Phenyl-methoxyimino-acetic acid derivatives as pesticides

Abstract

Compounds of formula 1 1

Description

[0001] The present invention relates to new phenyl-methoxyimino-acetic acid derivatives having microbicidal activity, a process for their preparation, agrochemical compositions containing these active ingredients, as well as the use thereof in the control and prevention of plant-pathogenic fungi in agriculture and in horticulture.

[0002] The new compounds fall within formula I, 2

[0003] wherein:

[0004] A is a group CH2O or CH2ON═C(R1);

[0005] X1 and X2 independently of one another, are C1-C4-alkyl;

[0006] Y is OH, O(C1-C4-alkyl), NH2 or NHCH3;

[0007] R1 is C1-C4-alkyl, cyclopropyl, cyano, trifluoromethyl or C1-C4-alkoxy;

[0008] R is aryl, hetaryl or heterocyclyl, whereby the above-mentioned groups may be substituted by one or more identical or different substituents, selected from the group comprising halogen; C1-C6-alkyl; aryl which is optionally mono- to trisubstituted by identical or different substituents from C1-C4-alkyl, halogen, C1-C4-alkoxy, C1-C4-halogenalkyl or cyano; C1-C6-alkoxy; halogen-C1-C6-alkoxy; aryloxy which is optionally mono- to trisubstituted by identical or different substituents from C1-C4-alkyl, halogen, C1-C4-alkoxy, C1-C4-halogenalkyl or cyano; halogen-C1-C6-alkyl; C1-C6-alkylthio; halogen-C1-C6-alkylthio; C1-C6-alkylsulfinyl; halogen-C1-C6-alkylsulfinyl; C1-C6-alkylsulfonyl; halogen-C1-C6-alkylsulfonyl; C2-C6-alkenyl; C2-C6-alkenyloxy; C2-C6-alkynyl; C3-C6-alkynyloxy; halogen-C2-C6-alkenyl; halogen-C2-C6-alkenyloxy; halogen-C2-C6-alkynyl; halogen-C3-C6-alkynyloxy; C1-C6-alkylcarbonyl; halogen-C1-C6-alkylcarbonyl; C1-C6-alkoxycarbonyl; halogen-C1-C6-alkoxycarbonyl; C1-C6-alkylaminocarbonyl; di-(C1-C6-alkyl)-aminocarbonyl, whereby the alkyl groups may be identical or different; C1-C6-alkylaminothiocarbonyl; di-(C1-C6-alkyl)-aminothiocarbonyl, whereby the alkyl groups may be identical or different; C1-C6-alkylamino; di-(C1-C6-alkyl)-amino; NO2; an unsubstituted C1-C4-alkylendioxy group or one which is mono- to tetrasubstituted by C1-C4-alkyl and/or halogen; CN; SF5; OCN or C(═NOR2)—Z—R3;

[0009] R2 and R3 independently of one another, are hydrogen or C1-C6-alkyl;

[0010] Z is a direct bond, O, S, NH or N(C1-C6-alkyl).

[0011] Formula I is to include all possible isomeric forms and mixtures thereof, e.g. racemic mixtures and any [E/Z] mixtures.

[0012] Alkyl is either straight-chained, e.g. methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, e.g. isopropyl, isobutyl, sec.-butyl, tert.-butyl, isopentyl, neopentyl or isohexyl.

[0013] Alkenyl is either straight-chained, e.g. vinyl, 1-methylvinyl, allyl, 1-butenyl or 2-hexenyl, or branched, e.g. isopropenyl.

[0014] Alkynyl is either straight-chained, e.g. propargyl, 2-butinyl or 5-hexinyl, or branched, e.g. 2-ethinylpropyl or 2-propargylisopropyl.

[0015] Alkylenedioxy is —O(alkylene)O—.

[0016] Alkylene is either straight-chained, e.g. —CH2CH2—, —CH2CH2CH2— or —CH2CH2CH2CH2—, or branched, e.g. —CH(CH3)—, —CH(C2H5)—, —C(CH3)2—, —CH(CH3)CH2— or —CH(CH3)CH(CH3)—.

[0017] Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

[0018] Halogenalkyl may contain identical or different halogen atoms.

[0019] Aryl signifies phenyl or naphthyl, preferably phenyl.

[0020] Heteroaryl signifies a cyclic aromatic group with 5 to 9 ring members in one or two rings, of which 1 to 3 members are hetero atoms selected from the group oxygen, sulphur and nitrogen. 1 to 2 benzene rings may be condensed on the heterocycle, the binding to the residual molecule taking place either through the hetero or the benzene moiety.

[0021] Examples are benzimidazolyl, benzisoxazolyl, benzisothiazolyl, benzocumarinyl, benzofuryl, benzothiadiazolyl, benzothiazolyl, benzothienyl, benzoxazolyl, benzoxdiazolyl, quinazolinyl, quinolyl, quinoxalinyl, carbazolyl, dihydrobenzofuryl, furyl, imidazolyl, indazolyl, indolyl, isoquinolinyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, ethylenedioxyphenyl, naphthyridinyl, oxazolyl, phenanthridinyl, phthalazinyl, pteridinyl, purinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyrazolo[3,4-b]pyridyl, pyridyl, pyrimidinyl, pyrrolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, thiazolyl, thienyl, triazinyl and triazolyl.

[0022] Preference is given to pyridyl, pyrazinyl, pyrimidinyl, thiazolyl, quinolinyl and thienyl.

[0023] Heterocyclyl signifies a 5- to 7-membered, non-aromatic ring with one to three hetero atoms selected from the group comprising N, O and S. Preference is given to non-aromatic 5- and 6-rings that have one nitrogen atom as a hetero atom and optionally one further hetero atom.

[0024] Piperidinyl, morpholinyl, pyrrolidinyl, pyrazolinyl, thiazolinyl and oxazolinyl are preferred.

[0025] Of the compounds of formula I, those groups are preferred, wherein:

[0026] (1) a) A is the group CH2O; or

[0027]  b) A is the group CH2ON═C(R1), wherein R1 is CH3; or

[0028]  c) X1 and X2 are methyl; or

[0029]  d) Y is OCH3 or NHCH3.

[0030] In addition, in combination with one of the above-mentioned groups (1)a to (1)d, the groups of compounds are preferred in which R has the following significances:

[0031] (2) phenyl which is unsubstituted or mono- to tri-substituted by identical or different substituents from halogen, C1-C6-alkyl, C1-C6-halogenalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C3-C6-alkynyloxy, C1-C6-alkoxycarbonyl, cyano or OCN;

[0032]  especially phenyl which is mono- to disubstituted by identical or different substituents from halogen, C1-C2-alkyl, C1-C2-haloalkyl, C1-C2-alkoxy or C1-C2-haloalkoxy.

