DE19837794A1 - New pyridyl O,N-disubstituted amidoxime and pyridazinyl O,N-disubstituted amidoxime derivatives useful as plant fungicides and for control of fungal attack on materials, e.g. wood - Google Patents

Abstract

Heteroaryl O,N-disubstituted amidoximes (I) are new. Also new are heteroaryl nitriles (II) as well as heteroaryl amidoximes (III) and (IV) used or obtained in the preparation of compounds (I). Pyridyl and pyridazinyl O,N-disubstituted amidoxime derivatives (I) are new: X and Y = N, NO or CR<5>, but are not both CR<5>; R<1> = 1-4C haloalkyl; halo; 1-4C haloalkoxy; 1-4C alkyl; 1-4C alkylthio; or 1-4C haloalkylthio; R<2> = H; halo; or 1-4C alkyl optionally substituted with halo, 1-4C alkoxy or 1-4C alkylthio; R<3> = 1-4C alkyl optionally substituted with CN, halo, 1-4C alkoxy or 3-8C cycloalkyl; 3-6C alkenyl, 3-6C haloalkenyl or 3-6C alkynyl; R<4> = phenyl-1-6C alkyl, thienyl-1-4C alkyl or pyrazolyl-1-4C alkyl (each optionally ring-substituted with 1 or more halo, 1-4C alkyl, 1-4C haloalkyl, 1-4C alkoxy or 1-4C haloalkoxy); R<5> = H; halo; or 1-4C alkyl optionally substituted with halo, 1-4C alkoxy or 1-4C alkylthio; the following compounds (I) are excluded: N-(4-methoxy)phenylacetyl-3-chloro-pyridyl-4-amide O-propargyl oxime; and N-(4-methoxy)phenylacetyl-3,5-dimethyl-pyridyl-4-amide O-propargyl oxime. Independent claims are also included for: (a) heteroaryl nitriles of formula (II), except when R<1> = CF3, X = N and Y = CH; (b) heteroaryl amidoximes of formula (III); and (c) heteroaryl O-substituted amidoximes of formula (IV):

Description

The present invention relates to new hetarylamidoxime derivatives, Processes and intermediates for their production and their Use as a fungicide.

JP-A 02/006453 describes pyridinamide oxime derivatives with fungi zider effectiveness described, but especially in not fully satisfy low application rates can. There are also the connections N- (4-methoxy) phenylacetyl-3-chloropyridyl-4-amide- [O-propar gyl] -oxime (Example 528) and N- (4-methoxy) phenylacetyl-3,5-di methyl-pyridyl-4-amide- [O-propargyl] oxime (Example 529) be wrote.

The object of the present invention was therefore to create new ones Compounds with improved activity, especially in the case of low application rates.

Surprisingly, it has now been found that this object is achieved by hetarylamidoxime derivatives of the formula I.

is solved.

In formula I, the substituents have the following meaning:
R ¹ C ₁ -C ₄ haloalkyl, halogen, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio,
R ^{2 is} hydrogen, halogen, C ₁ -C ₄ alkyl, which may be substituted by halogen, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio,
R ³ C ₁ -C ₄ -alkyl which may be substituted by cyano, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ haloalkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl,
R ^{4 is} phenyl-C ₁ -C ₆ -alkyl which, on the phenyl ring, has one or more substituents selected from the group consisting of Ha, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ - Can carry alkoxy or C ₁ -C ₄ haloalkoxy, or
Thienyl-C ₁ -C ₄ -alkyl, which has one or more substituents selected from the group consisting of halo, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy or on the thienyl ring C ₁ -C ₄ haloalkoxy can wear, or
Pyrazole-C ₁ -C ₄ alkyl, which on the pyrazole ring one or more substituents selected from the group consisting of halo gene, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or Can carry C ₁ -C ₄ haloalkoxy,
XN, NO or CR ⁵ ,
YN, NO or CR ⁵ ,
R ^{5 is} hydrogen, halogen, C ₁ -C ₄ alkyl, which can be substituted by halogen, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio,
where X and Y cannot be CR ⁵ at the same time,
with the exception of the compounds N- (4-methoxy) phenylacetyl-3-chloropyridyl-4-amide- [O-propargyl] oxime and N- (4-methoxy) phenylacetyl-3, 5-dimethyl-pyridyl-4- amide- [O-propargyl] oxime.

