WO2020078426A1 - 一种杀菌组合物及其应用 - Google Patents

一种杀菌组合物及其应用 Download PDF

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WO2020078426A1
WO2020078426A1 PCT/CN2019/111693 CN2019111693W WO2020078426A1 WO 2020078426 A1 WO2020078426 A1 WO 2020078426A1 CN 2019111693 W CN2019111693 W CN 2019111693W WO 2020078426 A1 WO2020078426 A1 WO 2020078426A1
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azoxystrobin
composition according
bactericidal composition
compound
fungicide
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PCT/CN2019/111693
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English (en)
French (fr)
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杜辉
任新峰
何莹
朱艳梅
许映蓉
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南通江山农药化工股份有限公司
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products

Definitions

  • the invention relates to a preparation and application technology of an agricultural sterilization composition.
  • the varieties of fungicides containing a single active ingredient have different degrees of defects in the process of agricultural sterilization: continuous use is easy to produce drug resistance, and the bactericidal spectrum is not wide enough to provide very comprehensive protection for crops.
  • the prevention effect can be improved, the amount of effective ingredients used can be reduced, the cost of prevention and control can be saved, the sterilization effect can be enhanced, the service life of the agent can be extended, and the pollution to the environment can be reduced.
  • Patent CN104649973A discloses a pyrazole amide compound and its use, in which it is reported that the compound represented by the general formula I ( Figure 1) has good activity against various fungal diseases.
  • the invention with patent application number 2014105792666 belongs to the technical field of agricultural insecticides, and particularly relates to a compound insecticidal composition of dihalopyrazolamide and imazalil.
  • the effective components are dihalopyrazolamide and pyraclostrobin; the weight ratio of the two is 1: 4-7, preferably 1: 5.
  • the invention is composed of active ingredients with different action mechanisms. The increased action sites are beneficial to overcome and delay the emergence of insect resistance, and broaden the insecticidal spectrum; the drug efficacy is greatly improved, the prevention effect time is long, and the field dosage of active ingredients Declining, reducing production and use costs, reducing pesticide residues and environmental pollution. This invention gives a beneficial inspiration for the development of the present invention.
  • Purpose of the invention to mix fungicides with different action mechanisms, make full use of the synergistic effect produced by the mixing of the two, and to provide a highly effective, low toxicity, low cost, multi-purpose pesticide sterilization composition.
  • a bactericidal composition mentioned in the present invention contains at least two active ingredients, such as three kinds of coating agents, one is a compound whose component A is selected from the general formula I, the other Component B, selected from triazole fungicides prothioconazole, difenoconazole, tebuconazole, hexaconazole, epoxiconazole, oxiconazole, nitrile azole, flusilazole, powder azole alcohol , Myclobutanil, penconazole, propiconazole, tetraflufenazole, triazole alcohol, bifentriazole or triazolone; or selected from methoxyacrylic fungicides azoxystrobin, trifluconate , Azoxystrobin, azoxystrobin, pyraclostrobin, fluoxastrobin, azoxystrobin, syringare, azoxystrobin, azoxystrobin or pyra
  • A is selected from compounds represented by general formula I:
  • R 1 is selected from hydrogen or methyl
  • R 2 is selected from methyl, ethyl, n-propyl or isopropyl.
  • B is selected from the triazole fungicides prothioconazole, difenoconazole, tebuconazole, hexaconazole, fluconazole, oxiconazole, nitrile azole, flusilazole, powder triazole, myclobutanil , Penconazole, propiconazole, tetraflurazole, triazolol, bifentriol or triadimefon; or selected from the group consisting of methoxyacrylic acid fungicides azoxystrobin, azoxystrobin, trifloxystrobin , Ticlostrobin, pyraclostrobin, fluoxastrobin, fluoxastrobin, fenoxacon, syringare, azoxystrobin, azoxystrobin or pyraclostrobin; or selected from the protective fungicide chlorothalonil , Mancozeb, Famex, etc .; or selected from biogenic or antibiotic
  • the ratio of A and B is 1: 100 to 100: 1 based on the mass fraction of the active ingredient.
