EP1115723A2 - Pesticidal methoximinomethyloxathiazine - Google Patents

Abstract

The invention relates to novel methoximinomethyloxathiazines of formula (I), to two methods for producing them and to their use as pesticides.

Description

Methoximinomethyloxathiazine

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

Certain methoximinomethyloxathiazines with a similar substitution pattern and their fungicidal activity have already been disclosed (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 methoximinomethyloxathiazines of the general formula (I) have now been found

in which

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

Q represents oxygen or sulfur,

X represents halogen and Ll, L ^,> and L ^ are the same or different and each independently represent hydrogen, halogen, cyano, nitro, each optionally substituted by halogen alkyl, alkoxy, alkylthio, alkylsulfyl 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, such as, for example and preferably, phenyl, naphthyl, anthranyl, phenanthryl, preferably phenyl or naphthyl, in particular 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 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.

Furthermore, it was found that the new methoximinomethyloxathiazines of the general formula (I) can be obtained if

a) 3- (2-hydroxyphenyl) -3-methoxyiminomethyl-oxathiazines of the formula (II), in which

L, I, L ^, L ^ and i 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

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 if

Phenoxypyrimidines of the general formula (IV)

in which

X,, L _% L ^ and i 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 methoximinomethyloxathiazines of the general formula (I) have a very strong microbicidal action.

The compounds of the invention can optionally be used as mixtures of various possible isomeric forms, in particular stereoisomers such as B. E- and Z-. Both the E and the Z isomers and 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 disubstituted 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 or disubstituted in the aryl part, in each case optionally substituted in the aryl part, each having 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;

each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfmyl or haloalkylsulfonyl, each with 1 up 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 11 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 up to fourfold, if necessary, the same or different

Fluorine, chlorine, oxo, methyl, trifluoromethyl or ethyl substituted, each doubly linked alkylene with 3 or 4 carbon atoms, oxyalkylene with 2 or 3 carbon atoms or dioxyalkylene with 1 or 2 carbon atoms;

A 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 ^ stands for 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, preferably fluorine or chlorine and in particular fluorine and

L, I, L, 2, L, 3 and ß 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 with 1 up to 6 carbon atoms, preferably hydrogen or methyl and in particular hydrogen.

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

Z for cyclopentyl or cyclohexyl which is optionally mono- to disubstituted by fluorine, chlorine, methyl, ethyl or hydroxy;

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

or in particular represents phenyl or benzyl which is optionally monosubstituted to tetrasubstituted, in particular monosubstituted or disubstituted, in the same or different manner, 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, ethylsulfmyl, methylsulfonyl or ethylsulfonyl,

Methylaminomethyl, dimethylaminomethyl,

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

Trifiuormethyl, 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 up to fourfold, if necessary, the same or different

Fluorine, chlorine, oxo, methyl or trifluoromethyl substituted propane diyl, ethyleneoxy, methylenedioxy, ethylenedioxy, each linked twice

A ¹ or a grouping ^, where

A ² ^ AI stands for hydrogen or methyl and

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

Q represents sulfur or in particular oxygen,

X represents fluorine or chlorine, in particular fluorine and

L, iß, L ^ and iß 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, ethylsulfmyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoromethylthioifluorifluoromifluoromifluoromifluoromifluoromethyl, difluoromifluoromethylthioifluoromifluoromifluoromifluoromifluoromethyl, difluoromifluoromifluoromifluoromifluoromifluoromifluoromifluorifluoromifluorofluoromethyl, bifluoromethylfifluoromethyl, bifluoromethylfifluoromethyl, bifluoromethyl, bifluoromethyl, bifluoromethyl, bifuryl Trifluoromethylsulfonyl, preferably hydrogen or methyl and in particular hydrogen.

Compounds of the formula (I) in which

Q stands for oxygen.

Compounds of the formula (I) in which

iß, ß, iß and L ^ stand for hydrogen.

Compounds of the formula (I) in which

X stands for fluorine. Compounds of the formula (I) in which

Z represents unsubstituted or substituted phenyl. As a substituent

Halogen, alkyl, cyano and alkyloxy radicals are preferred.

