EP1003742A1 - Methoximinomethyloxadiazines used as pesticides - Google Patents

Abstract

The invention relates to new methoximinomethyloxadiazines, two methods for their production, and their use as pesticides. The invention also relates to new intermediary products and a method for their production.

Description

 METΉOXIMINOMETΉYLOXADIAZINE AS PESΉZIDE

The invention relates to new methoximinomethyloxadiazines, two processes for their preparation and their use as pesticides and new intermediates and processes for their preparation.

It has already become known that certain methoximinomethyloxadiazines have a fungicidal action (WO 96-25406). However, the action of these previously known compounds is not entirely satisfactory in all areas of application, especially at low application rates and concentrations.

The new methoximinomethyloxadiazines of the general formula (I) have now been found

in which

Z for optionally substituted cycloalkyl, aryl, arylalkyl,

Heterocyclyl or heterocyclylalkyl,

Q represents oxygen or sulfur,

X represents halogen, L *, \ 7, \ A ^> and \ 7 are the same or different and each independently represent hydrogen, halogen, cyano, nitro, each optionally substituted by halogen substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl.

In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkanediyl, alkenyl or alkynyl, are in each case straight-chain or branched, also in combination with heteroatoms, such as, for example, in alkoxy, alkylthio or alkylamino.

Aryl stands for aromatic, mono or polycyclic hydrocarbon rings, e.g. Phenyl, naphthyl, anthranyl, phenanthryl, preferably phenyl or naphthyl, especially phenyl.

Heterocyclyl stands for saturated or unsaturated, as well as aromatic, ring-shaped

Compounds in which at least one ring member has a heteroatom, i.e. H. is an atom other than carbon. If the ring contains several heteroatoms, these can be the same or different. Heteroatoms are preferably oxygen, nitrogen or sulfur. If the ring contains several oxygen breaths, these are not adjacent. If appropriate, the ring-shaped compounds together with other carbocyclic or heterocyclic, fused or bridged rings together form a polycyclic ring system. Mono- or bicyclic ring systems are preferred, in particular mono- or bicyclic aromatic ring systems.

Cycloalkyl stands for saturated, carbocyclic, ring-shaped compounds which optionally form a polycyclic ring system with other carbocyclic, fused or bridged rings.

It has also been found that the new methoximinomethyloxadiazines of the general formula (I) can be obtained if

a) 3- (2-hydroxy-phenyl) -3-methoxyiminomethyl-oxadiazines of the formula (II),

in which

L, l, \ 7, \ Ä and \ 7 have the meanings given above,

with a substituted halopyrimidine of the general formula (III),

in which

Z, Q and X have the meanings given above and

γl represents halogen,

if appropriate in the presence of a diluent, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a catalyst, or if

b) phenoxypyrimidines of the general formula (IV)

in which

X, L, l, \ 7, L ^J and \ 7 have the meanings given above and

Y ^ represents halogen,

with a ring compound of the general formula (V),

Z-Q-H (V)

in which

Z and Q have the meanings given above,

if appropriate in the presence of a diluent, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a catalyst

Finally, it was found that the new methoximinomethyloxadiazines of the general formula (I) show a very potent fungicidal action

The compounds according to the invention can optionally be present as mixtures of various possible isomeric forms, in particular of stereoisomers, such as, for example, E- and Z-. Both the E- and the Z-isomers, as well as any mixtures of these isomers, are claimed. The invention preferably relates to compounds of the formula (I) in which ^■

Z for each cycloalkyl or cycloalkylalkyl which is optionally mono- to pentasubstituted by halogen or alkyl, each having 3 to 7 carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the alkyl part;

for heterocyclyl or heterocyclylalkyl optionally substituted by halogen or alkyl having 1 to 4 carbon atoms, each having 3 to 7 ring members and 1 to 4 carbon atoms in the alkyl part;

or for aryl or arylylalkyl, each of which is monosubstituted to tetrasubstituted or substituted in the aryl part, in each case optionally with 6 to 10 carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part, the possible substituents preferably being selected from the list below:

Halogen, cyano, nitro, amino, formyl, carbamoyl, thiocarbamoyl;

in each case straight-chain or branched alkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 8 carbon atoms;

each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms;

in each case straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms; in each case straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 1 1 identical or different halogen atoms;

each straight-chain or branched alkylamino, dialkylamino,

Alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, arylalkylaminocarbonyl, alkenylcarbonyl or alkynylcarbonyl, with 1 to 6 carbon atoms in the respective hydrocarbon chains;

Cycloalkyl or cycloalkyloxy each having 3 to 6 carbon atoms;

each optionally monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, oxo, methyl, trifluoromethyl or ethyl and in each case doubly linked alkylene having 3 or 4 carbon atoms, oxyalkylene

2 or 3 carbon atoms or dioxyalkylene with 1 or 2 carbon atoms;

A ¹ or a grouping j | , in which

A ^ represents hydrogen or alkyl having 1 to 4 carbon atoms or cycloalkyl having 3 to 6 carbon atoms and

A ^{2 represents} hydroxy, amino, methylamino, methyl, phenyl, benzyl, alkoxy, alkylamino, dialkylamino with 1 to 4 carbon atoms in the respective alkyl chains,

represents oxygen or sulfur, X represents fluorine, chlorine or bromine, preferably fluorine or chlorine and in particular fluorine and

LI, \ 7-, L and L * are the same or different and independently of one another each for hydrogen, halogen, cyano, nitro, in each case optionally substituted by 1 to 5 halogen atoms, alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms, preferably hydrogen or methyl and especially hydrogen

The invention relates in particular to compounds of the formula (I) in which

Z for each optionally up to five times by fluorine, chlorine, methyl or

Ethyl substituted cyclobutyl, cyclopentyl or cyclohexyl,

for optionally substituted by methyl, ethyl, fluorine, chlorine or bromine

Thienyl, pyridyl, furyl, thienylmethyl, pyridylmethyl or furylmethyl,

or is in each case optionally monosubstituted to tetrasubstituted, identical or differently substituted phenyl or benzyl, the possible substituents preferably being selected from the list below

