JP2021517592A - Quinazoline dione compounds, their use and pesticide herbicides - Google Patents

Abstract

The present invention discloses quinazoline dione compounds, their use and pesticide herbicides in the field of pesticide herbicides. The quinazoline dione compound of the present invention has a structure represented by the formula (I), and R is an H or a group represented by the formula (I-1). The quinazoline dione compound according to the present invention has excellent herbicidal activity and excellent crop safety.

Description

The present invention relates to the field of pesticide herbicides, and specifically relates to a quinazoline dione compound, the use of the quinazoline dione compound, and a pesticide herbicide containing the quinazoline dione compound.

4-Hydroxyphenylpyruvate dioxygenase (4-HPPD) was recognized as an action target for herbicides in the 90s of the last century.

4-HPPD is widely present in aerobic organisms and is mainly involved in the metabolism of tyrosine in the organism. In plants, the tyrosine metabolite p-hydroxyphenylpyruvate produces homogentisic acid under the action of 4-HPPD, which is further converted to plastoquinone and tocopherols. Plastoquinone and tocopherol are important precursors of plant photosynthesis. Therefore, by inhibiting the synthesis of plastoquinone and tocopherol in the plant, the normal photosynthesis of the plant is hindered and the plant suffers from albinism and dies. Herbicides targeting HPPD have features such as high efficiency, low toxicity, environmental friendliness, and excellent safety for subsequent crops. Therefore, 4-HPPD herbicide is a herbicide that is expected to have research value and future development potential.

In 2015, CN104557739A screened for the first time an HPPD-based inhibitor molecule containing a segment of quinazoline dione, the structure of its representative substance being as follows, which mainly controls weeds such as morokoshi fields. Used for.

Then, based on this, WO2017 / 140612A1 further discloses a series of HPPD-based inhibitor molecules, but this prior art did not provide test results for the biological activity of specific compounds.

Paddy rice is a very important food crop, and weed control in paddy rice fields plays a very important role in increasing the production of paddy rice and solving the global food crisis problem. Currently, malignant weeds such as paddy field fly, resistant fly and Azegaya have a serious effect on the normal growth of paddy rice, especially resistant fly grows very rapidly, and resistant fly will be controlled in the future. It will be difficult.

Therefore, it is very important to provide a novel HPPD-based inhibitor having a good control effect and high safety against weeds such as paddy rice fields.

An object of the present invention is to provide a novel HPPD-based inhibitor having an excellent control effect and high safety for crops against weeds in crop cultivated areas such as paddy rice fields.

（式（Ｉ）中、ＲはＨ又は式（Ｉ−１）で表される基である。）

In order to achieve the above object, the first aspect of the present invention provides a quinazoline dione-based compound having a structure represented by the formula (I).

(In formula (I), R is H or a group represented by formula (I-1).)

When the R is H, the quinazoline dione compound of the present invention has the structure shown by the following compound 1.

When the R is a group represented by the formula (I-1), the quinazoline dione compound of the present invention has a structure represented by the following compound 2.

The present inventors have better herbicidal activity than any of the compounds according to the present invention, Compound 1 and Compound 2, which have a similar structure according to the prior art, and the reference samples described later in the present specification. , It has been found that Compound 1 and Compound 2 according to the present invention also have clearly higher crop safety. Furthermore, we found that Compound 1 of the present invention is particularly safe for corn and wheat crops, and Compound 2 of the present invention is higher for crops in the field (eg paddy rice) than Compound 1. It was also found to be safe.

The present invention is not particularly limited in the method for synthesizing the quinazoline dione compound represented by the formula (I), and those skilled in the art can combine it with the synthetic method in the chemical field according to the structure of the compound according to the present invention to formula (I). ), Since an appropriate method for producing the quinazoline dione compound can be obtained, it will not be described repeatedly here.

A second aspect of the present invention provides the use of the quinazoline dione compound described in the first aspect in weed control.

Preferably, the weeds are Hie, Azegaya, Enokorogusa, Onimehishiba, Tarhokomugi, Suzumenochahiki, Karasumugi, Suzumenoteppo, Setogaya, Hosomugi, Marubatsuyukusa, Ebisugusa, Asagao, Onamomi, Kayatsurigusa, , Suberihiyu, Haribiyu, Kosendangusa, Kishusuzumenohie, Taiwan Ashikaki, Ibokusa, Omodaka, Alisma orientales, Mizuaoi, Commelina communis, Pontederia vaginalis, Scirpus juncoides, Tamagayatsuri, etc.