  • 1 to 40: 1 to 5 basically have a synergistic effect.
  • the preferred ratio is 1: 5 to 5: 1, which has a significant synergistic effect.
  • the bactericidal composition is added with auxiliary agents and excipients, and is prepared into any dosage form suitable for agricultural use according to the production process known to those skilled in the art.
  • the better dosage forms include film spreading oil agent and suspended seed coat. Agent, suspending agent, wettable powder, smoking agent, water dispersible granules (spray granulation method).
  • the adjuvants and excipients include surfactants, dispersants, wetting agents, emulsifiers, disintegrants, stabilizers, thickeners, binders, etc. and other beneficial ingredients to stabilize and
  • the known substances that exert drug effects are various components commonly used or allowed in pesticide formulations, and are not particularly limited. The specific components and dosages are confirmed by tests according to the formulation requirements.
  • the present invention provides a kind of use of the above sterilization composition for preventing and controlling crop diseases of rice, wheat, corn, fruits and vegetables and protecting crop health. It can be used to control rice sheath blight, wheat rust, soybean rust, corn rust, gray mold, powdery mildew, black spot, rice blast, stalk rot, root rot, seedling rot, seed and soil transmission Diseases, etc.
  • B uses hexaconazole, and the mass ratio of A and B is 1-50: 1. It is used to control rice sheath blight and has a good control effect.
  • a and B uses thiophanate methyl, and the mass ratio of A and B is 1 to 5: 5 to 1. It is used to control wheat scab and has a good control effect.
  • B uses pyraclostrobin, and the mass ratio of A and B is 1 to 5: 1. It is used to control gray mold of grape and has a good control effect.
  • B uses azoxystrobin, and the mass ratio of A and B is 1 to 5: 5 to 1. It is used to control corn rust and has a good control effect.
  • the two active ingredients are compounded, the mechanism of action is complementary, there is no mutual resistance, the use of pesticides is reduced, which reduces the cost and the pollution to the environment, which is beneficial to the treatment of disease resistance, and its promotion and application have huge Economic and social benefits.
  • the bactericidal composition of the present invention has an obvious synergistic effect, is conducive to expanding the bactericidal spectrum, is beneficial to delaying the emergence of drug resistance or drug resistance treatment, and is used in the field of plant protection to prevent and control crop diseases such as rice, wheat, corn, fruits and vegetables and protect crops Health, improve the yield and quality of crops.
  • FIG. 1 is a chemical structural formula (general formula I) of compound A in the present invention.
  • Bioassay Example 3 Compound A has a broad bactericidal / bacteriostatic activity against plant pathogens:
  • Compound A has bio-inhibitory / bactericidal activity against 16 plant pathogenic bacteria at a dose of 10-0.1 mg / L, among which the activity against Rhizoctonia cerealis and Fusarium is significant.
  • Bioassay Example 4 Compound A is generally safe for crops:
  • Compound A is safe for rice, wheat, corn, soybean, cucumber and other five crops at a dose of 100-400 mg / L.
  • Bioassay Example 5 compound A and triazole fungicide hexazol have a significant synergistic effect on rice sheath blight:
  • Composition A, hexaconazole and their respective ratios have excellent activity against Rhizoctonia solani, within the range of 100: 1 to 1: 100, with a co-toxicity coefficient of 110.05 to 293.33, all with phase Add to the synergistic effect, when the ratio is in the range of 1: 1 ⁇ 50: 1, the co-toxicity coefficient is greater than 150, the synergistic effect is significant.
  • Bioassay Example 6 compound A and thiophanate-methyl have a significant synergistic effect on wheat scab:
  • Composition A, thiophanate-methyl and their respective ratios all have good activity against wheat Fusarium graminearum, within the range of 80: 1 to 1:80, with a co-toxicity coefficient of 95.53 to 214.90 Adding to the synergistic effect, when the ratio is within the range of 1: 5 to 5: 1 and 20: 1, the co-toxicity coefficient is greater than 150, and the synergistic effect is significant.
