A polychloropyridine amide derivative, its preparation method and application
By designing polychlorinated pyridine amide derivatives and their pesticide salts and complexes, the problems of drug resistance and environmental pollution of traditional fungicides have been solved, providing a highly efficient, safe, and green pesticide solution that enables effective control of a variety of plant diseases.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JINAN LEFENG CROP SCI CO LTD
- Filing Date
- 2026-04-02
- Publication Date
- 2026-06-05
Smart Images
Figure CN122145381A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of pesticide technology, and in particular to a polychlorinated pyridine amide derivative, its preparation method, and its application. Background Technology
[0002] Current agricultural disease control methods still primarily rely on fungicides. The widespread use of traditional fungicides has been accompanied by problems such as the development of pathogen resistance and environmental pollution risks. Many pathogens have developed severe resistance to some classic fungicides due to long-term use. With increasing environmental requirements, the creation of green pesticides will be a new trend in the future development of plant protection.
[0003] Therefore, it is necessary to provide a more efficient bactericide. Summary of the Invention
[0004] To discover more efficient, broad-spectrum, low-toxicity, and non-cross-resistance pesticide lead and candidate compounds, the inventors designed and synthesized a series of polychlorinated pyridine amide derivatives. In accordance with national standards for fungicide bioassays, the inventors conducted fungicidal activity tests on these polychlorinated pyridine amide derivatives. The relevant bioassay data show that the series of polychlorinated pyridine amide derivatives designed and synthesized by the inventors exhibit good fungicidal activity at low concentrations, low toxicity to non-target organisms, safety for mammals, and no negative environmental effects. This aligns with the development requirements of environmentally friendly green pesticides and has high research value.
[0005] To address at least one of the aforementioned technical problems, in a first aspect, this application provides a polychlorinated pyridine amide derivative or its pesticide-acceptable salt or metal ion complex, wherein the polychlorinated pyridine amide derivative is selected from the following structures: , , ; Wherein, R1 is selected from , , ; R2 is selected from , , , , , , , ;R 11 R 12 R 13 R 14 R 15 They are independently selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 alkoxy, halogen-substituted C1-C3 alkyl, and halogen-substituted C1-C3 alkoxy, respectively; R3 is selected from , , , , , , , , , , ; R4 is selected from , , , , , , , ; R 161 R 171 R 162 R 172 R 181 R 182 R 183 R 191 R 192 R 193 R 194 R 195 R 196 R 201 R 202 Each of the following groups is independently selected from hydrogen, hydroxyl, halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, halogen-substituted C1-C3 alkyl, and halogen-substituted C1-C3 alkoxy.
[0006] Preferably, R 11 Selected from methyl, trifluoromethyl, and difluoromethyl; R 12 Methyl; R 13 Selected from hydrogen and halogens; R 14 R 15 Each is independently selected from halogens, C1-C3 alkyl groups, and trifluoromethyl groups; R 161 R 171 R 162 R 172 Each is independently selected from hydrogen, halogen, and cyano groups; R 181 R 182 R 183 Each is independently selected from hydrogen and halogen; R 181 R 182 R 183 R 191 R 192 R 193 R 194 R 195 R196 Each of the following is independently selected from hydrogen, hydroxyl, halogen, C1-C3 alkyl, C1-C3 alkoxy, halogen-substituted C1-C3 alkyl, and halogen-substituted C1-C3 alkoxy; R 201 R 202 They are selected independently from hydrogen and halogens, respectively.
[0007] Preferably, R4 is selected from , , , , , , , , , , , .
[0008] Preferably, the compound numbers and corresponding structural formulas of the polychlorinated pyridine amide derivatives are shown in Table 1: Table 1 .
[0009] Preferably, the compound numbers and corresponding structural formulas of the polychlorinated pyridine amide derivatives are shown in Table 2: Table 2 .
[0010] Preferably, the compound numbers and corresponding structural formulas of the polychlorinated pyridine amide derivatives are shown in Table 3: Table 3 .
[0011] Secondly, this application provides a method for preparing the above-mentioned polychlorinated pyridine amide derivatives or their pesticide-acceptable salts or metal ion complexes. The reaction formula for preparing the polychlorinated pyridine amide derivatives is shown below: ; ; ; X is selected from F, Cl, Br, and I.
