CN1708225A - Fungicidal compositions for the control of paddy rice diseases - Google Patents
Fungicidal compositions for the control of paddy rice diseases Download PDFInfo
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- CN1708225A CN1708225A CNA2003801024643A CN200380102464A CN1708225A CN 1708225 A CN1708225 A CN 1708225A CN A2003801024643 A CNA2003801024643 A CN A2003801024643A CN 200380102464 A CN200380102464 A CN 200380102464A CN 1708225 A CN1708225 A CN 1708225A
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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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
Abstract
The invention relates to fungicidal compositions effective in the control of paddy rice diseases, containing as the active ingredients both a compound represented by the general formula (1) or an acid addition salt thereof and at least one member selected from among strobilurin insecticides: (1) wherein R is hydrogen, -COR<1>, -COOR<1> (wherein R<1> is alkyl having 1 to 4 carbon atoms), -COCH2OCH3, or -COCH2OCOCH3.
Description
Background of invention
Invention field
The present invention relates to a kind of excellent bactericidal composition of preventing and treating the rice disease effect that has, more specifically, relate to a kind of bactericidal composition that excellent control comprises the rice fungus diseases evil effect of rice blast that has.
Association area
The WO 01/92231 that the applicant submits to (international publication day: December 6 calendar year 2001) disclose formula (1) compound or its acid-addition salts with excellent bactericidal activity:
Wherein
R represents hydrogen atom;-COR
1Or-COOR
1, R wherein
1Expression has the alkyl of 1～4 carbon atom;-COCH
2OCH
3Or-COCH
2OCOCH
3In the disclosure text, the physicochemical property of above-claimed cpd and the above-claimed cpd control efficiency to rice blast has been described also.In addition, the disclosure textual description above-claimed cpd good to the result of treatment of rice blast and residual activity and preventive effect, these effects are different from the result of treatment of conventional rice blast control agent.
The mechanism of action of the compound of formula (1) expression is not illustrated as yet fully.But, expect that these compounds have the mechanism of action that is different from conventional rice blast control agent, for example also can show control efficiency because of other resistant strain to kasugarnycin, organophosphorus reagent and strobilurins compound, show bactericidal activity in addition, and can not suppress melanic biosynthesis in the medium.
It is reported that the strobilurins Fungicidal compounds has good control efficiency or high bactericidal activity for the many rice fungus diseases that comprise rice blast or multiple mycosis or pathogen (it is as the fungi of these diseases that cause barley and wheat, fruit and vegetables main points of cultivation).The good control efficiency of strobilurins compound and the mechanism of action thereof for example are described in Noyaku Handobukku (agrochemistry handbook) 2001 (being published in calendar year 2001 by protection association of Japanese plant) and Ippan Itaku ShikenSeisekisho (general contrast experiment's report) (being published by protection association of Japanese plant).
Rice blast is severe diseases in the rice cropping.Rice blast is by the Pyricularia Sacc. fungi parasitogenic plant disease of (a kind of mould also belongs to Fungi Imperfecti).Up to the present, many good rice blast control agent and prevent and treat method have been reported.
Yet in some cases, even after using described control agent, also can specific meteorological condition (as abnormality cold summer gas and very long rainy season) and owing to the cause of disadvantageous cultivation condition (as the mismanagement to seedling and fertilising) breaks out rice blast.For those reasons, wish to develop the control agent that rice blast is had better control efficiency.In addition, the increase of the increase of recent part-time peasant's quantity and older's quantity of being engaged in agriculture has caused a kind of technology that can prolong the disease control time and reduce the application times and the amount of labour of needs development.In addition, from saving the angle of labour and the amount of application that reduces agricultural chemicals, wish to develop the chemical reagent that can show control efficiency simultaneously to multiple diseases.
Summary of the invention
By assessing the resultant effect of above-mentioned various active, these active duration etc., the inventor has now found that a kind of compound (2 that contains formula (1) expression, 3-dimethyl-6-the tert-butyl group-8-fluoro-4-8-hydroxyquinoline derivative) and at least a blend compositions that is selected from the strobilurins bactericide activity that can not lose each active component, have synergistic function simultaneously, and rice blast is shown excellent control efficiency.Also find in this connection when above-mentioned composition in due course machine use and when when time of application lags behind opportune moment, said composition can be the control efficiency that rice blast has excellence to a kind of representative disease of paddy rice with low dosage chronically.Finished the present invention based on this discovery.
Therefore, an object of the present invention is to provide a kind of chemical reagent, it has excellent control efficiency to rice disease, and even lags behind in time of application and also can have excellent control efficiency chronically with low dosage when suitably using opportunity.
According to an aspect of the present invention, provide a kind of bactericidal composition, it contains compound or its acid-addition salts of the formula (1) as active component:
Wherein
R represents hydrogen atom;-COR
1Or-COOR
1, R wherein
1Expression has the alkyl of 1～4 carbon atom;-COCH
2OCH
3Or-COCH
2OCOCH
3And
At least a compound that is selected from the strobilurins bactericide.
According to a further aspect in the invention, provide a kind of method of preventing and treating rice disease, this method comprises the step to the above-mentioned bactericidal composition of pending Zoned application effective dose.
According to another aspect of the invention, provide the purposes that above-mentioned bactericidal composition is used for preparing rice disease control agent.
Bactericidal composition according to the present invention contains the mixture of two kinds of compounds that differ from one another on the mechanism of action and bactericidal range.Bactericidal composition according to the present invention has excellent control efficiency for other fungal diseases (for example, sheath fusarium wilt (sheath blast), the ear burn that spore tikka bacterium, tail spore tikka bacterium etc. cause because length is wriggled, double-coloredization of the grain of rice (dicoloration) and the false smut that is for example caused by curved spore mould of paddy rice and lattice pink mold) of rice blast and paddy rice.According to bactericidal composition of the present invention, the composition in the described bactericidal composition works in Synergistic mode one and provides unexpected and remarkable prevention effect.Therefore, for bactericidal composition according to the present invention, can reduce chemicals rate of application essential on the unit are.In addition, can obtain excellent control efficiency with the lower dosage of every kind of composition according to bactericidal composition of the present invention than the described composition of independent use.In addition, in this case, control efficiency is sustainable long-time.Therefore, for bactericidal composition according to the present invention, can reduce the necessary number of times of handling plant.In addition, can reduce the chemicals total amount that during cultivating, is used for target plant.When machine is in due course used bactericidal composition according to the present invention preventing and treating processing, and even when time of application lags behind opportune moment, said composition can show excellent control efficiency.Can realize preventing and treating simultaneously multiple diseases according to sterilization of the present invention, meanwhile can reduce to produce the danger of antifungal activity.Can be expected to make major contribution according to bactericidal composition of the present invention to saving agricultural workforce, environmental protection and stable food production.
Detailed Description Of The Invention
Bactericidal composition
As mentioned above, bactericidal composition according to the present invention contains formula (1) compound or its acid-addition salts and at least a compound that belongs to the strobilurins bactericide as active component.