When defining the substituents R ¹ to R ⁵ , the terms given stand as a collective term for a group of compounds.

Halogen stands for fluorine, bromine, chlorine or iodine, ins especially for 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 ethyl;
• - C ₁ -C ₄ haloalkyl for: a C ₁ -C ₄ alkyl radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for. B. trichloromethyl, tri fluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 2-fluoropropyl, 3-fluoropropyl, 2 -Chlorpropyl or 3-chloropropyl, especially for 2-fluoroethyl, trifluoromethyl or 2-chloroethyl;
• - C ₁ -C ₄ haloalkoxy for: a C ₁ -C ₄ alkoxy radical, where the alkyl part, as mentioned above, is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, e.g. B. 2,2-difluoroethoxy, especially difluoromethoxy;
• - C ₁ -C ₄ haloalkylthio for: a C ₁ -C ₄ alkylthio radical, where the alkyl part, as mentioned above, is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, e.g. B. 2,2-difluoroethylthio or difluoromethylthio;
• - Cyano-C ₁ -C ₄ alkyl for: e.g. B. Cyanomethyl, 1-cyanoeth-1-yl, 2-cyanoeth-1-yl, 1-cyanoprop-1-yl, 2-cyanoprop-1-yl, 3-cyano prop-1-yl, 1-cyanoprop-2 -yl or 2-cyanoprop-2-yl, especially for cyanomethyl or 2-cyanoethyl;
• - C ₁ -C ₄ alkoxy for: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy, in particular for methoxy or ethoxy;
• - C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl for: substituted by C ₁ -C ₄ alkoxy as mentioned above C ₁ -C ₄ alkyl, that is, for. B. for methoxymethyl, ethoxymethyl, n-propoxymethyl, (1-methyl ethoxy) methyl, n-butoxymethyl, (1-methylpropoxy) methyl, (2-methylpropoxy) methyl, (1,1-dimethylethoxy) methyl, 2- (methoxy ) ethyl or 2- (ethoxy) ethyl, especially for methoxymethyl or 2-methoxyethyl;
• - C ₃ -C ₆ alkenyl for: e.g. B. Prop-2-en-1-yl, n-buten-4-yl, 1-methyl-prop-2-en-1-yl, 2-methyl-prop-2-en-1-yl or 2- Buten-1-yl, especially for prop-2-en-1-yl;
• - C ₃ -C ₆ haloalkenyl for: C ₃ -C ₆ alkenyl as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, for. B. 2-chloroallyl, 3-chloro allyl, 2,3-dichloroallyl or 3,3-dichloroallyl, especially for 2-chloroallyl;
• - C ₃ -C ₆ alkynyl for: e.g. B. Prop-1-in-1-yl, prop-2-in-1-yl, n-but-1-in-1-yl, n-but-1-in-3-yl, n-but- 1-in-4-yl or n-but-2-in-1-yl, especially for prop-2-in-1-yl;
• - C ₃ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl for: e.g. B. Cyclopropylmethyl, Cyclobutylmethyl, Cyclopentylmethyl, Cyclohexylmethyl, (Cyclopropyl) ethyl, 1- (Cyclobutyl) ethyl, 1- (Cyclo pentyl) ethyl, 1- (Cyclohexyl) ethyl, 1- (Cycloheptyl) ethyl, 1- (Cyclooctyl) ethyl , 2- (cyclopropyl) ethyl or 2- (cyclobutyl) ethyl, especially for cyclopentylmethyl or cyclopropylmethyl;
• - Phenyl-C ₁ -C ₆ alkyl for: e.g. B. benzyl, 1-phenylethyl, 2-phenyl ethyl, 1-phenylprop-1-yl, 2-phenylprop-1-yl, 3-phenyl prop-1-yl, especially for benzyl or 2-phenylethyl;
• - Thienyl-C ₁ -C ₄ alkyl for: e.g. B. 2-thienylmethyl, 3-thienylmethyl or 2-thienylethyl;
• - Pyrazole-C ₁ -C ₄ alkyl for: e.g. B. 1-pyrazolylmethyl, 2-pyrazolylmethyl, 3-pyrazolylmethyl or 2-pyrazolylylethyl;

