1-Aryl-naphthoic acid amide and microbicides containing these.

0001The present invention relates to substituted 1-aryl-2-naphthoylamines, their preparation, and microbicidal agents which contain at least one of these compounds as active ingredient. The invention further relates to the production of the agents mentioned and the use of the new active ingredients and agents for controlling harmful microorganisms, in particular fungi which damage plants.

0002The compounds according to the invention have the general formula I.<chemistry id="chem0001" num="0001"><img file="EP0346841A2_D0001.tif" /></chemistry><ul id="ul0001" list-style="none"><li>where R₁ Halogen, nitro, cyano, unsubstituted or by halogen and / or C.₁-C₃Alkoxy mono- or polysubstituted C₁-C₆-Alkyl, C₃-C₆-Cycloalkyl, OR₄, NO₅R₆, CO₂R₅, CONR₅R₆ or NHCOR₇ means, or in which two adjacent positions in the nucleus are bridged by an unsubstituted or fluorine mono- or polysubstituted methylenedioxy or ethylenedioxy group, in which R₄ Hydrogen or C₁-C₆-Alkyl means that unsubstituted or by C₁-C₃-Alkoxy or substituted one or more times by halogen, or for C₃-C₄Alkenyl, 2-propynyl, 3-halo-2-propynyl,<chemistry id="chem0002" num="0002"><img file="EP0346841A2_D0002.tif" /></chemistry>or COR₇ stands,</li><li>Rs and R₆ independently of one another or C₁ -C₄-Alkyl is</li><li>R₇ for C₁-C₄-Alkyl and</li><li>Z represents O or NH,</li><li>a and b represent the number of positions occupied in the respective six-ring, and</li><li>a stands for the numbers 1-3 and b for the numbers 0-3, the individual groups R₁ are the same or different if the sum of a and b is greater than 1,</li><li>X represents oxygen, sulfur or NH,</li><li>R₂ and R₃ independently unsubstituted or by C₁-C₄-Alkoxy, halogen, cyano substituted Ci-C₆-Alkyl or C₃-C₇Cycloalkyl, C₃-C₇-Alkenyl or the rest<chemistry id="chem0003" num="0003"><img file="EP0346841A2_D0003.tif" /></chemistry>represents what</li><li>n = 0 or 1, further</li><li>R₂ and R₃ also together a C₄-C₇Alkylene chain which, with the nitrogen atom connecting it, is unsubstituted or substituted by C₁-C₄-Alkyl can form mono- or disubstituted heterocycle, one of the methylene groups from this chain being denoted by 0, S or NR₇ can be replaced, as well as R₂ can also mean hydrogen; including the addition salts of the compounds of formula I.</li></ul>

0003The term alkyl itself or as part of another substituent means, depending on the number of carbon atoms given, for example the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, etc., and their isomers, such as isopropyl, isobutyl, tert .-Butyl, isopentyl, etc. Cycloalkyl can mean, for example, cyclopropyl, cyclopentyl or cyclohexyl. Haloalkyl stands for a simple to perhalogenated alkyl substituent, such as CH₂CI, CHCI₂, CCl₃, CH₂Br, CHBr₂, CBr₃, CH₂F, CHF₂, CF₃, CCl₂F, CCI₂-CHCI₂, CH₂CH₂F, CJ₃ etc. Here and below, halogen should be understood to mean fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.

0004In the presence of a methylenedioxy group or ethylenedioxy group in one of the rings, two adjacent positions are thus occupied.

0005The compounds of the formula I are oils, resins or predominantly crystalline solids which are stable under normal conditions and are distinguished by extremely valuable microbicidal properties. For example, they can be used preventively and curatively in the agricultural sector or related fields to combat plant-damaging microorganisms. The active compounds of the formula I according to the invention are distinguished in high use concentrations by high fungicidal activity and problem-free use. No damage to the treated plants is observed.

00061-phenyl-4-hydroxy-2-naphthoylamine of the formula<chemistry id="chem0004" num="0004"><img file="EP0346841A2_D0004.tif" /></chemistry>where R₁ Dimethylamino, anilino, 4-chloroanilino, 4-methylanilino or benzylamino are known from the literature as pharmaceuticals (Indian J. Pharm. Sci. 1985 47 (1) 12-15; CA 103 25, 205882f (1985). Some of these Connections are anti-inflammatory.

00071-acetoxy- and 1-hydroxy-3-morpholinocarbonyl-4-phenylnaphthalene of the formula<chemistry id="chem0005" num="0005"><img file="EP0346841A2_D0005.tif" /></chemistry>are in J. Chem. Soc. Perkin Trans. 1 1978 (11), 1360-1366; CA 90 (9), 71721 (1979). These compounds do not specify commercially usable properties.

