CN101060780A - Isomeric mixtures of dinitro-octylphenyl esters and synergistic fungicidal mixtures therefrom - Google Patents

Abstract

The present invention relates to an isomeric composition comprising isomers of dinitro-octylphenyl esters, wherein the 2,6-dinitro-4-(1-propylpentyl)phenyl ester isomer is present in an amount of less than 0.1 weight percent, based on the total weight of the isomeric composition and to synergistic fungicidal mixtures therefrom.

Description

The isomer mixture of dinitro-octyl phenyl ester and by its Synergistic fungicidal mixture of making

The present invention relates to the isomer composition and the Synergistic fungicidal composition of dinitro-octyl phenyl ester.

Comprise 2,4-dinitro-6-octyl phenyl crotonates and 2, the composition of 6-dinitro-4-octyl phenyl crotonates have been used as the fungicide of the phytotrophy mite class that is used to control powdery mildew or some kind.This based composition is also referred to as karathane, is Karathane ^TMThe active component that uses in fungicide/miticide.Karathane is six kinds of mixture of isomers that have cis and trans component separately, and contain 2,4-and 2, the mixture of about 2: 1 ratios of 6-dinitro-octyl phenyl crotonates is as its active component, and wherein " octyl group " is meant 1-methylheptyl, 1-ethylhexyl and 1-propyl group amyl group mixture of isomers.Delivered and 2, the relevant various researchs of 4-dinitro-6-(1-methylheptyl) phenylcrotonic acid ester comprise about the skin absorbs of karathane and the report of mammal development impact." Dinocap Dermal Absorption inFemale Rabbits and Rhesus Monkeys ", Biological Monitoring for Pesticide Exposure, Chapter 11, the 137-151 page or leaf, discloses and has related to 2 of 97% purity, the research of the absorption data of 4-dinitro-6-(1-methylheptyl) phenylcrotonic acid ester isomer on December 4th, 1987.Another research, " Developmental Toxicity of Dinocap in the Mouse isNot Due to Two Isomers of the Major Active Ingredients ", Teratogenesis. Carcinogenesis, and Mutagenesis7:341-346 (1987) has reported that karathane is as the purposes of fungicide and reported 2 of 95% purity, the toxicity data of 4-dinitro-6-(1-methylheptyl) phenylcrotonic acid ester isomer.

Karathane is known to form Synergistic mixtures with other fungicide, comprise as WO02/067679 and U.S.6, described in 346,535 with the mixture of benzophenone; As U.S.6, described in 528,536 with the mixture of benzyl phenyl ether and/or carbamate; As U.S.6, described in 515,000 with the mixture of acid amides; Described in WO 2004091298 with the mixture of benzamidoxime; As U.S.6, described in 207,691 with the mixture of 1-((N-(2,3-two chloro-4-hydroxyphenyl) amino)-carbonyl)-1-hexahydrotoluene; Described in FR 2445696 with the mixture of tpn and Plondrel; Described in GB 2003032 with N-(to fluorine-based phenyl)-2, the mixture of 3-dichloro maleimide; As U.S.3, described in 456,055 with the mixture of tetrachloro isophthalonitrile; As U.S.6, described in 489,360 with the mixture of benzyl phenyl ether or carbamate; As U.S.5, described in 569,656 with the mixture of aminomethyl heterocycle; Described in WO2003103393 with the mixture of fused pyrimidones; And analog, wherein above-listed all United States Patent (USP)s all are incorporated herein by this reference.

Karathane is the mixture of isomers with various toxicological effect ranks (for example teratogenesis in mouse and the PVR in dog).Therefore, need all the time to be manufactured on and keep or improve the similar fungicide that has more favourable toxicology character when antifungal is renderd a service and exploitation by its Synergistic fungicidal mixture of making.

The present invention relates to comprise the isomer composition of the isomer of dinitro-octyl phenyl ester, wherein 2,6-dinitro-4-(1-propyl group amyl group) phenylester isomer exists with the amount of the 0.1wt% that is less than the isomer composition gross weight; Also relate to the Synergistic fungicidal mixture of making by it.

Find surprisingly that of the present invention containing is less than 0.1wt%2, the isomer composition of 6-dinitro-4-(1-propyl group amyl group) phenylester isomer has very favorable toxicology character when keeping antifungal to render a service.

Usually, dinitro-octyl phenyl ester exists as the isomer mixture that comprises following isomeric forms:

2,4-dinitro-6-(1-methylheptyl) phenylester,

2,4-dinitro-6-(1-ethylhexyl) phenylester,

2,4-dinitro-6-(1-propyl group amyl group) phenylester,

2,6-dinitro-4-(1-methylheptyl) phenylester,

2,6-dinitro-4-(1-ethylhexyl) phenylester and

2,6-dinitro-4-(1-propyl group amyl group) phenylester;

Wherein be meant can be in hydrolysis under the environmental condition to form any ester functional group of corresponding phenol for ester.Environmental condition be included in the crops environment or in crop itself naturally occurring those conditions, comprise the existence of moisture.

Find surprisingly that comprise 2 of the 0.1wt% that is less than the isomer composition gross weight, the isomer composition of 6-dinitro-4-(1-propyl group amyl group) phenylester does not have teratogenesis or retinopathy change effect, keeps antifungal to render a service simultaneously.

For example, karathane is a kind of isomer composition, and it is meant the cis that comprises following isomer and the dinitro-octyl phenyl crotonates isomer mixture of trans forms:

2,4-dinitro-6-(1-methylheptyl) phenylcrotonic acid ester,

2,4-dinitro-6-(1-ethylhexyl) phenylcrotonic acid ester,

2,4-dinitro-6-(1-propyl group amyl group) phenylcrotonic acid ester,

2,6-dinitro-4-(1-methylheptyl) phenylcrotonic acid ester,

2,6-dinitro-4-(1-ethylhexyl) phenylcrotonic acid ester and

2,6-dinitro-4-(1-propyl group amyl group) phenylcrotonic acid ester.

Well known in the artly be, the crotonates in the karathane is hydrolyzed into corresponding dinitro octyl phenol when being exposed in plant or the environment, and this phenol is the active component with fungicidal action.Therefore, any ester of these compounds or analog (wherein this ester is derived and formed the relevant substituting group can change into phenol in plant or environment) have essentially identical fungicidal action and within the scope of the invention.Preferably, isomer composition of the present invention is the mixture of dinitro-octyl phenyl crotonates.

Generally speaking, isomer composition of the present invention can comprise the dinitro-octyl phenyl ester that constitutes with any combination of isomer and amount, as long as 2,6-dinitro-4-(1-propyl group amyl group) amount of phenylester is lower than the 0.1wt% of isomer composition gross weight, and as long as keeps improved toxicology and antifungal to render a service.In other words, this isomer composition can comprise any amount of dinitro-octyl phenyl ester isomer, and every kind of isomer exists with any amount, as long as 2,6-dinitro-4-(1-propyl group amyl group) amount of phenylester is lower than the 0.1wt% of isomer composition gross weight.Usually, this isomer composition comprises:

0.1 to 99.9wt%2,4-dinitro-6-(1-methylheptyl) phenylester,

0.1 to 99.9wt%2,4-dinitro-6-(1-ethylhexyl) phenylester,

0.1 to 99.9wt%2,4-dinitro-6-(1-propyl group amyl group) phenylester,

0.1 to 99.9wt%2,6-dinitro-4-(1-methylheptyl) phenylester,

0.1 to 99.9wt%2,6-dinitro-4-(1-ethylhexyl) phenylester and

Be less than 0.1wt%2,6-dinitro-4-(1-propyl group amyl group) phenylester.

In one embodiment, isomer composition of the present invention comprises and accounts at least 20 of all isomer gross weights of existing in the composition, usually at least 30, more generally at least 40, typically at least 50, more typical at least 60, preferably at least 70, more preferably at least 80, more preferably at least 90, most preferably at least 2 of 95wt%, 4-dinitro-6-(1-methylheptyl) phenylester.

In another embodiment, isomer composition of the present invention comprises and accounts for 1, common 1.5 of all isomer gross weights of existing in the composition, common 2, preferred 2.5, more preferably 3, most preferably 5 to 45, usually to 40, usually to 35, preferably to 30, more preferably to 27, most preferably to 2 of 25wt%, 4-dinitro-6-(1-ethylhexyl) phenylester.

In another embodiment, isomer composition of the present invention comprises and accounts for 0.1, common 0.5 of all isomer gross weights of existing in the composition, common 1, preferred 1.5, more preferably 2.0, most preferably 2.5 to 45, usually to 40, usually to 35, preferably to 30, more preferably to 27, most preferably to 2 of 25wt%, 4-dinitro-6-(1-propyl group amyl group) phenylester.

In an embodiment again, isomer composition of the present invention comprises and accounts for 0.1, common 0.5 of all isomer gross weights of existing in the composition, common 0.7, preferred 1.0, more preferably 1.5, most preferably 2.0 to 45, usually to 40, usually to 35, preferably to 30, more preferably to 27, most preferably to 2 of 25wt%, 6-dinitro-4-(1-methylheptyl) phenylester.

