EP1017671A1

EP1017671A1 - Novel benzamidoxim derivatives, intermediate products and methods for preparing them, and their use as fungicides

Info

Publication number: EP1017671A1
Application number: EP98947519A
Authority: EP
Inventors: Karl Eicken; Joachim Rheinheimer; Frank Wetterich; Eberhard Ammermann; Gisela Lorenz; Siegfried Strathmann
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1997-09-18
Filing date: 1998-09-05
Publication date: 2000-07-12
Also published as: AU9440198A; CA2304052A1; AR017121A1; US20030078437A1; WO1999014188A1; US6417398B1

Abstract

The invention concerns benzamidoxim derivatives of formula (I) in which the substituents have the following meanings: R<1> represents hydrogen or fluorine; R<2> represents C1-C6 phenyl-alkyl, bearing on the cyclic phenyl compound one or several substituents selected in the group comprising halogen, C1-C4 alkyl, C1-C4 alkyl halide, C1-C4 alkoxy or C1-C4 alkoxy halide, or C1-C4 thienyl-alkyl, optionally bearing one or several substituents selected in the group comprising halogen, C1-C4 alkyl, C1-C4 alkyl halide, C1-C4 alkoxy or C1-C4 alkoxy halide, or C1-C4 pyrazol-alkyl, optionally bearing one or several substituents selected in the group comprising halogen, C1-C4 alkyl, C1-C4 alkyl halide, C1-C4 alkoxy or C1-C4 alkoxy halide.

Description

New benzamide oxime derivatives, intermediates and processes for their preparation and their use as fungicides

description

The present invention relates to new benzamidoxime derivatives, processes and intermediates for their preparation and their use as fungicides.

JP-A 02/006453 describes benzamide oxime derivatives with fungicidal activity, which, however, cannot be completely satisfactory, especially when the application rates are low.

It was therefore an object of the present invention to provide new benzamide oxime derivatives with improved activity, in particular even at low application rates.

Surprisingly, it has now been found that benzamide oxime derivatives of the formula I

where the substituents have the following meanings:

R ^{1 is} hydrogen or fluorine

R ² is phenyl-Ci-C _ß -alkyl, which may carry one or more substituents selected from the group consisting of halo, Cι-C4-alkyl, _{Cι-C4-haloalkyl,} Cι-C ₄ alkoxy or Cι-C ₄ ~ Can carry haloalkoxy, or

Thienyl-C _. -C ₄ alkyl, which optionally one or more substituents selected from the group consisting of halogen, Cι-C ₄ -alkyl, C ₄ haloalkyl, Cι-C can carry ₄ -haloalkoxy ₄ alkoxy or Cι-C , or

Pyrazole -CC ₄ alkyl, which optionally one or more substituents selected from the group consisting of halogen, -C ₄ alkyl, Cj _. -C ₄ -Halogenalkyl, Cχ-C ₄ alkoxy or -CC ₄ ~ haloalkoxy can wear. When defining the substituents R 1 and R, the terms given stand as a term for a group of compounds.

Halogen is fluorine, bromine, chlorine or iodine, in particular fluorine or chlorine.

Furthermore, for example:

- C 1 -C ₄ alkyl for: methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl, in particular for methyl or ethyl;

Cχ-C ₄ haloalkyl for: a Cι ~ C ₄ alkyl radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, Chlorofluoromethyl, dichlorofluoromethyl, chlorine - difluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2, 2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro 2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloro propyl, 3-chloropropyl, 2, 3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3, 3, 3-trifluoropropyl, 3, 3, 3-trichloropropyl,

2, 2, 3, 3, 3-pentafluoropropyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromomethyl, 4-fluorobutyl, 4- Chlorobutyl, 4-bromobutyl or nonafluorobutyl, especially for trifluoromethyl;

C 1 -C ₄ -Alko y for: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy, in particular for methoxy or ethoxy;

