A triketone-benzimidazolone compound, its preparation method and application, and a herbicide

Abstract

The present invention relates to the field of new pesticide compounds, and discloses a triketone-benzimidazolone compound, its preparation method and application, and a herbicide. The compound has the structure represented by formula (I). The triketone-benzimidazolone compound provided by the present invention has a significant inhibitory effect on weeds, including broadleaf weeds, grass weeds, and sedge weeds, and is highly safe for crops. #imgabs0#

Description

Technical Field

[0001] The present invention relates to the field of new pesticide compounds, and in particular to a triketone-benzimidazolone compound, a preparation method and application thereof, and a herbicide. Background Art

[0002] Among the many problems that hinder the sustainable development of modern agriculture, various types of weeds have become the number one problem affecting crop yields.

[0003] Although there are various herbicides on the market for weed control, the resistance problems of some existing herbicides have far exceeded people's expectations due to factors such as target resistance and non-target resistance.

[0004] Therefore, the fundamental way to solve this problem is to create ultra-high-efficiency herbicides with novel mechanisms of action and low resistance risk.

[0005] Para-hydroxyphenylpyruvate dioxygenase (EC 1.13.11.27, HPPD) exists in aerobic organisms and is a dioxygenase that relies on divalent iron for catalysis.

[0006] In higher plants, HPPD converts its substrate, p-hydroxyphenylpyruvate (HPPA), into homogentisate (HGA), which is then further converted into plastoquinone and tocopherol. Plastoquinone participates in photosynthesis as an electron carrier, while tocopherol is a structural component of cell membranes, protecting them from oxidative damage. Inhibition of HPPD activity in weeds reduces the synthesis of plastoquinone and tocopherol, thereby affecting carotenoid biosynthesis and, in turn, photosynthesis, ultimately leading to the weeds exhibiting albinism symptoms and dying.

[0007] To date, more than a dozen HPPD-inhibiting herbicides have been commercialized. Market feedback indicates that HPPD herbicides are highly effective, broad-spectrum, low-toxic, and environmentally friendly. Furthermore, compared to herbicides targeting AHAS, ACCase, and PSII, these herbicides exhibit much slower resistance development and lack cross-resistance with other herbicides, providing specific inhibition of resistant weeds in the field. This advantage is crucial for combating the widespread outbreaks of resistant weeds.

[0008] At present, the vast majority of commercial HPPD herbicides are only suitable for controlling weeds in corn fields, with only a few being used in rice, wheat and other crop fields. However, the application rate is large and the residue problem is prominent, which makes it impossible for existing HPPD herbicides to play their advantages in controlling resistant weeds in wheat fields.

[0009] Therefore, creating a new ultra-efficient HPPD herbicide with novel structure and safety for specific crops is one of the important means to solve the current frequent problem of weed resistance in major crop fields, and it has huge market value. Summary of the Invention

[0010] The object of the present invention is to provide a novel triketone-benzimidazolone compound having the potential to become a novel ultra-high-efficiency HPPD-inhibiting herbicide.

[0011] In order to achieve the above object, the first aspect of the present invention provides a triketone-benzimidazolone compound having a structure shown in formula (I):

[0012]

[0013] Wherein, in formula (I),

[0014] R 1 is C1-C3 alkyl, -C6H5 or -CH2-C6H5;

[0015] R 21 、R 22 、R 23 、R 24 and R 25 are each independently selected from H, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl substituted with 1-6 halogens, nitro, cyano; and R 21 、R 22 、R 23 、R 24 and R 25 Not at the same time H;

[0016] R 3 and R 4 Each independently selected from H, -CH3;

[0017] X is H, C1-C3 alkyl, halogen, nitro or -CF3;

[0018] n is 0, 1 or 2.

[0019] The second aspect of the present invention provides a method for preparing the compound of the first aspect, comprising: subjecting the enol ester represented by formula (I-1) to a rearrangement reaction in the presence of a catalyst to obtain the compound represented by formula (I);

[0020] Formula (I): Formula (I-1):

[0021] The definitions of the groups in formula (I) and formula (I-1) are the same as those described in the first aspect above.

[0022] The third aspect of the present invention provides use of the triketo-benzimidazolone compound described in the first aspect in inhibiting HPPD activity in weeds.

[0023] The fourth aspect of the present invention provides a herbicide, which contains a herbicidally effective amount of at least one of the compounds described in the first aspect, and optionally contains an adjuvant.

[0024] The triketone-benzimidazolone compound provided by the present invention has excellent HPPD inhibitory effect, has significant inhibitory effect on weeds including broadleaf weeds, grass weeds and sedge weeds, and is highly safe for crops.

