GB2288400A - Silyloxy-cyclopropyl-azolyl derivatives - Google Patents

Description

1 2288400 Silyloxy-cvclopropvl-azolyl derivatives The present invention

relates to novel silyloxy-cyclopropyl-azolyl derivatives, to a process for their preparation and to their use as fungicides.

it has already been disclosed that certain hydroxyethylazolyl derivatives possess fungicidal properties (cf. EP-A 0 438 686 and EP-A 0 123 160). For example, 1-(2-chlorophenyl)-2-(1-methoxy-cycloprop-l-yl)-3-(1,2, 4triazol-l-yl)-propan-2-ol and 1-(2-chloro-phenyl)-2-(1,2,4triazol - 1 yl -methyl) - 3, 3 - dimethyl -butan- 2 - ol can be used to combat fungi. The action of these substances is good, but in some cases leaves something to be desired at low application rates.

Novel silyloxy-cyclopropyl-azolyl derivatives have now been found of the formula CN 1 7;;7 R' c O-SiR3 2 N , z N 11 (I) in which R represents alkyl, Le A 30 289-Foreign countries - 1 RI represents alkyl, alkenyl, alkinyl, cycloalkyl optionally substituted by alkyl, optionally substituted aryl, optionally substituted aralkyl or optionally substituted aralkenyl, and z represents a nitrogen atom or a CH group.

The substances according to the invention contain an asymmetrically substituted carbon atom. They may therefore be obtained in optical isomer forms. The present invention relates both to the individual isomers and to mixtures thereof.

it has also been found that silyloxy-cyclopropyl-azolyl is derivatives of the formula (I) are obtained if oxiranes of the formula R 0 CH 2 1 N, z (I1) in which RI and Z have the meanings given above 1 are reacted with trialkyl-silyl cyanides of the formula R3S'_CN (III) in which R has the meaning given above 1.

Le A 30 289-Foreign countries 2 - in the presence of an acid-binding agent and in the presence of a diluent.

Finally it has been found that the novel silyloxy-cyclopro pyl-azolyl derivatives of the formula (1) have very good fungicidal properties.

Surprisingly the substances according to the invention display a better fungicidal activity than the previously known compounds of the same general mode of action which are closest to them in terms of constitution.

A general definition of the silyloxy-cyclopropyl-azolyl derivatives according to the invention is given by the formula (1).

R preferably represents alkyl having 1 to 3 carbon atoms.

RI preferably represents straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched alkenyl having 2 to 8 carbon atoms, straight-chain or branched alkinyl having 2 to 8 carbon atoms, or represents cycloalkyl having 3 to 7 carbon atoms, it being possible for each of these cycloalkyl radicals to be monosubstituted to trisubstituted by identical or different substituents consisting of alkyl having 1 to 4 carbon atoms, or represents phenyl which may be mono subs ti tuted to trisubstituted by identical or different substituents consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, Le A 30 289-Foreign countries 3 is halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and/or cyano, or represents phenylalkyl having 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety, it being possible for the phenyl moiety to be in each case monosubstituted to trisubstituted by identical or different substituents consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro andlor cyano, or represents phenylalkenyl having 2 to 4 carbon atoms in the straight-chain or branched alkenyl moiety, it being possible for the phenyl moiety to be in each case monosubstituted to trisubstituted by identical or different substituents consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 or Le A 30 289-Foreign countries 1 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and/or cyano.

z also preferably represents nitrogen or a CH group.

R particularly preferably represents methyl.

is R1 particularly preferably represents straight-chain or branched alkyl having 1 to 6 carbon atoms, straightchain or branched alkenyl having 2 to 6 carbon atoms, straight-chain or branched alkinyl having 2 to 6 carbon atoms, or represents cycloalkyl having 3 to 7 carbon atoms, it being possible for each of these radicals to be monosubstituted to trisubstituted by identical or different substituents consisting of methyl and/or ethyl, or represents phenyl which may be monosubstituted to trisubstituted by identical or different substituents consisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1 -methoximino ethyl, nitro and/or cyano, or represents phenylalkyl having 1 to 3 carbon atoms in the straight-chain or branched alkyl moiety, it being possible for the phenyl moiety to be in each case monosubstituted to trisubstituted by identical or different substituents consisting of fluorine, Le A 30 289-Foreign countries - 5 chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy, chlorodi fluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and/or cyano. or represents phenylalkenyl having 2 to 4 carbon atoms in the straight-chain or branched alkenyl moiety, it being possible for the phenyl moiety to be in each case monosubstituted to trisubstituted by identical or different substituents consisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, is trifluoromethylthio, chloro-difluoromethoxy, chlorodi fluoromethylthio, methoxy-carbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and/or cyano.

z also particularly preferably represents nitrogen or a CH group.

