Derivatives of acrylic acid, methods for their production (options), fungicidal composition, method of combating fungi

 

(57) Abstract:

The invention relates to new derivatives of acrylic acid, exhibiting fungicidal activity mainly in relation to fungal infections of plants, processes for their preparation, fungicidal compositions and method of combating fungi. Proposed according to the invention derivatives of acrylic acid correspond to the General formula I where a is hydrogen, R2is methyl and R1is 4-tert-butalbiral-2-yl, 4-tert-butylpyridinium-2-yl, 5-methyl-6-isopropoxypyridine-4-yl or 4-(C1-4-chlorophenacyl)pyrid-2-yl or isoquinoline, optionally substituted with halogen or1- C4-alkoxyl. Methods for obtaining compounds of formula I which consists in the interaction of the compounds of formula II in an alkaline medium with the compound of the formula III (x - tsepliaeva group) or the compounds of formula XV with a compound of formula XI, (X - ONH2-group). Fungicidal composition comprises a compound of formula I in an effective amount and fungicide acceptable carrier or diluent. A method of combating fungi consists in processing plants compound of formula I or the above composition. 4 S. and 2 C.p. f-crystals, 3 PL.

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Izobretatelyam their compositions, and to methods of using them to combat fungi, mainly fungal infections of plants.

Fungicidal derivatives of acrylic acid, including a group oximoula ether having the General formula [1] described in EP-A-0370629 and WO GB 92/00681/ published as WO GB 92/18487/, and they have the General formula [1], in which A is hydrogen, halogen, hydroxy, C1-4-alkyl, C1-4-alkoxy, phenoxy, nitro or cyano;

R1and R2that may be the same or different, are hydrogen, possibly substituted by alkyl, possibly substituted by cycloalkyl, possibly substituted by cycloalkylation, possibly substituted by aralkyl, possibly substituted by heteroallyl, possibly substituted by aryloxyalkyl, possibly substituted by heteroeroticism, possibly substituted by alkenyl, possibly substituted by quinil, possibly substituted alkoxy, possibly substituted aryl, possibly substituted by heteroaryl, possibly substituted, aryloxy, possibly substituted, heteroaromatic, nitro, halogen, cyano, NR3R4, -CO2R3, -CONR3R4, -COR3-S/O/nR3where n is 0,1 or 2, /CH2/mPO/OR3/2where m is 0 or 1, or R1and R2Torie may be the same or different, are hydrogen, possibly substituted by alkyl, possibly substituted by aralkyl, possibly substituted by alkenyl, possibly substituted by quinil, possibly substituted by aryl or perhaps replaced by heteroaryl.

The present invention provides a compound of formula (I), (see Appendix) in which A is hydrogen, R2is stands and R1is 4-tert-butalbiral-2-yl, 4-tert-butylpyridinium-2-yl, 5-methyl-6-ISO-propoxyphene-4-yl, or 4-/C1-4-chlorophenacyl/pyrid-2-yl/ 4-Cl F2C-pyrid-2-yl or 4-Cl2FC-pyrid-2-yl or isoquinoline, possibly substituted by halogen or C1- C4alkoxy.

Compounds of the invention contain at least one carbon-nitrogen double bond and at least one carbon-carbon double bond, and they sometimes get in the form of mixtures or geometric isomers. However, these mixtures can be separated into individual isomers, and this invention also includes isomers and their mixtures in all proportions.

Separate the isomers, asymmetrically substituted double bond propenoate group and oximes identify commonly used terms "E" and "Z". These terms are determined in accordance with the ICI is Wiley - Interscience, S. 109, et seq).

As for the carbon-carbon links propenoate group, usually one isomer is fungicide more active than the other, the more active isomer is usually that in which the group-CO2CH3and-OCH3located at opposite sides of olefinic communication propenoate group / /E/-isomer/. These /E/-isomers form a preferred variant of the invention.

Halogen is generally fluorine, chlorine or bromine.

Preferably, R2would the stands, hydrogen or cyano.

Isoquinoline ring R1and R2can be connected to any one of the carbon atoms, preferably it is connected via a 3-carbon /ie isoquinoline-3-ilen component/.

When replacing isoquinoline ring R1or R2replace the carbon atom of a cyclic structure, preferably a 5-position /ie 5-substituted sochineniia component/.

In one aspect the present invention provides a compound of formula I in which A is hydrogen, R2is stands and R1is isoquinoline, unsubstituted or substituted by one or more of halogen, C1where A is hydrogen, R2is stands and R1is isoquinoline, unsubstituted or substituted by one or more of halogen (especially fluorine or chlorine/, C1-C4-alkoxy (especially methoxy or ethoxy/.

In accordance with the present invention provided individual /E/ and /Z/-isomers of compounds NN 694-885 or mixtures thereof in any ratio with the formula /I/ and R1, R2and A, the data in table I. (see also Annex the end of the text)

Compounds of the invention are characterized by melting points given in table I and/or NMR data given in table II.

Table II: Selected data proton NMR.

Table II shows selected data proton NMR for certain compounds described in table I. Chemical shifts were measured in ppm/ppm/ from tetramethylsilane and everywhere used as a solvent deuterochloroform.

Operating frequency of the spectrometer by using NMR amounted to 270 MHz. Used the following abbreviations:

s - singlet

d = doublet

dd = double doublet

t = triplet

q = Quartet

sept = septet

m = multiplet

br = broad

ppm = parts per million

Soii scheme I, the terms A, R1and R2are as defined above, R*is R1or R2and X is tsepliaeva group /for example halogen/chlorine, bromine or iodine/ or OSO2CF3/.

The compound of formula (I) can be obtained by treatment of the oxime of the formula /III/ appropriate /base such as sodium hydride or sodium methoxide/ in a suitable solvent (for example N, N - dimethylformamide or tetrahydrofuran/ for the formation of anion and then adding the compounds of formula (II).

The oximes of the formula (III known in the chemical literature. The compound of formula II, where X is bromine and propenoate the group has the /E/-configuration, described in EP-A-0203606.

The oxime of formula (III can be obtained by reacting the compounds of formula /XI/ with hydroxylamine in an appropriate solvent (for example a mixture of a primary alcohol (for example methanol or ethanol with water/ possible in the presence of buffer /for example salts of organic acid such as sodium acetate/.

The connection formula /XI/ can be obtained by treating the compounds of formula /XII/ /R*is R1or R2but not the stands/ acid, preferably a strong mineral CI.

The connection formula /XII/ can be obtained by treating the compounds of formula /XIII/, where X is typically chlorine, bromine or OSO2CF3/ loveallsaveall connection /for example/I-ethoxyphenyl/tri-n-batilolum/ in the presence of a suitable catalyst, for example bis/ triphenylphosphine/ palladium (II) chloride/ in a suitable solvent (for example N,N-dimethylformamide/.

The alternate connection formula /XI/ can be obtained by reacting the compounds of formula /XIV/ halide Metalmania in a suitable solvent (for example diethyl ether or tetrahydrofuran/.

The connection formula /XIV/ can be obtained by reacting the compounds of formula /XIII/ trialkylamines, /such as trimethylamine/, which is preferably in aqueous solution and in the presence of an appropriate organic solvent (for example diethyl ether/ and then the introduction of a source of cyanide anions /such as potassium cyanide or sodium/.