0008No 1-aryl-2-naphthoylamines with microbicidal activity are known from the literature.

0009The aim of the present invention is to provide novel microbicidal active ingredients. It has surprisingly been found that the compounds of the formula I have strong microbicidal activity.

0010Those compounds of formula 1 are preferred in which R₁ Halogen, nitro, C₁-C₆-Alkyl, C₃-C₆-Cycloalkyl, methylenedioxy, mono- or difluoromethylenedioxy, unsubstituted or substituted by fluorine or multiply substituted ethylenedioxy, OR4 or NRsRs, where R₄ Hydrogen or C₁-C₃Represents alkyl which is unsubstituted or by C₁-C₃Alkoxy is monosubstituted or mono- to pentasubstituted by halogen,<ul id="ul0002" list-style="none"><li>Rs and Rs independently of one another for H or C.₁-C₄-Alkyl,</li><li>a for the numbers 2 or 3, b for 0 or 1, and</li><li>X stands for O or S while</li><li>R₂ and R₃ independently of one another phenyl, 4-chlorophenyl, furthermore R₂ and R₃ also together a C₄-C₇-Alkylene chain, which together with the nitrogen atom is an unsubstituted or by C₁C.₄-Alkyl mono- or disubstituted heterocycle can form, one of the methylene groups from the chain by O, S or NR₇ can be replaced.</li></ul>

0011Of this group of compounds, those in which R₁ Methyl, chlorine, methoxy, ethoxy, difluoromethoxy, methylenedioxy, difluoromethylenedioxy, ethylenedioxy, nitro, mono- or dimethylamino and R₂ and R₃ the residues together with the common nitrogen atom<chemistry id="chem0006" num="0006"><img file="EP0346841A2_D0006.tif" /></chemistry>form.

0012From this group, those compounds are of interest in which R₁ Means methoxy or methylenedioxy and a represents the number 2.

0013From the latter group, those compounds stand out as microbicides where X stands for oxygen.

0014From this group, the compound of the formulas Ia should be mentioned as a particularly effective individual compound:<chemistry id="chem0007" num="0007"><img file="EP0346841A2_D0007.tif" /></chemistry>Of the compounds of formula I in which R₁ Methoxy or methyl means and a stands for the numbers 2 or 3 and b for O, those compounds are to be emphasized as microbicides, in which X stands for sulfur.

0015From this group, the compound of formula Ib is to be mentioned as the sole representative:<chemistry id="chem0008" num="0008"><img file="EP0346841A2_D0008.tif" /></chemistry>Of the compounds of formula I in which R₁ Halogen, nitro, C₁-C₆-Alkyl, C₁-C₃-Alkoxy, C₃-C₆-Cycloalkyl, methylenedioxy, mono- or difluoromethylenedioxy, unsubstituted or mono- or polysubstituted fluorine or NR₅R₆ mean what<ul id="ul0003" list-style="none"><li>Rs and R₆ independently of one another for H or C.₁-C₄-Alkyl,</li><li>a for the numbers 2 or 3 and b for 0 or 1, and</li><li>X stands for 0 or S, and</li><li>R₂ and R₃ independently for hydrogen, unsubstituted or through C, -C₄-Alkoxy, halogen or cyano substituted C₁-C₆-Alkyl, or or C₃-C₇-Alkenyl, and phenyl or 4-chlorophenyl, furthermore R₂ and R₃ also together represents a C4-C7 alkylene chain which, with the nitrogen atom, is unsubstituted or substituted by C₁-C₄-Alkyl mono- or disubstituted heterocycle can form, with one of the methylene groups from the chain through 0, S or NR₇ as microbicides, those of the formula Ic are preferred,<chemistry id="chem0009" num="0009"><img file="EP0346841A2_D0009.tif" /></chemistry></li><li>where R₈ and R_s either the methoxy radical or together the methylenedioxy radical and Q the following radicals:<chemistry id="chem0010" num="0010"><img file="EP0346841A2_D0010.tif" /></chemistry><chemistry id="chem0011" num="0011"><img file="EP0346841A2_D0011.tif" /></chemistry><chemistry id="chem0012" num="0012"><img file="EP0346841A2_D0012.tif" /></chemistry></li></ul>

0016From this group, the compound of the formula Id is to be mentioned as an individual representative:<chemistry id="chem0013" num="0013"><img file="EP0346841A2_D0013.tif" /></chemistry>

