Carbonyl azo compounds, methods of making and using the same

Abstract

The present application relates to a kind of carbonyl oxides azo compounds or its agriculturally acceptable salt and its preparation method and application, and its application as insecticide and fungicide, and part compound exhibits excellent fungicidal activity and nematocidal activity.

Description

Technical Field

[0001] This invention belongs to the field of pesticide chemistry, specifically relating to carbonyl oxide azo compounds, their preparation methods, and applications. Background Technology

[0002] Crop production relies heavily on the use of chemical pesticides to manage insects, plant pathogens, and weeds that affect crop yields. Chemical pesticides, with their high efficiency and relatively low cost, have become a significant driver of increased yields per unit area of ​​farmland. However, the intense selective pressures imposed by chemical pesticides, coupled with a lack of effective resistance management practices, have led to the widespread evolution of resistance to these pesticides in insects, plant pathogens, and weeds. Therefore, there is an increasing need for effective and safe pesticides with novel molecular targets to address the evolving resistance of insects, plant pathogens, and weeds and ensure food security.

[0003] Based on the previously discovered azo compounds or oxyazo compounds CN115197103B and CN120058565A, this invention is proposed to discover more similar compounds with both insecticidal and bactericidal activities, further optimize compound structures, and study conformational relationships. Summary of the Invention

[0004] The object of this invention is to provide a carbonyl oxide azo compound that possesses both insecticidal and fungicidal activity. A first aspect of this invention is to provide a compound of formula I, or an agriculturally acceptable salt thereof: ; Formula I; Among them, R a Selected from C1-C6 alkyl groups, -(CH2) n -C6-C 10 Aryl; R b Selected from C3-C6 alkyl, C6-C 12 Aryl, -(CH2) n -C5-C containing N, O, and S atoms 12 heteroaryl, -(CH2) n -C3-C6 cycloalkyl; The C3-C6 alkyl, C6-C 12 Aryl, -(CH2) n -C5-C containing N, O, and S atoms 12 heteroaryl, -(CH2) n -C3-C6 cycloalkyl groups may be further optionally surrounded by one, two, or three independent R... c replace; The R cSelected from hydrogen, halogen, C1-C6 alkyl, halogen-substituted C1-C6 alkyl, C1-C6 alkoxy, -NHCOC1-C6 alkyl, -OCOC1-C6 alkyl, C6-C 12 Aryl, C6-C 12 aryloxy group, C6-C 12 Aryl-(CH2) n- Oxygen group, -NHCOOC1-C6 alkyl group, -NH-C6-C 12 Aryl, -COC1-C6 alkyl, C5-C6 containing N, O, or S atoms 12 Mixed aromatics; n is an independent selection from 0, 1, 2, 3, or 4.

[0005] More preferably, wherein the R a Selected from methyl or benzyl; The R b Selected from phenyl, naphthyl, thienyl, thiazolyl, -CH2-thiazolyl, furanyl, oxazolyl, pyrroleyl, imidazolyl, pyrazolyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, -CH2-cyclohexane, -(CH2)2-cyclohexane, -(CH2)3-cyclohexane, n-propane, n-butane, n-pentane, n-hexane, n-heptane.

[0006] More preferably, wherein the R c Selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, -CFH2, -CClH2, -CF2H, -CF3, -CH2CFH2, -CH2CF2H, -CH2CF3, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, phenyl, -NHCOCH3, -OCOCH3, PhO-, PhCH2O-, -NHCOOt-Bu, -COCH3, o-chloropyridyl.

[0007] Furthermore, in this invention, R b Selected from , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , or .

[0008] The present invention also provides the compound of formula I, specifically as follows: ; ; ; A second aspect of the present invention provides a pesticide composition comprising at least one of the aforementioned compounds of Formula I, or an agriculturally chemically acceptable salt thereof, and a carrier; said carrier being in liquid or solid form.

[0009] The third aspect of the present invention provides the use of the compound of Formula I, or an agriculturally chemically acceptable salt thereof, or the pesticide composition thereof, in an agricultural insecticide, preferably wherein the agricultural pest is pine wood nematode, root-knot nematode, soybean cyst nematode, rice tip nematode, and stem rot nematode.

[0010] The fourth aspect of the present invention provides the application of the compound of Formula I, or an agriculturally chemically acceptable salt thereof, or the pesticide composition thereof, in the control of plant fungal diseases, preferably, the plant fungal diseases being Rhizoctonia solani, Sclerotinia sclerotiorum, Botrytis cinerea, Botrytis cinerea, Colletotrichum gloeosporioides, Colletotrichum gloeosporioides, Alternaria alternata, Alternaria sclerotiorum, and wheat powdery mildew.

