WO2004062361A2 - Spiro compounds - Google Patents

Abstract

The invention relates to novel spiro compounds of formula (I) wherein R represents optionally substituted heterocyclyl, to a method for producing said novel active ingredients, and to the use of the same as microbicides.

Description

spiro compounds

The present invention relates to new spiro compounds, a process for their production and their use to control undesirable microorganisms.

Various substituted 5-phenyl-6-oxa-4-azaspiro [2,4] hept-4-en-7-ones have already become known (cf. J. Chem. Soc. Perkin Trans. 2 (1993), 741-748 and Int. J. Pept. Protein Res. 34 (1989), 56-65). However, the use of the substances described there against plant pests has not yet been disclosed.

There have now been new spiro compounds of the formula

in which

R represents optionally substituted heterocyclyl,

found.

Furthermore, it has been found that the spiro compounds of the formula (I) are obtained when

a) Acylaminocyclopropanecarboxylic acids of the formula

in which

R has the meaning given above,

with condensing agents, if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor and if appropriate in the presence of a catalyst.

Finally, it was found that the new spiro compounds of the formula (I) have very good microbicidal properties and can be used both in crop protection and in material protection to combat unwanted microorganisms. The substances according to the invention can not only be used for the direct control of undesired microorganisms, but also practice

Plant out a resistance-inducing effect.

Surprisingly, the spiro compounds of the formula (I) according to the invention show a substantially better fungicidal activity than the most similarly known, previously known active compounds of the same action.

The spiro compounds according to the invention are generally defined by the formula (I). Preferred substances of the formula (I) are those in which

R represents optionally substituted by halogen and / or alkyl having 1 to 4 carbon atoms, optionally benzo-fused, five or six-membered heterocyclyl,

or R is a radical of the formula which is halogen and / or

Alkyl with 1 to 4 carbon atoms can be substituted.

Substances of the formula (I) in which

R represents single to triple, identical or different, pyridyl, isothiazolyl, thienyl or benzothiophenyl substituted by chlorine, bromine and / or methyl or

durch Chlor, Brom und/oder Methyl substituiert sein kann.R stands for the rest of the formula, single or double

can be substituted by chlorine, bromine and / or methyl.

Compounds of the formula (I) in which

R for 2,6-dichloropyrid-4-yl, 3,4-dichloroisothiazol-5-yl, 5-bromo-2-thienyl, 5-chloro-2-thienyl, 4,5-dibromo-2-thienyl, 3- Chloro-l-benzothiophene-2-yl, 2-

steht.Chloro-6-methyl-pyrid-4-yl or for the rest of the formula

stands.

If one uses l- [2,6-dichloro-isonicotinyl) amino] -cyclopropane-carboxylic acid as the starting substance and oxalyl chloride as the condensing agent, the nerlauf can of process (a) according to the invention can be illustrated by the following formula

Formula (II) provides a general definition of the acylaminocyclopropanecarboxylic acids required as starting materials for carrying out process (a) according to the invention. In this formula, R preferably has those meanings which have already been mentioned as preferred for this radical in connection with the description of the substances of the formula (I) according to the invention.

The acyla inocyclopropanecarboxylic acids of the formula (II) are hitherto unknown. They can be made by

b) acylaminocyclopropane-carboxylic acid ester of the formula

in which

R has the meanings given above and

R ^{1 represents} methyl or ethyl, with water in the presence of a base and optionally in the presence of an organic diluent.

If 1 - [(2,6-dichloro-iso-nicotinyl) amino] cyclopropane-carboxylic acid methyl ester is used as the starting substance, the course of process (b) can be illustrated by the following formula.

Formula (III) provides a general definition of the acylamino-cyclopropane-carboxylic acid esters required as starting substances for carrying out process (b). In this formula, R preferably has those meanings which have already been mentioned as preferred for this radical in connection with the description of the substances of the formula (I) according to the invention. R ¹ represents methyl or ethyl.

The acylamino-cyclopropanecarboxylic acid esters of the formula (III) are also not yet known. They can be made by

c) aminocyclopropane-carboxylic acid esters of the formula

in welcher

in which

R ^{1 has} the meanings given above, or their hydrohalides or hydrogen sulfates,

with acid halides of the formula

^{R ~} H ^_X V) ° in which

R has the meanings given above and

X represents halogen,

if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

If 3,4-dichloro-5-isothiazole-carbonyl chloride and 1-amino-cyclopropane are used

1-carboxylic acid methyl ester as starting materials, the course of process (c) can be illustrated by the following formula.