0017Of the compounds of the formula I, the valuable microbicides to be emphasized are also those of the formula le<chemistry id="chem0014" num="0014"><img file="EP0346841A2_D0014.tif" /></chemistry><ul id="ul0004" list-style="none"><li>where R₈ and R₉ both mean either methoxy or together methylenedioxy, and</li><li>R₁₀ and R₁₁ Methoxy or together methylenedioxy and R₁₁ can also be chlorine, nitro, amino, acetylamino, while</li><li>R₁ o is hydrogen, and</li><li>X₁ Mean O or S.</li></ul>

0018In the preparation of the compounds of the formula I according to the invention, the procedure is that an amine of the formula II<chemistry id="chem0015" num="0015"><img file="EP0346841A2_D0015.tif" /></chemistry>where R₂ and R₃ have the meanings given for formula I,<ul id="ul0005" list-style="none"><li>a) with a naphthoic acid derivative of the formula III<chemistry id="chem0016" num="0016"><img file="EP0346841A2_D0016.tif" /></chemistry>where R₁, a and b have the meanings given for formula I and Y is OH, halogen or C.₁-C₄Alkoxy means in a compound of the formula I '<chemistry id="chem0017" num="0017"><img file="EP0346841A2_D0017.tif" /></chemistry>transferred: and, if desired, the compound with phosphorus pentasulfide in a thiocarbonamide of the formula I "<chemistry id="chem0018" num="0018"><img file="EP0346841A2_D0018.tif" /></chemistry>transformed; or to obtain compounds of the formula I where X = NH,</li><li>b) with an imino ester of the formula IV<chemistry id="chem0019" num="0019"><img file="EP0346841A2_D0019.tif" /></chemistry>where R₁, a and b have the meanings given for formula 1 and R₁ a C₁C.₄Alkyl means in a compound of the formula I '"<chemistry id="chem0020" num="0020"><img file="EP0346841A2_D0020.tif" /></chemistry>transferred.</li></ul>

0019The preparation of the compounds of the formula I 'is the acylation of an amine of the formula II with a carboxylic acid derivative or with a carboxylic acid of the formula III, the latter preferably being used in the presence of an acid-activating or dehydrating agent.

0020Examples of suitable acid-activating and / or dehydrating agents are a chloroformate such as ethyl chloroformate or phosphorus pentoxide, N, N'-dicydohexylcarbodiimide, N, N'-carbonyldiimidazole or N, N'-thionyldümidazole.

0021The reaction is conveniently carried out in a solvent or solvent mixture such as methylene chloride, chloroform, carbon tetrachloride, ether, tetrahydrofuran, dioxane, benzene, toluene, acetonitrile or dimethylformamide, optionally in the presence of an inorganic base such as sodium carbonate or a tertiary organic base such as triethylamine or pyridine, which simultaneously can serve as a solvent, and optionally in the presence of an acid-activating agent at temperatures between -25 ° C and 150 ° C, but preferably at temperatures between -10 ° C and the boiling point of the reaction mixture. In this case, a reactive derivative of a compound of the general formula III which may have formed in the reaction mixture does not need to be isolated, and the reaction can also be carried out in an excess of the compound of the general formula II used as solvent.

0022To prepare such compounds of the formula I "(thioamides), the corresponding amides are reacted with phosphorus pentasulfide in an inert solvent. In some cases, P₂S₅ advantageous in the presence of K₂S or K₂(P_x) deploy.

0023Examples of suitable solvents are toluene, xylene and benzene. The reaction temperature is between 0 ° C and the boiling point of the reaction mixture, although in general a temperature of 120 ° C should not be exceeded.

0024To prepare such compounds of the formula I '"(amidines), corresponding imino esters are reacted with amines of the formula II.

0025The reaction takes place in an inert solvent such as ether or tetrahydrofuran at temperatures between about 0 and 100 C.

0026Some carboxylic acids of the formula III are known or can be prepared by customary processes (J. Org. Chem. 1981 46 3881-3886; J. Org. Chem. 1964 29 1757-1762; Synthesis 1983 105-107); getting produced. Iminoesters of the formula IV can be obtained from the corresponding nitriles by addition of a C.₁-C4-Alkanols win in the presence of HCI.

0027The amines of the formula II are generally known.

0028Compounds of the formula III in which Y is halogen or C1-C4-alkoxy can be prepared from the corresponding carboxylic acids.

