CN102448297B - The composition of control fungal pathogens and method - Google Patents
The composition of control fungal pathogens and method Download PDFInfo
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- CN102448297B CN102448297B CN200980159624.5A CN200980159624A CN102448297B CN 102448297 B CN102448297 B CN 102448297B CN 200980159624 A CN200980159624 A CN 200980159624A CN 102448297 B CN102448297 B CN 102448297B
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- zoospore
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Classifications
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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
- A01N37/18—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 the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/30—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 the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the groups —CO—N< and, both being directly attached by their carbon atoms to the same carbon skeleton, e.g. H2N—NH—CO—C6H4—COOCH3; Thio-analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
- A01N37/18—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 the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/28—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 the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group; Thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/72—Hydrazones
- C07C251/74—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/76—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/06—Compounds containing any of the groups, e.g. semicarbazides
- C07C281/08—Compounds containing any of the groups, e.g. semicarbazides the other nitrogen atom being further doubly-bound to a carbon atom, e.g. semicarbazones
- C07C281/10—Compounds containing any of the groups, e.g. semicarbazides the other nitrogen atom being further doubly-bound to a carbon atom, e.g. semicarbazones the carbon atom being further bound to an acyclic carbon atom or to a carbon atom of a ring other than a six-membered aromatic ring
Abstract
What the present invention disclosed is the method that can be used for attracting the aldehyde of phytopathogen zoospore and the acylhydrazone of ketone and semicarbazones derivative and these compounds of use.These compounds comprise formula I, and wherein X is selected from (CH
2)
n, 1,3-phenylene and Isosorbide-5-Nitrae-phenylene; R
1be selected from isobutyl group, sec-butyl and the tert-butyl group-CH
2; R
2for hydrogen or methyl; 0-25 is equaled with n.After being exposed to water, the release of these compounds attracts the aldehydes or ketones of zoospore.These compounds can combine with fungicide, thus form Fungicidal formulations, the oomycetes of the special anti-generation fungal pathogens effectively of described Fungicidal formulations.
Description
Technical field
The many aspects that the present invention discloses relate to new fungi zoospore attractant release composition, and described fungi zoospore attractant release composition is very suitable for being mixed with together with fungicide the various compositions that can be used in fungus control method.
Background technology
Important economic plants can attack by variety classes phytopathogen in certain limit.To cause in disease multiple is caused by Oomycete pseudomycete (oomycetepseudofungi).Multiple such as potato in the disease caused by Oomycete pathogene or the late blight (lateblightofpotatoortomato) of western red silk, the mould frost disease of grape or the mould white disease of vegetables very have damaging.
The life cycle of multiple Oomycete pathogene involves a series of spore form, and described spore form is very important in the distribution and propagation of these diseases.Such as, in the asexual life-cycle processes of the raw single shaft of multiple Oomycete pseudomycete such as phytophthora infestans (cause of disease of potato late blight) and grape mould (cause of disease that the mould frost of grape is sick), described fungal pathogens produces and is referred to as sporangial non-athletic pycnospore.Under suitable conditions, sporangial inclusion forms the extra spore being referred to as zoospore.Zoospore has flagellum and can move about in water, and namely they are motilities.Zoospore is main infection medium (infectionagent), its pore vicinity swimming over to plant or the correct position vicinity be positioned on leaf, stem, root, seed or stem tuber, and packing herein, thus make plant infection.Then, on blade, the germ tube grown from the sporangiocyst germinateed enters into described pore, or in some cases, the germ tube grown from the zoospore of packing directly can penetrate leaf or root table face.
Researcher has identified the known different chemical product that can attract fungi zoospore.Usually the material these zoospore attractants being described as causing chemotaxis to reply to zoospore or compound.The example of some zoospore attractant chemicals is disclosed in article " Fattyacids; aldehydesandalcoholsasattractantsforzoosporesofPhytophth orapalmivora " inNature, in volume217, page448, byCameronandCarlile.The further example of zoospore attractant can at article " BiologyofPhytophthorazoosporesinPhytopathology ", volume60, pages1128-1135byHickman and " ChemotacticresponseofzoosporesoffivespeciesofPhytophthor a " inPhytopathology, find in volume63, page1511byKhew.The content of above mentioned every section of article is incorporated to the application as a reference specially.
Usually, these zoospore attractant chemicals or material are produced by the root district of plant and in rhizosphere, can be strengthened course of infection by making zoospore be locked in an infection point.Ad-hoc location on plant leaf or leaf also may produce the material attracting zoospore.Utilized multiple disclosed method to attract the ability of zoospore to test material by chemotaxis, described method is those methods such as adopting capillary, and wherein said capillary releases material to be tested.Described method normally can and be described in many sections of public publications, described public publication comprises:
1.Donaldson，S.P.andJ.W.Deacon.1993.NewPhytologist，123：289-295。
2.Tyler，B.M.，M-H.Wu，J-M.Wang，W.CheungandP.F.MorR1s.1996.
AppliedandEnvironmentalMicrobiology，62：2811-2817。
3.Khew，K.I.andG.A.Zentmeyer.1973.Phytopathology，63：1511-1517。
Usually, if attract the ability of zoospore to test compound by chemotaxis, then they must have enough water-soluble, if described compound has low water-soluble, then they must adopt suitable physical form or matrix (matrix), thus realize the enough release of test compounds.Researcher has been found that the short chain aldehyde of some natural existence or synthesis and ketone (C4-C8) are effective zoospore attractant.Prove further, when by these aldehyde and ketone with have Oomycete pathogene fungicide that inherence acts on use as a mixture time, described aldehyde and ketone strengthen the effect of described fungicide.But, the restriction of some physical propertys such as high volatile volatile or highly-water-soluble is subject to for most of short chain aldehyde of this object and the purposes of ketone.
The invention provides new method and the composition of control Oomycete fungal plant substance.The present composition is generally and is suitable for preventing and treating the composition that can produce the Oomycete fungal of zoospore, described composition comprises fungicide and at least one zoospore attractant derivative of agriculture effective dose, and this derivative is derived from short chain aldehydes or ketones zoospore attractant molecule.
Summary of the invention
An embodiment is the composition being suitable for attracting Oomycete fungal zoospore.Described derivative is hydrolyzed in time in water, thus release zoospore attractant.Another embodiment is the mixture to the effective fungicide of Oomycete fungal of these zoospore attractant derivatives and agriculture effective dose.
