WO2021004195A1 - 杀真菌、细菌组合物及应用 - Google Patents

杀真菌、细菌组合物及应用 Download PDF

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WO2021004195A1
WO2021004195A1 PCT/CN2020/093663 CN2020093663W WO2021004195A1 WO 2021004195 A1 WO2021004195 A1 WO 2021004195A1 CN 2020093663 W CN2020093663 W CN 2020093663W WO 2021004195 A1 WO2021004195 A1 WO 2021004195A1
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copper
component
following groups
hydrogen
alkyl
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PCT/CN2020/093663
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English (en)
French (fr)
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陈亮
刘君丽
李思博
程学明
吴鸿飞
冯聪
颜克成
于海波
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沈阳中化农药化工研发有限公司
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Priority claimed from CN201910609654.7A external-priority patent/CN112189661B/zh
Priority claimed from CN201910609428.9A external-priority patent/CN112189660B/zh
Priority claimed from CN201910609426.XA external-priority patent/CN112189662B/zh
Priority claimed from CN201910609408.1A external-priority patent/CN112189668B/zh
Application filed by 沈阳中化农药化工研发有限公司 filed Critical 沈阳中化农药化工研发有限公司
Publication of WO2021004195A1 publication Critical patent/WO2021004195A1/zh

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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
    • 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
    • A01N37/34—Nitriles
    • 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
    • A01N37/48—Nitro-carboxylic acids; Derivatives 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
    • 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
    • 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
    • A01N47/40—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides

Definitions

  • the invention belongs to the field of agricultural bactericides, and specifically is a fungicidal and bacterial composition and application.
  • the purpose of the present invention is to provide a fungicidal and bacterial composition and its application.
  • a fungicidal and bacterial composition the composition is composed of component A and component B; the weight ratio between the two components A and B is 1:100-100:1; wherein, component A is the general formula The malononitrile oxime ether compound shown in I;
  • component B is selected from succinate dehydrogenase inhibitor fungicides, copper-containing fungicides, antibiotics, antibiotics, salts of antibiotics or zinc thiazole;
  • L is selected from -(CR 1 R 2 ) n -;
  • n is selected from 1 or 2;
  • Z is selected from hydrogen, C 1 -C 3 alkyl, phenylmethyl
  • K is selected from oxygen
  • R 3 is selected from hydrogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, unsubstituted or optionally substituted phenyl or pyridyl with the following groups, wherein the following groups are halogen or C 1 -C 3 haloalkyl;
  • R 4 and R 5 are each independently selected from hydrogen, C 1 -C 3 alkyl
  • Q is selected from one of the groups represented by Q 1-2 , unsubstituted or optionally substituted phenyl and pyridyl with the following groups, wherein the following groups are halogen and C 1 -C 3 alkyl;
  • T is selected from unsubstituted or optionally substituted phenyl and pyridyl with the following groups, wherein the following groups are halogen, cyano, C 1 -C 3 alkyl, and halogenated C 1 -C 3 alkyl , Halogenated C 1 -C 3 alkoxy.
  • component A in the composition is the malononitrile oxime ether compound represented by the general formula I:
  • L is selected from: -(CR 1 R 2 ) n -;
  • n is selected from 1;
  • R 1 and R 2 are selected from hydrogen
  • W is selected from W 1 , W 2 , W 3 , W 4 , W 12 , W 16 , W 21 , W 23 , W 48 , W 49 , W 59 , W 67 , W 68 , W 69 , W 70 , W 71 , W 72 , W 73 , W 74 , W 79 , W 80 , W 81 , W 82 , W 83 or W 84 ;
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , and X 9 are each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, -OR 3 , unsubstituted or optionally substituted phenyl and pyridyl with the following groups, wherein the following groups are halogen, cyano, C 1 -C 3 haloalkyl; when When W is W 1 , X 1 , X 2 , X 3 , X 4 , and X 5 are not hydrogen at the same time;
  • Z is selected from hydrogen, C 1 -C 3 alkyl
  • K is selected from oxygen
  • R 3 is selected from C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, unsubstituted or optionally substituted phenyl or pyridyl with the following groups, wherein the following groups are halogen or C 1 -C 3 haloalkyl;
  • Q is selected from one of the groups represented by Q 1-2 , unsubstituted or optionally substituted phenyl and pyridyl with the following groups, the following groups being halogen, C 1 -C 3 alkyl;
  • T is selected from unsubstituted or optionally substituted phenyl and pyridyl with the following groups, wherein the following groups are halogen, cyano, C 1 -C 3 alkyl, and halogenated C 1 -C 3 alkyl , Halo C 1 -C 3 alkoxy;
  • the B-component succinate dehydrogenase inhibitor fungicide is selected from the group consisting of benzonifluconazole, penthiopyrad, pyrazoxane, boscalid, fluopyram, fluopyram, Flufenapyr, flufenoxanil, thiafluzamide, dipropyslide, furopyram, fluoxanil, flufenazuril, cyprofenac, bixafen, or thiafluzamide Bacteryl
  • the B component is selected from: Kasugamycin, Zhongshengmycin, Polyoxin, Shenzinomycin, Jinggangmycin, Tetramycin, Ningnanmycin, Gongzhulingmycin, Wuyimycin or chain sulfate Mycin, or the salt of each of the above antibiotics;
  • the B component is selected from: copper hydroxide, king copper, Bordeaux solution, basic copper sulfate, copper calcium sulfate, cuprous oxide, thiazolium copper, thiason copper, copper quinoline, copper complex, copper acetate, Copper rosinate, copper nonbacterium, or copper succinate fertilizer;
  • the B component is selected from: zinc thiazole;
  • the weight ratio between the two components A and B is 1:90-90:1.
  • the weight ratio between the two components A and B is 1:75-75:1; wherein the A component is the malononitrile oxime ether compound represented by the general formula I:
  • L is selected from -(CR 1 R 2 ) n -;
  • n is selected from 1;
  • R 1 and R 2 are selected from hydrogen
  • W is selected from W 1 , W 2 , W 3 , W 4 , W 16 , W 49 , W 59 , W 69 , W 70 , W 71 , W 72 , W 79 , W 80 or W 81 ;
  • X 1 , X 2 , X 3 , X 4 , X 5 , and X 6 are each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, -OR 3.
  • Z is selected from hydrogen
  • K is selected from oxygen
  • R 3 is selected from C 1 -C 3 alkyl, C 1 -C 3 haloalkyl
  • Q is selected from one of the groups represented by Q 1-2 , unsubstituted or optionally substituted phenyl and pyridyl with the following groups, wherein the following groups are halogen and C 1 -C 3 alkyl;
  • T is selected from unsubstituted or optionally substituted phenyl and pyridyl with the following groups, wherein the following groups are halogen, C 1 -C 3 alkyl, halogenated C 1 -C 3 alkyl, halogenated C 1 -C 3 alkoxy;
  • the B component is selected from the group consisting of benzonifluconazole, pyraclostrobin, pyraclostrobin, boscalid, fluopyram, fluopyram, flupyraclostrobin, flupyraclosamide, pyraclostrobin Furosemide, bispropynyl, furopyram, fluoctam, fluconazole or cyprofen;
  • the B component is selected from: Kasugamycin, Zhongshengmycin, Polyoxin, Shenzinomycin, Jinggangmycin, Tetramycin, Ningnanmycin, Gongzhulingmycin or Wuyimycin, or the above antibiotics.
  • the B component is selected from: copper hydroxide, king copper, Bordeaux solution, basic copper sulfate, copper calcium sulfate, cuprous oxide, thiazolium copper, thiason copper, copper quinoline, copper complex, copper acetate, rosinic acid Copper, nonbacterial copper or succinic acid copper;
  • the B component is selected from: zinc thiazole.
  • the weight ratio between the two components A and B is 1:50-50:1; wherein, the A component is the malononitrile oxime ether compound represented by the general formula I:
  • L is selected from -(CR 1 R 2 ) n -;
  • n is selected from 1;
  • R 1 and R 2 are selected from hydrogen
  • W is selected from W 1 , W 2 , W 3 , W 4 , W 16 , W 49 or W 69 ;
  • X 1 , X 2 , X 3 , X 4 , and X 5 are each independently selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, isopropyl, chloromethyl, bromomethyl , Difluoromethyl, trifluoromethyl, -OR 3 , unsubstituted or optionally substituted phenyl with the following groups, wherein the following groups are halogen or cyano; when W is W 1 , X 1 , X 2 , X 3 , X 4 , and X 5 are not hydrogen at the same time;
  • R 3 is selected from methyl or trifluoromethyl
  • the B component is selected from: benzonifluconazole, pyraclostrobin, pyraclostrobin, boscalid, fluopyram, fluopyram, flufenoxanil, pyraclostrobin, Thiofuramid, bispropynamide, furopyram or fluoxamide;
  • the B component is selected from: Kasugamycin, Zhongshengmycin, Polyoxin, Shenzinomycin, Jinggangmycin, Tetramycin, Ningnanmycin or Gongzhulingmycin;
  • the B component is selected from: copper hydroxide, king copper, Bordeaux solution, basic copper sulfate, copper calcium sulfate, cuprous oxide, thiazolium copper, thiason copper, copper quinoline, copper complex, copper acetate, rosinic acid Copper, nonbacterial copper or succinic acid copper;
  • the B component is selected from: zinc thiazole.
