WO2024008049A1 - 一种含吡啶基苯基异噁唑啉类化合物和草甘膦的除草组合物及其应用 - Google Patents

一种含吡啶基苯基异噁唑啉类化合物和草甘膦的除草组合物及其应用 Download PDF

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WO2024008049A1
WO2024008049A1 PCT/CN2023/105585 CN2023105585W WO2024008049A1 WO 2024008049 A1 WO2024008049 A1 WO 2024008049A1 CN 2023105585 W CN2023105585 W CN 2023105585W WO 2024008049 A1 WO2024008049 A1 WO 2024008049A1
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alkyl
composition
compound
glyphosate
alkoxy
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PCT/CN2023/105585
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English (en)
French (fr)
Inventor
迟会伟
刘杰
吴建挺
袁雪
赵士胜
逯玉环
王涛
王泽军
于志波
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潍坊中农联合化工有限公司
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Priority to CN202380009766.3A priority Critical patent/CN117729851A/zh
Publication of WO2024008049A1 publication Critical patent/WO2024008049A1/zh

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides

Definitions

  • the invention belongs to the technical field of pesticides, especially the field of herbicides, and specifically relates to a herbicidal composition containing pyridylphenyl isoxazoline compounds and glyphosate and its application.
  • Glyphosate and its salts are systemic conductive broad-spectrum herbicides that inhibit the biosynthesis of aromatic amino acids, shikimic acid and chlorophyll, and also inhibit photophosphorylation. Therefore, glyphosate has high herbicidal ability. It is the comprehensive result of multiple effects. Glyphosate has a broad herbicidal spectrum and good systemic conductivity. It has outstanding advantages in controlling perennial deep-rooted malignant weeds. In addition, it is safe for humans and animals and does not pollute the environment. Therefore, it is widely used in agriculture, forestry and animal husbandry. It has been widely used and has become one of the few large-tonnage herbicides in the world. However, its poor quick-acting effect is also an inevitable shortcoming, and glyphosate-resistant biotype weeds are growing rapidly.
  • the herbicides currently used for weeding in non-arable land are limited by the herbicidal activity and herbicidal spectrum of a single dose of herbicide. Using a single herbicide alone cannot completely and effectively control the occurrence of weeds, and it can also easily lead to weed resistance. Or a larger dose may be needed. Therefore, there is an urgent need for a new herbicide with high efficiency and low regreening rate.
  • the object of the present invention is to address the shortcomings of current farmland herbicides and provide a herbicide composition that has a low greening rate, good weeding effect, is safe to use, and is beneficial to the comprehensive management of farmland weeds, and the herbicidal composition can be used when applied to harmful plants. It has the effect of reducing the amount of active ingredients and increasing efficiency, and can be used to eliminate crop stubble, quickly clear up stubble for the next crop, has an outstanding effect on promoting withering of crops, and can also be used to improve crop quality and increase yield.
  • a composition comprising: a) compound 1 and b) glyphosate and salts thereof;
  • the compound 1 is a compound represented by general formula (I), its stereoisomers, racemates, tautomers, isotope markers, nitrogen oxides, pharmaceutically acceptable salts or esters, and solvates. solvates of compounds or pharmaceutically acceptable salts,
  • R 1 , R 2 , R 3 and R 4 are the same or different, and are independently selected from hydrogen, halogen, C 1 -C 6 alkyl or halogenated C 1 -C 6 alkyl;
  • R 5 , R 6 , R 7 , and R 8 are the same or different, and are independently selected from hydrogen, halogen, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, and C 1 -C 6 alkoxy. or halogenated C 1 -C 6 alkoxy;
  • R 9 and R 10 are the same or different, and are independently selected from hydrogen, cyano, C 1 -C 6 alkyl or halo C 1 -C 6 alkyl;
  • R 11 and R 12 are the same or different, and are independently selected from hydrogen, cyano, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, COOR 13 or CONR 14 R 15 ;
  • R 13 is selected from hydrogen, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 3 alkoxy C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, unsubstituted or C 6 -C 10 aryl C 1 -C 6 alkyl substituted by 1-4 Ra, 5-10 membered heteroaryl C 1 -C 6 alkyl or 3-10 One-membered heterocyclyl C 1 -C 6 alkyl; each Ra is the same or different, independently selected from halogen, cyano, nitro, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy or halogenated C 1 -C 6 alkoxy;
  • R 14 and R 15 are the same or different, and are independently selected from hydrogen, C 1 -C 6 alkyl or C 1 -C 4 alkoxy C 1 -C 6 alkyl.
  • Compound 1 of the present invention is a compound disclosed in patent application CN202011497249.X (publication number CN114644622A), the full text of which is incorporated into the present invention.
  • R 1 , R 2 , R 3 and R 4 are the same or different, and are independently selected from hydrogen, halogen, C 1 -C 4 alkyl or halogenated C 1 -C 4 alkyl;
  • R 5 , R 6 , R 7 , and R 8 are the same or different, and are independently selected from hydrogen, halogen, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, and C 1 -C 4 alkoxy. or halogenated C 1 -C 4 alkoxy;
  • R 9 and R 10 are the same or different, and are independently selected from hydrogen, C 1 -C 4 alkyl or halo C 1 -C 4 alkyl;
  • R 11 and R 12 are the same or different, and are independently selected from hydrogen, cyano, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, COOR 13 or CONR 14 R 15 ;
  • R 13 is selected from hydrogen, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 3 alkoxy C 1 -C 3 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, unsubstituted or C 6 -C 8 aryl C 1 -C 4 alkyl substituted by 1-4 Ra, 5-8 membered heteroaryl C 1 -C 4 alkyl or 3-6 One-membered heterocyclyl C 1 -C 4 alkyl; each Ra is the same or different, independently selected from halogen, cyano, nitro, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogenated C 1 -C 4 alkoxy;
  • R 14 and R 15 are the same or different, and are independently selected from hydrogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy C 1 -C 6 alkyl.
  • R 1 , R 2 , R 3 and R 4 are the same or different, and are independently selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, tris Fluoromethyl or trifluoroethyl;
  • R 5 , R 6 , R 7 , and R 8 are the same or different, and are independently selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, trifluoromethyl, Fluoroethyl, methoxy, ethoxy, trifluoromethoxy or trifluoroethoxy;
  • R 9 and R 10 are the same or different, and are independently selected from hydrogen, C 1 -C 4 alkyl or halo C 1 -C 4 alkyl;
  • R 11 and R 12 are the same or different, and are independently selected from hydrogen, cyano, C 1 -C 4 alkyl, halo C 1 -C 4 alkyl, COOR 13 or CONR 14 R 15 ;
  • R 13 is selected from hydrogen, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 3 alkoxy C 1 -C 3 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, unsubstituted or benzyl substituted by 1 to 4 Ra, furylmethyl, tetrahydrofurylmethyl or 1,3-dioxolaneethyl; each Ra is the same or different from each other Independently selected from fluorine, chlorine, cyano, nitro, methyl, ethyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, trifluoromethoxy or trifluoroethoxy;
  • R 14 and R 15 are the same or different, and are independently selected from hydrogen, C 1 -C 4 alkyl or C 1 -C 3 alkoxy C 1 -C 3 alkyl.
  • R 1 , R 2 , R 3 and R 4 are the same or different, and are independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, trifluoromethyl base or trifluoroethyl;
  • R 5 , R 6 , R 7 , R 8 are the same or different, and are independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, Trifluoromethoxy or trifluoroethoxy;
  • R 9 and R 10 are the same or different, and are independently selected from hydrogen, methyl, ethyl, propyl, butyl, trifluoromethyl or trifluoroethyl;
  • R 11 and R 12 are the same or different, and are independently selected from hydrogen, cyano, C 1 -C 4 alkyl, halo C 1 -C 4 alkyl, COOR 13 or CONR 14 R 15 ;
  • R 13 is selected from hydrogen, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 3 alkoxy C 1 -C 3 alkyl, allyl, propargyl, unsubstituted Or benzyl, furylmethyl, tetrahydrofurylmethyl or 1,3-dioxolaneethyl substituted by 1-4 Ra; each Ra is the same or different, independently selected from fluorine, chlorine, cyano, nitro, methyl, ethyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, trifluoromethoxy or trifluoroethoxy;
