The formula I embraces all stereoisomeric forms and mixtures thereof, such as racemic and diasteromeric mixtures, for example E/Z mixtures.

1, 2-Dioxime ether derivatives having fungicidal activities are known, e. g. from WO 95/18789.

It has been found that the compounds according to the invention exhibit improved biological properties which render them very suitable for practical use in agriculture and horticulture by having an extraordinarily good fungicidal activity, especially in cereals.

The invention furthermore relates to the preparation of these compounds, to agrochemical compositions which comprise, as active ingredients, at least one of these compounds, and to the use of the active ingredients or of the compositions for protecting plants against attack by harmful microorganisms, in particular fungi.

The general terms used herein have the following meanings : C1-C4alkyl, on its own or as structural element of other groups such as alkoxy, is methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl or tert-butyl.

Alkenyl is straight-chain or branched, for example vinyl, allyl, methallyl, 1-methylvinyl or but- 2-en-1-yl.

Alkynyl is straight-chain or branched, for example ethynyl, propargyl, but-1-yn-1-yl, but-1-yn- 3-yl. Ethynyl and propargyl are preferred.

Halogen or halo is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

Halomethyl may contain identical or different halogen atoms ; examples are fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, difluorochloromethyl, dichlorofluoromethyl ; trifluoromethyl being preferred.

Preferred are compounds of formula I wherein R2 is methyl ; R3 is fluoro, chloro or bromo, C1-C4alkyl, C1-C4alkoxy, ethynyl or trifluoromethyl.

Particularly preferred are the compounds of the Table 1, especially 1 to 8 and 10.

The compounds of formula I can be prepared as follows : A compound of formula 11, wherein U is a leaving group, for example chlorine, bromine, iodine, mesyloxy or tosyloxy, is reacted with a compound of formula III, wherein the substituents are as defined for formula 1, preferably in an organic solvent in presence of a base.

Compounds of formula 11 and III are known or can be prepared by known methods.

The compounds of formula I can be used in the agricultural sector and related fields preventively and/or curatively as active ingredients in the controi of plant diseases. The compounds of formula I according to the invention are distinguished by having good activity even at low rates of concentration, by being well tolerated by plants and by being environ- mentally friendly. They possess very advantageous, especially systemic, properties and can be used for the protection of a large number of cultivated plants. With the compounds of formula I it is possible to inhibit or destroy the pests that occur on plants or on parts of plants (the fruit, blossom, leaves, stems, tubers or roots) of various crops of useful plants, while parts of plants that grow later are also protected against phytopathogenic microorganisms, in particular fungi.

The compounds I can also be used as dressings in the treatment of seed (fruit, tubers, grains) and plant cuttings to provide protection against fungus infections as well as against phytopathogenic fungi that occur in the soil.

The compounds I are effective, for example, against phytopathogenic fungi belonging to the following classes : Fungi imperfecti (e. g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora und Alternaria) ; Basidiomycetes (e. g. Rhizoctonia, Hemileia, Pucc- inia) ; Ascomycetes (e. g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and Oomycetes (e. g. Phytophthora, Pythium, Plasmopara).

Within the scope of the invention, target crops for plant protection use include, for example, the following species of plants : cereals (wheat, barley, rye, oats, rice, maize, sorghum and related crops) ; beet (sugar beet and fodder beet) ; pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries) ; leguminous plants (beans, lentils, peas, soybeans) ; oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts) ; cucumber plants (marrows, cucumbers, melons) ; fibre plants (cotton, flax, hemp, jute) ; citrus fruit (oranges, lemons, grapefruit, mandarins) ; vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika) ; lauraceae (avocados, cinnamon, camphor) ; and plants such as tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.

The compounds I are usually used in the form of compositions and can be applied to the area or plant to be treated simultaneously or in succession with further active ingredients.

These further active ingredients may be, for example, fertilisers, micronutrient donors or other preparations that influence plant growth. It is also possible to use selective herbicides, and insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or other applica- tion-promoting adjuvants customarily employed in formulation technology.

Suitable carriers and adjuvants may be solid or liquid and are the substances usefully employed in formulation technology, for example natural or regenerated mineral sub- stances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers.

A preferred method of applying a compound of formula 1, or an agrochemical composition comprising at least one of those compounds, is application to the foliage of the plants (foliar application). The frequency and the rate of application depend upon the risk of infestation by the pathogen in question. However, the compounds of formula I can also penetrate the plants through the roots via the soil (systemic action) if the locus of the plants is impreg- nated with a liquid formulation or if the active ingredients are incorporated into the soil in solid form, e. g. in granular form (soil application). In the case of paddy rice crops, such granules may be applied in metered amounts to the flooded rice field. The compounds of formula I may, however, for seed treatment, also be applied to the seed grains (coating), either by impregnating the seeds or tubers with a liquid formulation of the active ingredient or by coating them with a solid formulation.