  • the weight ratio between the two components A and B is 1:20-20:1; wherein the A component is the malononitrile oxime ether compound represented by the general formula I:
  • L is selected from -(CR 1 R 2 ) n -;
  • n is selected from 1;
  • R 1 and R 2 are selected from hydrogen
  • W is selected from W 1 ;
  • X 1 , X 2 , X 3 , X 4 , and X 5 are each independently selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, isopropyl, chloromethyl, bromomethyl , Difluoromethyl, trifluoromethyl, -OR 3 , unsubstituted or optionally substituted phenyl with the following groups, wherein the following groups are halogen or cyano; when W is W 1 , X 1 , X 2 , X 3 , X 4 , and X 5 are not hydrogen at the same time;
  • R 3 is selected from methyl or trifluoromethyl
  • the B component is selected from: benzonifluconazole (201), penthiopyrad (202), pyraclostrobin (203), boscalid (204), fluopyram (205), fluorine Pyraclostrobin (206), flufenoxan (207), flupyramide (208), thiafluzamide (209), dipropargyl (210).
  • the B component is selected from: Kasugamycin (2001), Zhongshengmycin (2002), Polyoxin (2003), Shenzixin (2004), Jinggangmycin (2005), Tetramycin (2006) Or Ningnanmycin (2007).
  • the B component is selected from: copper hydroxide (20001), king copper (20002), Bordeaux solution (20003), basic copper sulfate (20004), copper calcium sulfate (20005), cuprous oxide (20006), thiazolium copper (20007), Thiisson Copper (20008), Copper Quinoline (20009), Copper Complex (2010), Copper Acetate (2011), Copper Rosinate (2012), Copper Nonbacterium (2013), Copper Succinate Fertilizer (2014).
  • the B component is selected from: zinc thiazole (200001).
  • composition is used to control harmful fungi, bacterial infections, and infested plants, seeds, soil, areas, materials or spaces.
  • composition is used for the prevention and treatment of plant fungi and bacterial diseases of cereals, rice, fruit trees, vegetables, flowers, Chinese medicinal materials or lawns.
  • the fungicidal and bacterial composition adopts leaf surface or whole plant spray, root irrigation or seed soaking methods to prevent and control plant fungi and bacterial diseases.
  • composition of the present invention is suitable for controlling various harmful fungi and bacteria, especially various diseases of cereals, vegetables, fruit trees, ornamental plants, lawns and tropical crops, and various storage diseases.
  • the A component compound and at least one B component compound may be added with other active substances effective against harmful pathogenic microorganisms or other pests, or active compounds or fertilizers with herbicidal and growth regulating effects. .
  • the composition in any form, that is, the mixed use of the A-component compound and at least one B-component compound, it exhibits a significant increase in the range of disease prevention and control and improved prevention of certain diseases, including pathogenic fungi and bacteria.
  • pathogenic fungi and bacteria A variety of plant diseases caused by a variety of pathogenic microorganisms.
  • the composition is particularly important for controlling fungal and bacterial diseases of various crops such as cereals, rice, vegetables, fruit trees, and flowers, and for protecting crops by dressing seeds.
  • Particularly suitable for controlling the following plant fungal and bacterial diseases rice blast, rice sheath blight, rice bacterial leaf blight, rice bacterial leaf spot, cucumber fusarium wilt, cucumber downy mildew, cucumber powdery mildew, cucumber gray mold, cucumber Bacterial angular leaf spot, tomato leaf mold, tomato bacterial wilt, apple tree ring leaf disease, apple tree spot leaf disease, pepper blight, watermelon wilt, wheat head blight, wheat total erosion, soybean root rot, Citrus canker, kiwi fruit canker, tobacco bacterial wilt, Chinese cabbage soft rot, melon bacterial fruit spot, etc.
  • the application period of the composition of the present invention may be before or after the plant is sowed, or before or after the emergence of the plant, spraying or powdering the seeds, plants or the soil.
  • the fungicidal and bacterial composition of the present invention has a very obvious synergistic effect, significantly improves the prevention and control effect of crop diseases, and can expand the bactericidal spectrum and delay the occurrence of pathogen resistance;
  • the invention combines compounds with different action mechanisms and chemical structure types, can more effectively prevent and control harmful microorganisms that affect crop growth, and has a synergistic effect to achieve the purposes of effective treatment of resistance and effective control of plant diseases.
  • the synergistic effect of the fungicidal and bacterial composition of the present invention on harmful fungi and bacterial diseases can be illustrated by the following examples, but the present invention is by no means limited to this.
  • the active compounds alone or in combination were prepared into acetone or DMSO stock solutions containing 0.25% by weight of the active compounds. 1% (weight) of emulsifier (Ethoxylated alkylphenol-based wetting agent with emulsifying and dispersing effects) was added to the stock solution, and the active compound or mixture was diluted with water to the required concentration in the following examples.
  • emulsifier Ethoxylated alkylphenol-based wetting agent with emulsifying and dispersing effects
  • the expected efficacy of the active compound mixture is determined using the Colby formula [S.R. Colby. Calculating Synergistic and Antagonistic Response of Herbicide Combinations. Weeds, 1967, 15(1): 20-22] and compared with the observed efficacy.
  • the effect of the combination is a synergistic effect.
  • the difference between the synergistic effect and (O-E) is positive. If the actually observed effect (O) is equal to the expected effect (E), then the effect of the combination is a purely additive effect and does not show synergy. In terms of mathematics, the difference corresponding to (OE) is zero. If the actually observed efficacy (O) is less than the expected efficacy (E), then the effect of the combination is an antagonistic effect, and mathematically, the difference corresponding to (O-E) is negative.
  • Potted wheat seedlings with the cultivar "Liaochun No. 10" were cultivated to the three-leaf stage, and sprayed to the dripping point with an aqueous suspension of the active compound of the following concentration. After 24 hours, the wheat leaves were inoculated with an aqueous suspension of spores of Blumeria graminis, and then the wheat seedlings were placed in a climate room at 22-24°C and a relative humidity of 85-90% for 7 days. Finally, visually determine the development degree of pathogen infection on wheat leaves. (See Table 1 and Table 2).
  • the potted cucumber seedlings of the cultivar "Shandong dense thorn" were cultivated to the two-leaf stage, and sprayed to the dripping point with an aqueous suspension of the active composition or compound of different concentrations as described below. After 24 hours, the cucumber leaves were inoculated with an aqueous suspension of spores of cucumber downy mildew (Pseudoperonospora cubensis), and then the cucumber seedlings were placed in a climate room at 22-24°C and a relative humidity of 95-99% for 7 days. Then visually determine the degree of development of pathogen infection on cucumber leaves (see Tables 3 and 4).
  • the potted rice seedlings of the cultivar "Koshihikari" are cultivated to the three-leaf stage, and sprayed to the dripping point with an aqueous suspension of the active composition or the compound at different concentrations as described below. After 24 hours, the rice leaves were inoculated with an aqueous suspension of the mycelium of Rhizoctonia solani, and then the rice seedlings were placed in a climate room at 24-28°C and a relative humidity of 95-99% for 7 days. Finally, visually determine the degree of development of pathogen infection on rice leaves (see Tables 5 and 6).
  • the potted cucumber seedlings of the cultivar "Shandong dense thorn" were cultivated to the two-leaf stage, and sprayed to the dripping point with an aqueous suspension of the active composition or compound of different concentrations as described below. After 24 hours, the cucumber leaves were inoculated with an aqueous suspension of cucumber powdery mildew (Sphaerotheca fuliginea), and then the cucumber seedlings were placed in a climate room at 24-28°C and a relative humidity of 90-95% for 7 days. Finally, visually determine the development degree of pathogen infection on cucumber leaves (see Tables 7 and 8).
  • the potted tomato seedlings of the cultivar "Liaoyuan Duoli" were cultivated to the two-leaf stage, and sprayed to the dripping point with an aqueous suspension of the active compound of the following concentration. After 24 hours, the tomato seedlings were inoculated with an aqueous suspension of Ralstonia solanacearum, and then the seedlings were placed in a climate room at 22-26°C and a relative humidity of 95-99% for 3 days. Finally, visually determine the degree of development of pathogen infection on tomato seedlings (see Tables 9 and 10).
  • the field plots with wheat powdery mildew (Blumeria graminis) were selected to carry out field trials, and the wheat cultivar was "Liaochun 10".
  • the experiment adopted a randomized block design, with a plot area of 25 square meters, four repetitions, a total of two drug treatments, one week apart.
  • powdery mildew spots were first seen in the field, the first chemical treatment was started.
  • a knapsack sprayer was used to spray the wheat plants with an aqueous suspension of the active compound at the following concentration, and a second spray treatment was performed one week later.
  • One week after the last spray treatment the development degree of pathogen infection on the wheat leaves was visually measured, and the average value of four replicates of each treatment was calculated (see Tables 11 and 12).