The following compounds are preferred in the sense of the present invention:

• a) Compounds of formula I, wherein R ^{1 has} the following meanings: C ₁ -C ₄ haloalkyl, such as. B. trifluoromethyl; Chlorine; C ₁ -C ₄ haloalkoxy, such as. B. difluoromethoxy; or the corresponding compounds in combination with one or more of the b.-g. meanings mentioned.
• b) Compounds of formula I, wherein R ^{2 has} the following meanings: hydrogen, C ₁ -C ₄ alkyl, such as. B. methyl; Fluorine, chlorine; or the corresponding compounds in combination with one or more of the under a. and c.-g. meanings mentioned.
• c) Compounds of formula I, wherein R ^{3 has} the following meanings: cyclopropyl-C ₁ -C ₄ alkyl, such as. B. Cyclopropylmethyl; or the corresponding compounds in combination with one or more of those listed under a., b., d.-g. meanings mentioned.
• d) Compounds of formula I, wherein R ^{4 has} the following meanings: phenyl-C ₁ -C ₄ alkyl, such as. B. benzyl, where the phenyl ring may be substituted by one to three substituents selected from the following group: fluorine; Chlorine; C ₁ -C ₄ alkyl, such as. B. methyl; C ₁ -C ₄ acoxy, such as. B. methoxy; or C ₁ -C ₄ haloalkyl, such as. B. trifluoromethyl; or the corresponding compounds in combination with the under a.-c. or e.-g. meanings mentioned.
• e) Compounds of formula I, wherein R ^{5 has} the following meanings: hydrogen, C ₁ -C ₄ alkyl, such as. B. methyl; or C ₁ -C ₄ haloalkyl, such as. B. trifluoromethyl; or the corresponding compounds in combination with one or more of the a.-d. or f.-g. meanings mentioned.
• f) compounds of the formula I, where X is nitrogen; respectively. the corresponding compounds in combination with an or several of the under a.-e. or g. meanings mentioned.
• g) compounds of the formula I, where Y is CR ⁵ ; or the corresponding compounds in combination with one or more of the a.-f. meanings mentioned.

Compounds in which the substituent R ¹ for trifluoromethyl, chlorine, difluoromethoxy, the substituent R ³ for cyclopropylmethyl and the substituent R ⁴ for benzyl, which has one to three substituents selected from the above group, in particular one to three substituents selected from fluorine, on the phenyl ring , Chlorine, methyl, methoxy or trifluoromethyl, has been found to be particularly effective as a rule. Y is preferably the methine group CH or C-CH ₃ .

Compounds of the formula I in which R ¹ to R ^{5 have} the meanings listed in Tables 1-3 below are particularly preferred for the purposes of the present invention.

Table 1

cPr stands for cyclopropylmethyl in the following tables 1-3.  

Table 2

Table 3

The synthesis of the active ingredients described can be carried out on the basis of corresponding heterocyclic aldehydes. These are neither known nor can be prepared analogously to the known compounds (see, for example: Bertini et al., Heterocycles 41, pp. 675-688 (1995); Radinov et al., Journal of Organic Chemistry 56, p 4793-4796 (1991)). The conversion into the nitriles (synthesis route A) is also described (see, for example: Bertini et al., Heterocycles 41, pp. 675-688 (1995). The nitriles of the formula III can also be prepared by methods known from the literature (see Synthesis 1997, No. 11, p. 1321) Compounds of the formula III in which R ¹ CF ₃ , X nitrogen and Y denote the methine group (= CH-) are known from the literature (J. Med. Chem . 1967, 10: 149; Tetrahedron 1996, 52: 10841; Russ. Chem. Bull. 1998, 47: 465).

