SK598A3 - Triazoline and isoxazoline bis-oxime derivatives and their use as pesticides - Google Patents

Abstract

Bis-oxime derivatives of formula (I) in which A is (a) or (b), where W is oxygen or sulfur, and the other substituents defined as follows: R1 = hydrogen, C1-C4alkyl; cyclopropyl; R2 = hydrogen, C1-C6alkyl; halo(C1-C6) alkyl; C2-C6alkoxyalkyl; C3-C6cycloalkyl; substituted or unsubstituted aryl; substituted or unsubstituted heteroaryl; cyano; C1-C6alkoxycarbonyl; C1-C6alkyl-S(O)n; substituted or unsubstituted aryl-S(O)n; C1-C6alkoxy; substituted or unsubstituted aryloxy; substituted or unsubstituted heteroaryloxy; unsubstituted or mono- to trimethyl-substituted heterocyclyl; substituted or unsubstituted aryl-C1-C6alkyl; substituted or unsubstituted heteroaryl-C1-C6alkyl; R3 = hydrogen; C1-C6alkyl; C1-C6haloalkyl having 1 to 5 halogen atoms; C1-C4alkoxy-C1-C2-alkyl; unsubstituted or mono- to trihalo-substituted C1-C6alkenyl; C2-C6alkynyl; unsubstituted or mono- to tetrahalo-substituted C3-C6cycloalkyl-C1-C4alkyl; n = 0 to 2; R8 = H, C1-C4alkyl, C1-C4haloalkyl, C3-C6cycloalkyl; X = OR5, SR5, NR6R7, halogen (especially Cl); R6, R7 = independently of one another H, C1-C4alkyl, C3-C4alkenyl, C3-C4alkynyl; R5 = C1-C4alkyl, C1-C3haloalkyl are fungicidal, acaricidal and insecticidal active ingredients for agriculture. They can be employed as formulated crop protection compositions.

Description

The invention relates to novel bis-oxime derivatives having a microbicidal, insecticidal and acaricidal action of the general formula I

wherein W represents an oxygen atom or a sulfur atom, and

R ¹ represents a hydrogen atom, a C 1 -C 4 alkyl group or a cyclopropyl group,

R ² is H, alkyl having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, alkoxyalkyl of 2 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, cyano, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkyl-S (O) _n , substituted or unsubstituted aryl-S (O) _n , C 1-6 alkoxy carbon atoms, substituted or unsubstituted aryloxy, substituted or unsubstituted heteroaryloxy, unsubstituted or mono- to trimethyl-substituted heterocyclyl, substituted or unsubstituted arylalkyl of 1 to 6 carbon atoms in the alkyl moiety or substituted or unsubstituted or unsubstituted or unsubstituted alkylated parts,

R ³ is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 5 haloalkyl, C 1 -C 4 alkoxyalkyl and C 1 -C 2 alkyl, unsubstituted or mono- to trihalo-substituted alkenyl of 1 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, or unsubstituted or mono- to tetrahalo-substituted cycloalkylalkyl of 3 to 6 carbon atoms in the cycloalkyl of 1 to 4 carbon atoms n is 0 to 2,

R ⁸ represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 haloalkyl group or a C 3 -C 6 cycloalkyl group, represents a group OR ^a , SR ^s , NR ^e R ^v or a halogen atom (in particular Cl), the symbols R ⁶ and R ⁷ independently of one another are hydrogen, alkyl having 1 to 4 carbon atoms, alkenyl of 3-4 carbon atoms or alkynyl of 3-4 carbon atoms, and

^R is alkyl having 1 to 4 carbon atoms or haloalkyl having 1 to 3 carbon atoms.

In a narrower sense, the invention, as a particularly important subgroup, relates to compounds of formula I in which:

A represents the structural element _M- zCH ₃ where W represents an oxygen atom or a sulfur atom,

R ² is as defined above other than haloalkyl group having 1 to 6 carbon atoms and the symbols R ^1, R ^{3 and} n are as defined above.

Substituents of optionally substituted aryl groups, heteroaryl groups, aryl-S (O) groups, aryloxy groups, heteroaryloxy groups, arylalkyl groups having 1 to 6 carbon atoms in the alkyl moiety and heteroarylalkyl groups having 1 to 6 carbon atoms in the alkyl moiety include alkyl groups (C 1 -C 4), (C 1 -C 6) alkoxy, (C 1 -C 4) haloalkyl, (C 1 -C 4) haloalkoxy, (C 1 -C 4) alkylthio, (C 1 -C 4) alkylsulfinyl (C 1 -C 4) alkylsulfonyl C1-C4 groups, halogen atoms, nitro, cyano, substituted or unsubstituted aryl groups, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted arylthio groups or unsubstituted heteroarylthio, unsubstituted, mono- or dihalo-substituted and / or non- or dimethyl-substituted cyclopropylmethoxy, substituted or unsubstituted alkynyl of 2 to 6 carbon atoms, unsubstituted or mono- to trihalosubstituted-6-substituted-alkenyl .

