CN107629035B - Pyrazolone compound or salt thereof, herbicide composition and application - Google Patents

Pyrazolone compound or salt thereof, herbicide composition and application Download PDF

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CN107629035B
CN107629035B CN201711002418.6A CN201711002418A CN107629035B CN 107629035 B CN107629035 B CN 107629035B CN 201711002418 A CN201711002418 A CN 201711002418A CN 107629035 B CN107629035 B CN 107629035B
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ethyl
radical
methyl
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CN107629035A (en
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连磊
征玉荣
何彬
彭学岗
金涛
崔琦
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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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system

Abstract

The application belongs to the field of pesticides, and particularly relates to a pyrazolone compound or salt thereof, a herbicide composition and application. The pyrazolone compound is shown as a general formula I:
Figure DDA0001443710150000011
in the formula, R1R2N represents butyrolactam or valerolactam which are unsubstituted or substituted on the ring by one or more groups selected from fluorine, chlorine, methyl, ethyl, methoxy and ethoxy; r3Represents hydrogen, C1～4Alkyl radical, C2～4Alkenyl radical, C2～4Alkynyl, unsubstituted or with C1～4Alkyl substituted C3～6A cycloalkyl group; r4Represents methyl, ethyl, n-propyl, isopropyl, cyclopropyl; x represents-R5、‑S(O)nR6、‑CH2R7、‑(C＝O)R8、‑PO(OR9)2、‑Si(OR9)3And the like. The medicinal active substance provided by the invention has the advantages of good medicinal effect, convenience in use, low cost and good commercial value.

Description

Pyrazolone compound or salt thereof, herbicide composition and application
Technical Field
The application belongs to the field of pesticides, and particularly relates to a pyrazolone compound or salt thereof, a herbicide composition and application.
Background
The weed control is a crucial link in the process of realizing high-efficiency agriculture, wherein the chemical weeding method is convenient, economic and effective, becomes an indispensable component of modern agricultural technology, and promotes the innovation of cultivation technology. The pyrazole compound has the characteristics of high efficiency, low toxicity, various structures and the like, and is used as a herbicide in the most main application field.
Patent CN105218449A discloses a series of pyrazolone herbicide compounds with herbicidal activity and their synthesis method. On the basis of the research, pyrazolone compounds with novel structures and herbicidal activity are synthesized in order to design and synthesize more efficient and broader-activity-spectrum herbicide compounds.
Disclosure of Invention
The invention aims to provide a pyrazolone compound or a salt thereof, a herbicide composition and weeding application in the field of pesticides. The medicinal active substance provided by the invention has good medicinal effect, convenient use and low cost.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a pyrazolone compound of formula I or a salt thereof:
Figure GDA0001480207400000011
in the formula (I), the compound is shown in the specification,
R1R2n represents a butyrolactam radical which is unsubstituted or substituted on the ring by one or more radicals selected from fluorine, chlorine, methyl, ethyl, methoxy and ethoxy
Figure GDA0001480207400000012
Valerolactam radical
Figure GDA0001480207400000013
R3Represents hydrogen, C1～4Alkyl radical, C2～4Alkenyl radical, C2～4Alkynyl, unsubstituted or with C1～4Alkyl substituted C3～6A cycloalkyl group;
R4represents methyl, ethyl, n-propyl, isopropyl, cyclopropyl;
x represents-R5、-S(O)nR6、-CH2R7、-(C＝O)R8、-PO(OR9)2、-Si(OR9)3Wherein, in the step (A),
R5、R6represents a substituted or unsubstituted aryl or heterocyclic group, n represents 1, 2, 3;
R7represents substituted or unsubstituted aryl or heterocyclic radical, C substituted by halogen1～6Alkyl, halogen, C1～6Alkylamino radical, C2～4Alkynyl, C2～4Alkenyl radical, C1～6Alkoxy, nitro, cyano, C3～6Cycloalkyl, amino, C1～6An alkylthio group;
R8represents C1～6Alkylamino radical, C1～6Alkylthio radical, C1～6Alkylamino radical C1～6Alkyl radical, C1～6Alkylthio group C1～6Alkyl, halogen, amino, cyano, nitro, C1～6Alkoxy radical C1～6Alkyl, substituted or unsubstituted phenyl, phenyl C1～6Alkyl, phenoxy or phenoxy C1～6An alkyl group;
R9represents hydrogen, C1～6Alkyl radical, C3～6Cycloalkyl, substituted or unsubstituted phenyl or heterocyclyl.
