EP1131309A2 - Thiophendioximether - Google Patents

Abstract

The present invention relates to new thiophendioximethers, to a method for producing the same as well as to their use as fungicides.

Description

Thiophene dioxime ether

The invention relates to new thiophene dioxime ethers, a process for their preparation and their use as fungicides.

It has already been known that certain compounds which are constitutionally similar to those described below have fungicidal properties (see e.g. WO 95-04728). The fungicidal activity of these compounds, however, leaves something to be desired, especially at low application rates.

The new thiophene dioxime ethers of the general formula (I) have now been found

in which

E represents optionally substituted, geminally linked thiophene diyl,

R ^{1 represents} optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or arylalkyl,

R ^{2 represents} optionally substituted alkyl, alkenyl, alkynyl, aryl, cycloalkyl, arylalkyl, heterocyclyl or heterocyclylalkyl,

R ^{3 represents} optionally substituted alkyl or cycloalkyl, and for a single bond, oxygen, sulfur or a grouping

N— R ⁴ stands for

/

R ^{4 represents} alkyl, or together with R ² and the nitrogen atom to which they are attached, forms an optionally substituted heterocyclic ring.

It was also found that the new thiophene dioxime ethers of the general formula (I) can be obtained if esters of the formula (II)

in which

E, R ¹ , R ² , R ³ and Z have the meanings given above and

Alk stands for alkyl,

with hydroxylamine or an acid addition complex thereof, if appropriate in the presence of a diluent and if appropriate in the presence of a base, and the resulting intermediate product, preferably without working up, with a reactive ethane derivative, such as, for example, 1,2-dichloroethane, 1,2-dibromoethane, 1 , 2-bis (4-tolylsulfonyloxy) ethane, 1,2-bis-methylsulfonyloxyethane or ethylene carbonate, if appropriate in the presence of a diluent and if appropriate in the presence of a base. Finally, it was found that the new thiophene dioxime ethers of the general formula (I) have a very strong fungicidal activity.

The compounds of the invention can optionally be used as mixtures of various possible isomeric forms, especially stereoisomers, such as e.g. E and Z, or optical isomers are present. Both the E and the Z isomers, the individual enantiomers, the racemates and any mixtures of these isomers are claimed.

Preference is given to thiophene dioxime ethers of the formula (I) in which

E for optionally by halogen, alkyl or alkoxy, each with 1 to 4

Carbon atoms substituted, particularly preferably unsubstituted, geminally linked thiophene diyl,

R ¹ for alkyl with 1 to 12 carbon atoms, alkenyl or alkynyl with 2 to 12 carbon atoms, cycloalkyl with 3 to 8 carbon atoms optionally substituted by halogen or alkyl with 1 to 4 carbon atoms or arylalkyl with 6 to 10 optionally substituted in the aryl part

Carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part, the substituents preferably being selected from the following list: halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl,

Alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 8 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; for alkyl with 1 to 12 carbon atoms, alkenyl or alkynyl with 2 to 12 carbon atoms, optionally substituted by halogen or alkyl with 1 to 4 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, for optionally with halogen, alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl 1 to 4 carbon atoms, haloalkoxy, haloalkylthio, haloalkylsulfmyl or haloalkylsulfonyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms or phenyl, substituted heterocyclyl, benzoheterocyclyl, dibenzoheterocyclyl or heterocyclylalkyl each having 3 to 7 ring members in the heterocyclyl part

Carbon atoms in the alkyl part; or in each case optionally substituted aryl or arylalkyl in the aryl part having 6 to 10 carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part, the substituents preferably being selected from the following list:

Halogen, cyano, nitro, amino, 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 with

2 to 6 carbon atoms; in each case straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfmyl 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 11 identical or different halogen atoms; in each case straight-chain or branched alkylamino, dialkylamino, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl or arylalkylaminocarbonyl 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, 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; each optionally substituted by halogen, alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl having 1 to 4 carbon atoms, haloalkoxy, haloalkylthio, haloalkylsulfmyl or haloalkylsulfonyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms, phenoxy or phenylalkoxy having 1 to 4 carbon atoms in the alkyl part , each optionally by halogen, alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl having 1 to 4 carbon atoms, haloalkoxy, haloalkylthio, haloalkylsulfmyl or haloalkylsulfonyl having 1 to

