III, wherein the reaction equation is as follows:
the reaction is carried out in an aprotic solvent under the action of a base and a condensing agent.
The reaction temperature is 0 ℃ to 90 ℃, preferably 10 ℃ to 30 ℃.
The solvent is one or more mixed solvents selected from dichloromethane, dichloroethane, acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, toluene and xylene.
The alkali is selected from one or more of organic alkali such as triethylamine, trimethylamine, DIPEA, DBU and the like.
The condensing agent is PyBop, HATU or HOBt-EDCI.
A herbicidal composition comprising a herbicidally effective amount of at least one of said substituted nitrogen-containing heteroaromatic imidate derivatives.
The herbicide composition also comprises a preparation auxiliary agent.
A method for controlling undesirable vegetation which comprises applying to the vegetation or the area of undesirable vegetation a herbicidally effective amount of at least one of said substituted nitrogen-containing heteroaromatic imidate derivatives or of said herbicidal composition.
The use of at least one of said substituted nitrogen-containing heteroaromatic imidate derivatives or of said herbicidal compositions for controlling harmful plants.
Preferably, the substituted nitrogen-containing heteroaromatic imidate derivatives are 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.
The compounds of the formula I according to the invention have outstanding herbicidal activity against a large number of economically important monocotyledonous and dicotyledonous harmful plants. The active substances according to the invention are also effective against perennial weeds which grow from rhizomes, or other perennial organs 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 and dicotyledonous weed groups which the compounds of the invention can control, without being restricted 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.
With regard to dicotyledonous weed species, the action can be extended to species such as the annual cleavers, viola, veronica, picea, chickweed, amaranthus, sinapis, ipomoea, sida, matricaria and abutilon species, and the perennial weeds cyclocarya, thistle, sorrel and artemisia. The active substances according to the invention are effective in controlling harmful plants, such as barnyard grass, sagittaria, alisma, eleocharis, saccharum and cyperus, in this particular condition of sowing of rice. If the compounds of the present invention are applied to the soil surface before germination, seedlings of weeds can be completely prevented before the weeds grow out, or the weeds stop growing when they grow out of cotyledons and finally die completely after three to four weeks. The compounds of the invention are particularly active against plants such as, for example, alpinia, sesamum indicum, polygonum convolvulus, chickweed, veronica vinifera, veronica albo, viola tricolor and amaranth, cleavers and kochia.
Although the compounds of the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, they are not at all harmful or only insignificantly harmful to the important economic crop plants, such as wheat, barley, rye, rice, maize, sugar beet, cotton and soybean. Especially good compatibility with cereal crops such as wheat, barley and maize, especially wheat. The compounds according to the invention are therefore 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 modified by genetic engineering (e.g. WO 92/11376, WO92/14827, WO 91/19806);
transgenic crop plants which are resistant to particular herbicides, which are resistant to glufosinate herbicides (e.g. EP-0242236A,
EP-0242246A) or a herbicide from the glyphosate group (WO 92/00377), or a herbicide from the sulfonylurea group (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. USA85(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 may be applied using a general formulation, wettable powders, concentrated emulsions, sprayable solutions, powders or granules may be used, so the present invention also provides herbicidal compositions comprising compounds of formula I. depending on the general biological and/or chemical physical parameters, the compounds of formula I may be formulated in a variety of ways. examples of suitable formulation choices are Wettable Powders (WP), water Soluble Powders (SP), water soluble concentrates, concentrated Emulsions (EC), emulsions such as oil dispersed in water and water dispersed in oil (EW), sprayable solutions, Suspension Concentrates (SC), dispersible oil suspensions (OD), suspensions with oil or water as diluents, miscible oil solutions, powders (DP), Capsule Suspensions (CS), core encapsulated (casing) compositions, granules for broadcasting and soil application, Spray granules, coated granules and absorbent granules, water dispersible granules (WG), water Soluble Granules (SG), water soluble granules (formula), microcapsules and wax preparations, these individual formulations are known in the literature, published as "mineral, published under" market, 9, published ", published by" company.