The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology. For that purpose they are advantageously formulated in known manner e. g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts or granules, for example by encapsulation in e. g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomis- ing, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

Advantageous rates of application are generally from 1 g to 2 kg of active ingredient (a. i.) per hectare (ha), preferably from 10 g to 1 kg a. i./ha, especially from 20 g to 600 g a. i./ha.

When used as seed dressings, rates of from 10 mg to 1 g of active ingredient per kg of seed are advantageously used.

The formulations, i. e. the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant, are pre- pared in known manner, e. g. by homogeneously mixing and/or grinding the active ingredient with extenders, such as solvents, solid carriers and, where appropriate, surface-active com- pounds (surfactants).

The agrochemical compositions normally comprise 0. 1 to 99 % by weight, especially 0. 1 to 95 % by weight, compound of formula 1, 99. 9 to 1 % by weight, especially 99. 8 to 5 % by weight, of a solid or liquid adjuvant, and 0 to 25 % by weight, especially 0. 1 to 25 % by weight, of a surfactant.

The compounds of formula I can be mixed with other fungicides, producing in some cases unexpected synergistic effects.

Especially preferred mixing partners are azoles such as azaconazole, bitertanol, propiconazole, difenoconazole, diniconazole, cyproconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, tebuconazole, tetraconazole, fenbuconazole, metconazole, myclobutanil, perfurazoate, penconazole, bromuconazole, pyrifenox, prochloraz, triadimefon, triadimenol, triflumizole or triticonazole ; pyrimidinyl carbinoles such as ancymidol, fenarimol or nuarimol ; 2-amino- pyrimidine such as bupirimate, dimethirimol or ethirimol ; morpholines such as dodemorph, fenpropidin, fenpropimorph, spiroxamin or tridemorph ; anilinopyrimidines such as cyprodinil, pyrimethanil or mepanipyrim ; pyrroles such as fenpiclonil or fludioxonil ; phenylamides such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, of urace or oxadixyl ; benzimidazoles such as benomyl, carbendazim, debacarb, fuberidazole or thiabendazole ; dicarboximides such as chlozolinate, dichlozoline, iprodine, myclozoline, procymidone or vinclozolin ; carboxamides such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin or thifluzamide ; guanidines such as guazatine, dodine or iminoctadine ; strobilurines such as azoxystrobin, kresoxim- methyl, metominostrobin, SSF-129, methyl 2-[(2-trifluoromethyl)-pyrid-6-yloxymethyl]-3- methoxyacrylate or 2- [a { [ (a-methyl-3-trifluoromethyl-benzyl) imino]-oxy}-o-tolyl]-glyoxylic acid-methylester-O-methyloxime (trifloxystrobin) ; dithiocarbamates such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb or ziram ; N-halomethylthio- dicarboximides such as captafol, captan, dichlofluanid, fluoromide, folpet or tolyfluanid ; copper compounds such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper or oxine-copper ; nitrophenol derivatives such as dinocap or nitrothal-isopropyl ; organo phosphorous derivatives such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos or toclofos-methyl ; and other compounds of diverse structures such as acibenzolar-S-methyl, anilazine, blasticidin-S, chinomethionat, chloroneb, chlorothalonil, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone, fenamidone, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, kasuga- mycin, methasulfocarb, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin, (S)-5-methyl-2-methylthio-5-phenyl-3-phenyl-amino-3, 5-dihydroimidazol-4-one (RPA 407213), 3, 5-dichloro-N- (3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide (RH-7281), N-allyl-4, 5-dimethyl-2-trimethylsilylthiophene-3-carboxamide (MON 65500), 4-chloro-4-cyano-N, N-dimethyl-5-p-tolylimidazole-1-sulfon-amide (IKF-916), N- (1-cyano-1, 2- dimethylpropyl)-2- (2, 4-dichlorophenoxy)-propionamide (AC 382042), or iprovalicarb (SZX 722).

1. Preparation Example Example P-1 : Preparation of compound No. 1. 7 0. 2 g of a 60 % sodium hydride dispersion in mineral oil is washed with hexane, and 5 ml of N, N-dimethylformamide are added thereto. To that suspension there are added 1. 5 g of 2- (bromomethylphenyl) glyoxylic acid ethyl ester O-methyl oxime and 1. 2 g of 1- (4-bromophenyl)-propane-1, 2-dione-1- (O-methyloxime)-2-oxime. The reaction mixture is heated to 50°C and stirred at room temperature for one hour. Ice-water is then added and extraction is carried out twice with 50 ml of ethyl acetate each time. The combined organic extracts are washed with water and dried over sodium sulfate and the solvent is distille off under reduced pressure. The residue is purified by chromatography on silica gel using ethyl acetate/hexane (1 : 5 % by volume to 1 : 4 % by volume). 1. 3 g of the desired product are obtained in the form of white crystals, m. p. 103-104°C.