[0011] A fifth aspect of the present invention provides a bactericide, characterized in that the bactericide contains at least one of the compounds of formula I, or an agriculturally chemically acceptable salt thereof, and optionally contains excipients; preferably, the formulation of the bactericide is selected from at least one of emulsifiable concentrates, suspension concentrates, wettable powders, powders, granules, aqueous solutions, mother liquors, and masterbatches.

[0012] The sixth aspect of the present invention provides a method for controlling or preventing the infection of useful plants by plant pathogenic microorganisms, wherein an effective amount of a fungicide according to the compound having formula I or a composition containing such compound as an active ingredient is applied to the plant, its parts or the site thereof.

[0013] The following is an explanation and description of the terminology used in this invention: The compounds and derivatives provided in this invention can be named according to the IUPAC (International Union of Pure and Applied Chemistry) or CAS (Chemical Abstracts Service, Columbus, OH) nomenclature system.

[0014] Regarding the definition of terms used in this invention: Unless otherwise stated, the initial definitions provided for groups or terms herein apply to the groups or terms used throughout this specification; for terms not specifically defined herein, the meanings that a person skilled in the art would give them should be given based on the disclosure and context.

[0015] "Substitution" refers to the replacement of hydrogen atoms in a molecule by other different atoms or molecules.

[0016] The minimum and maximum carbon atom content in hydrocarbon groups are indicated by prefixes. For example, the prefix Ca-b alkyl indicates any alkyl group containing "a" to "b" carbon atoms. Therefore, for example, "C1-4 alkyl" refers to an alkyl group containing 1 to 4 carbon atoms.

[0017] The term "alkyl" refers to a saturated hydrocarbon chain having a specified number of member atoms. For example, C1-6 alkyl refers to an alkyl group having 1 to 6 member atoms, such as 1 to 4 member atoms. Alkyl groups can be straight-chain or branched. Representative branched alkyl groups have one, two, or three branches. Alkyl groups may optionally be substituted by one or more substituents as defined herein. Alkyl groups include methyl, ethyl, propyl (n-propyl and isopropyl), butyl (n-butyl, isobutyl, and tert-butyl), pentyl (n-pentyl, isopentyl, and neopentyl), and hexyl, 2,2-dimethylbutyl, and 2,3-dimethylbutyl, etc. The term "C1-C3 alkyl" refers to a straight-chain or branched saturated hydrocarbon group having 1 to 3 carbon atoms. Alkyl groups may also be part of other groups, such as C1-C6 alkoxy groups.

[0018] The term "alkoxy" refers to an O-alkyl group. The term "C1-C8 alkoxy" refers to a group having an O-C1-C8 alkyl group.

[0019] The term "C6-C" 10 "Aryl" refers to an all-carbon monocyclic or fused polycyclic group with 6 to 10 carbon atoms and a fully conjugated π-electron system. Typical examples include, but are not limited to, phenyl, naphthyl, and biphenyl groups.

[0020] The term "heteroaryl" refers to a monocyclic or fused cyclic group containing one, two, three, or four cyclic heteroatoms selected from N, O, or S, with the remaining ring atoms being C, and possessing a fully conjugated π-electron system. The term "C6-C" is also used. 12 "Heteroaryl" refers to a heteroaryl group containing 3 to 10 carbon atoms in its ring. (C3-C) 10 Heteroaryl groups include, but are not limited to, pyrrole, furanyl, thiophene, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyrimidinyl, and pyridinyl.

[0021] The term "halogen" refers to fluorine, chlorine, bromine, or iodine.

[0022] The term "halogenated alkyl" refers to an alkyl group in which the hydrogen atom can be replaced by one or more halogen atoms. For example, C1-4 halogenated alkyl refers to an alkyl group containing 1 to 4 carbon atoms in which the hydrogen atom is replaced by one or more halogen atoms.

[0023] The term "agronomically acceptable salt" refers to acidic and / or basic salts formed by the above-mentioned compounds or their stereoisomers with inorganic and / or organic acids and bases, including zwitterionic salts (internal salts) and quaternary ammonium salts, such as alkylammonium salts. These salts can be obtained directly during the final separation and purification of the compounds. Alternatively, they can be obtained by mixing the above-mentioned compounds, or their stereoisomers, with an appropriate amount (e.g., equimolar amounts) of an acid or base. These salts may be obtained by precipitating in solution and collecting by filtration, by recovery after solvent evaporation, or by freeze-drying after reaction in an aqueous medium. The salts described in this invention can be hydrochlorides, sulfates, citrates, benzenesulfonates, hydrobromides, hydrofluoric acids, phosphates, acetates, propionates, succinates, oxalates, malates, succinates, fumarates, maleates, tartrates, or trifluoroacetates of the compounds.