0029The carboxylic acids of the formula Illa,<chemistry id="chem0021" num="0021"><img file="EP0346841A2_D0021.tif" /></chemistry>where R,₂ Fluorine, chlorine or C₁-C₃-Alkoxy or OR₄ means, where R₁, R4 and also a and b as defined under formula I can be prepared by reacting suitable organometallic compounds such as Grignard compounds or lithium compounds with carbonic acid. The organometallic compounds themselves can be prepared by metalation of the corresponding bromine compounds of the formula VIII with a suitable metal, such as activated magnesium, or with a metal compound, such as butyllithium, by known methods:<chemistry id="chem0022" num="0022"><img file="EP0346841A2_D0022.tif" /></chemistry>

0030The bromine compounds of the formula VIII can in turn be prepared by dehydrogenation of the corresponding 3,4-dihydronaphhtalines of the formula VI. The dehydrogenation can be carried out by known methods, for example by reaction with dehydrogenating agents such as sulfur or quinones, preferably 2,3-dichloro-5,6-dicyan-1,4-benzoquinone (Chem. Rev. 78 317 1978). The compounds of the formula VI themselves can be prepared by reacting dihydronaphthalenes of the formula V with suitable brominating agents, such as, for example, pyridinium hydrobromide perbromide (J. Med. Chem. 29 2053-2059, 1986)<chemistry id="chem0023" num="0023"><img file="EP0346841A2_D0023.tif" /></chemistry>

0031By varying the analog synthesis steps, the 3,4-dihydro-bromonaphthalene compounds of the formula VI can first be converted via the metal compounds with carbonic acid into the 3,4-dihydronaphthalenecarboxylic acids of the formula VII, which are then dehydrogenated to the compounds of the formula IIla:<chemistry id="chem0024" num="0024"><img file="EP0346841A2_D0024.tif" /></chemistry>

0032Some of the compounds of the formula V are known or can be prepared by known processes [Tetrahedron 38 2403-2410, (1982), Aust. J. Chem. From 34, 115-129 (1981)].

0033The bromnaphthalene carboxylic acids of the formula Illc<chemistry id="chem0025" num="0025"><img file="EP0346841A2_D0025.tif" /></chemistry>where a and R₁ as defined under formula I can be prepared from the corresponding nitrated naphthalene carboxylic acids of the formula 111 b by a known reaction sequence (reduction, diazotization, Sandmeyer reaction).<chemistry id="chem0026" num="0026"><img file="EP0346841A2_D0026.tif" /></chemistry>

0034It has now surprisingly been found that the compounds of the formula I according to the invention have a very advantageous spectrum of biocidal activity against harmful microorganisms, in particular against phytopathogenic fungi and bacteria, which satisfies the practical needs well. They have very advantageous curative, systemic and especially preventive properties and can be used to protect numerous crop plants. With the active ingredient of formula I, the pests occurring on plants or on parts of plants (fruits, flowers, leaves, stems, tubers, roots) of different crops can be contained or destroyed, with parts of the plant that grow later being spared by phytopathogenic microorganisms.

0035The active compounds according to the invention are active, for example, against the phytopathogenic fungi belonging to the following classes: Ascomycetes, for example Erysiphe, Sclerotinia, Fusarium, Monilinia, Helminthosporium; Basidiomycetes such as Puccinia, Tilletia , Rhizoctonia; and in particular those of the class of the Phycomycetes Oomycetes such as Phytophthora, Plasmopara, Peronospora, Pythium. The compounds of formula I can also be used as crop protection agents against important harmful fungi from the Fungi imperfecti family, for example against Cercospora, Pyricularia and Botrytis. The connections also act systemically. In addition, compounds of the formula I can be used successfully to protect perishable goods of plant or animal origin. They fight molds like Penicillium, Aspergillus, Rhizopus, Fusarium, Helminthosporium, Nigrospora and Alternaria as well as bacteria like butyric acid bacteria and yeasts like Candida. These active substances also show excellent activity against soil and seed-borne fungi.

0036The active compounds of the formula I can also be used as dressings for the treatment of seeds (fruits, tubers, grains) and plant cuttings for protection against fungal infections and against phytopathogenic fungi occurring in the soil, they being particularly useful as grain dressings in the control of fungal organisms, such as for example, Fusarium, Helminthosporium and Tilletia species.

0037The invention thus also relates to microbicidal agents and to the use of the compounds of the formula I for combating phytopathogenic microorganisms, in particular fungi which damage plants and the preventive prevention of infestation on plants and on stocks of plant or animal origin.

0038In the context of this invention, the following crop types are, for example, the target crops for crop protection: cereals: (wheat, barley, rye, oats, rice, sorghum and relatives); Beets: (sugar and fodder beets): pome, stone and berry fruits: (apples, pears, plums, peaches, almonds, cherries, strawberries, brain and blackberries); Legumes: (beans, lentils, peas, soy): Oil crops: (rape, mustard, poppy seeds, olives, sunflowers, coconut, castor bean, cocoa, peanuts); Cucumber Family: (Pumpkin, Cucumber, Melon); Fiber plants: (cotton, flax, hemp, jute); Citrus fruits: (oranges, lemons, grapefruit, mandarins); Vegetables: (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers); Laurel plants: (avocado, cinnamonum, camphor) or plants such as corn, tobacco, nuts, coffee, sugar cane, tea, grapevines, hops, banana and natural rubber plants and ornamental plants (composites).