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.

These residual definitions can be among themselves, that is, between the specified

Areas of preferred connections, can be combined as desired.

Formula (II) provides a general definition of the 3- (2-hydroxyphenyl) -3-methoxyiminomethyl-oxathiazines required as starting materials for carrying out process a) according to the invention. In this formula (II), L, I, ß, ß ¹ and ß 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 ß, ß , ß and ß were specified.

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

They are obtained (process c) if acylthioethylbenzofurandione dioximes of the general formula (VI) in which

L, ß, ß and ß have the meanings given above and

R ^{1 represents} alkyl,

with a base, optionally in the presence of a diluent.

Formula (VI) provides a general definition of the acylthioethylbenzofurandione dioximes required as starting materials for carrying out process c) according to the invention. In this formula (VI), ß, ß, L ^J and ß 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 ß, ß, ß and have been specified. R * stands for

Alkyl, preferably for methyl or ethyl.

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

They are obtained (process d) if benzofurandione dioximes of the general formula (VII) in which

L, I, ß, ß and ß have the meanings given above and

Y ^ represents halogen, alkylsulfonyloxy or arylsulfonyloxy,

with a thiocarboxylic acid of the general formula (VIII)

in which

Rl has the meaning given above,

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 benzofurandione dioximes required as starting materials for carrying out process d) according to the invention. In this formula (VII), L, I, ß, ß and ß 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, ß, ß and ß were given. Y ^ represents halogen, preferably chlorine or bromine, or alkylsulfonyloxy or arylsulfonyloxy, preferably methylsulfonyloxy, benzylsulfonyloxy or tolylsulfonyloxy. The starting materials of the formula (VII) are obtained if hydroxyethylbenzofurandione dioximes of the formula (IX)

in which

eat, eat, eat and eat have the meanings given above,

with an ethane derivative such as dibromoethane or bis-methylsulfonylethane-1,2-diol, optionally in the presence of a diluent such as dimethylformamide or N-methylpyrrolidone, and optionally in the presence of a base such as sodium or potassium carbonate.

The starting materials of the formula (IX) are known or can be prepared by known processes (compare WO 97-46542).

The thiocarboxylic acids which are furthermore required as starting materials for carrying out process d) according to the invention are generally known synthetic chemicals.

Formula (III) provides a general definition of the halopyrimidines required as starting materials for carrying out process a) according to the invention. In this formula (III), Z, Q and X preferably or in particular have those meanings which have already been stated as preferred or as particularly preferred for Z, Q and X in connection with the description of the compounds of the formula (I) according to the invention. γ represents halogen, preferably 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, for example by reaction of the trihalopyrimidines of the Formula (XIII) (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), X, I, ß, ß and ß 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 X, ß, ß, ß and ß were specified. Y ^ represents halogen, preferably fluorine or chlorine.

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

The phenoxypyrimidines of the general formula (IV) are obtained (process e), by whom 3- (2-hydroxyphenyl) -3-methoxyiminomethyl-oxathiazine of the formula (II) with a trihalopyrimidine of the general formula (XIII)

in which

X, γl and Y ^ 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-oxathiazines of the formula (II) required as starting materials for carrying out process e) according to the invention have already been described in connection with the description of process a) according to the invention.

Formula (XIII) provides a general definition of the trihalopyrimidines required as starting materials for carrying out process e) according to the invention. In this formula (XIII) X, γl and Y ^ are halogen, preferably fluorine or chlorine.

The trihalopyrimidines of the formula (XIII) are known and / or can be prepared by known methods (compare, for example, Chesterfield et al., J. Chem. Soc, 1955; 3478, 3480; WO 97-27189).

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, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred for

Z and Q were given.

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 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; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol,

Propane-l, 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 e) 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 ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane.

The processes a), b), c), d) and e) according to the invention are optionally carried out in the presence of a suitable base. All conventional inorganic or organic bases are suitable as such. These preferably include earth Alkali 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.

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 carried out when carrying out the inventive

Processes a), b) and e) can be varied over a wide range. In general, temperatures from -20 ° C to 100 ° C, preferably at temperatures from -10 ° C to 80 ° C.

