MXPA97003497A - Derivatives of the acid 2 [(2-alcoxi-6-trifluorometilpirimidin-4-il) oximetilen] -fenilacetico, its preparation, intermediaries yusos de e - Google Patents

Abstract

The present invention relates to the derivatives of 2 - [(2-alkoxy-6-trifluoromethylpyrimidin-4-yl) oxymethylene] -phenyl acetic acid of the formula I: wherein the index and the substituents have the following meanings: U is CH or N, V is O or NH, R is alkyl, R1 is cyano, halo, alkyl, haloalkyl, alkoxy, haloalkoxy or phenyl n is 0 or an integer from 1 to 4, the processes and intermediates for their preparation and their use.

Description

DERIVATIVES OF ACID 2 [(2-ALCOXI-6-TRIFLUOROMETILPIRIMIDIN- 4-IDOXIMETILEN] - PHENYLLATE, ITS PREPARATION, INTERMEDIARIES AND USES OF THIS The present invention relates to the derivatives of 2 - [(2-aikoxy-6-trifluoromethyl-pyrim? Din-4-yl) oxymethylene-acetylacetic acid of the formula I. wherein the Index and substituents have the following meanings: U is CH or N; V is O or NH; R is C? -C alkyl ?; R1 is a cyano, halogen, C-C alkyl, C1-C1 haloalkyl, Ci-Cj alkoxy, C- C haloalkoxy] or phenyl group / n is 0 or an integer from 1 to 4, it is possible In addition, the invention relates to the processes and intermediates for the preparation of these compounds and to the compositions containing them and their uses.

The methyl α-hetaryloxymethylene-phenyl-β-motokyacrylates are described in the literature as fungicides (EP-A 178 826, EP-A 278 595, EP-A 350 691). EP-A 407 873 further discloses the corresponding a- [2- (6-trifluoromethylpyrimidin-4-yl) -oxymethylenephenyl] -β-methoxyacrylates of methyl which have acaricidal and insecticidal action. Methyl a-1,2- (hetaryloxymethylene) phenyl J-a-methoxyiminoacetates having fungicidal activity have also been described (EP-A 253 213, EP-A 254 426, EP-A 299 694, EP-A 363 818) and insecticide or acaricides (EP-A 407 873). In addition, the literature describes a- [2- (etaryloxymethylene-phen-Ja-methoxyimino-N-methylacetamides having fungicidal action (EP-A 396 692) and insecticide or acaricide (EP-A 477 631). In many cases, the action of the described compounds against animal pests is not satisfactory.One aim of the present invention is to provide compounds that have better properties for the control of harmful fungi and pests of animals, in particular, harmful fungi, insects, nematodes and mites, especially insects and mites, we have now found that this objective is achieved by using the compounds I defined at the start, and we have found the processes and intermediates for their preparation, the compositions that contain them and the methods for their use. L03 compounds I are prepared in a manner similar to the processes described in the literature mentioned at the start.The compounds T are obtained, for example, by reacting a pyrimidin-4-ol of the formula II in a manner known per se in an inert organic solvent in the presence of a base with a benzyl derivative of the formula II I.

In formula III, X is a nucleophilically substitutable leaving group, such as a halogen, (eg, chlorine, bromine or iodine) or an alkyl or arylsulfonyl (eg, methylsulfonyl, trifluoromethylsulfonyl, phenylsulfonyl or methylphenylsulfonyl). This reaction is usually carried out from ü ° C to 80 ° C, preferably from 20 to 60 ° C. Suitable solvents are aromatic hydrocarbons such as toluene, o- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, disopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, n-propanol, isopropanoi, n-butanol and r-buLanoJ, ketones with acetone and metii ethyl ketone, and also dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethylimidazolidin-2-one and 1, J-dimethyltetrahydro-2 (1H) -pyrimidinone, particularly preferably methylene chloride, acetone and dimethylformamide. Mixtures of the mentioned solvents can also be used. Suitable bases are usually inorganic compounds such as alkali metal hydroxides and metals such as lithium hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, alkali metal and alkaline earth metal oxides. be lithium oxide, sodium oxide, calcium oxide and magnesium oxide, hydrides of alkali metals and alkaline earth metals such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, carbonates alkali metals and alkaline earth metals such as potassium carbonate and calcium carbonate and also acidic carbonates of alkali metals such as sodium hydrogen carbonate, organometallic compounds, in particular alkali metal alkyls such as methyl lithium, butyl lithium and phenyllithium, has 1 to 1 quan irons, such as methylmagensium chloride and also alkoxides of alkali metals and alkaline earth metals such as sodium methoxide, sodium ethoxide, potassium ethoxide, tert-butoxide, potassium and dimethoxymagnesium, additionally, organic bases, for example, tertiary amides such as trimethylamine, triethylamine, disopropylethylamine and N- methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and also bicyclic amines. The hydroxide of sodium, sodium hydride, potassium carbonate and potassium tert-butoxide are particularly preferred. In general, the bases are used in an equimolar quantity, in excess or if it is suitable as a solvent.

