DE10301419A1 - spiro compounds - Google Patents

Abstract

New spiro compounds of the formula DOLLAR F1 in which DOLLAR A R represents optionally substituted heterocyclyl, DOLLAR A a process for the preparation of the new active compounds and their use as microbicides.

Description

The present invention relates to new spiro compounds, a process for their production and their Use to combat of unwanted Microorganisms.

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

in welcher
R für gegebenenfalls substituiertes Heterocyclyl steht,
gefunden.There have now been new spiro compounds of the formula

in which
R represents optionally substituted heterocyclyl,
found.

It was also found that one the spiro compounds of formula (I) is 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.

Eventually it was found that the new spiro compounds of formula (I) have very good microbicidal properties own and in both crop protection and material protection for fighting undesirable Microorganisms can be used. The substances according to the invention can not only be used to combat unwanted Use microorganisms, but also practice one on plants resistance-inducing effect.

Surprisingly show the spiro compounds according to the invention the formula (I) a much better fungicidal activity than the most constitutionally similar, previously known active ingredients with the same direction of 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, optionally benzo-fused, five or six-membered heterocyclyl.

Substances of the formula (I) in which
R represents pyridyl, isothiazolyl, thienyl or benzothiophenyl substituted by single to triple, identical or different by chlorine and / or bromine.

Compounds of the formula (I) in which
R represents 2,6-dichloropyrid-4-yl, 3,4-dichloroisothiazol-5-yl, 5-bromo-2-thienyl, 5-chloro-2-thienyl, 4,5-dibromo-2-thienyl or 3- Chlor-1-benzothiophen-2-yl.

If 1- [2,6-dichloroisonicotinyl) amino] cyclopropane-carboxylic acid is used as the starting substance and oxalyl chloride as the condensing agent, the course of process (a) according to the invention can be illustrated by the following formula

To carry out the method according to the invention (a) required as starting materials Acylaminocyclopropancarbonsäuren are generally defined by formula (II). In this formula R preferably has those meanings that are already related with the description of the substances of formula (I) according to the invention for this Rest were mentioned as preferred.

The acylaminocyclopropane carboxylic acids of Formula (II) are not yet known. They can be made by one

• b) acylaminocyclopropane-carboxylic acid ester of the formula
  
  in which R has the meanings given above and R ^{1 is} 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 the process (b) can the following formula scheme can be illustrated.

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.

Also the acylamino-cyclopropanecarboxylic acid esters the formula (III) are not yet known. You let yourself be manufacture by

• c) aminocyclopropane-carboxylic acid esters of the formula
  
  in which R ^{1 has} the meanings given above, or their hydrohalides or hydrogen sulfates, with acid halides of the formula
  
  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 is used and 1-amino-cyclopropane-1-carboxylic acid methyl ester as starting materials, the course of process (c) can the following formula scheme can be illustrated.

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). They can be prepared by reacting 1-amino-cyclopropane-carboxylic acid with methanol or ethanol in the presence of thionyl chloride.

The continue to carry out the Process (c) acid halides required as reaction components are by the Formula (V) generally defined. In this formula, R preferably has those meanings that are already related to the description of the substances according to the invention of formula (I) for this Rest were mentioned as preferred. X preferably represents chlorine or bromine.

The acid halides of the formula (V) are known or can be prepared by known methods (cf. DE-A 3615 293 , WO 99-24 413, EP-A 0393 936 and Tetrahedron Lett. (1968), (49), 5149-5152).

As a diluent come in the execution of the method according to the invention (a) all common, inert organic solvents. Preferably used are aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methyl cyclohexane, 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; Ketones such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoramide; ester such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide or Sufone such as sulfolane.

As condensation agents come in the implementation of the method according to the invention (a) all common for amidation reactions usable cyclization reagents in question. Preferably used are acid halide formers such as phosgene, oxalyl chloride, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, Phosphorus oxychloride or thionyl chloride; Anhydride formers such as ethyl chloroformate, methyl chloroformate, 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 tertiary amines; such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundec ).