0039Active substances of the formula 1 are usually used in the form of compositions and can be applied simultaneously or in succession with further active substances to the area or plant to be treated. These further active ingredients can be both fertilizers, trace element mediators or other preparations which influence plant growth. However, it can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, together with any other carriers, surfactants or other application-promoting additives which are customary in formulation technology.

0040Suitable carriers and additives can be solid or liquid and correspond to the substances useful in formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers. Particularly advantageous, application-promoting additives which can lead to a large reduction in the application rate are also natural (animal or vegetable) or synthetic phospholipids from the range of the cephalins and lecithins, such as, for example, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol or lysolecithin.

0041A preferred method for applying an active ingredient of the formula I or an (agro) chemical agent which contains at least one of these active ingredients is application to the foliage (leaf application). The number of applications and the application rate depend on the infestation pressure for the relevant pathogen (type of fungus). The active ingredients of formula I can also get into the plant through the roots through the root system (systemic effect) by soaking the location of the plant with a liquid preparation or introducing the substances into the soil in solid form, for example in the form of granules (Floor application). However, the compounds of the formula I can also be applied to seeds (coating) by either impregnating the grains with a liquid preparation of the active ingredient or coating them with a solid preparation. In addition, other types of application are possible in special cases, such as the targeted treatment of plant stems or buds.

0042The compounds of the formula I are used in unchanged form or preferably together with the auxiliaries customary in formulation technology and are therefore used, for example, to give emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules Encapsulations in, for example, polymeric materials processed in a known manner. The application methods such as spraying, atomizing,

0043Dusting, scattering, brushing or pouring, like the type of agent, are chosen in accordance with the intended goals and the prevailing conditions. Favorable application rates are generally 50 g to 5 kg of active substance (AS) per ha; preferably 100 g to 2 kg ai / ha, in particular at 200 g to 600 g ai / ha.

0044The formulations, ie the agents, preparations or compositions containing the active ingredient of the formula I and, if appropriate, a solid or liquid additive, are prepared in a known manner, for example by intimately mixing and / or grinding the active ingredients with extenders, such as, for example, with solvents, solid carriers, and optionally surface-active compounds (surfactants).

0045Possible solvents are: aromatic hydrocarbons, preferably fractions Cs to C₁₂, such as xylene mixtures or substituted naphthalenes, phthalic esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters such as ethylene glycol monomethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone Dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils or soybean oil, or water.

0046Calcite, talc, kaolin, montmorillonite or attapulgite, highly disperse silica or absorbent polymers can be used as solid carriers, for example for dusts and dispersible powders. Pumice, broken brick, sepiolite or bentonite are suitable as granular, adsorptive granulate carriers, and non-sorptive carriers, for example calcite or dolomite, are not suitable. Shredded plant residues can also be used.

0047Depending on the nature of the active ingredient of the formula I to be formulated, suitable surface-active compounds are nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties. Surfactants are also to be understood as mixtures of surfactants.

0048The surfactants commonly used in formulation technology are described in the following publications:<ul id="ul0006" list-style="none"><li>"Mc Cutcheon's Detergents and Emulsifiers Annual" MC</li><li>Publishing Corp., Ridgewood New Jersey, 1980</li><li>Sisley and Wood, "Encyclopedia of Surface Active Agents",</li><li>Chemical Publishing Co., Inc. New York, 1980.</li></ul>

0049The agrochemical preparations contained in the. Rule 0.1 to 99%, in particular 0.1 to 95% active ingredient of the formula I, 99.9 to 1%, in particular 99.9 to 5% of a solid or liquid additive and 0 to 25%, in particular 0.1 to 25% of a surfactant.

0050While concentrated agents are preferred as a commodity, the end user generally uses diluted agents.

0051Such (agro) chemical agents are part of the present invention.

0052The following examples serve to illustrate the invention without restricting it (percentages and parts relate to weight; temperatures are given in degrees Celsius).