In another embodiment, isomer composition of the present invention comprises and accounts for 0.1, common 0.5 of all isomer gross weights of existing in the composition, common 1.0, preferred 1.5, more preferably 2.0, most preferably 2.5 to 45, usually to 40, usually to 35, preferably to 30, more preferably to 27, most preferably to 25wt% or still less 2,4-dinitro-6-(1-ethylhexyl) phenylester.

Isomer composition of the present invention comprises and is less than 0.1, usually less than 0.08, more generally is less than 0.06, preferably is less than 0.04, more preferably less than 0.02, most preferably is less than 2 of 0.001wt%, 6-dinitro-4-(1-propyl group amyl group) phenylester.In most preferred embodiment, isomer composition of the present invention is not contain 2, the isomer mixture of 6-dinitro-4-(1-propyl group amyl group) phenylester." do not contain " amount of using high pressure liquid chromatography can not detect that is meant.

In another embodiment of the present invention, isomer composition comprises:

80 to 98wt%2,4-dinitro-6-(1-methylheptyl) phenylester,

Be less than 1.5wt%2,4-dinitro-6-(1-ethylhexyl) phenylester,

Be less than 0.1wt%2,4-dinitro-6-(1-propyl group amyl group) phenylester,

Be less than 0.1wt%2,6-dinitro-4-(1-methylheptyl) phenylester,

Be less than 0.1wt%2,6-dinitro-4-(1-ethylhexyl) phenylester and

Be less than 0.1wt%2,6-dinitro-4-(1-propyl group amyl group) phenylester.

Isomer composition of the present invention can be by the whole bag of tricks manufacturing, as long as final isomer composition contains and is less than 2 of 0.1wt%, 6-dinitro-4-(1-propyl group amyl group) phenylester.As known in the art with " E.Y.Guide to the Chemicals Used in Crop Protection. " the 7th edition Publication 1093, Research Institute, Agriculture Canada, Ottawa, Canada:Information Canada, 1982.229 described in, karathane is obtained by changing into dinitro-octyl phenyl crotonates with the crotonyl chloride reaction by the mixture of dinitro-octyl phenol usually.Also can make other ester on benzyl ring, to settle different esters by replace crotonyl chloride with suitable material.Isomer composition can use said method to be less than 0.1wt%2 by adopting to contain in reaction, dinitro-octyl phenol the mixture of 6-dinitro-4-(1-propyl group amyl group) phenol is made, and this dinitro-octyl phenol mixture is again by the two nitrated manufacturings that contain the octyl phenol that is less than 0.1wt%4-(1-propyl group amyl group) phenol.Can comprise that purification and partition method obtain high pure raw materials by reaching the necessary any known method of required purity.For example, the method that is contemplated to comprises and is used to make 2,4-dinitro-6-(1-methylheptyl) phenol or 2,4-dinitro-6-octyl phenol, 2, the any isomer of 6-dinitro-4-octyl phenol or the method for their mixture, be that suitable purification and/or separating method is less than 2 of 0.1wt%, the required high pure raw materials of 6-dinitro-4-(1-propyl group amyl group) phenol to obtain to contain then.Perhaps, can high-purity methylheptyl phenol is nitrated to make high-purity dinitro-octyl phenol.High-purity methylheptyl phenol can obtain by any known method of the phenol alkylation is purified then (for example distillation, chromatography and similar approach).

Other methods that are contemplated to comprise and are used to make 2,4-dinitro-6-octyl phenyl ester and 2, any known method of the isomer mixture of 6-dinitro-4-octyl phenyl ester is that suitable purification and/or separating method are to obtain isomer composition of the present invention then.Purification and isolation technics can be any technology well known by persons skilled in the art, comprise distillation, chromatography and similar approach.Other correlation technique of making this class isomer mixture also is included in United States Patent (USP) 2,810,767 and United States Patent (USP) 2,526,660 in those disclosed, they all are incorporated herein by this reference.

In one embodiment, adopt to have at least 98.5% purity and contain to be less than 0.1wt%2,2 of 6-dinitro-4-(1-propyl group amyl group) phenol, 4-dinitro-6-(1-methylheptyl) phenol prepares isomer composition of the present invention.

In addition, another embodiment of the present invention is to can be used for protective plant to avoid the invasion and attack of phytopathogenic organisms body and/or the Fungicidal composition for the treatment of the plant that is infected by the phytopathogenic organisms body, and it comprises

I) contain 2 of the 0.1wt% that is less than the isomer composition gross weight, the isomer composition of the dinitro-octyl phenyl ester of 6-dinitro-4-(1-propyl group amyl group) phenylester and

II) botany acceptable carrier material.

Isomer composition of the present invention has been imagined all carriers---and by these carriers, this isomer composition can be mixed with and be used for carrying and can serving as fungicide.Usually, preparation is used with the form of water slurry or emulsion.But this class suspension or emulsion are made by water-soluble, aqueous suspension or emulsification preparation, these preparations are (1) solids that contain this isomer composition, be commonly referred to as wetting powder or water-dispersible granule, or (2) liquid, be commonly referred to as emulsifiable concentrate, aqueous emulsion, suspension-concentrates and aqueous suspension particle.Be understood that easily any material that can add this isomer composition can use, if they not obvious interference isomer composition as the situation of the activity of antifungal agent under the performance required effectiveness.

Can compacting, the wetting powder of extrusion or following processing---by disperseing in water, atomized drying or fluidized bed agglomeration are to form water-dispersible granule then---comprises the immixture of isomer composition, inert carrier and surfactant.The concentration of isomer composition in wetting powder is generally the 10wt% to 90wt% of wetting powder gross weight, more preferably 25wt% to 75wt%.In the preparation of wetting powder, with isomer composition and any subdivided solids, for example prophyllite, talcum, chalk, gypsum, bleaching earth, bentonite, Attagel, starch, casein, glutelin, illiteracy unsticking soil, diatomite, purifying silicon hydrochlorate or analog mix.In this generic operation, usually carrier in small, broken bits and surfactant are mixed with isomer composition and grind.

The emulsifiable concentrate of isomer composition is included in the debita spissitudo in the suitable liquid, for example accounts for the isomer composition of the 5wt% to 75wt% of concentrate gross weight.Isomer composition is dissolved in inert carrier, and it is the mixture of the miscible solvent of water, water, water immiscible solvent or they and emulsifier.Concentrate can water and oily the dilution to form the Spray Mixing thing of oil-in-water emulsion form.Available organic solvent comprises aromatic compounds, and especially the high boiling point naphthalene of oil system and olefinic part for example weigh aromatic naphtha.Also can use other organic solvent, for example terpene solvent comprises rosin derivative, aliphatic ketone, for example cyclohexanone and complexing alcohol, for example cellosolvo.

Those skilled in the art determine easily can favourable use at this emulsifier, it comprises the mixture of various nonionics, anion, cation and amphoteric emulsifier or two or more emulsifier.The example that can be used for preparing the nonionic emulsifier of emulsifiable concentrate comprises polyalkylene glycol ether; The condensation product of alkyl and aryl phenol, aliphatic alcohol, aliphatic amine or fatty acid and oxirane, expoxy propane, for example ethoxylated alkylphenol; With carboxylate with polyalcohol or polyoxyalkylene solubilising.Cationic emulsifier comprises quaternary ammonium compound and fatty amine salt.Anion emulsifier comprises the oil-soluble salt (for example calcium) of alkarylsulphonic acid, the oil-soluble salt of sulphation polyglycol ether and the suitable salt of phosphorylation polyglycol ether.

The typical organic liquid that can be used for preparing the emulsifiable concentrate of this isomer composition is an aromatics liquid, for example dimethylbenzene, propylbenzene cut; Or mix naphthalene cut, mineral oil, replacement aromatics organic liquid, for example dioctyl phthalate; Kerosene; The dialkyl amide of various fatty acid, the dimethylformamide of particularly fatty glycol and glycol derivative, for example methyl ether of the n-butyl ether of diethylene glycol, ether or methyl ether and triethylene glycol and analog.Also can in the preparation of emulsifiable concentrate, use the mixture of two or more organic liquids.Preferred organic liquid comprises dimethylbenzene and propylbenzene cut, and wherein the propylbenzene cut most preferably.Usually in liquid preparation, use surface-active emulsifiers, and amount for emulsifier and isomer composition gross weight 0.1 to 20wt%.The preparation that comprises isomer composition of the present invention also can contain other compatible additive, for example other biocompatible compounds of using in miticide, insecticide, plant growth regulator, other fungicide and the agricultural.

Water slurry comprises the suspension that is dispersed in the isomer composition in the aqueous carrier with 5 to 50wt% the concentration that accounts for the water slurry gross weight.By isomer composition of the present invention or its solution are acutely sneaked in the carrier that is made of water and the surfactant that is selected from above-mentioned same type the preparation water slurry.Also can add other component, for example mineral salt and synthetic or natural gum are to improve the density and the viscosity of aqueous carrier.The example of water slurry comprises the suspension of oil droplet (EW ' s), solid (SC ' s) and capsule (CS ' s).