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;is/are as follows[ ethylene oxide adduct surfactant]"Chemische Technologie" of Wiss.Verlagagesell.Stuttgart 1976, Winnacker-K ü chler [ 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.
Suitable active substances which can be mixed with the active substances according to the invention in a compounded or tank-mixed formulation are, for example, the substances known from "the world Wide Specification of New agricultural chemical products", from the national agricultural science and technology Press, 2010.9 and the documents cited therein. For example, the herbicidal active substances mentioned below may be mixed with the mixtures of the formula I (remarks: name of the compound, either by common name according to the International organization for standardization (ISO), or by chemical name, where appropriate with a code number): acetochlor, butachlor, alachlor, propisochlor, metolachlor, s-metolachlor, pretilachlor, propyzamide, pretilachlor, napropamide, R-levulinyl-propyzamide, propanil, mefenacet, dibenzamide, diflufenican, flumetsulam, bromobutyrolac, dimethenamid, mefenacet, metazachlor, isoxaflutole, ryegrass methyl ester, loflutolane, diacrylamide, pethoxamide, butachlor, propisochlor, cyprosulfamide, flumetsulam, heptanoyl, isobutramine, propyzamide, terbutamid, dimethenamid, larvamide, trimethylcyclam, clofenamid, propyzamide, penoxulamide, carpronide, diflormid, trinitrol, butachlor, butafenacet, butachlor, benfluralin, bencarbzamide, pencyhalonil, metolachlor, bencarbzamide, pencyhalonil, buta, Grazing amine, bensulfuron, quinoxalamine, bensulfuron-methyl, naproxen, acetochlor, naphazel, thiachlor, pyraflufen, bensulfuron-methyl, prochloraz, clofenamide, butamidam, flupiram, atrazine, simazine, prometryn, cyanazine, simetryn, ametryn, prometryn, ipratron, flurazin, terbutryn, triazineone-flumetsulam, ciprofloxacin, glycazine, pradapazine, prometryn, simatong, azidezin, diuron, isopentetryn, cycloprozine, ametryn, terbuthylazine, terbuton, metocloprid, cyanazine, bentazon, clonazine, atrazine, metribuzin, cyanuric acid, indaziflazaflam, chlorsulfuron, meturon, bensulfuron, chlorimuron, tribenuron-methyl, thifensulfuron-methyl, pyrazosulfuron-methyl, sulfosulfuron-methyl, sulfometuron, Cinosulfuron, triasulfuron, sulfometuron-methyl, nicosulfuron, ethametsulfuron, amidosulfuron, ethoxysulfuron, cyclosulfamuron, rimsulfuron, azimsulfuron, primisulfuron-methyl, flusulfuron-methyl, flupyrsulfuron-methyl, epoxysulfuron, imazosulfuron, primisulfuron-methyl, prosulfuron, sulfosulfuron, trifloxysulfuron, triflusulfuron, metsulfuron-methyl sodium, flupyrazosulfuron, methisulfuron-methyl, primisulfuron, propysilfuron (Propyrisulfuron), metribusulfuron, acifluorfen-methyl, fomesafen, lactofen, fluoroglycofen-ethyl, oxyfen, prosulfuron, benfuresafen, trifloxysulfuron, metofen-ethyl, metofen, trifloxysulfuron, fluroxypyr, fluridone, benfop, benfluridone, benfurazolin, benfluridone, benfurbenflur, Dimethofen, oxyfluorfen, clofenflurate, Halosafen, chlortoluron, isoproturon, linuron, diuron, sifenuron, fluometuron, benzthiauron, methabenzuron, prosulfuron, sulfosulfuron, clomauron, clodinafuron, clofensulfuron, metoxuron, bromuron, metoxuron, meturon, fensulfuron, prosulfuron, subtilon, cuarone, metolachlor, cycloaroron, cyclouron, thifluuron, buthiuron, kuron, cumuron, metoxuron, methamidothion, metominosulfuron, trifolium, isoxafluron, isoxauron, moneuronon, aniron, methicuron, chloretron, clotururon, teuron, benuron, pennison, phenmedibensulfuron, bensulfuron, benazolin, propham, buthan, thiuron, buthan, benazolin, buthan, benazolin, buthan, benazol, Thiobencarb, merthiolane, diclofop, triallate, penoxsulam, pyributicarb, dichlorfon, edifenphos, ethiofen, prosulfocarb, clenbuterol, prosulfocarb, dichotomene, thiobencarb, promethazine, Isopolinate, Methiobencarb, 