This bactericidal composition can be used for controlling plant diseases, preferably prevents and treats rice class disease, more preferably prevents and treats rice disease.The example of described disease comprises: rice blast; Because the ear burn that long wriggle spore tikka bacterium, tail spore tikka bacterium etc. cause; Double-coloredization of the grain of rice that causes by curved spore mould of paddy rice and lattice pink mold for example; False smut; With the sheath fusarium wilt.More preferably, bactericidal composition according to the present invention is used to prevent and treat rice blast.
In the present invention, " containing as active component " mean and certainly contain the carrier that is suitable for required prescription, can contain in addition can with other chemical reagent of The compounds of this invention coupling.
Term used herein " rice class " comprises the rice class of paddy rice and dry land growth.Term " paddy rice " is meant the rice of cultivating in the paddy field.
Formula (1) compound
Bactericidal composition according to the present invention comprises formula (1) compound or its acid-addition salts.
In formula (1), R represent hydrogen atom ,-COR
1,-COOR
1,-COCH
2OCH
3Or-COCH
2OCOCH
3Among the present invention, R
1Expression has the alkyl of 1～4 carbon atom.Among the present invention, alkyl can be in straight chain, side chain and the ring-type any.In addition, the one or more hydrogen atoms on the alkyl are selectively replaced by one or more identical or different substituting groups.R
1Instantiation comprise methyl, ethyl, n-pro-pyl, isopropyl and normal-butyl.
In formula (1), when R represented hydrogen atom, the compound of formula (1) can have formula (2) structure of the dynamic isomer of formula (1) compound.Obvious to those skilled in the art is that formula (1) compound comprises formula (2) compound.
Among the present invention, term " acid-addition salts " is meant at agricultural and gardening field salt commonly used, for example hydrochloride, nitrate, sulphate, phosphate and acetate.
It should be noted that formula (1) compound can have the form of hydrate or solvate.In the present invention, described hydrate and solvate are also included within formula (1) compound.
The instantiation of formula (1) compound comprises hereinafter with the compound 1～11 among the embodiment that describes.
The preparation method of formula (1) compound
Can adopt any suitable formation key or introduce substituent method synthesis type (1) compound.
For example, the 4-tert-butyl group-2-fluoroaniline that can pass through to be synthesized by conventional method is according to following scheme preparation formula (1) compound.
Wherein
R represent hydrogen atom ,-COR
1,-COOR
1,-COCH
2OCH
3Or-COCH
2OCOCH
3
R
1Expression has the alkyl of 1～4 carbon atom; With
R
2Expression-R
1,-OR
1,-CH
2OCH
3Or-CH
2OCOCH
3
According to this scheme, at first obtain formula (2) compound (step (a)), if desired, then formula (2) compound and formula (3) or (4) compound are reacted (step (b)) having alkali or do not exist under the condition of alkali, obtain formula (1) compound.
Such scheme is below described in more detail.
Step (a):
At first by the 4-tert-butyl group-2-fluoroaniline and 2-methyl-ethyl acetoacetate for example according to J.Am.Chem.Soc.70,2402 (1948) and Tetrahedron Lett.27,5323 (1986) preparation formula (2) compounds.Formula (2) compound is represented formula (1) compound of hydrogen atom corresponding to R wherein.The 4-tert-butyl group used herein-2-fluoroaniline can prepare by conventional method, for example at Chem.Abs.42, and 2239 or J.Chem.Soc., Chem.Commun., the method for describing in 1992,595.
Step (b):
Next, when needs when wherein R represents formula (1) compound of the group beyond the hydrogen atom, this formula (1) compound can prepare by formula (2) compound and formula (3) or (4) compound are reacted under alkali existence or the non-existent condition of alkali.
Here available alkali comprises for example organic amine, as triethylamine and pyridine; Inorganic base is as sodium carbonate, potash and sodium hydride.The consumption of formula (3) or (4) compound is preferably 1～50 equivalent with respect to formula (2) compound, more preferably 1～10 equivalent.The reaction of step (b) can for example carried out under 0～140 ℃ of temperature under the solvent-free condition or in that this reaction is in the presence of organic solvent inert such as dimethyl formamide or the oxolane.
The strobilurins bactericide
In the present invention, the strobilurins bactericide can be in the strobilurins bactericide any known in the art.For example in Noyaku Handobukku (agrochemistry handbook) 2001 (being published in calendar year 2001 by protection association of Japanese plant) and Noyaku Yoran (agrochemistry guide) (being published in calendar year 2001 by protection association of Japanese plant), the strobilurins bactericide is called bactericide.By with reference to these documents, those of ordinary skills can suitably select the strobilurins bactericide.
The instantiation that can be used for strobilurins bactericide of the present invention comprises Fluoxastrobin, SSF 126, kresoxim-methyl, oxime bacterium ester, orysastrobin, fluoxastrobin (fluoxastrobin), pyraclostrobin and ZEN 90160.
In one of the present invention's preferred implementation, the strobilurins bactericide is selected from Fluoxastrobin, SSF 126 and orysastrobin.
In one of the present invention's more preferably embodiment, the strobilurins bactericide is selected from Fluoxastrobin and SSF 126.
Other compositions
When actual when using according to bactericidal composition of the present invention, the composition that can use above-mentioned active component to form with former state.As selection, said composition also can for example be mixed with suitable carrier that is used to fill a prescription or auxiliary agent to make any suitable formulation, for example dusting powder, granule, application (pack), wetting powder, granular water-dispersible agent, floable, liquid preparation, micro-capsule or missible oil.This makes that bactericidal composition according to the present invention goes in the multiple suitable applications.
Preparation can be by the known method preparation of general agrochemical field.Particularly, for example can prepare preparation, if desired, for example active component can be mixed with solid carrier, solvent, surfactant and other auxiliary agents by the mixed active composition.Can select described carrier etc. according to application target (for example improving character, stabilizing active ingredient and the reinforced effects of preparation).
Here available solid carrier comprises for example clay, talcum, calcium carbonate, diatomite, zeolite, bentonite, acid clay, activated clay, Concave-convex clay rod, vermiculite, perlite, float stone, white carbon, titanium dioxide, water soluble salt, wood powder, maize cob (corn cob), walnut shell, cellulose powder, starch, dextrin and sugar.
The example of available here solvent comprises: arsol, and as dimethylbenzene, C
9Alkylbenzene, C
10Alkylbenzene, Fluhyzon and high boiling aromatic hydrocarbon; Aliphatic solvents is as N PARAFFIN ﹠ HEAVY NORMAL PARAFFIN, isomery paraffin and cycloalkanes; Mixed solvent is as the solvent that makes from kerosene or tar oil; Machine oil is as the high boiling point aliphatic hydrocarbon; Alcohols is as ethanol, isopropyl alcohol and cyclohexanol; Polyalcohol is as ethylene glycol, diethylene glycol (DEG), propane diols, hexylene glycol, polyethylene glycol and polypropylene glycol; Polyol derivative is as propylene glycol; Ketone is as cyclohexanone and gamma-butyrolacton; The ester class, as fatty acid methyl ester (as, fatty acid distribution of coconut oil methyl esters) and binary acid methyl esters (as, dimethyl succinate, glutamic acid dimethyl ester and dimethyl adipate); Nitrogen-containing solvent is as the N-alkyl pyrrolidone; Fat and oils are as cocoa butter, soybean oil and rapeseed oil; And water.
