WO2019033590A1 - 取代的苯甲酰基环己二酮类化合物或其互变异构体、盐、制备方法、除草组合物及应用 - Google Patents

取代的苯甲酰基环己二酮类化合物或其互变异构体、盐、制备方法、除草组合物及应用 Download PDF

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WO2019033590A1
WO2019033590A1 PCT/CN2017/110610 CN2017110610W WO2019033590A1 WO 2019033590 A1 WO2019033590 A1 WO 2019033590A1 CN 2017110610 W CN2017110610 W CN 2017110610W WO 2019033590 A1 WO2019033590 A1 WO 2019033590A1
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alkyl
alkoxy
compound
salt
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PCT/CN2017/110610
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French (fr)
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连磊
征玉荣
何彬
彭学岗
金涛
崔琦
刘娜
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青岛清原化合物有限公司
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    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
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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
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Definitions

  • the invention belongs to the technical field of pesticides, and in particular relates to a substituted benzoylcyclohexanedione compound or a tautomer thereof, a salt, a preparation method, a herbicidal composition and application.
  • Patent WO 97/46530 A1 discloses ketone compounds of the general formula I as herbicides:
  • Patent CN1416422 A discloses a substituted benzoylcyclohexenone compound represented by the following formula (I) as a herbicide:
  • formula (I) a substituted benzoylcyclohexenone compound represented by the following formula (I) as a herbicide:
  • the present invention provides a substituted benzoylcyclohexanedione compound or a tautomer thereof, a salt thereof, and a preparation thereof. Methods, herbicidal compositions and applications.
  • R 1 R 2 N stands for among them
  • R b is selected from the group consisting of hydrogen, C 1-6 alkyl, halogenated C 1-6 alkyl, C 2-6 alkenyl, halogenated C 2-6 alkenyl, C 1-6 alkoxy C 1-6 alkane , halogenated C 1-6 alkoxy C 1-6 alkyl, C 1-6 alkylcarbonyl, halogenated C 1-6 alkylcarbonyl, C 1-6 alkylsulfonyl, C 1-6 alkane Oxycarbonyl group, C 1-6 alkylaminocarbonyl group, C 1-6 alkylcarbonyl C 1-6 alkyl group, C 1-6 alkoxycarbonyl C 1-6 alkyl group, C 1-6 alkylaminocarbonyl C 1 ⁇ 6 alkyl, unsubstituted or 1-3 independently selected from halogen, nitro, cyano, C 1-6 alkyl, halogenated C 1-6 alkyl, C 1-6 alkoxy, halogen An aryl
  • R a is selected from one or more of the following groups: hydrogen, halogen, cyano, nitro, hydroxy, carboxy, amino, C 1 -C 6 alkylsulfonyl, C 1-6 alkyl, halo C 1 to 6 alkyl, C 2 to 6 alkenyl, halogenated C 2 to 6 alkenyl, C 1 to 6 alkoxy, halo C 1-6 alkoxy, C 1-6 alkylamino, C 2-6 alkenyloxy, halo C 2-6 alkenyloxy, C 2-6 alkenylamino, halogenated C 2-6 alkenylamino, C 1-6 alkylcarbonyl, halogenated C 1-6 alkylcarbonyl a C 1-6 alkoxycarbonyl group, a C 1-6 alkylaminocarbonyl group, a C 1-6 alkoxy C 1-6 alkyl group, a halogenated C 1-6 alkoxy C 1-6 alkyl group, C 1 ⁇
  • R 1 and R 2 each independently represent a C 1-8 alkyl group, a C 1-8 alkenyl group or a C 1-8 alkynyl group having 0 to 4 hetero atoms, with or without halogen substitution, with or without halogen substitution.
  • Y is selected from C, N, O or S;
  • two R 11 located on different C atoms are connected to CH 2 , (CH 2 ) 2 , (CH 2 ) 3 , (CH 2 ) 4 , (CH 2 ) 5 , (CH 2 ) 6 , O, O(CH 2 ) 2 O, O(CH 2 ) 3 O, O(CH 2 ) 4 O, S(CH 2 ) 2 S or S(CH 2 ) 3 S;
  • two R 11 located on the same C atom are bonded to the following groups: (CH 2 ) 2 , (CH 2 ) 3 , (CH 2 ) 4 , (CH 2 ) 5 , (CH 2 6 , O, O(CH 2 ) 2 O, O(CH 2 ) 3 O, O(CH 2 ) 4 O, S(CH 2 ) 2 S or S(CH 2 ) 3 S;
  • R 12 is selected from -OR 13 or -SR 13 wherein R 13 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylsulfonyl, C 2 - C 6 alkenyl, halo C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 alkoxycarbonyl C 1 -C 6 alkyl, C 1 -C 6 alkylaminocarbonyl C 1 -C 6 alkyl, unsubstituted or 1-3 independently selected from halogen, nitro, cyano, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkane
  • Het is selected from a 4- to 8-membered lactam group, an imidazolyl group, a pyrazolyl group, and R a is selected from a C 1-4 alkyl group, a C 1-4 alkoxy group, a nitro group, a halogen group, a cyano group, an amino group, One or more of C 1 to 6 alkylamino groups and C 1 to 6 alkylsulfonyl groups;
  • R 1 and R 2 represents a C 1-4 acyl group containing 0 to 4 O, S, N with or without a halogen substitution; the other represents hydrogen, 0 to 4 O with or without a halogen substitution.
  • S, N is C 1 ⁇ 8-alkyl, C ⁇ 1. 8 alkenyl or C 1 ⁇ 8 alkynyl, unsubstituted or substituted selected from halogen, C having 0 to 4 hetero atoms with or without a halogen-substituted ⁇ 4 alkyl with one or more groups substituted with C 3 ⁇ 6 cycloalkyl;
  • two R 11 located on different C atoms are bonded to CH 2 , (CH 2 ) 2 , (CH 2 ) 3 , (CH 2 ) 4 , ( CH 2 ) 5 , (CH 2 ) 6 , O, O(CH 2 ) 2 O, O(CH 2 ) 3 O, O(CH 2 ) 4 O, S(CH 2 ) 2 S or S(CH 2 ) 3 S;
  • two R 11 located on the same C atom are bonded to the following groups: (CH 2 ) 2 , (CH 2 ) 3 , (CH 2 ) 4 , (CH 2 ) 5 , (CH 2 6 , O, O(CH 2 ) 2 O, O(CH 2 ) 3 O, O(CH 2 ) 4 O, S(CH 2 ) 2 S or S(CH 2 ) 3 S.
  • Het is selected from the group consisting of butyrolactam, valerolactam, caprolactam, heptanolactam, piperazinone, morpholinone, thiomorpholinone, imidazolyl, pyrazolyl, R a or one or more selected from the group consisting of fluorine, chlorine, methyl, ethyl, methoxy, ethoxy, nitro, cyano, amino, C 1-6 alkylamino, C 1 -C 6 alkylsulfonyl Group
  • R 1 represents acetyl, fluoroacetyl, difluoroacetyl, trifluoroacetyl, methoxyacetyl, ethoxyacetyl, methoxypropionyl, ethoxypropionyl, and R 2 represents hydrogen or is unsubstituted or Methyl, ethyl, propyl, butyl, pentyl substituted with one or more groups selected from the group consisting of fluorine, methoxy, ethoxy, propoxy, butoxy, methoxyethoxy , cyclopropyl;
  • two R 11 located on different C atoms are connected to CH 2 , (CH 2 ) 2 , (CH 2 ) 3 , O, O(CH 2 ) 2 O, O(CH 2 ) 3 O, S(CH 2 ) 2 S or S(CH 2 ) 3 S;
  • two R 11 located on the same C atom are bonded to the following groups: (CH 2 ) 2 , (CH 2 ) 3 , O, O(CH 2 ) 2 O, O(CH 2 ) 3 O, S(CH 2 ) 2 S or S(CH 2 ) 3 S.
  • R is selected from one of the groups shown by the formula:
  • R 12 is selected from the group consisting of a hydroxyl group, a C 1 -C 3 alkoxy group, a C 1 -C 3 alkylcarbonyloxy group, a C 1 -C 3 alkylsulfonyloxy group, a C 2 -C 4 alkenyloxy group, a halogenated C 2- C 4 alkenyloxy, unsubstituted or 1-3 independently selected from fluoro, chloro, bromo, nitro, cyano, methyl, trifluoromethyl, methoxy or trifluoromethoxy Substituted by a phenoxy group, a benzyloxy group, a phenylthio group, a benzylthio group, a benzoyloxy group, a benzenesulfonyloxy group, a benzoylmethoxy group, containing 1-3 O, A 5-10 membered heteroaryloxy group of a S, N heteroatom or a 5-10
  • the salt is a potassium salt, a sodium salt, an ammonium salt, a calcium salt, a pyridinium salt or a choline salt.
  • the aryl group is a 6-10 membered aryl group, including a phenyl group or a naphthyl group, etc.; the heteroaryl group is a 5-10 membered heteroaryl group having 1-3 O, S, N heteroatoms, for example Pyridyl, pyrimidinyl, pyrazinyl, furyl, thienyl, pyrrolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, imidazolyl, triazolyl, oxadiazolyl, thiadiazole Base, pyridazinyl, triazinyl, quinolyl, quinoxalinyl, fluorenyl, benzotriazolyl, benzothienyl, benzofuranyl, isoquinolyl, tetrahydroquinolyl, etc. .
  • various tautomers may exist due to enol interconversion and the like, and the present invention includes all tautomers and mixtures thereof in any ratio.
  • the salt is an agrochemically acceptable salt, preferably an acid addition salt obtained by reacting a compound of this type with a chemically acceptable acid, or a compound having an acidic group and a basic compound The salt produced.
  • the acid is preferably selected from the group consisting of inorganic acids (such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid) and organic acids (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzene).
  • the basic compound is preferably selected from the group consisting of sodium hydroxide and potassium hydroxide. Calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate.
  • the above pharmaceutically acceptable salts are easily separated and can be purified by conventional separation methods such as solvent extraction, dilution, recrystallization, column chromatography, and preparative thin layer chromatography.
  • a method of preparing the substituted benzoylcyclohexanedione compound or a tautomer thereof, a salt thereof, comprising the steps of:
  • X represents a halogen, a hydroxyl group
  • M represents an alkali metal or an alkaline earth metal (preferably Na, Li, K, Ca, Mg, etc.), and the reaction equation is as follows:
  • the step (1) is carried out in an aprotic solvent, a base and a catalyst.
  • the reaction with R 13 X is carried out in an aprotic solvent under the action of a base, and in the reaction with R 13 SM in an aprotic solvent, a base and an activator.
  • the reaction temperature is -30 ° C to 180 ° C, preferably -5 ° C to 90 ° C.
  • a dehydrating agent such as thionyl chloride, DCC or CDI or the like is added to the reaction.
  • the solvent is one or a combination of two or more kinds of aprotic solvents such as dichloromethane, 1,2-dichloroethane, acetonitrile, toluene, tetrahydrofuran, 1,4-dioxane, and ethyl acetate.
  • aprotic solvents such as dichloromethane, 1,2-dichloroethane, acetonitrile, toluene, tetrahydrofuran, 1,4-dioxane, and ethyl acetate.
  • dichloromethane 1,2-dichloroethane or toluene.
  • the base is sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, triethylamine, DIPEA or DBU, preferably triethylamine or potassium carbonate.
  • the catalyst is acetone cyanohydrin.
