DE3211987A1 - Cyclobutanedicarboxylic acid derivatives, their preparation and their use as fungicide - Google Patents

Abstract

Cyclobutanedicarboxylic acid derivatives of the formula <IMAGE> in which one of the X and Y radicals represents <IMAGE> and the other denotes -ZR, Z denotes -O- or -S- and R denotes alkyl, alkenyl, alkynyl, cycloalkyl or aryl, and R1 to R6 are as defined in Patent Claim 1, are suitable for controlling various fungi and have, in particular, an outstanding activity against Botrytis.

Description

Cyclobutanedicarboxylic acid derivatives, process for their preparation

and their use as a fungicide. The present invention relates to new cyclobutanedicarboxylic acid derivatives, a process for their preparation, fungicidal Means containing such compounds as an active ingredient, as well as the use this compound for combating fungi and preventing fungal infestation.

From Japanese laid-open specification 74/71 141 and the European Patent publications 1395 and 17994 are known to have the cyclobutane ring optionally substituted 3, 5-dihalophenylcyclobutanedicarboximide antimicrobial, also have fungicidal properties.

There were new cyclobutanedicarb, onsäurederivate of the formula I and the other is -ZR, Z -0- or -S- and R is alkyl, alkenyl, alkynyl, cycloalkyl or aryl, R1 and R6 are independently methyl or ethyl, R2 and R3 are independently hydrogen, fluorine or methyl or R2 is -OCOCH3 or chlorine and at the same time R3 is hydrogen, R4 is hydrogen, methyl or chlorine and R5 is hydrogen or methyl, where R3 and R4 together can also form an additional bond in the four-membered ring. t2 8, / OLX 3j j Ci) 8, I (I) 6 CO y 66cO-y found wherein one of X and Y -NHZ \ C1 Alkyl groups R can be straight-chain or branched and preferably have 1-8 and especially 1-4 carbon atoms. Examples of such alkyl groups are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, 2-pentyl, n-hexyl, n-heptyl, 3-heptyl and n-octyl.

Alkenyl groups R are also straight-chain or branched and have preferably 2-8, especially 2-5 carbon atoms, such as vinyl, CH2 = C (CH3), allyl, Methallyl, crotyl and buten-l-yl groups.

For example, alkynyl groups R are propynyl and butynyl groups, preferred 2-propynyl.

Cyclolalkyl groups R include, for example, those with 5-8 ring carbon atoms into consideration, such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Cyclohexyl is preferred.

Aryl groups R preferably have 6 or 10 ring carbon atoms and can unsubstituted or substituted, e.g. by one or two halogen atoms, especially Chlorine or bromine, or by one or two alkyl or alkoxy groups, each with 1-4 C atoms and, above all, 1 or 2 C atoms each. Unsubstituted naphthyl groups are preferred and especially unsubstituted phenyl.

Preference is given to compounds of the formula I in which one of X and Y and the other -ZR, Z -0- or -S-, R straight-chain or branched C 1-4 -alkyl, cyclohexyl or phenyl, R1 and R6 each methyl, R2 and R3 independently of one another hydrogen, fluorine or methyl and R4 and R5 are independently hydrogen or methyl. Particularly preferred are compounds of the formula 1 in which the above applies to X and Y, R is methyl, isopropyl, cyclohexyl or phenyl, R1 and R6 are each methyl (cis), R2 and R3 independently of one another are hydrogen or fluorine and R4 and R5 each represent hydrogen. Very particular preference is given to compounds of the formula I in which R is methyl, isopropyl, cyclohexyl or phenyl, R1 and R6 are each methyl (cis) and R2, R3, R4 and R5 are each hydrogen.

The compounds of the formula I can exist as mixtures of stereoisomers. However, compounds of the formula I and their carbonyl functions are particularly preferred are cis.

The compounds of the formula I have excellent fungicidal properties and in particular have a pronounced botrytis effect. Botrytis spp. (B. cinerea, B. allem) with gray mold rot on vines, strawberries, apples, Onions and other fruits and vegetables represent a significant economic damaging factor represent.