4 carbon atoms and 1 to 9 halogen atoms or phenyl substituted heterocyclyl, heterocyclyloxy, heterocyclylthio, heterocyclylsulfinyl or heterocyclylsulfonyl with 5 or 6 ring members,

or a group 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,

for alkyl having 1 to 4 carbon atoms or for cycloalkyl having 3 to 4 substituents which is optionally mono- to tetrasubstituted by halogen or alkyl 6 carbon atoms, in particular methyl or cyclopropyl, and

for a single bond, oxygen, sulfur or a grouping

N— R ⁴ stands for

/

R ^{4 represents} alkyl having 1 to 4 carbon atoms, or together with R ² and the nitrogen atom to which they are attached, forms an optionally substituted, 3 to 6-membered, heterocyclic ring.

In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, are also straight-chain or branched, also in combination with heteroatoms, such as in alkoxy or alkylthio.

Haloalkyl stands for partially or completely halogenated alkyl. In the case of polyhalogenated haloalkyl, the halogen atoms can be the same or different.

Preferred halogen atoms are fluorine and chlorine and especially fluorine. If the haloalkyl carries further substituents, the maximum possible number of halogen atoms is reduced to the remaining free valences.

Halogen generally represents fluorine, chlorine, bromine or iodine, preferably

Fluorine, chlorine or bromine, especially for fluorine or chlorine.

Heterocyclyl stands for saturated or unsaturated, as well as aromatic, ring-shaped compounds in which at least one ring member is a hetero atom, ie an atom different from 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 atoms, they are not adjacent. If appropriate, the ring-shaped compounds with further carbocyclic or heterocyclic, fused or bridged rings form together a polycycic ring system. A polycyclic ring system can be linked via the heterocyclic ring or a fused-on carbocyclic ring. Mono- or bicyclic ring systems are preferred, in particular mono- or bicyclic aromatic ring systems.

Thiophene dioxime ethers of the formula (I-a) are particularly preferred

in which

R ^{1 is} methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, allyl, 2-buten-l-yl, 2-methyl-2-buten-l-yl, propargyl or for cyclopentyl or cyclohexyl which is optionally up to four times substituted by fluorine, chlorine, methyl or ethyl; or for optionally substituted by methyl, ethyl, fluorine, chlorine or bromine

Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; or stands for benzyl, 1-phenylethyl or 2-phenylethyl which is optionally monosubstituted to tetrasubstituted in the same or different ways, the possible substituents preferably being selected from the list below:

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, n - or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, methylaminomethyl, dimethylaminomethyl, trifluoromethyl. Trifluoroethyl,

Difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, Pentafluoroethoxy, 2-chloro-l, l, 2-trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl,

for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, pentyl, hexyl,

Heptyl, octyl, nonyl, decyl, undecyl, dodecyl, allyl, 2-buten-1-yl, 2-methyl-2-butan-1-yl, propargyl, each optionally optionally up to four times substituted by fluorine, chlorine, methyl or ethyl Cyclopentyl or cyclohexyl; or for optionally by methyl, ethyl, fluorine, chlorine, bromine, trifluoromethyl,

Phenyl substituted thienyl, pyridyl, furyl, piperazinyl, thiazolyl, dioxazinyl, benzimidazolyl, benzthiazolyl, benzofuranyl, benzopyrazolyl, dibenzothiazinyl, thienylmethyl, pyridylmethyl or furylmethyl; or represents phenyl, benzyl, 1-phenylethyl or 2-phenylethyl which is monosubstituted or disubstituted in the phenyl part in each case optionally in the phenyl moiety, the possible substituents preferably being selected from the list below:

Fluorine, chlorine, bromine, cyano, nitro, amino, 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, trifluoromethyl

Methylamino. Ethylamino, n- or i-propylamino, dimethylamino. Diethyl amino,

Methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, cyclopentyl, cyclohexyl, cyclopentyloxy, cyclohexyloxy, each optionally up to four times, identically or differently

Fluorine, chlorine, methyl or trifluoromethyl substituted, in each case doubly linked propanediyl, ethyleneoxy, methylenedioxy, ethylenedioxy, each optionally substituted by fluorine, chlorine, methyl, trifluoromethyl or methoxy, phenoxy or benzyl, in each case optionally by halogen, alkyl, alkoxy, alkylthio,

