WO2021179553A1 - N-苄基苯甲酰胺类化合物作为除草剂的用途 - Google Patents

N-苄基苯甲酰胺类化合物作为除草剂的用途 Download PDF

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Publication number
WO2021179553A1
WO2021179553A1 PCT/CN2020/113018 CN2020113018W WO2021179553A1 WO 2021179553 A1 WO2021179553 A1 WO 2021179553A1 CN 2020113018 W CN2020113018 W CN 2020113018W WO 2021179553 A1 WO2021179553 A1 WO 2021179553A1
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Prior art keywords
benzylbenzamide
compound
weeds
och
compounds
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PCT/CN2020/113018
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English (en)
French (fr)
Inventor
姬志勤
魏少鹏
张会霞
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西北农林科技大学
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Priority to US17/423,247 priority Critical patent/US20220330549A1/en
Priority to CN202080001955.2A priority patent/CN112203515B/zh
Publication of WO2021179553A1 publication Critical patent/WO2021179553A1/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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
    • A01N43/70—Diamino—1,3,5—triazines with only one oxygen, sulfur or halogen atom or only one cyano, thiocyano (—SCN), cyanato (—OCN) or azido (—N3) group directly attached to a ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3

Definitions

  • the invention belongs to the technical field of pesticides, and specifically relates to the use of N-benzylbenzamide compounds as herbicides.
  • the invention also provides herbicidal compositions and mixed formulations containing the N-benzylbenzamide compounds as well as Its application.
  • Patent CN2016109689860 provides a variety of N-benzylbenzamide compounds with specific chemical structures, which can be used as pharmaceutical ingredients for anti-tuberculosis.
  • patent EP0467473A1 discloses the herbicidal activity and synthesis method of compound 2.
  • Patent CN2018116183053 discloses the new use of compound 3 and its composition as agricultural fungicides.
  • N-benzylbenzamide compounds are a kind of pigment synthesis inhibitor herbicides, which can be used to control the field. Weeds in crop growing areas and non-cultivated crop areas. According to the existing literature searched by the inventor, there is no report of the N-benzylbenzamide compound disclosed in the present invention as a herbicide.
  • N-benzylbenzamide compounds have simple structure, stable properties, low toxicity, short synthetic route, low cost, better development and utilization value, and great prospects for popularization and application.
  • the present invention relates to the use of N-benzylbenzamide compounds as herbicides, characterized in that the components of the herbicides comprise N-benzylbenzamide compounds having the general formula (I) or (II) Or its salt.
  • R 0 is selected from methyl or methoxy
  • R 1 is selected from hydrogen, C 1 ⁇ C 4 alkyl, C 1 ⁇ C 4 alkoxy, halogenated C 1 ⁇ C 4 alkyl, halogenated C 1 ⁇ C 4 alkoxy, halogen, cyano;
  • R 2 , R 3 and R 4 are each independently selected from hydrogen, C 1 ⁇ C 4 alkyl, C 1 ⁇ C 4 alkoxy, halogen, cyano, halo C 1 ⁇ C 4 alkyl, halo C 1 ⁇ C 4 alkoxy, methylsulfonyl;
  • X is selected from C or N.
  • R 0 is selected from methyl or methoxy
  • R 1 is selected from hydrogen, methyl, methoxy, fluorine, chlorine, bromine, cyano;
  • R 2 , R 3 and R 4 are each independently selected from hydrogen, methyl, methoxy, fluorine, chlorine, bromine, cyano, and methanesulfonyl;
  • X is selected from C or N.
  • N-benzylbenzamide compounds with general formulas (I) and (II) of the present invention can be prepared by referring to similar methods in the above-mentioned documents.
  • N-benzylbenzamide compound with general formula (I) of the present invention can be prepared by using Scheme I in a suitable solvent and alkaline conditions.
  • the synthetic reaction route is:
  • the Scheme I reaction is carried out in a suitable solvent, and the suitable solvent can be selected from, for example, tetrahydrofuran, acetonitrile, toluene, xylene, N,N-dimethylformamide, dichloromethane, chloroform, pyridine, etc.;
  • a suitable base can be selected from, for example, triethylamine, pyridine, potassium carbonate, sodium hydroxide, etc.;
  • the reaction temperature can be between ice bath and the boiling temperature of the solvent, and is usually preferably 0 to 125°C; the reaction time is 30 minutes to 20 hours, Usually, it is preferably 1 to 6 hours.
  • Table 1 lists some of the compounds represented by the general formula (I). It should be noted that the N-benzylbenzamide compounds represented by the general formula (I) are not limited to the compounds listed in Table 1.
  • N-benzylbenzamide compound with the general formula (II) of the present invention can be prepared by using Scheme II in a suitable solvent and alkaline conditions.
  • the synthetic reaction route is:
  • the Scheme II reaction is carried out in a suitable solvent, and the suitable solvent can be selected from, for example, tetrahydrofuran, acetonitrile, toluene, xylene, N,N-dimethylformamide, dichloromethane, chloroform, pyridine, etc.;
  • a suitable base can be selected from, for example, triethylamine, pyridine, potassium carbonate, sodium hydroxide, etc.;
  • the reaction temperature can be between ice bath and the boiling temperature of the solvent, usually 0 to 125°C; the reaction time is 30 minutes to 20 hours, Usually, it is preferably 1 to 6 hours.
  • Table 2 lists some of the compounds represented by the general formula (II). It should be noted that the N-benzylbenzamide compounds represented by the general formula (II) are not limited to the compounds listed in Table 2.
  • the weeds treated with the N-benzylbenzamide compound of the present invention show a typical "albino effect", that is, the symptoms of the weeds after the treatment with the medicament are leaf bleaching, chlorosis, and death.
  • the weed symptoms caused by N-benzylbenzamide compounds are similar to mesotrione (HPPD inhibitor), diflufenican (PDS inhibitor) and other herbicides acting on the carotenoid biosynthetic pathway, but It is different from flumioxamide (PPO inhibitor) which interferes with chlorophyll biosynthesis. Therefore, it can be speculated that the N-benzylbenzamide compound of the present invention acts on the carotenoid biosynthesis pathway and belongs to the pigment synthesis inhibitor.
  • the N-benzylbenzamide compounds have higher herbicidal activity and can be used to prevent and control pests that are resistant to existing herbicides.
  • Grass is especially suitable for controlling weeds that are resistant to ALS inhibitors, PSII inhibitors, ACCase inhibitors and EPSP inhibitor herbicides.
  • the weeds should have the broadest or broader meaning, including all types of plant species that grow in undesirable places.
  • the present invention divides the "undesirable places" into field crop growing places and non-farming crop places.
  • the field where crops grow is the field or field in the usual sense.
  • Non-cultivated crop sites refer to places where weeds are not expected to grow except for field crops, including vineyards, apple orchards, citrus orchards, banana farms, coffee plantations, tea plantations, rubber plantations, oil Palm plantations, coconut plantations and other places.
  • the N-benzylbenzamide compound and the herbicide containing the N-benzylbenzamide compound as a component can be used to control the following weeds growing in the following crop fields .
  • Crop genera in the Dicotyledon class Gossypium, Soybean, Beet, Phaseolus, Pea, Solanum, Linum, Tomato, Arachis, Brassica, Lactuca, Cantaloupe, Cucurbita, etc.
  • Crop genera in the class of monocotyledons Oryza, Zea, Triticum, Barley, Oats, Millet, Sugarcane, Bromeliad, Asparagus, Allium, etc.
  • Dicotyledonous weed genera White mustard, Mustard, Sorrel, Stellaria, Chenopodium, Kochia, Urtica, Senecio, Amaranth, Purslane, Cocklebur Genus, Ipomoea, Polygonum, Ragweed, Thistle, Solanum, Solanum, Papaver, Datura, Viola, Papaver, Centaurea, Nitraria, Saskatchewan Genus, Motherweed, Sesbania, Trifolium, Abutilon, Wild Sesame, Matricaria, Artemisia, Morning Glory, etc.
  • Monocotyledonous weeds Barnyard, Setaria, Millet, Crabgrass, Timothy, Poa, Wool, Ryegrass, Bromus, Oats, Cyperus, Alcohol , Wheatgrass, Amphiprion, Drifting Grass, Sagittaria, Scirpus, Paspalum, Platypus, Bentgrass, Camellia, Bermudagrass, Commelina, Arm The genus Xingcao, the genus Stephanotis and so on.
  • the N-benzylbenzamide compound and the herbicide containing the N-benzylbenzamide compound as a component can be used to control the following representative farmland weeds .
  • the farmland weeds include: barnyardgrass, pondweed, duckweed, sedge, flat saccharum, stephen, wild oats, crabgrass, cricket grass, setaria, mitten, wormwood, shepherd's purse , Lone cabbage, Humulus, Fructus vulgaris, Involvulus vulgaris, Polygonum vulgare, Cyperus rotundus, Quinoa, Polygonum sorrel, Amaranthus retroflexus, Portulaca oleracea, Amaranthus, Dodder, Abutilon, Pork stalk, Channa , Cocklebur, bermudagrass, Imperata cylindrica, nightshade, cow chickweed, airplane grass, red thistle, rotundifolia, mugwort, dandelion, year round, cole,
  • the present invention provides the use of a composition as an agricultural herbicide.
  • the herbicidal component in the composition contains the N-benzylbenzamide compound or salt thereof, and the composition also includes The carrier accepted in agriculture.
  • the agricultural application method of the composition the inventor has learned through experiments that by applying the method of pre-emergence soil treatment or post-emergence stem and leaf spraying to soil or weeds, a better weeding effect can be obtained.
  • the dosage of the N-benzylbenzamide compound or its salt varies due to various factors, such as the compound used, the crop to be protected, the weed to be controlled, and the degree of weed growth , Climatic conditions, application methods, dosage forms, etc.
  • the inventor verified the dosage of the composition and learned that the dosage per hectare is 10 g to 5000 g based on the N-benzyl benzamide compound or its salt. At this amount, the composition can exhibit a relatively ideal herbicidal effect.
  • the N-benzylbenzamide compound or its salt has good herbicidal activity both before and after emergence, and its symptoms are manifested as leaf albino, wilting and death.
  • the dosage of the N-benzylbenzamide compound or its salt is 10 g to 1000 g per hectare.
  • the weight percentage of the N-benzylbenzamide compound or its salt is recommended to be between 0.1% and 99.0%. The inventors have discovered through research that the N-benzylbenzamide compound or its salt can be used as a selective herbicide by controlling it at an appropriate concentration.
  • the present invention provides the use of a mixed formulation as an agricultural herbicide.
