CN107652217B - Substituted benzoyl diketone nitrile compounds or its tautomer, salt, preparation method, Herbicidal combinations and application - Google Patents

Substituted benzoyl diketone nitrile compounds or its tautomer, salt, preparation method, Herbicidal combinations and application Download PDF

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CN107652217B
CN107652217B CN201711003067.0A CN201711003067A CN107652217B CN 107652217 B CN107652217 B CN 107652217B CN 201711003067 A CN201711003067 A CN 201711003067A CN 107652217 B CN107652217 B CN 107652217B
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salt
substituted
compound
alkyl
tautomer
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CN107652217A (en
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连磊
征玉荣
何彬
彭学岗
金涛
崔琦
刘娜
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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/CN2017/112014 priority patent/WO2019080226A1/en
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    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
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Abstract

The invention belongs to technical field of pesticide, and in particular to a kind of substituted benzoyl diketone nitrile compounds or its tautomer, salt, preparation method, Herbicidal combinations and application.Substituted the benzoyl diketone nitrile compounds or its tautomer, salt, as shown in general formula I-1:In formula, R1R2N is representedR is represented

Description

Substituted benzoyl diketone nitrile compound or tautomer, salt, preparation method, herbicidal composition and application thereof
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a substituted benzoyl diketone nitrile compound or tautomer and salt thereof, a preparation method, a herbicidal composition and application.
Background
The control of weeds is a crucial step in the realization of efficient agricultural processes, and despite the wide variety of herbicides available on the market, for example, WO2011012248A2 discloses 2- (3-aminobenzoyl) -3-cyclopropyl-3-oxopropanenitrile, a compound of formula (I), as a herbicideAnd the table discloses that X is Cl and Y is CF3Compound (No. 69); WO 97/46530A 1 discloses as herbicides ketones of the general formula I: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 benzoyl diketone nitrile compound or tautomer, salt, a preparation method, a weeding composition and application thereof, in order to develop a medicinal active substance with higher medicinal property, wider active spectrum and better safety.
The technical scheme adopted by the invention is as follows:
a substituted benzoyl diketone nitrile compound or its tautomer, salt is shown in general formula I-1:
in the formula,
R1R2n representsWherein,
selected from the group consisting of three-to eight-membered heterocyclic rings containing, in addition to C and the N atom at the 1-position, 0 to 3 of the following atoms or groups as ring members: o, NRb、S、SO、SO2、C＝O、C＝NRbAnd C is NORb；
RbSelected from hydrogen, C1～6Alkyl, halo C1～6Alkyl radical, C2～6Alkenyl, halo C2～6Alkenyl radical, C1～6Alkoxy radical C1～6Alkyl, halo C1～6Alkoxy radical C1～6Alkyl radical, C1～6Alkylcarbonyl, halo C1～6Alkylcarbonyl group, C1～6Alkylsulfonyl radical, C1～6Alkoxycarbonyl group, C1～6Alkylamino carbonyl, C1～6Alkyl carbonyl radical C1～6Alkyl radical, C1～6Alkoxycarbonyl radical C1～6Alkyl radical, C1～6Alkylamino carbonyl group C1～6Alkyl, unsubstituted or substituted by 1-3 substituents independently selected from halogen, nitro, cyano, C1～6Alkyl, halo C1～6Alkyl radical, C1～6Alkoxy, halo C1～6Alkoxy radical, C1～6Aryl, heteroaryl, arylcarbonyl, heteroarylcarbonyl, arylsulfonyl, arylmethyl, heteroarylmethyl substituted with a group selected from alkylcarbonyl;
Raone or more groups selected from the following groups: hydrogen, halogen, cyano, nitro, hydroxy, carboxy, amino, C1-C6Alkylsulfonyl radical, C1～6Alkyl, halo C1～6Alkyl radical, C2～6Alkenyl, halo C2～6Alkenyl radical, C1～6Alkoxy, halo C1～6Alkoxy radical, C1～6Alkylamino radical, C2～6Alkenyloxy, halogeno C2～6Alkenyloxy radical, C2～6Alkenylamino, halogeno C2～6Alkenylamino radical, C1～6Alkylcarbonyl, halo C1～6Alkylcarbonyl group, C1～6Alkoxycarbonyl group, C1～6Alkylamino carbonyl, C1～6Alkoxy radical C1～6Alkyl, halo C1～6Alkoxy radical C1～6Alkyl radical, C1～6Alkylcarbonyloxy C1～6Alkyl radical, C1～6Alkoxy radical C1～6Alkoxy, halo C1～6Alkoxy radical C1～6Alkoxy radical, C1～6Alkoxycarbonyl radical C1～6Alkoxy radical, C1～6Alkylcarbonyloxy, halo C1～6Alkylcarbonyloxy, C1～6Alkylcarbonylamino, C1～6Alkylsulfonyloxy, C1～6Alkylsulfonylamino group, C1～6Alkyl carbonyl radical C1～6Alkoxy, unsubstituted or substituted by 1 to 3 substituents independently selected from halogen, nitro, cyano, C1～6Alkyl, halo C1～6Alkyl radical, C1～6Alkoxy radical, C1～6Aryl, heteroaryl, arylcarbonyloxy, arylsulfonyloxy, arylmethyloxy, heteroarylmethyloxy, arylcarbonylamino, arylsulfonylamino, arylmethylamino or heteroarylmethylamino substituted with a group in alkylcarbonyl;
r representsWherein R is13Selected from hydrogen, C1-C6Alkyl, halo C1-C6Alkyl radical, C3-C6Cycloalkyl, 6-10 membered aryl with or without halogen substitution, 5-10 membered heteroaryl with or without halogen substitution containing 1-3 heteroatoms O, S, N.