Suitable substituents for the latter aryl and heteroaryl radicals include halogen atoms, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl (e.g., trifluoromethyl) and C 1 -C 4 haloalkoxy groups. carbon (e.g., trifluoromethoxy).

Suitable substituents of the substituted or unsubstituted (C 2 -C 6) alkynyl group on the aryl (especially phenyl) group R ² are: (C 1 -C 4) alkyl, (C 1 -C 4) alkoxy, (C 1 -C 4) haloalkyl C 1 -C 4 (e.g., trifluoromethyl), C 1 -C 4 haloalkoxy (eg, trifluoromethoxy), C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, atoms halogen, nitro, cyano, substituted or unsubstituted phenyl, pyridoyl or benzoyl (wherein the substituents on the six-membered rings may be C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl ( especially trifluoromethyl C1 -C4 haloalkoxy (in particular trifluoromethoxy), C1 -C4 alkylthio, halogen atoms, nitro, cyano, C1 -C4 alkylsulfinyl and C1 -C4 alkylsulfonyl, and also unsubstituted or C 1 -C 4 acylated or C 1 -C 4 O-alkylated C 1 -C 4 hydroxyalkyl, C 1 -C 5 alkoxycarbonyl in the alkoxy moiety; N, N-di (alkyl) carbamoyl groups having 1 to 4 carbon atoms in each alkyl moiety; N-alkyl-N-alkoxycarbamoyl groups having 1 to 4 carbon atoms in the alkyl moiety and 1 to 4 carbon atoms in the alkoxy moiety; unsubstituted or halo-substituted cyclopropyloxycarbonyl or C 2 -C 5 alkenyl groups which are unsubstituted or substituted by C 2 -C 4 alkoxy and / or halogen; as well as five- or six-membered heteroaryl groups containing one or more heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, which may be unsubstituted or substituted by one or more substituents selected from the group consisting of halogen atoms, cyano, hydroxy, as well as alkyl groups of alkenyl groups , alkoxy, alkenyloxy and alkynyloxy groups each containing up to 4 carbon atoms.

Each substituent may be present one to three times independently of the others.

Thus, an important sub-group of the active compounds are the compounds of formula I in which:

R ¹ represents a hydrogen atom, a methyl, ethyl or cyclopropyl group,

R ² is a phenyl group having an unsubstituted or substituted ethynyl group in which the optional substituents are selected from alkyl groups having 1 to 4 carbon atoms (e.g. methyl and ethyl), hydroxyalkyl groups of 1 to 4 carbon atoms, halogen, haloalkyl (C 1 -C 4) groups, cyano, (C 1 -C 5) alkoxycarbonyl, cyclopropylmethoxycarbonyl, (C 2 -C 5) alkenyl groups which are unsubstituted or substituted by (C 2 -C 4) alkoxy and / or halogen , N-methyl-N-methoxycarbamoyl, unsubstituted or substituted phenyl (whose substituents are selected from C1-C4 alkyl, C1-C4 alkoxy, trifluoromethyl, cyano, halogen atoms (e.g. unsubstituted or substituted 5- to 6-membered heteroaryl groups (e.g., pyridyl, pyrazinyl, pyrimidinyl, thienyl or (iso) thiazolyl), the substituents of which may be selected from the group consisting of halogen, methyl, cyano methoxy and hydroxy, and

R ³ represents a methyl, ethyl or allyl group.

The invention, as a further important subgroup, relates to compounds of formula I wherein:

R ¹ represents a hydrogen atom, a methyl, ethyl or cyclopropyl group,

R ² is H, methyl, ethyl, cyclopropyl, cyano, methoxycarbonyl, -S (0) C 1 -C 4 alkyl carbon atoms, or a phenoxyphenyl or any of which, or alkoxy of 1 to 5 means a naphthyl, biphenyl, phenylthiophenyl ring system, the systems may be unsubstituted or substituted by one to three substituents selected from the group consisting of halogen atoms and alkyl groups having 1 to 2 carbon atoms, or represents a phenyl group bonded directly or through an oxygen atom, S (O) ) or CH which is unsubstituted or substituted by at most three substituents selected from C1 -C4 alkyl, C1 -C4 alkoxy, cyano, halogen atoms, trifluoromethyl, trifluoromethoxy, C2 -C4 alkynyl carbon atoms, nitros a -S (O) _n- C 1 -C 4 alkyl group and a cyclopropylmethoxy group which is unsubstituted or substituted on the ring by one or two halogen atoms, or represents a pyridine or pyrimidine ring which is bonded directly or through an oxygen atom or a group CH, or is a thiazoline or oxazoline ring which is unsubstituted or mono- or disubstituted by the same or different substituents selected from the group consisting of methyl and halogen atoms, and R ³ and n are as defined in the general formula

I.

