Compound containing triazole ring structure, preparation method and application thereof, and herbicide

Abstract

The invention relates to the field of pesticides and herbicides, and discloses a compound containing a triazole ring structure, a preparation method and application thereof, and a herbicide. The compound has a structure as shown in a formula (I). The compound provided by the invention is a high-activity PDS inhibitor with a brand new skeleton structure, and has a good weed control effect.

Description

Technical Field

[0001] This invention relates to the field of pesticides and herbicides, specifically to a compound containing a triazole ring structure, its preparation method and application, and a herbicide. Background Technology

[0002] Weeds have long been considered a key factor affecting grain yield, and the use of herbicides is the most effective way to control them. With the continued use of single-mode herbicides, enormous selective pressure has been placed on weeds, and the resulting problem of weed resistance has been frequently reported in recent years.

[0003] To date, there have been 530 cases of herbicide-resistant weeds worldwide, involving 272 plant species (155 dicotyledons and 117 monocotyledons). The most effective way to address this problem is to develop highly active compounds with novel modes of action or skeletal structures to improve resistance to existing herbicides.

[0004] At the same time, although first-generation herbicides had a positive impact on agriculture, their high persistence and non-target toxicity caused significant adverse effects on the environment and human health.

[0005] As people's awareness of food safety gradually increases, new requirements have been put forward for the development of green pesticides, which means that while we focus on the high activity of herbicides, we must also balance the safety of non-target organisms.

[0006] In the development of green herbicides, carotenoids, as indispensable auxiliary pigments in plant growth and photosynthesis, and given the lack of carotenoid biosynthesis pathways in humans and other mammals, have become a key pathway for developing broad-spectrum, green herbicides. Hydroxylenol dehydrogenase (PDS, EC: 1.3.5.5), a key rate-limiting enzyme in the plant carotenoid synthesis pathway, has led to the commercialization of seven whitening herbicides targeting PDS in the past few decades. Based on their structural characteristics, these herbicides can be divided into three categories: phenyl ethers (such as pyrifluquinazon, beflurazole, and pyrifluquinazon), N-phenyl heterocyclic herbicides (such as norflurazole and flurflurazole), and diphenyl heterocyclic herbicides (such as fluflurazole and fluflurazole).

[0007] Over the past few decades, seven bleaching herbicides targeting PDS have been commercialized. Based on their structural characteristics, these herbicides can be divided into three categories: phenyl ethers (such as pyrifluquinazon, flubutyrazole, and flupyrfluquinazon), N-phenyl heterocyclic herbicides (such as pyrazosulfuron and flurflufenoxam), and diphenyl heterocyclic herbicides (such as furazolidone and fluazinam). These herbicides inhibit PDS, thereby blocking the biosynthesis of carotenoids in plants. This leads to an excess of reactive oxygen species produced during photosynthesis that cannot be quenched in time, resulting in the oxidative degradation of chlorophyll and ultimately causing bleaching and death of the plant.

[0008] Among them, pyrfluthrin was first developed by Bayer in 1982. Due to its broad spectrum, dual-effect of predation and suppression, and long residual effect, it has the largest sales volume among PDS targeted herbicides. However, pyrfluthrin has been developed for more than 40 years, and the resulting weed resistance problem has been frequently discovered and studied in recent years. Since 2003, almost no PDS inhibitors with completely new skeleton structures have been reported.

[0009] Given the limited variety of PDS-targeting pharmacophores and the frequent occurrence of herbicide resistance, it is highly significant to develop highly active PDS inhibitors with novel scaffold structures. Summary of the Invention

[0010] The purpose of this invention is to develop highly active PDS inhibitors with novel scaffold structures.

[0011] To achieve the above objectives, a first aspect of the present invention provides a compound containing a triazole ring structure, the compound having the structure shown in formula (I).

[0012]

[0013] In equation (I),

[0014] X is either O or S;

[0015] R 11 R 12 R 13 R 14 and R 15 Each is independently selected from H, halogen, or C substituted with at least one halogen. 1-12 Alkyl groups, C substituted with at least one halogen 1-12 Any one of the alkoxy groups; and R 11 R 12 R 13 R 14 and R 15 They are not both H.

[0016] A second aspect of the present invention provides a method for preparing the compound containing a triazole ring structure as described in the first aspect, comprising:

[0017] In the presence of a solvent, the compound shown in formula (II-1) is reacted with the compound shown in formula (II-2) to obtain the compound with a triazole ring structure shown in formula (I);

[0018]

[0019] The definitions of the groups in formulas (II-1), (II-2) and (I) are the same as the definitions of the groups in the compounds containing the triazole ring structure described in the first aspect.

[0020] The third aspect of the present invention provides the use of the triazole ring-containing compound described in the first aspect as a PDS inhibitor in weed control.

[0021] A fourth aspect of the present invention provides a herbicide containing an effective amount of at least one of the compounds containing a triazole ring structure described in the first aspect for controlling weeds.

[0022] The compounds of the present invention have at least the following advantages:

[0023] 1) Introducing two or three substituents into the benzene ring at the 3-position of the triazole ring of the compound of the present invention is significantly beneficial to improving the activity. The introduction of CF3 and Cl at the ortho position helps to improve the activity of the compound, and the introduction of halogen atoms, especially F and Cl, can improve the activity of the compound.

[0024] 2) The carbamate structure on the side chain at the 3-position of the triazole ring of the compounds of the present invention is crucial to the activity of the compounds;

[0025] 3) The introduction of a trifluoromethyl group at the 4-position of the benzene ring of the triazole ring in the compound of the present invention is more beneficial to the activity of the compound.