  • the activator is methanesulfonyl chloride, p-toluenesulfonyl chloride, trimethylchlorosilane, trifluoroacetyl chloride, trifluoroacetic anhydride, trifluoromethanesulfonyl chloride, Etc., used to activate the carbonyl group on the cyclohexanedione to make it easy to react with other reagents.
  • a herbicidal composition comprising at least one of the substituted benzoylcyclohexanedione compounds or tautomers and salts thereof as an active component.
  • the active ingredient is present in an amount of from 0.1 to 99% by weight.
  • a method of controlling a harmful plant comprising: using a herbicidally effective amount of the substituted benzoylcyclohexanedione compound or a tautomer thereof, a salt thereof, or the herbicidal composition On plants or in harmful plant areas.
  • the substituted benzoylcyclohexanedione compounds or their tautomers and salts are used to control weeds in useful crops.
  • the useful crop is a crop that has been treated with genetically modified crops or genome editing techniques.
  • the compounds of formula I of the present invention have outstanding herbicidal activity.
  • the active substances of the present invention are also effective for perennial weeds which grow from rhizomes, rhizomes, or other perennial organs and are difficult to control. In this regard, it is generally not important to use the substance before, before, or after germination. Particular mention is made of representative examples of monocotyledonous and dicotyledonous weed populations which can be controlled by the compounds of the invention, without limiting the identified species.
  • weed species in which the active substance is effective include monocotyledons: annual oats, rye, grasses, maiden, ferraris, medlar, genus, foxtail, and sedge, and perennial ice. Genus, Bermudagrass, Rhizoma and sorghum, and perennial sedge.
  • dicotyledonous weed species species whose effects can be extended to, for example, the annual genus Polyporus, Amaranth, Pomna, Wild Sesame, Stellaria, Amaranthus, White Mustard, Ipomoea, and Yellow Flower Genus, Matricaria and genus, and perennial weeds, genus, genus and genus.
  • the active substance of the present invention effectively controls harmful plants under the conditions of rice sowing, such as cockroaches, genus, genus, genus, genus, cane, and sedge.
  • the compound of the present invention is applied to the surface of the soil before germination, the weeds of the weeds can be completely prevented before the weeds grow, or when the weeds grow out of the cotyledons, and finally completely die after three to four weeks.
  • the compound of the present invention is particularly resistant to the following plants, and is active in the following plants, such as Apila, Xiaoye Sesame, Rolling Stalk, Poria, Ivy, Herba, Arabian, Pansy, Pansy, Poria and Kochia. .
  • the compounds of the present invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, there is no damage to important economic crop plants such as wheat, barley, rye, rice, corn, sugar beet, cotton and soybean. Or the damage is trivial. In particular, it is well compatible with cereal crops such as wheat, barley and corn, especially wheat. Thus, the compounds of the invention are highly suitable for the selective control of unwanted plants in agricultural or ornamental plants.
  • Transgenic plants Due to their herbicidal nature, these active substances can be used to control harmful plants in genetically engineered plant cultivation that is known or to be present.
  • Transgenic plants usually have superior traits, such as resistance to specific insecticides, particularly specific herbicides, resistance to pathogenic microorganisms of plant diseases or plant diseases, such as specific insects or fungi, bacteria or Viral microorganisms.
  • Other specific traits are related to the following conditions of the product, such as quantity, quality, storage stability, composition and specific ingredients.
  • the obtained transgenic plant product has 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 in economically important transgenic crops and ornamental plants, such as cereals, such as wheat, barley, rye, oats, millet, rice, cassava and corn, or for beets, Cultivation of cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetable plants.
  • the compounds of the formula I are preferably used as herbicides for the cultivation of useful plants which are resistant or resistant to the toxic effects of the herbicide by genetic engineering.
  • glufosinate herbicides eg EP-0242236 A, EP-0242246 A
  • glyphosate herbicides WO 92/00377
  • sulfonate An ureide herbicide EP-0257993 A, US-5013659 A
  • transgenic crop plant such as cotton which is capable of producing a Bacillus thuringiensis toxin (Bt toxin) which protects against damage by a particular pest (EP-0142924 A, EP-0193259 A);
  • Plant cells of the activity-reducing gene product can be prepared by, for example, expressing at least one appropriate antisense-RNA, sense-RNA to achieve co-suppression, or by expressing at least one appropriately constructed ribozyme, It specifically cleaves the transcription product of the above gene product.
  • DNA molecules comprising the entire coding sequence of the gene product, including any flanking sequences that may be present, and the use of DNA molecules comprising only a portion of the coding sequence, which must be sufficiently long to achieve antisense in the cell Effect. Sequences that are highly homologous but not identical to the gene product coding sequence can also be used.
  • the synthesized protein can be localized in any desired plant cell compartment.
  • the synthesized protein can be localized in any desired plant cell compartment.
  • 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 control can be improved or expanded.
  • the range of weeds, the application rate at the time of application is preferably a combination of the resistance of the transgenic crops and the performance of the herbicide, and the effects of the growth and yield of the transgenic crop plants.
  • the invention therefore also provides the use of said compounds as herbicides to control harmful plants in plants of transgenic crops.
  • the compounds of the invention can significantly modulate the growth of crop plants. By modulating the involvement of plant metabolism, these compounds are used to orient the components of the plant and promote harvesting, such as drying and dwarfing the plants. Moreover, they are also suitable for regulating and inhibiting unwanted plant growth without destroying the growth of the crop. Inhibition of plant growth plays a very important role in many monocotyledonous and dicotyledonous crops, as this reduces or completely prevents lodging.
  • the compound of the present invention can be applied using a general formulation, and a wettable powder, a concentrated emulsion, a sprayable solution, a powder or granules can be used.
  • a herbicidal composition comprising a compound 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.
  • suitable formulations 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 solution, suspension concentrate (SC), dispersible oil suspension (OD), oil or water diluent, solution of miscible oil, powder (DP), capsule suspension (CS) ), seed dressing composition, particles for spreading and soil application, sprayed particles, coated particles and absorbent particles, water dispersible particles (WG), water soluble particles (SG), ULV (super Low volume) formula, microcapsules and wax products.
  • WP wettable powders
  • SP water soluble powders
  • EC concentrated emulsions
  • EW oil dispersed in water and water dispersed in oil
  • SC sprayable solution, suspension concentrate
  • OD dispersible oil suspension
  • DP powder
  • Wettable powders can be uniformly dispersed in water, in addition to active substances, including diluents or inert substances, ionic and nonionic surfactants (wetting agents, dispersing agents), such as polyethoxylated alkylphenols, poly Ethoxylated fatty alcohol, polyoxyethyl aliphatic amine, fatty alcohol polyglycol ether sulfate, alkyl sulfonate, alkyl phenyl sulfonate, sodium lignosulfonate, 2, 2'- dinaphthylmethane Sodium 6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurate.
  • the herbicide active substance is finely ground, for example, using a conventional apparatus such as a hammer mill, a fan mill and a jet mill, and an auxiliary agent is simultaneously or sequentially mixed.
  • a concentrated emulsion such as butanol, cyclohexanone, dimethylformamide, xylene or a higher boiling aromatic compound or a mixture of hydrocarbons or solvents, and adding one more One or more ionic and/or nonionic surfactants (emulsifiers).
  • emulsifiers which can be used are, for example, calcium alkylaryl sulfonates of calcium dodecylbenzene sulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aromatic polyglycol ethers, fatty alcohols Polyglycol ether, propylene oxide-ethylene oxide condensation product, alkyl polyether, sorbitan ester such as sorbitan fatty acid ester, or polyoxyethylene sorbent such as polyoxyethylene sorbitan fatty ester A glycan ester.
  • nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aromatic polyglycol ethers, fatty alcohols Polyglycol ether, propylene oxide-ethylene oxide condensation product, alkyl polyether, sorbitan ester such as sorbitan fatty acid ester, or polyoxyethylene sorbent such as polyoxyethylene sorbitan fatty ester A gly
  • the active substance and the finely divided solid matter are ground to obtain a powder, a solid substance such as talc, a natural clay such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • a water or oil based suspension can be prepared by, for example, wet milling using a commercially available bead mill with or without the addition of a surfactant of the other formulation type described above.
  • an aqueous organic solvent may be used, using a stirrer, a colloid mill and/or a static mixer, and if necessary, a surfactant of another formulation type as described above may be added.
  • the granules are prepared by spraying the active material onto the adsorbate, granulating with an inert material, or concentrating the active material onto the surface of, for example, a sand or kaolinite carrier, granulating the inert material by a binder, and adhering Mixtures such as polyvinyl alcohol, sodium polyacrylate or mineral oil.
  • Suitable actives can be plasmidized by the method of preparing fertilizer granules, and if necessary, fertilizer can be mixed.
  • the water-suspended granules are prepared by a usual method such as spray-drying, fluidized bed granulation, disc granulation, mixing using a high speed mixer, and extrusion without a solid inert material.
  • the agrochemical formulations usually comprise from 0.1 to 99% by weight, in particular from 0.1 to 95%, of the active substance I.
  • the concentration of the active substance in the wettable powder is, for example, from about 10 to 99% by weight, and the usual formulation components constitute the remaining amount by weight to 100%.
  • the concentration of the active substance in the concentrated emulsion may range from about 1 to 90%, preferably from 5 to 80% by weight.
  • the powder formulation comprises from 1 to 30% by weight of active substance, usually from 5 to 20% by weight of active substance, whereas the sprayable solution comprises from about 0.05 to 80%, preferably from 2 to 50% by weight of active substance. .
  • the content of the active material in the water-suspended granules mainly depending on whether the active material is liquid or solid, and auxiliaries, fillers and the like used in granulation.
  • the content of the active substance in the aqueous suspension granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the preparation of the active substance may include a tackifier, a wetting agent, a dispersing agent, an emulsifier, a penetrating agent, a preservative, an antifreezing agent, a solvent, a filler, a carrier, a coloring agent, an antifoaming agent, an evaporation inhibitor, and pH and viscosity modifiers commonly used in all cases.
  • insecticide active substances such as insecticides, acaricides, herbicides and fungicides, or with safeners, fertilizers and/or plant growth regulators.
  • safeners for premixed or filled mix.
  • Suitable active substances which can be mixed with the active substance of the present invention in a mixed preparation or a tank mix are, for example, "World Pesticide New Variety Technology Encyclopedia", China Agricultural Science and Technology Press, 2010.9 and the literature cited herein.
  • the herbicide active substance mentioned below may be mixed with the mixture of the formula I (note: the name of the compound, or a common name according to the International Organization for Standardization (ISO), or a chemical name, if appropriate, a code): Amine, butachlor, alachlor, propisochlor, metolachlor, stilben, acetochlor, chlorfenapyr, acetochlor, naproxen, R-levoperin Acetochlor, dipivoxil, thiaceuramide, dibenzoylamine, piracetamide, herbicide, flufenic acid, bromobutyramide, dimethoprim, high-efficiency dimethyl Thiamethoxazole, acetophene, flufenacet,
  • the commercially available formulations are diluted in a conventional manner, for example, in wettable powders, concentrated emulsions, suspensions, and granules suspended in water, diluted with water.
  • Granules for granules or soil application or sprayed and sprayed solutions are generally not required to be further diluted with inert materials prior to use.
  • the amount of the compound of formula I required varies with external conditions, such as temperature, humidity, the nature of the herbicide used, and the like. It can have a big
  • the extent of the change is, for example, between 0.001 and 1.0 kg/ha, or more active substance, but preferably between 0.005 and 750 g/ha, in particular between 0.005 and 250 g/ha.