2, 4-d butyl ester, 2 methyl 4-sodium chloride, 2, 4-d isooctyl ester, 2 methyl 4-chloroisooctyl ester, 2, 4-d sodium salt, 2, 4-d dimethylamine salt, 2 methyl 4-chloroethyl thioester, 2 methyl 4 chloride, 2, 4-d propionic acid, 2, 4-d propionate, 2, 4-d butyric acid, 2 methyl 4-chloropropionic acid, 2 methyl 4-chlorobutyric acid, 2,4, 5-d nasal discharge, 2,4, 5-d propionic acid, 2,4, 5-d butyric acid, 2 methyl 4-chloropropionic acid, 2 methyl 4-d propionic acid, 2-d propionic acid, 2-cloroprionic acid, triclocarb, triclopyr, triclop, Aminodiclofenac, metocloprofenac, diclofop-methyl, fluazifop-p-butyl, haloxyfop-methyl, haloxyfop-p-butyl, quizalofop-ethyl, quizalofop-p-ethyl, fenoxaprop-p-ethyl, propaquizafop-ethyl, fenoxaprop-ethyl, clodinafop-ethyl, benazolin, clodinafop-ethyl, haloxyfop-methyl, benazolin, propalaxyl, butyfen-ethyl, chloroethafloxacin, aminofluanid, benazolin, dichlofop-ethyl, methamphetalin, propamocarb-ethyl, benfop-methyl, thiophosphine, pirimiphos-methyl, benfop-ethyl, benazolin, benfop-methyl, imax-methyl, mefenofos, mefeno, Imazamox ammonium salt, imazapic acid, imazamethabenz ester, fluroxypyr, clopyralid, picloram, triclopyr, dithiopyr, haloxydine, triclopyril, thiazopyr, fluridone, aminopyralid, diflufenzopyr, butoxyethyl triclopyr, Clodinate, sethoxydim, clethodim, cycloxydim, clethodim, topramezone, Buthidazole, metribuzin, hexazinone, metamitron, metribuzin, amitridione, Amibuzin, bromoxynil, octanoyl ioxynil, dichlobenitrile, pyraclonil, hydroxybensulam, Iodobonil, flumetsulam, penoxsulam, clofenapyr, pyraclonil, pyraflufen-ethyl, pyraoxystrobin, flumetsulam, pyraclonil, pyraoxystrobin, isoxathion, pyriftalid, pyriminobac-methyl, pyrithiobac-methyl, benzobicylon, mesotrione, sulcotrione, Tembotrione, Tefuryltrione, Bicyclopyrone, ketodradox, isoxaflutole, isoxaclomazone, fenoxasulfofone, methiozoline, isopyrafen, pyraflufen, pyrazote, difenzoquat, pyrazoxazole, pyroxaflutole, pyroxsulam, pyraclofos, pyraclonil, amicarbazone, carfentrazone, flumiclone, sulfentrazone, bencarane, bisphenomezone, butafenacil, isoxaflutole, cyclam, triclopyr, fluroxypyr, flumethazine, parnaprox, flumiclone, flumethol, carfentrazone, carzone, carfentrazone, car, Fluazifop-methyl, pyriminostrobin, bromopicrin, didaphylm, pyridaben, Pyridafol, quinclorac, chloroquine, bentazon, pyridate, oxaziclomefone, benazolin, clomazone, isoprox, isoproxypyrim, propyribac, cumylfen, clomazone, sodium chlorate, thatch, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, mequat, bromophenol oxime, triazasulam, imazazole, flurtamone, mesotrione, ethofumesate, pyrimethanil, clodinafop-methyl, clodinium, pyributaine, benfurazolin, meton, metamitron, metolachlor, dichlorvofen, triclopyr, aloac, Dietmquat, Etpronil, ipriflam, iprimazam, iprodione, Trizopyr, Thiaclonifen, chlorpyrifos, pyradifquat, chlorpyrifos, propiram, pyradifurone, pyradifon, pyradifurone, pyrazone, thion, pyrazone, clomazone, fenclorim, cloquintocet-mexyl, mefenpyr-diethyl, DOWFAUC, UBH-509, D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, DOWCO535, DK-8910, V-53482, PP-600, MBH-001, KIH-9201, ET-751, KIH-6127 and KIH-2023.