A third aspect of the present invention provides the use of the quinazoline dione compound according to the first aspect in controlling at least one weed selected from grass weeds, broad-leaved weeds and sedge weeds.

Preferably, in the present invention, the broad-leaved weeds are Hagayto, white goosefoot, Ichibi, Commelina benghalus, Ebisgusa, Asagao, Onamomi, Amaranthus retroflexus, Osennari, Takasaburo, Suberihiyu, Haribiyu, Murdannia keiskei, Omodaka, Sagiomodaka, Mizua. Includes at least one of. The Cyperus microiria includes Scirpus juncoides, Cyperus difformis, and the like.

Preferably, in the present invention, the grass weeds include barnyard grass, leptochloa vulgaris, green foxtail, onimehishiba, tarhokomugi, alopecurus aequalis, oat, alopecurus aequalis, setogaya, hosomugi, kayatsurigusa, oat noendou, kosendangusa, kishuzume. Includes at least one of.

A fourth aspect of the present invention provides the use of the quinazoline dione compound according to the first aspect as a herbicide.

A fifth aspect of the present invention provides a herbicide composed of an active ingredient containing at least one of the quinazoline dione compounds described in the first aspect described above and an auxiliary material.

Preferably, in the pesticide herbicide, the content of the active ingredient is 1 to 99.9999% by weight.

Preferably, the dosage form of the pesticide herbicide is at least one selected from emulsions, suspensions, wettable powders, powders, granules, liquids, poison bait, mother liquor and mother powder.

The suspension may include, for example, a dry suspension, a dispersible oily suspension and a water emulsion.

Auxiliary materials in the pesticide herbicide of the present invention include, for example, surfactants, protective colloids, pressure-sensitive adhesives, thickeners, thixotropes, penetrants, chelating agents, dyes, colorants, polymers and the like. It is not limited, and may be, for example, a conventional auxiliary agent capable of functioning as a carrier.

Carriers herein refer to one or more organics, inorganics, natural products or synthetics. These carriers are advantageous for the use of the active ingredient, are generally inert and are agriculturally acceptable, and are particularly acceptable for the plant to be applied. The carrier is a solid such as porcelain, natural or synthetic silicate, silica, resin, wax, solid fertilizer, or water, alcohols, ketones, petroleum fractions, aromatic hydrocarbons or wax hydrocarbons, chlorinated hydrocarbons. It may be a liquid such as hydrogen or liquefied gas.

The components of the surfactant of the present invention include emulsifiers, dispersants or wetting agents, which may be ionic or nonionic. Examples include polyacrylic acid salts, lignosulfonates, phenol sulfonic acids or naphthalene sulfonates, polymers of ethylene oxide with aliphatic alcohols or aliphatic acids or aliphatic amines and substituted phenols (particularly alkylphenols or arylphenols). Sulfonate, taurine derivative, phosphate ester of alcohol or polyhydroxyethylated phenol phosphate, alkyl sulfonic acid ester salt, alkylaryl sulfonate, alkyl sulfate, lauryl ether sulfate, fatty alcohol sulfate, sulfate In addition to cetyl alcohol-heptadecanol-octadecyl alcohol and sulfated fatty alcohol ethylene glycol ether, naphthalene or a condensate of naphthalene sulfonic acid, phenol and formaldehyde, polyoxyethylene octylanisole, ethoxylated isooctyl ether, octylphenol or nonylphenol, alkyl Phenylpolyethylene glycol ether, tributylphenylpolyethylene glycol ether, tristearylphenylpolyethylene glycol ether, alkylaryl polyether alcohol, condensate of alcohol and fatty alcohol / ethylene oxide, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxy Propylene, Lauryl Alcohol Polyethylene Glycol Ether Acetal, Sorbitol Ester, Lignin Sulfonate Waste Liquid, Protein, Modified Protein, Polysaccharide, Hydrophobized Modified Starch, Polyvinyl Alcohol, Polycarboxylate, Polyoxyal Chelate, Polyvinylamine, Polyvinylpyrrolidone and Copolymer Can be mentioned.

The present invention is not particularly limited to the method for producing the pesticide herbicide, and those skilled in the art can produce the corresponding reagent using a conventional production method in the field of pesticides.

The pesticide herbicide of the present invention includes, but is not limited to, being applied to crops by methods such as spraying.

The quinazoline dione compound according to the present invention and the pesticide herbicide containing the quinazoline dione compound have all the advantages of the HPPD herbicide, and are also environmentally friendly and safe for subsequent crops. It has the advantages of low usage, good fast-acting properties, wide herbicidal spectrum, and high safety.