An embodiment is zoospore attractant derivative, and described derivative discharges zoospore attractant after being exposed to water.These attractant derivatives be generally acylhydrazone or semicarbazones and comprise the formula of being selected from 1,
The compound of formula 2, formula 3, formula 4, formula 5 and formula 6, its Chinese style 1 is:
Wherein R
1=isobutyl group, sec-butyl or the tert-butyl group-CH
2; R
2=H; And n=0-25;
Formula 2 is:
Wherein R
1=sec-butyl or the tert-butyl group-CH
2; And R
2=H;
Formula 3 is:
Wherein R
1=isobutyl group, sec-butyl or the tert-butyl group-CH
2, and R
2=H;
Formula 4 is:
Wherein R
1=isobutyl group, R
2=H; And R
3=comprise the alkyl of 2-25 carbon, but get rid of n-heptyl or n-undecane base, or comprise the branched alkyl of 4-25 carbon, or comprise the substituted or unsubstituted cycloalkyl of 3-25 carbon, or comprise the substituted or unsubstituted aryl alkyl of 12-26 carbon; Or
R
1=sec-butyl or the tert-butyl group-CH
2; R
2=H; And R
3=comprise the alkyl of 1-25 carbon, or comprise the branched alkyl of 3-25 carbon, or comprise the substituted or unsubstituted cycloalkyl of 7-25 carbon, or comprise the substituted or unsubstituted aryl alkyl of 7-25 carbon; Or
R
1=isobutyl group; R
2=methyl; And R
3=comprise 2,3,6 and 12-25 carbon alkyl, or comprise the branched alkyl of 3-25 carbon, or comprise the substituted or unsubstituted cycloalkyl of 3-25 carbon, or comprise the substituted or unsubstituted aryl alkyl of 7-25 carbon;
Formula 5 is:
Wherein R
4=H, the alkyl comprising 1-4 carbon separately or haloalkyl or alkoxyl or alkyl sulfenyl or halogenated alkoxy or haloalkylthio, halogen, hydroxyl, nitro, hydroxy-acid group, carboxylic acid derivates group or cyano group; With
R
1=sec-butyl or the tert-butyl group-CH
2; And R
2=H; Or
R
1=isobutyl group; And R
2=methyl;
Formula 6 is:
Wherein R
4=H, the alkyl comprising 1-4 carbon separately or haloalkyl or alkoxyl or alkyl sulfenyl or halogenated alkoxy or haloalkylthio, halogen, hydroxyl, nitro, hydroxy-acid group, carboxylic acid derivates group or cyano group; With
R
1=isobutyl group, sec-butyl or the tert-butyl group-CH
2; And R
2=H; Or
R
1=isobutyl group; And R
2=methyl.
Another embodiment is the method for control fungal pathogens, said method comprising the steps of: at least one formula 1-6 component mixed with the fungicide of agriculture effective dose to the Zoned application contiguous with described fungal pathogens.In one embodiment, described fungal pathogens is Oomycete fungal pathogene and before described fungal pathogens has started infection, said mixture is applied to plant tissue.
Another embodiment is the preparation for preventing and treating fungi, and it comprises compound and at least one fungicide that at least one is selected from formula 1-6.In one embodiment, the fungi of described fungicide anti-generation motility zoospore effectively.In one embodiment, one or more fungicides are selected from mancozeb (mancozeb), maneb (maneb), zineb (zineb), tmtd (thiram), Propineb (propineb), Carbatene (metiram), Kocide SD (copperhydroxide), Cupravit (copperoxychloride), bordeaux mixture (Bordeauxmixture), captan (captan), folpet (folpet), Amitraz (amisulbrom), nitrile Fluoxastrobin (azoxystrobin), oxime bacterium ester (trifloxystrobin), ZEN 90160 (picoxystrobin), kresoxim-methyl (kresoxim-methyl), fluoxastrobin (fluoxastrobin), pyraclostrobin (pyraclostrobin), cycloheximide triazole (famoxadone), Fenamidone (fenamidone), metalaxyl (metalaxyl), Metalaxyl-M (mefenoxam), M 9834 (benalaxyl), frost urea cyanogen (cymoxanil), Propamocarb (propamocarb), dimethomorph (dimethomorph), flumorph (flumorph), mandipropamid (mandipropamid), iprovalicarb (iprovalicarb), benzene metsulfovax ester (benthiavalicarb-isopropyl), valiphenal, zoxamide (zoxamide), Guardian (ethaboxam), cyazofamid (cyazofamid), fluopicolide (fluopicolide), fluazinam (fluazinam), tpn (chlorothalonil), dithianon (dithianon), phosethyl-Al (fosetyl-Al), phosphorous acid (phosphorousacid), Tolylfluanid (tolylfluanid) and (1S)-1-({ [(1R, S)-(4-cyano-phenyl) ethyl] sulfonyl } methyl) propyl carbamic acid (4-fluorophenyl) ester.In one embodiment, described fungicide is not based on the fungicide (non-copperbasedfungicide) of copper.In another embodiment, described fungicide can be formula I, wherein
Wherein R1 is ethyl, 1-octyl group, 1-nonyl or 3,5,5-trimethyl-1-hexyl; And R
2for methyl, ethyl, 1-propyl group, 1-octyl group, trifluoromethyl or methoxy.
Another embodiment is the method for control fungal infection, said method comprising the steps of: at least one preparation is provided, described preparation comprises compound and at least one fungicide that at least one is selected from formula 1-6, and the preparation of agriculture effective dose or mixture is applied to the region contiguous with fungi.In one embodiment, the mixture comprising described attractant derivative and fungicide is applied to at least one place in upper/lower positions: the seed of plant, plant leaf, flower, stem, fruit, the region contiguous with plant, soil, seed, germination, root, liquid state or solid state crystal growth medium and water cultivation growth solution.
