PT100395A - AROMATIC COMPOUNDS CONTAINING AN OXYGEN RING CONDENSED WITH BENZENE AND PROCESS FOR THEIR PREPARATION - Google Patents

Description

The present invention relates to oxime ethers of formula I in the form of their racemic mixtures or isomers thereof,

in which R 1 represents hydrogen, C 1-4 alkyl, C 1-3 alkoxy methyl, methylthio, cyano, cyclopropyl or trifluoromethyl, R 2 and R 3 together with the two carbon atoms to which they are attached form a five to seven membered non- substituted or unsubstituted alkyl substituted by 1 or 2 oxygen atoms and X represents a single bond, -C (R 2) -, CO, -CR = CR-, C (R 2) 0, C (R 2) S or C (R 2) C (R 2), in which R 2 represents hydrogen and / or C 1 -C 3 alkyl, with the proviso that X represents one of the groups -C (R 2) S and C (R 2) C (R 2), if R 1 is methyl and R 2 and R 3 together represent methylenedioxy. 4

The compounds according to the invention have fungicidal properties and are suitable as fungicidal active ingredients, especially for use in agriculture and horticulture. The invention also relates to a process for the preparation of the compounds according to the invention, to fungicidal compositions comprising such compounds as active ingredients and to the use of such compounds and compositions for the control of phytopathogenic fungi in agriculture and horticulture.

In formula I above and hereinafter, the alkyl or alkoxy groups are, depending on the number of carbon atoms, straight-chain or branched.

Substituents of the oxygen-containing ring are, for example, C1-4-alkoxy and furyl; such substituents may be several and may be identical or different.

The oxime ethers wherein the five to seven membered ring formed by R 2 and R 3 is mono- or polysubstituted by C 1-6 alkyl, C 1-6 alkoxy, . 1-4 'and / or fluorine are therefore preferred. (Subgroup IA).

If asymmetric carbon atoms are present in the compounds of formula I, the compounds occur in optically active form. The compounds occur in any case in the form [E] or [Z] simply as a result of the presence of the imino and aliphatic double bond. In addition, atropic isomerism may occur. Formula I should include all these possible isomeric forms and mixtures thereof, for example racemic mixtures and any mixtures [E / ZJ. 5

The process according to the invention for the preparation of the compounds according to the invention is characterized by the reaction of an oxime of general formula II

in which R 1, R 2, R 3 and X are as defined above, with a benzyl alcohol derivative of the general formula III

m

V wherein U represents a leaving group.

This reaction is a nucleophilic substitution which may be carried out under reaction conditions which are customary in this respect, the leaving group U, present in the benzyl alcohol derivative of formula III, should preferably be understood as being chlorine, bromine, iodine, methanesulfonyloxy, benzenesulfonyloxy or p-toluenesulfonyloxy. The reaction is advantageously carried out in a basic medium in an inert organic diluent which may be especially unsubstituted or halogenated, aliphatic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, petroleum, ligroin , benzene, toluene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene, o-dichlorobenzene, also ethers, such as diethyl ether and dibutyl ether, dimethyl ether glycol and diethylene glycol dimethyl ether, tetrahydrofuran and dioxane, also ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, also nitriles, such as, for example, acetonitrile and propionitrile, benzonitrile, glutaric acid dinitrile and, in addition, amides such as, for example, dimethylformamide, dimethylacetamide and N- methylpyrrolidone, as well as dimethyl sulfoxide, tetramethylenesulfone and hexamethylphosphoric acid triamide.

Alkali and alkaline earth metal hydroxides, hydrogeonocarbons, carbonates and alkalates (Li, Na, K, Ca, Mg), sodium hydride, tertiary amines, such as trimethylamine and triethylamine, pyridine, picolines , N-methylmorpholine, N-ethylpyrrolidine, diazabicyclo [4.3.0] undecane (DBU), 1,4-diazabicyclo2.2.2octane (DABCO), diazabicyclo [3.2.0] nonane DBN) and organolithium compounds, such as n-butyllithium.

Still further, silver oxide may be used as the weak catalytically active base. The reaction temperature is advantageously in the range of from -20 ° C to + 80 ° C, preferably from 0 ° C to +60 ° C.

Alternatively, the reaction may be carried out with phase transfer catalysis in an organic solvent, such as, for example, methylene chloride, in the presence of a sodium hydroxide solution, and a phase transfer catalyst such as, for example, tetrabutylammonium hydrogensulfate, at room temperature. Isolation and purification of the compounds of formula I thus obtained may be carried out according to methods known per se. Any isomeric mixtures obtained, for example E / Z isomeric mixtures, may be separated into the pure isomers also by methods known per se, for example by chromatography or fractional crystallization. ))

The oximes of formula II used as starting materials in the process according to the invention are known or may be prepared according to methods known per se, for example by reacting the corresponding carbonyl compound with hydroxylamine hydrochloride in the presence of a base, for example sodium or potassium hydroxide, iodine or pyridine. Other methods can be found in Houben-Weyl, " Methoden der Organischen Chemie ", vol. x / 4, pp. 3-308 (1968) [(" Herstellung und Umwandlung von Oximen ") (Preperation and conversion of oximes)]. The present invention also relates to compounds of formula II which are novel.