  • the herbicidal active components of this mixed preparation include the N-benzylbenzamide compounds or their salts, as well as acetyl-Coenzyme A carboxylase inhibitors, acetolactate synthase inhibitors, auxin herbicides,
  • the herbicidal component of carotenoid biosynthesis inhibitor, photosynthesis inhibitor, cell wall biosynthesis inhibitor, the herbicidal component is mixed with the N-benzylbenzamide compound or its salt or exhibits a compound formulation Synergistic effect.
  • N-benzylbenzamide compounds or their salts of the present invention and the herbicides acting on the photosynthetic system II (PSII) are particularly synergistic when used as a herbicidal composition, and also have a good control effect on older weeds, and the action time is significantly accelerated, and weeds appear on the day of application Obvious symptoms of albinism.
  • the weight percentage of the N-benzylbenzamide compound or its salt and the PSII herbicide in the composition of the present invention is 1:20-20:1, N-benzylbenzamide
  • the weight percentage of the compound or its salt and the PSII herbicide in the formulation is recommended to be between 0.1% and 99.0%, and the appropriate dosage is 10 g to 1000 g of active ingredient per hectare.
  • the weight ratio of the N-benzylbenzamide compound or its salt to atrazine in the composition of the present invention is 1:10-10:1, N-benzylbenzamide
  • the weight percentage of the compound or its salt and the PSII herbicide in the formulation is recommended to be between 0.1% and 99.0%, and the appropriate dosage is 10 g to 1000 g of active ingredient per hectare.
  • the composition can significantly reduce the amount of atrazine, reduce the phytotoxicity of atrazine residues on subsequent crops, and significantly improve the control effect on older gramineous weeds, and the action time is significantly accelerated.
  • compositions provided by the present invention as an agricultural herbicide
  • a mixed formulation as an agricultural herbicide
  • the composition or mixed formulation is usually used in agriculture in the form of a formulation, which also Including agriculturally accepted carriers.
  • Said N-benzylbenzamide compounds or their salts, or other herbicidal active ingredients compounded with them, are used as active ingredients to be dissolved or dispersed in a carrier or formulated into preparations so as to be easier to disperse when used as herbicides .
  • Dispersant such as polycarboxylate (such as TERSPERSE 2700, T36, GY-D06, etc.), lignosulfonate, alkyl naphthalene sulfonate, one or more; wetting agent such as alkyl sulfate, alkyl One or more of sulfonate and naphthalenesulfonate; disintegrant such as one or more of ammonium sulfate, urea, sucrose, glucose; binder such as diatomaceous earth, corn starch, polyvinyl alcohol (PVA ), one or more of carboxymethyl (ethyl) cellulose; safener MON13900 (product of Monsanto); fillers such as diatomaceous earth, kaolin, white carbon black, light calcium, talcum powder, attapulgite One or more clay
  • Dispersants that can be used such as polycarboxylates (TERSPERSE 2700, T36, GY-D06, etc.), lignosulfonates (Ufoxane 3A, Borresperse NA, Borresperse CA-SA, etc.), naphthalene and alkyl naphthalene formaldehyde condensation Sulfonates (NNO, MF, Morwet D-425, Tamol NN, TERSPERSE2020, etc.), open powder BX (sodium dibutyl naphthalene sulfonate), EO-PO block polyethers, alkylphenol polyoxygen One or more of vinyl ether phosphate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate (SOPA); wetting agent such as sulfate (K-12), sulfate
  • dispersing agents such as polycarboxylates, lignin sulfonates, alkyl naphthalene sulfonates (NNO), and TERSPERSE 2020 (alkyl naphthalene sulfonates) can be used; emulsifiers such as agricultural milk 700# (generic name: alkylphenol formaldehyde resin polyoxyethylene ether), agricultural milk 2201, Span-60# (generic name: sorbitan stearate), Tween-60# (generic name: poly One or more of oxyethylene sorbitan stearate), agricultural milk 1601# (common name: triphenylethyl phenol polyoxypropylene polyoxyethylene block polymer), TERSPERSE 4894; wetting agent Such as alkylphenol polyoxyethylene ether formaldehyde conden
  • the selected dispersant such as polycarboxylate, lignin sulfonate, alkyl naphthalene sulfonate (diffuser NNO), TERSPERSE 2020 (alkyl naphthalene sulfonate) Species; emulsifiers such as BY (castor oil polyoxyethylene ether) series emulsifiers (BY-110, BY-125, BY-140), Nongru 700# (common name: alkylphenol formaldehyde resin polyoxyethylene ether), Nongru 2201, Span-60# (common name: sorbitan monostearate), Tween-60# (common name: sorbitan monostearate polyoxyethylene ether), Nongru 1601 #(Common name: phenethyl phenol polyoxyethylene polyoxypropylene ether), TERSPERSE 4894; wetting agent such as alkylphenol polyoxyethylene ether formaldehyde condensate
  • the present invention provides a new application of the N-benzylbenzamide compound or its salt in weed control, and expands the application of the N-benzylbenzamide compound in the agricultural field.
  • the N-benzylbenzamide compound or its salt is used as a herbicide for controlling weeds in field crop growing places and non-farming crop places, has high herbicidal activity, and can be used to prevent and control diseases that are resistant to existing herbicides Weeds are especially suitable for controlling weeds that are resistant to ALS inhibitors, PSII inhibitors, ACCase inhibitors, and EPSP inhibitor herbicides.
  • the present invention further clarifies that the composition containing the N-benzylbenzamide compound or its salt and the PSII inhibitor herbicide composition still exhibits a good effect on weeds in field crop growth sites and non-farming crop sites. Control effect. This fully shows that the N-benzylbenzamide compound or its salt has great development potential, and provides a new idea for the development of new green chemical pesticides.
  • the present invention contains the N-benzylbenzamide compound or its salt composition and mixed preparations that can be formulated into suspensions, water dispersible granules, wettable powders or dispersible oil suspensions that meet the needs of agricultural production, etc.
  • the formulation has good safety to crops and meets the safety requirements of pesticide preparations.
  • the invention enriches existing herbicide varieties and can bring considerable market benefits.
  • the amount of each component added is in percentage by weight, and the active compound is metered in after being folded.
  • the compound B14 and other components are thoroughly mixed and pulverized by a jet mill to obtain a 10% N-benzylbenzamide compound (compound B14) wettable powder product.
  • the amount of each component added is in percentage by weight, and the active compound is metered in after being folded.
  • the compound A09 and other components are thoroughly mixed in a stirred tank to obtain a 10% N-benzylbenzamide compound (compound A09) water emulsion product.
  • the amount of each component added is in percentage by weight, and the active compound is metered in after being folded.
  • the compound A85 and other components are thoroughly mixed in a stirred tank to obtain a 10% N-benzylbenzamide compound (compound A85) dispersible oil suspension product.
  • Example 12 10% N-benzylbenzamide compound (compound B07) emulsifiable concentrate
  • the amount of each component added is in percentage by weight, and the active compound is metered in after being folded.
  • the compound B07 and other components are thoroughly mixed in a stirred tank to obtain a 10% N-benzylbenzamide compound (compound B07) emulsifiable concentrate product.
  • Examples 9-12 give several herbicides containing N-benzylbenzamide compounds, which are only used as demonstration instructions for the preparation of N-benzylbenzamide-containing herbicides or herbicidal composition formulations.
  • the setaria seeds were sown in plastic pots with a diameter of 9 cm, each pot was sown with 20 seeds, covered with soil 0.5 cm, and cultivated in a greenhouse at 25-35°C under natural light and natural humidity.
  • the spraying system is automatically controlled for spraying. There are 29 treatments, A02 single dose 50, 100, 200, 400g(ai)/ha four single dose treatments, atrazine single Four single-agent treatments of 400, 800, 1200, 1600g(ai)/ha, the mixed dosage of 900g(ai)/ha, 20 treatments mixed with two single agents in different proportions, and a blank control (Spraying water), each treatment is repeated 4 times.
  • Level 2 equivalent to 0 ⁇ 2.5% of the weeds in the blank control area
  • Level 3 equivalent to 2.6 to 5% of the weeds in the blank control area
  • Level 4 equivalent to 5.1-10% of the weeds in the blank control area
  • Grade 5 equivalent to 10.1-15% of the weeds in the blank control area
  • Grade 6 equivalent to 15.1-25% of the weeds in the blank control area
  • Grade 8 equivalent to 35.1 ⁇ 67.5% of the weeds in the blank control area
  • Grade 9 equivalent to 67.6-100% of the weeds in the blank control area.
  • Table 4 shows the preemergence herbicidal activity of the test compounds against weeds.
  • test compound has a good control effect on both monocotyledonous weeds and dicotyledonous weeds. After the emergence of the weeds, the seedlings show albino symptoms. Gradually wither and die. The better the light and temperature conditions, the better the effect.
  • the post-emergence herbicidal activity test of some N-benzylbenzamide compounds of general formula I or II was carried out with reference to the method of NY/T 1155.4-2006.
  • the neutral sandy loam soil with the organic content ⁇ 3% is filled to 4/5 of the pot, and the bottom of the pot is used for infiltration irrigation to make the soil completely wet.
  • the test weed seeds were evenly sown on the soil surface, and then 0.5cm ⁇ 2.0cm soil was covered according to the size of the seeds. After sowing, they were transferred to the greenhouse for regular cultivation.
  • Level 2 equivalent to 0 ⁇ 2.5% of the weeds in the blank control area
  • Level 3 equivalent to 2.6 to 5% of the weeds in the blank control area
  • Level 4 equivalent to 5.1-10% of the weeds in the blank control area
  • Grade 5 equivalent to 10.1-15% of the weeds in the blank control area
  • Grade 6 equivalent to 15.1-25% of the weeds in the blank control area
  • Grade 8 equivalent to 35.1 ⁇ 67.5% of the weeds in the blank control area
  • Grade 9 equivalent to 67.6-100% of the weeds in the blank control area.
  • the test compound has a good control effect on both monocotyledonous weeds and dicotyledonous weeds, and the weeds show pigment synthesis for 1 to 3 days after treatment.
  • the characteristic albinism symptoms of the inhibitor gradually dry out and die. The better the light and temperature conditions, the better the effect.
  • N-benzylbenzamide compounds of general formula I or II were tested for herbicidal activity in paddy field after seedling.
  • the soil texture of the experimental paddy field was a medium-soil field, with an organic matter content of 2.0%, and a pH value of 6.5 in the cultivated layer.
  • the rice seedlings were sprayed at the 4-leaf to 5-leaf stage about 1 month after sowing. Take the representative compounds in the examples to make 10% emulsifiable concentrates, spray with water, and spray with a dosage of 150g(ai)/ha, 4 replicates for each treatment, and a plot area of 50m 2 .