- Cχ-C ₄ haloalkoxy for: a Cι-C ₄ alkoxy radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluorometh ^¬ oxy , Trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2, 2-difluoroethoxy, 2, 2, 2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2 -Chlor-2, 2-difluoroethoxy, 2,2-di-chloro-2-fluoroethoxy, 2, 2, 2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2, 2-difluoropropoxy, 2,3-di fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3, 3, 3-trifluoropropoxy,

3, 3, 3-trichloropropoxy, 2, 2, 3, 3, 3-pentafluoropropoxy, hepta- fluoropropoxy, 1- (fluoromethyl) -2-fluoroethoxy, 1- (chloromethyl) -2-chloroethoxy, 1- (bromomethyl) -2-bromethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy, especially for Difluoromethoxy;

Phenyl-Ci-Cg-alkyl for: e.g. Benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-l-yl, 2-phenylprop-l-yl, 3-phenylprop-1-yl, 1- (phenylmethyl) -eth-l-yl, 1- (Phenylmethyl) -1- (methyl) eth-l-yl or 1- (phenylmethyl) prop-1-yl, especially for benzyl or 2-phenylethyl;

Thienyl -CC ₄ alkyl for: for example 2-thienylmethyl, 3-thienylmethyl, 2-thienylethyl, 2-thienylprop-l-yl or 3-thienylprop-1-yl;

Pyrazole-C ₁ -C ₄ -alkyl for: for example 1-pyrazolyl-methyl, 2-pyrazolyl methyl, 3-pyrazolylmethyl, 2-pyrazolylylethyl, 2-pyrazolyl-ylprop-1-yl or 3-pyrazolylprop-l-yl;

Compounds in which the substituent R ^{2 is} benzyl, which has one to three substituents selected from the above-mentioned group on the phenyl ring, in particular one to three substituents selected from fluorine, chlorine, methyl, methoxy or trifluoromethyl, have been found to be particularly special proven effective. In particular, 4-fluorobenzyl, 4-chlorobenzyl, 4-methylbenzyl, 4-methoxybenzyl, 4-trifluoromethylbenzyl and 4-difluoromethoxybenzyl may be mentioned as particularly preferred substituents R ² .

Compounds of the formula I in which R ¹ and R ^{2 have} the meanings listed in Table 1 below are particularly preferred.

Table 1

The benzamide oxime derivatives of the formula I according to the invention are obtained by the process according to the invention by reacting benzonitriles of the formula II with hydroxylamm or its salts in aqueous solution, preferably water or water / alkanol mixtures, if appropriate in the presence of a base, to give the benzamide oximes of the formula III, which are then reacted in a manner known per se in the presence of a base with cyclopropylmethyl halide to give the compounds of the formula IV.

The benzamide oximes IV can then be acylated in a manner known per se with the corresponding acid halides, preferably the corresponding acid chlorides, by heating inert solution (preferably to temperatures in the range from 20 to 100 ° C.). Suitable inert solvents are in particular hydrocarbons or ethers, particularly preferably aromatic hydrocarbons such as toluene or xylene, to name just two examples.

The intermediates of the formula III listed above, where R ^{1 is} fluorine and the intermediates of the formula IV are new. Preferred compounds are those in which R ¹ and R ² correspond to the meanings given for the compounds I.

The compounds I are distinguished by an excellent action against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. They are partly systemically effective and can therefore also be used as leaf and soil fungicides.

The plants are normally sprayed or dusted with the active compounds or the seeds of the plants are treated with the active compounds.

The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, in the case of water as

Diluents other organic solvents can also be used as auxiliary solvents. The following are essentially considered as auxiliaries: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), wet nurses (e.g. ethanolamm, dimethylformamide) ) and water; Carriers such as natural starch flours (e.g. kaolins, clays, talc, chalk) and synthetic starch flours (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignite sulfite liquors and methyl cellulose.

The alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignm,

Phenol, naphthalene and dibutylnaphthalene sulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, as well as fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives Formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, polyoxy ethylene octylphenol ether, ethoxylated iso-octyl, octyl or nonylphenol, alkylphenol, tributylphenyl polyglycol ether, alkyl aryl polyether alcohols, iso-tridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene glycol or methyl alcoholoxy labacyl ether, polyethyleneproethylene glycol, lauryl alkoxyl ether, polyethyleneproethylene glycol, lauryl alkoxyl ether, or into consideration.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are mineral soils such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, boluses, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, Ammonium phosphate, ammonium nitrate, ureas and herbal products such as

Cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

Examples of such preparations are:

I. a solution of 90 parts by weight of a compound I according to the invention and 10 parts by weight of N-methyl-2-pyrrolidone, which is suitable for use in the form of tiny drops;

II. A mixture of 10 parts by weight of a compound I according to the invention, 70 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium - Salt of dodecylbenzenesulfonic acid, 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole

Castor oil; A dispersion is obtained by finely distributing the solution in water.

III. an aqueous dispersion of 10 parts by weight of a compound I according to the invention, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil;

IV. An aqueous dispersion of 10 parts by weight of a compound I according to the invention, 25 parts by weight of cyclohexanol, 55 parts by weight of a mineral oil fraction from Boiling point 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil;

V. a mixture of 80 parts by weight, preferably a solid compound I according to the invention, 3 parts by weight of the sodium salt of di-iso-butylnaphthalm-2-sulfonic acid and 10 parts by weight of the sodium salt of a lignosulfonic acid, ground in a hammer mill from a sulfite waste liquor and 7 parts by weight of powdered silica gel; a spray broth is obtained by finely distributing the mixture of water;

VI. an intimate mixture of 3 parts by weight of a compound I according to the invention and 97 parts by weight of finely divided kaolin; this dusting agent contains 3% by weight of active ingredient;

VII. An intimate mixture of 30 parts by weight of a compound I according to the invention, 62 parts by weight of powdered silica gel and 8 parts by weight of paraffmol, which was sprayed onto the surface of this silica gel; this

Reprocessing gives the active ingredient good adhesion;

VIII. A stable aqueous dispersion of 40 parts by weight of a compound I according to the invention, 10 parts by weight of the sodium salt of a phenolsulfonic acid-urea formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water can be further diluted;

IX. a stable oily dispersion of 20 parts by weight of a compound I, 2 parts by weight of the invention

Calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 50 parts by weight of a paraffinic mineral oil.

The new compounds are distinguished by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Deuteromycetes, Ascomycetes, Phycomycetes and Basidiomycetes. Some of them are systemically effective and can be used as foliar and soil fungicides.

They are particularly important for combating a large number of fungi on various crops such as wheat, rye, barley, oats, rice, corn, lawn, cotton, soybeans, coffee, sugar cane, who, fruit and ornamental plants and vegetable plants such as Cucumbers, beans and squash, as well as on the seeds of these plants.

The compounds are used by treating the fungi or the seeds, plants, materials or the soil to be protected against fungal attack with a fungicidally active amount of the active compounds.

It is used before or after the infection of the materials, plants or seeds by the fungi.

The new compounds are particularly suitable for combating the following plant diseases:

Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizoctonia species on cotton and turf, Ustilago sugar species on cereals, Ustilago sugar on cereals, Ustilago varieties on cereals, Ustilago sugar varieties on cereals, Ustilago varieties on cereals, Ustilago varieties inaequalis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinerea (gray mold) on strawberries, vines, ornamental plants and vegetables, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley, Reisicularophyte oryzaza infestans on potatoes and tomatoes, Fusarium and Verticillium species on various plants, Plasmopara viticola on vines, Alternaria species on vegetables and fruits.

The new connections can also be used in material protection (wood protection), e.g. against Paecilomyces variotii.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.

Depending on the type of effect desired, the application rates are between 0.025 and 2, preferably 0.1 to 1 kg of active ingredient per ha.

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

In the use form as fungicides, the compositions according to the invention can also be present together with other active compounds, for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers. When mixed with fungicides, the fungicidal activity spectrum is enlarged in many cases.