Formula (IV) provides a general definition of the aminocyclopropane-carboxylic acid esters required as starting substances for carrying out process (c). In this formula, R ^{1 represents} methyl or ethyl.

The aminocyclopropane-carboxylic acid esters of the formula (IV) are known or can be prepared by known methods (cf. DE-A 28 24 517, WO 86-03 378, EP-A 0 199 257 and Plant Growth Regul. 8 (4), (1989), 297-307). So let yourself be produce by reacting 1-amino-cyclopropane-carboxylic acid with methanol or ethanol in the presence of tliionyl chloride.

Formula (N) provides a general definition of the acid halogens required as reaction components for carrying out process (c). In this

Formula R preferably has those meanings which have already been mentioned as preferred for this radical in connection with the description of the substances of the formula (I) according to the invention. X preferably represents chlorine or bromine.

The acid halides of the formula (V) are known or can be prepared according to known ones

Produce methods (cf. DE-A 3615 293, WO 99-24 413, EP-A 0393 936 and Tetrahedron Lett. (1968), (49), 5149-5152).

Suitable diluents for carrying out process (a) according to the invention are all customary, inert organic solvents.

Aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, tetrachloromethane, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as Ν, Ν-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide or Sufone such as sulfolane.

Suitable condensation agents for carrying out process (a) according to the invention are all cyclization reagents which can normally be used for amidation reactions. Acid halide formers can preferably be used such as phosgene, oxalyl chloride, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride or thionyl chloride; Anhydride formers such as ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate or methanesulfonyl chloride; Carbodiimides, such as N, N'-dicyclohexylcarbodiimide (DCC) or other customary condensing agents, such as phosphorus pentoxide, polyphosphoric acid, N, N'-carbonyldiimidazole, 2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ), bis- (2 -Oxo-3-oxazolidinyl) phosphinic acid chloride (BOP-Cl) or triphenylphosphine / carbon tetrachloride.

Suitable acid binders for carrying out process (a) according to the invention are all customary inorganic and organic bases. Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, are preferably usable. Sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or cesium carbonate, furthermore ammonium compounds, such as ammonium hydroxide, ammonium acetate or ammonium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N , N-dimethyl-benzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

Suitable catalysts for carrying out process (a) according to the invention are all reaction accelerators customary for such reactions. Examples include 4-dimethylaminopyridine, 1-hydroxy-benzotriazole or dimethylformamide.

The reaction temperatures can be varied within a substantial range when carrying out process (a) according to the invention. Generally works one at temperatures between -78 ° C and + 120 ° C, preferably at temperatures between -60 ° C and + 25 ° C.

When carrying out process (a) according to the invention, as in carrying out processes (b) and (c), the procedure is generally carried out under

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

When carrying out process (a) according to the invention, 0.5 to 5 mol, preferably an equimolar amount, of condensing agent are generally employed per mol of acylamino-cyclopropanecarboxylic acid of the formula (II). The processing takes place according to usual methods.

Bases which can be used in carrying out process (b) are all customary inorganic bases. Alkaline earth metal or alkali metal hydroxides, such as, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, can preferably be used.

Suitable diluents for carrying out process (b) are all customary, water-miscible, organic solvents. Alcohols such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-l, 2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether are preferably usable.

The reaction temperatures can be varied within a substantial range when carrying out process (b). In general, temperatures from 0 ° C to 80 ° C, preferably at temperatures from 0 ° C to 50 ° C.

When carrying out process (b), acylamino-cyclopropanecarboxylic acid esters of the formula (III) are used in the presence of an equivalent amount or one Excess base with an excess of water. The processing is again carried out using customary methods.

Suitable diluents for carrying out process (c) are all customary, inert organic solvents. Aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether,

Methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole, or amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethyl- triamide.

Suitable acid binders when carrying out process (c) are all customary inorganic and organic bases. Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, are preferably usable.

Potassium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or cesium carbonate, furthermore ammonium compounds, such as ammonium hydroxide, ammonium carbonate or ammonium acetate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimin , N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylamino-pyridine, diazabipyclooctane (DABCO), diazabicyclonones (DBN) or diazabicyclonecene (DBU). The reaction temperatures can be varied within a substantial range when carrying out process (c). In general, temperatures from 0 ° C to 120 ° C, preferably at temperatures from 0 ° C to 80 ° C.