  • the activity level criteria for harmful plant damage are as follows:
  • Grade 9 growth control rate is above 95%
  • Level 7 growth control rate is above 80%
  • Level 5 The growth control rate is above 60%
  • Level 2 growth control rate is 5-20%
  • Level 1 The growth control rate is below 5%
  • the above growth control rate is the fresh weight control rate.
  • the test plants were treated at the 5-leaf stage, and the tested compounds of the present invention were each dissolved in acetone, then Tween 80 was added, diluted with a certain amount of water to a certain concentration, and sprayed onto the plants using a spray tower. After the application, the cells were cultured for 3 weeks in the greenhouse, and the experimental effects of the weeds after 3 weeks are shown in Table 2.
  • the application dose is 300 g/ha of active ingredient.
  • the compounds of the present invention generally have better weed control effects, especially for the broad-leaved weeds such as sage, ramie, which are widely occurring in corn wheat fields, and have good commercial value.
  • the broad-leaved weeds such as Phyllostachys pubescens, which are resistant to ALS inhibitors, have extremely high activity.
  • the compounds of the present invention have been tested to have good activity and crop safety against key weeds in live and transplanted paddy fields at suitable dosages.
  • the post-emergence test conditions were the same as above, and the test was 50 g/ha; the observation time was 20 days after the test.
  • the compounds of the present invention are significantly superior to the comparative compounds in herbicidal activity.

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Abstract

一种取代的苯甲酰基环己二酮类化合物或其互变异构体、盐、制备方法、除草剂组合物及应用。取代的苯甲酰基环己二酮类化合物或其互变异构体、盐，如通式I所示：，式中，R 1R 2N代表，R代表、或。

Description

取代的苯甲酰基环己二酮类化合物或其互变异构体、盐、制备方法、除草组合物及应用 技术领域
本发明属于农药技术领域，具体涉及一种取代的苯甲酰基环己二酮类化合物或其互变异构体、盐、制备方法、除草组合物及应用。
背景技术
杂草的防治是实现高效农业过程中一个至关重要的环节，尽管市场上的除草剂种类多样，例如，专利WO97/46530 A1公开了如下通式Ⅰ所示的酮类化合物作为除草剂：
Figure PCTCN2017110610-appb-000001
专利CN1416422 A公开了如下通式(Ⅰ)所示的取代的苯甲酰基环己烯酮化合物用作除草剂：
Figure PCTCN2017110610-appb-000002
但由于市场的不断扩大、杂草的抗性、药物的使用寿命以及药物的经济性等问题以及人们对环境的日益重视，需要科学家们不断研究进而开发出新的高效、安全、经济以及具有不同作用方式的除草剂品种。
发明内容
为开发一种药性更高、活性谱更广、安全性更好的药物活性物，本发明提供了一种取代的苯甲酰基环己二酮类化合物或其互变异构体、盐、制备方法、除草组合物及应用。
本发明采用的技术方案如下：
一种取代的苯甲酰基环己二酮类化合物或其互变异构体、盐，如通式I所示：
Figure PCTCN2017110610-appb-000003
式中，
R1R2N代表
Figure PCTCN2017110610-appb-000004
其中，
Het选自三至八元杂环，该环上除含有C和1-位上的N原子外，还含有0-3个以下原子 或基团作为环的组成部分：O、NRb、S、SO、SO2、C＝O、C＝NRb或C＝NORb，且当C＝O、C＝NRb或C＝NORb在2-位时，3-位不能为N或S；
Rb选自氢、C1～6烷基、卤代C1～6烷基、C2～6烯基、卤代C2～6烯基、C1～6烷氧基C1～6烷基、卤代C1～6烷氧基C1～6烷基、C1～6烷基羰基、卤代C1～6烷基羰基、C1～6烷基磺酰基、C1～6烷氧基羰基、C1～6烷氨基羰基、C1～6烷基羰基C1～6烷基、C1～6烷氧基羰基C1～6烷基、C1～6烷氨基羰基C1～6烷基、未取代的或被1-3个独立选自卤素、硝基、氰基、C1～6烷基、卤代C1～6烷基、C1～6烷氧基、卤代C1～6烷氧基、C1～6烷基羰基中的基团所取代的芳基、杂芳基、芳基羰基、杂芳基羰基、芳基磺酰基、芳甲基、杂芳基甲基；
Ra选自以下基团中的一个或多个基团：氢、卤素、氰基、硝基、羟基、羧基、氨基、C1-C6烷基磺酰基、C1～6烷基、卤代C1～6烷基、C2～6烯基、卤代C2～6烯基、C1～6烷氧基、卤代C1～6烷氧基、C1～6烷氨基、C2～6烯氧基、卤代C2～6烯氧基、C2～6烯氨基、卤代C2～6烯氨基、C1～6烷基羰基、卤代C1～6烷基羰基、C1～6烷氧基羰基、C1～6烷氨基羰基、C1～6烷氧基C1～6烷基、卤代C1～6烷氧基C1～6烷基、C1～6烷基羰基氧基C1～6烷基、C1～6烷氧基C1～6烷氧基、卤代C1～6烷氧基C1～6烷氧基、C1～6烷氧基羰基C1～6烷氧基、C1～6烷基羰基氧基、卤代C1～6烷基羰基氧基、C1～6烷基羰基氨基、C1～6烷基磺酰基氧基、C1～6烷基磺酰基氨基、C1～6烷基羰基C1～6烷氧基、未取代的或被1-3个独立选自卤素、硝基、氰基、C1～6烷基、卤代C1～6烷基、C1～6烷氧基、C1～6烷基羰基中的基团所取代的芳基、杂芳基、芳基羰基氧基、芳基磺酰基氧基、芳甲基氧基、杂芳基甲基氧基、芳基羰基氨基、芳基磺酰基氨基、芳甲基氨基或杂芳基甲基氨基；
或者R1、R2分别代表氢，含有或没有卤素取代的含0～4个杂原子的C1～8烷基、C1～8烯基或C1～8炔基，含有或没有卤素取代的含0～4个杂原子的C1～4酰基，未取代或被选自卤素、含有或没有卤素取代的含0～4个杂原子的C1～4烷基中的一个或多个基团所取代的C3～6环烷基；
R代表
Figure PCTCN2017110610-appb-000005
其中，
R11选自氢、C1-C6烷基、C3-C6环烷基、C1-C6烷氧基、C1-C6烷氧基C1-C6烷基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷硫基、含有或没有卤素取代的6-10元芳基、含有或没有卤素取代的含1-3个O、S、N杂原子的5-10元杂芳基，n＝0-6；
Y选自C、N、O或S；
Z选自C、N、O、S、SO、SO2或C＝O；
或者当n＝2、且Z和/或Y选自C时，位于不同C原子上的两个R11连接成CH2、(CH2)2、 (CH2)3、(CH2)4、(CH2)5、(CH2)6、O、O(CH2)2O、O(CH2)3O、O(CH2)4O、S(CH2)2S或S(CH2)3S；
或者当n＝2时，位于同C原子上的两个R11连接成如下基团：(CH2)2、(CH2)3、(CH2)4、(CH2)5、(CH2)6、O、O(CH2)2O、O(CH2)3O、O(CH2)4O、S(CH2)2S或S(CH2)3S；
R12选自-OR13或-SR13，其中，R13选自氢、C1-C6烷基、C1-C6烷基羰基、C1-C6烷基磺酰基、C2-C6烯基、卤代C2-C6烯基、C2-C6炔基、C1-C6烷氧基羰基C1-C6烷基、C1-C6烷氨基羰基C1-C6烷基、未取代的或被1-3个独立选自卤素、硝基、氰基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基或卤代C1-C6烷氧基中的基团所取代的芳基、芳甲基、芳基羰基、芳基磺酰基、杂芳基、杂芳基羰基或芳基羰基甲基。
优选地，Het选自4～8元内酰胺基、咪唑基、吡唑基，Ra选自C1～4烷基、C1～4烷氧基、硝基、卤素、氰基、氨基、C1～6烷氨基、C1～6烷基磺酰基中的一个或多个基团；
或者R1、R2中的一个代表含有或没有卤素取代的含0～4个O、S、N的C1～4酰基；另一个代表氢，含有或没有卤素取代的含0～4个O、S、N的C1～8烷基、C1～8烯基或C1～8炔基，未取代或被选自卤素、含有或没有卤素取代的含0～4个杂原子的C1～4烷基中的一个或多个基团所取代的C3～6环烷基；
当n＝2、且Z和/或Y选自C时，位于不同C原子上的两个R11连接成CH2、(CH2)2、(CH2)3、(CH2)4、(CH2)5、(CH2)6、O、O(CH2)2O、O(CH2)3O、O(CH2)4O、S(CH2)2S或S(CH2)3S；
或者当n＝2时，位于同C原子上的两个R11连接成如下基团：(CH2)2、(CH2)3、(CH2)4、(CH2)5、(CH2)6、O、O(CH2)2O、O(CH2)3O、O(CH2)4O、S(CH2)2S或S(CH2)3S。
更优选地，Het选自丁内酰胺基、戊内酰胺基、己内酰胺基、庚内酰胺基、哌嗪酮基、吗啉酮基、硫代吗啉酮基、咪唑基、吡唑基，Ra选自氟、氯、甲基、乙基、甲氧基、乙氧基、硝基、氰基、氨基、C1～6烷氨基、C1-C6烷基磺酰基中的一个或多个基团；