  • R 14 and R 15 are the same or different, and are independently selected from hydrogen, C 1 -C 4 alkyl or C 1 -C 3 alkoxy C 1 -C 3 alkyl.
  • the compound represented by general formula (I) is a compound represented by the following general formula (IA):
  • R 13 is selected from C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 3 alkoxy C 1 -C 6 alkyl, unsubstituted or substituted by 1-4 Ra C 6 -C 10 aryl C 1 -C 6 alkyl, 5-10 membered heteroaryl C 1 -C 6 alkyl or 3-10 membered heterocyclyl C 1 -C 6 alkyl; each Ra is the same or different, independently selected from halogen, cyano, nitro, C 1 -C 6 alkyl, haloC 1 -C 6 alkyl, C 1 -C 6 alkoxy or haloC 1 -C 6 Alkoxy.
  • R 13 is selected from methyl, ethyl, methoxyethyl or tetrahydrofurylmethyl.
  • the specific structure is as follows:
  • the weight ratio of Compound 1 and glyphosate is 1:(5-180), or 1:(6.7-180); for example: 1:7; 1:8; 1:10;1:12;1:15;1:20;1:25;1:24;1:30;1:40;1:50;1:60;1:70;1:80;1: 90; 1:100; 1:120; 1:150; 1:160, etc.
  • the glyphosate refers to N-(phosphonomethyl)glycine.
  • the salt of glyphosate includes any salt acceptable in agriculture, forestry or horticulture, specifically sodium salt, ammonium salt, isopropyl ammonium salt, potassium salt, etc.
  • component a) and component b) exist independently.
  • component a) and component b) are mixed, for example, tank mixed.
  • component a) and component b) are first made into solutions respectively, and then the solution of component a) and the solution of component b) are poured into a bucket for mixing.
  • the composition is in the form of a preparation.
  • the preparation is a liquid preparation or a solid preparation.
  • the composition preparation is, for example, an emulsifiable concentrate, a water suspension, an oil suspension, a wettable powder, a granule or an aqueous formulation that is acceptable for pesticides, agriculture, forestry or horticulture.
  • the composition further includes pesticides, agricultural, forestry or horticulturally acceptable auxiliaries, such as wetting agents, emulsifiers, dispersants, thickeners, and antifreeze agents. , one or more of disintegrants, binders, defoaming agents, stabilizers, fillers and carriers.
  • the content of the auxiliary agent in the composition in terms of weight percentage, can be 2-60%, such as 8-50%, exemplarily 2%, 6%, 8% , 10%, 18.7%, 19%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%.
  • the wetting agent may be selected from: trisiloxane polyoxyethylene ether, sodium N-lauroyl glutamate, sodium lauryl sulfate, sodium lauroyl sarcosinate, castor oil Polyoxyethylene ether, triphenylethylphenol polyoxyethylene ether, sodium dodecylbenzene sulfonate, sodium alkylnaphthalene sulfonate, sodium isooctyl succinate sulfonate and fatty alcohol polyoxyethylene ether, etc. one or more.
  • the emulsifier can be selected from: sodium lignosulfonate, agricultural milk, phenylphenol polyoxyethyl ether phosphate, naphthalene sulfonate formaldehyde condensate, benzyl dimethylphenol polyoxyethyl ether, dehydration Sorbitol fatty acid ester polyoxyethylene ether, sorbitan oleate (Span 80), One or more of fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether phosphate, castor oil polyoxyethylene ether phosphate, etc.
  • the dispersant can be selected from: glycerin fatty acid polyoxyethylene ether, polyoxyethylene alkyl aryl ether, sodium lignosulfonate, fatty alcohol polyoxyethylene ether sulfate, naphthalene sulfonate formaldehyde condensate, naphthalene sulfonic acid One or more of formaldehyde condensate sodium salt, nonylphenol polyoxyethylene ether, fatty alcohol polyether, fatty alcohol polyoxyethylene ether, phosphate ester and polyoxyethylene sorbitan fatty acid ester.
  • the thickener may be selected from one or more of polyvinyl acetate, gelatin, gum arabic, polyvinyl alcohol, and the like.
  • the antifreeze may be selected from one or more of propylene glycol, ethylene glycol, glycerin, and the like.
  • the disintegrant may be selected from one or more of sodium bicarbonate, ammonium sulfate, sodium sulfate, calcium sulfate and magnesium chloride.
  • the binder may be selected from one or more of xanthan gum, starch, urea-formaldehyde resin, gelatin, gum arabic, carboxymethyl cellulose, carboxyethyl cellulose, and the like.
  • the defoaming agent may be selected from one or more of silicone oil, n-octanol, silicone, butyl phosphate, isobutyl phosphate, and the like.
  • the stabilizer can be selected from: triethanolamine, epichlorohydrin, butyl glycidyl ether, triphenyl phosphite, N-soybean oil-based trimethylenediamine and dialkyl succinate acetate sulfonate, etc. one or more of them.
  • the filler includes solid filler or liquid filler, wherein the solid filler can be selected from one or more of kaolin, attapulgite, diatomite, white carbon black, bentonite, montmorillonite, talc, calcium carbonate, etc. kind; the liquid filler can be selected from one or more of water, soybean oil, castor oil and mineral oil.
  • solvents that can be used in the composition are toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, butanone, cyclohexanone, methanol, isopropyl alcohol, One or more of butanol, ethylene glycol, tetrahydrofuran, engine oil, vegetable oil, refined oil and water.
  • the present invention also provides the application of the composition, which is used to control harmful plants, improve the quality and yield of crops, or destroy crops or eliminate stubble.
  • the harmful plants are, for example, grass weeds, broadleaf weeds, sedge weeds or other unwanted crop plants.
  • the present invention also provides a method for controlling harmful plants, especially a method for controlling harmful plants in crops, which method is to apply the composition to the harmful plants and/or the places where the harmful plants grow.
  • the application rate is a herbicidal active amount.
  • the present invention also provides a method for improving the quality and yield of crops, which method is to apply the composition to crops, crop seeds or tubers or other propagable parts, and crop growing ground.
  • the present invention also provides a method for destroying crops or eliminating stubble, which method is to apply the composition to crops, seeds or tubers of crops or other reproductive parts, and crop growing ground.
  • the composition is directionally applied on non-cultivated land, to promote withering or stubble elimination after crop harvest, before crop sowing, after crop sowing and before emergence, before crop transplantation, and between crop rows.
  • the composition can be used for stem and leaf spraying: including: non-arable land weeding; farmland crop inter-row directional spray weeding, fruit tree inter-row directional spray weeding, seedling inter-row directional spray weeding; crop (such as cotton, rice, rapeseed, sugar beet, potatoes, peanuts, etc.) after harvest withering or stubble elimination.
  • the composition can be used for soil spraying, including: before sowing farm crops, farm crops After sowing and before emergence, before transplanting fruit trees, before transplanting seedlings, before sowing lawns, before sowing flowers, etc.
  • the composition has a soil sealing effect.
  • the composition When used for soil spraying and stem and leaf spraying, it also has a certain soil sealing effect on pre-emergent weeds (inhibiting the growth of weeds). emergence).
  • the non-cultivated land includes but is not limited to forest trees (fields), roads, forest fire roads, railways, etc.; the farmland crops include but is not limited to corn, sorghum, wheat, barley, and rye.
  • triticale and durum wheat rice, sugar cane, soybeans, legumes (such as peas, beans and lentils), peanuts, sunflowers, sugar beets, potatoes, cotton, brassicas (such as broccoli, cabbage, Cabbage, etc.);
  • the fruit trees include but are not limited to apples, pears, peaches, apricots, walnuts, pecans, olives, cherries, plums, citrus, coffee trees, etc.;
  • the seedlings include but are not limited to pine, fir, oak, Maple, willow, hawthorn, crabapple, etc.;
  • the lawn includes but is not limited to bermudagrass, multiflora ryegrass, tall fescue, etc.;
  • the flowers include but is not limited to roses, petunias, marigolds, snapdragons, etc.
  • Compound 1 has a good control effect on broad-leaf weeds and grass weeds, but the greening rate is high; glyphosate can be transmitted through systemic absorption and is very prominent in controlling perennial deep-rooted malignant weeds. advantages, but its quick effect is poor. After mixed use, it not only expands the herbicidal spectrum, but also makes up for the shortcomings of compound 1 and glyphosate, improves the quick effect, and reduces the greening rate of weeds.
