A pyrazole-quinazolinone compound, a preparation method and application thereof, and a herbicide

Abstract

The application relates to the field of pesticide compounds, discloses a pyrazole-quinazoline-dione compound, a preparation method and application of the pyrazole-quinazoline-dione compound and a herbicide. The compound has the structure shown in formula (I). The compound provided by the application has excellent herbicidal activity and good safety to food crops.

Description

Technical Field

[0001] This invention relates to the field of pesticides and herbicides, specifically to a pyrazole-quinazolinedione compound, its preparation method and application, and a herbicide. Background Technology

[0002] The development and application of highly effective herbicides are important technical means to ensure grain yield and safeguard national food security.

[0003] However, the long-term, single, and unreasonable use of herbicides has led to the rampant growth of resistant weeds. Herbicide resistance has become a major problem restricting agricultural production, and there is an urgent need to independently develop new and efficient herbicides.

[0004] p-Hydroxypyruvate dioxygenase (HPPD) is one of the most important herbicide targets. Herbicides targeting HPPD have advantages such as high efficiency, low toxicity, low residue, good environmental compatibility, and slow resistance development. They also have excellent control efficacy against ALS, ACCase, and glyphosate weeds.

[0005] Therefore, HPPD herbicides are one of the powerful tools for solving the current problem of concentrated weed resistance.

[0006] CN112608282A discloses a compound containing a quinazolinidone and NO structure, its preparation method and application. The compound provided by this prior art has excellent herbicidal activity against five common grass and broadleaf weeds: barnyard grass, crabgrass, amaranth, lambsquarters, and velvetleaf. However, the compound provided by this prior art has unsatisfactory control efficacy against foxtail grass and low safety for crops such as wheat. Summary of the Invention

[0007] One of the objectives of this invention is to overcome the aforementioned deficiencies in the prior art and provide a novel, ultra-efficient herbicide suitable for grain crop fields.

[0008] The second objective of this invention is to provide a broad-spectrum HPPD herbicide that can be used to control grassy weeds and some broadleaf weeds.

[0009] To achieve the above objectives, a first aspect of the present invention provides a pyrazole-quinazolinedione compound having the structure shown in formula (I).

[0010]

[0011] In equation (I),

[0012] R is selected from -(CH2) n -R 1 C 1-12 Alkyl, C 3-8cycloalkyl; n is 0, 1, 2 or 3; R 1 Selected from unsubstituted or substituted phenyl groups of at least one group in combination A; said combination A is composed of halogen, C 1-6 Alkyl, C 1-6 Alkyl groups, C substituted with at least one halogen 1-6 Alkyl composition;

[0013] R1 is selected from H, -(CH2). m -R 2 m is an integer from 1 to 6, R 2 It is vinyl or acetylene.

[0014] A second aspect of the present invention provides a method for preparing the compound described in the first aspect, the method comprising: subjecting a compound with the structure shown in formula (II) to a catalyst in the presence of a base and a solvent under rearrangement reaction conditions;

[0015] Optionally, the method further includes: making a second contact between the product obtained after the first contact and R1-X;

[0016]

[0017] Where X is a halogen, and the definitions of R and R1 are the same as those in the first aspect.

[0018] A third aspect of the invention provides the use of the compounds described in the first aspect in the control of weeds.

[0019] A fourth aspect of the present invention provides a herbicide comprising an active ingredient and excipients, wherein the active ingredient comprises at least one of the compounds described in the first aspect or their agriculturally chemically acceptable salts, hydrates, solvates, or enantiomers or optically active derivatives thereof.

[0020] The aforementioned compounds provided by this invention, or their agriculturally chemically acceptable salts, hydrates, solvates, or their enantiomers and optically active derivatives, possess excellent herbicidal activity.

[0021] The aforementioned compounds provided by this invention, or their agriculturally chemically acceptable salts, hydrates, solvates, or their enantiomers and optically active derivatives, are applicable to weed control in grain crop fields, especially wheat fields.

