Substituted anilides of the cycloalkyl- or heterocyclyl-carboxylic acids.

0001The present invention relates to new cycloalkyl- or heterocyclyl-carboxylic acid anilides, a process for their preparation and their use for controlling pests, in particular fungi.

0002It is known that certain phenols have good fungicidal properties (see W. Krämer in crop protection and pest control, Ed. K.-H. Büchel, pp. 143 ff, 1977, Georg Thieme Verlag, Stuttgart, and the literature cited therein).

0003Furthermore, many carboxylic acid anilides with fungicidal activity, in particular with high activity against benzimidazole-tolerant plant pathogens, are known (cf. EP 117 024, EP 125 901, EP 100 615).

0004New cycloalkyl- or heterocyclyl-carboxylic acid anilides of the general formula (I)<chemistry id="chem0001" num="0001"><img file="EP0339418A2_D0001.tif" /></chemistry> in which X represents optionally alkyl-substituted cycloalkyl or an optionally alkyl-substituted heterocycle, Hal stands for halogen and Y¹, Y² and Y³ independently of one another represent hydrogen, halogen, optionally halogen-substituted alkyl, optionally halogen-substituted alkoxy or optionally halogen-substituted alkylthio, found.

0005The substituted cycloalkyl- or heterocyclyl-carboxylic acid anilides of the formula (I) contain one or more centers of asymmetry and can therefore be present in the form of diastereomers or diastereomer mixtures which are obtained in different proportions. They are predominantly obtained as racemates.

0006It has also been found that the new substituted cycloalkyl- or heterocyclyl-carboxylic acid anilides of the formula (I)<chemistry id="chem0002" num="0002"><img file="EP0339418A2_D0002.tif" /></chemistry> in which X represents optionally alkyl-substituted cycloalkyl or an optionally alkyl-substituted heterocycle, Hal for halogen and Y¹, Y² and Y³ are the same or different and represent hydrogen, halogen, optionally halogen-substituted alkyl, optionally halogen-substituted alkoxy or optionally halogen-substituted alkylthio, obtained when aminophenols of the formula (II)<chemistry id="chem0003" num="0003"><img file="EP0339418A2_D0003.tif" /></chemistry> in which Hal, Y¹, Y² and Y³ have the meanings given above, with carboxylic acid derivatives of the formula (III) X-<img file="EP0339418A2_D0004.tif" />-Hal¹ (III) in which X has the meaning given above and Hal¹ is halogen, preferably chlorine, or a leaving group which is customary in acylation reactions, preferably an activating ester radical if appropriate in the presence of an acid acceptor and if appropriate in the presence of a solvent or diluent.

0007Finally, it was found that the substituted cycloalkyl- or heterocyclyl-carboxylic acid anilides of the formula (I) have, inter alia, a high fungicidal activity. The new compounds can also be used in synergistic mixtures with other known, highly effective compounds.

0008In the context of the present invention, the substituents can generally have the following meanings.

0009<u style="single">halogen</u> Unless otherwise stated, can mean fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.

0010<u style="single">Alkyl</u>, <u style="single">Alkoxy</u> and <u style="single">Alkylthio</u> stand for a radical which has 1-6, preferably 1-4 and particularly preferably 1-3 carbon atoms per alkyl unit, e.g. B. methyl, ethyl, n- and iso-propyl, n-, sec-, iso- and tert-butyl, pentyl, n-hexyl or iso-hexyl, methoxy, ethoxy, n- and iso-propoxy, n- , sec.-, iso- and tert-butoxy, pentoxy and hexoxy, methylthio, ethylthio, n- and iso-propylthio, n-, sec.-, iso- and tert-butylthio, pentylthio and hexylthio.