In one embodiment, to by least one zoospore attractant derivative and at least one, the preparation that the effective fungicide of Oomycete fungal pathogene is formed is adjusted, thus control is by the disease being selected from following Oomycete fungal pathogene and causing: phytophthora infestans (Phytophthorainfestans), the raw single shaft of grape mould (Plasmoparaviticola), Phytophthora capsici (Phytophthoracapsici), Pseudoperonospora cubensis (Pseudoperonosporacubensis), lettuce dish stalk mould (Bremialactucae), Kidney bean epidemic disease mould (Phytophthoraphaseoli), Phytophthora nicotianae mutation-phytophthora parasitica (Phytophthoranicotianevar.parasitica), standing grain raw finger, obstructs mould (Sclerosporagraminicola), the brown bar downy mildew (Sclerophthorarayssiae) of corn, palm mould (Phytophthorapalmivora), Phytophthoracitrophora, large spore epidemic disease mould (Sclerophthoramacrospora), Sclerophthoragraminicola, Phytophthora cactorum (Phytophthoracactorum), cloves epidemic disease mould (Phytophthorasyringe), the humulus false downy mildew of grass (Pseudoperonosporahumuli) and white rust (Albugocandida).
In another embodiment, described zoospore attractant derivative can discharge zoospore attractant, such as be selected from following C4-C8 aldehydes or ketones: isopentyl aldehyde, 2 methyl butyraldehyde, valeral, isobutylaldehyde, butyraldehyde, 4-methyl pentanal, 3, 3-dimethyl butyraldehyde, 3-methylsulfany butyraldehyde, 2-cyclopropyl acetaldehyde, 3-guaiacene, 2-ethyl crotonaldehyde, crotonaldehyde, 2 methyl crotonaldehyde, indole-3-formaldehyde, furfural (furans-2-formaldehyde), thiophene-2-formaldehyde, 2-ethyl butyraldehyde, cyclopropyl carboxaldehyde, 2, 3-dimethylated pentanal, 2 methyl pentanal, oxolane-3-formaldehyde, cyclopenta formaldehyde, 3-methylpent-2-ketone, 4, 4-dimethyl-penten-2-ketone, 3, 3-dimethyl butyrate-2-ketone and 4-methylpenta-2-one.
The material of induction zoospore packing can be added in the composition containing fungicide and zoospore attractant derivative, thus improve disease control further, described material is such as pectin, metal ion and inorganic compound or inorganic salt compound, and it is selected from Ca, Zn, Mg, Mn, NaNO
3, KNO
3, and NaCl.
Accompanying drawing explanation
Fig. 1 shows and is used in aldehyde in method that the application discloses and some acylhydrazones of ketone and semicarbazones derivative and the test attracting the ability of zoospore to carry out to their.
Fig. 2 summarizes the data by attracting the ability of the motility zoospore of Phytophthora capsici (PHYTCA) and the raw single shaft of grape mould (PLASVI) to test to multiple acylhydrazone and the semicarbazones derivative of aldehyde and ketone and collect.
Embodiment
In order to understand the principle of innovative techniques better, will multiple exemplary of described innovative techniques be mentioned below and will concrete language be used to describe them.It should be understood, however, that it is not the scope being intended to limit thus described innovative techniques, as usually expected in those skilled in the art, the change that the principle of described innovative techniques is carried out, modification and other be applied within the scope of the application.
The present invention relates to compound, described compound is the derivative that the derivative of zoospore attractant compound maybe can form zoospore attractant compound, and the derivative release zoospore attractant of described zoospore attractant compound also can be used for strengthening the effect that the plant disease caused by Oomycete pathogene prevented and treated by fungicide.The inventive method comprises makes the plant be in by the risk of the Oomycete pathogen invasion producing zoospore contact with composition, and described composition includes fungicide and the zoospore attractant derivative of effective amount.Selectively, can use together with the mixture of the mixture of different zoospore attractants and zoospore attractant derivative and fungicide or different fungicide.
Although do not wish to be bound by any theory, think the effect that can strengthen composition with under type: with the embedding of zoospore attractant derivative, dressing or surround fungicide particle, thus around fungicide particle, producing the concentration gradient of zoospore attractant, zoospore is attracted to described fungicide by it.By zoospore is attracted to fungicide particle, can expand the disease control region of fungicide, this can reduce the utilization rate of fungicide or extend the disease control phase.In addition, the fungicide of relative broad range can be used, be included in fungicide plant surface with limited reallocation.
Although do not wish to be bound by any theory, think that use zoospore attractant derivative can strengthen the effect of zoospore active fungicide (zoosporeactivefungicide), described zoospore active fungicide is such as thiocarbamate, mancozeb, maneb, zineb, tmtd, Propineb or Carbatene; Based on the fungicide of copper, such as Kocide SD (copperhydroxide), Cupravit (copperoxychloride) or bordeaux mixture (Bordeauxmixture); Phthalmide fungicide, such as captan (captan) or folpet (folpet); Amitraz (amisulbrom); Strobilurin class, such as nitrile Fluoxastrobin (azoxystrobin), oxime bacterium ester (trifloxystrobin), ZEN 90160 (picoxystrobin), kresoxim-methyl (kresoxim-methyl), fluoxastrobin (fluoxastrobin), pyraclostrobin (pyraclostrobin) etc.; Cycloheximide triazole (famoxadone); Fenamidone (fenamidone); Metalaxyl (metalaxyl); Metalaxyl-M (mefenoxam); M 9834 (benalaxyl); Frost urea cyanogen (cymoxanil); Propamocarb (propamocarb); Dimethomorph (dimethomorph); Flumorph (flumorph); Mandipropamid (mandipropamid); Iprovalicarb (iprovalicarb); Benzene metsulfovax ester (benthiavalicarb-isopropyl); Valiphenal; Zoxamide (zoxamide); Guardian (ethaboxam); Cyazofamid (cyazofamid); Fluopicolide (fluopicolide); Fluazinam (fluazinam); Tpn (chlorothalonil); Dithianon (dithianon); Phosethyl-Al (fosetyl-Al); Phosphorous acid (phosphorousacid); Tolylfluanid (tolylfluanid); Amino sulfone class, such as (1S)-1-({ [(1R, S)-(4-cyano-phenyl) ethyl] sulfonyl } methyl) propyl carbamic acid (4-fluorophenyl) ester; Or following triazolopyrimidine compound, such as formula I:
Wherein R1 is ethyl, 1-octyl group, 1-nonyl or 3,5,5-trimethyl-1-hexyl; And R
2for methyl, ethyl, 1-propyl group, 1-octyl group, trifluoromethyl or methoxy.