Alternatively, the compounds of formula /XI/, /XII/, /XIII/ XIV/ can be obtained by methods known in the literature.

The alternate connection of the formula (I) can be obtained by treating a substituted hydroxylamine of paxillin /XV/, in which A is hydrogen, can be obtained as described in EP-A-0463488.

The alternate connection of the formula (I) can be obtained from the phenylacetate of the formula /VI/ or keeeper formula /X/ stages shown in scheme 2. Throughout the scheme, the terms A, R1, R2and X are as defined above, R5is hydrogen or a metal such as sodium or potassium/ and R is an alkyl group. Each transformation was carried out at an appropriate temperature and is usually, but not always, in a suitable solvent.

Thus, the compound of formula (I) can be obtained by processing the phenylacetate of the formula /VI/ /base such as sodium hydride or sodium methoxide/ and methylformate. If then to the reaction mixture add flavor formula CH3L, where L is tsepliaeva group, such as halogen (for example chlorine, bromine or iodine/ or anion CH3SO4then get the connection formula /I/. If the reaction mixture is added proton acid, then get the connection formula /IX/, where R5is hydrogen. Alternative from the reaction mixture may be a dedicated connection formula /IX/, in which R5t which can be converted into a compound of formula I by treatment with varieties of the formula CH3L, in which L is as defined above.

The compound of formula IX, in which R5is hydrogen, can be converted into a compound of formula (I) in the sequential treatment /base such as potassium carbonate/ and varieties of General formula CH3L.

The alternate connection of the formula (I) can be obtained from the acetal of the formula /IV/ by elimination of methanol in acidic or alkaline medium. Examples of reagents or reagent mixtures that can be used for this transformation is sitedisability acid potassium sulfate/ see for example, T/Yamada, H. Hagiwara, and H. Uda, J. Chem, Soc. Chemical Communications, 1980, 838 and references therein/; and triethylamine, often in the presence of a Lewis acid such as titanium tetrachloride /see, for example, K. Nsunda and L. Heresi, J. Chem. Soc. Chemical Communications, 1985, 1000/.

The acetal of formula /IV/ can be obtained by processing methylsiliconate formula /V/ triethylorthoformate in the presence of a Lewis acid such as titanium tetrachloride /see, for example, K. Saigo, M. Osaki and T. Mukaiyama, Chemistry Letters, 1976, 769/.

Methylsiliconate formula /V/ can be obtained by processing the phenylacetate of the formula /VI/ base and trialkylsilanes the/ and trialkylsilyl, formula R3Si-OSO2CF3/see, for example, C. Ainsworth, F. Chen, Y. Kuo, J. Organometallic Chemistry, 1972, 46, 59/.

Is not always necessary to isolate the intermediate chemical compounds /IV/ and /V/; under appropriate conditions, the compound of formula (I) can be obtained from the phenylacetate of the formula /VI/, "one tank" by successive addition of the reagents listed above.

The phenylacetate of the formula /VI/ can be obtained from the phenylacetate of the formula /VII/. Thus, if the oxime of General formula (III treated with an appropriate base (for example sodium hydride or sodium methoxide/ and add the phenylacetate of the formula /VII/, I get the phenylacetate of the formula /VI/.

The phenylacetate of the formula /VII/ can be obtained by processing isoproteronol formula /VIII/HX,/ in which X is preferably bromine/ methanol. This conversion can be performed in two stages, if isochroman formula /VIII/ handle HX in Nesporova solvent, and the resulting phenylacetic acid then etherification using standard methods /see, for example, I. Matsumoto, and J. Yoshizawa, Jpn Kokai (Tokkyo Koho) 79 138536, 27.10.1979, Chem Abs., 1980, 92, 180829 h; and G. M. F. Lim, Y. G. Perron and R. D. Droghini, Res. Discl., 1979, 188, 672, Chem. Abs., 1980, 92, 128526t/ Isochromosome formula /VIII/ horoshem processing keeeper formula /XI/ reagent ethoxymethyleneamino, for example ethoxymethylenemalononitrile /see, for example, W., Steglich, G. Schramm, T. Anke and F. Oberwinkler, EP-A-0044448, published. July 4, 1980/.

Ketoester formula /XI/ can be obtained from keeeper formula /X/ by treatment with anion oxime of formula (III, which is described above. The ketoesters of the formula /X/ is described in EP-A-0331061.

Therefore, in sum, schemes 1 and 2 illustrate certain ways in which can be respectively obtained components Aksenovo ester and 3-methoxypropionate in the final stages of the synthesis of compounds of the invention of formula (I). Alternative final stage or stages in the synthesis of compounds of the invention of formula (I) is a modification to one of the groups R1or R2or to the Deputy A. Thus, for example, if A or Deputy in one of the groups R1or R2when this group is pyridine or pyrimidine ring, is appropriately located to the amino group, it can be converted into the final stages of the reaction sequence through nitriding in an atom of halogen.

According to another aspect of the present invention provides a method for obtaining compounds of formula (I).

The connection of the following pathogens: Pyricilaria oryzae on rice and wheat and other Pyricularia spp. on other hosts, Puccinia recondita, Puccinia striiformis and other rust fungi on wheat, Puccinia hordei, Puccinia striiformis and other rust fungi on barley, and rusts on other hosts, such as peat, rye seed, coffee tree, pear trees, Apple trees, ground nuts, sugar beet, vegetables and ornamental plants; Erysiphe graminis /powdery mildew on barley, wheat, rye seed and turf and other powdery dew on different hosts, for example, Sphaerotheca macularis on hops ordinary, Sphaerotheca fuliginea on pumpkins /for example cucumbers/, Podosphaera leucotricha on apples and Uncinula necator on grape vine; Cochliobolus spp., Helminthosporium spp., Cereals spp., (Pyrenophora spp.), Rhynchosporium spp., Septoria spp.