An important sub-group of the latter are those in which R ¹ and R ³ are each methyl, and

R ² is a methyl group, a cyano group or a pyridine radical, or is phenyl, which is attached directly or via oxygen, S (O) n

or CH _and which is unsubstituted or substituted by at most three substituents selected from the group consisting of methyl, methylthio, methoxy, fluorine, chlorine, bromine, trifluoromethyl, trifluoromethoxy, propyn-2-yl, nitro, cyano and cyano or is a thiazole ring or a naphthyl, biphenyl or phenoxyphenyl ring system which is unsubstituted or substituted by up to two identical or different substituents selected from the group consisting of methyl and halogen atoms, and A and n have the meanings defined in the general formula

I.

A particularly important group includes those compounds of formula I wherein R ¹ , R ² and R ³ are each methyl, and

A is the above ring system.

The novel compounds of the formula I possess fungicidal, acaricidal and insecticidal properties and are suitable as agrochemical active substances for use in agriculture.

The invention further relates to a process for the preparation of these novel compounds, and to fungicidal, acaricidal and insecticidal compositions containing the compounds as active substances, and to the use of these compounds and compositions for controlling phytopathogenic fungi, mites and insects and preventing fungal infestation. , mites or insects.

When asymmetric carbon atoms are present in the compounds of formula I, these compounds exist in optically active forms. These compounds occur in each case in E- and / or Z-forms only because of the presence of aliphatic double bonds and oximine double bonds. In addition, atropisomerism may occur. Formula I is understood to include all these isomeric forms that are possible as well as mixtures thereof, for example racemic mixtures and any E / Z mixtures.

Depending on the number of carbon atoms, the alkyl and alkoxy groups are straight or branched and include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, sec. -pentyl, tert-pentyl or n-hexyl, etc.

Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Alkenyl is a straight or branched chain alkenyl group, for example, vinyl, 1-methylvinyl, allyl, 1-butenyl or isopropenyl.

Alkynyl is, for example, ethynyl, 1-propynyl, 1-butynyl or 1,3-butadiinyl.

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

The haloalkyl group may contain the same or different halogen atoms.

The aryl group is a phenyl or naphthyl group, preferably a phenyl group.

Heteroaryl groups are groups containing 5 to 9 ring members in one or two rings, of which 1 to 3 are heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen. 1 or 2 benzene rings may be fused to this heterocycle, wherein the entire group may be attached to the remainder of the molecule through both the heterocyclic moiety and the benzene moiety.

Examples include benzimidazolyl, benzisoxazolyl, benzisothiazolyl, benzokumarinylovú, benzofuryl, benzothiadiazolyl, benzothiazolyl, benzothienyl, benzoxazolyl, benzoxadiazolyl, quinazolinyl, quinolinyl, quinoxalinyl, carbazolyl, dihydrobenzofuranyl, furyl, imidazolyl, indazolyl, indolyl, isoquinolinyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, ethylenedioxyphenyl, naphthyridinyl, oxazolyl, purinyl, pyrazolof 3,4-pyrrolyl, thiazolyl, phenantridinyl, phthalazinyl, pteridinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridyl, pyridyl, thiazolyl, pyridyl, thiazolyl, thiazolyl, thiazolyl, thiazolyl, pyridyl, thiazolyl, pyridyl, thiazolyl, thiazolyl, pyridyl, thiazolyl;

Preferred are pyridyl, pyrazinyl, thiazolyl, quinolyl and thienyl groups.

pyrimidinyl,

Heterocyclyl groups are 5- to 7-membered non-aromatic rings containing 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur. Preferred are aromatic 5- to 6-membered rings containing a nitrogen atom as a heteroatom and, if desired, a further heteroatom, preferably a nitrogen or sulfur atom, especially nitrogen.

Thiazolinyl and oxazolinyl are preferred.

A) A compound of formula I can be prepared by reacting an oxime of formula II

HONv.

(II) wherein R ¹ , R ² and R ^{3 have the} meanings defined for formula I with a benzyl derivative of formula III or IV

H ₃ C _x

u (III)

wherein W is as defined for formula I and U is a leaving group.