In particular, the quinazoline dione compound according to the present invention exhibits excellent crop safety with respect to at least one of corn, wheat and paddy rice.

The quinazolindione compound according to the present invention has a very high herbicidal activity against grass weeds, broad-leaved weeds and Pontederia vaginalis weeds, and weeds growing especially in paddy rice, corn and wheat cultivated areas, for example. Gramineae weeds in paddy fields (Echinochloa chinensis, Azegaya, Kishuusuzumenohie, Enokorogusa, Onimehishiba, Taiwanashikaki, etc.); Broad-leaved weeds (Ibokusa, Omodaka, Sagiomodaka, Mizuaoi, Tsuyukusa, Konagi, etc.); On the other hand, the control effect is remarkable.

The endpoints and arbitrary values of the ranges disclosed herein are not limited to this exact range or value, and it should be understood that these ranges or values include values close to these ranges or values. Is. For numeric ranges, one or more new numeric ranges can be obtained by combining between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values, and these numerical ranges. Should be considered as specifically disclosed herein.

The present invention uses the following substances as reference samples.

As a method for producing the compound 1 and the compound 2 of the present invention and the above-mentioned reference sample, for example, the synthetic method described in CN104557739A can be referred to, and the type of raw material may be simply changed depending on the substituent.

In a preferred specific embodiment, the methods for producing Compound 1 and Compound 2 are provided below, and the raw material is Analytical Reagent in any of the following production examples.

化合物２ａの製造： ２−メチル−６−アミノ安息香酸（化合物１ａ）（１００ｍｍｏｌ）を酢酸（１２００ｍｌ）に溶解し、１ｍｏｌ／Ｌ ＩＣｌ酢酸溶液を撹拌しながら滴下し、滴下終了後、撹拌しながら２ｈ反応させ続けた。反応中に大量の固体が析出し、ＴＬＣにより反応の進行を監視し、反応終了後、ろ液を減圧下吸引ろ過して除去し、得られた固体を酢酸５００ｍＬで２回洗浄し、乾燥させ、灰白色固体を収率９３％で得た。