When carrying out process (c), 0.2 to 5 mol, preferably 0.5 to 2 mol, of acid halide of the formula (V) are generally employed per mol of amino-cyclopropane-carboxylic acid ester of the formula (IV) , The processing takes place according to usual methods.

The substances according to the invention have a strong microbicidal action and can be used to control unwanted microorganisms, such as fungi and bacteria, in crop protection and in material protection.

Fungicides can be used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and

Use Deuteromycetes.

Bactericides can be used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:

Xanthomonas species, such as, for example, Xanthomonas campestris pv. Oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv. Lachrymans;

Erwinia species, such as, for example, Erwinia amylovora;

Pythium species, such as, for example, Pythium ultimum; Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Bremia species, such as, for example, Bremia lactucae;

Peronospora species, such as, for example, Peronospora pisi or P. brassicae; Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca Fülliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidial form: Drechslera, Syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus

(Conidial form: Drechslera, Syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita; Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae; Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens; Alternaria species, such as, for example, Alternaria brassicae;

Pseudocercosporella species, such as, for example, Pseudocercosporella heφotrichoides.

The active compounds according to the invention also have a strong strengthening effect in plants. They are therefore suitable for mobilizing the plant's own defenses against attack by unwanted microorganisms. Plant-strengthening (resistance-inducing) substances are to be understood in the present context as substances which are able to stimulate the defense system of plants in such a way that the treated plants develop extensive resistance to these microorganisms when subsequently inoculated with undesired microorganisms.

Undesired microorganisms are to be understood in the present case as phytopathogenic fungi, bacteria and viruses. The substances according to the invention can therefore be used to protect plants from attack by the named pathogens within a certain period of time after the treatment. The period of time within which protection is brought about generally extends from 1 to 10 days, preferably 1 to 7 days, after the plants have been treated with the active compounds.

The good plant tolerance of the active ingredients in the fight against

Concentrations necessary for plant diseases allow the treatment of above-ground parts of plants, of seedlings, and of the soil.

The active compounds according to the invention can be used with particularly good results in combating cereal diseases, for example against Erysiphe species.

The active compounds according to the invention are also suitable for increasing the crop yield. They are also less toxic and have good plant tolerance.

If appropriate, the active compounds according to the invention can also be used in certain concentrations and application rates as herbicides, for influencing plant growth and for controlling animal pests. If appropriate, they can also be used as intermediates and precursors for the synthesis of further active compounds. According to the invention, all plants and parts of plants can be treated. Plants are understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Cultivated plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which can or cannot be protected by plant breeders' rights. Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

The treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space according to the customary treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, scattering, spreading and, in the case of propagation material, in particular in the case of seeds, furthermore by coating in one or more layers.

In material protection, the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.

In the present context, technical materials are understood to mean non-living materials that have been prepared for use in technology. For example, technical materials which are to be protected against microbial change or destruction by active substances according to the invention can

Adhesives, glues, paper and cardboard, textiles, leather, wood, paints and Plastic articles, cooling lubricants and other materials that can be attacked or decomposed by microorganisms. In the context of the materials to be protected, parts of production systems, for example cooling water circuits, are also mentioned which can be impaired by the multiplication of microorganisms. In the context of the present invention, technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids, particularly preferably wood.

Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials. The active compounds according to the invention preferably act against fungi, in particular molds, wood-coloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.

Microorganisms of the following genera may be mentioned, for example:

Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger, Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puetana, Lentinus, such as Lentinus tigrinus, Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma such as Sclerophoma pityophila, Trichoderma such as Trichoderma viride, Escherichia such as Escherichia coli, Pseudomonas such as Pseudomonas aeruginosa, Staphylococcus such as Staphylococcus aureus. Depending on their respective physical and / or chemical properties, the active ingredients can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV -Cold and warm mist formulations.

These formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water. Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. Solid carriers are possible: e.g. natural rock powders such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates. Solid carriers for granules are possible: e.g. broken and fractionated natural rocks such as calcite, pumice, marble, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems. As an emulsifier and / or foam generator

Agents are possible: for example nonionic and anionic emulsifiers, such as poly oxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Possible dispersants are: eg lignin sulfite waste liquor and methyl cellulose.