[0033] (3) phenyl which is substituted by

[0034]  C(═NOR2)—Z—R3; wherein R2 and R3, independently of each other, signify hydrogen or C1-C4-alkyl and Z signifies a direct bond.

[0035] (4) pyridyl, pyrimidinyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, pyrazolinyl, which are unsubstituted or mono- to trisubstituted by identical or different substituents from halogen, cyano, nitro, aminocarbonyl, C1-C4-alkyl, C1-C4-halogenalkyl, C1-C4-alkylcarbonyl, C1-C4-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-halogenalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C2-C6-alkenyl, C(═NOR2)—Z—R3 or by aryl that is optionally mono- to trisubstituted by identical or different substituents from C1-C4-alkyl, halogen, C1-C4-alkoxy, C1-C4-halogenalkyl or cyano;

[0036] especially

[0037] pyridyl, pyrimidinyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, pyrazolinyl, which are unsubstituted or mono- to disubstituted by identical or different substituents from halogen, cyano, nitro, methyl, ethyl, halomethyl, haloethyl, methoxy, ethoxy, halomethoxy, haloethoxy, or by phenyl that is optionally mono- to disubstituted by identical or different substituents from C1-C2-alkyl, halogen, C1-C2-alkoxy, C1-C2-halogenalkyl or cyano.

[0038] Compounds of formula I may be produced as follows:

[0039] A) A compound of formula I is produced whereby a compound of the general formula II 3

[0040]  wherein A, R, X1, X2 and Y have the significances given for formula I, is reacted with an oxidation agent, such as a quinone, preferably chloranil or DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone), atmospheric oxygen, manganese dioxide, selenium dioxide, N,N,N′,N′-tetramethyl ethylenediamine/base or triphenylmethanol in trifluoroacetic acid.

[0041] The compounds of the general formula II are known (WO 97/47592 and WO 97/49672) or may be produced by the methods described therein.

[0042] B) A compound of formula I, wherein Y is OH, NH2 or NHCH3 and A, R, X1 and X2 have the significances given for formula I, are produced whereby a compound of formula Ia 4

[0043]  wherein Y signifies O(C1-C4 alkyl) and A, R, X1 and X2 have the significances given for formula I, is reacted with an aqueous acid or base, or with NH3 or with NH2CH3.

[0044] C) A compound of formula I, wherein Y signifies O(C1-C4-alkyl) or NHCH3, is produced whereby a compound of formula III, 5

[0045]  wherein U is a leaving group, for example chlorine, bromine, iodine, OH, mesyloxy, benzene-sulphonyloxy or tosyloxy, preferably chlorine or bromine, and the remaining substituents have the above-mentioned significances, is reacted with an alcohol of the general formula IV, or with an oxime of the general formula V,

R—OH  IV

R(R1)C═NOH  V

[0046]  wherein R and R1 have the significances given for formula I.

[0047] D) A compound of formula I is produced whereby a compound of formula VI, 6

[0048]  wherein the substituents have the significances given for formula I, is reacted with a methylation agent, e.g. methyl iodide or dimethyl sulphate.

[0049] A compound of formula VI is produced, whereby either

[0050] a) a compound of formula VII, 7

[0051]  wherein the substituents have the significances given for formula I, is reacted with hydroxylamine or with one of its salts, or

[0052] F) a compound of formula VIII, 8

[0053]  wherein the substituents have the significances given for formula I, is reacted with nitrous acid or with an alkyl nitrite.

[0054] G) A compound of formula I, wherein A is the group CH2ON═CR1 and the remaining substituents have the significances given for formula I, is produced whereby a compound of formula IX, 9

[0055]  is reacted with a compound of formula R1—CO—R, wherein the substituents have the significances given for formula I.

[0056] All the above-described reactions are known per se.

[0057] The process for the production of the compounds of formula I, as well as the new intermediates of formulae III, VI, VII, VIII and IX likewise form objects of the invention. The said intermediates may be produced by reacting the corresponding (analogous to formula II) 1,4-cyclohexadiene derivative with an oxidation agent, such as a quinone, preferably chloranil or DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone), atmospheric oxygen, manganese dioxide, selenium dioxide, N,N,N′,N′-tetramethyl ethylenediamine/base or triphenylmethanol in trifluoroacetic acid.

[0058] The corresponding 1,4-cyclohexadiene derivatives are known (WO 97/47592 and WO 97/49672) or may be produced by the methods described therein.

[0059] The compounds of formula I are of preventive and/or curative merit as active ingredients for the control of plant pests and may be used in the agricultural sector and related fields The active ingredients of formula I according to the invention are notable for their good activity even at low concentrations, for their good plant tolerance and for their environmental acceptability. They possess very advantageous, especially systemic properties, and may be used for the protection of numerous cultivated plants. Using the active ingredients of formula I, pests appearing on plants or plant parts (fruits, flowers, foliage, stems, tubers, roots) of various crops can be checked or destroyed, whereby parts of the plant which grow later are also protected e.g. from phytopathogenic micro-organisms.

[0060] The compounds of formula I may also be be employed as a dressing for seeds (fruits, tubers, grain) and plant cuttings to protect against fungal infections, and to protect against phytopathogenic fungi appearing in the soil.

[0061] Compounds I are effective for example against the phytopathogenic fungi belonging to the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria); Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia); Ascomycetes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and Oomycetes (e.g. Phytophthora, Pythium, Plasmopara).

[0062] Target cultivations for the plant-protecting usage in the context of the invention are, for example, the following species of plant: cereals, (wheat, barley, rye, oats, rice, corn, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybean); oleaginous fruits (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (squashes, cucumbers, melons); fibrous plants (cotton, flax, hemp, jute); citrus fruits (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); Lauraceae (avocado, cinnamon, camphor); and plants such as tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, banana plants, natural rubber plants and ornamentals.

[0063] Further fields of application for the active ingredients according to the invention are the protection of stock and material, where the goods stored are protected against rotting and mildew.

[0064] Compounds I are used in this instance in unmodified form or preferably together with the excipients that are usual in formulation technology. To this end, they are suitably processed in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts or granules, e.g. by encapsulation in e.g. polymeric substances. As with the type of compositions, the methods of application, such as spraying, atomizing, dusting, scattering, coating or pouring, are selected in accordance with the intended objectives and the prevailing circumstances.