As catalysts come in the execution of the method according to the invention (a) all for such implementations usual Reaction accelerators in question. Examples include 4-dimethylaminopyridine, 1-hydroxy-benzotriazole or dimethylformamide.

The reaction temperatures can be at the implementation of the method according to the invention (a) in a larger area can be varied. In general, temperatures between -78 ° C and + 120 ° C, preferably at temperatures between –60 ° C and + 25 ° C.

When carrying out the method according to the invention (a) one works in the same way as when carrying out processes (b) and (c) generally under atmospheric pressure. However, it is also possible in each case under increased or work under reduced pressure.

When carrying out the method according to the invention (a) is set to 1 mol of acylamino-cyclopropanecarboxylic acid Formula (II) generally 0.5 to 5 moles, preferably an equimolar Amount of condensing agent. The processing takes place according to usual Methods.

As bases come in performing the Procedure (b) all usual inorganic bases. Alkaline earth metal or alkali metal hydroxides are preferably usable, such as lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide.

As a diluent come in the execution of procedure (b) all usual, water-miscible, organic solvents. Preferably alcohols such as methanol, ethanol, n- or i-propanol can be used, n, i, sec. or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, Diethylene glycol monomethyl ether or diethylene glycol monoethyl ether.

The reaction temperatures can be at the implementation of the method (b) in a larger area can be varied. Generally one works at temperatures of 0 ° C to 80 ° C, preferably at temperatures of 0 ° C up to 50 ° C.

When performing method (b) sets to acylamino-cyclopropanecarboxylic acid ester of formula (III) in the presence of an equivalent amount or an excess at base with an excess of water around. The processing is again carried out according to the usual Methods.

As a diluent come in the execution of process (c) all usual, inert organic solvents. Preferably used are aliphatic, alicyclic or aromatic hydrocarbons, such as 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 hexamethylphosphoric triamide.

The acid binders come from execution procedure (c) all usual inorganic and organic bases in question. Preferably used are alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or bicarbonates, such as, for example Sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, Sodium hydroxide, 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-dimethylaniline, N, N-dimethyl-benzylamine, Pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, Diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can be at the implementation of the method (c) in a larger area can be varied. Generally one works at temperatures of 0 ° C to 120 ° C, preferably at temperatures of 0 ° C up to 80 ° C.

When performing procedure (c) sets to 1 mol of amino-cyclopropane-carboxylic acid ester of the formula (IV) in Generally 0.2 to 5 moles, preferably 0.5 to 2 moles, of acid halide of the formula (V). The processing takes place according to usual Methods.

The substances according to the invention have a strong microbicidal effect on and can for fighting of unwanted Microorganisms, such as fungi and bacteria, in crop protection and be used in material protection.

Fungicides can be plant protection for fighting from Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Use Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be used in crop protection for fighting from Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and use 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 fuliginea;
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 herpotrichoides.

The active compounds according to the invention also have a strong strengthening Effect in plants. They are therefore suitable for mobilization plant's own defenses against infestation by unwanted Microorganisms.

Among plant-strengthening (resistance-inducing) In the present context, substances are to be understood as substances able to stimulate the immune system of plants that the treated plants with subsequent inoculation undesirable Microorganisms largely resistant to these microorganisms unfold.

Are among unwanted microorganisms in the present case phytopathogenic fungi, bacteria and viruses too understand. The substances according to the invention can So be used to plants within a certain period of time after treatment against infestation by the named pathogens to protect. The period within which protection is brought about extends in the generally from 1 to 10 days, preferably 1 to 7 days after Treatment of plants with the active ingredients.

The good plant tolerance of the active ingredients in the fight necessary concentrations of plant diseases allows a Treatment of above-ground parts of plants, planting and seeds, and the floor.

The active compounds according to the invention can be used here with particularly good success in combating cereal diseases, such as against Erysiphe species.

The active compounds according to the invention are suitable also to increase the crop yield. They are also less toxic and are well tolerated by plants.

The active compounds according to the invention can, if appropriate in certain concentrations and application rates also as herbicides, to influence plant growth, as well as to combat animal pests be used. If necessary, they can also be used as intermediate and intermediate products for use the synthesis of other active ingredients.