Examples of substances according to the invention which may be mentioned are the silyloxy-cyclopropyl-azolyl deri- vatives listed in the following table.

Le A 30 289-Foreign countries - 6 - Table 1 is CN 1 '17 R' cO-SiR3 1 UM2 1 N C ', z N 11 (1) R 1 1 R z -C,H,-n - CE3 H -C4R9-t - CE3 H -CE2 -CH = CE2 -CE3 H -C4E9-n -CE3 CH -C429-t -CE3 CH -CH2-CE = CII - CE3 -CE3 N - C112 C = C11 - C113 H -CE3 H -CH3 N -G-CH3 C113 N cl CE3 N Le A 30 289-Foreign countries - 7 Table 1 (continued) R R z -CH3 cl - CR3 R - CE3 -CE3 OCHF2 -CE3 C113 -CE3 -CH 2 O-Cl -CH 27-0 -CH3 H cl -CH3 -CH 27_. Cl - CE3 -CH--O-F 21 Le A 30 289-Foreign countries - 8 - Table 1 (continued) RI R z F -C113 -CH 2 F - C113 N C-0-CH H 2 3 -CE13 N -CH 2 OCHF 2 -CH2 ---- CF 3 C53 -CH 2 c 3 --0-OCF -CH2 3 -CH cl - CE3 1-0- CH 3 -CE3 -CH 1 - CH 3 3 cl CE3 1 - -CH-P-Cl CH 3 Le A 30 289-Foreign countries - 9 Table 1 (continued) RI R - CH3 -CH F 1-0- CH 3 F -CE3 CH- 3-F 1 c C113 -CH CH 3 1 -C- CH 3 C113 -CH CF 3 1-0- CH3 -CE3 -CH CH 3 10CHF 2 - CIE3 -CH OW 3 1-0 CH 3 -CHI-CH2-0-cl -CE3 -CHI-CH 2-0-F - CE3 - CE3 -CHI---CH-O-CH 3 2 H H N H N X H H H 1 Le A 30 289-Foreign countries - Table 1 (continued) Ri 1 R z -CHI-CH2-P -CH3 H -CH=CH-C -C113 -CH=CH--ci -CE3 - CE3 -CH=CH-C-CH3 CE3 -CH=CH-O-F -CE13 -CH=CH-O-CF3 CE3 -CHCH-O-OCF3 - -C113 -CH=CH-P OCHF2 Le A 30 289-Foreign countries - 11 Using 3-(2-chlorobenzyl)-3-(1,2,4-triazol-l-yl-methyl)2-oxa-spiro[2.21- pentane and trimethylsilyl cyanide as starting materials and calcium oxide as acid-binding agent, the course of the process according to the invention can be illustrated by means of the following equation:

cl 0 CH2-t CH2 1 N ', N N 11 +(CH3)3Si-CN Ca 0 0 cl M 117 CHI---C O-Si(CHI UM2 1 N C ', N N J1 A general definition of the oxiranes required as starting materials for carrying out the process according to the invention is given by the formula (11). in this formula RI and Z preferably have those meanings which have already been mentioned as being preferred for these radicals in connection with the description of the substances of the is formula (I) according to the invention.

Examples of oxiranes of the formula (11) which may be mentioned are the substances listed in the following Table 2.