[0065] Suitable carriers and additives may be solid or liquid and are substances that are appropriate in formulation technology, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binding agents or fertilisers.

[0066] The compounds of formula I may be mixed with further active ingredients, e.g. fertilisers, trace element intermediates or other plant-protecting compositions, especially with further fungicides. Unexpected synergistic effects may thus occur.

[0067] Preferred mixture components are:

[0068] azoles, such as azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole;

[0069] pyrimidinyl carbinols, such as ancymidol, fenarimol, nuarimol;

[0070] 2-aminopyrimidines, such as bupirimate, dimethirimol, ethirimol;

[0071] morpholines, such as dodemorph, fenpropidin, fenpropimorph, spiroxamin, tridemorph;

[0072] anilinopyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil;

[0073] pyrroles, such as fenpiclonil, fludioxonil;

[0074] phenylamides, such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl;

[0075] benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole;

[0076] dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozolin;

[0077] carboxamides, such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, thifluzamide;

[0078] guanidines, such as guazatine, dodine, iminoctadine;

[0079] strobilurines, such as azoxystrobin, kresoxim-methyl, SSF-126 (metominostrobin or fenominostrobin; SSF-129 (α-methoximino-N-methyl-2-[(2,5-dimethylphenoxy)methyl]-benzeneacetamide), trifloxystrobin (2-[α-{[(α-methyl-3-trifluoromethyl-benzyl)imino]-oxy}-o-tolyl]-glyoxylic acid methylester-O-methyloxime);

[0080] dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram;

[0081] N-halomethylthio, such as captafol, captan, dichlofluanid, fluoromide, folpet, tolyfluanide;

[0082] Cu compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulphate, cuprous oxide, mancopper, oxine-copper;

[0083] nitrophenol derivatives, such as dinocap, nitrothal-isopropyl;

[0084] organo-P derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl;

[0085] miscellaneous, such as acibenzolar-S-methyl, anilazine, blasticidin-S, quinomethionat, chloroneb, chlorothalonil, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, kasugamycin, methasulfocarb, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulphur, triazoxide, tricyclazole, triforine, validamycin.

[0086] One preferred method of applying an active ingredient of formula I or an agrochemical composition containing at least one of these active ingredients is application to the foliage (leaf application). The frequency and rate of application depend on the severity of infestation by the invader in question. However, the active ingredients I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plants with a liquid preparation, or by applying the substances to the soil in solid form, for example in granular form (soil application). With paddy rice cultures, granules may be metered into the flooded paddy field. The compounds I may also be applied to seed grain for seed pretreatment (coating) by either drenching the grains or tubers in a liquid preparation of the active ingredient or coating them with a solid preparation.

[0087] The compositions are prepared in known manner, e.g. by intimately mixing and/or grinding the active ingredient with extenders, such as solvents, solid carriers and optionally surface-active compounds (surfactants).

[0088] The agrochemical compositions normally contain 0.1 to 99 percent by weight, especially 0.1 to 95 percent by weight, of active ingredient of formula I, 99.9 to 1 percent by weight, especially 99.8 to 5 percent by weight, of a solid or liquid additive and 0 to 25 percent by weight, especially 0.1 to 25 percent by weight, of a surfactant.

[0089] Favourable application rates generally lie between 1 g and 2 kg of active substance (AS) per hectare (ha), preferably between 10 g and 1 kg AS/ha, especially between 20 g and 600 g AS/ha.

[0090] For usage as a seed dressing, the dosages advantageously used are 10 mg to 1 g of active substance per kg seeds.

[0091] The compositions may also contain further additives, such as stabilisers, anti-foaming agents, viscosity regulators, binding agents or tackifiers, as well as fertilizers or other active ingredients, in order to achieve special effects.

PREPARATION EXAMPLES

P-1) {4,5-dimethyl-2-[1-(3-trifluoromethyl-phenyl)-ethylidene-amino-oxymethyl]-phenyl}-methoxyimino-acetic acid methylester

[0092] A solution of 3.15 g of {4,5-dimethyl-2-[1-(3-trifluoromethyl-phenyl)-ethylidene-amino-oxymethyl]-cyclohexa-1,4-dienyl}-methoxyimino-acetic acid methylester (as an E/Z-mixture in respect of the ethylidene-aminooxy double bond) in 40 ml of toluene is mixed with 2.0 g of 2,3-dichlor-5,6-dicyano-1,4-benzoquinone (DDQ), whereby a slight exothermic reaction is observed. After stirring for 4 hours at room temperature, the reaction mixture is filtered through Hyflo and the solvent is distilled off on a rotary evaporator. After purifying with diethyl ether/hexane (1:3) on silica gel, 2.6 g of the title compound are obtained as a yellowish oil.

P-2) 2-{4,5-dimethyl-2-[1-(3-trifluoromethyl-phenyl)-ethylidene-amino-oxymethyl]-phenyl}-2-methoxyimino-N-methyl-acetamide

[0093] A solution of 2.1 g of the ester obtained in P-1 in 10 ml of ethanolic methylamine (8.03 molar) is stirred over night at room temperature. After distilling off the excess methylamine and the solvent, 2.0 g of the title compound are obtained in the form of a slightly yellow crystal powder having a melting range of 129-134° C. (E/Z mixture).

P-3) (4,5-dimethyl-2-o-tolyloxymethyl-phenyl)-methoxyimino-acetic acid methylester

[0094] A solution of 1.3 g of (4,5-dimethyl-2-o-tolyloxymethyl-cyclohexa-1,4-dienyl)-methoxyimino-acetic acid methylester in 15 ml of toluene is mixed with 1.1 g of DDQ. After stirring for 5 hours at room temperature, the reaction mixture is purified using toluene/hexane/diisopropylether (10:10:3) on silica gel. After stirring in hexane, the title compound is obtained in the form of white crystals having the melting point 82-84° C.

[0095] The compounds of the following tables may be produced in analogous manner.

[0096] Table 1

[0097] Compounds of the general formula I.1, in which Y signifies methoxy and R corresponds in each case to one line of Table A. 10

[0098] Table 2

[0099] Compounds of the general formula I.1, in which Y signifies ethoxy and R corresponds in each case to one line of Table A.

[0100] Table 3

[0101] Compounds of the general formula I.1, in which Y signifies NHCH3 and R corresponds in each case to one line of Table A.

[0102] Table 4

[0103] Compounds of the general formula I.2, in which R1 signifies methyl and Y signifies methoxy and R corresponds in each case to one line of Table A. 11

[0104] Table 5

[0105] Compounds of the general formula I.2, in which R1 signifies methyl and Y signifies ethoxy and R corresponds in each case to one line of Table A.