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 varieties which can be estimated or not estimated by plant breeders' rights. Plant parts are to be understood to mean all above-ground and underground parts and organs of the plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as 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 according to the invention and parts of plants with the active ingredients are carried out directly or through Impact on their environment, living space or storage space according to the usual Treatment methods, e.g. by dipping, spraying, evaporating, atomizing, Scattering, spreading and propagating material, in particular in the case of seeds, still by single or multi-layer coating.

They can be used in material protection substances according to the invention to protect technical materials against infestation and destruction by undesirable Use microorganisms.

Among technical materials are to understand non-living materials in the present context, the for the use has been prepared in the art. For example can Technical materials that are active against microbial by active ingredients according to the invention change or destruction protected adhesives, glues, paper and cardboard, textiles, Leather, wood, paints and plastic articles, cooling lubricants and other materials infested with microorganisms or can be decomposed. As part of the to be protected Materials are also parts of production plants, such as cooling water circuits, which can be affected by the multiplication of microorganisms. As part of the present invention are preferred as technical materials Adhesives, glues, papers and cartons, leather, wood, paints, coolant and heat transfer fluids called, particularly preferably wood.

As microorganisms that break down or a change of the technical materials can be, for example Bacteria, fungi, yeasts, algae and slime organisms. Preferably act the active compounds according to the invention against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against mucous organisms and algae.

Microorganisms of the following genera may be mentioned, for example:
Alternaria, such as Alternaria tenuis,
Aspergillus, such as Aspergillus niger,
Chaetomium, like 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, like Trichoderma viride,
Escherichia, such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, such as Staphylococcus aureus.

The active ingredients can depend on their respective physical and / or chemical properties in the usual Formulations are transferred like solutions, Emulsions, suspensions, powders, foams, pastes, granules, aerosols, Fine encapsulation in polymeric substances and in coating compositions for seeds, as well as ULV cold and warm fog formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, 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, for example petroleum fractions, alcohols, such as butanol or glycol, and the like 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 under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide. Solid carrier materials are suitable: for example natural rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatoms earth and synthetic rock powder, 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 as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems. Suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene 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.

It can be in the formulations Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, grained or latex-shaped Polymers are used, such as gum arabic, polyvinyl alcohol, Polyvinyl acetate, as well as natural Phospholipids such as cephalins and lecithins, and synthetic phospholipids. Further Additives can mineral and vegetable oils his.

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 be used.

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

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

For example, come as a mixed partner following connections in question:

fungicides:

• 2-phenylphenol; 8-hydroxyquinoline sulfate;
• Acibenzolar-S-methyl; aldimorph; amidoflumet; Ampropylfos; Ampropylfos-potassium; andoprim; anilazine; azaconazole; azoxystrobin;
• benalaxyl; Benodanil; benomyl; Benthiavalicarb-isopropyl; Benzamacril; Benzamacril-isobutyl; bilanafos; binapacryl; biphenyl; bitertanol; Blasticidin-S; bromuconazole; Bupirimate; Buthiobate; butylamine;
• Calcium polysulfide; capsimycin; captafol; captan; carbendazim; carboxin; carpropamid; 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; dimethomorph; dimoxystrobin; diniconazole; Diniconazole-M; dinocap; diphenylamines; Dipyrithione; Ditalimfos; dithianon; dodine; Drazoxolon;
• edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole;
• famoxadone; fenamidone; Fenapanil; fenarimol; Fenbuconazole; fenfuram; fenhexamid; Fenitropan; fenoxanil; fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam; Flubenzimine; fludioxonil; flumetover; flumorph; fluoromides; fluoxastrobin; fluquinconazole; flurprimidol; 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; Irumamycin; 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; procymidone; 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; tridemorph; 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 ;
• 1- (1-naphthalenyl) -1H-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-1,1,3-trimethyl-1H-inden-4-yl) -3-pyridinecarboxamides;
• 3,4,5-trichloro-2,6-pyridinedicarbonitrile;
• Actinovate;
• cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol;
• Methyl 1- (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) -1H-imidazole-5-carboxylate;
• Monokaliumcarbonat;
• N- (6-methoxy-3-pyridinyl) -cyclopropanecarboxamide;
• sodium tetrathiocarbonate; as well as copper salts and preparations, like 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, Tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