Isomer composition also can be used as granular preparation and uses, and it is particularly useful for being administered on the soil.Granular preparation contain usually account for the granular preparation gross weight 0.5 to 10wt% be dispersed in isomer composition in the atent solvent, atent solvent is complete or most of by the coarse grain inert material, and for example Attagel, bentonite, diatomite, clay or similar cheap material constitute.This class preparation is prepared as follows usually: isomer composition is diluted in suitable solvent, and it is administered on the particulate vector of the suitable particle size that is prefabricated into 0.5 to 3 millimeter.Suitable solvent is the basic therein or completely soluble solvent of compound.This class preparation also can be prepared as follows: dough (dough) or the pastel and the crushing and dry to obtain desired particle size of making carrier and isomer composition and solvent.

Isomer composition of the present invention also can be used as water-dispersible granule or the dry flow property preparation is used.Water-dispersible granule contains 10 to 70% the isomer composition that accounts for the total formulation weight amount usually.The common following acquisition of this class preparation: under the situation of adding dispersant and/or wetting agent, be mixed into and/or spray to isomer mixture on the carrier and mixes with water and be fit to the mixture that uses known granulating technique (for example disk granulation, extrusion, atomized drying, fluidized bed agglomeration and similar techniques) further to process to form.

By isomer mixture is closely mixed with suitable powdery agricultural carrier (for example kaolinton, broken volcanic rock and analog), can prepare the dust that contains isomer mixture.Dust can suitably contain 1 to 10wt% isomer composition or other fungicide that accounts for the dust gross weight.Dust also can be by preparing isomer composition as above the described similar mode of particle is impregnated on the carrier.

Preparation of the present invention can also contain cosurfactant so that isomer composition deposit better, wetting and be penetrated on target crop and the organism.These cosurfactants can be chosen wantonly as the component of preparation or as a jar mixed auxiliary agent (tank mix) and use.The amount of cosurfactant is generally 0.01 to 1.0 volume % of water sprinkling amount, preferred 0.05 to 0.5 volume %.Suitable cosurfactant includes, but are not limited to ethoxylated nonylphenol, ethoxylation is synthetic or the salt of natural alcohol, ester or sulfosuccinic acid or the mixture of ester, ethoxylation organosiloxane, ethoxylated fatty amine and surfactant and mineral or vegetable oil.

One embodiment of the invention relate to the fungicide Synergistic mixtures that comprises isomer composition of the present invention and at least a other fungicide; and be used for protective plant and avoid the invasion and attack of phytopathogenic organisms body or the purposes of the plant that treatment has been infected by the phytopathogenic organisms body, comprise soil, plant, plant part, leaf, flower and/or fruit are used this Synergistic mixtures.

Fungicidal compounds is common and one or more other fungicides are co-administered to control a greater variety of not desirable diseases.When uniting when using with other fungicide, the isomer composition that the present invention proposes can be prepared with other fungicide, with other fungicide in-tank mixing, or uses in regular turn with other fungicide.2-（）-；2-；8-；；Ampelomyces；quisqualis；；；；；；；- （BABS）；；；；；S （blasticidin-S）；；；；；；；；；；；；；；；；；；；；； （copper sulfate （tribasic））；；；；；；；；；；-（）；； （dichlorophen）；；；；；； （difenzoquat）；；；；；R- （diniconazole-M）；；；；；；；；；enestrobin；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；GY-81；；；；；；；；；；；；；；；；；；；；；；；；；；；；；； （metam）；；metam-potassium； （metam-sodium）；；；；；；；； （mildiomycin）；；；；；；； （）；；；；；；；；；；；；；；；；B；；；；；；；；；；；；；；；；；；；；；；；；silthiofam；；2-；；；；；SYP-Z071；SYP-048；；；；；；；；；；；；；；；；；；；；；；；；；；；Candida oleophila；Fusarium oxysporum；；Phlebiopsis gigantean；Streptomyces griseoviridis；； （RS）-N-（3；5-）-2-（）-；1；2-；1；3--1；1；3；3-；1--2；4-；1--2-；2-（2--2--1-）；2；3--5--1；4-dithi-ine1；1；4，4-tetraoxide；-2-；2-；；3-（4-）-5-；4-（2--1-）thiocyanateme；。 The acid of ammonia propyl-phosphine, anilazine, azithiram, polysulfide barium, Bayer 32394, benodanil, benquinox, bentaluron, benzamacril; Benzamacril-isobutyl, benzamorf, binapacryl, sulfuric acid two (methyl mercury), bis oxide (tributyltin), buthiobate, chromic acid cadmium sulfate calcium copper zinc, carbamorph, CECA, chlobenthiazone, Imugan, chlorfenazole, Si Lv quinoxaline, Climbazole, two (3-phenylo salicylic acid) copper, copper chromate zinc, cufraneb, cupric hydraziniumsulfate, cuprobam, ring bacterium amine, cypendazole, cyprofuram, decafentin, dichlone, sclex, diclobutrazol, dimethirimol, dinocton, the nitre monooctyl ester, dinoterbon, dipyrithione, Plondrel, dodicin, drazoxolon, EBP, ESBP, etaconazole, Ethisul, ethirim, fenaminosulf, fenapanil, plant the clothing ester, fluotrimazole, furcarbanil, furconazole, furconazole_cis, seed dressing amine, furan first thiophanate, glyodine, griseofulvin, halacrinate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, the front three methuroxam, the methyl mercury dicyandiamide, metsulfovax, milneb, the mucochloric anhydride, myclozolin, N-3,5-dichlorophenyl succinimide, N-3-nitrobenzophenone clothing health acid imide, natamycin, the N-ethylmercurio-4-toluol sulfonanilide, two (dimethyl dithiocarbamic acid) nickel, OCH, the dimethyl dithiocarbamic acid phenyl mercury, phenylmercuric nitrate, phosdiphen, prothiocarb; Hydrochloric acid prothiocarb, pyracarbolid, pyridinitril, chloromethane oxy picolinate, chlorine pyrrole root furan ether, quinacetol; Quinacetol sulfate, quinazamid, quinoline azoles, rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, Eradex, tioxymid, triamiphos, triarimol, triazbutil, trichlamide, bis methylarsine, XRD-563 and zarilamid, IK-1140, NC-224 and any combination thereof.

As disclosed in the list of references, have been found that the synergy with karathane before, list of references for example but is not limited to WO 02/067679, WO 2003103393, WO2004091298; FR 2445696, GB 2003032; US 6,346, and 535, US 6,528,536; US 6,515, and 000, US 6,207,691; US 3,456, and 055 and US 6,489,360.But, do not report synergy with composition of the present invention before.

Another aspect of the present invention relates to the Synergistic mixtures of isomer composition as herein described and at least a other fungicide, and it has improved toxicity surprisingly.Cooperative compositions of the present invention can comprise 1) with the synergistic any fungicide of karathane and 2) as isomer composition that this paper described in detail.Knownly show synergistic exemplary fungicide and include but not limited to that Qol fungicide such as methoxy acrylate comprise Fluoxastrobin and oximide acetic acid ester, comprise kresoxim-methyl; SBI fungicide: the I class, for example triazole comprises nitrile bacterium azoles; The II class, for example spiro ketal amine comprises volution bacterium amine; With the III class, for example hydroxyanilines comprises fenhexamid; Benzophenone is as metrafenone; Quinolines is as benzene oxygen quinoline; Dithiocar-bamate and derivative are as mancozeb; The dichloro nitrile is as tpn; Respiration inhibition succinate dehydrase carboxylic acid amides on the composite I I comprises Boscalid, and analog.

In a specific embodiments, the present invention is a Synergistic mixtures, comprises:

I) comprise the isomer composition of the isomer of dinitro-(octyl group) phenylester, wherein 2,6-dinitro-4-(1-propyl group amyl group) phenylester exist with the amount of the 0.1wt% that is less than the isomer composition gross weight and

Ii) QoI fungicide (be commonly referred to as strobilurins and relevant chemistry).

QoI fungicide comprises the compound of Fluoxastrobin, ether bacterium amine, fluoxastrobin, orysastrobin, ZEN 90160, pyraclostrobin, oxime bacterium ester, kresoxim-methyl, Famoxate, Fenamidone and so on.

In another embodiment, the present invention is a Synergistic mixtures, comprises:

I) comprise the isomer composition of the isomer of dinitro-(octyl group) phenylester, wherein 2,6-dinitro-4-(1-propyl group amyl group) phenylester exist with the amount of the 0.1wt% that is less than the isomer composition gross weight and

Ii) quinoline or cinnolines.

At U.S.5, reported quinoline and cinnolines in 145,843, quinoxyfen for example, this patent is incorporated herein by this reference.

In another embodiment, the present invention is a Synergistic mixtures, comprises:

I) comprise the isomer composition of the isomer of dinitro-(octyl group) phenylester, wherein 2,6-dinitro-4-(1-propyl group amyl group) phenylester exist with the amount of the 0.1wt% that is less than the isomer composition gross weight and

Ii) dithiocar-bamate.

