EP0730592A1

EP0730592A1 - Derivatives of 2,3,5,6-tetrafluorobenzoic acid and their use in combating pests

Info

Publication number: EP0730592A1
Application number: EP95901380A
Authority: EP
Inventors: Udo Kraatz; Gerd Hänssler
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1993-11-25
Filing date: 1994-11-14
Publication date: 1996-09-11
Also published as: CN1141037A; HU9601420D0; BR9408162A; PL314587A1; DE4340180A1; SK65896A3; CZ147396A3; WO1995014688A1; AU1064995A; HUT74715A; TW258646B; JPH09511221A

Abstract

The application relates to derivatives of 2,3,5,6-tetrafluorobenzoic acid of formula (I) wherein Y represents oxygen or sulphur and X represents the groups -O- N=CR?1R2, -OR3, -OCHR4-CO-NR5R6 or -NR7R8¿ as well as a process for manufacturing the said substance and uses thereof in combating pests.

Description

DERIVATIVES OF THE 2, 3, 5, 6-TETRAFLUOROBENZOESAURE AND THEIR USE FOR CONTROLLING Pests

The invention relates to new derivatives of 2,3,5,6-tetrafluorobenzoic acid, a process for their preparation and their use for controlling pests.

The application relates to derivatives of 2,3,5,6-tetrafluorobenzoic acid of the general formula (I)

in which

Y stands for oxygen or sulfur and

X represents the groups -ON = CR- -R ² , -OR ³ , -OCHR ⁴ -CO-NR ⁵ R ⁶ or -NR ⁷ R ⁸

wherein

R ¹ and R ² independently of one another are optionally substituted alkyl, cycloalkyl and aryl, R ^{3 is} alkyl with at least 2 carbon atoms, substituted alkyl and optionally substituted cycloalkyl, aryl and aralkyl,

R ⁴ , R ⁵ and R ⁶ independently of one another are hydrogen and optionally substituted alkyl, aryl and aralkyl, or

R ⁵ and R ⁶ together with the nitrogen atom to which they are attached form an optionally substituted ring, or

R ⁷ and R ⁸ independently of one another are hydrogen and optionally substituted alkyl, cycloalkyl, aryl, aralkyl, alkylheteroaryl and heteroaryl, or represent the groups -CHR ⁴ -COOH and -CHR ⁴ -COOCH ₃ , where R ⁷ and R ^{8 are} not simultaneously stand for hydrogen, or

R ⁷ and R ⁸ together with the nitrogen atom to which they are attached form an optionally substituted ring

as well as their acid addition salts and metal salt complexes.

Furthermore, it has been found that the derivatives of 2,3,5,6-tetrafluorobenzoic acid of the formula (I) are obtained if 2,3,5,6-tetrafluorobenzoyl chloride or anhydride with a corresponding oxime, alcohol or amine, if appropriate in the presence a solvent and / or a base.

Finally, it was found that the new derivatives of 2,3,5,6-tetrafluorobenzoic acid of the general formula (I) have an excellent microbicidal activity, in particular against microorganisms which are pathogenic to plants. In addition, the active compounds according to the invention have an excellent resistance-inducing activity in plants against attack by undesired microorganisms.

For the sake of simplicity, the following always refers to compounds of the formula (I), although both the pure compounds and the mixtures are meant with different proportions of isomeric, enantiomeric and diastereomeric compounds. The derivatives of 2,3,5,6-tetrafluorobenzoic acid according to the invention are generally defined by the formula (I).

Unless otherwise defined, the following preferably means in the general formulas:

Alkyl, individually or in composite radicals, straight-chain or branched alkyl having 1 to 8, in particular 1 to 4, carbon atoms. Examples include methyl, ethyl, n.- and i.-propyl, n-, i-, s- and t-butyl.

Cycloalkyl - a 3- to 7-membered ring, in particular a ring with 3, 5 or 6 carbon atoms. Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl may be mentioned by way of example and preferably.

Aryl unsubstituted or substituted aryl having 6 to 10 carbon atoms. Examples are unsubstituted or substituted

Phenyl and naphthyl, especially unsubstituted or substituted phenyl called.