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 tables 1-2. 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 the Compounds
TABLE 2 Compounds1HNMR data
Examples of representative compounds are as follows:
preparation of compound 3:
compound a (1.0g,3.0mmol) was dissolved in 10mL of dichloromethane at room temperature, TEA (0.61g,6.0mmol) and PyBop (1.7g,3.3mmol) were added in this order and stirred at room temperature for 30min, compound B (0.5g,3.6mmol) was added and stirred at room temperature overnight to check completion of the reaction, 10mL of water was added to the reaction system, after separation, the aqueous phase was extracted twice with 10mL of dichloromethane, the organic phases were combined, dried and subjected to column chromatography (petroleum ether: ethyl acetate: 10:1 to 4:1) to give 3 as a white solid (0.9g, yield 67%).
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 present 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:
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 monocotyledonous and dicotyledonous weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet and sorghum) in a plastic pot filled with soil, then covering the plastic pot with 0.5-2 cm of soil to make the plastic pot grow in a good greenhouse environment, treating test plants in a 4-5 leaf period after sowing for 2-3 weeks, respectively dissolving the compound of the invention to be tested by acetone, then adding Tween 80, diluting the solution into a solution with certain water to a certain concentration, and spraying the solution onto the plants by 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 3.
TABLE 3 post-emergence weed test
Note: the application dosage is 250 g/hectare of effective components, and the water adding amount is 450 kg/hectare.
Pre-emergence test experiment:
placing the monocotyledon and dicotyledon weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet and sorghum) in a plastic pot filled with soil, then covering the plastic pot with 0.5-2 cm of soil, respectively dissolving the compound of the invention to be tested by acetone, then adding Tween 80, diluting the solution into solution with a certain concentration by using a certain amount of water, and immediately spraying the solution after sowing. After the application, the mixture is cultured in a greenhouse for 4 weeks, and after 3 weeks, experimental results are observed, so that the medicament has a superior effect under the measurement of 250 g/hectare, particularly on weeds such as cockspur grass, kukukuh, piemarker and the like, and a plurality of compounds have good selectivity on corn, wheat, rice, soybean and rape.
Experiments show that the compound has better weed control effect generally, has good effect on main gramineous weeds such as cockspur grass, digitaria sanguinalis and setaria viridis and main broadleaf weeds such as piemarker, rorippa rorifolia and sponish needles herb which are widely generated in corn fields, paddy fields and wheat fields, and has good commercial value. Particularly, the broadleaf weeds such as rorippa rorifolia, descurainia sophia, capsella bursa-pastoris, ophiopogon japonicus, cleavers and chickweed which have resistance to ALS inhibitors have extremely high activity.
Evaluating the safety of transplanted rice and the weed control effect of paddy field:
after the paddy field soil was filled in a tank of 1/1,000,000 hectare, seeds of barnyard grass, japanese iris, bidens tripartita and edible tulip were sown, and soil was lightly covered thereon. Standing in a state of water storage depth of 0.5-1 cm in a greenhouse, and implanting tuber of Pseudobulbus Cremastrae seu pleiones in the next or 2 days. Thereafter, the water storage depth was maintained at 3 to 4 cm, and an aqueous dilution of a wettable powder or a suspension, which was prepared by a usual formulation method, was dropped uniformly by a pipette at a time point when barnyard grass, japanese iris, or burley reached 0.5 leaf and the bulb reached the primary leaf stage to obtain a predetermined amount of active ingredient.