Preferably, R5、R6Represents unsubstituted phenyl or a 3-to 10-membered heterocyclic group containing 1 to 4 heteroatoms selected from O, N and S, selected from C1～6Alkyl radical, C1～6Alkoxy radical, C1～6Alkylamino radical, C1～6Alkylthio, halogen, C2～4Alkenyl radical, C2～4Alkynyl, amino, nitro, cyano, carboxyl, C1～6Alkoxycarbonyl group, C1～6Alkoxy radical C1～6Alkyl radical, C1～6Alkylsulfonyl radical C1～6Alkyl radical, C1～6Alkylthio sulfonic acidAcyl radical C1～6Alkyl radical, C3～6Phenyl substituted by one or more of cycloalkyl or 3-10 membered heterocyclic group containing 1-4 heteroatoms selected from O, N and S, n represents 1, 2, 3;
R7represents unsubstituted phenyl or a 3-to 10-membered heterocyclic group containing 1 to 4 heteroatoms selected from O, N and S, selected from C1～6Alkyl radical, C1～6Alkoxy radical, C1～6Alkylamino radical, C1～6Alkylthio, halogen, C2～4Alkenyl radical, C2～4Alkynyl, amino, nitro, cyano, carboxyl, C1～6Alkoxycarbonyl group, C1～6Alkoxy radical C1～6Alkyl radical, C1～6Alkylsulfonyl radical C1～6Alkyl radical, C1～6Alkylthio sulfonyl C1～6Alkyl radical, C3～6Phenyl substituted by one or more of cycloalkyl, 3-to 10-membered heterocyclic group containing 1 to 4 hetero atoms selected from O, N and S, C substituted by halogen1～6Alkyl, halogen, C1～6Alkylamino radical, C2～4Alkynyl, C2～4Alkenyl radical, C1～6Alkoxy, nitro, cyano, C3～6Cycloalkyl, amino, C1～6An alkylthio group;
R8represents C1～6Alkylamino radical, C1～6Alkylthio radical, C1～6Alkylamino radical C1～6Alkyl radical, C1～6Alkylthio group C1～6Alkyl, halogen, amino, cyano, nitro, C1～6Alkoxy radical C1～6Alkyl, phenyl C1～6Alkyl, phenoxy or phenoxy C1～6Alkyl, selected from C1～6Alkyl radical, C1～6Alkoxy radical, C1～6Alkylamino radical, C1～6Alkylthio, halogen, C2～4Alkenyl radical, C2～4Alkynyl, amino, nitro, cyano, carboxyl, C1～6Alkoxycarbonyl group, C1～6Alkoxy radical C1～6Alkyl radical, C1～6Alkylsulfonyl radical C1～6Alkyl radical, C1～6Alkylthio sulfonyl C1～6Alkyl radical, C3～6Phenyl substituted by one or more cycloalkyl groups,Phenyl radical C1～6Alkyl, phenoxy or phenoxy C1～6An alkyl group;
R9represents hydrogen, C1～6Alkyl radical, C3～6Cycloalkyl, unsubstituted phenyl or 3-to 10-membered heterocyclic group containing 1 to 4 heteroatoms selected from O, N and S, selected from C1～6Alkyl radical, C1～6Alkoxy radical, C1～6Alkylamino radical, C1～6Alkylthio, halogen, C2～4Alkenyl radical, C2～4Alkynyl, amino, nitro, cyano, carboxyl, C1～6Alkoxycarbonyl group, C1～6Alkoxy radical C1～6Alkyl radical, C1～6Alkylsulfonyl radical C1～6Alkyl radical, C1～6Alkylthio sulfonyl C1～6Alkyl radical, C3～6Phenyl substituted by one or more of cycloalkyl or 3-10 membered heterocyclic group containing 1-4 hetero atoms selected from O, N and S.