It may be advantageous for the reaction to add a catalytic amount of a crown ether such as 18-crown-6 or 15-crown-5. The reaction can also be carried out in a two-phase system consisting of an alkali metal solution or alkaline earth metal hydroxides or alkali metal or alkaline earth metal carbonates in water and an organic phase such as, for example, hydrocarbons halogenated The phase transfer catalysts used may be ammonium halides and tet raf 1 -substituted as, for example, benzyltriethylammonium chloride, benzyltributyl ammonium bromide, tetrabutylammonium chloride, hexadecyltri ethyl ammonium bromide or tetrabutylammonium tetrafluoroborate. and also phosphonium halides such as tetrabutyl phosphonium chloride or tetraphenyl phosphonium bromide. It may be advantageous for the reaction to first treat the compounds II with a base and react the resulting salt with the compounds III. Compounds II can be obtained by condensation of the esters of trichloroacetic acid VT with o-a Iquii isoureas VII in a manner similar to the known processes [cf. J. Chem. Soc 1946, 5].

F3C-C0-CH2-CO2Rb + HN «C (NH2) -OR R, in the formula VII is an alkyl group of C1-C1, in particular methyl or ethyl. The reaction is usually carried out from 0 to 120 ° C, preferably from 20 to 80 ° C, in particular, at the boiling point of the solvent. The solvents that are normally used are alcohols, in particular methanol or ethanol.

It is common to use the o-alkylisoureas of the formula VII in the form of their salts, in particular as acid hairs (eg, acid and acid bromide). When the salts are used, it is recommended to carry out the reaction in the presence of a base (for example, alkaline earth metal or alkali metal alkoxides or hydroxides, such as sodium methoxide, sodium ethoxide, potassium tert-butoxide). , sodium hydroxide, potassium hydroxide or calcium hydroxide). Alternatively, compounds I are also obtained by reacting a sulfone derivative of formula IV in a manner known per se Lcf. 'J. Med. Chem. 27 (1984), 1621; CH-A 649 086] in the presence of a base with an alcohol of the formula V.

Ra in formula IV is C alquilo-CH alkyl, in particular methyl. Suitable bases are, in particular, sodium hydride, potassium tert-butoxide and potassium carbonate. In general, the reaction is carried out in an inert dipolar aprotic solvent (in particular, dimethylsulfoxide, dimethylformamide or 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone). The sulfone derivatives of the formula IV which are necessary for the reaction are obtained by oxidation starting from the corresponding sulphides VIII.

VIII IV Oxidation is carried out according to the process known in the literature, for example, using hydrogen peroxide in concentrated acetic acid Lcf. Chem. Pharm. Bull. 27 (1978), 183J or using sodium hypochlorite in water [cf. J. Prakt. Chem 33 (1966), 165]. The benzyl derivatives of the formula III wherein V is oxygen are known in the literature and were mentioned in the beginning. The benzyl II derivatives wherein U is N and V is NH are described in DE-A 43 05 502. Alternatively, the compounds of the general formula I where U is N and V is NH are obtained by aminolysis of the corresponding esters (V = O) [cf. Houben-Weyl Vol. E5, p. 983 ff. ] Ib Typically, this reaction is carried out at 0 to 60 ° C, preferably 10 ° to 30 ° C, in an inert solvent. Methylane can be introduced as gas or volumetric as an aqueous solution. Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, disopropyl ether, tert-butyl methyl ether , dioxane, tetrahydrofuran and anisole, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, particularly preferred methanol, toluene and tetrahydrofuran. Mixtures of the mentioned solvents can also be used. In the definitions of the symbols indicated in the above formulas, collective terms were used which, in general, are representative of the following substituents: Halogen: fluorine, chlorine, bromine and iodine.