/including Mycosphaerella graminicola and Leptosphaeria nodorum), Pseudocercosporella herpotrichoides and Gaeumannomyces graminis on cereals (for example, wheat, barley, rye, turf and other hosts; Cercospora arachidicola and Cercosporidium personatum on ground nuts and other Cercospora species on other hosts, for example sugar beet, bananas, soya beans and rice; Botrytis cinerea /grey mould in/ on tomatoes, strawberries, vegetables, grape vines and other hosts and other Botrytis spp. on other hosts; Alternaria on vegetables, for example cucumbers, oilseed rape, apples, tomatoes, grains /what's fruits, walnut trees and other hosts; Cladosporium spp. on the host range, including grains /for example, wheat/; Monilinia spp. on stone fruits, nut trees and other hosts; Didymella spp. on tomatoes, turf, wheat and other hosts; Phoma spp. on rape seed oil, peat, rice, potatoes, wheat and other hosts, Asperqillus spp. and Aureobasidium spp. on wheat, forest plantations, and other farms; Ascochyta spp. on pear trees, wheat, barley and other hosts; c Plasmopara viticola on grape vines; other downy dew, for example, Bremia lactucae on lettuce, Peronospora. spp. on soybeans, tobacco, onions and other hosts, Pseudoperonospora humuli on hops ordinary and Pseudoperonospora cubensis on a pumpkin; Pythium spp. on the turf and other hosts; Phytophthora infestans on potatoes and tomatoes and other Phytophthora spp. on vegetables, strawberries, avocado, pepper, ornamental plants, tobacco, cocoa and other hosts; Thanatephorus cucumeris on rice and turf, and other Rhizoctonia species on various hosts such as wheat and barley, vegetables, cotton and turf; Sclerotinia spp, peat, groundnut, rapeseed oilseed, and other hosts; Sclerotium spp. peat, ground nuts and other hosts; with Colletotrichum spp. on the host range, including peat, coffee and vegetables; with Laetisaria fuciformis on rusovich, soybean, melon, pear trees, lupine and other hosts; Elsinoe spp. in citrus, the vine, the European olive, walnut, pecan, roses and other owners, with Pyrenopeziza spp. on oilseed rape and other hosts; Oncobasidium theobromae on cocoa, causing vascular striped shevarchinot; Fusarium spp., Typhula spp., Microdochium nivale, Untilago spp., Urocystis spp., Tilletia spp. and Claviceps purpurea on the number of owners; but particularly wheat, barley, turf and maize; Ramularia spp. on beet sugar and other hosts, disease after harvest, in particular fruit, for example with Pencillium digitatum and P. italicum and Trichoderma viride on oranges, Colletotrichum musae and Gloeosporium on bananas and Botrytis cinerea on the vineyard; with other pathogenic organisms in the vineyard, especially with Eutypa lata, Guignardia bidwellii, Phellinus igniarus, Phomopsis viticola, Pseudopezicula tracheiphila and Stereum hirsutum; with other pathogenic organisms in forest plantations, especially with Cephaloascus fragrans, Ceratocys spp., Ophiostoma piceae, Penicillium spp., Trichoderma pseudokoningii, Trichoderma viride, Trichoderma harzianum, Aspergillus niger, Leptographium lindbergi and Aureobasidium pullulans; and fungal vectors of viral diseases, for example, Polymyxa graminis on cereals as the vector of the virus chlorotic zakalivanie barley.

Some of the songs display a wide spectrum of activity against areas rich in mushrooms is tion can be volatile in the vapor phase, to be quite active against fungi on the plant.

Therefore, the invention provides a method of combating fungi, which comprises applying to the plant, to seed of a plant or to the locus of the plant or seed fungicide effective amount of the compound defined above, or its containing composition.

Connections can be used for agricultural purposes directly, but for convenience they can be included in the composition using a carrier or diluent.

Thus, the invention provides fungicidal compositions containing the compound, which is described above, and acceptable carrier or diluent. Preferably, all of the composition of solid and liquid contain from 0.0001 to 95%, more preferably from 1 to 85%, for example from 1 to 25% or from 25% to 60% of the compound, which is defined above.

When applied to the foliage of plants compounds of the invention is applied at a rate of from 0.1 g to 10 kg, preferably from 1 g to 8 kg, more preferably from 10 g to 4 kg of active ingredient /compound of the invention/ per hectare.

When used for seed treatment compound izobreteny occhialino from 0.005 g to 4 g of active ingredient /compound of the invention/ kg seed.

The compounds can be applied in a variety of ways. For example, they can be applied in the form of compositions or directly to the foliage of a plant, to seeds or to other medium in which plants are cultivated or you want to sow, or they can be sprinkled, sprayed or applied in the form of a creamy or paste-like compositions, or they can be applied in the form of steam or slowly released granules.

Application can be made for any part of the plant, including leaves, stems, branches or roots, or to soil surrounding the roots, or on the seed before planting, or usually on the ground or on the system hydroponic culture. Compounds of the invention can also be injected into plants or sprayed onto vegetation using electrodynamic methods such as spraying or other low volume methods, or apply by land or aerial irrigation systems.

The term "plant" as used here, includes crops, shrubs and trees. In addition, fungicidal method of the invention includes preventive, protective, preventive, systemic and will eradicate processing.

Compounds preferably used for agricultural Inesta goal.

The composition can be in the form of pulverized powders or granules containing the active ingredient /compound of the invention/ and a solid diluent or carrier, for example fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, fallerovo earth, gypsum, diatomaceous earth and China clay. These granules can be prepared in advance in the form of granules, suitable for application to the soil, without additional processing. These granules can be obtained either by impregnation of the pellets filling the active ingredient or by granulating a mixture of the active ingredient and powdered filler. The composition for seed treatment may include a reagent such as petroleum/ to promote adhesion of the composition to the seed; alternatively the active ingredient can be included in the composition for seed treatment using an organic solvent (for example N-methylpyrrolidone, propylene glycol or N, N-dimethyformamide/. The composition may also be in the form of water-dispersible powders or water dispersible granules containing a wetting agent or dispersant to facilitate the dispersion in liquids. Powders and grime soluble powders or granules or in the form of solutions in polar solvents.

Soluble powders can be obtained by mixing the active ingredient with a water-soluble salt, such as sodium bicarbonate, sodium carbonate, magnesium sulfate or polysaccharides, and a wetting agent or a dispersant to improve FotoDepartament/solubility. Then the mixture can be milled to fine powder. Such compositions can also be pelletized prior to the formation of water-soluble granules. The solutions can be obtained by dissolving the active ingredient in polar solvents such as ketones, alcohols and glycol ethers. These solutions to improve water dilution and prevent crystallization in the tank to spray may contain a surfactant.

Concentrates of emulsions or emulsion can be obtained by dissolving the active ingredient in an organic solvent may contain a wetting agent or emulsifying agent and then adding the mixture to water which may also contain a wetting agent or emulsifying agent. Suitable organic solvents are aromatic solvents such as alkyl benzenes and alkylnaphthalene, ketones, for example, cyclohexane and metelnick, furrowy alcohol, butanol and glycol ethers.

Aqueous suspension concentrates largely insoluble solids can be obtained by grinding in a ball mill or bead mill with a dispersant and enabling a suspending agents in order to stop the precipitation of the solid.

Compositions which are used as sprayers, can be in the form of aerosols, while the composition is kept in the tank under pressure of jet fuel, for example tortiglioni or DICHLORODIFLUOROMETHANE.

Compounds of the invention can be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating in a fenced space smoke containing compounds.

Alternative connections can be used in microcapsule form. They can also be incorporated into a biodegradable polymer composition to obtain a slow, regulated excretion of the active substance.

Various compositions may be better suited for different uses by incorporating appropriate additives, for example additives to improve the absorption, distribution, adhesion and is Ksenia biological effectiveness of different compositions. Such additives can be surface-active substances which improve the wetting and fixation on surfaces treated with the composition, and absorption and mobility of the active material, or may additionally include additives for spraying based on oil, additives such as petroleum products from natural vegetable oils, for example soybean oil and rapeseed oil/ or their mixtures with other useful drugs.

Compounds of the invention can be used as mixtures with fertilizers /for example, fertilizers containing nitrogen, potassium or phosphorus/. Preferred are the composition containing only the fertilizer granules, including, for example covered with a compound of the formula /I/. These granules suitably contain up to 25% by weight of the connection. Therefore the invention also provides a fertilizer composition containing fertilizer and compound of General formula /I/, or its salt, or its metal complex.

Water-dispersible powders, mulgirigala concentrates and suspension concentrates usually contain surfactants such as wetting agent, dispersant, emulsifier or suspendisse agent. These reagents can be nationalmore, for example cetyltrimethylammonium bromide.