  • the potted rice seedlings of the cultivar "Koshihikari” are cultivated to the three-leaf stage, and sprayed to the dripping point with an aqueous suspension of the active composition or the compound at different concentrations as described below. After 24 hours, the rice leaves were inoculated with an aqueous suspension of the mycelium of Rhizoctonia solani, and then the rice seedlings were placed in a climate room at 24-28°C and a relative humidity of 95-99% for 7 days. Finally, visually determine the degree of development of pathogen infection on rice leaves (see Tables 13 and 14).
  • the potted cucumber seedlings of the cultivar "Shandong dense thorn" were cultivated to the two-leaf stage, and sprayed to the dripping point with an aqueous suspension of the active composition or compound of different concentrations as described below. After 24 hours, the cucumber leaves were inoculated with an aqueous suspension of cucumber bacterial Xerocarpa pv.lachrymans (Pseudomonas syringae pv.lachrymans), and then the cucumber seedlings were placed in a climate room at 24-28°C and a relative humidity of 95-99% for 7 days . Finally, visually determine the development degree of pathogen infection on cucumber leaves (see Tables 17 and 18).
  • the potted Chinese cabbage seedlings of the cultivar "Degao No. 1" were cultivated to the three-leaf stage, and sprayed to the dripping point with an aqueous suspension of active compositions or compounds of different concentrations as described below. After 24 hours, the Chinese cabbage leaves were inoculated with an aqueous suspension of Chinese cabbage soft rot fungus (Erwinia carotovora subsp. carotovora), and then the seedlings were placed in a climate room at 22-26°C and a relative humidity of 95-99% for 3 days. Finally, the degree of development of pathogen infection on Chinese cabbage leaves was visually determined (see Tables 21 and 22).
  • the potted cucumber seedlings of the cultivar "Shandong dense thorn" were cultivated to the two-leaf stage, and sprayed to the dripping point with an aqueous suspension of the active composition or compound of different concentrations as described below. After 24 hours, the cucumber leaves were inoculated with an aqueous suspension of cucumber powdery mildew (Sphaerotheca fuliginea), and then the cucumber seedlings were placed in a climate room at 24-28°C and a relative humidity of 90-95% for 3 days. Finally, visually determine the degree of development of pathogen infection on cucumber leaves (see Tables 23 and 24)
  • the potted cucumber seedlings of the cultivar "Shandong dense thorn" were cultivated to the two-leaf stage, and sprayed to the dripping point with an aqueous suspension of the active compound of the following concentration. After 24 hours, the cucumber leaves were inoculated with an aqueous suspension of spores of cucumber downy mildew (Pseudoperonospora cubensis), and then the cucumber seedlings were placed in a climate room at 22-24°C and a relative humidity of 95-99% for 7 days. Then visually determine the development degree of pathogen infection on cucumber leaves.
  • the potted cucumber seedlings of the cultivar "Shandong dense thorn" were cultivated to the two-leaf stage, and sprayed to the dripping point with an aqueous suspension of the active compound of the following concentration. After 24 hours, the cucumber leaves were inoculated with an aqueous suspension of cucumber bacterial Xerocarpa pv.lachrymans (Pseudomonas syringae pv.lachrymans), and then the cucumber seedlings were placed in a climate room at 24-28°C and a relative humidity of 95-99% for 7 days . Finally, visually determine the development degree of pathogen infection on cucumber leaves.
  • the potted melon seedlings of the cultivar "Tiger Skin Crisp” were cultivated to the two-leaf stage, and sprayed to the dripping point with an aqueous suspension of the active compound of the following concentration. After 24 hours, the melon leaves were inoculated with an aqueous suspension of Acidovorax citrulli, and then the melon seedlings were placed in a climate room at 24-28°C and a relative humidity of 95-99% for 7 days. Finally, the development degree of pathogen infection on melon leaves was visually determined.