Alkyl: straight or branched chain saturated hydrocarbon radicals having from 1 to 6 carbon atoms, such as methyl, ethyl, propyl, 1-methyl ethyl, butyl, 1-methyl propyl, 2-methyl propyl, 1, 1-dimethyl ethyl, pentyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 2,2-dimethyl propyl, 1-ethylpropyl, hexyl, 1,1-dimethyl propyl, 1,2-dimethyl propyl, 1 -methyl pentyl, 2-methyl-pentyl, 3-methyl pentyl, 4-methyl pentyl, 1,1-dimethyl butyl, 1,2-dimethyl butyl, 1,3-dimethyl butyl, 2,2-dimethyl butyl, 2, 3-dimethyl butyl, 3,3-dimethyl butyl, 1-ethyl butyl, 2-ethyl butyl, 1,1-trimethyl propyl, 1,2,2-trimethyl propyl, 1-ethyl-1-methyl-propyl and l-et? l-2-methyl propyl; Haloalkyl: straight or branched chain alkyl groups having from 1 to 4 carbon atoms (as mentioned above), it is possible that in these groups the hydrogen atoms are partially or completely substituted by halogen atoms as mentioned in the above, for example, Ci-C haloalkyl. such as chloromethyl, dichloromethyl, trichloroethyl, fluoromethyl, difluoromethyl, trifluoroethyl, chloroform, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2, 2, 2 -tr? tluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl; Alkoxy: straight or branched chain alkyl groups having from 1 to 4 carbon atoms (as mentioned above), which are attached to the structure by means of an oxygen atom (-o-); Haloalkoxy: straight or branched chain haloalkyl groups having from 1 to 4 carbon atoms (as mentioned above) which are attached to the structure by means of an oxygen atom (-o-). With respect to their biological activity, those compounds I are particularly preferred, wherein R is C 1 -C 4 alkyl, in particular C 4 C 4 alkyl. Compounds I are further preferred in which n is 0 or 1, in particular 0. In the case where n is different from 0, compounds I in which R 1 has the following meaning are preferred: cyano, fluorine, chlorine, methyl, trifluoromethyl or methoxy. The additionally preferred compounds I are those in which a radical R 1 is attached in the 3-, 4- or 5- position of the ring teny. In particular, with respect to their use, the compounds I compiled in the following table are preferred. The groups mentioned in the table for a substituent are further considered per se (regardless of the combination in which they are mentioned) in particular a preferred embodiment of the related substituent. Table 1 The compounds of the formula I where U is CH and V is 0 (= la) and the combination of the substituents R '"and R for a compound corresponds to a line of table A. Table 2 The compounds of the formula I where U is N and V is 0 (= Ib) and the combination of the substituents R1n and R for a compound corresponds to a line of table A. Table 3 The compounds of the formula I where U is N and V is, NH (= le) and the combination of the substituents R! N and R for a compound corresponds to a line of table A. Table A The compounds of the formula I, according to the invention, are suitable for controlling animal pests of the class insects, mites and nematodes, in particular insects, especially mites. These compounds can be used as fungicides and pesticides for the protection of crops and in the hygiene sectors, in the protection of stored and veterinary materials. Harmful insecticides include: on the order of butterflies (Lepidoptera), for example, Adoxophyes orana, Agrotis ypsilon, Agrotis Segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Cacoecia murinana, Capua reticulana, Choristoneura fumiferana, Chilo partellus, Choristoneura occidentalis, Cirphis unipuncta, Cnaphalocrocis medinalis, Crocidolomia binotalis, Cydia pomonella, Dendroli us pini, Diaphania nitidalis, Diatraea grandiosella, Elands insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Feltia subterránea, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, L mantria monacha, Lyonetia clerkella, Manduca sexta, Malacosoma neustria, Mamestra brassicae, Mocis repanda, Operophthera brumata, Orgyia pseudotsugata, Ostrinia nubilalis, Pandemis heparana, Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Phyllocnistis citrella, Pieris braesicae, Plathypena scabra, Platynota stultana, Plutella xylostella, Prays citri, Prays oleae, Prodenia sunia, Prodenia ornithogalli, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sesamia inferens, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Syllepta derogata, Synanthedon myopaeformis , Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni, Tryporyza incertulas, Zeraprara canadensis, also Galleria meilonella and Sitotroga cerealella, Ephestia cautella, Tineola bisselliella; from the order of the beetles (Coleoptera), for example, Agricots lineatus, Agriotes obscurus, Anthonomus grandis, Anthonomus pomorum, Apion vorax, Atomaria linearis, Blastophagus piniperda, Cassida nebulosa, Cerotoma trifurcata, Ceuthorhynchus assimlis, Ceuthorhynchus napi, Chaetocnema tibialis, Conoderus vespertinus , Crioceris asparagi, Dendroctonus refipennis, Diabrotica longicornis, Diabrotica 12-punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus , Lissorhoptrus oryzophilus, Melanotus co