化合物３ａの製造： 化合物２ａ（２０ｍｍｏｌ）とピリジン３０ｍｌを窒素保護下で１００ｍＬ ２口フラスコに加え、固体が完全に溶解するまで撹拌した後、反応系にイソシアン酸ｍ−クロロフェニル（２５ｍｍｏｌ）をゆっくりと加えた。反応溶液を１００℃に加熱して２４時間反応させた。反応終了後、反応液を室温まで冷却した後、氷水にゆっくりと加えて３０分撹拌し、得られた固体を吸引ろ過し、水洗し、エーテルで洗浄し、乾燥させ、化合物３ａを収率９２％で得た。
化合物４ａの製造： 化合物３ａ（１２ｍｍｏｌ）、ＤＭＦ（３６ｍＬ）およびＫ₂ＣＯ₃（１４ｍｍｏｌ）を反応フラスコに加えた。撹拌しながら３０ｍｉｎ反応させた後、硫酸ジメチル（２４ｍｍｏｌ）をゆっくりと滴下し、添加終了後、室温で一晩撹拌しながら反応させた。ＴＬＣにより反応の進行を監視し、反応終了後、反応液を氷水２００ｍＬにゆっくり注いだ。３０ｍｉｎ激しく撹拌した後、得られた固体を吸引ろ過し、水洗し、エーテルで洗浄し、乾燥させ、化合物４ａを収率８７％で得た。
化合物５ａの製造： ４ａ（１２ｍｍｏｌ）、ＣｕＣＮ（２４ｍｍｏｌ）を反応フラスコに加え、窒素保護下、乾燥ＤＭＦを６０ｍＬ加え、系を加熱して還流させ、約１２ｈ反応させた。ＴＬＣにより反応の進行を監視したところ、反応終了後、ＤＭＦを減圧留去により除去し、冷却後、反応フラスコにアセトン６０ｍＬを加え、３０ｍｉｎ激しく撹拌し、反応フラスコ中の不溶性固体を濾去した。濾液を濃縮して、白色固体を粗収率８５％で得た。
化合物６ａの製造： 粗生成物５ａ（１０ｍｍｏｌ）を酢酸（２９ｍＬ）、水（１２４ｍＬ）、及びトリフルオロメタンスルホン酸（７．３ｍＬ）に溶解し、濃硫酸９８ｍＬを撹拌しながらゆっくりと滴下した。添加終了後、温度を上げて還流させ、１２ｈ反応させ、ＴＬＣにより反応の進行を監視したところ、反応終了後、系を室温まで冷却し、氷水２００ｍＬに注ぎ、３０ｍｉｎ激しく撹拌した。得られた固体を吸引ろ過し、水洗して、乾燥させ、化合物５ａを粗収率８８％で得た。
化合物７ａの製造： 化合物６ａ（１１６．３ｍｍｏｌ）と再蒸留ＤＣＭ（５８１．５ｍｌ）を１０００ｍＬ反応フラスコに加え、氷水浴下、塩化オキサリル（１７４．５ｍｍｏｌ）をゆっくりと滴下し、滴下終了後、１５ｍｉｎ撹拌し続けた。１０滴のＤＭＦを反応系にゆっくりと滴下し、滴下終了後、氷水浴下、固体が完全に溶解するまで、撹拌しながら２ｈ反応させた。反応終了後、溶媒を減圧下除去した。製造した酸塩化物を乾燥ＤＣＭ ２００ｍＬに溶解し、使用に準備した。
氷水浴下、１,３−ジメチル−５−ピラゾロン（１７４．５ｍｍｏｌ）とＤＣＭ（３５０ｍＬ）を反応フラスコに加えた。トリエチルアミン（３４８．９ｍｍｏｌ）をゆっくりと滴下し、滴下終了後、この温度で１５ｍｉｎ撹拌し続けた。上記酸塩化物のジクロロメタン溶液をこの反応系に素早く滴下し、滴下時間を約５ｍｉｎに制御した。滴下終了後、１５ｍｉｎ反応を続けた。原料が消失するまでＴＬＣにより反応の進行を監視し、反応終了後、反応系内に固体が析出し、吸引ろ過により得られた固体をジクロロメタンに溶解し、０℃で１２時間静置した。吸引ろ過によりろ渣を除去し、残留液体を減圧蒸留して、白色固体を収率９２％で得た。
化合物１の製造： 化合物７ａ（４５．７ｍｍｏｌ）と乾燥アセトニトリル６８５．５ｍＬを反応フラスコに加えた。反応液にトリエチルアミン（９１．４ｍｍｏｌ）、アセトンシアノヒドリン（１．５ｍｌ）を順次加えた。上記反応系を撹拌しながら８０℃に加熱し、約３０ｈ反応させた。原料が消失するまでＴＬＣにより反応の進行を監視したところ、反応終了後、溶媒を減圧下で留去し、得られた固体を塩化メチレンに溶解し、塩化メチレン有機相を１Ｍ ＨＣｌ溶液で洗浄した。分液して有機相を収集し、有機相を乾燥させて溶剤を除去された後、メタノールで再結晶させた。収率は９４％であった。 Production Example 1: Synthesis of Compound 1 by the following synthetic route