1. Manufacturing examples

0053H.1: Preparation of 1- (3,4-dimethoxyphenyl) -2-naphthoic acid morpholide (active substance, compound no. 1.1, table 1).<chemistry id="chem0027" num="0027"><img file="EP0346841A2_D0027.tif" /></chemistry>

005412.3 g of 1- (3,4-dimethoxyphenyl) -2-naphthoic acid are placed in 70 ml of toluene, and 4.8 g of thionyl chloride are added. The reaction mixture is heated to boiling and stirred under reflux for 16 h. Then 7.0 g of morpholine are added dropwise at 50 °, the reaction mixture is stirred at reflux for a further 4 h, then diluted in the cold with 100 ml of toluene and washed 3 times with 200 ml of water each time. The organic phase is dried over sodium sulfate, filtered and the solvent evaporated under vacuum. For purification, the oily residue is chromatographed on a silica gel column using ethyl acetate. The title compound is obtained as a yellow oil, which solidifies on standing. M.p. 161-163^*.

0055H.2: Preparation of 2- (4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl) -1- (3,4-dimethoxyphenyl) naphthalene (intermediate).<chemistry id="chem0028" num="0028"><img file="EP0346841A2_D0028.tif" /></chemistry>

0056To 25.5 g of Grignard reagent prepared from 23.2 g of 4-bromo-veratrol and 2.5 g of magnesium in 50 ml of tetrahydrofuran, 21.3 g of 2- (4,4-dimethyl-4,5- dihydro-1,3-oxazol-2-yl) -1-methoxy-naphthalene was added dropwise, the red reaction mixture was heated to boiling, stirred at reflux for 4 h, then mixed with -200 ml of saturated ammonium chloride solution in the cold and 3 times with extracted 100 ml ether. The ether phases are combined, washed twice with 200 ml of water each time, dried over sodium sulfate and the solvent evaporated under vacuum. For purification, the oily residue is chromatographed 1: 1 on a silica gel column using hexane / ethyl acetate. The compound is obtained as a yellow oil<maths id="math0001" num=""><img file="EP0346841A2_D0029.tif" /></maths> : 1,6158.

0057H.3: Preparation of 1- (3,4-dimethoxyphenyl) -2-naphthoic acid (intermediate).<chemistry id="chem0029" num="0029"><img file="EP0346841A2_D0030.tif" /></chemistry>

005816.0 g of the 2- (4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl) -1- (3,4-dimethoxyphenyl) -naphthalene prepared under H 2 are 8 hours in Boiled 40 ml of 3 N hydrochloric acid. The two-phase mixture is then cooled to room temperature and the phases are separated. The heavy phase is mixed with 40 ml of 20% methanolic (methanol / H₂0 1: 1) sodium hydroxide solution stirred for 40 hours at reflux, the methanol is distilled off, the aqueous residue is diluted with 100 ml of water and extracted 3 × with 100 ml of ethyl acetate. The aqueous phase is concentrated with conc. Hydrochloric acid adjusted to pH 1. The crystals which have precipitated out are filtered off with suction and washed twice with 100 ml of water each time and dried in a vacuum drying cabinet at 60.degree. M.p.> 215` C.

0059H.4: Preparation of 1- (3,4-dimethoxyphenyl) -6-chloro-2-naphthoic acid morpholide (compound no.3.1, table 3).<chemistry id="chem0030" num="0030"><img file="EP0346841A2_D0031.tif" /></chemistry>

00606.9 g of 1- (3,4-dimethoxyphenyl) -6-chloro-2-naphthoic acid are placed in 50 ml of toluene, and 2.4 g of thionyl chloride are added. The reaction mixture is heated to boiling and stirred under reflux for 5 hours. 4.0 g of morpholine are then added dropwise at -50 °, the mixture is heated to boiling again and the mixture is stirred at reflux for a further 3 hours. After cooling to room temperature, the reaction mixture is diluted with 100 ml of toluene, the organic phase is washed 3 times with 250 ml of water each time, dried over sodium sulfate, filtered and the solvent is evaporated off in vacuo. The oily residue is chromatographed on a silica gel column for purification using ethyl acetate. The title compound is obtained in the form of beige crystals. Mp 157-159 °.

0061H.5: Preparation of 1- (3,4-dimethoxyphenyl) -6-chloro-2-naphthoic acid (intermediate)<chemistry id="chem0031" num="0031"><img file="EP0346841A2_D0032.tif" /></chemistry>

0062To a solution of 20.0 g of 1- (3,4-dimethoxyphenyl) -6-chloro-2-bromomagnesium naphthalene in 110 ml of tetrahydrofuran, made from 18.8 g of 1- (3,4-dimethoxyphenyl) -6-chloro 2-bromonaphthalene and 1.2 g magnesium become dry C0 at -5 to 0₂ initiated. After the exothermic reaction has subsided, a further hour becomes C0₂ initiated. Then 30 ml of -10% hydrochloric acid, then another 200 ml of water are added dropwise with cooling, the acidic reaction solution is concentrated. Sodium hydroxide solution made alkaline and extracted twice with 150 ml ether. The aqueous phase is adjusted to pH 1 with 20% hydrochloric acid. The acid precipitated is filtered off, washed with a little water and dried in a vacuum drying cabinet at 80 °. Mp of the beige title compound> 200 °.