[0026] Furthermore, the compounds of the present invention not only exhibit excellent herbicidal effects at high application rates, but also show high inhibitory activity against lambsquarters, mustard, and sorrel even at medium and low doses of 187.5-375 g ai / ha. The inhibitory activity of some compounds is even better than that of the commercial herbicide pyrifluquinazon.

[0027] In particular, while exhibiting excellent and broad-spectrum control effects against broadleaf weeds, the compounds of the present invention also show relatively high tolerance to corn and wheat. This indicates that the compounds of the present invention can serve as a new potential herbicide for the management of broadleaf weeds in corn and wheat fields. Detailed Implementation

[0028] 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.

[0029] In this invention, unless otherwise specified, groups of the same type have similar interpretations, and will not be described in detail here.

[0030] C 1-12 Alkyl groups refer to alkyl groups with a total number of carbon atoms of 1-12, including straight-chain alkyl groups and branched alkyl groups. For example, they can be straight-chain alkyl groups or branched alkyl groups with a total number of carbon atoms of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc. Regarding "C 1-10 Alkyl group, C 1-8 Alkyl group, C 1-6 "alkyl" has a similar interpretation, except that the number of carbon atoms is different.

[0031] C substituted by at least one halogen 1-12 Alkyl groups, representing alkyl groups with a total number of carbon atoms of 1-12, include straight-chain alkyl groups and branched-chain alkyl groups, and the C... 1-12 At least one H in the alkyl group is replaced by a halogen atom selected from halogens, for example, the C 1-12 The 1, 2, 3, 4, 5, 6, 7, 8, and 9 H atoms in the alkyl group are replaced by one or more halogen atoms selected from fluorine, chlorine, bromine, and iodine. For example, they can be trifluoromethyl, difluoromethyl, monofluoromethyl, monofluoroethyl, difluoroethyl, trifluoroethyl, etc. This refers to C atoms substituted with 1-9 halogens. 1-8 Alkyl groups, C6 groups substituted with 1-9 halogens 1-6 "alkyl" has a similar interpretation, except that the number of carbon atoms is different.

[0032] C substituted by at least one halogen 1-12 The alkoxy group refers to an alkoxy group with a total number of carbon atoms of 1-12, including straight-chain alkoxy groups and branched-chain alkoxy groups, and the C... 1-12 At least one H in the alkoxy group is replaced by a halogen atom selected from halogens, such as the C... 1-12The 1, 2, 3, 4, 5, 6, 7, 8, and 9 H atoms in the alkoxy group are replaced by one or more halogen atoms selected from fluorine, chlorine, bromine, and iodine. For example, they can be trifluoromethoxy, difluoromethoxy, monofluoromethoxy, monofluoroethoxy, difluoroethoxy, trifluoroethoxy, etc. This refers to C atoms substituted with 1-9 halogens. 1-8 "alkoxy groups", "C groups substituted with 1-9 halogens" 1-6 The "alkoxy group" has a similar explanation, except that the number of carbon atoms is different.

[0033] As previously described, a first aspect of the present invention provides a compound containing a triazole ring structure having the structure shown in formula (I).

[0034]

[0035] In equation (I),

[0036] X is either O or S;

[0037] R 11 R 12 R 13 R 14 and R 15 Each is independently selected from H, halogen, or C substituted with at least one halogen. 1-12 Alkyl groups, C substituted with at least one halogen 1-12 Any one of the alkoxy groups; and R 11 R 12 R 13 R 14 and R 15 They are not both H.

[0038] Preferably, in formula (I),

[0039] X is either O or S;

[0040] R 11 R 12 R 13 R 14 and R 15 Each is independently selected from H, fluorine, chlorine, bromine, or C substituted with 1-12 halogens. 1-10 Alkyl groups, C substituted with 1-12 halogens 1-10 Any one of the alkoxy groups; and R 11 R 12 R 13 R 14 and R 15 They are not both H.

[0041] More preferably, in equation (I),

[0042] X is either O or S;

[0043] R 11 R 12 R 13 R 14 and R 15 Each is independently selected from H, fluorine, chlorine, bromine, or C substituted with 1-12 halogens. 1-6 Alkyl groups, C substituted with 1-12 halogens 1-6 Any one of the alkoxy groups; and R 11 R 12 R 13 R 14 and R 15 They are not both H.

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

[0045] X is either O or S;

[0046] R 11 R 12 R 13 R 14 and R 15 Each is independently selected from any one of H, fluorine, chlorine, bromine, trifluoromethyl, and trifluoromethoxy; and R 11 R 12 R 13 R 14 and R 15 They are not both H.

[0047] In a further preferred embodiment, the compound represented by formula (I) is selected from any one of the following:

[0048] Compound 1a: X is O, R 13 For Cl, R 11 R 12 R 14 and R 15 All are H;

[0049] Compound 1b: X is O, R 11 For CF3, R 13 For Cl, R 12 R 14 and R 15 All are H;

[0050] Compound 1c: X is O, R 11 For Cl, R 15 For CF3, R 12 R 13 and R 14 All are H;

[0051] Compound 1d: X is O, R 11 For Cl, R 13 For Br, R 15 For OCF3, R 12 and R 14 All are H;

[0052] Compound 1e: X is O, R 11 For Br, R 13 For Cl, R 15 For CF3, R 12 and R 14 All are H;

[0053] Compound 1f: X is O, R 12 and R 14 For CF3, R 11 R 13 R 15 All are H;

[0054] Compound 1g: X is O, R 11 and R 13 For F, R 12 R 14 R 15 All are H;