Aralkyl unsubstituted or substituted aralkyl having 1 to 4, in particular 1 or 2, carbon atoms in the straight-chain or branched alkyl part and 6 to

10 carbon atoms, preferably phenyl in the aryl part. Exemplary and preferred are benzyl, 1,1- and 1,2-phenethyl and 1,1-, 1,2-, 1,3- and 2,2-phenylpropyl.

Heteroaryl - unsubstituted or substituted 5- to 9-membered ring, in particular 5- to 7-membered ring, which contains 1 to 4, preferably 1 to 3, identical or different heteroatoms. Preferred heteroatoms are oxygen, sulfur and nitrogen. Be exemplary and preferred Pyrimidinyl, pyrrolyl, isothiazolyl, oxazolyl, thienyl, furyl, pyridazinyl, pyrazinyl, isooxazolyl, thiazolyl and especially pyridyl.

Heteroarylalkyl the heteroaryl part corresponds to the definitions and preferred ranges given above. The alkyl part is straight-chain or branched and contains 1 to

4 especially 1 or 2 carbon atoms. Exemplary and preferred are heteroarylmethyl, 1,1- and 1,2-heteroarylethyl and 1,1-, 1,2-, 1,3- and 2,2-heteroarylpropyl.

The optionally substituted radicals of the general formulas can carry one or more, preferably 1 to 3, in particular 1 or 2, identical or different substituents. Examples of preferred substituents are: alkyl having preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methyl, ethyl, n.- and i.-propyl and n.-, i.-, sea and t. Butyl; Alkoxy preferably having 1 to 4, in particular 1 or 2, carbon atoms, such as methoxy, ethoxy, n.- and i.-propyloxy and n.-, L-, see- and t.-butyloxy; Alkylthio with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methylthio, ethylthio, n.- and i.-propylthio and n.-, i.-, see- and t.-butylthio; Haloalkyl, haloalkoxy and haloalkylthio with preferably 1 to 4, in particular 1 or 2 carbon atoms and preferably 1 to 9, in particular 1 to 5 halogen atoms, where the halogen atoms are identical or different and are halogen atoms, preferably fluorine, chlorine or bromine, in particular fluorine, such as trifluoromethyl, difluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluorochloroethyl, trifluoroethyl, trifluoroethoxy, difluoromethoxy, pentafluoroethoxy, tetrafluoroethoxy, trifluorochloroethoxy, trifluoromethoxy and trifluoromethylthio; Hydroxy; Halogen, preferably fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine; Cyano; Nitro; Dialkylamino with preferably 1 to 4, in particular 1 or 2, carbon atoms per alkyl group, such as dimethylamino and diethylamino; Carboxy; Alkylalkoxy having 1 to 4, in particular 1 or 2, carbon atoms in each alkyl part; Carbonylalkoxy with 1 to 4, especially 1 or 2 carbon atoms in the alkyl part, such as carbonylmethoxy and carbonylethoxy; Carbonylalkyl having 1 to 4, in particular 1 or 2, carbon atoms in the alkyl part, such as acetyl and propionyl; Formyl; Carbonylaryloxy with 5 to 10 carbon atoms in the aryl part, such as carbonylphenoxy; Carbonylaryl having 6 to 10 carbon atoms in the aryl part, such as benzoyl; Oxycarbonylalkyl having 1 to 4, in particular 1 or 2, carbon atoms in the alkyl part, such as acetoxy; Oxycarbonylaryl having 6 to 10 carbon atoms in the aryl part, such as benzoyloxy; Carboxylamino, carbonylaminoalkyl, carbonylaminodialkyl, aminocarbonyl, alkylaminocarbonyl, aminocarbonylalkyl and alkylaminocarbonylalkyl each having 1 to 4, in particular 1 or 2, carbon atoms in the alkyl part; Sulfonamido; Sulfonalkyl; Sulfonylalkyl and sulfonylalkoxy each having 1 to 4, in particular 1 or 2, carbon atoms; in each case unsubstituted or substituted by halogen, in particular fluorine, chlorine and / or bromine, phenyl or phenoxy.

The definitions listed here apply in a corresponding manner to the definitions in the following preferred combinations of radicals.