[0012] Thirdly, this application provides an agricultural bactericidal composition comprising the above-mentioned polychlorinated pyridine amide derivative or its pesticide-acceptable salt or metal ion complex.
[0013] Preferably, the agricultural fungicide composition further includes a commercial agricultural fungicide selected from benzothiadiazole, thiamethoxam, methomyl, isothiazamide, ribavirin, anthraquinone, ningnanmycin, or salicylic acid, cymoxanil, thiram, zinc thiram, mancozeb, aluminum fosetyl-aluminum, thiophanate-methyl, chlorothalonil, dichlorvos, iprodione, benzyl benzoate, thiophanate-methyl, thiophanate-methyl, metalaxyl, flumorph, dimethomorph, high-efficiency metalaxyl, high-efficiency benzyl benzoate, diclofenac, sulfadiazine, mesotrione, thiabendazole, chlorothalonil, propiconazole, propiconazole, cyclopropiconazole, cycloflufenoxam, cyclopropiconazole, cyproconazole, silthiamethoxam, carbendazim, oxychloride, carbendazim, methomyl, methylflufenoxam, fluopyram, furazolidone, thiabendazole, cyproconazole, pyraclostrobin. Pyraclostrobin, Bifenopyram, Fluopyram, Fluopyram, Fluopyram, Fluopyram, Fluopyram aniline, Benzopropoxyl, Isoprophiamol, Fluopyram hydroxylamine, Fluopyram, Fluopyram, Diyrylamide, Benzoylamide, Ethylpyridinium, Iprodione, Azoxystrobin, Fluopyram, Azoxystrobin, Fenoxystrobin, Oxystrobin, Azoxystrobin, Pyroximetris, Azoxystrobin Azoxystrobin, tebuconazole, tebuconazole, oxycyclazole, furazolidone, cyproconazole, difenoconazole, tebuconazole, high-efficiency tebuconazole, fluconazole, cyproconazole, fluquinazole, flusilazole, fenconazole, hexaconazole, imidacloprid, tebuconazole, tebuconazole, propiconazole, thiophanate-methyl, siloxyconazole, tebuconazole, tetraflufenazole, triazole, tebuconazole, bifenthrin Thiamethoxam, Wheat-Stalking Agent, Imazalil, High-efficiency Imazalil, Prochloraz, Fluopyram, Cyazofamid, Imidacloprid, Oxamid, Isoprothiolane, Oxamid, Pyrimethanil, Oxamid, Oxamid, Thiazolamide, Oxythiazoline, Cymoxanil, Cyclopyralid, Benzylthiocyanate, Dodecylmorpholine, Butylmorpholine, Tridemorpholine, Seed Treatment Pyrazosulfuron, Fludioxonil, Fluazinam, Pyridaben, Cyclopyralid, Fluazinam, Pyrimethanil, Azoxystrobin, Fluazinam, Thifluzamide, Azoxystrobin, Pyrimethanil, Chlorpheniramine, Fluazinam, Acaricide, Dicyananthraquinone, Ethoxyquinoline, Hydroxyquinoline, Propoxyquinoline, Phenoxyquinoline, Ethiocarb, Isopropamidone, Benzylthiazoline, Cymoxanil, Sulfocarb, Dichlorvos, Isoprothiolane, Pyridaben, Methyl Phosphate, Pyrimethanil, Kasugamycin, Polyoxin, Polyoxin Oxymycin, effectivemycin, jinggangmycin, streptomycin, metalaxyl, furazolidone, benzalkonium chloride, furazolidone, carbendazim, benomyl, thiophanate-methyl, triadimefon, ethirimol sulfonate, dimethomorph, ethirimol, captan, captan, vinclozolin, fluchlorothalonil, chlorothalonil, isoprothiolane, isoprothiolane, tebuconazole, pentachloronitrobenzene, propineb, aluminum triethylphosphonate, sulfur, Bordeaux mixture, copper sulfate, copper oxychloride, cuprous oxide, copper hydroxide, benomyl, pendimethalin, pyridaben, tetrachlorophthalide, quinclorac, spirocycline, tricyclazole, azithion, polyoxin, biguanide octyl salt, biguanide octylamine, chlorothalonil, benzylsulfonamide, toluenesulfonamide, indole ester, sodium dichloroisothiazoline, quinclorac, allylbenzylthiazide, and allylisothiazide.
