CN112110846A - N-aryl phthalimide derivative and preparation method and application thereof - Google Patents
N-aryl phthalimide derivative and preparation method and application thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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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
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- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract
The inventionThe invention provides N-aryl o-phthalimide compounds, a preparation method and application thereof, and relates to the N-aryl o-phthalimide compounds which have a chemical structural general formula shown in III.
Description
Technical Field
The technical scheme of the invention relates to an N-aryl phthalimide compound, in particular to an N-aryl phthalimide derivative.
Background
The herbicide is an important component of the pesticide, and has important value for controlling the weeds of crops. With the unreasonable and large-scale use of herbicides, the problems of environmental pollution, weed drug resistance, pesticide residue and the like are increasingly highlighted (Sperry, Benjamin P. weed technology 2017,31(1):1-7.), so that the development of a novel environment-friendly, efficient, economic and degradable herbicide suitable for market demands has important significance. At present, the development of novel enzyme inhibitors according to the difference of metabolic mechanisms of weeds and crops is one of characteristics of herbicide creation (Hao, Ge-Fei.CHIMIA International Journal for Chemistry 2011,65(12): 961-969.).
At present, a novel herbicide is designed in a targeted mode by utilizing a molecular docking method based on a herbicide target, and the novel herbicide is one of hot spots of herbicide creation research (Liujing pottery, scientific and technological innovation and application, 2016(34): 67-67). Protoporphyrinogen oxidase inhibitors (PPO inhibitors) cause plant growth inhibition or death by affecting the biosynthesis of chlorophyll in plant cells, resulting in cell destruction. The PPO inhibitor has the advantages of high efficiency, low toxicity, quick response, lasting drug effect, better control effect on dicotyledonous weeds and monocotyledonous weeds, and the like. PPO inhibitors therefore occupy an important position in the herbicide market. Currently commercially available PPO inhibitors are: fomesafen (fomesafen), oxyfluorfen (oxyfluorfen), aclonifen (aclonifen), lactofen (lactofen), flumioxazin (flumioxazin), sulfentrazone (sulfentrazone), carfentrazone (carfentrazone), pyraclonil (pyraclonil) and saflufenacil (saflufenacil). The PPO inhibitor herbicide is one of the herbicides with slow development of global resistance, and with the increasing prominence of global resistance problems, the development of novel high-activity PPO inhibitors is imminent.
In order to find and discover a pesticide lead compound which is more efficient, broad-spectrum, low-toxicity and low-ecological risk and has no cross resistance with the existing herbicide, the invention takes a protoporphyrinogen oxidase inhibitor N-aryl o-phthalimide structure as a lead structure, introduces different substituent groups to an N-aryl part by utilizing the pesticide molecular design principle, designs and synthesizes a class of N-aryl o-phthalimide derivatives, and carries out systematic weeding bioactivity screening so as to provide more efficient candidate compounds for the creation of a novel herbicide.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a synthesis method of a novel N-aryl o-phthalimide derivative, a method for regulating and controlling the biological activity of agricultural, horticultural and forestry weeds and a determination method thereof, and also provides application of the compounds in the agricultural field, the horticultural field and the forestry field.
The technical scheme adopted by the invention for solving the technical problem is as follows: the general formula of the chemical structure of the N-aryl o-phthalimide compound with herbicidal activity in the agricultural field, the horticultural field and the forestry field is shown as the formula III:
Ⅲ：
wherein R is1Selected from: hydrogen, fluorine, chlorine, methyl and nitro.
Ar is selected from: p-isopropylphenyl, p-tert-butylphenyl, 3-fluoro-4-methylphenyl, 2-fluoro-4-nitrophenyl, 3-carboxamidophenyl, 5-methylthiazol-3-yl, 4-bromo-2, 6-difluorophenyl, 4-fluoro-2-methoxylphenyl, 3, 4-dichlorobenzyl, 1-methyl-pyrazol-5-yl, 2-thienyl and 3-fluoro-2-methoxyphenyl.
The synthesis method of the N-aryl o-phthalimide derivative III comprises the following steps:
wherein R is1Selected from: hydrogen, fluorine, chlorine, methyl and nitro.