Preferred are the compounds of formula (I) in which

R ¹ and R ^{2 are the} same or different and each represents unsubstituted or substituted alkyl having 1 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms or phenyl,

R ^{3 represents} alkyl with 2 to 8 carbon atoms, substituted alkyl with 1 to 8 carbon atoms, each unsubstituted or substituted cycloalkyl with 3 to 7 carbon atoms, phenyl or phenylalkyl with 1 to 4 carbon atoms in the alkyl part,

R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are the} same or different and represent hydrogen, in each case unsubstituted or substituted alkyl having 1 to 8 carbon atoms, phenyl or phenylalkyl having 1 to 4 carbon atoms in the alkyl part, where R and R ⁸ does not simultaneously represent hydrogen,

R ⁷ and R ⁸ independently of one another, in addition, each for unsubstituted or substituted cycloalkyl having 3 to 7 carbon atoms, 5- to 9-membered heteroaryl which contains 1 to 4 identical or different heteroatoms such as oxygen, nitrogen and sulfur, or corresponding heteroarylalkyl having 1 to 4 carbon atoms in the alkyl part, or

R ^{8 represents} the groups -CHR ⁴ -COOH and -CHR ⁴ -COOCH ₃ or

R ⁵ and R ⁶ together with the nitrogen atom to which they are attached form an unsubstituted or substituted 5- to 7-membered ring which can additionally contain 1 or 2 identical or different heteroatoms such as oxygen, nitrogen and sulfur, or

R ⁷ and R ⁸ together with the nitrogen atom to which they are attached form an unsubstituted or substituted 5- to 7-membered ring which can additionally contain 1 or 2 identical or different heteroatoms such as oxygen, nitrogen and sulfur.

Those compounds of the formula (I) in which

R ¹ and R ^{2 are the} same or different and each represents unsubstituted branched alkyl having 4 to 6 carbon atoms or substituted alkyl having 1 to 6 carbon atoms, each unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopropyl, cyclohexyl or phenyl,

R ^{3 represents} alkyl having 2 to 6 carbon atoms, substituted alkyl having 1 to 6 carbon atoms, in each case unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or

Benzyl stands,

R ^{4 represents} hydrogen or alkyl having 1 to 4 carbon atoms or optionally substituted phenyl or benzyl,

R ⁵ and R ^{6 are the} same or different and represent hydrogen, alkyl having 1 to 8 carbon atoms and unsubstituted or substituted phenyl, the preferred substituents being halogen, alkyl, alkoxy, Alkylthio, haloalkyl, haloalkoxy and haloalkylthio may be mentioned,

R ⁷ and R ^{8 are} identical or different and represent hydrogen, in each case unsubstituted or substituted alkyl having 1 to 6 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl and benzyl, the substituents preferably being halogen, alkyl, alkoxy, alkylthio, Haloalkyl, haloalkoxy, haloalkylthio and dialkylamino may be mentioned, but R ⁷ and R ⁸ do not simultaneously represent hydrogen, and

R ⁸ additionally stands for the groups -CHR ⁴ -COOH and -CHR ⁴ -COOCH ₃ or

R ³ and R ⁶ together with the nitrogen atom to which they are attached represent an unsubstituted or substituted piperidine,

Form morpholine, hexahydroazepine or piperazine ring, alkyl and hydroxyalkyl preferably being mentioned as substituents, or

R ⁷ and R ⁸ together with the nitrogen atom to which they are attached are in each case an unsubstituted or substituted piperidine,

Form pyrrolidine, morpholine, hexahydroazepine or piperazine ring, alkyl and hydroxyalkyl preferably being mentioned as substituents.