0063H.6: Preparation of 1- (3,4-dimethoxyphenyl) -6-chloro-2-bromonaphthalene (intermediate).<chemistry id="chem0032" num="0032"><img file="EP0346841A2_D0033.tif" /></chemistry>

006419.0 g of 1- (3,4-dimethoxyphenyl) -6-chloro-2-bromo-3 are added to 13.6 g of 2,3-dichloro-5,6-dicyan-1,4-benzoquinone in 300 ml of dichloroethane , 4-dihydronaphthalene, dissolved in 100 ml dichloroethane, added dropwise, heated and kept under reflux for 16 hours. The cooled reaction mixture is then mixed with 300 ml of hexane, filtered and the filtrate evaporated. The residue is chromatographed on a silica gel column for purification using ethyl acetate / hexane 2: 1. The product is obtained as a white powder. M.p. 117-119 °.

0065H.7: Preparation of 1- (3,4-dimethoxyphenyl) -6-chloro-2-bromo-3,4-dihydronaphthalene (intermediate).<chemistry id="chem0033" num="0033"><img file="EP0346841A2_D0034.tif" /></chemistry>

006630.0 g of 1- (3,4-dimethoxyphenyl) -6-chloro-3,4-dihydronaphthalene are dissolved in 200 ml of methylene chloride and cooled to 0 °. For this, at 0^* 31.2 g of pyridine hydrobromide perbromide were added in portions over the course of 1 1/2 hours. When the addition is complete, the violet solution is stirred at 0 for 2 hours, then 300 ml of 10% sodium bicarbonate solution are added, the organic phase is separated off and washed with water, dried over sodium sulfate, filtered and evaporated. The semi-crystalline product thus obtained can be directly reacted further. When left to stand for a long time, the title compound crystallizes completely and can be digested in hexane. Mp 92-95 °.

0067H.8: Preparation of 1- (3,4-dimethoxyphenyl) -6-chloro-3,4-dihydronaphthalene (intermediate).<chemistry id="chem0034" num="0034"><img file="EP0346841A2_D0035.tif" /></chemistry>

0068To 96.4 g of 4-bromomagnesium veratrol, made from 9.6 g of magnesium and 86.8 g of 4-bromveratrol, in 500 ml of tetrahydrofuran are at 0 to max. 5 ° 43.0 g of 6-chloro-1-tetralone, dissolved in 300 ml of tetrahydrofuran, were added dropwise over the course of 1 hour. The reaction mixture is then stirred for one hour at room temperature and then for 5 hours at reflux, then cooled to room temperature and 150 ml of 10% hydrochloric acid and 500 ml of water are added in the cold. The reaction mixture is extracted 3 times with 250 ml of ether each time, the organic phases are combined, washed with 2 times 150 ml of water, dried over sodium sulfate, filtered and evaporated. The oily residue is boiled in 150 ml of methanol / sulfuric acid (1: 1) under reflux for 2 hours to completely eliminate water. The olefin is then extracted with 3 × 250 ml of ether from the cooled reaction solution. The organic phases are combined, washed with water, over Na₂S0₄ dried, filtered and evaporated. The oily residue is purified by column chromatography using ethyl acetate / hexane 1: 2. The title compound is obtained as a yellow oil.

0069The compounds listed in Tables 1-3 can be prepared analogously to Examples H.1 and H.4 or using one of the methods given above.<tables id="tabl0001" num="0001"><img file="EP0346841A2_D0036.tif" /></tables><tables id="tabl0002" num="0002"><img file="EP0346841A2_D0037.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP0346841A2_D0038.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP0346841A2_D0039.tif" /></tables>

2nd Formulation examples for active ingredients of formula I (% = weight percent)

2.1. Emulsion concentrates

0070<tables id="tabl0005" num="0005"><img file="EP0346841A2_D0040.tif" /></tables>

0071Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

2.2. solutions

0072<tables id="tabl0006" num="0006"><img file="EP0346841A2_D0041.tif" /></tables>

0073These solutions are suitable for application as microdispersions.

2.3. Granules

0074<tables id="tabl0007" num="0007"><img file="EP0346841A2_D0042.tif" /></tables>

0075The active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated off in vacuo.

2.4. Dusts

0076<tables id="tabl0008" num="0008"><img file="EP0346841A2_D0043.tif" /></tables>

0077Ready-to-use dusts are obtained by intimately mixing carrier substances with the active ingredient.