The reaction temperatures can be carried out when carrying out the process according to the invention

Process c) can be varied over a wide range. In general, temperatures from 20 ° C to 250 ° C, preferably at temperatures from 50 ° C to 150 ° C.

The reaction temperatures can be carried out when carrying out the process according to the invention

Process d) can be varied over a wide range. In general, temperatures from -20 ° C to 100 ° C, preferably at temperatures from -10 ° C to 80 ° C.

To carry out process a) according to the invention for the preparation of the compounds of the formula (I), generally 0.5 to 15 mol are employed per mole of 3- (2-hydroxyphenyl) -3-methoxyimino-methyl-oxathiazine of the formula (II), preferably 0.8 to 8 moles of substituted halopyrimidine of the formula (III).

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

To carry out the process d) according to the invention for the preparation of the compounds of the formula (VI), 1 to 15 mol, preferably 1 to 8 mol, of 1 to 8 mol of thiocarboxylic acid of the formula (VIII) are generally employed per mole of benzofuranedioxime of the formula (VII).

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

The processes a), b), c), d) and e) 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.

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, in crop protection and in material protection.

Fungicides can be used to control Plasmodiophoromycetes,

Use 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 diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:

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 fuliginea;

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 (conidial form: Drechslera, Syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus

(Conidial form: 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, Sclerotinia 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 of above-ground parts of plants, of propagation stock and seeds, and of the soil.

The active compounds according to the invention can be particularly successful

Control of wine, fruit and vegetable cultivation, such as against Sphaerotheca species.

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.

In material protection, the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.

In the present context, technical materials are to be understood as non-living materials that have been prepared for use in technology. For example, technical materials which are to be protected against microbial change or destruction by active substances according to the invention, adhesives, glues, paper and cardboard, textiles, leather, wood, paints and

Plastic articles, cooling lubricants and other materials that can be attacked or decomposed by microorganisms. In the context of the materials to be protected, parts of production plants, for example cooling water circuits, are also mentioned which can be impaired by the multiplication of microorganisms. In the context of the present invention, the preferred technical materials are adhesives, glues, papers and cartons, leather, wood, paints, cooling agents. Lubricants and heat transfer fluids called, particularly preferably wood.

Bacteria, fungi, yeasts, algae and, for example, are microorganisms which can cause degradation or a change in the technical materials

Called slime organisms. The active compounds according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.

For example, microorganisms of the following genera may be mentioned:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum, Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, like Trichoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa,

Staphylococcus, such as Staphylococcus aureus.

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,

Fine encapsulation in polymeric materials and in coating compositions for seeds, as well as ULV cold and warm mist formulations. 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. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions,

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 dimethylformamide and dimethyl sulfoxide, and water. Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and pressure, e.g. Aerosol

Propellants, such as halogenated hydrocarbons, butane, propane, nitrogen and carbon dioxide. Possible solid carriers are: e.g. natural rock meals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock meals, such as highly disperse silica, aluminum oxide and silicates. The following are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems. Possible emulsifiers and / or foaming agents are: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters,

Polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Possible dispersants are: e.g. Lignin sulfite liquor 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 phosphohpides, such as cephalins and lecithins, and synthetic phosphohpides. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. 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 are used.

The formulations generally contain between 0.1 and 95 percent by weight

Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the spectrum of activity or to prevent the development of resistance. In many cases, synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components.

The following connections can be considered as mixed partners:

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, carvon,

Quinomethionate (quinomethionate), chlobenthiazon, chlorfenazole, chloroneb, chloro- picrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,

Debacarb, dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazol-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithorphoxinodonine, dithorphononodine

Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,

Famoxadone, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzon, fluazinam, flumetover, fluoromid, fluquinconazole, flurprimolol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusilazolutol, flusulfazolutol, flusulfazolutol, flusilazolutol, flusilazolutol, flusilazolutolol 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 phthalate, copper oxychloride, copper sulfate, copper oxide, oxy-copper and Bordeaux mixture, Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,

Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,

Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,

Paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidon, propamocarb,

Propanosine sodium, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,

Quinconazole, quintozen (PCNB),

Sulfur and sulfur preparations,

Tebuconazole, tecloftalam, tecnazen, tetcyclacis, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, dioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutichl, triazoxid, triazoxid, triazoxid, triazoxide

Tridemorph, triflumizole, triforin, triticonazole,

Uniconazole,

Validamycin A, vinclozolin, viniconazole,

Zarilamid, Zineb, Ziram as well

Dagger G, OK-8705,

OK-8801, - (1, 1-dimethylethyl) -ß- (2-phenoxyethyl) - 1 H- 1, 2,4-triazole-1-ethanol, α- (2,4-dichloro phhenyl) -ß-fluoro-b-propyl- 1 H- 1, 2,4-triazole-1-ethanol, α- (2,4-dichlorophenyl) -ß-methoxy-a-methyl- 1 H- 1, 2,4-triazole-1-ethanol, α- (5-methyl-1, 3-dioxan-5-yl) -ß - [[4- (trifluoromethyl) phenyl] methylene] - 1 H- 1, 2,4-triazol-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- 1 - [[[[- (4-methylphenyl) ethyl] amino] carbonyl] propyl} carbamic acid 1 - isopropyl ester 1 - (2,4-dichloφhenyl) -2- (1 H - 1, 2,4-triazol-1-yl) -ethanone-O- (phenylmethyl) -oxime,

1 - (2-methyl-1-naphthalenyl) - 1 H-pyrrole-2,5-dione, l- (3,5-dichlorophenyl) -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 - [[2nd - (4-Chlθφhenyl) -3-phenyloxiranyl] methyl] - 1 H- 1, 2,4-triazole,

1 - [1 - [2- [(2,4-dichlorothenyl) methoxy] phenyl] ethenyl] -1 H-imidazole, 1-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,

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

2,2-dichloro-N- [1- (4-chloro-phenyl) -ethyl] -l-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 - [(1-methylethyl) sulfonyl] -5- (trichloromethyl) -1,3,4-thiadiazole, 2 - [[6-deoxy-4-O- (4-O-methyl-β-D-glycopyranosyl ) -aD-glucopyranosyl] -amino] -4- methoxy- 1 H-pyrrolo [2,3-d] pyrimidine-5-carbonitrile,

2-aminobutane,

2-bromo-2- (bromomethyl) pentandinitrile,

2-chloro-N- (2,3-dihydro- 1, 1, 3 -trimethy 1- 1 H-inden-4-yl) -3-pyridinecarboxamide, 2-chloro-N- (2,6-dimethylphenyl) - N- (isothiocyanatomethyl) acetamide,

2-phenylphenol (OPP), 3,4-dichloro-1 - [4- (difluoromethoxy) phenyl] -1 H-pyrrole-2,5-dione,

3, 5-dichloro-N- [cyan [(1-methyl-2-propynyl) -oxy] -methyl] -benzamide,

3 - (1,1-dimethylpropyl-1-oxo-1 H-indene-2-carbonitrile,

3- [2- (4-chloro-phenyl) -5-ethoxy-3-isoxazolidinyl] pyridine, 4-chloro-2-cyano-N, N-dimethyl-5- (4-methylphenyl) -1 H-imidazole-1 -sulfonamide,

4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one,

8- (1, 1-dimethylethyl) -N-ethyl-N-propyl-1, 4-dioxaspiro [4.5] decane-2-methanamine,

8-hydroxyquinoline sulfate,

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

Ethyl [(4-chloφheny l) azo] cyanoacetate, potassium hydrogen carbonate,

Methane tetrathiol sodium salt,

Methyl 1 - (2,3-dihydro-2,2-dimethyl-1 H-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- (2,3-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'-methoxymanimidamide, N-formyl-N-hydroxy-DL-alanine sodium salt,

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

Bactericides:

Bromopol, 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) -lH-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyflutrrrin, bifenthrin, BPMC , Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxim, Butylpyridaben,

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloetho- carb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N - [(6-Chloro-3-pyridinyl) -methyl] -N'-cyano-N-methyl -ethanimidamides, Chloφyrifos, Chloφyrifos 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, dimethoate, dimethylvinphos, dioxathione, disulfoton, Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos,

Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil,

Fluazinam, Fluazuron, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

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

Lamda-cyhalothrin, Lufenuron,

Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, 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, Pyrachl

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, Tralomenhrononium, Triomenophoniazonium, Tri

Vamidothione, XMC, xylylcarb, zetamethrin.