The hetarylamidoxime derivatives of the formula I according to the invention are obtained according to the following reaction scheme:

Compounds of formula I are obtained according to the invention Process from the benzonitriles of formula II by reacting II with hydroxylamine or its salts in aqueous solution, preferably in water or water / alkanol mixtures if in the presence of a base to the hetaryloximes of the formula III, which then then in a manner known per se to the pre IV products are alkylated.

The Hetarylamidoxime IV can then in a conventional manner with the corresponding acid halides, preferably the ent speaking acid chlorides, by heating in inert solution average (preferably at temperatures in the range of 20 to 100 ° C) be acylated. Suitable inert solvents are ins special hydrocarbons or ethers, particularly preferably aro Matic hydrocarbons such as toluene or xylene to only two To name examples.  

Alternatively, the active compounds according to the invention can also be prepared by synthesis route B, likewise starting from the heterocyclic aldehydes (NCS = N-chlorosuccinimide):

The synthesis of the oximes is carried out according to known methods by Reaction with an appropriate hydroxylamine. The chlorination and subsequent aminolysis with ammonia is in WO 98/04509 wrote and can be carried out largely analogously here. However, ammonia may be required in some cases use in an aprotic solvent and progress Follow the implementation to avoid side reactions. The final acylation is then as with synthesis route A be wrote carried out.

The compounds listed in the above reaction scheme or intermediates of formula II, III and IV are also new and represent a further object of the invention.

Preferred compounds of the formulas II, III or IV are those in which R ² and R ³ (compounds IV) have the meanings given above for compounds of the formula I.

Preferred compounds of formula III are the compounds listed in the table below.

Preferred compounds of formula IV are the compounds listed in the table below.

For the purposes of the present invention, the compounds of the formula I mentioned in the following table are examples:

The compounds I are distinguished by an excellent action against a wide range of phytopathogenic fungi, ins special from the class of Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes, from. You are e.g. T. systemic effective and can therefore also be used as leaf and soil fungicides be set.

The plants are usually sprayed with the active ingredients or pollinated or the seeds of the plants with the active ingredients acts.

The formulations are prepared in a known manner, e.g. B. by stretching the active ingredient with solvents and / or Carriers, if desired using emulsifier agents and dispersants, where in the case of water as Ver other organic solvents as auxiliary solvents can be used. As auxiliary agents come there  for essentially: 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), amines (e.g. ethanolamine, dimethylformamide) and Water; Carriers such as natural rock powder (e.g. kaolins, Clays, talc, chalk) and synthetic stone powder (e.g. finely divided silica, silicates); Emulsifiers such as non- ionogenic and anionic emulsifiers (e.g. polyoxyethylene fat alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants agents such as lignin sulfite liquor and methyl cellulose.

The alkali, alkaline earth, Ammonium salts of aromatic sulfonic acids, e.g. B. lignin, Phenolic, naphthalene and dibutylnaphthalenesulfonic acid, as well as from Fatty acids, alkyl and alkyl aryl sulfonates, alkyl and lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, as well as fatty alcohol glycol ether, condensate tion products of sulfonated naphthalene and its derivatives Formaldehyde, condensation products of naphthalene or Naphthalenesulfonic acids with phenol and formaldehyde, polyoxy ethylene octyl phenol 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, lauryl alcohol polyglycol ether acetate, Sorbitol ester, lignin sulfite liquor or methyl cellulose in Be dress.

Powders, materials for spreading and dusts can be mixed or mixed joint grinding of the active substances with a solid Carrier are manufactured.