munis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus. Phaedon cochleariae. Phyllopertha horticultural, Phyllophaga sp., Phyllotreta chrysocephala, Phyllotretra nemorum, Phyllotreta striolata, Popillia japonica, Psylliodes napi, Scolytus intricatus, Sitona lineatus, also Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Sitophiius granaria, Lasioderma serricorne, Oryzaephilus surina ensis, Rhyzopertha dominica , Sitophilus oryzae, Tribolium castaneum, Trogoderma granariu, Zabrotes subfasciatus; of the order of diptera insects (Diptera), for example, Anastrepha ludens, Ceratitis capitata, Contarinia sorghicola, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia coarctata, Delia radicum, Hydrellia griseola, Hyle yia platura, Liriomyza sativae, Liriomyza trifolii, Mayetiola destructor, Orseolia oryzae, Oscinella frit, Pegomya hyoscyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tipula oleracea, Typula paludosa, also Aedes aegypti, Aedes vexans, Anopheles maculipennis, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Cordylobia anthropophaga, Culex pipiens, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hypoderma lineata, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Musca domestica, Muscina stabulans, Oestrus ovis, Tabanus bovinus, Simulium damnosum; from the order of the tisatoptera (Thysanoptera), for example, Frankliniella fusca, Frankliniel the occidentalis, Frankliniella tritici, Haplothrips tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci; • k - -k 'k' k '-k' k from the order Hymenoptera insects (Hymenoptera), for example, Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoploca pa minuta, Hoplocampa testudinea, Iridomyrmes humilis, Iridomyrmex purpureus, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri; of the order of the worms (Heteroptera), for example, Acrosterum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus interedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus hesperus, Lygus lineolaris, Lygus pratensis, Nezara viridu, Piesma quadrata, Solubea insularis, Thyanta perditor; of the order of the sucking insects (Homoptera), for example, Acyrthosiphon onobrychis, Acyrthosiphon pisum, Adelges laricis, Aonidiella aurantii, Aphidula nasturtii, Aphis fabae, Aphis gossypii, Aphis pomi, Aulacorthum solani, Bemisia tabaci, Brachycaudus cardui, Brevicoryne brassicae, Dalbulus maidis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicóla, Empoasca fabae, Eriosoma lanigerum, Laodeiphax striatella, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzus persicae, Myzus cerasi, Nephotettix cincticeps, Nilaparvata lugens, Perkinsiella saccharicida, Phorodon humuli, Planococcus citri, Psyila mali, Psylla piri, Psylla pyricol, Quadraspidiotus perniciosus, Rhopalosiphum aidis, Saissetia oleae, Schizaphis graminum, Seienaspidus articulatus, Sitobion avenae, Sogatella furcifera, Toxoptera citricida, Trialeurodes abutilonea, Trialeurodes vaporariorum, Viteus vitifolii; on the order of termites (Isoptera), for example, Calotermes flavicoJlis, Leucotermes flavipes, Macrotermes subhyalmus, Odontotermes formosanus, Reticulitermes lucitugus, Termes natalensis; of the order of the orthoptera insects (Orthoptera), for example, Gryllotalpa gryllotaipa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinípes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus, Schistocerca gregaria , also Acheta domestica, Blatta orientalis, Blattella germanica, Periplaneta americana; of the order Arachnoidea, for example, phytophagous mites mites such as Aculops lycopersicae, Aculops pelekassi, Aculus schlechtendali, Brevipalpus phoenicis, Bryobia praetiosa, Eotetranychus carpini, Eutetranychus banksii, Eriophyes sheldoni, Oligonychus pratensis, Panonychus ulmi, Panonychus citri, Phyllocoptruta oleivora, Poiyphagotarsonemus latus , Tarsonemus pallidus, Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus urticae, ticks such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophílus decoloratus, Boophiius microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata , Olobius megnini, Rhipicephalus appendiculatus and Rhipicephalus evertsi and parasitic mites of animals such as Dermanyssus gallinae, Psoroptes ovis and Sarcoptes scabiei; of the class of nematodes, for example, root nematodes gall, p. ex. , Meloidogyne hapla, Meioidogyne incognita, Meloidogyne javaníca, cyst-forming nematodes, for example, Globodera pallida, Globodera rostochiensis, Heterodera avenae, Heterodera glycines, Heterodera schachtii, migratory endoparasites and semi-endoparasitic nematodes, p. ex. , Heliocotylenchus multicinctus, Hirschmanniella oryzae, Hoplolaimus spp., Pratylenchus brachyurus, Pratylenchus fallax, Pratylenchus penetrans, Pratylenchus vulnus, Radopholus similis, Rotylenchus reniformis, Scutellonema bradys, Tylenchuius semipenetrans, nematodes of stems and leaves, p. ex. , Anguina tritici, Aphelenchoides besseyi, Ditylenchus angustus, Ditylenchus dipsaci, viral vectors, p. eg, Longidorus spp., Trichodorus christei, Trichodorus viruliferus, Xiphinema index, Xiphinema mediterraneum.

