CN115005214B

CN115005214B - Efficient bactericidal composition for preventing and treating fusarium disease of crops

Info

Publication number: CN115005214B
Application number: CN202210805610.3A
Authority: CN
Inventors: 马忠华; 吴宁捷; 胡伟群; 王洪雷; 陈云; 许天明; 曹杨
Original assignee: JIANGSU PESTICIDE RESEARCH INSTITUTE CO LTD; Zhejiang Chemical Industry Research Institute Co Ltd; Zhejiang University ZJU
Current assignee: JIANGSU PESTICIDE RESEARCH INSTITUTE CO LTD; Zhejiang Chemical Industry Research Institute Co Ltd; Zhejiang University ZJU
Priority date: 2022-07-08
Filing date: 2022-07-08
Publication date: 2023-03-28
Anticipated expiration: 2042-07-08
Also published as: CN115005214A

Abstract

The invention discloses a high-efficiency bactericidal composition for preventing and treating fusarium diseases of crops, and belongs to the technical field of crop disease prevention and treatment. The active components of the composition comprise succinate dehydrogenase inhibitor bactericides and a compound ZJS178 with a structural formula shown in a formula (I), the two components respectively inhibit the bioenergy (ATP synthesis) and mechanical energy (motor protein) of germs, the two action mechanisms are different but are mutually related, and the two components are compounded to have obvious synergistic effect and obviously enhance the bactericidal effect. The composition consists of active ingredients with different action mechanisms, is favorable for delaying the drug resistance of pathogenic bacteria, has good safety to crops, and meets the requirement of reduction and synergism of pesticides.

Description

Efficient bactericidal composition for preventing and treating fusarium disease of crops

Technical Field

The invention relates to the technical field of crop disease control, in particular to an efficient bactericidal composition for controlling crop diseases caused by fusarium.

Background

Fusarium (Fusarium spp.) can infect various tissue parts such as roots, stems, flowers and fruits of crops, cause various crop diseases and affect the yield and quality, and common Fusarium diseases of crops have the following effects: rice bakanae disease, wheat scab, corn ear rot, melon wilt, root rot of various crops, etc.

In China, wheat scab is frequently epidemic and disastrous due to Fusarium graminearum complex, and the germs generate mycotoxins such as deoxynivalenol, zearalenone and the like on infected wheat, thereby seriously threatening the safety of people and livestock. Therefore, the disease is classified as 'one kind of crop diseases and insect pests' by the rural agricultural department. In addition, bakanae disease caused by Fusarium fujikuroi complex is also a common fungal disease in rice. With the large-area popularization of centralized seedling raising technologies such as mechanical transplanting, seedling throwing and the like, bakanae disease is more and more common in China, the incidence rate of local areas reaches 100 percent, and serious yield loss is caused. Fusarium can also cause blight of various fruits and vegetables, for example, banana wilt caused by Fusarium oxysporum (Fusarium oxysporum) and blight of melons, tomatoes and the like, which seriously restricts the healthy development of industries.

Therefore, the method for effectively preventing and controlling the fusarium disease of the crop has important significance for guaranteeing the effective supply and quality safety of agricultural products in China.

Currently, the chemical control is mainly used for preventing and controlling fusarium diseases due to the lack of high-resistance crop varieties. Compared with crop diseases such as powdery mildew, gray mold and the like, the fusarium in the market is deficient in special chemical agents. Succinate dehydrogenase inhibitor (SDHIs) bactericides such as pyraflufen-ethyl fluoride (pydiflumetofen) can be used for preventing and treating diseases caused by Fusarium (Fusarium) on grains, such as Fusarium head blight (Fusarium head light) and the like.

Fluxapyroxad, chemical name: 3- (difluoromethyl) -N-methoxy-1-methyl-N- [ (RS) -1-methyl-2- (2, 4, 6-trichlorophenyl) ethyl ] pyrazole-4-carboxamide, a new generation of succinate dehydrogenase inhibitors (SDHI) developed by Dart. The medicament acts on the respiratory chain complex II, prevents ATP synthesis, inhibits the growth of pathogenic bacteria to cause the death of the pathogenic bacteria, and finally achieves the aim of preventing and treating plant diseases.