[0106] Table 6

[0107] Compounds of the general formula I.2, in which R1 signifies methyl and Y signifies NHCH3 and R corresponds in each case to one line of Table A.

[0108] Table 7

[0109] Compounds of the general formula I.2, in which R1 signifies ethyl and Y signifies methoxy and R corresponds in each case to one line of Table A.

[0110] Table 8

[0111] Compounds of the general formula I.2, in which R1 signifies ethyl and Y signifies ethoxy and R corresponds in each case to one line of Table A.

[0112] Table 9

[0113] Compounds of the general formula I.2, in which R1 signifies ethyl and Y signifies NHCH3 and R corresponds in each case to one line of Table A.

[0114] Table 10

[0115] Compounds of the general formula I.2, in which R1 signifies cyclopropyl and Y signifies methoxy and R corresponds in each case to one line of Table A.

[0116] Table 11

[0117] Compounds of the general formula I.2, in which R1 signifies cyclopropyl and Y signifies ethoxy and R corresponds in each case to one line of Table A.

[0118] Table 12

[0119] Compounds of the general formula I.2, in which R1 signifies cyclopropyl and Y signifies NHCH3 and R corresponds in each case to one line of Table A.

[0120] Table 13

[0121] Compounds of the general formula I.2, in which R1 signifies methoxy and Y signifies methoxy and R corresponds in each case to one line of Table A.

[0122] Table 14

[0123] Compounds of the general formula I.2, in which R1 signifies methoxy and Y signifies ethoxy and R corresponds in each case to one line of Table A.

[0124] Table 15

[0125] Compounds of the general formula I.2, in which R1 signifies methoxy and Y signifies NHCH3 and R corresponds in each case to one line of Table A.

[0126] Table 16

[0127] Compounds of the general formula I.2, in which R1 signifies cyano and Y signifies methoxy and R corresponds in each case to one line of Table A.

[0128] Table 17

[0129] Compounds of the general formula I.2, in which R1 signifies cyano and Y signifies ethoxy and R corresponds in each case to one line of Table A.

[0130] Table 18

[0131] Compounds of the general formula I.2, in which R1 signifies cyano and Y signifies NHCH3 and R corresponds in each case to one line of Table A.

[0132] Table 19

[0133] Compounds of the general formula I.2, in which R1 signifies trifluoromethyl and Y signifies methoxy and R corresponds in each case to one line of Table A.

[0134] Table 20

[0135] Compounds of the general formula I.2, in which R1 signifies trifluoromethyl and Y signifies ethoxy and R corresponds in each case to one line of Table A.

[0136] Table 21

[0137] Compounds of the general formula I.2, in which R1 signifies trifluoromethyl and Y signifies NHCH3 and R corresponds in each case to one line of Table A.