[0022] In other words, the aforementioned compounds provided by this invention, or their agriculturally chemically acceptable salts, hydrates, solvates, or their enantiomers and optically active derivatives, have excellent safety for crops in grain-type crop fields, especially wheat fields. Detailed Implementation

[0023] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0024] “C 1-12 "Alkyl" refers to a straight-chain or branched alkyl group with a total of 1-12 carbon atoms. For example, the number of carbon atoms can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and n-hexyl. "C" 1-6 Alkyl groups, etc., have similar definitions.

[0025] “C 3-8 "Cycloalkyl" refers to saturated cycloalkyl groups with 3, 4, 5, 6, 7, or 8 carbon atoms in the ring, including but not limited to cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0026] “C 1-6 "Alkoxy" refers to a straight-chain or branched alkoxy group with a total number of carbon atoms of 1-6. For example, the number of carbon atoms can be 1, 2, 3, 4, 5, or 6, including but not limited to methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexyloxy, etc.

[0027] In this invention, "halogen" refers to fluorine, chlorine, bromine, or iodine.

[0028] As previously described, a first aspect of the present invention provides a pyrazole-quinazolinedione compound having the structure shown in formula (I).

[0029]

[0030] In equation (I),

[0031] R is selected from -(CH2) n -R 1 C 1-12 Alkyl, C 3-8 cycloalkyl; n is 0, 1, 2 or 3; R 1 Selected from unsubstituted or substituted phenyl groups of at least one group in combination A; said combination A is composed of halogen, C 1-6 Alkyl, C 1-6 Alkyl groups, C substituted with at least one halogen 1-6 Alkyl composition;

[0032] R1 is selected from H, -(CH2). m -R 2 m is an integer from 1 to 6, R 2 It is vinyl or acetylene.

[0033] Preferably, in formula (I),

[0034] R is selected from -(CH2) n -R 1 C 1-6 Alkyl, C 3-6 cycloalkyl; n is 0, 1 or 2; R 1 Selected from unsubstituted or substituted phenyl groups of at least one group in combination A; said combination A is composed of halogen, C 1-4 Alkyl, C 1-4 Alkyl groups, C substituted with at least one halogen 1-4 Alkyl composition;

[0035] R1 is selected from H, -(CH2). m -R 2 m is 1, 2, 3 or 4, R 2 It is vinyl or acetylene.

[0036] More preferably, in equation (I),

[0037] R is selected from -(CH2) n -R 1 Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, cyclopropyl, cyclobutyl, cyclohexyl; n is 0 or 1; R 1 Selected from unsubstituted or substituted phenyl groups of at least one group in combination A; said combination A is composed of fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, or C substituted with at least one halogen. 1-4 Alkyl composition;

[0038] R1 is selected from H, -(CH2). m -R 2 m is 1, 2, 3 or 4, R 2 It is vinyl or acetylene.

[0039] More preferably, in formula (I),

[0040] R is selected from -(CH2) n -R 1 Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, cyclopropyl, cyclobutyl, cyclohexyl; n is 0 or 1; R1 The phenyl group is selected from unsubstituted or substituted with at least one group in combination A; said combination A consists of fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy, isopropoxy, and trifluoromethyl.

[0041] R1 is selected from H, -(CH2). m -R 2 m is 1 or 2, R 2 It is vinyl or acetylene.

[0042] In particularly preferred cases, the compound with the structure shown in formula (I) is selected from any one of the following:

[0043]

[0044]

[0045] The pyrazole-quinazolindione compounds provided by this invention can be used as broad-spectrum HPPD herbicides for controlling grassy weeds and some broadleaf weeds. Furthermore, the compounds provided by this invention have good control efficacy against a variety of difficult-to-control weeds, including shepherd's purse, lambsquarters, lambskin, velvetleaf, cleavers, speedwell, chickweed, amaranth, black nightshade, lantern grass, purslane, amaranth retroflexus, carp intestines, barnyard grass, goosegrass, golden foxtail, foxtail grass, crabgrass, wild oats, Japanese wild oats, jointed goatgrass, wild oats, wild oats, barnyard grass, double-spike barnyard grass, fireweed, and sedge.