Granules, e.g. B. coating, impregnation and homogeneous granules can Herge by binding the active ingredients to solid carriers be put. Solid carriers are mineral soils like sili cagel, silicas, silica gels, silicates, talc, kaolin, lime stone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, Calcium and magnesium sulfate, magnesium oxide, ground art substances, 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:

• A) a solution of 90 parts by weight of an inventive Compound I and 10 parts by weight of N-methyl-2-pyrrolidone, which is suitable for use in the form of tiny drops;
• B) a mixture of 10 parts by weight of an inventive Compound I, 70 parts by weight of xylene, 10 parts by weight of the Addition product of 8 to 10 moles of ethylene oxide with 1 mole Oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt the dodecylbenzenesulfonic acid, 5 parts by weight of the Anla tion product of 40 moles of ethylene oxide to 1 mole Castor oil; by finely distributing the solution in water you get a dispersion.
• C) an aqueous dispersion of 10 parts by weight of one Compound I according to the invention, 40 parts by weight of cyclo hexanone, 30 parts by weight of isobutanol, 20 parts by weight of the Addition product of 40 mol ethylene oxide to 1 mol Castor oil;
• D) an aqueous dispersion of 10 parts by weight of one Compound I according to the invention, 25 parts by weight of cyclo hexanol, 55 parts by weight of a mineral oil fraction from Boiling point 210 to 280 ° C and 10 parts by weight of the system approximately 40 moles of ethylene oxide and 1 mole of castor oil;
• E) a mixture ground in a hammer mill 80 parts by weight, preferably a solid fiction according to compound I, 3 parts by weight of the sodium salt Di-iso-butylnaphthalene-2-sulfonic acid, 10 parts by weight of the Sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 7 parts by weight of powdered silica gel; by finely distributing the mixture in water a spray liquor;
• F) an intimate mixture of 3 parts by weight of a fiction according to compound I and 97 parts by weight of finely divided Kaolin; this dust contains 3% by weight of active ingredient;
• G) an intimate mixture of 30 parts by weight of a fiction according to compound I, 62 parts by weight of powder Silica gel and 8 parts by weight of paraffin oil, which on the Surface of this silica gel was sprayed; this Preparation gives the active ingredient good adhesion;  
• H) a stable aqueous dispersion of 40 parts by weight of one Compound I according to the invention, 10 parts by weight of Sodium salt of a phenolsulfonic acid-urea form aldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water, which can be further diluted;
• I) a stable oily dispersion of 20 parts by weight of one Compound I according to the invention, 2 parts by weight of Calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight Fatty alcohol polyglycol ether, 20 parts by weight of sodium salt of a phenolsulfonic acid-urea-formaldehyde Condensate and 50 parts by weight of a paraffinic Mineral oil.

The new connections are characterized by an excellent Efficacy against a wide range of plant pathogens Mushrooms, especially from the Deuteromycetes class, Ascomycetes, Phycomycetes and Basidiomycetes. You are for Partly systemic and can act as foliar and soil fungicides be used.

They are particularly important for combating a large number of mushrooms on various crops such as wheat, rye, Barley, oats, rice, corn, grass, cotton, soy, coffee, Sugar cane, wine, fruit and ornamental plants and vegetables such as Cucumbers, beans and squash, as well as on the seeds of these Plants.

The compounds are applied by using the mushrooms or the Seeds, plants, materials to be protected from fungal attack or the soil with a fungicidally effective amount of the active fabrics treated. It is used before or after the infection tion of materials, plants or seeds by the fungi.

The new compounds are particularly suitable for combating of the following plant diseases: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea Pumpkin family, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizoctonia species on cotton and lawn, Ustilago species on grain and sugar Rohr, Venturia inaequalis (scab) on apples, Helminthosporium- Grain species, Septoria nodorum on wheat, Botrytis cinerea (Gray mold) on strawberries, vines, ornamental plants and vegetables, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley, Pyricularia oryzae on rice, Phytophthora 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) are used, e.g. B. against Paecilomyces variotii.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% active ingredient.

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

When treating seeds, amounts of active ingredient are generally used from 0.001 to 50, preferably 0.01 to 10 g per kilogram of seed needed.

The agents according to the invention can be used as Fungicides are also present together with other active ingredients, e.g. B. with herbicides, insecticides, growth regulators, fungicides or with fertilizers.