Fluorine, chlorine, bromine, cyano, nitro, amino, formyl, carbamoyl, thiocarbamoyl,

Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxymethyl,

Methoxy, ethoxy, n- or i-propoxy,

Methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl,

Methylaminomethyl, dimethylaminomethyl, Vinyl, allyl, 2-methylallyl, propen-1-yl, crotonyl, propargyl, vinyloxy, allyloxy, 2-methylallyloxy, propen-1-yloxy, crotonyloxy, propargyloxy;

Trifluoromethyl, trifluoroethyl,

Difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, pentafluoroethoxy, 2-chloro-l, l, 2-trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl, or trifluoromethyl

Methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino,

Acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl,

Ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, acryloyl, propioloyl,

Cyclopentyl, cyclohexyl,

each optionally optionally up to four times, the same or different, substituted by fluorine, chlorine, oxo, methyl or trifluoromethyl, in each case twice linked propanediyl, ethyleneoxy, methylenedioxy, ethylenedioxy

or a grouping J, where

A represents hydrogen or methyl and

A ^{2 represents} hydroxy, methoxy, ethoxy, amino, methylamino, methyl, phenyl or benzyl, Q represents oxygen or sulfur,

X represents fluorine or chlorine, in particular fluorine and

i, L ² , L ^J and L are the same or different and are each independently hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, di-fluorochloromethoxy, trifluoromethylthio, difluoromethylthio, difluoromethyl

Trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, preferably stand for hydrogen or methyl and in particular for hydrogen.

The general or preferred radical definitions given above apply both to the end products of the formula (I) and correspondingly to the starting materials or intermediates required in each case for the preparation.

The radical definitions specified for these radicals in the respective combinations or preferred combinations of radicals are independently replaced by radical definitions of other preferred ranges, regardless of the combination specified in each case.

Formula (II) provides a general definition of the 3- (2-hydroxy-phenyl) -3-methoxyiminomethyl-oxadiazines required as starting materials for carrying out process a) according to the invention. In this formula (II), \ 7, L ² , L-> and l7 preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or as particularly preferred for L ^ , L ² , L ^ and \ 7 were specified.

The starting materials of formula (II) are new and also the subject of the present application. They are obtained (process c) if benzofürandione dioximes of the general formula (VI),

in which

L, I, L ² , L, 3 and \ 7 have the meanings given above and

Y ^ represents halogen, alkylsulfonyl or arylsulfonyl,

with ammonia, if appropriate in the presence of a diluent and if appropriate under elevated pressure.

Formula (VI) provides a general definition of the benzofürandione dioximes required as starting materials for carrying out process c) according to the invention. In this formula (VI), i, L ² , L ^ and L ^ preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred for L. , L ² , L and \ 7 were specified. Y ^J represents halogen, preferably chlorine or bromine, or alkylsulfonyl or arylsulfonyl, preferably methylsulfonyl, benzylsulfonyl or tolylsulfonyl.

The starting materials of formula (VI) are new and also the subject of the present application. They are obtained if (process d) hydroxyethylbenzofürandione dioximes of the formula (VII)

in which

L, I, L ² , L ^J and \ 7 have the meanings given above,

with an alkyl or arylsulfonyl chloride or a halogenating agent, if appropriate in the presence of a diluent and if appropriate in the presence of a base.

Formula (VII) provides a general definition of the hydroxyethylbenzofürandione dioximes required as starting materials for carrying out process d) according to the invention. In this formula (VII), i, L ² , L ^J and \ 7 preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred for L, L ² , L ^J and l7 were given.

The starting materials of the formula (VII) are obtained if, for example, an optionally substituted benzofüranone (X) (compare, for example, Chem.Ber., 30 <1897>, 1081) is first reacted with methoxyamine to give a benzofüranone oxime (IX) which contains benzofüranone oxime (IX ) then nitrosated with an alkyl nitrite and the dioxime (VIII) obtained is finally alkylated with, for example, oxirane

(see also the manufacturing examples):

Alkylnitπt

(VII) (VIII)

To carry out process d) according to the invention, an alkyl or arylsulfonyl chloride or a halogenating agent is furthermore required. Alkyl, arylsulfonyl chloride, methyl, ethyl, phenyl or tolylsulfonyl chloride are preferably suitable. All reagents which contain hydroxyl groups bonded to carbon are suitable as halogenating agents can be exchanged for halogens Examples include phosgene, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, thionyl chloride or thionyl bromide

The halopyrimidines still required as starting materials for carrying out the process a) according to the invention are generally defined by the formula (III) In this formula (III) Z, Q and X preferably or in particular have those meanings which have already been associated with the description of the compounds according to the invention of the formula (I) as preferred or as particularly preferred for Z, Q and X γ stands for halogen, preferably for fluorine or chlorine

The starting materials of the formula (III) are known (compare, for example, DE-A 4340181, Chem Ber., 90 <1957> 942, 951) and / or can be prepared by known methods. are provided, for example by reaction of the trihalopyrimidines of the formula (XI) (see below) with ring compounds of the formula (V) (see below).

Formula (IV) provides a general definition of the phenoxypyrimidines required as starting materials for carrying out process b) according to the invention. In this

Formula (IV) has X, L ', L ² , L ^J and \ 7 preferably or in particular those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred for X, L, L ² , L ^J and L + were given. Y ² represents halogen, preferably fluorine or chlorine.

The starting materials of formula (IV) are new and also the subject of the present application.

The phenoxypyrimidines of the general formula (IV) are obtained (process e) if 3- (2-hydroxyphenyl) -3-methoxyiminomethyl-oxadiazines of the formula (II) with a trihalopyrimidine of the general formula (XI)

in which

X, γl and Y ^{2 are the} same or different and each represents halogen,

if appropriate in the presence of a diluent, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a catalyst.

The 3- (2-hydroxyphenyl) -3-methoxyiminomethyl-oxadiazines of the formula (II) required as starting materials for carrying out the process e) according to the invention have already been described in connection with the description of the method a) according to the invention.