Ar is selected from: p-isopropylphenyl, p-tert-butylphenyl, 3-fluoro-4-methylphenyl, 2-fluoro-4-nitrophenyl, 3-carboxamidophenyl, 5-methylthiazol-3-yl, 4-bromo-2, 6-difluorophenyl, 4-fluoro-2-methoxylphenyl, 3, 4-dichlorobenzyl, 1-methyl-pyrazol-5-yl, 2-thienyl and 3-fluoro-2-methoxyphenyl.
The specific method for synthesizing the N-aryl o-phthalimide derivative and measuring the biological activity comprises the following steps:
A. the preparation method of the compound III comprises the following steps:
in a 50 ml single neck round bottom flask was added 3.38 mmol of compound I, dissolved with 15 ml of glacial acetic acid and added 3.72 mmol of an aromatic amine compound ii selected from: p-isopropylphenyl, p-tert-butylphenyl, 3-fluoro-4-methylphenyl, 2-fluoro-4-nitrophenyl, 3-formamidophenyl, 5-methylthiazol-3-yl, 4-bromo-2, 6-difluorophenyl, 4-fluoro-2-methoxylphenyl, 3, 4-dichlorobenzyl, 1-methyl-pyrazol-5-yl, 2-thienyl and 3-fluoro-2-methoxy, heating to 100 ℃, stirring for 4 hours, monitoring the reaction process by thin-layer chromatography, removing the solvent under reduced pressure after the reaction is completed, purifying the residue by 200-300-mesh silica gel column chromatography to obtain a compound III, wherein an eluent is petroleum ether and ethyl acetate, the volume ratio is 5:1-2:1 according to different products, the yield is 28-87%; the amount of compound III prepared and the volume of the reaction vessel are scaled up or down accordingly.
B. The herbicidal activity of the N-aryl o-phthalimide derivative III is determined as follows:
the weeding activity of the N-aryl o-phthalimide derivative III adopts a small cup method, and the method comprises the following specific steps: 20 mg of the sample was dissolved in 1 ml of N, N-dimethylformamide and then diluted with an aqueous solution containing an amount of Tween 80 to a test concentration of 200. mu.g/ml. In the small cup method, seeds with consistent germination are picked by tweezers and evenly placed on filter paper sheets in a small beaker of 50 ml, 10 seeds are placed in each cup, each treatment is repeated for 3 times, and a pipettor is used for sucking 1 ml of medicine liquid drops to the filter paper sheets. All treatments were placed in a climatic chamber for incubation at 25 + -0.5 deg.C with 60 + -5% humidity and day-to-night ratio of 16:8 in the light cycle. After 7 days of treatment, the root length and stem length were measured, and the root inhibition rate and stem inhibition rate were calculated. The concentration adopted by the stem leaf spraying method and the pre-emergence soil spraying method is 90g ai/ha. The stem leaf treatment method adopts dicotyledonous weeds at two leaf stages and monocotyledonous weeds at 3-5 leaf stages, the test agent is uniformly sprayed on the leaves of the weeds by using a walking spray tower, a solution without a sample is used as a blank control, the treatment is repeated for 3 times, the treated weeds are cultured in a climatic chamber, and the inhibition degree of the sample on the growth of the weeds is investigated by an absolute value method after 7 days. Pre-emergence soil spraying method: after weed seeds are sowed, directly carrying out medicament spraying treatment by using a walking type spraying tower, taking a solution without adding a sample as a blank control, repeating the treatment for 3 times, culturing the plants in an artificial climate chamber, investigating the inhibition degree of the sample on weed growth by an absolute value method after 14 days, and testing plants are the species of most typical weeds actually occurring in the field in agricultural production of China, and have the following names: the latin name of the crabgrass is Digitaria sanguinalis and Amaranthus retroflexus.
The beneficial effects of the invention are as follows: the N-aryl phthalimide derivative III is subjected to derivative synthesis, and the phthalimide derivative is screened for herbicidal activity.