Suitable anionic additives are Soaps, salts of aliphatic monoamino sulfuric acid (for example sodium lauryl sulphate/ and salts of sulphonated aromatic compounds (for example, nitrilotriethanol, sodium lignosulphonate, calcium or ammonium, butylnaphthalene and the mixture aminobutiramida and triisopropylphenylsulfonyl sodium/.

Suitable non-ionic additives are condensation products of ethylene oxide with fatty alcohols, for example aerowyn or etilovym alcohol, or with alkyl phenols such as octyl - or Nonylphenol, and activclassroom. Other non-ionic additives are partial esters of a polyhydric alcohol derived from fatty acids with long chain and mexicanvalium, Alkylglucoside, polysaccharides and lecithins, and the condensation products mentioned partial esters of a polyhydric alcohol with ethylene oxide. Suitable suspendresume agents are hydrophilic colloids /for example, polyvinylpyrrolidone and sodium carboxymethyl cellulose/ and swelling clay, such as bentonite and attapulgite.

Composition for use in aqueous dispersions or emulsions is usually applied in the form of a concentrate. the ti concentrates are preferably able to withstand storage for prolonged periods and after such storage will be capable of dilution with water to form aqueous compositions, which remain homogeneous for a time sufficient to allow their application to traditional equipment for spraying. Concentrates can fit up to 95%, suitable 1-85%, for example 1-25% or 25-60% by weight of the active ingredient. After dilution water structures such compositions can contain variable amounts of active ingredient, depending on intended purposes, but can be used an aqueous composition containing from 0.0001 to 10% by weight, for example from 0.005-10% by weight of the active ingredient.

The compositions of this invention may contain other compounds having biological activity, i.e., compounds having similar or complementary fungicidal activity, or which have activity, regulating the growth of plants, herbicide or insecticide activity.

When another fungicide composition formed may have a broader spectrum of activity or to a higher level of internal antistia on the fungicidal activity of the compounds of General formula /I/. Examples of fungicidal compounds which may be included in the composition of the invention are /RS/-1-aminopropylphosphonic acid, /RS/-4-/4-chlorophenyl/-2-phenyl-2-/1H-1,2,4-triazole-1-yl-methyl/butyronitrile, /Z/-N-but-2-enyl-oxymethyl-2-chloro-2',6'-diethylacetanilide, 1-/2-cyano-2-methoxybenzyl/-3-atilmotin, 4-/2.2-debtor-1,3-benzodioxol-4-yl/pyrrol-3-carbonitrile, 4-bromo-2-cyano-N, N-dimethyl-6-triftoratsetata-1-sulfonamide, 5-ethyl-5,8-dihydro-8-oxo/1,3/-dioxol-/4,5-g/quinoline-7-carboxylic acid -[N-/3-chloro-2,6-xylyl/-2-methoxyacetate] - butyrolactone, N-/2-methoxy-5-pyridyl/-cyclo-propanecarboxylate, alankar, Aldemar, aspropirgos, anilazine, azaconazole, BAS 490F, benalaxyl, benomyl, bisoxazole, binapacryl, bitertanol, blasticidin S, bromuconazole, bupirimate, buenaflor, butiaba, captafol, Captan, carbendazim, carbondisulphide, carboxin, chinomethionat, chlorbenzene, chloroneb, CHLOROTHALONIL, Hartline, clothingon, copper compounds such as copper oxychloride, okshihinolin copper, copper sulfate, Tallat copper and Bordeaux liquid, cycloheximide, having cymoxanil, coprocessor, zipform, debaker, di-2-pyridyldithio 1,1'-dioxide, dichlofluanid, Dylan, diclobutrazol, declomycin, dicloran, didecyldimethylammonium, dimethirimol, diniconazole, dinocap, dipyrithione, datalists, dithianon, dodemont, Dodin, Dogadin, edifenphos, epoxiconazol, itaconate, ethirimol, ethoxyquin, ethyl-(Z)-N-benzyl-N-([methyl/methyl-Diethylaminoethanol/amino]thio/- - alaninate, etridiazole, fenaminosulf, verapamil, fenarimol, fenbuconazole, fanforum, penciclovir, fenpropidin, fenpropimorph, fentiazac, fistinginaction, ferbam, verison, fluazinam, fludyoksonil forumID, Fluconazol, flusilazol, flutolanil, flutriafol, folpet, fuberidazole, parallaxis, vorconizole, guazatine, hexaconazole, hydroxyethoxy, hymexazol, 1C1A5504, imazalil, kabekona, ipconazole, iprobenfos, iprodion, isopropylaminocarbonyl, isoprothiolane, kasugamycin, MANCOZEB, MANEB, mepanipyrim, mepronil, metalaxyl, metconazole, mefenoxam, metiram, metiram-zinc, metalhawk, myclobutanil, poisonin the Nickel dimethyldithiocarbamate, nitrates-isopropyl, nuarimol, furac, organomercury compounds, oxadixyl, oxolinic acid, oxycarboxin, peyratout, penconazole, pencycuron, finaince, fosetyl-A1, phosphoric acid, phtalic, polyoxin D, polishers, provenzal, prochloraz, procymidone, propamocarb, propanesulphonic, propiconazol, propineb, rolniczy, the Quaternary ammonium compounds, henansal, chinomethionat, hintzen, rabenasolo, pentachlorophenol sodium, streptomycin, sulfur, SSF-126, tebuconazole, thorpdale, tennesen, tetraconazole, thiabendazol, tilian, leflunomid, 2-/thiocyanomethylthio/benzothiazole, thiophanate-methyl, thiram, timbercoat, cyclophosphates, tolylfluanid, triacetate salt of 1,1'-iminodi /octamethylene/biguanidine, triadimefon, triadimenol, triazolyl, triazoxide, tricyclazole, tridemorph, triforine, triflumizole, triticonazole, validamycin vapam, vinclozolin, XPD-563, zineb and Zir.

Compounds of General formula /I/ can be replaced with soil, peat or root system for protection of plants against diseases spread by seeds, soil, deciduous or against fungal diseases.

The following examples illustrate the invention. In all examples, the term "ether" refers to diethyl ether, for dewatering solutions used magnesium sulfate, and the solution was concentrated under reduced pressure. Reactions involving intermediate chemical compounds sensitive to air or water, and were carried out under nitrogen atmosphere and, when necessary, solvents before use obezvozhivani. However, the phase. If data shown, infrared spectroscopy and NMR, they are selective. Do not attempt to list every absorption in all cases. Unless specified otherwise, the data of the NMR spectrum was recorded using solutions of CDCl3. Everywhere used the following abbreviations:

DMF = N,N-dimethylformamide

NMR = nuclear magnetic resonance

m.p. = melting point

ppm = parts per million

t = triplet; s = singlet

q = Quartet; d = doublet

JR = IR; ether = diethyl ether

b.p. = boiling point; m = multiplet

THF = tetrahydrofuran; br = broad

Example 1

This example illustrates the receipt of /E/, /E/-methyl-2-[2-/5-methyl-6-isopropoxypyridine-4-ene-acetoxidans-methyl/phenyl] -3-methoxypropionate /Connection N 735 table I/.