[0024] Compounds having Formula I are used in related fields as active ingredients, for example, for controlling plant pests, or on non-living materials for controlling putrefactive microorganisms or organisms potentially harmful to humans. These novel Formula I compounds are characterized by excellent activity at low application rates, good plant tolerance, and no environmental harm. They possess highly useful therapeutic, preventative, and systemic properties and can be used to protect cultivated plants. Compounds having Formula I can be used to inhibit or destroy pests appearing on various useful plant crops or plant parts (fruits, flowers, leaves, stems, tubers, roots), while also protecting, for example, later-growing plant parts from plant pathogenic microorganisms.

[0025] The term "plant" refers to all the tangible parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, culms, leaves, and fruits.

[0026] A compound having Formula I may be the sole active ingredient in a composition, or, where appropriate, it may be mixed with one or more other active ingredients (such as pest control agents, fungicides, synergists, herbicides, or plant growth regulators). In some cases, the additional active ingredients may result in unexpected synergistic activities.

[0027] Other suitable active ingredients include acyclic amino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, aniline fungicides, and antibiotic fungicides.

[0028] A formulation, such as a composition comprising a compound having formula I, and a solid or liquid adjuvant or a monomer for encapsulating the compound having formula I, can typically be prepared in a known manner by closely mixing and / or grinding the compound with an additive (e.g., a solvent, a solid carrier, and optionally a surfactant).

[0029] Typically, formulations comprise from 0.01% to 90% by weight of the active ingredient, from 0% to 20% of an agriculturally acceptable surfactant, and from 10% to 99.99% of solid or liquid formulation inert agents and adjuvants.

[0030] The compositions of the present invention can be used in any conventional form, for example, as a double-pack, emulsion concentrate (EC), suspension concentrate (SC), suspension emulsion (SE), capsule suspension (CS), water-dispersible particles (WG), emulsifiable particles (EG), water-in-oil emulsion (EO), oil-in-water emulsion (EW), microemulsion (ME), dispersible oil suspension (OD), oil suspension (OF), oil-soluble liquid (OL), soluble concentrate (SL), ultra-low volume suspension (SU), ultra-low volume liquid (UL), technical grade (TK), dispersible concentrate (DC), wettable powder (WP), or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0031] Obviously, based on the above description of the present invention, and according to common technical knowledge and conventional methods in the field, various other modifications, substitutions, or alterations can be made without departing from the basic technical concept of the present invention.

[0032] Beneficial technical effects of the present invention: 1. The bioactivity assays of compounds 5-1 to 5-50 of this invention against pine wood nematode, root-knot nematode, soybean cyst nematode, rice tip nematode, stem rot nematode, and fungi show that carbonyl oxide azo compounds have consistent bioactivity against multiple targets. Based on the nematicidal activity of compounds 5-1 to 5-50 against pine wood nematode, it can be seen that most compounds also have excellent nematicidal activity against root-knot nematode, soybean cyst nematode, rice tip nematode, and stem rot nematode, providing guidance for the development of nematicides in agriculture and forestry.

[0033] 2. Based on the nematicidal activity of compounds 5-1 to 5-50 against pine wood nematodes, it can be known that most of these compounds are effective against Rhizoctonia solani (…). Rhizoctonia solani ), Sclerotinia sclerotiorum ( Sclerotinia sclerotiorum ), Botrytis cinerea ( Botrytis gray ), Staphylococcus aureus ( Botryosphaeria dothidea ), Colloidal anthracnose bacteria ( Colletotrichum gloeosporioides ), *Cyclocarya paliurus* ( Corynespora cassicola Alternaria ( ) Alternaria alternata ), Streptococcus faecalis ( Monilinia fructigen ) and wheat powdery mildew fungus (Phyllostachys bryony, a member of the Poaceae family, Blumeria grassinis Fungi such as [list of fungi] also have excellent bactericidal activity, providing guidance for the development of fungicides in agriculture and forestry. Attached Figure Description

[0034] Figure 1 Single crystal structures of compounds 5-9. Detailed Implementation

[0035] The present invention is further illustrated by the following examples, but these are not intended to limit the invention.