Penflufen (Penflufen), chemical name: 5-fluoro-1, 3-dimethyl-N- [2- (4-methylpent-2-yl) phenyl ] -1H-pyrazole-4-carboxamide, is a SDHI-type fungicide developed by Bayer. The preparation acts on respiratory chain complex II, inhibits bacteria ATP synthesis, and has systemic, prophylactic and therapeutic effects. At present, the pesticide is mainly used for seed treatment, and after the seed treatment, the pesticide permeates into germinated seeds and is conducted to the whole plant through xylem of young plants, so that the pesticide plays a role in protection.

The succinate dehydrogenase inhibitor bactericide has a single action site, and resistance risks are continuously increased along with wide application of the succinate dehydrogenase inhibitor bactericide, so that the development of a proper medicament combination is particularly important for preventing and controlling crop diseases. At present, no report related to the disease control of the compounding of the SDHIs bactericide and the cyanoacrylate bactericide is available.

Disclosure of Invention

The invention aims to provide a high-efficiency, low-toxicity and environment-friendly bactericidal composition which is beneficial to germ resistance control and has a special effect on crop diseases caused by fusarium.

In order to achieve the purpose, the invention adopts the technical scheme that:

the invention provides a high-efficiency sterilization composition, the active components of the composition comprise a compound ZJS178 with a structural formula shown in formula (I) and succinate dehydrogenase inhibitor bactericides,

the compound ZJS178 is a new compound prepared in the earlier stage of the subject group of the invention, the chemical name is 2-cyano-3-amino-3- [4- (N-ethyl-N-methylamino) phenyl ] ethyl acrylate, and the synthetic route is as follows:

the compound is a cyanoacrylate bactericidal compound, acts on I-type myosin of fusarium, is motor protein of pathogen, can hydrolyze ATP, converts biological energy into mechanical energy, and provides power for vital activities such as pathogen growth, infection, toxin synthesis and the like. ZJS178 specifically acts on the I-type myosin of fusarium, so that the growth of germs is unpowered, and the germs die.

The ZJS178 has novel structure and unique action mode, and research shows that the ZJS178 has no cross resistance with succinate dehydrogenase inhibitor (SDHI) medicaments, is effective on diseases caused by fusarium, and has protective action and therapeutic action.

As the ZJS178 and the SDHI bactericides have different action mechanisms but are associated with action sites, the invention combines the ZJS178 and the SDHI bactericides, can obviously enhance the bactericidal effect, delay the drug resistance of germs and reduce the prevention and treatment cost. Specifically, the SDHI bactericide can effectively inhibit ATP synthesis of pathogenic bacteria, and the ZJS178 and the SDHI medicament are reasonably compounded, so that ATP synthesis and motor protein activity can be simultaneously blocked, the effect of efficiently inhibiting growth of the pathogenic bacteria is achieved, and the generation of resistance of the pathogenic bacteria to any medicament can be delayed.

Preferably, the mass ratio of the compound ZJS178 to the succinate dehydrogenase inhibitor bactericide in the composition is 50.

The succinate dehydrogenase inhibitor bactericide includes but is not limited to: fluxapyroxad, fluopyram, carboxin, and the like.

Preferably, the mass ratio of the compound ZJS178 to the succinate dehydrogenase inhibitor bactericide in the composition is 9.

Research shows that the compound ZJS178 and succinate dehydrogenase inhibitor bactericide produce synergistic effect in certain compounding ratio and have synergistic effect on preventing and treating fusarium disease. When the mass ratio of the compound ZJS178 to the succinate dehydrogenase inhibitor bactericide in the composition is 7.

Furthermore, the efficient bactericidal composition also comprises a carrier and an auxiliary agent which are acceptable in pesticides. The mass ratio of the active components in the composition is 1-90%.

Preferably, the mass ratio of the active components in the composition is 10-40%.

According to the method known by the person skilled in the art, the bactericidal composition can be prepared into various agriculturally acceptable formulations in practical application, and the common formulation formulations comprise water dispersible granules, suspending agents, microemulsions, aqueous emulsions and seed treatment suspending agents.