或者R1代表乙酰基、氟乙酰基、二氟乙酰基、三氟乙酰基、甲氧乙酰基、乙氧乙酰基、甲氧丙酰基、乙氧丙酰基，R2代表氢或者未取代或被选自氟、甲氧基、乙氧基、丙氧基、丁氧基、甲氧乙氧基中的一个或多个基团所取代的甲基、乙基、丙基、丁基、戊基、环丙基；
当n＝2、且Z和/或Y选自C时，位于不同C原子上的两个R11连接成CH2、(CH2)2、(CH2)3、O、O(CH2)2O、O(CH2)3O、S(CH2)2S或S(CH2)3S；
或者当n＝2时，位于同C原子上的两个R11连接成如下基团：(CH2)2、(CH2)3、O、O(CH2)2O、O(CH2)3O、S(CH2)2S或S(CH2)3S。
进一步优选地，R选自下式所示的基团之一：
Figure PCTCN2017110610-appb-000006
R11选自氢、C1-C6烷基、C3-C6环烷基、C1-C6烷氧基、C1-C6烷氧基C1-C6烷基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷硫基、含有或没有卤素取代的6-10元芳基、含有或没有卤素取代的含1-3个O、S、N杂原子的5-10元杂芳基，n＝0-6；
R12选自羟基、C1-C3烷氧基、C1-C3烷基羰基氧基、C1-C3烷基磺酰基氧基、C2-C4烯氧基、卤代C2-C4烯氧基、未取代的或被1-3个独立选自氟、氯、溴、硝基、氰基、甲基、三氟甲基、甲氧基或三氟甲氧基中的基团所取代的苯氧基、苄基氧基、苯硫基、苄基硫基、苯甲酰氧基、苯磺酰基氧基、苯甲酰基甲氧基、含1-3个O、S、N杂原子的5-10元杂芳基氧基或含1-3个O、S、N杂原子的5-10元杂芳基羰基氧基。
所述的盐为钾盐、钠盐、铵盐、钙盐、吡啶盐或胆碱盐。
上面给出的通式化合物的定义中，汇集所用术语定义如下：
所述的芳基为6-10元芳基，包括苯基或萘基等；所述的杂芳基是含有1-3个O、S、N杂原子的5-10元杂芳基，例如吡啶基、嘧啶基、吡嗪基、呋喃基、噻吩基、吡咯基、吡唑基、噻唑基、噁唑基、异噁唑基、咪唑基、三唑基、恶二唑基、噻二唑基、哒嗪基、三嗪基、喹啉基、喹喔啉基、吲哚基、苯并三唑基、苯并噻吩基、苯并呋喃基、异喹啉基、四氢喹啉基等。
在本发明的化合物中，由于烯醇互变等可以存在多种互变异构体，本发明包括所有互变异构体及其任何比例的混合物。
所述的盐为农药学上可接受的盐，较佳的为本类化合物与化学上可接受的酸进行反应制得的酸加成盐，或者其中具有酸性基团的化合物和碱性化合物反应生成的盐。其中，所述的酸较佳的选自无机酸(如盐酸、硫酸、磷酸或氢溴酸等)和有机酸(如草酸、马来酸、富马酸、苹果酸、酒石酸、柠檬酸或苯甲酸等)；所述的碱性化合物较佳的选自氢氧化钠、氢氧化钾、 氢氧化钙、碳酸钠、碳酸钾、碳酸氢钠或碳酸氢钾等。上述药学上可接受的盐容易分离，可采用常规分离方法提纯，如溶剂萃取、稀释、重结晶、柱色谱和制备薄层色谱等。
一种制备所述取代的苯甲酰基环己二酮类化合物或其互变异构体、盐的方法，其包括以下步骤：
(1)使用如通式II所示的化合物与化合物
Figure PCTCN2017110610-appb-000007
进行反应，制备如通式I-1所示的化合物；
(2)将如通式I-1所示的化合物与化合物R13X或R13S-M进行反应，制得如通式I-2所示的化合物；
其中，X代表卤素、羟基，M代表碱金属或碱土金属(优选Na、Li、K、Ca、Mg等)，反应方程式如下：
Figure PCTCN2017110610-appb-000008
所述步骤(1)在非质子性溶剂中、碱和催化剂的作用下进行。
所述步骤(2)中与R13X反应时在非质子性溶剂中、碱的作用下进行，与R13S-M反应时在非质子性溶剂中、碱和活化剂的作用下进行。
反应温度均为-30℃-180℃，优选-5℃-90℃。
其中，当X代表羟基时，反应中需加入脱水剂，如氯化亚砜、DCC或CDI等。
所述溶剂为二氯甲烷、1,2-二氯乙烷、乙腈、甲苯、四氢呋喃、1,4-二氧六环、乙酸乙酯等非质子性溶剂中的一种或两种以上的组合，优选二氯甲烷、1,2-二氯乙烷或甲苯。
所述碱为氢氧化钠、氢氧化钾、氢氧化钙、碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、三乙胺、DIPEA或DBU，优选三乙胺或碳酸钾。
所述催化剂为丙酮氰醇。
所述活化剂为甲磺酰氯、对甲苯磺酰氯、三甲基氯硅烷、三氟乙酰氯、三氟乙酸酐、三氟甲磺酰氯、
Figure PCTCN2017110610-appb-000009
等，用于活化环己二酮上的羰基使其易与其他试剂发生反应。
一种除草组合物，含有所述的取代的苯甲酰基环己二酮类化合物或其互变异构体、盐中的至少一种作为活性组分。
所述活性组分的重量百分含量为0.1-99％。
一种控制有害植物的方法，包括将除草有效量的所述的取代的苯甲酰基环己二酮类化合物或其互变异构体、盐中的至少一种或所述的除草组合物使用在植物上或者有害植物区域。
所述的取代的苯甲酰基环己二酮类化合物或其互变异构体、盐中的至少一种或所述的除草组合物在控制杂草上的应用。
将所述的取代的苯甲酰基环己二酮类化合物或其互变异构体、盐用于防除有用作物中的杂草。
所述有用作物为转基因作物或者基因组编辑技术处理过的作物。
对于许多经济上重要的单子叶和双子叶有害植物，本发明的式I化合物具有突出的除莠活性。本发明的活性物质也对于多年生杂草有效，这些杂草从根茎、根状茎、或其它的多年生的器官上生长出来，很难控制。关于这点，是否在播种前、萌发前或萌发后使用该物质一般不重要。特别提及本发明化合物可以控制的单子叶和双子叶杂草群的代表例子，没有限制到的确定的物种。活性物质有效作用的杂草物种的例子包括单子叶植物：一年生燕麦属、黑麦、草属、看麦娘属、法拉里斯、稗、马唐属、狗尾草属和莎草属，和多年生的冰草属、狗牙根属、白茅属和高粱属、以及多年生的莎草属。
关于双子叶杂草物种，其作用可以扩展到的物种例如一年生的猪殃殃属、堇菜属、婆婆纳属、野芝麻属、繁缕属、苋属、白芥属、番薯属、黄花稔属、母菊属和苘麻属，和多年生杂草旋花属、蓟属、酸模属和艾属。本发明活性物质在水稻播种这种待定条件下有效控制有害植物，例如稗、慈姑属、泽泻属、荸荠属、蔗草和莎草属。如果将本发明化合物在萌芽前施用于土壤表面，可以在杂草长出前完全预防杂草的秧苗，或在杂草长出子叶时就停止生长，最后在三到四星期之后完全死亡。本发明化合物特别抗下述植物的活性优良，阿皮拉草、小野芝麻、卷茎蓼、繁缕、长春藤叶婆婆纳、阿拉伯婆婆纳、三色堇和苋、猪殃殃属和地肤。
虽然本发明化合物对于单子叶和双子叶的杂草具有优良的除莠活性，但对于重要的经济类作物植物，例如小麦、大麦、黑麦、稻子、玉米、甜菜、棉花和大豆却根本没有损害，或者是损害是微不足道的。特别是和谷类作物相容得很好，例如小麦、大麦和玉米，特别是小麦。因此，本发明化合物非常适于有选择地控制在农用作物或观赏植物中的无用植物。
由于它们的除莠性质，在已知或将要出现的遗传工程的植物耕种中，这些活性物质可以用于控制有害植物。转基因植物通常具有优越的性状，例如对特定杀虫剂特别是特定除草剂的抵抗力，对植物病害或植物病害的致病微生物的抵抗力，例如特定的昆虫或真菌、细菌或 病毒的微生物。其它的特别性状与产品的下述条件有关，例如，数量、质量、贮存稳定性、组分和特殊的成分。如此，已经知道获得的转基因植物产品具有增加的淀粉含量或改进的淀粉质量或不同的脂肪酸成份。
本发明的式I化合物或其盐优选用于，经济上重要的转基因的作物和观赏植物，例如谷类，例如小麦、大麦、黑麦、燕麦、粟、稻子、木薯和玉米、或用于甜菜、棉花、大豆、油菜籽、马铃薯、番茄、豌豆及其他蔬菜类植物的耕种。式I化合物优选用于有用植物耕种的除草剂，这些植物具有抗药性或通过遗传工程对除草剂的毒害作用具有抗药性。
传统的繁育具有比已知植物具有改进形状植物的方法包括，例如传统的交配方法和突变株繁育。换句话说，可以借助于遗传工程的方法(参见，例如EP-0221044 A，EP-0131624 A)来得到具有改进性状的新植物。例如，已经描述了几个方法：
-为了改进植物中的淀粉合成，利用遗传工程改变作物植物(例如WO 92/11376，WO 92/14827，WO 91/19806)；
-对特定的除草剂具有抗性的转基因作物植物，对草丁膦除草剂(例如EP-0242236 A，EP-0242246 A)或对草甘膦类除草剂(WO 92/00377)，或对磺酰脲类除草剂(EP-0257993 A，US-5013659 A)；
-例如棉花的转基因作物植物，它能够产生苏芸金杆菌毒素(Bt毒素)，这种毒素可以防御特定害虫对植物的侵害(EP-0142924 A，EP-0193259 A)；
-具有改进的脂肪酸成份的转基因作物植物(WO91/13972)。
已经知道许多能够制备具有改进性状转基因植物分子生物技术(参见，例如Sambrook等，1989，分子扩增，实验手册第二版，美国冷泉港实验室出版，冷泉港，纽约；或Winnacker“Gene und Klone”[基因和克隆]，VCH Weinheim，第二版1996或Christou，“植物科学的趋势”1(1996)423-431))。为了实现遗传工程的操作，可能将核酸分子引入质粒，通过DNA序列的重组，发生突变或序列改变。利用上述的标准方法，例如可以交换底物、除去部分序列或增加自然的或合成的序列。为了将DNA片段互相连接，有可能在片段上附带有结合体或连接体。
可以用下述方法制备降低活性的基因产品的植物细胞，例如通过表达至少一种适当的反义-RNA、正义-RNA来达到共抑制的效果，或通过表达至少一种适当构造的核糖酶，它特定裂解上述基因产品的转录产物。
为此目的，有可能使用包含基因产物全部编码序列的DNA分子，包括有可能存在的任何旁侧序列，和使用包含仅仅一部分编码序列的DNA分子，这些部分必须足够长以达到在细胞中反义的效果。也可以使用与基因产物编码序列具有高度同源性但不完全相同的序列。
当在植物中表达核酸分子时，合成的蛋白质可以在任何期望的植物细胞室中定位。然而为了在特定的室定位，有可能例如将编码区和DNA序列连接，以确保在特定位置定位。这些序列为本领域所属技术人员已知的(参见，例如Braun等，EMBO J.11(1992)3219-3227；Wolter等，Proc.Natl.Acad.Sci.USA 85(1988)，846-850；Sonnewald等Plant J.1(1991)，95-106)。
利用已知的技术可以将转基因植物细胞重组到整个植物上。转基因植物可以为任何期望的植物品种，即单子叶和双子叶植物。用这样的方式，通过超表达、禁止或抑制同源(＝自然的)基因或基因序列，或通过异种的(＝外部的)基因或者基因序列的表达，有可能获得改进性状的转基因植物。
当在转基因的作物上使用本发明的活性物质时，除了具有在其它作物上可观察到的抑制有害植物的效果外，经常在相应的转基因作物上会有特殊的效果，例如可以改进或扩大控制杂草的范围，改进应用时的施用量，优选转基因作物的抗药性和除草剂的性能很好的结合，并且转基因的作物植物的生长和产率的影响。因此本发明也提供了所述化合物的用途，作为除草剂控制转基因作物植物中的有害植物。
另外本发明化合物可以明显调节作物植物的生长。通过调节参与植物代谢，使用这些化合物定向控制植物的组分和促进收获，例如使植物干化和矮化生长。而且它们也适于调节和抑制不希望的植物生长，而不破坏作物的生长。抑制植物的生长在许多单子叶植物和双子叶植物作物中起着非常重要的作用，因为这样可以减少或完全预防倒伏。