  • Potted rice seedlings of the cultivar "Koshihikari” were cultivated to the three-leaf stage, and sprayed to the dripping point with an aqueous suspension of the active compound of the concentration described below. After 24 hours, the rice leaves were inoculated with an aqueous suspension of the mycelium of Rhizoctonia solani, and then the rice seedlings were placed in a climate room at 24-28°C and a relative humidity of 95-99% for 7 days. Finally, visually determine the development degree of pathogen infection on rice leaves.
  • the potted melon seedlings of the cultivar "Tiger Skin Crisp” were cultivated to the two-leaf stage, and sprayed to the dripping point with an aqueous suspension of the active compound of the following concentration. After 24 hours, the melon leaves were inoculated with an aqueous suspension of Acidovorax citrulli, and then the melon seedlings were placed in a climate room at 24-28°C and a relative humidity of 95-99% for 7 days. Finally, the development degree of pathogen infection on melon leaves was visually determined.
  • the potted Chinese cabbage seedlings of the cultivar "Degao No. 1" were cultivated to the three-leaf stage, and sprayed to the dripping point with an aqueous suspension of the active compound of the following concentration. After 24 hours, the Chinese cabbage leaves were inoculated with an aqueous suspension of Chinese cabbage soft rot fungus (Erwinia carotovora subsp. carotovora), and then the seedlings were placed in a climate room at 22-26°C and a relative humidity of 95-99% for 3 days. Finally, the development degree of pathogen infection on Chinese cabbage leaves was determined visually.

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Abstract

本发明涉及一种杀真菌、细菌组合物及其应用方法，组合物包含A、B两种活性组分，其中组分A选自如通式Ⅰ所示的化合物， B组分选自琥珀酸脱氢酶抑制剂类杀菌剂、含铜杀菌剂、抗生素类化合物、抗生素类化合物的盐或噻唑锌。组合物中两种活性组分的重量份数比为1:100至100:1，本发明的组合物用于防治由病原真菌和细菌引起的多种植物病害。

Description

杀真菌、细菌组合物及应用 技术领域
本发明属于农用杀菌剂领域，具体为一种杀真菌、细菌组合物及应用。
背景技术
中国发明专利CN201611199611.9以及PCT申请WOCN16111411中公开了一种丙二腈肟醚类化合物，该类化合物同时对植物病原真菌和细菌都具有良好的防治效果。丙二腈肟醚类化合物对由卵菌、担子菌、子囊菌、半知菌等植物病原真菌引起的多种植物病害，包括黄瓜霜霉病、黄瓜灰霉病、黄瓜炭疽病、黄瓜白粉病、番茄早疫病、番茄晚疫病、辣椒疫病、葡萄霜霉病、葡萄白腐病、苹果轮纹病、苹果斑点落叶病、水稻纹枯病、水稻稻瘟病、小麦锈病、小麦叶斑病、小麦白粉病、油菜菌核病、玉米小斑病等具有良好的防治效果；同时对假单胞菌、欧文氏菌、黄单胞菌、嗜酸菌等植物病原细菌引起的多种植物病害，包括番茄青枯病、烟草青枯病、柑橘溃疡病、猕猴桃溃疡病、大白菜软腐病、黄瓜细菌性角斑病等具有良好的防治效果。
实际的农业经验和大量的科学研究数据表明，长期重复且专一的施用一种类型的化合物来防治植物真菌和细菌病害，在很多情况下会导致病原细菌和真菌菌株的快速选择性，部分菌株对特定活性化合物发展出适应的抗性，导致活性化合物的防治效果显著降低，甚至完全丧失。
发明内容
为了降低病原真菌和细菌对活性化合物产生抗药性的风险，同时也为了提高对病原真菌和细菌的防治效果，本发明目的在于提供一种杀真菌、细菌组合物及其应用。
为实现上述目的，本发明的技术方案如下：
一种杀真菌、细菌组合物，组合物为A组分和B组分；所述A、B两组分之间的重量比为1:100～100:1；其中，A组分为通式Ⅰ所示丙二腈肟醚类化合物；B组分选自琥珀酸脱氢酶抑制剂类杀菌剂、含铜杀菌剂、抗生素类化合物、抗生素类化合物的盐或噻唑锌；
Figure PCTCN2020093663-appb-000001
所述通式Ⅰ所示的丙二腈肟醚类化合物：
Figure PCTCN2020093663-appb-000002
式中：
L选自-(CR 1R 2) n-；
n选自1或2；
当n＝2时，W为苯基；当n＝1时，W选自W 1、W 2、W 3、W 4、W 12、W 16、W 21、W 23、W 47、W 48、W 49、W 59、W 67、W 68、W 69、W 70、W 71、W 72、W 73、W 74、W 79、W 80、W 81、W 82、W 83或W 84；
Figure PCTCN2020093663-appb-000003
Figure PCTCN2020093663-appb-000004
其中：
X 1、X 2、X 3、X 4、X 5、X 6、X 7、X 8、X 9各自独立地选自氢、卤素、氰基、硝基、C 1-C 3烷基、C 1-C 3卤代烷基、-OR 3、-N(R 4)S(＝O) 2R 5、-S(＝O) 2NR 3R 5、-CH 2ON＝C(CN) 2、未取代的或被下述基团任意取代的苯基和吡啶基，其中，下述基团为卤素、氰基、C 1-C 3卤代烷基；当W为W 1时，X 1、X 2、X 3、X 4、X 5不同时为氢；或W 1为
Figure PCTCN2020093663-appb-000005
Figure PCTCN2020093663-appb-000006
Z选自氢、C 1-C 3烷基、苯基甲基；
K选自氧；
R 3选自氢、C 1-C 3烷基、C 1-C 3卤代烷基、未取代的或被下述基团任意取代的苯基或吡啶基，其中下述基团为卤素或C 1-C 3卤代烷基；
R 4、R 5各自独立地选自氢、C 1-C 3烷基；
Q选自Q 1-2所示的基团之一、未取代的或被下述基团任意取代的苯基和吡啶基，其中，下述基团为卤素、C 1-C 3烷基；
Figure PCTCN2020093663-appb-000007
T选自未取代的或被下述基团任意取代的苯基和吡啶基，其中，下述基团为卤素、氰基、C 1-C 3烷基、卤代C 1-C 3烷基、卤代C 1-C 3烷氧基。
优选，组合物中A组分为所述通式Ⅰ所示的丙二腈肟醚类化合物：
式中，L选自：-(CR 1R 2) n-；
n选自1；
R 1、R 2选自氢；
W选自W 1、W 2、W 3、W 4、W 12、W 16、W 21、W 23、W 48、W 49、W 59、W 67、W 68、W 69、W 70、W 71、W 72、W 73、W 74、W 79、W 80、W 81、W 82、W 83或W 84；
X 1、X 2、X 3、X 4、X 5、X 6、X 7、X 8、X 9各自独立地选自氢、卤素、氰基、硝基、C 1-C 3烷基、C 1-C 3卤代烷基、-OR 3、未取代的或被下述基团任意取代的苯基和吡啶基，其中，下述基团为卤素、氰基、C 1-C 3卤代烷基；当W为W 1时，X 1、X 2、X 3、X 4、X 5不同时为氢；
Z选自氢、C 1-C 3烷基；
K选自氧；
R 3选自C 1-C 3烷基、C 1-C 3卤代烷基、未取代的或被下述基团任意取代的苯基或吡啶基，其中下述基团为卤素或C 1-C 3卤代烷基；
Q选自Q 1-2所示的基团之一、未取代的或被下述基团任意取代的苯基和吡啶基，下述基团为卤素、C 1-C 3烷基；
T选自未取代的或被下述基团任意取代的苯基和吡啶基，其中，下述基团为卤素、氰基、C 1-C 3烷基、卤代C 1-C 3烷基、卤代C 1-C 3烷氧基；
所述B组分琥珀酸脱氢酶抑制剂类杀菌剂选自苯并烯氟菌唑、吡噻菌胺、吡唑萘菌胺、啶酰菌胺、氟吡菌胺、氟吡菌酰胺、氟唑环菌胺、氟唑菌酰胺、噻呋酰胺、双炔酰菌胺、呋吡菌胺、氟啶菌酰胺、氟唑菌苯胺、环丙酰菌胺、联苯吡菌胺或噻氟菌胺；
所述B组分选自：春雷霉素、中生菌素、多抗霉素、申嗪霉素、井冈霉素、四霉素、宁南霉素、公主岭霉素、武夷霉素或硫酸链霉素，或上述各抗生素的盐；
所述B组分选自：氢氧化铜、王铜、波尔多液、碱式硫酸铜、硫酸铜钙、氧化亚铜、噻菌铜、噻森铜、喹啉铜、络氨铜、乙酸铜、松脂酸铜、壬菌铜或琥胶肥酸铜；
所述B组分选自：噻唑锌；
其中，A、B两组分之间的重量比为1：90～90：1。
进一步优选，所述A、B两组分之间的重量比为1：75～75：1；其中，A组分为所述通式Ⅰ所示的丙二腈肟醚类化合物：
式中，
L选自-(CR 1R 2) n-；
n选自1；
R 1、R 2选自氢；
W选自W 1、W 2、W 3、W 4、W 16、W 49、W 59、W 69、W 70、W 71、W 72、W 79、W 80或W 81；
X 1、X 2、X 3、X 4、X 5、X 6各自独立地选自氢、卤素、氰基、硝基、C 1-C 3烷基、C 1-C 3卤代烷基、-OR 3、未取代的或被下述基团任意取代的苯基，其中，下述基团为卤素、氰基、C 1-C 3卤代烷基；当W为W 1时，X 1、X 2、X 3、X 4、X 5不同时为氢；