  • Level 2 equivalent to 0 ⁇ 2.5% of the weeds in the blank control area
  • Level 3 equivalent to 2.6 to 5% of the weeds in the blank control area
  • Level 4 equivalent to 5.1-10% of the weeds in the blank control area
  • Grade 5 equivalent to 10.1-15% of the weeds in the blank control area
  • Grade 6 equivalent to 15.1-25% of the weeds in the blank control area
  • Grade 8 equivalent to 35.1 ⁇ 67.5% of the weeds in the blank control area
  • Grade 9 equivalent to 67.6-100% of the weeds in the blank control area.
  • test compounds in the table have a good control effect on weeds in rice fields. 15 days after treatment, the control effect of compounds A02, A14, A23, A24, A89, B14, B22, B27, B30 on grass weeds, broadleaf weeds and Cyperaceae weeds can reach level 1.
  • Example 17 Field test of some compounds of general formula I or II to control weeds in corn fields
  • N-benzylbenzamide compounds of general formula I or II were tested for the efficacy of controlling weeds in corn fields.
  • the soil texture of the experimental corn field was sandy loam soil, the organic matter content was 2.0%, the pH value of the cultivated layer was 6.5, and the corn was sprayed at the 2-leaf to 5-leaf stage after sowing.
  • Each treatment has 4 repetitions and the plot area is 20 m 2 .
  • the 25% mesotrione dispersible oil suspension was used as the control agent, and the dosage was 150g(ai)/ha. 21 days after treatment, the results were investigated by visual inspection. According to the symptom and severity of the weed damage, the herbicidal activity is evaluated on a scale of 1-9.
  • Level 2 equivalent to 0 ⁇ 2.5% of the weeds in the blank control area
  • Level 3 equivalent to 2.6 to 5% of the weeds in the blank control area
  • Level 4 equivalent to 5.1-10% of the weeds in the blank control area
  • Grade 5 equivalent to 10.1-15% of the weeds in the blank control area
  • Grade 6 equivalent to 15.1-25% of the weeds in the blank control area
  • Grade 8 equivalent to 35.1 ⁇ 67.5% of the weeds in the blank control area
  • Grade 9 equivalent to 67.6-100% of the weeds in the blank control area.
  • Table 7 Post-emergence weeding effect of some N-benzylbenzamide compounds to control weeds in corn fields (150g a.i./ha)
  • test compounds in the table have a good control effect on weeds in corn fields. 21d after treatment, compounds A02, B08, B14, B27, and B30 are effective against setaria, barnyardgras, goosegrass, crabgrass, pigweed, purslane, amaranthus retroflexus, nightshade, convolvulus, iron amaranth and sedge
  • the prevention effect can reach level 1.
  • Example 18 Field test of mixing some compounds of general formula I or II with atrazine to control weeds in corn fields
  • N-benzylbenzamide compounds of general formula I or II were mixed with atrazine in the field to carry out the field efficacy test for the control of weeds in the corn field.
  • the soil texture of the experimental corn field was sandy loam soil, the organic matter content was 2.0%, the pH value of the cultivated layer was 6.5, and the corn was sprayed at the 2-leaf to 5-leaf stage after sowing.
  • the 40% atrazine suspension was used as the control agent, and the dosage was 600g(ai)/ha. 21 days after treatment, the results were investigated by visual inspection. According to the symptom and severity of the weed damage, the herbicidal activity is evaluated on a scale of 1-9. The herbicidal activity of each compound is shown in Table 8.
  • the compound of general formula I or II and atrazine are barrel-mixed in a certain ratio, which can treat cornfield weeds Setaria, barnyardgrass, goosegrass, crabgrass, quinoa, purslane, and reverse branch.
  • the control effect of amaranth, nightshade, abutilon and sedge reaches level 1.
  • the 40% atrazine suspension is used at a dosage of 600g (a.i.)/ha, it can achieve level 1 control effect on broadleaf grasses, but has poor control effect on grass weeds and sedges.
  • the compound of general formula I or II and atrazine are mixed in a certain ratio after barrel mixing, which significantly improves the control effect on grass weeds and sedges, especially the control of older grass weeds and sedges, which are basically ineffective at atrazine.
  • the effect can also reach level 1.
  • Example 19 Field test on the control of weeds in corn fields with a mixture of some compounds of general formula I or II and atrazine
  • the post-emergence test of the compound of general formula I or II and atrazine was carried out on the control of weeds in the corn field.
  • the stems and leaves are sprayed after the seedlings, and the corn is sprayed at the 4-leaf stage, and the spray amount is 30kg per mu. 21 days after treatment, the results were investigated by visual inspection.
  • the herbicidal activity is evaluated on a scale of 1-9.
  • the 40% atrazine suspension was used as the control agent, and the dosage was 600 g (a.i.)/ha.
  • the herbicidal activity is shown in Table 9.
  • N-benzylbenzamide compounds of the present invention as herbicides has been described through specific examples. Those skilled in the art can learn from the content of the present invention and appropriately change the raw materials, process conditions and other links to achieve corresponding other purposes. All the related changes do not depart from the content of the present invention, and all similar replacements and modifications are obvious to those skilled in the art, and are deemed to be included in the scope of the present invention.

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Abstract