The compounds of formula I have one for practical needs very favorable spectrum of activity for the protection of cultivated plants, without them through Adversely affect unwanted side effects. Cultivated plants are in the frame of the present invention, for example, cereals, corn, rice, vegetables, sugar beets, Soy, peanuts, fruit trees, especially stone fruit, ornamental plants, vines, hops, cucumber plants (Cucumber, pumpkin, melon), solanaceae, such as potatoes, tomatoes and tobacco, as well also banana, cocoa and natural rubber plants.

The active ingredients of the formula I can be used on plants or parts of plants (Fruits, blossoms, foliage, stems, tubers, roots) of these and related crops the fungi that occur are contained or destroyed, with later growing ones Plant parts are spared from such fungi. The active ingredients are against the phytopathogenic fungi belonging to the following classes are effective: Ascomycetes (e.g. Erysiphaceae, Fusarium, Helminthosporium); Basidiomycetes, especially rust fungi (e.g. Puccinia, Tilletia); Fungi imperfecti (e.g. Moniliales et al., Cercospora, Sclerotinia as well as Botrytis and Piricularia) and those belonging to the class of the Oomycetes angel Phytophthora or Plasmopara. They can also be used as a mordant to treat Seeds (fruits, tubers, grains) and plant cuttings to protect against fungal infections as well as against phytopathogenic fungi occurring in the soil.

The compounds of the formula I can be prepared in a preferred process by adding a compound of the formula II where one of X 'and Y' and the other is -OH, at a temperature between -20 ° C and +100 "C, preferably between 0 ° C and 40" C, in the presence of a dehydrating agent and preferably in the presence of an inert organic solvent to form an isoimide of the formula III cyclized, wherein one of X "and Y" is oxygen and the other and the isoimide of the formula III, optionally after previous isolation, is reacted in the presence of catalytic amounts of acid with a compound of the formula IV R-ZH (IV), where Z, R and R1 to R6 have the meanings given under formula I.

The compounds of the formula I can also be obtained by using an anhydride of the formula V first with a compound of the formula IVa R-ZM (IVa) to a compound of the formula VI converts the compound of the formula VI into a corresponding acid halide, preferably an acid chloride, and then allows the acid halide to react with 3,5-dichloroaniline. R, Z and R1 to R6 have the meaning given under formula I, one of X1 and X2 represents -OM and the other represents -ZR and M represents hydrogen or an alkali metal, preferably Na or K.

As a further alternative, compounds of formula I, wherein Z = -0- and R is alkyl, alkenyl, alkynyl, cycloalkyl or aryl, also thereby be obtained that a compound of formula II at a temperature between O-100 ° C, preferably between 20-400C, in the presence of an inert solvent and an acid-binding agent reacts with a compound of the formula VII R - A (VII), where A is a leaving group, such as chlorine, bromine, iodine, p-toluenesulfonyl, Methylsulfonyl or alkyl sulfate, and R has the meaning given above.

Acid-binding agents include, for example, tertiary amines such as triethylamine or pyridine, also hydroxides, oxides, carbonates and dicarbonates of alkali and Alkaline earth metals and alkali metal alcoholates, such as, for example, potassium tert-butoxide and sodium methylate.

As a dehydrating agent in the former manufacturing method for example: anhydrides of optionally with halogen atoms or C1 4-alkyl groups substituted aliphatic C 5 monocarboxylic acids, such as acetic acid, Propionic acid, butyric acid and valeric anhydride, trichloro, trifluoro, trimethyl, Triethyl and tri-n-butyl acetic anhydride; Carbodiimides such as N, N'-diisopropylcarbodiimide and N, N'-dicyclohexylcarbodiimide, and ketene. Furthermore, mixtures of tertiary Amines and the above-mentioned anhydrides or mixtures of tertiary amines and optionally halogenated acetyl halides, such as acetyl chloride, chloroacetyl chloride, Dichloroacetyl chloride and trifluoroacetyl chloride can be used. Suitable tertiary Amines are e.g. N, N-dimethylaniline, N-methyl-N-ethylaniline, N-methyl- or N-ethylmorpholine, Pyridine, quinuclidine or N, N'-dimethylpiperazine and especially trialkylamines each with 1-8 carbon atoms in the alkyl groups, such as triethylamine, tri-n-butylamine, tri- (2-ethyln-hexyl) amine and tri-n-octylamine. Preferred dehydrating agents are acetic anhydride, N, N'-dicyclohexylcarbodiimide and kets. Excess acetic anhydride can also serve as a solvent.