[0055] Compound 1h: X is O, R 12 For CF3, R 13 For Cl, R 11 R 14 R 15 All are H;

[0056] Compound 1i: X is O, R 12 and R 13 For Cl, R 11 R 14 R 15 All are H;

[0057] Compound 1j: X is O, R 11 and R 13 For F, R 12 and R 14 For Cl, R 15 For H;

[0058] Compound 1k: X is O, R 13 For F, R 11 R 12 R 14 and R 15 All are H;

[0059] Compound 1l: X is O, R 12 For F, R14 For CF3, R 11 R 13 R 15 All are H;

[0060] Compound 1m: X is O, R 11 and R 13 For Cl, R 12 R 14 R 15 All are H;

[0061] Compound 1n: X is O, R 11 For Br, R 13 For F, R 15 For CF3, R 12 and R 14 All are H;

[0062] Compound 1o: X is O, R 11 For Cl, R 13 and R 15 For F, R 12 and R 14 All are H;

[0063] Compound 1p: X is O, R 11 For F, R 13 For Cl, R 12 R 14 R 15 All are H;

[0064] Compound 2a: X is S, R 13 For Cl, R 11 R 12 R 14 and R 15 All are H;

[0065] Compound 2b: X is S, R 11 and R 13 For Cl, R 12 R 14 R 15 All are H;

[0066] Compound 2c: X is S, R 11 and R 13 For Br, R 15 For CF3, R 12 and R 14 All are H;

[0067] Compound 2d: X is S, R 11 For Br, R 13 For Cl, R 15 For CF3, R 12and R 14 All are H;

[0068] Compound 2e: X is S, R 11 For Cl, R 13 For Br, R 15 For OCF3, R 12 and R 14 All are H;

[0069] Compound 2f: X is S, R 11 For Cl, R 13 and R 15 For F, R 12 and R 14 All are H;

[0070] Compound 2g: X is S, R 11 For CF3, R 13 For Cl, R 12 R 14 and R 15 All are H;

[0071] Compound 2h: X is S, R 12 For F, R 14 For CF3, R 11 R 13 and R 15 All are H;

[0072] Compound 2i: X is S, R 11 and R 13 For F, R 12 R 14 and R 15 All are H;

[0073] Compound 2j: X is S, R 12 and R 13 For Cl, R 11 R 14 and R 15 All are H;

[0074] Compound 2k: X is S, R 12 For CF3, R 13 For Cl, R 11 R 14 and R 15 All are H;

[0075] Compound 2l: X is S, R 13 For F, R 11 R 12 R 14 and R 15 All are H.

[0076] This invention does not impose any particular limitation on the specific methods for preparing the aforementioned compounds containing triazole ring structures. Those skilled in the art can obtain the aforementioned compounds containing triazole ring structures based on the specific structural formulas provided by this invention, combined with known knowledge in the field of organic synthesis. Furthermore, several examples are exemplarily listed below to illustrate the preparation methods of the compounds containing triazole ring structures of this invention. Those skilled in the art can also obtain specific preparation methods for all other compounds containing triazole ring structures by changing the types of raw materials according to the preparation methods of the compounds containing triazole ring structures described below. This invention will not further describe in detail the preparation methods for all compounds containing triazole ring structures, and this should not be construed as a limitation of the invention. However, in order to obtain target compounds with higher purity and / or yield, as mentioned above, a second aspect of this invention provides a method for preparing the compounds containing triazole ring structures described in the first aspect, comprising:

[0077] In the presence of a solvent, the compound shown in formula (II-1) is reacted with the compound shown in formula (II-2) to obtain the compound with a triazole ring structure shown in formula (I);

[0078]

[0079] The definitions of the groups in formulas (II-1), (II-2) and (I) correspond to the definitions of the groups in the compounds containing triazole ring structures described in the first aspect.

[0080] The present invention does not have any particular requirements for the solvent, and various organic solvents commonly used in the art can be used. For example, it can be one or more of N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethyldecylamide, N,N-dimethylformamide, trimethylbenzene, tetramethylbenzene, xylene, toluene, octane, heptane, methanol, isopropanol, n-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1,4-dioxane, and cyclohexanone.

[0081] Preferably, the temperature of the contact reaction is 50-120°C.

[0082] This invention does not impose any particular requirements on the source of the raw materials described in formula (II-1) and the raw materials shown in formula (II-2). They can be prepared using methods commonly used in the art, or they can be obtained commercially. This invention does not impose any particular limitations in this regard, and those skilled in the art should not understand this as a limitation of the invention.

[0083] As previously stated, the third aspect of the present invention provides the use of the triazole ring-containing compound described in the first aspect as a PDS inhibitor in weed control.

[0084] Preferably, the weeds are selected from at least one of broadleaf weeds, dicotyledonous weeds, grass weeds, and monocotyledonous weeds.

[0085] Preferably, the weeds are selected from at least one of the following: *Hemiberlesia lataniae*, *Hemiberlesia sapiens*, *Poa annua*, *Chenopodium album*, *Mustard greens*, *Rumex japonica*, *Abutilon theophrasti*, *Digitaria sanguinalis*, *Amaranthus retroflexus*, *Barnyard grass*, *Eclipta prostrata*, and *Setaria

[0086] As previously described, a fourth aspect of the present invention provides a herbicide containing an effective amount of at least one of the compounds containing a triazole ring structure described in the first aspect for controlling weeds.

[0087] The present invention does not impose any particular requirement on the specific content of the triazole ring compound in the herbicide, which can be, for example, 1-100 wt%; for example, 1 wt%, 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%, or 95 wt%.

[0088] Preferably, the herbicide of the present invention further contains a surfactant.