The following list of fungicides with which the compounds according to the invention can be used together is intended to explain, but not to limit, the possible combinations:

Sulfur, dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese-zinc-ethylene-diamine-bis-dithiocarbamate, tetramethylthiuron-bis-dithiocarbamate, (bis) dithiocarbamate (bis) dithiocarbamate (bis) dithiocarbamate, bis-dithiocarbamate (bis) dithiocarbamate (bis) dithiocarbamate (bis) dithiocarbamate (bis) dithiocarbamate (bis) dithiocarbamate (dithiurocarbamate), , Ammonia complex of zinc (N, N '-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N' -polypropylene-bis- (thio-carbamoyl) - disulfide;

Nitroderivatives, such as dinitro- (1-methylheptyl) phenylcrotonate, 2-sec. -Butyl-4, 6-dinitrophenyl-3, 3-dimethylacrylate, 2-sec. - Butyl-4, 6-dinitrophenyl-iso-propyl carbonate, 5-nitro-iso-phthalic acid di-iso-propyl ester;

heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, 0, O-diethyl-phthalimidophosphonothioate, 5-amino-l- [bis - (dimethylamino) -phosphinyl] - 3-phenyl-l, 2,4-triazole, 2,3-dicyano-l, 4-dithioanthraquinone,

2-thio-l, 3-dithiolo [4, 5-b] quinoxaline, 1- (butylcarbamoyl) -2-benz - methyl imidazole-carbamic acid, 2-methoxycarbonylamino-benz - imidazole, 2- (furyl- (2)) - benzimidazole, 2- (thiazolyl- (4)) -benzimidazole, N- (1, 1, 2, 2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethyl hio-phthalimide,

N-dichlorofluoromethylthio-N ', N' -dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-rhodanomethylthiobenzothiazole, 1,4-dichloro-2, 5-dimethoxybenzene,

4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thione-l-oxide, 8-hydroxyquinoline or its copper salt, 2, 3-dihydro-5-carboxanilido-6-methyl-l, 4-oxathiin, 2, 3-dihydro-5-carboxanilido-6-methyl-l, 4-oxathiin-4, 4-dioxide, 2-methyl-5, 6-dihydro-4H-pyran-3-carboxylic acid anilide, 2-methyl-furan-3-carboxylic acid anilide, 2, 5-dimethyl-furan-3-carboxylic acid anilide, 2,4, 5-trimethyl-furan-3-carboxylic acid anilide, 2, 5-dimethyl-furan-3-carboxylic acid cyclohexylamide, N- Cyclohexyl-N-methoxy-2, 5-dimethyl-furan-3-carboxamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, N-formyl-N-morpholine-2, 2, 2-trichloroethyl - acetal, piperazin-1, 4-diylbis- (1- (2, 2, 2-trichloro-ethyl) -formamide, 1- (3, 4-dichloroanilino) -1-formylamino-2, 2, 2-trichloroethane,

2,6-dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts, N- [3- (p-tert-butylphenyl) -2- methylpropyl] cis-2, 6-dimethylmorpholine, N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperidine, 1- [2- (2,4-dichlorophenyl) -4-ethyl-l , 3-dioxolan-2-yl-ethyl] - lH-l, 2,4-triazole 1- [2- (2,4-dichlorophenyl) -4-n-propyl-l, 3-dioxolan-2- yl-ethyl] -1H-1, 2, 4-triazole, N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N '-imidazol-yl-urea, 1- (4th -Chlorphenoxy) - 3,3-dimethyl-l- (1H-1,2,4-triazol-l-yl) -2-butanone, (2-chlorophenyl) - (4-chlorophenyl) -5-pyrimidine- methanol, 5-butyl-2-dimethyl-amino-4-hydroxy-6-methyl-pyrimidine, bis- (p-chlorophenyl) -3-pyridine-methanol, 1, 2-bis- (3-ethoxycarbonyl-2-thioureido) - benzene, 1, 2-bis (3-methoxycarbonyl-2-thioureido) benzene, [2- (4-chloro-phenyl) ethyl] - (1, 1-dimethylethyl) -1H-1, 2, 4-triazole -l-ethanol, 1- [3- (2-chlorophenyl) -1- (4-fluorophenyl) oxiran-2-yl-methyl] - 1H-1,2 , 4-triazole and