Le A 30 289-Foreign countries - 12 - Table 2 is RL- 1 11.1 \, N CH 2 1 N 11 z N 11 (11) RI 1 z -C4E9-n -C4H9-t -CH2-CE = C52 -C4E._n CH -C4119-t CH -CE2-CII = C11 - C113 H - CH2-C = CH N CH3 cl Le A 30 289-Foreign countries - 13 - Table 2 (continued) -Q-Cl --0-F -P-F --p OCHF2 -CH2--o-ci -CH2--0 cl -CH2-. 3-cl -CH2-0-F N H H H H H H H N N Le A 30 289-Foreign countries - 14 Table 2 (continued) 11 RI F -CH2-- 3- F -CH2 O-CH3 N H ---p CH2 OCHF2 H -CH2-0-CF3 K ---p CH 2 c 3 N --O-OCF CH 2 3 N -cH cl 1 -C- UM3 N -CH -C-, 1 ;t13 cl H -CH -P- cl 1 - UM3 cl X Le A 30 289-Foreign countries - is - Table 2 (continued) -CH F 1-0- CH3 N F -CH- 3-F 1 CH 3 H -CH CH3 1 -C- CH3 H -CH CF3 1-0- CH3 H -CH 1 3 CH3 OCHF2 H -CH OCF3 1-0CH3 N -CHI--CH-O-Cl 2 H -CHI-CH 2-0-F H -CHI-CH 2-0-CH3 H 1 Le A 30 289-Foreign countries - 16 Table 2 (continued) RI z -CH-CH2-P -CH=CH-0 -CH=CH-O-Cl H 14 H -CH=CH-O-CH3 -CH=CH-O-F -CH=CH-O-CF 3 -CH=CH-O-OCF3 -CH=CH-P OCHF2 K H N H N Le A 30 289-Foreign countries - 17 - The oxiranes of the formula (I1) have not been hitherto disclosed. They can be prepared by reacting cyclopropylhydroxyethyl-azoles of the formula 1 17 R' C C] OH 1 UM 2 1 r, N 'I z N 1 ' (IV) in which RI and Z have the meanings given above in the presence of strong bases and in the presence of a diluent.

Using 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-2-hydroxy3- (1,2,4triazol-l-yl) -propane as starting material and potassium tert-butylate as strong base, the course of the process for the preparation of oxiranes of the formula (11) can be illustrated by the following equation:

Le A 30 289-Foreign countries - 18 cl OH 1'17 CHI-C cl 2 N , N N 11 KOC(CHI -HQ cl O-CH CH2 1 r, N, N N 11 0 A general definition of the cyclopropyl-hydroxyethyl-azoles required as starting materials in the preparation of oxiranes of the formula (II) is given by the formula (IV).

in this formula RI and Z preferably have those meanings which have already been mentioned as being preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention.

The cyclopropyl-hydroxyethyl-azoles of the formula (M are known or can be prepared by methods which are known in principle (cf. EP-A 0 180 136, EPA 0 297 345, EP-A 0 297 is 332, EP-A 0 298 332, EP-A 0 440 949 and EP-A 0 470 463).

Suitable bases for carrying out the process for the preparation of oxiranes of the formula (II) are all conventional, strong, inorganic and organic bases. Preferred possibilities for use are alkali metal alcoholates such as sodium methylate, sodium ethylate and potassium tertbutylate, and also alkali metal hydrides such as sodium hydride.

Suitable diluents for carrying out the process for the preparation of oxiranes of the formula (I1) are all of those inert organic solvents which are customary for such reactions. Preferred possibilities for use are alcohols Le A 30 289-Foreign countries such as methanol, ethanol, propanol and tert-butanol, and also ethers such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, and furthermore aliphatic, cycloaliphatic and aromatic hydrocarbons such as pentane, hexane, cyclohexane, benzene, toluene and xylene.

When carrying out the process for the preparation of oxiranes of the formula (11) the reaction temperatures can be varied within a relatively wide range. The process is in general carried out at temperatures of between WIC and 1000C, preferably between 200C and 800c.

The process for the preparation of oxiranes of the formula (I1) is generally carried out under atmospheric pressure.

is However, it is also possible to work under elevated or reduced pressure.

To carry out the process for the preparation of oxiranes of the formula (II), in general from 1 to 1.5 equivalents of strong base are used per mole of cyclopropyl-hydroxyethylazole of the formula (IV). The product is worked up by conventional methods. The general procedure is to wash the reaction mixture, if desired after diluting it beforehand with an organic solvent whose miscibility with water is poor, with water, to dry and concentrate the organic phase and, if desired, to free the product which remains from any impurities which may be present, by conventional methods such as, for example, by chromatography.