The starting materials of formula III may be prepared in a manner known per se, for example as described in European Patent Application No. 203,606 and the literature cited therein. i

An important group of compounds within the formula I or the above mentioned subgroup IA comprises the oxime ethers in which and together represent a methylenedioxy or ethylenedioxy bridge bonded via the oxygen atom to the phenyl ring, which bridge may be mono or polysubstituted by methyl, methoxy and / or fluoro, while R 1, X and R 2 are as defined above. (Subgroup IB). 8

Within this group, the preferred compounds are those in which X represents a single bond or one of the groups -C (R) O-, -C0-, CR20 and CR2CR2 and especially those in which R1 represents methyl, isopropyl, methoxymethyl, cyclopropyl or CF3

Another preferred group within the IB subgroup comprises those compounds wherein X represents one of the groups -CR = CR- and C (R2) S, and especially where R1 is methyl, isopropyl, methoxymethyl, cyclopropyl or CF3. (Subgroup Ib).

Another important group of compounds comprises oxime ethers of formula I or IA wherein R 2 and R 3 together with the two carbon atoms to which they are attached form a five-membered ring comprising an oxygen atom or a seven-membered ring which comprises two oxygen atoms, which rings are unsubstituted or mono or polysubstituted by methyl, methoxy and / or fluoro, while R 1, X and R 2 are as defined above. (IC subgroup).

The oxime ethers of formula I or subgroup IA wherein R 2 and R 3 together with the phenyl ring to which they are attached form a benzo-1,3-dioxane ring, while X and R are as defined above, also constitute a important range of compounds. (ID Subgroup).

Compounds Nos. 2, 3, 4, 15, 16, 17, 21, 23, 37 and 38 listed in Table 1 below can be mentioned among the especially preferred compounds.

Typical examples of the novel compounds of the present invention are given in Table 1 below.

9 TABLE 1 Comp. R1 X V \ R

Physical data [incl. r3 N2 mass spectrum] 1 CH3 2 CH3 3 CH3 4 CH3 5 CH3 oil â € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒ (M +, 1%), 145 (100) mp 97-98 ° C Oil CH = (M +, 6%), 145 (100) mp 121-122 ° C. CH 2 CH 2 -

Comp. R ^ X

N2

Physical data [incl. mass spectrum] 6 'CH3 CH2 7 CH3 CH (CH3) 8 CH3 C (CH3) 29 CH3CH2 10 CH3CH2CH2-11 (CH3) 2CH-12 CH3OCH2-13 CH3 CH20

The title compound was prepared according to the procedure described in Example 1, as a white solid which was purified by chromatography on silica gel (M + 74%), 190 (100), 425 (M +, 1%) oil, 145 (100) oil 413 (M + 725%) 145 (100) 14 ch3 11

TABLE 1 (continued) Comp. R ^ X

NS

Physical data [incl. mass spectrum] 15. CF3 16 Λ 17 CH3 18 Δ

19 CH3 CH2 20 CH3 21 CH3 -

P. (M +, 4%), 145 (100) oil 423 (M +, 2%), 202 (100) oil 419 (M +, 2%), 145 (100)

397 (M +, 4%), 145 (100) 37 CF3

oil 38 Δ 39 CH3OCH2

43 (M + 1%), 145 (100) oil 188 (91%), 145 (100) oil 413 (M +, 1%), 145 (100)

TABLE 1 (continued) Comp. R1 X

R,

NS

Physical data [incl. mass spectrum]

40 H 41 CH 3 CH 2 CH 2

42 (CH 3) 2 CH

43 H

44 H

45 CH3S

46 H C (CH 3) 2 47 CH 3 CH (CH 3) -O-

48 H CH (CH 3) -CH 2 C (CH 3) = CH-

415 (M +, 1%), 145 (100) oil 190 (55%), 145 (100) oil 405 (M +, 2.5%) 145 (100) oil 369 (M +, 1%), (M +, 1%), 145 (100) oil 15

TABLE 1 (continued)

Comp. R X X R3 wa _______

Physical data [incl. mass spectrum] 49 50 51 52 53 54 55 56 CH3CH2CH (CH3) 57 ch3ch2ch (ch3) CH3 CH (CH3) CH2 CH3 C (CH3) = CH CH3 CH = C (CH3) CH3 CH = C (CH3) CH3 CH (CH 3) CH 2 CH 3 CH 2 CH (CH 3) CH 3 C (CH 3) 2 CH 2

oil 425 (M +, 1%), 145 (100) oil 439 (M +, 2%), 145 (100), 16

ORDER 1 (continued) -O * Comp. R1 X " " Physical data [incl. Mass spectrometer 58H-TV o / o oil] / 383 (M +, 5%), 145 (100) 59 CH3OCH2 - "θ"? (60%) of the title compound was prepared as a white oil (60%) as a white solid, mp 60 DEG- 5%), 145 (100) " Q " oil 63 CH 3 CH 2 409 (M +, 8%), 188 (100) oil 0 F 17