[0025] More specifically, the aforementioned triketone-benzimidazolone compounds provided by the present invention have significant control effects on at least one of Artemisia destructor, Shepherd's purse, Chenopodium album, Ramie, Galium, Veronica, Chickweed, Amaranthus chinensis, Solanum nigrum, Lantern Festival, Purslane, Amaranthus retroflexus, Cyperus rotundus, Echinochloa crus-galli, Goosegrass, Golden foxtail, Setaria viridis, Digitaria sanguinalis, Alopecurus japonica, Japanese Alopecurus tataricus, Aesculus multiflorus, Wild oats, Bromus, Leptochloa chinensis, Paspalum distachyon, Firefly rush, and Cyperus dimorphus, and are highly safe for crops such as corn, wheat, sorghum, peanuts, and rapeseed. DETAILED DESCRIPTION

[0026] The endpoints of the ranges and any values ​​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 endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0027] In the present invention, unless otherwise stated, the terms used are interpreted as follows:

[0028] The C1-C3 alkyl group represents any one of a methyl group, an ethyl group, a n-propyl group, and an isopropyl group.

[0029] -C6H5, represents phenyl.

[0030] -CH2-C6H5 represents benzyl.

[0031] Halogen refers to any one of fluorine, chlorine, bromine and iodine.

[0032] C1-C6 alkyl refers to an alkyl group with a total carbon atom number of 1-6, including straight-chain alkyl groups and branched-chain alkyl groups, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc.

[0033] C1-C6 alkoxy refers to an alkoxy group with a total carbon atom number of 1-6, including straight-chain alkoxy groups and branched-chain alkoxy groups, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy, etc.

[0034] The C1-C6 alkyl group substituted with 1 to 6 halogen groups means that, based on the aforementioned C1-C6 alkyl group, 1 to 6 H groups on the C1-C6 alkyl group are substituted with arbitrary halogen groups.

[0035] First aspect

[0036] As mentioned above, the first aspect of the present invention provides a triketone-benzimidazolone compound having a structure shown in formula (I):

[0037]

[0038] Wherein, in formula (I),

[0039] R 1 is C1-C3 alkyl, -C6H5 or -CH2-C6H5;

[0040] R 21 、R 22 、R 23 、R 24 and R 25 are each independently selected from H, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl substituted with 1-6 halogens, nitro, cyano; and R 21 、R 22 、 R 23 、R 24 and R 25 Not at the same time H;

[0041] R 3 and R 4 Each independently selected from H, -CH3;

[0042] X is H, C1-C3 alkyl, halogen, nitro or -CF3;

[0043] n is 0, 1 or 2.

[0044] According to a preferred embodiment, in formula (I),

[0045] R 1 is methyl, ethyl, n-propyl, isopropyl, -C6H5 or -CH2-C6H5;

[0046] R 21 、R 22 、R23 、R 24 and R 25 are each independently selected from H, F, Cl, Br, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl substituted with 1-6 halogens, nitro, and cyano; and R 21 、 R 22 、R 23 、R 24 and R 25 Not at the same time H;

[0047] R 3 and R 4 Each independently selected from H, -CH3;

[0048] X is H, methyl, ethyl, F, Cl, Br, nitro or -CF3;

[0049] n is 0 or 1.

[0050] According to another preferred embodiment, in formula (I),

[0051] R 1 is methyl, ethyl, -C6H5 or -CH2-C6H5;

[0052] R 21 、R 22 、R 23 、R 24 and R 25 Each is independently selected from H, F, Cl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, C1-C6 alkyl substituted with 1-6 halogens, nitro, cyano; and R 21 、R 22 、R 23 、R 24 and R 25 Not at the same time H;

[0053] R 3 and R 4 Each independently selected from H, -CH3;

[0054] X is H, methyl, ethyl, F, Cl, Br, nitro or -CF3;

[0055] n is 0 or 1.

[0056] According to a particularly preferred embodiment, the compound represented by formula (I) is selected from any one of the following:

[0057]

[0058]

[0059] The present invention does not particularly limit how to obtain the compound represented by formula (I). Those skilled in the art can obtain a suitable synthesis method by combining the structural formula provided by the present invention with conventional experimental means and known knowledge in the field of organic synthesis. In order to obtain higher yield and purity, the present invention provides the method described in the second aspect to prepare the compound represented by formula (I).