[0089] The surfactants mentioned above can be various surfactants known in the field of pesticide formulation, and the present invention is preferably one or more of emulsifiers, dispersants and wetting agents.

[0090] In addition to the surfactants mentioned above, the herbicide of the present invention may also contain other carriers, such as various carriers known in the field of pesticide formulation, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetic carriers. Specifically, for example: silica, kaolin, diatomaceous earth, clay, talc, organobentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust, urea, amine fertilizer, a mixture of urea and amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, attapulgite, a mixture of anhydrous potassium carbonate and anhydrous potassium bicarbonate, and a mixture of anhydrous sodium carbonate and anhydrous sodium bicarbonate, or one or more of these.

[0091] Preferably, the formulation of the herbicide is selected from at least one of the following: emulsifiable concentrate, water-in-oil emulsion, microemulsion, soluble liquid, water suspension, suspension emulsion, ultra-low volume spray, oil suspension, microcapsule suspension, water-spreading oil, wettable powder, water-dispersible granules, dry suspension, soluble powder, soluble granules, emulsifiable powder, emulsifiable granules, granules, solid microcapsule formulations, effervescent tablets, effervescent granules, water-floating dispersible granules, and seed coating agents.

[0092] The compounds of this invention have the advantage of high crop safety. Specifically, the compounds provided by this invention have high safety for crops such as corn, wheat, and rice.

[0093] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, the raw materials used are all commercially available products.

[0094] Preparation Example 1

[0095]

[0096] (1) Synthesis of intermediates

[0097] Equal amounts of acetylhydrazine (10 mmol) and phenyl isothiocyanate (10 mmol) were dissolved in 50 mL of ethanol and heated under reflux for 3 hours. After the reaction was complete, the solution was cooled to 0°C, filtered to obtain a white precipitate, washed with ice-cold ethanol, and dried. The resulting solid was then added to 70 mL of 1 M NaOH solution and heated under reflux again for 2 hours. After the reaction was complete, the solution was cooled to 0°C, neutralized with 1 M HCl solution to approximately pH 5, and a white solid precipitated as the product was obtained. The product was filtered to remove the solvent, washed with water, and purified by recrystallization from ethanol to obtain the intermediate.

[0098] (2) Synthesis of the target compound

[0099] Nitrobenzene compound (2.13 mmol) was dissolved in 15 mL of a water / ethanol mixture (v:v = 4:1) containing NH4Cl (4.26 mmol), and 2 equivalents of iron powder (4.26 mmol) were added. The mixture was heated to 90 °C and refluxed for 4 hours. The reaction progress was monitored using thin-layer chromatography (TLC). After the reaction was complete, the solution was cooled to room temperature, the solid was removed by filtration, the solvent in the mother liquor was removed under reduced pressure, and the residue was purified by silica gel column chromatography to obtain aniline compound.

[0100] The aniline compound (1.25 mmol) was dissolved in 15 mL of dichloromethane (DCM), and triphosgene (1.5 mmol) and triethylamine (1.5 mmol) were added. The mixture was stirred at room temperature for 2 hours. The reaction progress was monitored using TLC. After the reaction was complete, the solvent was removed, and the next step was performed directly.

[0101] The intermediate (0.38 mmol) and isocyanate (0.46 mmol) were dissolved in 15 mL of acetone, and triethylamine (47 mg, 0.46 mmol) was added. The mixture was heated to 60 °C and refluxed for 3 hours. The reaction progress was monitored using TLC. After the reaction was complete, the solution was cooled to room temperature, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography to obtain the target compound.

[0102] Preparation Example 2

[0103]

[0104] The triazole-containing intermediate (0.38 mmol) and isothiocyanate (0.46 mmol) were dissolved in 15 mL of acetone, and triethylamine (0.46 mmol) was added. The mixture was heated to 60 °C and refluxed for 3 hours. The reaction progress was monitored using TLC. After the reaction was complete, the solution was cooled to room temperature, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography to obtain the target compound.

[0105] The following lists the structure and characterization data of some compounds:

[0106]

[0107] White solid, yield 76%. 1 H NMR (400MHz, DMSO) δ14.18(s,1H),9.88(s,1H),7.90(d,J=12.8Hz,2H),7.80(d,J=6.5Hz,2H),7.33(s,4H),5.06(s,2H).

[0108]

[0109] White solid, yield 79%. 1 H NMR (400MHz, DMSO) δ14.19(s,1H),9.34(s,1H),7.94(d,J=9.3Hz,2H),7.88–7.66(m,4H),7.35(d,J=8.5Hz,1H),5.04(s,2H).

[0110]

[0111] White solid, yield 60%. 1 H NMR (400MHz, DMSO) δ14.19(s,1H),9.34(s,1H),7.94(d,J=9.3Hz,2H),7.84–7.56(m,4H),7.39(d,J=8.5Hz,1H),5.01(s,2H).

[0112]

[0113] White solid, yield 75%. 1H NMR (400MHz, DMSO) δ14.16(s,1H),9.57(s,1H),7.92(d,J=1.8Hz,2H),7.90(s,1H),7.77(d,J=6.9Hz,2H),7.70(s,1H),5.00(s,2H).

[0114]

[0115] White solid, yield 64%. 1 H NMR (400MHz, DMSO) δ14.20 (s, 1H), 9.64 (s, 1H), 8.21 (d, J = 23.1Hz, 1H), 7.85 (dd, J = 48.5, 27.3Hz, 5H), 5.00 (s, 2H).