[0046] This invention does not impose any particular limitation on the specific method for obtaining the above-mentioned pyrazole-quinazoline dione compounds. Those skilled in the art can obtain a suitable method for preparing pyrazole-quinazoline dione compounds by combining the specific structure of the pyrazole-quinazoline dione compounds provided by this invention with synthetic methods in the field of organic synthesis.

[0047] However, in order to improve the yield of the obtained pyrazole-quinazolinedione compounds, as mentioned above, the second aspect of the present invention provides a method for preparing the compounds described in the first aspect, the method comprising: subjecting a compound with the structure shown in formula (II) to a catalyst in the presence of a base and a solvent under rearrangement reaction conditions;

[0048] Optionally, the method further includes: making a second contact between the product obtained after the first contact and R1-X;

[0049]

[0050] Where X is a halogen, and the definitions of R and R1 are the same as those in the first aspect.

[0051] According to the method for preparing compounds of formula (I) of the present invention, those skilled in the art can first contact compounds of formula (II) with catalysts in the presence of base and solvent according to conventional conditions and operations of rearrangement reactions.

[0052] In a preferred embodiment, the molar ratio of the compound with the structure shown in formula (II) to the catalyst and the base is 1:(0.01-1):(0.5-4); more preferably, the molar ratio of the compound with the structure shown in formula (II) to the catalyst and the base is 1:(0.05-1):(1-3).

[0053] In a preferred embodiment, the conditions for the first contact include: a reaction temperature of 0-100°C and a reaction time of 0.5-24 h; more preferably, the conditions for the first contact include: a reaction temperature of 20-40°C and a reaction time of 5-12 h.

[0054] Those skilled in the art should understand that the method described in this invention may also include a step of purifying the obtained product. There are no special requirements for the purification method, and various purification methods commonly used by those skilled in the art can be adopted. For example, extraction with an extractant, drying with a drying agent, and removal of impurities by column chromatography or other methods can be used.

[0055] In the preparation method described in this invention, the compound with the structure shown in formula (II) can be commercially available or prepared by conventional reactions in the art.

[0056] For example, compounds with the structure shown in formula (II) can be prepared using the synthetic route shown below:

[0057]

[0058] Specifically, in the presence of glacial acetic acid, compound I-1 is reacted with iodine monochloride to obtain compound I-2, which is then further reacted with isocyanates of different substitutions (R-NCO) to obtain intermediate compound I-3. Then, in the presence of N,N-dimethylformamide (DMF) and cesium carbonate, intermediate compound I-3 is reacted with iodomethane to obtain intermediate compound I-4. Intermediate I-4 is mixed with N,N'-dicyclohexylcarbodiimide (DCC), 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (Xantphos), and palladium acetate, and under a protective atmosphere, anhydrous formic acid and triethylamine are added to react and obtain intermediate compound I-5. Intermediate compound I-5 is then reacted sequentially with oxalyl chloride and methylpyrazolone to obtain the compound with the structure shown in formula (II).

[0059] In a preferred embodiment, the catalyst is selected from at least one of sodium cyanide, potassium cyanide, acetone cyanohydrin, trimethylcyanosilane, 1,2,4-triazole and benzo-1,2,4-triazole.

[0060] Preferably, the alkali is selected from at least one of potassium carbonate, sodium carbonate, cesium carbonate, triethylamine, and pyridine.

[0061] Preferably, the solvent is selected from at least one of dichloromethane, trichloromethane, dichloroethane, acetonitrile, toluene, tetrahydrofuran, and benzene.

[0062] As previously stated, a third aspect of the present invention provides the use of the compounds described in the first aspect in the control of weeds.

[0063] The weeds described in this invention are plants that grow in areas harmful to human survival and activities, and can be non-cultivated wild plants or plants useless to humans. For example, they can be various wild plants in crop fields.

[0064] Preferably, the weed is at least one weed selected from sorghum fields, soybean fields, rapeseed fields, wheat fields, rice fields, corn fields, and peanut fields; more preferably, the weed is at least one selected from grass weeds and broadleaf weeds. More preferably, the weed is at least one weed selected from wheat fields.

[0065] Preferably, the weeds are selected from at least one of grass weeds and broadleaf weeds.

[0066] Preferably, in the foregoing application of the present invention, the amount of the compound used is 10-400 g / ha.