[0060] Second aspect

[0061] As mentioned above, the second aspect of the present invention provides a method for preparing the compound described in the first aspect, the method comprising: subjecting the enol ester represented by formula (I-1) to a rearrangement reaction in the presence of a catalyst to obtain the compound represented by formula (I);

[0062] Formula (I): Formula (I-1):

[0063] The definitions of the groups in formula (I) and formula (I-1) are the same as those described in the first aspect.

[0064] The present invention does not particularly limit how to obtain the starting materials represented by formula (I-1). Those skilled in the art can obtain a suitable synthesis method by using the structural formula provided by the present invention in combination with conventional experimental methods and known knowledge in the field of organic synthesis. The present invention will not be further described herein, and those skilled in the art should not be construed as limiting the present invention.

[0065] Preferably, the rearrangement reaction is carried out under alkaline conditions.

[0066] Preferably, the rearrangement reaction is carried out in the presence of acetone cyanohydrin.

[0067] Preferably, the rearrangement reaction is carried out in the presence of a solvent such as acetonitrile.

[0068] Preferably, the conditions for the rearrangement reaction include: a reaction temperature of 0°C to 60°C, and a reaction time of 2-48 hours; more preferably, the conditions for the rearrangement reaction include: a reaction temperature of 15°C to 45°C, and a reaction time of 10-30 hours.

[0069] The third aspect

[0070] As mentioned above, the third aspect of the present invention provides the use of the triketo-benzimidazolone compound described in the first aspect in inhibiting the HPPD activity of weeds.

[0071] Preferably, the weeds include at least one of broadleaf weeds, grass weeds and sedge weeds.

[0072] More preferably, the weeds are selected from at least one of: sophora flavescens, shepherd's purse, quinoa, velvet, cleaver, speedwell, chickweed, amaranth, nightshade, lantern grass, purslane, amaranth retroflexus, carp intestine, barnyard grass, goosegrass, golden foxtail, foxtail, crabgrass, alopecurus, Japanese alopecurus, aesculus fragrans, wild oats, brome, chinensis, paspalum distachyon, firefly rush, and sedge.

[0073] The fourth aspect

[0074] As mentioned above, the fourth aspect of the present invention provides a herbicide, which contains a herbicidally effective amount of at least one of the triketo-benzimidazolone compounds described in the first aspect, and optionally contains an auxiliary material.

[0075] Preferably, the content of the auxiliary material is 0.01-80% by weight.

[0076] In the present invention, the excipients may be various excipients conventionally used in the art, such as surfactants, solvents, etc. The present invention will not elaborate on this, and those skilled in the art should not interpret this as a limitation of the present invention.

[0077] Preferably, the formulation of the herbicide is selected from at least one of emulsifiable concentrate, suspension concentrate, wettable powder, dust, granule, aqueous solution, mother liquor and mother powder.

[0078] Instance section

[0079] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, all raw materials used in the examples are commercially available and are of analytical purity.

[0080] The room temperature mentioned below means about 25°C.

[0081] Preparation Example 1: Preparation of Compound 1

[0082]

[0083] At room temperature, 100 g of the compound 1-1 was added to a 2 L reaction flask. 1 L of glacial acetic acid was added with stirring. 128 g of ICl was dissolved in 400 mL of glacial acetic acid and added dropwise to the reaction system over 30 minutes with stirring. After the addition was complete, the reaction was stirred and continued for approximately 3 hours. After completion of the reaction, the reaction solution was filtered, and the resulting solid was washed with 800 mL of glacial acetic acid and dried to obtain Intermediate 1-2 in a 98% yield.

[0084] 100 g of intermediate 1-2 was added to a 2 L flask, 1 L of tetrahydrofuran was added, and then 113 g of triphosgene was added, followed by overnight reaction. After the reaction, the mixture was washed with saturated sodium carbonate solution and extracted with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and evaporated to obtain intermediate 1-3 with a yield of 90%.

[0085] 98.8g of intermediate 1-3 was added to a 2L single-necked flask, 1L of DMF was added, and 67.5g of KCO was added under stirring to continue the stirring reaction for about 30min. Then 69.5g of iodomethane was slowly added dropwise to the reaction system, and the reaction was stirred at room temperature overnight after dropwising. After completion of the reaction, 3L of water was added to the system, and the reaction system was extracted 3 times with 800mL of ethyl acetate at each time. The organic layers were merged, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain intermediate 1-4 in an 87% yield.

[0086] 89.9 g of intermediate 1-4 was added to a 2 L flask, and 700 mL of 1,4-dioxane was added, followed by 108.9 g of ammonium carbonate added in batches. The reaction was carried out at 80 ° C for 6 h. After the reaction was completed, it was cooled to room temperature and filtered. The filtrate was dried over anhydrous sodium sulfate, mixed, and passed through a column to obtain intermediate 1-5 with a yield of 83%.