The attractant of useful zoospore attractant derivative and their release can change with vegetation type, fungal pathogens and environmental condition.Common zoospore attractant can comprise the derivative of such as C4-C8 aldehyde or C4-C8 ketone.Zoospore attractant derivative also can be adsorbed on inert base or be embedded in inert base, and described inert base is such as PergoPakM, corn starch, clay, latex agglomerate (latexagglomerate) or fertiliser granulates.
Zoospore attractant derivative can be used for the object of such as attractant molecular Control release.Zoospore attractant derivative is generally to be prepared or derivative compound by zoospore attractant molecule.Zoospore attractant derivative can combinationally use with zoospore attractant and fungicide.Compared with corresponding aldehydes or ketones, the acyl hydrazone derivative of suitable zoospore attractant derivative such as various aldehyde and ketone or semicarbazones derivative can have lower volatility and/or water-soluble.These derivatives can produce or discharge zoospore attractant after contacting with the water on the region of the water on plant surface or contiguous described plant.The example of hydazone derivative technology is see PCT patent application WO2006016248 and " Controlledreleaseofvolatilealdehydesandketonesbyreversib lehydrazoneformation-' classical ' profragrancesaregettingdynamic " byLevrandetal.publishedinChemicalCommunications (Cambridge, UnitedKingdom) (2006) onpages2965-2967 (ISSN:1359-7345).By above-mentioned bibliography separately disclosed content be incorporated to the application especially as a reference.The application provides multiple method to synthesize novel and/or useful acylhydrazone and semicarbazones derivative.
Reaction 1 as follows generally describes zoospore attractant derivative (such as above-mentioned formula 1-6) and how to discharge zoospore attractant after contact with water.The generation speed of zoospore attractant depends on many factors, and described factor comprises the existence on plant surface of the physical-chemical property of zoospore attractant derivative, the composition of the preparation containing described derivative, water and duration and uses the temperature in region, humidity and other environmental condition.As follows, this hydrolysis is reversible in theory, but this invertibity may be low under the agriculture condition of reality.
Reaction 1
When combinationally using with fungicide, above-mentioned zoospore attractant derivative can provide special effectively preventing to the disease that, Phytophthora capsici mould by pathogene phytophthora infestans, the raw single shaft of grape and Pseudoperonospora cubensis cause.Also other pathogene can be prevented and treated in various plants, described plant is such as tomato, potato, pepper, grape, cucurbitaceous plant (cucurbits), lettuce, beans (beans), Chinese sorghum, corn, oranges and tangerines, turfgrass, English walnut (pecan), apple, pears, hop (hop) and crucifer (crucifiers), it is mould that other pathogene described comprises lettuce dish stalk, Kidney bean epidemic disease is mould, Phytophthora nicotianae mutation-phytophthora parasitica, standing grain is raw refers to that stalk is mould, the brown bar downy mildew of corn, palm mould, Phytophthoracitrophora, large spore epidemic disease is mould, Sclerophthoragraminicola, Phytophthora cactorum, cloves epidemic disease is mould, the humulus false downy mildew of grass and white rust.
Treat that the effective dose of the zoospore attractant derivative used together with fungicide depends on such as vegetation type, plant growth stage, harsh environmental conditions degree, fungal pathogens and application conditions usually.Usually, the plant needing fungi to protect, prevent and treat or eliminate is contacted with the zoospore attractant derivative of following amount, and described amount is about 1 to about 5000ppm zoospore attractant derivative, is preferably about 10 to about 1000ppm zoospore attractant derivatives.Described contact can be any effective means.Such as, the mixture of the fungicide of described attractant derivative and valid density can be sprayed to any expose portion such as leaf or stem of plant.Described attractant derivative can be formulated in itself in agricultural carrier and to account for 1 to the 95wt% of preparation.One or more attractant derivatives can be become liquid or solid form with one or more zoospore attractants with one or more fungicide co-formulation, the mixture of wherein said attractant, attractant derivative or one or more attractants or attractant derivative accounts for 1 to 50% of preparation.
The fungicide strengthened above by zoospore attractant derivative plant leaf be can be applied to or the soil contiguous with described plant or region are applied to.In addition, the described fungicide strengthened by zoospore attractant derivative can be mixed together with any combination of following material or use together with any combination of following material, and described material is weed killer herbicide, insecticide, bactericide, nematocide, acarus-killing, biocide, drive ant agent, rodenticide, invertebrate poison, arthropodicides, fertilizer, growth regulator and pheromones.
Experimental section
Following scheme 1 shows synthesis several aldehyde of the present invention and the different acylhydrazone of ketone and the general approach of semicarbazones derivative.
Scheme 1
For scheme 1, R
1for alkyl; R
2for hydrogen or methyl; R
3for aliphatic group; Be 0-8 with n.
the synthesis of compound 10 and 12
In brief, 10.0g (51.5mmol) isopthalic dihydrazide, 150mL absolute ethyl alcohol and 124mmol aldehyde are added hot reflux 8-24 hour.TLC analyzes and shows that raw material hydrazine exhausts.Lasting a few hours is cooled to room temperature by mixture, then filters.Gained white solid ethanol washs, and then in vacuum drying oven, is dried to constant weight at 40-50 DEG C.By proton NMR spectrum and elementary analysis be separated solid to be analyzed and these results analyzed are consistent with desired structure.Further define fusing point.
the synthesis of compound 5
In brief, 10.0g (57.4mmol) AH, 0.5mL glacial acetic acid and 150mL absolute ethyl alcohol is added to being equipped with in the dry round-bottomed flask of the 250mL of magnetic stir bar, thermometer and reflux condenser.After major part dissolution of solid, in flask, add 13.5mL (126mmol) isopentyl aldehyde, be then heated backflow 4 hours.Following inspection reaction process: take out waiting separatory and by HPLC, it being analyzed of reactant mixture.After reaction completes substantially, by mixture cool to room temperature.Gained solid is collected by vacuum filtration, with hexane flushing and 40 DEG C of vacuum dryings.Be separated to about 16g white solid product (90% yield).The structure of product is consistent with the structure of compound 5 (passes through 300MHz
1hNMR and HPLC/MS analyzes and determines).Determine that fusing point is 204-206 DEG C.Similar method is for the preparation of the compound 1-9 in Fig. 1 and compound 11.
the determination of activity of zoospore attractant is designed
Refer now to Fig. 1, the ability that wherein listed compound attracts two kinds of different fungies and Phytophthora capsici (PHYTCA) and grape to give birth to the motility zoospore of single shaft mould (PLASVI) is evaluated.Be that the solution form of 5mM is tested having sufficient water miscible compound with concentration.Grind having inadequate water miscible compound and be mixed with 10% suspension concentrates.The solution of suspension concentrates is placed in 1.0cmDrummondSize2 microcapillary.Pipe be placed in the hole of 12 orifice plates and fix with a droplet DowCorning vacuum grease.