Alkylsulfinyl or alkylsulfonyl having 1 to 4 carbon atoms, haloalkoxy, haloalkylthio, haloalkylsulfmyl or haloalkylsulfonyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms or phenyl-substituted heterocyclyl, heterocyclyloxy, heterocyclylthio, heterocyclic sulfonyl or ring member with or 6-heterocyclyls for methyl , Ethyl, fluorine, chlorine, bromine, trifluoromethyl, phenyl substituted thienyl, imidazolyl, thiadiazolyl, pyridyl, furyl, piperazinyl, thiazolyl, dioxazinyl, thiadiazolylsulfonyl;

A or a grouping ^. in which

, ₂ jf

A 'represents hydrogen or methyl and

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

for methyl, ethyl, n- or i-propyl, or for cyclopropyl, cyclobutyl, cyclopentyl or phenyl which is optionally up to four times substituted by fluorine, chlorine, methyl or ethyl; in particular represents methyl or cyclopropyl, Z for a single bond. Oxygen, sulfur or a grouping

N— R ⁴ stands for

/

R ^{4 represents} methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or together with R ² and the nitrogen atom to which they are attached, an optionally substituted 5 to 6 membered, heterocyclic ring forms.

R ¹ preferably represents ethyl and in particular methyl.

R ³ preferably represents ethyl and in particular methyl.

R ² preferably represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or phenyl which is substituted once or twice by fluorine, chlorine, methyl, methoxy, trifluoromethyl and / or trifluoromethoxy or especially for unsubstituted phenyl.

The general or residual definitions given above or in the preferred ranges 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.

These radical definitions can be combined with one another as desired, that is to say also between the specified ranges of preferred compounds.

Formula (II) provides a general definition of the esters required as starting materials for carrying out the process according to the invention for preparing the thiophene dioxime ethers of the formula (I). In this formula (II), E, R ¹ , R ² , R ³ and Z have preferably or in particular those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as preferred or as particularly preferred for E, R ¹ , R ² , R ³ and Z.

The esters of the formula (II) are not yet known; they are also the subject of the present application as new substances.

They are obtained if halomethylthiophenes of the formula (III)

in which

E and Alk have the meanings given above and

X represents halogen,

with oximes of the formula (IV),

in which

R ¹ , R ² , R ³ and Z have the meanings given above, optionally in the presence of a diluent, preferably an ether, such as tetrahydrofuran, a nitrile, such as acetonitrile, an amide, such as N, N-dimethylformamide, or N-methylpyrrolidone; or a sulfoxide such as dimethyl sulfoxide; optionally in the presence of a base, preferably an alkaline earth metal or alkali metal hydride, or alcoholates, such as, for example, sodium hydride, sodium methylate, sodium ethylate or potassium tert-butoxide.

The halomethylthiophenes required as starting materials for carrying out the process according to the invention for the preparation of the esters of the formula (II) are generally defined by the formula (III). In this formula (III), E preferably or in particular has those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as preferred or as particularly preferred for E. Alk preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl. X represents halogen, preferably chlorine or bromine.

The halomethylthiophenes of the formula (III) are known and can be prepared by known methods (compare, for example, WO 95-01973 or EP-A 579 071).

Formula (IV) provides a general definition of the oximes which are further required as starting materials for carrying out the process according to the invention for preparing the esters of formula (II). In this formula (IV), R ¹ , R ² , R ³ and Z preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the invention

Formula (I) was mentioned as preferred, or as particularly preferred for R ¹ , R ² , R ³ and Z.

The oximes of the formula (IV) are known and can be prepared by known methods (compare, for example, WO 96-32373 and WO 97-06133). The ethane derivatives still required as starting materials for carrying out the process according to the invention for the preparation of the thiophene dioxime ethers of the formula (I) are known synthetic chemicals.

As a diluent for carrying out the method according to the invention

Preparation of the thiophene dioxime ethers of the formula (I) 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; 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; 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.

The process according to the invention for the preparation of the thiophene dioxime ethers of the formula (I) 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 aramo- nium carbonate, as well as 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 Diazabicycloundecen (DBU).

The reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 0 ° C to 80 ° C.

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 can be used in crop protection and material protection.

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 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 permits 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

Combating cereal diseases, such as against Puccinia species, diseases in wine, fruit and vegetable cultivation, such as against Venturia 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,

Fine encapsulation in polymeric materials and in coating compositions for seeds, as well as ULV cold and warm mist formulations.

These formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, e.g. organic solvents can 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. as well as water. With liquefied Gaseous extenders or carriers are those 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. Solid carrier materials are suitable: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates. Possible solid carriers for granules are: e.g. 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. Suitable emulsifiers and / or foaming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Possible dispersants are, for example, lignin sulfite liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. 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 can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%. Depending on their respective physical and / or chemical properties, the active ingredients 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, and ULV -Cold and warm mist formulations.

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, chloropicrin, 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, Dithianon,

Dodemo h, Dodine, Drazoxolon,

Ediphenphos, epoxiconazole, etaconazole, ethirimol, etridiazole, famoxadone, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,

Fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam. Ferimzon, Fluazinam, flumetover, fluoromide, fluquinconazole, Fkuprimidol, flusilazole,

Flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum, fosetyl-sodium,

Fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis,

Furmecyclox, guazatin,

Hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, imibenconazole, iminoctadine, iminoctadineal besilate, iminoctadine triacetate,

Iodocarb, Ipconazole, 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 mix,

Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl,

Metconazole, methasulfocarb, methfuroxam, metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,

Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,

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

Paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphene, 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, Tioxymid, Tolclofos-methyl,

Tolylfluanid, Triadimefon, Triadimenol, Triazbutil, Triazoxid, Trichlamid, Tricyclazol,

Tridemoφh, triflumizole, triforin, triticonazole,

Uniconazole,

Validamycin A, vinclozolin, viniconazole, zarilamide, 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-dichloro-phenyl) -ß-fluoro-b-propyl-1 H-1, 2,4-triazole-1-ethanol, α- (2,4-dichloφhenyl) -ß-methoxy-a-methyl-1 H-1, 2,4 -triazol-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- (1H-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-dichloro phhenyl) -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-dichloro-phenyl) -3- (2-propenyl) -2,5-pyrrolidinedione, 1 - [ (Diiodomethyl) sulfonyl] -4-methyl-benzene,

1 - [[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1 H-imidazole,

1 - [[2- (4-Chlθφhenyl) -3-phenyloxiranyl] methyl] - 1 H- 1, 2,4-triazole,

1 - [1 - [2 - [(2,4-dichlorothenyl) methoxy] phenyl] ethenyl] - 1 H-imidazole, l-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol, 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1, 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 - [(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-l, l, 3-trimethyl-lH-inden-4-yl) -3-pyridinecarboxamide, -Chlor-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) acetamide, -phenylphenol (OPP),, 4-dichloro-1 - [4- (difluoromethoxy) -phenylj- 1 H-pyrrole-2, 5-dione, 5-dichloro-N- [cyan [(1-methyl-2-propynyl) -oxy] -methyl] -benzamide, - (1, 1-dimethylpropyl-1-oxo-1 H-inden-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-methy-1-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) carbonyl] hydrazide, bis- (l-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) -oxy] -2,5-thiophene dicarboxylate, ice-1 - (4-chloro-phenyl) -2- (1 H-1, 2,4-triazole-1-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,

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) -l-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- l - [(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-1, 2,3-benzothiadiazole-7-carbothioate, spiro [2H] - 1-benzopyran-2, 1 '(3Η) -isobenzofuran] -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, Acephate, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb, Alpha-cypermethrin, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azamethiphos, Azinphos A, Azinphos M, Azocyclotin,

Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Betacyfluthrin, Bifenazate, Bifenthrin, Biethanomofufoxin, Bethanomethofinoxin, Bethenomethrin Butyl pyridaben

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chloφyrifos, Chloφyrifos M, Chlovaporthrin, Cis-Resmethrin, Clispethythrinhrin, Cispermythrinhrin, Cispermethrinhrin , Cyhalothrin, cyhexatin, cypermethrin, cyromazine,

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlorvos, Diflubenzuron, Dimethoat, Dimethylvinphos, Diofenolan, Disulfoton, Docusat-sodium, Dofenapyn, Eflusilanate, Emamectin, Empentanate, Endorphin, Endof. Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos, Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flubrocythrinate, Flucycloxoxinon, Flutoxinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, , Furathiocarb,

Granulosis viruses

Halofenozide, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene, Imidacloprid, Isazofos, Isofenphos, Isoxathion, Ivermectin, Kernpolyederviruses Lambda-cyhalothrin, Lufenuron