Formula (XI) provides a general definition of the trihalopyrimidines required as starting materials for carrying out process e) according to the invention.

In this formula (XI) X, Y ¹ and Y ^{2 represent} halogen, preferably fluorine or chlorine.

The trihalopyrimidines of the formula (XI) are known and / or can be prepared by known methods (compare, for example, Chesterfield et al., J. Chem.

Soc, 1955; 3478, 3480).

Formula (V) provides a general definition of the ring compounds which are further required as starting materials for carrying out process b) according to the invention. In this formula (V), Z and Q preferably or in particular have those meanings which have already been stated as preferred or as particularly preferred for Z and Q in connection with the description of the compounds of the formula (I) according to the invention.

The ring compounds of the formula (V) are known synthetic chemicals or can be prepared by simple methods.

Suitable diluents for carrying out processes a), b) and e) according to the invention are all inert organic solvents. These preferably include ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Sulfoxides, such as dimethyl sulfoxide; or sulfones, such as sulfolane. Suitable diluents for carrying out process c) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin, ether, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-

Amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide, sulfoxides, such as Dimethyl sulfoxide, sulfones such as sulfolane, alcohols such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol,

Ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water

Suitable diluents for carrying out process d) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin, halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane, ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1, 2- dimethoxyethane, 1,2-diethoxyethane or anisole, ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone, nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile, amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, esters such as methyl acetate or acetic acid aureethyl ester, sulfoxides such as dimethyl sulfoxide, sulfones such as sulfolane

The processes a), b) and e) according to the invention are, if appropriate, carried out in the presence of a suitable acid acceptor. All customary inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, alcoholates, carbonates or hydrogen carbonates, such as sodium hydride, sodium amide, potassium tert-butoxide, Sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium hydrogen carbonate or sodium hydrogen carbonate.

Process d) according to the invention is optionally carried out in the presence of a suitable acid acceptor. All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide , Potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, Pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

All copper (I) salts, such as, for example, copper (I) chloride, copper (I) bromide or copper (I) iodide, are suitable as catalysts for processes a), b) and e) according to the invention.

The reaction temperatures can be varied within a substantial range when carrying out processes a), b) and e). In general, temperatures from -20 ° C to 100 ° C, preferably at temperatures from -10 ° C to 80 ° C.

The reaction temperatures can be varied within a substantial range when carrying out process c) according to the invention. In general, temperatures from 20 ° C to 250 ° C, preferably at temperatures from 50 ° C to 150 ° C.

The reaction temperatures can be varied within a substantial range when carrying out process d) according to the invention. Generally you work at temperatures from -20 ° C to 80 ° C, preferably at temperatures from -10 ° C to 40 ° C.

To carry out process a) according to the invention for the preparation of the compounds of the formula (I), 0.5 (general) is employed per mole of 3- (2-hydroxyphenyl) -3-methoxyiminomethyl-oxadiazine of the formula (II) to 15 moles, preferably 0.8 to 8 moles, of substituted halopyrimidine of the formula (III).

To carry out process b) according to the invention for the preparation of the compounds of the formula (I), 0.5 to 15 mol, preferably 0.8 to 8 mol, of a ring compound of the general formula are generally employed per mol of the phenoxypyrimidine of the formula (IV) (V) a.

To carry out process d) according to the invention for the preparation of the compounds of the formula (VI), the mole of hydroxyethylbenzofürandione dioxime is used

Formula (VII) generally 1 to 15 moles, preferably 2 to 8 moles of alkyl or arylsulfonyl chloride or halogenating agents.

To carry out process e) according to the invention for the preparation of the compounds of the formula (IV), 1 to 15 are generally employed per mole of 3- (2-hydroxyphenyl) -3-methoxyiminomethyl-oxadiazine of the formula (II) Mol, preferably 2 to 8 mol of a trihalopyrimidine of the general formula (XI).

The processes a), b), d) and e) according to the invention are generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure - generally between 0.1 bar and 10 bar.

Process c) according to the invention is generally carried out under elevated pressure. It is preferably carried out at a pressure between 2 and 100 bar, in particular between 3 and 50 bar. The reaction products are worked up, worked up and isolated using generally customary processes (see also the preparation examples).

The substances according to the invention have a strong microbicidal action and can be used to control unwanted microorganisms, such as fungi and bacteria

Plant protection and material protection are used.

Fungicides can be used to protect plants against Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

Some pathogens of fungal and bacterial are exemplary but not limiting

Diseases that fall under the generic names listed above:

Xanthomonas species, such as, for example, Xanthomonas campestris pv. Oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv. Lachrymans; Erwinia species, such as, for example, Erwinia amylovora;

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or

Pseudoperonospora cubensis; Plasmopara species, such as, for example, Plasmopara viticola;

Bremia species, such as, for example, Bremia lactucae;

Peronospora species, such as, for example, Peronospora pisi or P. brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca Fülliginea; Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (Konidienfoπn: Drechslera, Syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus

(Konidieήform: Drechslera, Syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus; Puccinia species, such as, for example, Puccinia recondita;

Sclerotinia species, such as, for example, Scierotinia sclerotiorum;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;

Pellicularia species, such as, for example, Pellicularia sasakii; Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum; Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae;

Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases allows treatment above ground

Parts of plants, of seedlings, and of the soil.

The active compounds according to the invention can be used with particularly good success to combat cereal diseases, such as, for example, against Leptosphaeria, Puccinia or Fusarium species, and diseases in wine, fruit and vegetable cultivation, such as, for example, against Venturia, Sphaerotheca or Plasmopara. Species, or rice diseases, such as against Pyricularia species, use.