Preferably, the first and second electrodes are formed of a metal,selected from 3 to 8 nitrogen-containing heterocyclic groups containing 1 to 3 hetero atoms, such as 4 to 8-membered lactam group, imidazolyl group, pyrazolyl group, which ring contains 1 to 3 following atoms or groups as a ring component in addition to C, N atom at 1-position and 1 or 2C ═ O: o, NRb、S、SO、SO2A five or six membered heterocyclic ring of (a); raSelected from hydrogen, C1～4Alkyl radical, C1～4Alkoxy, nitro, halogen, cyano, amino, C1～6Alkylamino radical, C1～6One or more groups in an alkylsulfonyl group; rbSelected from hydrogen, C1～6Alkyl, halo C1～6One or more groups in an alkyl group;
R13selected from hydrogen, C1-C6Alkyl, halo C1-C6Alkyl radical, C3-C6Cycloalkyl, 6-10 membered aryl with or without halogen substitution, 5-10 membered heteroaryl with or without halogen substitution containing 1-3 heteroatoms O, S, N.
More preferably still, the first and second liquid crystal compositions are,selected from butyrolactam, valerolactam, caprolactame, enantholactam, piperazinone, morpholinone, thiomorpholinone, imidazolyl, pyrazolyl, and mixtures thereof, RaSelected from hydrogen, fluorine, chlorine, methyl, ethyl, methoxy, ethoxy, nitro, cyano, amino, C1～6Alkylamino radical, C1-C6One or more groups in an alkylsulfonyl group; rbSelected from hydrogen, C1～6Alkyl, halo C1～6One or more groups in an alkyl group;
R13selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, cyclopropyl, with or without halogen substitution
The salt is potassium salt, sodium salt, ammonium salt, calcium salt, pyridine salt or choline salt.
In the definitions of the compounds of the general formula given above, the terms used are collectively defined as follows:
the aryl is 6-10-membered aryl, including phenyl or naphthyl and the like; the heteroaryl group is a 5-to 10-membered heteroaryl group containing 1 to 3O, S, N heteroatoms, such as pyridyl, pyrimidinyl, pyrazinyl, furyl, thienyl, pyrrolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, imidazolyl, triazolyl, oxadiazolyl, thiadiazolyl, pyridazinyl, triazinyl, quinolyl, quinoxalyl, indolyl, benzotriazolyl, benzothienyl, benzofuryl, isoquinolyl, tetrahydroquinolyl and the like.
In the compounds of the invention, all tautomers and mixtures thereof in any ratio are included.
The salt is an agriculturally and pharmaceutically acceptable salt, and preferably is an acid addition salt prepared by reacting the compound with a chemically acceptable acid, or a salt generated by reacting a 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 preparing the substituted benzoyldione nitriles or tautomers, salts thereof, comprising the steps of:
(1) reacting a compound of formula III with a hydroxylamine salt such as hydroxylamine hydrochloride in a suitable solvent such as ethanol, methanol, isopropanol, DMF or acetonitrile, a suitable base such as sodium/potassium acetate, sodium/potassium hydroxide, sodium/potassium tetrabutoxide, sodium/potassium carbonate at a temperature in the range from room temperature up to the boiling point of the solvent to produce a compound of formula II;
(2) reacting a compound of formula II in a suitable solvent, a suitable base, 1, 2-dichloroethane, acetonitrile, diethyl ether, tetrahydrofuran, DMF or DMSO, at a temperature in the range from room temperature up to the boiling point of the solvent to form a compound of formula I-1; the base is triethylamine, pyridine or DBU.