[0067] In the application of the compound provided by the present invention as described above, the compound is used after being dissolved and diluted with a solvent, and the concentration after dissolution and dilution is preferably 0.05-0.4 g / L. The solvent for dissolving the compound may include N,N-dimethylformamide, dimethyl sulfoxide, etc., and the dilution reagent may be water containing common additives. Preferably, one or more additives commonly used in herbicides in the art, such as surfactants, emulsifiers, etc., may be added to the solution containing the compound. The diluted compound of the present invention can be sprayed onto the stems and / or leaves of plants using conventional methods in the art.

[0068] As previously described, a fourth aspect of the present invention provides a herbicide comprising an active ingredient and excipients, wherein the active ingredient includes at least one of the compounds described in the first aspect of the present invention.

[0069] Preferably, the content of the active ingredient is 1-99.9% by weight. For example, it can be 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, etc.

[0070] The excipients described in this invention are various additives commonly used in the preparation of various formulations of herbicides in the art.

[0071] Preferably, the formulation of the herbicide of the present invention is selected from at least one of emulsifiable concentrate, suspension concentrate, wettable powder, powder, granule, aqueous solution, mother liquor and mother powder.

[0072] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, all raw materials used are commercially available and of analytical grade. Room temperature below refers to 25±3℃.

[0073] Preparation Example 1

[0074]

[0075] 0.6 mol of methyl 2-amino-3-methylbenzoate was placed in a 2 L three-necked round-bottom flask, and 500 mL of glacial acetic acid was added. The mixture was mechanically stirred at room temperature. Simultaneously, 0.7 mol of ICl was dissolved in 300 mL of glacial acetic acid and added to the reaction system using a constant-pressure dropping funnel. After the addition was completed within 30 min, the reaction was continued for 3 h, and the reaction progress was monitored by TCL. After the reaction was completed, the solid was filtered and washed with a small amount of glacial acetic acid, then dried to obtain intermediate I-2, with a yield of 91%.

[0076] 13.7 mmol of intermediate I-2 was weighed and added to a 100 mL Shrek tube. 25 mL of ultradry pyridine was added under a nitrogen atmosphere, followed by stirring and the addition of 17.2 mmol of o-chlorophenyl isocyanate. The mixture was heated to reflux for 10 h, and the reaction progress was monitored by TLC. After the reaction was complete, the system was cooled to room temperature and then poured into 400 mL of ice water. The solid precipitated by stirring was filtered, dried, and intermediate I-3 was obtained in 86% yield.

[0077] In a 100 mL flask, 11.6 mmol of intermediate I-3, 23.2 mmol of cesium carbonate, and 30 mL of DMF were added sequentially. After stirring at room temperature for about 15 min, 34.8 mmol of iodomethane was added. The reaction was allowed to proceed for about 1 h. The reaction was monitored by TLC. After the reaction was completed, intermediate I-4 was purified by column chromatography with a yield of 81%.

[0078] 5 mmol of intermediate I-4, 10 mmol of N,N'-dicyclohexylcarbodiimide, 0.15 mmol of 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene, and 0.13 mmol of palladium acetate were placed in a 100 mL Shrek tube. Under nitrogen protection, 20 mL of ultradry DMF was added, followed by the slow addition of 35 mmol of anhydrous formic acid and 10 mmol of triethylamine. After the addition was complete, the system was heated to 80 °C and reacted for approximately 1.5 h. The reaction progress was monitored by TLC until the reactants had completely reacted. After the reaction was complete, the mixture was cooled to room temperature, and the insoluble substances were filtered off. The filtrate was collected and added to 300 mL of water. The reaction mixture was then extracted three times with 30 mL of dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The mixture was recrystallized from diethyl ether to obtain intermediate I-5 in 80% yield.