0011<u style="single">Haloalkoxy</u> or. <u style="single">Haloalkylthio</u> generally represents a straight-chain or branched hydrocarbon radical with 1-6 carbon atoms and 1-9 identical or different halogen atoms which is bonded via oxygen or sulfur. Residues with 1-4 carbon atoms and 1-5 identical or different halogen atoms are preferred. Residues with 1 or 2 carbon atoms and 1 - 3 identical or different halogen atoms are very particularly preferred. Examples include: trifluoromethoxy, trichloromethoxy, difluorochloromethoxy, dichlorofluoromethoxy, difluoroethoxy, trifluoroethoxy, tetrafluoroethoxy, pentafluoroethoxy, trifluoromethylthio, trichloromethylthio, difluorochloromethylthio, dichlorofluoromifluoromethylthio, dichlorofluoromifluoromethyl, dichlorofluoromethylthio, dichlorofluoromifluoromethyl, dichlorofluoromifluoromethyl, dichlorofluoromethylthio, dichlorofluoromifluoromethyl, dichlorofluoromifluoromethyl, dichlorofluoromethylthio, dichlorofluoromifluoromethyl, dichlorofluoromifluoromethyl,

0012<u style="single">Haloalkyl</u> has the meaning of haloalkoxy.

0013<u style="single">Cycloalkyl</u> generally represents a cyclic hydrocarbon radical having 3 to 10 carbon atoms. Residues with 3 to 7 carbon atoms are preferred. Examples include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclodecanyl.

0014The cycloalkyl radicals can be substituted one to more times. Alkyl with 1-6 carbon atoms may be mentioned as substituents.

0015Alkyl has the preferred and particularly preferred meaning which has already been given above.

0016<u style="single">Heterocycle</u> can stand for a radical with 4-7 ring members, preferably with 4-6 ring members, with one or more heteroatoms such as oxygen, sulfur or nitrogen being present in addition to carbon. 5- or 6-rings with one or two of the heteroatoms mentioned, especially oxygen, are preferred. Examples include: oxetanyl, oxolanyl, oxanyl, dioxolanyl and dioxanyl. The heterocycles can be substituted one to more times, identically or differently, by alkyl having 1-6, preferably 1-4 and particularly preferably having 1 or 2 carbon atoms. Examples include: 3-methyl-oxetan-3-yl, 2-methyl-oxolan-2-yl, 2-methyl-oxan-2-yl, 5-methyl-1,3-dioxolan-5-yl, 2- Ethyl-oxolan-2-yl, 2-ethyl-oxan-2-yl, 5-ethyl-1,3-dioxolan-5-yl.

0017Formula (I) provides a general definition of the substituted cycloalkyl- or heterocyclyl-carboxylic acid anilides according to the invention. Preferred compounds of the formula (I) are those in which X stands for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl which is optionally mono- to tetrasubstituted, identically or differently, by straight-chain or branched alkyl having 1-4 carbon atoms or represents a heterocycle with 4-6 ring members, with one or two being the same apart from carbon or various heteroatoms such as oxygen or nitrogen are contained. The heterocycle can be substituted one to six times, identically or differently, by straight-chain or branched alkyl having 1 to 4 carbon atoms, Hal represents fluorine, chlorine or bromine, Y¹, Y² and Y³ are the same or different and are for hydrogen, fluorine, chlorine, bromine, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy or alkylthio each having 1 to 4 carbon atoms, for haloalkyl, Halogenalkoxy or haloalkylthio, each with 1 - 4 carbon atoms in the straight-chain or branched alkyl part and with 1 - 5 identical or different halogen atoms.

0018Compounds of the formula (I) in which X for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl substituted once or twice, identically or differently, by straight-chain or branched alkyl having 1 to 3 carbon atoms, for optionally mono- or doubly, identically or differently, by straight-chain or branched alkyl having 1 - 3 Carbon atoms substituted oxanyl, oxolanyl, dioxanyl, dioxolanyl or oxetanyl, Y¹, Y² and Y³ are the same or different and represent hydrogen, fluorine, chlorine, bromine, methyl or trifluoromethyl and Hal stands for fluorine, chlorine or bromine.