A solution of 4-chloro-5-methyl-6-ISO-propoxyimino /6.82 g/, /1-ethoxyphenyl/anti /13.19 g/ and bis/triphenylphosphine/palladium /11/ chloride /0.8 g/ DMF /N, N-dimethylformamide/ /25 ml/ was heated at 80oC for 8 hours. The reaction mixture was cooled to room temperature and added potassium fluoride /300 ml of 10% aqueous solution/. The resulting mixture was stirred for 1 hour, then filtered through accelerator Hyflo filter brine, then was dried, concentrated and subjected to chromatography, using as eluent a mixture of hexane and tert-butyl methyl ether in a ratio of components in a mixture of 1:1 to obtain 1-ethoxyphenyl-1-/5-methyl-6-ISO-propoxyphene-4-yl/, /5,11 g, yield 63%/, in the form of a light oil;1H NMR /270MHz/: 1.37 /9H, m/; 2.17 /3H, s/; 3.95 /2H, q/, 4.47 /1H, d,/; 4.53 /1H, d,/; 5.38 /1H; m/; 8.56 /1H, s/ frequent. in a million.

A solution of 1-ethoxyphenyl-1-/5-methyl-6-isopropoxypyridine-4-Il /5.11 g/ acetone /150 ml/ processed hydrochloric acid /6 ml of 2M solution/. The reaction mixture was stirred for 16 hours and then concentrated. The residue was diluted with water and neutralized with sodium bicarbonate. The aqueous phase was extracted with simple ether /x2/ and the combined extracts were concentrated to obtain 4-acetyl-5-methyl-6-ISO-propoxyimino /3.92 g, yield 88%/ in the form of a yellow oil;1H NMR /270 MHz/: 1.39 /6H, d/; 2.30 /3H, s/; 2.65 /3H, s/; 5.40 /1H; m/; 8.64 /1H, s/ ppm.

A solution of 4-acetyl-5-methyl-6-ISO-propoxyimino /3.92 g/, hydroxylamine /1,58 g/, and sodium acetate /1.5 g/ in a mixture of ethanol and water /30 ml/ when the ratio of components in a mixture of 2:1 was heated in a flask with reflux condenser, then stood. After that, the reaction mixture is poured into water and was extracted with ethylacetate a mixture of ethyl acetate and hexene in a ratio of components in a mixture of 2:3 to obtain two fractions.

A. E-4-acetyl-5-methyl-6-ISO-propositionalization in the form of a white solid substance /1.69 g, yield 40%, melting point: 95.4-96.5oC 1H-NMR /270 MHz/: 1.27 /6H, d/; 2.07 /3H, s/; 2.12 /3H, s/; 5.28 /1H; m/; 8.55 /1H, s/; 11.55 /1H, s/ ppm /frequent. million/.

B. E-4-acetyl-5-methyl-6-ISO-propositionalization in the form of a white solid substance /1.7 g, yield 40%, melting point 126.8 - 127.7oC1H-NMR /270 MHz/: 1.28 /6H, d/; 1.87 /3H, s/; 1.98 /3H, s/; 5.28 /1H; m/; 8.55 /1H, s/; 10.77 /1H, s/ ppm.

A solution of E-4-acetyl-5-methyl-6-ISO-propositionalization /1,69 g/ DMF /N, N-dimethylformamide/ /10 ml/ added dropwise to a stirred suspension of sodium hydride /0,19 g/ DMF /20 ml/. After two hours, was added dropwise a solution of /E/-methyl 2-[2-/methyl bromide/phenyl]-3-methoxypropionate /2.31 g/ DMF /10 ml/. After another 2 hours the mixture was poured into water and was extracted with simple ether /x4/. The organic extracts were washed with brine, dried, concentrated and subjected to chromatography, using as eluent a simple ether to obtain the titled compound /2.17 g, yield 65%/ in the form of a white solid, melting point 56.3-58.3oC,1H-NMR /270 MHz/, 1.35 /6H, d/, 2.09 /3H, s/; 2.24 /3H, s/; 3.68 /3H, s/; 3.81 /3H, s/; 5.13 /2H, s/; 5.37 /1H; m/; 7.1-7.6 /4H, m/; 7.58 /1H, s/; 8.56 /1H, s/ ppm.

Example 2.

This example illustrates obtaining Astor 1-chlorothymol /4.9 g/ /1-ethoxyphenyl/anti-at 10.82 g/ and bis/triphenylphosphine/palladium /11/chloride /0.75 g/ DMF /40 ml/ was heated at 90oC for 7 hours.

The reaction mixture was cooled to room temperature and added potassium fluoride /300 ml of 10% aqueous solution/. The resulting mixture was mixed for 1 hour, then filtered through accelerator filtering Hyflo, washed simple ether. The filtrate was extracted with simple ether /x2/ and the combined extracts were washed with brine, then dried, concentrated and subjected to chromatography using a mixture of ethyl acetate and hexane in a ratio of components in a mixture of 3:7 to obtain 1-ethoxyphenyl-1-isoquinoline /4.84 g, yield 81%/ in the form of a yellow oil,1H NMR: 1.46 /3H, t/; 4.10 /2H, q/; 4.65 /2H, dd/; 7.5 to 8.4 per 5H, m/; charged 8.52 /1H, d/ ppm.

A solution of 1-ethoxyphenyl-1-isoquinoline /1.84 g/ acetone /50 ml/ was treated with hydrochloric acid /5 ml of 2 M solution/. The reaction mixture was heated in a flask under reflux for 2 hours and then concentrated.

The residue was diluted with water and neutralized with sodium bicarbonate. The aqueous phase was extracted with ethyl acetate /X3/ and the United extracts were concentrated to obtain 1-acetyl-isoquinoline /3.84 g, yield 91%/ in the form of a yellow oil;1H NMR: 2.87/3H, s/; 7.64-7.75 /2H; m/; 7.79-7.89 /2H; m/; 8.59 /1H, d,/; ppm. 8.96 /1H, d/ ppm.

A solution of 1-acetylethanolamine /3.42 g/, gennarelli in the flask under reflux for 8 hours, then it stood for 16 hours. After that, the reaction mixture is poured into water and was extracted with ethyl acetate. The United extracts were dried, concentrated and subjected to chromatography, using as eluent a mixture of ethyl acetate and hexane with the ratio of components in a mixture of 3:7 to obtain 1-acetylethanolamine /1.87 g, yield 58%/ in the form of a white crystalline solid, melting point:

154,4 was 155.3oC;1H NMR: 2.50/3H, s/; 7.58 - 7.73 /3H, m/; 7.85 /1H; m/; 8.55 /1H; m/; 8.57 /1H; m/; 8.66 /1H, s/ ppm.

A solution of 1-acetylethanolamine /0.74 g/ DMF /10 ml/ added dropwise to a stirred suspension of the sodium hydride /0.19 g/ DMF /20 ml/. After 2 hours, was added dropwise a solution of /E/-methyl-2-[2/methyl bromide/phenyl]-3-methoxypropionate 1.14 g/ DMF /10 ml/. Two hours later, the mixture was poured into water and was extracted with simple ether /X3/. the organic extracts were washed with brine, dried, concentrated and triturated to powder with hexane and simple ether to obtain the titled compound /0,58 g, yield 37%/ in the form of a white yellow substances, the melting point 96,0 is 98.2oC,

1H NMR: 2.46/3H, s/; 3.64 /3H, s/; 3.78/3H, s/; 5.24/2H, s/; 7.1 - 7.8 /8H, m/; 7.60 /1H, s/; 8.36 /1H, s/; 8.52 /1H, d/ ppm.