[0116]

[0117] White solid, yield 77%. 1 H NMR (400MHz, DMSO) δ14.19 (s, 1H), 10.41 (s, 1H), 7.90 (d, J = 9.9Hz, 3H), 7.85–7.73 (m, 3H), 7.67 (s, 1H), 5.16 (s, 2H).

[0118]

[0119] White solid, yield 87%. 1 H NMR (400MHz, DMSO) δ14.17(s,1H),9.43(s,1H),7.91(s,2H),7.81(s,2H),7.41(s,1H),7.34–7.21(m,1H),7.04(t,J=8.3Hz,1H),5.04(s,2H).

[0120]

[0121] White solid, yield 82%. 1 H NMR (400MHz, DMSO) δ14.18(s,1H),10.19(s,1H),7.91(s,1H),7.89–7.74(m,4H),7.63(d,J=8.7Hz,1H),7.56(d,J=7.6Hz,1H),5.12(s,2H).

[0122]

[0123] White solid, yield 77%. 1H NMR (400MHz, DMSO) δ14.19(s,1H),10.07(s,1H),7.91(d,J=10.0Hz,2H),7.82(d,J= 5.9Hz,2H),7.61(s,1H),7.54(d,J=8.8Hz,1H),7.28(d,J=7.9Hz,1H),5.10(s,2H).

[0124]

[0125] White solid, yield 81%. 1 H NMR (400MHz, DMSO) δ14.18(s,1H),9.90(s,1H),7.90(d,J=5.8Hz,2H),7.80(d,J=5.0Hz,2H),7.68(t,J=7.7Hz,1H),5.09(s,2H).

[0126]

[0127] White solid, yield 79%. 1 H NMR (400MHz, DMSO) δ14.15(s,1H),9.74(s,1H),7.89(d,J=8.3Hz,2H),7.80(d,J=5.3Hz,2H),7.32(s,2H),7.10(t,J=8.8Hz,2H),5.04(s,2H).

[0128]

[0129] White solid, yield 83%. 1 H NMR (400MHz, DMSO) δ14.20(s,1H),10.33(s,1H),7.95(s,1H),7.86(s,3H),7.55(s,1H),7.47(d,J=9.2Hz,1H),7.26(d,J=6.3Hz,1H),5.18(s,2H).

[0130]

[0131] White solid, yield 85%. 1 H NMR (400MHz, DMSO) δ14.17(s,1H),9.29(s,1H),7.94(s,1H),7.91(d,J=4.4Hz,1 H),7.80(d,J=5.0Hz,2H),7.61(d,J=1.6Hz,1H),7.44–7.34(m,2H),5.06(s,2H).

[0132]

[0133] White solid, yield 61%. 1 H NMR (400MHz, DMSO) δ14.20(s,1H),9.55(s,1H),8.09(dd,J=7.8,2.6Hz,1H),7.94(s,2H),7.83(s,2H),7.75(dd,J=8.6,2.8Hz,1H),5.00(s,2H).

[0134]

[0135] White solid, yield 81%. 1 H NMR (400MHz, DMSO) δ14.17(s,1H),9.35(s,1H),7.92(d,J=6.5Hz,2H),7.81(s,2H),7.41(dd,J=15.8,8.5Hz,2H),5.03(s,2H).

[0136]

[0137] White solid, yield 89%. 1 H NMR (400MHz, DMSO) δ14.16(s,1H),9.56(s,1H),7.85(dd,J=39.1,5.5Hz,4H),7.44(dd,J=10.6,2.2Hz,2H),7.22(d,J=8.5Hz,1H),5.04(s,2H).

[0138]

[0139] White solid, yield 85%. 1 H NMR (400MHz, DMSO) δ14.09(s,1H),9.87(s,1H),7.59(dd,J=14.6,8.0Hz,1H),7.50–7.36(m,3H),7.34(t,J=6.0Hz,4H),5.04(s,2H).

[0140]

[0141] White solid, yield 84%. 1H NMR (400MHz, DMSO) δ14.11(s,1H),9.34(s,1H),7.64(s,1H),7.62–7.52(m,1H),7.40(t,J=6.9Hz,4H),7.32(d,J=9.0Hz,1H),5.03(s,2H).

[0142]

[0143] White solid, yield 63%. 1 H NMR (400MHz, DMSO) δ14.07(d,J=28.1Hz,1H),9.52(d,J=77.0Hz,1H),8.32(d,J=12.8Hz,1H),7 .95(d,J=12.0Hz,1H),7.63(dd,J=14.7,7.7Hz,1H),7.39(dd,J=32.1,8.3Hz,3H),4.97(s,2H).

[0144]

[0145] White solid, yield 61%. 1 H NMR (400MHz, DMSO) δ14.08(s,1H),9.52(d,J=76.8Hz,1H),8.21(d,J=11.5Hz,1H),7.86(d,J =12.7Hz,1H),7.62(d,J=6.6Hz,1H),7.50–7.36(m,2H),7.35(d,J=7.5Hz,1H),4.97(s,2H).

[0146]

[0147] White solid, yield 67%. 1 H NMR (400MHz, DMSO) δ14.14(s,1H),9.64(s,1H),7.95(s,1H),7.75(s,1H),7.60(s,1H),7.53–7.32(m,2H),7.29(s,1H),5.00(s,2H).

[0148]

[0149] White solid, yield 78%. 1 H NMR (400MHz, DMSO) δ14.14(s,1H),9.42(s,1H),7.62(s,1H),7.56–6.98(m,5H),5.03(s,2H).