A general definition of the trialkyl-silyl cyanides which are also required as starting materials for carrying out the process according to the invention for the preparation of silyloxy-cyclopropyl-azolyl derivates of the formula (1) is given by the formula (III). in this formula R preferably has those meanings which have already been mentioned as being preferred for this radical in connection with the Le A 30 289-Foreign countries - 20 description of the substances of the formula (I) according to the invention.

The trialkyl-silyl cyanides of the formula (111) are known or can be prepared by known methods.

is When carrying out the process according to the invention, suitable acid- binding agents are weak bases. Preferred possibilities for use are alkali metal carbonates and hydrogen carbonates, such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, and also alkaline earth metal oxides, such as calcium oxide, and, furthermore, ammonium carbonate or ammonium hydrogen carbonate, and also tertiary amines such as triethyl amine and pyridine.

Suitable diluents when carrying out the process according to the invention are all apolar organic solvents. Preferred possibilities for use are aliphatic, cylcoaliphatic or aromatic hydrocarbons such as pentane, hexane, cyclohexane, benzene, toluene and xylene, and also ethers, such as diethyl ether, 1,2- dimethoxyethane, tetrahydrofuran and dioxane, and, furthermore, halogenated hydrocarbons such as dichloromethane, as well.

When carrying out the process according to the invention the reaction temperatures can be varied within a relatively wide range. The process is in general carried out at temperatures between O'C and 601C, preferably between 101C and 300C.

The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to work under elevated or reduced pressure.

To carry out the process according to the invention involves the use, per mole of oxirane of the formula (II), Le A 30 289-Foreign countries - 21 is of in general from 1 to 2 mol of trialkyl-silyl cyanide of the f ormula (III) and from 1 to 2 equivalents of acidbinding agent. The product is worked up by conventional methods. The general procedure is to filter the reaction mixture and to concentrate the filtrate, if desired after washing it beforehand with water, under reduced pressure, and, if desired, to free the product which remains from any impurities which may be present, by conventional methods, for example by chromatography.

The active compounds according to the invention have a strong microbicidal action and can be employed as fungicides.

Fungicides in plant protection are employed for combating Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Some causative organisms of fungal and bacterial diseases which come under the generic names listed above may be mentioned as examples, but not by way of limitation:

Xanthomonas species, such as Xanthomonas oryzae; Pseudomonas species, such as Pseudomonas lachrymans; Erwinia species, such as Erwinia amylovora; Pythium species, such as Pythium ultimum; Phytophthora species, such as Phytophthora infestans; Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis; Plasmopara species, such as Plasmopara viticola; Peronospora species, such as Peronospora pisi or P. brassicae; Erysiphe species, such as Erysiphe graminis; Sphaerotheca species, such as Sphaerotheca fuliginea; Podosphaera species, such as Podosphaera leucotricha; Venturia species, such as Venturia inaequalis; Le A 30 289-Foreign countries Pyrenophora species, such as Pyrenophora teres or P graminea (conidia form: Drechslera, syn:

Helminthosporium); Cochliobolus species, such as Cochliobolus sativus (conidia form: Drechslera, syn: Helminthosporium); Uromyces species, such as Uromyces appendiculatus; Puccinia species, such as Puccinia recondita; Tilletia species, such as Tilletia caries; Ustilago species, such as Ustilago nuda or Ustilago avenae; Pellicularia species, such as Pellicularia sasakii; Pyricularia species, such as Pyricularia oryzae; Fusarium species, such as Fusarium culmorum; Botrytis species, such as Botrytis cinerea; Septoria species, such as Septoria nodorum; is Leptosphaeria species, such as Leptosphaeria nodorum; Cercospora species, such as Cercospora canescens; Alternaria species, such as Alternaria brassicae and Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.

The good toleration, by plants, of the active compounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.

The active compounds according to the invention are particularly suitable for combating cereal diseases such as Erysiphe, Leptosphaeria and Fusarium, and for combatting Plasmopara, Venturia and Podosphaera in fruit growing, viticulture and vegetable growing. They can also be employed against diseases in rice, such as Pyricularia oryzae, and also possess a good and broad in vitro action.