In brief, use in measuring at these, make Phytophthora capsici at V-8 grow on agar.When culture is 5-7 days ages and produces enough sporangiums, in plate, add 15ml sterile water to cause the generation of zoospore.After room temperature keeps 10 minutes, the plate of overflow is placed in refrigerator and keeps 20 minutes at 4 DEG C.Then lasting 30-60 minute makes plate get back to room temperature.Then zoospore suspension Whatman113V Filter paper filtering.
In order to cause the generation of the mould zoospore of the raw single shaft of grape, to be infected completely by three and the leaf producing the grape (VitisviniferacvCarignane) of enough spores collects sporangium.Infected leaf is placed in deionized water and by light brush leaf, sporangium is taken off.10 minutes are left standstill in room temperature by comprising the sporangial solution be removed.Solution to be transferred in refrigerator and to keep 20 minutes at 4 DEG C, then lasting 60 to 90 minutes and get back to room temperature, now there is a large amount of zoospore.Then zoospore suspension Whatman113V Filter paper filtering.
About 1mL zoospore suspension is placed in hole, and described hole is containing the capillary needed to the chemicals that attractant activity is tested.After 60 to 90 minutes, as follows attraction level is marked: examine under a microscope capillary and solution and the zoospore number in the zoospore number swum in capillary and external solution is compared.With grade 1 to 10, semiquantitative scoring is carried out to this ratio, wherein 1 represents zoospore in capillary without accumulation, 2 represent that the accumulation of zoospore in capillary approximates the density of zoospore in external solution, 5 represent the density of accumulation about 5 times in external solution, and 10 represent that zoospore is full of capillary, its density is so large that cannot to count.The average of 1-3 is classified as slight attraction; The average of 4-7 is classified as moderate to attract; The average of 8-10 is classified as and highly attracts.These results are summed up in fig. 2.As the replacement method of the method, mention in background technology for determining that operation that zoospore attracts normally is suitable for and also can being used.
The compounds of this invention with zoospore attractant character advantageously particularly can have anti-Oomycete fungal pathogene activity fungicide with multiple fungicide combines.Useful fungicide comprises mancozeb, maneb, zineb, tmtd, Propineb, Carbatene, Kocide SD, Cupravit, bordeaux mixture, captan, folpet, Amitraz, nitrile Fluoxastrobin, oxime bacterium ester, ZEN 90160, kresoxim-methyl, fluoxastrobin, pyraclostrobin, cycloheximide triazole, Fenamidone, metalaxyl, Metalaxyl-M, M 9834, frost urea cyanogen, Propamocarb, dimethomorph, flumorph, mandipropamid, iprovalicarb, benzene metsulfovax ester, valiphenal, zoxamide, Guardian, cyazofamid, fluopicolide, fluazinam, tpn, dithianon, phosethyl-Al, phosphorous acid, Tolylfluanid, (1S)-1-({ [(1R, S)-(4-cyano-phenyl) ethyl] sulfonyl } methyl) propyl carbamic acid (4-fluorophenyl) ester and triazolopyrimidine compound, such as formula I:
Wherein R1 is ethyl, 1-octyl group, 1-nonyl or 3,5,5-trimethyl-1-hexyl; And R
2for methyl, ethyl, 1-propyl group, 1-octyl group, trifluoromethyl or methoxy.
The compounds of this invention is preferably used in the form of compositions, and described composition comprises one or more formula 1-6 compounds and botany acceptable carrier.Described composition is concentrate formulation or dust/granular preparation, and be dispersed in by described concentrate formulation for using in water or another kind of liquid, namely described dust/granular preparation is used without further process.Described composition is prepared according to the conventional method of agrochemical field, but owing to wherein there is the compounds of this invention but novel and important.The application has carried out some to the preparation of described composition and has described, thus ensures that chemurgy scholar easily can prepare desired composition.
Compound administration is modal in dispersion is wherein the aqueous suspension or emulsion prepared by the concentrate formulation of described compound.Such water soluble, water can suspend or can emulsification preparation be solid (being usually known as wettable powders) or liquid (being usually known as missible oil or aqueous suspension).The present invention expects and uses all medium, sends fungicide by described medium preparation the compounds of this invention.It is easily understood that can use the arbitrary substance that these compounds can be added wherein, condition is that they obtain desired purposes, and does not significantly disturb the activity of the compounds of this invention.
Wettable powders (can be suppressed to form water and dispersible particle) comprises the abundant mixture (intimatemixture) of reactive compound, inert carrier and surfactant.The concentration of reactive compound is generally about 1 to about 95%w/w, is more preferably about 1 to about 50%w/w.In the preparation of wettable powders composition, reactive compound can with the solids mixing of any fine dispersion, the solid of described fine dispersion is such as pyrophyllite (prophyllite), talcum, chalk, gypsum, bleaching earth (Fuller ' searth), bentonite, attapulgite, starch, casein (casein), seitan (gluten), imvite (montmorilloniteclay), diatomite (diatomaceousearth) or purified silicates (purifiedsilicate) etc.In described operation, usually the carrier of fine dispersion and described reactive compound to be ground in volatile organic solvent and blended.Effective surfactant accounts for about 0.5% of described wettable powders to about 10%, comprises Sulfonated lignin, naphthalene sulfonate, alkylbenzenesulfonate, alkyl sulfate and the non-ionic surfactants ethylene oxide adduct as alkyl phenol.