Dithiocar-bamate comprises mancozeb (the coordination product of zinc ethylene bisdithiocarbamate and manganese), maneb (ethylidene dithiocarbamate manganese) and zineb (ethene bisdithiocarbamic zinc), ziram (zine dimethyldithiocarbamate), Propineb ([[(1-methyl isophthalic acid, 2-ethane two bases) two [carbamatothioato]] (2-)] zinc homopolymers), Carbatene (three [amine-[ethylenebis (dithiocar-bamate)]-zinc (II)-[tetrahydrochysene-1,2,4,7-idthiadia-zocine-3, the 8-dithione] polymer], ferbam (ferric dimethyl dithiocarbamate), the compound of metham-sodium (sodium N methyl dithiocarbamate) and thiuram (curing two (dimethyl thiocarbamoyl)) and so on.

In another embodiment, the present invention is a Synergistic mixtures, comprises:

I) comprise the isomer composition of the isomer of dinitro-(octyl group) phenylester, wherein 2,6-dinitro-4-(1-propyl group amyl group) phenylester exist with the amount of the 0.1wt% that is less than the isomer composition gross weight and

Ii) triazole.

Triazole comprises oxygen ring azoles, bitertanol, bromuconazole, chlorfenazole, Climbazole, cypendazole, Cyproconazole, diclobutrazol, Difenoconazole, alkene azoles alcohol, R-alkene azoles alcohol, fluorine ring azoles, etaconazole, Grandox fumigant, RH-7592, fluotrimazole, Fluquinconazole, Flusilazole, Flutriafol, furidazol, furconazole and furconazole_cis; Own azoles alcohol, press down the compound of mould azoles, glyoxalin, kind bacterium azoles, metconazole, nitrile bacterium azoles, pefurazoate, penconazole, probenazole, Prochloraz, propiconazole, prothioconazoles, quinoline azoles, rabenzazole, simeconazoles, Tebuconazole, tetraconazole, triazolone, Triadimenol, tricyclazole, Te Fuling, triticonazole and so on.

In another embodiment, the present invention is a Synergistic mixtures, comprises:

I) comprise the isomer composition of the isomer of dinitro-(octyl group) phenylester, wherein 2,6-dinitro-4-(1-propyl group amyl group) phenylester exist with the amount of the 0.1wt% that is less than the isomer composition gross weight and

Ii) volution bacterium amine.

Isomer mixture and the amount of other fungicide in Synergistic mixtures can become according to required purposes and the disease that will control.Usually, isomer composition to be to account for 0.1 of isomer composition and other fungicide gross weight, and more generally 1, common again 5, the most common 10, typically 15, more typical 20, typical case 30, the most typical 40 again, usual 45wt% is to common 99.9, and more generally 99, common again 95, the most common 90, typically 85, more typical 80, typical case 70 is the most typical 60 again, and the amount of usual 55wt% exists.

Usually, this at least a other fungicide to be to account for 99.9 of isomer composition and other fungicide gross weight, and more generally 99, common again 95, the most common 90, typically 85, more typical 80, typical case 70, the most typical 60 again, usual 55wt% to 0.1, more generally 1, common again 5, the most common 10, typically 15, more typical 20, typical case 30 is the most typical 40 again, and the amount of usual 45wt% exists.

In addition, isomer composition and Synergistic mixtures can combine with other agricultural chemicals compatible with this isomer composition at the medium of selecting to be used for using and that can not resist the activity of this isomer composition, comprise insecticide, nematocide, miticide, arthropodicides, bactericide or its combination.Correspondingly, in this class embodiment, use other composition pesticide as the additional toxic agent that is used for different pesticidal uses.When being used in combination with other agricultural chemicals, isomer composition or Synergistic mixtures can be prepared with other agricultural chemicals, use in regular turn with other agricultural chemicals in-tank mixing or with other agricultural chemicals.Typical insecticide includes but not limited to: antibiotic insecticide, as allosamidin and thuringiensin; The macrolide insecticides is as pleocidin; The avermectin insecticides is as Avermectin, doractin, emaricin, acetylamino evericin, ivermectin and Sai La rhzomorph; The milbemycin insecticide is as lepimectin, the close spit of fland of going out, milbemycin oxime and Moxidectin (moxidectin); Contain the arsenic insecticide, as calcium arsenate, Paris green, copper arsenate, lead arsenate, potassium arsenite and sodium arsenite; Vegetable insecticide is as anabasine, nimbin, d-limonene, nicotine, pyrethrin, cinerin, cinerin I, cinerin ii, jasmolin I, jasmolin ii, pyrethrin I, pyrethrin II, quassia medicine, rotenone, ryania and sabadilla; Carbamate insecticide is as bendiocarb and carbaryl; Carbamic acid benzofuranyl methyl esters insecticides is as Benfuracard micro, carbofuran, carbosulfan, decarbofuran and furathiocarb; Carbamic acid dimethyl ester insecticide is as dimitan, dimetilan, hyquincarb and Aphox; Oxime carbamate insecticide is as alanycarb, Aldicarb, aldoxycarb, butocarboxim, butanone sulfone prestige, Methomyl, nitrilacarb, oxamyl, tazimcarb, Talcord, the two prestige of sulphur and thiofanox; Phenylcarbamic acid methyl esters insecticide is as allyxycarb, aminocarb, metalkamate, butacarb, sok, cloethocarb, dicresyl, Elacron, EMPC, ethiofencarb, fenethacarb, Bassa, Mobucin, methiocarb, meta-tolyl-N-methylcarbamate (MTMC), mexacarbate, promacyl, Carbamult, unden, Landrin, XMC and Meobal; The dinitrophenol dinitrophenolate insecticide is as Dinitrocyclohexylphenol, dinoprop, dinosam and DNOC; Fluorine-containing insecticide is as hexafluorosilicic acid barium, ice crystal, sodium fluoride, sodium hexafluorisilicate and sulfluramid; The carbonamidine insecticide is as Amitraz, galecron, Carzol and formparanate; The fumigant insecticide, as acrylonitrile, carbon disulphide, carbon tetrachloride, chloroform, trichloronitromethane, paracide, 1,2-dichloropropane, Ethyl formate, ethylene dibromide, dichloroethane, oxirane, hydrogen cyanide, iodomethane, methyl bromide, methyl chloroform, carrene, naphthalene, phosphine, vikane and tetrachloroethanes; Inorganic insecticide is as borax, calcium polysulfide, copper oleate, calogreen, potassium rhodanide and sodium sulfocyanate; The chitin synthetic inhibitor is as two three flufenoxurons, Buprofezin, fluorine pyridine urea, fly eradication amine, diflubenzuron, flucycloxuron, flufenoxuron, fluorine bell urea, Acarus tritici urea, Rimon, noviflumuron, penfluron, fluorobenzene urea with kill the bell urea; Intend juvenile hormone, as epofenonane, fenoxycarb, hydroprene, kinoprene, methoprene, pyrrole propyl ether and triprene; Juvenile hormone is as juvenile hormone I, juvenile hormone II and juvenile hormone III; Ecdysone agonist is as ring worm hydrazides, chlorine worm hydrazides, methoxyfenozide and worm hydrazides; Moulting hormone is as α-ecdysone and ecdysterone; The inhibitor of casting off a skin is as diofenolan; Precocene is as precocene I, precocene II and precocene III; Non-classified insect growth regulator, IGR is as Dicyclanil; The similar thing insecticide of nereistoxin is as bensultap, cartap, thiocyclam and thiosultap; Nicotinic insecticide is as flonicamid; The nitroguanidine insecticide is as thiophene worm amine, MTI-446, Imidacloprid and thiophene worm piperazine; The Nitromethylene insecticide is as Nitenpyram and nithiazine; Pyridine radicals methylamine insecticide is as Acetamiprid, Imidacloprid, Nitenpyram and thiophene worm quinoline; Organochlorine insecticide is as bromo DDT, toxaphene, DDT, pp '-DDT, ethyl-DDD, HCH, γ-HCH, lindane, methoxychlor, pentachlorophenol and TDE; Cyclodiene is as aldrin, bromocyclne, chlorbicyclen, Niran, CD, dieldrin, neutraphylline, 5a,6,9,9a-hexahydro-6,9-methano-2,4, endrin, HEOD, heptachlor, HHDN, Telodrin, isodrin, kelevan and mirex; Organic phosphate insecticide is as bromfenvinfos, chlorfenviphos, crotoxyphos, dichlorvos, Carbicron, dimethylvinphos, fospirate, heptenophos, methocrotophos, Menite, nuvacron, 2-dichloroethylk dimethyl phosphate, naftalofos, phosphamidon, Kayaphos, TEPP and Ravap; Organic sulfur substituted phosphate insecticides is as salithion, fosmethilan and phenthoate dimephenthoate cidial; Aliphatic series organic sulfur substituted phosphate insecticides is as Acethion, Citram, cadusafos, chlorethoxyfos, chlormephos, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-S, demeton-methyl, O-demeton-methyl, S-demeton-methyl, metilomerkaptofosoksid, disulfoton, ethion, phonamiphos, IPSP, isothioate, malathion, methacrifos, oxydemeton_methyl, oxydeprofos, Disystom-s, thimet, sulfotep, terbufos and thiometon; The organic phosphorothioate pesticides of aliphatic series acid amides is as amidithion, cyanthoate, Rogor, ethoate methyl, formothion, Afos, omethoate, prothoate, sophamide and vamidothion; The organic phosphorothioate pesticides of oxime is as chlorophoxim, phoxim and phoxiom_methyl; Heterocyclic organic sulfide substituted phosphate insecticide is as azamethiphos, Resistox, Dithion, dioxathion, endothion, menazon, morphothion, Phosalone, pyraclofos, pyridaphethione and quinothion; The organic phosphorothioate pesticides of benzothiopyran derivative is as dithicrofos and thicrofos; The organic phosphorothioate pesticides of phentriazine is as azinphos ethyl and azinphos-methyl; The organic phosphorothioate pesticides of iso-indoles is as dialifos and phosmet; The organic phosphorothioate pesticides of isoxazole is as oxazole phosphorus and zolaprofos; The organic phosphorothioate pesticides of pyrazolopyrimidine is as chlorprazophos and pyrazophos; The organic phosphorothioate pesticides of pyridine is as chlopyrifos and chlorpyrifos-methyl; The organic phosphorothioate pesticides of pyrimidine is as butathiofos, diazinon, etrimfos, lirimfos, Diothyl, pirimiphos-methyl, primidophos, Pyrimitate and fourth Pyrimitate (tebupirimfos); The organic phosphorothioate pesticides of quinoxaline is as quinalphos and methyl quinalphos; The organic phosphorothioate pesticides of thiadiazoles is as athidathion, lythidathion, methidathion and prothidathion; The organic phosphorothioate pesticides of triazole is as isazofos and Hostathion; The organic phosphorothioate pesticides of phenyl kills sulphur phosphorus, iodfenphos, mesulfenfos, parathion, parathion-methyl, phenkapton, nichlorfos, Profenofos, Toyodan, sulprofos, Swebate, trichlormetaphos-3 and the trichlorine third oxygen phosphorus as Alamos, bromophos, Rilariol, trithion, Actellic, cyanophos, cythioate, Di-captan, dichlofenthion, etaphos, famphur, ronnel, sumithion, fensulfothion, fenthion, ethyl fenthion, speed; The phosphonate ester insecticide is as butyl ester phosphine and chlorophos; Thiophosphonate (phosphonothioate) insecticide is as mecarphon; Phenyl ethylphosphonothioate insecticide is as fonofos and trichloronat; Phenyl phenylphosphonothioate insecticide is as cyanofenphos, EPN and leptophos; The phosphoramidate insecticide is as Ruelene, fenamiphos, fosthietan, mephosfolan, phosfolan and pirimetaphos; The phosphoramidothioate insecticide is as orthene, isocarbophos, isofenphos, acephatemet and propetamphos; Idol phosphorus diamides insecticide is as dimefox, mazidox, mipafox and schradane; The oxadiazine insecticide is as indenes worm prestige; The phthalimide insecticide is as dialifos, phosmet and tetramethrin; The pyrazoles insecticide is as acetoprole, ethiprole, fluorine worm nitrile, pyrafluprole, pyriprolc, tebufenpyrad, azoles insect amide and vaniliprole; Pyrethroid insectide, as acrinathrin, allethrin, bioallethrin, barthrin, Biphenthrin, bioethanomethrin, cyclethrin, cycloprothrin, cyfloxylate, β-cyfloxylate, cyhalothrin, gamma-cyhalothrin, λ-cyhalothrin, cypermethrin, α-cypermethrin, β-cypermethrin, θ-cypermethrin, ζ-cypermethrin, cyphenothrin, decis, the tetrafluoro methothrin, dimethrin, dextrorotation eneyne chrysanthemum, fenfluthrin, fenpirithrin, fenpropathrin, sumicidin, cis fenvalerate,, flucythrinate, fluorine amine sumicidin, taufluvalinate, furethrin, alkynes miaow chrysanthemum ester, metofluthrin, permethrin, biopermethrin, transpermethrin, phenothrin, prallethrin, profluthrin, pyresmethrin, resmethrin, bioresmethrin, cis resmethrin (cismethrin), tefluthrin, terallethrin, tetramethrin, tralomethrin and transfluthrin; Pyrethroid ether insecticide is as ether chrysanthemum ester, trifluoro chrysanthemum ester, halfenprox, protrifenbute and silafluofene; The pyrimidinediamine insecticide is as flufenerim and pyrimidifen; Azole pesticides is as chlorfenapyr; The tetronic acid insecticide is as season ketone first mite ester, spiral shell mite ester and spirotetramet; The thiocarbamide insecticide is as the butyl ether urea; The urea insecticide is as flucofuron and sulcofuron; And non-classified insecticide, as closantel, Crotamiton, EXD, fenazaflor, fenoxacrim, Flubendiamide, hydramethylnon, Isoprothiolane, special mite nitrile, metaflumizone, metoxadiazone, nifluridide, pyridaben, pyridalyl, rafoxanide, triarathene and triaguron, and their any combination.