TABLE A
No.  R
1.   Phenyl
2.   1-Naphthyl
3.   2-Naphthyl
4.   2-F—C6H4
5.   3-F—C6H4
6.   4-F—C6H4
7.   2,3-F2—C6H3
8.   2,4-F2—C6H3
9.   2,5-F2—C6H3
10.  2,6-F2—C6H3
11.  3,4-F2—C6H3
12.  3,5-F2—C6H3
13.  2-Cl—C6H4
14.  3-Cl—C6H4
15.  4-Cl—C6H4
16.  2,3-Cl2—C6H3
17.  2,4-Cl2—C6H3
18.  2,5-Cl2—C6H3
19.  2,6-Cl2—C6H3
20.  3,4-Cl2—C6H3
21.  3,5-Cl2—C6H3
22.  2,3,4-Cl3—C6H2
23.  2,3,5-Cl3—C6H2
24.  2,3,6-Cl3—C6H2
25.  2,4,5-Cl3—C6H2
26.  2,4,6-Cl3—C6H2
27.  3,4,5-Cl3—C6H2
28.  2-Br—C6H4
29.  3-Br—C6H4
30.  4-Br—C6H4
31.  2,3-Br2—C6H3
32.  2,4-Br2—C6H3
33.  2,5-Br2—C6H3
34.  2,6-Br2—C6H3
35.  3,4-Br2—C6H3
36.  3,5-Br2—C6H3
37.  2-F-3-Cl—C6H3
38.  2-F-4-Cl—C6H3
39.  2-F-5-Cl—C6H3
40.  2-F-3-Br—C6H3
41.  2-F-4-Br—C6H3
42.  2-F-5-Br—C6H3
43.  2-Cl-3-Br—C6H3
44.  2-Cl-3-Br—C6H3
45.  2-Cl-5-Br—C6H3
46.  3-F-4-Cl—C6H3
47.  3-F-5-Cl—C6H3
48.  3-F-6-Cl—C6H3
49.  3-F-4-Br—C6H3
50.  3-F-5-Br—C6H3
51.  3-F-6-Br—C6H3
52.  3-C-4-Br—C6H3
53.  3-C-5-Br—C6H3
54.  3-C-6-Br—C6H3
55.  4-F-5-Cl—C6H3
56.  4-F-6-Cl—C6H3
57.  4-F-5-Br—C6H3
58.  4-F-6-Br—C6H3
59.  4-C-5-Br—C6H3
60.  5-F-6-Cl—C6H3
61.  5-F-6-Br—C6H3
62.  5-Cl-6-Br—C6H3
63.  3-Br-4-Cl—5-Br—C6H2
64.  2-CN—C6H4
65.  3-CN—C6H4
66.  4-CN—C6H4
67.  3-OCN—C6H4
68.  4-OCN—C6H4
69.  2-CH3O—C6H4
70.  3-CH3O—C6H4
71.  4-CH3O—C6H4
72.  2,3-(CH3O)2—C6H3
73.  2,4-(CH3O)2—C6H3
74.  2,5-(CH3O)2—C6H3
75.  3,4-(CH3O)2—C6H3
76.  3,5-(CH3O)2—C6H3
77.  3,4,5-(CH3O)3—C6H2
78.  2-C2H5O—C6H4
79.  3-C2H5O—C6H4
80.  4-C2H5O—C6H4
81.  2-(n-C3H7O)—C6H4
82.  3-(n-C3H7O)—C6H4
83.  4-(n-C3H7O)—C6H4
84.  2-(i-C3H7O)—C6H4
85.  3-(i-C3H7O)—C6H4
86.  4-(i-C3H7O)—C6H4
87.  4-(n-C4H9O)—C6H4
88.  3-(t-C4H9O)—C6H4
89.  4-(t-C4H9O)—C6H4
90.  2-Allyl-O—C6H4
91.  3-Allyl-O—C6H4
92.  4-Allyl-O—C6H4
93.  2-CF3—C6H4
94.  3-CF3—C6H4
95.  4-CF3—C6H4
96.  2-Acetyl-C6H4
97.  3-Acetyl-C6H4
98.  4-Acetyl-C6H4
99.  2-Methoxycarbonyl-C6H4
100. 3-Methoxycarbonyl-C6H4
101. 4-Methoxycarbonyl-C6H4
102. 2-Aminocarbonyl-C6H4
103. 3-Aminocarbonyl-C6H4
104. 4-Aminocarbonyl-C6H4
105. 2-Dimethylaminocarbonyl-C6H4
106. 3-Dimethylaminocarbonyl-C6H4
107. 4-Dimethylaminocarbonyl-C6H4
108. 2-(Methylaminocarbonyl)-C6H4
109. 3-(Methylaminocarbonyl)-C6H4
110. 4-(Methylaminocarbonyl)-C6H4
111. 2-CH3S—C6H4
112. 3-CH3S—C6H4
113. 4-CH3S—C6H4
114. 2-CH3SO2—C6H4
115. 3-CH3SO2—C6H4
116. 4-CH3SO2—C6H4
117. 2-CF3O—C6H4
118. 3-CF3O—C6H4
119. 4-CF3O—C6H4
120. 2-CHF2O—C6H4
121. 3-CHF2O—C6H4
122. 4-CHF2O—C6H4
123. 3-CF3-4-CF3O—C6H3
124. 2-CH3NH—C6H4
125. 3-CH3NH—C6H4
126. 4-CH3NH—C6H4
127. 2-(CH3)2N—C6H4
128. 3-(CH3)2N—C6H4
129. 4-(CH3)2N—C6H4
130. 2-Ethoxycarbonyl-C6H4
131. 3-Ethoxycarbonyl-C6H4
132. 4-Ethoxycarbonyl-C6H4
133. 2-CH2FCH2—C6H4
134. 3-CH2FCH2—C6H4
135. 4-CH2FCH2—C6H4
136. 2-CF3CH2—C6H4
137. 3-CF3CH2—C6H4
138. 4-CF3CH2—C6H4
139. 2-CHF2CF2—C6H4
140. 3-CHF2CF2—C6H4
141. 4-CHF2CF2—C6H4
142. 2-CHF2—C6H4
143. 3-CHF2—C6H4
144. 4-CHF2—C6H4
145. 2-NO2—C6H4
146. 3-NO2—C6H4
147. 4-NO2—C6H4
148. 2-CH3—C6H4
149. 3-CH3—C6H4
150. 4-CH3—C6H4
151. 2,3-(CH3)2—C6H3
152. 2,4-(CH3)2—C6H3
153. 2,5-(CH3)2—C6H3
154. 2,6-(CH3)2—C6H3
155. 3,4-(CH3)2—C6H3
156. 3,5-(CH3)2—C6H3
157. 2-C2H5—C6H4
158. 3-C2H5—C6H4
159. 4-C2H5—C6H4
160. 2-i-C3H7—C6H4
161. 3-i-C3H7—C6H4
162. 4-i-C3H7—C6H4
163. 3-tert.-C4H9—C6H4
164. 4-tert.-C4H9—C6H4
165. 2-Vinyl-C6H4
166. 3-Vinyl-C6H4
167. 4-Vinyl-C6H4
168. 2-Allyl-C6H4
169. 3-Allyl-C6H4
170. 4-Allyl-C6H4
171. 2-Propargyl-C6H4
172. 2-Ethinyl-C6H4
173. 3-Propargyloxy-C6H4
174. 4-Butinyloxy-C6H4
175. 2-C6H5—C6H4
176. 3-C6H5—C6H4
177. 4-C6H5—C6H4
178. 3-CH3-5-t-C4H9—C6H3
179. 2-F-4-CH3—C6H3
180. 2-F-5-CH3—C6H3
181. 2-CH3-4-F—C6H3
182. 2-CH3-5-F—C6H3
183. 2-CH3-4-Cl—C6H3
184. 2-F-4-CH3—O—C6H3
185. 2-F-4-CH3CH2O—C6H3
186. 2-F-4-i-C3H7—C6H3
187. 2-[C(═NOH)CH3]phenyI
188. 2-[C(═NOCH3)CH3]phenyl
189. 2-[C(═NOCH2CH3)CH3]phenyl
190. 2-[CH(═NOCH3)]phenyl
191. 2-[C(═NOCH3)CH2CH3]phenyl
192. 2-[C(═NOCH3)CH2CH2CH3]phenyl
193. 2-[C(═NOCH3)OCH3]phenyl
194. 2-[C(═NOCH3)SCH3]phenyl
195. 2-[C(═NOCH3)NHCH3]phenyl
196. 2-[C(═NOCH3)N(CH3)2]phenyl
197. 3-[C(═NOH)CH3]phenyl
198. 3-[C(═NOCH3)CH3]phenyl
199. 3-[C(═NOCH2CH3)CH3]phenyl
200. 3-[CH(═NOCH3)]phenyl
201. 3-[C(═NOCH3)CH2CH3]phenyl
202. 3-[C(═NOCH3)CH2CH2CH3]phenyl
203. 3-[C(═NOCH3)OCH3]phenyl
204. 3-[C(═NOCH3)SCH3]phenyl
205. 3-[C(═NOCH3)NHCH3]phenyl
206. 3-[C(═NOCH3)N(CH3)2]phenyl
207. 4-[C(═NOH)CH3]phenyl
208. 4-[C(═NOCH3)CH3]phenyl
209. 4-[C(═NOCH2CH3)CH3]phenyl
210. 4-[CH(═NOCH3)]phenyl
211. 4-[C(═NOCH3)CH2CH3]phenyl
212. 4-[C(═NOCH3)CH2CH2CH3]phenyl
213. 4-[C(═NOCH3)OCH3]phenyl
214. 4-[C(═NOCH3)SCH3]phenyl
215. 4-[C(═NOCH3)NHCH3]phenyl
216. 4-[C(═NOCH3)N(CH3)2]phenyl
217. 2-Pyridyl
218. 3-Pyridyl
219. 4-Pyridyl