Suitable inert organic solvents for carrying out the cyclization are e.g. optionally chlorinated aromatic hydrocarbons, such as benzene, Toluene, xylenes and chlorobenzene; chlorinated aliphatic hydrocarbons such as Chloroform, methylene chloride and 1,2-dichloroethane; aliphatic and cycloaliphatic Ketones such as acetone, methyl ethyl ketone and cyclohexanone; as well as dialkyl ethers with each 2-6 carbon atoms in the alkyl parts and cyclic ethers as well as tetrahydrofuran and dioxane. The reaction is particularly preferably carried out in acetic anhydride or toluene.

After the cyclization, the isoimides of the formula III can, if desired isolated in the usual way, e.g. by distilling off the solvent and the residue from a suitable solvent such as methanol or ethyl acetate or acetone, recrystallized. However, such isolation is prior to further Reaction with the compounds of the formula IV is generally not necessary.

The implementation of the isoimides of the formula III with the compounds of Formula IV is advantageously used in an organic medium at temperatures between 10 and 700C, preferably between 10 and 300C.

Suitable inert organic solvents are, for example, aliphatic or cycloaliphatic hydrocarbons, such as n-hexane and cyclohexane, and optionally chlorinated aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, Ketones and ethers of the type mentioned above for the cyclization. Used with preference an excess of the compound of the formula IV is used as the solvent. The acid can inorganic or organic acids are added, e.g. hydrohalic acids, Sulfuric or phosphoric acid or aliphatic and aromatic carboxylic and sulfonic acids, such as formic acid, acetic acid, propionic acid, chloroacetic acid, trifluoroacetic acid, Benzoic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid or naphthalene-1,5-disulfonic acid. P-Toluenesulfonic acid is preferred. The acids are by definition in catalytic amounts, preferably in an amount of 0.5 to 1 mol%, based on the isoimide of the formula III, is used.

The implementation of the anhydrides of the formula V with the compounds of Formula IVa is also expedient in the presence of an inert organic solvent performed. Suitable solvents are, for example, aliphatic or cyclic ethers such as diethyl ether or tetrahydrofuran, and aromatic hydrocarbons such as benzene or toluene. Salts of the formula IVa can also be formed in situ.

The conversion of the compounds of the formula VI into the corresponding Acid halides can be used in a manner known per se more suitable Halogenating agents, e.g. oxalyl chloride, thionyl chloride or bromide, phosgene, Phosphorus oxychloride or bromide.

The acid halides obtained from the compounds of the formula VI can be reacted with the 3,5-dichloroaniline in a manner known per se, expediently in an organic medium at temperatures between 0 and 300C and optionally below Addition of an acid-binding agent. Suitable organic solvents are e.g. optionally chlorinated aliphatic or aromatic hydrocarbons, such as Benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, o-dichlorobenzene; aliphatic or cycloaliphatic ketones such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone; also dialkyl ethers with 2-6 C atoms in the alkyl parts and cyclic ethers such as tetrahydrofuran and dioxane. Preferred solvents are Diethyl ether, tetrahydrofuran and dioxane.

The compounds of the formulas II, IV, IVa and V are known or can can be produced in a manner known per se. The amic acids of the formula II can for example that described in European Patent Publication No. 17994 Procedures are obtained.