The active compounds according to the invention are also suitable for increasing the crop yield. They are also less toxic and have good plant tolerance. Depending on their respective physical and / or chemical properties, the active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, as well as ULV cold and warm fog formulation ^• * g & e ^w n

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. Liquid solvents are essentially aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride. aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum effects, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dime thylformamide and dimethyl sulfoxide, as well as water Mt liquefied gaseous extenders or carriers are meant such liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide B natural rock meals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock meals, such as highly disperse silicic acid, aluminum oxide and silicates. Solid carrier materials for granules are possible: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. Non-ionic and anionic emulsifiers can be used as emulsifiers and / or foam-generating agents ores, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Suitable dispersants include, for example, lignin sulfite waste liquors and methyl cellulose

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used in the formulations, such as

Gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids, such as Kephahne and lecithins, and synthetic phospholipids. Other additives can be mineral and vegetable oils

Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used

The formulations generally contain between 0.1 and 95 percent by weight

Active ingredient, preferably between 0.5 and 90%

Depending on their respective physical and / or chemical properties, the active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for Seeds, as well as ULV cold and warm mist formulations ^W n

As such or in their formulations, the active compounds according to the invention can also be mixed with known fungicides, bactericides, acaricides, nematicides or

Insecticides can be used, for example, to broaden the spectrum of activity or prevent the development of resistance. In many cases, synergistic effects are obtained, ie the effectiveness of the mixture is greater than the effectiveness of the individual components

The following compounds can be considered as mixing partners, for example Fungicides:

Aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin,

Benalaxyl, benodanil, benomyl, benzamacril, benzamacrylic isobutyl, bialaphos, binapacrylic, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,

Calcium polysulfide, capsimycin, captafol, captan, carbendazim, carboxin, carvone, quinomethionate (quinomethionate), chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cuffaneb, cymoxanil, cyofurilazol, cypodaminazol, cypodinconazole

Debacarb, dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole

M, Dinocap, Diphenylamine, Dipyrithione, Ditalirnfos, Dithianon, Dodemo h, Dodine, Drazoxolon,

Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,

Famoxadone, Fenapanil, Fenarimol, Fenbuconazol, Fenfüram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzon, Fluazinam, Flumetover, Fluoromid, Fluquinconazol, Fluφrimidolutin, Flusilimidol, Flusulfimidol, Flusulfimidol, Flusulfimidol, Flusulfimidol, Flusulfimidol, Flusulfilidol, Flusulfinidol, Flusulfilidol, Flusulfinidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusulfilidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusulfilidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusulfilidol, Fosetyl sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox,

Guazatin,

Hexachlorobenzene, hexaconazole, hymexazole, Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovaledione,

Kasugamycin, Kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,

Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfüroxam, Metiram, Metomeclam, Metsulfovax,

Mildiomycin, myclobutanil, myclozolin,

Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,

Ofürace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,

Paclobutrazol, Pefürazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin, Polyoxorim, probenazole, Prochloraz, Procymidon, Propamocarb, Propanosine-Sodium, Propiconazole, Propineb, Pyrazophos, Pyrifen, Pyifen, Pyroyilonil

Quinconazole, quintozen (PCNB),

Sulfur and sulfur preparations,

Tebuconazole, tecloftalam, tecnazene, Tetcyclacis, tetraconazole, thiabendazole, Thicyofen, Thifluzamide, thiophanate-methyl, thiram, Tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, Triazbutil, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,

Uniconazole,

Validamycin A, vinclozolin, viniconazole, Zarilamid, Zineb, Ziram as well

Dagger G,

OK-8705,

OK-8801, α- (1, 1-dimethylethyl) -ß- (2-phenoxyethyl) - 1 H-1, 2,4-triazole-1-ethanol, α- (2,4-dichloφhenyl) -ß-fluorine -b-propyl- 1 H- 1, 2,4-triazole- 1 -ethanol, - (2,4-dichloφhenyl) -ß-methoxy-a-methyl- 1 H- 1, 2,4-triazole- 1 - ethanol, α- (5-methyl-l, 3-dioxan-5-yl) -ß - [[4- (trifluoromethyl) phenyl] methylene] -lH-l, 2,4-triazole-

1-ethanol, (5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (lH-l, 2,4-triazol-l-yl) -3-octanone,

(E) -a- (methoxyimino) -N-methyl-2-phenoxy-phenylacetamide,

{2-Methyl-l - [[[l- (4-methylphenyl) ethyl] amino] carbonyl] propyl} carbamic acid l-isopropyl ester

1 - (2,4-dichloφhenyl) -2- (1 H- 1, 2,4-triazole-1-yl) -ethanone-O- (phenylmethyl) -oxime, 1 - (2-methyl-1-naphthalenyl) - 1 H-pyrrole-2, 5-dione,

1 - (3, 5 -Dichlθφhenyl) -3 - (2-propenyl) -2, 5-pyrrolidinedione, l - [(diiodomethyl) sulfonyl] -4-methyl-benzene, l - [[2- (2.4 -Dichloφhenyl) -l, 3-dioxolan-2-yl] methyl] -lH-imidazole,

1 - [[2- (4-chloro-phenyl) -3-phenyloxiranyl] methyl] - 1 H- 1, 2,4-triazole, l- [l- [2 - [(2,4-dichloro-henyl) methoxy] -phenyl] -ethenyl] -lH-imidazole, l-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,

2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4 ^l -trifluoromethyl-l, 3-thiazole-5-carboxanilide,

2,2-dichloro-N- [1 - (4-chloro-phenyl) -ethyl] - 1-ethyl-3-methyl-cyclopropanecarboxamide,

2,6-dichloro-5- (methylthio) -4-pyrimidinyl-thiocyanate, 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide,

2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,

2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,

2 - [(l-methylethyl) sulfonyl] -5- (trichloromethyl) -1, 3,4-thiadiazole,

2 - [[6-Deoxy-4-O- (4-O-methyl-ß-D-glycopyranosyl) -aD-glucopyranosyl] -amino] -4- methoxy-lH-pyrrolo [2, 3 -d] pyrimidine- 5-carbonitrile,

2-aminobutane,

2-bromo-2- (bromomethyl) pentandinitrile, 2-chloro-N- (2,3-dihydro-1,3-trimethyl-1H-inden-4-yl) -3-pyridinecarboxamide, 2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) acetamide, 2-phenylphenol (OPP),