The synthesis, biological activity and application of N-aryl-phthalimide derivative III are more specifically illustrated by specific preparation and biological activity determination examples, which are only used for specifically illustrating the invention and not limiting the invention, and particularly, the biological activity is only illustrated and not limiting the patent, and the specific implementation modes are as follows:
example 1: the preparation method of the compound III comprises the following steps:
in a 50 ml single neck round bottom flask was added 3.38 mmol of compound I, dissolved with 15 ml of glacial acetic acid and added 3.72 mmol of aromatic amine compound II selected from: p-isopropylaniline, p-tert-butylaniline, 3-fluoro-4-methylaniline, 2-fluoro-4-nitroaniline, 3-aminobenzamide, 3-amino-5-methylisoxazole, 4-bromo-2, 6-difluoroaniline, 2-amino-5-methyl fluorobenzoate, 3, 4-dichlorobenzylamine, 1-methyl-5-aminopyrazole, 2-thiophenemethylamine and 3-fluoro-2-methoxyaniline, heating to 100 ℃, stirring for 4 hours, monitoring the reaction process by using thin-layer chromatography, removing the solvent under reduced pressure after the reaction is completed, purifying the residue by using 200-300-mesh silica gel column chromatography to obtain a compound III, wherein an eluent is petroleum column chromatographyEther and ethyl acetate, wherein the volume ratio is 5:1-2:1 according to different products, and the yield is 28-87%; when R is1For H, Ar is 4-bromo-2, 6-difluorophenyl, the nuclear magnetic data are as follows:1H NMR(400MHz,CDCl3)7.98(dd, J ═ 5.5,3.1Hz,2H),7.83(dd, J ═ 5.5,3.1Hz,2H),7.29(d, J ═ 6.7Hz, 2H). The amount of compound III prepared and the volume of the reaction vessel are scaled up or down accordingly. The physicochemical and structural parameters of compound III are shown in Table 1.
Example 2: the herbicidal activity test result of the N-aryl o-phthalimide derivative III of the invention is as follows:
the common names of weeds tested in the present invention are as follows: the latin name of the crabgrass is Digitaria sanguinalis, Amaranthus retroflexus. The measurement was carried out by the cuvette method.
The results of the small cup method are shown in Table 2, and Table 2 shows that the N-aryl phthalimide derivatives synthesized by the invention have different degrees of herbicidal activity at 200 micrograms/ml. 3a shows that the stem inhibition rate of the amaranthus retroflexus is 87 percent, and the control effect is more than 20 percent higher than that of a control medicament atrazine (66 percent); 3a has the inhibition rate of 68 percent on the crabgrass roots and 83 percent on the crabgrass stems, the rhizome inhibition rate of the crabgrass stems is more than 10 percent of that of a control medicament atrazine (the root inhibition rate is 58 percent, and the stem inhibition rate is 60 percent), and the crabgrass has better weeding effect. The inhibition rate of 3d on the amaranthus retroflexus root is 81 percent and exceeds that of the control medicament atrazine by more than 50 percent, and the chlortoluron has no inhibition activity. 3g of the compound has an inhibition rate of 91 percent on crabgrass roots, which is respectively 30 percent higher than atrazine and flumioxazin and is more than 20 percent higher than that of control medicaments of atrazine and flumioxazin; the inhibition on the crabgrass stems reaches 83 percent, and is more than 20 percent higher than that of a control medicament atrazine. The inhibition rate of 3j on the crabgrass root reaches 87 percent, is higher than that of a control medicament atrazine by 20 percent and exceeds that of flumioxazin by more than 15 percent. The 3o inhibition rate of the amaranthus retroflexus root reaches 83 percent, and the content of the atrazine exceeds that of a contrast medicament by more than 50 percent. The root inhibition rate of 3r on the large crabgrass reaches 87%, the inhibition rate on the large crabgrass stems is 86%, and the inhibition rates respectively exceed that of a control medicament atrazine (the root inhibition rate is 58%, and the stem inhibition rate is 60%) by 15% and 25% above. In conclusion, in the cuvette test, the compounds 3a, 3d, 3g, 3o and 3r of the present invention showed very good herbicidal activity, and particularly the compound 3a showed very high inhibitory effect on crab and redroot amaranth.