The example of available here surfactant comprises: sorbitan fatty ester, the polyoxyethylene sorbitan fatty acid ester, sucrose fatty ester, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid ester, the polyoxyethylene fatty acid diester, Emulsifier EL-60, Crodaret, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene dialkyl phenyl organic ether, polyoxyethylene alkyl phenyl ether/formalin condensation product, the polyoxyethylene/polyoxypropylene block polymer, alkyl polyoxyethylene/polyoxypropylene block polymer ether, alkyl phenyl polyoxyethylene/polyoxypropylene block polymer ether, polyoxyethylene alkyl amine, the polyoxyethylene fatty acid acid amides, the polyoxyethylene diphenyl ether, polyoxyethylene benzyl phenyl ether, polyoxyethylene styryl phenyl ether, APEO type siloxanes, ester type siloxanes, fluorine surfactant or other non-ionic surface active agents, alkyl sulfate, polyoxyethylene alkyl ether sulfate salt, polyoxyethylene alkylphenyl ether sulfate salt, polyoxyethylene benzyl phenyl ether sulfate, polyoxyethylene/polyoxypropylene block polymer sulphate, paraffin sulfonate, α-Xi Jihuangsuanyan (AOS), dialkyl sulfosuccinates, alkylbenzenesulfonate, naphthalene sulfonate, naphthalene sulfonate/formalin condensation product, alkyl diphenyl base ether disulfonate, lignosulphonates, polyoxyethylene alkyl phenyl ether sulfonate, polyoxyethylene alkyl ether sulfosuccinic acid half ester, soap, N-methyl-fatty acid sarcosinate, resinate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, polyoxyethylene benzyl phenyl ether phosphate, polyoxyethylene/polyoxypropylene block polymer phosphate, lecithin, alkylphosphonic, alkyl trimethyl ammonium chloride, methyl/polyxyethylated ammonium chloride, bromination alkyl N-methyl-pyridine, alkyl methyl ammonium chloride, dichloride alkyl pentamethyl propane-diammonium, the alkyl dimethyl benzalkonium chloride, benzethonium chloride, dialkyl group diamino ethyl betain and alkyl dimethyl benzyl betain.
Here available auxiliary agent comprises for example p isopropylbenzoic acid ester, carboxymethyl cellulose, PVA, sodium tripolyphosphate, calgon, xanthans, guar gum, carboxymethyl cellulose, Sodium Benzoate, potassium sorbate, p-hydroxybenzoate, 1,2-[4-morpholinodithio quinoline-3-ketone, ethylene glycol, diethylene glycol (DEG), propane diols, polyvinylpyrrolidone, urea, hexa, antioxidant, ultra-violet absorber, zeolite, quicklime, magnesia, the hydrophobicity high boiling solvent, Sodium Polyacrylate, alginic acid, kraft lignin, methacrylic acid/nvp copolymer, glycerine, sorbitol and water-swellable polymer.
Above-mentioned carrier, surfactant, dispersant and auxiliary agent can independently use, also can from mutually on the same group or different classes of selection two or more be used in combination.
In bactericidal composition of the present invention, bactericidal composition based on 100 weight portions, formula (1) compound or its acid-addition salts and at least a mixed proportion that is selected from the compound of strobilurins bactericide can be preferably 1～70 weight portion so that their total amount (total amount of active component) is 0.1～90 weight portion.
The total amount of active component can suitably be selected by formulation, application process, environment for use and other conditions of considering this bactericidal composition.For example, when described bactericidal composition was the wetting powder form, the total amount of active component was 5～50 weight %, was preferably 10～30 weight %.On the other hand, when described bactericidal composition was the dusting powder form, the total amount of active component was 0.5～5.0 weight %, was preferably 1.0～2.0 weight %.
In bactericidal composition of the present invention, the mixing ratio between formula (1) compound or its acid-addition salts and at least a compound that is selected from the strobilurins bactericide is 2: 50～50: 2, is preferably 1: 10～10: 1.
When using, can directly use bactericidal composition with former state according to bactericidal composition of the present invention.If desired, described bactericidal composition can dilute with diluent liquid such as water, handles then, for example is administered to pending zone, sneaks into pending zone, is administered to the water surface in pending zone or immerses pending zone.The instantiation of described processing comprise be applied to plant itself (being applied to cauline leaf), be applied to seedling growing box, be applied to soil (using) with earth mixture or band, be applied to field water (be applied to the water surface or be applied to conventional rice field) and be applied to seed (seed treatment).
According to a further aspect in the invention, provide a kind of method of preventing and treating rice class disease, this method comprises the step to the bactericidal composition of the present invention of pending Zoned application effective dose.Term " pending zone " is meant for the purpose of preventing and treating rice class disease the zone that should handle with bactericidal composition of the present invention.The example in this zone comprises rice plants, seedling growing box, soil, field water and seed.Preferably, pending zone is rice plants, soil or field water.
The consumption of bactericidal composition of the present invention can be according to mixing ratio, formulation, time of application, application process and the target disease to be prevented and treated of the growth conditions of its environment for use, target crop, active component and appropriate change.Usually, in the total amount of active component, the consumption of described bactericidal composition is per 10 ares and uses 1～1500g, preferred 10～150g.For example, when described bactericidal composition was applied to rice plants, in the total amount of active component, the consumption of bactericidal composition was per 10 ares and uses 5～500g, preferred 10～100g.
Can use with mixture according to bactericidal composition of the present invention, for example mix use with other bactericide, bactericide, insecticide, miticide, weed killer herbicide, plant growth regulator or fertilizer.
Usually, be pre-formed the preparation of hope in the above described manner according to bactericidal composition of the present invention.As selection, can adopt preparation that wherein makes a kind of active component of containing described composition (that is, in formula (1) compound or its acid-addition salts and at least a compound that is selected from the strobilurins bactericide a kind of) in advance and the method that contains another kind of formulations of active ingredients and in use these preparation original positions are mixed.
Therefore, according to a further aspect in the invention, provide a kind of formula (1) compound or its acid-addition salts and at least a combination of compounds body that is selected from the strobilurins bactericide of containing.
In a preferred implementation, in the combinations thereof body, provide formula (1) compound or its acid-addition salts to contain formula (1) compound or its acid-addition salts as first composition form of active component, and provide at least a this compound as second composition form of active component to contain this at least a compound that is selected from the strobilurins bactericide.In the case, as above-mentioned bactericidal composition, it can be any formulation of using suitable carriers or auxiliary agent to make by additional that first composition and second is formed.This assembly can provide with the form of complete chemicals.
According to a further aspect in the invention, provide the purposes that the combinations thereof body is used to prepare rice disease control agent.Described " rice disease control agent " contains with good grounds bactericidal composition of the present invention.
According to another aspect of the invention, provide a kind of method of preventing and treating rice class disease, this method comprises the step that formula (1) compound or its acid-addition salts and at least a compound that is selected from the strobilurins bactericide is applied at the same time or separately pending zone.