This reaction is a nucleophilic substitution which can be carried out under the corresponding conventional reaction conditions. The leaving group U present in the benzyl derivative of the general formula III or IV is preferably chlorine, bromine, iodine, mesyloxy or tosyloxy. The reaction is preferably carried out in an inert organic diluent such as a cyclic ether, for example tetrahydrofuran or dioxane, acetone, dimethylformamide, in the presence of a base such as sodium hydride, sodium or potassium carbonate, sodium amide, tertiary amine such as trialkylamine, especially diazabicyclononan or diazabicycloundecane, or silver, at temperatures between -20 ° C and +80 ° C, preferably at a temperature ranging from 0 ° C to 50 ° C.

Alternatively, the reaction may be carried out at room temperature using a phase transfer catalyst in an organic solvent such as toluene in the presence of an aqueous alkaline solution such as sodium hydroxide solution and a phase transfer catalyst such as tetrabutylammonium hydrogen sulfate.

The compounds of formula I thus prepared can be isolated and purified by known methods. The mixtures of isomers obtained, for example mixtures of E- and Z-isomers, can also be resolved by known methods into pure isomers, for example by chromatography or fractional crystallization.

The oximes of the formula II used as starting materials are either known or can be prepared by known methods (J. Chem. Soc., Perkin Trans. II 537 (1990); Ber. Deutsch. Chem. Ges. 62, 866 (1929)). Gazz Chim Ital 37, 147 (1907) Liebigs Ann Chem 262, 305 (1891)).

Similarly, the benzyl derivatives of formulas III and IV used as starting materials are either known or can be prepared by known methods.

B) Compounds of formula I wherein R ¹ to R ^{3 are} as defined above and W represents a sulfur atom may be further prepared by cautiously reacting compounds of formula I wherein W represents an oxygen atom with a sulfurizing agent such as phosphorus pentasulfide or Lawesson's reagent, for example 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide (see, in this regard, Cava + Lawesson, Tetrahedron 41, 5061 (1985)).

C) Compounds of formula I wherein A is a group

and W represents an oxygen atom, may be further prepared according to Scheme 1 below.

The individual reaction steps may be carried out analogously to Rolf H. Prager and Jason A. Smith in Aust. J. Chem. 48, 217-226 (1995).

Scheme 1

base dimethyl sulphate no.

methyl iodide or (CH ₃ ) ₃ OBF ₄ or q-ch = n ₂ Q = Hci (CH ₃ ) ₃ Si

IN

- ^CH 3

As can be seen from the above scheme, malonic acid esters of formula 3 and isoxazolone derivatives of formula 8 are important intermediates and are a further object of the invention.

d) Compounds of formula I wherein A is a group

can be further prepared according to Scheme 2 below.

The individual reaction steps may be carried out analogously to that described by Arndt et al. v Rev. Fac. Sci. Istanbul [A] 13, 127 et seq. (Beilstein E III / IV 26674)

Scheme 2

(ch ₃ ) _{3 s}

XH, base

R NHNHj

-►

N-N '

R

The compound of formula I is obtained by reaction of the oxime of formula II

HON (II), wherein R ¹ to R ^{3 are} as defined in formula (I), with an iodobenzyl derivative of formula (V) in which U represents a leaving group.

The compound of formula 14 is obtained by subjecting a nitro derivative of formula VI to catalytic hydrogenation.

(VI)

As can be seen, nitrophenyl derivatives of formula VI, aniline derivatives of formula 14, iso (thio) cyanates of formula 17 and (thio) guanidine derivatives of formula 19 are important intermediates for obtaining (thio) triazolone derivatives of formulas 22 and 23. The invention further relates to also those intermediates in which the substituents R ¹ to R ⁸ , X and W have the meanings defined in the general formula I.

Compounds of formula VI are prepared by reacting an oxime of formula II with a nitrobenzyl derivative of formula VII (VII),

NO _Z wherein U represents a leaving group.

It has now been found that the compounds of the formula I exhibit a microbicidal spectrum which is advantageous for practical needs for the control of phytopathogenic microorganisms, especially fungi. They have very advantageous curative, preventive and especially systemic properties and can be used to protect a number of plants. Pests of plants or parts of plants (fruits, flowers, leaves, stems, tubers, roots) of different crops can be controlled or destroyed using the active compounds of the formula I, even those parts of the plants which develop later are protected against phytopathogenic microorganisms. .

The compounds of the formula I can also be used as seed dressing agents, for seed treatment (fruits, tubers, grains) and nurseries, i.e. for the treatment of propagation material of any kind, for protection against fungal infections and phytopathogenic fungi occurring in plants. soil.