For the water-dispersible granule form, the person skilled in the art can carry out the invention using the corresponding auxiliaries. The dispersant can be selected from polycarboxylate, lignosulfonate and alkyl naphthalene sulfonate; the wetting agent is selected from alkyl sulfate, alkyl sulfonate and naphthalene sulfonate; the disintegrating agent is selected from ammonium sulfate, urea, sucrose and glucose; the binder is selected from diatomite, corn starch, polyvinyl alcohol and carboxymethyl (ethyl) cellulose; the filler is selected from diatomite, kaolin, white carbon black, light calcium carbonate, talcum powder, attapulgite and argil.

Auxiliaries which can be used in the form of suspensions are: the dispersant is selected from polycarboxylate, lignosulfonate and alkyl naphthalene sulfonate; the wetting agent is selected from alkylphenol polyoxyethylene polyether formaldehyde condensate sulfate, alkylphenol polyoxyethylene ether phosphate, phenethyl phenol polyoxyethylene ether phosphate, alkyl sulfate, alkyl sulfonate and naphthalene sulfonate; the thickening agent is selected from xanthan gum, polyvinyl alcohol and bentonite; the preservative is selected from formaldehyde, benzoic acid and sodium benzoate; the defoaming agent is an organic silicon defoaming agent; the antifreeze agent is selected from ethylene glycol, propylene glycol, glycerol, urea, and inorganic salts such as sodium chloride.

The water emulsion type can use the auxiliary agent: the emulsifier is selected from nonylphenol polyoxyethylene ether phosphate, tristyrylphenol polyoxyethylene ether phosphate (Nongru No. 600 phosphate), nongru No. 700, nongru No. 2201, span-60, emulsifier T-60, surfactant TX-10, nongru No. 1601, nongru No. 600 and Nongru No. 400; the solvent is selected from dimethylbenzene, methylbenzene, cyclohexanone and solvent oil (S-150, S-180 and S-200); the stabilizer is selected from triphenyl phosphite, epichlorohydrin and acetic anhydride; the thickener is selected from xanthan gum, polyvinyl alcohol, bentonite and magnesium aluminum silicate; the antiseptic is selected from methanol, benzoic acid, and sodium benzoate.

Auxiliary agents which can be used in the form of microemulsions are: the emulsifier is selected from calcium dodecylbenzene sulfonate (Nongru 500 #), nongru 700#, nongru 2201#, span-60 #, tween-80-60 #, TX-10, nongru 1601, nongru 600#, nongru 400#; the auxiliary emulsifier is selected from methanol, isopropanol, n-butanol, and ethanol; the solvent is selected from cyclohexanone, N-methyl pyrrolidone, xylene, toluene and solvent oil (S-150, S-180 and S-200); the stabilizer is selected from triphenyl phosphite and epichlorohydrin.

The seed treatment suspending agent may be used with the following auxiliaries: the film forming agent can be polyethylene glycol, polyvinyl alcohol resin, polyvinylpyrrolidone, hydroxyethyl cellulose, homo polyvinyl acetate, sodium carboxymethyl cellulose, acacia, gelatin, polyvinyl alcohol or polyacrylamide or their mixture. The proportion of homopolymeric vinyl acetate can be adjusted by the skilled worker depending on the viscosity desired for the product.

The invention also provides application of the high-efficiency bactericidal composition in preventing and treating fusarium diseases of crops.

Further, the Fusarium refers to a plant pathogenic Fusarium, and mainly includes Fusarium graminearum complex (Fusarium graminearum complex), fusarium graminearum complex (Fusarium fujikuroi complex), fusarium oxysporum (Fusarium oxysporum), fusarium moniliforme (Fusarium moniliforme), and the like.

Further, crop diseases caused by fusarium include, but are not limited to: wheat scab, rice bakanae disease.

Specifically, when the compound ZJS178 and the fluxapyroxad are compounded to prevent and treat wheat scab, the pesticide is applied for 1 time at the initial stage of wheat heading and flowering, and is applied for one time after 6 days. The compound ZJS178 and penflufen are compounded into a medicament as a seed treating agent for preventing and treating crop diseases.

The invention has the following beneficial effects:

(1) The active ingredients of the bactericidal composition provided by the invention comprise succinate dehydrogenase inhibitor bactericides and a compound ZJS178, the two ingredients respectively inhibit the biological energy (ATP synthesis) and the mechanical energy (motor protein) of germs, the two ingredients have different action mechanisms but are mutually associated, and the two ingredients have obvious synergistic action after being compounded, so that the bactericidal effect is obviously enhanced.