Example 3: the N-aryl phthalimide derivative III is applied to the preparation of a compound herbicide by combining with an agriculturally acceptable auxiliary agent and any one or more of the following commercial herbicides:
the commercial herbicide is selected from the group consisting of nicosulfuron, tribenuron-methyl, cinosulfuron, sulfometuron-methyl, penoxsulam, alachlor, acetochlor, butachlor, metolachlor, 2-methyl-4-chloro, trifluralin, mesotrione, topramezone, pendimethalin, atrazine, prometryn, cyanazine, ametryn, metribuzin, aclonifen, oxyfluorfen, acifluorfen, lactofen, fluoroglycofen, pyraflufen-ethyl, imazapyr, imazaquin, pyribenzoxim, imazapyr, bentazon, pyrazofen-ethyl, pyribenzoxim, pyriproxyfen, phenmedipham, desmedipham, benazolin, swamp, pyributicarb, dicarb, thiocarb, thiodan, halofop, quizalofop-ethyl, quizalofop-p-ethyl, bentazone, bencarb, flumetofen, benazolin, dithiopyr, fluazinone, thiazopyr, diflufenzopyr, paraquat, glyphosate, anilofos, flumiclorac, flumioxazin, fluthiacet, metribuzin, pyraflufen, tralkoxydim, carfentrazone, isoxaflutole, bromoxynil, and the like; the total mass percentage of the N-aryl phthalimide derivative III in the obtained compound herbicide is 1-90%, and the mass percentage of the N-aryl phthalimide derivative III and the commercial herbicide is 1-99-1%; the formulation suitable for the compound herbicide is any one of wettable powder, microcapsule suspending agent, dispersible liquid formulation, dispersible solid formulation, seed treatment emulsion, aqueous emulsion, large granule, microemulsion, oil suspending agent, water soluble granule, soluble concentrate, water dispersible granule, poison grain, aerosol, sustained release block, capsule granule, dry-mixed seed powder, missible oil, electrostatic spray, aqueous oil-in-oil emulsion, oil-in-water emulsion, aerosol can, fine granule, aerosol candle, aerosol cylinder, aerosol stick, seed treatment suspending agent, aerosol tablet, aerosol pill, gas generating agent, drift powder, ointment, hot fogging concentrate, solid/liquid mixed package agent, liquid/liquid mixed package agent, cold fogging concentrate, solid/solid mixed package agent, medicinal paint, seed treatment liquid, microgranule, oil dispersible powder, colloid, pour-on agent, smearing agent, Suspending emulsion, film-forming oil agent, soluble powder, seed treatment water-soluble powder, ultra-low volume suspending agent, tracing powder, ultra-low volume liquid, steam releasing agent, and wet-mixed seed water-dispersible powder; the plant suitable for the compound herbicide is selected from rice, wheat, barley, oat, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, tuber mustard, beet, rape, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, orange, peach, tea, potherb, bamboo shoot, hop, pepper, banana, papaya, orchid, bonsai; the compound herbicide is suitable for controlling weeds and is selected from: grassy weeds: crab grass, green bristlegrass herb, goosegrass herb, barnyard grass, moleplant seed, tiger tail grass, wild oat, teff grass, golden green bristlegrass herb, long silvergrass club grass, amur foxtail and the like; broad-leaved weeds such as Amaranthus retroflexus, herba Portulacae, fructus Chenopodii, herba Desmodii Trifoliatae, herba Acalyphae, herba Xanthii, Ambrosia, piemarker, Kochiae fructus, herba Solani Nigri, herba Spinaciae, herba Stellariae, herba Moslae, herba Ecliptae, herba seu radix Valerianae, herba Convolvuli Alsinoides, and semen Cuscutae; cyperaceae weeds such as herba Tagetis Erectae, herba Cyperi Erectae, herba Salsolae Collinae, herba Alii Fistulosi, etc.
TABLE 1 chemical Structure and physicochemical parameters of N-arylphthalimide derivatives III of the present invention
TABLE 2 microcup herbicidal Activity of N-arylphthalimide derivative III of the present invention (inhibition rate of 200. mu.g/ml/%)
Claims (3)
1. The N-aryl o-phthalimide compound is characterized by having a chemical structural general formula shown as a formula III:
Ⅲ：
wherein R is1Selected from: hydrogen, fluorine, chlorine, methyl and nitro.