Preparation of Compound 2a: 2-Methyl-6-aminobenzoic acid (Compound 1a) (100 mmol) is dissolved in acetic acid (1200 ml), and a 1 mol / L ICl acetic acid solution is added dropwise with stirring. The reaction was continued for 2 hours. A large amount of solid precipitates during the reaction, and the progress of the reaction is monitored by TLC. After the reaction is completed, the filtrate is removed by suction filtration under reduced pressure, and the obtained solid is washed twice with 500 mL of acetic acid and dried. , A grayish white solid was obtained in a yield of 93%.
Preparation of Compound 3a: Compound 2a (20 mmol) and 30 ml of pyridine are added to a 100 mL two-necked flask under nitrogen protection, stirred until the solid is completely dissolved, and then slowly m-chlorophenyl isocyanate (25 mmol) is added to the reaction system. added. The reaction solution was heated to 100 ° C. and reacted for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature, slowly added to ice water, stirred for 30 minutes, and the obtained solid was suction-filtered, washed with water, washed with ether, dried, and the yield of compound 3a was 92. Obtained in%.
Preparation of Compound 4a: Compound 3a (12 mmol), DMF (36 mL) and K ₂ CO ₃ (14 mmol) were added to the reaction flask. After reacting for 30 minutes with stirring, dimethyl sulfate (24 mmol) was slowly added dropwise, and after the addition was completed, the reaction was carried out with stirring overnight at room temperature. The progress of the reaction was monitored by TLC, and after the reaction was completed, the reaction solution was slowly poured into 200 mL of ice water. After vigorous stirring for 30 minutes, the obtained solid was suction filtered, washed with water, washed with ether and dried to give compound 4a in a yield of 87%.
Preparation of compound 5a: 4a (12 mmol) and CuCN (24 mmol) were added to the reaction flask, 60 mL of dry DMF was added under nitrogen protection, and the system was heated to reflux and reacted for about 12 hours. When the progress of the reaction was monitored by TLC, after completion of the reaction, DMF was removed by distillation under reduced pressure, and after cooling, 60 mL of acetone was added to the reaction flask, and the mixture was vigorously stirred for 30 minutes to remove the insoluble solid in the reaction flask. The filtrate was concentrated to give a white solid in a crude yield of 85%.
Preparation of compound 6a: The crude product 5a (10 mmol) was dissolved in acetic acid (29 mL), water (124 mL), and trifluoromethanesulfonic acid (7.3 mL), and 98 mL of concentrated sulfuric acid was slowly added dropwise with stirring. After the addition was completed, the temperature was raised to reflux, the reaction was carried out for 12 hours, and the progress of the reaction was monitored by TLC. After the reaction was completed, the system was cooled to room temperature, poured into 200 mL of ice water, and stirred vigorously for 30 minutes. The obtained solid was suction filtered, washed with water and dried to obtain Compound 5a in a crude yield of 88%.
Preparation of compound 7a: Compound 6a (116.3 mmol) and redistilled DCM (581.5 ml) were added to a 1000 mL reaction flask, oxalyl chloride (174.5 mmol) was slowly added dropwise under an ice water bath, and 15 min after completion of the addition. Continued stirring. Ten drops of DMF were slowly added dropwise to the reaction system, and after completion of the addition, the reaction was carried out under an ice-water bath for 2 hours with stirring until the solid was completely dissolved. After completion of the reaction, the solvent was removed under reduced pressure. The prepared acid chloride was dissolved in 200 mL of dry DCM and prepared for use.
Under an ice water bath, 1,3-dimethyl-5-pyrazolone (174.5 mmol) and DCM (350 mL) were added to the reaction flask. Triethylamine (348.9 mmol) was slowly added dropwise, and after completion of the addition, stirring was continued at this temperature for 15 minutes. A dichloromethane solution of the acid chloride was rapidly added dropwise to this reaction system, and the addition time was controlled to about 5 min. After completion of the dropping, the reaction was continued for 15 minutes. The progress of the reaction was monitored by TLC until the raw materials disappeared, and after the reaction was completed, a solid was precipitated in the reaction system, and the solid obtained by suction filtration was dissolved in dichloromethane and allowed to stand at 0 ° C. for 12 hours. The filtrate was removed by suction filtration, and the residual liquid was distilled under reduced pressure to obtain a white solid in a yield of 92%.
Preparation of Compound 1: Compound 7a (45.7 mmol) and 685.5 mL of dry acetonitrile were added to the reaction flask. Triethylamine (91.4 mmol) and acetone cyanohydrin (1.5 ml) were sequentially added to the reaction solution. The reaction system was heated to 80 ° C. with stirring and reacted for about 30 hours. The progress of the reaction was monitored by TLC until the raw materials disappeared. After the reaction was completed, the solvent was distilled off under reduced pressure, the obtained solid was dissolved in methylene chloride, and the organic phase of methylene chloride was washed with 1M HCl solution. .. The liquid was separated to collect the organic phase, and the organic phase was dried to remove the solvent and then recrystallized from methanol. The yield was 94%.