Those compounds of the formula (I) in which

R ^{1 represents} methyltriazolyl,

R ^{2 represents} butyl, pentyl, hexyl and heptyl which is optionally substituted by unsubstituted or halogen-substituted phenoxy, or in each case optionally one to three times by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy,

Trifluoromethyl or trifluoromethoxy substituted phenyl or cyclopropyl, R ^{3 stands} for ethyl, n- and i-propyl, n-, i-, s- and t-butyl, or for methyl, ethyl, n- and i-propyl substituted by dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl , n.-, i.-, s.- and t.-butyl, or for each optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy or phenyl, benzyl or

Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,

R ⁴ for hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t. -Butyl stands,

R ^{5 represents} hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t.-butyl,

R ^{6 represents} hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t.-butyl, or

R ⁵ and R ⁶ together with the nitrogen atom to which they are attached form a piperidine, morpholine, hexahydroazepine or piperazine ring,

R ^{7 represents} hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t.-butyl,

R ^{8 represents} methyl, ethyl, n.- and i.-propyl, n.-, i.-, s.- and t.-butyl, optionally substituted by dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, or each in each case optionally monosubstituted to trisubstituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy

Phenyl, benzyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl,

or represents the groups -CHR ^{4 '} -COOH and -CHR ^4' -COOCH ₃ , wherein

R ^{4 represents} hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t.-butyl, phenyl, biphenyl and hydroxybiphenyl and benzyl, or R ⁷ and R ⁸ together with the nitrogen atom to which they are bonded form a piperidine, pyrrolidine, morpholine or piperazine ring, which are optionally mono- or disubstituted by methyl, ethyl, hydroxymethyl and hydroxyethyl

Preferred compounds are also addition products of acids and those derivatives of the formula (I) in which the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 have} the meanings which are already preferred for these substituents

The acids which can be added preferably include hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono-, bi- and trifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, Fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, sulfonic acids such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid as well as saccharin or thiosaccharin

In addition, preferred compounds are addition products of salts and metals of main groups II to IV and groups I and II as well as groups IV to VIII and those derivatives of formula (I) in which the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 have} the meanings which have already been mentioned preferably for these substituents

Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred. Anions of these salts are those which are derived from acids which lead to environmentally compatible addition products. Particularly preferred acids in this context are Hydrogen halide acids, such as, for example, hydrochloric acid and hydrobromic acid, nitric acid and sulfuric acid

The new derivatives of tetrafluorobenzoic acid of the formula (I) can be prepared in an analogous manner by known processes. The starting compounds required for the preparation of the compounds of the formula (I) are known or can be prepared by generally known methods The starting compounds are preferably reacted in an inert water-immiscible diluent, such as aromatic, non-aromatic or halogenated hydrocarbons such as: esters, such as ethyl acetate; Chlorinated hydrocarbons, such as dichloromethane, trichloroethane; Aromatics such as toluene; Hydrocarbons such as cyclohexane or their mixtures and / or in the presence of an acid binder such as potassium carbonate, triethylamine, pyridine, N-methylpiperidine or potassium or sodium hydroxide, at temperatures from 0 ° C to 100 ° C, preferably 20 ° C to 40 ° C and under normal pressure. In the reaction with amino acids, an aqueous solution is preferably used with sodium hydroxide solution as an auxiliary base at 0 ° C. to 20 ° C.

The invention encompasses both the pure isomers and the mixtures. These mixtures can be prepared using common methods, e.g. selective crystallization from suitable solvents or chromatography on silica gel or aluminum oxide are separated into the components. Racemates can be separated into the individual enantiomers by conventional methods, e.g. by salt formation with optically active acids such as champhersulfonic acid or dibenzoyl acid and selective crystallization or by derivatization with suitable, optically active reagents, separation of the diastereomeric derivatives and cleavage or separation on optically active column material.

The active compounds of the formula (I) according to the invention have a strong action against pests and can be used practically to combat unwanted harmful organisms. The active ingredients are suitable for use as crop protection agents, in particular as fungicides.

Fungicidal agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

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

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;

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 (conidia form: Drechslera, Syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus

(Coni form: Drechslera, Syn: Helminthosporium);

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

Puccinia species, such as, for example, Puccinia recondita; 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 used with particular good protection for controlling Pyricularia species on rice. The active compounds according to the invention furthermore have a strong resistance-inducing action in plants. They are therefore suitable for generating resistance in plants against attack by undesired microorganisms

In the present context, resistance-inducing substances are to be understood as those substances which, on the one hand, show only a low activity when directly affected by the undesired microorganisms, but on the other hand are able to stimulate the immune system of plants in such a way that the affected If the plants are subsequently inoculated with undesirable microorganisms, they will develop extensive resistance to these microorganisms