(2) The bactericidal composition provided by the invention consists of active ingredients with different action mechanisms, is favorable for delaying the drug resistance of germs, has good safety to crops, and meets the requirement of reduction and synergism of pesticides.

Detailed Description

The present invention is further illustrated by the following specific examples. The following examples are merely illustrative of the present invention and are not intended to limit the scope of the invention. Modifications or substitutions to methods, steps or conditions of the present invention may be made without departing from the spirit and nature of the invention.

The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.

Example 1: synthesis of Compound ZJS178

Step 1: synthesis of intermediate b

7.0g of the starting material a (CAS No: 67710-36-5) and 150mL of dichloromethane were charged into a reaction flask, 11.7g of Boc anhydride was added in ice bath, 6.0g of triethylamine and 3.3g of DMAP were slowly added, and stirring was continued for 0.5 hour in ice bath, then the mixture was warmed to room temperature, and further stirred for 5 hours. After the reaction, 1M hydrochloric acid was added to the reaction solution, the organic phase was separated, and the organic phase was washed once with pure water and saturated brine. The organic phase is passed through anhydrous Na ₂ SO ₄ Dried and concentrated to give 9.6g of intermediateBody b, the crude product was directly taken to the next reaction without further purification.

Step 2: synthesis of intermediate c

9.6g of intermediate b, 120mL of ethanol and 24mL of water were put into a reaction flask, heated to 90 ℃ and added with 3.7g of iron powder and 12mL of saturated ammonium chloride solution, and the reaction was continued for 4 hours. After the reaction, diatomite is added for filtration, the filtrate is concentrated and then water is added, and ethyl acetate is added for extraction for three times. The combined organic phases were concentrated and separated by column chromatography (eluent ethyl acetate and petroleum ether, volume ratio 1.

And step 3: synthesis of intermediate d

0.19g of sodium hydride was added to 20mL of tetrahydrofuran under ice-cooling, 1.0g of intermediate c was added thereto, and the mixture was warmed to room temperature and stirred for 30 minutes. Further, 0.74g of iodoethane was added thereto, and the mixture was stirred at room temperature overnight. After the reaction, water was added to quench the reaction, followed by extraction with ethyl acetate three times. The combined organic phases were concentrated and separated by column chromatography (eluent ethyl acetate and petroleum ether, volume ratio 1.

And 4, step 4: synthesis of intermediate e

0.11g of sodium hydride was added to 10mL of tetrahydrofuran under ice-cooling, and 0.5g of intermediate d was added, and the mixture was warmed to room temperature and stirred for 30 minutes. Further, 0.40g of methyl iodide was added thereto, and the mixture was stirred at room temperature overnight. After the reaction, water was added to quench the reaction, followed by extraction with ethyl acetate three times. The organic phases were combined, concentrated and separated by column chromatography (eluent ethyl acetate and petroleum ether, volume ratio 1.

And 5: synthesis of Compound ZJS178

And adding 0.34g of the intermediate e and 10mL of tetrahydrofuran into a reaction bottle, dropwise adding sodium chloride into concentrated sulfuric acid to prepare hydrogen chloride gas, slowly introducing the reaction solution, stopping introducing the reaction solution after 1 hour, and stirring at room temperature overnight. After the reaction was completed, a saturated aqueous sodium hydrogencarbonate solution was added and extracted twice with ethyl acetate. The organic phases are combined, concentrated and separated by column chromatography (eluent ethyl acetate and petroleum ether, volume ratio 1: 2) to yield 0.22g of compound ZJS178, yield 93.2%.

Example 2: indoor toxicity determination of ZJS178 and triflumizole acylhydroxylamine compound pair wheat scab

Test subjects: fusarium graminearum (Fusarium graminearum) is obtained by field separation, identified as Fusarium graminearum by biological methods such as morphology, pathogenicity and the like, and stored in a laboratory for later use.

Test agents: ZJS178 was synthesized from example 1, fluxapyroxad (synanton south-channel crop protection limited, commercially available).