Production Example 2: Method for Producing Compound 2 Compound 1 (91.3 mmol) is dissolved in THF (457 ml), and triethylamine (182.7 mmol), N, N-diethylformyllolide (182.7 mmol), and DMAP (27. 4 mmol) were added sequentially. The temperature is raised and the mixture is refluxed for 5 hours. After the reaction is completed, the mixture is cooled to room temperature, allowed to stand at 0 ° C. for 2 hours, the solid is removed by suction filtration, the filtrate is distilled under reduced pressure, and the obtained solid is subjected to ether. Recrystallized to obtain a crude product, methylene chloride was dissolved, the organic phase of dichloromethane was washed twice with water, the solvent was distilled off under reduced pressure, and the obtained solid was recrystallized from ether. The rate was 91%.
For the method for producing the compound in the reference sample, refer to Production Example 1 and Production Example 2 described above.
Table 1 shows the characterization data of the above reference sample and the compounds of the present invention.

The biological activity test in a greenhouse was performed using the above-mentioned reference sample and the compound of the present invention.

Test Example 1: General screening experiment in a greenhouse Weigh a certain amount of drug substance on an analytical balance and dissolve in DMF containing 1% by weight of Tween-80 emulsifier to prepare 1% by weight of mother liquor, and then prepare 1% by weight of mother liquor. Diluted with distilled water to make stock solutions of various concentrations and prepared for use.
Test weeds: See Table 2. Use a spray on the stems and leaves after germination. Specifically, after taking a paper cup with an inner diameter of 7 cm and filling it with complex soil (vegetable soil: seedling raising substrate = 1: 2, v / v) up to 3/4, weed seeds are directly sown and 0.2 cm. The soil was covered and grown to the 4-5 leaf stage to prepare for use. 10 g. Of the reference sample and the compound of the present invention. a. i / mu, mesotrione 10 g. a. After application at an automatic spray tower at a dose of i / mu, the chemical solution on the leaf surface of the crop under test is dried, then transferred to a greenhouse for cultivation (temperature 25-28 ° C, humidity 70%), and 30 days later. , The results are examined and the results are shown in Table 2.
Investigation method: 30 days after the test procedure, visually confirm the damage symptom and the state of growth inhibition of the subject, weigh the fresh weight of the above-ground part, calculate the fresh weight reduction rate (%), and control effect by the fresh weight reduction rate. Represents (%).
Fresh weight loss rate (%) = (Control fresh weight-Treatment fresh weight) / Control fresh weight x 100
Evaluation of herbicidal activity (symptoms such as resistance, mild inhibition, mild bleaching, mild malformation, severe malformation, complete bleaching, complete death):
Grade G: Same as control, drug resistant, with less than 10% control effect.
Grade F: Growth is slightly affected, slightly suppressed, less active, with less than 10% to less than 20% control effect.
Grade E: Growth is affected, slightly whitened, less active, with less than 20% to less than 50% control effect.
Grade D: Growth is affected, slightly malformed, moderately active, with less than 50% to less than 70% control effect.
Grade C: Relatively sensitive, severely malformed, relatively good in activity, with a control effect of 70% to less than 90%.
Grade B: Very sensitive, completely whitened, good activity, meets screening conditions, control effect is less than 90% to less than 100%.
Grade A: Completely dead, good activity, 100% control effect.

As is clear from the above test results of herbicidal activity, the compounds 1 and 2 of the present invention have an excellent control effect on weeds. Furthermore, the compounds of the present invention have a better control effect than commercially available mesotrions, especially on green foxtail.

Comparing Compounds D1 to D11, all of Compounds D1 to D11 have a lower control effect on test weeds than the compounds of the present invention, and the control effect of each compound on different weeds is lower. Significantly different. In particular, Compound D8 and Compound D11 had almost no control effect on the test weeds.

Furthermore, when the pyrazole ring segment in the structure of the compound of the present invention is modified with a substituent and a methyl group, an ethyl group, a propyl group and a cyclopropyl group are introduced, the herbicidal activity of the synthesized compounds D12 to D15 corresponds. It was far superior to the drug substance compounds D36 to D39. From this, it was shown that the segment of the N, N-diethylformyl group discovered by the present inventors has a clear promoting effect on the improvement of the herbicidal activity of the HPPD-based inhibitor.

In order to further verify the promoting effect of the N, N-diethylformyl group segment on the biological activity, the N, N-diethylformyl group segment is widely present in pesticides and pharmaceuticals and has good biological activity. When compounds D16 to D19 were synthesized by cyclization using a 5-membered ring or a 6-membered ring, the herbicidal activity of this series of compounds was almost lost. Based on this, other substituted alkyl groups such as alkoxy groups, 3-membered rings, 4-membered rings, 5-membered rings, and 6-membered rings were introduced while retaining the formyl group. In general screening experiments, the furan ring and thiophene ring derivatives had the best herbicidal activity and were close to the herbicidal activity of the compounds of the present invention.

As a result of comparative analysis, when a 3-membered ring or a 4-membered ring was introduced (Compound D21, Compound D22, Compound D23, Compound D24), the herbicidal activity was generally reduced, but other substituted alkyl groups such as an alkoxy group were added. When introduced, the herbicidal activity was improved as compared with the drug substance molecule, and the control effect on rice weeds was equivalent to that of the compound of the present invention, but the control effect on broadleaf weeds was lower than that of the compound of the present invention.

As a result of comprehensive analysis, the N, N-diethylformyl group segment played an important role in improving the herbicidal activity of the HPPD-based inhibitor of the present invention.