• Abamectin, ABG-9008, Acephate, Acequinocyl, Acetamiprid, Acetoprole, Acrinathrin, AKD-1022, AKD-3059, AKD-3088, Alanycarb, Aldicarb, Aldoxycarb, Allethrin, Allethrin 1R-isomers, Alpha-Cypermethrin (Alphamethrin), Amidoflumet, Aminocarb, Amitraz, Avermectin, AZ-60541, Azadirachtin, Azamethiphos, Azinphos-methyl, Azinphos-ethyl, Azocyclotin,
• Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Bacillus thuringiensis strain EG-2348, Bacillus thuringiensis strain GC-91, Bacillus thuringiensis strain NCTC-11821, Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Beta-Cyfluthrin, Beta-Cypermethrin, Bifenazate, Bifenthrin, binapacryl, bioallethrin, bioallethrin-S-cyclopentyl-isomer, Bioethanomethrin, biopermethrin, bioresmethrin, bistrifluron, BPMC, Brofenprox, Bromophos-ethyl, Bromopropylate, Bromfenvinfos (-methyl), BTG-504, BTG-505, Bufencarb, Buprofezin, Butathiofos, Butocarboxim, Butoxycarboxime, butylpyridaben,
• Cadusafos, Camphechlor, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA-50439, Chinomethionate, Chlordane, Chlordimeform, Chloethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, chlorobenzilate, chloropicrin, chlorproxyfen, chlorpyrifos-methyl, Chlorpyrifos (ethyl), chlovaporthrin, chromafenozide, cis-cypermethrin, Cis-resmethrin, cis-permethrin, Clocythrin, cloethocarb, clofentezine, clothianidin, clothiazoben, Codlemone, Coumaphos, Cyanofenphos, Cyanophos, Cycloprene, Cycloprothrin, Cydia pomonella, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, Cyphenothrin (1R trans isomer), cyromazines,
• DDT, deltamethrin, demeton-S-methyl, demeton-S-methylsulphone, Diafenthiuron, dialifos, diazinon, dichlofenthion, dichlorvos, dicofol, Dicrotophos, Dicyclanil, Diflubenzuron, Dimethoate, Dimethylvinphos, Dinobuton, Dinocap, Dinotefuran, Diofenolan, Disulfoton, Docusat-sodium, Dofenapyn, DOWCO-439,
• Eflusilanate, Emamectin, Emamectin-benzoate, Empenthrin (1R-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, Fenvalerate, Fipronil, Flonicamid, Fluacrypyrim, Fluazuron, flubenzimine, flubrocythrinate, flucyclox uron, flucythrinate, Elufenerim, flufenoxuron, flufenprox, flumethrin, flupyrazofos, Flutenzin (Flufenzine), Fluvalinate, Fonofos, Formetanate, Formothion, Fosmethilan, Fosthiazate, Fubfenprox (Fluproxyfen), Furathiocarb,
• Gamma-HCH, Gossyplure, Grandlure, granulovirus,
• Halfenprox, Halofenozide, HCH, HCN-801, Heptenophos, Hexaflumuron, Hexythiazox, hydramethylnone, hydroprene,
• IKA-2002, imidacloprid, imiprothrin, 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 (cis-, trans-), petroleum, PH-6045, phenothrin (1R-trans isomer), phenthoates, phorates, phosalones, phosmet, phosphamidon, Phosphocarb, Phoxim, Piperonyl butoxide, Pirimicarb, Pirimiphos-methyl, Pirimiphos-ethyl, Prallethrin, Profenofos, Promecarb, Propaphos, Propargite, Propetamphos, Propoxur, Prothiofos, Prothoate, Protrifenbute, Pymetrozine, Pyraclofos, Pyresmethrin, Pyrethrum, Pyridaben, Pyridalyl, Pyridaphenthione, pyridathione, pyrimidifen, pyriproxyfen,
• quinalphos,
• Resmethrin, RH-5849, Ribavirin, RU-12457, RU-15525,
• S-421, S-1833, Salithion, Sebufos, SI-0009, Silafluofen, Spinosad, Spirodiclofen, Spiromesifen, Sulfluramid, Sulfotep, Sulprofos, SZI-121,
• Tau fluvalinate, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, Tefluthrin, Temephos, Temivinphos, Terbam, Terbufos, Tetrachlorvinphos, Tetradifone, tetramethrin, tetramethrin (1R-isomer), tetrasul, theta-cypermethrin, Thiacloprid, Thiamethoxam, Thiapronil, Thiatriphos, Thiocyclam hydrogen oxalate, Thiodicarb, Thiofanox, Thiometon, Thiosultap-sodium, Thuringiensin, Tolfenpyrad, Tralocythrin, Tralomethrin, Transfluthrin, Triarathene, 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 connection 3-methyl-phenyl-propyl carbamate (Tsumacide Z), the connection 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) (see WO-96/37494, WO-98/25923), as well as preparations, which insecticide effective plant extracts, nematodes, fungi or Viruses included.