  • Leaf method refer to NY / T1156.9-2008; evaluation of the combined effect of mixing refers to NY / T1156.6-2006.
  • composition A, pyraclostrobin and their respective ratios have excellent activity against Botrytis cinerea, in the range of 1: 60 ⁇ 60: 1, the co-toxicity coefficient is 109.31 ⁇ 196.57, All have additive to synergistic effects. When the ratio is 1: 1 to 5: 1, the co-toxicity coefficient is greater than 150, and the synergistic effect is significant.
  • Bioassay Example 8 compound A and pyrithiol have a synergistic effect on cucumber powdery mildew:
  • composition A, pyrithiol and their respective ratios have excellent activity against cucumber powdery mildew.
  • the co-toxicity coefficient is 80.72 ⁇ 147.06.
  • the ratio is 1: 75 ⁇ 1: 1
  • the co-toxicity coefficient is greater than 120, which has synergistic effect.
  • test agents are the original compound A and 95% azoxystrobin, the test concentrations are 25, 6.25, 1.56, 0.78, 0.39, 0.195 mg / L; select the corn seedlings in the three-leaf stage of potted plants with uniform growth and uniformity, as set
  • the concentration was sprayed on the crop sprayer and inoculated with corn rust spore suspension (5 ⁇ 10 6 pieces / ml) after 24 hours and sprayed on the host crop. After inoculation, place in an artificial climate room (temperature: 25 fog in the day, 20 fog at night, relative humidity: 95%) and cultivate for 1 day, then transfer the plants to the greenhouse for normal management, and investigate the control effect of the compound after 7 days, and calculate the control based on the disease index effect.
  • Level 1 The lesion area accounts for less than 5% of the entire leaf area
  • Level 3 The lesion area accounts for 6% -10% of the entire leaf area
  • Level 5 The area of diseased spots accounts for 11% -25% of the whole leaf area
  • Level 7 The area of the diseased area accounts for 26% -50% of the entire leaf area
  • Grade 9 The lesion area accounts for more than 50% of the entire leaf area.
  • the test site was set up in the Jiangsu Coastal Area Agricultural Science Research Institute, the rice variety "Huaidao No. 14".
  • the chemical treatment set up 25% Compound A ⁇ Hexazolol SC 75, 150, 225, 300 gai / ha, 25% Compound A 9 treatments including suspension agent 150, 225gai / ha, 5% hexaconazole SC 75, 150gai / ha, and blank control, with a cell area of 35m 2 , repeated 3 times, and arranged in random blocks in the cell. A total of 2 drugs were administered.
  • the 25% compound A. hexaconazole SC of the bactericidal composition has excellent control effect on rice sheath blight and is superior to the control effect of two single agents.
  • the control effects of the composition, compound A, and hexaconazole were 91.18%, 84.97%, and 83.65%, respectively.
  • the bactericidal composition had a significant advantage, and also showed a synergistic effect in the field.
  • Bioassay Example 11 40% compound A ⁇ azoxystrobin SC (of which: compound A 30 + azoxystrobin 10) field efficacy test for controlling wheat rust:
  • the test site was located in Yangling Demonstration Zone, Xianyang City, Shaanxi province. With an area of 2.0 mu, the wheat variety is Xinong 979.
  • the soil type is soil, the pH value is neutral, and the management level is average.
  • the experiment assumes that 0% compound A ⁇ azoxystrobin SC has 100, 150, 200, 200 gai / ha, 25% compound A suspending agent 150, 225gai / ha, 25% azoxystrobin SC 150, 200 gai / ha, and blank control, etc. 9 treatments, 3 repetitions, 2 application times. A total of 2 medications were administered, and an investigation was conducted 7 days after the second medication. Refer to GB / T17980.23-2000 "Guidelines for field efficacy test of fungicides to control cereal rust disease".
  • the 40% compound A. azoxystrobin SC of the bactericidal composition has a good control effect on wheat rust, and is superior to the control effect of two single agents.
  • the control effects of the composition, compound A, and azoxystrobin were 82.65%, 73.86%, and 77.21%;
  • the control effects of the composition, compound A, and azoxystrobin were respectively 89.49%, 81.56%, 82.05%;
  • the bactericidal composition has a significant advantage, and also shows synergistic effects in the field.