[0079] In a 100 mL round-bottom flask, 3.9 mmol of intermediate I-5 and 30 mL of ultra-dry dichloromethane were added. Then, under ice bath conditions, 7.8 mmol of oxalyl chloride and catalytic amounts of DMF (4 drops) were added. After the addition was complete and the reaction system stabilized, the ice bath was removed, and the mixture was stirred at room temperature for 3 h. The solvent was then removed by vacuum distillation. The resulting system was evacuated and sealed to obtain a pale yellow oil. Simultaneously, 5.8 mmol of methylpyrazolone was placed in another 100 mL round-bottom flask, and 15 mL of ultra-dry dichloromethane and 7.8 mmol of triethylamine were added sequentially. The mixture was stirred at room temperature for 10 min, then placed in an ice bath. The resulting pale yellow oil was dissolved in 15 mL of ultra-dry dichloromethane and added to the above system. After the addition was complete, the ice bath was removed, and the reaction was allowed to proceed at room temperature. The reaction progress was monitored using a TCL (Total Chromatography-Clean Air) system. After the reaction was completed, the reaction system was washed with saturated sodium bicarbonate solution, and the reaction system was extracted three times with 15 mL of dichloromethane each time. The organic phase was collected, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain intermediate I-6 with a yield of 79%.

[0080] 2 mmol of intermediate I-6 was placed in a 100 mL round-bottom flask, and 20 mL of acetonitrile was added with stirring. Then, 4 mmol of triethylamine and 8 drops of acetone cyanohydrin were added sequentially. The reaction was allowed to proceed overnight at room temperature, and the reaction progress was monitored by TLC until the reactants were completely reacted. The solvent acetonitrile was removed to dryness, and 15 mL of 1 mol / L hydrochloric acid solution was added to the reaction system. The reaction system was extracted three times with 15 mL of dichloromethane each time. The organic phases were combined, dried over anhydrous sodium sulfate to remove the solvent, and then purified by recrystallization from anhydrous methanol to obtain compound 4 in 69% yield.

[0081] Preparation Example 2

[0082]

[0083] 13.7 mmol of intermediate I-2 was placed in a 200 mL round-bottom flask, 50 mL of tetrahydrofuran was added, and 34.3 mmol of ethyl isocyanate was added with stirring. The system was heated to 70 °C and reacted for 48 h. The reaction progress was monitored by TLC. After the starting material was completely reacted, the solvent was removed by vacuum distillation to obtain intermediate I-7 with a yield of 96%.

[0084] In a 100 mL round-bottom flask, 13 mmol of intermediate I-7 and 30 mL of methanol solution were added, followed by the addition of 39 mmol of sodium methoxide under stirring. The reaction was allowed to proceed for approximately 1 h, and the reaction progress was monitored by TLC. After the reaction was complete, the methanol was removed, and 20 mL of 1 mol / L hydrochloric acid solution was slowly added. Subsequently, a large amount of white solid precipitated. This solid was filtered, dried, and the yield of intermediate I-8 was obtained, with a yield of 85%.

[0085] In a 100 mL flask, 11 mmol of intermediate I-8, 22 mmol of cesium carbonate, and 30 mL of DMF were added sequentially. After stirring at room temperature for about 15 min, 33 mmol of iodomethane was added. The reaction was allowed to proceed for about 1 h. The reaction was monitored by TLC. After the reaction was completed, intermediate I-9 was purified by column chromatography with a yield of 84%.

[0086] 5 mmol of intermediate I-9, 10 mmol of N,N'-dicyclohexylcarbodiimide, 0.15 mmol of 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene, and 0.13 mmol of palladium acetate were placed in a 100 mL Shrek tube. Under nitrogen protection, 20 mL of ultradry DMF was added, followed by the slow addition of 35 mmol of anhydrous formic acid and 10 mmol of triethylamine. After the addition was complete, the system was heated to 80 °C and reacted for approximately 1.5 h. The reaction progress was monitored by TLC until the reactants had completely reacted. After the reaction was complete, the mixture was cooled to room temperature, and the insoluble substances were filtered off. The filtrate was collected and added to 300 mL of water. The reaction mixture was then extracted three times with 30 mL of dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The mixture was recrystallized from diethyl ether to obtain intermediate I-10, with a yield of 79%.