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as guariarabicum, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to to broaden the spectrum of activity or to prevent the development of resistance. In many cases, synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components.

The following connections can be considered as mixed partners:

fungicides:

2-phenylphenol; 8-hydroxyquinoline sulfate; Acibenzolar-S-methyl; aldimorph; amidoflumet; Ampropylfos; Ampropylfos potasium; andoprim; anilazine; azaconazole; azoxystrobin;

benalaxyl; Benodanil; benomyl; Benthiavalicarb-isopropyl; Benzamacril; Benzama-cril-isobutyl; bilanafos; binapacryl; biphenyl; bitertanol; Blasticidin-S; Bromuconazoles; Bupirimate; Buthiobate; butylamine;

Calcium polysulfide; capsimycin; captafol; captan; carbendazim; carboxin; Caφropamid; carvones; chinomethionat; Chlobenthiazone; Chlorfenazole; Chloroneb; chlorothalonil; chlozolinate; Clozylacon; cyazofamid; cyflufenamid; Cymoxanil; cyproconazole; cyprodinil; cyprofuram;

Dagger G; debacarb; dichlofluanid; dichlone; dichlorophen; diclocymet; Diclomezine; dicloran; diethofencarb; Difenoconazole; diflumetorim; dimethirimol; Dimethomoφh; dimoxystrobin; diniconazole; Diniconazole-M; dinocap; Diphenylamines; Dipyrithione; Ditalimfos; dithianon; dodine; Drazoxolon;

edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole;

famoxadone; fenamidone; Fenapanil; fenarimol; Fenbuconazole; Fenfiiram; Fenhexamide; Fenitropan; fenoxanil; fenpiclonil; fenpropidin; Fenpropimoφh; ferbam;

fluazinam; Flubenzimine; fludioxonil; flumetover; Flumoφh; fluoromides;

fluoxastrobin; fluquinconazole; Fluφrimidol; flusilazole; flusulfamide; flutolanil;

flutriafol; folpet; Fosetyl-Al; Fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; Furcarbanil; Furmecyclox;

guazatine;

Hexachlorobenzene; hexaconazole; hymexazol; imazalil; Imibenconazole; Iminoctadine triacetate; Iminoctadine tris (albesil; iodocarb; ipconazole; ipprobefos; iprodione; iprovalicarb; rrumamycin; isoprothiolane; isovaledione;

kasugamycin; Kresoxim-methyl;

mancozeb; maneb; Meferimzone; mepanipyrim; mepronil; metalaxyl; Metalaxyl-M; metconazole; methasulfocarb; Methfuroxam; metiram; metominostrobin; Metsulfovax; mildiomycin; myclobutanil; myclozoline;

natamycin; nicobifen; Nitro Thal-isopropyl; Noviflumuron; nuarimol;

ofurace; orysastrobin; oxadixyl; Oxolinic acid; Oxpoconazole; oxycarboxin; Oxyfenthiin;

paclobutrazol; Pefurazoate; penconazole; pencycuron; phosdiphen; phthalides; Picoxystrobin; piperalin; Polyoxins; Polyoxorim; Probenazole; prochloraz; Procymi-done; propamocarb; Propanosine-sodium; propiconazole; propineb; proquinazid; prothioconazole; pyraclostrobin; Pyrazohos; pyrifenox; pyrimethanil; pyroquilon; Pyroxyfur; Pyrrolnitrine;

Quinconazole; quinoxyfen; quintozene;

Simeconazole; spiroxamine; Sulfur;

tebuconazole; tecloftalam; Tecnazene; Tetcyclacis; tetraconazole; thiabendazole;

Thicyofen; Thifluzamide; Thiophanate-methyl; thiram; Tioxymid; Tolclofos-methyl; tolylfluanid; triadimefon; triadimenol; Triazbutil; triazoxide;

Tricyclamide; Tricyclazole; Tridemoφh; trifloxystrobin; triflumizole; triforine; triticonazole; Uniconazole;

Validamycin A; vinclozolin;

Zineb; ziram; zoxamide;

(2S) -N- [2- [4 - [[3- (4-chlorophenyl) -2-propynyl] oxy] -3-methoxyphenyl] ethyl] -3-methyl-2 - [(methylsulfonyl) amino] butanamide ;

l- (l-Naρhthalenyl) -lH-pyrrole-2,5-dione;