[0087] 68.3 g of Intermediate 1-5 was added to a 2 L round-bottom flask, followed by 600 mL of dichloromethane solution. Subsequently, 77.7 g of iodosobenzene was added to the reaction mixture and stirred overnight at room temperature. After completion of the reaction, the mixture was filtered and the filter cake was washed with a small amount of dichloromethane to obtain a brown solid. This solid was dried to obtain Intermediate 1-6 in an 80% yield.

[0088] 5g of intermediate 1-6 was added to a 250mL single-necked flask, 35mL of DMF was added, and 11.3g of CsCO was added under stirring, and the stirring reaction was continued for about 30min. Then 6.4g of 2-methylbenzyl bromide was slowly added dropwise to the reaction system, and the reaction was stirred at room temperature overnight after completion of the addition. After completion of the reaction, 150mL of water was added to the system, and the reaction system was extracted with 50mL of ethyl acetate 3 times at each time. The organic layers were combined and dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain intermediate 1-7 in an 86% yield.

[0089] 5.8 g of Intermediate 1-7 and 2.7 g of CuCN were added to a 200 mL two-necked flask, followed by 50 mL of dry DMF. The reaction was refluxed for 12 hours. After completion, the DMF was removed by distillation under reduced pressure. After cooling, 50 mL of acetone was added to the reaction flask, and stirred vigorously for 20 minutes. Unreacted CuCN was removed by filtration. The filtrate was mixed and filtered to obtain Intermediate 1-8 in an 81% yield.

[0090] 3.5 g of intermediate 1-8 was added to a 250 mL reaction flask, and 30 mL of glacial acetic acid, 30 mL of water, and 30 mL of concentrated sulfuric acid were added with stirring. The temperature was raised to 120°C and the reaction was allowed to proceed for 12 h. After completion of the reaction, the reaction system was cooled to room temperature and poured into a beaker containing 150 mL of ice water. The system was extracted three times with 50 mL of ethyl acetate each time. After the extraction, the organic layers were combined and then extracted three times with 30 mL of 50% sodium hydroxide solution each time. The aqueous layers were combined and acidified to a pH of approximately 1 with concentrated hydrochloric acid. A large amount of solid (i.e., intermediate 1-9) was precipitated on standing. The pure product was obtained by filtration with suction in a yield of 70%.

[0091] 2.6 g of intermediate 1-9 was added to a 100 mL single-necked flask, followed by 30 mL of dry THF. 2 g of SOCl2 was slowly added dropwise at room temperature. After the addition was complete, the mixture was refluxed at 70°C for approximately 1.5 h. The reaction progress was monitored by TLC. After completion, the solvent was removed from the flask. 20 mL of dry CH2Cl2, 1.9 g of 1-10a, and 3.4 g of Et3N were added. The reaction was allowed to react for approximately 0.5 h. TLC was used to monitor the disappearance of the acid chloride. After completion, the reaction was washed once with 25 mL of water and twice with 10 mL of saturated NaHCO3. The mixture was dried over anhydrous Na2SO4 and filtered through a column to obtain intermediate 1-11 in a 73% yield.

[0092] 2.5g of intermediate 1-11 was added to a 100mL two-necked flask, and 30mL of anhydrous acetonitrile was added. Under N2 protection, 1.2g of Et3N and 52mg of acetone cyanohydrin were added. The reaction was carried out at room temperature (about 25°C) for 15h and TLC was followed until the reaction starting materials disappeared. After the reaction was completed, the acetonitrile was removed and washed with 40mL of 1 mol / L hydrochloric acid. The reaction system was extracted with 20mL of dichloromethane three times each. The organic phases were combined and washed with saturated sodium chloride solution 3 times with 10mL each. The organic layer was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to obtain a light yellow oil. The obtained oil was recrystallized with 10mL of methanol to obtain compound 1.

[0093] Preparation Example 2: Preparation of Compound 30

[0094]

[0095] 5 g of intermediate 1-6 was added to a 250 mL single-necked flask, followed by 35 mL of DMF. 11.3 g of CsCO was added with stirring and the reaction was continued with stirring for approximately 30 minutes. 6.5 g of 2-fluorobenzyl bromide was then slowly added dropwise to the reaction system. After the addition was complete, the reaction was stirred at room temperature overnight. After completion of the reaction, 150 mL of water was added to the system, and the reaction system was extracted three times with 50 mL of ethyl acetate each time. The organic layers were combined, dried over anhydrous sodium sulfate, and the solvent removed under reduced pressure to obtain intermediate 1-12 in an 81% yield.