The compounds of the formula I are active, for example, against the following classes of phytopathogenic fungi: Fungi imperfecti (in particular Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora, Cercosporella and Alternaria), Basidiomycetes (e.g. Rhizoctonia, Hemileia, Pucciniaes) , Podosphaera, Monilinia, Uncinula), in particular against Oomycetes (e.g., Phytophthora, Peronospora, Bremia, Pythium, Plasmopara). The compounds of the formula I also exhibit an insecticidal and acaricidal action, in particular against insect bites and suckers.

The target crops for the plant protection uses described herein include, for example, the following plant types: cereals (wheat, barley, rye, oats, triticale, rice, maize, sorghum and related species), beets (sugar beet and fodder beet), pome, stone and soft fruits (apple, pears, plums, peaches, almonds, cherries, strawberries, gooseberry, raspberries and blackberries), legumes (beans, lentils, peas, soybeans), oilseeds (rape, mustard, poppy, olives, sunflower, coconut, castor, cacao, groundnut), pumpkin plants (pumpkins, cucumbers, melons), fiber plants (cotton, flax, hemp, jute), citrus-producing plants (oranges, lemons, grapefruits, mandarins), vegetables ( spinach, lettuce, asparagus, cabbage vegetables, carrots, onions, tomatoes, potatoes, peppers), laurel plants (avocado, cinnamon, camphor), and plants such as tobacco, nuts, coffee, sugar cane, tea k, pepper and other spice-producing plants, vines, hops, edible, banana, rubber and flowers and ornamental plants.

The active compounds of the formula I are usually used in the form of compositions and can be applied to the area or plants to be treated simultaneously or sequentially with the other active ingredients. These other active ingredients may be fertilizers, trace element providing agents or other preparations which have an impact on plant growth. In this connection, selective herbicides as well as insecticides, fungicides, bactericides, nematicides, mulosicides or mixtures of two or more of these formulations, if desired, can be used together with other carriers, surfactants or other application-improving additives which do not adversely affect the efficacy compounds of formula I commonly used in the art of formulation.

Suitable carriers and additives may be solid or liquid and include materials suitable for use in formulating compositions, for example, natural or regenerated minerals, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.

Suitable solvents are: aromatic hydrocarbons, preferably fractions containing 8 to 12 carbon atoms, for example xylenes or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols as well as their ethers and esters such as is ethanol, ethylene glycol, monomethyl ether or monoethylether of ethylene glycol, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, and unmodified or epoxidized vegetable oils such as epoxidized coconut oil or coconut oil or or water.

Solid carriers which are generally used, for example, for dusts and dispersible powders are ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.

In addition, natural (animal or vegetable) or synthetic phospholipids from the group of cephalins and lecithins, which can be obtained, for example, from soybeans, are particularly preferred application-improving additives which can lead to a large reduction in the application rate.

Depending on the nature of the active ingredient of the formula I to be incorporated into the composition, suitable surface-active compounds are nonionic, cationic and / or anionic surfactants which exhibit good emulsifying, dispersing and wetting properties. It is understood that the term surfactant also includes mixtures of surfactants.

Suitable anionic surfactants can be so-called water-soluble soaps and also water-soluble synthetic surface-active compounds.

Soaps are alkali metal, alkaline earth metal salts or substituted or unsubstituted ammonium salts of higher fatty acids (containing 10 to 22 carbon atoms), for example sodium or potassium salts of oleic or stearic acid, or natural mixtures of fatty acids, which can be obtained, for example, from coconut oil or tallow oil. Other substances that may be mentioned are fatty acid methyltaurides.

Suitable nonionic surfactants are polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, the derivatives of which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl .

Examples of nonionic surfactants which may be mentioned include nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene adducts with polyethylene oxide, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Other suitable substances are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

In particular, the cationic surfactants are quaternary ammonium salts which carry as a substituent on the nitrogen atom at least one alkyl radical containing 8 to 22 carbon atoms, as further substituents lower unsubstituted or halogenated, alkyl groups, benzyl groups or lower hydroxyalkyl radicals.

The anionic, non-ionic or cationic surfactants commonly used in formulation are known to the person skilled in the art, or can be found in the corresponding literature:

Mc Cutcheon 's Detergens and Emulsifiers Annual, Mc

Publishing Corp., Glen Rock, New Jersey, 1988,

M. and J. Ash, Encyclopedia of Surfactants, Vol

I-III, Chemical Publishing Co., New York, 1980-1982,

- Dr. Helmut Stache dating in Tensid-Taschenbuch, Carl Hanser

Verlag, Munich / Vienna, 1982.