When mixed with fungicides you get in many cases an increase in the fungicidal spectrum of activity.

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 ferridimethyl dithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithio carbamate, manganese ethylene bisdithiocarbamate, manganese-zinc-ethylene diamine-bis-dithiocarbamate, tetramethylthiuram disulfide, zinc ammonium, ammonia-bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) ammonium bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) and ammonium bis (ammonia) bis (ammonia) bis (ammonia) bis (n) - 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) phenyl crotonate, 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, O, O-diethyl-phthalimidophosphonothioate, 5-amino-1- [bis- (dimethyl amino) phosphinyl] -3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-di thioanthraquinone, 2-thio-1,3-dithiolo [4,5-b] quinoxaline , 1- (Butyl carbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxy carbonylamino-benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) -benzimidazole, N- (1, 1,2,2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthio-phthalimide, N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3- trichloromethyl-1,2,3-thiadiazole, 2-rhodanmethylthio benzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4- (2-chlorophenyl hydrazono) -3-methyl-5-isoxazolone, pyridine-2-thione- 1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carbox anilido-6-methyl-1,4-oxathiine, 2,3-dihydro-5-carbox anilido-6-methyl-1, 4-oxathiin-4,4-dioxide, 2-M ethyl-5,6-di hydro-4H-pyran-3-carboxylic acid anilide, 2-methyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,4,5-tri methyl furan -3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide, N-cyclohexyl-N-methoxy-2,5-dimethyl furan-3-carboxylic acid amide, 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-trichloroethyl) -formamide, 1- (3,4- Dichloroanilino) -1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cy clododecyl-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-1,3-dioxolan-2-ylethyl] -1H-1,2,4-triazole, 1- [2- (2,4-dichlorophenyl) - 4-n-propyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, N- (n-propyl) -N- (2,4,6-trichlorophenoxy ethyl) - N'-imidazol-yl urea, 1- (4-chlorophen oxy) -3,3-dime thyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone, (2-chlorophenyl) - (4-chlorophenyl) -5-pyrimidine-methanol, 5-butyl-2-dimethyl amino-4-hydroxy-6-methyl-pyrimidine, bis- (p-chlorophenyl) -3-pyridinium methanol, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) -benzene, 1,2-bis- ( 3-methoxycarbonyl-2-thioureido) benzene, [2- (4-chlorophenyl) ethyl] - (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol, 1- [3- (2-chlorophenyl) -1- (4-fluorophenyl) oxiran-2-ylmethyl] -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-dimethyl-phenyl) -N-fu royl (2) -alaninate, DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) -alanine methyl ester, N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2 -aminobutyrolactone, DL-N- (2,6-dimethylphenyl) -N- (phenyl acetyl) -alanine methyl ester, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1 , 3-oxazolidine, 3 - [(3,5-dichlorophenyl) -5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione, 3- (3,5-dichlorophenyl) -1-iso -propylcarbamoylhydantoin, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboxylic acid imide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] acetamide, 1- [2- ( 2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole, 2,4-di fluoro-a- (1H-1,2,4-triazolyl-1-methyl) -benzhydryl alcohol, N- ( 3-chloro-2,6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoro methyl-3-chloro-2-aminopyridine, 1 - ((bis- (4-fluorophenyl) methyl silyl) methyl) -1H -1,2,4-triazole,
Strobilurins such as methyl-E-methoximino- [a- (o-tolyloxy) - o-tolyl] acetate, methyl-E-2- {2- [6- (2-cyanophenoxy) pyridimin-4-yl-oxy] phenyl} -3-methoxyacrylate, methyl-E-methoximino- [a- (2,5-di methyloxy) -o-tolyl] 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 acid morpholide.