0019Compounds of the formula (I) in which X represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl substituted in the 1-position by methyl or ethyl, which are additionally substituted by a further alkyl radical having 1 to 3 carbon atoms, Hal stands for fluorine, chlorine or bromine and Y¹, Y² and Y³ are the same or different and represent hydrogen, fluorine, chlorine, bromine or trifluoromethyl.

0020If, for example, 2,6-dichloro-4-amino-phenol and 1-methyl-1-chlorocarbonylcyclohexane are used as starting materials, the course of the reaction can be represented by the following formula:<chemistry id="chem0004" num="0004"><img file="EP0339418A2_D0005.tif" /></chemistry>

0021Formula (II) provides a general definition of the aminophenols required as starting materials for carrying out the process according to the invention. In this formula (II), the radicals Hal and Y 1 - Y 3 have the meanings already given in connection with the description of the compounds of the formula (I) according to the invention. The majority of the compounds are known and can be produced by analogy processes (cf. "Methods of Organic Chemistry", Houben-Weyl, Volume VI / 1c, Phenols, Part 1, Georg Thieme Verlag, Stuttgart, 1976, and "Reactions of Organic Synthesis", Cesare Ferri, pp. 81, 89, 91, 97, 118, 120, 122, 124, 126, 128, Georg Thieme Verlag, Stuttgart, 1978).

0022The 4-amino-2-chloro- or -2-bromo-6-trifluoromethylphenols are known from Jp. Kokai Tokkyo Koho Jp 61/126055 and e.g. B. 4-amino-2,3,5,6-tetrafluorophenol from Zh. Org. Khim. 10 (9), 1923-1927 (1974). The compounds of formula (II A)<chemistry id="chem0005" num="0005"><img file="EP0339418A2_D0006.tif" /></chemistry> in which Y⁴ stands for fluorine or chlorine, are still new and the subject of a separate, not previously published German application P 3 804 288 and z. B. are prepared from corresponding hydroxybenzoic acids of the formula (VA)<chemistry id="chem0006" num="0006"><img file="EP0339418A2_D0007.tif" /></chemistry> by decarboxylation followed by nitration of the resulting phenols of the formulas (VI A)<chemistry id="chem0007" num="0007"><img file="EP0339418A2_D0008.tif" /></chemistry> to the nitro compounds of the formula (VII A)<chemistry id="chem0008" num="0008"><img file="EP0339418A2_D0009.tif" /></chemistry> which are then hydrogenated, e.g. B. with hydrogen and Raney nickel, to the corresponding amines of the formulas (II A).

0023The compounds of the formulas (VII A) are also still new and are the subject of the above, not previously published German application.

0024The cycloalkanecarboxylic acid derivatives also required for carrying out the process according to the invention are generally defined by the formula (III) in which X represents cycloalkyl. In this formula (III), the radicals X and Hal 1 have the meanings already given in connection with the description of the compounds of the formula (I) according to the invention. The compounds are known and can be prepared by analogy processes (cf. Diversi et. Al., Synthesis<u style="single">1971</u>, 258; U.S. 3,674,831; "Reactions of organic synthesis" Cesare Ferri, p. 460, 461, 1978, Georg Thieme Verlag, Stuttgart). The heterocyclic carboxylic acid derivatives also required to carry out the process according to the invention are also defined by the formula (III) in which X represents heterocyclyl. The compounds are known (cf. DE 1 900 202; DE 2 212 641) and can be prepared by analogy processes.

0025The process according to the invention is optionally carried out in the presence of acid acceptors. All customary acid binders can be used as acid acceptors. Alkali carbonates and alcoholates, such as sodium and potassium carbonate, sodium and potassium methylate or ethylate, furthermore aliphatic, aromatic and heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, 1,8-diazabicyclo (5,4,0) -undec-7-ene, dimethylbenzylamine and pyridine.

0026To carry out the process according to the invention, 1 to 2 mol, in particular 1 to 1.4 mol, of the compounds of the general formula (III) are preferably used per mol of aminophenol of the general formula (II).