Test Example 2: Preliminary screening experiment in a greenhouse Weigh a certain amount of API with an analytical balance, dissolve in DMF containing 1% by weight of Tween-80 emulsifier, prepare 1% by weight of mother liquor, and dilute with distilled water. Prepared for use with stock solutions of various concentrations.
Potted planting method: See Tables 3, 4a, and 4b for test subjects. A flowerpot with an inner diameter of 6 cm was taken, the complex soil (vegetable soil: seedling raising substrate = 1: 2, v / v) was filled up to 3/4, and the seeds to be tested (germination rate ≥ 85%) were directly sown. 2 cm of soil was covered and the subject was grown to about 3 leaf stages and prepared for use. Each compound was sprayed in an automatic spray tower at 2, 4, 8 g. a. After application at a dose of i / mu, the chemical solution on the leaf surface to be tested was dried, then transferred to a greenhouse for cultivation, and after 30 days, the results were examined and the results were shown in Tables 3, 4a, and 4b. Shown in.
The investigation method was the same as in Test Example 1.

As a result of analyzing the results of the preliminary screening experiment and comparing the results of the general screening experiment, the compounds D25 to D30 have a relatively ideal control effect on weeds by the general screening, and the control effect of the compound of the present invention is relatively ideal. There was no significant difference from.

As can be seen from further preliminary screening experiments, the control effects of compounds D25 to D30 on green foxtail and fly generally decrease as the dose decreases, whereas the doses of compound 1 and compound 2 of the present invention are reduced. Even if the amount was reduced, it had an ideal control effect on green foxtail and fly.

As is clear from the results of the crop safety test, Compounds D25 to D30 show obvious phytotoxicity to all of the test crops (Indica, Japonica), further as an environmentally friendly and safe selective herbicide. I couldn't develop it.

As evidenced by the results of crop safety tests on corn and wheat, Compounds D25-Compound D30 show obvious phytotoxicity to all of the test crops and are further developed as environmentally friendly and safe selective herbicides. I couldn't.

On the other hand, the compound of the present invention exhibits excellent crop safety for at least one species of paddy rice, corn and wheat, and has an excellent control effect on major weeds in paddy rice fields, and has been industrially developed as a candidate drug molecule. We were able to.

Test Example 3: Further test of the activity of Compound 2 Weigh a certain amount of the drug substance with an analytical balance, dissolve it in DMF containing 1% by weight of the Tween-80 emulsifier, prepare 1% by weight of the mother liquor, and use distilled water. Diluted to various concentration stock solutions and prepared for use.
Potted planting method: See Tables 5 and 6 for test subjects. A flowerpot with an inner diameter of 6 cm was taken, the complex soil (vegetable soil: seedling raising substrate = 1: 2, v / v) was filled up to 3/4, and the seeds of the test weeds (germination rate ≥ 85%) were directly sown. It covered 2 cm of soil and was ready for use when weeds grew to about 3 leaf stages. 2.5, 5.0, and 10 g of each compound in an automatic spray tower. i. After application at a dose of / mu, the chemical solution on the leaf surface was dried, and then transferred to a greenhouse for cultivation. After 30 days, the results were examined and the results are shown in Tables 5 and 6.
The investigation method was the same as in Test Example 1.

Test Example 4: Further Test of Compound Safety of the Present Invention A certain amount of API is weighed with an analytical balance, dissolved in DMF containing 1% by weight of Tween-80 emulsifier, 1% by weight of mother liquor is prepared, and distilled. Diluted with water to make stock solutions of various concentrations and prepared for use.
Potted planting method: See Table 7 for test subjects. A flowerpot with an inner diameter of 6 cm is taken, the complex soil (vegetable soil: seedling raising substrate = 1: 2, v / v) is filled up to 3/4, and the seeds of the above test crop (germination rate ≥ 85%) are directly sown. When the soil was covered with 0.2 cm and grew to the three-leaf stage, it was subjected to the test. 2.5, 5.0, 10 g of each compound in an automatic spray tower. i. After application at a dose of / mu, the chemical solution on the leaf surface was dried, and then transferred to a greenhouse for cultivation. After 30 days, the results are examined and the results are shown in Table 7.
The investigation method was the same as in Test Example 1.