A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also 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, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to

Applying active ingredients according to the ultra-low-volume method or injecting the active ingredient preparation or the active ingredient itself into the soil. 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 seed. In the treatment of 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.

The agents used to protect industrial materials generally contain the active ingredients in an amount of 1 to 95%, preferably 10 to 75%. The application concentrations of the active compounds according to the invention depend on the type and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimal amount can be determined by test series. In general, the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.

The effectiveness and the spectrum of activity of the active substances to be used according to the invention in the protection of materials or of the agents, concentrates or very generally formulations which can be produced therefrom can be increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active substances are used to increase the Spectrum of effects or achieving special effects such as added protection against insects. These mixtures can have a broader spectrum of activity than the compounds according to the invention.

Cereal diseases, such as Leptosphaeria species, or rice diseases, such as Pyricularia species, are also successfully combated.

MANUFACTURING EXAMPLES:

example 1

Procedure a)

To a mixture of 1 g (0.004 mol) (5,6-dihydro- [4,2,2] oxathiazin-3-yl) - (2-hydroxyphenyl) methanone O-methyloxime and 0.85 g (0 , 0041 mol) of 4-phenoxy-5,6-di-fluoro phyrimidine in 10 ml of dimethylformamide are added under cooling, 0.12 g

(0.004 mol) 80% sodium hydride and stirred for 12 hours at 25 ° C. The reaction mixture is poured onto water, extracted with ethyl acetate, the organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo. The residue is chromatographed on silica gel using cyclohexane / ethyl acetate (1: 1). 0.9 g (51% of theory) (5,6-dihydro- [l, 4,2] -oxathiazin-3-yl) are obtained -

[2- (5-fluoro-6-phenoxy-pyrimidin-4-yloxy) phenyl] methanone O-methyloxime.

^Ϊ H NMR Spectrum (CDCI3 / TMS): δ = 3.17 / 3.18 / 3.19 / 3.20 (2H); 3.85 (3H); 4.13 / 4.14 / 4.15 / 4.16 (2H); 7.19-7.51 (9H); 8.09 (1H) ppm.

Example 2

Procedure b)

To a mixture of 1.5 g (0.0041 mol) of [2- (5,6-difluoropyrimidin-4-yloxy) phenyl] - (5,6-dihydro- [4,2,2] oxathiazine 3-yl) -methanone O-methyloxime and 0.52 g (0.004 mol) of 2-chloro-phenol in 15 ml of acetonitrile are added at 25 ° C to 0.62 g (0.0045 mol) of potassium carbonate and stirred at 25 ° C for 12 hours . The reaction mixture is poured onto water, extracted with ethyl acetate, the organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo.

1.4 g (73.6%) of crude (5,6-dihydro- [1,2,2] oxathiazin-3-yl) - {2- [5-fluoro-6- (2-chlorophenoxy) - are obtained. pyrimidin-4-yloxy] phenyl} methanone O-methyloxime.

iH-NMR spectrum (CDCI3 / TMS): δ = 3.17 / 3.18 / 3.19 / 3.20 (2H); 3.84 (3H); 4.13 / 4.14 / 4.15 / 4.16 (2H); 7.19-7.52 (8H); 8.06 (1H) ppm.

Analogously to Examples 1 to 2 and in accordance with the information in the general description of the process, the compounds of the formula (I-a) mentioned in Table 1 below are obtained.

Table 1

The H-NMR spectra were recorded in deuterochloroform (CDCI3) or hexacheuterodimethyl sulfoxide (DMSO-dg) with tetramethylsilane (TMS) as the internal standard. The chemical shift is given as a δ value in ppm.