[0150]

[0151] White solid, yield 72%. 1 H NMR (400MHz, DMSO) δ14.11(s,1H),9.34(s,1H),7.76(dd,J=12.0,3.3Hz,2H),7.60(dd,J=14.6 ,7.9Hz,1H),7.43(d,J=10.1Hz,1H),7.36(d,J=8.5Hz,2H),7.29(d,J=7.4Hz,1H),5.01(s,2H).

[0152]

[0153] White solid, yield 84%. 1 H NMR (400MHz, DMSO) δ14.11(s,1H),9.35(s,1H),7.79(d,J=2.2Hz,1H),7.76(dd,J=8.6,2.2Hz,1H),7.60( dd,J=14.7,8.0Hz,1H),7.43(d,J=8.5Hz,1H),7.36(d,J=8.5Hz,2H),7.29(d,J=7.6Hz,1H),5.01(s,2H).

[0154]

[0155] White solid, yield 82%. 1 H NMR (400MHz, DMSO) δ14.13(s,1H),9.47(s,1H),7.59(dd,J=14.5,7.7Hz,1H ),7.50–7.32(m,3H),7.33–7.19(m,2H),7.03(t,J=7.9Hz,1H),5.00(s,2H).

[0156]

[0157] White solid, yield 82%. 1 H NMR (400MHz, DMSO) δ14.15(s,1H),10.09(s,1H),7.64–7.58(m,2H),7.54(d,J=8.8Hz,1H),7.44–7.37(m,2H),7.34–7.27(m,2H),5.07(s,2H).

[0158]

[0159] White solid, yield 77%. 1 H NMR (400MHz, DMSO) δ14.14(s,1H),10.21(s,1H),7.84(s,1H),7.68–7.50(m,3H),7.45–7.25(m,3H),5.07(s,2H).

[0160]

[0161] White solid, yield 87%. 1 H NMR(400MHz,DMSO)δ14.12(s,1H),9.78(s,1H),7.61(dd,J=14.9,7.6Hz,1H ),7.50–7.39(m,2H),7.40–7.23(m,3H),7.14(t,J=8.6Hz,2H),5.05(s,2H).

[0162] Test case

[0163] Test methods

[0164] Post-emergence foliar spraying: The tested targets are listed in the table. Take 7.5cm inner diameter flowerpots, fill them with compound nutrient soil to 3 / 4 full, directly sow the above six weed targets (germination rate ≥85%), cover with 0.2cm of soil, add water to the bottom until the soil is saturated, and then place them in a greenhouse for cultivation. Maintain suitable soil moisture content. Once the weeds reach approximately the 3-leaf stage, they are ready for use. The compound is applied at a dosage of 750g ai / ha using an automatic spray tower (model: 3WPSH-700E). After the pesticide solution on the weed leaves dries, the plants are transferred to a greenhouse for cultivation. The activity (%) against the weeds is investigated after 25 days. Specific results are shown in Table 1.

[0165] Pre-emergence soil sealing treatment: The test targets are listed in the table. Take 7.5cm inner diameter flowerpots, fill them with compound nutrient soil to 3 / 4 full, sow seeds (germination rate ≥85%) one day before spraying, cover with soil and water to keep the soil moist, and set aside. Apply the compound at a dosage of 750g ai / ha in an automatic spray tower (model: 3WPSH-700E), allow it to air dry naturally in a ventilated hall for 2-3 hours, then transfer it to a greenhouse for cultivation. Investigate the activity (%) against weeds after 30 days.

[0166] Activity screening (pot method, post-emergence foliar spray treatment): The test targets are listed in the table. Take 7.5cm inner diameter flowerpots, fill them with compound nutrient soil to 3 / 4 full, directly sow the above six weed targets (germination rate ≥85%), cover with 0.2cm of soil, add water to the bottom until the soil is saturated, and then place them in a greenhouse for cultivation. Maintain suitable soil moisture content. Use the plants when they reach approximately the 3-leaf stage. Apply the compound at doses of 375g ai / ha and 187.5g ai / ha using an automatic spray tower (model: 3WPSH-700E). After the pesticide solution on the weed leaves dries, transfer them to a greenhouse for cultivation. Investigate the activity (%) against the weeds 25 days later.

[0167] Safety screening (pot method, post-emergence foliar spraying): The target crops are listed in the table. Take 9cm (or 7.5cm) inner diameter flowerpots, fill them with composite soil to 3 / 4 full, directly sow the above six targets (germination rate ≥85%), cover with 0.2cm of soil, add water to the bottom until the soil is saturated, and then place them in a greenhouse for cultivation. Maintain suitable soil moisture content until the crops reach approximately the 3-leaf stage. After applying the compounds at doses of 750g ai / ha and 375g ai / ha using an automatic spray tower (model: 3WPSH-700E), allow the pesticide solution on the crop leaves to dry, then transfer them to a greenhouse for 25 days of cultivation before investigating the safety (%) on the crops.

[0168] The calculation method for the inhibition rate of weed / or crop growth is as follows:

[0169]

[0170] Wherein, E1 is the inhibition rate of weed / crop growth (in %), C1 is the fresh weight of the aboveground parts of the control weed / control crop plants (in g), and T1 is the fresh weight of the aboveground parts of the treated weed / treated crop plants (in g).

[0171] Table 1: Post-emergence herbicidal activity (750g ai / ha)

[0172]

[0173]

[0174] a The average of three replicates. b Pyrfluthrin was used as a positive control. " / " indicates that it was not provided.

[0175] The pre-emergence herbicidal activity of the compound was also tested, and the results are shown in Table 2.

[0176] Table 2: Pre-emergence herbicidal activity (750g ai / ha)

[0177]

[0178] a The average of three replicates. b Pyrfluthrin was used as a positive control. " / " indicates that it was not provided.