3,4-dichloro-l- [4- (difluoromethoxy) phenyl] -IH-pyrrole-2,5-dione, 3,5-dichloro-N- [cyan [(l-methyl-2-propynyl) -oxy ] -methyl] -benzamide,

3 - (1,1-dimethylpropyl-1-oxo-1 H-inden-2-carbonitrile, 3- [2- (4-chloro-phenyl) -5-ethoxy-3-isoxazolidinyl] pyridine, 4-chloro-2- cyan-N, N-dimethyl-5- (4-methylphenyl) -1 H -imidazole-1 -sulfonamide, 4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one, 8- (1st , 1-dimethylethyl) -N-ethyl-N-propyl-1,4-dioxaspiro [4.5] decane-2-methanamine,

8-hydroxyquinoline sulfate,

9H-xanthene-9-carboxylic acid 2 - [(phenylamino) carbonyl] hydrazide, bis- (l-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) -oxy] -2,5-thiophene dicarboxylate, eis- 1 - (4-Chlθφhenyl) -2- (lH-l, 2,4-triazol-l-yl) cycloheptanol, cis-4- [3- [4- (1,1, dimethylpropyl) phenyl- 2-methylpropyl] -2,6-dimethyl-moφholin hydrochloride,

Ethyl - [(4-chlθφhenyl) azo] cyanoacetate, potassium hydrogen carbonate, methanetretrathiol sodium salt, methyl 1 - (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) - 1 H-imidazole -5-carboxylate,

Methyl N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate, Methyl-N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate, N- (2nd , 3-dichloro-4-hydroxyphenyl) - 1 -methyl-cyclohexane carboxamide. N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) acetamide, N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2 -oxo-3-thienyl) -acetamide,

N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide, N- (4-cyclohexylphenyl) -1, 4,5,6-tetrahydro-2-pyrimidinamine, N- (4-hexylphenyl ) - 1,4,5, 6-tetrahydro-2-pyrimidinamine, N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) acetamide, N- (6 Methoxy) -3-pyridinyl) -cyclopropanecarboxamide,

N- [2,2,2-trichloro-1 - [(chloroacetyl) amino] ethyl] benzamide, N- [3-chloro-4,5-bis (2-propynyloxy) phenyl] -N ' -methoxy-methanimidamide, N-formyl-N-hydroxy-DL-alanine sodium salt,

O, O-diethyl- [2- (dipropylamino) -2-oxoethyl] ethylphosphoramidothioate, O-methyl-S-phenyl-phenylpropylphosphoramidothioate, S-methyl-1, 2,3-benzothiadiazole-7-carbothioate, spiro [2H] - 1-benzopyran-2, 1 '(3'H) -isobenzofüran] -3'-one,

Bactericides:

Bronopol, dichlorophene, nitrapyrin, nickel-dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam,

Copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

Abamectin, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz,

Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,

Bacillus thuringiensis, 4-bromo-2- (4-chloro-phenyl) - 1 - (ethoxymethyl) -5- (trifluoromethyl) - 1H-pyrrole-3-carbonitrile, bendiocarb, benufracarb, bensultap, betacyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, Bufencarb, Buprofezin, Butocarboxim,

Butyl pyridaben,

Cadusafos, Carbaryl, Carbofüran, Carbophenothion, Carbosulfan, Cartap, Chloethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N - [(6-Chloro-3-pyridinyl) -methyl] -N'-cyano-N-methyl-ethanimidamide , Chloφyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazin,

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat,

Dimethylvinphos, dioxathione, disulfoton, Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos,

Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fiuazinam, Fluazuron, Flucycloxuron, Flucythrinat, Flufenproxaton, Flufenproxaton, Flufenproxhonat, Flufenproxhonat, Flufenproxaton, Flufenproxaton, Flufenproxatonur Furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,

Lamda-cyhalothrin, Lufenuron,

Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathione, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,

Naled, NC 184, Nitenpyram

Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,

Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos, Promecarb,

Propaphos, Propoxur, Prothiophos, Prothoat, Pymetrozin, Pyrachlophos, Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,

Quinalphos,

Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos, Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomenhriazon, Tralomenhriazon, Tronomenhrononium,

Vamidothione, XMC, xylylcarb, zetamethrin.

A mixture with other known active ingredients, such as herbicides or with

Fertilizers and growth regulators are possible.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.

When the active compounds according to the invention are used as fungicides, the application rates can be varied within a relatively wide range, depending on the type of application. In the treatment of parts of plants, the active compound application rates are generally between 0.1 and 10,000 g ha, preferably between 10 and 1,000 g / ha. In the case of seed treatment, the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per

Kilogram of seeds. When treating the soil, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha. Manufacturing examples:

example 1

Procedure b

To a solution of 0.7 g (2 mmol) of 3- {l- [2- (4,5-difluoropyrimid-6-yloxy) phenyl] -1- (methoximino) methyl} -5,6-dihydro- 4H-l, 2,4-oxadiazine in 30 ml of acetonitrile are first added to 0.33 g (2 mmol) of 2,3-dichlorophenol at 20 ° C. and then 0.33 g (2.4 mmol) of potassium carbonate. The mixture is stirred overnight, filtered off, taken up in 150 ml of ethyl acetate and washed with water. Finally, the organic phase is dried over sodium sulfate and concentrated under reduced pressure, leaving a viscous oil which slowly crystallizes. You get

0.9 g (91.8% of theory) 3- {l- [2- (4- <2,3-dichlorophenoxy> -5-fluoropyrimid-6-yloxy) phenyl] -1 - (methoximino) methyl } -5, 6-dihydro-4H-1, 2,4-oxadiazine.

HPLC: logP: 3.45.