[0036] Example 1 Step 1: In a 100 mL round-bottom flask, benzoic acid 1-1 (8.19 mmol) was dissolved in 10 mL of N,N-dimethylformamide (DMF) and stirred at room temperature until completely dissolved. The condensing agent 2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethylurea tetrafluoroborate (TBTU, 6.05 mmol) and the organic base N,N-diisopropylethylamine (DIEA, 7.57 mmol) were added sequentially to the reaction system. After stirring for 10 min, a DMF solution (5 mL) of p-methoxyphenylhydrazine hydrochloride 2-1 (0.97 g, 5.55 mmol) was added. After the reaction was complete, distilled water was added to terminate the reaction. The mixture was extracted with ethyl acetate, and the combined organic phases were washed sequentially with saturated sodium carbonate (Na₂CO₃) solution and saturated brine (NaCl). After drying with anhydrous sodium sulfate (Na₂SO₄), the product was dissolved under reduced pressure to obtain a pale yellow solid product 3-1.

[0037] Step 2: Compound 3-1 (5.92 mmol) was dissolved in dichloromethane (15 mL) in a 100 mL round-bottom flask. Iodobenzene diacetate (DIPA, 5.92 mmol) was slowly added under stirring, and the mixture was stirred at room temperature for 15 min. After the reaction was complete, the reaction mixture was extracted with dichloromethane, and the organic phase was washed successively with saturated sodium carbonate (Na₂CO₃) solution, distilled water, and saturated sodium chloride (NaCl) solution. After drying with anhydrous sodium sulfate (Na₂SO₄), the crude product was dissolved under reduced pressure, and purified by silica gel column chromatography to give a brownish-red oily liquid, 4-1.

[0038] Step 3: Compound 4-1 (5.92 mmol) and 15 mL of dichloromethane were added to a 100 mL round-bottom flask. After stirring to dissolve, the reaction system was cooled to 0 °C. Under low temperature conditions, a dichloromethane solution (15 mL) of m-chloroperoxybenzoic acid (m-CPBA, 8.88 mmol) was slowly added dropwise. After the addition was complete, stirring was continued for 15 min. Subsequently, the reaction solution was heated to 60 °C and refluxed for 4 h. After the reaction was completed, the reaction solution was cooled to room temperature and washed successively with saturated sodium sulfite (Na2SO3) solution, distilled water, and saturated sodium chloride (NaCl) solution. The organic layer was dried over anhydrous sodium sulfate (Na2SO4), dissolved under reduced pressure, and the crude product was purified by silica gel column chromatography to obtain a yellow oily liquid product 5-1. The NMR data of compound 5-1 are shown in Table 1.

[0039] ; Example 2-Example 21

[0040] Following the same preparation method as in Example 1, products 5-2 to 5-21 were prepared. The NMR data of compounds 5-2 to 5-21 are shown in Table 1. The single-crystal structure of compound 5-9 is shown in... Figure 1 .

[0041] Table 1 Chemical structures of the compounds of this invention and 1 H NMR data ; ; ; ; Examples 22 to 50

[0042] Step 1: In a 100 mL round-bottom flask, acid 1-20~1-48 (1 eq) was dissolved in 10 mL acetonitrile and stirred at room temperature until completely dissolved. Then, the organic base N,N-diisopropylethylamine (DIEA, 2 eq) and the condensing agent 2-(1H-benzotriazo-L-1-yl)-1,1,3,3-tetramethylurea tetrafluoroborate (TBTU, 1 eq) were added sequentially to the reaction system. After stirring for 10 min, p-methoxyphenylhydrazine hydrochloride 2-1 (1.2 eq) was added, and the reaction was carried out at room temperature for 30 min. The reaction progress was monitored by thin-layer chromatography (TLC). After the reaction was complete, distilled water was added to terminate the reaction. A solid precipitated from the reaction system; this was directly filtered to obtain a silver solid product 3-22~3-50.

[0043] Step 2: In a 100 mL round-bottom flask, dissolve compounds 3-22~3-33 or 3-41~3-46 in dichloromethane. Under stirring, slowly add iodophenyl diacetic acid (1 eq) and stir at room temperature for 15 min. After the reaction is complete, extract the reaction mixture with dichloromethane. Wash the organic phase successively with saturated sodium carbonate solution, distilled water, and saturated sodium chloride solution. After drying with anhydrous sodium carbonate solution, remove the solvent under reduced pressure. Purify the crude product by silica gel column chromatography to obtain a brownish-red solid 4-22~4-33 or 4-41~4-46.