Z选自氢；
K选自氧；
R 3选自C 1-C 3烷基、C 1-C 3卤代烷基；
Q选自Q 1-2所示的基团之一、未取代的或被下述基团任意取代的苯基和吡啶基，其中，下述基团为卤素、C 1-C 3烷基；
T选自未取代的或被下述基团任意取代的苯基和吡啶基，其中，下述基团为卤素、C 1-C 3烷基、卤代C 1-C 3烷基、卤代C 1-C 3烷氧基；
B组分选自苯并烯氟菌唑、吡噻菌胺、吡唑萘菌胺、啶酰菌胺、氟吡菌胺、氟吡菌酰胺、氟唑环菌胺、氟唑菌酰胺、噻呋酰胺、双炔酰菌胺、呋吡菌胺、氟啶菌酰胺、氟唑菌苯胺或环丙酰菌胺；
B组分选自：春雷霉素、中生菌素、多抗霉素、申嗪霉素、井冈霉素、四霉素、宁南霉素、公主岭霉素或武夷霉素，或上述各抗生素的盐；
B组分选自：氢氧化铜、王铜、波尔多液、碱式硫酸铜、硫酸铜钙、氧化亚铜、噻菌铜、噻森铜、喹啉铜、络氨铜、乙酸铜、松脂酸铜、壬菌铜或琥胶肥酸铜；
B组分选自：噻唑锌。
在进一步优选，所述A、B两组分之间的重量比为1：50～50：1；其中，A组分为所述通式Ⅰ所示的丙二腈肟醚类化合物：
式中，
L选自-(CR 1R 2) n-；
n选自1；
R 1、R 2选自氢；
W选自W 1、W 2、W 3、W 4、W 16、W 49或W 69；
X 1、X 2、X 3、X 4、X 5各自独立地选自氢、氟、氯、溴、氰基、硝基、甲基、乙基、异丙基、氯甲基、溴甲基、二氟甲基、三氟甲基、-OR 3、未取代的或被下述基团任意取代的苯基，其中，下述基团为卤素、氰基；当W为W 1时，X 1、X 2、X 3、X 4、X 5不同时为氢；
R 3选自甲基或三氟甲基；
B组分选自：苯并烯氟菌唑、吡噻菌胺、吡唑萘菌胺、啶酰菌胺、氟吡菌胺、氟吡菌酰胺、氟唑环菌胺、氟唑菌酰胺、噻呋酰胺、双炔酰菌胺、呋吡菌胺或氟啶菌酰胺；
B组分选自：春雷霉素、中生菌素、多抗霉素、申嗪霉素、井冈霉素、四霉素、宁南霉素或公主岭霉素；
B组分选自：氢氧化铜、王铜、波尔多液、碱式硫酸铜、硫酸铜钙、氧化亚铜、噻菌铜、噻森铜、喹啉铜、络氨铜、乙酸铜、松脂酸铜、壬菌铜或琥胶肥酸铜；
B组分选自：噻唑锌。
更进一步优选，所述A、B两组分之间的重量比为1：20～20：1；其中，A组分为所述通式Ⅰ所示的丙二腈肟醚类化合物：
式中，
L选自-(CR 1R 2) n-；
n选自1；
R 1、R 2选自氢；
W选自W 1；
X 1、X 2、X 3、X 4、X 5各自独立地选自氢、氟、氯、溴、氰基、硝基、甲基、乙基、异丙基、氯甲基、溴甲基、二氟甲基、三氟甲基、-OR 3、未取代的或被下述基团任意取代的苯基，其中，下述基团为卤素、氰基；当W为W 1时，X 1、X 2、X 3、X 4、X 5不同时为氢；
R 3选自甲基或三氟甲基；
B组分选自：苯并烯氟菌唑(201)、吡噻菌胺(202)、吡唑萘菌胺(203)、啶酰菌胺(204)、氟吡菌胺(205)、氟吡菌酰胺(206)、氟唑环菌胺(207)、氟唑菌酰胺(208)、噻呋酰胺(209)、双炔酰菌胺(210)。
B组分选自：春雷霉素(2001)、中生菌素(2002)、多抗霉素(2003)、申嗪霉素(2004)、井冈霉素(2005)、四霉素(2006)或宁南霉素(2007)。
B组分选自：氢氧化铜(20001)、王铜(20002)、波尔多液(20003)、碱式硫酸铜(20004)、硫酸铜钙(20005)、氧化亚铜(20006)、噻菌铜(20007)、噻森铜(20008)、喹啉铜(20009)、络氨铜(2010)、乙酸铜(2011)、松脂酸铜(2012)、壬菌铜(2013)、 琥胶肥酸铜(2014)。
B组分选自：噻唑锌(200001)。
一种所述杀真菌、细菌组合物的应用，所述组合物作为防治植物病原性有害真菌、细菌。
所述组合物用于防治有害真菌、细菌侵染、侵害的植物、种子、土壤、区域、材料或空间。
所述组合物用于谷物、水稻、果树、蔬菜、花卉、中药材或草坪的植物真菌、细菌性病害的防治。
所述杀真菌、细菌组合物采用叶面或植株整体喷雾、灌根或浸种的方式，防治植物真菌、细菌病害。
本发明的杀真菌、细菌组合物优选的技术方案为，组分A选自下表中所列化合物：
Figure PCTCN2020093663-appb-000008
本发明组合物适合于防治多种有害真菌和细菌，尤其是禾谷类、蔬菜、果树、观赏植物、草坪及热带作物的多种病害，以及多种仓储病害。
当制备该组合物时，A组分化合物和至少一种B组分化合物，可以向其中加入其它对有害病原微生物或其它害虫有效的活性物质，或具有除草作用以及生长调节作用的活性化合物或肥料。
无论以任何形式使用该组合物，即A组分化合物和至少一种B组分化合物的混合使用，呈现显著的防治病害范围增大和对某些病害的防效提高，包括对病原真菌和细菌等多种病原微生物引起的多种植物病害。组合物对防治各种作物如谷物、水稻、蔬菜、果树、花卉的真菌和细菌病害，以及用于拌种保护作物尤为重要。特别适合防治下列植物真菌和细菌病害：稻瘟病、水稻纹枯病、水稻白叶枯病、水稻细菌性条斑病、黄瓜枯萎病、黄瓜霜霉病、黄瓜白粉病、黄瓜灰霉病、黄瓜细菌性角斑病、番茄叶霉病、番茄青枯病、苹果树轮纹病、苹果树斑点落叶病、辣椒疫病、西瓜枯萎病、小麦赤霉病、小麦全蚀病、大豆根腐病、柑橘溃疡病、猕猴桃溃疡病、烟草青枯病、大白菜软腐病、甜瓜细菌性果斑病等。
在防治植物病害的过程中，本发明的组合物的施用时期，可以是植物播种之前或之后，也可以在植物出苗之前或之后对种子、植株或土壤喷雾或散粉等方式而进行。
本发明所具有的优点：
本发明的杀真菌、细菌组合物具有非常明显的协同增效作用，对农作物病害的防治效果有显著提高，同时能扩大杀菌谱、延缓病原物抗药性的发生；
本发明将具有不同作用机理、化学结构类型的化合物进行组合，可更加有效的防治影响作物生长的有害微生物，且具有协同增效作用，以达到有效处理抗性和有效防治植物病害的目的。
具体实施方式
本发明的杀真菌、细菌组合物对有害真菌和细菌病害的协同增效作用可通过下列实例说明，但本发明绝非仅限于此。
将单独或联合的活性化合物制备成含有0.25％(重量)活性化合物的丙酮或DMSO储备液。将1％(重量)的乳化剂
Figure PCTCN2020093663-appb-000009
(具有乳化和分散作用的基于乙氧基化烷基酚的湿润剂)加入该储备液中，并用水将该活性化合物或混合物稀释至以下实例中所需浓度。
活性化合物混合物的预期效力使用Colby公式[S.R.Colby.Calculating Synergistic and Antagonistic Responses of Herbicide Combinations.Weeds,1967,15(1):20-22]确定并与观察到的效力比较。
Colby公式：E＝x+y-xy/100
E：使用浓度分别为a和b的活性化合物A和B的混合物时的预期效力，以未处理对照的％表示。
x使用浓度为a的活性化合物A时的效力，以未处理对照的％表示；
y使用浓度为b的活性化合物B时的效力，以未处理对照的％表示。
如果实际观察到的效力(O)大于预期的效力(E)，那么该组合的作用是一种协同增效的效应，在数学方面，协同增效效应对应于(O-E)的差为正值。如果实际观察到的效力(O)等于预期的效力(E)，那么该组合的作用是一种单纯的相加效应，未表现出协同增效，在数学方面，对应于(O-E)的差为零。如果实际观察到的效力(O)小于预期的效力(E)，那么该组合的作用是一种拮抗的效应，在数学方面，对应于(O-E)的差为负值。
应用实施例1防治小麦白粉病试验
将栽培品种为“辽春10号”的盆栽小麦幼苗培养至三叶期，用如下所述浓度的活性化合物含水悬浮液喷雾至滴流点。24小时后，用小麦白粉病菌(Blumeria graminis)的孢子含水悬浮液接种小麦叶片，之后将小麦幼苗放置于22～24℃和相对湿度为85～90％气候室中培养7天。最后目测测定小麦叶片上病菌侵染的发展程度。(参见表1和表2)。
表1单独活性组分的活性
Figure PCTCN2020093663-appb-000010
Figure PCTCN2020093663-appb-000011
表2本发明组合物的活性
Figure PCTCN2020093663-appb-000012
Figure PCTCN2020093663-appb-000013
Figure PCTCN2020093663-appb-000014
各单独活性组分以及本发明组合物防治小麦白粉病的数据结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。应用实施例2防治黄瓜霜霉病试验
将栽培品种为“山东密刺”的盆栽黄瓜幼苗培养至二叶期，用如下所述不同浓度的活性组合物或化合物的含水悬浮液喷雾至滴流点。24小时后，用黄瓜霜霉病菌(Pseudoperonospora cubensis)的孢子含水悬浮液接种黄瓜叶片，之后将黄瓜幼苗放置于22～24℃和相对湿度为95～99％气候室中培养7天。然后目测测定黄瓜叶片上病菌侵染的发展程度(参见表3和4)。
表3单独活性组分的活性
Figure PCTCN2020093663-appb-000015
Figure PCTCN2020093663-appb-000016
表4本发明组合物的活性
Figure PCTCN2020093663-appb-000017
Figure PCTCN2020093663-appb-000018
由各单独活性组分以及本发明组合物防治黄瓜霜霉病的数据结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。应用实施例3防治水稻纹枯病试验
将栽培品种为“越光”的盆栽水稻幼苗培养至三叶期，用如下所述不同浓度的活性组合物或化合物的含水悬浮液喷雾至滴流点。24小时后，用水稻纹枯病菌(Rhizoctonia solani)的菌丝体含水悬浮液接种水稻叶片，之后将水稻幼苗放置于24～28℃和相对湿度为95～99％气候室中培养7天。最后目测测定水稻叶片上病菌侵染的发展程度(参见表5和6)。
表5单独活性组分的活性
Figure PCTCN2020093663-appb-000019
Figure PCTCN2020093663-appb-000020
表6本发明组合物的活性
Figure PCTCN2020093663-appb-000021
Figure PCTCN2020093663-appb-000022