[0096] 5.5 g of Intermediate 1-12 and 2.5 g of CuCN were added to a 200 mL two-necked flask, followed by 50 mL of dry DMF. The reaction was refluxed for 12 hours. After completion, the DMF was removed by distillation under reduced pressure. After cooling, 50 mL of acetone was added to the reaction flask, and stirred vigorously for 20 minutes. Unreacted CuCN was removed by filtration. The filtrate was mixed and filtered to obtain Intermediate 1-13 in an 82% yield.

[0097] 3.4 g of intermediate 1-13 was added to a 250 mL reaction flask. 30 mL of glacial acetic acid, 30 mL of water, and 30 mL of concentrated sulfuric acid were added with stirring. The temperature was raised to 120°C and the reaction was allowed to react for 12 h. After completion of the reaction, the reaction system was cooled to room temperature and poured into a beaker containing 150 mL of ice water. The system was extracted three times with 50 mL of ethyl acetate each time. After extraction, the organic layers were combined and then extracted three times with 30 mL of 50% sodium hydroxide solution each time. The aqueous layers were combined and acidified to a pH of approximately 1 with concentrated hydrochloric acid. A large amount of solid (i.e., intermediate 1-14) was precipitated on standing. The pure product was obtained by filtration with suction in a yield of 73%.

[0098] 2.6 g of intermediate 1-14 was added to a 100 mL single-necked flask, followed by 30 mL of dry THF. 2 g of SOCl2 was slowly added dropwise at room temperature. After the addition was complete, the mixture was refluxed at 70°C for approximately 1.5 hours, monitored by TLC. After completion, the solvent was removed. 20 mL of dry CH2Cl2, 2.1 g of 1-10b, and 3.4 g of Et3N were added, and the reaction was continued for approximately 0.5 hours, monitored by TLC, until the acid chloride disappeared. After completion, the reaction was washed once with 25 mL of water and twice with 10 mL of saturated NaHCO3, dried over anhydrous Na2SO4, and filtered through a column to obtain intermediate 1-15 in a 71% yield.

[0099] 2.5g of intermediate 1-15 was added to a 100mL two-necked flask, and 30mL of anhydrous acetonitrile was added. 1.2g of Et3N and 52mg of acetone cyanohydrin were added under N2 protection. The reaction was carried out at room temperature (about 25°C) for 15h and TLC was followed until the reaction starting materials disappeared. After the reaction was completed, the acetonitrile was dried, washed with 40mL of 1 mol / L hydrochloric acid, and the reaction system was extracted with 20mL of dichloromethane 3 times each. The organic phases were combined and washed 3 times with 10mL of saturated sodium chloride solution each time. The organic layer was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to obtain a light yellow oil, which was recrystallized with 10mL of methanol to obtain compound 30.

[0100] Preparation Example 3: Preparation of Compound 36

[0101]

[0102] Add 2g of intermediate 1-14 to a 100mL single-necked flask, followed by 25mL of dry THF. Slowly add 1.5g of SOCl2 dropwise at room temperature. After complete addition, reflux at 70°C for approximately 1.5h. TLC is used to monitor the reaction progress. After completion, remove the solvent. Add 20mL of dry CH2Cl2, 2.1g of 1-10c, and 2.6g of Et3N. Reaction is continued for approximately 0.5h. TLC is used to monitor the disappearance of the acid chloride. After completion, the reaction is washed once with 25mL of water and twice with 10mL of saturated NaHCO3. Dry over anhydrous Na2SO4 and filter through a column to obtain intermediate 1-16 in a 73% yield.

[0103] 2g of intermediate 1-16 was added to a 100mL two-necked flask, and 30mL of anhydrous acetonitrile was added. Under N2 protection, 1g of Et3N and 54mg of acetone cyanohydrin were added. The reaction was carried out at room temperature (about 25°C) for 15h and TLC was followed until the reaction starting materials disappeared. After the reaction was completed, the acetonitrile was dried, washed with 30mL of 1 mol / L hydrochloric acid, and the reaction system was extracted with 20mL of dichloromethane three times each. The organic phases were combined and washed with saturated sodium chloride solution 3 times with 10mL each, and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to obtain a light yellow oil, which was recrystallized with 10mL of methanol to obtain compound 36.