[0044] Step 3: In a 100 mL round-bottom flask, dissolve compounds 4-22~4-33 or 4-41~4-46 in dichloromethane. Cool the reaction system to 0°C, and slowly add m-chloroperoxybenzoic acid (1.5 eq) under low temperature conditions, stirring for 15 min. Then, heat the reaction system to 60°C and reflux for 6-12 h. After the reaction is complete, cool the reaction system to room temperature, wash successively with saturated sodium sulfite solution, distilled water, and saturated sodium chloride solution, dry with anhydrous sodium carbonate solution, and remove solvent under reduced pressure. The crude product is purified by silica gel column chromatography to obtain a yellow solid 5-22~5-33 or 5-41~5-46.

[0045] Step 4: In a 100 mL round-bottom flask, dissolve compounds 3-34~3-40 or 3-47~3-49 in chloroform. Under stirring, slowly add maleic anhydride (2 eq), stir at room temperature for 10 min, then add hydrogen peroxide (6 eq). Heat the reaction system to 100 °C and reflux for 8-24 h. After the reaction is complete, extract the reaction mixture with dichloromethane. Wash the organic phase successively with saturated sodium carbonate solution, distilled water, and saturated sodium chloride solution. After drying with anhydrous sodium carbonate solution, remove solvent under reduced pressure. The crude product is purified by silica gel column chromatography to obtain yellow solids 5-34~5-40 or 5-47~5-49. The NMR data of the compounds are shown in Table 2.

[0046] ; ; Table 2 Chemical structures of the compounds of this invention and 1 H NMR data ; ; ; ; ; Example 1

[0047] Pine wood nematode ( Bursaphelenchus xylophilus Bioactivity assay: The nematicidal activity of the target compound was determined using the immersion method. First, the test compound was dissolved in DMSO to prepare a 2% stock solution. This stock solution was then diluted with sterile distilled water containing 0.1% Tween-80 to obtain 100 μg / mL. -1 The working solution was prepared by adding 50 μL of the test solution and 50 μL of nematode suspension (approximately 500 nematodes, final concentration 50 μg·mL⁻¹) to each well of a 96-well plate. -1 Each process is set to 3 repetitions.

[0048] Compounds showing significant activity in the initial screening were serially diluted with sterile distilled water containing 0.1% Tween-80 to prepare test solutions at five concentration gradients. These solutions were then processed in 96-well plates, with 50 μL of the test solution and 50 μL of J2 nematode suspension (approximately 500 nematodes) added to each well, and each treatment was performed in triplicate. The treated 96-well plates were incubated in the dark at 23 ℃ for 24 hours. The survival status of the nematodes was observed using an electron microscope, with mortality rates ranging from 0% to 100%, where 0% indicated all pine wood nematodes were alive and 100% indicated all wood nematodes were dead. Statistical analysis of the experimental data was performed using software.

[0049] At 50 μg·mL -1 At certain concentrations, compounds 5-1 to 5-50 were used for preliminary screening of the indoor bioactivity of mixed-age pine wood nematodes. The specific results are shown in Table 3. The results indicate that when the 4-position of the left-side benzene ring is methoxy (R... 2 When the compound is OCH3, the nematicidal activity of the target compounds 5-1~5-8, 5-10, 5-21, 5-25, 5-30, 5-35, and 5-36 is 100%, while the nematicidal activity of the positive control emamectin benzoate is 25.51%.

[0050] Table 3. Compounds of the present invention at 50 μg·mL -1 Nematode activity against mixed-age pine wood nematodes at certain concentrations ;

[0051] Based on the preliminary screening results of indoor bioactivity of mixed-age pine wood nematodes, different concentrations were set to further determine the nematicidal activity of the target compound and positive control against pine wood nematodes. The LC50 of the target compound was obtained by data processing using software. 50 The results are shown in Table 4.

[0052] Table 4. LC50 of the target compound against second-instar larvae of pine wood nematode. 50 Measurement results ; As can be seen from Table 4, the LC50 of compounds 5-1 to 5-50 of this invention against second-instar larvae of pine wood nematode... 50 The concentrations ranged from 0.668 to 42.026 μg·mL. -1 All were superior to the positive control emamectin benzoate (LC50). 50 =48.42 μg·mL -1 It exhibited good nematicidal activity.