2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine;

2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide;

2-chloro-N- (2,3-dihydro-l, l, 3-trimethyl-lH-inden-4-yl) -3-pyridinecarboxamides;

3,4,5-trichloro-2,6-pyridinedicarbonitrile; Actinovate;

ice-1 - (4-chloro-phenyl) -2- (1 H-1, 2,4-triazol-1-yl) -cycloheptanol;

Methyl l- (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) -IH-imidazole-5-carboxylate;

Monokaliumcarbonat;

N- (6-methoxy-3-pyridinyl) -cyclopropanecarboxamide;

sodium tetrathiocarbonate; as well as copper salts and preparations, such as Bordeaux mixture; copper; copper naphthenate; copper oxychloride; Copper sulfate; Cufraneb; copper; mancopper; Oxine-copper.

bactericides:

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, teclofalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

Abamectin, ABG-9008, Acephate, Acequinocyl, Acetamiprid, Acetoprole, Acrinathin, AKD-1022, AKD-3059, AKD-3088, Alanycarb, Aldicarb, Aldoxycarb, Allethrin, Allethrin lR-isomers, Alpha-Cypermethrin), Alphamypethrin amidoflumet,

Aminocarb, Amitraz, Avermectin, AZ-60541, Azadirachtin, Azamethiphos, Azinphos-methyl, Azinphos-ethyl, Azocyclotin,

BaciUus popilliae, BaciUus sphaericus, BaciUus subtilis, BaciUus thuringiensis, BaciUus thuringiensis strain EG-2348, BaciUus thuringiensis strain GC-91, BaciUus thuringiensis strain NCTC-11821, Baculoviren, Beauveria bassiana, Beauaciarbarbox, Beauendiarbuloxella, Beauendiarbulobella, Beauendiarboxarbella, Beauendiarbuloxella, Beauendiarboxarbella, Beauendiarbuloxella -Cyfluthrin, beta-cypermethrin, bifenazate, bifenthrin, binapacryl, bioallethrin, bioallethrin-S-cyclopentyl isomer, bioethanomethrin, biopennethrin, bioresmethrin, bistrifluron, BPMC, brofenprox, bromophyl-ethyl-bromophyl-ethyl-bromophos-ethyl-bromophos-ethyl

BTG-504, BTG-505, Bufencarb, Buprofezin, Butathiofos, Butocarboxim, Butoxycarboxim, Butylpyridaben,

Cadusafos, Camphechlor, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA-50439, Chinomethionate, Chlordane, Chlordimeform, Chloethocarb,

Chloroethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, Chlorobenzilate, Chloropicrin, Chloφroxyfen, Chloφyrifos-methyl, Chloφyrifos (- ethyl), Chlovaporthrin, Chromafenozide, Cis-Cypermethrin, Cis-Resmethrin, Cis- Permethrin, Clocythrin, Cloethocarb, Clofentezine, Cyanophosphos, Cyanosophone, Clothianidin, Clothianidin, Clothianidin, Clothianidin, Clothianidin, Clothianidine, Cycloprene, Cycloprothrin, Cydia pomonella, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyphenothrin

(IR-trans isomer), cyromazines,

DDT, Deltamethrin, Demeton-S-methyl, Demeton-S-methylsulphone, Diafenthiuron, Dialifos, Diazinon, Dichlofenthion, Dichlorvos, Dicofol, Dicrotophos, Dicyclanil, Diflubenzuron, Dimethoate, Dimethylvinphos, Dinobutonef, Dinobuton, Dinobuton

Diofenolan, Disulfoton, Docusat-sodium, Dofenapyn, DOWCO-439,

Eflusilanate, Emamectin, Emamectin-benzoate, Empenthrin (IR-isomer), Endosulfan, Entomopthora spp., EPN, Esfenvalerate, Ethiofencarb, Ethiprole, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos,

Famphur, Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenfluthrin, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fensulfothion, Fenthion, Fentrifanil, Fenronucuron, Flefronazyronid, Fluronilyronimine, Fluroniluron, Flefronyronimine, Fluroniluron, Fluenthronid, Fluentilyronimide, Fifronazuron, Fluentilonyronimide, , Flucycloxuron, Flucythrinate, Flufenerim, Flufenoxuron, Flufenprox, Flumethrin, Flupyrazo- fos, Flutenzin (Flufenzine), Fluvalinate, Fonofos, Formetanate, Formothion, Fos- methilan, Fosthiazate, Fubfenfenarbx, Furathyfox, Fur