Example 3.

This example illustrates obtaining methyl-2-[2-from arid /2.6 ml, 3.0 M solution in THF/ added dropwise to a solution of isoquinoline-3-carbonitrile at 0 - 5oC. After the addition the reaction mixture was stirred at room temperature for 1 hour, then abruptly cooled water. To the reaction mixture to obtain a PH of the aqueous phase equal to 2, added hydrochloric acid /2M aqueous solution/. After stirring for 30 minutes the aqueous solution was neutralized with sodium bicarbonate /solid/ and was extracted with simple ether /x2/. The United extracts were washed with water, dried and concentrated to obtain a crystalline solid. Recrystallization from hexane received 3-acetylthiophene /0.55 g, yield 14%/ in the form of a pale yellow solid, melting point: 84.8 - 86.8oC.

1H NMR: 2.83/3H, s/; 7.69 - 7.81 /2H; m/; 7.99 /1H; m/; 8.04 /1H; m/; 8.49 /1H; m/; 9.29 /1H, s/ ppm.

A solution of 3-acetylthiophene /0.65 g/, hydroxylamine /0.29 g/, and sodium acetate /0.47 g/ in a mixture of methanol /20 ml/ and water /3 ml/ was heated in a flask under reflux for 1.5 hours. Then the reaction mixture is poured into water and was extracted with ethyl acetate. The United extracts were dried, concentrated and triturated to powder with hexane to obtain 3-acetylethanolamine /0.63 g, yield 89%/ as Bel is/1H, d/; 7.99 /1H, d/ a; 8.11 /1H, s/; 9.28 /1H, s/ ppm.

A solution of 3-acetylethanolamine /2.97 g/ DMF /20 ml/ added dropwise to a stirred suspension of sodium hydride /0.67 g/ DMF /20 ml/. Half an hour later added dropwise a solution of /E/-methyl-2-[2-/methyl bromide/phenyl]-3-methoxypropionate /5.02 g/ DMF /20 ml/. After another hour the mixture was poured into water and was extracted with simple ether /X3/. The organic extracts were washed with brine, dried, concentrated and subjected to chromatography, using as eluent a mixture of ethyl acetate and hexane with the ratio of components in a mixture of 3:7 to obtain the titled compound /2.37 g, yield 38%/ in the form of a white solid, melting point: 95.6 - 96.2oC;

1H NMR: 2.45/3H, s/; 3.69/3H, s/; 3.82/3H, s/; 5.26/2H, s/; 7.1 - 8.0 /8H, m/; 7.60 /1H, s/; 8.18 /1H, s/; 9.25 /1H, s/ ppm.

Example 4.

This example illustrates obtaining methyl-2-[2-/4-pyrid-2 - yl/pyrimidine-2-yl-acetoxymethyl/phenyl]-3-methoxypropionate /Connection N 786 table I/.

Portafotodigitalefv /0.42 g/ added to the mixture of triethylorthoformate /5.25 ml/ trimethylsilylacetamide /5 ml/ at 0oC. provided the heating of the reaction mixture to room temperature and then realized stirring for 3 hours. The mixture was diluted simple ether and washed Rast is a /4.06 g, the output 94%/ in the form of a pale yellow liquid.1H NMR: 1.55/3H, s/; 3.22/6H, s/ ppm. 2.2-Dimethoxypropionate /10 g/ added to a solution of sodium methoxide, /obtained by dissolving 4.7 g of sodium in 40 ml of dry methanol/. The mixture was heated to 50oC for 4 hours, then before adding solid carbon dioxide /5 g/ cooled. The resulting sodium carbonate was filtered and the filtrate was concentrated in distilled at 50 - 60oC, 13 mm Hg to obtain 2,2-dimethoxypropionate /2.9 g, yield 23%/ in the form of a light oil.1H NMR: 1.45/3H, s/; 3.29/6H, s/; 3.80/3H, s/; 7.99/1H, s/ ppm.

Methyl 2,2-dimethoxypropionate /3,35 g/ ammonium chloride /1.55 g/ was heated in a flask under reflux in methanol /20 ml/ within 6 hours. The reaction mixture is cooled, filtered, and concentrated to obtain the resin, which was led when crushed into a powder with hexane and simple ether to obtain 2,2-dimethoxyphenylethylamine /3,24 g, yield 66%/ in the form of a hygroscopic solid.

2.2-Dimethoxyphenylethylamine /3.24 g/ and 1-/pyrid-2-yl/-3-N, N-dimethylaminopropan-2-may /3,38 g/ was heated in a flask under reflux for 1.5 hours in a solution of ethoxide sodium /received by dissolved connected, was dried and concentrated to obtain 2-acetyl-4-/pyrid-2-yl/pyrimidinemethanol /2.45 g, yield 52%/ in the form of butter.1H NMR: 1.80/3H, s/; 3.38/6H, s/; 7.41/1H; m/; 7.88/1H, t/; 8.30/1H, d,/; 8.60/1H, d,/; 8.72/1H, d,/; 8.98/1H, d/ ppm.

A solution of 2-acetyl-4-/pyrid-2-yl/-pyrimidinediamine /0.2 g/ dioxane/8 ml/ processed hydrochloric acid /1 ml of 2M solution/. The reaction mixture was heated in a flask under reflux for one hour, then concentrated.

The residue was diluted with water and neutralized with sodium bicarbonate. The aqueous phase was extracted with ethyl acetate /x2/ and the United extracts were concentrated to obtain 2-acetyl-4-/pyrid-2-yl/pyrimidine /0.12 g, yield 74%/ in the form of glossy colored solids; 1H NMR: 2.89/3H, s/; 7.47/1H; m/; 7.91/1H; m/; 8.52/1H, d,/; 8.63/1H, d,/; 8.78/1H, d,/; 9.06/1H, d/ ppm.

A solution of 2-acetyl-4-/pyrid-2-yl/pyrimidine /1.0 g/, hydroxylamine /0.39 g/, and sodium acetate /0.62 g/ in a mixture of ethanol /10 ml/ and water /2 ml/ was heated in a flask under reflux for 1.5 hours. Then the reaction mixture is poured into water, the precipitate was filtered and washed with hexane to obtain 2-acetyl-4-/pyrid-2-yl/pyrimidinamine /0.98 g, yield 91%/ in the form of a white crystalline solid. Melting point: 196.8oC;1H NMR: Riya /0.20 g/ and DMF /5 ml/ added dropwise a solution of 2-acetyl-4-/pyrid-2-yl/-pyrimidinamine /0.8 g/ DMF /10ml/. After 1.5 hours was added dropwise a solution of /E/-methyl-2-[2-methyl bromide/phenyl] 3-methoxypropionate /1.05 g/ DMF /10 ml/. After three hours the mixture is poured into water and was extracted with ethyl acetate /x3/. The organic extracts were washed with brine, dried, concentrated and subjected to chromatography, using as eluent ethyl acetate to obtain the titled compound /0.93 g, yield 61%/ in the form of a white solid crystalline substance, melting point: 88-90oC:1H NMR: 2.50/3H, s/; 3.69/3H, s/; 3.82/3H, s/; 5.36/2H, s/; 7.18(1H, m/; 7.35/2H; m/; 7.42/1H; m/; 7.59/1H, s/; 7.60/1H; m/; 7.89/1H; m/; 8.31/1H, d,/; 8/58/1H, d,/; 8.74/1H, d,/; 8.96/1H, d/ppm.