[0053] Example 2 The test compound was dissolved in acetone to prepare a 2% (w / w) stock solution, which was then serially diluted with sterile water containing 0.1% Tween-80 to obtain 200 μg / mL solutions. -1 and 50 μg·mL -1 The working concentration was determined by preparing a second-instar larval suspension to a concentration of 100 larvae / mL. 90 μL of larval suspension (approximately 2000 larvae) was added to each well of a 96-well plate, followed by 10 μL of different concentrations of drug solution (final concentration 20 μg / mL). -1 and 5 μg·mL -1 Each treatment was performed in duplicate, and incubated at 25 °C for 72 h. After incubation, the drug solution was removed and 100 μL of 2% sodium chloride solution was added. The insects were observed under an electron microscope after 2 min. Inanimate objects were considered dead if they were stiff and motionless, and alive if they were curled or twisted. The mortality rate was defined as 0-100%, where 0% indicates no insecticidal activity and 100% means all insects tested were dead.

[0054] LC of second instar larvae of pine wood nematode selected from compounds 5-1 to 5-21 50 Less than 10 μg·mL -1 The activity of the compounds in second-instar root-knot nematode larvae was determined, and the results are shown in Table 5. Compounds 5-1 to 5-3, 5-5 to 5-7, and 5-10 showed activity at 20 μg·mL⁻¹. -1 The caustic activity at the specified concentration is 100%, indicating good development potential.

[0055] Table 5. In vitro activity assays of the compounds of this invention against second-instar larvae of root-knot nematodes. ; Choose 5 μg·mL from compounds 5-22 to 5-50 -1 Compounds exhibiting 100% nematicidal activity against second-instar larvae of pine wood nematode at certain concentrations were tested against second-instar larvae of root-knot nematodes and soybean cyst nematodes. The results are shown in Table 6. Compounds 5-23–5-25 and 5-31 showed activity against second-instar larvae of root-knot nematodes at concentrations of 5 μg·mL⁻¹. -1 The nematicidal activities against root-knot nematodes at the specified concentrations were 100%, 82.56%, 100%, and 69.23%, respectively, and against soybean cyst nematodes were 68.75%, 88.93%, 75.64%, and 94.12%, respectively, showing good development prospects.

[0056] Table 6. In vitro activity assays of the compounds of this invention against second-instar larvae of root-knot nematodes and soybean cyst nematodes. ; Example 3

[0057] Rice stem nematode ( Aphelenchoides besseyi ) and stem nematodes ( Ditylenchus destroyer ) were placed in an incubator at 23 ℃ and cultured. The corresponding Botrytis cinerea ( Botrytis cinerea Incubate at 25 °C. The nematicidal activity test method is as described in Example 51.

[0058] Compound 5-10, exhibiting the best nematicidal activity, was selected for bioactivity assays against rice tip nematode and stem rot nematode. The results are shown in Table 7. Compound 5-10 showed the best nematicidal activity at a concentration of 25 μg·mL⁻¹. -1 At that time, the mortality rate against rice stem nematode was 89.48%, and the mortality rate against rice stem rot nematode was 100%; the concentration was 10 μg·mL -1 The mortality rate against rice stem nematode was 92.78%, and the mortality rate against rice stem rot nematode was 100%. At a concentration of 25 μg·mL⁻¹... -1 The lethality rates of abamectin against rice stem nematode and rice stem nematode were 34.59% and 50.38%, respectively.

[0059] Table 7. In vitro activity assays of the compounds of this invention against rice stem nematode and rice stem nematode. ; Example 4

[0060] The bactericidal activity was determined using the toxic culture medium method. A 2% (w / v) stock solution of the test compound was prepared using dimethylformamide (DMF) as the solvent. The solution was then diluted with sterile distilled water containing 0.1% (v / v) Tween-80 to obtain a 500 μg / mL solution. -1 The intermediate concentration working solution was prepared. The above working solution was mixed uniformly with sterilized PDA medium at a ratio of 1:9 (v / v) to achieve a final test concentration of 50 μg·mL⁻¹. -1 Commercial fungicides tebuconazole and azoxystrobin (concentration 50 μg·mL) were used. -1 The positive control was set up with three replicates for each treatment. The inoculated petri dishes were placed in a 25 ℃ incubator. The observation endpoint was defined as the colony diameter reaching 7 cm in the negative control group. The colony diameter of each treatment group was measured using calipers, and the inhibition rate was calculated.