Abstract

公开了一种杀菌组合物，含有化合物A及化合物B两种活性成分，A为具有如通式（I）所示的化合物；B选自三唑类杀菌剂、甲氧基丙烯酸酯类杀菌剂、保护性杀菌剂、生物源或抗生素类杀菌剂。其可以配制成展膜油剂、悬浮种衣剂、悬浮剂、可湿性粉剂、烟剂或水分散粒剂。杀菌组合物具有明显的增效作用，有利于扩大杀菌谱，有利于延缓抗药性产生或抗药性治理，提高农作物的产量和质量。

Description

一种杀菌组合物及其应用 技术领域
本发明涉及一种农用杀菌组合物的制备和应用技术。
背景技术
含有单一活性成分的杀菌剂品种在农业杀菌过程中存在不同程度的缺陷：连续使用容易产生抗药性，杀菌谱不够广，不能为作物提供非常全面的保护作用。通过两种或两种以上活性组分的复配，可以提高防效，减少有效成分的使用量，节约防除成本，增强杀菌效果，延长药剂使用寿命，并减少对环境的污染。
专利CN104649973A公开了一种吡唑酰胺类化合物及其用途,其中报道了如通式I(附图1)所示的化合物对多种真菌病害具有很好的活性。
其中，R 1＝CH 3、R 2＝n-Pr的化合物(CN104649973A中化合物5)对多种病害具有很好的活性，可以有效地防治水稻纹枯病、小麦锈病、大豆锈病、玉米锈病、灰霉病，白粉病，黑星病，水稻稻瘟病、茎腐病、根腐病，苗腐病、种传和土传病害等。
专利申请号为2014105792666的发明属于农业杀虫剂技术领域，特别涉及一种二卤代吡唑酰胺与唑虫酰胺复配杀虫组合物。其有效成分为二卤代吡唑酰胺与唑虫酰胺；两者的重量比为1:4～7，优选1:5。该发明由不同作用机制的有效成分组成，作用位点增加，有利于克服和延缓虫害抗药性的产生，并且拓宽了杀虫谱；药效大幅度提高，防效时间长，有效成分的田间用量下降，降低了生产和使用成本，减少农药残留和环境污染。该发明给予本发明的研发有益启示。
发明内容
发明目的：将作用机制不同的杀菌剂进行混配，充分利用二者混配产生的增效作用，提供一种高效、低毒、低成本、多用途的农药杀菌组合物。
本发明提到的一种杀菌组合物：该组合物至少含有两种活性成分，如做成种衣剂可以是三种，一种为组分为A选自通式I的化合物，另一种组分为B，选自三唑类杀菌剂丙硫菌唑、苯醚甲环唑、戊唑醇、己唑醇、氟环唑、烯唑醇、腈苯唑、氟硅唑、粉唑醇、腈菌唑、戊菌唑、丙环唑、四氟醚唑、三唑醇、联苯三唑醇或三唑酮；或选自甲氧基丙烯酸酯类杀菌剂嘧菌酯、醚菌酯、肟菌酯、啶氧菌酯、吡唑醚菌酯、氟嘧菌酯、肟醚菌胺、丁香菌酯、烯肟菌酯、烯肟菌胺或唑菌酯；或选自保护性杀菌剂百菌清、代森锰锌、福美双等；或选自生物源或抗生素类杀菌剂井冈霉素、中生菌素、多抗霉素、春雷霉素等；或选自其他类杀菌剂啶菌恶唑、拌种咯、多菌灵、甲基硫菌灵、咪鲜胺、咯菌腈、乙嘧酚、三环唑、稻瘟酰胺、腐霉利等。本发明的技术方案：一种杀菌组合物，含有A、B两种活性成分，其特征在于：
A选自如通式I所示的化合物：
式中：R 1选自氢或甲基，R 2选自甲基、乙基、正丙基或异丙基。
本发明较优选的技术方案为：上述杀真菌组合物中，活性组分A选自通式I中R 1＝甲基、R 2＝正丙基的化合物A。
B选自三唑类杀菌剂丙硫菌唑、苯醚甲环唑、戊唑醇、己唑醇、氟环唑、烯唑醇、腈苯唑、氟硅唑、粉唑醇、腈菌唑、戊菌唑、丙环唑、四氟醚唑、三唑醇、联苯三唑醇或三唑酮；或选自甲氧基丙烯酸酯类杀菌剂嘧菌酯、醚菌酯、肟菌酯、啶氧菌酯、吡唑醚菌酯、氟嘧菌酯、肟醚菌胺、丁香菌酯、烯肟菌酯、烯肟菌胺或唑菌酯；或选自保护性杀菌剂百菌清、代森锰锌、福美双等；或选自生物源或抗生素类杀菌剂井冈霉素、中生菌素、多抗霉素、春雷霉素等；或选自其他类杀菌剂啶菌恶唑、拌种咯、多菌灵、甲基硫菌灵、咪鲜胺、咯菌腈、乙嘧酚、三环唑、稻瘟酰胺、腐霉利等。