  • the herbicide composition of the present invention is easily degraded in plants. Corn can be planted directly after application, and peanuts, cabbage, and water spinach can be planted 7 days later.
  • the present invention can be used for stem and leaf spraying and soil spraying. Examples of target weeds include: wormwood, tribulus terrestris, milfoil, burdock, shepherd's purse, rice crock, commelder grass, crabgrass, barnyard grass, tigertail grass, Imperata, amaranth, nightshade, and water chestnut.
  • gallbladder brome, reed, milfoil, zinnia, amaranth, chickweed, hard grass, crabgrass, amaranth, wheatgrass, cocklebur, purslane, humulus, marigold Weeds such as chrysanthemum, cosmos, and kidweed.
  • the two single agents of the present invention can form a synergistic effect after compounding, thereby enhancing the weed control effect.
  • Compound 1 and glyphosate belong to two categories of herbicides with different mechanisms of action, making weeds less likely to develop resistance. The combination of the two expands the herbicidal spectrum and delays the occurrence of weed community succession.
  • the herbicidal composition of the present invention can also improve crop quality and increase yield.
  • Compound 1 used in the examples has the following structure:
  • Example 1 Determination of indoor herbicidal activity of compound 1 (IA-1, IA-2, IA-3, IA-4) and glyphosate single agents and combinations.
  • the pot experiment method was used to study the herbicidal effect of compound 1 mixed with glyphosate, and the Gowing method was used to evaluate the type of joint action after the two were mixed.
  • test materials were cultured in a glass greenhouse at a temperature of 20-28°C.
  • Transplant marigolds, cosmos, and rhizome that are growing well into a plastic pot with a diameter of 9cm, and put it into a large plastic pot filled with water. Let the water gradually seep in at the bottom, and wait until the water seeps to the soil surface. Then put it in a cool place to slow down the seedlings for 1-2 days, then place it in a glass greenhouse to cultivate for 1 week, and then carry out spraying treatment, and conduct the test according to the test dosage described in Table 1.
  • test doses of compound 1 are 0.5, 1.5, 2.5, 3.5, 4.5g a.i/mu (grams of active ingredient/mu), and the test of glyphosate
  • the dosage is: 30, 45, 60, 75, 90g a.i/mu, compounded in pairs according to Table 1.
  • the nozzle model is TP65015E, the speed is 500mm/s, and the flow rate is 590mL/min.
  • Table 1 Compound 1 (IA-1, IA-2, IA-3, IA-4) and glyphosate composition indoor biological activity measurement dosage table (unit: g ai/mu)
  • Y is the weed control effect when the dosage of glyphosate is Q
  • EE 0 >10% is synergistic effect; EE 0 ⁇ -10% is antagonism; EE 0 value between ⁇ 10% is additive effect.
  • Example 2 Compound 1 (IA-1, IA-2, IA-3, IA-4) and glyphosate tank-mixed field weed control test
  • Test method The test site is Gengzhuang Village, Sangzidian Town, Tianqiao District, Jinan City, Shandong province.
  • the main weed species are goosegrass, chrysanthemum, brome, reed, amaranth, zinnia, amaranth, chickweed, and hard.
  • a tank-mixing test was conducted on compound 1 and glyphosate.
  • the application method was: the dose of compound 1 was 2g ai/mu, the dose of glyphosate was 40g ai/mu, and the dose of compound 1 and glyphosate in tank-mixing was 2+40g ai/mu. mu, choose a place with good growth and uniform grass for spraying.
  • the backpack spray equipment is AGROLEX Singapore Linong HD-400 manual sprayer, imported flat fan-shaped nozzle, capacity 16L; choose large-leaf age weeds for stem and leaf treatment, the spray pressure is 4kdf/cm 2 , and deionized water is used for test chemicals Dissolve, each treatment solution is prepared by the secondary dilution method. Before application, stir the solution evenly and then spray it.
  • the control effect was investigated using visual inspection (0 means no control effect, 100% means all weeds are controlled), the control effect was investigated 15 days after application, and the greening time was investigated after 15, 30, and 45 days. From Table 10 to Table 13, it can be clearly seen that the compounding of compound 1 (compounds IA-1, IA-2, IA-3, IA-4) and glyphosate can significantly improve the control effect of the two on weeds. And it significantly extended the time for weeds to turn green, and even failed to turn green in 45 days.
  • Table 12 Compound IA-3 + glyphosate composition visual weed control effect in field for 15 days and number of days to return to green Note: “-” means the weeds have not turned green.
  • Example 2 The method of Example 2 was used to conduct a field weed control test.
  • the main weed species were Artemisia striata, Tribulus terrestris, Goosegrass, Pondgrass, shepherd's purse, rice crock pot, commelder grass, crabgrass, barnyardgrass, tigertail grass, Imperata, lettuce, nightshade, broken rice chestnuts, etc.
  • the test method is: the dosage of compound 1 is 2g ai/mu, the dosage of glyphosate is 40g ai/mu, and the dosage of compound 1 and glyphosate aqueous preparation is 250mL/mu.
  • the preparation of the aqueous preparation is as follows: add glyphosate into a dimethylamine solution to form a glyphosate salt, then add compound 1, stir evenly and then add emulsifiers (fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene). Oxyethylene ether phosphate), and finally prepared compound 1 and glyphosate aqueous solution.
  • the final concentrations are: glyphosate 16% and compound 1 0.8%.
  • compound 1 and glyphosate can significantly improve the control effect and greening time of the two active ingredients on weeds, whether in formulation form or tank mix form.
  • Table 14 Compound IA-1 ⁇ glyphosate composition visual weed control effect and greening time in field for 15 days Note: “-” means the weeds have not turned green.
  • Table 17 Compound IA-4 ⁇ glyphosate composition visual weed control effect and greening time in field for 15 days Note: “-” means the weeds have not turned green.
  • Example 4 Indoor soil sealing test of compound 1 and glyphosate composition
  • Example 5 Compound 1 and glyphosate composition safety test for subsequent crops in the field
  • Test method The test location is Gengzhuang Village, Sangzidian Town, Tianqiao District, Jinan City, Shandong province.
  • the target subsequent crops are corn, peanuts, water spinach and cabbage.
  • Compound 1+glyphosate 2+40g a.i./mu was applied to bare soil using a tank mix method. Four crops were sown one after another at intervals of 0, 7, 15, and 30 days. Each crop was compared 14 days after sowing. The similarities and differences between the treatment and the clean water treatment are shown in Table 22.
  • the survey results 14 days after sowing showed that: when sown 0 days after the treatment, there was no obvious phytotoxicity in corn, and the other three target crops had varying degrees of inhibition (slight phytotoxicity); when sown 7 days, 15 days, and 30 days after the treatment, 4 There was no obvious phytotoxicity in any of the crops.
  • the compound 1 + glyphosate combination is safe for corn after use, and safe for peanuts, water spinach, and cabbage after 7 days.
  • Example 6 Directional spray test of compound 1 and glyphosate composition in corn fields
  • Test method The test location is Gengzhuang Village, Sangzidian Town, Tianqiao District, Jinan City, Shandong province, and the target crop is corn (Zhengdan 958).
  • the previous crop was wheat, and the wheat stubble was not treated.
  • the wheat stubble was treated by tank mixing.
  • the dosage of compound 1 + glyphosate composition was 2 + 40g a.i./mu.
  • the grass phases are: crabgrass, cowgrass, cocklebur, commeldergrass, amaranth retroflexus, humulus, pigweed, field bindweed, cyperus rotundus, setaria, small thistle, snakehead, Chickweed, most of the weeds at this time have 2-5 leaves, and the whole field is directional sprayed.
  • the dosage of compound 1 + glyphosate combination is 2 + 40g a.i./mu.
  • Example 7 Compound 1 and glyphosate composition used as cotton defoliant
  • Test method The test location is Gengzhuang Village, Sangzidian Town, Tianqiao District, Jinan City, Shandong province, and the target crop is cotton.
  • the compound 1 + glyphosate composition was applied by spraying on the stems and leaves of the whole field, and the dose was 1.5+40g a.i./mu.
  • the effect of the agent on promoting cotton bolls to flocculate was finally investigated, and the absolute value survey method was used to investigate the cotton defoliation rate.
  • the test reference was NY /T1464.26-2007 Pesticide Field Efficacy Test Guidelines Part 26: Cotton Withering Agent Test.