The substances according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, Le A 30 289-Foreign countries - 23 aerosols, very fine capsules in polymeric substances and in coating compositions for seed, as well as UW formulations.

These formulations are produced in a known manner, for exampleby mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents, and/or foam-forming agents. In the case of the use of water as an extender, organic solvents such as alcohols can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as is chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents-, such as dimethylformamide and dimethyl sulphoxide, as well as water; by liquefied gaseous extenders or carriers are meant those liquids which are gaseous at ambient temperature and under atmospheric pressure, for example aerosol propellants, such as halogenated hydrocarbons such as butane, propane, nitrogen and carbon dioxide; as solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates; as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable:

Le A 30 289-Foreign countries - 24 for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcoholand polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. other additives can be mineral and vegetable oils.

it is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper., cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be employed in the formulations as a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides in order for example to widen the spectrum of action or to prevent the build- up of resistance. In many cases, synergistic effects are obtained.

Examples of suitable substrates for the mixtures are the following compounds.

Le A 30 289-Foreign countries - 25 - Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyri-mI dine; 21,61-dibromo-2-methyl-41-trifluoromethoxy-41 trifluoro-methyl-1,3-thiazole-5-carboxanilide; 2,6-di chloro-N-(4-trifluoromethylbenzyl)benzamide;(E)-2-methox imino-K-methyl-2-(2-phenoxyphenyl)-acetamide; 8-hydroxyqui noline sulphate; methyl (E)-2-{2-E6-(2-cyanophenoxy) pyrimidin-4-yloxyl -phenyl} - 3 -methoxy- acryl ate; methyl (E) methoximino[alpha-(o-tolyloxy)-o-tolyllacetate; 2-phenyl phenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate, is calcium polysulphide, captafol, captan, carbendazim, carboxin, quinomethionate, chloroneb, chloropicrin, chloro thalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram, dichlorophen, diclobutrazol, dichlofluanid, dichlomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine, drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclo nil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulphamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fthalide. fuberidazole, furalaxyl, furmecyclox, guazatine, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione, isoprothiolane, kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture, Le A 30 289-Foreign countries mancopper. mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methasulphocarb, methfuroxam, metiram, metsulphovax, myclobutanil, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxycarboxin, perfurazoate, penconazole, pencycuron, phosdiphen, pimari cin, piperalin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon quintozene (PCNB), sulphur and sulphur preparations, tebuconazole, tecloftalam, tecnazene.

thiabendazole, thicyofen, thiophanate-methyl, is tolclophos -methyl, tolylfluanide, triadimefon, triadimenol triazoxide, trichlamide, tricyclazole, tridemorph triflumizole, triforine, triticonazole, validamycin A, vinclozolin, zineb, ziram.

tetraconazole, thiram Bactericides:

bronopol, dichlorophen, nitrapyrin, nickeldimethyldi- thiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, teclof talam, copper sulphate and other copper preparations.

insecticides/Acaricides/Nematicides:

abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin, Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap, beta-cyf luthrin, bif enthrin, BPMC, brof enprox, bromophos A, bufencarb, buprofezin, butocarboxin, butylpyridaben, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, CGA 157 419, CGA 184699, chloethocarb, chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlor mephos, chlorpyrifos, chlorpyrifos M, cis-resmethrin, Le A 30 289-Foreign countries 27 - clocythrin, cyfluthrin, cyromazine, deltamethrin, demeton M, demeton S, demetonS-methyl, diafenthiuron, diazinon, dichlorofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton, edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethotenprox, ethoprophos, etrimphos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam, flucycloxuron, flucythrinate, flufenoxuron, is flufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathiocarb, ECE, heptenophos, hexaflumuron, hexythiazox, imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion, ivemectin, lambda-cyhalothrin, lufenuron, malathion, mecarbam, mervinphos, mesulphenphos, metalde hyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled, KC 184, NI 25, nitenpyram, omethoate, oxamyl, oxydemethon M, oxydeprofos, parathion A, parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, phosphamdon, phoxim, pirimicarb, pirimiphos M, pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozin, pyrachlophos, pyradaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen, quinalphos, RH 5992, salithion, sebufos, silafluofen, sulphotep, sulprofos, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron.

tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, clofentezine, cyanophos, cycloprothrin, cyhalothrin, cyhexatin, cypermethrin, Le A 30 289-Foreign countries thiafenox, thiodicarb, thiofanox, thiomethon,thionazin, thuringiensin, tralomethrin, triarathen, triazophos, triazuron, trichlorfon, triflumuron, trimethacarb, vamidothlon, XMC, xylylcarb, zetamethrin.