Analogously to Example (1), and in accordance with the general description of the production processes a) and b) according to the invention, the compounds of the formula (Ia) according to the invention listed in Table 1 below are also obtained:

Table 1:

Table 1:

Table 1:

Table 1 :

) The logP values were determined in accordance with EEC Directive 79/831 Annex V. A8 by HPLC (gradient method, acetonitrile / 0, 1% aqueous phosphoric acid)

Production of the starting materials according to formula (II):

Example (II- 1):

Procedure c)

1.26 g (4 mmol) of benzofuran-2,3-dione-2- [O- (2-methylsulfonyloxy-ethyl) -oxime] -3- (O-methyl-oxime) are placed in 15 ml of methanol in an autoclave. Then 2.5 g (147 mmol) of ammonia are condensed in and the autoclave is heated to 100 ° C. under autogenous pressure for 16 hours. The mixture is cooled to 20 ° C., the reaction mixture is removed and the solvent is distilled off in vacuo. Finally, the residue is stirred with water, the white fatty substance obtained is filtered off and dried overnight in a drying cabinet. 0.9 g (96% of theory) of 3- {l- [2-hydroxyphenyl] -1- (methoximino) methyl} -5,6-dihydro-4H-1,2,4-oxadiazine are obtained.

iH-NMR: δ = 3.57 (m, 2H); 3.98 (s, 3H); 4.05 (m, 2H) ppm

Production of starting materials according to formula (III)

Example (III- 1)

A solution of 42.4 g (0.45 mol) of phenol and 50.4 g (0.45 mol) of potassium tert-butoxide in 400 ml of tetrahydrofuran is added dropwise at 0 ° C. to a solution of 80 g (0.05 6 mol) 4,5,6-trifluoropyrimidine in 11 tetrahydrofuran. When the addition is complete, the mixture is stirred at 0 ° C. for 30 minutes, then the reaction mixture is poured onto water and extracted with ethyl acetate. The organic phase is dried over sodium sulfate, concentrated in vacuo and the residue is stirred with low-boiling petroleum ether. 63.8 g (68.1% of theory) of 4-phenoxy-5,6-difluoropyrimidine with a melting point of 65-66 ° C. are obtained.

Production of the preliminary product:

500 ml of liquid are distilled off at 145 ° C. and 20 mbar for drying from a mixture of 609 g of potassium fluoride in 2.3 l of sulfolane. 1054 g of 5-chloro-4,6-difluoropyrimidine (DE-A 3843558) and 25 g of tetraphenylphosphonium bromide are then added, 5 bar of nitrogen are injected and the mixture is stirred at 240 ° C. for 24 hours, the pressure rising to 11 bar. The reaction mixture is cooled to 80 ° C. and let down. Now the mixture is slowly heated again at normal pressure, the product distilling off. When the bottom temperature has reached 200 ° C., the pressure is reduced to 150 mbar in order to accelerate the distillation and to obtain further product. A total of 664 g (70.7% of theory) of 4,5,6-trifluoropyrimidine with a boiling point of 86 to 87 ° C. Production of the starting materials according to formula (IV):

Example αv-l):

Procedure e)

To a solution of 1.2 g (5.1 mmol) of 3- {l- [2-hydroxyphenyl] -l- (methoximino) - methyl} -5,6-dihydro-4H-l, 2,4-oxadiazine in 30 ml of acetonitrile are first added at 20 ° C. to 0.7 g (5.1 mmol) of 4,5,6-trifluoropyrimidine and then 1.4 g (10.2 mmol) of potassium carbonate. The mixture is stirred overnight, filtered off, taken up in 150 ml of ethyl acetate and washed with water. Finally, the organic phase is dried over sodium sulfate and concentrated under reduced pressure, leaving a viscous oil which slowly crystallizes. 1.4 g are obtained

(82% of theory) 3- {l- [2- (4,5-difluoropyrimid-6-yloxy) phenyl] -1- (methoximino) - methyl} -5,6-dihydro-4H-l, 2, 4-oxadiazine.

HPLC: logP: 1.97

Production of the starting materials according to formula (VI):

Example fVI-1):

3.2 g (0.0135 mol) of benzofuran-2,3-dione-2- [O- (2-hydroxyethyl) oxime] -3- (O-methyloxime) are dissolved in 100 ml of methylene chloride at 20 C. and 1.05 ml (0.0135 mol) of methanesulfonyl chloride are added. After 15 minutes, 5.6 ml (0.0406 mol) of triethylamine are added to this mixture while cooling with ice at 10 ° C. Finally, the mixture is warmed to 20 The reaction mixture is then taken up in methyl t-butyl ether, washed with water, dried over magnesium sulfate and concentrated under reduced pressure. 4.0 g (94.2% of theory) of benzofuran-2 are obtained , 3-dione-2- [O- (2-methylsulfonyloxyethyl) oxime] -3- (O-methyloxime) as a white solid

HPLC log P. 2.39

Production of precursors according to formulas (VTI), (VUI) and (IX):

Compound (IX- 1)

6.7 g (0.05 mol) of benzofuran-3-one are mixed with 4.2 g (0.05 mol) of O-methylhydroxylamine hydrochloride and 4.1 g (0.05 mol) of sodium acetate in 50 ml of methanol Boiled under reflux for 3 hours. The solvent is distilled off in vacuo, the reaction mixture is poured onto water and extracted with ethyl acetate. The organic phase is washed with saturated, aqueous sodium carbonate solution. The organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo

7.27 g (89.2% of theory) of crude benzofuran-3-one-O-methyl-oxιm are obtained. For analysis, it is distilled at 2 torr and 70 ° C. in a bulb tube. An oil is obtained which, according to NMR -Analysis as well as according to the HPLC analysis consists of two stereoisomers (79% isomer B and 21% isomer A) ^Ϊ H NMR Spectrum (DMSO-d ₆ / TMS): δ = 3.93 (3H, isomer B); 3.93 (3H, isomer A); 5.11 (2H, isomer A); 5.16 (2H, isomer B); 7.0-7.07 (2H); 7.39-7.45 (IH); 7.54 / 7.57 (IH, isomer B); 7.95-8.02 (IH, Isomer A) ppm.