The missible oil of the compounds of this invention is contained in the compound of the normal concentration (such as about 10% to about 50%w/w) in suitable liquid.Described compound can be dissolved in inert carrier (described inert carrier is the mixture of water miscible solvent or water immiscible organic solvent and emulsifier).Available water and the described concentrate of oil dilution, thus form the spraying mixture of O/w emulsion form.Available organic solvent comprises aromatic solvent (particularly the high boiling point naphthalene part of oil and hydrocarbon fraction such as heavy aromatic naphthas).Also other organic solvent can be used, such as terpene type solvent (comprising rosin derivative), aliphatic ketone (such as cyclohexanone) and complicated alcohol (such as cellosolvo).
The application the emulsifier of favourable use easily can be determined by those skilled in the art and comprise the blend of various nonionic emulsifier, anion emulsifier, cationic emulsifier and amphoteric emulsifier or two or more emulsifier.Example for the preparation of the nonionic emulsifier of missible oil comprises poly-(alkylidene) glycol ethers and alkyl and aryl phenol, fatty alcohol, aliphatic amine or fatty acid and oxirane, the condensation product (such as ethoxylated alkyl phenols) of expoxy propane and the carboxylate of available polyalcohol or polyoxyalkylene solubilising.Cationic emulsifier comprises quaternary ammonium compound and fatty amine salt.Anion emulsifier comprises the oil-soluble salt (such as, calcium salt) of alkyl aryl sulphonic acid, the oil-soluble salt of sulphation polyglycol ether and the acceptable acid addition salts of phosphorylation polyglycol ether.
The aromatic organic liquids such as dioctyl phthalate of the naphthalene cut that the representative organic liquid that can use in the preparation of missible oil of the present invention is aromatic series liquid such as dimethylbenzene and propyl benzene fractions or mixing, mineral oil, replacement; Kerosene (kerosene); The dialkyl amide of various fatty acid is the n-butyl ether of the dimethylformamide of fatty acid and ethylene glycol and ethylene glycol derivative such as triethylene glycol, the ethyl ether of triethylene glycol or the methyl ether of triethylene glycol particularly.Also can the mixture of suitable two or more organic liquids of employing in the preparation of missible oil.Preferred organic liquid is dimethylbenzene and propyl benzene fractions, most preferably dimethylbenzene.Usually surface active dispersing agent is adopted and in the combination weight of dispersant and reactive compound, the amount of described surface active dispersing agent is 0.1 to 20wt% in fluid composition.Described preparation also can contain other compatible additive, the bioactive compound such as, used in plant growth regulator and other agricultural.The cystogenous material of induction zoospore can be added to strengthen disease control further in the composition containing fungicide and zoospore attractant derivative, described material is such as pectin, metal ion and inorganic compound or inorganic salt compound, it is selected from Ca, Zn, Mg, Mn, NaNO
3, KNO
3, and NaCl.
Aqueous suspension comprises the soluble compound of water of the present invention and is dispersed in suspension in aqueous vehicles, and concentration range is about 5% to about 50%w/w.Prepare suspension in the following manner, compound described in fine gtinding, it be acutely mixed in carrier, described medium is made up of with the surfactant being selected from type identical with surfactant discussed above water.Inert fraction such as mineral salt and synthesis or lac can be added to increase density and the viscosity of aqueous vehicles.Usually the most effectively simultaneous grinding and the described compound of mixing is come by preparing aqueous mixture and carry out homogenize to it in equipment such as sand mill (sandmill), ball mill (ballmill) or piston type homogenizer (piston-typehomogenizer).
Described compound also can be used by the form of particulate composition, and described particulate composition can be used in particular for being applied in soil.Particulate composition is about compound described in 10wt% containing the about 0.5wt%-be dispersed in inert carrier usually, described inert carrier completely or major part be made up of the attapulgite of coarse pulverizing, bentonite, diatomite, clay or similar inexpensive substance.Above-mentioned composition is prepared usually as follows: dissolved in a suitable solvent by described compound, be applied to particulate vector, and described particulate vector is made suitable granularity (scope is about 0.5 to 3mm) in advance.Above-mentioned composition also can be prepared as follows: described carrier and compound are made pasty state or paste, then crushes also drying and obtains required grain graininess.
Pulvis containing described compound is prepared as follows simply: the described compound of abundant mixing powdery and suitable dust-like agricultural carrier (pelelith etc. of such as kaolinton, grinding).Pulvis can suitably containing 1%-about compound described in 10% of having an appointment.
Described active compound can containing cosurfactant to strengthen the deposition of described composition in target crop and organism, wetting and infiltration.These cosurfactants can optionally be used as the component of described preparation or use as filling mixture.In the sprayed volume of water, the amount of described cosurfactant is 0.01% to 1.0%v/v, is preferably 0.05% to 0.5%.Suitable cosurfactant comprises the blend of ethoxylated nonylphenol, ethoxylation synthol or ethoxylation natural alcohol, the salt of sulfosuccinate, ethoxylation organosiloxane, ethoxylated fatty amine and surfactant and mineral oil or vegetable oil.
Described composition optionally comprises antifungal combination, and described combination comprises one or more the compounds of this invention of at least 1% and another kind of Pesticidal compound.This extra Pesticidal compound can be fungicide, insecticide, nematocide, acarus-killing, arthropodicides, bactericide or their combination, described extra Pesticidal compound in for the medium selected by application with the compounds of this invention compatible and activity that is not antagonism the compounds of this invention.Therefore, in such embodiments, other Pesticidal compound described toxic agent use as a supplement, for identical or different pesticidal use.Compound in combination can exist with the ratio of 1: 10 to 100: 1 usually.
The present invention comprises the method for control or prevention fungal attack within the scope of it.These methods comprise to described fungi position or to treat by prevent the position (such as, to potato, tomato, cucurbit or mattae) encroached on use one or more compounds of the present invention of effective dose and agriculture effective dose to the activated fungicide of Oomycete fungal tool.The compounds of this invention is suitable for processing each Plants, shows low phytotoxicity simultaneously.The compounds of this invention (it is compound or the composition comprising described compound) is used by any one in various known technology.Such as, described compound can be used the leaf of plant, flower, stem, fruit, the region contiguous with plant, soil, seed, the seed of germination, root, liquid state or solid state crystal growth medium and water cultivation growth solution, thus prevent and treat various fungi and do not damage the commercial value of described plant.Described material can be used by any one form in normally used preparation type, and such as it is solution, dust agent, wettable pulvis, can flow concentrate or missible oil.These materials can be used expediently by various known way.