The compounds of the following table may be obtained in analogous manner.

Table 1 No. R3 phys. data (m. p. °C) * mixture of isomers 1. 2-F-4-C4H9O Oil 2. 3-CF3-4-Cl 80-82 3. 2-CH3-4-C3H70 91-93 4. 2-F-4-CH30 98-100 5. 4-CF3 95-97 6. 4-CH3 oil* 7. 4-Br 103-104 8. 4-F 74-75 9. 4-C#CH Oil* 10. 2, 4-F2 90-93 11. 4-CH30 oil* 12. 4-C2H50 100-102* 13. 4-C3H7O Oil* 14. 2,5-(CH3)2 Oil* 15. 4-C4H9O oil* 16. 4-Cl oil* 17. 4-CN oil* 18. 4-CH=CH2 oil* 2. Formulation examples for similar purposes of pesticidal use are descibed for example in WO 97/33890 3. Bioloqical Examples : In the following pathosystems the compounds of the table exhibit good activities.

Example B-1 : Action against Puccinia graminis on wheat a) Residual-protective action 6 days after sowing, wheat plants are sprayed to drip point with an aqueous spray mixture (0. 02 % active ingredient), prepared from a wettable powder formulation of the active ingre- dient, and infected 24 hours later with a uredospore suspension of the fungus. After an incubation period of 48 hours (conditions : 95-100 % relative humidity at 20°), the plants are placed in a greenhouse at 22°. Fungus infestation is evaluated 12 days after infection.

In this test compounds 1, 3, 5, 7, 8 and 10 of Table 1 showed an efficacy of 80% or more. b) Systemic action 5 days after sowing, wheat plants are watered with an aqueous spray mixture (0. 006 % active ingredient, based on the volume of the soil), prepared from a wettable powder formulation of the active ingredient. Care is taken that the spray mixture does not come into contact with parts of the plants that are above the soil. The plants are infected 48 hours later with a uredospore suspension of the fungus. After an incubation period of 48 hours (conditions 95-100 % relative humidity at 20°), the plants are placed in a greenhouse at 22°.

Fungus infestation is evaluated 12 days after infection.

Example B-2 : Action against Phytophthora infestans on tomatoes a) Residual-protective action After a cultivation period of three weeks, tomato plants are sprayed to drip point with an aqueous spray mixture (0. 02 % active ingredient), prepared from a wettable powder formu- lation of the active ingredient, and infected 24 hours later with a sporangia suspension of the fungus. Fungus infestation is evaluated 5 days after infection, a relative humidity of 90 to 100 % and a temperature of 20° having been maintained during that period. b) Systemic action After a cultivation period of three weeks, tomato plants are watered with an aqueous spray mixture (0. 006 % active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the active ingredient. Care is taken that the spray mixture does not come into contact with parts of the plants that are above the soil. After 48 hours, the plants are infected with a sporangia suspension of the fungus. Fungus infestation is evaluated 5 days after infection, a relative humidity of 90 to 100 % and a temperature of 20° having been maintained during that period.

Example B-3 : Action against Plasmopara viticola on vines Vine seedlings at the 4-to 5-leaf stage are sprayed to drip point with an aqueous spray mixture (0. 02 % active ingredient), prepared from a wettable powder formulation of the active ingredient, and infected 24 hours later with a sporangia suspension of the fungus.

Fungus infestation is evaluated 6 days after infection, a relative humidity of 95 to100 % and a temperature of 20° having been maintained during that period.

In this test compounds 3 to 8 and 10 of Table 1 showed an efficacy of 90% or more.

Example B-4 : Residual-protective action against Venturia inaegualis on apples Apple cuttings with 10-20 cm long fresh shoots are sprayed to drip point with an aqueous spray mixture (0. 02 % active ingredient), prepared from a wettable powder formulation of the active ingredient, and infected 24 hours later with a conidia suspension of the fungus.

The plants are incubated for 5 days at 90-100 % relative humidity and placed in a green- house for a further 10 days at 20-24°. Fungus infestation is evaluated 12 days after infection.

Example B-5 : Action against Erysiphe graminis on barley a) Residual-protective action Barley plants about 8 cm in height are sprayed to drip point with an aqueous spray mixture (0. 02 % active ingredient), prepared from a wettable powder formulation of the active ingredient, and dusted 3 to 4 hours later with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. Fungus infestation is evaluated 12 days after infection.

In this test compound 2, 5 and 10 of Table 1 showed an efficacy of 90% or more. b) Systemic action Barley plants about 8 cm in height are watered with an aqueous spray mixture (0. 002 % active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the active ingredient. Care is taken that the spray mixture does not come into contact with parts of the plants that are above the soil. The plants are dusted 48 hours later with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. Fungus infestation is evaluated 12 days after infection.