Isomer composition or by its Synergistic mixtures of making, and the amount of other insecticide can become according to required purposes and the disease that will control in the insecticide mixtures.Usually, isomer composition of the present invention or Synergistic mixtures to be to account for 0.1 of isomer composition or Synergistic mixtures and other insecticidal total weight, and more generally 1, common again 5, the most common 10, typically 15, more typical 20, typical case 30, the most typical 40 again, usual 45wt% is to common 99.9, and more generally 99, common again 95, the most common 90, typically 85, more typical 80, typical case 70 is the most typical 60 again, and the amount of usual 55wt% exists.

Usually, when using, other insecticide to be to account for 99.9 of isomer composition or Synergistic mixtures and other fungicide gross weight, and more generally 99, common again 95, the most common 90, typically 85, more typical 80, typical case 70, the most typical 60 again, usual 55% to 0.1, more generally 1, common again 5, the most common 10, typically 15, more typical 20, typical case 30 is the most typical 40 again, and the amount of usual 45wt% exists.

Another embodiment of the present invention is the method for control and prevention fungal attack.This method comprises to be selected or to using this isomer composition of (for example cereal or mattae being used) antifungal effective dose or by its Synergistic fungicidal mixture of making in the position that needs prevention infection plant, leaf, fungi.Isomer composition of the present invention or Synergistic mixtures are fit to not show teratogenesis or retinopathy simultaneously with each plant species of mycocidal horizontal stretcher.This isomer composition or Synergistic mixtures can use with protective agent, therapeutic agent and/or eradicant mode.

Have been found that this isomer composition or have significant fungicidal action, particularly for agricultural is used, and be used for crops and horticultural crop especially effectively by the Synergistic mixtures that it is made.Especially, isomer composition or by the various not desirable fungi of the effective control infection useful plant of its Synergistic mixtures of making crop, for example powdery mildew in a kind of fruit, such as apple, pear, etc., drupe, cedra fruits, soft fruit, liane, cucurbitaceous plant, decorative plant, tobacco, lupulus and some vegetables and the American gooseberrymildew in gooseberry and the currant.

Isomer composition or depend on required specific function, the fungal species that will control, its vegetative stage and the plant part or the other products that will contact with isomer composition by the definite amount of application of its Synergistic mixtures of making.

Isomer composition and be used for plant effectively to suppress disease and the acceptable amount of botany by its Synergistic mixtures of making.Term " suppress disease and the acceptable amount of botany " is meant the amount of killing or suppressing the plant disease that needs control but can obviously not cause the reactive compound of dunsiekte.This amount is generally 1 to 1000ppm (per 1,000,000 parts umber), and wherein 10 to 500ppm is preferred.The definite concentration of required isomer composition or consonance mixture becomes with type, application process, specified plant species, weather conditions and the similar factor of the mycosis that will control, used preparation.Suitable rate of application is generally 0.10 to 4 pound of/acre (0.01 to 0.45 gram/square metre g/m ²).

Also find surprisingly, isomer composition of the present invention and can have the acaracidal effect of reduction by its Synergistic mixtures of making, this helps keeping useful mite class.

Embodiment

Provide the following example with further elaboration the present invention, but be not regarded as restriction.As disclosed herein, all degree centigrade to provide, except the yield percentage as molar percentage, unless indicate separately, all percentages all are percentage by weights to all temperature.

2, the preparation of 4-dinitro-6-(1-methylheptyl) phenol

2-(1-methylheptyl) phenol (206.3 grams, 98.5% calibrating) is stirred and is heated to 60 ℃.Through dropwise adding the concentrated sulfuric acid (315.2 gram) in 1 hour, temperature is remained on 65-72 ℃.

In the container that separates, stir 35% aqueous solution (553.2 gram) of sodium nitrate and be heated to 70 ℃.Dropwise added sulfonated phenol reactant mixture through 3 hours in sodium nitrate solution then, temperature remains on 78 ℃.Mixture was stirred 1 hour at 78 ℃, be cooled to 35 ℃ then.Make the mixture sedimentation, and separate water layer.Organic layer with the water washing twice that contains small amount of methanol, is restrained as 2 of orange oil 4-dinitro-6-(1-methylheptyl) phenol product 75 ℃ of dryings to stay 252 then under vacuum.