220. 5-CH3-Pyridin-2-yl
221. 5-Cl-Pyridin-2-yl
222. 6-Cl-Pyridin-2-yl
223. 6-CF3-Pyridin-2-yl
224. 6-CH3-Pyridin-2-yl
225. 6-CH3O-Pyridin-2-yl
226. 3,5-Cl2-Pyridin-2-yl
227. 6-Cl-Pyridin-3-yl
228. 6-CH3-Pyridin-3-yl
229. 6-CH3O-Pyridin-3-yl
230. 2-Pyrimidinyl
231. 4-CH3O-Pyrimidin-2-yl
232. 4-Cl-Pyrimidin-2-yl
233. 4-CH3-Pyrimidin-2-yl
234. 5-CH3-Pyrimidin-2-yl
235. 5-Cl-Pyrimidin-2-yl
236. 5-CH3O-Pyrimidin-2-yl
237. 5-C2H5O-Pyrimidin-2-yl
238. 4-Pyrimidinyl
239. 2-Cl-Pyrimidin-4-yl
240. 2-CH3O-Pyrimidin-4-yl
241. 2-CH3-Pyrimidin-4-yl
242. 6-Cl-Pyrimidin-4-yl
243. 6-CH3-Pyrimidin-4-yl
244. 6-CH3O-Pyrimidin-4-yl
245. 5-Pyrimidinyl
246. 2-CH3-Pyrimidin-5-yl
247. 2-Cl-Pyrimidin-5-yl
248. 2-CH3O-Pyrimidin-5-yl
249. 2-C2H5O-Pyrimidin-5-yl
250. 2-Furyl
251. 4-C2H5-Fur-2-yl
252. 4-CH3-Fur-2-yl
253. 4-Cl-Fur-2-yl
254. 4-CN-Fur-2-yl
255. 5-CH3-Fur-2-yl
256. 5-Cl-Fur-2-yl
257. 5-CN-Fur-2-yl
258. 3-Furyl
259. 5-CH3-Fur-3-yl
260. 5-Cl-Fur-3-yl
261. 5-CN-Fur-3-yl
262. 2-Thienyl
263. 4-CH3-Thien-2-yl
264. 4-Cl-Thien-2-yl
265. 4-CN-Thien-2-yl
266. 5-CH3-Thien-2-yl
267. 5-Cl-Thien-2-yl
268. 5-CN-Thien-2-yl
269. 3-Thienyl
270. 5-CH3-Thien-3-yl
271. 5-Cl-Thien-3-yl
272. 5-CN-Thien-3-yl
273. 2-Oxazolyl
274. 4-CH3-Oxazol-2-yl
275. 4-Cl-Oxazol-2-yl
276. 4-CN-Oxazol-2-yl
277. 5-CH3-Oxazol-2-yl
278. 5-Cl-Oxazol-2-yl
279. 5-CN-Oxazol-2-yl
280. 4-Oxazolyl
281. 2-CH3-Oxazol-4-yl
282. 2-Cl-Oxazol-4-yl
283. 2-CN-Oxazol-4-yl
284. 5-Oxazolyl
285. 2-CH3-Oxazol-5-yl
286. 2-Cl-Oxazol-5-yl
287. 2-CN-Oxazol-5-yl
288. 3-Isoxazolyl
289. 5-CH3-Isoxazol-3-yl
290. 5-Cl-Isoxazol-3-yl
291. 5-CN-Isoxazol-3-yl
292. 5-Isoxazolyl
293. 3-CH3-Isoxazol-5-yl
294. 3-Cl-Isoxazol-5-yl
295. 3-CN-Isoxazol-5-yl
296. 2-Thiazolyl
297. 4-CH3-Thiazol-2-yl
298. 4-Cl-Thiazol-2-yl
299. 4-CN-Thiazol-2-yl
300. 5-CH3-Thiazol-2-yl
301. 5-Cl-Thiazol-2-yl
302. 5-CN-Thiazol-2-yl
303. 4-Thiazolyl
304. 2-CH3-Thiazol-4-yl
305. 2-Cl-Thiazol-4-yl
306. 2-CN-Thiazol-4-yl
307. 2-CH3S-Thiazol-4-yl
308. 5-Thiazolyl
309. 2-CH3-Thiazol-5-yl
310. 2-Cl-Thiazol-5-yl
311. 2-CN-Thiazol-5-yl
312. 3-Isothiazolyl
313. 5-CH3-Isothiazol-3-yl
314. 5-Cl-Isothiazol-3-yl
315. 5-CN-Isothiazol-3-yl
316. 5-Isothiazolyl
317. 3-CH3-Isothiazol-5-yl
318. 3-Cl-Isothiazol-5-yl
319. 3-CN-Isothiazol-5-yl
320. 2-Imidazolyl
321. 4-CH3-Imidazol-2-yl
322. 4-Cl-Imidazol-2-yl
323. 4-CN-Imidazol-2-yi
324. 1-CH3-Imidazol-2-yl
325. 1-CH3-4-Cl-Imidazol-2-yl
326. 1,4-(CH3)2-Imidazol-2-yl
327. 1-CH3—5-Cl-Imidazol-2-yl
328. 1,5-(CH3)2-Imidazol-2-yl
329. 4-Imidazolyl
330. 2-CH3-Imidazol-4-yl
331. 2-Cl-Imidazol-4-yl
332. 1-CH3-Imidazol-4-yl
333. 1,2-(CH3)2-Imidazol-4-yl
334. 1-CH3-2-Cl-Imidazol-4-yl
335. 1-CH3-Imidazol-5-yl
336. 1-CH3-3-Cl-Imidazol-5-yl
337. 1,2-(CH3)2-Imidazol-5-yl
338. 3-Pyrazolyl
339. 5-CH3-Pyrazol-3-yl
340. 5-Cl-Pyrazol-3-yl
341. 5-CN-Pyrazol-3-yl
342. 1-(4-Chlorphenyl)-pyrazol-3-yl
343. 1-(4-Methylphenyl)-pyrazol-3-yl
344. 1-CH3-Pyrazol-3-yl
345. 1-CH3-4-Cl-Pyrazol-3-yl
346. 1-CH3-5-Cl-Pyrazol-3-yl
347. 1,5-(CH3)2-Pyrazol-3-yl
348. 1-CH3-Pyrazol-5-yl
349. 1-CH3-3-Cl-Pyrazol-5-yl
350. 1,3-(CH3)2-Pyrazol-5-yl
351. 4-Pyrazolyl
352. 3-Cl-Pyrazol-4-yl
353. 3-CH3-Pyrazol-4-yl
354. 1-CH3-Pyrazol-4-yl
355. 1-CH3-3-Cl-Pyrazol-4-yl
356. 1-(4-Chlorphenyl)-pyrazol-4-yl
357. 1-(4-Methylphenyl)-pyrazol-4-yl
358. 1,3-(CH3)2-Pyrazol-4-yl
359. 1,3,4-Oxadiazol-5-yl
360. 2-CH3-1,3,4-Oxadiazol-5-yl
361. 2-Cl-1,3,4-Oxadiazol-5-yl
362. 2-CF3-1,3,4-Oxadiazol-5-yl
363. 2-i-C3H7-1,3,4-Oxadiazol-5-yl
364. 2-CH3O-1,3,4-Oxadiazol-5-yl
365. 1,2,4-Oxadiazol-3-yl
366. 5-CH3-1,2,4-Oxadiazol-3-yl
367. 5-i-C3H7-1,2,4-Oxadiazol-3-yl
368. 5-Cl-1,2,4-Oxadiazol-3-yl
369. 5-CF3-1,2,4-Oxadiazol-3-yl
370. 1,2,4-Triazol-3-yl
371. 1-CH3-1,2,4-Triazol-3-yl
372. 1-Pyrrolyl
373. 3-CH3-Pyrrol-1-yl
374. 1-Pyrazolyl
375. 3-CH3-Pyrazol-1-yl
376. 3-CF3-Pyrazol-1-yl
377. 4-CH3-Pyrazol-1-yl
378. 4-Cl-Pyrazol-1-yl
379. 4-Ethoxyoarbonyl-Pyrazol-1-yl
380. 3-CH3-4-Br-Pyrazol-1-yl
381. 1-Imidazolyl
382. 4-CH3-Imidazol-1-yl
383. 4,5-Cl2-Imidazol-1-yl
384. 2,4-(CH3)2-Imidazol-1-yl
385. 1,2,4-Triazol-1-yl
386. 1,3,4-Triazol-1-yl
387. 3,5-(CH3)2-1,2,4-Triazol-1-yl
388. 1-(4-Chiorophenyl)-1,2,4-triazol-3-yl
389. 1-(4-Methylphenyl)-1,2,4-triazol-3-yl
390. 1-Piperidinyl
391. 1-Pyrrolidinyl
392. 1-Morpholinyl
393. 2-Δ2-Thiazolinyl
394. 5-CH3-Δ2-Thiazolin-2-yl
395. 5,5-(CH3)2-Δ2-Thiazolin-2-yl
396. 4,5-(CH3)2-Δ2-Thiazolin-2-yl
397. 2-Δ2-Oxazolinyl
398. 4-CH3-Δ2-Oxazolin-2-yl
399. 4,4-(CH3)2-Δ2-Oxazolin-2-yl
400. 12
401. 13
402. 14
403. 1-(4-Chlorphenyl)-Δ2-pyrazolin-3-yl
404. 1-(4-Methylphenyl)-Δ2-pyrazolin-3-yl
405. 4-I-C6H4
406. 3-Ethinyl-C6H4
407. 4-Br-2-CH3O-C6H3
408. 4-Ethinyl-2-CH3O-C6H3