The compounds according to the invention have fungicidal action and, accordingly, can be used to control or prevent fungal infestation in agriculture, horticulture and wood protection. They are especially suitable for inhibiting the growth or destruction of phytopathogenic fungi in plant parts, for example leaves, stems, roots, tubers, fruits or flowers, and in seeds, as well as harmful fungi occurring in the soil. The compounds according to the invention may also be used to control fungi which are the cause of the decomposition of wood or its discoloration. The compounds according to the invention are effective, for example, in the control of fungi of the classes Deuteromycetes, Ascomycetes, Basidiomycetes and Phycomycetes.

The compounds according to the invention are especially suitable for the control of the following pathogens:

True fungal fungi (for example Erysiphe graminis, Erysiphe cichoracearum, Podosphera leucotri-cha, Uncinula necator, Sphaerotheca species).

Rust fungi (for example, Puccinia tritici, Puccinia recondita, Puccinia hordei, Puccinia coronata, Puccinia striiformis, Puccinia arachidis, Hemileia vastatrix, Uromyces fabae).

Fungi of scabies (for example Venturia inaegualis).

Species of Cercospora (for example Cercospora arachi-dicola, cercospora beticola).

Species of Mycosphaerella (for example Mycosphaerella fijiensis). 18

Species of Alternaria (eg Alternaria brassicae, Alternaria mali).

Species of Septoria (eg Septoria nodorum).

Species of Helminthosporium (for example

Helminthosporium teres, Helminthosporium oryzea).

Species of Plasmopara (for example Plasmopara viticola).

Pseudoperonospora species (for example

Pseudoperonospora cubensis).

Species of Phytophthora (for example Phytophthora infestans).

Species of Pseudocercosporella (for example Pseudocercosporella herpotrichoides).

Species of Perularia (for example Pericularia oryzae).

The compounds are also effective against, for example, fungi of the genus Tilletia, Ustilago, Rhizoctonia, Verticillium, Fusarium, Pythium, Gaeumannomyces, Sclerotinia, Monilia, Botrytis, Peronospora, Bremia, Gloeosporium, Cercosporidium, Penicillium, Ceratocyistis, Rhynchosporium, Pyrenophora, Diaphorthe , Ramularia and Leptosphaeria. Certain representative of the compounds according to the invention are also effective against wood-destroying fungi, such as, for example, the genera Coniophora, Gloeophyllum, Poria, Merulius, Trametes, Aureobasidium, Sclerophoma and Trichoderma. 19 19

The compounds according to the invention are distinguishable by a prophylactic and curative action, but especially by a marked systemic action.

The compounds are effective against phytopathogenic fungi under greenhouse conditions in concentrations as low as 0.5 mg to 500 mg of active ingredient per liter of spray. Under field conditions it is advantageous to use concentrations of from 20 g to 1 kg of compound of formula I per hectare and treatment. In order to control disseminated fungi in seeds and soil by the seed coating process, it is advantageous to use concentrations of from 0.001 g to 1.0 g of compound of formula I per 1 kg of seed.

The compounds according to the invention may be formulated into a variety of compositions, for example, solutions, suspensions, emulsions, emulsifiable concentrates and powdered preparations. The fungicidal compositions according to the invention comprise an effective amount of at least one compound of formula I, as defined above, and formulation aids. The compositions advantageously comprise at least one of the following formulation auxiliaries:

Solid support agents; solvents or dispersing agents; surfactants (wetting and emulsifying agents); dispersing agents (without surfactant); and stabilizers.

Suitable solid carriers are: natural mineral substances such as kaolin, clay earth, diatomite ("kieselguhr"), talc, bentonite, chalk, for example prepared chalk, magnesium carbonate, limestone, quartz, dolomite, attapulgite , montmorillonite and diatomaceous earth; synthetic mineral substances, such as highly dispersed silicic acid, aluminum oxide and silicates; organic substances such as cellulose, starch, urea and synthetic resins; and fertilizers, such as phosphates and nitrates; it being possible for such carrier agents to be present, for example, in the form of granules or powders.

Suitable solvents and dispersing agents are essentially: aromatic compounds, such as toluene, xylenes, benzene and alkylnaphthalenes; chlorinated aromatic compounds and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes and methylene chloride; aliphatic hydrocarbons, such as cyclohexene and parfins, for example crude petroleum fractions; alcohols, such as butanol and glycol, as well as their ethers and esters; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and strongly polar solvents and dispersing agents, such as dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide, having such solvents and flash point dispersions (" flash points ") of at least 30øC and boiling points of at least 50 ° C, and water. Other suitable solvents and dispersing agents are so-called extendible agents or liquefied gaseous carriers, which are products which are gaseous at ambient temperature and under normal pressure. Examples of such products are especially aerosol propellants, such as (halo) -hydrocarbons. If water is used as solvent, it is also possible to use, for example, organic solvents as auxiliary solvents.