[0087] In a 100 mL round-bottom flask, 3.9 mmol of intermediate I-10 and 30 mL of ultra-dry dichloromethane were added. Then, under ice bath conditions, 7.8 mmol of oxalyl chloride and catalytic amounts of DMF (4 drops) were added. After the addition was complete and the reaction system stabilized, the ice bath was removed, and the mixture was stirred at room temperature for 4 h. The solvent was then removed by vacuum distillation. The resulting system was evacuated and sealed to obtain a pale yellow oil. Simultaneously, 5.8 mmol of methylpyrazolone was placed in another 100 mL round-bottom flask, and 15 mL of ultra-dry dichloromethane and 7.8 mmol of triethylamine were added sequentially. The mixture was stirred at room temperature for 10 min, then placed in an ice bath. The resulting pale yellow oil was dissolved in 15 mL of ultra-dry dichloromethane and added to the above system. After the addition was complete, the ice bath was removed, and the reaction was allowed to proceed at room temperature. The reaction progress was monitored using a TCL (Total Chloride Clamp). After the reaction was completed, the reaction system was washed with saturated sodium bicarbonate solution, and the reaction system was extracted three times with 15 mL of dichloromethane each time. The organic phase was collected, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain intermediate I-11 with a yield of 78%.

[0088] 2 mmol of intermediate I-11 was placed in a 100 mL round-bottom flask, and 20 mL of acetonitrile was added with stirring. Then, 4 mmol of triethylamine and 8 drops of acetone cyanohydrin were added sequentially. The reaction was allowed to proceed overnight at room temperature, and the reaction progress was monitored by TLC until the reactants were completely reacted. The solvent acetonitrile was dried, and 15 mL of 1 mol / L hydrochloric acid solution was added to the reaction system. The reaction system was extracted three times with 15 mL of dichloromethane each time. The organic phases were combined, dried over anhydrous sodium sulfate to remove the solvent, and then purified by recrystallization from anhydrous methanol to obtain compound 15 in 73% yield.

[0089] Preparation Example 3

[0090]

[0091] 0.3 mmol of compound 4 and 0.6 mmol of cesium carbonate were weighed into a 50 mL round-bottom flask. 15 mL of acetonitrile was added with stirring at room temperature, followed by 0.45 mmol of allyl bromide. The mixture was heated to 70 °C and the reaction was monitored by TLC until the reactants were completely reacted. After the reaction was complete, the acetonitrile was removed, 10 mL of saturated brine was added, and the mixture was extracted with dichloromethane (3 × 15 mL). The organic phase was collected, dried over anhydrous sodium sulfate, and finally purified by column chromatography to obtain compound 30 in 80% yield.

[0092] Preparation Example 4

[0093]

[0094] 0.3 mmol of compound 4 and 0.6 mmol of cesium carbonate were weighed into a 50 mL round-bottom flask. 15 mL of acetonitrile was added with stirring at room temperature, followed by 0.45 mmol of propargyl bromide. The mixture was heated to 70 °C and the reaction was monitored by TLC until the reactants were completely reacted. After the reaction, the acetonitrile was removed, 10 mL of saturated brine was added, and the mixture was extracted with dichloromethane (3 × 15 mL). The organic phase was collected, dried over anhydrous sodium sulfate, and finally purified by column chromatography to obtain compound 31 in 91% yield.

[0095] The preparation methods of the other compounds of the present invention are the same as those described in the preparation examples above. Table 1 lists the characterization data of the compounds of the present invention.

[0096] Table 1

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103] Test Example 1

[0104] This test example illustrates the herbicidal activity (expressed as growth inhibition rate (%)) of compounds with the structure shown in formula (I) and comparative compounds.

[0105] Herbicidal activity test (pot method): Test targets are shown in Table 3. Post-emergence foliar spraying: Take a 7cm inner diameter paper cup, fill it with composite soil (garden soil: seedling substrate, 1:2, v / v) to 3 / 4 full, directly sow weeds, cover with 0.2cm of soil, and wait until the plants reach the 4-5 leaf stage for use. The compounds of this invention and comparative compounds D1, D2, and D3 were applied at a dosage of 320g·ai / ha (grams per hectare) using an automatic spray tower. After the pesticide solution on the crop leaves dried, the plants were transferred to a greenhouse for cultivation (25℃, 70% humidity). The results were investigated after 30 days.