The compounds of the formula I are used in unchanged form or, preferably used together with the auxiliaries customary in formulation technology and are therefore e.g. emulsion concentrates that can be sprayed or thinned directly Solutions, diluted emulsions, wettable powders, soluble powders, dusts, Granules, including encapsulations in e.g. polymeric materials, processed in a known manner. The application methods, such as spraying, misting, dusting, scattering or Like the nature of the means, pouring becomes the same as the goals aimed at and the given ones Chosen according to the circumstances.

The formulations, i.e. the active ingredient of the formula I. and, if applicable agents, preparations or containing a solid or liquid additive Compositions are prepared in a known manner, for example by intimate mixing and / or grinding the active ingredients with extenders, such as solvents, solid carriers, and optionally surface-active compounds (surfactants).

The following solvents can be used: aromatic hydrocarbons, preferably the fractions C8 to C12, such as xylene mixtures or substituted naphthalenes, Phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones, such as Cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized Coconut oil or soybean oil; or water.

As solid carriers, e.g. for dusts and dispersible powders, As a rule, natural rock flour is used, such as calcite, talc, kaolin, Montmorillonite or Attapulgite. To improve physical properties Highly disperse silica or highly disperse absorbent polymers can also be added will. As granular, adsorptive granulate carriers, there are porous types, e.g.

Pumice stone, broken bricks, sepiolite or bentonite, as non-sorptive Carrier materials e.g. calcite or sand are possible. In addition, a multitude of of pre-granulated materials of an inorganic or organic nature, such as in particular Dolomite or crushed plant residues can be used.

As surface-active compounds come depending on the nature of the to be formulated Active ingredient of the formula I with non-ionic, cationic and / or anionic surfactants good emulsifying, dispersing and wetting properties. Among surfactants are also to understand surfactant mixtures.

Suitable anionic surfactants can be so-called water-soluble soaps like water soluble synthetic surface active compounds.

The soaps are alkali, alkaline earth or optionally substituted Ammonium salts of higher fatty acids CC10-C22), such as e.g.

the Na or K salts of oleic or stearic acid, or of natural ones Fatty acid mixtures that can be obtained from coconut or tallow oil, for example. called. The fatty acid methyl taurine salts should also be mentioned.

However, so-called synthetic surfactants are used more frequently, in particular Fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually as alkali, alkaline earth or optionally substituted ammonium salts and have an alkyl radical 8 to 22 carbon atoms, where alkyl also includes the alkyl part of acyl radicals, e.g. the Na or Ca salt of ligninsulphonic acid, the dodecylsulphuric acid ester or a fatty alcohol sulfate mixture made from natural fatty acids. This subheading also includes the salts of sulfuric acid esters and sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid residue with 8-22 carbon atoms. Alkylarylsulfonates are e.g. the Na-, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or a naphthalenesulfonic acid-formaldehyde condensation product.

There are also corresponding phosphates, such as salts of the phosphoric acid ester a p-nonylphenol- (4-14) -ethylene oxide adduct in question.

Inert line polyglycol ether derivatives are used as nonionic surfactants of aliphatic or cycloaliphatic alcohols, saturated or unsaturated Fatty acids and alkylphenols in question, the 3 to 30 glycol ether groups and 8 to. 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.

Other suitable nonionic surfactants are the water-soluble, 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups containing polyethylene oxide adducts with polypropylene glycol, ethylene diamino polypropylene glycol and alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. the compounds mentioned usually contain 1 to per propylene glycol unit 5 ethylene glycol units.

Examples of nonionic surfactants are nonylphenol polyethoxyethanols, Castor oil polyglycol ether, polypropylene-polyethyleneoxy adducts, tributylphenoxypolyethoxyethanol, Polyethylene glycol and Octylphenoxypolyäthoxyäthanol mentioned.

Furthermore, there are also fatty acid esters of polyoxyethylene sorbitan, such as the polyoxyethylene sorbitan trioleate into consideration.

The cationic surfactants are mainly quaternary Ammonium salts which contain at least one alkyl radical with 8 to 22 as N-substituent Contain carbon atoms and, as further substituents, lower ones, optionally halogenated ones Have alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably as halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyldi (2-chloroethyl) ethylammonium bromide.