More preferably, R3Represents hydrogen, methyl, ethyl, cyclopropyl;
R4represents methyl, ethyl, isopropyl;
x represents-S (O)nR6、-CH2R7、-(C＝O)R8Wherein, in the step (A),
R6represents unsubstituted phenyl or a 3-to 10-membered heteroaromatic group containing 1 to 4 heteroatoms selected from O, N and S, and is selected from C1～6Alkyl radical, C1～6Phenyl substituted by one or more of alkoxy and halogen or 3-10-membered aromatic heterocyclic group containing 1-4 heteroatoms selected from O, N and S, wherein n represents 2;
R7represents unsubstituted phenyl or a 3-to 10-membered heteroaromatic group containing 1 to 4 heteroatoms selected from O, N and S, and is selected from C1～6Alkyl radical, C1～6Phenyl substituted by one or more of alkoxy and halogen, 3-to 10-membered aromatic heterocyclic group containing 1 to 4 hetero atoms selected from O, N and S, and C substituted by halogen1～6Alkyl radical, C1～6Alkylamino radical, C2～4Alkynyl, C2～4Alkenyl radical, C1～6Alkoxy radical, C1～6An alkylthio group;
R8represents C1～6Alkylamino radical, C1～6Alkylthio radical, C1～6Alkylamino radical C1～6Alkyl radical, C1～6Alkylthio group C1～6Alkyl, phenyl C1～6Alkyl or phenoxy radicals, selected from C1～6Alkyl radical, C1～6Alkoxy radical, C1～6Alkylamino radical, C1～6Alkylthio, halogen, C2～4Alkenyl radical, C2～4Alkynyl, amino, nitro, cyano, carboxyl, C1～6Alkoxycarbonyl group, C1～6Alkoxy radical C1～6Alkyl radical, C1～6Alkylsulfonyl radical C1～6Alkyl radical, C1～6Alkylthio sulfonyl C1～6Alkyl radical, C3～6Phenyl C substituted by one or more radicals in cycloalkyl1～6Alkyl or phenoxy.
The term "heterocycle" or "heterocyclic group" means a 3-to 10-membered aromatic or non-aromatic heterocycle containing 1 to 4 heteroatoms selected from O, N and S and a 4-to 10-membered cyclic compound having a lactone, cyclic ether, lactam structure, and includes bicyclic groups. Thus, "heterocyclyl" includes "arylheterocyclyl" and its dihydro or tetrahydro analogs. The heterocyclyl substituents may be attached via a carbon atom or a heteroatom. The term "arylheterocyclyl" means a stable monocyclic or bicyclic ring of up to 7 atoms in each ring, which may include one aromatic ring and contain 1 to 4 heteroatoms selected from O, N and S. Aromatic heterocyclic groups within the scope of this definition include, but are not limited to: acridinyl, carbazolyl, cinnolinyl, quinoxalinyl, pyrazolyl, indolyl, benzotriazolyl, thienyl, furyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl, oxazolyl, isoxazolyl, indolyl, pyrazinyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, tetrahydroquinolinyl, thiazolyl, imidazolyl, triazolyl, oxadiazolyl, thiadiazolyl, triazinyl, as defined for heterocycles, "aryl heterocyclyl" is also to be understood as including any N-oxide derivative of a nitrogen-containing aryl heterocyclyl.
The salt is an agriculturally and pharmaceutically acceptable salt, preferably an acid addition salt prepared by reacting the compound with a chemically acceptable acid, or a salt generated by reacting a hydroxypyrazole compound with an acidic group and a basic compound. Wherein, the acid is preferably selected from inorganic acid (such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid, etc.) and organic acid (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzoic acid, etc.); the basic compound is preferably selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate, and the like. The pharmaceutically acceptable salts are easily separated and can be purified by conventional separation methods, such as solvent extraction, dilution, recrystallization, column chromatography, preparative thin layer chromatography, and the like.
A method for producing the pyrazolone compound or a salt thereof, comprising the steps of:
(1) using a compound of the formula II with an excess of the compound R1R2NH to prepare a compound shown as a general formula III;
(2) reacting the compound shown as the general formula III with a compound X-A to prepare a compound shown as a general formula I;
wherein A represents halogen, methylsulfonyl or p-toluenesulfonyl, and the reaction equation is as follows:
Figure GDA0001480207400000041
the steps (1) and (2) are carried out in an aprotic solvent under the action of alkali; the reaction temperature is-30-180 ℃, preferably-5-90 ℃.
The solvent is acetonitrile, diethyl ether, tetrahydrofuran, DMF or DMSO, preferably acetonitrile, tetrahydrofuran or DMF; the alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, triethylamine, NaH, DIPEA or DBU, preferably NaH, triethylamine or potassium carbonate.
A herbicidal composition comprising a herbicidally effective amount of at least one of said pyrazolone compounds or salts thereof.
The herbicide composition also comprises a preparation auxiliary agent.
A method for controlling harmful plants, which comprises applying a herbicidally effective amount of at least one of the pyrazolone compounds or salts thereof or the herbicide composition on plants or in the area of harmful plants.