[0014] Preferably, in the agricultural bactericidal composition, the mass percentage of the polychlorinated pyridine amide derivative or its pesticide-acceptable salt is 0.1%-99.9%.
[0015] Preferably, the agricultural bactericide composition further includes an adjuvant, wherein the adjuvant is present in the agricultural bactericide composition at a mass percentage of 0.1%-99.9%.
[0016] Preferably, the auxiliary agent includes at least one of a solvent and a surfactant.
[0017] Preferably, the polychlorinated pyridine amide derivative or its pesticide-acceptable salt is a salt obtained by reacting the polychlorinated pyridine amide derivative provided in this application with a chemically acceptable acid, wherein the chemically acceptable acid can be an inorganic acid or an organic acid. Preferably, the inorganic acid is selected from hydrochloric acid, sulfuric acid, phosphoric acid, or hydrobromic acid. The organic acid is selected from oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid, or benzoic acid.
[0018] Preferably, the metal ion complex of the polychlorinated pyridine amide derivative is a metal ion complex obtained by reacting the polychlorinated pyridine amide derivative provided in this application with a chemically acceptable metal salt. The chemically acceptable metal salt can be an inorganic salt or an organic acid salt. Preferably, the inorganic salt is selected from copper sulfate, zinc sulfate, manganese sulfate, ferric sulfate, copper phosphate, ferric phosphate, zinc phosphate, manganese phosphate, or copper chloride, ferric chloride, zinc chloride, manganese chloride, copper bromide, zinc bromide, ferric bromide, and manganese bromide. The organic acid salt is selected from the copper, zinc, iron, and manganese organic acid metal salts corresponding to oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid, or benzoic acid.
[0019] Preferably, the formulation of the agricultural bactericidal composition is selected from: seed treatment emulsions, water-in-oil emulsions, microemulsions, suspensions, capsule suspensions, water-soluble granules, fine granules, soluble concentrates, poisoned grains, block poisoned bait, granular poisoned bait, flake poisoned bait, concentrated poisoned bait, slow-release blocks, electrostatic sprays, oil-in-water emulsions, smoke cans, smoke candles, smoke tubes, smoke sticks, smoke sheets, smoke pellets, gas generators, ointments, hot fogging agents, cold fogging agents, aerosols, solid / liquid mixtures, liquid / liquid mixtures, solid / solid mixtures, medicated paints, microparticles, tracking powders, oil suspensions, oil-dispersible powders, concentrated gels, pouring agents, seed coating agents, coating agents, film-forming oils, ultra-low volume liquids, and vapor release agents.
[0020] Fourthly, this application provides the use of the above-mentioned polychlorinated pyridine amide derivatives or their pesticide-acceptable salts, metal ion complexes or the above-mentioned agricultural fungicidal compositions in the preparation of fungicides.
[0021] Preferably, the fungus includes at least one of the following: Rhizoctonia solani, Pyrrosia lingua, Fusarium graminearum, Fusarium pseudograminearum, Fusarium verticillatum, Sclerotinia sclerotiorum, Botrytis cinerea, Polytrichum candida, Fusarium oxysporum strawberry-specific, Staphylococcus aureus, Corynebacterium tumefaciens, Colletotrichum gloeosporioides, Colletotrichum gloeosporioides, and Phytophthora sacchariformis.
[0022] In summary, this application includes at least one of the following beneficial technical effects: 1. This application provides a polychlorinated pyridine amide derivative or its pesticide-acceptable salt or metal ion complex, which has excellent antibacterial effect.
[0023] 2. This application also provides a method for preparing the above-mentioned polychlorinated pyridine amide derivatives or their pesticide-acceptable salts or metal ion complexes, which is simple to prepare and easy to produce.
[0024] 3. This application provides an agricultural bactericide composition comprising the above-mentioned polychlorinated pyridine amide derivative or its pesticide-acceptable salt or metal ion complex, which has excellent antibacterial activity.
