WO2000017156A1

WO2000017156A1 - Novel benzamidoxime derivatives, intermediate products, methods for the production thereof, and their use as fungicides

Info

Publication number: WO2000017156A1
Application number: PCT/EP1999/006688
Authority: WO
Inventors: Karl Eicken; Joachim Rheinheimer; Ingo Rose; Eberhard Ammermann; Thomas Grote; Siegfried Strathmann; Gisela Lorenz
Original assignee: Basf Aktiengesellschaft
Priority date: 1998-09-22
Filing date: 1999-09-10
Publication date: 2000-03-30

Abstract

The invention relates to benzamidoxime derivatives of formula (I), whereby the substituents have the following meanings: R1 represents difluoromethyl or trifluoromethyl; R2 represents hydrogen or fluorine; R3 represents C¿1?-C4-alkyl, which can be substituted by cyano, C1-C4-alkyl halide, C1-C4-alkoxy-C1-C4-alkyl, C3-C6-alkenyl, C3-C6-alkenyl halide, C3-C6-alkynyl, C3-C8-cycloalkyl-C1-C4-alkyl; R?4¿ represents phenyl-C¿1?-C6-alkyl, which can be substituted on the phenyl ring once or multiple times, thienyl-C1-C4-alkyl, which can be substituted on the thienyl ring once or multiple times, or pyrazole-C1-C4-alkyl, which can be substituted on the pyrazole ring once or multiple times. The invention also relates to agrochemical compositions containing the compounds (I), to the compounds thereof having a fungicidal effect, and to intermediate products for producing the compounds (I).

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 is an object of the present invention to provide novel benzamidoxime derivatives ^"having improved activity, especially at low application rates, are available.

This task was surprisingly achieved by benzamide oxime derivatives of the formula I.

solved, where the substituents have the following meanings:

R ¹ difluoromethyl or trifluoromethyl,

R ^{2 is} hydrogen or fluorine,

R ³ -CC ₄ alkyl, which can be substituted by cyano,

_{Cι-C4-haloalkyl,} _{Cι-C4-alkoxy-Cι-C} ₄ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ haloalkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₈ -Cycloalkyl -CC-C ₄ alkyl,

R ⁴ is phenyl-Cι-C ₅ alkyl, which may carry one or more substituents selected from the group consisting of halogen, _Cι-C4 alkyl, C -C ₄ haloalkyl, Cχ-C ₄ alkoxy or Cι-C ₄ -Halogenalkoxy can wear, or Thienyl-Cχ-C ₄ alkyl, which comprises one or more substituents on the thienyl ring, selected from the group consisting of halogen, Cι-C ₄ -alkyl, C ₄ haloalkyl, Cι-C ₄ alkoxy or Cι-C ₄ - Halogenalkoxy can wear, or

Pyrazole -CC ₄ alkyl, which on the pyrazole ring has one or more substituents selected from the group consisting of halogen, -C ₄ -alkyl, -C-C ₄ -haloalkyl, -C-C-alkoxy or C] _- C ₄ -Halogen alkoxy can wear;

and their agriculturally applicable salts.

When defining the substituents R ¹ to R ⁴ , the terms given stand as a collective term for a group of compounds.

Halogen represents 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 ethyl;

Cι-C ₄ -haloalkyl: a Cι-C ₄ -alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine, for example, trichloromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2 -Bromethyl, 2, 2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2, 2, 2-trichlorethyl, 2-fluoropropyl, 3-fluoropropyl, 2-chloropropyl or 3-chloropropyl, especially for 2-fluoroethyl or 2-chloroethyl ;

- Cyano -CC-C ₄ ~ alkyl for: a C ₁ -C ₄ alkyl radical as mentioned above, which is substituted by a cyano group; e.g. cyanomethyl, 1-cyanoeth-1-yl, 2-cyanoeth-1-yl, 1-cyanoprop-1-yl, 2-cyanoprop-1-yl, 3-cyanoprop-1-yl, 1-cyanoprop-2-yl or 2-cyanoprop-2-yl, especially for cyanomethyl or 2-cyanoethyl;