Undesired microorganisms are to be understood in the present case as phytopathogenic fungi, bacteria and viruses. The substances according to the invention can therefore be used to produce resistance to the attack by the named pathogens in plants within a certain period of time after the treatment. The period within which resistance is brought about is generally from 1 to 10 days, preferably 1 to 7 days after the treatment of the plants with the active compounds

Unwanted microorganisms in crop protection include fungi from the classes of the Plasmodiophoromycetes, Oomycetes and Chytridiomycetes. Zygomycetes. Ascomycetes. Basidiomycetes and Deuteromycetes

Depending on their respective physical and / or chemical properties, the active compounds can be converted into 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 shapes

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, ie emulsifiers and / or dispersants and / or foam-generating agents If water is used as an extender, organic solvents can also be used, for example Auxiliary solvents are used. Liquid solvents are essentially 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 are liquids that are gaseous at normal temperature and pressure, e.g. aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; solid rock materials can be considered, for example, natural rock powder , such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock flours, such as highly disperse silicic acid, aluminum oxide and silicates, as solid carriers for granules are, for example, 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 stalks, as emulsifiers and / or foam-generating agents, for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters , Poly oxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and protein hydrolyzates, and dispersants are, for example, lignin sulfite liquors and methyl cellulose

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phosphophides, such as wafers and lecithins, and synthetic phospholipids, and other additives can be mineral and vegetable oils

Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as Alizaπn, azo and metal phthalocyanine substances 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%.

The active compounds according to the invention can be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and in mixtures with fertilizers and growth regulators.

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 compounds are particularly favorable mixing partners.

Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-

4'-tri-luoromethoxy-4'-trifluoromethyl-1,3-thizole-5-carboxanilide?, 6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidine-

4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [α- (o-tolyloxy) -otolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,

Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S,

Bromuconazole, bupirimate, buthiobate, calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate

(Quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb,

Cymoxanil, cyproconazole, cyprofuram,

Dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb.

Difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,

Edifenphos, epoxyconazole, ethirimol, etridiazole,

Fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin,

Fenpropimorph, fentin acetates, fentin hydroxide, ferbam, ferim zone, fluazinam,

Fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl aluminum, fthalides, fuberidazole, furalaxyl, furmecyclox,

Guazatine,

Hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan,

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

Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol,

Methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil.

Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,

Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin, Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin,

Probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb,

Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon,

Quintozen (PCNB),

Sulfur and sulfur preparations, Tebuconazole, Alam Teclof, tecnazene, tetraconazole, thiabendazole, Thicyofen, thio phanatmethyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, validamycin A, vinclozolin, zineb, Ziram

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, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin,

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

Azocyclotin,

Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin,

Butyl pyridaben,

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap,

CGA 157 419, CGA 184 699, chloethocarb, chlorethoxyfos, chloretoxyfos,

Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis- Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin,

Cyhalothrin, cyhexatin, cypermethrin, cyromazine,

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon,

Dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron,

Dimethoate, Dimethylvinphos, Dioxathion, Disulfoton, Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox,

Ethoprophos, Etofenprox, Etrimphos,

Fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,

Fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil,

Floazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

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

Lambda cyhalothrin, lufenuron, Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathione, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin, Naled, NC 184, NI 25, Nitenpyram, Omethoat, Oxofonon, Oxamyl, Oxamyl, Oxydos

Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyraclhrhos, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhium, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhrin, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraphofin, Pyrraclofhion, Pyrraclofhion, Pyrraclofhium, Pyrraclofhion, Pyrraclofhrin, Pyrraphofin, Pyrophone, Pyrophone, Pyrophone, Pyrophone, Pyrophone, Pyrophone, Pyrate, Pyrate Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos, RH 5992,

Salithion, Sebufos, Silafiuofen, Sulfotep, Sulprofos,

Tebufenozid, Tebufenpyrad, Tebupirimiphos, Teflubenuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralometonium, Triaromenoriazonium, Triaromenoriazonium YI 5301/5302, zetamethrin.

A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible.

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

When treating parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%. In the seed treatment, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

When treating the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.

When used as resistance inducers, the active substance concentrations for the treatment of parts of plants in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001 percent by weight, preferably between 0.5 and 0.001%.