本发明涉及如下所示的N-苄基苯甲酰胺类化合物或其盐作为除草剂的用途，(I), (II) 所述N-苄基苯甲酰胺类化合物或其盐作为色素合成抑制剂用于防除田间作物生长场所、非耕作作物场所的杂草；进一步地，该化合物还与农业上的接受的载体组成农用除草剂，更进一步地，该化合物还与其它除草活性组分特别是莠去津以混合制剂的形式作为农用除草剂。所述N-苄基苯甲酰胺类化合物或其盐的除草活性高，并可用于防治对现有除草剂产生抗性的杂草，与其它除草活性组分组合时表现出良好的增效作用。

Description

N-苄基苯甲酰胺类化合物作为除草剂的用途 技术领域
本发明属于农药技术领域，具体涉及N-苄基苯甲酰胺类化合物作为除草剂的用途，本发明还给出了含有所述N-苄基苯甲酰胺类化合物的除草组合物和混合制剂以及其应用。
背景技术
我国是农业大国，小麦、玉米、水稻等农作物种植面积广，咖啡、茶叶、橡胶、果树等经济作物亦有较大的种植面积。田间和非耕作作物场所杂草发生普遍，杂草种类繁多，与作物争夺水分、养分、光照和空间，造成严重减产。化学除草经济、有效、省力，但是由于大部分除草剂本身杀草谱有限，且长期使用容易造成杂草抗性的产生，因此，研发稳定性更高，除草活性更强，除草谱更广，毒副作用更小的绿色农用除草剂，成为未来发展的必然趋势。此外，现有研究发现，将作用机理不同的除草剂混用，能够有效提高除草效果和杀草谱、延缓杂草抗性的产生。
文献(1)(Polyhedron,2017,129:97-104)中报道了化合物1的制备方法及其抗病毒活性。现有研究证实，N-苄基苯甲酰胺类化合物是一类具有优秀抗结核杆菌活性的化合物(ACS Med.Chem.Lett.2018.9(7):741-745)。专利CN2016109689860提供了多种具体化学结构的N-苄基苯甲酰胺类化合物，可作为抗结核病的医药成分。
Figure PCTCN2020113018-appb-000001
在农业领域，专利EP0467473A1公开了化合物2的除草活性和合成方法。专利CN2018116183053公开了化合物3及其组合物作为农用杀菌剂的新用途。
Figure PCTCN2020113018-appb-000002
发明人合成了系列具体结构的N-苄基苯甲酰胺类化合物，结合生测试验数据得出，N-苄基苯甲酰胺类化合物是一种色素合成抑制剂类除草剂，可用于防除田间作物生长场所、非耕作作物场所的杂草。依据发明人检索的现有文献获知，目前还未见本发明公开 的N-苄基苯甲酰胺类化合物用作除草剂的报道。
发明内容
在前期试验的基础上，本申请提供N-苄基苯甲酰胺类化合物作为除草活性组分的新用途，以及含有N-苄基苯甲酰胺类化合物的除草组合物或混合制剂的新用途。N-苄基苯甲酰胺类化合物结构简单、性质稳定、毒性低、合成路线短、成本低廉，具有更好的开发利用价值，推广应用前景巨大。
本发明涉及N-苄基苯甲酰胺类化合物作为除草剂的用途，其特征在于，所述除草剂的组分包含具有通式(Ⅰ)或(Ⅱ)的N-苄基苯甲酰胺类化合物或其盐。
Figure PCTCN2020113018-appb-000003
式(I)，(II)中，
R 0选自甲基或甲氧基；
R 1选自氢、C 1～C 4烷基、C 1～C 4烷氧基、卤代C 1～C 4烷基、卤代C 1～C 4烷氧基、卤素、氰基；
R 2、R 3和R 4各自独立地选自氢、C 1～C 4烷基、C 1～C 4烷氧基、卤素、氰基、卤代C 1～C 4烷基、卤代C 1～C 4烷氧基、甲磺酰基；
X选自C或N。
更为优选地，式(I)，(II)中，
R 0选自甲基或甲氧基；
R 1选自氢、甲基、甲氧基、氟、氯、溴、氰基；
R 2、R 3和R 4各自独立地选自氢、甲基、甲氧基、氟、氯、溴、氰基、甲磺酰基；
X选自C或N。
本发明所述具有通式(I)、(II)的N-苄基苯甲酰胺类化合物可以参照上述文献中类似方法制得。
本发明所述具有通式(I)的N-苄基苯甲酰胺类化合物，可以在适宜的溶剂以及碱性条件下采用Scheme I的反应制得，合成反应路线为：
Scheme I:
Figure PCTCN2020113018-appb-000004
Scheme I反应在适宜的溶剂中进行，所述适宜的溶剂可选自如四氢呋喃、乙腈、甲苯、二甲苯、N,N-二甲基甲酰胺、二氯甲烷、三氯甲烷、吡啶等；所述适宜的碱可选自如三乙胺、吡啶、碳酸钾、氢氧化钠等；反应温度可在冰浴至溶剂沸点温度之间，通常优选为0～125℃；反应时间为30分钟至20小时，通常优选为1～6小时。
表1列出通式(I)所示部分化合物。需要说明的是，通式(I)所示N-苄基苯甲酰胺类化合物并不仅限于表1所列出的化合物。
表1通式(I)所示部分N-苄基苯甲酰胺类化合物
编号 R 1 R 2 R 3 R 4 X
A01 -H -F -H -H C
A02 -H -H -F -H C
A03 -H -F -H -F C
A04 -H -F -F -H C
A05 -H -CF 3 -H -H C
A06 -H -H -CF 3 -H C
A07 -H -Cl -H -F C
A08 -H -Cl -H -Cl C
A09 -H -Cl -H -H C
A10 -H -Br -H -H C
A11 -H -H -Br -H C
A12 -H -Br -H -Br C
A13 -H -Br -Br -H C
A14 -H -CH 3 -H -H C
A15 -H -H -CH 3 -H C
A16 -H -CH 3 -H -CH 3 C
A17 -H -CH 3 -CH 3 -H C
A18 -H -OCH 3 -H -H C
A19 -H -H -OCH 3 -H C
A20 -H -OCH 3 -H -OCH 3 C
A21 -H -OCH 3 -OCH 3 -H C
A22 -OCH 3 -F -H -H C
A23 -OCH 3 -H -F -H C
A24 -OCH 3 -F -H -F C
A25 -OCH 3 -F -F -H C
A26 -OCH 3 -CF 3 -H -H C
A27 -OCH 3 -H -CF 3 -H C
A28 -OCH 3 -Cl -H -F C
A29 -OCH 3 -Cl -H -Cl C
A30 -OCH 3 -Cl -Cl -H C
A31 -OCH 3 -Br -H -H C
A32 -OCH 3 -H -Br -H C
A33 -OCH 3 -Br -H -Br C
A34 -OCH 3 -Br -Br -H C
A35 -OCH 3 -CH 3 -H -H C
A36 -OCH 3 -H -CH 3 -H C
A37 -OCH 3 -CH 3 -H -CH 3 C
A38 -OCH 3 -CH 3 -CH 3 -H C
A39 -OCH 3 -OCH 3 -H -H C
A40 -OCH 3 -H -OCH 3 -H C
A41 -OCH 3 -OCH 3 -H -OCH 3 C
A42 -OCH 3 -OCH 3 -OCH 3 -H C
A43 -F -F -H -H C
A44 -F -H -F -H C
A45 -F -F -H -F C
A46 -F -F -F -H C
A47 -F -CF 3 -H -H C
A48 -F -H -CF 3 -H C
A49 -F -Cl -H -F C
A50 -F -Cl -H -Cl C
A51 -F -Cl -Cl -H C
A52 -F -Br -H -H C
A53 -F -H -Br -H C
A54 -F -Br -H -Br C
A55 -F -Br -Br -H C
A56 -F -CH 3 -H -H C
A57 -F -H -CH 3 -H C
A58 -F -CH 3 -H -CH 3 C
A59 -F -CH 3 -CH 3 -H C
A60 -F -OCH 3 -H -H C
A61 -F -H -OCH 3 -H C
A62 -F -OCH 3 -H -OCH 3 C
A63 -F -OCH 3 -OCH 3 -H C
A64 -CH 3 -F -H -H C
A65 -CH 3 -H -F -H C
A66 -CH 3 -F -H -F C
A67 -CH 3 -F -F -H C
A68 -CH 3 -CF 3 -H -H C
A69 -CH 3 -H -CF 3 -H C
A70 -CH 3 -Cl -H -F C
A71 -CH 3 -Cl -H -Cl C
A72 -CH 3 -Cl -Cl -H C
A73 -CH 3 -Br -H -H C
A74 -CH 3 -H -Br -H C
A75 -CH 3 -Br -H -Br C
A76 -CH 3 -Br -Br -H C
A77 -CH 3 -CH 3 -H -H C
A78 -CH 3 -H -CH 3 -H C
A79 -CH 3 -CH 3 -H -CH 3 C
A80 -CH 3 -CH 3 -CH 3 -H C
A81 -CH 3 -OCH 3 -H -H C
A82 -CH 3 -H -OCH 3 -H C
A83 -CH 3 -OCH 3 -H -OCH 3 C
A84 -CH 3 -OCH 3 -OCH 3 -H C
A85 -H -CH 3 -H -H N
A86 -H -H -CH 3 -H N
A87 -H -OCH 3 -H -H N
A88 -H -H -OCH 3 -H N
A89 -H -Cl -H -F N
A90 -H -Cl -F -H N
A91 -H -Cl -H -H N
A92 -H -H -H -Cl N
A93 -H -F -H -H N
A94 -H -H -F -H N
A95 -H -F -H -F N
A96 -H -F -F -H N
A97 -H -Br -H -H N
A98 -H -Br -H -F N
A99 -H -Br -H -Br N
本发明所述具有通式(II)的N-苄基苯甲酰胺类化合物，可以在适宜的溶剂以及碱性条件下采用Scheme II的反应制得，合成反应路线为：
Scheme II:
Figure PCTCN2020113018-appb-000005
Scheme II反应在适宜的溶剂中进行，所述适宜的溶剂可选自如四氢呋喃、乙腈、甲苯、二甲苯、N,N-二甲基甲酰胺、二氯甲烷、三氯甲烷、吡啶等；所述适宜的碱可选自如三乙胺、吡啶、碳酸钾、氢氧化钠等；反应温度可在冰浴至溶剂沸点温度之间，通常优选为0～125℃；反应时间为30分钟至20小时，通常优选为1～6小时。
表2列出通式(II)所示部分化合物。需要说明的是，通式(II)所示N-苄基苯甲酰胺类化合物并不仅限于表2所列出的化合物。
表2通式(II)所示部分N-苄基苯甲酰胺类化合物
编号 R 0 R 1 R 2 R 3 R 4 X
B01 -CH 3 -H -F -H -H C
B02 -CH 3 -H -H -F -H C
B03 -CH 3 -H -F -H -F C
B04 -CH 3 -H -F -F -H C
B05 -CH 3 -H -CF 3 -H -H C
B06 -CH 3 -H -H -CF 3 -H C
B07 -CH 3 -H -Cl -H -F C
B08 -CH 3 -H -Cl -H -Cl C
B09 -CH 3 -H -Cl -Cl -H C
B10 -CH 3 -H -Br -H -H C
B11 -CH 3 -H -H -Br -H C
B12 -CH 3 -H -Br -H -Br C
B13 -CH 3 -H -Br -Br -H C
B14 -CH 3 -H -CH 3 -H -H C
B15 -CH 3 -H -H -CH 3 -H C
B16 -CH 3 -H -CH 3 -H -CH 3 C
B17 -CH 3 -H -F -H -CH 3 C
B18 -CH 3 -H -OCH 3 -H -H C
B19 -CH 3 -H -H -OCH 3 -H C
B20 -CH 3 -H -OCH 3 -H -OCH 3 C
B21 -CH 3 -H -OCH 3 -OCH 3 -H C
B22 -CH 3 -H -F -H -H N
B23 -CH 3 -H -H -F -H N
B24 -CH 3 -H -F -H -F N
B25 -CH 3 -H -F -F -H N
B26 -CH 3 -H -H -H -H N
B27 -CH 3 -H -F -H -Cl N
B28 -CH 3 -H -F -Cl -H N
B29 -CH 3 -H -Cl -H -Cl N
B30 -CH 3 -H -Cl -F -H N
B31 -CH 3 -H -Cl -H -H N
B32 -CH 3 -H -H -Br -H N
B33 -CH 3 -H -Br -H -Br N
B34 -CH 3 -H -Br -Br -H N
B35 -CH 3 -H -CH 3 -H -H N
B36 -CH 3 -H -H -CH 3 -H N
B37 -CH 3 -H -OCH 3 -H -H N
B38 -CH 3 -H -H -OCH 3 -H N
B39 -OCH 3 -H -OCH 3 -H -H N
B40 -OCH 3 -H -H -OCH 3 -H N
B41 -OCH 3 -H -F -H -H N