The compounds of this invention has the wide scope of validity in fungicide formulations.The exact amount of zoospore attractant derivative to be administered not only depends on used concrete zoospore attractant derivative, also depend on desired specific function, fungal species to be prevented and treated and vegetative stage thereof, and the position of the plant contacted with the composition of effective fungicidal amount or other article.Therefore, may not be equally authentic when the compounds of this invention and the composition containing described compound are at similar concentration or in anti-identical fungi type.The compounds of this invention and the composition that is mixed to form with fungicide thereof are effective when disease suppression and the acceptable amount of botany to plant.
Although illustrate in accompanying drawing and above-mentioned specification and describe new technology in detail; but these contents should be considered to be exemplary and not restrictive in essence; it should be understood that and only show and describe preferred embodiment and expect to protect all changes fallen in new technology spirit and change.Equally, although use specific embodiment, theoretical property argument, describe and illustration new technology is described, these illustrations and enclose discuss never should be understood to be to limit described technology.All patents of reference in this application, patent application and bibliography, technical paper, publication etc. are incorporated to the application as a reference in full.
Claims (15)
1., for preventing the method for the Oomycete pathogenic infection in plant, described method comprises:
Make to be subject to region that Oomycete infects the plant of infringement and comprise at least one fungicide, formula 4 compound contacts with the composition of at least one zoospore packing material, wherein said at least one fungicide has anti-Oomycete activity, and its Chinese style 4 is:
Wherein
R
1=isobutyl group; R
2=H; And R
3=comprise the alkyl of 2-25 carbon, but get rid of n-heptyl or n-undecane base, or comprise the branched alkyl of 4-25 carbon; Or
R
1=sec-butyl or the tert-butyl group-CH
2; R
2=H; And R
3=comprise the alkyl of 1-25 carbon, or comprise the branched alkyl of 3-25 carbon, or comprise the substituted or unsubstituted cycloalkyl of 7-25 carbon; Or
R
1=isobutyl group; R
2=methyl; And R
3=comprise the alkyl of 2,3,6 and 12-25 carbon, or comprise the branched alkyl of 3-25 carbon; With
Zoospore attractant is discharged in described region after being exposed to water, thus produce zoospore attractant concentration gradient, wherein said zoospore attractant concentration gradient attracts the zoospore of described Oomycete by described water, wherein said at least one zoospore packing material induction zoospore packing, and the Oomycete pathogenic infection in wherein said plant prevent by described at least one fungicide.
2. the process of claim 1 wherein in formula 4, R
1for isobutyl group; And R
2for hydrogen.
3. the process of claim 1 wherein that described zoospore is the spore being selected from following at least one Oomycete: the raw single shaft of phytophthora infestans, grape is mould, Phytophthora capsici, Pseudoperonospora cubensis, lettuce dish stalk is mould, Kidney bean epidemic disease is mould, Phytophthora nicotianae mutation-phytophthora parasitica, standing grain rawly refer to that stalk is mould, corn brown bar downy mildew, palm mould, Phytophthoracitrophora, large spore epidemic disease are mould, Sclerophthoragraminicola, Phytophthora cactorum, cloves epidemic disease are mould, the careless false downy mildew of humulus and white rust.
4. the process of claim 1 wherein that described zoospore is the spore being selected from following at least one Oomycete: the raw single shaft of phytophthora infestans, grape is mould, Phytophthora capsici and Pseudoperonospora cubensis.
5. the process of claim 1 wherein the Oomycete of described at least one fungicide anti-generation motility zoospore effectively.
6. the method for claim 1, wherein said at least one fungicide is selected from mancozeb, maneb, zineb, tmtd, Propineb, Carbatene, Kocide SD, Cupravit, bordeaux mixture, captan, folpet, Amitraz, nitrile Fluoxastrobin, oxime bacterium ester, ZEN 90160, kresoxim-methyl, fluoxastrobin, pyraclostrobin, cycloheximide triazole, Fenamidone, metalaxyl, Metalaxyl-M, M 9834, frost urea cyanogen, Propamocarb, dimethomorph, flumorph, mandipropamid, iprovalicarb, benzene metsulfovax ester, valiphenal, zoxamide, Guardian, cyazofamid, fluopicolide, fluazinam, tpn, dithianon, Tolylfluanid, (1S)-1-({ [(1R, S)-(4-cyano-phenyl) ethyl] sulfonyl } methyl) propyl carbamic acid (4-fluorophenyl) ester and formula I triazolopyrimidine compound:
Wherein Rl is ethyl, 1-octyl group, 1-nonyl or 3,5,5-trimethyl-l-hexyl; And R
2for methyl, ethyl, 1-propyl group, 1-octyl group, trifluoromethyl or methoxy.
7. the method for claim 1, described method also comprises following prevention Oomycete pathogenic infection:
To the plant being subject to encroach on or the described composition with the agriculture effective dose of the Zoned application of Oomycete vicinity.
8. the process of claim 1 wherein that described Oomycete zoospore attractant is a part of acylhydrazone or semicarbazones or is included in a part of acylhydrazone or semicarbazones, wherein said acylhydrazone or semicarbazones are by C
5-C
8aldehyde or C
5-C
8ketone is formed.
9. the process of claim 1 wherein that described at least one fungicide is not based on the fungicide of copper.
10. the method for claim 1, wherein select described at least one fungicide to prevent the disease caused by Oomycete pathogene, described Oomycete pathogene is selected from that phytophthora infestans, the raw single shaft of grape are mould, Phytophthora capsici, Pseudoperonospora cubensis, lettuce dish stalk is mould, Kidney bean epidemic disease is mould, Phytophthora nicotianae mutation-phytophthora parasitica, standing grain rawly refer to that stalk is mould, corn brown bar downy mildew, palm mould, Phytophthoracitrophora, large spore epidemic disease are mould, Sclerophthoragraminicola, Phytophthora cactorum, cloves epidemic disease are mould, the careless false downy mildew of humulus and white rust.
The method of 11. claims 1, described method also comprises:
The described composition of agriculture effective dose is applied to at least one place in upper/lower positions: the seed of plant, plant leaf, flower, stem, fruit, the region contiguous with plant, soil, seed, germination, root, liquid state and solid state crystal growth medium and water cultivation growth solution.