Also a mix with other known ones Active ingredients, such as herbicides or with fertilizers and growth regulators, Safener or semiochemicals is possible.

In addition, the compounds of the invention of the formula (I) also have very good antifungal effects. she have a very broad spectrum of antifungal effects, in particular against dermatophytes and sprout fungi, mold and diphasic fungi (e.g. against Candida species such as Candida albicans, Candida glabrata) as well as Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species like Trichophyton mentagrophytes, microsporon species such as microsporon canis and audouinii. The list this fungus does not in any way limit the detectable mycotic Spectrum, but is only explanatory.

The active ingredients as such, in the form of their Formulations or the use forms prepared from them, such as ready-to-use solutions, Suspensions, wettable powders, pastes, soluble powders, dusts and granules are used. The application is done in the usual way Manner, e.g. by pouring, splashing, spraying, Scattering, dusting, foaming, Brushing etc. It is also possible apply the active ingredients using the ultra-low-volume process or the drug preparation or the drug itself into the soil to inject. The seeds of the plants can also be treated.

When using the active compounds according to the invention as fungicides the application rates depending on the type of application within a larger area can be varied. In the treatment of parts of plants are the Application rates of active ingredient generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. When treating seeds 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 Application rates of active ingredient 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, wild plant species or plant species and their parts obtained by conventional biological breeding methods, such as crossing or protoplast fusion, are treated. In a further preferred embodiment, transgenic plants and plant cultivars which have been obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetically modified organisms) and their parts are treated. The term “parts” or “parts of plants” or “parts of plants” was explained above.

Plants are particularly preferred according to the invention the commercially available in each case or plant varieties in use. Among plant varieties is understood to mean plants with new properties ("traits") that can be obtained through conventional breeding, by mutagenesis or by recombinant DNA techniques are. You can Be varieties, breeds, bio and genotypes.

Depending on the plant species or plant varieties, their location and growth conditions (soils, climate, growing season, Nutrition) can by the treatment according to the invention also super-additives ("Synergistic") effects occur. For example, reduced application rates and / or extensions of the Spectrum of activity and / or an enhancement of the effect of those which can be used according to the invention Substances and agents, better plant growth, increased tolerance across from high or low temperatures, increased drought tolerance or against water or soil salt content, increased flowering performance, easier harvesting, Acceleration of maturity, higher Crop yields, higher quality and / or higher Nutritional value of Crops, higher Shelf life and / or workability of the harvested products is possible, which is beyond what is actually to be expected Effects go beyond.