Compound (VIII-1)

3.92 g (0.035 mol) of potassium tert-butoxide are dissolved in 40 ml of tert-butanol. A solution of 5.7 g (0.035 mol) of benzofuran-3-one-O-methyloxime and 7.2 g (0.07 mol) of tert-butyl nitrite in 10 ml of tert-butanol is added to this solution. The mixture is stirred for two hours without cooling, and 20 ml of 2N aqueous hydrochloric acid are then added. The crystallized product is filtered off, washed several times with water and dried in an exciccator. 3.19 g (47.1% of theory) are obtained.

Benzofuran-2,3-dione-3- (O-methyl-oxime) -2-oxime as a mixture of two stereoisomers, consisting of 86.33% isomer A and 12.98% isomer B (HPLC).

iH-NMR spectrum (DMSO-d ₆ / TMS): δ = 4.10 (3H, isomer B); 4.1 1 (3H; isomer A); 7.21 / 7.24 / 7.26 (IH); 7.31 / 7.34 (IH); 7.51 / 7.53 / 7.56 (IH); 7.63 / 7.65 (IH, isomer

B); 8.02 / 8.05 (IH, isomer A); 11.36 (IH, isomer A); 1 1.75 (IH, Isomer B) ppm.

Compound (VII- 1)

Procedure b)

264 are passed into a solution of 192.2 g (1.0 mol) of benzofuran-2,3-dione-3- (O-methyl-oxime) -2-oxime in 2 l of water within 85 minutes at 20 ° C , 3 g (6.0 mol) of ethylene oxide. The solution is cooled to 5 ° C and 70 g (1.06 mol) of potassium hydroxide biscuits are added, the temperature rising to 10 ° C. The mixture is stirred for a further 165 minutes without further cooling, the resulting precipitate is filtered off with suction, washed in portions with 500 ml of ice water and dried at 40 ° C. in a vacuum drying cabinet. 143.0 g (61% of theory) of benzofuran-2,3-dione-2- [O- (2-hydroxyethyl) oxime] -3- (O-methyl oxime) are obtained as a mixture of two stereoisomers .

HPLC: logP = 1.65 (0.5%); 1.79 (99.5%)

Examples of use

Example A

Leptosphaeria nodorum test (wheat) / protective

Solvent: 25 parts by weight of N, N-dimethylacetamide emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight is mixed

Active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective efficacy, young plants are sprayed with the active compound preparation in the stated application rate. After the

The plants are sprayed with a spore suspension of Leptosphaeria nodorum. The plants remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 48 hours.

The plants are placed in a greenhouse at a temperature of approx. 15 ° C and a relative humidity of 80%.

Evaluation is carried out 10 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the substance according to the invention listed in Example (3) shows an efficiency of 90% or more at an application rate of 250 g / ha. Example B

Puccinia test (wheat) / curative

Solvent: 25 parts by weight of N, N-dimethylacetamide

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for curative effectiveness, young plants are sprayed with a conidia suspension from Puccinia recondita. The plants remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 48 hours. The plants are then sprayed with the active compound preparation in the specified amount.

The plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80% in order to promote the development of rust pustules.

Evaluation is carried out 10 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the substance according to the invention listed in Example (3) shows an efficiency of 90% or more at an application rate of 250 g / ha. Example C

Fusarium nivale (var.nivale) test (wheat) / protective

Solvent: 25 parts by weight of N, N-dimethylacetamide emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the mixture is diluted

Concentrate with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Fusarium nivale (var. Nivale).

The plants are placed in a greenhouse under translucent incubation hoods at a temperature of approx. 15 ° C and a relative humidity of approx. 100%.

Evaluation is carried out 4 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the substances according to the invention listed in Examples (1) and (2) show an efficiency of 90% or more at an application rate of 250 g / ha. Example D

Plasmopara test (vine) / protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the mixture is diluted

Concentrate with water to the desired concentration.

To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Plasmopara viticola and then remain in an incubation cabin at about 20 ° C. and 100% relative atmospheric humidity for 1 day. The plants are then placed in a greenhouse at about 21 ° C. and about 90% relative atmospheric humidity for 5 days. The plants are then moistened and placed in an incubation cabin for 1 day.

Evaluation is carried out 6 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the examples (1), (2), (3), (4), (5), (6), (7), (9), (10),

(1 1), (13), (14), (15), (17), (19), (20), (34), (48), (50), (51), (53) and ( 59) listed substances according to the invention at an application rate of 100 g / ha

Efficiency of 90% or more. Example E

Sphaerotheca test (cucumber) / protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the mixture is diluted

Concentrate with water to the desired concentration.

To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Sphaerotheca fuliginea. The plants are then placed in the greenhouse at about 23 ° C. and a relative atmospheric humidity of about 70%.

Evaluation is carried out 10 days after the inoculation. 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the substances listed in Examples (1), (2), (3) and (4) show an efficiency of 90% or more at an application rate of 100 g / ha

Example F

Venturia test (apple) / protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the mixture is diluted

Concentrate with water to the desired concentration.

To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants are washed with an aqueous comedy suspension of the apple scab pathogen

Venturia inaequalis and then remain in an incubation cabin for 1 day at approx. 20 ° C and 100% relative humidity.

The plants are then placed in the greenhouse at approx. 21 ° C. and a relative humidity of approx. 90%.

Evaluation is carried out 12 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the examples (2), (3), (4), (5), (7), (10), (11), (12), (13), (17), (20 ), (21), (22), (23), (24), (31), (36), (40), (48) and (59) listed substances according to the invention at an application rate of 10 g / ha an efficiency of 90% or more. Example G

Pyricularia test (rice) / protective

Solvent: 2.5 parts by weight of acetone

Emulsifier: 0.06 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted with

Water and the specified amount of emulsifier to the desired concentration.

To test for protective activity, young rice plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants are then placed in a greenhouse at 100% relative atmospheric humidity and 25 ° C.

Evaluation is carried out 4 days after the inoculation. 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the substances according to the invention listed in Examples (1), (3), (4) and (7) show an efficiency of 90% or more at an application rate of 750 g / ha.