由各单独活性组分以及本发明组合物防治水稻纹枯病的数据结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。应用实施例4防治黄瓜白粉病试验
将栽培品种为“山东密刺”的盆栽黄瓜幼苗培养至二叶期，用如下所述不同浓度的活性组合物或化合物的含水悬浮液喷雾至滴流点。24小时后，用黄瓜白粉病菌(Sphaerotheca fuliginea)的含水悬浮液接种黄瓜叶片，之后将黄瓜幼苗放置于24～28℃和相对湿度为90～95％气候室中培养7天。最后目测测定黄瓜叶片上病菌侵染的发展程度(参见表7和8)。
表7单独活性组分的活性
Figure PCTCN2020093663-appb-000023
Figure PCTCN2020093663-appb-000024
表8本发明组合物的活性
Figure PCTCN2020093663-appb-000025
Figure PCTCN2020093663-appb-000026
由各单独活性组分以及本发明组合物防治黄瓜白粉病的数据结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。应用实施例5防治番茄青枯病试验
将栽培品种为“辽园多丽”的盆栽番茄幼苗培养至二叶期，用如下所述浓度的活性化合物含水悬浮液喷雾至滴流点。24小时后，用番茄青枯病菌(Ralstonia solanacearum)的含水悬浮液接种番茄幼苗，之后将幼苗放置于22～26℃和相对湿度为95～99％气候室中培养3天。最后目测测定番茄幼苗上病菌侵染的发展程度(参见表9和10)。
表9单独活性组分的活性
Figure PCTCN2020093663-appb-000027
Figure PCTCN2020093663-appb-000028
表10本发明组合物的活性
Figure PCTCN2020093663-appb-000029
Figure PCTCN2020093663-appb-000030
由各单独活性组分以及本发明组合物防治番茄青枯病的数据结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。应用实施例6防治小麦白粉病田间小区试验
选择常年发生小麦白粉病(Blumeria graminis)的田块开展田间小区试验，小麦栽培品种为“辽春10号”。试验采用随机区组设计，小区面积25平方米，四次重复，共进行两次药剂处理，间隔一周。在田间初见白粉病病斑时开始进行首次药剂处理，使用背负式喷雾器，用如下所述浓度的活性化合物含水悬浮液对小麦植株进行喷雾处理，一周后进行第二次喷雾处理。末次喷雾处理之后一周，目测测定小麦叶片上病菌侵染的发展程度，并计算各处理四次重复的平均值(参见表11和12)。
表11单独活性组分的活性
Figure PCTCN2020093663-appb-000031
Figure PCTCN2020093663-appb-000032
表12本发明组合物的活性
Figure PCTCN2020093663-appb-000033
Figure PCTCN2020093663-appb-000034
由各单独活性组分以及本发明组合物防治小麦白粉病的数据结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。应用实施例7防治水稻纹枯病试验
将栽培品种为“越光”的盆栽水稻幼苗培养至三叶期，用如下所述不同浓度的活性组合物或化合物的含水悬浮液喷雾至滴流点。24小时后，用水稻纹枯病菌(Rhizoctonia solani)的菌丝体含水悬浮液接种水稻叶片，之后将水稻幼苗放置于24～28℃和相对湿度为95～99％气候室中培养7天。最后目测测定水稻叶片上病菌侵染的发展程度(参见表13和14)。
表13单独活性组分的活性
Figure PCTCN2020093663-appb-000035
表14本发明组合物的活性
Figure PCTCN2020093663-appb-000036
Figure PCTCN2020093663-appb-000037
由上述数据可见本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。
应用实施例8防治黄瓜霜霉病试验
将栽培品种为“山东密刺”的盆栽黄瓜幼苗培养至二叶期，用如下所述不同浓度的活性组合物或化合物的含水悬浮液喷雾至滴流点。24小时后，用黄瓜霜霉病菌(Pseudoperonospora cubensis)的孢子含水悬浮液接种黄瓜叶片，之后将黄瓜幼苗放置于22～24℃和相对湿度为95～99％气候室中培养7天。然后目测测定黄瓜叶片上病菌侵染的发展程度(参见表15和16)。
表15单独活性组分的活性
Figure PCTCN2020093663-appb-000038
Figure PCTCN2020093663-appb-000039
表16本发明组合物的活性
Figure PCTCN2020093663-appb-000040
Figure PCTCN2020093663-appb-000041
由各单独活性组分以及本发明组合物防治黄瓜霜霉病的数据结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。应用实施例9防治黄瓜细菌性角斑病试验
将栽培品种为“山东密刺”的盆栽黄瓜幼苗培养至二叶期，用如下所述不同浓度的活性组合物或化合物的含水悬浮液喷雾至滴流点。24小时后，用黄瓜细菌性角斑病菌(Pseudomonas syringae pv.lachrymans)的含水悬浮液接种黄瓜叶片，之后将黄瓜幼苗放置于24～28℃和相对湿度为95～99％气候室中培养7天。最后目测测定黄瓜叶片上病菌侵染的发展程度(参见表17和18)。
表17单独活性组分的活性
Figure PCTCN2020093663-appb-000042
表18本发明组合物的活性
Figure PCTCN2020093663-appb-000043
Figure PCTCN2020093663-appb-000044
由各单独活性组分以及本发明组合物防治黄瓜细菌性角斑病的数据结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。
应用实施例10防治甜瓜细菌性果斑病试验
将栽培品种为“虎皮脆”的盆栽甜瓜幼苗培养至二叶期，用如下所述不同浓度的活 性组合物或化合物的含水悬浮液喷雾至滴流点。24小时后，用甜瓜细菌性果斑病菌(Acidovorax citrulli)的含水悬浮液接种甜瓜叶片，之后将甜瓜幼苗放置于24～28℃和相对湿度为95～99％气候室中培养7天。最后目测测定甜瓜叶片上病菌侵染的发展程度(参见表19和20)。
表19单独活性组分的活性
Figure PCTCN2020093663-appb-000045
表20本发明组合物的活性
Figure PCTCN2020093663-appb-000046
Figure PCTCN2020093663-appb-000047
由各单独活性组分以及本发明组合物防治甜瓜细菌性果斑病的数据结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。
应用实施例11防治大白菜软腐病试验
将栽培品种为“德高1号”的盆栽大白菜幼苗培养至三叶期，用如下所述不同浓度的活性组合物或化合物的含水悬浮液喷雾至滴流点。24小时后，用大白菜软腐病菌(Erwinia carotovora subsp.carotovora)的含水悬浮液接种大白菜叶片，之后将幼苗放置于22～26℃和相对湿度为95～99％气候室中培养3天。最后目测测定大白菜叶片上病菌侵染的发展程度(参见表21和22)。
表21单独活性组分的活性
Figure PCTCN2020093663-appb-000048
Figure PCTCN2020093663-appb-000049
表22本发明组合物的活性
Figure PCTCN2020093663-appb-000050
Figure PCTCN2020093663-appb-000051
由各单独活性组分以及本发明组合物防治大白菜软腐病的数据结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。
应用实施例12防治黄瓜白粉病试验
将栽培品种为“山东密刺”的盆栽黄瓜幼苗培养至二叶期，用如下所述不同浓度的活性组合物或化合物的含水悬浮液喷雾至滴流点。24小时后，用黄瓜白粉病菌(Sphaerotheca fuliginea)的含水悬浮液接种黄瓜叶片，之后将黄瓜幼苗放置于24～28℃和相对湿度为90～95％气候室中培养3天。最后目测测定黄瓜叶片上病菌侵染的发展程度(参见表23和24)
表23单独活性组分的活性
Figure PCTCN2020093663-appb-000052
表24本发明组合物的活性
Figure PCTCN2020093663-appb-000053
Figure PCTCN2020093663-appb-000054
由各单独活性组分以及本发明组合物防治黄瓜白粉病的数据结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。应用实施例13防治柑橘溃疡病田间小区试验
选择常年发生柑橘溃疡病(Xanthomonas axonopodis pv.citri)的果园开展田间小区试验，柑橘品种为“脐橙”。试验采用随机区组设计，每小区3株柑橘树，四次重复，共进行两次药剂处理，间隔十天。在田间初见溃疡病病斑时开始进行首次药剂处理，使用背负式喷雾器，用如下所述浓度的活性化合物含水悬浮液对柑橘植株进行喷雾处理，十天后进行第二次喷雾处理。末次喷雾处理之后十天，目测测定柑橘叶片上病菌侵染的发展程度，并计算各处理四次重复的平均值(参见表25和26)。
表25单独活性组分的活性
Figure PCTCN2020093663-appb-000055
Figure PCTCN2020093663-appb-000056
表26本发明组合物的活性
Figure PCTCN2020093663-appb-000057
由各单独活性组分以及本发明组合物防治柑橘溃疡病的数据结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。应用实施例14防治黄瓜霜霉病试验