Gamma-HCH, Gossyplure, Grandlure, granulovirus,

Halfenprox, Halofenozide, HCH, HCN-801, Heptenophos, Hexaflumuron, Hexythiazox, Hydramethylnone, Hydroprene,

IKA-2002, hnidacloprid, --miprothrin, indoxacarb, iodofenphos, Iprobefos, Isazofos,

Isofenphos, isoprocarb, isoxathion, ivermectin, Japonilure,

Kadethrin, nuclear polyhedron viruses, kinoprene,

Lambda-cyhalothrin, lindane, lufenuron,

Malathion, Mecarbam, Mesulfenfos, Metaldehyde, Metam-sodium, Methacrifos, Methamidophos, Metharhician anisopliae, Metharhician flavoviride, Methidathione, Methiocarb, Methomyl, Methoprene, Methoxychlor, Methoxyfenozide, Metolcarb,

Metoxadiazone, Mevinphos, Milbemectin, Milbemycin, MKI-245, MON-45700, Monocrotophos, Moxidectin, MTI-800,

Naled, NC-104, NC-170, NC-184, NC-194, NC-196, Niclosamide, Nicotine, Nitenpyram, Nithiazine, NNI-0001, NNI-0101, NNI-0250, NNI-9768, Novaluron, Noviflumuron,

OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802, omethoate, oxamyl, oxydemeton-methyl,

Paecilomyces fumosoroseus, Parathion-methyl, Parathion (-ethyl), Permethrin (eis, trans-), Petroleum, PH-6045, Phenothrin (lR-trans isomer), Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phosphocarb, Phoxim, Piperonyl butoxide, pirimicarb, pirimiphos-methyl, pirimiphos-ethyl, prallethrin, profenofos, promecarb, propaphos, propargite, propetamphos, propoxur, prothiofos, prothoate, protrifen-bute, pymetrozine, pyraclofos, pyreshridium pyrin, pyreshridium pyridhridium, pyreshridium pyridhridium, pyreshridium pyrin , Pyrimidifen, pyriproxyfen, quinalphos,

Resmethrin, RH-5849, Ribavirin, RU-12457, RU-15525, S-421, S-1833, SaHthion, Sebufos, SI-0009, Silafluofen, Spinosad, Spirodiclofen, Spiromesifen, Sulfluramid, Sulfotep, Sulprofos, SZI-121,

Tau Fluvalinate, Tebufenozide, Tebufenpyrad, Tebupirimfos, Teflubenzuron, Tefluhrin, Temephos, Temivinphos, Terbam, Terbufos, Tetrachlorvinphos, Tetradifon,

Teframethrin, Teframethrin (IR-isomer), Tefrasul, Theta-Cypermethrin, Thiacloprid, Thiamethoxam, Thiapronil, Thiatriphos, Thiocyclam hydrogen oxalate, Thiodicarb, Thiofanox, Thiometon, Thiosultap-sodium, Thuringadhrinehrin, Thuringadhrininin , Triazamates, triazophos, triazuron, trichlophenidines, trichlorfon, triflumuron, trimethacarb,

Vamidothion, Vaniliprole, Verbutin, Verticillium lecanii,

WL-108477, WL-40027,

YI-5201, YI-5301, YI-5302,

XMC, xylylcarb,

ZA-3274, Zeta-Cypermethrin, Zolaprofos, ZXI-8901,

the compound 3-methyl-ρhenyl-propylcarbamate (Tsumacide Z), the compound 3- (5-chloro-3-pyridinyl) -8- (2,2,2-trifluoroethyl) -8-azabicyclo [3.2.1] octane -3-carbonitrile (CAS reg. No. 185982-80-3) and the corresponding 3-endo isomer (CAS reg. No. 185984-60-5) (cf. WO-96/37494, WO -98 / 25923)

and preparations containing insecticidally active plant extracts, nematodes, fungi or viruses.