Cχ-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 ₄ -alkyl for: C 1 -C ₄ -alkoxy substituted as mentioned above -CC ₄ -alkyl, for example for methoxy ethyl, ethoxymethyl, n-propoxymethyl,

(l-methylethoxy) methyl, n-butoxymethyl, (l-methylpropoxy) methyl, (2-methylpropoxy) methyl,

(1, l-dimethylethoxy) methyl, 2- (methoxy) ethyl or 2- (ethoxy) ethyl, especially for methoxymethyl or 2-methoxyethyl;

- C ₃ -C ₆ alkenyl for: for example prop-2-en-1-yl, n-buten-4-yl, 1-methyl-prop-2-en-1-yl, 2-methyl-prop-2 -en-l-yl or 2-butene-l-yl, in particular for prop-2 -en-l-yl;

C -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 example 2-chloroallyl, 3-chloroallyl, 2, 3-dichloroallyl or 3 , 3-dichlorallyl, especially for 2-chloroallyl;

- C ₃ -C ₆ alkynyl for: for example prop-1-in-l-yl, prop-2-in-l-yl, n-but-1-in-l-yl, n-but-l-in -3-yl, n-but-l-in-4-yl or n-but-2-in-l-yl, in particular for prop-2-in-l-yl;

C ₃ -C8 cycloalkyl -CC-C4-alkyl for: -CC ₄ -alkyl as mentioned above, which is substituted by C -C ₈ -cycloalkyl; eg

Cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl,

Cyclo exylmethyl, (cyclopropyl) ethyl, 1- (cyclobutyl) ethyl,

1- (cyclopentyl) ethyl, 1- (cyclohexyl) ethyl,

1- (cycloheptyl) ethyl, 1- (cyclooctyl) ethyl, 2- (cyclopropyl) ethyl or 2- (cyclobutyl) ethyl, especially for cyclopentylmethyl;

Phenyl-Ci-C _δ- alkyl for: -C-C ₄ alkyl as mentioned above, which is substituted by phenyl; e.g. benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-l-yl,

2-phenylprop-l-yl, 3-phenylprop-l-yl, especially for benzyl or 2-phenylethyl;

Thienyl -CC-alkyl for: -CC ₄ -alkyl as mentioned above, which is substituted by thienyl; eg 2-thienylmethyl, 3-thienylmethyl or 2-thienylethyl;

Pyrazole -CC ₄ alkyl for: -C ₄ alkyl as mentioned above, which is substituted by pyrazole; eg 1-pyrazolylmethyl, 2-pyrazolylmethyl, 3-pyrazolylmethyl or 2-pyrazolylylethyl; Compounds in which the substituent R ¹ for difluoromethyl and / or the substituent R ³ for cyclopropylmethyl and / or the substituent R ⁴ for benzyl, which has one to three substituents selected from the above-mentioned group, in particular one to three substituents, on the phenyl ring Fluorine, chlorine, methyl, methoxy or trifluoromethyl, has generally proven to be particularly effective.

Preferred compounds in the sense of the present invention are, in particular, the compounds with the following structural features:

1. Compounds of formula I wherein R ^{1 is} CHF ₂ .

2. Compounds according to item 1, wherein R ^{2 is} hydrogen or fluorine. 3. Compounds according to item 1 or 2, where R ^{3 is} C 1 -C ₄ alkyl,

C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or C ₃ -C ₈ cycloalkyl -C ₁ -C ₄ alkyl.