The application of at least one of the pyrazolone compounds or the salts thereof or the herbicide composition in controlling harmful plants is preferably used for controlling the harmful plants in useful crops, wherein the useful crops are transgenic crops or crops treated by genome editing technology.
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, 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 GDA0001480207400000071
is/are as follows
Figure GDA0001480207400000072
[ 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.
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, butachlor, benfluralin-bencarbzachlor, bencarbzamide, bencarb-N-P-N-P-N-P-N-, 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, bensulfuron-methyl, benazol-methyl, bensulfuron-methyl, benazol-methyl, benflurazid, benfluridimethyl, benfluridil, benflurazid, benfluridil, ben, 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, benfurbenfluridone, benfluridone, benfurin, benfluridone, benfurbenfurbenfurin, benfurbenfurbenfurbenfurbenfurbenfurin, benfluridone, benfurbenfurbenfurbenfurbenfurin, benfurin, benfluridone, benfurin, benfurbenfurbenfurin, benfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurbenfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurin, benfurin, benfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurbenfurin, benfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurin, benfurin, benfurbenfurbenfurin, benfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurbenfurbenfur, 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, benazolin, thiuron, thifenbenazolin, thiuron, thifenbenazolin, thiuron, thifenbenazolin, thiuron, thifenbencarb, thiuron, thifenbencarb, thiuron, thifenbencarb, thiuron, thifenbencarb, 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, clorac, 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, mefenap-ethyl, mefenoxaprop-p-ethyl, mefenofos, mefenoxaprop-p-ethyl, mefenoxaprop-p-ethyl, mefenoxaprop-p-ethyl, mefenoxaprop-p-ethyl, mefenofos, mefenap-p-ethyl, mefenoxaprop-p-ethyl, mefenoxaprop-p-ethyl, mefenoxaprop-p-ethyl, mefenozide, mefenoxaprop-ethyl, mefenoxaprop-p-ethyl, mefenoxaprop-p-ethyl, mefenoxaprop-p-, 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, pyraclonil, pyraoxystrobin, pyraclonil, pyraclostrobin, propyzachlor, pyraclostrobin, flufenapyr-ethyl, pyraclostrobin, flufenapyr-ethyl, pyraclostrobin, 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, tebufenozide, tebufadix, tebufenozide, tebufalin, tebufenozide, tebufalin, 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, thiothifluzone, pyrazone, thiothifluzone, thion, thiothifluzone, thion, thiobenflurazolidone, thion, thifluzone, thion, thifluzone, thidiazuron, thidiaz, 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.
Several methods for preparing the compounds of the present invention are illustrated in the schemes and examples below. The starting materials are either commercially available or can be prepared by methods known in the literature. 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.
In view of the economics and versatility of the compounds, the process examples provided below are intended 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 not 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. Wherein the hydrogen spectrum conditions of nuclear magnetic resonance are as follows:1HNMR was measured by AVANCE AV-500 nuclear magnetic resonance apparatus with TMS as internal standard and mass spectra by Shimadzu-2010A mass spectrometer.
Table 1 below gives a series of compounds having the following structural formula:
table 1 Structure of Compounds and methods of use thereof1HNMR data
Figure GDA0001480207400000111
Figure GDA0001480207400000112
Figure GDA0001480207400000121
Figure GDA0001480207400000131
Figure GDA0001480207400000141
Figure GDA0001480207400000151
Figure GDA0001480207400000161
Figure GDA0001480207400000171
Figure GDA0001480207400000181
Figure GDA0001480207400000191
Figure GDA0001480207400000201
Figure GDA0001480207400000211
Figure GDA0001480207400000221
Examples of representative compounds are as follows:
1. preparation of Compound 005
Figure GDA0001480207400000222
2.0g of compound A1, 1.5g of triethylamine and 10mL of acetonitrile are mixed, the mixture is cooled to 0 ℃ in an ice bath under stirring, 1.0g of p-ethyl benzene sulfonyl chloride is slowly dripped at the temperature of 0-5 ℃, and the mixture is slowly heated to room temperature after dripping and stirred for reaction for 2 hours. Then, 50mL of water was added dropwise to the reaction mixture to precipitate a pale yellow solid. Suction filtration, cake washing with water, drying, 2.0g light yellow solid, yield: 71% and 95% HPLC purity.