The comds I are additionally suitable as fungicides. The comds I are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular of the Ascomycetes and Basidiomycetes classes. In some cases they are systemic active and can be used as leaf and soil fungicides. These comds are particularly important for the control of a multiplicity of fungi in various crop plants such as wheat, rye, barley, oats, rice, corn, grass, cotton, soybean fiber, coffee, sugar cane, vines, fruit plants and decorative plants and plant plants such as cucumbers, beans and cucurbits and the seeds of these plants. They are especially suitable for the control of the following plant diseases: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbites, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, Rhizoctonia species in cotton and pasture, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in strawberries and vines, Cercospora arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricuiaria oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Fusarium and Verticiilium species in various plants, Plasmopara viticulture on vines and species Alternate it in vegetables and fruits.

The comds I are applied by treating the fungus or the plants, seeds, materials or the soil to be protected from the attack of the fungi, with a mycotic active amount of the active comds. The application is carried out before or after the fungal infection of the materials, plants or seeds. The comds can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, flours, pastes and granules. The form of application depends on the particular use that is proposed; in each case, a fine and uniform dispersion of the 2- [(2-alkoxy-6-trifluoromethylpyridimin-4-yl) -oxi-ethylene] phenylacetic acid derivatives must be ensured. The formulations are prepared in the known manner, for example, by spreading the active compound with solvents and / or diluents, if desired using emulsifiers and dispersants. It is also possible, if water is used as a diluent, to use other organic solvents as auxiliary solvents. Auxiliary solvents for this purpose are essentially: solvents such as aromatics (eg, xylene), chlorinated aromatics (eg, chlorobenzenes), paraffins (eg, petroleum fractions), alcohols (eg, aluminum) 1, butane!) Ketones (eg, cyclohexanone), amines (such as ethanolamine, dimethylformamide) and water; diurents as native natural minerals (eg, kaolins, aluminas, talc, chalk) and native synthetic minerals (eg, highly dispersed silicic acid, silicates); emulsifiers such as non-ionic and anionic emulsifiers (eg, ethers of polyoxyethylene fatty alcohols, aikylsuitonates and arylsulfonates) and dispersants such as residual lignosulphite liquors and methyl cellulose. In general, the fungicidal compositions contain from 0.1 to 95, preferably from 0.5 to 90 percent by weight of the active compound. Depending on the desired effect, the application modes are from 0.1 to 2.0 kilograms of active compound per ha. In the treatment of the seeds, in general, the necessary amounts of the active compound are from 0.001 to 0.1 g, preferably from 0.01 to 0.05 g per kilogram of seed. The active compounds can be used as such, in the form of their formulations or in the useful forms prepared therefrom by spraying, spraying, dusting, spreading or watering, for example, in the form of direct solutions. , ab I is, p lvos, suspensions or dispersions, emulsions, oily dispersions, pastes, powdered compositions, compositions or granules for dissemination. Useful forms completely depend on the proposed uses; in each case, if possible they should guarantee the finest dispersion of the active compounds according to the invention. The compounds can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, flours, pastes or granules. The useful forms depend on the particular use that is proposed; in each case, if possible, they should guarantee the finer dispersion than the active