In this method, " simultaneously " use and comprise following embodiment: be about to formula (1) compound or its acid-addition salts and at least a compound that is selected from the strobilurins bactericide and be pre-mixed together, then this mixture is applied to the target area to make mixture." difference " used and comprised following embodiment: promptly, will formula (1) compound or its acid-addition salts and at least a compound that is selected from the strobilurins bactericide be pre-mixed, formula (1) compound or its acid-addition salts early than or be later than another composition and use.
In another preferred implementation of the present invention, a kind of method of preventing and treating rice class disease is provided, this method comprises to pending Zoned application:
(A) contain that formula (1) compound or its acid-addition salts are formed as first of active component and
(B) containing at least a compound that is selected from the strobilurins bactericide forms as second of active component.
Embodiment
Following examples further illustrate the present invention, but are not limitation of the present invention.
The preparation of formula 1 compound
Preparation has substituent formula shown in the following table 1 (1) compound (compound 1～11).
Table 1
| Substituting group | ||
| ????R | ????R 1 | |
| Compound 1 | ????-H | ????- |
| Compound 2 | ????-COR 1 | ????-CH 3 |
| Compound 3 | ????-COR 1 | ????-C 2H 5 |
| Compound 4 | ????-COR 1 | ????-C 3H 7 |
| Compound 5 | ????-COR 1 | ????-C 4H 9 |
| Compound 6 | ????-COOR 1 | ????-CH 3 |
| Compound 7 | ????-COOR 1 | ????-C 2H 5 |
| Compound 8 | ????-COOR 1 | ????-C 3H 7 |
| Compound 9 | ????-COOR 1 | ????-C 4H 9 |
| Compound 10 | ????-COCH 2OCH 3 | ????- |
| Compound 11 | ????-COCH 2OCOCH 3 | ????- |
Prepare compound 1～11 according to following process.
The preparation of the 4-tert-butyl group-2-fluoroaniline
With SELECTFLUOR (making) (1-chloro-methyl-4-fluoro-1 by Aldrich Chemical Company Inc., the 4-diazonium dicyclo [2 of mixing, 2,2] octane-two-tetrafluoroborate) (15g) add in the acetonitrile (200ml), this mixture was heated 30 minutes so that SELECTFLUOR is dissolved in the acetonitrile down at 70 ℃.The reaction solution that obtains is cooled to 60 ℃, in the reaction solution of described cooling, adds the 4-tert-butyl group-antifebrin (5.7g).Stir this mixture one hour down at 100 ℃, then this reaction solution is left standstill cooling.Then the reaction solution with cooling adds in the entry (200ml), extracts (100ml, 2 times) with ethyl acetate again.Wash ethyl acetate layer with saturated brine, and dry on anhydrous sodium sulfate, remove described solvent by distillation under reduced pressure afterwards.On silica gel, pass through chromatogram (Wako Gel C-200, by Wako Pure Chemical Industries, Ltd. make eluting solvent: n-hexane-ethyl acetate (10: 1)) crude product that obtains of purifying is to obtain the 4-tert-butyl group-2-fluoro-antifebrin (3.06g).This 4-tert-butyl group-2-fluoro-antifebrin (3.67g) is added in the mixed liquor of ethanol (30ml) and concentrated hydrochloric acid (15ml), stirred this mixture 2 hours down at 95 ℃.Described reaction solution is left standstill cooling, and the reaction solution of cooling is poured in the water, with in the saturated sodium bicarbonate aqueous solution and after, adopt ethyl acetate to extract.With saturated sodium bicarbonate aqueous solution and saturated brine washing ethyl acetate layer, and dry on anhydrous sodium sulfate.Remove described solvent by distillation under reduced pressure then, obtain the 4-tert-butyl group-2-fluoroaniline (3.49g).This compound is in containing deteriochloroform
1The H-NMR data are as follows.
δ(ppm)：7.01(1H，dd)，6.95(1H，dd)，6.73(1H，m)，1.28(9H，s)
Compound 1:2, the 3-dimethyl-6-tert-butyl group-8-fluoro-4-oxyquinoline
Under the condition that etherate of trifluoroboron (0.3ml) exists, the 4-tert-butyl group-2-fluoroaniline (4.79g) and the 2-methyl-ethyl acetoacetate (4.96g) that obtains according to the method described above refluxed 3 hours with preparation feedback solution in toluene (60ml).Wash the reaction solution that obtains thus with saturated sodium bicarbonate aqueous solution and saturated brine, and dry on anhydrous sodium sulfate.Under reduced pressure, remove described solvent then by distillation.Product was refluxed 1 hour in diphenyl ether (80ml), and it is left standstill cooling.Under reduced pressure, pass through then to filter the collecting precipitation product, obtain 2, and the 3-dimethyl-6-tert-butyl group-8-fluoro-4-oxyquinoline (compound 1,1.66g).This compound is in the weight-DMSO (methyl-sulfoxide)
1The H-NMR data are as follows.
δ(ppm)：11.27(1H，br.s)，7.83(1H，s)，7.59(1H，br.d)，2.41(3H，s)，1.96(3H，s)，1.31(9H，s)
Compound 2:2, the 3-dimethyl-6-tert-butyl group-8-fluoro-4-acetyl group quinoline
In acetic anhydride (3ml) in 120 ℃ of following agitate compounds 1 (50mg) 3 hours with preparation feedback solution.Acetic anhydride is removed in distillation from the reaction solution that obtains under reduced pressure.Use the acetic acid ethyl dissolution residue.Wash this solution with saturated sodium bicarbonate aqueous solution and saturated brine, dry on anhydrous sodium sulfate then, then described solvent is removed in distillation under reduced pressure.On silica gel by chromatogram (Wako Gel C-200, eluting solvent: purifying crude product n-hexane-ethyl acetate (5: 1)), obtain 2, the 3-dimethyl-6-tert-butyl group-8-fluoro-4-acetyl group quinoline (compound 2,35.7mg).This compound is in containing deteriochloroform
1The H-NMR data are as follows.
δ(ppm)：7.43(1H，dd)，7.37(1H，d)，2.78(3H，s)，2.51(3H，s)，2.26(3H，s)，1.38(9H，s)
Compound 3:2, the 3-dimethyl-6-tert-butyl group-8-fluoro-4-propiono quinoline
60% sodium hydride (20mg) is suspended in the oxolane (3ml).Under ice-cooled condition, compound 1 (124mg) is added in this suspension, stirred this mixture 30 minutes.To wherein adding propionyl chloride (200 μ l), stirred this mixture 3 hours in addition.The reaction solution that obtains is thus poured in the frozen water, with this mixture of ethyl acetate extraction.With saturated sodium bicarbonate aqueous solution and saturated brine washing ethyl acetate layer, then dry on anhydrous sodium sulfate.Under reduced pressure remove described solvent then by distillation.On silica gel by chromatogram (Wako Gel C-200, eluting solvent: purifying crude product n-hexane-ethyl acetate (3: 1)), obtain 2, the 3-dimethyl-6-tert-butyl group-8-fluoro-4-propiono quinoline (compound 3,21mg).This compound is in containing deteriochloroform
1The H-NMR data are as follows.