A mixture with other known active ingredients, such as herbicides or with

Fertilizers and growth regulators, safeners and semiochemicals are possible. In addition, the compounds of the formula (I) according to the invention also have very good antifungal effects. They have a very broad spectrum of antifungal effects, especially against dermatophytes and sprout fungi, squid and diphasic fungi (e.g. against Candida species such as Candida albicans,

Candida glabrata) and Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species such as Trichophyton mentagrophytes, Microsporon species such as Microsporon canis and audouinii. The list of these fungi in no way represents a restriction of the detectable mycotic spectrum, but is only of an explanatory nature.

The active compounds can be used as such, 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 usual way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.

When the active compounds according to the invention are used as fungicides, the application rates can be varied within a relatively wide range, depending on the type of application. In the treatment of parts of plants, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. In the case of seed treatment, the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In the treatment of the soil, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

As already mentioned above, according to the invention all plants and their parts can be treated. In a preferred embodiment, plant species and plant cultivars which occur wildly or are obtained by conventional organic breeding methods, such as crossing or protoplast fusion, and parts thereof are treated. In a further preferred embodiment, transgenic plants and plant cultivars which may be obtained by genetic engineering methods

Combination with conventional methods have been obtained (Genetically Modified Organisms) and their parts treated. The term “parts” or “parts of plants” or “parts of plants” was explained above.

Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention. Plant cultivars are understood to mean plants with new properties (“traits”) which have been cultivated by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, breeds, bio- and genotypes.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, nutrition), the treatment according to the invention can also cause superadditive ("synergistic") effects. For example, reduced application rates and / or widening of the activity spectrum and / or an increase in the action of the substances and agents which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripening, higher harvest yields, higher quality and / or higher nutritional value of the harvested products, higher storability and / or workability of the

Harvest products possible that go beyond the expected effects.

The preferred transgenic (genetically engineered) plants or plant cultivars to be treated according to the invention include all plants which, by virtue of the genetic engineering modification, have received genetic material which contains them

Gives plants particularly advantageous valuable properties (“traits”). Examples of such properties are better plant growth, increased tolerance to over high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripeness, higher harvest yields, higher quality and or higher nutritional value of the harvested products, higher shelf life and / or workability of the harvested products. Further and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or viruses, and an increased tolerance of the plants to certain herbicidal active ingredients. Examples of transgenic plants are the important crop plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, tobacco, rapeseed and

Fruit plants (with the fruits apples, pears, citrus fruits and grapes) are mentioned, with particular emphasis on corn, soybeans, potatoes, cotton, tobacco and rapeseed. The traits are particularly emphasized as the increased defense of the plants against insects, arachnids, namatodes and snails by toxins that arise in the plants, especially those that are caused by the genetic material from BaciUus thuringiensis (eg by the genes CryΙA (a) , CryIA (b), CryΙA (c), CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF as well as their combinations) are produced in the plants (hereinafter "Bt plants"). Properties ("traits") are also the increased defense of plants against fungi, bacteria and viruses is particularly emphasized

Systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. The properties (“traits”) which are particularly emphasized are the increased tolerance of the plants to certain herbicidal active compounds, for example imidazolinones, sulfonylureas, glyphosates or phosphinotricin (for example “PAT” gene). The desired properties (“traits”) in each case. conferring genes can also occur in combinations with one another in the transgenic plants. Examples of "Bt plants" are corn varieties, cotton varieties, soy varieties and potato varieties which are sold under the trade names YIELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard®

(Cotton), Nucoton® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants are corn varieties, cotton varieties and soy varieties that are marketed under the trade names Roundup Ready® (tolerance to glyphosate e.g. corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, e.g. rapeseed), IMI® (tolerance to Imidazolinone) and STS® (tolerance to sulfonylureas such as maize). The herbicide-resistant plants (conventionally bred to herbicide tolerance) include the varieties sold under the name Clearfield® (eg maize). Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties ("traits").

The plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the active compound mixtures according to the invention. The preferred ranges given above for the active ingredients or mixtures also apply to the treatment of these plants. Plant treatment with the compounds or mixtures specifically listed in the present text should be particularly emphasized.

The preparation and use of the active compounds according to the invention can be seen from the following examples.