The agrochemical preparations generally contain 0.1 to 99%, in particular 0.1 to 95%, of the active compound of the formula I, 99.9 to 1%, in particular 99.9 to 5%, of a solid or liquid additive, and 0 to 25% in particular 0.1 to 25% of a surfactant.

While concentrated formulations are preferable as commercial products, the end consumer typically uses dilute formulations.

The compositions may also contain other additives such as stabilizers, anti-foaming agents, viscosity regulators, binders, tackifiers and fertilizers or other active ingredients to achieve special effects.

Formulations, i. j. compositions, preparations or combinations containing the active ingredient of the formula I and, if desired, a solid or liquid additive, are prepared in a known manner, for example by thoroughly mixing and / or grinding the active ingredient with a filler, for example a solvent (or mixture thereof), and, if desired, surface-active compounds (surfactants).

A preferred method of administering an active ingredient of the formula I or an agrochemical composition comprising at least one of these active ingredients is by foliar application. The application rate and application rate in this case depend on the degree of pathogen. However, the active compounds of the formula I can also be introduced into the plant by a root system (systemic effect) when a liquid preparation is applied to the plant site or the substances in solid form are incorporated into the soil, for example in the form of granules (soil application). In the case of rice, such granules may be applied to a flooded rice field. However, the compounds of formula (I) may also be applied to the seeds (coating), wherein a liquid preparation containing the active substance or coated with a solid preparation is applied to the seeds or applied. In principle, any kind of plant propagation material, such as seeds, roots, stems, branches, or shoots, can be protected using the compounds of formula I.

The compounds of formula (I) are used herein in pure form or preferably together with carriers and excipients commonly used in formulating compositions. For this purpose, they are preferably formulated in known manner, for example, into emulsion concentrates, spreadable pastes, solutions suitable for direct spraying or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts or granules. They may also be encapsulated, for example in polymeric substances. Application methods such as spraying, dew-spraying, dusting, spreading, spreading or pouring, as well as the type of composition, are selected according to the desired results and prevailing conditions. Preferred application rates are generally from 1 g to 2 kg of active ingredient per hectare, preferably 25 g to 800 g of active ingredient per hectare, particularly preferably 50 g to 400 g of active ingredient per hectare. When used as seed dressing agents, doses of 0.001 g to 1.0 g of active ingredient per kg of seed are preferably used.

The invention is illustrated in more detail by the following examples without limiting its scope in any way.

DETAILED DESCRIPTION OF THE INVENTION

1. Preparation examples

Example 1

Preparation of a compound of formula

0.22 g of a 60% sodium hydride dispersion was washed with hexane and 5 ml of Ν, Ν-dimethylformamide was added. To this suspension is added

1.5 g of 4- (ortho-bromomethylphenyl) -2,3-dihydro-5-methoxy-2-methyl-3-isoxazolone and 0.65 g of 3-methoxyimino-2-butanone oxime are added and the reaction mixture is stirred for 1 hour. Ice water was then added and the mixture was extracted with ethyl acetate. The organic phase is washed with saturated sodium bicarbonate solution and then with saturated sodium chloride solution. After drying over anhydrous sodium sulfate, the solvent was distilled off in vacuo and the residue was chromatographed on silica gel using ethyl acetate / hexane (1: 2) as eluent to give compound no. 1.1 with a melting point of 100-107 ° C.

Example 2

Preparation of a compound of formula

To a solution of 1 g of the compound obtained in Example 1 in 10 ml of toluene is added 0.7 g of Lawesson's reagent and the suspension formed is then heated at 100 ° C for 2 hours. The mixture was diluted with ethyl acetate and washed with water. The organic phase is dried over sodium sulphate and the solvent is distilled off in vacuo. The residue was chromatographed on silica gel using ethyl acetate / hexane (1: 3) as the eluent to give compound no. 2.1 in the form of a yellow oil.

Example 3

Preparation of a compound of formula

F

(compound 6.91)

a) 8.95 g of 5-chloro-2-methyl-4- (o-tolyl) -2,4-dihydro [1,2,4] triazol-3-one (prepared according to WO 95) are introduced into 50 ml of carbon tetrachloride (14009) and 7.83 g of N-bromosuccinimide, and a catalytic amount of dibenzoyl peroxide is added. The suspension was then stirred under reflux for 1.5 hours under irradiation with a 500-Watt photo lamp. The suspension is concentrated by evaporation and the residue is directly chromatographed on silica gel using hexane / ethyl acetate 6: 4 as eluent. Recrystallization from toluene / heptane 1: 1 gives 4- (2-bromomethylphenyl) -5-chloro-2-methyl-2,4-dihydro [1,2,4] triazol-3-one as white crystals mp 131.5-133 ° C.