[0179] As shown in Table 2, the compounds of this invention exhibit excellent herbicidal activity against broadleaf weeds such as lambsquarters, mustard, and sorrel. Compound 11 showed 100% inhibition against both lambsquarters and mustard, and 95% inhibition against sorrel. Compound 1c also showed inhibition activity exceeding 90% against all three broadleaf weeds, significantly superior to pyrifluquinazon. Compound 1b, which exhibits excellent post-emergence herbicidal activity, maintained 100% inhibition activity against lambsquarters before emergence, and 80% inhibition activity against mustard and sorrel.

[0180] The inventors discovered that, in the compounds provided by this invention, the introduction of CF3 and Cl at the ortho position on the benzene ring of the 3-position side chain of the triazole ring significantly enhances the activity of the compounds. Furthermore, the inventors also found that the 3-F-5-CF3-Ph structure can significantly improve the pre-emergence herbicidal activity of the compounds of this invention.

[0181] The present invention tested the greenhouse weed control activity of some compounds against three dicotyledonous weeds: lambsquarters, mustard, and sorrel. The results are shown in Table 3.

[0182] Table 3: Post-emergence greenhouse weed control activity

[0183]

[0184] a The average of three replicates. b Pyrfluthrin was used as a positive control. " / " indicates that it was not provided.

[0185] As shown in Table 3, the compounds of this invention maintain excellent herbicidal activity against broadleaf weeds at application rates of 375-187.5 g ai / ha. Specifically, compound 1e exhibits 95%, 90%, and 95% herbicidal activity against lambsquarters, mustard, and sorrel at an application rate of 375 g ai / ha, respectively. At an application rate of 187.5 g ai / ha, it also shows over 80% herbicidal activity against lambsquarters (80%), mustard (85%), and sorrel (90%). Compound 1n achieves 100% herbicidal activity against sorrel at 375 g ai / ha and retains 95% herbicidal activity against sorrel at a rate of 187.5 g ai / ha. Furthermore, compound 1n retains over 80% broad-spectrum herbicidal activity against all three broadleaf weeds. Compound 1m also exhibits excellent herbicidal activity, showing over 80% activity against three broadleaf weeds at application rates of 375-187.5 g ai / ha. Compound 2b, which showed the best activity at an application rate of 750 g ai / ha, also demonstrated 80%, 90%, and 70% herbicidal activity against lambsquarters, mustard, and sorrel at 375 g ai / ha, respectively, and 85% herbicidal activity against mustard at 187.5 g ai / ha.

[0186] Comparing the overall control effects of some compounds of this invention on three weeds at 375 g ai / ha and 187.5 g ai / ha, it was found that the compounds of this invention still have excellent herbicidal activity against broadleaf weeds at an application rate of 187.5 g ai / ha. In particular, compounds 1e and 1n have better overall herbicidal activity against lambsquarters, mustard, and sorrel than pyrifluquinazon. Compound 1m also has herbicidal activity comparable to pyrifluquinazon.

[0187] The results also show that compound 11 of the present invention has the best pre-emergence herbicidal activity, and compound 1m has the best herbicidal activity at low and medium doses.

[0188] The present invention further provides crop safety test results for some compounds, as shown in Table 4.

[0189] Table 4: Post-emergence crop safety

[0190]

[0191] a The average of three replicates. b Pyrfluthrin was used as a positive control. " / " indicates that it was not provided.

[0192] Post-emergence crop safety studies showed that maize and wheat exhibited high tolerance after treatment with 750 g ai / ha of the herbicide. Notably, compound 1m, at an application rate of 375 g ai / ha, demonstrated herbicidal activity comparable to pyrifluquinazon, while exhibiting significantly better selectivity for maize than pyrifluquinazon. Compound 1l also showed excellent selectivity for maize.

[0193] Similarly, the compounds synthesized in this invention exhibit 100% safety for wheat.

[0194] The compounds provided by this invention exhibit high herbicidal activity, such as compounds 1e, 1m, 1n, and 2b. Notably, compound 2b of this invention, at a post-emergence treatment of 750 g ai / ha, showed 100% inhibition of lambsquarters and mustard, and 80% inhibition of sorrel. Compounds 1e, 1m, and 1n not only demonstrated excellent herbicidal effects at high application rates, but also showed inhibition activities exceeding 80% against lambsquarters, mustard, and sorrel at medium-low doses of 187.5-375 g ai / ha, even surpassing the commercially available herbicide pyrifluquinazon.

[0195] In particular, compound 1m showed excellent and broad-spectrum control of broadleaf weeds at post-emergence application rates of 187.5-750 g ai / ha, while maize and wheat showed relatively high tolerance to compound 1m at application rates of 375-750 g ai / ha. This suggests that compound 1m can be used as a new potential herbicide for the management of broadleaf weeds in maize and wheat fields.

[0196] In summary, the results of this study indicate that the compounds of this invention, especially compound 1m, have the potential to selectively control broadleaf weeds in maize and wheat fields at application rates of 375 g a.i. / ha and lower.

[0197] 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 compound containing a triazole ring structure, characterized in that, The compound has the structure shown in formula (I). In equation (I), X is either O or S; R 11 R 12 R 13 R 14 and R 15 Each is independently selected from H, halogen, or C substituted with at least one halogen. 1-12 Alkyl groups, C substituted with at least one halogen 1-12 Any one of the alkoxy groups; and R 11 R 12 R 13 R 14 and R 15 They are not both H.