Preparation Examples

example 1

Verfahren (a)

Procedure (a)

2.7 g of oxalyl chloride and 2 drops of dimethylformamide are added to a solution of 5 g of l - {[(3,4-dichloro-5-isothiazolyl) carbonyl] amino} cyclopropanecarboxylic acid in 200 ml of dichloromethane and the mixture is stirred for 16 hours at room temperature , The reaction mixture is then poured into 300 ml of water, the organic phase is then separated off and the aqueous phase is extracted twice with 200 ml of dichloromethane each time. The combined organic phases are dried over sodium sulfate and then concentrated under reduced pressure. 2.04 g (43.2% of theory) of 5- (3,4-dichloro-5-isothiazolyl) -6-oxa-4-azaspiro [2.4] hept-4-en-7-one are obtained

HPLC: logP = 2.90

The compounds of the formula (I) listed in Table 1 below are also obtained by the method given above.

Tabelle 1

Table 1

Tabelle 1 (Fortsetzung)

Table 1 (continued)

The logP values were determined in accordance with EEC Directive 79/831 Annex V. A8 by HPLC (gradient method, acetonitrile / 0.1% aqueous phosphoric acid)

Production of precursors of formula (II)

Example 8

Method (b)

150 ml of 1N aqueous sodium hydroxide solution are added to a solution of 11.5 g (39.0 mmol) of l - {[(3,4-dichloro-5-isothiazolyl) carbonyl] amino} cyclopropanecarboxylic acid methyl ester in 250 ml of isopropanol and the mixture is stirred for 1 hour at room temperature. The reaction mixture is then poured into 1.5 l of water and acidified with 1N hydrochloric acid until a pH between 3 and 4 is reached. The precipitate is filtered off, washed with 300 ml of water and dried. 7.23 g (59% of theory) of 1 - {[(3, 4-dichloro-5-isothiazolyl) carbonyl] amino} cyclopropanecarboxylic acid are obtained. HPLC: logP = 1.57

The compounds of the formula (II) mentioned in Table 2 below are also prepared by the method given above. Table 2

The logP values were determined in accordance with EEC Directive 79/831 Annex V. A8 by HPLC (gradient method, acetonitrile 0.1% aqueous phosphoric acid) # stands for the point of attachment

Preparation of an intermediate of formula (III)

Example 12

Procedure (c) To a mixture of 11.9 g (78.5 mmol) of 1-aminocyclopropane-1-carboxylic acid methyl ester and 19.9 g of triethylamine in 120 ml of tefrahydrofuran is added a solution of 17 g (78.5 mmol) of 3,4- Dichloro-5-isothiazole carbonyl chloride in 160 ml of tefrahydrofuran and stirred for 16 hours at room temperature. The reaction mixture is then poured into 1.5 l of water and extracted three times with 300 ml of ethyl acetate each time. The combined organic phases are dried over sodium sulfate and then concentrated under reduced pressure. 17.6 g (72% of theory) of l - {[(3,4-dichloro-5-isothiazolyl) carbonyl] amino} cyclopropanecarboxylic acid methyl ester are obtained.

HPLC: logP = 2.03

usage example

Example A

Erysiphe test (barley) / resistance induction

Solvent: 50 parts by weight of N, N-dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable formulation of the active substance, 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 resistance-inducing activity, young plants are sprayed with the preparation of active compound in the stated application rate. 5 days after the

The plants are treated with spores of Erysiphe graminis f. sp. hordei pollinated. The plants are then placed in a greenhouse at a temperature of approximately 20 ° C. and a relative atmospheric humidity of approximately 80% in order to promote the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the substance according to the invention listed in Example (1) shows one

Application rate of 375 g / ha an efficiency of 100%. Table A

Erysiphe test (barley) 7 resistance induction

Active ingredient application rate in efficiency g / ha in%

According to the invention:

Claims

claims 1. Sprio compounds of the formula

in which R represents optionally substituted heterocyclyl. 2. A process for the preparation of spiro compounds of the formula (I) according to claim 1, characterized in that a) Acylamino-cyclopropanecarboxylic acids of the formula

in which R has the meaning given above, with condensing agents, if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor and if appropriate in the presence of a catalyst. 3. Microbicidal agents, characterized by a content of at least one spiro compound of the formula (I) according to claim 1 in addition to extenders and / or surface-active substances. 4. Use of spiro compounds of formula (I) according to claim 1 for Control of unwanted microorganisms. 5. A method for controlling unwanted microorganisms, characterized in that spiro compounds of the formula (I) according to claim 1 are applied to the microorganisms and / or their habitat. 6. A process for the preparation of microbicidal agents, characterized in that spiro compounds of the formula (I) according to Claim 1 are mixed with extenders and / or surface-active substances.