In addition, after filling the 1/1,000,000 hectare pot with paddy field soil, leveling is carried out to ensure that the water storage depth is 3-4 cm, and the rice (japonica rice) at the 3-leaf stage is transplanted with the transplanting depth of 3 cm on the next day. The compound of the present invention was treated on the 5 th day after transplantation in the same manner as described above.
The growth states of cockspur grass, Chinese iris, bidens tripartita and edible tulip on 14 th day after the treatment with the medicament and the growth state of rice on 21 th day after the treatment with the medicament are respectively observed by naked eyes, the weeding effect is evaluated according to the activity standard level of 1-10, and a plurality of compounds show excellent activity and selectivity.
Note: the seeds of barnyard grass, Chinese iris, edible tulip and bidens tripartita are all collected from Heilongjiang in China, and are detected to have drug resistance to pyrazosulfuron-ethyl with conventional dosage.
Comparative experiment:
control compound a:(from patent WO2003/011853)
Control compound B:(from patent CN105503712A)
Control compound C:(Tao Shi Yinong commercial variety)
The postemergence test conditions were as above.
TABLE 4 comparative experimental results (50 g/hectare)
Number of Compounds Rice (Oryza sativa L.) with improved resistance to stress Wheat (Triticum aestivum L.) Abutilon Galium aparine Corn (corn) Capsella bursa-pastoris
1 0 0 10 10 0 10
3 0 0 10 10 0 10
4 0 0 10 10 1 10
5 0 0 10 10 0 10
7 0 0 10 10 0 10
9 0 0 10 10 0 10
11 0 0 10 10 0 10
12 0 0 10 10 0 10
57 0 0 10 10 0 10
58 0 0 10 10 0 10
Control Compound A 7 4 10 10 8 10
Control Compound C 4 3 10 10 7 10
As can be seen from table 4, the compounds of the present invention have higher crop safety than the control compounds a and C, and especially establish good selectivity for key crops such as wheat, corn, rice, etc., while the control compounds have poor selectivity for major crops, which indicates that the present invention has unexpected effects.
TABLE 5 comparative experimental results (100 g/hectare)
Number of Compounds Small flying tent All-grass of Coturnix Makino Root of thorny thorn All-grass of Kwangsi
17 10 10 9 10
Control Compound B 2 1 0 2
As can be seen from Table 5, the herbicidal activity of the compounds of the present invention is much higher than that of the control compound B, especially against weeds such as erigeron breviscapus, quassia japonica, aralia elata, and brassica campestris.
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 and broadleaf 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. A substituted nitrogen-containing heteroaromatic imine formate derivative is shown as a general formula I:
wherein,
R1and R2Independently represent H, halogen, cyano, nitro, alkyl, haloalkyl, alkenyl, cycloalkyl, alkoxy, acyloxy, alkylthio, unsubstituted or substituted aryl, benzyl, heteroaromatic radicalsAryl, aryloxy, arylthio, heteroaryloxy and heteroarylthio; and formula-COR5A group shown in the formula, wherein R5Represents alkyl, haloalkyl, alkenyl, cycloalkyl, alkoxy, alkenyloxy, cycloalkoxy, alkylthio, alkenylthio, cycloalkylthio, unsubstituted or substituted benzyl, aryl, heteroaryl, aryloxy, heteroaryloxy, arylmethoxy, heteroarylmethoxy, benzylthio, arylthio, heteroarylthio and amino which may be substituted by alkyl, acyl, acyloxy, unsubstituted or substituted aryl, heteroaryl, arylalkyl, heteroarylalkyl; or R1And R2Are linked to form a 5-or 6-membered saturated or unsaturated ring;
y represents H, halogen, cyano, nitro, alkyl, haloalkyl, alkenyl, cycloalkyl, alkoxy, acyloxy, alkylthio, NR3R4Wherein R is3And R4Independently represents H, alkyl, alkenyl, alkynyl, hydroxy, haloalkyl, alkoxy, amino, acyl, alkoxycarbonyl, alkylcarbamoyl, alkylsulfonyl, trialkylsilyl or dialkylphosphono, or NR3R4Represents a 5-or 6-membered saturated ring or a 5-membered unsaturated ring;