2. Preparation of Compound 011
Figure GDA0001480207400000231
Dissolving 0.8g of dimethylamino methanol in 10mL of acetonitrile, cooling to 0 ℃ in an ice bath under stirring, slowly adding 0.4g of 60% NaH at 0-5 ℃, reacting for 30min under stirring, then adding 2.3g of compound A2, heating to room temperature, and stirring overnight. Adding 50mL of water into the reaction solution, adjusting the pH value to 6 by using dilute hydrochloric acid, extracting by using ethyl acetate, washing an organic phase by using water, drying by using anhydrous sodium sulfate, concentrating, and purifying an obtained crude product by using column chromatography to obtain 1.8g of off-white solid, wherein the yield is 72 percent, and the HPLC purity is 97 percent.
3. Preparation of Compound 016
Figure GDA0001480207400000232
2.2g of the compound A3, 1.5g of triethylamine and 10mL of acetonitrile are mixed, cooled to 0 ℃ in an ice bath under stirring, 0.8g of dimethyl chlorophosphate is slowly added at 0-5 ℃, and the mixture is stirred at room temperature overnight. Adding 50mL of water into the reaction solution, adjusting the pH value to 6 with dilute hydrochloric acid, extracting with ethyl acetate, washing an organic phase with water, drying with anhydrous sodium sulfate, concentrating, and purifying the obtained crude product by column chromatography to obtain 2.1g of a light yellow solid, wherein the yield is 77% and the HPLC purity is 94%.
4. Preparation of Compound 088
Figure GDA0001480207400000233
2.0g of Compound A4, 2.0g of anhydrous potassium carbonate and 10mL of acetonitrile were mixed, and 0.8g of phenyl chloroformate was slowly dropped under vigorous stirring. The reaction was stirred overnight at room temperature. 50mL of water was added to the reaction solution, followed by extraction with ethyl acetate. The organic phase was washed with water and concentrated to give a crude product which was purified by column chromatography to give 2.1g of an off-white solid in 77% yield and 95% HPLC purity.
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 weed 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 2.
TABLE 2 post-emergence weed test results
Figure GDA0001480207400000241
Figure GDA0001480207400000251
Figure GDA0001480207400000261
Note: the application dosage is 250 g/hectare of effective components, and the water adding amount is 450 kg/hectare.
Evaluating the safety of transplanted rice and the weed control effect of paddy field:
after the paddy field soil was filled in a pot of 1/1,000,000 hectare, seeds of barnyard grass, moleplant seed and monochoria vaginalis were sown and covered with soil gently. Thereafter, the resulting mixture was left standing in a greenhouse with the water depth of 0.5 to 1 cm, the water depth of the mixture was maintained at 3 to 4 cm, and the amount of the wettable powder or the aqueous diluted suspension of the suspension, which was prepared by preparing the compound of the present invention according to a usual formulation method, was 1.5 leaves in barnyard grass, moleplant seed and monochoria vaginalis, and was subjected to a uniform dropping treatment with a pipette so as to obtain a predetermined amount of the 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 state of barnyard grass, moleplant seed and monochoria vaginalis on the 14 th day after the treatment with the agent and the growth state of rice on the 21 st day after the treatment with the agent were respectively observed with naked eyes, and the weeding effect was evaluated at an activity standard level of 0 to 10, thereby obtaining the results shown in table 3.
TABLE 3 results of rice field transplantation experiments (250 g/ha active ingredient)
Serial number Barnyard grass All-grass of Japanese stephania Herba Monochoriae Rice (Oryza sativa L.) with improved resistance to stress
006 10 10 10 0
017 10 9 10 0
018 10 10 10 0
019 10 10 9 0
020 10 10 10 0
022 10 10 10 0
023 10 10 10 0
025 10 9 10 0
028 10 10 10 0
029 10 10 10 0
030 10 10 10 0
Note: cockspur grass, moleplant seed and monochoria vaginalis seed are collected from Heilongjiang China and detected to have drug resistance to pyrazosulfuron-ethyl with conventional dosage.
And (3) comparison test:
the test procedure is in accordance with the aforementioned post-emergence weed test, and the results of comparative tests on the compounds are shown in tables 4 to 10, wherein the comparative examples a to j all come from patent CN 105218449A.