4. Compounds according to item 3, wherein R ^{3 is} alkyl. 5. Compounds according to item 3, wherein R ^{3 is} methyl or ethyl. 6. Compounds according to item 3, wherein R ^{3 is} propargyl. 7. Compounds according to item 3, wherein R ^{3 is} cyclopropylmethyl. 8 compounds according to items 1-7, wherein R ^{4 is} benzyl, which can be substituted on the phenyl by -CC ₄ alkoxy, halogen, halogen-C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyl. 9. Compounds according to items 1-7, wherein R ^{4 is} 2-hienyl-C ₁ -C ₄ -alkyl or 3-thienyl-C ₁ -C ₄ -alkyl.

10. Compounds according to items 1-7, wherein R ^{4 is} pyrazolyl -CC ₄ -alkyl.

11. Compounds according to items 1-10, wherein the C 1 -C ₄ -alkyl radicals mentioned stand for a methyl, ethyl or n-propyl group.

12. Compounds according to items 1-11, where the halogen atoms mentioned are chlorine or fluorine.

Compounds of the formula I in which R ¹ to R ^{4 have} the meanings listed in Table 1 below are particularly preferred.

Table 1

cPr stands for cyclopropylmethyl in the table above and in the tables below.

The benzamide oxime derivatives of the formula I according to the invention are obtained by reacting the benzonitriles II with haloalkanes CH _m F _n Hal (m has the value 0 or 1, n the value 2 or 3), such as CHF ₂ C1 or CF ₃ I in basic medium (preferably in the presence of an alkali metal hydroxide), to benzonitriles III and subsequent reaction of III with hydroxylamine or its salts in aqueous solution, preferably in water or water / alkanol mixtures, optionally in Presence of a base to the benzamide oximes of the formula IV, which are then alkylated to the precursors V in a manner known per se. Benzonitriles of the formula II are commercially available. can be easily prepared according to the methods described in the literature.

The benzamide oximes V can then be acylated in a manner known per se with the corresponding acid halides, preferably the corresponding acid chlorides, by heating in inert solvents (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.

R ⁱ shark

OH

II

OR ¹

III IV

OR ¹

In the above scheme, R ¹ preferably represents a group CH _m F _n , where m is 0 or 1 and n is 2 or 3, and the sum of m + n is 3.

The intermediates of the formula III listed in the above reaction scheme, in which R ^{2 represents} fluorine and the intermediates of the formulas IV, V and VI are new and represent a further object of the invention.

The production of these new intermediates with a difluor substitution can start from

2,3-difluoro-6-methoxybenzaldehyde (which can be prepared, for example, by the process of Example 27 in WO 97/03071), according to the variants described in Example 2, is carried out to the stage of the compounds IV. The next steps to

Preparation of the corresponding compounds V and VI are known per se to the person skilled in the art.

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

Preferred compounds of the formula IV are listed in Table 2.

Table 2

Table 3 below lists some preferred compounds of Formula V.

Table 3

c-Pr = cyclopropylmethyl

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 Basidio ycetes. 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 agrochemical compositions or compositions containing these active compounds, or the seeds of the plants are treated with the active compounds.

The formulations or agrochemical compositions are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, where 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), amines (e.g. ethanolamine, dimethylformamide) and water; Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (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 lignin sulfite liquors and methyl cellulose.

The alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ethers,

Condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated iso-octyl, octyl or nonylphenol, alkylphenol, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, iso-tridecyl alcohol, fatty alcohol ethylene oxide condensate, polyoxyethylene ethoxylated oil, ethoxylated roxyl ether, ethoxylated roxyl ether, ethoxylated roxyl ether, Leaches of sulfite or methyl cellulose 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 earths such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and vegetable products such as corn flour, tree bark, wood and nutshells, 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

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 of 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 wt. Parts by a compound I according to the invention, 25 wt. Parts by cyclohexanol, 55 wt. Parts by a mineral oil fraction of boiling point 210 to 280 ° C and 10 wt. Parts by the ^"adduct of 40 moles of ethylene oxide to 1 mol castor oil;

V. a mixture of 80 parts by weight, preferably a solid compound I, 3 parts by weight of the

Sodium salt of di-iso-butylnaphthalene-2-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of powdered silica gel; a spray mixture is obtained by finely distributing the mixture in 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 dust 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 paraffin oil which was sprayed onto the surface of this silica gel; this preparation 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

Sodium salt one

Phenolsulfonic acid-urea-formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water, which can be further diluted;

IX. a stable oily dispersion of 20 parts by weight of a compound I according to the invention, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt

Phenolsulfonic acid-urea-formaldehyde condensate and 50 parts by weight of a paraffinic mineral oil.