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Abstract

一种含吡啶基苯基异噁唑啉类化合物和草甘膦的除草组合物及其应用，所述吡啶基苯基异噁唑啉类化合物具有式(I)所示的结构。所述组合物不仅可以优势互补，扩大杀草谱，降低了返青率，而且取得了明显的协同增效作用，极大的延长了返青时间，提高了杀草效果。所述农药组合物可用于非耕地开荒，作物苗前处理，公路和铁路等地方。

Description

一种含吡啶基苯基异噁唑啉类化合物和草甘膦的除草组合物及其应用
本申请要求2022年7月4日向中国国家知识产权局提交的专利申请号为2022107882479，发明名称为“一种含吡啶基苯基异噁唑啉类化合物和草甘膦的除草组合物及其应用”的在先申请的优先权。该在先申请的全文通过引用的方式结合于本申请中。
技术领域
本发明属于农药技术领域，尤其是除草剂领域，具体涉及一种含吡啶基苯基异噁唑啉类化合物和草甘膦的除草组合物及其应用。
背景技术
草甘膦(Glyphosate)及其盐属于内吸传导型广谱灭生性除草剂，可抑制芳香氨基酸、莽草酸和叶绿素的生物合成，还抑制光合磷酸化，因此，草甘膦高效的杀草能力是多种作用的综合结果。草甘膦杀草谱广、具有良好的内吸传导性能，在防除多年生深根性恶性杂草上显示非常突出的优点，加上对人畜安全，不污染环境，从而在农、林、牧业上得到广泛的应用，已成为世界上少有的大吨位除草剂品种。但是其速效性差也是其不可避免的一处短板，而且抗草甘膦的生物型杂草正在快速增长。
目前非耕地除草所用除草剂受单剂除草剂的除草活性和杀草谱所限，单独使用一种除草剂单剂不能完全有效地控制杂草的发生，而且还易导致杂草产生抗药性，或者需要使用较大的剂量。因此，目前急需一种高效、返青率低的新型除草剂。
发明内容
本发明目的是针对目前农田除草剂的缺陷，提供一种返青率低、除草效果好、使用安全，有利于农田杂草综合治理的除草剂组合物，且所述除草组合物在应用于有害植物时具有活性成分减量增效的作用，且可应用于作物灭茬，为下茬作物快速腾茬，对作物有突出的催枯作用，还可以应用于作物提质增产。
本发明目的通过如下技术方案得以实现：
一种组合物，包括：a)化合物1和b)草甘膦及其盐；
所述化合物1为通式(I)所示的化合物、其立体异构体、消旋体、互变异构体、同位素标记物、氮氧化物、药学上可接受的盐或酯、溶剂合物或者药学上可接受的盐的溶剂合物，
其中，R1、R2、R3、R4相同或不同，彼此独立地选自氢、卤素、C1-C6烷基或卤代C1-C6烷基；
R5、R6、R7、R8相同或不同，彼此独立地选自氢、卤素、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基或卤代C1-C6烷氧基；
R9、R10相同或不同，彼此独立地选自氢、氰基、C1-C6烷基或卤代C1-C6烷基；
R11、R12相同或不同，彼此独立地选自氢、氰基、C1-C6烷基、卤代C1-C6烷基、COOR13或CONR14R15；
R13选自氢、C1-C6烷基、卤代C1-C6烷基、C1-C3烷氧基C1-C6烷基、C3-C6烯基、C3-C6炔基、未取代或被1-4个Ra取代的C6-C10芳基C1-C6烷基、5-10元杂芳基C1-C6烷基或3-10元杂环基C1-C6烷基；每个Ra相同或不同，彼此独立地选自卤素、氰基、硝基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基或卤代C1-C6烷氧基；
R14、R15相同或不同，彼此独立地选自氢、C1-C6烷基或C1-C4烷氧基C1-C6烷基。
本发明所述化合物1为专利申请CN202011497249.X(公开号CN114644622A)中所公开的化合物，该申请全文引入到本发明中。
在本发明一些实施方式中，通式(I)中，R1、R2、R3、R4相同或不同，彼此独立地选自氢、卤素、C1-C4烷基或卤代C1-C4烷基；
R5、R6、R7、R8相同或不同，彼此独立地选自氢、卤素、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基或卤代C1-C4烷氧基；
R9、R10相同或不同，彼此独立地选自氢、C1-C4烷基或卤代C1-C4烷基；
R11、R12相同或不同，彼此独立地选自氢、氰基、C1-C6烷基、卤代C1-C6烷基、COOR13或CONR14R15；
R13选自氢、C1-C6烷基、卤代C1-C6烷基、C1-C3烷氧基C1-C3烷基、C3-C6烯基、C3-C6炔基、未取代或被1-4个Ra取代的C6-C8芳基C1-C4烷基、5-8元杂芳基C1-C4烷基或3-6元杂环基C1-C4烷基；每个Ra相同或不同，彼此独立地选自卤素、氰基、硝基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基或卤代C1-C4烷氧基；
R14、R15相同或不同，彼此独立地选自氢、C1-C4烷基或C1-C4烷氧基C1-C6烷基。
在本发明一些实施方式中，通式(I)中，R1、R2、R3、R4相同或不同，彼此独立地选自氢、氟、氯、溴、甲基、乙基、三氟甲基或三氟乙基；
R5、R6、R7、R8相同或不同，彼此独立地选自氢、氟、氯、溴、甲基、乙基、三氟甲基、三 氟乙基、甲氧基、乙氧基、三氟甲氧基或三氟乙氧基；
R9、R10相同或不同，彼此独立地选自氢、C1-C4烷基或卤代C1-C4烷基；
R11、R12相同或不同，彼此独立地选自氢、氰基、C1-C4烷基、卤代C1-C4烷基、COOR13或CONR14R15；