B42 -OCH 3 -H -H -F -H N
B43 -OCH 3 -H -F -H -F N
B44 -OCH 3 -H -F -F -H N
B45 -OCH 3 -H -H -H -H N
B46 -OCH 3 -H -F -H -Cl N
B47 -OCH 3 -H -F -Cl -H N
B48 -OCH 3 -H -Cl -H -Cl N
B49 -OCH 3 -H -Cl -H -H N
B50 -OCH 3 -H -Br -H -H N
B51 -OCH 3 -H -H -Br -H N
B52 -OCH 3 -H -Br -H -Br N
B53 -OCH 3 -H -Br -Br -H N
B54 -OCH 3 -H -CH 3 -H -H N
B55 -OCH 3 -H -H -CH 3 -H N
B56 -OCH 3 -H -OCH 3 -H -H N
B57 -OCH 3 -H -H -OCH 3 -H N
B58 -OCH 3 -H -OCH 3 -H -H N
B59 -OCH 3 -H -H -OCH 3 -H N
本发明所述N-苄基苯甲酰胺类化合物处理后的杂草表现出典型的“白化效应”，即杂草经药剂处理后的症状为叶片白化、失绿、死亡。N-苄基苯甲酰胺类化合物引起的杂草症状与硝磺草酮(HPPD抑制剂)、吡氟酰草胺(PDS抑制剂)等作用于类胡萝卜素生物合成途径的除草剂类似，但与干扰叶绿素生物合成的丙炔氟草胺(PPO抑制剂)不同，因此可以推测本发明所述N-苄基苯甲酰胺类化合物作用于类胡萝卜素生物合成途径，属于色素合成抑制剂。通过试验获知，与现有商品化色素合成抑制剂类除草剂相比，所述N-苄基苯甲酰胺类化合物具有较高的除草活性，可用于防治对现有除草剂产生抗性的杂草，尤其适用于防治对ALS抑制剂、PSII抑制剂、ACCase抑制剂以及EPSP抑制剂类除草剂产生抗性的杂草。
在本发明中，所述杂草应具有最为广泛或较为广泛的含义，包括在不希望的地方生长的所有类型的植物种类。本发明将所述“不希望的地方”分为田间作物生长场所和非耕作作物场所。田间作物生长场所是指通常意义上的田间或大田。非耕作作物场所是指除田间作物生长场所之外的，不希望杂草生长的地方，包括葡萄园、苹果园、柑橘园、香蕉培育场、咖啡种植场、茶叶种植场、橡胶种植场、油棕种植场、椰子种植场等场所。
所述N-苄基苯甲酰胺类化合物，及其以所述N-苄基苯甲酰胺类化合物为组分的所述除草剂，可以用于防除生长于下述作物田间的下述杂草。
双子叶植物纲中的作物属：棉属，大豆属，甜菜属，菜豆属，豌豆属，茄属，亚麻属，番茄属，落花生属，芸苔属，莴苣属，香瓜属，南瓜属等。
单子叶植物纲中的作物属：稻属，玉蜀黍属，小麦属，大麦属，燕麦属，稷属，甘蔗属，凤梨属，天门冬属，葱属等。
双子叶植物纲的杂草属：白芥属，芥属，猪殃殃属，繁缕属，藜属，地肤属，荨麻属，千里光属，苋属，马齿苋属，苍耳属，番薯属，蓼属，豚草属，蓟属，苦苣菜属，茄属，婆婆纳属，曼陀罗属，堇菜属，罂粟属，矢车菊属，牛腾菊属，节节菜属，母草属，田菁属，车轴草属，苘麻属，野芝麻属，母菊属，蒿属，牵牛属等。
单子叶植物纲的杂草属：稗属，狗尾草属，稷属，马唐属，梯牧草属，早熟禾属，羊毛属，黑麦草属，雀麦属，燕麦属，莎草属，蜀黍属，冰草属，雨久花属，飘拂草属，慈姑属，藨草属，雀稗属，鸭嘴草属，剪股颖属，看买年属，狗牙根属，鸭跖草属，臂形草属，千金子属等。
进一步地，所述N-苄基苯甲酰胺类化合物，及其以所述N-苄基苯甲酰胺类化合物为组分的所述除草剂，可以用于防除下述代表性的农田杂草。所述农田杂草包括：稗草、眼子菜、鸭舌草、异型莎草、扁秆蔗草、千金子、野燕麦、马唐、蟋蟀草、狗尾草、看麦娘、播娘蒿、荠菜、独行菜、葎草、萹蓄、田旋花、卷茎蓼、香附子、藜、酸模叶蓼、反枝苋、马齿苋、凹头苋、菟丝子、苘麻、猪殃殃、鱧肠、苍耳、狗牙根、白茅、龙葵、牛繁缕、飞机草、盛红蓟、圆叶节节菜、艾蒿、蒲公英、一年蓬、泥胡菜、茵陈、苦荬菜、小蓟、大蓟、香薷、水苏、铁苋菜等。
再者，本发明提供一种组合物作为农用除草剂的用途，其所述组合物中的除草组分含有所述的N-苄基苯甲酰胺类化合物或其盐，所述组合物还包括农业上接受的载体。关于所述组合物的在农业上的使用方法，发明人通过试验获知，采用苗前土壤处理或苗后茎叶喷雾的方法施于土壤或杂草上，可以获得较好的除草效果。
为获得理想的除草效果，所述的N-苄基苯甲酰胺类化合物或其盐的用量因各种因素而改变，例如所用化合物、欲保护的作物、欲防治的杂草、杂草生长程度、气候条件、施药方法、采用的剂型等。发明人对所述组合物的用量进行了验证，得知以所述N-苄基苯甲酰胺类化合物或其盐计，每公顷用量为10克～5000克。在此用量下，所述组合物可以表现出较为理想的除草效果。所述的N-苄基苯甲酰胺类化合物或其盐同时具有很好的苗前和苗后除草活性，其症状表现为叶片白化、萎蔫、死亡。在温度和光照适合的条件下，在很低剂量下仍具有很好的防治效果。进一步优选地，通常较为适宜所述N-苄基苯 甲酰胺类化合物或其盐的用量为每公顷10克～1000克。在所述组合物中，所述的N-苄基苯甲酰胺类化合物或其盐的重量百分含量建议在0.1％～99.0％之间。发明人研究发现，所述N-苄基苯甲酰胺类化合物或其盐控制在适宜的使用浓度，可作为选择性除草剂。
此外，本发明提供一种混合制剂作为农用除草剂的用途。这种混合制剂的除草活性组分包括所述的N-苄基苯甲酰胺类化合物或其盐，还包括作为乙酰辅酶A羧化酶抑制剂、乙酰乳酸合成酶抑制剂、生长素除草剂、类胡萝卜素生物合成抑制剂、光合作用抑制剂、细胞壁生物合成抑制剂的除草组分，所述除草组分与所述N-苄基苯甲酰胺类化合物或其盐混合使用或表现出复配增效作用。
特别地，本发明所述的N-苄基苯甲酰胺类化合物或其盐与作用于光合系统II(PSII)的除草剂(如三嗪类、哒嗪酮类、苯并噻二嗪酮类、苯基哒嗪类、取代脲类除草剂)作为除草组合物使用时增效作用尤为显著，对大龄杂草也具有很好的防治效果，而且作用时间显著加快，施药当天杂草即出现明显白化症状。
更为特别地，本发明所述的N-苄基苯甲酰胺类化合物或其盐与PSII除草剂在组合物中的重量百分比为1﹕20～20﹕1，N-苄基苯甲酰胺类化合物或其盐与PSII除草剂在制剂中的重量百分含量建议在0.1％～99.0％之间，适宜使用剂量为每公顷10克～1000克有效成分。
更为特别地，本发明所述的N-苄基苯甲酰胺类化合物或其盐与莠去津在组合物中的重量比为1﹕10～10﹕1，N-苄基苯甲酰胺类化合物或其盐与PSII除草剂在制剂中的重量百分含量建议在0.1％～99.0％之间，适宜使用剂量为每公顷10克～1000克有效成分。该组合物可以显著降低莠去津的用量，减少莠去津残留对后茬作物的药害，显著提高对大龄禾本科杂草的防治效果，而且作用时间显著加快。
本领域技术人员应当知晓，本发明所提供的组合物作为农用除草剂的用途，以及混合制剂作为农用除草剂的用途，所述组合物或混合制剂通常以制剂的形式在农业上使用，其还包括农业上接受的载体。所述的N-苄基苯甲酰胺类化合物或其盐，或与其复配的其它除草活性组分，作为活性组分溶解或分散于载体中或配制成制剂以便作为除草剂使用时更易于分散。这些化学制剂可被制成可湿性粉剂、水分散粒剂、水乳剂、可分散油悬浮剂、乳油或悬浮剂中的任何一种剂型，但并不限定于此。对制剂加工领域的技术人员来说，可以选用一种或多种适宜的载体或助剂。
以水分散粒剂为例，本领域技术人员很熟悉使用相应的载体或助剂完成本发明。分散剂如聚羧酸盐(比如TERSPERSE 2700、T36、GY-D06等)、木质素磺酸盐、烷基萘磺酸盐中一种或多种；润湿剂如烷基硫酸盐、烷基磺酸盐、萘磺酸盐中一种或多种；崩解剂如硫酸铵、尿素、蔗糖、葡萄糖中一种或多种；粘结剂如硅藻土、玉米淀粉、聚乙烯醇(PVA)、羧甲基(乙基)纤维素类中的一种或多种；安全剂MON13900(孟山都公司产品)；填料如硅藻土、高岭土、白炭黑、轻钙、滑石粉、凹凸棒土、陶土一种或多种。
以可湿性粉剂为例，本领域技术人员很熟悉使用相应的载体或助剂完成本发明。可使用的分散剂如聚羧酸盐类(TERSPERSE 2700、T36、GY-D06等)、木质素磺酸盐类(Ufoxane 3A、Borresperse NA、Borresperse CA-SA等)、萘和烷基萘甲醛缩合物磺酸盐类(NNO、MF、Morwet D-425、Tamol NN、TERSPERSE2020等)、拉开粉BX(二丁基萘磺酸钠)、EO-PO嵌段聚醚类、烷基酚聚氧乙烯基醚磷酸酯、烷基酚聚氧乙烯基醚甲醛缩合物硫酸盐(SOPA)中一种或多种；润湿剂如硫酸盐类(K-12)、磺酸盐类(ABS-Na、BX、Terwet 1004等)、复合润湿剂(Morwet EFW)中一种或多种；填料如硅藻土、高岭土、轻钙、滑石粉、白炭黑、凹凸棒土、陶土、硫酸铵、尿素、蔗糖、葡萄糖、玉米淀粉、硫酸钠、多聚磷酸钠等一种或多种。
以可分散油悬浮剂为例，本领域技术人员很熟悉使用相应的载体或助剂完成本发明。可使用分散剂如聚羧酸盐、木质素磺酸盐、烷基萘磺酸盐(扩散剂NNO)、TERSPERSE2020(烷基萘磺酸盐类)中一种或多种；乳化剂如农乳700#(通用名：烷基酚甲醛树脂聚氧乙烯醚)、农乳2201、斯盘-60#(通用名：失水山梨醇硬脂酸酯)、吐温-60#(通用名：聚氧乙烯失水山梨醇硬脂酸酯)、农乳1601#(通用名：三苯乙基苯酚聚氧丙烯聚氧乙烯嵌段聚合物)、TERSPERSE 4894中的一种或多种；润湿剂如烷基酚聚氧乙烯基醚甲醛缩合物硫酸盐、烷基酚聚氧乙烯基醚磷酸酯、苯乙基酚聚氧乙烯基醚磷酸酯、烷基硫酸盐、烷基磺酸盐、萘磺酸盐、TERSPERSE 2500中一种或多种；增稠剂如黄原胶、聚乙烯醇、膨润土、硅酸镁铝中一种或多种；防腐剂如甲醛、苯甲酸、苯甲酸钠中一种或多种；安全剂MON13900；消泡剂如有机硅类消泡剂；防冻剂如乙二醇、丙二醇、甘油、尿素、无机盐类如氯化钠中一种或多种；水为去离子水。
以悬浮剂为例，选用的分散剂如聚羧酸盐、木质素磺酸盐、烷基萘磺酸盐(扩散剂 NNO)、TERSPERSE 2020(烷基萘磺酸盐类)中一种或多种；乳化剂如BY(蓖麻油聚氧乙烯醚)系列乳化剂(BY-110、BY-125、BY-140)、农乳700#(通用名：烷基酚甲醛树脂聚氧乙烯醚)、农乳2201、斯盘-60#(通用名：山梨醇酐单硬脂酸酯)、吐温-60#(通用名：失水山梨醇单硬脂酸酯聚氧乙烯醚)、农乳1601#(通用名：苯乙基苯酚聚氧乙烯聚氧丙烯醚)、TERSPERSE 4894中的一种或多种；润湿剂如烷基酚聚氧乙烯基醚甲醛缩合物硫酸盐、烷基酚聚氧乙烯醚磷酸酯、苯乙基酚聚氧乙烯基醚磷酸酯、烷基硫酸盐、烷基磺酸盐、萘磺酸盐、TERSPERSE 2500(美国亨斯迈公司出品)中一种或多种；增稠剂如白炭黑、聚乙烯醇、膨润土、硅酸镁铝中一种或多种；安全剂MON13900；防冻剂如乙二醇、丙二醇、甘油、尿素、无机盐类如氯化钠中一种或多种；分散介质如大豆油、菜籽油、棉籽油、玉米油、蓖麻油、棕榈油、环氧大豆油、油酸甲酯及其甲酯化油类、柴油、机油、矿物油，及酯类溶剂如邻苯二甲酸二甲酯、邻苯二甲酸二丁酯、乙酸乙酯、苯甲酸甲酯中一种或多种。
本发明的有益效果或优点：
本发明给出了所述N-苄基苯甲酰胺类化合物或其盐在除草方面的新用途，拓展了所述N-苄基苯甲酰胺类化合物在农业领域的应用。所述N-苄基苯甲酰胺类化合物或其盐作为除草剂用于防除田间作物生长场所、非耕作作物场所的杂草，除草活性高，并可用于防治对现有除草剂产生抗性的杂草，尤其适用于防治对ALS抑制剂、PSII抑制剂、ACCase抑制剂以及EPSP抑制剂类除草剂产生抗性的杂草。
本发明还进一步明确了含有所述N-苄基苯甲酰胺类化合物或其盐与PSII抑制剂类除草剂组合物，对田间作物生长场所、非耕作作物场所的杂草仍表现出较好的防除效果。这充分说明所述N-苄基苯甲酰胺类化合物或其盐具有很大的开发潜力，为开发新的绿色化学农药提供了一种新的思路。
本发明含有所述N-苄基苯甲酰胺类化合物或其盐组合物以及混合制剂可以配制成符合农业生产需求的悬浮剂、水分散粒剂、可湿性粉剂或可分散油悬浮剂等多种剂型，且对作物安全性好，符合农药制剂的安全性要求。本发明丰富了现有除草剂品种，可以带来可观的市场效益。
具体实施方式
为了便于理解本发明的目的、技术方案及其效果，现将结合实施例对本发明做进一 步详细阐述。
(一)N-苄基苯甲酰胺类化合物的合成
实施例1 N-(3-氟苄胺)-2-甲氧基苯甲酰胺(化合物A01)的制备
Figure PCTCN2020113018-appb-000006
将125克(1.0mol)3-氟苄胺和150克三乙胺(1.5mol)溶于1.5L甲苯中，冰浴下搅拌30分钟，再滴加溶于500毫升甲苯中的170克(1.0mol)2-甲氧基苯甲酰氯，加完后室温下继续搅拌1.5小时，加入饱和碳酸氢钠溶液200毫升洗涤，再依次用去离子水和饱和食盐水各200毫升洗涤，无水硫酸钠干燥后减压脱去溶剂，残余物经硅胶柱层析得产物230克，收率88.8％。 1H NMR(500MHz,CDCl 3)δ8.24(d,J＝8.0Hz,2H),7.45(t,J＝8.0Hz,1H),7.27-7.31(m,1H),7.03-7.14(m,3H),6.90-6.99(m,2H),4.68(d,J＝5.0Hz,2H),3.93(s,3H).