Malathion, Mecarbam, Metaldehyde, Methamidophos, Metharhician anisopliae, Metharhician flavoviride, Methidathione, Methiocarb, Methomyl, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Monocrotophos, Naled, Nitenpyramo, Oxitomethonid, Oxitomethonate, Oxitomethamate, Oxitomethonate, Oxitomethonate, Oxyne, Oxidonyl, Oxitone, Oxitone, Oxyne, Oxyne, Oxitone

Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propoxur, Prothiofos, Prothoat, Pyymrahrofinos. Pyrethrum, pyridaben, pyridathione, pyrimidifen, pyriproxyfen,

Quinalphos, Ribavirin

Salithion, Sebufos, Silafluofen, Spinosad, Sulfotep, Sulprofos, Tau-fluvalinate, Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Temivinphos, Terbufos, Tetrachlorvinamethetox, Thoxinoxioxoxate, Thetinoxioxilate, cetamidoxi Thiofanox, Thuringiensin, Tralocythrin, Tralomethrin, Triarathene, Triazamate, Triazophos, Triazuron, Trichlophenidine, Trichlorfon, Triflumuron, Trimethacarb, Vamidothion, Vaniliprole, Verticillium lecanii

YI 5302 Zeta-cypermethrin, zolaprofos

(IR-cis) - [5- (phenylmethyl) -3-furanyl] methyl-3 - [(dihydro-2-oxo-3 (2H) - furanylidene) methyl] -2,2-dimethylcyclopropane carboxylate (3-phenoxyphenyl ) -methyl-2,2,3,3-tetramethylcyclopropane carboxylate l - [(2-chloro-5-thiazolyl) methyl] tetrahydro-3,5-dimethyl-N-nitro-l, 3,5-triazine-2 (1H ) - imin

2- (2-Chloro-6-fluoφhenyl) -4- [4- (l, l-dimethylethyl) phenyl] -4,5-dihydro-oxazole 2- (acetyloxy) -3-dodecyl-1, 4-naphthalenedione

2-Chloro-N - [[[4- (l-phenylethoxy) phenyl] amino] carbonyl] benzamide 2-chloro-N - [[[4- (2,2-dichloro-l, l-difluoroethoxy ) -phenyl] -amino] -carbonyl] -benzamide

3-methylphenyl propyl carbamate

4- [4- (4-ethoxyphenyl) -4-methylpentyl] -1-fluoro-2-phenoxy-benzene 4-chloro-2- (1,1-dimethylethyl) -5 - [[2- (2,6- dimethyl-4-phenoxyphenoxy) ethyl] thio] - 3 (2H) -pyridazinone 4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 ( 2H) - pyridazinone

4-chloro-5 - [(6-chloro-3-pyridinyl) methoxy] -2- (3,4-dichloφhenyl) -3 (2H) -pyridazinone Bacillus thuringiensis strain EG-2348 benzoic acid [2-benzoyl- 1 - ( 1, 1-dimethylethyl) hydrazide butanoic acid 2,2-dimethyl-3- (2,4-dichloφhenyl) -2-oχo-l-oxaspiro [4.5] dec-3-en-4-yl ester

[3 - [(6-Chloro-3-pyridinyl) methyl] -2-thiazolidinylidene] -cyanamide dihydro-2- (nitromethylene) -2H- 1,3-thiazine-3 (4H) -carboxaldehyde ethyl- [2- [[1,6-dihydro-6-oxo-1- (phenylmethyl) -4-pyridazinyl] oxy] ethyl] carbamate N- (3,4,4-trifluoro-l-oxo-3-butenyl) glycine

N- (4-Chlorophenyl) -3- [4- (difluoromethoxy) phenyl] -4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide

N - [(2-chloro-5-thiazolyl) methyl] -N'-methyl-N "-nitro-guanidine N-methyl 1-N '- (1-methyl 1-2-propenyl) -1, 2-hydrazinedicarbothioamide N-methyl-N'-2-propenyl-1, 2-hydrazine dicarbothioamide

O, O-Diethyl- [2- (dipropylamino) -2-oxoethyl] ethyl phosphoramidothioate 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, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process 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 using the active compounds according to the invention 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.