The test method comprises the following steps: refer to the hypha growth rate method in agricultural industry Standard NY/T1156.2-2006 of the people's republic of China. Each medicament is respectively treated by 5 dosages according to the content of active ingredients, and the inhibition rate of each medicament on the growth of pathogenic bacteria is 10-90%. Inoculating the wheat scab pathogenic bacteria on a PDA culture medium, when bacterial colonies grow to 2/3 of a culture dish, punching bacterial blocks at the edges of the bacterial colonies by using a puncher with the diameter of 5mm, moving the bacterial blocks to the center of a pre-prepared medicine-containing culture medium by using an inoculating needle, culturing in an incubator at 25 ℃ for 3 days, measuring the diameter cm of each processed bacterial colony by using a caliper by using a cross method, calculating the corrected inhibition percentage, and calculating the EC of each medicament by using linear regression analysis between the probability value of the inhibition percentage and the logarithmic value of the series concentration ₅₀ Values, repeated 4 times per treatment. ZJS178 as the standard drug, according to the following formulaCo-toxicity coefficients (CTCs) were calculated.

Actual virulence index (ATI) = (EC of standard agent) ₅₀ EC of test agent ₅₀ )×100；

Theoretical virulence index (TTI) = standard agent virulence index x percentage of standard agent in the mixed formulation + test agent virulence index x percentage of test agent in the mixed formulation;

co-toxicity coefficient (CTC) = (ATI/TTI) × 100%;

a CTC value of less than 80 indicates that the combination of the medicaments has antagonistic action; 80-120 is additive effect; a value greater than 120 is synergistic.

The test results are shown in table 1.

Table 1 shows indoor toxicity measurement results of wheat scab by compounding ZJSK 178 and triflumizole hydroxylamine

The results in table 1 show that ZJS178 and fluxapyroxad both have excellent bacteriostatic effects on wheat scab germs, and the two have synergistic effects within the range of 5.

Example 3: indoor toxicity determination of ZJS178 and penflufen on rice bakanae disease

Test subjects: the rice bakanae disease (Fusarium fujikuroi) is obtained by field separation, identified as Fusarium fujikuroi by biological methods such as morphology, pathogenicity and the like, and stored in a laboratory.

Test agents: ZJS178 was synthesized from example 1, fluxapyroxad aniline (available commercially from Bayer AG).

Bioassay methods refer to example 2.

The test results are shown in table 2.

Table 2: indoor toxicity determination result of compounding ZJS178 and penflufen on rice bakanae disease

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As can be seen from the results in Table 2, ZJS178 and fluxapyroxad both have good bacteriostatic effects on bakanae disease of rice, and ZJS178 and fluxapyroxad aniline are at 5:1-1: the compound in the range of 5 has obvious synergistic effect.

Example 4: test of field drug effect

1. Preparation of the preparation

The percentage contents in all the preparation ratios are mass percentages.

(1) 40% of ZJSS178-Fluxapyroxad water dispersible granule

Weighing 20% of ZJS178, 20% of fluxapyroxad, 3% of TERSPERSE 2700, 2% of diffuser NNO (alkylnaphthalenesulfonate formaldehyde condensate), 3% of nekal BX (sodium dibutylnaphthalenesulfonate), 4% of K-12 (sodium dodecylsulfate), 3% of diatomaceous earth, 5% of glucose, kaolin to 100%.

According to the formula proportion, the raw medicine, the dispersing agent, the wetting agent, the binding agent and the like are mixed and subjected to superfine airflow crushing by a conventional method for preparing water dispersible granules, and the mixture is added into a granulator with a screen with a certain specification for granulation. Then drying and screening to obtain granular products.

(2) 10% of ZJSS178 Fluxapyroxad suspension

Weighing 5% of ZJS178, 5% of fluxapyroxad, 2% of TERSPERSE 2500, 3% of TERSPERSE 2425, 0.2% of xanthan gum, 3% of white carbon, 5% of ethylene glycol, 0.5% of formaldehyde, 0.3% of benzoic acid, 0.5% of silicone defoamer (trade name: s-29 Nanjing Sixin applied Chemicals Co., ltd.), and deionized water to 100% by mass.

According to the formula proportion, water is used as a medium, the raw pesticide, the dispersing agent, the suspending agent, the antifreezing agent and the like are added into a batching kettle to be uniformly mixed, and the mixture is dispersed for 30min through a ball mill or high-speed shearing, and then is made into the suspending agent after being sanded by a sand mill.