[0061] Compound 5-10, selected from compounds 5-1 to 5-21, exhibited the best nematicidal activity against six pathogenic fungi, Rhizoctonia solani (…). Rhizoctonia solani Fusarium graminearum ( ), Fusarium gramineae ), Staphylococcus aureus ( Botryosphaeria dothidea Fusarium solani () Fusarium oxysporum ), Colloidal anthrax bacteria ( Colletotrichum gloeosporioides ), Botrytis cinerea ( Botrytis cinerea The bactericidal activity was determined. The results are shown in Table 8. (50 μg·mL⁻¹)-1 At the specified concentrations, the inhibition rates against Rhizoctonia solani, Staphylococcus aureus, and Botrytis cinerea all exceeded 80%, reaching 89.94%, 91.97%, and 98.06%, respectively.

[0062] Table 8 shows compounds 5-10 at 50 μg·mL -1 Results of bactericidal activity assay at concentrations ; Compounds 5-22 to 5-50 were selected to target the LC50 of second-instar larvae of pine wood nematode. 50 Less than 4 μg·mL -1 The compound is effective against eight pathogenic fungi, Rhizoctonia solani (Rhizoctonia solani). Rhizoctonia solani ), Sclerotinia sclerotiorum ( Sclerotinia sclerotiorum ), Botrytis cinerea ( Botrytis cinerea ), Staphylococcus aureus ( Botryosphaeria dothidea ), Colloidal anthracnose bacteria ( Colletotrichum gloeosporioides ), *Cyclocarya paliurus* ( Corynespora cassicola Alternaria ( ) Alternaria alternata ), Streptococcus faecalis ( Monilinia fructigen The bactericidal activity was determined, and the results are shown in Table 9. (50 μg·mL⁻¹) -1 At the specified concentrations, compounds 5-22~5-25, 5-31 and 5-36 all exhibited excellent fungicidal activity against eight pathogenic fungi, showing promising development potential.

[0063] Table 9 shows the compounds of the present invention at 50 μg·mL⁻¹ -1 Results of bactericidal activity assay at concentrations ; Example 5

[0064] The activity test for wheat powdery mildew was conducted using a live pot method. The test agent was dissolved in DMF to prepare a 5% stock solution, which was then diluted with 1% Tween water to the required concentration, serially diluted to 0.5%, and mixed according to the specified ratio before dilution. For each treatment, three pots of wheat plants with uniform growth were selected, and the solution was sprayed evenly using a spraying method. Each treatment was replicated three times. Twenty-four hours after application, wheat powdery mildew was inoculated using the spore-shaking method, and then the plants were moved to a suitable environment for cultivation. After the blank control showed complete disease development, 10 leaves from each pot were examined and graded as follows to calculate the control effect.

[0065] Compounds 5-23, 5-31, and 5-33, which exhibited superior fungicidal activity as shown in Table 9, were selected for in vivo activity testing against wheat powdery mildew. The results are shown in Table 10. At a concentration of 100 μg·mL⁻¹, compounds 5-23, 5-31, and 5-33 showed control efficacy of 88.52%, 80.00%, and 22.22% against wheat powdery mildew, respectively, indicating promising development prospects.

[0066] Table 10 shows the fungicidal activity of compounds 5-23 of the present invention against wheat powdery mildew at a concentration of 100 μg·mL⁻¹. ; Conclusion: The bioactivity assays of compounds 5-1 to 5-50 against pine wood nematode, root-knot nematode, soybean cyst nematode, rice tip nematode, stem rot nematode, and fungi indicate that carbonyl oxide azo compounds exhibit consistent bioactivity against multiple targets. Based on the results of Examples 50 to 54, and considering the nematicidal activity of compounds 5-1 to 5-50 against pine wood nematode, most compounds also demonstrate excellent nematicidal activity against root-knot nematodes, soybean cyst nematodes, rice tip nematodes, and stem rot nematodes, providing guidance for the development of nematicides in agriculture and forestry. Based on the results of Examples 50 and 55 to 56, and considering the nematicidal activity of compounds 5-1 to 5-50 against pine wood nematode, most compounds also demonstrate good nematicidal activity against Rhizoctonia solani (…). Rhizoctonia nightshade ), Sclerotinia sclerotiorum ( Sclerotinia sclerotiorum ), Botrytis cinerea ( Botrytis cinerea ), Staphylococcus aureus ( Botryosphaeria dothidea ), Colloidal anthracnose bacteria ( Colletotrichum gloeosporioides ), *Cyclocarya paliurus* ( Corynespora cassicola Alternaria ( ) Alternaria alternate ), Streptococcus faecalis ( Monilinia fructigen ) and wheat powdery mildew fungus (Phyllostachys bryony, a member of the Poaceae family, Blumeria grassinis Fungi such as [list of fungi] also have excellent bactericidal activity, providing guidance for the development of fungicides in agriculture and forestry.