^X H-NMR (CDCl) 6 value: 7.52 (m, 3H), 7.23 (m, IH), 4.6 (d, IH), 4.33 (d, IH), 3.57 (s, 3H)

b) 1.6 g of 1-methoxyimino-1- (2,4-difluorophenyl) -2-propanone oxime and 2.12 g of 4- (2-bromomethylphenyl) -5-chloro-2-methyl-2,4-dihydro [ 1,2,4] triazol-3-one was stirred at reflux in the presence of 1.45 g of potassium carbonate in 20 ml of acetonitrile for 2.5 hours. The mixture was then concentrated and the residue was directly chromatographed on silica gel using hexane / ethyl acetate (65:35) as eluent to give compound no. 6.91 in waxy form. @ 1 H-NMR (CDCl3) .delta. 6: 7.5-6.7 (m, 7H),

5.05 (d, 1H), 4.91 (d, 1H), 3.93 (s, 3H), 3.52 (s, 3H),

2.12 (s, 3H)

The following compounds, which fall within the scope of the invention, can be prepared in the same manner or analogously to one of the above methods.

@ 1 H-NMR values are chemical shifts reported in S (ppm) in deuterochloroform.

Claims (20)

of formula I Bis-oxime derivative of triazoline or isoxazoline in general ^O- r, 3 NR (I) in which A R ¹ R ² is an H ₃ C X wherein W represents an oxygen atom or a sulfur atom, and represents a hydrogen atom, a C 1 -C 4 alkyl group or a cyclopropyl group, means hydrogen, alkyl group with 1 to 6 carbon alkyl, haloalkyl p 1 to 6 carbon alkyl, alkoxyalkyl group with 2 to 6 carbon alkyl, cycloalkyl group with 3 to 6 carbon alkyl, substituted or unsubstituted aryl group substituted or unsubstituted heteroaryl, cyano, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkyl-S (O) C 1-6, substituted or unsubstituted aryl-S (O) _n , C 1 -C 6 alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted heteroaryloxy, unsubstituted or mono- to trimethyl-substituted heterocyclyl, substituted or unsubstituted arylalkyl of 1 to 6 carbon atoms in the alkyl moiety, or substituted or unsubstituted heteroarylalkyl of 1 to 6 carbon atoms . R ³ is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 5 haloalkyl, C 1 -C 4 alkoxyalkyl and C 1 -C 2 alkyl , unsubstituted or mono- to tri-halo-substituted alkenyl of 1 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, or unsubstituted or mono- to tetrahalo-substituted cycloalkylalkyl of 3 to 6 carbon atoms in the cycloalkyl portion of 1 to 4 carbon atoms n is 0 to 2, R @ 5 represents a hydrogen atom, a C1 -C4 alkyl group, a C1 -C4 haloalkyl or a C3 -C6 cycloalkyl group, X is 0R ^a, SR ^5, NR ^e R ⁷ or halogen, in particular chlorine, and R symbols R® ^-7, independently of one another are hydrogen, alkyl having 1 to 4 carbon atoms, alkenyl having 3 to 4 carbon atoms or a (C až-C alk,) alkynyl group; and ^R is alkyl having 1 to 4 carbon atoms or haloalkyl having 1 to 3 carbon atoms. 100 A bis-oxime derivative of the general formula I according to claim 1, in which R ^a represents a methyl group, X is methoxy, R ² is as defined in claim 1, with the exception of haloalkyl having 1 to 6 carbon atoms, and R ¹ , R ³ , and W have the meanings defined in claim 1. A bis-oxime derivative of the general formula I according to claim 1, in which R ¹ represents a hydrogen atom, a methyl, ethyl or cyclopropyl group, R ³ represents a phenyl group bearing an unsubstituted or substituted ethynyl group, wherein the optionally present substituents are selected from the group consisting of alkyl groups of 1 to 4 carbon atoms, hydroxyalkyl groups of 1 to 4 carbon atoms, halogen atoms, haloalkyl groups of 1 to 4 carbon atoms , cyano, (C 1 -C 5) alkoxycarbonyl, cyclopropylmethoxycarbonyl, (C 2 -C 5) alkenyl groups which are unsubstituted or substituted by alkoxy and / or halogen, N-methyl-N-methoxycarbamoyl or unsubstituted a phenyl group whose substituents are selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, trifluoromethyl, cyano, halogen atoms, and trifluoromethoxy, and unsubstituted or substituted five to six. 1 membered heteroaryl groups whose substituents may be selected from the group consisting of halogen atoms, cyano, methyl, methoxy and hydroxy, and R ³ represents a methyl, ethyl or allyl group. A bis-oxime derivative of the general formula I according to claim 2, in which R ¹ represents a hydrogen atom, a methyl, ethyl or cyclopropyl group, R ² is H, methyl, ethyl, cyclopropyl, cyano, methoxycarbonyl, -S (O) _n C 1 -C 4 alkyl or C 1 -C 5 alkyl, or is a naphthyl, biphenyl, a phenoxyphenyl or phenylthiophenyl ring system, each of which