2. The compound containing a triazole ring structure according to claim 1, characterized in that, In equation (I), X is either O or S; R 11 R 12 R 13 R 14 and R 15 Each is independently selected from H, fluorine, chlorine, bromine, or C substituted with 1-12 halogens. 1-10 Alkyl groups, C substituted with 1-12 halogens 1-10 Any one of the alkoxy groups; and R 11 R 12 R 13 R 14 and R 15 They are not both H.

3. The compound containing a triazole ring structure according to claim 2, characterized in that, In equation (I), X is either O or S; R 11 R 12 R 13 R 14 and R 15 Each is independently selected from H, fluorine, chlorine, bromine, or C substituted with 1-12 halogens. 1-6 Alkyl groups, C substituted with 1-12 halogens 1-6 Any one of the alkoxy groups; and R 11 R 12 R 13 R 14 and R 15 They are not both H.

4. The compound containing a triazole ring structure according to claim 3, characterized in that, In equation (I), X is either O or S; R 11 R 12 R 13 R 14 and R 15 Each is independently selected from any one of H, fluorine, chlorine, bromine, trifluoromethyl, and trifluoromethoxy; and R 11 R 12 R 13 R 14 and R 15 They are not both H.

5. The compound containing a triazole ring structure according to any one of claims 1-4, characterized in that, The compound represented by formula (I) is selected from any one of the following: Compound 1a: X is O, R 13 For Cl, R 11 R 12 R 14 and R 15 All are H; Compound 1b: X is O, R 11 For CF3, R 13 For Cl, R 12 R 14 and R 15 All are H; Compound 1c: X is O, R 11 For Cl, R 15 For CF3, R 12 R 13 and R 14 All are H; Compound 1d: X is O, R 11 For Cl, R 13 For Br, R 15 For OCF3, R 12 and R 14 All are H; Compound 1e: X is O, R 11 For Br, R 13 For Cl, R 15 For CF3, R 12 and R 14 All are H; Compound 1f: X is O, R 12 and R 14 For CF3, R 11 R 13 R 15 All are H; Compound 1g: X is O, R 11 and R 13 For F, R 12 R 14 R 15 All are H; Compound 1h: X is O, R 12 For CF3, R 13 For Cl, R 11 R 14 R 15 All are H; Compound 1i: X is O, R 12 and R 13 For Cl, R 11 R 14 R 15 All are H; Compound 1j: X is O, R 11 and R 13 For F, R 12 and R 14 For Cl, R 15 For H; Compound 1k: X is O, R 13 For F, R 11 R 12 R 14 and R 15 All are H; Compound 1l: X is O, R 12 For F, R 14 For CF3, R 11 R 13 R 15 All are H; Compound 1m: X is O, R 11 and R 13 For Cl, R 12 R 14 R 15 All are H; Compound 1n: X is O, R 11 For Br, R 13 For F, R 15 For CF3, R 12 and R 14 All are H; Compound 1o: X is O, R 11 For Cl, R 13 and R 15 For F, R 12 and R 14 All are H; Compound 1p: X is O, R 11 For F, R 13 For Cl, R 12 R 14 R 15 All are H; Compound 2a: X is S, R 13 For Cl, R 11 R 12 R 14 and R 15 All are H; Compound 2b: X is S, R 11 and R 13 For Cl, R 12 R 14 R 15 All are H; Compound 2c: X is S, R 11 and R 13 For Br, R 15 For CF3, R 12 and R 14 All are H; Compound 2d: X is S, R 11 For Br, R 13 For Cl, R 15 For CF3, R 12 and R 14 All are H; Compound 2e: X is S, R 11 For Cl, R 13 For Br, R 15 For OCF3, R 12 and R 14 All are H; Compound 2f: X is S, R 11 For Cl, R 13 and R 15 For F, R 12 and R 14 All are H; Compound 2g: X is S, R 11 For CF3, R 13 For Cl, R 12 R 14 and R 15 All are H; Compound 2h: X is S, R 12 For F, R 14 For CF3, R 11 R 13 and R 15 All are H; Compound 2i: X is S, R 11 and R 13 For F, R 12 R 14 and R 15 All are H; Compound 2j: X is S, R 12 and R 13 For Cl, R 11 R 14 and R 15 All are H; Compound 2k: X is S, R 12 For CF3, R 13 For Cl, R 11 R 14 and R 15 All are H; Compound 2l: X is S, R 13 For F, R 11 R 12 R 14 and R 15 All are H.

6. A method for preparing the compound containing the triazole ring structure according to any one of claims 1-5, characterized in that, The method includes: In the presence of a solvent, the compound shown in formula (II-1) is reacted with the compound shown in formula (II-2) to obtain the compound with a triazole ring structure shown in formula (I); The definitions of the groups in formulas (II-1), (II-2) and (I) correspond to the definitions of the groups in the compounds containing the triazole ring structure according to any one of claims 1-5.

7. The use of the triazole ring-containing compound as a PDS inhibitor in weed control according to any one of claims 1-5.

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

9. A herbicide, characterized in that, The herbicide contains an effective amount of at least one of the compounds containing a triazole ring structure as described in any one of claims 1-5 for controlling weeds.

10. The herbicide according to claim 9, characterized in that, The formulation of this herbicide is selected from at least one of the following: emulsifiable concentrate, water-in-oil emulsion, microemulsion, soluble liquid, water suspension, suspension emulsion, ultra-low volume spray, oil suspension, microcapsule suspension, water-spreading oil, wettable powder, water-dispersible granules, dry suspension, soluble powder, soluble granules, emulsifiable powder, emulsifiable granules, granules, solid microcapsule formulations, effervescent tablets, effervescent granules, water-floating dispersible granules, and seed coating agents.

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