w represents H, halogen, alkoxy, alkyl, haloalkyl, alkenyl, alkynyl;
x represents halogen, alkoxy, alkyl, haloalkyl, alkenyl, alkynyl or cyano;
q is selected from halogen, alkyl, cycloalkyl, alkoxy, phenyl, 2, 3-indanyl or naphthyl, with or without halogen, orIs unsubstituted or substituted, wherein one or more substituents are selected from the group consisting of: halogen, cyano, aryloxy, alkyl, alkoxy, haloalkyl, haloalkoxy, acyl, alkylthio, phenyl, -OCH2CH2-、-OCH2O-or-OCH2CH2O-。
2. The derivative of substituted nitrogen-containing heterocyclic imidate according to claim 1,
R1and R2Independently represent H, cyano, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1-C8 acyloxy, C1-C8 alkylthio, unsubstituted or substituted aryl, benzyl, heteroaryl, aryloxy, arylthio, heteroaryloxy and heteroarylthio; and formula-COR5A group shown in the formula, wherein R5Represents C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C2-C8 alkenyloxy, C3-C8 cycloalkoxy, C1-C8 alkylthio, C2-C8 alkenylthio, C3-C8 cycloalkylthio, unsubstituted or substituted benzyl, aryl, heteroaryl, aryloxy, heteroaryloxy, arylmethoxy, heteroarylmethoxy, benzylthio, arylthio, heteroarylthio and amino which may be substituted by C1-C8 alkyl, C1-C8 acyl, C1-C8 acyloxy, unsubstituted or substituted aryl, heteroaryl, arylC 1-C8 alkyl, heteroarylC 1-C8 alkyl; wherein "substituted" means substituted with one or more groups selected from the group consisting of halogen, cyano, nitro, C1-C8 alkyl, halo C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C2-C8 alkenyloxy, C1-C8 alkylthio, aryl, aryloxy, benzyl, benzyloxy, C1-C8 acyl, C1-C8 acyloxy, C2-C8 alkenyl, and amino which may be substituted with C1-C8 alkyl, aryl, aryloxy, C1-C8 acyl, C1-C8 acyloxy, and C2-C8 alkenyl;
y represents H, halogen, cyano, nitro, C1-C8 alkyl, halo C1-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1-C8 acyloxy, C1-C8 alkylthio, NR3R4Wherein R is3And R4Independently represent H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, hydroxyl, halogenated C1-C8 alkyl, C1-C8 alkoxy, amino, C1-C8 acyl, C1-C8 alkoxycarbonyl, C1-C8 alkylcarbamoyl, C1-C8 alkylsulfonyl, tri C1-C8 alkylsilyl or di C1-C8 alkylphosphonyl, or R3R4N represents a 5-or 6-membered ringA saturated ring or a 5-membered unsaturated ring;
w represents H, halogen, C1-C8 alkoxy, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl;
x represents halogen, C1-C8 alkoxy, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl or cyano;
q is selected from halogen, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, phenyl, 2, 3-indanyl or naphthyl, or aryl, which may or may not contain halogenIs unsubstituted or substituted, wherein one or more substituents are selected from the group consisting of: halogen, cyano, aryloxy, C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkyl, halogenated C1-C8 alkoxy, C1-C8 acyl, C1-C8 alkylthio, phenyl, -OCH2CH2-、-OCH2O-or-OCH2CH2O-。
3. The derivative of substituted nitrogen-containing heterocyclic imidate according to claim 1,
R1and R2Independently represent hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, cyano, C1-C6 alkoxycarbonyl, and phenyl which is unsubstituted or substituted by one or more groups selected from halogen, halogeno C1-C6 alkyl, C1-C6 alkyl, C1-C6 alkoxy and C2-C6 alkenyl;
y represents H, NR3R4Wherein R is3And R4Independently represent H, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 acyl;
w represents H, halogen;
x represents halogen, C1-C6 alkyl, C1-C6 alkoxy, cyano;
q is selected from halogen, C1-C6 alkyl with or without halogen, C3-C6 cycloalkyl, phenyl unsubstituted or substituted by one or more groups selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkyl.