The invention is illustrated by the following examples explained in more detail:

example 1 a) 2,6-Dimethyl-4-trifluoromethyl-nicotinamide oxime

12.6 g 2, 6-dimethyl-4-trifluoromethylnicotinitrile (Synthesis 1997 (No. 11), p. 1321), 8.6 g hydroxylamine hydrochloride, 7.8 g sodium carbonate, 26 ml water and 130 ml ethanol become 24 h at 70 ° C stirred. After evaporation of the solvent, the residue was partitioned between 80 ml of 2N HCl and 50 ml of ethyl acetate. After the HCl phase had been separated off, neutralized to pH 7 and extracted three times with 80 ml each of tert-butyl methyl ether, the solvent was evaporated in vacuo. 8.2 g of crystals were obtained, which consisted of 50% of the desired product and 50% of 2,6-dimethyl-trifluoromethyl-nicotinamide.
NMR (CDCl ₃ ): ppm: 2.65 s (6H); 4.8 s (2H); 7.3 s (1H); 7.65 s (1H)

b) 2,6-Dimethyl-4-trifluoromethyl-nicotinamide- [O-cyclopropyl methyl] oxime

3.0 g of bromocyclopropylmethane were added at -5 ° C. to a solution of 8.0 g of crystals of a) (content of 2,6-dimethyl-4-trifluoromethyl-nicotinamide oxime: 50%) in 50 ml of dimethylformamide and then 0. 73 g of 80% sodium hydride were added in portions, and the mixture was stirred at 0 ° C. for 3 h and at room temperature overnight. The mixture was stirred in 400 ml of water and extracted three times with 100 ml of cyclohexane. After evaporation of the cyclohexane, 5.3 g of the desired product were isolated.
NMR (CDCl ₃ ) ppm: 0.3 m (2H); 0.55 m (2H); 1.1 m (1H); 2.6 s (3H); 2.65 s (3H); 3.85 d (2H); 4.9 s (2H); 7.3 s (1H).

c) N-phenylacetyl-2,6-dimethyl-4-trifluoromethyl-nicotinamide- [O- cyclopropylmethyl] oxime

0.60 g of the 2,6-dimethyl-4-trifluoromethyl-nicotinamide- [Ocyclopropylmethyl] -oxime obtained from stage b) and 0.45 g of phenylacetic acid chloride are stirred in 20 ml of toluene at 90 ° C. for 15 h. After the addition of 30 ml of water, the pH was adjusted to 11.5 with 2N NaOH. After evaporation of the solvent, 0.7 g of the desired product (mp: 68-71 ° C.) is isolated from the toluene phase.
NMR (CDCl ₃ ) ppm: 0.2 m (2H); 0.5 m (2H); 1.05 m (1H); 2.45 s (3H); 2.6 s (3H); 3.6 s (2H); 3.8 m (2H); 7.2-7.45 m (6H); 8.55 s (1H).

Example 2 Efficacy against powdery mildew

Leaves of potted wheat seedlings of the variety "Early gold" were made with aqueous active ingredient preparation a stock solution consisting of 10% active ingredient, 63% cyclohexanone and 27% emulsifier was added until dripping wet sprays and 24 h after the spray coating has dried on with spores of powdery mildew (Erysiphe graminis f. sp. tritici) pollinated. The Test plants were then in the greenhouse at tempera tures between 20 and 22 ° C and 75 to 80% relative air set up moisture. After 7 days the extent of the flour Dew development determined visually in% of the total leaf area.  

The plants treated with the active ingredient from Example 1 showed no infestation, while the untreated plants become one were largely infected.

Example 3 Efficacy against powdery mildew

Leaves of potted wheat seedlings of the variety "Early gold" were made with aqueous active ingredient preparation a stock solution consisting of 10% active ingredient, 63% cyclohexanone and 27% emulsifier was added until dripping wet sprays and 24 h after the spray coating has dried on with spores of powdery mildew (Erysiphe graminis f. sp. tritici) pollinated. The Test plants were then in the greenhouse at Tem temperatures between 20 and 22 ° C and 75 to 80% relative air set up moisture. After 7 days the extent of the flour Dew development determined visually in% of the total leaf area.