2.5. Wettable powder

0078<tables id="tabl0009" num="0009"><img file="EP0346841A2_D0044.tif" /></tables>

0079The active ingredient is mixed well with the additives and ground in a suitable mill. Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.

3rd Biological examples

Example 3.1: Action against Plasmopara viticola on vines

a) Residual protective effect

0080In the 4-5 leaf stage, vine seedlings were sprayed with a spray mixture (0.02% active ingredient) made from wettable powder of the active ingredient. After 24 hours, the treated plants were infected with a sporangia suspension of the fungus. After incubation for 6 days at 95-100% relative humidity and 20^. C the fungal attack was assessed.

b) Residual curative effect

0081In the 4-5 leaf stage, vine seedlings were infected with a sporangia suspension of the fungus.After incubation for 24 hours in a moist chamber at 95-100% relative humidity and 20 C, the infected plants were dried and sprayed with a spray mixture prepared from wettable powder of the active ingredient (0.02 % Active substance) sprayed. After the spray coating had dried on, the treated plants were brought back into the moist chamber. The fungal infection was assessed 6 days after the infection.

0082Compounds from Tables 1 to 3 showed a very good fungicidal action against vines' Plasmopara viticola, in particular the active ingredients Nos. 1.1, 1.2, 1.6, 1.8, 1.24, 1.46 and 3.1 brought about complete suppression of fungal attack (0 to 5% remaining).

Example 3.2: Action against Cercospora arachidicola on peanut plants

Residual protective effect

0083Peanut plants 10-15 cm high are sprayed with a spray mixture (0.02% active substance) made from wettable powder of the active substance and infected 48 hours later with a conidia suspension of the fungus. The infected plants are incubated for 72 hours at approx. 21 ° C and high atmospheric humidity and then placed in a greenhouse until the typical leaf spots appear. The fungicidal activity is assessed 12 days after infection based on the number and size of the spots that occur.

0084Compared to untreated but infected control plants (number and size of the spots = 100%), peanut plants treated with the active ingredients from the tables show a greatly reduced Cercospora infestation. Compounds 1.24 and 1.26 and others of Tables 1 to 3 prevented stains almost completely (0-10%).

Example 3.3: Residual protective action against Venturia inaequalis on apple shoots

0085Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture (0.02% active substance) made from wettable powder of the active ingredient. After 24 hours, the treated plants are infected with a conidia suspension of the fungus. The plants are then incubated for 5 days at 90-100% relative atmospheric humidity and for a further 10 days in a greenhouse at 20-24^* C set up. Scab infestation is assessed 15 days after infection. Compound No. 1.24 of Table 1 inhibits the disease infestation to less than 10%. In contrast, untreated but infected control instincts are 100% infected.

Example 3.4 .: Effect against Erysiphe graminis on barley

a) Residual protective effect

0086Approx. Barley plants 8 cm high are sprayed with a spray mixture (0.02% active substance) made from wettable powder of the active ingredient. After 3-4 hours, the treated plants are dusted with conodoes of the fungus. The infected barley plants are grown in a greenhouse at around 22^*C set up and the fungal attack was assessed after 10 days.

b) Systemic effect

0087A spray liquor made from wettable powder of the active ingredient is poured into about 8 cm high barley plants (0.02% active substance based on the volume of the earth). Care was taken to ensure that the spray mixture did not come into contact with the parts of the plant above ground. After 48 hours, the treated plants are dusted with conidia of the fungus. The infected barley plants are placed in a greenhouse at about 22 ° C. and the fungal attack is assessed after 10 days.

0088Compounds from Tables 1 to 3 showed good activity against Erysiphe. For example, the compounds No. 1.1, 1.2, 1.10, 1.24, 1.26, 1.31, 1.32, 1.40, 2.1 and 3.1 reduce the Erysiphae infestation to 0 to 5%. On the other hand, untreated but infected control plants show an Erysiphe infestation of 100%.

Example 3.5: Action against Phytophthora on tomato plants Residual protective action

0089After growing for 3 weeks, tomato plants are sprayed with a spray mixture (0.02% active substance) prepared from wettable powder of the active ingredient. After 24 hours, the treated plants are infected with a sporangia suspension of the fungus. Fungus infestation is assessed after incubating the infected plants for 5 days at 90-100% relative humidity and 20 C.

0090Compounds from Tables 1 to 3 showed a lasting effect (less than 20% fungal attack). With the compounds No. 1.1, 1.6, 1.46 and 3.1, 3.4 and other preparations from Table 3, an infection was practically completely prevented (0 to 5% infection).