The compounds of the formula I are particularly important for combating a large number of fungi on different ones

Crops such as wheat, rye, barley, oats, rice, corn,

Lawn, cotton, soy, coffee, sugar cane, wine, fruit and Ornamental plants and vegetables such as cucumbers, beans and pumpkin plants, 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-ethylenediamine-bis-dithiocarbamate,

Tetramethylthiuram disulfide, ammonia complex from

Zinc (N, N-ethylene-bis-dithiocarbamate), ammonia complex of zinc (N, N '-propylene-bis-dithiocarbamate), zinc (N, N' -propylene-bis-dithiocarbamate), N, N 'polypropylene bis (thiocarbamoyl) 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-1, 4-dithioanthraquinone, 2- Thio-1,3-dithiolo [4,5-b] quinoxaline, 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-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 dia mid, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-rhodanmethylthiobenzothiazole, 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-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-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-eth.yl] - 1H-1, 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- (4-chlorophenoxy) -3, 3-dimethyl-l- (1H-1,2,4-triazol-l-yl) -2-butanone, (2-chlorophenyl) - (4-chlorophenyl) -5 pyrimidine-methanol, 5-butyl-2-dimethylamino-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-Chlorophenyl) ethyl] - (1, 1-dimethylethyl) -1H-1, 2,4-triazole-1-ethanol, 1- [3- (2-chlorophenyl) -1- (4-fluorophenyl) oxirane - 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-dimethyl-phenyl) -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-aminobutyrolactone, DL-N- (2, 6-dimethylphenyl) -N- (phenylacetyl) - 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-dicarboximide, 2-cyano- [ N- (ethylaminocarbonyl) -2-methoximino] acetamide, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2, -triazole, 2,4-difluoro-α- (1H-1 , 2, 4-triazolyl-l-methyl) -benzhydryl alcohol, N- (3-chloro-2, 6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1- (( bis- (4-fluorophenyl) methylsilyl) methyl) 1 H-l, 2,4-triazole,

Strobilurins such as methyl -E-methoximino- [α- (o-tolyloxy) - o-tolyl] acetate, methyl -E -2 - {2 - [6 - (2-cyanophenoxy) pyridimin-4 - yloxy] phenyl} -3 -methoxyacrylate, methyl -Ξ-methoximino- [α- (2,5-dimethyloxy) -otolyl] acetamide. Anilino-pyrimidines such as N- (4, 6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propinyDpyrimidin-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) 2,6 bis-difluoromethoxy-benzonitrile

In a mixture of 13.5 g 2, 6-hydroxy-benzonitrile, 70 ml

1, 2-Dimethoxyethane and 65 ml NaOH (33%) were gassed with stirring at 75 ° C. 6.3 g of chlorodifluoromethane (the reflux condenser was cooled with dry ice) and stirred at 70-75 ° C. for two hours. After cooling, the mixture was diluted with 500 ml of water and extracted three times with 150 ml of tert-butyl methyl ether each. After evaporation of the solvent, 13.0 g of the desired product were obtained as an oil.

NMR (CDC1 ₃ ) ppm: 6.7 t (2H); 7.20 d (2H); 755-7.70 t (lH).

b) 2-bis-difluoromethoxy-benzamidoxime

A mixture of 13.0 g 2,6-bis-difluoromethoxy-benzonitrile and 5.0 g hydroxylamine hydrochloride, 4.1 g sodium carbonate, 12 ml water and 55 ml ethanol was stirred at 75 ° C. for 20 h.