various fungicides, such as dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, DL-methyl-N- (2,6-dimethylphenyl) -N-furoyl (2) -alaninate, DL-N- (2, 6-dimethyl-phenyl) -N- (2'-methoxyacetyl) -alanine-methyl ester, N- (2, 6-dimethylphenyl) -N -chloroacetyl-D, L-2-aminobutyrene - acton, DL-N- (2, 6-dimethylphenyl) -N- (phenylacetyl) -alanine methyl ester, 5-methyl-5-vinyl-3- (3, 5- dichlorophenyl) -2, 4-dioxo-l, 3-oxazolidine, 3- [(3, 5-dichlorophenyl) -5-methyl-5-methoxymethyl-l, 3-oxazolidin-2, 4-dione, 3- (3, 5-dichlorophenyl) -1-iso-propylcarbamoyl - hydantoin, N- (3, 5-dichlorophenyl) -1, 2-dimethylcyclopropane

1,2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] acetamide, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4 tri-azole, 2,4-difluoro-α- (1H-1,2,4-triazolyl-1-methyl) -benzhydryl alcohol, N- (3-chloro-2,6-dinitro-4-trifluoromethyl-phenyl ) -5-tri - fluoromethyl-3-chloro-2-aminopyridine, 1- ((bis- (4-fluorophenyl) methylsilyl) methyl) -1H-1, 2, 4-triazole,

Strobilurins such as methyl -E-methoximino- [α- (o-tolyloxy) - o-tolyl] acetate, methyl -E-2 - {2- [6- (2 -cyanophenoxy) pyridimin-4 -yl-oxy] phenyl} - 3-methoxyacrylate, methyl -E-methoximino- [α- (2,5-dimethyloxy) -otolyl] acetamide.

Anilino-pyrimidines such as N- (4, 6-dimethylpyrimidin-2-yl) aniline, N- [4 -methyl -6 - (1-propynyl) pyrimidin-2-yl] aniline, N- (4-methyl-6 - cyclopropyl-pyrimidin-2-yl) aniline. Phenylpyrroles such as 4 - (2, 2-difluoro-1, 3 -benzodioxol -4 -yl) -pyrrole - 3-carbonitrile.

Cinnamic acid amides such as 3- (4-chlorophenyl) -3- (3, 4-dimethoxyphenyl) acrylic morpholide.

example 1

a) 2-Chloro-6-fluorobenzamide oxime

A mixture of 15.6 g of 2-chloro-6-fluorobenzonitrile, 9.0 g of hydroxylamine hydrochloride, 7.4 g of sodium carbonate, 50 ml of ethanol and 15 ml of water was stirred at 70-75 ° C. for 16 h. After evaporation of the solvent, the residue was tert with. Butyl methyl ether stirred and obtained from the filtrate after evaporation of the solvent 17.6 g of the desired product with an mp. 115-120 ° C.

b) 2-chloro-6-fluorobenzamide- [O-cyclopropylmethyl] oxime

To a mixture of 1.9 g of the product obtained under a) and 1.6 g of cyclopropylmethyl bromide in 20 ml of dimethylformamide, 0.3 g of sodium hydride (80%) was added in portions at 0 ° C. in the course of 15 minutes and for 3 hours at 5 ° C stirred. The mixture was stirred into water and extracted three times with 70 ml of cyclohexane. After evaporation of the cyclohexane, 1.9 g of the desired product were isolated as an oil.

NMR (CDC1 ₃ ) in ppm: 0.3 m (2H); 0.50 m (2H); 1.2 m (1H); 3.9 d (2H); 4.8 s, br (2H); 6.95-7.10 m (1H); 7.2-7.3 m (2H)

c) N-phenylacetyl-2-chloro-6-fluorobenzamide- [O-cyclopropylmethyl] oxime

1.2 g of the product obtained in b) and 1.1 g of phenylacetic acid chloride were refluxed in 40 ml of toluene for 7 h. After cooling, 40 ml of water were added and the pH was adjusted to 11. After evaporation of the solvent, 1.6 g of a crystalline crude product were obtained from the toluene phase, from which 0.7 g of the desired product having an mp of 79-81 ° C. was obtained after recrystallization.