TABLE 4 comparative test results
Figure GDA0001480207400000271
Figure GDA0001480207400000281
TABLE 5 comparative test results
Figure GDA0001480207400000282
TABLE 6 comparative test results
Figure GDA0001480207400000283
Figure GDA0001480207400000291
TABLE 7 comparative test results
Figure GDA0001480207400000292
TABLE 8 comparative test results
Figure GDA0001480207400000293
Figure GDA0001480207400000301
TABLE 9 comparative test results
Figure GDA0001480207400000302
TABLE 10 comparative test results
Figure GDA0001480207400000303
Figure GDA0001480207400000311
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 (12)

1. A pyrazolone compound of formula I or a salt thereof:
Figure FDF0000008516130000011
in the formula (I), the compound is shown in the specification,
R1R2n represents butyrolactam or valerolactam which are unsubstituted or substituted on the ring by one or more groups selected from fluorine, chlorine, methyl, ethyl, methoxy and ethoxy;
R3represents hydrogen, C1～4Alkyl radical, C2～4Alkenyl radical, C2～4Alkynyl, unsubstituted or with C1～4Alkyl substituted C3～6CycloalkanesA group;
R4represents methyl, ethyl, n-propyl, isopropyl, cyclopropyl;
x represents-S (O)nR6、-(C＝O)R8Wherein, in the step (A),
R6represents unsubstituted or selected from C1～6Phenyl or pyridyl substituted by one of the alkyl groups, n represents 2;
R8represents C1～6Alkylamino radical, C1～6Alkylthio, phenyl, phenoxy.
2. A pyrazolone compound of formula I or a salt thereof:
Figure FDF0000008516130000012
in the formula (I), the compound is shown in the specification,
R1R2n represents butyrolactam or valerolactam which are unsubstituted or substituted on the ring by one or more groups selected from fluorine, chlorine, methyl, ethyl, methoxy and ethoxy;
R3represents hydrogen, C1～4Alkyl radical, C2～4Alkenyl radical, C2～4Alkynyl, unsubstituted or with C1～4Alkyl substituted C3～6A cycloalkyl group;
R4represents methyl, ethyl, n-propyl, isopropyl, cyclopropyl;
x represents-CH2R7Wherein, in the step (A),
R7represents unsubstituted or selected from C1～6Phenyl substituted by one of the alkyl groups, C substituted by halogen1～6Alkyl radical, C1～6Alkylamino radical, C2～4Alkenyl radical, C1～6Alkoxy radical, C2～4Alkynyl, C1～6An alkylthio group.
3. A pyrazolone compound of formula I or a salt thereof:
Figure FDF0000008516130000013
in the formula (I), the compound is shown in the specification,
R1R2n represents butyrolactam or valerolactam which are unsubstituted or substituted on the ring by one or more groups selected from fluorine, chlorine, methyl, ethyl, methoxy and ethoxy;
R3represents hydrogen, C1～4Alkyl radical, C2～4Alkenyl radical, C2～4Alkynyl, unsubstituted or with C1～4Alkyl substituted C3～6A cycloalkyl group;
R4represents methyl, ethyl, n-propyl, isopropyl, cyclopropyl;
x represents-PO (OR)9)2、-Si(OR9)3Wherein, in the step (A),
R9represents hydrogen, C1～6Alkyl radical, C3～6Cycloalkyl, unsubstituted phenyl or pyrazolyl, selected from C1～6Phenyl or pyrazolyl substituted with one or more groups selected from alkyl.
4. The pyrazolone compound or a salt thereof according to any one of claims 1 to 3,
R1R2n represents an unsubstituted butyrolactam or valerolactam;
R3represents hydrogen, methyl, ethyl or cyclopropyl;
R4represents methyl or ethyl.
5. A pyrazolone compound or a salt thereof, wherein the compound is selected from any one of the following:
Figure FDF0000008516130000021
Figure FDF0000008516130000022
Figure FDF0000008516130000031
Figure FDF0000008516130000041
Figure FDF0000008516130000051
6. the pyrazolone compound or a salt thereof according to claim 5, which is selected from any one of the following:
Figure FDF0000008516130000052
Figure FDF0000008516130000061
7. a herbicidal composition, characterized by comprising a herbicidally effective amount of at least one of the pyrazolone compounds or salts thereof according to any one of claims 1 to 6.
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 pyrazolone compounds or salts thereof according to any one of claims 1 to 6 or a herbicidal composition according to any one of claims 7 to 8 to plants or to the area of harmful plants.
10. Use of at least one of the pyrazolone compounds according to any one of claims 1 to 6 or a salt thereof or of the herbicide composition according to any one of claims 7 to 8 for controlling harmful plants.
11. The use according to claim 10, characterized in that the pyrazolone compounds or salts thereof are used for controlling harmful plants in crops of useful plants.
12. Use according to claim 11, wherein the useful crop is a transgenic crop or a crop treated with genome editing technology.
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