[0025] 4. The present invention also provides the application of the above-mentioned polychlorinated pyridine amide derivatives or their pesticide-acceptable salts and metal ion complexes in the preparation of antibacterial agents. Detailed Implementation
[0026] The present invention will be further described below with reference to specific embodiments. However, these embodiments are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified, specific conditions in the following embodiments are performed under conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, the methods used are conventional methods known in the art, and the consumables and reagents used are commercially available. Unless otherwise stated, the technical and scientific terms used herein have the same meaning as those familiar with the art. Furthermore, any methods or materials similar to or equivalent to those described herein may also be applied to the present invention.
[0027] Example 1 The structural formulas and corresponding compound numbers of the polychlorinated pyridine amide derivatives provided in this application are shown in Table 1 of the invention description.
[0028] The reaction formula for preparing the polychlorinated pyridine amide derivative is shown below: ; ; ; Where X is Cl.
[0029] The preparation method of the polychlorinated pyridine amide derivative of this application will be illustrated below using the preparation of compound 3 as an example.
[0030] The structural formula of compound 3 is as follows:
[0031] The chemical reaction equation for the preparation of compound 3 is as follows: ; The specific experimental procedure was as follows: 2,3,5,6-Tetrachloro-4-aminopyridine (2.3 g, 10 mmol) was added to dichloroethane (10 mL), followed by the dropwise addition of triethylamine (1.0 g, 10 mmol). After stirring at room temperature for 10 min, a dichloroethane solution (5 mL) of compound 3,5,6-trichloro-2-pyridinecarboxyl chloride (10 mmol) was added, and the mixture was stirred at room temperature for 8 h. After the reaction was complete, the solvent was removed, and then 10 mL of ethyl acetate and 10 mL of water were added sequentially. After thorough stirring, the ethyl acetate phase was separated. The ethyl acetate phase was dried over sodium sulfate, the solvent was removed, and the solid was recrystallized in dichloroethane to obtain 3.6 g of a white powdery solid with a melting range of 197.4–199.2 °C, which was compound 3, with a yield of 81.5%.
[0032] The preparation methods for the other compounds in Table 1 are the same as those for compound 3, except that the definitions of R1, R2, R3, and R4 in the reactants are different. Characterization data for some preferred polychlorinated pyridine amide derivatives in Table 1 are shown in Table 2.
[0033] Table 4 Characterization data of some polychlorinated pyridine amide derivatives in this application
[0034] Example 2: Bactericidal effect test of the polychlorinated pyridine amide derivatives provided in this application Referring to the People's Republic of China Agricultural Industry Standard "Guidelines for Indoor Bioassay Testing of Pesticides - Fungicides Part 2: Test for Inhibition of Mycelial Growth of Pathogenic Fungi - Plate Method" NY / T 1156.2-2006, the fungicidal or bacteriostatic activity of the polychlorinated pyridine amide derivatives and their pesticide-acceptable salts in this invention is determined by the cell growth rate method. The specific steps are as follows: (1) Preparation of PDA medium: The medium was prepared using potato dextrose agar powder, with a ratio of 100 mL deionized water for every 4.6 g of powder. (2) Preparation of the drug solution: Weigh 0.1 g of the original drug (the polychlorinated pyridine amide derivative and positive control drug provided in this application), dissolve it in acetone, and dilute to 10 mL in a volumetric flask to obtain a concentration of 10. 4 The mother liquor of mg / L was diluted 10 times with 0.1wt% Tween 80 aqueous solution to obtain 10 mg / L. 3 Prepare a solution of mg / L of the drug for later use; (3) Drug processing: Under aseptic conditions, take 1 mL of 10 3 A 10 mg / L drug solution was added to 99 mL of sterilized PDA medium and shaken thoroughly to obtain a final drug-containing medium with a concentration of 10 mg / L. The medium was then poured into 9 cm diameter petri dishes to prepare 10 mg / L drug-containing plates. Simultaneously, a blank control plate (containing no drug) was prepared. (4) Inoculation: Select vigorous pathogens with neat edges. Under aseptic conditions, use a 5 mm punch to cut off the mycelial cake from the edge of the colony. Place the mycelial cake in the center of the drug-containing plate and the blank control plate using an inoculator, and cover the plate. Wrap the inoculated plate with plastic wrap and place it in a constant temperature incubator at 24±1℃. Each treatment is repeated 3 times. The experiment includes positive control drug groups (CK1, CK2, CK3, CK4) with the same concentration and a blank control group corresponding to the blank control plate. (5) Investigation: Based on the mycelial growth of the blank control group, the data were measured by the cross-cross method, the average value was calculated, and the mycelial growth inhibition rate of the drug-treated group was calculated by comparing with the blank control. The results were calculated. The formula for calculating the colony growth diameter is: ; Where D is the colony growth diameter, D1 is the colony diameter after culture, and D2 is the diameter of the mycelial cake; The formula for calculating the mycelial growth inhibition rate is: ; Where I represents the mycelial growth inhibition rate, in %, D0 represents the colony growth diameter of the blank control group, and D t The diameter of the colony growth in the drug-treated group.