The surfactants commonly used in formulation technology are, among others, in the following publications described: "MC Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ringwood New Jersey, 1979; Sisely and Wood, "Encyclopedia of Surface Active Agents, "Chemical Publishing Co., Inc. New York, 1964.

The pesticidal preparations generally contain 0.1 to 99%, in particular 0.1 to 95%, active ingredient of the formula I, 1 to 99% of a solid or liquid additive and 0 to 25%, especially 0.1 to. 25% of a surfactant.

While concentrated agents are preferred as a commodity, used the end user usually dilutes funds.

The agents can also contain other additives such as stabilizers, defoamers, Viscosity regulators, binders, adhesives and fertilizers or other active ingredients included to achieve special effects.

Production examples Example 1: 31.6 g of 1- (3, 5-dichlorophenylcarbamoyl) -1, 2-dimethylcyclobutane-2-carboxylic acid (prepared according to European patent publication No. 17994) are stirred with 100 ml of acetic anhydride at 200 ° C. for 4 hours. A clear solution emerges after a short time. The acetic anhydride is distilled off in vacuo at 40 ° C. and the residue is recrystallized from methanol. 22 g of 1,2-dimethylcyclobutane-1,2-dicarboxylic acid (3,5-dichlorophenyl) isoimide, of mp. 110-llloC.

Yield = 74% of theory

Nuclear Magnetic Resonance Spectrum (60 MHz, CHCl3, g in ppm): 1.35 (s, 3H, -CH3); 1.45 (s, 3H, -CH3); 2.0-2.7 (m, 4H, -CH2CH2-); 6.9-7.1 (m, 3H, aromat.).

-1 -1 IR spectrum (KBr): 1840 cm (s) and 1730 cm (vs).

10 g (0.033 mol) of the above isoimide are suspended in 100 ml of methanol and stirred. 0.1 g of p-toluenesulfonic acid are added.

A clear solution is slowly formed. After 5 hours, in vacuo concentrated to about 20 ml, and the precipitated crystals are sucked. 9 g (80% of theory) of the amide ester of the above formula are obtained; M.p. 132-1330C.

Elemental analysis for C15X17NO3C12 (molecular weight 330.2): calculated C. 54.6 Z H 5.2% Cl 21.5% found C 55.0% H 5.0% C1 22.0%.

Nuclear Magnetic Resonance Spectrum (CDC13) b in ppm: 1.45 and 1.51 (s, 6H, 2 CH3), 1.88 and 2.48 (m, 4H, CH2-CH2), 3.62 (s, 3H, CH3), 7.05 (t, 1H, aromat.) and 7.45 (d, 2H, aromat.).

Example 2: 9 g (0.03 mol) of the isoimide prepared according to Example 1 are suspended in 15 ml of isopropanol. 0.1 g of p-toluenesulfonic acid are added. It is then heated to 650C. This creates a clear solution. When the reaction mixture is cooled, the crystals of the amide ester of the above formula precipitate; Yield 7.7 g (72% of theory): mp 122-124 ° C.

Elemental analysis for Cl7H2IN03C12 (molecular weight 358.3): calculated C. 57.0% H 5.9% C1 19.8% found C 57.0% H 5.7% C1 20.3%.

Nuclear Magnetic Resonance Spectrum CCDCl3) J in ppm: 1.15 and 1.23 (d, 6H, 2CH3), 1.42 and 1.5 (s, 6H, 2CH3), 1.7-2.75 (m, 4H, CH2-CH2), 5.0 (m, 1H, CH), 7.0 (t, 1H, aromat.) and 7.5 (d, 2H, aromat.).

Example 3: 6 g (0.02 mol) of the isoimide prepared according to Example 1 are suspended in 10 ml of isopropyl mercaptan and stirred. To this are added 0.06 g of p-toluenesulfonic acid. The internal temperature rises to 404C and a clear solution is formed. After 2 hours, the precipitated crystals are rinsed onto the suction filter with petroleum ether. 5.4 g (72% of theory) of the amide thioester of the above formula are obtained; M.p. 106-107oC.