[0104] Preparation Example 4: Preparation of Compound 48

[0105]

[0106] At room temperature, 100 g of compound 1-17 was added to a 2 L reaction flask. 1 L of glacial acetic acid was added with stirring. 104 g of ICl was dissolved in 400 mL of glacial acetic acid and added dropwise to the reaction system over 30 minutes with stirring. After the addition was complete, the reaction was stirred and continued for approximately 3 hours. After completion of the reaction, the reaction solution was filtered, and the resulting solid was washed with 800 mL of glacial acetic acid and dried to obtain Intermediate 1-18 in a 95% yield.

[0107] 100 g of intermediate 1-18 was added to a 2 L flask, 1 L of tetrahydrofuran was added, and then 120 g of triphosgene was added, followed by overnight reaction. After the reaction, the mixture was washed with saturated sodium carbonate solution and extracted with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and evaporated to obtain intermediate 1-19 in a yield of 87%.

[0108] 94.6g of intermediate 1-19 was added to a 2L single-necked flask, 1L of DMF was added, and 81.1g of KCO was added under stirring, and the reaction was continued with stirring for about 30 minutes. Then 84.1g of iodomethane was slowly added dropwise to the reaction system. After the addition was complete, the reaction was stirred at room temperature overnight. After completion of the reaction, 3L of water was added to the system, and the reaction system was extracted with 800mL of ethyl acetate three times each. The organic layers were combined, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain intermediate 1-20 in an 82% yield.

[0109] 81 g of intermediate 1-20 was added to a 2 L flask, and 700 mL of 1,4-dioxane was added, followed by 92.5 g of ammonium carbonate added in batches. The reaction was carried out at 80 ° C for 6 h. After the reaction was completed, it was cooled to room temperature and filtered. The filtrate was dried over anhydrous sodium sulfate, mixed, and passed through a column to obtain intermediate 1-21 with a yield of 80%.

[0110] 59.8 g of Intermediate 1-21 was added to a 2 L round-bottom flask, followed by 600 mL of dichloromethane solution. 84.8 g of iodosobenzene was then added to the mixture, and stirred overnight at room temperature. After the reaction was complete, the mixture was filtered, and the filter cake was washed with a small amount of dichloromethane to obtain a brown solid. Drying afforded Intermediate 1-22 in a 79% yield.

[0111] 5 g of intermediate 1-22 was added to a 250 mL single-necked flask, followed by 35 mL of DMF. 10.6 g of Cs2CO3 was added with stirring and the reaction was continued with stirring for approximately 30 minutes. 6.1 g of 2-fluorobenzyl bromide was then slowly added dropwise to the reaction system. After the addition was complete, the reaction was stirred at room temperature overnight. After completion of the reaction, 150 mL of water was added to the system, and the reaction system was extracted three times with 50 mL of ethyl acetate each time. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to obtain intermediate 1-23 in an 80% yield.

[0112] 5.4 g of Intermediate 1-23 and 2.3 g of CuCN were added to a 200 mL two-necked flask, followed by 50 mL of dry DMF. The reaction was refluxed for 12 hours. After completion, the DMF was removed by distillation under reduced pressure. After cooling, 50 mL of acetone was added to the reaction flask, and stirred vigorously for 20 minutes. Unreacted CuCN was removed by filtration. The filtrate was mixed and filtered to obtain Intermediate 1-24 in a yield of 78%.

[0113] 3.2 g of intermediate 1-24 was added to a 250 mL reaction flask. 30 mL of glacial acetic acid, 30 mL of water, and 30 mL of concentrated sulfuric acid were added with stirring. The temperature was raised to 120°C and the reaction was allowed to proceed for 12 h. After completion of the reaction, the reaction system was cooled to room temperature and poured into a beaker containing 150 mL of ice water. The system was extracted three times with 50 mL of ethyl acetate each time. After the extraction, the organic layers were combined and then extracted three times with 30 mL of 50% sodium hydroxide solution each time. The aqueous layers were combined and acidified to a pH of approximately 1 with concentrated hydrochloric acid. A large amount of solid (i.e., intermediate 1-25) was precipitated on standing. The pure product was obtained by filtration with suction in a yield of 71%.

[0114] 2.4 g of intermediate 1-25 was added to a 100 mL single-necked flask, followed by 30 mL of dry THF. 1.7 g of SOCl2 was slowly added dropwise at room temperature. After the addition was complete, the mixture was refluxed at 70°C for approximately 1.5 h. The reaction progress was monitored by TLC. After completion, the solvent was removed from the flask. 20 mL of dry CH2Cl2, 1.6 g of 1-10a, and 2.9 g of Et3N were added. The reaction was allowed to react for approximately 0.5 h. TLC was used to monitor the disappearance of the acid chloride. After completion, the reaction was washed once with 25 mL of water and twice with 10 mL of saturated NaHCO3. The mixture was dried over anhydrous Na2SO4 and filtered through a column to obtain intermediate 1-26 in a 75% yield.