[0035] (6) Secondary screening: Select agents with a mycelial growth inhibition rate of over 80% and determine their EC50. 50 EC 90 Equivalent values. Based on the drug activity, five gradient concentrations were set up, and other experimental methods were the same as above.
[0036] The common plant pathogenic fungi tested in this invention are coded and named as follows: RS: Rhizoctonia solani, its Latin name is: Rhizoctonia solani, PO: The Latin name of *Pyrrosia lingua* is: Rice blastCavara Fg: Fusarium graminearum, its Latin name is: Fusarium graminearum, F. p: Fusarium graminearum, its Latin name is: Fusarium pseudograminearum, F. s: Fusarium pseudoverticum, its Latin name is: Fusarium sporotrichioides、S. s： Sclerotium sclerotiorum, its Latin name is: Sclerotinia sclerotiorum, B. c: Botrytis cinerea, its Latin name is: Botrytis cinerea, Cc: Corynebacterium multiflorum, its Latin name is: Corynespora cassiicola, F. o: Fusarium oxysporum strawberry-specific strain, its Latin name is: Fusarium oxysporum f. sp. Fragariae, B. d: Staphylococcus aureus, its Latin name is: Botryosphaeria dothidea、C. m: Apple black rot fungus, its Latin name is: Cytospora mali Grove C. g: Colletotrichum candida, its Latin name is: Colletotrichum gloeosporioides (Penz.) Penz.&Sacc.、 P.s.: Phytophthora indicum, its Latin name is: Phytophthora sojae (Kaufm. & Gerd.); These strains are highly representative and can represent most of the pathogens occurring in the field during agricultural production. The results of the cell growth rate method are shown in Table 5, and the results of the gradient experiment are shown in Table 6.
[0037] Four compounds were set up as positive control drugs: CK1, CK2, CK3, and CK4. The structural formulas of CK1, CK2, CK3, and CK4 are as follows:
[0038] Table 5. Bactericidal activity test results (%) of some polychlorinated pyridine amide derivatives provided in this application
[0039] As shown in Table 5, the polychlorinated pyridine amide derivatives provided by this invention all exhibit varying degrees of fungicidal activity. Using compounds with similar chemical structures to the polychlorinated pyridine amide derivatives provided by this invention and different types of commercial fungicides (chlorothalonil) as positive controls, the bioactivity of the polychlorinated pyridine amide derivatives was determined. Unexpected results were obtained: although the three compounds with structures similar to the polychlorinated pyridine amide derivatives provided by this invention and the fungicide chlorothalonil all showed certain fungicidal activity, under the same test conditions, the polychlorinated pyridine amide derivatives provided by this invention showed remarkable specificity, exhibiting ideal control effects against certain plant diseases and suitable for further development and utilization as a commercial agricultural fungicide.
[0040] Furthermore, for some polychlorinated pyridine amide derivatives with excellent bactericidal activity, further bioassays were conducted. Five concentration gradients were set based on the agent's activity, and other experimental methods were the same as above. EC was calculated. 50 EC 90 The relevant results are shown in Table 6.
[0041] Table 6 shows the results of the bactericidal activity gradient test of some of the preferred compounds.
[0042] As shown in Table 6, the polychlorinated pyridine amide derivatives provided in this application exhibit good bactericidal activity, which is unexpected and incredible to those skilled in the art without creative effort.