δ(ppm)：7.42(1H，dd)，7.36(1H，d)，2.81(2H，q)，2.75(3H，s)，2.25(3H，s)，1.43(3H，t)，1.37(9H，s)
Compound 4:2, the 3-dimethyl-6-tert-butyl group-8-fluoro-4-bytyry quinoline
60% sodium hydride (20mg) is suspended in the oxolane (3ml).Under ice-cooled condition, compound 1 (124mg) is added in this suspension, stirred this mixture 30 minutes.To wherein adding butyl chloride (200 μ l), stirred this mixture 3 hours in addition.The reaction solution that obtains is thus poured in the frozen water, with this mixture of ethyl acetate extraction.With saturated sodium bicarbonate aqueous solution and saturated brine washing ethyl acetate layer, then dry on anhydrous sodium sulfate.Under reduced pressure remove described solvent then by distillation.On silica gel by chromatogram (Wako Gel C-200, eluting solvent: purifying crude product n-hexane-ethyl acetate (3: 1)), obtain 2, the 3-dimethyl-6-tert-butyl group-8-fluoro-4-bytyry quinoline (compound 4,64mg).This compound is in containing deteriochloroform
1The H-NMR data are as follows.
δ(ppm)：7.43(1H，dd)，7.37(1H，d)，2.76(2H，t)，2.75(3H，s)，2.25(3H，s)，1.94(2H，m)，1.37(9H，s)，1.15(3H，t)
Compound 5:2, the 3-dimethyl-6-tert-butyl group-8-fluoro-4-valeryl quinoline
60% sodium hydride (20mg) is suspended in the oxolane (3ml).Under ice-cooled condition, compound 1 (124mg) is added in this suspension, stirred this mixture 30 minutes.To wherein adding valeric chloride (200 μ l), stirred this mixture 3 hours in addition.The reaction solution that obtains is thus poured in the frozen water, with this mixture of ethyl acetate extraction.With saturated sodium bicarbonate aqueous solution and saturated brine washing ethyl acetate layer, then dry on anhydrous sodium sulfate.Under reduced pressure remove described solvent then by distillation.On silica gel by chromatogram (Wako Gel C-200, eluting solvent: purifying crude product n-hexane-ethyl acetate (3: 1)), obtain 2, the 3-dimethyl-6-tert-butyl group-8-fluoro-4-valeryl quinoline (compound 5,120mg).This compound is in containing deteriochloroform
1The H-NMR data are as follows.
δ(ppm)：7.42(1H，dd)，7.37(1H，d)，2.78(2H，t)，2.75(3H，s)，2.25(3H，s)，1.89(2H，m)，1.56(2H，m)，1.37(9H，s)，1.03(3H，t)
Compound 6:2, the 3-dimethyl-6-tert-butyl group-8-fluoro-4-methoxycarbonyl group quinoline
60% sodium hydride (20mg) is suspended in the oxolane (3ml).Under ice-cooled condition, compound 1 (124mg) is added in this suspension, stirred this mixture 30 minutes.To wherein adding methylchloroformate (200 μ l), stirred this mixture 3 hours in addition.The reaction solution that obtains is thus poured in the frozen water, with this mixture of ethyl acetate extraction.With saturated sodium bicarbonate aqueous solution and saturated brine washing ethyl acetate layer, then dry on anhydrous sodium sulfate.Under reduced pressure remove described solvent then by distillation.On silica gel by chromatogram (Wako Gel C-200, eluting solvent: purifying crude product n-hexane-ethyl acetate (3: 1)), obtain 2, the 3-dimethyl-6-tert-butyl group-8-fluoro-4-methoxycarbonyl group quinoline (compound 6,100mg).This compound is in containing deteriochloroform
1The H-NMR data are as follows.
δ(ppm)：7.45(1H，br.s)，7.43(1H，dd)，4.00(3H，s)，2.76(3H，s)，2.31(3H，s)，1.38(9H，s)
Compound 7:2, the 3-dimethyl-6-tert-butyl group-8-fluoro-4-carbethoxyl group quinoline
60% sodium hydride (60mg) is suspended in the oxolane (10ml).Under ice-cooled condition, compound 1 (200mg) is added in this suspension, stirred this mixture 30 minutes.To wherein adding ethyl chloroformate (200 μ l), stirred this mixture 3 hours in addition.The reaction solution that obtains is thus poured in the frozen water, with this mixture of ethyl acetate extraction.With saturated sodium bicarbonate aqueous solution and saturated brine washing ethyl acetate layer, then dry on anhydrous sodium sulfate.Under reduced pressure remove described solvent then by distillation.On silica gel by chromatogram (Wako Gel C-200, eluting solvent: purifying crude product n-hexane-ethyl acetate (3: 1)), obtain 2, the 3-dimethyl-6-tert-butyl group-8-fluoro-4-carbethoxyl group quinoline (compound 7,220mg).This compound is in containing deteriochloroform
1The H-NMR data are as follows.
δ(ppm)：7.45(1H，br.s)，7.43(1H，dd)，4.40(2H，q，J＝6.7Hz)，2.32(3H，s)，2.04(3H，s)，1.44(3H，t)，1.38(9H，s)
Compound 8:2, the positive third oxygen carbonyl quinoline of the 3-dimethyl-6-tert-butyl group-8-fluoro-4-
60% sodium hydride (20mg) is suspended in the oxolane (3ml).Under ice-cooled condition, compound 1 (124mg) is added in this suspension, stirred this mixture 30 minutes.To wherein adding chloro-carbonic acid n-propyl (200 μ l), stirred this mixture 3 hours in addition.The reaction solution that obtains is thus poured in the frozen water, with this mixture of ethyl acetate extraction.With saturated sodium bicarbonate aqueous solution and saturated brine washing ethyl acetate layer, then dry on anhydrous sodium sulfate.Under reduced pressure remove described solvent then by distillation.On silica gel by chromatogram (Wako Gel C-200, eluting solvent: purifying crude product n-hexane-ethyl acetate (3: 1)), obtain 2, the positive third oxygen carbonyl quinoline of the 3-dimethyl-6-tert-butyl group-8-fluoro-4-(compound 8,96mg).This compound is in containing deteriochloroform
1The H-NMR data are as follows.
δ(ppm)：7.45(1H，br.s)，7.43(1H，dd)，4.35(2H，t，J＝6.7Hz)，2.75(3H，s)，2.31(3H，s)，1.82(2H，m)，1.38(9H，s)，1.04(3H，t)
Compound 9:2, the 3-dimethyl-positive butoxy carbonyl quinoline of the 6-tert-butyl group-8-fluoro-4-
60% sodium hydride (60mg) is suspended in the oxolane (10ml).Under ice-cooled condition, compound 1 (200mg) is added in this suspension, stirred this mixture 30 minutes.To wherein adding butyl chloroformate (200 μ l), stirred this mixture 3 hours in addition.The reaction solution that obtains is thus poured in the frozen water, with this mixture of ethyl acetate extraction.With saturated sodium bicarbonate aqueous solution and saturated brine washing ethyl acetate layer, then dry on anhydrous sodium sulfate.Under reduced pressure remove described solvent then by distillation.On silica gel by chromatogram (Wako Gel C-200, eluting solvent: purifying crude product n-hexane-ethyl acetate (3: 1)), obtain 2, the 3-dimethyl-positive butoxy carbonyl quinoline of the 6-tert-butyl group-8-fluoro-4-(compound 9,142mg).This compound is in containing deteriochloroform
1The H-NMR data are as follows.