[0067] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. The compound represented by Formula I, or its agriculturally acceptable salt: ； Formula I; in, R a Selected from C1-C6 alkyl groups, -(CH2) n -C6-C 10 Aryl; R b Selected from C3-C6 alkyl, C6-C 12 Aryl, -(CH2) n -C5-C containing N, O, and S atoms 12 heteroaryl, -(CH2) n -C3-C6 cycloalkyl; The C3-C6 alkyl, C6-C 12 Aryl, -(CH2) n -C5-C containing N, O, and S atoms 12 heteroaryl, -(CH2) n -C3-C6 cycloalkyl groups may be further optionally surrounded by one, two, or three independent R... c replace; The R c Selected from hydrogen, halogen, C1-C6 alkyl, halogen-substituted C1-C6 alkyl, C1-C6 alkoxy, -NHCOC1-C6 alkyl, -OCOC1-C6 alkyl, C6-C 12 Aryl, C6-C 12 aryloxy group, C6-C 12 Aryl-(CH2) n- Oxygen group, -NHCOOC1-C6 alkyl group, -NH-C6-C 12 Aryl, -COC1-C6 alkyl, C5-C6 containing N, O, or S atoms 12 Mixed aromatics; n is an independent selection from 0, 1, 2, 3, or 4.

2. The compound according to claim 1, or an agriculturally chemically acceptable salt thereof, characterized in that: in, The R a Selected from methyl or benzyl; The R b Selected from phenyl, naphthyl, thienyl, thiazolyl, -CH2-thiazolyl, furanyl, oxazolyl, pyrrolyl, imidazolyl, pyrazolyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, -CH2-cyclohexane, -(CH2)2-cyclohexane, -(CH2)3-cyclohexane, n-propane, n-butane, n-pentane, n-hexane, n-heptane; n is an independent selection from 0, 1, 2, 3, or 4.

3. The compound according to claim 1, or an agriculturally chemically acceptable salt thereof, characterized in that: in, The R c Selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, -CFH2, -CClH2, -CF2H, -CF3, -CH2CFH2, -CH2CF2H, -CH2CF3, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, phenyl, -NHCOCH3, -OCOCH3, PhO-, PhCH2O-, -NHCOOt-Bu, -COCH3, o-chloropyridyl; n is an independent selection from 0, 1, 2, 3, or 4.

4. The compound according to claim 1, or an agriculturally chemically acceptable salt thereof, characterized in that: in, R b Selected from , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , or .

5. The compound according to any one of claims 1-4, or an agriculturally chemically acceptable salt thereof, characterized in that: The compound described in Formula I is specifically: ； ； 。 6. A pesticide composition comprising at least one compound of Formula I according to any one of claims 1-5, or an agriculturally chemically acceptable salt thereof, and a carrier; said carrier being in liquid or solid form.

7. The use of the compound of formula I according to any one of claims 1-5, or an agriculturally chemically acceptable salt thereof, or the pesticide composition according to claim 6, in an agricultural insecticide, preferably wherein the agricultural pest is pine wood nematode, root-knot nematode, soybean cyst nematode, rice tip nematode, and stem rot nematode.

8. The application of the compound of formula I according to any one of claims 1-5, or an agriculturally chemically acceptable salt thereof, or the pesticide composition according to claim 6, in the control of plant fungal diseases, preferably, the plant fungal diseases being Rhizoctonia solani, Sclerotinia sclerotiorum, Botrytis cinerea, Botrytis cinerea, Colletotrichum gloeosporioides, Corynebacterium multiflorum, Alternaria alternata, Alternaria sclerotiorum, and wheat powdery mildew fungus.

9. A bactericide, characterized in that, The fungicide contains a fungicide effective amount of at least one of the compounds of formula I according to any one of claims 1-5, or an agriculturally chemically acceptable salt thereof, and optionally contains excipients; preferably, the formulation of the fungicide is selected from at least one of emulsifiable concentrates, suspension concentrates, wettable powders, powders, granules, aqueous solutions, mother liquors, and masterbatches.

10. A method for controlling or preventing the infection of useful plants by plant pathogenic microorganisms, wherein a fungicide effective amount of a compound having formula I according to any one of claims 1 to 5, or a composition containing such compound as an active ingredient, is applied to said plant, its parts, or its location.

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