Surfactants (wetting and emulsifying agents) may be nonionic compounds, such as condensates of fatty acids, fatty alcohols or fatty phenols substituted with ethylene oxide; esters and fatty acid ethers of sugars or

polyhydric alcohols; products which are obtained from sugars or polyhydric alcohols by condensation with ethylene oxide; block copolymers of ethylene oxide and propylene oxide; or alkyldimethyl aminioxides.

Surfactants may also be anionic compounds, such as soaps; fatty sulfate esters, for example sodium dodecylsulfate, sodium octadecylsulfate and sodium cetylsulfate; alkylsulfonates, arylsulfonates and fatty aromatic sulphonates, such as alkylbenzenesulfonates, for example calcium dodecylbenzenesulfonates and butylnaphthalenesulfonates; and more complex fatty sulfonates, for example the oleic acid amide and N-methyltaurine condensates and the dioctyl succinate sodium sulphonate.

Finally, the surfactants may be cationic compounds, such as alkyldimethylbenzylammonium chlorides, dialkyldimethylammonium chlorides, alkyltrimethylammonium chlorides and ethoxylated quaternary ammonium chlorides.

Suitable dispersing agents (without surfactant action) are essentially: lignin, ammonium and sodium salts of lignosulfonic acid, sodium salts of maleic anhydride-diisobutylene copolymers, ammonium and sodium salts of sulfonated polycondensates of naphthalene and formaldehyde and sulfite waste liquors.

They may be used as dispersing agents which are especially suitable as thickening agents or anti-settling agents, for example methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol, alginates, caseinates and blood albumin. 22

Examples of suitable stabilizing agents are acid forming agents, for example epichlorohydrin, phenylglycidyl ethers and soy epoxides; antioxidants, for example esters of gallic acid and butylhydroxytoluene; UV absorbers, for example substituted benzophenones, diphenylacrylonitrile acid esters and cinnamic acid esters; and deactivators, for example, salts of ethylenediaminetetraacetic acid and polyglycols.

The fungicidal compositions according to the invention may, in addition to the compounds of formula I, also comprise other active ingredients, for example other types of. fungicidal compositions, insecticidal and acaricidal compositions, bactericides, plant growth regulators and fertilizers. Such combined compositions are suitable for broadening the spectrum of activity, or for plant growth in a specific manner.

The fungicidal compositions according to the invention, depending on their type, generally comprise from 0.0001 to 95%, by weight, of the compound (s) according to the invention as active ingredient (s). They may be in a form suitable for storage and transportation. In such forms, by emulsifiable concentrated examples, the concentration of active ingredient is usually in the upper region of the above concentration range. These forms may then be diluted with the same or different formulation auxiliaries to give concentrations of active ingredient suitable for practical use and such concentrations usually lie in the lower region of the above concentration range. The emulsifiable concentrates generally comprise from 5 to 85% by weight, preferably from 25 to 75%, by weight, of the compound (s) according to the invention. Suitable forms of 23

Application are, inter alia, ready-to-use solutions, emulsions and suspensions, which are suitable, for example, in the form of sprayable mixtures. The concentration of active ingredient in such sprayable mixtures may be, for example, from 0.0001 to 20%, by weight. In the ultra-low volume process, the sprayable mixtures may be formulated such that the active ingredient concentration is preferably from 0.5 to 20% by weight, while the sprayable blends formulated in the low volume process and the high volume ratio preferably have a concentration of active ingredient from 0.002 to 0.1%, by weight, respectively.

The fungicidal compositions according to the invention may be prepared by mixing at least one compound according to the invention with formulation aids.

The compositions may be prepared in a known manner, for example by mixing the active ingredients with solid carriers, by dissolving or suspending in suitable solvents or dispersing agents, often with the use of surfactants as wetting agents or emulsifiers or dispersion by dilution of pre-prepared emulsifiable concentrates with solvents or dispersing agents, etc.

In the case of powdery compositions, the active ingredient may be mixed with a solid carrier, for example grinding together; alternatively, the solid carrier can be impregnated with a solution or suspension of the active ingredient, and then the solvent or dispersing agent can be removed by evaporation, heating or by suction filtration under reduced pressure. By the addition of surfactants or dispersing agents, such compositions

powders can readily be made wettable with water so that they can be converted into aqueous suspensions which are suitable, for example in the form of sprayable compositions.

The compounds according to the invention may also be mixed with a surfactant and a solid carrier to form a wettable powder which is dispersible in water, or may be mixed with a pre-granulated carrier to form a shaped product of granules.