δ(ppm)：7.45(1H，d)，7.43(1H，dd)，4.35(2H，t)，2.75(3H，s)，2.32(3H，s)，1.77(2H，m)，1.48(2H，m)，1.38(9H，s)，0.99(3H，t)
Compound 10:2, the 3-dimethyl-6-tert-butyl group-8-fluoro-4-methoxyl group acetyl group quinoline
60% sodium hydride (165mg) is suspended in the oxolane (10ml).Under ice-cooled condition, compound 1 (680mg) is added in this suspension, stirred this mixture 30 minutes.To wherein adding methoxyacetyl chloride (200 μ l), stirred this mixture 3 hours in addition.The reaction solution that obtains is thus poured in the frozen water, with this mixture of ethyl acetate extraction.With saturated sodium bicarbonate aqueous solution and saturated brine washing ethyl acetate layer, then dry on anhydrous sodium sulfate.Under reduced pressure remove described solvent then by distillation.On silica gel by chromatogram (Wako Gel C-200, eluting solvent: purifying crude product n-hexane-ethyl acetate (3: 1)), obtain 2, the 3-dimethyl-6-tert-butyl group-8-fluoro-4-methoxyl group acetyl group quinoline (compound 10,390mg).This compound is in containing deteriochloroform
1The H-NMR data are as follows.
δ(ppm)：7.42(1H，dd)，7.35(1H，d)，4.51(2H，s)，3.62(3H，s)，2.75(3H，s)，2.26(3H，s)，1.37(9H，s)
Compound 11:2, the 3-dimethyl-6-tert-butyl group-8-fluoro-4-acetoxyl group acetyl group quinoline
60% sodium hydride (44mg) is suspended in the oxolane (10ml).Under ice-cooled condition, compound 1 (200mg) is added in this suspension, stirred this mixture 30 minutes.To wherein adding acetoxy acetyl chloride (100 μ l), stirred this mixture 3 hours in addition.The reaction solution that obtains is thus poured in the frozen water, with this mixture of ethyl acetate extraction.With saturated sodium bicarbonate aqueous solution and saturated brine washing ethyl acetate layer, then dry on anhydrous sodium sulfate.Under reduced pressure remove described solvent then by distillation.On silica gel by chromatogram (Wako Gel C-200, eluting solvent: purifying crude product n-hexane-ethyl acetate (3: 1)), obtain 2, the 3-dimethyl-6-tert-butyl group-8-fluoro-4-acetoxyl group acetyl group quinoline (compound 11,140mg).This compound is in containing deteriochloroform
1The H-NMR data are as follows.
δ(ppm)：7.43(1H，dd)，7.42(1H，br.s)，5.02(2H，s)，2.75(3H，s)，2.27(3H，s)，2.23(3H，s)，1.40(9H，s)
Preparation embodiment
Preparation embodiment 1: wetting powder
Following compositions is evenly pulverized, obtained wetting powder.
Compound 2 20 weight portions
Fluoxastrobin 20 weight portions
Diatomite 28 weight portions
White carbon (trade name; By Shionogi﹠amp; Co., LTD. system) 13 weight portions
Polyoxyethylene lauryl ether 12 weight portions
Lignosite 7 weight portions
Preparation embodiment 2: wetting powder
Following compositions is evenly pulverized, obtained wetting powder.
Compound 2 15 weight portions
Fluoxastrobin 5 weight portions
Diatomite 47 weight portions
Clay 10 weight portions
White carbon (trade name; By Shionogi﹠amp; Co., LTD. system) 10 weight portions
Polyoxyethylene lauryl ether 8 weight portions
Lignosite 5 weight portions
Preparation embodiment 3: wetting powder
Following compositions is evenly pulverized, obtained wetting powder.
Compound 2 20 weight portions
Fluoxastrobin 10 weight portions
Diatomite 42 weight portions
Clay 5 weight portions
White carbon (trade name; By Shionogi﹠amp; Co., LTD. system) 10 weight portions
Polyoxyethylene lauryl ether 8 weight portions
Lignosite 5 weight portions
Preparation embodiment 4: wetting powder
Following compositions is evenly pulverized, obtained wetting powder.
Compound 2 20 weight portions
SSF 126 20 weight portions
Diatomite 37 weight portions
White carbon (trade name; By Shionogi﹠amp; Co., LTD. system) 10 weight portions
Polyoxyethylene lauryl ether 8 weight portions
Lignosite 5 weight portions
Preparation embodiment 5: wetting powder
Following compositions is evenly pulverized, obtained wetting powder.
Compound 2 15 weight portions
SSF 126 5 weight portions
Diatomite 47 weight portions
Clay 10 weight portions
White carbon (trade name; By Shionogi﹠amp; Co., LTD. system) 10 weight portions
Polyoxyethylene lauryl ether 8 weight portions
Lignosite 5 weight portions
Preparation embodiment 6: wetting powder
Following compositions is evenly pulverized, obtained wetting powder.
Compound 2 20 weight portions
SSF 126 10 weight portions
Diatomite 42 weight portions
Clay 5 weight portions
White carbon (trade name; By Shionogi﹠amp; Co., LTD. system) 10 weight portions
Polyoxyethylene lauryl ether 8 weight portions
Lignosite 5 weight portions
Preparation embodiment 7: dusting powder
Following compositions is evenly pulverized, obtained dusting powder.
Compound 2 1.2 weight portions
Fluoxastrobin 0.5 weight portion
Clay 97.1 weight portions
Calcium carbonate 0.5 weight portion
White carbon (trade name; By Shionogi﹠amp; Co., LTD. system) 0.2 weight portion
Driless A (trade name; By SANKYO Co., the LTD. system) 0.5 weight portion
Preparation embodiment 8: dusting powder
Following compositions is evenly pulverized, obtained dusting powder.
Compound 21 weight portions
Fluoxastrobin 0.5 weight portion
Clay 97.1 weight portions
Calcium carbonate 0.5 weight portion
White carbon (trade name; By Shionogi﹠amp; Co., LTD. system) 0.4 weight portion
Driless A (trade name; By SANKYO Co., the LTD. system) 0.5 weight portion
Preparation embodiment 9: dusting powder
Following compositions is evenly pulverized, obtained dusting powder.
Compound 2 1.2 weight portions
SSF 126 0.5 weight portion
Clay 97.1 weight portions
Calcium carbonate 0.5 weight portion
White carbon (trade name; By Shionogi﹠amp; Co., LTD. system) 0.2 weight portion
Driless A (trade name; By SANKYO Co., the LTD. system) 0.5 weight portion
Preparation embodiment 10: dusting powder
Following compositions is evenly pulverized, obtained dusting powder.
Compound 21 weight portions
SSF 126 0.5 weight portion
Clay 97.1 weight portions
Calcium carbonate 0.5 weight portion
White carbon (trade name; By Shionogi﹠amp; Co., LTD. system) 0.4 weight portion
Driless A (trade name; By SANKYO Co., the LTD. system) 0.5 weight portion
Evaluation experimental
Experiment A: by before rice blast is propagated, using to the control efficiency of rice blast (when the suitable control
Experiment during machine)
Potted plant compost is put into the plastics cylinder, and (about 30cm * 50cm), (kind: Koshihikari) kind is gone in this cylinder, carries out intensive growing and cultivation then with the kind rice after the vernalization.This rice is used for experiment.