The chemical reaction equation is as follows:
wherein X is C1-C6 alkoxy, C1-C6 alkylamino, or the like.
A herbicidal composition containing the substituted benzoyldiketonitrile compound or at least one of its tautomers and salts as an active ingredient.
The weight percentage of the active component is 0.1-99%.
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 benzoyldione nitriles or tautomers, salts thereof or said herbicidal composition.
The application of the substituted benzoyl diketone nitrile compound or at least one of tautomer and salt thereof or the weeding composition in weed control.
The substituted benzoyl diketone nitrile compound or the tautomer and the salt thereof are used for controlling weeds in useful crops, preferably the useful crops are transgenic crops or crops treated by genome editing technology.
The compounds of formula I-1 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-1 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, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetable plants. The compounds of the formula I-1 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 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-1. depending on the general biological and/or chemical physical parameters, the compounds of formula I-1 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 coating (cutting) compositions, granules for broadcasting and soil application, spray granules, coated granules and absorbent granules, water dispersible granules (WG), water Soluble Granules (SG), ultra low volume Formulations, microcapsules and wax preparations of these individual types are described in the literature, "mineral powders, 9", Inc.' 9, published by "company, Inc.: see 5, Inc.: see.
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 the formula I-1. 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 amount of the compound of formula I-1 required to be used varies with the external conditions, such as temperature, humidity, the nature of the herbicide used, and the like. It may vary widely, for example between 0.001 and 1.0kg/ha, or more of active substance, but preferably between 0.005 and 750g/ha, in particular between 0.005 and 250 g/ha.
Detailed Description
The following examples are intended to illustrate the invention and should not be construed as limiting it in any way. The scope of the invention is indicated by the appended claims.
In view of the economic and diversity of the compounds, we prefer to synthesize some of the compounds, a selection of which are listed in table 1 below. Specific compound structures and corresponding compound information are shown in table 1. The compounds in table 1 are only for better illustrating the present invention, but not for limiting the present invention, and it should not be understood to limit the scope of the above-mentioned subject matter of the present invention to the following compounds for those skilled in the art.
Table 1 Structure of Compounds and methods of use thereof1HNMR data
R represents
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:
a process for preparing compound 001:
10g of 60% NaH is suspended in 50mL of dry DMF, 21.2g of 2-pyrrolidone is slowly added with stirring, after the addition is finished, the mixture is stirred for 30min at room temperature, then 24.3g of compound A1 is slowly added, the temperature is raised to 80 ℃, and the reaction is stirred for 3 h. Most DMF is evaporated under reduced pressure, the residual liquid is diluted by adding 100mL of water, the pH value is adjusted to about 3 by dilute hydrochloric acid, and ethyl acetate is used for extraction. The organic phase was washed successively with water, saturated sodium chloride solution, dried over anhydrous sodium sulfate and concentrated to give 26.2g of A2 as a pale yellow solid with an HPLC purity of 95%.
26g of Compound A2, 5g of concentrated sulfuric acid and 200mL of anhydrous methanol were mixed and heated under reflux overnight. The reaction mixture was concentrated under reduced pressure, and the residue was diluted with 100mL of water and extracted with dichloromethane. The organic phase was washed successively with water, saturated sodium bicarbonate solution, saturated sodium chloride solution, dried over anhydrous sodium sulfate and concentrated to give 25g of a pale yellow liquid A3.
20g of Compound A3, 5g of cyclopropylmethanone and 150mL of anhydrous toluene were mixed, and 7g of sodium tert-butoxide was slowly added with stirring, and after the addition, the mixture was refluxed overnight with increasing temperature. After the reaction, the temperature was lowered to 0 ℃, 100mL of water was added, the pH was adjusted to about 3 with dilute hydrochloric acid, and the mixture was separated. The organic phase was washed successively with water, saturated sodium chloride solution, dried over anhydrous sodium sulfate and concentrated. The crude product was distilled under reduced pressure to give 14.8g of a pale yellow liquid A4.
3.73g of Compound A4, 4.9g of triethyl orthoformate were mixed with 10mL of acetic anhydride and reacted under reflux with stirring for 3 hours. The reaction solution was concentrated under reduced pressure. To the residue was added 10mL of dry toluene, and the mixture was concentrated to remove volatile substances, whereby 4.3g of Compound A5 was obtained as a red liquid.