R13选自氢、C1-C6烷基、卤代C1-C6烷基、C1-C3烷氧基C1-C3烷基、C3-C6烯基、C3-C6炔基、未取代或被1-4个Ra取代的苄基、呋喃基甲基、四氢呋喃基甲基或1,3-二氧环戊烷乙基；每个Ra相同或不同，彼此独立地选自氟、氯、氰基、硝基、甲基、乙基、三氟甲基、三氟乙基、甲氧基、乙氧基、三氟甲氧基或三氟乙氧基；
R14、R15相同或不同，彼此独立地选自氢、C1-C4烷基或C1-C3烷氧基C1-C3烷基。
在本发明一些实施方式中，通式(I)中，R1、R2、R3、R4相同或不同，彼此独立地选自氢、氟、氯、甲基、乙基、三氟甲基或三氟乙基；
R5、R6、R7、R8相同或不同，彼此独立地选自氢、氟、氯、甲基、乙基、三氟甲基、三氟乙基、甲氧基、乙氧基、三氟甲氧基或三氟乙氧基；
R9、R10相同或不同，彼此独立地选自氢、甲基、乙基、丙基、丁基、三氟甲基或三氟乙基；
R11、R12相同或不同，彼此独立地选自氢、氰基、C1-C4烷基、卤代C1-C4烷基、COOR13或CONR14R15；
R13选自氢、C1-C6烷基、卤代C1-C6烷基、C1-C3烷氧基C1-C3烷基、烯丙基、炔丙基、未取代或被1-4个Ra取代的苄基、呋喃基甲基、四氢呋喃基甲基或1,3-二氧环戊烷乙基；每个Ra相同或不同，彼此独立地选自氟、氯、氰基、硝基、甲基、乙基、三氟甲基、三氟乙基、甲氧基、乙氧基、三氟甲氧基或三氟乙氧基；
R14、R15相同或不同，彼此独立地选自氢、C1-C4烷基或C1-C3烷氧基C1-C3烷基。
在本发明一些实施方式中，通式(I)所示的化合物为如下通式(IA)所示的化合物：
其中，R13选自C1-C6烷基、卤代C1-C6烷基、C1-C3烷氧基C1-C6烷基、未取代或被1-4个Ra取代的C6-C10芳基C1-C6烷基、5-10元杂芳基C1-C6烷基或3-10元杂环基C1-C6烷基；每个Ra相同或不同，彼此独立地选自卤素、氰基、硝基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基或卤代C1-C6烷氧基。
在本发明一些实施方式中，通式(IA)中，R13选自甲基、乙基、甲氧基乙基或四氢呋喃基甲基。具体结构如下：
根据本发明的实施方式，所述组合物中，化合物1和草甘膦的重量比为1:(5-180)，或1:(6.7-180)；例如：1:7；1:8；1:10；1:12；1:15；1:20；1:25；1:24；1:30；1:40；1:50；1:60；1:70；1:80；1:90；1:100；1:120；1:150；1:160等。
根据本发明的实施方式，所述草甘膦是指N-(膦酸基甲基)甘氨酸。所述草甘膦的盐包括其农业、林业或园艺学上可接受的任意盐，具体可以为：钠盐、铵盐、异丙铵盐、钾盐等。
根据本发明的实施方式，所述组合物中，所述组分a)和组分b)是独立存在的。使用时再将组分a)和组分b)进行混配，例如进行桶混。在一个实施方式中，先将组分a)和组分b)分别制成溶液，再将组分a)溶液和组分b)溶液倒入桶中混合。
根据本发明的实施方式，所述组合物为制剂形式。所述制剂为液体制剂或固体制剂。所述组合物制剂例如为乳油、水悬浮剂、油悬浮剂、可湿性粉剂、颗粒剂或水剂等农药、农业、林业或园艺学上可接受的剂型。
根据本发明的实施方式，所述组合物还包括农药、农业、林业或园艺学上可接受的助剂，所述助剂例如为润湿剂、乳化剂、分散剂、增稠剂、防冻剂、崩解剂、粘结剂、消泡剂、稳定剂、填料和载体中的一种或多种。
根据本发明的实施方式，所述助剂在所述组合物中的含量，以重量百分数计，可以为2-60％，例如为8-50％，示例性为2％、6％、8％、10％、18.7％、19％、20％、25％、30％、35％、40％、45％、50％、55％、60％。
根据本发明的实施方式，所述润湿剂可以选自：三硅氧烷聚氧乙烯醚、N-月桂酰基谷氨酸钠、十二烷基硫酸钠、月桂酰基肌氨酸钠、蓖麻油聚氧乙烯醚、三苯乙基苯酚聚氧乙烯醚、十二烷基苯磺酸钠、烷基萘磺酸钠、异辛醇琥珀酸酯磺酸钠和脂肪醇聚氧乙烯醚等中的一种或多种。
所述乳化剂可以选自：木质素磺酸钠、农乳、苯基酚聚氧乙基醚磷酸酯、萘磺酸盐甲醛缩合物、苄基二甲基酚聚氧乙基醚、失水山梨醇脂肪酸酯聚氧乙烯醚、山梨醇酐油酸酯(斯盘80)、 脂肪醇聚氧乙烯醚、壬基酚聚氧乙烯醚磷酸酯和蓖麻油聚氧乙烯醚磷酸酯等中的一种或多种。
所述分散剂可以选自：甘油脂肪酸聚氧乙烯醚、聚氧乙烯烷基芳基醚、木质素磺酸钠、脂肪醇聚氧乙烯醚硫酸盐、萘磺酸盐甲醛缩合物、萘磺酸甲醛缩合物钠盐、壬基酚聚氧乙烯醚、脂肪醇聚醚、脂肪醇聚氧乙烯醚、磷酸酯和聚氧乙烯山梨聚糖脂肪酸酯等中的一种或多种。
所述增稠剂可以选自：聚乙酸乙烯酯、明胶、阿拉伯胶和聚乙烯醇等中的一种或多种。
所述防冻剂可以选自：丙二醇、乙二醇和丙三醇等中的一种或多种。
所述崩解剂可以选自：碳酸氢钠、硫酸铵、硫酸钠、硫酸钙和氯化镁中的一种或多种。
所述粘结剂可以选自：黄原胶、淀粉、脲醛树脂、明胶、阿拉伯胶、羧甲基纤维素和羧乙基纤维素等中的一种或多种。
所述消泡剂可以选自：硅油、正-辛醇、硅酮、磷酸丁酯和磷酸异丁酯等中的一种或多种。
所述稳定剂可以选自：三乙醇胺、环氧氯丙烷、丁基缩水甘油醚、亚磷酸三苯酯、N-大豆油基三亚甲基二胺和二烷基丁二酸醋磺酸盐等中的一种或多种。
所述填料包括固体填料或液体填料，其中，固体填料可以选自：高岭土、凹凸棒土、硅藻土、白炭黑、膨润土、蒙脱石、滑石粉和碳酸钙等中的一种或多种；液体填料可以选自水、大豆油、蓖麻油和矿物油等中的一种或多种。
根据本发明的实施方式，所述组合物中可使用的溶剂为甲苯、二甲苯、二甲亚砜、N,N-二甲基甲酰胺、丁酮、环已酮、甲醇、异丙醇、丁醇、乙二醇、四氢呋喃、机油、植物油、提炼油和水等中的一种或多种。
本发明还提供了所述组合物的应用，其用于防治有害植物、用于作物的提质增产或者用于作物的摧枯或灭茬。