NMR (CDC1 ₃ ) in ppm: 0.2 m (2H); 0.5 m (2H); 1.05 m (1H); 3.65 s (2H); 4.9 d (2H); 6.9-7.05 m (1H); 7.2-7.4 m (7H); 8.5 s, br (1H). The following products of the formulas III and IV were prepared in an analogous manner to that described in Example 1.

Formula III: 2-chloro-5, 6-difluoro-benzamidoxime

Formula IV: 2-chloro-5, 6-difluoro-benzamide [O-cyclopropylmethyl] oxime

NMR (CDC1 ₃ ) in ppm: 0.3 m (2H); 0.55 m (2H); 1.4 m (1H); 3.9 d (2H); 4.85 s, br (2H); 7.1-7.2 m (2H).

The benzamide oxime derivatives of the formula I prepared in this way are shown in Table 2.

Table 2

Example 2

Efficacy against powdery mildew

Leaves of wheat seedlings of the "Frühgold" variety grown in pots were sprayed to runoff point with aqueous preparation of active compound, which was prepared from a stock solution consisting of 10% active compound, 63% cyclohexanone and 27% emulsifier, and 24 hours after the spray coating had dried on dusted with spores of powdery mildew (Erysiphe graminis f. sp. tritici). The test plants were then placed in a greenhouse at temperatures between 20 and 22 ° C and 75 to 80% relative humidity. After 7 days, the extent of mildew development was determined visually in% of the total leaf area.

The active ingredients 1.1, 1.2. , 1.4. and 1.11. Plants treated in Table 1 showed an infection of at most 15%, plants treated with active ingredients II.1 and II.3 in Table 2 showed no infection, while the untreated plants were 80% infected.

Claims

claims

1. Benzamide oxime derivatives of the formula I.

in which the substituents have the following meaning:

R ^{1 is} hydrogen or fluorine

R ² phenyl-Ci-Ce-alkyl, which has one or more substituents on the phenyl ring selected from the group consisting of halogen, Cχ-C ₄ alkyl, Cι-C ₄ haloalkyl, C -C ₄ ~ alkoxy or Cι-C ₄ -Halogenalkoxy can wear, or

Thienyl-C] _- C ₄ alkyl, which optionally one or more

Substituents selected from the group consisting of halogen, -CC ₄ -alkyl, -C-C ₄ ~ haloalkyl, -C ~ C ₄ -alkoxy or -C-C ₄ ~ haloalkoxy can carry, or

Pyrazole -CC ₄ alkyl, which optionally one or more

Substituents selected from the group consisting of halogen, -CC ₄ -Al yl, -C-C ₄ haloalkyl, Cχ-C ₄ alkoxy or -C-C ₄ haloalkoxy can wear.

2. benzamidoxime derivatives of the formula I according to claim 1, in which R ² is benzyl which may carry one to three substituents selected from the group consisting of halogen, Cι-C ₄ -alkyl, C ₄ haloalkyl, Cι- C ₄ alkoxy or Cι-C can carry ₄ -haloalkoxy. Benzamide oximes of the formula III

4. Benzamide oximes of the formula IV

wherein R ¹ and R ^{2 have} the meaning given in claim 1.

5. Use of the benzamidoxime derivatives of the formula I according to claim 1 for combating harmful fungi.

6. Process for the preparation of the benzamidoxime derivatives

Formula I according to claim 1, characterized in that benzonitriles of formula II with hydroxylamm or its

Salts in aqueous solution, preferably at a pH greater than 8 to benzamide oximes of the formula III (R ^{1 =} H or F), then alkylated with a cyclopropylmethyl halide to give benzamide oximes of the formula IV and then with a corresponding acid halide in benzamide oxime - Derivatives of formula I transferred.

Fungicidal compositions comprising a fungicidally effective amount of at least one benzamidoxime derivative of the formula I.

Process for combating harmful fungi, characterized in that the harmful fungi, their habitat or the plants, areas, materials or spaces to be kept free of them with a fungicidally effective amount of a compound of the general formula I or a fungicidal compound containing a benzamide oxime derivative of the formula I Agents treated according to claim 7.