2. Field test

2.1 field efficacy test for controlling wheat scab

The control of the wheat scab is carried out according to the regulation of 'NY/T1464.15-2007 pesticide field efficacy test rule-fungicide control of the wheat scab', the pesticide is applied for 1 time at the early stage of ear sprouting and flower raising of the wheat, and the pesticide is applied for one time after 6 days; and (3) surveying after spraying for 2 weeks, sampling 5 points of diagonal lines in each test cell, surveying 100-200 ears in each point, grading by the percentage of the area of the dry ears in the whole ear area, and recording the number of diseased ears and the total number of ears at each level. Disease grading criteria are as follows:

level 0: the whole spike is disease-free;

level 1: the area of the withered spike accounts for less than 1/4 of the total spike area;

and 2, stage: the area of the withered spike accounts for 1/4-1/2 of the area of the whole spike;

and 3, level: the area of the withered spike accounts for 1/2-3/4 of the area of the whole spike;

4, level: the area of the withered spike accounts for more than 3/4 of the area of the whole spike.

The test results are shown in table 3.

Table 3. ZJSK 178. Results of field drug effect of compound preparation of epoxiconazole and hydroxylamine on wheat scab

* Different lower case letters after the same column of data indicate significant differences at a P <0.05 level.

The results in Table 3 show that the ZJS 178-fluxapyroxad compound agent has excellent control effect on wheat scab; compared with single dosage, the two are compounded under the same dosage to have obvious synergistic effect.

2.2 field test of pesticide effect for preventing and treating bakanae disease of rice

The prevention and treatment of the rice bakanae disease are carried out according to the regulation of GB-T17980.104-2004 pesticide field efficacy test criterion (II) -bactericide prevention and treatment of the rice bakanae disease. In the east Puzhen of Shaoxing city, the rice variety is Zhongzao 39 (susceptible variety). The liquid medicine is diluted to a certain amount of liquid for soaking seeds for 72 hours, and then germination and seeding are carried out. The method adopts nutrient soil to carry out seedling culture, and the seedling culture process is strictly carried out according to a mechanical seedling transplanting and seedling culture flow. The seed amount, soil fertility and the like of each treatment are consistent. The seed amount of each seedling tray is 150g for each 20 seedling trays treated. 1d before transplanting and before heading, investigating the incidence of bakanae disease, and calculating the disease rate and control effect according to the following formula.

The test results are shown in table 4.

Table 4: test result of field pesticide effect of ZJS 178-fluxapyroxad aniline compound agent on rice bakanae disease

Table 4 shows that the compound of ZJS178 and penflufen has excellent control effect on rice bakanae disease; under the condition of the same effective dose, the control effect of the compound preparation is obviously better than that of a single preparation. Is safe to the test crops within the range of the test application.

The results of indoor bioassay and field pesticide effect test show that: the bactericide composition has remarkable synergism, consists of active ingredients with different action mechanisms, and can delay the generation of resistance of germs to a single medicament; the compound agent has no obvious adverse effect on the test crops, and the leaf color, the growth vigor and the like are normal.

Claims

1. The efficient sterilization composition is characterized in that active components of the composition comprise a compound ZJS178 and a succinate dehydrogenase inhibitor bactericide with a structural formula shown in a formula (I), the mass ratio of the compound ZJS178 to the succinate dehydrogenase inhibitor bactericide in the composition is 9-1,

2. the efficient sterilization composition according to claim 1, wherein the mass ratio of the compound ZJS178 to the succinate dehydrogenase inhibitor bactericide in the composition is 7.

3. The efficient bactericidal composition according to claim 1, wherein the active ingredients in the composition account for 10-40% by mass.

4. The highly potent fungicidal composition as claimed in claim 1, wherein the composition further comprises a pesticidally acceptable carrier and adjuvant.

5. The use of the high-efficiency bactericidal composition as defined in any one of claims 1-4 for controlling fusarium disease of crops.

6. The use of claim 5, wherein the Fusarium is Fusarium graminearum complex (Fusarium graminearum complex), fusarium fujikukoi complex (Fusarium fujikuroi complex), fusarium oxysporum (Fusarium oxysporum), fusarium moniliforme (Fusarium moniliforme).

7. The use of claim 6, wherein the disease comprises: wheat scab and rice bakanae disease.