Claims

claims

1. Compounds of formula (I)

in which

represents in each case optionally substituted cycloalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl,

represents oxygen or sulfur,

X represents halogen,

L, L ² , 7 and L ^{4 are the} same or different and each independently represents hydrogen, halogen, cyano, nitro, each optionally substituted by halogen, alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl.

Compounds of formula (I) according to claim 1, in which

for cycloalkyl or cycloalkylalkyl which are each mono- to pentasubstituted or substituted by halogen or alkyl and each have 3 to 7 carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the alkyl part; for heterocyclyl or heterocyclyialkyl optionally substituted by halogen, dialkylamino or alkyl having 1 to 4 carbon atoms, each having 3 to 7 ring members and 1 to 4 carbon atoms in the alkyl part;

or for aryl or arylylalkyl, each of which is monosubstituted to tetrasubstituted or substituted in the aryl part, in each case optionally with 6 to 10 carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part, the possible substituents being selected from the list below:

Halogen, cyano, nitro, amino, formyl, carbamoyl, thiocarbamoyl;

in each case straight-chain or branched alkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 8 carbon atoms;

each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms;

each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;

each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 1 1 identical or different halogen atoms;

each straight-chain or branched alkylamino, dialkylamino,

Alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, arylalkylaminocarbonyl, alkenylcarbonyl or alkynylcarbyl onyl, with 1 to 6 carbon atoms in the respective hydrocarbon chains;

Cycloalkyl or cycloalkyloxy each having 3 to 6 carbon atoms;

each optionally monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, oxo, methyl, trifluoromethyl or ethyl and in each case doubly linked alkylene having 3 or 4 carbon atoms, oxyalkylene having 2 or 3 carbon atoms or dioxyalkylene having 1 or 2 carbon atoms;

A ¹ or a grouping | T, in which

A represents hydrogen or alkyl having 1 to 4 carbon atoms or cycloalkyl having 3 to 6 carbon atoms and

A ^{2 represents} hydroxy, amino, methylamino, methyl, phenyl, benzyl, alkoxy, alkylamino, dialkylamino with 1 to 4 carbon atoms in the respective alkyl chains,

Q represents oxygen or sulfur,

X represents fluorine, chlorine or bromine and

L, L ² , L-3 and L ^{4 are the} same or different and are each independently of the other hydrogen, halogen, cyano, nitro, each optionally substituted by 1 to 5 halogen atoms, alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 Carbon atoms. Compounds of formula (I) according to claim 1, in which

Z for in each case optionally up to five times by fluorine, chlorine,

Methyl or ethyl substituted cyclobutyl, cyclopentyl or cyclohexyl;

for thienyl, pyridyl, furyl, thienylmethyl, pyridylmethyl or furylmethyl optionally substituted by methyl, ethyl, dimethylamino, fluorine, chlorine or bromine;

or represents phenyl or benzyl which is optionally monosubstituted to tetrasubstituted by identical or different substituents, the possible substituents being selected from the list below:

Fluorine, chlorine, bromine, cyano, nitro, amino, formyl, carbamoyl, thiocarbamoyl,

Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxymethyl,

Methoxy, ethoxy, n- or i-propoxy,

Methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl,

Methylaminomethyl, dimethylaminomethyl,

Vinyl, allyl, 2-methylallyl, propen-1-yl, crotonyl, propargyl, vinyloxy, allyloxy, 2-methylallyloxy, propen-1-yloxy, crotonyloxy, propargyloxy;

Trifluoromethyl, trifluoroethyl, Difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, pentafluoroethoxy, 2-chloro-l, l, 2-trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfinyl

Methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino,

Acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, acryloyl, propioloyl,

Cyclopentyl, cyclohexyl,

each optionally optionally up to four times, the same or different, substituted by fluorine, chlorine, oxo, methyl or trifluoromethyl, in each case twice linked propanediyl, ethyleneoxy, methylenedioxy, ethylenedioxy

A ¹ or a grouping, where

N

* 2 ^

A represents hydrogen or methyl and

A ^{2 represents} hydroxy, methoxy, ethoxy, amino, methylamino, methyl, phenyl or benzyl,

Q represents oxygen or sulfur,

X represents fluorine or chlorine, in particular fluorine and L *, L ² , \ 7 and L ^{4 are} identical or different and are each independently of one another hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl,

Ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, di - Fluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl.

4. pesticide, characterized by a content of at least one compound of the formula (I) according to claim 1.

5. A method for controlling pests, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on pests and / or their habitat.

6. Use of compounds or agents of the formula (I) according to Claims 1 to 4 for combating pests.

7. A process for the preparation of pesticides, characterized in that compounds of the formula (I) according to Claims 1 to 3 are mixed with extenders and / or surface-active agents.

8. A process for the preparation of compounds of formula (I), characterized in that

a) 3- (2-hydroxy-phenyl) -3-methoxyiminomethyl-oxadiazines of the formula (II),

in which

L, L ² , \ 7 and L ^{4 have} the meanings given in claim 1,

with a substituted halopyrimidine of the general formula (III),

in which

Z, Q and X have the meanings given in claim 1 and

γ represents halogen,

if appropriate in the presence of a diluent, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a catalyst, or

b) phenoxypyrimidines of the general formula (IV)

in which

X, L, L ² , iß and L ^{4 have} the meanings given in claim 1 and

Y ^{2 represents} halogen,

with a ring compound of the general formula (V),

Z-Q-H (V)

in which

Z and Q have the meanings given in claim 1,

if appropriate in the presence of a diluent, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a catalyst.

Compounds of formula (II)

in which

L, L ² , iß and L ^{4 have} the meanings given in claim 1.

10. Compounds of the formula (VI)

in which

L, L ² , iß and L ^{4 have} the meanings given in claim 1 and

represents halogen, alkylsulfonyl or arylsulfonyl.

11. Compounds of the formula (IV)

in which

X, L, L ² , L ^ and L ^{4 have} the meanings given in claim 1 and

Y ^{2 represents} halogen.