0027Practically all inert organic diluents are suitable as diluents for carrying out the process according to the invention. These include in particular aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and dibutyl ether, Glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, Esters such as methyl acetate and ethyl ester, nitriles such. B. acetonitrile and propionitrile, amides such as. B. dimethylformamide, dimethylacetamide and N-methylpyrrolidone and dimethyl sulfoxide, tetramethylene sulfone and hexamethylphosphoric triamide.

0028The process according to the invention is generally carried out at temperatures between -50 ° C. and 120 ° C. The range between 0 ° C and 110 ° C is preferred. The reactions are generally carried out under normal pressure.

0029Working up is carried out by customary methods, for example by extracting the products with toluene or methylene chloride from the reaction mixture diluted with water, washing the organic phase with water, drying and distilling or so-called "distillation", ie prolonged heating under reduced pressure to moderately elevated temperatures, to get rid of the last volatile constituents, or by chromatographic purification over silica gel or e.g. by crystallization. Refractive index, melting point, R are used to characterize the compounds_f-Value or boiling point.

0030The active compounds according to the invention are suitable for use to control pests, in particular as fungicides.

0031Fungicidal agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

0032Bactericidal agents are used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

0033Some 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; 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; 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.

0034The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases enables treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.

0035The active compounds 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 formulations.

0036These 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. In the case of the use of water as an extender, for example 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, for example 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 under normal pressure, for example Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. The following are suitable as solid carriers: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates. Possible solid carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, 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 emulsifying 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 dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.

0037Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

0038Dyes such as inorganic pigments, for example 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.

0039The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

0040The active compounds according to the invention can be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and also in mixtures with fertilizers and other growth regulators.

0041The 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, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients using the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient itself into the soil. The seeds of the plants can also be treated.

0042When treating parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.

0043In the case of seed treatment, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

0044When treating the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.

Manufacturing examples

Example 1:

0045<chemistry id="chem0009" num="0009"><img file="EP0339418A2_D0010.tif" /></chemistry>

004618.5 g (0.085 mol) of 4-amino-2,6-dichlorophenol are dissolved in 150 ml of tetrahydrofuran and first with 8.6 g (0.085 mol) of triethylamine, then at 0 ° C internal temperature with 15 g (0.094 mol) 1 -Methyl-cyclohexane carboxylic acid chloride added. The mixture is stirred at 20 ° C. overnight and then 5 g of carboxylic acid chloride and 2.8 g of triethylamine are again added to the reaction mixture to complete the reaction. After 2 hours, the mixture is poured onto ice and the extracted solid is recrystallized from toluene. The above-mentioned compound with a melting point of 140 ° C. is obtained; Yield: 22.3 g (= 87% of theory).

0047The compounds of the formula (I) are obtained analogously:<tables id="tabl0001" num="0001"><img file="EP0339418A2_D0011.tif" /></tables><tables id="tabl0002" num="0002"><img file="EP0339418A2_D0012.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP0339418A2_D0013.tif" /></tables>

Preparation of the starting compounds

Example A1

3,5-dichloro-2,6-difluoro-4-hydroxybenzoic acid

0048300 g of potassium hydroxide, 600 ml of water, 15 g of tetrabutylammonium chloride and 135 g of 3,5-dichloro-2,4,6-trifluorobenzotrifluoride are placed in a stirring apparatus and then refluxed for 5 hours. After the reaction has ended, the mixture is cooled and acidified by the dropwise addition of hydrochloric acid. The solid product is filtered off and dried in vacuo. Yield: 93 g with a melting point of 102-105 ° C.

Example A2

3-chloro-2,5,6-trifluoro-4-hydroxy-benzoic acid

0049Analogously to Example A1, from 400 g of NaOH, 1200 ml of water, 15 g of tetraethylammonium chloride and 276 g of 3-chlorotetrafluorobenzotrifluoride when heated under reflux for 6 hours, 238 g of product are obtained with a melting point of 87-90 ° C.