Embodiment 1

2, the preparation of 4-dinitro-6-(1-methylheptyl) phenylcrotonic acid ester

With 2,4-dinitro-6-(1-methylheptyl) phenol (98.5% purity) (252 gram) is dissolved in heptane (225 gram).Through dropwise adding benzyl dimethylamine (140.8 gram) in 40 minutes, keep the temperature of mixture to be lower than 40 ℃, and mixture was stirred 15 minutes.Through dropwise adding crotonyl chloride (139 gram) in 30 minutes, keep temperature to be lower than 60 ℃ then, and mixture stirred 30 minutes and be cooled at 60 ℃ be lower than 50 ℃.Wash mixture with water twice, be cooled to 20 ℃ then.With mixture, water and the methyl alcohol of mixture, wash with watery hydrochloric acid at last with methyl alcohol and sodium hydrate aqueous solution.With organic layer 70 ℃ under vacuum stripping to remove heptane and to stay, 4-dinitro-6-(1-methylheptyl) phenylcrotonic acid ester (282.6 gram) as 2 of orange/brown oil.

For analysis, use following method to utilize normal phase liquid chromatography:

The HPLC condition

40 ℃ of column temperature

Flow volume 1 ml/min

Wavelength 235 nanometers

Volume injected 10 microlitres

250 * 4.6 millimeters on HPLC Milton Roy post is filled 7 μ LICHROSORB SI60 (Merck)

Detect: detector Milton Roy SM 4000

Integrating system Shimadzu Mega2.

Sample solution:

With 0.45-0.50 gram 2,4-dinitro-6-(1-methylheptyl) phenylcrotonic acid ester and the 0.09-0.11 gram acetophenone phial of packing into.Add hexane (20 milliliters), phial is added a cover, and sonication 2 minutes.Solution (1 milliliter) is transferred in the phial, and added 20 milliliters of hexanes, phial is added a cover and shaken with perparation of specimen solution.

Standard liquid:

0.48-0.52 is restrained Karathane ^TMUniversal standard product and 0.09-0.11 gram acetophenone (I.S.) phial of packing into.Add hexane (20 milliliters), phial is added a cover, and sonication 2 minutes.Solution (1 milliliter) is transferred in the phial, and added 20 milliliters of hexanes, phial is added a cover and shaken with manufacturer's standard solution.

In HPLC, inject 10 microlitre standard liquids to obtain chromatogram.Similarly, in HPLC, inject 10 microlitre sample solutions to obtain chromatogram.The comparison colours spectrogram.

For calculated response factor and component content, the peak is grouped into:

Interior mark (I.S.)=acetophenone

Universal standard product=Karathane ^TM

Sample=be used to the evaluate and test sample of content of isomer

Group 1:2, the area summation of 4-dinitro-6-octyl phenol

Group 2:2, the area summation of 4-dinitro-6-octyl phenyl crotonates

Group 3:2, the area summation of 6-dinitro-4-octyl phenyl crotonates

Calculate the RF factor of each group.

Use suitable RF factor to calculate the percentage composition of each group.For group 3, if not relevant with group 3 peaks, content is 0.Then by the relative peak in relatively should group, the isomer percentage of mensuration group 2, promptly 2,4-dinitro-6-(1-methylheptyl) phenylcrotonic acid ester 98.5% and 2,4-dinitro-6-(1-ethylhexyl) phenylcrotonic acid ester 1.2%.

Use the product analysis of positive, liquid chromatography as follows:

2,4-dinitro-6-(1-methylheptyl) phenylcrotonic acid ester: 98.5%

2,4-dinitro-6-(1-ethylhexyl) phenylcrotonic acid ester: 1.2%

2,4-dinitro-6-(1-methylheptyl) phenol: 0.3%

Embodiment 2 and 3

The additional isomer analysis of the sample of making according to embodiment 1

In another is analyzed, use active component and the impurity of positive HPLC with two other sample of making according to embodiment 1 of the following listed accurate analysis of interior calibration.

Normal phase high performance liquid chromatography (HPLC)

The preparation of acetophenone inner mark solution:

About 1 gram acetophenone is weighed into 500 ml volumes measuring bottles, and record weight is to being accurate to 0.1 milligram, and the hexane of packing in flask is to volume.

The preparation of calibration solution:

By be weighed into about 50 milligram 2 in phial, 4-dinitro-6-(1-methylheptyl) phenylcrotonic acid ester (DNOP) standard items prepare calibration sample #1 in duplicate, and use pipette to add 20mL acetophenone inner mark solution.1 ml aliquots sample is added in 5 milliliters of hexanes.

By in phial, being weighed into 2,6-dinitro-4-(1-propyl group amyl group) phenylcrotonic acid ester, 2,4-dinitro-6-(1-propyl group amyl group) phenylcrotonic acid ester (propyl group amyl group isomer), 2,4-dinitro-6-(1-ethylhexyl) crotonates (ethylhexyl isomer) and 2, each about 15 milligrams and add 10 milliliters of hexanes in 4-dinitro-6-(1-methylheptyl) phenol, preparation calibration solution #2.1 ml aliquots sample of gained solution is added in the phial that contains 20 milliliters of acetophenone inner mark solutions.1 ml aliquots sample of this solution is added in 5 milliliters of hexanes.

By in phial, being weighed into about 10 milligrams of karathane (12 kinds of mixture of isomers, purity 95.3%) and using pipette to add 20 milliliters of acetophenone inner mark solutions, preparation calibration solution #3.1 ml aliquots sample of this solution is added in 5 milliliters of hexanes.

Calibration procedure:

Use following condition, before the sample, among and injection calibration solution afterwards:

Post: Lichrosorb SI-60 5 μ m; 250 millimeters * 4.6 millimeters

Autosampler: Alcott728

Pump: Varian9012

Injection: 10 microlitres

Detector: Applied Biosystems757

Column temperature: 30 ℃

Column oven: Phenomenex

Data system: PE/Nelson Access*Chrom

Mobile phase: 720 milliliters of hexane/280 milliliter carrene/1 milliliter of polar compounds (85 milliliters of carrene/10 milliliter acetate/5 milliliters of ethanol)

Retention time roughly:

2,4-dinitro-6-(1-propyl group amyl group) phenol 5.79 minutes

2,4-dinitro-6-(1-ethylhexyl) phenol 5.90 minutes

2,4-dinitro-6-(1-methyl hexyl) phenol 6.13 minutes

Unknown peak

2,6-dinitro-4-(1-propyl group amyl group) phenylcrotonic acid ester cis 7.49 minutes

2,6-dinitro-4-(1-ethylhexyl) phenylcrotonic acid ester cis 7.92 minutes

2,6-dinitro-4-(1-methyl hexyl) phenylcrotonic acid ester cis 8.15 minutes

2, trans 9.70 minutes of 6-dinitro-4-(1-propyl group amyl group) phenylcrotonic acid ester

2, trans 10.40 minutes of 6-dinitro-4-(1-ethylhexyl) phenylcrotonic acid ester

2, trans 10.89 minutes of 6-dinitro-4-(1-methyl hexyl) phenylcrotonic acid ester

2,4-dinitro-6-(1-propyl group amyl group) phenylcrotonic acid ester cis 11.30 minutes

2,4-dinitro-6-(1-ethylhexyl) phenylcrotonic acid ester cis 11.53 minutes

2,4-dinitro-6-(1-methyl hexyl) phenylcrotonic acid ester cis 12.04 minutes

2, trans 15.50 minutes of 4-dinitro-6-(1-propyl group amyl group) phenylcrotonic acid ester

2, trans 16.00 minutes of 4-dinitro-6-(1-ethylhexyl) phenylcrotonic acid ester

2, trans 16.98 minutes of 4-dinitro-6-(1-methyl hexyl) phenylcrotonic acid ester

Acetophenone (ISTD) 31.82 minutes

Calculate the response factor of each as mentioned above.Use the mean value of response factor to calibrate.

The preparation of sample for analysis:

Embodiment 2 that will make according to embodiment 1 and duplicate material 3, that record is accurate to 0.1 milligram about 50 milligrams (± 10 milligrams) phial separately of packing into.In each phial, use pipette to add 20 milliliters of acetophenone inner mark solutions.1 ml aliquots sample of gained solution is added in 5 milliliters of hexanes.Use the condition analysis sample identical with standard items.The percentage by weight analysis of embodiment 2 and # is listed in the table 1.