根据本发明的实施方案，所述有害植物例如为禾本科杂草、阔叶类杂草、莎草科杂草或者其他不想要的作物植物。
本发明还提供一种防治有害植物的方法，特别是防治作物中的有害植物的方法，所述方法是将所述组合物施用于有害植物和/或有害植物生长地。优选地，施用量为除草活性量。
本发明还提供一种用于作物的提质增产的方法，所述方法是将所述组合物施用于作物、作物的种子或块茎或其他可繁殖部位、作物生长地上。
本发明还提供一种用于作物的摧枯或灭茬的方法，所述方法是将所述组合物施用于作物、作物的种子或块茎或其他可繁殖部位、作物生长地上。
根据本发明的实施方案，将所述组合物在非耕地、作物收获后的催枯或灭茬、作物播种前、作物播种后出苗前、作物移栽前、作物行间定向施用。
在本发明的一个实施方案中，所述组合物可用于茎叶喷雾：包括：非耕地除草；农田作物行间定向喷雾除草、果树行间定向喷雾除草、苗木行间定向喷雾除草；对作物(如棉花、水稻、油菜、甜菜、薯类、花生等)收获后的催枯或灭茬。
在本发明的一个实施方案中，所述组合物可用于土壤喷雾：包括：农田作物播种前、农田作 物播种后出苗前、果树移栽前、苗木移栽前、草坪播种前、花卉播种前等。
根据本发明的实施方案，所述组合物具有土壤封闭的效果，所述组合物对用于土壤喷雾以及茎叶喷雾时，对未出苗的杂草也有一定的土壤封闭的效果(抑制杂草的出苗)。
在本发明的一个实施方案中，所述非耕地包括但不限于林木(场)、公路、森林防火道、铁路等地；所述农田作物包括但不限于玉米、高梁、小麦、大麦、黑麦、黑小麦和硬粒小麦、稻、甘蔗、大豆、豆类蔬菜(如豌豆、菜豆和扁豆)、花生、向日葵、糖用甜菜、土豆、棉花、芸苔属作物(如西蓝花、卷心菜、甘蓝等)；所述果树包括但不限于苹果、梨、桃、杏、胡桃、山核桃、橄榄、樱桃、李子、柑橘、咖啡树等；所述苗木包括但不限于松属、冷杉、橡树、枫树、柳树、山楂、海棠等；所述草坪包括但不限于狗牙根、多花黑麦草、高羊茅等；所述花卉包括但不限于玫瑰、矮牵牛、万寿菊和金鱼草等。
本发明的有益效果：
1、化合物1对阔叶类杂草、禾本科杂草有较好的防治效果，但是返青率较高；草甘膦可以通过内吸传导性，在防除多年生深根性恶性杂草上显示非常突出的优点，但是其速效性差。混配使用后，不仅扩大了杀草谱，还弥补了化合物1和草甘膦的缺点，提高了速效性，降低了杂草的返青率。
2、本发明所述除草剂组合物在植物体内容易降解，施用后可直接种植玉米，7天后可种植花生、白菜、空心菜。本发明可用于茎叶喷雾，也可以用于土壤喷雾。靶标杂草例如有：播娘蒿、蒺藜、牛筋草、婆婆纳、荠菜、米瓦罐、鸭跖草、马唐、稗草、虎尾草、白茅、苣买菜、龙葵、碎米荠、鳢肠、雀麦、芦苇、苘麻、百日草、凹头苋、繁缕、硬草、马唐、铁苋菜、大穗看麦娘、苍耳、马齿苋、葎草、金盏菊、波斯菊、小子虉草等杂草。
3、本发明两种单剂复配后可以形成增效作用，增强了杂草防治效果。
4、延缓和控制杂草抗药性的产生及田间杂草群落的演替。化合物1和草甘膦分属两类除草剂，作用机理不同，杂草不易产生抗药性。两者复配扩大了杀草谱，延缓了杂草群落演替的产生。
5、本发明所述的除草组合物还可以提升作物的质量和增加产量。
具体实施方式
下文将结合具体实施例对本发明做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。
实施例中所使用的化合物1具有如下所示结构：
实施例1：化合物1(IA-1、IA-2、IA-3、IA-4)和草甘膦单剂和组合物室内除草活性测定。
在室内温室条件下，采用盆栽试验的方法，研究化合物1和草甘膦混用的除草效果，并用Gowing法评价两者混用后的联合作用类型。
在玻璃温室中进行试验试材的培养，温度20-28℃。将生长状态良好的金盏菊、波斯菊、小子虉草移栽到直径为9cm的塑料盆中，放入装有水的大塑料盆中，让水在底部逐渐渗入，等水渗到土表后放在阴凉处缓苗1-2天，然后放在玻璃温室中培养1周，之后进行打药处理，按照表1中所述试验剂量进行试验。化合物1(化合物IA-1、IA-2、IA-3、IA-4)的试验剂量为0.5、1.5、2.5、3.5、4.5g a.i/mu(克有效成分/亩)，草甘膦的试验剂量为：30、45、60、75、90g a.i/mu，按表1进行两两复配。
使用型号为3WP-2000型行走式喷雾塔进行喷雾处理，喷头型号为TP65015E，速度为500mm/s，流量为590mL/min，按精准喷雾塔实际喷药面积(0.5m2)准确计算并配制所需药液。将塑料盆整齐排放在喷雾塔隔板上，每种处理3个重复。
试验结果如表2-表9所示。
表1化合物1(IA-1、IA-2、IA-3、IA-4)和草甘膦组合物室内生物活性测定剂量表(单位：g a.i/mu)
试验结果用Gowing法评价混用后的联合作用类型。Gowing法理论防治效果计算式为：
X一化合物1用量为P时的杂草防效；
Y一草甘膦用量为Q时的杂草防效；
E0一化合物1用量为P时的理论防效+草甘膦用量为Q时的理论防效；
E一化合物1与草甘膦按上述比例混用后的实际防效。
E-E0>10％为增效作用；E-E0<-10％为拮抗作用；E-E0值介于±10％之间为加成作用。
根据表2、表4、表6、表8可知，化合物1(IA-1、IA-2、IA-3、IA-4)和草甘膦复配时E-E0>10％，全部表现出增效作用，并且根据表3、表5、表7、表9可知，化合物1(IA-1、IA-2、IA-3、IA-4)和草甘膦复配，极大的延长了杂草返青时间，甚至可以直接杀死杂草，因此综上所述，优选比例为1：6.7-180。
表2化合物IA-1+草甘膦组合物室内生物活性测定结果表
表3化合物IA-1+草甘膦单剂和组合物室内供试杂草枯萎和返青时间