Manufacturing examples

Example 1):

1.8 g of methyl methoxyimino- [3- (2-methoxyimino-l-methyl-2-phenylethylidene-aminooxymethyl) thiophene-2-yl] acetic acid (0.002 mol) are added at 25 ° C. to a mixture of 0.63 g (0.009 mol) of hydroxylammonium chloride and 1.5 g of 85% potassium hydroxide (0.03 mol) in 20 ml of methanol. The mixture is heated at 60 ° C. for 1 hour, then 0.7 g (0.005 mol) of potassium carbonate are added, followed by 4.2 g

(0.022 mol) of dibromoethane and reflux for 16 hours. The mixture is poured onto water, acidified with 2N aqueous hydrochloric acid and extracted with ethyl acetate. The organic phase is dried over sodium sulfate, the solvent is distilled off in vacuo and the residue is chromatographed with ether: petroleum ether = 1: 1 on silica gel. 0.45 g (52% of theory) of l-phenylpropane-l, 2-dione 2- (O- {2 - [(5,6-dihydro- [l, 4,2] dioxazin-3-yl) - methoxyiminomethyl] -thiophene-3-ylmethyl} -oxime) 1 - (O-methyloxime) with a content of 92.8% (HPLC).

HPLC: logP = 3.56

iH-NMR spectrum (CDCI3 / TMS): δ = 2.09 (3H); 3.85 (3H); 3.90 (3H); 4.0-4.1 (2H); 4.38-4.42 (2H); 4.84 (2H); 6.92-6.97 (1H); 7.1-7.18 (2H); 7.32-7.38 (3H); 7.65-7.7 (lH) ppm. Analogously to Example 1 and in accordance with the general description of the preparation process according to the invention for the preparation of the compounds of the formula (I), the following compounds of the formula Ia according to the invention which are listed in Table 1 were also obtained:

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 raw materials:

Example (II-l):

2.3 g (0.077 mol) of 80% sodium hydride are suspended in 100 ml of dimethylformamide. At 0 ° C., 15 g (0.078 mol) of l-phenylpropane-1,2-dione 1 - (O-methyloxime) 2-oxime are added in portions and the mixture is stirred for about 1 hour until the evolution of gas has ended. The mixture is then cooled to -10 ° C., 23 g (0.078 mol) of (3-bromomethylthiophen-2-yl) methoxyiminoacetic acid methyl ester are added, and another 16

Stirred for hours without cooling. Now the mixture is poured onto water, extracted with diethyl ether and the organic phase is washed 3 times with 5% cold sodium hydroxide solution. After distilling off the solvent in vacuo, 14 g (20.7% of theory) of methoxyimino- [3- (2-methoxyimino-l-methyl-2-phenyl-ethylidene-aminooxymethyl) -thiophen-2-yl] are obtained. -acetic acid methyl ester with a content of 46.6

% (HPLC) and a logP of 3.89. The raw product is implemented without further purification.

Analogous to example (II-1), and in accordance with the general description of the production process according to the invention for the preparation of the compounds of the formula

(II) the following compounds according to the invention of the formula II-a mentioned in Table 2 were also obtained:

Table 2:

Examples of use

Example A

Puccinia test (wheat) / protective

Solvent: 10 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 protective activity, young plants are sprayed with an active compound preparation in the stated application rate. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Puccinia recondita. The plants remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 48 hours.

The plants are then placed in a greenhouse at a temperature of approximately 20 ° C. and a relative atmospheric humidity of 80% in order to prevent the development of

Favor 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 (1) shows an efficiency of 90% or more at an application rate of 250 g / ha. Example B

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 concentrate is diluted 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 conidia suspension of the Venturia inaequalis apple scab pathogen 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 the greenhouse at approx. 21 ° C. and a relative humidity of approx. 90%.

Evaluation is carried out 12 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 formula (I)

in which

E represents optionally substituted, geminally linked thiophene diyl,

R ^{1 represents} optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or arylalkyl,

R ^{2 represents} optionally substituted alkyl, alkenyl, alkynyl, aryl, cycloalkyl, arylalkyl, heterocyclyl or heterocyclylalkyl,

R ^{3 represents} optionally substituted alkyl or cycloalkyl, and

Z for a single bond, oxygen, sulfur or a grouping

N— R ⁴ stands for

/

R ^{4 represents} alkyl, or together with R ² and the nitrogen atom to which they are attached, forms an optionally substituted heterocyclic ring.