[0043] The above are all preferred embodiments of this application, and are not intended to limit the scope of protection of this application. Therefore, all equivalent changes made in accordance with the structure, shape and principle of this application should be covered within the scope of protection of this application.
Claims
1. A polychlorinated pyridine amide derivative or its pesticide-acceptable salt or metal ion complex, characterized in that, The polychlorinated pyridine amide derivatives are selected from the following structures: 、 、 ； Wherein, R1 is selected from , , ; R2 is selected from , , , , , , , ;R 11 R 12 R 13 R 14 R 15 They are independently selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 alkoxy, halogen-substituted C1-C3 alkyl, and halogen-substituted C1-C3 alkoxy, respectively; R3 is selected from , , , , , , , , , , ; R4 is selected from , , , , , , , ; R 161 R 171 R 162 R 172 R 181 R 182 R 183 R 191 R 192 R 193 R 194 R 195 R 196 R 201 R 202 Each of the following groups is independently selected from hydrogen, hydroxyl, halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, halogen-substituted C1-C3 alkyl, and halogen-substituted C1-C3 alkoxy.
2. The polychlorinated pyridine amide derivative or its pesticide-acceptable salt or metal ion complex according to claim 1, characterized in that, R 11 Selected from methyl, trifluoromethyl, and difluoromethyl; R 12 Methyl; R 13 Selected from hydrogen and halogens; R 14 R 15 Each is independently selected from halogens, C1-C3 alkyl groups, and trifluoromethyl groups; R 161 R 171 R 162 R 172 Each is independently selected from hydrogen, halogen, and cyano groups; R 181 R 182 R 183 Each is independently selected from hydrogen and halogen; R 181 R 182 R 183 R 191 R 192 R 193 R 194 R 195 R 196 Each of the following is independently selected from hydrogen, hydroxyl, halogen, C1-C3 alkyl, C1-C3 alkoxy, halogen-substituted C1-C3 alkyl, and halogen-substituted C1-C3 alkoxy; R 201 R 202 They are selected independently from hydrogen and halogens, respectively.
3. The polychlorinated pyridine amide derivative or its pesticide-acceptable salt or metal ion complex according to claim 1, characterized in that, The polychlorinated pyridine amide derivatives are selected from the following structures: 。 4. The polychlorinated pyridine amide derivative or its pesticide-acceptable salt or metal ion complex according to claim 1, characterized in that, The polychlorinated pyridine amide derivatives are selected from the following structures:
5. A method for preparing a polychlorinated pyridine amide derivative or its pesticide-acceptable salt or metal ion complex according to any one of claims 1-4, characterized in that, The reaction formula for preparing the polychlorinated pyridine amide derivative is shown below: ; ； ； X is selected from F, Cl, Br, and I.
6. An agricultural bactericidal composition, characterized in that, Includes the polychlorinated pyridine amide derivatives as described in any one of claims 1-4, or their pesticide-acceptable salts or metal ion complexes.
7. The agricultural bactericidal composition according to claim 6, characterized in that, In the agricultural bactericidal composition, the mass percentage of the polychlorinated pyridine amide derivative or its pesticide-acceptable salt is 0.1%-99.9%.
8. The agricultural bactericidal composition according to claim 6, characterized in that, It also includes adjuvants, wherein the adjuvants in the agricultural bactericidal composition are 0.1%-99.9% by mass.
9. The use of a polychlorinated pyridine amide derivative of any one of claims 1-4 or its pesticide-acceptable salt, metal ion complex or the agricultural fungicide composition of any one of claims 6-8 in the preparation of a fungicide.
10. The application according to claim 9, characterized in that, The fungi include at least one of the following: Rhizoctonia solani, Pyrrosia lingua, Fusarium graminearum, Fusarium pseudograminearum, Fusarium verticillatum, Sclerotium sclerotiorum, Botrytis cinerea, Polytrichum candida, Fusarium oxysporum strawberry-specific, Staphylococcus aureus, Corynebacterium tumefaciens, Colletotrichum gloeosporioides, Colletotrichum gloeosporioides, and Phytophthora sacchariformis.