可以使用一般的制剂来应用本发明的化合物，可使用可湿性粉剂、浓缩乳剂、可喷洒的溶液、粉末或颗粒。这样本发明也提供了包括式I化合物的除草剂组合物。根据通常的生物学和/或化学的物理参数，可以用多种方式配制式I化合物。适合的制剂选择实例为：可湿性粉剂(WP)、水溶性的粉末(SP)、水溶性的浓缩物、浓缩乳剂(EC)、例如油在水中分散和水在油中分散的乳剂(EW)、可喷洒溶液、悬浮剂浓缩物(SC)、可分散油悬浮剂(OD)、以油或水为稀释剂的悬浮液、可混溶油的溶液、粉末(DP)、胶囊悬浮液(CS)、包核(seeddressing)组合物、用于撒播和土壤施药的颗粒、喷射颗粒、涂覆颗粒和吸收颗粒，水中可分散的颗粒(WG)、水溶性的颗粒(SG)、ULV(超低容量)配方、微囊和蜡制品。这些单个的制剂类型为已知的，在下述文献中有描述，例如Winnacker-Küchler，“Chemische Techonologie”[化学工艺]，第7卷，C.Hauser Verlag Munich，第4版1986；Wade van Valkenburg，“Pesticide Formulations”，Marcel Dekker，N.Y.，1973；K.Martens，“Spray Drying”手册，第3版1979，G.Goodwin Ltd.London。
必要的制剂助剂，例如惰性物质、表面活性剂、溶剂及其它添加剂同样为已知的，并在下述文件中描述，例如Watkins的“粉末稀释剂杀虫剂和载体手册”，第二版，Darland书Caldwell N.J.；H.v.01phen“粘土胶体化学的入门”，第二版，J.Wiley和Sons，N.Y.；C.Marsden的“溶剂指南”第二版，Interscience，N.Y.1963；McCutcheon的“洗涤剂和乳化剂年报”，MC发行公司，Ridgewood N.J.；Sisley和Wood，“表面活性剂百科全书”，化学出版公司，N.Y.1964；
Figure PCTCN2017110610-appb-000010
的
Figure PCTCN2017110610-appb-000011
[环氧乙烷加成物表面活性剂]，Wiss.Verlagagesell.Stuttgart 1976；Winnacker-
Figure PCTCN2017110610-appb-000012
的“Chemische Technologie”[化学工艺]，第7卷，C.Hauser Verlag Munich，第4版1986。
可湿性粉剂能均匀地可分散在水中，除了活性物质，还包括稀释剂或惰性物质、离子和非离子型表面活性剂(润湿剂、分散剂)，例如聚乙氧基烷基酚、聚乙氧基脂肪醇、聚氧乙基脂肪族胺、脂肪醇聚二醇醚硫酸盐、烷基磺酸盐、烷基苯基磺酸盐、木质磺酸钠、2,2’-二萘甲烷-6,6’-二磺酸钠、二丁基萘磺酸钠或油酰甲基牛磺酸钠。为了制备可湿性粉剂，将除草剂的活性物质细磨，例如使用常用的仪器，如用锤磨机、风扇磨碎机和喷气式磨碎机，同时或顺序混入助剂。
将活性物质溶解在有机溶剂中制备浓缩乳剂，溶剂例如丁醇、环己酮、二甲基甲酰胺、二甲苯或较高沸点的芳族化合物或碳氢化合物或溶剂的混合物，并再加入一种或多种离子的和/或非离子型表面活性剂(乳化剂)。可以使用的乳化剂的例子为例如十二烷基苯磺酸钙的烷基芳基磺酸钙，或非离子乳化剂，例如脂肪酸聚二醇酯、烷基芳香基聚二醇醚、脂肪醇聚二醇醚、氧化丙烯-环氧乙烷缩合产物、烷基聚醚、例如山梨糖醇酐脂肪酸酯的山梨聚糖酯，或例如聚氧化乙烯山梨糖醇酐脂肪酯的聚氧化乙烯山梨聚糖酯。
将活性物质和细碎的固态物质研磨得到粉末，固态物质例如滑石、如高岭土、皂土和叶蜡石的天然粘土、或硅藻土。以水或油为基底的悬浮液可以通过下述方法制备，例如利用商业上通用的玻珠研磨机进行湿磨，加入或不加入上述另一个制剂类型的表面活性剂。
制备例如水包油乳化剂(EW)的乳剂，可以使用含水的有机溶剂，使用搅拌器、胶体研磨器和/或静态混合器，如果需要，加入如上所述另一个制剂类型的表面活性剂。
用下述方法制备颗粒剂，将活性物质喷到吸附物上，使用惰性物料颗粒化，或将活性物质浓缩到例如沙、高岭石载体的表面，通过粘合剂将惰性物料粒化，粘合剂例如聚乙烯醇、聚丙烯酸钠或矿物油。可以用制备肥料颗粒剂的方法将合适的活性物质粒化，如果需要可以混有肥料。使用通常的方法制备水悬浮颗粒剂，例如喷洒-干燥，流化床造粒、磨盘造粒、使用高速混合机混合，并在无固体惰性物料的情况下挤压。
关于使用磨盘、流化床、挤压机和喷涂颗粒剂的制备方法，参见下述工艺，例如“Spray Drying手册”第三版1979，G.Goodwin有限公司，伦敦；J.E.Browning，“Agglomeration”，化学和工程1967，147ff页；“Perry’s化学的工程师手册”，第五版，McGraw-Hill，纽约1973，8-57页。如果要知道关于作物保护产品的制剂，参见例如，G.C.Klingman,“Weed Control as a Science”，John Wiley和Sons公司，纽约，1961 81-96页和J.D.Freyer，S.A.Evans“杂草防除手册”，第五版，Blackwell Scientific Rublications，牛津大学1968，101-103页。
农用化学品制剂通常包含按重量计0.1到99％，特别是0.1到95％的活性物质式I。可湿性粉剂中活性物质的浓度为，按重量计例如从大约10到99％，通常的制剂组分构成按重量计剩余量到100％。活性物质在浓缩乳剂中的浓度按重量计可以为大约1到90％，优选5到80％。粉末制剂包含按重量计1到30％的活性物质，通常优选按重量计5到20％的活性物质，然而可喷洒的溶液包含按重量计大约0.05到80％，优选2到50％的活性物质。关于水悬浮颗粒剂中活性物质的含量，主要根据活性物质为液体还是固态，和造粒时使用的助剂、填料等等。水悬浮颗粒剂中活性物质的含量例如按重量计在1到95％之间，优选按重量计在10到80％之间。
另外所述的活性物质的制剂可以包括增粘剂、润湿剂、分散剂、乳化剂、渗透剂、防腐剂、防冻剂、溶剂、填料、载体、着色剂、消泡剂、蒸发抑制剂和通常在所有情况下都常用的pH和粘度调节剂。
以这些制剂为基础，也可能和其他杀虫剂活性物质例如杀虫剂、杀螨剂、除草剂和杀菌剂混合，也可以和安全剂、肥料和/或植物生长调节剂混合，混合方式可以为预先混合好的或灌装混合。
在混配制剂或桶混制剂中，可以和本发明的活性物质混合的合适的活性物质为，例如《世界农药新品种技术大全》，中国农业科学技术出版社，2010.9和这里引用的文献中的已知物质。例如以下提到的除草剂活性物质可以和式I混合物混合，(备注：化合物的名称，或者为根据国际标准化组织(ISO)的普通名称，或者为化学名称，适当的时候有代号)：乙草胺、丁草胺、甲草胺、异丙草胺、异丙甲草胺、精异丙甲草胺、丙草胺、毒草胺、克草胺、萘丙酰草胺、R-左旋萘丙酰草胺、敌稗、苯噻酰草胺、双苯酰草胺、吡氟酰草胺、杀草胺、氟丁酰草胺、溴丁酰草胺、二甲噻草胺、高效二甲噻草胺、乙氧苯草胺、氟噻草胺、甲氧噻草胺、吡草胺、异恶草胺、高效麦草伏甲酯、高效麦草伏丙酯、二丙烯草胺、烯草胺、丁酰草胺、环丙草胺、氟磺酰草胺、庚酰草胺、异丁草胺、丙炔草胺、特丁草胺、二甲苯草胺、二甲草胺、落草胺、三甲环草胺、氯甲酰草胺、炔苯酰草胺、戊酰苯草胺、卡草胺、新燕灵、三环赛草胺、丁烯草胺、牧草胺、苄草胺、醌萍胺、苯氟磺胺、萘丙胺、乙酰甲草胺、萘草胺、噻草 胺、吡氰草胺、苯草多克死、草克乐、氯酞亚胺、丁脒胺、氟吡草胺、莠去津、西玛津、扑草净、氰草净、西草净、莠灭净、扑灭津、异丙净、氟草净、特丁净、特丁津、三嗪氟草胺、环丙津、甘扑津、草达津、扑灭通、西玛通、叠氮净、敌草净、异戊乙净、环丙青津、灭莠津、另丁津、仲丁通、特丁通、甲氧丙净、氰草净、抑草津、可乐津、莠去通、灭草通、甘草津、三聚氰酸、Indaziflam、绿磺隆、甲磺隆、苄嘧磺隆、氯嘧黄隆、苯磺隆、噻磺隆、吡嘧黄隆、甲基二磺隆、甲基碘磺隆钠盐、甲酰氨基嘧磺隆、醚磺隆、醚苯磺隆、甲嘧磺隆、烟嘧磺隆、胺苯磺隆、酰嘧磺隆、乙氧嘧磺隆、环丙嘧磺隆、砜嘧磺隆、四唑嘧磺隆、啶嘧黄隆、单嘧磺隆、单嘧磺酯、氟唑磺隆、氟啶嘧磺隆、氟吡嘧磺隆、环氧嘧磺隆、唑吡嘧磺隆、氟嘧磺隆、丙苯磺隆、三氟丙磺隆、磺酰磺隆、三氟啶磺隆、氟胺磺隆、三氟甲磺隆、甲磺隆钠盐、氟吡磺隆、甲硫嘧磺隆、嘧苯胺磺隆、Propyrisulfuron(丙嗪嘧磺隆)、嗪吡嘧磺隆、三氟羧草醚、氟磺胺草醚、乳氟禾草灵、乙羧氟草醚、乙氧氟草醚、草枯醚、苯草醚、氯氟草醚乙酯、甲羧除草醚、三氟甲草醚、甲氧除草醚、三氟硝草醚、氟化除草醚、氟呋草醚、除草醚、甲草醚、二甲草醚、氟酯肟草醚、氟草醚酯、Halosafen、绿麦隆、异丙隆、利谷隆、敌草隆、莎扑隆、氟草隆、苯噻隆、甲基苯噻隆、苄草隆、磺噻隆、异恶隆、特丁噻草隆、炔草隆、氯溴隆、甲基杀草隆、酰草隆、甲氧杀草隆、溴谷隆、甲氧隆、绿谷隆、灭草隆、环草隆、非草隆、氟硫隆、草不隆、枯草隆、草完隆、异草完隆、环莠隆、噻氟隆、丁噻隆、枯莠隆、对氟隆、甲胺噻唑隆、隆草特、三甲异脲、恶唑隆、Monisouron、Anisuron、Methiuron、Chloreturon、四氟隆、甜菜宁、甜菜宁-乙酯、甜菜安、磺草灵、特草灵、燕麦灵、苯胺灵、氯苯胺灵、二氯苄草酯、灭草灵、氯炔灵、Carboxazole、Chlorprocarb、Fenasulam、BCPC、CPPC、Carbasulam、丁草特、禾草丹、灭草猛、禾草特、野麦畏、哌草丹、禾草畏、稗草丹、环草敌、燕麦敌、菌达灭、乙硫草特、坪草丹、克草猛、苄草丹、仲草丹、硫烯草丹、草灭散、Isopolinate、Methiobencarb、2,4-滴丁酯、2甲4氯钠、2,4-滴异辛酯、2甲4氯异辛酯、2,4-滴钠盐、2,4-滴二甲胺盐、2甲4氯乙硫酯、2甲4氯、2,4-滴丙酸、高2,4-滴丙酸盐、2,4-滴丁酸、2甲4氯丙酸、2甲4氯丙酸盐、2甲4氯丁酸、2,4,5-涕、2,4,5-涕丙酸、2,4,5-涕丁酸、2甲4氯胺盐、麦草畏、抑草蓬、伐草克、赛松、三氯苯酸、氨二氯苯酸、甲氧三氯苯酸、禾草灵、吡氟禾草灵、精吡氟禾草灵、氟吡甲禾灵、高效吡氟氯禾灵、喹禾灵、精喹禾灵、恶唑禾草灵、精恶唑禾草灵、喔草酯、氰氟草酯、恶唑酰草胺、炔草酯、噻唑禾草灵、炔禾灵、羟戊禾灵、三氟禾草肟、异恶草醚、百草枯、敌草快、安磺灵、乙丁烯氟灵、异丙乐灵、甲磺乐灵、环丙氟灵、氨基丙氟灵、乙丁氟灵、氯乙氟灵、氨基乙氟灵、地乐灵、氯乙地乐灵、Methalpropalin、丙硝酚、草甘膦、莎稗膦、草铵膦、甲基胺草磷、草硫膦、哌草膦、双丙氨膦、地散磷、抑草磷、蔓草磷、伐垅磷、双甲胺草磷、草特磷、咪唑烟酸、咪 