As is clear from further crop safety studies, Compound 2 showed excellent crop safety for paddy rice. In addition, Compound 2 is excellent in controlling major weeds in paddy fields, particularly Azegaya and resistant barnyard grass, and can effectively solve the problem that it is difficult to control resistant barnyard grass in paddy fields.
From the structural analysis of the compound, a segment of N, N-diethylformyl group was introduced based on compound 1, compound 2 was synthesized, and the introduction of this segment only maintained the biological activity of the original molecule. However, the crop selectivity of the original molecule was also improved (highly safe for paddy rice). This indicates that this segment has very good biological functions.

Test Example 5: Further Test of Compound Safety Weigh a certain amount of drug substance with an analytical balance (0.0001 g) and dissolve in DMF containing 1% by weight of Tween-80 emulsifier to prepare 1% by weight of mother liquor. Then, it was diluted with distilled water to prepare stock solutions having various concentrations, and prepared for use.
Potted planting method: See Table 8 for test subjects. A flowerpot with an inner diameter of 6 cm was taken, the complex soil (vegetable soil: seedling raising substrate = 1: 2, v / v) was filled up to 3/4, and the seeds to be tested above (germination rate ≥ 85%) were directly sown. The soil was covered with 0.2 cm and grown to about 1 to 2 leaf stages and subjected to the test. 2.5, 5.0, 10 g of each compound in an automatic spray tower. i. After application at a dose of / mu, the chemical solution on the leaf surface was dried, and then transferred to a greenhouse for cultivation. After 30 days, the results are examined and the results are shown in Table 8.
The investigation method was the same as in Test Example 1.
The results are shown in Table 8.

As a result of analyzing the above test results, it was found that the compound 2 of the present invention has a significant control effect on Japanese millet, green foxtail, Azegaya and the like, and also shows excellent safety against paddy rice. From the subsequent further evaluation of crop safety, it was found that Compound 2 showed excellent crop safety for various varieties of paddy rice and was promising.

Test Example 6: Field test Crop test: Six types of paddy rice (4 leaves, 1 core), that is, Ningyu 48, Ryutan 29, Y Ryoyu, Huanghua Zhao, Glutinous rice No. 2, and Glutinous rice No. 6 were tested.
Weed test: See Tables 9 to 10 Test method: With 20 m ² as one plot, each treatment was repeated 3 times, sprayed on the foliage 12 days after direct sowing of paddy rice, irrigated 48 hours after application, and retained for 5 to 7 days. did.
Twenty days after the treatment, the treatment area and the control area were visually observed, and the weed control effect and crop safety were calculated by the same investigation method as in Test Example 1.
Experiment location: Hainan Sanya Results are shown in Tables 9 and 10.

As is clear from the above results, 5 g. a. At i / mu doses, Compound 2 caused overt whitening in barnyard grass after 4 days and was particularly effective against Leptochloa zebra.

Under the same conditions, the compound 2 of the present invention contains 6 kinds of glutinous rice varieties (4 leaves, 1 core) to be tested, Ning glutinous rice 48, dragon glutinous rice 29, Y Ryoyu, Huanghua Zhao, glutinous rice No. 2, glutinous rice No. When used in glutinous rice, no bleaching was observed in paddy rice, so there was no phytotoxicity.

As described above, the compound according to the present invention has a good control effect on weeds in the cultivation area of crops such as paddy rice fields, and has excellent safety on crops.

Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. Many simple modifications can be made to the proposed technical invention of the present invention, including combining various technical features in other suitable manners without departing from the technical concept of the present invention. These simple modifications and combinations should also be considered as disclosed in the present invention. All belong to the claims of the present invention.

Claims (9)

A quinazoline dione compound having a structure represented by the formula (I).

(In formula (I), R is H or a group represented by formula (I-1).)

The compound according to claim 1, wherein R is H in the formula (I). The compound according to claim 1, wherein R is a group represented by the formula (I-1) in the formula (I). Use of the quinazoline dione compound according to any one of claims 1 to 3 in weed control. Use of the quinazoline dione compound according to any one of claims 1 to 3 in controlling at least one weed selected from grass weeds, broad-leaved weeds and sedge weeds. Use of the quinazoline dione compound according to any one of claims 1 to 3 as a pesticide herbicide. A pesticide herbicide composed of an active ingredient containing at least one of the quinazoline dione compounds according to any one of claims 1 to 3 and an auxiliary material. The pesticide herbicide according to claim 7, wherein the content of the active ingredient is 1 to 99.9999% by weight. The dosage form of the pesticide herbicide is at least one selected from emulsions, suspensions, wettable powders, powders, granules, liquids, poison bait, mother liquor and mother powder, according to claim 7 or 8. Agricultural herbicide.