4. The derivative of substituted nitrogen-containing heterocyclic imidate according to claim 1,
R1and R2Independently represent hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, methylthio, ethylthio, cyano, methoxycarbonyl, ethoxycarbonyl, and optionally are selected from halogen, CF3Phenyl substituted with one or more of methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, methoxy and ethoxy;
x represents chlorine, bromine, methoxy, ethoxy, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyano;
y represents H, NH2、NO2；
W represents H, chlorine, fluorine;
q represents cyclopropyl, trifluoromethyl, chlorine, fluorine,
5. A process for the preparation of substituted nitrogen-containing heteroaromatic formiminium formate derivatives according to any one of claims 1 to 4, comprising the steps of: the compound shown in the general formula I is prepared by reacting the compound shown in the general formula II with the compound shown in the general formula III, wherein the reaction equation is as follows:
6. the process for the preparation of a substituted nitrogen-containing heteroaromatic formiate derivative according to claim 5 wherein said reaction is carried out in an aprotic solvent under the action of a base and a condensing agent; preferably, the reaction temperature is 0 ℃ to 90 ℃, preferably 10 ℃ to 30 ℃; the solvent is one or more mixed solvents selected from dichloromethane, dichloroethane, acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, toluene and xylene; the base is selected from one or more of triethylamine, trimethylamine, DIPEA and DBU; the condensing agent is PyBop, HATU or HOBt-EDCI.
7. A herbicidal composition comprising a herbicidally effective amount of at least one of the substituted nitrogen-containing heteroaromatic imidoformate derivatives of any one of claims 1 to 5.
8. A herbicidal composition according to claim 7, characterized by further comprising formulation adjuvants.
9. A method for controlling harmful plants, which comprises applying a herbicidally effective amount of at least one of the substituted nitrogen-containing heteroaromatic imidoformate derivatives of any one of claims 1 to 5 or of the herbicidal composition of any one of claims 7 to 8 to the plants or to the area of the harmful plants.
10. Use of at least one of the substituted nitrogen-containing heteroaromatic formiminium formate derivatives according to any one of claims 1 to 5 or of the herbicidal composition according to any one of claims 7 to 8 for controlling harmful plants, preferably in crops of useful plants, transgenic or genome editing technology-treated plants.
CN201711260779.0A 2017-12-04 2017-12-04 Substituted nitrogen-containing heteroaromatic imine formate derivative, preparation method thereof, herbicidal composition and application Active CN109832277B (en)

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CN1551876A (en) * 2001-07-30 2004-12-01 �ݶ�ũ�����޹�˾ 6-aryl-4-aminopicolinates and their use as herbicides
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CN109485600A (en) * 2017-09-11 2019-03-19 山东先达农化股份有限公司 Compound of fluorine-containing chloropyridine oxime ester structure and its preparation method and application and a kind of herbicide

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EP0335409A3 (en) * 1988-03-31 1990-11-07 Kumiai Chemical Industry Co., Ltd. Pyrimidine derivatives, processes for their production and herbicidal compositions containing them
WO1996006096A1 (en) * 1994-08-23 1996-02-29 Nissan Chemical Industries, Ltd. Pyridine derivative
CN1551876A (en) * 2001-07-30 2004-12-01 �ݶ�ũ�����޹�˾ 6-aryl-4-aminopicolinates and their use as herbicides
CN101977503A (en) * 2008-03-19 2011-02-16 拜尔农科股份公司 Fungicide hydroximoyl-tetrazole derivatives
CN102007120A (en) * 2008-04-22 2011-04-06 拜尔农科股份公司 Fungicide hydroxyimino-heterocyclic derivatives
CN105503712A (en) * 2015-12-11 2016-04-20 中国农业大学 Pyridine-ethylbenzene-ether oxime esterPyrene ethylbenzene oxime-ethers esters compound, and preparation method and application thereof
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