唑乙烟酸、咪唑喹啉酸、甲氧咪草烟、甲氧咪草烟铵盐、甲咪唑烟酸、咪草酯、氯氟吡氧乙酸、氯氟吡氧乙酸异辛酯、二氯吡啶酸、氨氯吡啶酸、三氯吡氧乙酸、氟硫草定、卤草定、三氯吡啶酚、噻草啶、氟啶草酮、氯氨吡啶酸、氟吡草腙、三氯吡氧乙酸丁氧基乙酯、Cliodinate、稀禾啶、烯草酮、噻草酮、禾草灭、环苯草酮、丁苯草酮、肟草酮、吡喃草酮、Buthidazole、嗪草酮、环嗪酮、苯嗪草酮、乙嗪草酮、Ametridione、Amibuzin、溴苯腈、辛酰溴苯腈、辛酰碘苯腈、碘苯腈、敌草腈、二苯乙腈、双唑草腈、羟敌草腈、Iodobonil、唑嘧磺草胺、双氟磺草胺、五氟磺草胺、磺草唑胺、氯酯磺草胺、双氯磺草胺、啶磺草胺、氟草黄、双草醚、嘧啶肟草醚、环酯草醚、嘧草醚、嘧硫草醚、双环磺草酮、硝磺草酮、磺草酮、Tembotrione、Tefuryltrione、Bicyclopyrone、Ketodpiradox、异恶唑草酮、异恶氯草酮、Fenoxasulfone、Methiozolin、异丙吡草酯、吡草醚、吡唑特、野燕枯、苄草唑、吡草酮、吡氯草胺、Pyrasulfotole、苯唑草酮、Pyroxasulfone、唑草胺、氟胺草唑、杀草强、胺唑草酮、唑啶草酮、氟唑草酮、甲磺草胺、Bencarbazone、双苯嘧草酮、氟丙嘧草酯、除草定、异草定、环草啶、特草定、Flupropacil、吲哚酮草酯、氟烯草酸、丙炔氟草胺、炔草胺、酞苄醚、Flumezin、五氯酚(钠)、地乐酚、特乐酚、特乐酯、戊硝酚、二硝酚、氯硝酚、地乐施、地乐特、丙炔恶草酮、恶草酮、环戊恶草酮、氟唑草胺、嗪草酸甲酯、四唑酰草胺、氟哒嗪草酯、杀草敏、溴莠敏、二甲达草伏、哒草醚、草哒酮、草哒松、哒草伏、Pyridafol、二氯喹啉酸、氯甲喹啉酸、苯达松、哒草特、恶嗪草酮、草除灵、异恶草酮、环庚草醚、异丙酯草醚、丙酯草醚、茚草酮、氯酸钠、茅草枯、三氯醋酸、一氯醋酸、六氯丙酮、四氟丙酸、牧草快、溴酚肟、三唑磺、灭杀唑、呋草酮、呋草磺、乙呋草磺、嘧草胺、氯酞酸、氟咯草酮、稗草稀、丙烯醛、苯草灭、灭草环、燕麦酯、噻二唑草胺、棉胺宁、羟草酮、甲氧苯酮、苯嘧磺草胺、氯酰草膦、三氯丙酸、Alorac、Diethamquat、Etnipromid、Iprymidam、Ipfencarbazone、Thiencarbazone-methyl、Pyrimisulfan、Chlorflurazole、Tripropindan、Sulglycapin、甲硫磺乐灵、Cambendichlor、环丙嘧啶酸、硫氰苯胺、解草酮、解草啶、解草安、解草唑、解草喹、解草腈、解草烷、解草胺腈、解草烯、吡唑解草酯、呋喃解草唑、肟草安、双苯噁唑酸、二氯丙烯胺、氟氯吡啶酯、DOW氯氟吡啶酯、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和KIH-2023。
当使用时，如果需要，将市售的制剂以常见的方式稀释，例如在可湿性粉剂、浓缩乳剂、悬浮液和在水中悬浮的颗粒时，使用水稀释。粉末、土壤施药所用的颗粒剂或撒播和喷洒的溶液，一般在使用前不需要进一步用惰性物质稀释。随着外部条件的变化，要求的式I化合物的使用量也不同，外部条件为，例如温度、湿度、使用的除草剂的性质等等。它可以有大 的变化幅度，例如在0.001到1.0kg/ha之间，或更多的活性物质，但优选在0.005到750g/ha之间，特别是在0.005到250g/ha之间。
具体实施方式
以下实施例用于举例说明本发明，不应当视其为以任何方式限制本发明。本发明要求保护的权利范围通过权利要求书进行说明。
鉴于化合物的经济性与多样性，我们优选合成了一些化合物，在合成的诸多化合物中，选取部分列于下表1中。具体的化合物结构及相应的化合物信息如表1所示。表1中的化合物只是为了更好的说明本发明，但并不限定本发明，对于本领域的技术人员而言，不应将此理解为本发明上述主题的范围仅限于以下化合物。
表1化合物结构及其HNMR数据
Figure PCTCN2017110610-appb-000013
Figure PCTCN2017110610-appb-000014
Figure PCTCN2017110610-appb-000015
Figure PCTCN2017110610-appb-000016
Figure PCTCN2017110610-appb-000017
Figure PCTCN2017110610-appb-000018
Figure PCTCN2017110610-appb-000019
Figure PCTCN2017110610-appb-000020
Figure PCTCN2017110610-appb-000021
Figure PCTCN2017110610-appb-000022
Figure PCTCN2017110610-appb-000023
Figure PCTCN2017110610-appb-000024
Figure PCTCN2017110610-appb-000025
Figure PCTCN2017110610-appb-000026
Figure PCTCN2017110610-appb-000027
Figure PCTCN2017110610-appb-000028
Figure PCTCN2017110610-appb-000029
Figure PCTCN2017110610-appb-000030
Figure PCTCN2017110610-appb-000031
Figure PCTCN2017110610-appb-000032
Figure PCTCN2017110610-appb-000033
Figure PCTCN2017110610-appb-000034
Figure PCTCN2017110610-appb-000035
Figure PCTCN2017110610-appb-000036
Figure PCTCN2017110610-appb-000037
Figure PCTCN2017110610-appb-000038
Figure PCTCN2017110610-appb-000039
Figure PCTCN2017110610-appb-000040
Figure PCTCN2017110610-appb-000041
Figure PCTCN2017110610-appb-000042
Figure PCTCN2017110610-appb-000043
Figure PCTCN2017110610-appb-000044
Figure PCTCN2017110610-appb-000045
Figure PCTCN2017110610-appb-000046
Figure PCTCN2017110610-appb-000047
Figure PCTCN2017110610-appb-000048
Figure PCTCN2017110610-appb-000049
注：化合物41、43、48、64、65、106、108、113、130、131、134、140-142、147、151、154-162、206、210、212、214、234-236、243、245、247-249为多种异构体的混合物，其中，当R1R2N＝
Figure PCTCN2017110610-appb-000050
Figure PCTCN2017110610-appb-000051
时由于存在两个手性中心而产生异构体。
制备本发明化合物的数种方法详解说明于以下方案和实施例中。原料可以经市场购买到或者可以通过文献中已知的方法或者如详解所示进行制备。本领域技术人员应当理解，也可以利用其它合成路线合成本发明的化合物。尽管在下文中已经对合成路线中的具体原料和条件进行了说明，但是，可以很容易地将其替换为其它类似的原料及条件，这些对本发明制备方法的变型或者变体而产生的诸如化合物的各种异构等都包括在本发明范围内。另外，如下所述制备方法可以按照本发明公开内容、使用本领域技术人员熟知的常规化学方法进行进一步修饰。例如，在反应过程中对适当的基团进行保护等等。
以下提供的方法实施例用于促进对本发明的制备方法的进一步了解，使用的具体物质、种类和条件确定为是对本发明的进一步说明，并不是对其合理范围的限制。在下表中表明的合成化合物中使用的试剂或者可以市场购买到，或者可以由本领域普通技术人员轻易制备得到。
代表性化合物的实施例如下：
化合物001的合成：
Figure PCTCN2017110610-appb-000052
12.3g 1,3-环己二酮和20mL三乙胺溶解于100mL 1,2-二氯乙烷中，降温至0℃，搅拌下滴加由32.1g原料A1与50mL 1,2-二氯乙烷组成的溶液。滴完继续保温0～5℃搅拌0.5h后，向 反应液中加入10mL三乙胺和1mL丙酮氰醇。反应液升温至55℃搅拌反应1小时，降至室温。然后加1N盐酸调pH至3左右。分液，水相用1,2-二氯乙烷萃取。有机相合并，依次用水、饱和氯化钠溶液洗涤，无水硫酸钠干燥，浓缩，得到38g类白色固体。HPLC纯度>95％。
化合物002至040均按此方法制备得到。
化合物043的合成：
Figure PCTCN2017110610-appb-000053
2.3g原料A2溶解于10mL二氯甲烷中，搅拌降温至0℃，加入2.0g无水碳酸钾，搅拌30min。向反应液中滴加5mL溶有0.4g乙酰氯的二氯甲烷溶液，控制反应温度0～5℃。滴完慢慢升至室温搅拌反应2h。反应液抽滤，滤饼用10mL二氯甲烷洗涤。有机相合并，依次用饱和碳酸氢钠溶液、水、饱和氯化钠溶液洗涤，无水硫酸钠干燥，浓缩，得到2.0g类白色固体。HPLC纯度>95％(前后两种异构体的比例69:31)。
化合物044的合成：
Figure PCTCN2017110610-appb-000054
4.0g化合物001加入到25mL1,2-二氯乙烷中，搅拌降温至0℃，慢慢滴加2.5mL三乙胺，保温反应10min。向反应液中慢慢滴加1.2g甲磺酰氯与5mL1,2-二氯乙烷组成的溶液。滴完继续保温0～5℃搅拌4h。向反应液中慢慢加入1.4g苯硫酚钠盐，然后缓慢升至室温。反应液于室温搅拌反应16h。然后加1N盐酸调pH至3左右。分液，水相用1,2-二氯乙烷萃取。有机相合并，依次用水、饱和氯化钠溶液洗涤，无水硫酸钠干燥，浓缩。粗品经柱层析纯化，得到1.8g类白色固体。HPLC纯度>95％。
化合物046的合成：
Figure PCTCN2017110610-appb-000055
2.2g化合物001和0.85g原料A3溶解于10mL二氯甲烷中，搅拌降温至0℃，滴加5mL 溶有1.0g N,N'-二环己基碳酰亚胺(DCC)的二氯甲烷溶液，控制反应温度0～5℃。滴完慢慢升至室温搅拌反应16h。反应液抽滤，滤饼用10mL二氯甲烷洗涤。合并滤、洗液，浓缩，粗品经柱层析纯化，得到2.0g黄色固体。HPLC纯度>98％。
化合物062的合成：
Figure PCTCN2017110610-appb-000056
2.2g化合物001溶解于10mL二氯甲烷中，搅拌降温至0℃，加入1.0g三乙胺，搅拌30min。向反应液中滴加5mL溶有0.7g吡啶-4-甲酰氯的二氯甲烷溶液，控制反应温度0～5℃。滴完慢慢升至室温搅拌反应16h。反应液抽滤，滤饼用10mL二氯甲烷洗涤。有机相合并，依次用饱和碳酸氢钠溶液、水、饱和氯化钠溶液洗涤，无水硫酸钠干燥，浓缩，得到2.0g类白色固体。HPLC纯度>95％。
化合物137的合成：
Figure PCTCN2017110610-appb-000057