Example 5.

This example shows how to obtain methyl-2-[2-(4[1,1-dottorati]-pyrimidine-2-or-acetoxymethyl)phenyl] - 3-methoxypropionate /Connection N 763 table I/.

A solution of methyl 2-[2-(4-[2,2,2-triptoreline] pyrimidine-2-yl-acetoxymethyl)phenyl] -3-methoxypropionate /35g obtained as in WO 92/18487, Example 11, the compound N 417 /and hydrochloric acid /20 ml of 2M aqueous solution was heated in acetone in a flask under reflux for 4 hours. The reaction mixture was concentrated, neutralized with sodium bicarbonate and was extracted with ethyl acetate. The combined organic extracts were washed with water, dried and concentra methyl-2-[2-/4-hydroxypyrimidine-2-yl-acetoxymethyl/phenyl] -3-methoxypropionate /21.8 g, exit 77%/ in the form of a white solid.

In a flask under reflux for 30 minutes, heated methyl 2-[2-/4-hydroxypyrimidine-2-yl-acetoxymethyl/phenyl] -3-methoxypropanol /5g/ and phosphorylchloride /30ml/. The cooled reaction mixture is poured on ice, mixed and extracted with ethyl acetate /x3/.

The United extracts were washed with brine, dried, decolorized with charcoal, concentrated and subjected to chromatography, using as eluent a simple ether to obtain methyl 2-[2-/4-chloro-pyrimidine-2-yl-acetoxidans-methyl/phenyl] -3-methoxypropionate /2.3 g, yield 44%, the Compound N 711 table I / resin. Data1H NMR performed in table II.

A solution of methyl 2-[2-(4-chloropyrimidine-2-yl-acetoxymethyl/phenyl] -3-methoxypropionate /4.0 g/, /1-ethoxyphenyl/ anti /4.6 g/ bis/triphenylphosphine/palladium /11/ chloride /0.2 g/, tetraethylammonium /1.75 g/ and potassium carbonate /1.46 g/ DMF /30 ml was heated at 90oC for 3 hours. The cooled reaction mixture is poured into water and was extracted with triethylaluminum /x3/. The United extracts were washed with brine, dried, concentrated and subjected to chromatography, using as eluent a mixture of ethyl acetate and hexane ratio of compenate /2.09 g, yield 48%, the compound N 752 table I/ in the form of a white solid, melting point: 94-95oC.1H NMR: 1.45/3H, t/; 2.41/3H, S/; 3.68/3H, s/; 3.82/3H, s/; 3.98/2H, q/; 4.52/1H, d,/; 5.32/2H, s/; 5.78/1H, s/; 7.17/1H; m/; 7.35/2H; m/; 7.57/1H, d,/; 7.57/1H; m/; 7.59/1H, s/; 8,81/1H, d/ppm.

A solution of methyl 2-[2-(4-[1-ethoxyphenyl/-pyrimidine-2-alicetocienne/phenyl] -3-methoxypropionate /1.14 g/ and hydrochloric acid /2 ml 2M aqueous/ acetone /20 ml/ switched out within 3 hours. The reaction mixture was concentrated, neutralized with sodium bicarbonate and was extracted with ethyl acetate.

Connection extracts were washed with water, dried, concentrated and triturated to powder with hexane to obtain methyl-[2-/4-acetylpyridine-2-yl-acetoxymethyl)-phenyl] -3-methoxypropionate /0.87 g, yield 82%, the compound N 753 table I /in the form of a white solid crystalline substance, melting point: 104-106oC.1H NMR: 2.45/3H, s/; 2.78/3H, s/; 3.68/3H, s/; 3.82/3H, s/; 5.34/2H, s/; 7.18/1H; m/; 7.35/2H; m/; 7.55/1H; m/; 7.59/1H, s/; 7.82/1H, d,/; 9.07/1H, d/ ppm.

To a solution of methyl-2[2-/4-acetylpyridine-2-yl-acetoxymethyl/phenyl]-3-metoidioplasty /0.5 g/ dichloromethane /10 ml/added diethylaminoacetate /0.16 ml DAST/. The reaction mixture was heated in a flask under reflux for one hour, then kept what holodilniki for 7 hours. The cooled reaction mixture is poured into water and was extracted with ethyl acetate. Compound organic extracts were washed with sodium bicarbonate /saturated aqueous/ and then brine. Then they were concentrated and subjected to chromatography, using as eluent a mixture of ethyl acetate and hexane with the ratio of components in a mixture of 1: 1. This has resulted in a pale yellow resin, which was utverjdali when crushed to powder with hexane to obtain the titled compound /0.143 g, yield 27%/ in the form of a white solid crystalline substance, melting point: 96-97oC.

1H NMR 2.03/3H, t/; 2.39/3H, s/; 3.68/3H, s/; 3.82/3H, s/; 5.34/2H, s/; 7.17/1H; m/; 7.35/2H; m/; 7.52/1H. m/; 7.57/1H, d,/; 7.58/1H, s/; 8.89/1H, d/ ppm.

Example 6.

This example shows how to obtain methyl 2-[2-/4-chlorodifluoromethyl-5-methyl-pyrimidine-2-yl-acetoxymethyl/phenyl]-3 - methoxypropionate /Connection N 819 table I/.

Methyl 2-[2-phthalimidomethyl] 3-methoxypropanol /1.32 g, obtained as described in example 4 EP 0463488 dissolved in methanol /15 ml at room temperature, was added hydrazine hydrate /0,19/ ml and the resulting solution was mixed for 2 hours. Formed white precipitate was filtered and the filtrate was concentrated to obtain releasesto was filtered and the filtrate was concentrated to obtain methyl 2-[2-aminoacetonitrile[-3-methoxypropionate in the form of a yellow oil, which is immediately used in the next stage without further purification.

At room temperature for 24 hours shuffled mixture of methyl 2-[2-aminoacetonitrile] -3-methoxypropionate, 2-acetyl-4-chlorodifluoromethyl-5-methylpyrimidine /0.53 g/ n pyridine /2 drops/ in methanol. The reaction mixture was concentrated, using as eluent a simple ether to obtain after grinding to a powder with hexane named connections /0.52 g, yield 50%/ in the form of a pale yellow solid, melting point: 110-111oC 1H - NMR: 2.40/3H, s/; 2.55/3H, s/; 3.70/3H, s/; 3.85/3H, s/; 5.35/2H, s/; 7.2-7.60/4H, m/ 7.60/1H, s/; 8.80(1H, s/; ppm.

Example 7.

Compounds were tested against a variety of fungal diseases of the foliage. In this process we used the following methodology. In minihorse diameter of 4 cm was grown plants in the compost and John Innes Potting. Compound formulated or by grinding in a bead mill with a water solution Dispersola T or in the form of a solution in acetone or acetone/ethanol, which was diluted with water to the required concentration immediately before use. Composition /100 frequent. per million of active ingredient/ was sprayed on the foliage or applied to the plant roots in the soil.