将栽培品种为“山东密刺”的盆栽黄瓜幼苗培养至二叶期，用如下所述浓度的活性化合物含水悬浮液喷雾至滴流点。24小时后，用黄瓜霜霉病菌(Pseudoperonospora cubensis)的孢子含水悬浮液接种黄瓜叶片，之后将黄瓜幼苗放置于22～24℃和相对湿度为95～99％气候室中培养7天。然后目测测定黄瓜叶片上病菌侵染的发展程度。
各单独活性组分以及本发明组合物防治黄瓜霜霉病的数据结果见表27和表28。结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。
表27单独活性组分的活性
Figure PCTCN2020093663-appb-000058
Figure PCTCN2020093663-appb-000059
表28本发明组合物的活性
Figure PCTCN2020093663-appb-000060
Figure PCTCN2020093663-appb-000061
应用实施例15防治黄瓜细菌性角斑病试验
将栽培品种为“山东密刺”的盆栽黄瓜幼苗培养至二叶期，用如下所述浓度的活性化合物含水悬浮液喷雾至滴流点。24小时后，用黄瓜细菌性角斑病菌(Pseudomonas syringae pv.lachrymans)的含水悬浮液接种黄瓜叶片，之后将黄瓜幼苗放置于24～28℃和相对湿度为95～99％气候室中培养7天。最后目测测定黄瓜叶片上病菌侵染的发展程度。
各单独活性组分以及本发明组合物防治黄瓜细菌性角斑病的数据结果见表29和表30。结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。
表29单独活性组分的活性
Figure PCTCN2020093663-appb-000062
Figure PCTCN2020093663-appb-000063
表30本发明组合物的活性
Figure PCTCN2020093663-appb-000064
Figure PCTCN2020093663-appb-000065
应用实施例16防治甜瓜细菌性果斑病试验
将栽培品种为“虎皮脆”的盆栽甜瓜幼苗培养至二叶期，用如下所述浓度的活性化合物含水悬浮液喷雾至滴流点。24小时后，用甜瓜细菌性果斑病菌(Acidovorax citrulli)的含水悬浮液接种甜瓜叶片，之后将甜瓜幼苗放置于24～28℃和相对湿度为95～99％气候室中培养7天。最后目测测定甜瓜叶片上病菌侵染的发展程度。
各单独活性组分以及本发明组合物防治甜瓜细菌性果斑病的数据结果见表31和表32。结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。
表31单独活性组分的活性
Figure PCTCN2020093663-appb-000066
Figure PCTCN2020093663-appb-000067
表32本发明组合物的活性
Figure PCTCN2020093663-appb-000068
Figure PCTCN2020093663-appb-000069
应用实施例17防治大白菜软腐病试验
将栽培品种为“德高1号”的盆栽大白菜幼苗培养至三叶期，用如下所述浓度的活性化合物含水悬浮液喷雾至滴流点。24小时后，用大白菜软腐病菌(Erwinia carotovora subsp.carotovora)的含水悬浮液接种大白菜叶片，之后将幼苗放置于22～26℃和相对湿度为95～99％气候室中培养3天。最后目测测定大白菜叶片上病菌侵染的发展程度。
各单独活性组分以及本发明组合物防治大白菜软腐病的数据结果见表33和表34。结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。
表33单独活性组分的活性
Figure PCTCN2020093663-appb-000070
Figure PCTCN2020093663-appb-000071
表34本发明组合物的活性
Figure PCTCN2020093663-appb-000072
Figure PCTCN2020093663-appb-000073
应用实施例18防治水稻纹枯病试验
将栽培品种为“越光”的盆栽水稻幼苗培养至三叶期，用如下所述浓度的活性化合物含水悬浮液喷雾至滴流点。24小时后，用水稻纹枯病菌(Rhizoctonia solani)的菌丝体含水悬浮液接种水稻叶片，之后将水稻幼苗放置于24～28℃和相对湿度为95～99％气候室中培养7天。最后目测测定水稻叶片上病菌侵染的发展程度。
各单独活性组分以及本发明组合物防治水稻纹枯病的数据结果见表35和表36。结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。
表35单独活性组分的活性
Figure PCTCN2020093663-appb-000074
Figure PCTCN2020093663-appb-000075
表36本发明组合物的活性
Figure PCTCN2020093663-appb-000076
Figure PCTCN2020093663-appb-000077
应用实施例19防治柑橘溃疡病田间小区试验
选择常年发生柑橘溃疡病(Xanthomonas axonopodis pv.citri)的果园开展田间小区试验，柑橘品种为“脐橙”。试验采用随机区组设计，每小区3株柑橘树，四次重复，共进行两次药剂处理，间隔十天。在田间初见溃疡病病斑时开始进行首次药剂处理，使用背负式喷雾器，用如下所述浓度的活性化合物含水悬浮液对柑橘植株进行喷雾处理，十天后进行第二次喷雾处理。末次喷雾处理之后十天，目测测定柑橘叶片上病菌侵染的发展程度，并计算各处理四次重复的平均值(参见表37和38)。
表37单独活性组分的活性
Figure PCTCN2020093663-appb-000078
表38本发明组合物的活性
Figure PCTCN2020093663-appb-000079
Figure PCTCN2020093663-appb-000080
由各单独活性组分以及本发明组合物防治柑橘溃疡病的数据结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。应用实施例20防治甜瓜细菌性果斑病试验
将栽培品种为“虎皮脆”的盆栽甜瓜幼苗培养至二叶期，用如下所述浓度的活性化合物含水悬浮液喷雾至滴流点。24小时后，用甜瓜细菌性果斑病菌(Acidovorax citrulli)的含水悬浮液接种甜瓜叶片，之后将甜瓜幼苗放置于24～28℃和相对湿度为95～99％气候室中培养7天。最后目测测定甜瓜叶片上病菌侵染的发展程度。
各单独活性组分以及本发明组合物防治甜瓜细菌性果斑病的数据结果见表39和表40。结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。
表39单独活性组分的活性
Figure PCTCN2020093663-appb-000081
Figure PCTCN2020093663-appb-000082
表40本发明组合物的活性
Figure PCTCN2020093663-appb-000083
Figure PCTCN2020093663-appb-000084
应用实施例21防治大白菜软腐病试验
将栽培品种为“德高1号”的盆栽大白菜幼苗培养至三叶期，用如下所述浓度的活性化合物含水悬浮液喷雾至滴流点。24小时后，用大白菜软腐病菌(Erwinia carotovora subsp.carotovora)的含水悬浮液接种大白菜叶片，之后将幼苗放置于22～26℃和相对湿度为95～99％气候室中培养3天。最后目测测定大白菜叶片上病菌侵染的发展程度。
各单独活性组分以及本发明组合物防治大白菜软腐病的数据结果见表41和表42。结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。
表41单独活性组分的活性
Figure PCTCN2020093663-appb-000085
Figure PCTCN2020093663-appb-000086
表42本发明组合物的活性
Figure PCTCN2020093663-appb-000087
Figure PCTCN2020093663-appb-000088
应用实施例22防治小麦白粉病试验
将栽培品种为“辽春10号”的盆栽小麦幼苗培养至三叶期，用如下所述浓度的活性化合物含水悬浮液喷雾至滴流点。24小时后，用小麦白粉病菌(Blumeria graminis)的孢子含水悬浮液接种小麦叶片，之后将小麦幼苗放置于22～24℃和相对湿度为85～90％气候室中培养7天。最后目测测定小麦叶片上病菌侵染的发展程度。
各单独活性组分以及本发明组合物防治小麦白粉病的数据结果见表43和表44。结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。
表43单独活性组分的活性
Figure PCTCN2020093663-appb-000089
Figure PCTCN2020093663-appb-000090
表44本发明组合物的活性
Figure PCTCN2020093663-appb-000091
Figure PCTCN2020093663-appb-000092
应用实施例23防治水稻细菌性条斑病田间小区试验
选择常年发生水稻细菌性条斑病(Xanthomonas oryzae pv.oryzicola)的田块开展田间小区试验，水稻栽培品种为“万香优1号”。试验采用随机区组设计，小区面积25平方米，四次重复，共进行两次药剂处理，间隔一周。在田间初见细菌性条斑病病斑时开始进行首次药剂处理，使用背负式喷雾器，用如下所述浓度的活性化合物含水悬浮液对 水稻植株进行喷雾处理，一周后进行第二次喷雾处理。末次喷雾处理之后一周，目测测定水稻叶片上病菌侵染的发展程度，并计算各处理四次重复的平均值(参见表45和46)。
表45单独活性组分的活性
Figure PCTCN2020093663-appb-000093
表46本发明组合物的活性
Figure PCTCN2020093663-appb-000094
由各单独活性组分以及本发明组合物防治水稻细菌性条斑病的数据结果表明，本发明组合物的观察效力值均大于计算效力值，说明组合物在试验配比范围内表现为协同增效作用。

Claims (10)