compounds. The formulations are prepared in a known manner, for example, by spreading the active compound with solvents and / or diluents, if desired, using emulsifiers and dispersants, and if water is used as a diluent, other organic solvents can also be used as auxiliary solvents. Suitable auxiliaries for this purpose are mainly: - solvents such as aromatics (eg, xylene), chlorinated aromatics (eg, chlorobenzenes), paraffins (eg, petroleum fractions), alcohols (eg. , methanol, butanol), ketones (e.g., cloeanone), amines (e.g., ethanolamine), dimethylformamide and water; - diluents such as native natural minerals (eg kaolins, aluminas, talc, grega) and native synthetic minerals (eg, highly dispersed silicon, silicates), - emulsifiers such as nonionic and anionic emuters (eg. eg, fatty alcohol ethers of polyoxyethylene, alkylsultates and aryisulfonates) and - dispersants such as residual lignosulphite liquors and methylcellulose. Suitable surface active substances or surfactants are the ammonium salts of the aromatic sultonic acids and alkali metals and metals, irrespective of the acid, and the ignosultonic acid, phenol sulphonic acid, naphthalenes ionic and dibutyl. J naphthalensulfone, and also alkyl- and alkylaryl sulfonates of fatty acids, alkyl, lauryl ether and sulfates of fatty alcohols as well as the salts of sulfated hexa-, hepta- and octadecanols, and also of glycol ethers of fatty alcohols, the condensation products of naphthalenesulfonates and their derivatives with formaldehyde, the condensation products of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylenectyl ether phenylic, isooctyl-, octyl- or nonylphenolic, alkylphenol or ethoxylated tributylphenylpolyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, condensates of ethylene oxide of fatty alcohols , ethoxylated risino oil, polyoxyethylene or polyoxypropylene alkyl ethers, polyglycol ether of lauryl alcohol, sorbitol esters, residual lignosulphite liquors or methylic cellulose. Useful aqueous forms can be prepared from concentrates in emulsions, dispersions, pastes, wettable powders or granules dispersible in water by the addition of water. To prepare the emulsions, pastes or oily dispersions, the substances can be homogenized in water as such or dissolved in an oil or solvent by means of wetting agents, adhesives, dispersants or in the case of ficant. However, concentrates can also be prepared which consist of the active substance, wetting agent, adhesive, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution in water. Dust dispersing and dusting compositions can be prepared by mixing or binding, with grinding, the active substances with solid carrier. The granules, for example, homogenous and impregnated granules, coated, can be prepared by agglutinating the active compounds with the solid diluents. Solid diluents are mineral soils such as silica gel, silicas, silicates, talc, kaolin, limestone, quicklime, chalk, calcareoferruginous clay, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, Magnesium, native synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, powdered tree bark, powdered wood and nut peel powder, powder cellulose or other solid diluents. The concentrations of active compounds in the easy-to-use preparations can 1Hi 7.4 (2H); /.55 (1H); /.6 (1H) Table 2 Example 3 3-methoxy-2- (2- (2-isopropoxy-6-trifluoromethylpyrimidin-4-yloxymethyl) phenyl J methyl acrylate (1.03) To prepare the potassium salt of the hydroxypyrimidine from Example 1, 222 g of the hydroxy compound in 855 ml of ethanol and added dropwise to a solution of 56 g of potassium hydroxide in 855 ml of ethanol. After heating to reflux for 3 hours the mixture was concentrated and the residue was taken up in 2 liters of N, N-dimethyltormamide. To this solution of the potassium salt were added 280 g of methyl 3-methoxy-2- (2-bromomethylphenyl) acrylate and the mixture was stirred at 60 ° C for 12 hours.