Elemental analysis for C17H21NO2SCi2 (molecular weight 374.3): calculated C. 54.6% H 5.7% C1 18.9% found C 54.6% H 5.6% C1 19.1%.

Nuclear Magnetic Resonance Spectrum (CDCl3) g in ppm: 1.0-2.7 (m, 16H, 4 CH3 and CH2-CH2), 3.5 (m, 1H, CH), 7.0 (t, 1H, aromat.) And 7.4 (d, 2H, aromat.) ..

Example 4: 6 g (0.02 mol) of the isoimide prepared according to Example 1 are suspended in 10 ml of thiophenol and stirred. To this are added 0.06 g of p-toluenesulfonic acid. The internal temperature rises to 350C, and a clear solution is formed. After 3 hours, the precipitated crystals are rinsed onto the suction filter with petroleum ether. 3.8 g (50% of theory) of the amide thioester of the above formula are obtained; Melting point 103-1059C, elemental analysis for C20HlgNO2SCl2 (molecular weight 408.3): calculated C 58.8% H 4.7% C1 17.4% found C 59.0% H 4.8% C1 17.0%.

Nuclear Magnetic Resonance Spectrum (CDC13) g in ppm: 1.5 and 1.6 (s, 6H, 2 CH3), 1.9 and 2.7 (m, 4H, CH2-CH2), 7.0-7.4 (m, 8H, aromat.).

Formulation examples Example 5: Formulation examples for active ingredients of formula I (2 = percent by weight) a) wettable powder a) b) c) active ingredient 25% 50% 75% Na lignin sulfonate 5% 5% Na lauryl sulfate 3% -5% Na diisobutyl naphthalene sulfonate - 6% 10% octylphenol polyethylene glycol ether - 2% - (7-8 mol AeO) highly disperse silica 5% 10% 10% kaolin 62% 27% -The active ingredient is mixed well with the additives and grind well in a suitable mill. You get wettable powder that deals with Allow water to dilute into suspensions of any desired concentration.

b) Emulsion concentrate active ingredient 10% octylphenol polyethylene glycol ether (4-5 mol AeO) 3% calcium dodecylbenzenesulfonate 3 castor oil polyglycol ether (36 mol AeO) 4% cyclohexanone 30% xylene mixture 50% This concentrate can be diluted emulsions of any desired concentration can be made with water.

c) dust a) b) active ingredient 5% 8% talc 95% kaolin - 92% Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and ground on a suitable mill.

d) Extruder granulate active ingredient 10% Na lignin sulfonate 2% carboxymethyl cellulose 1% Kaolin 87% The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then in a stream of air dried.

e) Coating granules active ingredient 3% polyethylene glycol (M G 200) 3% Kaolin 94% The finely ground active ingredient is mixed with polyethylene glycol in a mixer moistened kaolin applied evenly. In this way you get dust-free Coating granules.

f) suspension concentrate active ingredient 40% ethylene glycol 10% nonylphenol polyethylene glycol ether (15 mol AeO) 6% Na lignin sulfonate 10% carboxymethyl cellulose 1% 37% aqueous formaldehyde solution 0.2% silicone oil in the form of a 75% aqueous emulsion 0.8% water 32% The finely ground active ingredient becomes intimate with the additives mixed.

A suspension concentrate is thus obtained, from which by dilution suspensions of any desired concentration can be prepared with water.

Biological Examples Example 6: a) Action against Botrytis cinerea on Vicia faba Residual protective effect: Vicia faba plants about 10 cm high were found with a spray mixture made from wettable powder of the active ingredient (0.02% active ingredient) sprayed. After 48 hours, the treated plants were sprinkled with a conidia suspension infected by the fungus. After incubating the infected plants for 2-3 The assessment was carried out for days at 95-100% relative humidity and 21 ° C of fungal attack.

br Effect against Botrytis ci-nerea - artificially injured on apples Apples were treated by making a spray powder of the active ingredient Spray mixture (0.02% active substance) was dripped onto the injury areas. The treated fruits were then with a spore suspension of Botrytis cinerea and inoculated for a week at high humidity and approx. 200C incubated. In the evaluation, rotten injuries were counted and from this the fungicidal effect of the test substance is derived.