4.3g of Compound A5, 0.74g of hydroxylamine hydrochloride, 1.5g of sodium acetate and 10mL of ethanol were mixed and stirred at room temperature for 2.5 h. The solution was diluted with water, extracted with ethyl acetate, the organic phase was washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography to give 3.0g of pale yellow solid a6 with HPLC purity of 95%.
2.0g of Compound A6 was dissolved in 15mL of 1, 2-dichloroethane, 1mL of triethylamine was added at room temperature, and the reaction mixture was stirred for 4 hours and then concentrated under reduced pressure. To the residue was added 5mL of 2.0M hydrochloric acid and stirred vigorously for 2h, extracted with 1, 2-dichloroethane, the organic phase was washed successively with water, saturated sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated to give 1.76g of an off-white solid in 88% yield and 92% purity by HPLC.
The preparation method of the compound 002 comprises the following steps:
10g of 60% NaH is suspended in 50mL of dry DMF, 28.7g of 5-methoxy-2-pyrrolidone is slowly added with stirring, after the addition is finished, the mixture is stirred for 30min at room temperature, then 24.3g of compound A1 is slowly added, the temperature is raised to 80 ℃, and the reaction is stirred for 3 h. Most DMF is evaporated under reduced pressure, the residual liquid is diluted by adding 100mL of water, the pH value is adjusted to about 3 by dilute hydrochloric acid, and ethyl acetate is used for extraction. The organic phase was washed successively with water, saturated sodium chloride solution, dried over anhydrous sodium sulfate and concentrated to give 27.1g of A7 as a pale yellow solid with an HPLC purity of 97%.
25.0g of Compound A7 was mixed with 50mL of thionyl chloride, heated under reflux for 2 hours, and excess thionyl chloride was distilled off under reduced pressure to give 26.5g of A8 as a pale yellow liquid. The crude product was used in the next reaction without purification.
13.5g of t-butyl acetoacetate and 3.8g of anhydrous lithium chloride were added to 30mL of THF, cooled to 0 ℃ in an ice bath, and stirred for 1 hour while 20g of pyridine was slowly dropped thereinto under stirring. A mixed solution of 25g of Compound A8 and 100mL of THF was added dropwise. After the dripping is finished, the temperature is increased and the reflux is carried out for 8 hours. After the reaction, the temperature was lowered to 0 ℃ and 100mL of water was added, and the pH was adjusted to about 3 with dilute hydrochloric acid, followed by liquid separation. The organic phase was washed successively with water, a saturated sodium bicarbonate solution and a saturated sodium chloride solution, dried over anhydrous sodium sulfate, and the residue obtained by concentration was mixed with 60mL of trifluoroacetic acid and stirred at room temperature overnight. The reaction solution was concentrated under reduced pressure, and the residual solution was diluted with ethyl acetate, washed successively with water, a saturated sodium bicarbonate solution, and a saturated sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated to give 20g of a pale yellow liquid a 9.
3.8g of Compound A9, 1.5mL of N, N-dimethylformamide dimethyl acetal and 15mL of 1, 2-dichloroethane are mixed and stirred at reflux overnight. The reaction mixture was concentrated under reduced pressure to obtain 4.4g of compound A10 in an orange-red viscous state.
4.4g of Compound A10, 0.74g of hydroxylamine hydrochloride, 1.5g of sodium acetate and 10mL of ethanol were mixed and stirred at room temperature for 2.5 h. The solution was diluted with water, extracted with ethyl acetate, the organic phase was washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography to give 2.63g of pale yellow solid a11 with HPLC purity of 95%.
1.5g of Compound A11 was dissolved in 10mL of 1, 2-dichloroethane, 0.7mL of triethylamine was added at room temperature, and the reaction mixture was stirred for 4 hours and then concentrated under reduced pressure. To the residue was added 3mL of 2.0M hydrochloric acid and stirred vigorously for 2h, extracted with 1, 2-dichloroethane, the organic phase was washed successively with water, saturated sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated to give 1.2g of an off-white solid in 80% yield and 90% purity by HPLC.
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.
Placing monocotyledon and dicotyledon weed seeds in a plastic pot filled with soil, then covering 0.5-2 cm of soil, enabling the monocotyledon and dicotyledon weed seeds to grow in a good greenhouse environment, processing test plants in a 4-5 leaf period after sowing for 2-3 weeks, respectively dissolving the tested compound of the invention with acetone, then adding Tween 80, diluting the solution into a solution with a certain concentration by using a certain amount of water, and spraying the solution onto the plants by using a spray tower. The weeds were cultured in the greenhouse for 3 weeks after application, and the experimental effects of the weeds after 3 weeks are shown in Table 2.