实施例2 N-(4-氟苄基)-2-羟基苯胺(化合物A02)的制备
Figure PCTCN2020113018-appb-000007
将125克(1.0mol)4-氟苄胺和150克三乙胺(1.5mol)溶于1.5L甲苯中，冰浴下搅拌30分钟，再滴加溶于500毫升甲苯中的170克(1.0mol)2-甲氧基苯甲酰氯，加完后室温下继续搅拌1.5小时，加入饱和碳酸氢钠溶液200毫升洗涤，再依次用去离子水和饱和食盐水各200毫升洗涤，无水硫酸钠干燥后减压脱去溶剂，残余物经硅胶柱层析得产物220克，收率84.9％。 1H NMR(500MHz,CDCl 3)δ8.23-8.25(m,1H),8.18(br,1H),7.44-7.47(m,1H),7.32-7.35(m,2H),6.97-7.11(m,4H),4.59(d,J＝5.5Hz,2H),3.92(s,3H).
实施例3 N-(3,5二氟苄基)-2-甲氧基苯甲酰胺(化合物A03)的制备
Figure PCTCN2020113018-appb-000008
将143克(1.0mol)3,5-二氟苄胺和150克三乙胺(1.5mol)溶于1.5L甲苯中，冰浴下搅拌30分钟，再滴加溶于500毫升甲苯中的170克(1.0mol)2-甲氧基苯甲酰氯，加完后室温下继续搅拌1.5小时，加入饱和碳酸氢钠溶液200毫升洗涤，再依次用去离 子水和饱和食盐水各200毫升洗涤，无水硫酸钠干燥后减压脱去溶剂，残余物经硅胶柱层析得产物245克，收率88.4％。 1H NMR(500MHz,CDCl 3)δ8.18–8.34(m,2H),7.46–7.52(m,1H),7.08–7.14(m,1H),7.01(d,J＝8.3Hz,1H),6.88(d,J＝6.1Hz,2H),6.67–6.75(m,1H),4.67(d,J＝6.0Hz,2H),3.97(s,3H).
实施例4 N-(3-氯-5-氟苄基)-2-甲氧基苯甲酰胺(化合物A07)的制备
Figure PCTCN2020113018-appb-000009
将159克(1.0mol)3-氯-5-氟苄胺和150克三乙胺(1.5mol)溶于1.5L甲苯中，冰浴下搅拌30分钟，再滴加溶于500毫升甲苯中的170克(1.0mol)2-甲氧基苯甲酰氯，加完后室温下继续搅拌1.5小时，加入饱和碳酸氢钠溶液200毫升洗涤，再依次用去离子水和饱和食盐水各200毫升洗涤，无水硫酸钠干燥后减压脱去溶剂，残余物经硅胶柱层析得产物260克，收率88.7％。 1H NMR(500MHz,CDCl 3)δ8.19–8.33(m,2H),7.48(t,J＝6.9Hz,1H),7.07–7.16(m,1H),7.00(d,J＝8.3Hz,1H),6.88(d,J＝6.1Hz,2H),6.69(t,J＝8.9Hz,1H),4.66(d,J＝6.0Hz,2H),3.97(s,3H).
实施例5 N-(3-氯苄基)-2-甲氧基苯甲酰胺(化合物A09)的制备
Figure PCTCN2020113018-appb-000010
将141克(1.0mol)3-氯苄胺和150克三乙胺(1.5mol)溶于1.5L甲苯中，冰浴下搅拌30分钟，再滴加溶于500毫升甲苯中的170克(1.0mol)2-甲氧基苯甲酰氯，加完后室温下继续搅拌1.5小时，加入饱和碳酸氢钠溶液200毫升洗涤，再依次用去离子水和饱和食盐水各200毫升洗涤，无水硫酸钠干燥后减压脱去溶剂，残余物经硅胶柱层析得产物260克，收率94.5％。 1H NMR(500MHz,CDCl 3)δ8.00-8.28(m,2H),7.45-7.51(m,1H),7.35(t,J＝1.7Hz,1H),7.22-7.31(m,3H),7.05-7.14(m,1H),6.99(d,J＝8.3Hz,1H),4.67(d,J＝5.8Hz,2H),3.95(s,3H).
实施例6 2-甲氧基-N-(3-甲基苄基)苯甲酰胺(化合物A14)的制备
Figure PCTCN2020113018-appb-000011
将121克(1.0mol)3-甲基苄胺和150克三乙胺(1.5mol)溶于1.5L甲苯中，冰浴下搅拌30分钟，再滴加溶于500毫升甲苯中的170克(1.0mol)2-甲氧基苯甲酰氯，加完后室温下继续搅拌1.5小时，加入饱和碳酸氢钠溶液200毫升洗涤，再依次用去离子水和饱和食盐水各200毫升洗涤，无水硫酸钠干燥后减压脱去溶剂，残余物经硅胶柱层析得产物210克，收率82.4％。 1H NMR(500MHz,CDCl 3)δ8.26(dd,J＝7.8,1.9Hz,1H),8.18(br,1H),7.44-7.48(m,1H),7.20-7.28(m,1H),7.14-7.20(m,2H),7.06-7.13(m,2H),6.97(d,J＝8.3Hz,1H),4.66(d,J＝5.7Hz,2H),3.92(s,3H),2.35(s,3H).
实施例7 N-(3-氟苄基)-2,5-二甲氧基苯甲酰胺(化合物A22)的制备
Figure PCTCN2020113018-appb-000012
将125克(1.0mol)3-氟苄胺和150克三乙胺(1.5mol)溶于1.5L甲苯中，冰浴下搅拌30分钟，再滴加溶于500毫升甲苯中的200克(1.0mol)2,5-二甲氧基苯甲酰氯，加完后室温下继续搅拌1.5小时，加入饱和碳酸氢钠溶液200毫升洗涤，再依次用去离子水和饱和食盐水各200毫升洗涤，无水硫酸钠干燥后减压脱去溶剂，残余物经硅胶柱层析得产物260克，收率90.0％。 1H NMR(500MHz,CDCl 3)δ8.37(s,1H),7.79(d,J＝3.3Hz,1H),7.32-7.27(m,1H),7.12(d,J＝7.7Hz,1H),7.09-7.03(m,1H),7.00(dd,J＝8.9,3.3Hz,1H),6.97-6.87(m,2H),4.66(d,J＝5.8Hz,2H),3.88(d,J＝2.7Hz,3H),3.80(d,J＝2.9Hz,3H).