注：“-”代表杂草未返青。
表4化合物IA-2+草甘膦组合物室内生物活性测定结果表

表5化合物IA-2+草甘膦单剂和组合物室内供试杂草枯萎和返青时间

注：“-”代表杂草未返青。
表6化合物IA-3+草甘膦组合物室内生物活性测定结果表

表7化合物IA-3+草甘膦单剂和组合物室内供试杂草枯萎和返青时间


注：“-”代表杂草未返青。
表8化合物IA-4+草甘膦组合物室内生物活性测定结果表
表9化合物IA-4+草甘膦单剂和组合物室内供试杂草枯萎和返青时间


注：“-”代表杂草未返青。
实施例2化合物1(IA-1、IA-2、IA-3、IA-4)和草甘膦桶混田间杂草防治试验
试验方法：试验地点为山东省济南市天桥区桑梓店镇耿庄村，杂草种类主要为牛筋草、鳢肠、雀麦、芦苇、苘麻、百日草、凹头苋、繁缕、硬草、马唐、铁苋菜、大穗看麦娘、苍耳、马齿苋、虎尾草等。对化合物1和草甘膦进行桶混试验，施用方式：化合物1剂量为2g a.i/mu，草甘膦剂量为40g a.i/mu，化合物1和草甘膦桶混时剂量为2+40g a.i/mu，选择长势较好、草相均一的地方，进行喷药处理。背负式喷雾器械为AGROLEX新加坡利农HD-400手动喷雾器，进口扁扇形喷头，容量16L；选择大叶龄杂草进行茎叶处理，喷液压力为4kdf/cm2，供试药剂用去离子水溶解，各处理药液均采用二次稀释法配置，施药前将药剂搅拌均匀后进行喷雾处理。采用目测法进行防治效果调查(0为无防治效果，100％为杂草全部防治)，施用15天后调查防治效果，15、30、45天后调查返青时间。通过表10-表13可以明显的看出化合物1(化合物IA-1、IA-2、IA-3、IA-4)和草甘膦的复配可以显著提高两者对杂草的防治效果，并且显著延长了杂草的返青时间，甚至在45天时无法返青。
表10化合物IA-1+草甘膦组合物大田15天杂草目测防治效果和返青天数


注：“-”代表杂草未返青。
表11化合物IA-2+草甘膦组合物大田15天杂草目测防治效果和返青天数

注：“-”代表杂草未返青。
表12化合物IA-3+草甘膦组合物大田15天杂草目测防治效果和返青天数


注：“-”代表杂草未返青。
表13化合物IA-4+草甘膦组合物大田15天杂草目测防治效果和返青天数

注：“-”代表杂草未返青。
实施例3化合物1和草甘膦制剂田间杂草防治试验
采用实施例2的方法进行田间杂草防治试验，杂草种类主要为播娘蒿、蒺藜、牛筋草、婆婆纳、荠菜、米瓦罐、鸭跖草、马唐、稗草、虎尾草、白茅、苣买菜、龙葵、碎米荠等。试验方式为：化合物1剂量为2g a.i/mu，草甘膦剂量为40g a.i/mu，化合物1和草甘膦水剂制剂用量为250mL/mu。所述水剂制剂制备如下：将草甘膦加入二甲胺溶液中制成草甘膦盐的形式，再加入化合物1，搅拌均匀后再加入乳化剂(脂肪醇聚氧乙烯醚、蓖麻油聚氧乙烯醚磷酸酯)，最后制成化合物1和草甘膦水剂，最终的浓度为：草甘膦16％，化合物1为0.8％。通过表14- 表17可以明显的看出化合物1和草甘膦的制剂形式可以显著提高两者对杂草的防治效果，并且明显延长了杂草的返青时间，甚至在45天时无法返青。
可见，化合物1和草甘膦无论是制剂形式还是桶混形式均可显著提高两种活性成分对杂草的防治效果和返青时间。
表14化合物IA-1·草甘膦组合物大田15天杂草目测防治效果和返青时间

注：“-”代表杂草未返青。
表15化合物IA-2·草甘膦组合物大田15天杂草目测防治效果和返青时间

注：“-”代表杂草未返青。
表16化合物IA-3·草甘膦组合物大田15天杂草目测防治效果和返青时间

注：“-”代表杂草未返青。
表17化合物IA-4·草甘膦组合物大田15天杂草目测防治效果和返青时间

注：“-”代表杂草未返青。
实施例4化合物1和草甘膦组合物室内土壤封闭试验
在大田试验过程中，发现化合物1还具有一定的土壤封闭活性，对化合物1和草甘膦组合 物进行如下室内试验：
在玻璃温室中，选择稗草、多花黑麦草、马齿苋、苘麻进行化合物1和草甘膦室内除草活性比对试验(土壤喷雾)，采用桶混的方法进行试验，其中，化合物1的剂量为10g a.i/mu，草甘膦的剂量为80g a.i/mu，进行土壤喷雾。结果为：化合物1+草甘膦对苘麻、马齿苋土壤封闭效果优异，防治效果值均在95％以上，对稗草具有较好的土壤封闭效果，株防治效果值在80％以上，化合物1+草甘膦对多花黑麦草具有一定的土壤封闭活性，结果详见表18-表21。
表18化合物IA-1和草甘膦组合物室内除草活性(土壤封闭)
表19化合物IA-2和草甘膦组合物室内除草活性(土壤封闭)
表20化合物IA-3和草甘膦组合物室内除草活性(土壤封闭)

表21化合物IA-4和草甘膦组合物室内除草活性(土壤封闭)
实施例5化合物1和草甘膦组合物大田后茬作物安全性试验
试验方法：试验地点为山东省济南市天桥区桑梓店镇耿庄村，靶标后茬作物选择玉米、花生、空心菜和白菜。采用桶混的方式在裸土上施用化合物1+草甘膦2+40g a.i./mu，间隔0天、7天、15天、30天后相继播种4种作物，分别于播种后14天比对各处理与清水处理对照的异同点，详细结果如表22所示。
播种后14天调查结果表明：药后0天播种，玉米无明显药害，其余3种靶标作物均有不同程度的抑制(轻微药害)；药后7天、15天、30天播种，4种作物均无明显药害。化合物1+草甘膦组合物使用后，对玉米安全，7天以后对花生、空心菜、白菜安全。
表22化合物1+草甘膦组合物后茬作物安全性试验