2.3g化合物011溶解于10mL二氯甲烷中，搅拌降温至0℃，加入1.0g三乙胺，搅拌30min。向反应液中滴加0.9g溴苄，控制反应温度0～5℃。滴完慢慢升至室温搅拌反应30h。向反应液中加入1N盐酸调pH至3左右，分液，水相用二氯甲烷萃取。有机相合并，依次用饱和碳酸氢钠溶液、水、饱和氯化钠溶液洗涤，无水硫酸钠干燥，浓缩，得到的粗品经柱层析纯化，得到1.5g类白色固体。HPLC纯度>97％。
化合物139的合成：
Figure PCTCN2017110610-appb-000058
2.5g原料A4溶解于10mL二氯甲烷中，搅拌降温至0℃，滴入1.5g三乙胺，搅拌30min。向反应液中滴加0.7g甲磺酰氯，控制反应温度0～5℃。滴完慢慢升至室温搅拌反应16h。向反应液中加入1N盐酸调pH至3左右，分液，水相用二氯甲烷萃取。有机相合并，依次用饱 和碳酸氢钠溶液、水、饱和氯化钠溶液洗涤，无水硫酸钠干燥，浓缩，得到2.6g淡黄色固体。HPLC纯度>95％。
生物活性评价：
有害植物破坏(即生长控制率)的活性级别标准如下：
10级：完全死亡；
9级：生长控制率在95％以上；
8级：生长控制率在90％以上；
7级：生长控制率在80％以上；
6级：生长控制率在70％以上；
5级：生长控制率在60％以上；
4级：生长控制率在50％以上；
3级：生长控制率在20％以上；
2级：生长控制率在5-20％；
1级：生长控制率在5％以下；
以上生长控制率为鲜重控制率。
将单子叶和双子叶杂草种子以及作物种子玉米放置在装有土壤的塑料盆中，然后覆盖0.5-2厘米土壤，使其在良好的温室环境中生长，播种2-3周后在4-5叶期处理测试植物，分别将供试的本发明化合物用丙酮溶解，然后加入吐温80，用一定的水稀释成一定浓度的溶液，用喷雾塔喷施到植物上。施药后在温室中培养3周，3周后杂草的实验效果列于表2。
表2.苗后杂草试验
化合物序号 播娘蒿 苘麻 玉米
1 10 10 0
2 10 10 0
3 10 10 0
4 10 10 0
5 10 10 0
6 10 10 0
7 10 10 0
8 10 10 1
9 10 10 0
10 10 10 0
11 10 10 0
12 10 10 0
13 10 10 0
14 10 10 0
15 10 10 2
16 10 10 0
17 10 10 0
18 10 10 0
19 10 10 0
20 10 10 0
21 10 10 0
22 10 10 1
23 10 10 0
24 10 10 0
25 10 10 1
26 10 10 0
27 10 10 0
28 10 10 0
29 10 10 0
30 10 10 0
31 10 10 0
32 10 10 0
33 10 10 0
34 10 10 0
35 10 10 1
36 10 10 2
37 10 10 1
38 10 10 1
39 10 10 0
40 10 10 0
41 10 10 0
42 10 10 0
43 10 10 0
44 10 10 0
45 10 10 0
46 10 10 0
47 10 10 0
48 10 10 0
49 10 10 0
50 10 10 0
51 10 10 0
52 10 10 0
53 10 10 0
54 10 10 0
55 10 10 0
56 10 10 0
57 10 10 0
58 10 10 0
59 10 10 0
60 10 10 0
61 10 10 0
62 10 10 0
63 10 10 0
64 10 10 0
65 10 10 0
66 10 10 0
67 10 10 0
68 10 10 0
69 10 10 0
70 10 10 0
71 10 10 0
72 10 10 0
73 10 10 1
74 10 10 0
75 10 10 0
76 10 10 0
77 10 10 0
78 10 10 0
79 10 10 0
80 10 10 1
81 10 10 0
82 10 10 0
83 10 10 0
84 10 10 0
85 10 10 0
86 10 10 0
87 10 10 2
88 10 10 0
89 10 10 0
90 10 10 1
91 10 10 0
92 10 10 0
93 10 10 0
94 10 10 0
95 10 10 0
96 10 10 0
97 10 10 0
98 10 10 0
99 10 10 0
100 10 10 2
101 10 10 1
102 10 10 0
103 10 10 0
104 10 10 0
105 10 10 0
106 10 10 0
107 10 10 0
108 10 10 0
109 10 10 0
110 10 10 0
111 10 10 0
112 10 10 0
113 10 10 0
114 10 10 0
115 10 10 0
116 10 10 0
117 10 10 0
118 10 10 0
119 10 10 0
120 10 10 0
121 10 10 0
122 10 10 0
123 10 10 0
124 10 10 0
125 10 10 0
126 10 10 0
127 10 10 0
128 10 10 0
129 10 10 0
130 10 10 0
131 10 10 0
132 10 10 0
133 10 10 0
134 10 10 2
135 10 10 0
136 10 10 0
137 10 10 0
138 10 10 0
139 10 10 0
140 10 10 0
141 10 10 0
142 10 10 0
143 10 10 1
144 10 10 0
145 10 10 0
146 10 10 0
147 10 10 0
148 10 10 0
149 10 10 0
150 10 10 0
151 10 10 0
152 10 10 0
153 10 10 0
154 10 10 0
155 10 10 0
156 10 10 0
157 10 10 0
158 10 10 0
159 10 10 0
160 10 10 0
161 10 10 0
162 10 10 0
163 10 10 0
164 10 10 0
165 10 10 0
166 10 10 0
167 10 10 0
168 10 10 1
169 10 10 0
170 10 10 0
171 10 10 0
172 10 10 0
173 10 10 0
174 10 10 0
175 10 10 0
176 10 10 0
177 10 10 0
178 10 10 0
179 10 10 2
180 10 10 0
181 10 10 0
182 10 10 0
183 10 10 0
184 10 10 0
185 10 10 0
186 10 10 0
187 10 10 0
188 10 10 0
189 10 10 0
190 10 10 0
191 10 10 0
192 10 10 0
193 10 10 0
194 10 10 0
195 10 10 0
196 10 10 1
197 10 10 0
198 10 10 0
199 10 10 0
200 10 10 2
201 10 10 0
202 10 10 0
203 10 10 0
204 10 10 0
205 10 10 0
206 10 10 0
207 10 10 0
208 10 10 0
209 10 10 0
210 10 10 0
211 10 10 0
212 10 10 0
213 10 10 0
214 10 10 0
215 10 10 0
216 10 10 0
217 10 10 0
218 10 10 0
219 10 10 0
220 10 10 0
221 10 10 0
222 10 10 0
223 10 10 1
224 10 10 0
225 10 10 0
226 10 10 1
227 10 10 1
228 10 10 0
229 10 10 0
230 10 10 0
231 10 10 0
232 10 10 0
233 10 10 0
234 10 10 0
235 10 10 0
236 10 10 0
237 10 10 0
238 10 10 0
239 10 10 1
240 10 10 0
241 10 10 0
242 10 10 0
243 10 10 0
244 10 10 0
245 10 10 0
246 10 10 0
247 10 10 0
248 10 10 1
249 10 10 0
250 10 10 0
251 10 10 0
252 10 10 2
253 10 10 1
254 10 10 0
255 10 10 0
256 10 10 0
257 10 10 0
258 10 10 0
259 10 10 0
260 10 10 0
261 10 10 0
262 10 10 1
263 10 10 1
264 10 10 0
265 10 10 0
266 10 10 0
267 10 10 0
268 10 10 0
注：施用剂量为有效成分300克/公顷。
通过实验我们发现本发明所述化合物普遍具有较好的杂草防效，尤其对于玉米小麦田广泛发生的播娘蒿、苘麻等主要的阔叶杂草有良好的效果，具备良好的商业价值。尤其是我们注意到对于ALS抑制剂有抗性的播娘蒿等阔叶杂草有极高的活性。另外，经测试本发明化合物在适合的剂量下对直播和移栽水稻田关键杂草也有很好的活性和作物安全性。
对比实验：
对比化合物1：
Figure PCTCN2017110610-appb-000059
(出自专利WO97/46530A1)
对比化合物2：
Figure PCTCN2017110610-appb-000060
(出自专利WO97/46530A1)
对比化合物3：
Figure PCTCN2017110610-appb-000061
(出自专利CN1416422A)
对比化合物4：
Figure PCTCN2017110610-appb-000062
(出自专利CN105218449A)
苗后测试条件同上，测试计量为50克/公顷；观察时间为试验20天后。
表3.对比实验结果
化合物 大穗看麦娘 硬草 节节麦 播娘蒿 苘麻
化合物237 8 9 5 10 10
化合物109 10 10 6 10 10
化合物153 5 6 3 8 8
化合物66 10 10 8 10 10
对比化合物1 0 0 0 1 1
对比化合物2 0 0 0 0 0
对比化合物3 1 1 2 4 3
对比化合物4 4 5 1 7 7
由表3可以看出，本发明的化合物在除草活性上明显优于对比化合物。
同时经过很多测试发现，本发明所述化合物很多对结缕草、狗牙根、高羊茅、早熟禾、黑麦草、海滨雀稗等禾本科草坪有很好的选择性，能防除很多关键禾本科杂草以及阔叶杂草。对不同施药方式下的大豆、棉花、油葵、马铃薯、果树、蔬菜等测试也显示出极好的选择性和商业价值。

Claims (12)

  1. 一种取代的苯甲酰基环己二酮类化合物或其互变异构体、盐，如通式I所示：
    Figure PCTCN2017110610-appb-100001