Ar is selected from: p-isopropylphenyl, p-tert-butylphenyl, 3-fluoro-4-methylphenyl, 2-fluoro-4-nitrophenyl, 3-carboxamidophenyl, 5-methylthiazol-3-yl, 4-bromo-2, 6-difluorophenyl, 4-fluoro-2-methoxylphenyl, 3, 4-dichlorobenzyl, 1-methyl-pyrazol-5-yl, 2-thienyl and 3-fluoro-2-methoxyphenyl.
The synthesis method of the N-aryl o-phthalimide derivative III comprises the following steps:
wherein R is1Selected from: hydrogen, fluorine, chlorine, methyl and nitro.
Ar is selected from: p-isopropylphenyl, p-tert-butylphenyl, 3-fluoro-4-methylphenyl, 2-fluoro-4-nitrophenyl, 3-carboxamidophenyl, 5-methylthiazol-3-yl, 4-bromo-2, 6-difluorophenyl, 4-fluoro-2-methoxylphenyl, 3, 4-dichlorobenzyl, 1-methyl-pyrazol-5-yl, 2-thienyl and 3-fluoro-2-methoxyphenyl.
The specific method for synthesizing the N-aryl o-phthalimide derivative and measuring the biological activity comprises the following steps:
A. the preparation method of the compound III comprises the following steps:
in a 50 ml single neck round bottom flask was added 3.38 mmol of compound I, dissolved with 15 ml of glacial acetic acid and added 3.72 mmol of an aromatic amine compound ii selected from: p-isopropylphenyl, p-tert-butylphenyl, 3-fluoro-4-methylphenyl, 2-fluoro-4-nitrophenyl, 3-formamidophenyl, 5-methylthiazol-3-yl, 4-bromo-2, 6-difluorophenyl, 4-fluoro-2-methoxylphenyl, 3, 4-dichlorobenzyl, 1-methyl-pyrazol-5-yl, 2-thienyl and 3-fluoro-2-methoxyphenyl, heating to 100 ℃, stirring for 4 hours, monitoring the reaction process by TLC, removing the solvent under reduced pressure after the reaction is completed, purifying the residue by 200-300-mesh silica gel column chromatography to obtain a compound III, wherein an eluent is petroleum ether and ethyl acetate, the volume ratio is 5:1-2:1 according to different products, the yield is 60-90%; the amount of compound III prepared and the volume of the reaction vessel are scaled up or down accordingly.
2. Use of an N-arylphthalimide derivative iii according to claim 1 with an agriculturally acceptable adjuvant for the preparation of herbicides.
3. The N-arylphthalimide derivative iii of claim 1, in combination with any one or more of commercial herbicides nicosulfuron, tribenuron-methyl, triasulfuron, prosulfuron, primisulfuron-methyl, penoxsulam, alachlor, acetochlor, butachlor, metolachlor, 2-methyl-4-chloro, trifluralin, mesotrione, topramezone, pendimethalin, atrazine, prometryn, cyanazine, ametryn, metribuzin, aclonifen, oxyfen, oxyfluorfen, acifluorfen, lactofen, fluoroglycofen, pyraflufen-ethyl, ipropyr, imazapyr, imazethapyr, imazamox, imazapyr, pyriftalid, pyrimethanil, pyriftalid, phenmedipham, desmedipham, pyributicarb, dicamba, dichlorcarb, haloxyfop, benazolin, quizalofop, thia diclofop, fluroxypyr, dithiopyr, fluazinone, thiazopyridine, diflufenzopyr, paraquat, glyphosate, anil, fluroxypyr, flumioxazin, fluthiacet, metribuzin, pyrafluxate, pyraflufen, carfenpyrazoxol, pyraflufen, carfenpyraflufen, pyraflutole, pyraflufen, isoxaflutole, bromoxynil, and the like; the total mass percentage of the N-aryl o-phthalimide derivative III in the obtained compound herbicide is 1-90%, and the mass percentage of the N-aryl o-phthalimide derivative III to the commercial herbicide is 1% -99% -1%; the formulation suitable for the compound herbicide is any one of wettable powder, microcapsule suspending agent, dispersible liquid formulation, dispersible solid formulation, seed treatment emulsion, aqueous emulsion, large