[0106] The growth inhibition rate was evaluated by visual inspection, and the rating was based on the conditions shown in Table 2. The test results are shown in Table 3.

[0107]

[0108] Table 2

[0109]

[0110] Table 3

[0111]

[0112]

[0113] As shown in Table 3, the compounds provided by this invention have significant inhibitory effects on weeds, including broadleaf and grass weeds. Furthermore, some compounds in this invention exhibited 100% herbicidal efficacy against the five tested weeds at an application rate of 320 g·ai / ha. Therefore, the compounds in this invention have strong prospects for development and commercialization.

[0114] Test Example 2

[0115] The crop safety of the compounds of the present invention was determined using a similar test method and the same evaluation method as in Test Example 1. The difference was that the compounds of the present invention were applied in an automatic spray tower at the dosages shown in Table 4. The test results for weed and crop inhibition are shown in Table 4.

[0116] Table 4

[0117]

[0118] The results shown above demonstrate that the compound provided by this invention has excellent safety for grain crops, particularly wheat.

[0119] Furthermore, the representative compounds of the present invention showed excellent crop safety against wheat at doses of 150 g.ai / ha and 120 g.ai / ha, while the comparative compounds D1, D2 and D3, which have higher herbicidal activity, caused wheat to essentially die at a dose of 150 g.ai / ha and severely inhibited wheat growth at a dose of 120 g.ai / ha.

[0120] In summary, the compounds of this invention can be applied to wheat fields for highly effective control of broadleaf and grassy weeds without causing phytotoxicity. Therefore, this invention is clearly suitable for field application as a selective herbicide for wheat fields and has high commercial value.

[0121] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A pyrazole-quinazolinedione compound, characterized in that, The compound has the structure shown in formula (I). Equation (I) Wherein, the compounds with the structure shown in formula (I) are selected from any one of the following: Compound 5: Compound 9: Compound 14: Compound 22: Compound 23: Compound 26: Compound 29: Compound 31: .

2. A method for preparing the compound of claim 1, characterized in that, The method includes: subjecting a compound with the structure shown in formula (II) to a catalyst in the presence of a base and a solvent under rearrangement reaction conditions; Optionally, the method further includes: making a second contact between the product obtained after the first contact and R1-X; Formula (II); Wherein, X is a halogen; the definitions of R and R1 are the same as those in claim 1.

3. The method according to claim 2, wherein, The conditions for the first contact include: a reaction temperature of 0-100℃ and a reaction time of 0.5-24h.

4. The method according to claim 3, characterized in that, The catalyst is selected from at least one of sodium cyanide, potassium cyanide, acetone cyanohydrin, trimethylcyanosilane, 1,2,4-triazole and benzo-1,2,4-triazole.

5. The use of the compound of claim 1 in weed control.

6. The application according to claim 5, characterized in that, The weeds are selected from at least one type of weed found in sorghum fields, soybean fields, rapeseed fields, wheat fields, rice fields, corn fields, and peanut fields.

7. The application according to claim 6, characterized in that, The weeds are selected from at least one of grass weeds and broadleaf weeds.

8. The application according to claim 7, characterized in that, The weeds mentioned are at least one of the following: shepherd's purse, shepherd's purse, lambsquarters, velvetleaf, cleavers, speedwell, chickweed, ironweed, black nightshade, lantern grass, purslane, amaranth, carp intestines, barnyard grass, goosegrass, golden foxtail grass, foxtail grass, crabgrass, wild oats, Japanese wild oats, jointed barnyard grass, wild oats, wild oats, barnyard grass, double-spike barnyard grass, fireweed, and sedge.

9. The application according to claim 8, characterized in that, The amount of the compound used is 10-400 grams per hectare.

10. A herbicide comprising an active ingredient and excipients, said active ingredient comprising the compound of claim 1 or an agriculturally chemically acceptable salt thereof.

11. The herbicide according to claim 10, wherein, The content of the active ingredient is 1-99.9% by weight.

12. The herbicide according to claim 10, wherein, The herbicide formulation is selected from at least one of emulsifiable concentrate, suspension concentrate, powder, granule, aqueous solution, mother liquor, and mother powder.

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