Example A3

2,6-dichloro-3,5-difluorophenol

005050 g 3,5-dichloro-2,6-difluoro-4-hydroxy-benzoic acid and 10 ml dimethylformamide are mixed and heated. Carbon dioxide develops at 105 - 130 ° C and is allowed to react at this temperature. Then 200 ml of toluene and then 80 ml of water are stirred in, the phases are separated, the organic phase is dried and then distilled. 34 g of the product with a boiling point of 87-88 ° C. and a refractive index of n are obtained<maths id="math0001" num=""><math display="inline"><mrow><mfrac linethickness="0"><mrow><mtext>20</mtext></mrow><mrow><mtext>D</mtext></mrow></mfrac></mrow></math><img file="EP0339418A2_D0014.tif" /></maths> : 1,5310.

Example A4

0051Analogously to Example A3, 2-chloro-3,5,6-trifluorophenol is obtained, with a boiling point of 68-70 ° C./20 mbar.

Example A5

2,6-dichloro-3,5-difluoro-4-nitro-phenol

005220 g of 2,6-dichloro-3,5-difluorophenol are placed in 70 ml of acetic acid and 8 g of 98% nitric acid are added dropwise. The mixture is then stirred at room temperature for 2 hours, taken up in 150 ml of dichloromethane and washed twice with water. After the dichloromethane has been distilled off, 18 g of product remain. According to GC analysis 94%.

Example A6

2-chloro-3,5,6-trifluoro-4-nitrophenol

0053Analogously to Example A5, 25 g of 2-chloro-3,5,6-trifluoro-4-nitrophenol are obtained from 28 g of 2-chloro-3,5,6-trifluorophenol by nitration with a purity of 93% and a melting point of 107- 109 ° C.

Example A7

2,6-dichloro-3,5-difluoro-4-aminophenol

005418th g of 2,6-dichloro-3,5-difluoro-4-nitrophenol are hydrogenated in 100 ml of methanol in the presence of 1.5 g of Raney nickel at 25-45 ° C. with 30-50 bar of hydrogen until the hydrogen uptake has ended. After filtration, the solution is freed from the solvent under reduced pressure. There remain 13 g of aminophenol (GC purity 98.4%); Mp 151 ° C.

Example A8

2-chloro-3,5,6-trifluoro-4-aminophenol

0055Analogously to Example A7, 20 g of aminophenol (GC purity 97%) are obtained from 25 g of 2-chloro-3,5,6-trifluoro-4-nitro-phenol in 120 ml of methanol and 2 g of Raney nickel by hydrogenation.

Examples of use

0056In the following application example, the compound of the formula A known as fungicide<chemistry id="chem0010" num="0010"><img file="EP0339418A2_D0015.tif" /></chemistry> N, N-Dimethyl-N-phenyl-N '- (fluorodichloromethylthio) sulfamide [KH Büchel "Plant Protection and Pest Control", Georg Thieme Verlag, Stuttgart, p. 141 (1977)] was used as the reference substance.

example

Botrytis test (bean) / protective

0057<tables id="tabl0004" num="0004"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Solvent:</entry><entry namest="col2" nameend="col2" align="char" char=",">4.7 parts by weight of acetone</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Emulsifier:</entry><entry namest="col2" nameend="col2" align="char" char=",">0.3 parts by weight of alkyl aryl polyglycol ether</entry></row></tbody></tgroup></table></tables>

0058To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

0059To test for protective efficacy, young plants are sprayed with the active compound preparation to runoff. After the spray coating has dried on, 2 small pieces of agar covered with Botrytis cinerea are placed on each leaf. The inoculated plants are placed in a darkened, moist chamber at 20 ° C. 3 days after the inoculation, the size of the infection spots on the leaves is evaluated.

0060A clear superiority in effectiveness compared to the prior art show in this test, for. B. the compounds according to the preparation examples: 1 and 3.