A、B的比例基于活性成分的质量分数为1:100～100:1，如实施例附表所示1～40:1～5基本均具有增效作用。优选比例为1:5～5:1，具有显著增效作用。
所述的杀菌组合物加入助剂及赋型剂，按照本领域技术人员均知的生产工艺，制备成适合农业上使用的任意一种剂型，比较好的剂型有展膜油剂、悬浮种衣剂、悬浮剂、可湿性粉剂、烟剂、水分散粒剂(喷雾造粒法)。
所述的助剂及赋型剂包括表面活性剂、分散剂、润湿剂、乳化剂、崩解剂、稳定剂、增稠剂、粘合剂等及其他有益于有效成分在制剂中稳定和发挥药效的已知物质，都是农药制剂中常用或允许使用的各种成分，并无特别限定，具体成分和用量根据配方要求通过试验确认。
本发明提供上述杀菌组合物的一类用途，用于防治水稻、小麦、玉米、果蔬的作物病害及保护作物健康。具体可用于防治水稻纹枯病、小麦锈病、大豆锈病、玉米锈病、灰霉病，白粉病，黑星病，水稻稻瘟病、茎腐病、根腐病，苗腐病、种传和土传病害等。
B采用己唑醇，A、B质量比例1～50:1，用于防治水稻纹枯病，具有很好的防治效果。
B采用甲基硫菌灵，A、B质量比例1～5：5～1，用于防治小麦赤霉病，具有很好的防治效果。
B采用吡唑醚菌酯，A、B质量比例1～5：1，用于防治葡萄灰霉病，具有很好的防治效果。
B采用嘧菌酯，A、B质量比例1～5：5～1，用于防治玉米锈病，具有很好的防治效果。
有益效果：
1、两种有效成分复配具有明显的增效作用，提高了防治效果；
2、两种有效成分复配，作用机制互补，不存在交互抗性，降低了农药使用量，从而降低了成本和减少了对环境的污染，有利于病害抗性治理，其推广应用有巨大的经济效益和社会效益。
本发明的杀菌组合物具有明显的增效作用，有利于扩大杀菌谱，有利于延缓抗药性产生或抗药性治理，用于植物保护领域，防治水稻、小麦、玉米、果蔬等作物病害及保护作物健康，提高农作物的产量和质量。
附图说明
图1是本发明中的化合物A的一种化学结构式(通式I)。
具体实施方式
下面结合实施例对本发明的内容作进一步详述，实施例中所提及的内容并非对本发明的限定，材料配方选择可因地制宜而对结果无实质性的影响。在这些实施例中，除另有 说明外，所有百分比均为重量百分比。
制剂实施例1:8％A·醚菌酯展膜油剂
Figure PCTCN2019111693-appb-000001
在常温常压下，将A、醚菌酯和溶剂投入带搅拌的反应容器中，在搅拌速度为100-250转/分钟下，溶剂将原药搅拌溶解，再加入表面活性剂、水面扩散剂，充分搅拌15-30分钟，使其混合均匀，即得8％A醚菌酯展膜油剂。
制剂实施例2:20％A·戊唑醇悬浮种衣剂
Figure PCTCN2019111693-appb-000002
按照比例将有效成分、润湿剂、分散剂、增稠剂、抗冻剂、警戒色、水等混合，采用高剪切分散剂进行粗粉碎和预分散，然后转入砂磨机中砂磨，待砂磨结束后，加入成膜剂进行搅拌均匀，得到稳定的20％A·戊唑醇悬浮种衣剂。
生测实施例3，化合物A对植物病原菌具有广泛的杀/抑菌活性：
(1)方法：平皿法，参照NY/T 1156.2-2006。
(2)结果：离体试验结果如表1。
表1化合物A离体杀菌谱
Figure PCTCN2019111693-appb-000003