^* * ⁾ 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 (IV):

Example (IV- 1)

Procedure e)

2.52 g (0.01 mol) (5,6-dihydro- [1,4,2] oxathiazin-3-yl) - (2-hydroxyphenyl) methanone O-methyloxime are dissolved in 10 ml acetone tril and treated with 1 , 7 g (0.0123 mol) of potassium carbonate were added. Now the mixture is cooled to 0 ° C. with stirring and then 1.34 g (0.01 mol) of 4,5,6-trifluoropyrimidine are added. The mixture is stirred for a further 12 hours without further cooling. Then the solvent is distilled off in vacuo, the residue is poured onto water and extracted with ethyl acetate. The organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo. 2.3 g (62% of theory) of [2- (5,6-difluoropyrimidin-4-yloxy) phenyl] - (5,6-dihydro- [1,4,2] oxathiazin-3- yl) -methanone O-methyloxime.

^Ϊ H NMR Spectrum (CDCI3 / TMS): δ = 3.15 / 3.16 / 3.17 / 3.18 (2H); 3.83 (3H); 4.11 / 4.12 / 4.13 / 4.14 (2H); 7.26-7.53 (4H); 8.20 (1H) ppm.

HPLC: logP = 2.80. Production of the starting materials according to formula (II)

Example (II- 1)

Procedure c)

3.67 g (0.0125 mol) of thioacetic acid S- [2- (3-methoxyimino-3H-benzofuran-2-ylideneaminooxy) ethyl] ester are dissolved in 40 ml of methanol with 12.5 ml of 2N aqueous potassium hydroxide solution for 15 minutes cooked under reflux. Then the solvent is distilled off in vacuo and the residue is treated with 2N aqueous hydrochloric acid. The mixture is extracted with diethyl ether, the organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo. The residue is stirred with diethyl ether and 0.78 g (24.7% of theory) (5,6-di-hydro- [1,2,2] oxathiazin-3-yl) - (2-hydroxyphenyl) methanone is obtained O-methyloxime.

! H NMR spectrum (CDCI3 / TMS): δ = 3.21 / 3.22 / 3.23 / 3.24 (2H); 4.06 (3H); 4.18 / 4.19 / 4.20 / 4.21 (2H); 6.3 (IH, b); 6.93-6.98 (2H); 7.17-7.21 (IH); 7.26-7.34 (lH) ppm.

HPLC: logP = 1.75. Production of the starting materials according to formula (VI)

Example (VI- 1)

Procedure d)

4.15 g (0.0138 mol) of benzofuran-2,3-dione 2- [O- (2-bromethyl) oxime] 3- (O-methyloxime) are dissolved in 14 ml of N, N-dimethylformamide. 1.6 g (0.021 mol) of thioacetic acid and 2.3 g (0.021 mol) of sodium carbonate are added at 20 ° C. and the mixture is stirred 2

Hours. The reaction mixture is then poured onto water and extracted with diethyl ether. The organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo.

3.97 g (95.7% of theory) of crude thioacetic acid S- [2- (3-methoxyimino-

3H-benzofuran-2-ylideneaminooxy) ethyl] ester, which is further reacted without purification, as a mixture of stereoisomers.

Isomer A: HPLC: logP = 3.01

^Ϊ H-NMR spectrum (CDCI3 / TMS): δ - 4.22 (3H) ppm.

Isomer B: HPLC: logP = 3.18.

iH-NMR spectrum (CDCI3 / TMS): δ = 4.21 (3H) ppm. Production of a starting material according to formula (VII)

Example VII-1

1 g (0.0052 mol) of benzofuran-2,3-dione 3- (O-methyloxime) 2-oxime is mixed with 1.5 g (0.0141 mol) of sodium carbonate and 3 g (0.016 mol) of 1,2-dibromethane in 5 ml of dimethylformamide stirred at 80 ° C for 6 hours. The reaction mixture is then poured onto water and extracted with diethyl ether. The organic phase is washed with aqueous potassium hydroxide solution and dried over sodium sulfate. After distilling off the solvent in vacuo, 1.1 g (70.7% of theory) of crude benzofuran-2,3-dione 2- [O- (2-bromethyl) oxime] 3- (O-methyloxime) as a mixture of stereoisomers, which is further implemented without purification.