The plants treated with the active ingredient from Example 1 showed no infestation, while the untreated plants become a large one Were affected.

Claims (15)

1. Hetarylbenzamide oxime derivatives of the formula I.
where the substituents have the following meanings:
R ¹ C ₁ -C ₄ haloalkyl, halogen, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio,
R ^{2 is} hydrogen, halogen, C ₁ -C ₄ alkyl, which may be substituted by halogen, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio,
R ³ C ₁ -C ₄ -alkyl which may be substituted by cyano, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ haloalkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl,
R ^{4 is} phenyl-C ₁ -C ₆ -alkyl, which has one or more substituents on the phenyl ring selected from the group consisting of halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy or can carry C ₁ -C ₄ haloalkoxy, or
Thienyl-C ₁ -C ₄ -alkyl, which has one or more substituents on the thienyl ring selected from the group consisting of halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy or C Can carry ₁ -C ₄ haloalkoxy, or
Pyrazole-C ₁ -C ₄ alkyl, which on the pyrazole ring one or more substituents selected from the group consisting of halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C Can carry ₁ -C ₄ haloalkoxy,
XN, NO or CR ⁵ ,
YN, NO or CR ⁵ ,
R ^{5 is} hydrogen, halogen, C ₁ -C ₄ alkyl, which can be substituted by halogen, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio,
where X and Y cannot be CR ⁵ at the same time, with the exception of the following compounds:
N- (4-methoxy) phenylacetyl-3-chloropyridyl-4-amide- [O-pro pargyl] oxime;
N- (4-methoxy) phenylacetyl-3, 5-dimethyl-pyridyl-4-amide- [O-pro pargyl] oxime. 2. Hetarylamidoxime derivatives of the formula I according to claim 1, in which R ^{1 is} C ₁ -C ₄ haloalkyl, chlorine or C ₁ -C ₄ haloalkoxy be. 3. hetarylamidoxime derivatives of the formula I according to claim 1 or 2, in which R ^{2 is} hydrogen, C ₁ -C ₄ alkyl, fluorine or chlorine. 4. Hetarylamidoxime derivatives of the formula I according to one of claims 1 to 3, in which R ^{3 is} cyclopropyl-C ₁ -C ₄ alkyl. 5. Hetarylamidoxime derivatives of the formula I according to one of claims 1 to 4, in which R ^{4 is} phenyl-C ₁ -C ₄ -alkyl, which can be substituted on the phenyl ring by one to three substituents selected from the group consisting of Ha lied, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy. 6. Hetarylamidoxime derivatives of the formula I according to one of the An sayings 1 to 5, in which X means nitrogen. 7. Hetarylamidoxime derivatives of the formula I according to one of claims 1 to 6, in which Y is CR ⁵ . 8. Hetarylamidoxime derivatives of the formula I according to one of claims 1 to 7, in which R ^{5 is} hydrogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl. 9. Hetaryl nitriles of the formula II
wherein R ¹ , R ² , X and Y have the meaning given in claim 1, with the proviso that R ^{1 is} not CF ₃ when X is nitrogen and Y is methine (CH). 10. Hetarylamidoxime of formula III
wherein R ¹ , R ² , X and Y have the meaning given in claim 1. 11. Hetarylamidoximes of formula IV
wherein R ¹ , R ² , R ⁵ , X and Y have the meaning given in claim 1. 12. Use of the hetarylamidoxime derivatives of the formula I according to one of claims 1 to 8 for combating harmful fungi. 13. Fungicidal compositions containing a fungicidally effective amount of at least one hetarylamidoxime derivative of the formula I. any of claims 1-8. 14. A method of combating harmful fungi, characterized records that the harmful fungi, their habitat or the plants, surfaces, materials or Spaces with a fungicidally effective amount of a compound of the general formula I according to one of claims 1 to 8 or a containing a hetarylamidoxime derivative of the formula I. fungicidal agents treated according to claim 13. 15. Use of compounds of formula II, III or IV as in claims 9 to 11 defined for the production of Compounds of formula I as defined in claim 1.