(3)评价：化合物A在10～0.1mg/L剂量下，对16种植物病原菌均具有生物抑/杀菌活性，其中对禾谷丝核菌、镰刀菌等活性显著。
生测实施例4，化合物A对作物具有普遍安全性：
(1)方法：盆栽法，参照NY/T 1965.1-2010
(2)结果：与空白对照相比，无明显区别，未发现药害症状。
表2化合物A对试验作物的安全性试验结果
Figure PCTCN2019111693-appb-000004
(3)评价：化合物A在100～400mg/L剂量下，对水稻、小麦、玉米、大豆、黄瓜等5种作物安全。
生测实施例5，化合物A与三唑类杀菌剂己唑醇复配对水稻纹枯病具有显著增效作用：
(1)方法：平皿法，参照NY/T1156.2-2006；混配的联合作用评价参照NY/T 1156.6-2006。
(2)结果：
表3组合物A与己唑醇复配对水稻纹枯病的测试与统计结果
Figure PCTCN2019111693-appb-000005
(3)评价：组合物A、己唑醇及其各配比对水稻纹枯病菌均具有优良活性，在100：1至1：100范围内，共毒系数为110.05～293.33，均具有相加至增效作用，当配比在1：1～50：1范围内时，共毒系数大于150，增效作用显著。
生测实施例6，化合物A与甲基硫菌灵复配对小麦赤霉病具有显著增效作用：
(1)方法：平皿法，参照NY/T1156.2-2006；混配的联合作用评价参照NY/T 1156.6-2006。
(2)结果：
表4化合物A与甲基硫菌灵复配对小麦赤霉病的测试与统计结果
Figure PCTCN2019111693-appb-000006
(3)评价：组合物A、甲基硫菌灵及其各配比对小麦赤霉病菌均具有良好活性，在80：1至1：80范围内，共毒系数为95.53～214.90，均具有相加至增效作用，当配比在1：5～5：1范围内及20：1时，共毒系数大于150，增效作用显著。
生测实施例7，化合物A与甲氧基丙烯酸酯类杀菌剂吡唑醚菌酯复配对葡萄灰霉病具有显著增效作用：
(1)方法：叶片法，参照NY/T1156.9-2008；混配的联合作用评价参照NY/T 1156.6-2006。
(2)结果：
表5化合物A与吡唑醚菌酯复配对葡萄灰霉病测试与统计结果
Figure PCTCN2019111693-appb-000007
(3)评价：组合物A、吡唑醚菌酯及其各配比对葡萄灰霉病均具有优良活性，在配比1：60～60：1范围内，共毒系数为109.31～196.57，均具有相加至增效作用，当配比在1：1～5：1时，共毒系数大于150，增效作用显著。
生测实施例8，化合物A与乙嘧酚复配对黄瓜白粉病具有增效作用：
(1)方法：盆栽法，参照NY/T 1156.11-2008；混配的联合作用评价参照NY/T 1156.6-2006。
(2)结果：
表6化合物A与乙嘧酚复配对黄瓜白粉病盆栽试验测试与统计结果
处理 实测EC 50值(mg/L) 理论EC 50值(mg/L) 共毒系数 增效作用
化合物A(A) 9.2015 100 / /
乙嘧酚(B) 0.1436 6407.73 / /
1:75(A:B) 0.1208 7617.14 120.43 增效
1:35(A:B) 0.112 8215.63 131.82 增效
1:15(A:B) 0.1158 7946.03 132.14 增效
1:5(A:B) 0.1406 6544.45 122.18 增效
1:1(A:B) 0.1923 4784.97 147.06 增效