TABLE 2 post-emergence weed test
Note: the application dosage is 300 g/hectare of effective components.
Experiments show that the compound generally has better weed control effect, particularly has good effect on main broadleaf weeds such as descurainia sophia, piemarker, chickweed and the like widely occurring in corn and wheat fields, and has good commercial value. In particular, we have noted that it has extremely high activity against broadleaf weeds such as descurainia sophia which are resistant to ALS inhibitors. In addition, the compound of the invention has good activity and crop safety for key weeds in direct seeding and transplanting paddy fields under the condition of proper dosage.
Comparative experiment:
the test conditions after seedling are the same as above, and the test dosage is 50 g/hectare; the observation time was 20 days after the test.
TABLE 3 comparative experimental results
As can be seen from Table 3, the compounds of the present invention are clearly superior in herbicidal activity to the comparative compounds.
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 (11)

1. A substituted benzoyl diketone nitrile compound or its tautomer, salt is shown in general formula I-1:
in the formula,
R1R2n representsWherein,
selected from 4-to 8-membered lactam group, imidazolyl group, pyrazolyl group,
RaOne or more groups selected from the following groups: hydrogen, C1～6Alkyl radical, C1～6Alkoxy, nitro, cyano, C1～6An alkylsulfonyl group;
Rbselected from hydrogen, C1～6Alkyl radical, C1～6Alkoxy radical C1～6Alkyl, unsubstituted or substituted by 1 to 3 substituents independently selected from cyano, C1～6Alkyl, halo C1～6Phenyl or benzyl substituted by a group in alkyl;
r representsWherein R is13Selected from hydrogen, C1-C6Alkyl, halo C1-C6Alkyl radical, C3-C6A cycloalkyl group.
2. A substituted benzoyldione nitrile compound as claimed in claim 1, or its tautomer, salt, wherein:
selected from butyrolactam, valerolactam, caprolactam, imidazolyl, pyrazolyl,
RaSelected from hydrogen, methyl, ethyl, methoxy, nitro, cyano, C1～6One or more groups in an alkylsulfonyl group;
Rbselected from hydrogen, C1～6Alkyl radical, C1～6Alkoxy radical C1～6Alkyl, cyanophenyl, benzyl;
R13selected from methyl, ethyl, tert-butyl, trifluoromethyl, cyclopropyl, cyclohexyl.
3. A substituted benzoyldione nitrile compound, or a tautomer, salt thereof, characterized by: the compound is selected from any one of the following compounds:
r represents
。
4. A substituted benzoyldione nitrile compound, or a tautomer, salt thereof, according to any one of claims 1-3, wherein: the salt is potassium salt, sodium salt, ammonium salt, calcium salt, pyridine salt or choline salt.
5. A process for preparing a substituted benzoyldione nitrile compound of any of claims 1-4, or a tautomer, salt thereof, comprising the steps of:
(1) reacting the compound shown in the formula III with hydroxylamine salt to obtain a compound shown in the formula II;
(2) reacting a compound of formula II in the presence of a base to produce a compound I-1;
the chemical reaction equation is as follows:
wherein X is C1-C6 alkoxy or C1-C6 alkylamino, R is1R2N and R13Is as defined in any one of claims 1 to 4.
6. A herbicidal composition characterized by: containing as an active ingredient at least one of the substituted benzoyldiketonitrile compounds according to any one of claims 1 to 4 or tautomers, salts thereof.
7. A herbicidal composition according to claim 6, characterized in that: the weight percentage of the active component is 0.1-99%.
8. A method for controlling harmful plants, which comprises applying a herbicidally effective amount of at least one of the substituted benzoyldiketonitriles according to any one of claims 1 to 4 or their tautomers, salts or herbicidal compositions according to claim 6 or 7 on plants or in the area of harmful plants.
9. Use of the substituted benzoyldiketonitrile according to any of claims 1 to 4 or at least one of its tautomers, salts or the herbicidal composition according to claim 6 or 7 for controlling weeds.
10. Use according to claim 9, characterized in that the substituted benzoyldiketonitriles or tautomers, salts thereof are used for controlling weeds in crops of useful plants.
11. The use according to claim 10, wherein the useful crop is a transgenic crop or a crop treated with genome editing techniques.
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CN1100261A (en) * 1993-05-18 1995-03-22 罗纳-普朗克农业有限公司 Herbicides

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