A mixture with other known active compounds, such as herbicides, or with fertilizers and growth regulators is also possible.

The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by watering, is spraying, atomizing, scattering, dusting, foaming, brushing on and the like. It is furthermore possible to apply the active compounds by the ultra-low volume method or to inject the active compound preparation or the active compound itself into the soil. The seeds of the plants can also be treated.

In the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range: they are, in general, between 1 and 0.0001% by weight, preferably between 0.5 and 0. 001% by weight.

In the treatment of seed, amounts of active compound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concentrations of 0.00001 to 0. 1% by weight, preferably 0.0001 to 0.02% by weight, are required at the place of action.

The preparation and the use of active compounds according to the invention are illustrated by the following examples.

Le A 30 289-Foreign countries - 29 Preparation Examples Exami)1e 1 cl M 1 7:7 CHi-C O-SI(CH J3 i;r12 N ', N N 11 (1 - 1) A mixture of 1.38 g (5 mmol) of 3-(2-chlorobenzyl)3-(1,2,4-triazol-l-ylmethyl)-2-oxa-spiro[2.2]pentane,l g of calcium oxide, 1.33 ml. (10 mmol) of trimethylsilyl cyanide and 20 ml of absolute n-hexane is stirred at 200C for 65 hours. The reaction mixture is then filtered and concentrated under reduced pressure. In this way 1.4 g (74% of theory) of 1-(2chlorophenyl)-2-cyano-3-(1,2,4-triazoll-yl)-2-(1-trimethylsilyloxycycloprop-l-yl)-propane are obtained in the form of an oil.

is 1H-NMR spectrum (200 MHz, MC13.' TMS):

(ppm) 0.25 (s, M; 0.45-1.0 (m, C1); 3.4 (AB, 2H); 4.55 (AB, 2H); 7.25-7.7 (m, 4H); 7.95 (s, 1H); 8.2 (s, 1H) Le A 30 289-Foreign countries Preparation of startincr substances Exam.ple 2 cl 0 CH2 CH--C c UM2 2 (11-1) 1 CH N r, ', N N 1' A mixture of 3.12 g (10 mmol) of 2-(1-chlorocyclopropyl)1-(2chlorophenyl)-2-hydroxy-3-(1,2,4-triazol-l-yl)propane, 1.12 g (10 mmol) of potassium tert-butylate and 50 ml of absolute tert-butanol is stirred at 600C for 25 hours. The reaction mixture is then diluted with ethyl acetate and washed several times with water. The organic phase is dried over sodium sulphate and concentrated under reduced pressure. 3.29 g of a crude product are obtained which is chromatographed over 300 g of silica gel using ethyl acetate as eluent. After the concentration of the eluate, 1.3 g (47% of theory) of 3-(2-chlorobenzyl)3-(1,2,4-triazol-l-yl-methyl)-2-oxa-spiro[2. 21-pentaneare obtained in the form of an oil.

1H-MR spectrum (200 MHz, CDC1,0 TMS): 0.7-0.95 (m, 4H); 3.3 (s, 2H); 4.55 (AB, 2H); 7.2-7.4 (m, 4H); 7.9 (s, 11-1); 8.1 (s, 1H) ppm GC/MS(Ci): 276 (M + H+, 100%) Le A 30 289-Foreign countries - 31 Exa=le 3 / 0 \ CH2 C'H =CH-CHI---C-CH--C-C 2 1 CH 2 CH2 CH2 1 N C ' N N 11 (11-2) A mixture of 1.34 g (5 mmol) of 6-(1-chlorocyclopropyl)6 -hydroxy-4 - methylene- 7 (1,2,4-triazol-l-yl) -hept-l-ene, 0.56 g (5 mmol) of potassium tert-butylate and 30 ml of absolute tert-butanol is stirred at 600C for 22 hours. The reaction mixture is then diluted with ethyl acetate and washed several times with water. The organic phase is dried over sodium sulphate and concentrated under reduced pressure. 1.1 g of a crude product are obtained which is chromatographed over 300 g of silica gel using ethyl acetate as eluent. After the concentration of the eluate, 0.8 g (70% of theory) of 3-(2-methylene-pent-4-enyl)3-(1,2,4-triazol-l-ylmethyl)-2-oxa-spiro[2.2]pen tane is obtained in the form of an oil.