实施例8 3-甲基-N-(3-甲基苄基)苯甲酰胺(化合物B14)的制备
Figure PCTCN2020113018-appb-000013
将121克(1.0mol)3-甲基苄胺和150克三乙胺(1.5mol)溶于1.5L甲苯中，冰浴下搅拌30分钟，再滴加溶于500毫升甲苯中的154克(1.0mol)3-甲基苯甲酰氯，加完后室温下继续搅拌1.5小时，加入饱和碳酸氢钠溶液200毫升洗涤，再依次用去离子水和饱和食盐水各200毫升洗涤，无水硫酸钠干燥后减压脱去溶剂，残余物经硅胶柱层析得产物212克，收率88.7％。 1H NMR(500MHz,CDCl 3)δ7.62(s,1H),7.59-7.54(m,1H),7.31(d,J＝4.7Hz,2H),7.24(d,J＝7.6Hz,1H),7.19-7.14(m,2H),7.12(d,J＝7.6Hz,1H),6.36(s,1H),4.61(d,J＝5.6Hz,2H),2.39(s,3H),2.35(s,3H)
(二)含N-苄基苯甲酰胺类化合物的除草剂或除草组合物的制备
实施例9 10％N-苄基苯甲酰胺类化合物(化合物B14)可湿性粉剂
所述可湿性粉剂的组分及占比：
Figure PCTCN2020113018-appb-000014
各组分加入量均为重量百分含量，活性化合物折百后计量加入。将化合物B14及其它组分充分混合，经气流粉碎机粉碎后，即得到10％N-苄基苯甲酰胺类化合物(化合物B14)可湿性粉剂产品。
实施例10 10％N-苄基苯甲酰胺类化合物(化合物A09)水乳剂
所述水乳剂组分及占比：
Figure PCTCN2020113018-appb-000015
各组分加入量均为重量百分含量，活性化合物折百后计量加入。将化合物A09及其它组分经搅拌釜充分混合，即得到10％N-苄基苯甲酰胺类化合物(化合物A09)水乳剂产品。
实施例11 10％N-苄基苯甲酰胺类化合物(化合物A85)可分散油悬浮剂
所述可分散油悬浮剂组分及占比：
Figure PCTCN2020113018-appb-000016
Figure PCTCN2020113018-appb-000017
各组分加入量均为重量百分含量，活性化合物折百后计量加入。将化合物A85及其它组分经搅拌釜充分混合，即得到10％N-苄基苯甲酰胺类化合物(化合物A85)可分散油悬浮剂产品。
实施例12 10％N-苄基苯甲酰胺类化合物(化合物B07)乳油
所述乳油组分及占比：
Figure PCTCN2020113018-appb-000018
各组分加入量均为重量百分含量，活性化合物折百后计量加入。将化合物B07及其它组分经搅拌釜充分混合，即得到10％N-苄基苯甲酰胺类化合物(化合物B07)乳油产品。
实施例9-12给出了几种含N-苄基苯甲酰胺类化合物的除草剂，仅作为含N-苄基苯甲酰胺类化合物的除草剂或除草组合物剂型制备的展示说明。
(三)含N-苄基苯甲酰胺类化合物的除草剂或除草组合物的药效试验
实施例13 化合物A02与莠去津增效试验
将狗尾草种子播种于直径9cm的塑料盆中，每盆播种20粒种子，覆土0.5cm，置于自然光照、自然湿度，25～35℃的温室内培养。待狗尾草3～4叶期时，采用自动控制喷洒系统施药，共设29个处理，分别为A02单剂50、100、200、400g(a.i.)/ha四个单剂处理，莠去津单剂400、800、1200、1600g(a.i.)/ha四个单剂处理，混剂用量为900g(a.i.)/ha，由2个单剂以不同比例混用的20个处理，另设1个空白对照(喷清水)，每个处理重复4次。施药后21天，剪取各处理所有杂草地上部分，称量鲜重，计算鲜重防治效果。采用Gowing法评价2种药剂混用的联合作用效果，2种单剂不同剂量混用时的理论和实测鲜重防治效果分别为E和E 0，E＝X+Y-XY/100，X，Y分别为2种单剂各剂量的实测鲜重防治效果，-5.0％≦E 0-E≦5.0％时为相加作用，E 0-E＞5.0％时为增 效作用，E 0-E＜-5.0％时为拮抗作用。
表3 A02与莠去津不同比例混用防治狗尾草增效作用
Figure PCTCN2020113018-appb-000019
从表3结果可以看出，A02与莠去津混合使用对狗尾草的防治效果表现出明显的增效作用，其中A02与莠去津比例为4+17时，E 0-E＝17.6％，A02与莠去津比例为3+18时，E 0-E＝16.2％，增效作用尤为明显。
实施例14 室内苗前土壤处理除草活性试验
参照NY/T 1155.3-2006的方法对部分通式Ⅰ或II的N-苄基苯甲酰胺类化合物进行室内苗前土壤处理除草活性试验。将有机质含量≤2％的中性砂壤土装至盆钵的4/5处，采用盆钵底部渗灌方式，使土壤完全润湿。将供试杂草种子均匀播撒于土壤表面，然后根据种子大小覆土0.5cm～2.0cm。取实施例中的代表性化合物制成10％乳油，播种24h后将供试药剂用水稀释后进行土壤喷雾处理，喷施剂量为150g(a.i.)/ha。处理后21d采用目测法调查结果。根据测试杂草受害症状和严重程度，以1～9级评价药剂的除草活性。
1级：无草；
2级：相当于空白对照区杂草的0～2.5％；
3级：相当于空白对照区杂草的2.6～5％；
4级：相当于空白对照区杂草的5.1～10％；
5级：相当于空白对照区杂草的10.1～15％；
6级：相当于空白对照区杂草的15.1～25％；
7级：相当于空白对照区杂草的25.1～35％；
8级：相当于空白对照区杂草的35.1～67.5％；
9级：相当于空白对照区杂草的67.6～100％。
供试化合物对杂草的苗前除草活性如表4所示。
表4部分N-苄基苯甲酰胺类化合物的苗前土壤处理除草效果(150g a.i./ha)
Figure PCTCN2020113018-appb-000020
Figure PCTCN2020113018-appb-000021
从表4数据可以看出，在150g(a.i.)/ha用量时，供试化合物对单子叶杂草和双子叶杂草均具有很好的防治效果，杂草出苗后表现幼苗呈白化症状，随后逐渐干枯、死亡。光照和温度条件越好，效果越优。
实施例15 室内苗后茎叶喷雾除草活性试验
参照NY/T 1155.4-2006的方法对部分通式I或II的N-苄基苯甲酰胺类化合物进行苗后除草活性试验。将有机质含量≤3％的中性砂壤土装至盆钵的4/5处，采用盆钵底部渗灌方式，使土壤完全润湿。将供试杂草种子均匀播撒于土壤表面，然后根据种子大小覆土0.5cm～2.0cm，播种后移入温室常规培养。取实施例中的代表性化合物制成10％乳油，于单子叶杂草2叶1心期，阔叶草3～5片真叶时喷雾，喷施药量为150g(a.i.)/ha。处理后21d采用目测法调查结果。根据测试杂草受害症状和严重程度，以1～9级评价药 剂的除草活性。
1级：全部死亡；
2级：相当于空白对照区杂草的0～2.5％；
3级：相当于空白对照区杂草的2.6～5％；
4级：相当于空白对照区杂草的5.1～10％；
5级：相当于空白对照区杂草的10.1～15％；
6级：相当于空白对照区杂草的15.1～25％；
7级：相当于空白对照区杂草的25.1～35％；
8级：相当于空白对照区杂草的35.1～67.5％；
9级：相当于空白对照区杂草的67.6～100％。
供试化合物对杂草的苗后除草活性如表5所示。
表5部分N-苄基苯甲酰胺类化合物的苗后除草效果(150g a.i./ha)
Figure PCTCN2020113018-appb-000022
Figure PCTCN2020113018-appb-000023
从表5数据可以看出，在150g(a.i.)/ha用量时，供试化合物对单子叶杂草和双子叶杂草均具有很好的防治效果，药后1～3d杂草表现出色素合成抑制剂的特征性白化症状，逐渐干枯、死亡。光照和温度条件越好，效果越优。
实施例16 部分通式I或II化合物水稻田苗后除草活性试验
参照GB/T 17980.40-2000的方法对部分通式I或II的N-苄基苯甲酰胺类化合物进行水稻田苗后除草活性试验。试验水稻田土壤质地为中壤田，有机质含量2.0％，耕作层pH值6.5，播种后约1个月水稻秧苗4叶～5叶期喷雾。取实施例中的代表性化合物制成10％乳油，兑水喷雾，喷施药量为150g(a.i.)/ha，每个处理设4个重复，小区面积50m 2。以25g/L五氟磺草胺悬浮剂为对照药剂，施药剂量为250g(a.i.)/ha。处理后15d和30d采用估计值调查法调查结果。每个药剂处理区同邻近的空白对照区进行比较，估计相对杂草种群量，以杂草群落总体的覆盖度为指标，其结果采用下列分级标准法进行调查。
1级：无草；
2级：相当于空白对照区杂草的0～2.5％；
3级：相当于空白对照区杂草的2.6～5％；
4级：相当于空白对照区杂草的5.1～10％；
5级：相当于空白对照区杂草的10.1～15％；
6级：相当于空白对照区杂草的15.1～25％；
7级：相当于空白对照区杂草的25.1～35％；
8级：相当于空白对照区杂草的35.1～67.5％；
9级：相当于空白对照区杂草的67.6～100％。
供试化合物对杂草的苗后除草活性如表6所示。
表6部分N-苄基苯甲酰胺类化合物防治水稻田杂草苗后除草效果(150g a.i./ha)
Figure PCTCN2020113018-appb-000024
Figure PCTCN2020113018-appb-000025
从表6数据可以看出，表中供试化合物对水稻田杂草具有很好的防治效果。药后15d，化合物A02，A14，A23，A24，A89，B14，B22，B27，B30对禾本科杂草、阔叶草和莎草科杂草的防效均可达到1级。
实施例17 部分通式I或II化合物防治玉米田杂草田间试验
参照GB/T 17980.42-2000的方法对部分通式I或II的N-苄基苯甲酰胺类化合物进行防治玉米田杂草田间药效试验。试验玉米田土壤质地为砂壤土，有机质含量2.0％，耕作层pH值6.5，播种后于玉米2叶～5叶期喷雾。取实施例中的代表性化合物制成10％乳油，兑水喷雾，喷施药量为150g(a.i.)/ha，每个处理设4个重复，小区面积20m 2。以25％硝磺草酮可分散油悬浮剂为对照药剂，施药剂量为150g(a.i.)/ha。处理后21d采用目测法调查结果。根据测试杂草受害症状和严重程度，以1～9级评价药剂的除草活性。
1级：无草；
2级：相当于空白对照区杂草的0～2.5％；
3级：相当于空白对照区杂草的2.6～5％；
4级：相当于空白对照区杂草的5.1～10％；
5级：相当于空白对照区杂草的10.1～15％；
6级：相当于空白对照区杂草的15.1～25％；
7级：相当于空白对照区杂草的25.1～35％；
8级：相当于空白对照区杂草的35.1～67.5％；
9级：相当于空白对照区杂草的67.6～100％。
各化合物除草活性如表7所示。
表7部分N-苄基苯甲酰胺类化合物防治玉米田杂草苗后除草效果(150g a.i./ha)
Figure PCTCN2020113018-appb-000026
Figure PCTCN2020113018-appb-000027