granule, microemulsion, oil suspending agent, water soluble granule, soluble concentrate, water dispersible granule, poison grain, aerosol, sustained release block, capsule granule, dry-mixed seed powder, missible oil, electrostatic spray, aqueous oil-in-oil emulsion, oil-in-water emulsion, aerosol can, fine granule, aerosol candle, aerosol cylinder, aerosol stick, seed treatment suspending agent, aerosol tablet, aerosol pill, gas generating agent, drift powder, ointment, hot fogging concentrate, solid/liquid mixed package agent, liquid/liquid mixed package agent, cold fogging concentrate, solid/solid mixed package agent, medicinal paint, seed treatment liquid, microgranule, oil dispersible powder, colloid, pour-on agent, smearing agent, Suspending emulsion, film-forming oil agent, soluble powder, seed treatment water-soluble powder, ultra-low volume suspending agent, tracing powder, ultra-low volume liquid, steam releasing agent, and wet-mixed seed water-dispersible powder; the plant suitable for the compound herbicide is selected from rice, wheat, barley, oat, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, tuber mustard, beet, rape, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, orange, peach, tea, potherb, bamboo shoot, hop, pepper, banana, papaya, orchid, bonsai; the compound herbicide is suitable for controlling weeds and is selected from: grassy weeds: crab grass, green bristlegrass herb, goosegrass herb, barnyard grass, moleplant seed, tiger tail grass, wild oat, teff grass, golden green bristlegrass herb, long silvergrass club grass, amur foxtail and the like; broad-leaved weeds such as Amaranthus retroflexus, herba Portulacae, fructus Chenopodii, herba Desmodii Trifoliatae, herba Acalyphae, herba Xanthii, Ambrosia, piemarker, Kochiae fructus, herba Solani Nigri, herba Spinaciae, herba Stellariae, herba Moslae, herba Ecliptae, herba seu radix Valerianae, herba Convolvuli Alsinoides, and semen Cuscutae; cyperaceae weeds such as herba Tagetis Erectae, herba Cyperi Erectae, herba Salsolae Collinae, herba Alii Fistulosi, etc.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110071304A1 (en) * | 2008-02-28 | 2011-03-24 | Research Foundation Itsuu Laboratory | Aromatic amide derivative |
| US20130023415A1 (en) * | 2010-03-23 | 2013-01-24 | Basf Se | Substituted Pyridines Having Herbicidal Action |
-
2019
- 2019-06-20 CN CN201910534179.1A patent/CN112110846A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110071304A1 (en) * | 2008-02-28 | 2011-03-24 | Research Foundation Itsuu Laboratory | Aromatic amide derivative |
| US20130023415A1 (en) * | 2010-03-23 | 2013-01-24 | Basf Se | Substituted Pyridines Having Herbicidal Action |
Non-Patent Citations (6)
| Title |
|---|
| ANTONIO CALA，等: "Phthalimide-derived strigolactone mimics as germinating agents for seeds of parasitic weeds", 《PEST MANAG SCI》 * |
| BERNARDO M.BARCHIN，等: "Microwave-Assisted Parallel Synthesis of a 2-Aryl-1H-Isoindole-1,3-Dione Library", 《SYNLETT》 * |
| HUA CHENG，等: "Synthesis, biochemical evaluation and computational simulations of new cytochrome bc1 complex inhibitors based on N-(4-aryloxyphenyl) phthalimides", 《CHINESE CHEMICAL LETTERS》 * |
| KAI JIANG，等: "Substituted Phthalimide AC94377 Is a Selective Agonist of the Gibberellin Receptor GID1", 《PLANT PHYSIOLOGY》 * |
| R.YOSHIDA，等: "新的N一苯基一邻苯二甲酰亚胺类除草剂S-53482", 《农药》 * |
| 孙致远，等: "邻苯二甲酰亚胺和酞氨酸类化合物结构与除草活性的关系", 《农药》 * |
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