is 1H-NMR spectrum (200 MHz, CDC13. TMS):

(ppm) 0.8-1.1 (m, 4F0; 2.45 (AB, 2H); 2.7 (AB, 210; 4.55 (s, 2H); 5.0 (m, 4H); 5.8 (m, 1I-I); 7.95 (s, 1F0; 8.15 (s, 1I-I) GC/MS(Ci): 232 (M + H+, 100%) Le A 30 289-Foreign countries Exam.ple 4 / 0 \ / CH2 C-CH-C-C j j 2 1 ' 1 CH 2 CH2 CH2 1 N, 1 N (11-3) A mixture of 1.52 g (5 mmol) of 4-(1-chloro-cyclopropyl)4-hydroxy-2phenyl-S-(1,2,4-triazol-l-yl)-pent-l-ene,0.67 g (6 mmol) of potassium tert-butylate and 50 ml of absolute tetrahydrofuran is stirred at 400C for 5 hours. The reaction mixture is then diluted with ethyl acetate and washed several times with saturated aqueous sodium carbonate solution. The organic phase is dried over sodium sulphate and concentrated under reduced pressure. 1.3 g of a crude product are obtained which is chromatographed over 200 g of silica gel using ethyl acetate as eluent. After is the concentration of the eluate, 0.5 g (37% of theory) of 3- (2 phenyl -prop- 1-en-3 -yl) -3- (1,2,4 - triazol - l-yl -methyl) 2-oxaspiro[2.2]pentane is obtained in the form of an oil.

GC/MS (Ci): 268 (M + H', 100%) Example 5 / 0 \ "_,CH2 CHS--C-CHi--C-C-', H 1 CH2 CH2 UM2 1 N C, ' N N 11 (11-4) Le A 30 289-Foreign countries - 33 The compound of the formula (11-4) is also prepared by the method indicated in Example 4. The substance is obtained in the form of an oil.

1 GC/MS (Ci): 206 (M + H+, 100%) T Le A 30 289-Foreign countries - 34 Use Examples

Example A

Erysiphe test (barley)/protective Solvent: 10 parts by weight of N-methyl-pyrrolidone Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

is To test for protective activity, young plants are sprayed with the preparation of active compound at the application rate indicated.

After the spray coating has dried on, the plants are dusted with spores of Erysiphe graminis f.sp. hordei.

The plants are placed in a greenhouse at a temperature of about 2CC and a relative atmospheric humidity of about 80%, in order to promote the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, at an application rate of 250 g/ha, the compound (I-1) according to the invention exhibits a degree of action of 100%.

Le A 30 289-Foreign countries Example B

Gibberella zeae test (barley)/protective 9 Solvent: 10 parts by weight of N-methyl-pyrrolidone Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether TO produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed is with the preparation of active compound at the application rate indicated.

After the spray coating has dried on, the plants are sprayed with a conidia suspension of Gibberella zeae.

The plants are placed in a greenhouse under transparent incubation covers at a temperature of about 200C and a relative atmospheric humidity of about 100%.

Evaluation is effected 4 days after the inoculation.

In this test, at an application rate of 250 g/ha, the compound (I-1) according to the invention exhibits a degree of action of 100%.

Le A 30 289-Foreign countries - 36 - Examiple C Venturia test (apple) / protective Solvent:

Emulsifier:

4.7 parts by weight of acetone 0.3 part by weight of alkyl-aryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

TO test for protective activity, young plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the apple scab causative organism Venturia inaequalis and then remain in an incubation cabin at 200C and 100% relative atmospheric humidity for 1 day.