To treat it, pour it over ice water and extract again with methyl methylbutyl ether. The combined ether tases were washed with water, dried with sodium sulfate and finally concentrated. To remove an N-alkylated by-product, the residue was dissolved in one liter of methanol and treated with 250 ml of water. The crystalline precipitate was filtered off with suction, washed with petroleum ether and dried. 211 g of the title compound were obtained. Mp. 107 ° C NMR-1 !. (CDC1., D in ppm): 1.4 (611); 3.7 (311); 3.8 (311); 5.3 (111); 5.35 (211); 6.65 (111); 7.2 (111); 7.4 (2H); 7.5 (1H); 7.55 (1H) Example 4 Methyl 2-methoxyimino-2- l3-chloro-2- (2-isopropoxy-6-trifluoromethylpyrimidin-4-yloxymethyl) phenyl] acetate (1.08) 3.3 g of 2-isopropoxy-4-hydroxy-6-trifluoromethylpyrimidine and 2.4 g of potassium carbonate was stirred at room temperature (approximately 25 ° C) for 30 min in 100 ml of dimethylformamide and the mixture was then added dropwise for 1 hour with a solution of 4.8 g of 2- methyl methoxyimino-2-! 2-bromomethyl-3-chlorophenyl] acetate in 30 ml of dimethyltormamide After a further 8 hours at room temperature, the reaction mixture was added to the ice water and the product was extracted using tert-butyl ether. The combined ether phases were dried and concentrated, The impure product thus obtained was purified by chromatography (silica gel / toluene) to obtain 4.8 g of the title compound, MP 106-108 ° C RMN-1H ( CDCl, d in ppm): 1.4 (6H), 3.85 (311), 4.0 (311), 5.35 (111), 5.45 (1H), 6.6 (111); 7.1 (111); 7.4 (1H); 7.55 (III) Example 5 2-methoxyimino-2- [3-chloro-2- (2-isopropoxy -trifluoromethyl-1-pyridimin-4-ylox? Methyl) femi] -N-methylacetamide (1.11) A mixture of 2.0 g of the methyl ester obtained from Example 4 and 70 ml of tetrahydrofuran was treated with 2 ml of an aqueous solution of methylamine at 40 *. After 8 hours at room temperature (about 25 ° C) loo my of tert-butyl methyl ether was added to the reaction mixture. The mixture thus obtained was washed three times with citric acid at 20 * concentration and twice with water. The organic phase was dried and concentrated. The impure product thus obtained was purified by chromatography [silica gc / toluene: ethyl acetate (9: 1) J. 1.0 g of the title compound was obtained. Mp 116-118 ° C NMR-! H (CDC1, d in ppm): 1.4 (6H); 2.95 (JH); 3.9 (JH); b.35 (JH); u, .45 (1H); 6.6 (1H); 6.8 (NH); l? (1 HOUR); /.35 (1H); /.5 (1H) • CHi Examples of the action centers animal pests It was possible to show the action of the compounds of the general formula I against animal pests through the The following experiments were performed: Active compounds were prepared a) As a solution at the O.lt concentration in acetone or b) As a 10- emulsion concentration in a mixture of 1 by weight of cyclohexanone, 0 • by weight of Nekarul2 LN (Lutenaol "AP6, wetting agent that has emulsifying and dispersing action based on the ethoxylated alkylphenols) and lp 'by weight of Emulfor" EL (Emulan "EL, emulsifier based on ethoxylated fatty alcohols) and diluted adequately to the desired concentration with acetone in case a) or with water in case b).