If desired, a compound according to the invention can be dissolved in a water-immiscible solvent, such as, for example, an alicyclic ketone, advantageously containing a dissolved emulsifier, so that the solution has a self-emulsifying action when added the water. Alternatively, the active ingredient may be mixed with an emulsifying agent and the mixture can then be diluted with water to the desired concentration. In addition, the active ingredient may be dissolved in a solvent and then mixed with an emulsifier. Such a mixture may also be diluted with water to the desired concentration. In this manner, the emulsifiable concentrates or ready-to-use emulsions are obtained.

The compositions according to the invention may be used according to the usual application methods in plant protection or in agriculture. The fungus control method according to the invention comprises treating the material to be protected, for example, plants, parts of plants or seeds, with an effective amount of a compound according to the invention or a composition according to the invention. the invention.

The following Examples illustrate the invention. - 25 -

Preparation of Compounds of Formula I:

Example 1 59.92 g (0.21 mol) of 2- (Î ± -bromo-o-tolyl) -3-methoxyacrylic acid methyl ester and 40.6 g (0.21 mol) of 3,4 ethylene-dioxyacetophenoneoxime in 210 ml of methylene chloride are stirred vigorously at room temperature for 10 minutes with 210 ml of 2,2 N sodium hydroxide solution and 92.3 g of tetrabutylammonium hydrogen sulfate. Thereafter, the same amounts of methylene chloride, 2,2 N sodium hydroxide solution and tetrabutylammonium hydrogen sulfate are added, and the mixture is stirred for another 10 minutes. The same amounts of 2,2 N sodium hydroxide solution and tetrabutylammonium hydrogen sulfate are then added again, followed by, after stirring for 10 minutes, saturated sodium hydrogen carbonate solution. The mixture is extracted three times with 150 mL of ethyl acetate each time, and the combined organic phases are washed with brine and dried over anhydrous sodium sulfate. After removal of the solvent by distillation, the remaining oil is purified by chromatography on silica gel using n-hexane / diethyl ether (3: 2) as the eluent. Recrystallization from diethyl ether / hexane affords [E] -3-methoxy-2- [α - {[(α-methyl-3,4-ethylenedioxybenzyl) imino] oxy) -o-tolyl methyl ester ] acrylic in the form of colorless crystals; m.p. 97-98 ° C [Comp. Na 2]. prepared

The compounds listed in Table 1 may be in an analogous manner.

Formulation Examples

Fls)

An emulsifiable concentrate has, for example, the following composition: ct / liter compound of Table 1 100 nonylphenol- (10) -ethoxylate > (anionic emulsifier) 50 N-methyl-2-pyrrolidone (solubilizer) 200 mixture of alkylbenzenes (solvent) qbp 1 liter The active ingredient and the emulsifiers are dissolved in the solvent and the solubilizer. A ready-to-use sprayable blend of any desired dilution can be prepared by emulsifying this concentrate in water. m

A wettable powder has, for example, the following composition: Table 1 Silicic acid (hydrated; carrier) sodium lauryl sulfate (wetting agent) sodium lignosulfonate (dispersing agent) kaolin (carrier) , 0 20.0 2.0 4.0 49.0

The components are mixed together and finally milled in a suitable mill. A suspension, which is suitable as ready-to-use sprayable mixture, is produced by dispersing the mixture in water.

Biological Examples:

Example BI:

Action against Puccinia qraminis in wheat (a) Residual protective action Wheat plants are sprayed for 6 days after being seeded with a sprayable mixture (0.02% active ingredient) prepared from a wettable powder formulation of the test compound. After 24 hours, the treated plants are infected with a suspension of uredospore of the fungus. The infected plants are incubated for 48 hours at a relative humidity of 95-100% and at about 20 ° C and then stored in an oven at about 22 ° C. The evaluation of the development of the rust pustule is made 12 days after infection. b) Systemic action Wheat plants are wetted 5 days after being seeded with a sprayable mixture (0.006% active ingredient, based on the soil volume) prepared from a wettable powder formulation of the test compound. After 48 hours, the treated plants are infected with a suspension of uredospore of the fungus. The infected plants are then incubated for 48 hours at a relative humidity of 95-100% and at about 20 ° C and then stored in an oven at about 22 ° C. The evaluation of the development of the rust pustule is made 12 days after infection. The attack of Puccinia is 100% on untreated and infected control plants. The compounds of Table 1 exhibit good activity against Puccinia fungi. The following compounds inhibit Puccinia infestation to less than 20%: numbers 1, 2, 3, 9, 10, 13, 15, 16, 21, 23, 36, 37, 38, 39, 41, 42, 43 and 44 .