实施例6化合物1和草甘膦组合物在玉米田定向喷雾试验
试验方法：试验地点为山东省济南市天桥区桑梓店镇耿庄村，靶标作物为玉米(郑单958)。前茬作物为小麦，麦茬未处理，采用桶混的方式进行小麦灭茬处理，化合物1+草甘膦组合物剂量为2+40g a.i./mu。在玉米7-8叶期时草相为：马唐、牛筋草、苍耳、鸭跖草、反枝苋、葎草、藜、田旋花、香附子、狗尾草、小蓟、鳢肠、繁缕，此时杂草叶龄多为2-5叶，进行全田定向喷雾处理，化合物1+草甘膦组合物的剂量为2+40g a.i./mu。
小麦灭茬处理20天调查结果表明：无自生小麦，玉米生长正常。
化合物1+草甘膦组合物在玉米田间定向喷雾使用后，1、3、7、10、14天调查结果发现：1天后杂草叶片开始出现明显的点状触杀斑，3天后叶片脱水干枯，7天后玉米田中的大部分杂草叶片已干枯死亡。10天玉米生长正常。玉米成熟后，经实地测产发现，施用化合物A+草甘膦组合物后，增产率在20％以上，明显增产，结果详见表23-表27。
表23化合物IA-1+草甘膦组合物玉米田间定向喷雾目测防效
表24化合物IA-2+草甘膦组合物玉米田间定向喷雾目测防效
表25化合物IA-3+草甘膦组合物玉米田间定向喷雾目测防效
表26化合物IA-4+草甘膦组合物玉米田间定向喷雾目测防效

表27化合物A+草甘膦组合物玉米田间定向喷雾测产结果
实施例7化合物1和草甘膦组合物作为棉花落叶剂使用
试验方法：试验地点为山东省济南市天桥区桑梓店镇耿庄村，靶标作物为棉花。化合物1+草甘膦组合物的施用方式为全田茎叶喷雾，剂量为1.5+40g a.i./mu，最终调查药剂促进棉铃吐絮效果，并选用绝对值调查法调查棉花脱叶率，试验参考NY/T1464.26-2007农药田间药效试验准则第26部分：棉花催枯剂试验。
棉田喷施化合物1+草甘膦组合物(1.5+40g a.i/mu)后，与对照区相比较，叶片提早脱落，药后15天发现，叶片相较于对照处理区有褶皱、脱水、干枯的现象，到20天时，叶片脱落率显著高于对照处理区；药后30天，叶片基本全部脱落，结果详见表28。
棉田喷施化合物1+草甘膦组合物(1.5+40g a.i/mu)后，对棉铃的吐絮也有一定的效果，药后20天，处理区的霜前花率显著高于对照区，从总体来看处理区的霜前花率显著高于对照区，有利于提高棉花的产量和质量，结果详见表29。
表28化合物1+草甘膦组合物(1.5+40g a.i/mu)棉花的脱叶率(％)
表29化合物1+草甘膦组合物(1.5+40g a.i/mu)棉花的霜前花率(％)
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种组合物，包括：a)化合物1和b)草甘膦及其盐；
    所述化合物1为通式(I)所示的化合物、其立体异构体、消旋体、互变异构体、同位素标记物、氮氧化物、药学上可接受的盐或酯、溶剂合物或者药学上可接受的盐的溶剂合物，
    其中，R1、R2、R3、R4相同或不同，彼此独立地选自氢、卤素、C1-C6烷基或卤代C1-C6烷基；
    R5、R6、R7、R8相同或不同，彼此独立地选自氢、卤素、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基或卤代C1-C6烷氧基；
    R9、R10相同或不同，彼此独立地选自氢、氰基、C1-C6烷基或卤代C1-C6烷基；
    R11、R12相同或不同，彼此独立地选自氢、氰基、C1-C6烷基、卤代C1-C6烷基、COOR13或CONR14R15；
    R13选自氢、C1-C6烷基、卤代C1-C6烷基、C1-C3烷氧基C1-C6烷基、C3-C6烯基、C3-C6炔基、未取代或被1-4个Ra取代的C6-C10芳基C1-C6烷基、5-10元杂芳基C1-C6烷基或3-10元杂环基C1-C6烷基；每个Ra相同或不同，彼此独立地选自卤素、氰基、硝基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基或卤代C1-C6烷氧基；
    R14、R15相同或不同，彼此独立地选自氢、C1-C6烷基或C1-C4烷氧基C1-C6烷基。
  2. 如权利要求1所述的组合物，其中，通式(I)化合物为如下通式(IA)化合物：
    其中，R13选自C1-C6烷基、卤代C1-C6烷基、C1-C3烷氧基C1-C6烷基、未取代或被1-4个Ra取代的C6-C10芳基C1-C6烷基、5-10元杂芳基C1-C6烷基或3-10元杂环基C1-C6烷基；每个Ra相同或不同，彼此独立地选自卤素、氰基、硝基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基或卤代C1-C6烷氧基。
  3. 如权利要求1所述的组合物，其中，通式(I)化合物为如下具体化合物：
  4. 如权利要求1所述的组合物，其中，所述组合物中，化合物1和草甘膦的重量比为1:(5-180)，或1:(6.7-180)。
  5. 如权利要求1所述的组合物，其中，所述草甘膦的盐为钠盐、铵盐、异丙铵盐、钾盐等。
  6. 如权利要求1所述的组合物，其中，所述组合物中，所述组合物中，所述组分a)和组分b)是独立存在的；使用时再将组分a)和组分b)进行混配；
    优选的，所述组合物为制剂形式；所述制剂为液体制剂或固体制剂；所述组合物制剂例如为乳油、水悬浮剂、油悬浮剂、可湿性粉剂、颗粒剂或水剂等农药、农业、林业或园艺学上可接受的剂型；
    优选的，所述组合物还包括农药、农业、林业或园艺学上可接受的助剂，所述助剂例如为润湿剂、乳化剂、分散剂、增稠剂、防冻剂、崩解剂、粘结剂、消泡剂、稳定剂、填料和载体中的一种或多种。
  7. 权利要求1-6任一项所述的组合物的应用，其用于防治有害植物、用于作物的提质增产或者用于作物的摧枯或灭茬。
  8. 一种防治有害植物的方法，所述方法是将权利要求1-6中任一项所述的组合物施用于有害植物和/或有害植物生长地；优选地，所述组合物可用于茎叶喷雾或土壤喷雾。
  9. 一种用于作物的提质增产的方法，所述方法是将权利要求1-6中任一项所述的组合物施用于作物、作物的种子或块茎或其他可繁殖部位、作物生长地上；优选地，所述组合物可用于茎叶喷雾或土壤喷雾。
  10. 一种用于作物的摧枯或灭茬的方法，所述方法是将权利要求1-6中任一项所述的组合物施用于作物、作物的种子或块茎或其他可繁殖部位、作物生长地上；优选地，所述组合物可用于茎叶喷雾或土壤喷雾。
PCT/CN2023/105585 2022-07-04 2023-07-03 一种含吡啶基苯基异噁唑啉类化合物和草甘膦的除草组合物及其应用 WO2024008049A1 (zh)

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