After the conclusion of the experiments, the lowest concentration in which the compounds still produced 80-100 inhibition or mortality was determined in each case compared to the control experiments, not treated (threshold of action or minimum concentration). Tetranychus telapus (red spider mite), catalysis Dwarf, potted, densely infested beans which showed the second pair of adult leaves were treated with an aqueous preparation of the active compound. After 5 days in the implant, the success of the control was determined by means of a binocular microscope. In this test, compounds 1.01-1.07 and 1.09-1.11 showed action thresholds from 2 to 400 ppm.

Nephotettix cmcticeps (fleas of green leaves in rice), catalysis. Round filters were treated with the aqueous preparation of the active compound and then 5 fleas of adult leaves were placed. After 24 hours mortality was evaluated. In this test, compounds 1.0 / and 1.08 showed action thresholds of 0.4mg. Examples of the action against the noxious fungus It was possible to show the fungicidal action of the compounds of the general formula I with the following experiments: The active compounds were prepared as an emulsion at 20% concentration in a mixture of 0, by weight of cyclohexanone, 20 ?. by weight of Nekanil'5 'LN (Lutensol6 AP6, wetting agent that has emulsifying and dispersing action with base of ethoxylated alkylphenols) and 10 by weight of Emulfor ™ "(EL) Emulan'5' EL, emulsifier with base of fatty alcohols ethoxylates) and diluted with water according to the desired concentration The comparative compound used was active compound A (Example No. 25, Table I of EP-A 407 872) Action against Plasmopara viticola (Vine Peronospora) flowerpot (variety: Müller Thurgau) were sprayed with the preparation of the active compound until the water dripped.After 8 days the plants were sprayed with zoospore suspension of the fungi Plaemopara vi tí col and remained 20-3ü? C for 5 days. days with high atmospheric humidity Before the evaluation, the plants were maintained for 16 hours with high atmospheric humidity, and the evaluation was carried out visually, in this test the plants treated with 250 ppm of the compounds s 1.01-1.0 ', 1.10 and 1.11, according to the invention, showed an attack of 5 or less while plants treated with the same amount of the active compound A known were attacked by 25'. The untreated plants (control) were attacked an 'i. Action against Pyriculapa oryzae. { Ri ce bias t) Rice seedlings (variety: Tai Nong 6 /) were sprayed with the preparation of the active compound until the water gushed. After 24 hours the plants were sprayed with an aqueous suspension of spores of the fungus Pip cul ap a oryzae and kept at 22-2 / ºC for 6 days with relative atmospheric humidity of 95-99. "The evaluation was carried out in In this test the plants treated with 250 ppm of the compounds 1.01, 1.02, 1.04, 1.06-1.08, 1.10 and 1.11, according to the invention, showed attack of 2 bJ> or less while the treated plants with the same amount of active compound A known were attacked in 60% of the untreated plants (control) were attacked by 85.

Claims (13)

REÍVINDI ACIÓ ES

1. A 2- [(2-alkoxy-6-trifluoromet? Lpyr? Midin-4-? L) oxymethyl en-tert-acetic acid derivative of the formula I where the index and substituents have the following meanings: U is CH or N; V is O or Nll; R is C? -C "alkyl; R1 is cyano, halogen, C-C4 alkyl, Ci-C haloalkyl, C.-Ci alkoxy, C-c < or phenyl; n is 0 or an integer from 1 to 4, it is possible that the radicals R1 are different if the value of n is greater than 1.

2. A compound of formula 1, according to claim 1, wherein U is CH and V is O.

3. A compound of the formula I, according to claim 1, wherein U is N and V is O.

4. A compound of the formula I, according to claim 1, wherein U is N and V is NH.

5. A process for preparing the compounds I, according to claim i, the :: u i consists of the reaction of a p? R? M? Din-4-ol of the formula II. in a manner known per se in an inert organic solvent in the presence of a base with a benzylic derivative of the formula III. wherein X is a leaving group nucleophilically susituible.

6. A process for preparing the compounds I according to claim 1, wherein the sulfone derivative of the formula IV wherein R 'is Ci-C alkyl, is reacted in the presence of a base with an alcohol of the formula V 110-KV

7. The use of the pyripudm-4-oles of the formula II, as established in claim 5, as intermediates for the preparation of the compounds of formula I, in accordance with the indication 1.

8. A sulfone derivative of formula IV, as set forth in claim 6.

9. The use of Sulphone derivatives of the formula IV, as established in claim 6, as intermediates.

10. A composition suitable for controlling pests of animals and noxious fungi, the composition contains a solid or liquid carrier and a compound of formula I, according to claim 1.

11. A process for controlling pests of animals and harmful fungi, the process comprises the treatment of the pests or noxious fungi or the materials, plants, soils or seeds to be protected therefrom, with an effective amount of a compound of the formula I, in accordance with claim 1.

12. The use of The compounds of formula I, according to claim 1, for preparing a composition suitable for controlling pests of animals or harmful fungi.

13. The use of the compounds I, according to claim 1, for controlling harmful animal pests or fungi.