Example B2:

Action against Cercospora arachidicola in Peanut plants a) Residual protective action

Peanut plants 10-15 cm high are sprayed with a sprayable mixture (0.02% active ingredient) prepared from a wettable powder formulation of the test compound and infected 48 hours later with a suspension of conidia of the fungus. The infected plants are incubated for 72 hours at about 21øC and at elevated humidity and then stored in an oven until the typical small spots on the sheet occur. The evaluation of the fungicidal action is done 12 days after the infection and is based on the number and size of the spots. b) Systemic action

Peanut plants 10-15 cm in height are sprayed with a sprayable mixture (0.06% active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the test compound. The treated plants are infected 48 hours later with a conidia suspension of the fungus and then incubated for 72 hours at about 21Â ° C and at elevated humidity. The plants are then kept in a greenhouse and evaluation of fungal infestation is made 11 days later.

Compared to untreated and infected control plants (number and size of spots = 100%), Cercospora infestation in the peanut plants treated with compounds of Table 1 is substantially reduced. Cercospora infestation is inhibited to less than 20% with compounds numbers 1, 2, 3, 10, 11, 12, 13, 15, 16, 21, 23, 36, 37, 38, 39, 41, 42, 43 , 44, 57, 58 and 59.

Example B3:

Action against Ervsiphe qraminis on barley plants a) Residual protective action

Barley plants about 8 cm in height are sprayed with a sprayable mixture (0.02% active ingredient) prepared from a wettable powder formulation of the test compound. The treated plants are sprinkled with 30 conidia of the fungus after 3 to 4 hours. Infected barley plants are stored in an oven at about 22øC. Fungi attack is evaluated after 10 days. b) Systemic action

A sprayable blend (0.006% active ingredient, based on the soil bulk) prepared from a wettable powder formulation of the test compound is used to wet barley plants about 8 cm in height. Care is taken so that the sprayable mixture does not come into contact with the parts of the plants above the ground. The treated plants are sprinkled 48 hours later with conidia of the fungus. The infected barley plants are then stored in an oven at about 22øC and evaluation of fungal infestation is made 10 days later.

The compounds of formula I exhibit good activity against Erysiphe fungi. Erysiphe infestation is 100% in untreated and infected control plants. Fungus infestation in barley is substantially inhibited by compounds of Table 1. Fungus infestation is inhibited to 0-5% with compounds numbers 1, 3, 4, 10, 11, 13, 15, 16, 21, 37, 38, 39, 41, 42, 43, 44, 59 and 61.

Example B4i)

Action against Venturia inaecrualis on softwood shoots

Resident Protective Action 31

Apple tree cuts with fresh shoots of 10-20 cm in length are sprayed with a sprayable mixture (0.06% active ingredient) preprable from a wettable powder formulation of the test compound. The treated plants are infected 24 hours later with a conidial suspension of the fungus. The plants were then incubated for 5 days at a relative humidity of 90-100% and stored in an oven for another 10 days at about 20-24 ° C. The pustules infestation is evaluated 15 days after infection. The compounds of formula I inhibit Venturia infestation to a substantial degree. Compound numbers 1, 3, 21, 36, 37, 38, 39, 41, 42, 43, 44 and others limit the infestation to less than 20%.

Example B5:

Action against Botrvtis cinerea in common bean

Residual protective action

Bean plants of about 10 cm in height are sprayed with a sprayable mixture (0.02% active ingredient) prepared from a wettable powder formulation of the test compound. After 48 hours the treated plants are infected with a conidial suspension of the fungus. Infected plants are incubated for 3 days at a relative humidity of 95-100% and 21 ° C and then evaluated for fungal infestation. The infestation by Botrytis on untreated and infected bean plants is 100%. After the treatment with one of the compounds Nos. 4, 13, 17, 21, 23, 24, 28, 36, 59 and 61 of formula I, the infestation is less than 20%. 32 32

Example B6:

Action against Rhizoctonia solani (soil fungus in rice plants) a) Local soil protection

A sprayable mixture prepared from a test compound formulation (0.006% active ingredient) is used to wet rice plants for 12 days without wetting parts of the above ground plants. A suspension of mycelium and sclerotia of Rhizoctonia solani is applied to the soil surface in order to infect the treated plants. The plants are incubated for 6 days at 27 ° C (day) and 23 ° C (night) and at 100% relative humidity (humidity box) in a climatic chamber and then the fungus infestation is assessed on leaf sheath, leaves and stems. b) Local protective application

12-day-old rice plants are sprayed with the sprayable mixture mentioned in a). The treated plants are infected one day later with a suspension of mycelium and sclerotia of Rhizoctonia solani. The plants are incubated for 6 days at 27 ° C (day) and 23 ° C (night) and at 100% relative humidity (humidity box) in a climatic chamber and then the fungus infestation is assessed on leaf sheath, leaves and stems.

The compounds of Table 1 exhibit good inhibitory activity of Rhizoctonia infestation. In contrast, the infestation is 100% in untreated and infected control plants. THE

I 33

fungal infestation is inhibited to substantially less than 20% by compounds numbers 2, 9, 17, 23, 24, 59, 61 and 63.