5:1(A:B) 0.8766 1049.68 91.17 相加
15:1(A:B) 1.8977 484.88 98.11 相加
35:1(A:B) 3.21 286.65 104.16 相加
75:1(A:B) 5.7661 159.58 87.20 相加
(3)评价：组合物A、乙嘧酚及其各配比对黄瓜白粉病均具有优良活性，在配比1：75～75：1范围内，共毒系数为80.72～147.06，均具有相加至增效作用，当配比在1：75～1：1时，共毒系数大于120，具有增效作用。
生测实施例9，化合物A与嘧菌酯复配对玉米锈病具有显著增效作用：
(1)方法
供试药剂为化合物A原药和95％嘧菌酯原药，试验浓度均为25、6.25、1.56、0.78、0.39、 0.195mg/L；选择生长整齐一致盆栽三叶期玉米幼苗，按所设浓度在作物喷雾机上进行喷雾处理，24小时后接种玉米锈病菌孢子悬浮液(5×10 6个/ml)喷雾于寄主作物上。接种后放置人工气候室(温度：昼25雾、夜20雾，相对湿度：95％)培养1天，然后将植株移置温室正常管理，于7天后调查化合物的防治效果，以病情指数计算防治效果。
玉米锈病分级标准：
0级：无病；
1级：病斑面积占整片叶面积的5％以下；
3级：病斑面积占整片叶面积的6％-10％；
5级：病斑面积占整片叶面积的11％-25％；
7级：病斑面积占整片叶面积的26％-50％；
9级：病斑面积占整片叶面积的50％以上。
(2)结果
表7化合物A与嘧菌酯复配对玉米锈病盆栽试验测试与统计结果
Figure PCTCN2019111693-appb-000008
(3)评价：组合物A、嘧菌酯及其各配比对玉米锈病均具有优良活性，在配比1：50～50：1范围内，共毒系数为91.69～204.76，均具有相加至增效作用，当配比在1：5～5：1时，共毒系数大于150，具有显著增效作用。
生测实施例10，25％化合物A·己唑醇SC(其中化合物A 15+己唑醇10)防治水稻纹枯病田间药效试验：
(1)方法
2016年，试验地点设在江苏沿海地区农业科学研究所，水稻品种“淮稻14号。药剂处理设：25％化合物A·己唑醇SC 75、150、225、300gai/ha，25％化合物A悬浮剂150、225gai/ha，5％己唑醇SC 75、150gai/ha，及空白对照等9个处理，小区面积35m 2，3次重复，小区随机区组排列。共施2次药，于第2次施药后14天，病情稳定后进行发病情况调查，调查试验田间各小区水稻纹枯病的病株率和病情指数，然后据病情指数计算防治效果。参照GB17980.20-2000《杀菌剂防治水稻纹枯病田间药效试验准则》。
(2)结果
表8 25％化合物A·己唑醇SC防治水稻纹枯病田间试验结果
Figure PCTCN2019111693-appb-000009
(3)评价：在田间条件下，杀菌组合物25％化合物A·己唑醇SC对水稻纹枯病的防效优秀，优于二个单剂的防效。在相同剂量150gai/ha时，组合物、化合物A、己唑醇的防效分别为91.18％、84.97％、83.65％，杀菌组合物具有显著的优势，在田间也表现出了增效效果。
生测实施例11，40％化合物A·嘧菌酯SC(其中：化合物A 30+嘧菌酯10)防治小麦锈病田间药效试验：
(1)方法