Table 1

Component	Embodiment 2 (wt%)	Embodiment 3 (wt%)
			2,4-dinitro-6-(1-methylheptyl) phenylcrotonic acid ester	97.9	98.0
2,4-dinitro-6-(1-propyl group amyl group) phenol	ND	ND
			2,4-dinitro-6-(1-ethylhexyl) phenol	ND	ND
2,4-dinitro-6-(1-methylheptyl) phenol	0.23	0.35
			The unknown in 6.4 minutes	0.02	0.03
2,6-dinitro-4-(1-propyl group amyl group) phenylcrotonic acid ester cis	ND	ND
			2,6-dinitro-4-(1-ethylhexyl) phenylcrotonic acid ester cis	ND	ND
2,6-dinitro-4-(1-methylheptyl) phenylcrotonic acid ester cis	ND	ND
			2,6-dinitro-4-(1-propyl group amyl group) phenylcrotonic acid ester is trans	0.07	0.03
2,6-dinitro-4-(1-ethylhexyl) phenylcrotonic acid ester is trans	0.03	0.007
			2,6-dinitro-4-(1-methylheptyl) phenylcrotonic acid ester is trans	ND	ND
2,4-dinitro-6-(1-propyl group amyl group) phenylcrotonic acid ester cis	ND	ND
			2,4-dinitro-6-(1-ethylhexyl) phenylcrotonic acid ester cis	ND	ND
2,4-dinitro-6-(1-propyl group amyl group) phenylcrotonic acid ester is trans	ND	ND
			2,4-dinitro-6-(1-ethylhexyl) phenylcrotonic acid ester trans (LC)	1.4	1.3
Other	1.45	1.283
			Mass balance (wt%)	101.1	101.0

Do not detect (ND)

Detection limit (LOD)=0.02%

Test on plant:

The antifungal of the composition of evaluation and test embodiment 1 is renderd a service on 9 kinds of diseases that phytopathogenic fungi (Table II) causes in the greenhouse.Used plant cultivation kind is Ugni Blanc (grape), Bovowinka (Malus spectabilis), HH88 (beet), M-9 (rice) and Yuma (wheat) in this research.Broad leaved plant and paddy are grown in no native peat base potting mixtures (Metromix), and wheat is grown in 50/50 mixture of mineral soil and Metromix.Wheat 20 ℃ the growth and all other plants 25 ℃ of growths.The apple seed is immersed in the water, and the short time cultivates in the 200ppm of benomyl solution, washes with water again.The seed that will wet stores at 7 ℃ (45 ) in airtight container, washes with water weekly once and exposes 3 millimeters (about 30 days) until radicle.Then with seeds cultivation, and usually after 3 weeks, 4-6 leaf seedling is ready for inoculation.

High power capacity is used research

Use the high-volume spraying application method with the composition of embodiment 1 with 100,50,25 and 12.5ppm be administered on the seedling, composition prepare in water and carried out serial dilution, then by adding aqueous solution raising volume.Spray plant to runoff with 15 ml solns having the pressure that the rotating disk sprayer of two relative 4JAUPM air atomizer spray nozzles (Spraying Systems) goes up with 138kPa.Spray solution volume on the per hectare is about 400 liters/hectare.1 day (protective agent test in 1 day) for plant inoculation pathogene, cultivated 24 hours with 100% relative moisture in the dew chamber behind the composition of using embodiment 1, transferred to then in the environment that is fit to the disease expression to reach duration of test runs.For the combination of each pathogene/composition, spray three and duplicate jar.The disease generation percentage of 7-14 days evaluation and test plants after infection, and measure average disease control percentage.The results are shown among Table III and the IV.

Pathogene breeding and host's inoculation

Behind the composition of using embodiment 1,4-5 1 day (protective agent test), for embodiment 6-7 using preceding 2 days (therapeutic test), for plant inoculates various pathogene.For all wheat tests, use composition in vegetative period 1.2, this moment, second leaf was flared to 1/2 (seed was watered back 12 days for the first time) of its final size.The vegetative period of other plant species and the breeding relevant and to infect the information of program as follows when using with each pathogene about composition.

Table II. used phytopathogen and host plant in the greenhouse evaluation and test

Host plant	The disease title	The pathogenic organisms body	The Bayer coding
				Wheat	Powdery mildew	Erysiphe graminis f.sp tritici	ERYSGT
Wheat	Leaf rust	Puccinia triticinia	PUCCRT
				Apple	Shot hole	Apple black star bacteria	VENTIN
Grape	Powdery mildew	The grape powdery mildew bacterium	UNCINE
				Cucumber	Powdery mildew	Two spore powdery mildews	ERYSCI

ERYSGT: wheat seedling infects the fresh spore from obligate pathogen.

ERYSGT acutely shakes the wheat plant that infects thereon.The plant that has sprinkled the ERYSGT spore 22 ℃ of cultivations in the greenhouse is completed into (common 7 days) until the disease symptom.

ERYSCI: cucumber seedling infects the fresh spore from obligate pathogen.

ERYSCI sprays spore suspension thereon.Spray plant until runoff.In the greenhouse, cultivate seedling and be completed into (common 10 days) until the disease symptom at 22 ℃.

PUCCRT: collect the spore of obligate pathogen PUCCRT and be stored in 4 ℃ from infection plant with vacuum plant.The fresh spore of about 0.1 gram (storing below 30 days at 4 ℃) is mixed with several Tween 20.Thick spore paste is diluted with water to 100 milliliters, and is sprayed on the wheat seed seedling until runoff.The plant that infects PUCCRT preserves in 20 ℃ of dew chambers and spends the night, and transfers to then in 20 ℃ of growth rooms, forms symptom gradually at this in 8-9 days.

PYRIOR: under white light, on the PDA of 24 ℃ of growths, made inoculum 10-12 days.In water, scrape mycelium, in blender, shred, and see through several layers of garrha (cheesecloth) expression.Regulate spore concentration to 50,000/ milliliter, add the three big Tween 20 of dripping for per 100 ml volumes then.Spray 12 the biggest paddy (open second leaf fully) with aqueous spore suspension and, in 24 ℃ of dew chambers, placed 24 hours, transfer to then in 24 ℃ of growth rooms and be completed into (7 days) until the disease symptom until runoff.

VENTIN: use the leaf that infects by flushing in running water frozen soln and the conidium of collecting (before maximum 6 months) in advance inoculates with 400,000 spores/ml concn then.Spray apple seedling until runoff with the VENTIN inoculum, in 20 ℃ of dew chambers, cultivated 24 hours, transfer to then in 18 ℃ of growth rooms until forming disease symptom (8 days) gradually.Evaluation and test disease seriousness on two minimus leaves in when inoculation only is because older leaf highly tolerates for the infection of this pathogene.

UNCINE: keep two complete fresh spores that open the big mattaes infection of six weeks of leaf from this obligate pathogen by shaking the plant that infects thereon, make to be trimmed to.With the plant that sprinkles the UNCINE spore in the greenhouse 22 ℃ of cultivations until forming disease symptom (common 10 days).

Table III. the high power capacity test of in high power capacity screening (screen), carrying out with three plant species pathomycetes

Pathogene	Ratio (ppm)	Disease control percentage
			ERYSCI	200	**
PUCCRT	200	***
			PYRIOR	200	***

^*Be the disease control of 0-49%

^*Be the disease control of 50-79%

^{* *}Be the disease control of 80-100%

Table IV. disease control percentage

						Material	Ratio ppm	ERYSGT	PUCCRT	UNCINE	VENTIN 10
Embodiment 1	100	***	***	***	***
						Embodiment 1	50	***	**	***	**
Embodiment 1	25	NT	*	***	**
						Embodiment 1	12.5	NT	*	***	**15
Fluoxastrobin	25	NT	NT	***	NT
						Fenarimol	25	NT	NT	NT	***
Be untreated	*	*	*	*	*20

^*Be the disease control of 0-49%

^*Be the disease control of 50-79%

^{* *}Be the disease control of 80-100%

NT does not test.

Collaborative embodiment

Synergistic activity on the pathogenic disease of the plant that is combined in crop of embodiment 1 and appointment fungicide.As long as greater than the summation of each component effect, just there is synergy in the effect of active component combination.

For given active component combination, expect that active E follows so-called COLBY formula and can followingly calculate (COLBY, S.R. " Calculating synergistic and antagonisticresponses of herbicide combination " .Weeds rolls up 15, the 20-22 pages or leaves; 1967).

When C=uses p ppm active component, the effect percentage of active component I

When Y=uses q ppm active component, the effect percentage of active component II

According to Colby, when using p+q ppm active component, the expection summation action of active component I+II is

E＝X+Y-(X*Y)/100

If observed practical function (O) is greater than predictive role (E), the effect of this combination is that superfacies adds so, promptly has synergy.

Perhaps, also can use so-called WADLEY method (EPPO-Bulletin16,1986,651-657) measure synergy by dose response curve.

Embodiment 4

The synergistic combination of embodiment 1 and mancozeb

Composition is to the protective agent activity of wheat leaf rust (PUCCRT)

Protective agent greenhouse research in 1 day

Table V

	Blending ratio (ppm)	Embodiment 1 (ppm)	Observed control %	Expection control %	SF Colby
						Embodiment 1	Do not have	75.00	68.63
Embodiment 1	Do not have	50.00	33.33
						Embodiment 1	Do not have	25.00	11.76
Embodiment 1	Do not have	12.50	0.00
						Mancozeb	200.00	Do not have	88.24
Mancozeb	100.00	Do not have	58.82
						Mancozeb	50.00	Do not have	5.88
Mancozeb	25.00	Do not have	0.00
						Mancozeb	100.00	12.50	82.35	58.82	1.40
Mancozeb	50.00	12.50	52.94	5.88	9.00
						Mancozeb	25.00	12.50	25.49	0.00	25.49
Mancozeb	100.00	25.00	86.27	63.67	1.36
						Mancozeb	50.00	25.00	80.39	16.96	4.74
Mancozeb	25.00	25.00	33.33	11.76	2.83
						Mancozeb	100.00	50.00	97.65	72.55	1.35
Mancozeb	50.00	50.00	86.67	37.25	2.33
						Mancozeb	25.00	50.00	76.47	33.33	2.29
Mancozeb	100.00	75.00	97.25	87.08	1.12
						Mancozeb	50.00	75.00	94.12	70.47	1.34
Mancozeb	25.00	75.00	76.47	68.63	1.11

The effectiveness of the combination of the mancozeb of 8: 1 to 3: 1 ratios and embodiment 1 demonstrates synergy.