12. the process of claim 1 wherein that described plant is selected from grape, potato, tomato, cucumber, pumpkin or other cucurbitaceous plant, cabbage or other crucifer, lettuce, beans, corn, soybean, pepper and hop.
The method of 13. claims 8, wherein said Oomycete zoospore attractant acylhydrazone or semicarbazones hydrolysis are selected from following C4-C8 aldehyde to be formed: isopentyl aldehyde, 2 methyl butyraldehyde, valeral, isobutylaldehyde, butyraldehyde, 4-methyl pentanal, 3, 3-dimethyl butyraldehyde, 3-methylsulfany butyraldehyde, 2-cyclopropyl acetaldehyde, 3-guaiacene, 2-ethyl crotonaldehyde, crotonaldehyde, 2 methyl crotonaldehyde, indole-3-formaldehyde, furfural (furans-2-formaldehyde), thiophene-2-formaldehyde, 2-ethyl butyraldehyde, cyclopropyl carboxaldehyde, 2, 3-dimethylated pentanal, 2 methyl pentanal, oxolane-3-formaldehyde and cyclopenta formaldehyde.
The method of 14. claims 8, wherein said Oomycete zoospore attractant acylhydrazone or semicarbazones hydrolysis are to form C4-C8 ketone.
15. the process of claim 1 wherein described zoospore packing material comprise in pectin and metal ion one or more and comprise at least one inorganic compound or inorganic salt compound extraly, it is selected from Ca, Zn, Mg, Mn, NaNO
3, KNO
3and NaCl.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2009/039170 WO2010114536A1 (en) | 2009-04-01 | 2009-04-01 | Compositions and methods to control fungal pathogens |
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| CN102448297B true CN102448297B (en) | 2015-11-25 |
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| EP (1) | EP2413695A1 (en) |
| JP (1) | JP5645914B2 (en) |
| KR (1) | KR20120026484A (en) |
| CN (1) | CN102448297B (en) |
| BR (1) | BRPI0925053A2 (en) |
| CA (1) | CA2756929A1 (en) |
| MX (1) | MX2011010392A (en) |
| RU (1) | RU2528955C2 (en) |
| UA (1) | UA107572C2 (en) |
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Citations (3)
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|---|---|---|---|---|
| WO1994008042A1 (en) * | 1992-09-25 | 1994-04-14 | The Australian National University | Detection of motile organisms in a sample |
| CN101001832A (en) * | 2004-08-05 | 2007-07-18 | 弗门尼舍有限公司 | Use of dynamic mixtures for a controlled release of fragrances |
| TW200840479A (en) * | 2007-02-02 | 2008-10-16 | Bayer Cropscience Ag | Synergistic fungicidal active compound combinations |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2805255B2 (en) * | 1990-06-16 | 1998-09-30 | 日本農薬株式会社 | Hydrazinecarboxamide derivatives, their production, their uses and their use |
| DE69616340T2 (en) * | 1995-07-12 | 2002-07-04 | Du Pont | FUNGICIDAL MIXTURES |
| JPH11292834A (en) * | 1998-04-02 | 1999-10-26 | Otsuka Chem Co Ltd | Hydrazone derivative |
| PL376969A1 (en) * | 2002-12-06 | 2006-01-23 | Dow Agrosciences Llc | Synergistic compositions |
| JP2007008891A (en) * | 2005-07-01 | 2007-01-18 | Nippon Soda Co Ltd | Hydrazinecarboxylic acid derivative and germicide for agriculture and horticulture |
-
2009
- 2009-04-01 CA CA2756929A patent/CA2756929A1/en not_active Abandoned
- 2009-04-01 JP JP2012503389A patent/JP5645914B2/en not_active Expired - Fee Related
- 2009-04-01 CN CN200980159624.5A patent/CN102448297B/en not_active Expired - Fee Related
- 2009-04-01 UA UAA201112633A patent/UA107572C2/en unknown
- 2009-04-01 EP EP09789561A patent/EP2413695A1/en not_active Withdrawn
- 2009-04-01 MX MX2011010392A patent/MX2011010392A/en active IP Right Grant
- 2009-04-01 KR KR1020117025843A patent/KR20120026484A/en not_active Application Discontinuation
- 2009-04-01 BR BRPI0925053-0A patent/BRPI0925053A2/en not_active IP Right Cessation
- 2009-04-01 WO PCT/US2009/039170 patent/WO2010114536A1/en active Application Filing
- 2009-04-01 RU RU2011144082/13A patent/RU2528955C2/en not_active IP Right Cessation
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994008042A1 (en) * | 1992-09-25 | 1994-04-14 | The Australian National University | Detection of motile organisms in a sample |
| CN101001832A (en) * | 2004-08-05 | 2007-07-18 | 弗门尼舍有限公司 | Use of dynamic mixtures for a controlled release of fragrances |
| TW200840479A (en) * | 2007-02-02 | 2008-10-16 | Bayer Cropscience Ag | Synergistic fungicidal active compound combinations |
Non-Patent Citations (2)
| Title |
|---|
| Controlled Release of Volatile Aldehydes and Ketones from Dynamic Mixtures Generated by Reversible Hydrazone Formation;Barbara Levranda et al;《Helvetica Chimica Acta》;20071231;第90卷;全文 * |
| fatty acid aldehydes and alcohols as attractants for zoospores of phytophthora palmivora;London;《Nature》;19780202;第271卷(第5644期);第448页 * |
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| Publication number | Publication date |
|---|---|
| WO2010114536A1 (en) | 2010-10-07 |
| ZA201107134B (en) | 2012-12-27 |
| CA2756929A1 (en) | 2010-10-07 |
| CN102448297A (en) | 2012-05-09 |
| RU2011144082A (en) | 2013-05-10 |
| KR20120026484A (en) | 2012-03-19 |
| RU2528955C2 (en) | 2014-09-20 |
| JP5645914B2 (en) | 2014-12-24 |
| EP2413695A1 (en) | 2012-02-08 |
| MX2011010392A (en) | 2011-10-24 |
| BRPI0925053A2 (en) | 2015-08-11 |
| UA107572C2 (en) | 2015-01-26 |
| JP2012522773A (en) | 2012-09-27 |
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