After evaporation of the solvent, the residue was partitioned between 100 ml of 2N HCl and 100 ml of ethyl acetate. After separating the HCl phase, neutralizing to pH 7 and extracting three times with 40 ml of tert. -Butyl methyl ether, the solvent was evaporated. 9.7 g of the desired product with an mp of 110-112 ° C. were obtained.

NMR (CDC1 ₃ ) ppm: 4.8 s (2H); 6.55 t (2H); 7.1 d (2H), 7.4 t (1H).

c) 2,6-bis-difluoromethoxy-benzamide- [O-cyclopropylmethyl] -oxime

1.1 g of 80% sodium hydride were added to a solution of 9.5 g of 2,6-bis-difluoromethoxi-benzamidoxime in 55 ml of dimethylformamide (DMF) at 0 to 5 ° C. and the mixture was stirred at this temperature for 3 hours. Then 5.7 g of bromocyclopropylmethane were added at the same temperature and then 2 h at 5 ° C. and stirred overnight at room temperature. The mixture was stirred into 500 ml of water and extracted three times with 80 ml of cyclohexane and 20 ml of MTBE. After evaporation of the cyclohexane

9.5 g of the desired product obtained from the mp: 53-54 ° C. 5

NMR (CDC1 ₃ ) ppm: 0.3 m (2H); 0.55 m (2H); 1.2 m (1H); 3.85 d (2H); 4.8 d (2H); 6.6 t (2H); 7.1 d (2H); 7.2 t (lH).

d) N-phenylacetyl-2, 6-bis -difluoromethoxy-benzamide- [O-cyclopropyl 0 methyl] -oxime (compound 1.6 from Table 1).

1.6 g of the 2,6-bis-difluoromethoxybenzamide- [O-cyclopropylmethyl] -oxime obtained after stage c) and 1.1 g of phenylacetic acid chloride were refluxed with 30 ml of toluene for 7 hours. 5 After cooling, 40 ml of water were added and the pH was adjusted to 11. After evaporation of the solvent and subsequent recrystallization from diisopropyl ether, 1.1 g of the desired product with an mp of 80-82 ° C. was isolated from the toluene phase. 0

NMR (CDC1 ₃ ) ppm: 0.2 m (2H); 0.50 m (2H); 1.1 m (1H); 3.80 S (2H); 3.8 d (2H); 6.4 t (2H); 7.0 d (2H); 7.2-7.4 m (6H); 8.5 s (1H).

Example 2 5 Activity against powdery mildew

Leaves of potted wheat seedlings of the "early gold" variety were treated with aqueous active ingredient preparation consisting of a stock solution consisting of 10% active ingredient, 63% cyclohexanone

30 and 27% of the emulsifier was added, sprayed to runoff point and 24 hours after the spray coating had dried on, dusted with spores of the powdery mildew (Erysiphe graminis f. Sp. Tritici). The test plants were then relative in the greenhouse at temperatures between 20 and 22 ° C and 75 to 80%

35 humidity set up. After 7 days, the extent of mildew development was determined visually in% of the total leaf area.

The plants treated with the active compounds from Example 1d (Table 1: No. 1.6) with 40 aqueous active compound preparation containing 63 ppm showed no infection, while the untreated plants were 80% infected.

Example 3: Activity against powdery mildew

45 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 were spore-dried 24 hours after the spray coating had dried on of powdery mildew (Erysiphe graminis f. sp. tritici) pollinated. 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 plants treated with the active ingredient 1.6 in Table 1 showed no infection, while the untreated plants were 80% infected.