[0115] 2.3g of intermediate 1-26 was added to a 100mL two-necked flask, and 30mL of anhydrous acetonitrile was added. 1.1g of Et3N and 46mg of acetone cyanohydrin were added under N2 protection. The reaction was reacted at room temperature for 15h, and TLC was followed until the reaction raw materials disappeared. After completion of the reaction, the acetonitrile was removed and washed with 40mL of 1 mol / L hydrochloric acid, and the reaction system was extracted with 20mL of dichloromethane 3 times each. The organic phases were combined, washed 3 times with saturated sodium chloride solution 10mL each, and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to obtain a light yellow oil, which was recrystallized with 10mL of methanol to obtain compound 48.

[0116] Table 1 lists the characterization data of some compounds of the present invention. The yields in Table 1 are calculated based on the main raw materials in the last step of the chemical reaction to obtain the compound.

[0117] Table 1

[0118]

[0119]

[0120]

[0121]

[0122] Test Example 1

[0123] Initial screening test (pot culture): The target crops and test crops are listed in Tables 3 to 13. Post-emergence foliar spray: Fill a 7-cm inner diameter paper cup 3 / 4 full with a composite soil solution (garden soil: seedling medium, 1:2, v / v). Directly sow weeds, cover with 0.2 cm of soil, and wait until they reach the 4-5 leaf stage. Apply the compound of this invention at a dose of 320 g.ai / ha (grams per hectare) using an automated spray tower. After the spray solution on the weed or crop leaves has dried, transfer the weeds or crop to a greenhouse (70% humidity) for incubation. Results are assessed after 30 days.

[0124] In addition, some of the compounds of the present invention were rescreened with a further reduced dosage.

[0125] The growth inhibition rate was evaluated by visual inspection, and the rating was performed according to the conditions shown in Table 2. The test results are shown in Tables 3 to 13.

[0126] Table 2

[0127] (％) Evaluation (inhibition, deformity, albinism, etc.) Growth inhibition rate level 0-4 There is no effect on weed or crop growth and no symptoms of efficacy. 0 5-29 Slightly affects the growth of weeds or crops, with no obvious symptoms of efficacy 1 30-49 It inhibits the growth of weeds or crops without obvious symptoms of efficacy. 2 50-69 It has an impact on the growth of weeds or crops and has obvious efficacy symptoms. 3 70-89 Weeds or crops are severely inhibited from growing. 4 90-100 Weed or crop death. 5

[0128] Table 3

[0129]

[0130]

[0131] Table 4

[0132]

[0133]

[0134] Table 5

[0135]

[0136] Table 6

[0137]

[0138] Table 7

[0139]

[0140]

[0141] Table 8

[0142]

[0143] Table 9

[0144]

[0145]

[0146] Table 10

[0147]

[0148] Table 11

[0149]

[0150]

[0151] Table 12

[0152]

[0153] Table 13

[0154]

[0155]

[0156] Test Example 2

[0157] Enzyme-Level Inhibitory Activity Test (Conjugated Method): The inventors tested the inhibitory activity of some compounds against Arabidopsis HPPD (AtHPPD) using a conjugated method reported in the literature (Amaya, Alphonso A. et al. Kinetic analysis of human homogentisate 1,2-dioxygenase. Archives of Biochemistry & Biophysics 2004, 421, 135-142). Weigh 2-3 mg of compound into a 1.5 mL EPES tube and centrifuge until ready for use. Based on the inhibitor's purity, relative molecular mass, and mass, the volume of a 10 mM stock solution was calculated. The corresponding volume of DMSO was added and mixed thoroughly. The 10 mM inhibitor solution was then diluted again with DMSO to 1 mM for use. Finally, the inhibitor was diluted to 10 μM in 20 mM HEPES buffer for initial screening. After the initial screening, the inhibitor was diluted according to the inhibition rate obtained in the initial screening to prepare 11 concentrations to ensure that the inhibition rate of each concentration of the inhibitor on the enzyme was evenly distributed. The test was performed using a coupled method on a microplate reader, and the test was repeated three times in parallel. The average value was taken as the IC value of the inhibitor on AtHPPD. 50 The commercial inhibitor mesotrione was used as a control agent.

[0158] The results are shown in Table 14.