[0138] Details of the physical data in the following Tables:

[0139] °C.=m.p. in °Celsius;

[0140] Number=chemical displacement of the CH2O group in 1H-NMR (.δ.in ppm);

[0141] *isomers

TABLE B
Compounds of formula
15
No.	Y	R	phys. data
1.1	OCH3	Phenyl	68-70°
1.3	OCH3	2-Naphthyl	132-134°
1.4	OCH3	2-F-C6H4	resin
1.6	OCH3	4-F-C6H4	resin
1.8	OCH3	2,4-F2-C6H3	1O4-106°
1.13	OCH3	2-Cl-Phenyl	108-110° C.
1.17	OCH3	2,4-Cl2-C6H3	118-120°
1.30	OCH3	4-Br-C6H4	resin
1.91	OCH3	3-Allyl-O-C6H4	resin
1.94	OCH3	3-CF3-C6H4	resin
1.148	OCH3	2-CH3-Phenyl	82-84° C.
1.152	OCH3	2,3-(CH3)2-C6H4	resin
1.405	OCH3	4-I-C6H4	105‘107°
1.406	OCH3	3-Ethinyl-C6H4	resin
1.407	OCH3	4-Br-2-CH3-O-C6H3	resin
1.408	OCH3	4-Ethinyl-2-CH3-O-C6H3	resin
3.13	NHCH3	2-Cl-Phenyl	148-150° C.
3.407	NHCH3	4-Br-2-CH3-O-C6H3	134-135°
3.408	NHCH3	4-Ethinyl-2-CH3-O-C6H3	160-170°

[0142]

Table C
Compounds of formula
16
No.	Y	R1	R	phys. data
4.94	OCH3	OH3	3-CF3-Phenyl	5.08/5.41 * (3:2)
6.94	NHCH3	OH3	3-CF3-Phenyl	129-134° C.*

[0143]

TABLE 22
Intermediates of formula
17
No.	Y	R	phys. data
22.1.	OCH3	Cl
22.2.	OCH3	Br
22.3.	OCH2CH3	Cl
22.4.	NHCH3	Cl

[0144] Formulations may be prepared analogously to those described for example in WO 97/33890.

BIOLOGICAL EXAMPLES

[0145] In the following patho-systems, compounds from the tables display good activity.

Example B-1

Activity Against Puccinia graminis on Wheat

[0146] a) Residual protective action

[0147] 6 days after planting, wheat plants are sprayed to drip point with an aqueous spray mixture prepared from a wettable powder of the active ingredient (0.02% active substance), and 24 hours later they are infected with a uredospore suspension of the fungus. After an incubation period of 48 hours (conditions: 95 to 100 percent relative humidity at 20°), the plants are placed in a greenhouse at 22°. 12 days after infection, the fungal attack is evaluated.

[0148] b) Systemic action

[0149] 5 days after planting, an aqueous spray mixture prepared from a wettable powder of the active ingredient (0.006% active substance, based on soil volume) is poured onto wheat plants. Care is taken that the spray mixture does not come into contact with the parts of the plants that are above ground. 48 hours later, the plants are infected with a uredospore suspension of the fungus. After an incubation period of 48 hours (conditions: 95 to 100 percent relative humidity at 20°), the plants are placed in a greenhouse at 22°. 12 days after infection, the fungal attack is evaluated.

Example B-2

Activity Against Phytophthora infestans on Tomatoes

[0150] a) Residual protective action

[0151] After cultivating for three weeks, tomato plants are sprayed to drip point with an aqueous spray mixture prepared from a wettable powder of the active ingredient (0.02% active substance), and 24 hours later they are infected with a sporangia suspension of the fungus. Evaluation of the fungal attack takes place 5 days after infection, during which time conditions of 90 to 100 percent relative humidity and a temperature of 20° are maintained.