The preferred transgenic plants or plant cultivars to be treated according to the invention include all plants; who received genetic material through the genetic modification, which gives these plants particularly advantageous valuable properties (“traits”). Examples of such properties are 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 shelf life and / or workability of the harvested products.Other and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance of the plants to certain herbicidal active ingredients Zen, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, tobacco, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes) mentioned, with corn, soybeans, potatoes, cotton, tobacco and rapeseed in particular be highlighted. The properties (“traits”) that are particularly emphasized are the plants' increased defense against insects, arachnids, namatodes and snails due to toxins produced in the plants, in particular those which are caused by the genetic material from Bacillus thuringiensis (for example by the genes CryIA (a) , CryIA (b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF as well as their combinations) are produced in the plants (hereinafter "Bt plants"). Properties ("traits") are also used the increased defense of plants against fungi, bacteria and viruses through systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins are particularly emphasized. The properties (“traits”) which are particularly emphasized are the increased tolerance of the plants to certain herbicidal active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example “PAT” gene). The genes conferring the desired properties (“traits”) can also occur in combinations with one another in the transgenic plants. Examples of "Bt plants" are maize varieties, cotton varieties, soy varieties and potato varieties that are marketed 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 maize varieties, cotton varieties and soy varieties that are sold under the trade names Roundup Ready ^® (tolerance to glyphosate e.g. corn, cotton, soy), Liberty Link ^® (tolerance to phosphinotricin, e.g. rape), IMI ^® (tolerance to Imidazolinone) and STS ^® (tolerance to sulfonylureas such as maize). Herbicide-resistant plants (bred conventionally for herbicide tolerance) plants also sold under the name Clearfield ^® varieties (eg maize) are mentioned. 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 special advantageous according to the invention with the Compounds of the general formula (I) or the active compound mixtures according to the invention be treated. The above for the active ingredients or mixtures Preferred areas also apply to the treatment of these plants. The is particularly emphasized Plant treatment with the compounds specifically listed in this text or mixtures.

The preparation and use of the active compounds according to the invention can be seen from the following examples. example 1

Procedure (a)

2.7 g of oxalyl chloride and 2 drops of dimethylformamide are added to a solution of 5 g of 1 - {[(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

Tabelle 1

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

Table 1

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) preparation of precursors of the formula (II) example 6

Method (b)

150 ml of 1N aqueous sodium hydroxide solution are added to a solution of 11.5 g (39.0 mmol) of 1 - {[(3,4-dichloro-5-isothiazolyl) carbonyl] amino} cyclopropanecarboxylic acid methyl ester in 250 ml of isopropanol and the mixture is stirred for 1 hour 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 connection preparation of a preliminary product of formula (III) Example 10

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 tetrahydrofuran are added a solution of 17 g (78.5 mmol) of 3,4-dichloro- 5-isothiazole carbonyl chloride in 160 ml of tetrahydrofuran 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 1 - {[(3,4-dichloro-5-isothiazolyl) carbonyl] amino} cyclopropanecarboxylic acid methyl ester are obtained.
HPLC: logP = 2.03

use Examples 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

For the preparation of a suitable active ingredient preparation 1 part by weight of active ingredient is mixed with the stated amounts solvent and emulsifier and diluted the concentrate with water to the desired concentration.

For testing for resistance-inducing Effectiveness sprayed to young plants with the active ingredient preparation in the specified Application rate. 5 days after the treatment, the plants are with Spores of Erysiphe graminis f. sp. hordei pollinated. Then be the plants in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80% to promote the development of mildew pustules.

7 days after the inoculation the expansion. 0% means an efficiency that the one corresponds to the control while an efficiency of 100% means that no infection is observed.

In this test it shows in example (1) listed fabric according to the invention with an application rate of 375 g / ha an efficiency of 100%.

Claims (6)

Spiro compounds of the formula

in which R represents optionally substituted heterocyclyl. 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. Microbicidal agents, characterized by a content on at least one spiro compound of formula (I) according to claim 1 in addition to extenders and / or surface-active substances. Use of spiro compounds of formula (I) according to claim 1 to combat of unwanted Microorganisms. Control procedures of unwanted Microorganisms, characterized in that spiro compounds of formula (I) according to claim 1 spreads on the microorganisms and / or their habitat. Process for the preparation of microbicidal agents, characterized in that spiro compound gene of formula (I) according to claim 1 mixed with extenders and / or surface-active substances.