In glass greenhouse, cultivate about 2 weeks of this rice under 25 ℃ and night 20 ℃ of conditions by day.During the stage, ill leaf (this leaf has been inoculated Pyricularia oryzae (family 037) in advance and rice blast occurred) is placed on the rice of intensive plantation to three or four leaves when rice is long, under wet condition, places then with inoculation Pyricularia oryzae 24 hours.Then the rice strain is put back in the described glass greenhouse once more.After this 7 or 8 days, observe and scab occurred, carry out first time chemicals subsequently and use.In this case, (use the Neoesterin (trade name of 5000 times of dilutions with 10% aqueous acetone solution; By KUMIAICHEMICAL INDUSTRY CO., LTD. system) as being added into wherein spreader-sticker) will test with chemical liquid and be diluted to predetermined concentration.Amount with every cylinder 15ml is used each the experiment chemical liquid that makes thus by spray gun.When for the first time chemicals is used and is carried out after 6 or 7 days that the second time, chemicals was used, with the first time chemicals execute and carry out second time chemicals in a like fashion and use.
After this chemicals is used, in glass greenhouse, rice is controlled.During this period, with 1 to 2 day be the interval, place following 24 hours of wet condition to quicken the formation and the propagation of rice blast rice.
Last chemicals was used back ten days, to every cylinder 40 plant, observed the lesion area of the blade surface of a slice leaf position that is positioned at leaf below, the top, measured the percentage that lesion area accounts for treatment region.Measure the percentage that lesion area accounts for the district of being untreated in the mode identical in addition with treatment region.For every kind of experimental chemistry reagent, determine the protection value by the treatment region gained result and the district gained result that is untreated by following formula.
Protection value=[1-(the lesion area percentage in the lesion area percentage of the treatment region/district of being untreated)] * 100
Preventive effect and residual effect by following method determination experiment chemical reagent: whether after the predetermined number of days after wherein chemical reagent is handled, observing lesion area percentage increases.Thus, whether increase to determine preventive effect and residual effect according to last protection value.
Experimentize for each group of forming by the chemical reagent shown in the following table A1-A3.Carrying out once or twice chemicals uses.
The results are shown among the Table A 1-A3.
Table A 1: dually use experiment
| Chemical reagent | Concentration, ppm | Lesion area percentage | The protection value |
| Compound 2 Fluoxastrobin compound 2+ Fluoxastrobins are untreated | ? 80 80 40+40 | 35.9 5.0 3.0 0.4 | ? ????86 ????92 ????99 |
Table A 2: single administration experiment
| Chemical reagent | Concentration, ppm | Lesion area percentage | The protection value |
| Compound 2 Fluoxastrobin compound 2+ Fluoxastrobins are untreated | ? ??80 ??80 ??40+40 | ??35.8 ??17.9 ??20.0 ??10.6 | ? ??50 ??44 ??70 |
Table A 3: single administration experiment
| Chemical reagent | Concentration, ppm | Lesion area percentage | The protection value |
| Compound 2 compounds 3 compounds 11 Fluoxastrobin SSF 126 compound 2+ Fluoxastrobin compound 3+ Fluoxastrobin compound 11+ Fluoxastrobin compound 2+ SSF 126 compound 3+ SSF 126 compound 11+ SSF 126s are untreated | ? ??80 ??80 ??80 ??80 ??80 ??40+40 ??40+40 ??40+40 ??40+40 ??40+40 ??40+40 | 40.6 15.1 21.4 18.3 14.1 20.9 4.1 6.9 5.4 10.9 13.6 14.5 | ? ??63 ??47 ??55 ??65 ??49 ??90 ??83 ??87 ??73 ??66 ??64 |
Experiment B: by after rice blast is propagated, using to the control efficiency (using the experiment that lags behind) of rice blast
Potted plant compost is put into the plastics cylinder, and (about 30cm * 50cm), (kind: Koshihikari) kind is gone in this cylinder, carries out intensive growing and cultivation then with the seed rice after the vernalization.This rice is used for experiment.
In glass greenhouse, cultivate about 2 weeks of this rice under 25 ℃ and night 20 ℃ of conditions by day.During the stage, ill leaf (this leaf has been inoculated Pyricularia oryzae (family 037) in advance and rice blast occurred) is placed on the rice of intensive plantation to three or four leaves when rice is long, under wet condition, places then with inoculation Pyricularia oryzae 24 hours.Then the rice strain is put back in the described glass greenhouse once more.After this 7 or 8 days, observe and scab occurs.Afterwards, place following 24 hours of wet condition infecting for the second time quickening once more rice, and in this cylinder, propagate rice blast.Quicken rice blast and propagate the back after about 3 or 4 days, confirm to have secondary scab seldom, carry out first time chemicals subsequently and use.
All the condition with experiment A is identical for other experiment conditions (as experiment chemical liquid condition, application process, administration interval, use rice blast development and the calculating of the method for preventing and treating, lesion area percentage and the calculating of protection value after the beginning).When carrying out that the second time, chemicals was used, its chemicals administration interval is identical with the interval of experiment A.
Test for every group that forms by the chemical reagent shown in the following table B1-B4 for each family.
The result is illustrated among the B1-B4.
Table B1: dually use experiment
| Chemical reagent | Concentration, ppm | Lesion area percentage | The protection value |
| Be untreated | 81.5 | ||
| Compound 2 | ??80 | 27.6 | ????66 |
| Fluoxastrobin | ??80 | 21.4 | ????74 |
| Compound 2+ Fluoxastrobin | ??40+40 | 12.2 | ????85 |
Table B2: single administration experiment
| Chemical reagent | Concentration, ppm | Lesion area percentage | The protection value |
| Be untreated | 74.5 | ||
| Compound 2 | ??80 | 27.9 | ??63 |
| Fluoxastrobin | ??80 | 54.1 | ??27 |
| Compound 2+ Fluoxastrobin | ??40+40 | 19.8 | ??73 |
Table B3: single administration experiment
| Chemical reagent | Concentration, ppm | Lesion area percentage | The protection value |
| Be untreated | ????30.0 | ||
| Compound 2 | ??80 | ????16.6 | ????45 |
| Fluoxastrobin | ??80 | ????10.9 | ????64 |
| Compound 2+ Fluoxastrobin | ??40+40 | ????4.5 | ????85 |
Table B4: single administration experiment
| Chemical reagent | Concentration, ppm | Lesion area percentage | The protection value |
| Be untreated | ????73.3 | ||
| Compound 2 | 80 | ????19.0 | ????74 |
| Compound 3 | 80 | ????31.3 | ????57 |
| Compound 11 | 80 | ????27.8 | ????62 |
| Fluoxastrobin | 80 | ????19.0 | ????74 |
| SSF 126 | 80 | ????27.4 | ????63 |
| Compound 2+ Fluoxastrobin | 40+40 | ????14.4 | ????80 |
| Compound 3+ Fluoxastrobin | 40+40 | ????13.1 | ????82 |
| Compound 11+ Fluoxastrobin | 40+40 | ????12.5 | ????83 |
| Compound 2+ SSF 126 | 40+40 | ????11.5 | ????84 |
| Compound 3+ SSF 126 | 40+40 | ????15.3 | ????79 |
| Compound 11+ SSF 126 | 40+40 | ????15.5 | ????79 |
Claims (16)
1. bactericidal composition, it contains as active component
The compound of formula (1) or its acid-addition salts:
Wherein
R represents hydrogen atom;-COR
1Or-COOR
1, R wherein
1Expression has the alkyl of 1～4 carbon atom;-COCH
2OCH
3Or-COCH
2OCOCH
3And
At least a compound that is selected from the strobilurins bactericide.