2017年，试验地点设在陕西省咸阳市杨凌示范区。面积2.0亩，小麦品种为西农979。土壤类型为土娄，pH值中性，管理水平一般。试验设0％化合物A·嘧菌酯SC有100、150、200、200gai/ha，25％化合物A悬浮剂150、225gai/ha，25％嘧菌酯SC 150、200gai/ha，及空白对照等9个处理，3次重复，施药2次。共施2次药，第2次用药后7天进行调查。参照GB/T17980.23-2000《杀菌剂防治禾谷类锈病田间药效试验准则》。
(2)结果
表9 40％化合物A·嘧菌酯SC防治小麦锈病田间试验结果
Figure PCTCN2019111693-appb-000010
(3)评价：在田间条件下，杀菌组合物40％化合物A·嘧菌酯SC对小麦锈病的防效良好，优于二个单剂的防效。在剂量150gai/ha下，组合物、化合物A、嘧菌酯的防效分别为82.65％、73.86％、77.21％；在剂量200gai/ha下，组合物、化合物A、嘧菌酯的防效分别为89.49％、81.56％、82.05％；杀菌组合物具有显著的优势，在田间也表现出了增效效果。

Claims (10)

  1. 一种杀菌组合物，含有A、B两种活性组分，以及助剂、载体或稀释剂，其特征在于A为具有如通式I所示基团的化合物：
    Figure PCTCN2019111693-appb-100001
    通式I中：R 1为氢或甲基，R 2为甲基、乙基、正丙基或异丙基；
    B为三唑类杀菌剂，甲氧基丙烯酸酯类杀菌剂，保护性杀菌剂，生物源或抗生素类杀菌剂，或者其他类杀菌剂；
    制成展膜油剂、悬浮种衣剂、悬浮剂、可湿性粉剂、烟剂或水分散粒剂；
    所述的其他类杀菌剂为啶菌恶唑、拌种咯、多菌灵、甲基硫菌灵、咪鲜胺、咯菌腈、乙嘧酚、三环唑、稻瘟酰胺或腐霉利。
  2. 根据权利要求1所述一种杀菌组合物，其特征在于：所述的三唑类杀菌剂为丙硫菌唑、苯醚甲环唑、戊唑醇、己唑醇、氟环唑、烯唑醇、腈苯唑、氟硅唑、粉唑醇、腈菌唑、戊菌唑、丙环唑、四氟醚唑、三唑醇、联苯三唑醇或三唑酮；
    所述的甲氧基丙烯酸酯类杀菌剂为嘧菌酯、醚菌酯、肟菌酯、啶氧菌酯、吡唑醚菌酯、氟嘧菌酯、肟醚菌胺、丁香菌酯、烯肟菌酯、烯肟菌胺或唑菌酯；
    所述的保护性杀菌剂为百菌清、代森锰锌或福美双；
    所述的生物源或抗生素类杀菌剂为井冈霉素、中生菌素、多抗霉素或春雷霉素。
  3. 根据权利要求1或2所述一种杀菌组合物，其特征在于：A与B的质量比例为1～40:1～5。
  4. 根据权利要求1或2所述一种杀菌组合物，其特征在于：A与B的质量比例为1:5～5:1。
  5. 一种权利要求1或2所述的杀菌组合物的用途，其特征在于：用于防治水稻、小麦、玉米、果蔬的作物病害及保护作物健康。
  6. 如权利要求5所述的杀菌组合物的用途，其特征在于：用于防治水稻的纹枯病、稻瘟病或稻曲病，或者，小麦的锈病、赤霉病、白粉病或全蚀病，黄瓜的炭疽病、白粉病或灰霉病。
  7. 如权利要求5所述的杀菌组合物的用途，其特征在于：B采用己唑醇，A、B质量比例1～50:1，用于防治水稻纹枯病。
  8. 如权利要求5所述的杀菌组合物的用途，其特征在于：B采用甲基硫菌灵，A、B质量比例1～5：5～1，用于防治小麦赤霉病。
  9. 如权利要求5所述的杀菌组合物的用途，其特征在于：B采用吡唑醚菌酯，A、B质量比例1～5：1，用于防治葡萄灰霉病。
  10. 如权利要求5所述的杀菌组合物的用途，其特征在于：B采用嘧菌酯，A、B质量比例1～5：5～1，用于防治玉米锈病。
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