  1. 一种杀真菌、细菌组合物，其特征在于：组合物为A组分和B组分；所述A、B两组分之间的重量比为1:100～100:1；其中，A组分为通式Ⅰ所示丙二腈肟醚类化合物；B组分选自琥珀酸脱氢酶抑制剂类杀菌剂、含铜杀菌剂、抗生素类化合物、抗生素类化合物的盐或噻唑锌；
    Figure PCTCN2020093663-appb-100001
  2. 按权利要求1所述的杀真菌、细菌组合物，其特征在于：所述通式Ⅰ所示的丙二腈肟醚类化合物：
    Figure PCTCN2020093663-appb-100002
    式中：
    L选自-(CR 1R 2) n-；
    n选自1或2；
    当n＝2时，W为苯基；当n＝1时，W选自W 1、W 2、W 3、W 4、W 12、W 16、W 21、W 23、W 47、W 48、W 49、W 59、W 67、W 68、W 69、W 70、W 71、W 72、W 73、W 74、W 79、W 80、W 81、W 82、W 83或W 84；
    Figure PCTCN2020093663-appb-100003
    其中：
    X 1、X 2、X 3、X 4、X 5、X 6、X 7、X 8、X 9各自独立地选自氢、卤素、氰基、硝基、C 1-C 3烷基、C 1-C 3卤代烷基、-OR 3、-N(R 4)S(＝O) 2R 5、-S(＝O) 2NR 3R 5、-CH 2ON＝C(CN) 2、未取代的或被下述基团任意取代的苯基和吡啶基，其中，下述基团为卤素、氰基、C 1-C 3卤代烷基；当W为W 1时，X 1、X 2、X 3、X 4、X 5不同时为氢；或W 1为
    Figure PCTCN2020093663-appb-100004
    Figure PCTCN2020093663-appb-100005
    Z选自氢、C 1-C 3烷基、苯基甲基；
    K选自氧；
    R 3选自氢、C 1-C 3烷基、C 1-C 3卤代烷基、未取代的或被下述基团任意取代的苯基或吡啶基，其中下述基团为卤素或C 1-C 3卤代烷基；
    R 4、R 5各自独立地选自氢、C 1-C 3烷基；
    Q选自Q 1-2所示的基团之一、未取代的或被下述基团任意取代的苯基和吡啶基，其中，下述基团为卤素、C 1-C 3烷基；
    Figure PCTCN2020093663-appb-100006
    T选自未取代的或被下述基团任意取代的苯基和吡啶基，其中，下述基团为卤素、氰基、C 1-C 3烷基、卤代C 1-C 3烷基、卤代C 1-C 3烷氧基。
  3. 按照权利要求1或2所述的杀真菌、细菌组合物，其特征在于：组合物中A组分为所述通式Ⅰ所示的丙二腈肟醚类化合物：
    式中，L选自：-(CR 1R 2) n-；
    n选自1；
    R 1、R 2选自氢；
    W选自W 1、W 2、W 3、W 4、W 12、W 16、W 21、W 23、W 48、W 49、W 59、W 67、W 68、W 69、W 70、W 71、W 72、W 73、W 74、W 79、W 80、W 81、W 82、W 83或W 84；
    X 1、X 2、X 3、X 4、X 5、X 6、X 7、X 8、X 9各自独立地选自氢、卤素、氰基、硝基、C 1-C 3烷基、C 1-C 3卤代烷基、-OR 3、未取代的或被下述基团任意取代的苯基和吡啶基，其中，下述基团为卤素、氰基、C 1-C 3卤代烷基；当W为W 1时，X 1、X 2、X 3、X 4、X 5不同时为氢；
    Z选自氢、C 1-C 3烷基；
    K选自氧；
    R 3选自C 1-C 3烷基、C 1-C 3卤代烷基、未取代的或被下述基团任意取代的苯基或吡啶基，其中下述基团为卤素或C 1-C 3卤代烷基；
    Q选自Q 1-2所示的基团之一、未取代的或被下述基团任意取代的苯基和吡啶基，下述基团为卤素、C 1-C 3烷基；
    T选自未取代的或被下述基团任意取代的苯基和吡啶基，其中，下述基团为卤素、氰基、C 1-C 3烷基、卤代C 1-C 3烷基、卤代C 1-C 3烷氧基；
    所述B组分琥珀酸脱氢酶抑制剂类杀菌剂选自苯并烯氟菌唑、吡噻菌胺、吡唑萘菌胺、啶酰菌胺、氟吡菌胺、氟吡菌酰胺、氟唑环菌胺、氟唑菌酰胺、噻呋酰胺、双炔酰菌胺、呋吡菌胺、氟啶菌酰胺、氟唑菌苯胺、环丙酰菌胺、联苯吡菌胺或噻氟菌胺；
    所述B组分选自：春雷霉素、中生菌素、多抗霉素、申嗪霉素、井冈霉素、四霉素、 宁南霉素、公主岭霉素、武夷霉素或硫酸链霉素，或上述各抗生素的盐；
    所述B组分选自：氢氧化铜、王铜、波尔多液、碱式硫酸铜、硫酸铜钙、氧化亚铜、噻菌铜、噻森铜、喹啉铜、络氨铜、乙酸铜、松脂酸铜、壬菌铜或琥胶肥酸铜；
    所述B组分选自：噻唑锌；
    所述A、B两组分之间的重量比为1：90～90：1。
  4. 按照权利要求3所述的杀真菌、细菌组合物，其特征在于：所述A、B两组分之间的重量比为1：75～75：1；其中，A组分为所述通式Ⅰ所示的丙二腈肟醚类化合物：
    式中，
    L选自-(CR 1R 2) n-；
    n选自1；
    R 1、R 2选自氢；
    W选自W 1、W 2、W 3、W 4、W 16、W 49、W 59、W 69、W 70、W 71、W 72、W 79、W 80或W 81；
    X 1、X 2、X 3、X 4、X 5、X 6各自独立地选自氢、卤素、氰基、硝基、C 1-C 3烷基、C 1-C 3卤代烷基、-OR 3、未取代的或被下述基团任意取代的苯基，其中，下述基团为卤素、氰基、C 1-C 3卤代烷基；当W为W 1时，X 1、X 2、X 3、X 4、X 5不同时为氢；
    Z选自氢；
    K选自氧；
    R 3选自C 1-C 3烷基、C 1-C 3卤代烷基；
    Q选自Q 1-2所示的基团之一、未取代的或被下述基团任意取代的苯基和吡啶基，其中，下述基团为卤素、C 1-C 3烷基；
    T选自未取代的或被下述基团任意取代的苯基和吡啶基，其中，下述基团为卤素、C 1-C 3烷基、卤代C 1-C 3烷基、卤代C 1-C 3烷氧基；
    B组分选自苯并烯氟菌唑、吡噻菌胺、吡唑萘菌胺、啶酰菌胺、氟吡菌胺、氟吡菌酰胺、氟唑环菌胺、氟唑菌酰胺、噻呋酰胺、双炔酰菌胺、呋吡菌胺、氟啶菌酰胺、氟唑菌苯胺或环丙酰菌胺；
    B组分选自：春雷霉素、中生菌素、多抗霉素、申嗪霉素、井冈霉素、四霉素、宁南霉素、公主岭霉素或武夷霉素，或上述各抗生素的盐；
    B组分选自：氢氧化铜、王铜、波尔多液、碱式硫酸铜、硫酸铜钙、氧化亚铜、噻菌铜、噻森铜、喹啉铜、络氨铜、乙酸铜、松脂酸铜、壬菌铜或琥胶肥酸铜；
    B组分选自：噻唑锌。
  5. 按照权利要求4所述的杀真菌、细菌组合物，其特征在于：所述A、B两组分之间的重量比为1：50～50：1；其中，A组分为所述通式Ⅰ所示的丙二腈肟醚类化合物：
    式中，
    L选自-(CR 1R 2) n-；
    n选自1；
    R 1、R 2选自氢；
    W选自W 1、W 2、W 3、W 4、W 16、W 49或W 69；
    X 1、X 2、X 3、X 4、X 5各自独立地选自氢、氟、氯、溴、氰基、硝基、甲基、乙基、异丙基、氯甲基、溴甲基、二氟甲基、三氟甲基、-OR 3、未取代的或被下述基团任意取代的苯基，其中，下述基团为卤素、氰基；当W为W 1时，X 1、X 2、X 3、X 4、X 5不同时为氢；
    R 3选自甲基或三氟甲基；
    B组分选自：苯并烯氟菌唑、吡噻菌胺、吡唑萘菌胺、啶酰菌胺、氟吡菌胺、氟吡 菌酰胺、氟唑环菌胺、氟唑菌酰胺、噻呋酰胺、双炔酰菌胺、呋吡菌胺或氟啶菌酰胺；
    B组分选自：春雷霉素、中生菌素、多抗霉素、申嗪霉素、井冈霉素、四霉素、宁南霉素或公主岭霉素；
    B组分选自：氢氧化铜、王铜、波尔多液、碱式硫酸铜、硫酸铜钙、氧化亚铜、噻菌铜、噻森铜、喹啉铜、络氨铜、乙酸铜、松脂酸铜、壬菌铜或琥胶肥酸铜；
    B组分选自：噻唑锌。
  6. 按照权利要求5所述的杀真菌、细菌组合物，其特征在于：所述A、B两组分之间的重量比为1：20～20：1；其中，A组分为所述通式Ⅰ所示的丙二腈肟醚类化合物：
    式中，
    L选自-(CR 1R 2) n-；
    n选自1；
    R 1、R 2选自氢；
    W选自W 1；
    X 1、X 2、X 3、X 4、X 5各自独立地选自氢、氟、氯、溴、氰基、硝基、甲基、乙基、异丙基、氯甲基、溴甲基、二氟甲基、三氟甲基、-OR 3、未取代的或被下述基团任意取代的苯基，其中，下述基团为卤素、氰基；当W为W 1时，X 1、X 2、X 3、X 4、X 5不同时为氢；
    R 3选自甲基或三氟甲基；
    B组分选自：苯并烯氟菌唑、吡噻菌胺、吡唑萘菌胺、啶酰菌胺、氟吡菌胺、氟吡菌酰胺、氟唑环菌胺、氟唑菌酰胺、噻呋酰胺或双炔酰菌胺；
    B组分选自：春雷霉素、中生菌素、多抗霉素、申嗪霉素、井冈霉素、四霉素或宁南霉素；
    B组分选自：氢氧化铜、王铜、波尔多液、碱式硫酸铜、硫酸铜钙、氧化亚铜、噻菌铜、噻森铜、喹啉铜、络氨铜、乙酸铜、松脂酸铜、壬菌铜或琥胶肥酸铜
    B组分选自：噻唑锌。
  7. 一种权利要求1所述杀真菌、细菌组合物的应用，其特征在于：所述组合物作为防治植物病原性有害真菌、细菌。
  8. 按权利要求7所述杀真菌、细菌组合物的应用，其特征在于：所述组合物用于防治有害真菌、细菌侵染、侵害的植物、种子、土壤、区域、材料或空间。
  9. 按权利要求8所述杀真菌、细菌组合物的应用，其特征在于：所述组合物用于谷物、水稻、果树、蔬菜、花卉、中药材或草坪的植物真菌、细菌性病害的防治。
  10. 按权利要求7-9任意一项所述杀真菌、细菌组合物的应用，其特征在于：所述杀真菌、细菌组合物采用叶面或植株整体喷雾、灌根或浸种的方式，防治植物真菌、细菌病害。
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CN114304173A (zh) * 2022-01-14 2022-04-12 吉林省农业科学院 一种用于防治菌核病的农药组合物及其应用
CN114304173B (zh) * 2022-01-14 2023-09-19 吉林省农业科学院 一种用于防治菌核病的农药组合物及其应用

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