Example B7:

Action against Phytophthora infestans on tomatoes > a) Healing action

Tomato plants of the variety "Roter Gnom " are treated for three weeks and then sprayed with a zoospore suspension of the fungus and incubated in a chamber at 18 to 20øC and saturation humidity. The moisture is discontinued after 24 hours. When the plants were dried they were sprayed with a mixture comprising a wettable powder formulation of the test compound at a concentration of 200 ppm. After the spray coating dried, the plants were again placed in a humidity chamber for 4 days. The number and size of typical leaf spots that occurred after this time were used as the standard for evaluating the activity of the test compounds. b) Preventive systemic action >

A wettable powder formulation of the test compound is applied at a concentration of 60 ppm (based on the soil volume) to the soil surface of three week old tomato plants of the " Roter Gnom " in pots. After a three day waiting period, the bottoms of the leaves are sprayed with a zoospore suspension of Phytophthora infestans. They are then held in a spray chamber for 5 days at 18-20Â ° C and saturation humidity. At the end of this period, typical spots on the sheets are formed, the number and size of which are used as the standard for evaluating the activity of the test compounds.

The compounds of Table 1, for example compounds numbers 4, 9, 11, 13, 15, 16, 17, 23, 24, 28, 36, 57, 59, 61, 62 and 63, inhibit infestation by Phytophthora infestans for less than 20%.

Example B8;

Action against Plasmopara viticola (Bert. Et Curt.) (Berl. Et Detoni) on vines a) Residual protective action

Vine cuts of the variety " Chasselas " are grown in an oven. In leaf stage 10, 3 plants are sprayed with a blend (200 ppm active ingredient) prepared from a wettable powder formulation of the test compound. After the spray coating has dried, the bottoms of the leaves are uniformly infected with a spore suspension of the fungus. The plants are then held for eight days in a humidity chamber. At the end of this period, clear symptoms of the disease appear in the control plants. The number and size of the infected sites in the treated plants are used as the standard for evaluating the activity of the test compounds. b) Healing action

Vine cuts of the variety " Chasselas " are grown in an oven and, at stage 10 of the sheet, the lower parts of the leaves are uniformly infected with a spore suspension of Plasmopara viticola. After 24 hours in the humidity chamber, the plants are sprayed with a mixture of active ingredient prepared from a wettable powder formulation of the test compound (500 ppm active ingredient). The plants are then held for 7 days in a humidity chamber. At the end of this period, clear symptoms of the disease appear in the control plants. The number and size of the infected sites in the treated plants are used as the standard for evaluating the activity of the test compounds.

The compounds of the formula I, especially the compounds 1, 2, 3, 4, 9, 10, 11, 12, 13, 15, 16, 17, 23, 24, 28, 36, 37, 38, 41, 43, 44, 56, 57, 58, 59, 60, 61, 62 and 63, strongly inhibit Plasmopara infestation to, in some cases, less than 10%.

Example B9:

Action against Pvthium debarianum in beet (Beta vulqarisl a) Action after application to soil The fungus is grown on sterile oats and added to a mixture of soil and sand. The soil thus infected is introduced into pots of flowers and sown with beet seeds. Immediately after sowing, an aqueous suspension (20 ppm active ingredient based on the volume of soil) prepared from a wettable powder formulation of the test formulation is poured onto the soil. The vessels are then kept in an oven at 20-24 ° C for 2-3 weeks. The soil is kept constantly and evenly moist by a slight spray with water. The test is evaluated by determining the ratio of emergence of beet plants and the proportion of healthy and diseased plants. b) Action after coating application The fungus is grown on sterile oat grains and added to a mixture of soil and sand. The thus infected soil is introduced into pots of flowers and seeded with beet seeds which were coated with a coating powder formulation of the test preparation (1000 ppm active ingredient based on the volume of soil). Seed-containing pots are kept in a greenhouse for 2-3 weeks at 20-24 ° C. The soil is kept constant and evenly moist by a slight spray with water. The test is evaluated by determining the ratio of emergence of beet plants and the proportion of healthy and diseased plants.

An emergency ratio of more than 80% is achieved with compounds of Table I. The corresponding control plants have an emergency ratio of less than 30% and an unhealthy appearance.

Lisbon, April 16, 1992

J. PEREIRA DA CRUZ

Official Property Agent Industriai RUA VICTOR CORDON, 10- A 3. " 1200 LISBOA

Claims (4)