2. according to the bactericidal composition of claim 1, the wherein said compound that belongs to the strobilurins bactericide is selected from Fluoxastrobin and SSF 126.
3. the bactericidal composition according to claim 1 or 2 is used to prevent and treat rice class disease.
4. the bactericidal composition according to claim 1 or 2 is used to prevent and treat rice disease.
5. according to the bactericidal composition of claim 3, wherein said disease is a rice blast.
6. assembly, it contains formula (1) compound or its acid-addition salts:
Wherein
R represents hydrogen atom;-COR
1Or-COOR
1, R wherein
1Expression has the alkyl of 1～4 carbon atom;-COCH
2OCH
3Or-COCH
2OCOCH
3And
At least a compound that is selected from the strobilurins bactericide.
7. be used to prepare the purposes of rice disease control agent according to the bactericidal composition of claim 1 or 2.
8. be used to prepare the purposes of rice disease control agent according to the assembly of claim 6.
9. according to the purposes of get up requirement 7 and 8, wherein said disease is a rice blast.
10. method of preventing and treating rice class disease, it comprises that the bactericidal composition with the claim 1 of effective dose or 2 is applied to the step in pending zone.
11. a method of preventing and treating rice class disease, it comprises formula (1) compound or its acid-addition salts:
Wherein
R represents hydrogen atom;-COR
1Or-COOR
1, R wherein
1Expression has the alkyl of 1～4 carbon atom;-COCH
2OCH
3Or-COCH
2OCOCH
3And
At least a compound that is selected from the strobilurins bactericide is applied to the step in pending zone at the same time or separately.
12. according to the method for claim 11, wherein all described compositions are applied to pending zone simultaneously.
13. according to each method in the claim 10～12, the wherein said compound that belongs to the strobilurins bactericide is selected from Fluoxastrobin and SSF 126.
14. according to each method in the claim 10～13, wherein said disease is a rice disease.
15. according to each method in the claim 10～14, wherein said disease is a rice blast.
16. according to each method in the claim 10～15, wherein said pending zone is rice plants itself, soil or field water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP315503/2002 | 2002-10-30 | ||
| JP2002315503 | 2002-10-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1708225A true CN1708225A (en) | 2005-12-14 |
| CN1327768C CN1327768C (en) | 2007-07-25 |
Family
ID=32211655
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801024643A Expired - Fee Related CN1327768C (en) | 2002-10-30 | 2003-10-29 | Fungicidal compositions for the control of paddy rice diseases |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JP4558496B2 (en) |
| KR (1) | KR100764948B1 (en) |
| CN (1) | CN1327768C (en) |
| AR (1) | AR041728A1 (en) |
| AU (1) | AU2003280600A1 (en) |
| TW (1) | TWI320305B (en) |
| WO (1) | WO2004039156A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103271036A (en) * | 2012-05-31 | 2013-09-04 | 陕西上格之路生物科学有限公司 | Sterilization composition containing SYP-1620 |
| WO2014172924A1 (en) * | 2013-04-22 | 2014-10-30 | 山东省联合农药工业有限公司 | Quinoline derivative and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4880281B2 (en) * | 2005-10-21 | 2012-02-22 | Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 | Agricultural and horticultural bactericidal mixed composition |
| JP5132303B2 (en) * | 2007-12-26 | 2013-01-30 | Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 | Stabilized agrochemical solid pharmaceutical composition |
| WO2011071026A1 (en) | 2009-12-09 | 2011-06-16 | 明治製菓株式会社 | Stabilized composition for aqueous suspension agricultural chemical |
| JP5608508B2 (en) * | 2010-10-19 | 2014-10-15 | Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 | Agricultural and horticultural fungicides |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL89029A (en) * | 1988-01-29 | 1993-01-31 | Lilly Co Eli | Fungicidal quinoline and cinnoline derivatives, compositions containing them, and fungicidal methods of using them |
| AU6987096A (en) * | 1995-09-12 | 1997-04-01 | Basf Aktiengesellschaft | Fungicidal quinolines |
| TW521072B (en) * | 1997-06-02 | 2003-02-21 | Meiji Seika Kaisha | 4-quinolinol derivatives and fungicides containing the same as an active ingredient used for agriculture and horticulture |
| EP1291344A4 (en) * | 2000-05-30 | 2004-06-09 | Meiji Seika Kaisha | Rice blast control agents |
| JP2003055114A (en) * | 2001-08-14 | 2003-02-26 | Meiji Seika Kaisha Ltd | Fungicidal mix composition for paddy rice |
| TW200304772A (en) * | 2002-03-08 | 2003-10-16 | Meiji Seika Kaisha | Fungicidal composition for control of rice plant disease |
-
2003
- 2003-10-29 KR KR1020057007435A patent/KR100764948B1/en not_active IP Right Cessation
- 2003-10-29 WO PCT/JP2003/013850 patent/WO2004039156A1/en active Application Filing
- 2003-10-29 CN CNB2003801024643A patent/CN1327768C/en not_active Expired - Fee Related
- 2003-10-29 TW TW092130115A patent/TWI320305B/en not_active IP Right Cessation
- 2003-10-29 JP JP2004548069A patent/JP4558496B2/en not_active Expired - Fee Related
- 2003-10-29 AU AU2003280600A patent/AU2003280600A1/en not_active Abandoned
- 2003-10-30 AR ARP030103984A patent/AR041728A1/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103271036A (en) * | 2012-05-31 | 2013-09-04 | 陕西上格之路生物科学有限公司 | Sterilization composition containing SYP-1620 |
| CN103271036B (en) * | 2012-05-31 | 2014-04-09 | 陕西上格之路生物科学有限公司 | Sterilization composition containing SYP-1620 |
| WO2014172924A1 (en) * | 2013-04-22 | 2014-10-30 | 山东省联合农药工业有限公司 | Quinoline derivative and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200418384A (en) | 2004-10-01 |
| AU2003280600A1 (en) | 2004-05-25 |
| JP4558496B2 (en) | 2010-10-06 |
| KR100764948B1 (en) | 2007-10-08 |
| KR20050059321A (en) | 2005-06-17 |
| WO2004039156A1 (en) | 2004-05-13 |
| AR041728A1 (en) | 2005-05-26 |
| CN1327768C (en) | 2007-07-25 |
| TWI320305B (en) | 2010-02-11 |
| JPWO2004039156A1 (en) | 2006-02-23 |
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