    式中，
    R1R2N代表
    Figure PCTCN2017110610-appb-100002
    其中，
    Het选自三至八元杂环，该环上除含有C和1-位上的N原子外，还含有0-3个以下原子或基团作为环的组成部分：O、NRb、S、SO、SO2、C＝O、C＝NRb或C＝NORb，且当C＝O、C＝NRb或C＝NORb在2-位时，3-位不能为N或S；
    Rb选自氢、C1～6烷基、卤代C1～6烷基、C2～6烯基、卤代C2～6烯基、C1～6烷氧基C1～6烷基、卤代C1～6烷氧基C1～6烷基、C1～6烷基羰基、卤代C1～6烷基羰基、C1～6烷基磺酰基、C1～6烷氧基羰基、C1～6烷氨基羰基、C1～6烷基羰基C1～6烷基、C1～6烷氧基羰基C1～6烷基、C1～6烷氨基羰基C1～6烷基、未取代的或被1-3个独立选自卤素、硝基、氰基、C1～6烷基、卤代C1～6烷基、C1～6烷氧基、卤代C1～6烷氧基、C1～6烷基羰基中的基团所取代的芳基、杂芳基、芳基羰基、杂芳基羰基、芳基磺酰基、芳甲基、杂芳基甲基；
    Ra选自以下基团中的一个或多个基团：氢、卤素、氰基、硝基、羟基、羧基、氨基、C1-C6烷基磺酰基、C1～6烷基、卤代C1～6烷基、C2～6烯基、卤代C2～6烯基、C1～6烷氧基、卤代C1～6烷氧基、C1～6烷氨基、C2～6烯氧基、卤代C2～6烯氧基、C2～6烯氨基、卤代C2～6烯氨基、C1～6烷基羰基、卤代C1～6烷基羰基、C1～6烷氧基羰基、C1～6烷氨基羰基、C1～6烷氧基C1～6烷基、卤代C1～6烷氧基C1～6烷基、C1～6烷基羰基氧基C1～6烷基、C1～6烷氧基C1～6烷氧基、卤代C1～6烷氧基C1～6烷氧基、C1～6烷氧基羰基C1～6烷氧基、C1～6烷基羰基氧基、卤代C1～6烷基羰基氧基、C1～6烷基羰基氨基、C1～6烷基磺酰基氧基、C1～6烷基磺酰基氨基、C1～6烷基羰基C1～6烷氧基、未取代的或被1-3个独立选自卤素、硝基、氰基、C1～6烷基、卤代C1～6烷基、C1～6烷氧基、C1～6烷基羰基中的基团所取代的芳基、杂芳基、芳基羰基氧基、芳基磺酰基氧基、芳甲基氧基、杂芳基甲基氧基、芳基羰基氨基、芳基磺酰基氨基、芳甲基氨基或杂芳基甲基氨基；
    或者R1、R2分别代表氢，含有或没有卤素取代的含0～4个杂原子的C1～8烷基、C1～8烯基或C1～8炔基，含有或没有卤素取代的含0～4个杂原子的C1～4酰基，未取代或被选自卤素、含有或没有卤素取代的含0～4个杂原子的C1～4烷基中的一个或多个基团所取代的C3～6环烷基；
    R代表
    Figure PCTCN2017110610-appb-100003
    其中，
    R11选自氢、C1-C6烷基、C3-C6环烷基、C1-C6烷氧基、C1-C6烷氧基C1-C6烷基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷硫基、含有或没有卤素取代的6-10元芳基、含有或没有卤素取代的含1-3个O、S、N杂原子的5-10元杂芳基，n＝0-6；
    Y选自C、N、O或S；
    Z选自C、N、O、S、SO、SO2或C＝O；
    或者当n＝2、且Z和/或Y选自C时，位于不同C原子上的两个R11连接成CH2、(CH2)2、(CH2)3、(CH2)4、(CH2)5、(CH2)6、O、O(CH2)2O、O(CH2)3O、O(CH2)4O、S(CH2)2S或S(CH2)3S；
    或者当n＝2时，位于同C原子上的两个R11连接成如下基团：(CH2)2、(CH2)3、(CH2)4、(CH2)5、(CH2)6、O、O(CH2)2O、O(CH2)3O、O(CH2)4O、S(CH2)2S或S(CH2)3S；
    R12选自-OR13或-SR13，其中，R13选自氢、C1-C6烷基、C1-C6烷基羰基、C1-C6烷基磺酰基、C2-C6烯基、卤代C2-C6烯基、C2-C6炔基、C1-C6烷氧基羰基C1-C6烷基、C1-C6烷氨基羰基C1-C6烷基、未取代的或被1-3个独立选自卤素、硝基、氰基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基或卤代C1-C6烷氧基中的基团所取代的芳基、芳甲基、芳基羰基、芳基磺酰基、杂芳基、杂芳基羰基或芳基羰基甲基。
  2. 根据权利要求1所述的一种取代的苯甲酰基环己二酮类化合物或其互变异构体、盐，其特征在于：
    Het选自4～8元内酰胺基、咪唑基、吡唑基，Ra选自C1～4烷基、C1～4烷氧基、硝基、卤素、氰基、氨基、C1～6烷氨基、C1～6烷基磺酰基中的一个或多个基团；
    或者R1、R2中的一个代表含有或没有卤素取代的含0～4个O、S、N的C1～4酰基；另一个代表氢，含有或没有卤素取代的含0～4个O、S、N的C1～8烷基、C1～8烯基或C1～8炔基，未取代或被选自卤素、含有或没有卤素取代的含0～4个杂原子的C1～4烷基中的一个或多个基团所取代的C3～6环烷基；
    当n＝2、且Z和/或Y选自C时，位于不同C原子上的两个R11连接成CH2、(CH2)2、(CH2)3、(CH2)4、(CH2)5、(CH2)6、O、O(CH2)2O、O(CH2)3O、O(CH2)4O、S(CH2)2S或S(CH2)3S；
    或者当n＝2时，位于同C原子上的两个R11连接成如下基团：(CH2)2、(CH2)3、(CH2)4、(CH2)5、(CH2)6、O、O(CH2)2O、O(CH2)3O、O(CH2)4O、S(CH2)2S或S(CH2)3S。
  3. 根据权利要求1或2所述的一种取代的苯甲酰基环己二酮类化合物或其互变异构体、 盐，其特征在于：
    Het选自丁内酰胺基、戊内酰胺基、己内酰胺基、庚内酰胺基、哌嗪酮基、吗啉酮基、硫代吗啉酮基、咪唑基、吡唑基，Ra选自氟、氯、甲基、乙基、甲氧基、乙氧基、硝基、氰基、氨基、C1～6烷氨基、C1-C6烷基磺酰基中的一个或多个基团；
    或者R1代表乙酰基、氟乙酰基、二氟乙酰基、三氟乙酰基、甲氧乙酰基、乙氧乙酰基、甲氧丙酰基、乙氧丙酰基，R2代表氢或者未取代或被选自氟、甲氧基、乙氧基、丙氧基、丁氧基、甲氧乙氧基中的一个或多个基团所取代的甲基、乙基、丙基、丁基、戊基、环丙基；
    当n＝2、且Z和/或Y选自C时，位于不同C原子上的两个R11连接成CH2、(CH2)2、(CH2)3、O、O(CH2)2O、O(CH2)3O、S(CH2)2S或S(CH2)3S；
    或者当n＝2时，位于同C原子上的两个R11连接成如下基团：(CH2)2、(CH2)3、O、O(CH2)2O、O(CH2)3O、S(CH2)2S或S(CH2)3S。
  4. 根据权利要求1-3任意一项所述的一种取代的苯甲酰基环己二酮类化合物或其互变异构体、盐，其特征在于：
    R选自下式所示的基团之一：
    Figure PCTCN2017110610-appb-100004
    R11选自氢、C1-C6烷基、C3-C6环烷基、C1-C6烷氧基、C1-C6烷氧基C1-C6烷基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷硫基、含有或没有卤素取代的6-10元芳基、含有或没有卤素取代的含1-3个O、S、N杂原子的5-10元杂芳基，n＝0-6；
    R12选自羟基、C1-C3烷氧基、C1-C3烷基羰基氧基、C1-C3烷基磺酰基氧基、C2-C4烯氧基、卤代C2-C4烯氧基、未取代的或被1-3个独立选自氟、氯、溴、硝基、氰基、甲基、三氟甲基、甲氧基或三氟甲氧基中的基团所取代的苯氧基、苄基氧基、苯硫基、苄基硫基、苯甲酰氧基、苯磺酰基氧基、苯甲酰基甲氧基、含1-3个O、S、N杂原子的5-10元杂芳基氧基或含1-3个 O、S、N杂原子的5-10元杂芳基羰基氧基。
  5. 根据权利要求1-4任意一项所述的一种取代的苯甲酰基环己二酮类化合物或其互变异构体、盐，其特征在于：所述的盐为钾盐、钠盐、铵盐、钙盐、吡啶盐或胆碱盐。
  6. 一种制备权利要求1-5任意一项所述取代的苯甲酰基环己二酮类化合物或其互变异构体、盐的方法，其包括以下步骤：
    (1)使用如通式II所示的化合物与化合物
    Figure PCTCN2017110610-appb-100005
    进行反应，制备如通式I-1所示的化合物；
    (2)将如通式I-1所示的化合物与化合物R13X或R13S-M进行反应，制得如通式I-2所示的化合物；
    其中，反应方程式如下：
    Figure PCTCN2017110610-appb-100006
    X代表卤素、羟基，M代表碱金属、碱土金属，优选Na、Li、K、Ca或Mg。
  7. 根据权利要求6所述制备取代的苯甲酰基环己二酮类化合物或其互变异构体、盐的方法，其特征在于：所述步骤(1)在非质子性溶剂中、碱和催化剂的作用下进行；所述步骤(2)中与R13X反应时在非质子性溶剂中、碱的作用下进行，与R13S-M反应时在非质子性溶剂中、碱和活化剂的作用下进行；反应温度均为-30℃-180℃，优选-5℃-90℃。
  8. 根据权利要求7所述制备取代的苯甲酰基环己二酮类化合物或其互变异构体、盐的方法，其特征在于：所述溶剂为二氯甲烷、1,2-二氯乙烷、乙腈、甲苯、四氢呋喃、1,4-二氧六环和乙酸乙酯中的一种或两种以上的组合，优选二氯甲烷、1,2-二氯乙烷或甲苯；所述碱为氢氧化钠、氢氧化钾、氢氧化钙、碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、三乙胺、DIPEA或DBU，优选三乙胺或碳酸钾；所述催化剂为丙酮氰醇；所述活化剂为甲磺酰氯、对甲苯磺酰氯、三甲基氯硅烷、三氟乙酰氯、三氟乙酸酐、三氟甲磺酰氯、
    Figure PCTCN2017110610-appb-100007
    Figure PCTCN2017110610-appb-100008
  9. 一种除草组合物，其特征在于：含有权利要求1-5任意一项所述的取代的苯甲酰基环己二酮类化合物或其互变异构体、盐中的至少一种作为活性组分，优选地，所述活性组分的重量百分含量为0.1-99％。
  10. 一种控制有害植物的方法，其特征在于，包括将除草有效量的权利要求1-5任意一项所述的取代的苯甲酰基环己二酮类化合物或其互变异构体、盐中的至少一种或权利要求9所述的除草组合物使用在植物上或者有害植物区域。
  11. 如权利要求1-5任意一项所述的取代的苯甲酰基环己二酮类化合物或其互变异构体、盐中的至少一种或权利要求9所述的除草组合物在控制杂草上的应用。
  12. 根据权利要求11所述的应用，其特征在于，将所述的取代的苯甲酰基环己二酮类化合物或其互变异构体、盐用于防除有用作物中的杂草，优选地，所述有用作物为转基因作物或者基因组编辑技术处理过的作物。
PCT/CN2017/110610 2017-08-17 2017-11-11 取代的苯甲酰基环己二酮类化合物或其互变异构体、盐、制备方法、除草组合物及应用 WO2019033590A1 (zh)

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