Claims

claims

1. Benzamide oxime derivatives of the formula I.

OR ¹

where the substituents have the following meanings:

R ¹ difluoromethyl or trifluoromethyl,

R ^{2 is} hydrogen or fluorine,

R ³ C1-C ₄ alkyl, which can be substituted by cyano, -C-C4-haloalkyl, C ₁ -C ₄ -alkoxy-Cι-C -alkyl _/

C ₃ -C6 alkenyl, C ₃ -C ₆ haloalkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₈ cycloalkyl -CC ₄ -alkyl,

R ⁴ phenyl-Ci-Ce-alkyl, which has 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 1 -C ₄ - on the phenyl ring Halogenalkoxy can wear, or

Thienyl -CC-C4-alkyl, which carries one or more substituents selected from the group consisting of halogen, C1.-C4-alkyl, Cχ-C ₄ -haloalkyl, Cι-C ₄ -alkoxy or Cχ-C4-haloalkoxy on the thienyl ring can, or

Pyrazole -CC ₄ alkyl, which on the pyrazole ring one or more substituents selected from the group consisting of halogen, C1-C-alkyl. Cχ-C4-haloalkyl, -CC alkoxy or -CC ₄ haloalkoxy can wear;

and their agriculturally applicable salts.

2. Benzamidoxime derivatives of formula I according to claim 1, in which R ^{4 is} benzyl, which can carry one to three substituents selected from the group consisting of halogen, C1-C4-alkyl, or C 1 -C ₄ -alkoxy on the phenyl ring .

3. benzamidoxime derivatives of the formula I according to claim 1 or 2, in which R ^{1 is} difluoromethyl.

4. Benzamidoxime derivatives of formula I according to any one of claims 1-3, in which R ^{3 is} cyclopropylmethyl.

5. Benzonitriles of the formula II

OH

where the fluorine atom can be in the meta or para position to the cyano group.

6. Benzonitriles of the formula III

OR ¹

OR ¹

R ¹ denotes difluoromethyl or trifluoromethyl,

R ^{2 represents} hydrogen or fluorine and

R ^{2 can be} in the meta or para position to the cyano group.

7. Benzamide oximes of the formula IV

R ¹ denotes difluoromethyl or trifluoromethyl,

R ^{2 represents} hydrogen or fluorine and

R ^{2 can be} in the meta or para position to the cyano group.

8. Benzamide oximes of the formula V

in which

R ¹ difluoromethyl or trifluoromethyl,

R ^{2 is} hydrogen or fluorine,

R ³ C ₁ -C ₄ -alkyl which may be substituted by cyano, C ₄ haloalkyl, _{Cι-C4-alkoxy-Cι-C} ₄ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C _6- haloalkenyl, C ₃ -C ₆ -alkynyl, C ₃ -C ₈ -cycloalkyl -CC-C ₄ -alkyl,

and R ^{2 can be} in the meta or para position to the oxime group.

9. Use of the benzamidoxime derivatives of the formula I according to one of claims 1-4 for combating harmful fungi.

10. Agrochemical composition containing a fungicidally effective amount of at least one benzamidoxime derivative of the formula I according to any one of claims 1-4.

11. A method 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 general formula I or a

Treated benzamidoxime derivative of formula I containing agrochemical composition with fungicidal activity according to claim 10.

12. Use of compounds of formula II according to claim 5 for the preparation of compounds of formula I according to one of claims 1-4.

13. Use of compounds of formula III according to claim 6 for the preparation of compounds of formula I according to one of claims 1-4.

14. Use of compounds of formula IV according to claim 7 for the preparation of compounds of formula I according to one of the

Claims 1-4.

15. Use of compounds of formula V according to claim 8 for the preparation of compounds of formula I according to any one of claims 1-4.

16. A process for the preparation of compounds of formula I according to any one of claims 1-4, comprising at least one of the following process steps:

a) implementation of compounds of formula II

OH = \ ⁽ I ⁾ χj— ^CN

OH

with halides R ⁱ -Hal to compounds III;

b) implementation of compounds of formula III

OR ¹

OR ¹

with NH ₂ OH to give compounds IV;

c) implementation of compounds of formula IV

OR ¹

with halides R ³ -Hal to compounds V;

10 d) implementation of compounds of formula V

20 with acid halides R -CO-Hal to give compounds I.

25

30

35

40

45