Compounds of formula (I) according to claim 1, in which E represents thiophene diyl optionally substituted by halogen, alkyl or alkoxy, each having 1 to 4 carbon atoms or unsubstituted, geminally linked thiophene diyl,

R ^{1 is} alkyl having 1 to 12 carbon atoms, alkenyl or alkynyl having 2 to 12 carbon atoms, cycloalkyl having 3 to 8 carbon atoms optionally substituted by halogen or alkyl having 1 to 4 carbon atoms or arylalkyl having 6 to 10 carbon atoms optionally substituted in the aryl part and 1 to 4

Carbon atoms in the alkyl part, the substituents being selected from the following list:

Halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 8 carbon atoms; in each case straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfmyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;

R ² for alkyl with 1 to 12 carbon atoms, alkenyl or alkynyl with 2 to 12 carbon atoms, cycloalkyl with 3 to 8 carbon atoms optionally substituted by halogen or alkyl with 1 to 4 carbon atoms, for optionally with halogen, alkyl, alkoxy, alkylthio, alkylsulfinyl or Alkylsulfonyl with 1 to 4 carbon atoms, haloalkoxy, haloalkylthio, haloalkylsulfmyl or haloalkylsulfonyl with 1 to 4 carbon atoms and 1 to 9 halogen atoms or phenyl, substituted heterocyclyl, benzoheterocyclyl, dibenzoheterocyclyl or heterocyclylalkyl, each with 3 to 7 ring members in the heterocyclyl part and 1 to 4 carbon atoms in the alkyl part; or in each case optionally substituted aryl or arylalkyl in the aryl part with 6 to 10 carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part, the substituents being selected from the following list:

Halogen, cyano, nitro, amino, 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 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,

Alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl or arylalkylaminocarbonyl 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, methyl, trifluoromethyl or ethyl, 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; each optionally by halogen, alkyl, alkoxy. Alkylthio. Alkylsulfinyl or alkylsulfonyl with 1 to 4 carbon atoms, haloalkoxy, haloalkylthio, haloalkylsulfmyl or haloalkylsulfonyl with 1 to 4 carbon atoms and 1 to 9 halogen atoms substituted phenoxy or phenylalkoxy with 1 to 4 carbon atoms in the alkyl part, in each case optionally by halogen, alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl with 1 to 4 carbon atoms, haloalkoxy, haloalkylthio, haloalkylsulfmyl or haloalkylsulfonyl with 1 to 4 carbon atoms and 1 to 9 halogen atoms or phenyl-substituted heterocyclyl, heterocyclyloxy,

Heterocyclylthio, heterocyclylsulfinyl or heterocyclylsulfonyl with 5 or 6 ring members,

or a group in which

A represents hydrogen or alkyl having 1 to 4 carbon atoms or

Cycloalkyl having 3 to 6 carbon atoms and

A2 stands for hydroxy, amino, methylamino, methyl, phenyl, benzyl, alkoxy, alkylamino, dialkylamino with 1 to 4 carbon atoms in the respective alkyl chains,

R ^{3 stands} for alkyl with 1 to 4 carbon atoms or for cycloalkyl with 3 to 6 carbon atoms which is optionally monosubstituted to tetrasubstituted by halogen or alkyl, in particular for methyl or cyclopropyl and

Z for a single bond, oxygen, sulfur or one Grouping N— R ⁴ stands for /

R ^{4 represents} alkyl having 1 to 4 carbon atoms, or together with R ² and the nitrogen atom to which they are attached, forms an optionally substituted, 3 to 6-membered, heterocyclic ring.

Compounds of formula (I-a)

in which

R ¹ , R ² , R ³ and Z have the meanings given in claim 1.

Compounds of formula (I-a) according to claim 3

in which

R ^{1 is} methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, allyl, 2-buten-1-yl. 2-methyl-2-buten-l-yl, propargyl or for each optionally up to four times by fluorine, chlorine, methyl or ethyl substituted cyclopentyl or cyclohexyl; or for cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl optionally substituted by methyl, ethyl, fluorine, chlorine or bromine; or stands for benzyl, 1-phenylethyl or 2-phenylethyl which is optionally monosubstituted to tetrasubstituted in the same or different ways, the possible substituents being selected from the list below:

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, n - or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, methylaminomethyl, dimethylamino-methyl,

Trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, pentafluoroethoxy, 2-chloro-1, 1, 2-trifluorethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylfiformethyl, trifluoromethyl

for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, allyl, 2-

Buten-1-yl, 2-methyl-2-buten-l-yl, propargyl, each optionally optionally up to four times substituted by fluorine, chlorine, methyl or ethyl cyclopentyl or cyclohexyl; or for thienyl, pyridyl, furyl optionally substituted by methyl, ethyl, fluorine, chlorine, bromine, trifluoromethyl, phenyl,

Piperazinyl, thiazolyl, dioxazinyl, benzimidazolyl, benzthiazolyl, benzofuranyl, benzopyrazolyl, dibenzothiazinyl, thienylmethyl, pyridylmethyl or furylmethyl; or for phenyl, benzyl, 1-phenylethyl or 2-phenylethyl which is monosubstituted to tetrasubstituted by identical or different substituents in the phenyl moiety in each case, the possible substituents being derived from the the following list is selected:

Fluorine, chlorine, bromine, cyano, nitro, amino, 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, ethylsulfyl, 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-1, 1, 2-trifluorethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylfiformethyl, trifluoromethyl

Methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, cyclopentyl, cyclohexyl, cyclopentyloxy, cyclohexyloxy, in each case optionally or differently by four times, chlorine, in each case simply or differently , Methyl or trifluoromethyl substituted, in each case doubly linked propanediyl, ethyleneoxy, methylenedioxy,

Ethylene dioxy, each optionally substituted by fluorine, chlorine, methyl, trifluoromethyl or methoxy, phenoxy or benzyl, each optionally by halogen, alkyl, alkoxy, alkylthio. Alkylsulfinyl or alkylsulfonyl with 1 to 4 carbon atoms,

Haloalkoxy, haloalkylthio, haloalkylsulfmyl or Haloalkylsulfonyl with 1 to 4 carbon atoms and 1 to 9 halogen atoms or phenyl-substituted heterocyclyl, heterocyclyloxy, heterocyclylthio, heterocyclylsulfinyl or heterocyclylsulfonyl with 5 or 6 ring members, optionally substituted by methyl, ethyl, fluorine, chlorine, bromine, trifluoromethyl, phenyl, phenyl Thiadiazolyl, pyridyl, furyl, piperazinyl, thiazolyl, dioxazinyl, thiadiazolylsulfonyl;

A or a grouping NJ, where

A ² ^

A ^{l represents} hydrogen or methyl and

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

R ^{3 represents} methyl, ethyl, n- or i-propyl, or each cyclopropyl, cyclobutyl, cyclopentyl or phenyl which is optionally monosubstituted to tetrasubstituted by fluorine, chlorine, methyl or ethyl,

Z for a single bond, oxygen, sulfur or a grouping

stands, where

R ^{4 represents} methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or together with R ² and the nitrogen atom to which they are attached, an optionally substituted 5 to 6 membered, heterocyclic ring forms.

5. A compound according to any one of claims 1 to 4, in which

R ¹ and R ^{3 are} methyl.

6. agents containing extenders and / or carriers and optionally surface-active substances, characterized by a content of at least one compound as defined in claims 1 to 5.

7. Verfaliren to control pests, characterized in that compounds as defined in claim 1 or agents as defined in claim 6 are allowed to act on pests and / or their habitat.

8. Use of compounds as defined in claims 1 to 5 or agents as defined in claim 6 for controlling pests.

9. A process for the preparation of agents, characterized in that compounds as defined in claims 1 to 5 are mixed with extenders and / or carriers and / or surface-active agents.

10. A process for the preparation of compounds as defined in claim 1, characterized in that esters of the formula (II)

in which

E. R ¹ . R ² , R ³ and Z have the meanings given in claim 1 and Alk stands for alkyl,

with hydroxylamine or an acid addition complex thereof, if appropriate in the presence of a diluent and if appropriate in the presence of a base, and the resulting intermediate is reacted further with a reactive ethane derivative if appropriate in the presence of a diluent and if appropriate in the presence of a base.

1 1. Compounds of formula (II)

in which

E, R ¹ , R ² , R ³ and Z have the meanings given in claim 1 and

Alk stands for alkyl.

12. A process for the preparation of compounds of formula (II) according to

Claim 11, characterized in that halomethylthiophenes of the formula

in which

E and Alk have the meanings given above and

X represents halogen,

with oximes of the formula (IV),

in which

R ¹ , R ² , R ³ and Z have the meanings given above,

if appropriate in the presence of a diluent and if appropriate in the presence of a base.