The plants are then placed in a greenhouse at 200C and a relative atmospheric humidity of about 70%.

Evaluation is carried out 12 days after the inoculation.

In this test, at an application rate of 1 ppm, the compound (I-1) according to the invention exhibits a degree of action of more than 90%.

It will of course be understood that the present invention has been described above purely by way of example, and that modifications of detail can be made within the scope of this invention.

Le A 30 289-Foreign countries - 37

Claims (12)

Patent claims

1. Silyloxy-cyclopropyl-azolyl derivatives of the formula CN 1 17 R' c O-SiR3 1 UM 2 1 N r, ', z N 11 in which R represents alkyl, R1 represents alkyl, alkenyl, alkinyl, cycloalkyl optionally substituted by alkyl, optionally substituted aryl, optionally substituted aralkyl or optionally substituted aralkenyl, and is Z represents nitrogen or a CH group.

2. Silyloxy-cyclopropyl-azolyl derivatives of the formula (1) according to Claim 1, in which R represents alkyl having 1 to 3 carbon atoms.

R1 represents straightchain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched alkenyl having 2 to 8 carbon atoms, straightchain or branched alkinyl having 2 to 8 carbon atoms, or Le A 30 289-Foreign countries is represents cycloalkyl having 3 to 7 carbon atoms, it being possible for each of these cycloalkyl radicals to be monosubstituted to trisubstituted by identical or different substituents consisting of alkyl having 1 to 4 carbon atoms, or represents phenyl which may be monosubstituted to trisubstituted by identical or different substituents consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and/or cyano, or represents phenylalkyl having 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety, it being possible for the phenyl moiety to be in each case monosubstituted to trisubstituted by identical or different substituents consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, Le A 30 289-Foreign countries - 39 i is phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and/or cyano, or represents phenylalkenyl having 2 to 4 carbon atoms in the straight-chain or branched alkenyl moiety, it being possible for the phenyl moiety to be in each case monosubstituted to trisubstituted by identical or different substituents consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and/or cyano, and Z represents nitrogen or a CH group.

3.

Process for the preparation of silyloxy-cyclopropyl azolyl derivatives of the formula CN 1 E7 R' c O-SiR3 1 UM2 1 N i ', z N 11 Le A 30 289-Foreign countries (1) k in which R represents alkyl, R1 represents alkyl, alkenyl, alkinyl, cycloalkyl optionally substituted by alkyl, optionally substituted aryl, optionally substituted aralkyl or optionally substituted aralkenyl, and Z represents nitrogen or a CH group, characterized in that oxiranes of the formula R 1 0 CH2 1 N ' ', Z N 1 ' in which (II) R1 and Z have the meanings given above 1 are reacted with trialkyl-silyl cyanides formula R3si-W in which (III) R has the meaning given above, of the in the presence of an acid-binding agent and in the presence of a diluent.

Le A 30 289-Foreign countries - 41

4. Fungicidal compositions, characterized in that they at least' one silYlOxy-cYclopropyl-azole derivative of the formula (1) according to Claim 1.

contain IL

5. Use of silyloxy-cyclopropyl-azole derivatives of the formula (1) according to Claim 1 as fungicides.

6. Method of combating fungi, characterized in that silyloxy-cyclopropylazole derivatives of the formula (I) according to Claim 1 are applied to the fungi and/or to their habitat.

7. Process for the preparation of fungicidal compositions, characterised in that silyloxy-cyclopropyl-azolyl derivatives of formula (I) according to Claim 1 are mixed with extender and/or surface active agents.

8. Silyloxy-cyclopropyl-azolyl derivatives according to Claim 1, as hereinbefore specifically identified.

9. Process for the preparation of silyloxy-cyclopropyl- azolyl derivatives according to Claim 1, substantially as hereinbefore specifically described in Example 1.

10. Silyloxy-cyclopropyl-azolyl derivative according to Claim 1, whenever produced by the process of Claim 9.

11. Method according to Claim 6, in which a silyloxy- cyclopropyl-azolyl derivative according to claim 8 or is used.

12. Process according to Claim 7, in which the silyloxycyclopropyl-azolyl derivative is a compound according to Claim 8 or 10.

J! Le A 30 289-Foreign countries - 42