may be unsubstituted or substituted by one to three substituents selected from the group consisting of halogen atoms and alkyl groups having 1 to 2 carbon atoms, or a phenyl group bonded directly or through an oxygen atom, S ( O) alebo or CH ^ which is unsubstituted or substituted by at most three substituents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen atoms, trifluoromethyl, trifluoromethoxy, C 2 -C 4 alkynyl 4 carbon atoms, nitro, p -S (O) _n- C 1 -C 4 -alkyl and cyclopropylmethoxy which is unsubstituted or substituted on the ring by one or two halogen atoms or represents a pyridine or pyrimidine ring which is bonded directly or through an oxygen atom or a CH ₂ group . 102 or is a thiazoline or oxazoline ring which is unsubstituted or mono- or disubstituted by the same or different substituents selected from the group consisting of methyl and halogen atoms, and R ³ and n have the meanings defined in general formula I. The bis-oxime derivative of the general formula I according to claim 4, wherein R ¹ and R ³ are each methyl, and R ² is a methyl group, a cyano group or a pyridine radical, or is phenyl, which is attached directly or via oxygen, S (O) _n or a group CH, and which is unsubstituted or substituted by up to three substituents selected from the group consisting of methyl methylthio, methoxy, fluoro, chloro, bromo, trifluoromethyl, trifluoromethoxy, propyn-2-yl, nitro and cyano, or a thiazole ring or a naphthyl, biphenyl or phenoxyphenyl ring system which is unsubstituted up to two of the same or different substituents selected from the group consisting of methyl and halogen atoms, and A and n are as defined in formula I. A bis-oxime derivative of the formula I according to claim 1, in which R ¹ , R ² and R ³ are each a methyl group, and 103 A is a ring system as defined in claim 1. A process for the preparation of a bis-oxime derivative of the formula I, characterized in that the oxime of the formula II is used HON NR (II), in which R ¹ , R ² and R ^{3 are} as defined in formula I, is reacted with a benzyl derivative of formula III or IV U (III) (IV), where I and W is as defined for U represents a leaving group. of the general formula A method according to claim 7, characterized in that Use of a benzyl derivative of the formula III or IV in which U represents a chlorine atom, a bromine atom, an iodine atom, a mesyloxy group or a tosyloxy group and the reaction is carried out in an inert organic diluent in the presence of a base at -20 ° C to +80 ° C 104 A pesticidal composition, in which, as an active ingredient of the formula I according to claim 1, a material. characterized in that it comprises a bis-oxime derivative 1 together with a suitable carrier 10. A composition as defined in claim 1, wherein the active ingredient is as defined in claim 1 9, comprising a bis-oxime derivative according to any one of claims 2 to 6. 11. A method for controlling and preventing infestation of plants by microorganisms, mites or insects, characterized in that a bis-oxime derivative of the general formula I is applied as an active substance to plants, parts of plants or to the plant nutrient medium. Method according to claim 11, characterized in that the propagation material is treated. A method according to claim 12, characterized in that the seeds are treated. Use of a bis-oxime derivative of the formula I for controlling or preventing attack by microorganisms. Use of a bis-oxime derivative of the general formula I for controlling Acarina insects and pests. 16. The ester malonic acid derivative of formula 3 wherein R ⁴ is methyl or ethyl, and the radicals R ^1, R ² and R ³ are as defined in general 105 Formula I. An isoxazolone derivative of general formula 8 wherein R ¹ , general formula I. R ² and R ³ are as defined for A nitrophenyl derivative of the general formula VI NOj (VI), in which R ¹ , R ² and R ^{3 have the} meanings defined in general formula I. An aniline derivative of the general formula 14 NH 3 R 4 - ^N · -0- J O NR R '(14), wherein R ¹ , R ² and R ^{3 are} as defined in formula (I). 106 20th An iso (thio) cyanate of formula 17 (17) wherein R ¹ , R ^2, and R ² 21st W is O or S, and R ³ is as defined in Formula I. (Thio) guanidine derivative of formula 19 wherein R ^1, R ^2, and W is O or S, and R ³ is as defined in Formula I.