从表7数据可以看出，表中供试化合物对玉米田杂草具有很好的防治效果。药后21d，化合物A02，B08，B14，B27，B30对狗尾草、稗草、牛筋草、马唐、藜、马齿苋、反枝苋、龙葵、田旋花、铁苋菜和莎草的防效均可达到1级。
实施例18 部分通式I或II化合物与莠去津桶混防治玉米田杂草田间试验
参照GB/T 17980.42-2000的方法对部分通式I或II的N-苄基苯甲酰胺类化合物与莠去津田间桶混进行防治玉米田杂草田间药效试验。试验玉米田土壤质地为砂壤土，有机质含量2.0％，耕作层pH值6.5，播种后于玉米2叶～5叶期喷雾。取实施例中的代表性化合物制成10％乳油，与40％莠去津悬浮剂桶混，二次吸收后兑水喷雾，每个处理设4个重复，小区面积20m 2。以40％莠去津悬浮剂为对照药剂，施药剂量为600g(a.i.)/ha。处理后21d采用目测法调查结果。根据测试杂草受害症状和严重程度，以1～9级评价药剂的除草活性。各化合物除草活性如表8所示。
表8部分通式I或II化合物与和莠去津桶混苗后防除玉米田杂草防治效果
Figure PCTCN2020113018-appb-000028
Figure PCTCN2020113018-appb-000029
从表8数据可以看出，通式I或II化合物与莠去津以一定比例进行桶混，对玉米田杂草狗尾草、稗草、牛筋草、马唐、藜、马齿苋、反枝苋、龙葵、苘麻和莎草的的防治效果达到1级。40％莠去津悬浮剂在用量为600g(a.i.)/ha时，对阔叶草可达到1级防效，但是对禾本科杂草和莎草的防治效果较差。通式I或II化合物与莠去津以一定比例进行桶混后显著提高了对禾本科杂草和莎草的防效，尤其是对莠去津基本无效的大龄禾本科杂草和莎草防治效果也可以达到1级。
实施例19 部分通式I或II化合物与和莠去津混剂防治玉米田杂草田间试验
参照NY/T 1155.4-2006的方法对部分通式I或II化合物与和莠去津混剂进行苗后防除玉米田杂草田间药效试验。采用苗后茎叶喷雾处理，于玉米4叶期施药，亩喷药液量30kg。处理后21d采用目测法调查结果。根据测试杂草受害症状和严重程度，以1～9级评价药剂的除草活性。以40％莠去津悬浮剂为对照药剂，施药剂量为600g(a.i.)/ha。除草活性如表9所示。
表9部分通式I或II化合物与和莠去津混剂苗后防除玉米田杂草防治效果
Figure PCTCN2020113018-appb-000030
Figure PCTCN2020113018-appb-000031
Figure PCTCN2020113018-appb-000032
从表9数据可以看出，通式I或II化合物与莠去津加工成的混剂，在用量450g(a.i.)/ha时对玉米田杂草狗尾草、稗草、牛筋草、马唐、藜、马齿苋、反枝苋、龙葵、苘麻和莎草的防治效果达到1级。
本发明的N-苄基苯甲酰胺类化合物作为除草剂的用途已经通过具体的实例进行了描述，本领域技术人员可借鉴本发明内容，适当改变原料、工艺条件等环节来实现相应的其它目的，其相关改变都没有脱离本发明的内容，所有类似的替换和改动对于本领域技术人员来说是显而易见的，都被视为包括在本发明的范围之内。

Claims (10)

  1. N-苄基苯甲酰胺类化合物作为除草剂的用途，其特征在于，所述除草剂的组分包含具有如下通式(Ⅰ)或(Ⅱ)的N-苄基苯甲酰胺类化合物或其盐，
    Figure PCTCN2020113018-appb-100001
    式(I)，(II)中，
    R 0选自甲基或甲氧基；
    R 1选自氢、C 1～C 4烷基、C 1～C 4烷氧基、卤代C 1～C 4烷基、卤代C 1～C 4烷氧基、卤素或氰基；
    R 2、R 3和R 4各自独立地选自氢、C 1～C 4烷基、C 1～C 4烷氧基、卤素、氰基、卤代C 1～C 4烷基、卤代C 1～C 4烷氧基或甲磺酰基；
    X选自C或N。
  2. 根据权利要求1所述的用途，其特征在于，式(I)，(II)中：
    R 0选自甲基或甲氧基；
    R 1选自氢、甲基、甲氧基、氟、氯、溴或氰基；
    R 2、R 3和R 4各自独立地选自氢、甲基、甲氧基、氟、氯、溴、氰基或甲磺酰基；
    X选自C或N。
  3. 根据权利要求1或2所述的用途，其特征在于，所述具有通式(I)的N-苄基苯甲酰胺类化合物，在适宜的溶剂以及碱性条件下采用Scheme I的反应制得，合成反应路线如下：
    Scheme I:
    Figure PCTCN2020113018-appb-100002
    Scheme I反应在适宜的溶剂中进行，所述适宜的溶剂选自四氢呋喃、乙腈、甲苯、二甲苯、N,N-二甲基甲酰胺、二氯甲烷、三氯甲烷或吡啶；所述适宜的碱选自三乙胺、 吡啶、碳酸钾或氢氧化钠；反应温度在冰浴至溶剂沸点温度之间；反应时间为30分钟至20小时。
  4. 根据权利要求1或2所述的用途，其特征在于，所述具有通式(II)的N-苄基苯甲酰胺类化合物，在适宜的溶剂以及碱性条件下采用Scheme II的反应制得，合成反应路线为：
    Scheme II:
    Figure PCTCN2020113018-appb-100003
    Scheme II反应在适宜的溶剂中进行，所述适宜的溶剂选自四氢呋喃、乙腈、甲苯、二甲苯、N,N-二甲基甲酰胺、二氯甲烷、三氯甲烷或吡啶；所述适宜的碱选自如三乙胺、吡啶、碳酸钾或氢氧化钠；反应温度在冰浴至溶剂沸点温度之间；反应时间为30分钟至20小时。
  5. 根据权利要求1或2所述的用途，其特征在于，所述N-苄基苯甲酰胺类化合物作为色素合成抑制剂用于防除田间作物生长场所、非耕作作物场所的杂草。
  6. 根据权利要求5所述的用途，其特征在于，所述杂草包括：白芥属，芥属，猪殃殃属，繁缕属，藜属，地肤属，荨麻属，千里光属，苋属，马齿苋属，苍耳属，番薯属，蓼属，豚草属，蓟属，苦苣菜属，茄属，婆婆纳属，曼陀罗属，堇菜属，罂粟属，矢车菊属，牛腾菊属，节节菜属，母草属，田菁属，车轴草属，苘麻属，野芝麻属，母菊属，蒿属，牵牛属，稗属，狗尾草属，稷属，马唐属，梯牧草属，早熟禾属，羊毛属，黑麦草属，雀麦属，燕麦属，莎草属，蜀黍属，冰草属，雨久花属，飘拂草属，慈姑属，藨草属，雀稗属，鸭嘴草属，剪股颖属，看麦娘属，狗牙根属，鸭跖草属，臂形草属或千金子属。
  7. 根据权利要求5所述的用途，其特征在于，所述杂草为稗草、眼子菜、鸭舌草、异型莎草、扁秆蔗草、千金子、野燕麦、马唐、蟋蟀草、狗尾草、看麦娘、播娘蒿、荠菜、独行菜、葎草、萹蓄、田旋花、卷茎蓼、香附子、藜、酸模叶蓼、反枝苋、马齿苋、凹头苋、菟丝子、苘麻、猪殃殃、鱧肠、苍耳、狗牙根、白茅、龙葵、牛繁 缕、飞机草、盛红蓟、圆叶节节菜、艾蒿、蒲公英、一年蓬、泥胡菜、茵陈、苦荬菜、小蓟、大蓟、香薷、水苏或铁苋菜。
  8. 一种组合物作为农用除草剂的用途，其特征在于，所述组合物中的除草组分为根据权利要求1或2的N-苄基苯甲酰胺类化合物或其盐，所述组合物还包括农业上接受的载体。
  9. 一种混合制剂作为农用除草剂的用途，其特征在于，所述混合制剂的除草组分为根据权利要求1或2的N-苄基苯甲酰胺类化合物或其盐，该混合制剂还包括作为乙酰辅酶A羧化酶抑制剂、乙酰乳酸合成酶抑制剂、生长素除草剂、类胡萝卜素生物合成抑制剂、光合作用抑制剂、细胞壁生物合成抑制剂的除草组分。
  10. 根据权利要求9所述的用途，其特征在于，在所述混合制剂中，除草组分为N-苄基苯甲酰胺类化合物或其盐和莠去津，二者的重量比为1﹕10～10﹕1。
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4270946A (en) * 1979-10-01 1981-06-02 Stauffer Chemical Company N-Aryl,2-phenoxy nicotinamide compounds and the herbicidal use thereof
US4556414A (en) * 1981-06-25 1985-12-03 Rhone-Poulenc Agrochimie Herbicidal dihydropyridine amides
CN1054974A (zh) * 1990-03-16 1991-10-02 国际壳牌研究有限公司 除草用的甲酰胺衍生物
CN1110502A (zh) * 1990-07-17 1995-10-25 国际壳牌研究有限公司 除草剂组合物及其应用
WO2005070889A1 (en) * 2004-01-23 2005-08-04 E.I. Dupont De Nemours And Company Herbicidal amides
CN111202068A (zh) * 2020-03-11 2020-05-29 西北农林科技大学 N-苄基苯甲酰胺类化合物及其制备方法与用途

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100378076C (zh) * 2002-05-16 2008-04-02 拜尔作物科学有限公司 吡啶甲酰胺衍生物及其作为杀虫剂的用途
DE102016210164A1 (de) * 2016-06-08 2017-12-14 Clariant International Ltd Verwendung von N-substituierten Pyrrolidonen zur Förderung der Penetration von agrochemischen Wirkstoffen
CN109691450A (zh) * 2018-12-28 2019-04-30 利民化工股份有限公司 N-苄基苯甲酰胺类化合物及其组合物、混合制剂的用途

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4270946A (en) * 1979-10-01 1981-06-02 Stauffer Chemical Company N-Aryl,2-phenoxy nicotinamide compounds and the herbicidal use thereof
US4556414A (en) * 1981-06-25 1985-12-03 Rhone-Poulenc Agrochimie Herbicidal dihydropyridine amides
CN1054974A (zh) * 1990-03-16 1991-10-02 国际壳牌研究有限公司 除草用的甲酰胺衍生物
CN1110502A (zh) * 1990-07-17 1995-10-25 国际壳牌研究有限公司 除草剂组合物及其应用
WO2005070889A1 (en) * 2004-01-23 2005-08-04 E.I. Dupont De Nemours And Company Herbicidal amides
CN111202068A (zh) * 2020-03-11 2020-05-29 西北农林科技大学 N-苄基苯甲酰胺类化合物及其制备方法与用途

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