The compounds of the formula I according to the invention generally showed a good fungicidal effect in the experiments described above.

Thus, among other things, caused the compounds listed below an inhibition of the infestation to less than 20% in comparison with untreated however infected (= 100% infestation) control plants: In Botrytis cinerea on Vicia faba: Connection according to example 4.

In Botrytis cinerea on apples: compound according to example 2.

Inhibition of infestation to 5% and less was effected in the above Try the following compounds of formula I: In Botrytis cinerea on Vicia faba: Compounds according to Examples 1 and 3.

In Botrytis cinerea on apples: Compounds according to Examples 1 and 3.

Claims (8)

Claims (II; jCompounds of the formula I wherein one of X and Y and the other is -ZR, Z is -0- or -S- and R is alkyl, alkenyl, alkynyl, cycloalkyl or aryl, R1 and R6 are independently methyl or ethyl, R2 and R3 are independently hydrogen, fluorine or methyl or but R2 is -OCOCH3 or chlorine and at the same time R is hydrogen, R4 R3 is hydrogen, R4 is hydrogen, methyl or chlorine and R5 is hydrogen or methyl, where R3 and R4 together can also form an additional bond in the four-membered ring. 2. Compounds of formula I according to claim 1, wherein with respect to X, Y, Z and R1 to R6 are as stated in claim 1 and R is straight-chain or branched Alkyl with 1-8 carbon atoms, straight-chain or branched alkenyl with 2-8 carbon atoms, 2-propynyl, cycloalkyl with 5-8 ring carbon atoms or aryl with 6 or 10 ring carbon atoms, that is unsubstituted or by one or two halogen atoms or one or two alkyl or alkoxy groups are substituted by 1-4 carbon atoms each. 3. Compounds of formula I according to claim 1, wherein with respect to X, Y and Z is as stated in the claim, R straight-chain or branched C1 alkyl, Cyclohexyl or phenyl, R1 and R6 each methyl, 1-4 R2 and R3 independently of one another Hydrogen, fluorine or methyl and R4 and R5 independently of one another are hydrogen or methyl. 4. Compounds of formula I according to claim 1, wherein with respect to X, Y and Z is as stated in claim 1, R is methyl, isopropyl, cyclohexyl or Phenyl, R1 and R6 each methyl (cis), R2 and R3 independently of one another hydrogen or fluorine and R4 and R5 each represent hydrogen. 5. Compounds of formula I according to claim 1, wherein with respect to X, Y and Z is as stated in claim 1, R is methyl, isopropyl, cyclohexyl or Phenyl, R1 and R6 each denote methyl (cis) and R2, R3, R4 and R5 each denote hydrogen. 5 6. A process for the preparation of compounds of the formula I according to claim 1, characterized in that either a) a compound of the formula II where one of X 'and Y' and the other is -OH, at a temperature between -200C and + 1000C in the presence of a dehydrating agent to form an isoimide of the formula III cyclized where one of X "and Y" is oxygen and the other representsXand the isoimide of the formula III, optionally after previous isolation, in the presence of catalytic amounts of acid is reacted with a compound of the formula IV R-ZH (IV), where Z, R and R1 to R6 have the meaning given in claim 1, or b) an anhydride of the formula V first with a compound of the formula IVa R-ZM (IVa) to a compound of the formula VI converts, converts the compound of formula VI into a corresponding acid halide and then lets the acid halide react with 3; 5-dichloroaniline, where Z, R and R1 to R6 have the meaning given in claim 1, one of X and X -OM and 1 2 represents the other -ZR and M represents hydrogen or an alkali metal. 7. Fungicidal agent containing a compound as active ingredient of formula I according to claim 1 and optionally a suitable carrier material and / or a surfactant. 8. Use of a compound of the formula I according to claim 1 for combating of fungi and to prevent fungal attack.