Opryskivatel the things approximately 40 ppm a. i. in dry soil. When the sprayers were applied to crops, to obtain a final concentration of 0.05% was added Tween 20.

In most experiments the compounds were applied to the soil /roots/ or leaves /by spraying/ for one or two days before infection of a plant disease. The exception was the experience on Erysiphe graminis in which the plants were infected for 24 hours before processing.

Leaf pathogens were applied in the form of zoosporangium suspensions by spraying on the leaves of test plants.

After infection, plants were placed in a suitable environment for the development of infection and then incubated until then, until the disease can be assessed. The period between infection and rating changed from 4 to 14 days depending on the disease environment.

The degree of presence of the disease /i.e., the surface area of foliage, covered with actively sporliuk disease/ at each of the test plants were recorded using the following scale:

0=0% disease; 5=3.1-5% disease

1=0.1-1% of the disease; 10=5.1-10% of the disease

3=1.1-3% of the disease; 20=10.1-20% of the disease

30=20.1-30% of the disease

60=30.1-60% of the disease

90=60.1-100% in the future on untreated control plants. This calculated value was expressed as the value of ROSSO /percentage/ control. An example of a typical calculation was as follows:

The extent of the disease on the untreated control plants = 90

The extent of the disease on the treated plant = 30.

< / BR>
This calculated value of ROSSO then rounded to the nearest value 9-point scale shown above. If the calculated value of ROSSO fell exactly in the middle between two points, it is rounded to the lower of the two values.

The results are shown in table III.

Unless specified otherwise, the data represent the activity of the connection joint spraying the leaves and irrigation of the root system at a concentration of 100 ppm (1 ppm = 1 mg/l).

The concentration of 10 ppm when applied only on the leaves

There is no result.

Abbreviations in table III:

Ps Puccinia recondita Tc Thanetophorus cucumeris

Egt Erysiphe graminis tritici Vi Venturia inaequalis

Sn Septoria nodorum Pv Plasmopara viticola

Po Pyricularia oryzae Pil Phytophthora infestans lycopersici

Listed below are the comparative test data connection 159 from EP-A1 0370629, and the closest connection 737 of the present invention (DI)

< / BR>
< / BR>
The only structural difference is a hundred attachment of the heterocycle to the side chain of the oxime.

Connection 737 significantly more active than compound 159, against four important plant diseases. While the connection 159 is inactive at a concentration of 10 ppm against Phytophtora infestans (see page 63 application D1), the connection 737 completely eliminate this disease at a concentration of 100 ppm (see table III description of the present invention).

Examples of compositions

The following examples are examples of compositions suitable for use in agriculture and horticulture, which can be prepared on the basis of the compounds according to paragraphs. 1 or 2 claims.

An example of A

Emulsifying concentrate is obtained by mixing and subsequent mixing of the ingredients until complete dissolution, wt.%:

The compound N 737 table I - 10

Benzyl alcohol - 30

Dodecylbenzenesulfonate calcium - 5

Nonylphenolethoxylate (13 moles of ethylene oxide) - 10

Alkylbenzene - 45

Example B.

The active ingredient is dissolved in methylene chloride and the resulting liquid is applied by spraying the granules attapulgite. Then the solvent is allowed to evaporate and get granular composition, wt.%:

The compound N 737 table. I - 5

Granules attapulgite - 95

the seeds, obtained by grinding and mixing the three ingredients. weight. %:

The compound N 737 table. I - 50

Mineral oil - 2

Kaolin - 48

Example D

Powder dust produced by grinding and mixing the active ingredient with talc, wt.%:

The compound N 737 table. I - 5

Talc - 95

Example E

A concentrated slurry obtained by grinding in a ball mill ingredients and prepare aqueous suspensions of crushed, mixed with water, wt.%:

The compound N 737 table. I - 40

Sodium lignosulphonate - 10

Bentonite clay - 1

Water - 49

This song can be used for spraying after dilution with water, or directly apply to the seeds.

Example F.

Wettable powder is obtained by thorough mixing and grinding the ingredients until a homogeneous mixture, wt.%:

The compound N 73 from table. I - 25

Sodium dodecyl sulfate - 2

Sodium lignosulphonate - 5

Silicon dioxide - 25

Kaolin - 43g

1. Derivatives of acrylic acid of the formula I

< / BR>
in which A is hydrogen;

R2is methyl;

R1- 4-tert-butalbiral-2-yl, 4-tert-butylpyridinium-2-yl, 5-methyl-6-isopropoxypyridine-4-yl, 4-(C

2. Connection on p. 1, where A represents hydrogen, R1- isoquinoline, optionally substituted with chlorine, fluorine, or methoxy; R2is methyl.

3. The method of obtaining acrylic acid derivatives of the formula I, wherein interact compounds II

< / BR>
in an alkaline medium with a salt of the oxime of formula III

< / BR>
where X is tsepliaeva group;

A is hydrogen;

R2is methyl and R1- 4-tert-butylphenyl-2-yl, 4-tert-butylpyridinium-2-yl, 5-methyl-6-isopropoxypyridine-4-yl, 4-(C1-4-chlorophenacyl)pyrid-2-yl or isoquinoline, optionally substituted with halogen or1-4-alkoxyl.

4. The method according to p. 1, wherein spend processing the compounds of formula XV

< / BR>
the compound of the formula XI

< / BR>
where A is hydrogen;

R2is methyl;

R1- 4-tert-butalbiral-2-yl, 4-tert-butylpyridinium-2-yl, 5-methyl-6-isopropoxypyridine-4-yl, 4-(C1-4-chlorophenacyl)pyrid-2-yl or isoquinoline, optionally substituted with halogen or1- C4-alkoxyl.

5. Fungicidal composition comprising an active substance and fungicide acceptable carrier or diluent, characterized in that the active substance is rubbish> - 4-tert-butalbiral-2-yl, 4-tert-butylpyridinium-2-yl, 5-methyl-6-isopropoxypyridine-4-yl, 4-(C1-4-chlorophenacyl)pyrid-2-yl or isoquinoline, optionally substituted with halogen or1- C4-alkoxyl,

in an effective amount.

6. A method of combating fungi by processing plants active substance, characterized in that the active substance use derivatives of acrylic acid of formula I under item 1 or containing composition under item 5 in an effective amount.

 

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< / BR>
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The invention relates to new biologically active compounds derived amide alanovoy acid, three different methods for their preparation, herbicide composition and method for killing weeds that may find application in agriculture

The invention relates to a method for producing derivatives of General formula (I), which allows to improve the yield of these products

The invention relates to new aminoven derivatives, processes for their production and insecticide containing as selective compounds listed derivatives

The invention relates to optically active compounds as components of ferroelectric liquid crystal materials (LCD monitor) recording devices for optical display of information, and modulation of radiation

The invention relates to heterocyclic nitrogen compounds endowed with high antifungal activity, processes for their preparation and their use in agriculture as fungicides

The invention relates to a series of racemic and optically active derivatives of pyrido[1,2-a] pyrazine, which are used as antidepressants and anxiolytics, as well as intermediates of these derivatives

The invention relates to new chemical compounds belonging to the class of aromatic Schiff bases the following formula:

The invention relates to a compact, crystalline 3-cyan - 2-morpholino-5-(pyrid-4-yl)-pyridine with high apparent (bulk) density and method thereof

Ammonium salts // 2106346
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