[0152] b) Systemic action

[0153] After cultivating for three weeks, an aqueous spray mixture prepared from a wettable powder of the active ingredient (0.006% active substance, based on soil volume) is poured onto tomato plants. Care is taken that the spray mixture does not come into contact with the parts of the plants that are above ground. 48 hours later, the plants are infected with a sporangia suspension of the fungus. Evaluation of the fungal attack takes place 5 days after infection, during which time conditions of 90 to 100 percent relative humidity and a temperature of 20° are maintained.

Example B-3

Residual Protective Action Against Cercospora arachidicola on Peanuts

[0154] Peanut plants of 10 to 15 cm height are sprayed to drip point with an aqueous spray mixture prepared from a wettable powder of the active ingredient (0.02% active substance), and 48 hours later they are infected with a conidia suspension of the fungus. The plants are incubated for 72 hours at 21° and at high humidity, and then placed in a greenhouse until the typical leaf spots appear. Evaluation of the activity of the active substance is made 12 days after infection and is based on the number and size of leaf spots.

Example B-4

Activity Against Plasmopara viticola on Grapevines

[0155] Vine seedlings at the 4 to 5 leaf stage are sprayed to drip point with an aqueous spray mixture prepared from a wettable powder of the active ingredient (0.02% active substance), and 24 hours later they are infected with a sporangia suspension of the fungus. Evaluation of the fungal attack takes place 6 days after infection, during which time conditions of 95 to 100 percent relative humidity and a temperature of 20° are maintained.

Example B-5

Activity Against Colletotrichum lagenarium on Cucumbers

[0156] After cultivating for 2 weeks, cucumber plants are sprayed with an aqueous spray mixture prepared from a wettable powder of the active ingredient (concentration 0.002%). After 2 days, the plants are infected with a spore suspension (1.5×105 spores/ml) of the fungus, and incubated for 36 hours at 23° C. and at high humidity. Incubation then continues at normal humidity and at ca. 22° C. The fungal attack that has set in is evaluated 8 days after infection.

Example B-6

Residual Protective Action Against Venturia inaequalis on Apples

[0157] Apple cuttings with new shoots 10 to 20 cm in length are sprayed to drip point with an aqueous spray mixture prepared from a wettable powder of the active ingredient (0.02% active substance), and 24 hours later they are infected with a conidia suspension of the fungus. The plants are incubated for 5 days at 90 to 100 percent relative humidity and placed in a greenhouse for a further 10 days at 20 to 24°. 12 days after infection, the fungal attack is evaluated.

Example B-7

Activity Against Erysiphe graminis on Barley

[0158] a) Residual protective action

[0159] Barley plants of approximately 8 cm height are sprayed to drip point with an aqueous spray mixture prepared from a wettable powder of the active ingredient (0.02% active substance), and 3 to 4 hours later they are dusted with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. 12 days after infection, the fungal attack is evaluated.

[0160] b) Systemic action

[0161] An aqueous spray mixture prepared from a wettable powder of the active ingredient (0.002% active substance, based on soil volume) is poured onto barley plants of approximately 8 cm height. Care is taken that the spray mixture does not come into contact with the parts of the plants that are above ground. 48 hours later, the plants are dusted with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. 12 days after infection, the fungal attack is evaluated.

Example B-8

Activity Against Podosphaera leucotricha on Apple Shoots

[0162] Apple cuttings with new shoots of ca. 15 cm length are sprayed with a spray mixture (0.06% active substance). After 24 hours, the treated plants are infected with a conidia suspension of the fungus and placed in a plant-growth chamber at 70% relative humidity and at 20° C. 12 days after infection, the fungal attack is evaluated.

Claims

1. A compound of formula I 18

2. A compound according to claim 1, wherein R is phenyl which is unsubstituted or mono- to tri-substituted by identical or different substituents from halogen, C1-C6-alkyl, C1-C6-halogenalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C3-C6-alkynyloxy, C1-C6-alkoxycarbonyl, cyano or OCN.

3. A compound according to claim 1, wherein R is phenyl which is substituted by C(═NOR2)—Z—R3, wherein R2 and R3 independently of one another signify hydrogen or C1-C4-alkyl and Z signifies a direct bond.

4. A compound according to claim 1, wherein R is pyridyl, pyrimidinyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl or pyrazolinyl, which are unsubstituted or mono- to trisubstituted by identical or different substituents from halogen, cyano, nitro, aminocarbonyl, C1-C4-alkyl, C1-C4-halogenalkyl, C1-C4-alkylcarbonyl, C1-C4-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-halogenalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C2-C6-alkenyl, C(═NOR2)—Z—R3 or by aryl that is optionally mono- to trisubstituted by identical or different substituents from C1-C4-alkyl, halogen, C1-C4-alkoxy, C1-C4-halogenalkyl or cyano.

5. Process for the preparation of a compound of formula I characterised by the fact that A) a compound of formula II 19 wherein A, R, X1, X2 and Y have the significances given for formula I, is reacted with an oxidation agent; or B) in order to produce a compound of formula I, wherein Y is OH, NH2 or NHCH3 and A, R, X1 and X2 have the significances given for formula I, a compound of formula Ia 20 wherein Y signifies O(C1-C4 alkyl) and A, R, X1 and X2 have the significances given for formula I, is reacted with an aqueous acid or base, or with NH3 or with NH2CH3; or C) in order to produce a compound of formula I, wherein Y is (C1-C4-alkyl) or NHCH3, a compound of formula III, 21 wherein U is a leaving group and the remaining substituents have the above-mentioned significances, is reacted with an alcohol of the general formula IV or with an oxime of the general formula V, R—OH  IV R(R1)C═NOH  V  wherein R and R1 have the significances given for formula I; or D) a compound of formula VI, 22 wherein the substituents have the significances given for formula I, is reacted with a methylation agent; or G) in order to produce a compound of formula I, wherein A is the group CH2ON═CR1 and the remaining substituents have the significances given for formula I, a compound of formula IX, 23 is reacted with a compound of formula R1—CO—R, wherein the substituents have the significances given for formula I.

6. A compound selected from the group 24 wherein the substituents have the significances given in claim 1 and U is a leaving group.

7. Agrochemical composition containing as active ingredient an effective quantity of a compound of formula I according to claim 1, together with an appropriate carrier.

8. Process for the protection of plants against harmful fungi, characterised in that a compound according to claim 1 is applied to the plants or to their locus.