[0159] Table 14: Evaluation of the inhibitory activity of some compounds on AtHPPD enzyme

[0160] Compound number <![CDATA[IC 50 (μM)]]> Compound number <![CDATA[IC 50 (μM)]]> 1 0.117±0.002 48 0.193±0.003 2 0.187±0.006 49 0.206±0.006 7 0.211±0.009 50 0.226±0.004 10 0.267±0.004 51 0.310±0.007 Mesotrione 0.289±0.012

[0161] As shown in Table 3, at a dosage of 320 g.ai / ha, most of the compounds in this series had a certain control effect on the tested barnyard grass, foxtail grass, crabgrass, amaranth, and velvetleaf. In particular, compounds 1, 2, 7, 8, 9, 16, 20, 24, 30, 35, 38, 40, and 43 all achieved a control effect of more than 90% on the five tested weeds.

[0162] As can be seen from Table 4, when the dosage was reduced to 120 g.ai / ha, the control effect of compound 1 on the tested barnyard grass, foxtail grass, crabgrass, amaranth, velvet, wild oats, brome, and multifloral ryegrass reached more than 90%; the control effect of compound 2 on the tested barnyard grass, crabgrass, amaranth, velvet, wild oats, brome, and multifloral ryegrass reached more than 90%; the control effect of compound 16 on the tested barnyard grass, foxtail grass, crabgrass, amaranth, velvet, wild oats, and brome reached more than 90%; the control effect of compound 20 on the tested barnyard grass, foxtail grass, crabgrass, amaranth, wild oats, brome, and multifloral ryegrass reached more than 90%.

[0163] As shown in Tables 5 to 13, compounds 2, 7, 8, 9, 10, 11, 13, 16, and 20 exhibited excellent crop safety in peanuts and wheat at dosages of 120, 60, and 30 g.ai / ha.

[0164] As shown in Table 14, in enzyme activity tests, compounds 1, 2, 7, 10, 48, 49, and 50 exhibited superior inhibitory activity against AtHPPD compared to the control agent, mesotrione. While compound 51's inhibitory activity against AtHPPD was inferior to that of the commercial control agent, mesotrione, it was still on the same order of magnitude as the control agent and exhibited excellent inhibitory activity, thus showing promising commercialization prospects.

[0165] Therefore, the compounds provided by the present invention have high herbicidal activity against broadleaf weeds, grass weeds and sedge weeds, for example, broadleaf weeds: Artemisia selengensis, shepherd's purse, quinoa, velvetleaf, cleaver, speedwell, chickweed, amaranth, nightshade, lantern grass, purslane, amaranth retroflexus, and carp intestine; grass weeds: barnyard grass, goosegrass, golden foxtail, foxtail, crabgrass, alopecurus, Japanese alopecurus, aesculus, wild oats, brome, jackfruit, and paspalum distachyon; and sedge family: firefly rush and cyperus dimorphus.

[0166] Furthermore, the compound of the present invention is highly safe to crops.

[0167] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A triketone-benzimidazolone compound, characterized in that The compound has the structure shown in formula (I): Formula (I) Wherein, in formula (I), The compound shown is selected from any one of the following: 。 2. A method for preparing the compound according to claim 1, characterized in that: The method comprises: in the presence of a catalyst, performing a rearrangement reaction on an enol ester represented by formula (I-1); obtaining a compound represented by formula (I); Formula (I): Formula (I-1): , The definitions of the groups in formula (I) and formula (I-1) are the same as those in claim 1.

3. Use of the triketone-benzimidazolone compound according to claim 1 in inhibiting HPPD activity in weeds.

4. Use of the triketone-benzimidazolone compound according to claim 1 in controlling weeds.

5. The use according to claim 4, characterized in that The weeds are at least one of broadleaf weeds, grass weeds and sedge weeds.

6. The use according to claim 4 or 5, characterized in that The weeds are selected from at least one of: sophora flavescens, shepherd's purse, quinoa, velvet, cleaver, speedwell, chickweed, amaranth, nightshade, lantern grass, purslane, amaranth retroflexus, carp intestine, barnyard grass, goosegrass, golden foxtail, foxtail, crabgrass, alopecurus, Japanese alopecurus, aesculus, wild oats, brome, chinensis, paspalum distachyon, firefly rush, and sedge.

7. A herbicide comprising a herbicidally effective amount of at least one of the compounds according to claim 1, and optionally containing an adjuvant.

8. The herbicide according to claim 7, wherein The content of the auxiliary material is 0.01-80% by weight.

9. The herbicide according to claim 7 or 8, wherein The formulation of the herbicide is selected from at least one of emulsifiable concentrate, suspension, powder, granule, aqueous solution, mother liquor and mother powder.

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