An oxime ether characterized in that it has the general formula I in the form of a racemic mixture or its isomers, wherein represents hydrogen, C 1-4 alkyl. (C1-3) alkoxy, methylthio, cyano, cyclopropyl or trifluoromethyl, R2 and R3 together with the two carbon atoms to which they are attached form an unsubstituted or substituted five to seven membered ring comprising 1 or 2 oxygen atoms , and X represents a single bond, -C (R 2) -, CO, -CR = CR-, C (R 2) 0, C (R 2) S or C (R 2) C (R 2), in which R represents hydrogen and (C 1 -C 4) alkyl, with the proviso that X represents one of the groups -C (R 2) -, -CR = CR-, C (R 2) , if R 1 is methyl and R 2 and R 3 together represent methylenedioxy. 2â. The oxime ether of claim 1, wherein the five to seven membered ring formed by R 2 and R 3 is mono- or polysubstituted by C 1-4 alkyl, C 1-4 alkoxy, and / or fluoro. 3 & The oxime ether of claim 1 or 2, wherein R 2 and R 3 together represent a methylenedioxy or ethylenedioxy bridge bonded by oxygen to the phenyl ring, which bridge may be mono or polysubstituted by methyl, methoxy and / for fluoro, while R 2, X and R 2 are as defined above. 4a. The oxime ether of claim 3, wherein X is a single bond or one of the groups -C (R 2) -, -CO-, C (R 2) 0 and CR 2 CR 2. 5â. The oxime ether of claim 4, wherein R 1 is methyl, isopropyl, methoxymethyl, cyclopropyl or CF 3. 6â. The oxime ether of claim 3, wherein X is one of the groups -CR = CR- and C (R2) S-. Oxime ether according to claim 6, wherein R 1 is methyl, isopropyl, methoxymethyl, cyclopropyl or CF 3. 8ã. The oxime ether of claim 1 or 2, wherein R2 and R3 together with the two carbon atoms to which they are attached form a five-membered ring 3 which comprises an oxygen atom or a seven-membered ring comprising two oxygen atoms, which rings are unsubstituted or mono or polysubstituted by methyl, methoxy and / or fluoro, while R 1, X and R 2 are as defined above. 9a. The oxime ether of claim 1 or 2, wherein R 2 and R 3 together with the phenyl ring to which they are attached form a benzo-1,3-dioxane ring, while R 1, X and R 2 are as defined above . The compound according to claim 1, characterized in that it is selected from: [E] -3-methoxy-2- [α - {[(α-methyl-3,4-ethylenedioxybenzyl) imino] oxy -o-tolyl] acrylic acid [comp. 2], [E] -3-methoxy-2- [α - {[(a-methyl-3,4-trimethylenedioxybenzyl) imino] oxy} -o-tolyl] acrylic acid methyl ester [comp. 3], [E] -3-methoxy-2- [Î ± - {[(Î ± -methyl-3,4-difluoromethylenedioxybenzyl) imino] oxy} -o-tolyl] acrylic acid methyl ester [comp. 17], [E] -3-methoxy-2- [α - {[(a-methyl-3,4-isopropylidenedioxybenzyl) imino] oxy} -o-tolyl] acrylic acid methyl ester [comp. 21], [E] -3-methoxy-2- [α - {[(α-trifluoromethyl-3,4-methylenedioxybenzyl) imino] oxy} -o-tolyl] acrylic acid methyl ester [comp. 37], [E] -2- [α - {[(α-cyclopropyl-3,4-methylenedioxybenzyl) imino] oxy} -o-tolyl] -3-methoxyacrylic acid methyl ester [comp. 38], [E] -3-methoxy-2- [α - {[(a-methyl-3/4-methylenedioxycinnamyl) imino] oxy} -o-tolyl] acrylic acid methyl ester [comp. 4], [E] -3-methoxy-2- [Î ± - {[(a-trifluoromethyl-3,4-ethylenedioxybenzyl) imino] oxy} -o-tolyl] acrylic acid methyl ester [comp. 15], [E] -2- [α - {[(α-cyclopropyl-3,4-ethylenedioxybenzyl) imino] oxy} -o-tolyl] -3-methoxyacrylic acid methyl ester [comp. 16], [E] -3-methoxy-2- [Î ± - {[(Î ± -methyl-3,4-methoxymethylenedioxybenzyl) imino] oxy} -o-tolyl] acrylic acid methyl ester [comp. 23]. lia. A process for the preparation of a compound of formula I according to claim 1, characterized in that an oxime of formula II wherein R 1, R 2, R 3 and X are as defined in claim 1, is reacted with an alcohol derived from benzyl alcohol of general formula III CH3 OH. Wherein U represents a leaving group. 12â. The process according to claim 11, characterized in that U represents chlorine, bromine, iodine, methanesulfonyloxy, benzenesulfonyloxy or p-toluenesulfonyloxy. Fungicidal composition, characterized in that it comprises as active ingredient a compound of formula I according to claim 1 together with a suitable carrier. 14a. The fungicidal composition according to claim 13, characterized in that it comprises as active ingredient a compound according to any one of claims 2 to 10, 15s. Method for controlling or preventing fungal infestation in agriculture, horticulture and wood protection, characterized in that a compound of formula I as claimed in claim 1 is used as the active ingredient. 16ã. The method of claim 15, wherein a compound of formula I as claimed in any one of claims 2 to 10 is applied. Lisbon, April 16, 1992 J. PEREIRA DA CRUZ Official Agent for Industrial Property RUA VK3TOR CORDON, 40-A 3. «1200 LISBOA