The synergistic combination of embodiment 5 embodiment 1 and nitrile bacterium azoles

Composition is to the protective agent activity of wheat leaf rust (PUCCRT)

Protective agent greenhouse research in 1 day

Table VI

	Blending ratio (ppm)	Embodiment 1 (ppm)	Observed control %	Expection control %	SF Colby
						Embodiment 1	Do not have	75.00	68.63
Embodiment 1	Do not have	50.00	33.33
						Embodiment 1	Do not have	25.00	11.76
Embodiment 1	Do not have	12.50	0.00
						Nitrile bacterium azoles	18.75	Do not have	84.31
Nitrile bacterium azoles	12.50	Do not have	74.51
						Nitrile bacterium azoles	6.25	Do not have	27.45
Nitrile bacterium azoles	3.13	Do not have	0.00
						Nitrile bacterium azoles	12.50	12.50	72.55	74.51	0.97
Nitrile bacterium azoles	6.25	12.50	56.86	27.45	2.07
						Nitrile bacterium azoles	3.13	12.50	11.76	0.00	11.76
Nitrile bacterium azoles	12.50	25.00	84.31	77.51	1.09
						Nitrile bacterium azoles	6.25	25.00	70.59	35.99	1.96
Nitrile bacterium azoles	3.13	25.00	45.10	11.76	3.83
						Nitrile bacterium azoles	12.50	50.00	98.04	83.01	1.18
Nitrile bacterium azoles	6.25	50.00	96.47	51.63	1.87
						Nitrile bacterium azoles	3.13	50.00	92.94	33.33	2.79
Nitrile bacterium azoles	6.25	75.00	92.94	77.24	1.20
						Nitrile bacterium azoles	3.13	75.00	84.31	68.63	1.23

The sterol biosynthesis is suppressed; The C14-demethylase suppresses the synergistic activity of (SBI classification I), example nitrile bacterium azoles.The effectiveness of the nitrile bacterium azoles of 1: 24 to 1: 4 ratio and the combination of embodiment 1 demonstrates synergy.

The synergistic combination of embodiment 6 embodiment 1 and volution bacterium amine

Composition is to the therapeutic activity of wheat powdery mildew (ERYSGT)

Treatment greenhouse research in 2 days

Table VII

	Blending ratio (ppm)	Embodiment 1 (ppm)	Observed control %	Expection control %	SF Colby
						Embodiment 1	Do not have	75.00	23.00
Volution bacterium amine	12.50	Do not have	15.00
						Volution bacterium amine	12.50	75.00	65.00	34.75	1.88

The affirmation of the synergistic activity that the sterol biosynthesis is suppressed; D14 reductase and D8 isomerase in sterol biosynthesis (SBI classification II), example volution bacterium amine.The effectiveness of the volution bacterium amine of 1: 4 ratio and the combination of embodiment 1 demonstrates synergistic activity.

The synergistic combination of embodiment 7 embodiment 1 and Fluoxastrobin

Composition is to the therapeutic activity of wheat powdery mildew (ERYSGT)

Treatment greenhouse research in 2 days

Table VIII

	Blending ratio (ppm)	Embodiment 1 (ppm)	Observed control %	Expection control %	SF Colby
						Embodiment 1	Do not have	75.00	23.00
Fluoxastrobin	6.25	Do not have	13.00
						Fluoxastrobin	12.50	Do not have	15.00
Fluoxastrobin	25	Do not have	15
						Fluoxastrobin	75	Do not have	52
Fluoxastrobin	100	Do not have	79
						Fluoxastrobin	6.25	75	42	33.41	1.27
Fluoxastrobin	12.50	75	54	34.91	1.54
						Fluoxastrobin	25	75	73	34.91	2.09
Fluoxastrobin	75	75	97	63.02	1.54
						Fluoxastrobin	100	75	98	83.77	1.17

The synergistic activity of fungicide in composite I II that serves as respiration inhibitor; Cytochrome b cl is in the Qo site (QoI fungicide); The example Fluoxastrobin.The effectiveness of the combination of the Fluoxastrobin of 1: 12 to 4: 3 ratio and embodiment 1 demonstrates synergistic activity.

Claims (21)

1. the isomer composition that comprises dinitro-octyl phenyl ester, wherein 2,6-dinitro-4-(1-propyl group amyl group) phenylester exists with the amount of the 0.1wt% that is less than the isomer composition gross weight.

2. isomer composition according to claim 1 comprises and accounts for the isomer composition gross weight:

0.1 to 99.9wt%2,4-dinitro-6-(1-methylheptyl) phenylester,

0.1 to 99.9wt%2,4-dinitro-6-(1-ethylhexyl) phenylester,

0.1 to 99.9wt%2,4-dinitro-6-(1-propyl group amyl group) phenylester,

0.1 to 99.9wt%2,6-dinitro-4-(1-methylheptyl) phenylester,

0.1 to 99.9wt%2,6-dinitro-4-(1-ethylhexyl) phenylester and

Be less than 0.1wt%2,6-dinitro-4-(1-propyl group amyl group) phenylester.

3. isomer composition according to claim 1 comprises and accounts for the isomer composition gross weight:

-at least 95wt% 2,4-dinitro-6-(1-methylheptyl) phenylester,

-be less than 2 of 3wt%, 4-dinitro-6-(1-ethylhexyl) phenylester and

-be less than 2 of 0.1wt%, 6-dinitro-4-(1-propyl group amyl group) phenylester.

4. isomer composition according to claim 1, wherein every kind of this isomer composition ester all is a crotonates.

5. can be used for protective plant and avoid the invasion and attack of phytopathogenic organisms body and/or the Fungicidal composition for the treatment of the plant that is infected by the phytopathogenic organisms body, it comprises

I) isomer composition according to claim 1 and

II) botany acceptable carrier material.

6. Fungicidal composition according to claim 5, wherein isomer composition comprises and accounts for the isomer composition gross weight:

0.1 to 99.9wt%2,4-dinitro-6-(1-methylheptyl) phenylester,

0.1 to 99.9wt%2,4-dinitro-6-(1-ethylhexyl) phenylester,

0.1 to 99.9wt%2,4-dinitro-6-(1-propyl group amyl group) phenylester,

0.1 to 99.9wt%2,6-dinitro-4-(1-methylheptyl) phenylester,

0.1 to 99.9wt%2,6-dinitro-4-(1-ethylhexyl) phenylester and

Be less than 0.1wt%2,6-dinitro-4-(1-propyl group amyl group) phenylester.

7. Fungicidal composition according to claim 5, wherein isomer composition comprises and accounts for the isomer composition gross weight:

-at least 95wt% 2,4-dinitro-6-(1-methylheptyl) phenylester,

-be less than 2 of 3wt%, 4-dinitro-6-(1-ethylhexyl) phenylester and

-be less than 2 of 0.1wt%, 6-dinitro-4-(1-propyl group amyl group) phenylester.

8. Fungicidal composition according to claim 5, wherein every kind of this isomer composition ester all is a crotonates.

9. the Synergistic fungicidal composition that comprises isomer composition according to claim 1 and at least a other fungicide.

10. the Synergistic fungicidal composition that comprises isomer composition according to claim 2 and at least a other fungicide.

11. comprise the Synergistic fungicidal composition of isomer composition according to claim 3 and at least a other fungicide.

12. comprise the Synergistic fungicidal composition of isomer composition according to claim 4 and at least a other fungicide.

13. the described Synergistic fungicidal composition of claim 9, wherein this at least a other fungicide is selected from QoI fungicide.

14. Synergistic fungicidal composition according to claim 9, wherein this at least a other fungicide is selected from strobilurin.

15. Synergistic fungicidal composition according to claim 9, wherein this at least a other fungicide is selected from the sterol biosynthesis inhibitor.

16. Synergistic fungicidal composition according to claim 9, wherein this at least a other fungicide is selected from benzophenone.

17. the described Synergistic fungicidal composition of claim 9, wherein this at least a other fungicide is quinoxyfen.

18. Synergistic fungicidal composition according to claim 9, wherein this at least a other fungicide is selected from dithiocar-bamate.

19. be used to control or prevent the method for fungal attack, comprise plant, leaf, fungi point or the position that needs prevention infection is used the isomer composition of claim 1 of antifungal effective dose or the Synergistic fungicidal composition of claim 9.

20. method according to claim 19, wherein isomer composition comprises and accounts for the isomer composition gross weight:

-at least 95wt% 2,4-dinitro-6-(1-methylheptyl) phenylester,

-be less than 2 of 3wt%, 4-dinitro-6-(1-ethylhexyl) phenylester and

-be less than 2 of 0.1wt%, 6-dinitro-4-(1-propyl group amyl group) phenylester.

21. method according to claim 19, wherein every kind of isomer composition ester all is a crotonates.