Isomer A: HPLC logP = 3.08

1 H-NMR spectrum (CDCI3 / TMS): δ = 4.23 (3H) ppm

Isomer B:

HPLC: logP = 3.23

¹ H NMR Spectrum (CDCI3 / TMS): δ = 4.21 (3H) ppm Examples of use:

Example A

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 concentrate is diluted 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 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 a

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 (1) shows an efficiency of 90% or more at an application rate of 100 g / ha.

Claims

claims

1. Compounds of the general formula (I),

in which

Z for optionally substituted cycloalkyl, aryl, arylalkyl,

Heterocyclyl or heterocyclylalkyl,

Q represents oxygen or sulfur,

X represents halogen and

L, iß, iß and iß 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.

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

for cycloalkyl or cycloalkylalkyl which are each mono- or disubstituted 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 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 or disubstituted in the aryl part, in each case optionally substituted in the aryl part, each having 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; 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 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 having 2 or 3 carbon atoms or dioxyalkylene having 1 or 2 carbon atoms;

A or a grouping | J where

₂ ^ ^N

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

Pß for hydroxy, amino, methylamino, methyl, phenyl, benzyl,

Alkoxy, alkylamino, dialkylamino having 1 to 4 carbon atoms in the respective alkyl chains,

Q represents oxygen or sulfur,

X represents fluorine, chlorine or bromine, preferably fluorine or chlorine and in particular fluorine and L, iß, iß and iß are the same or different and are each independently of one another 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, preferably for Are hydrogen or methyl and especially hydrogen.

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

Z for each, if appropriate, once to twice by fluorine, chlorine,

Methyl, ethyl or hydroxy substituted cyclopentyl or cyclohexyl;

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

or in particular represents phenyl or benzyl which is optionally monosubstituted to quadrupled, in particular monosubstituted or doubly, identically or differently, 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, methoxy-methyl,

Methoxy, ethoxy, n- or i-propoxy, Methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfmyl, methylsulfonyl or ethylsulfonyl,

Methylaminomethyl, dimethylaminomethyl,

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

Trifiuormethyl, 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, ethoxy carbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, acryloyl, propioloyl,

Cyclopentyl, cyclohexyl,

in each case 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 ^, where

, 2 ^

AI stands for hydrogen or methyl and

Pß stands for hydroxy, methoxy, ethoxy, amino, methylamino, methyl, phenyl or benzyl,

Q represents sulfur or in particular oxygen,

X represents fluorine or chlorine and

L, iß, iß and iß 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,

Ethylsulfmyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulfonyl are.

4. agent containing extenders and / or carriers and optionally surface-active substances, characterized by a content of at least one compound of formula (I) according to claim 1.

5. A method for controlling pests, characterized in that compounds of the formula (I) according to Claim 1 or agents according to Claim 4 are allowed to act on pests and / or their habitat. Use of compounds of formula (I) according to Claims 1 to 3 or agents according to Claim 4 for controlling pests.

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

Process for the preparation of compounds of formula (I) as defined in claim 1, characterized in that

a) 3- (2-Hydroxyphenyl) -3-methoxyiminomethyl-oxathiazine of the formula

(II),

in which

L, iß, iß and iß 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,

optionally in the presence of a diluent, optionally in the presence of an acid acceptor and optionally in the presence of a catalyst, or that

Phenoxypyrimidines of the general formula (IV)

in which

X, L, ß, ß and ß have the meanings given in claim 1 and

γ2 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.

Compounds of formula (II)

in which

L, iß, iß and iß have the meanings given in claim 1.

10. Compounds of the formula (IV) in which

L, iß, iß andL ^ have the meanings given in claim 1 and

Y ^{2 represents} halogen.

11. Compounds of the formula (VI)

in which

ß, lß, let wxAlß have the meanings given in Claim 1 and

R ^{1 represents} alkyl.