The preparation and use of the substances according to the invention is illustrated by the following examples.

Manufacturing examples

Production Example 1

55 g (0.26 mol) of 2,3,5,6-tetrafluorobenzoyl chloride are added dropwise at 20 ° to a solution of 42.4 g (0.27 mol) of l-hydroxyacetyl-2,3,4,5, 6,7-hexahydroazepine and 27 g (0.27 mol) of triethylamine in 500 ml of methylene chloride in the course of 30 minutes. After stirring overnight, work up with water / dichloromethane, separate the organic phase and concentrate it in vacuo a viscous oil, which soon crystallizes and is stirred with petroleum ether. Yield 67.5 g (77.9% of theory), mp 64 to 66 °

Preparation example 2

10.6 g (50 mmol) of 2,3,5,6-tetrafluorobenzoyl chloride and 25 ml of 2N sodium hydroxide solution are added dropwise to the solution of 8.08 g (49 mmol) of L-phenylalamn in 25 ml of 2N sodium hydroxide solution while cooling with ice Overnight stirring is adjusted to pH 2 with dilute hydrochloric acid and the precipitated precipitate is sucked from a yield of 15.6 g (93.4% of theory), mp 146 to 147 ° The following compounds of the formula (I) are prepared in a corresponding manner and in accordance with the general information:

Examples of use

Example A

Pyricularia test (rice) / systemic

Solvent: 12.5 parts by weight of acetone emulsifier: 0.3 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 the concentrate is diluted to the desired concentration with water and the stated amount of emulsifier.

To test for systemic properties, 40 ml of the active ingredient preparation are poured onto common soil in which young rice plants have been grown. 7 days after the treatment, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants then remain in a greenhouse at a temperature of 25 ° C. and a relative atmospheric humidity of 100% until evaluation.

The disease infestation is evaluated 4 days after the inoculation.

The compounds according to the manufacturing examples 1, 2, 3 and 37 show 100% efficiency at an application rate of 100 mg of active ingredient per 100 cm ³ .

Claims

_First Derivatives of 2,3,5,6-tetrafluorobenzoic acid of the general formula (I)

in which

Y stands for oxygen or sulfur and

X represents the groups -ON = CR ^] R ² , -OR ³ , -OCHR ⁴ -CO-NR ⁵ R ⁶ or -NR ⁷ R ⁸

wherein

R ¹ and R ² independently of one another are optionally substituted alkyl, cycloalkyl and aryl,

R ^{3 is} alkyl with at least 2 carbon atoms, substituted alkyl and optionally substituted cycloalkyl, aryl and aralkyl,

R ⁷ and R ⁸ independently of one another are hydrogen and optionally substituted alkyl, cycloalkyl, aryl, aralkyl, Alkylheteroaryl and heteroaryl mean, or stand for the groups -CHR ⁴ -COOH and -CHR ⁴ -COOCH ₃ , where R ⁷ and R ^{8 are} not simultaneously hydrogen, or

R ⁷ and R ⁸ together with the nitrogen atom to which they are bound form an optionally substituted ring

as well as their acid addition salts and metal salt complexes.

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

R ³ for alkyl with 2 to 8 carbon atoms, substituted alkyl with 1 to 8 carbon atoms, each unsubstituted or substituted

Cycloalkyl having 3 to 7 carbon atoms, phenyl or phenylalkyl having 1 to 4 carbon atoms in the alkyl part,

R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are} identical or different and represent hydrogen, in each case unsubstituted or substituted alkyl having 1 to 8 carbon atoms, phenyl or phenylalkyl having 1 to 4 carbon atoms in the alkyl part, where R and R ⁸ do not simultaneously represent hydrogen,

R ^{8 represents} the groups -CHR ⁴ -COOH and -CHR ⁴ -COOCH ₃ or

R ⁵ and R ⁶ together with the nitrogen atom to which they are attached are an unsubstituted or substituted one

5- to 7-membered ring form which can additionally contain 1 or 2 identical or different heteroatoms such as oxygen, nitrogen and sulfur, or

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

R ¹ and R ^{2 are the} same or different and each represents unsubstituted branched alkyl having 4 to 6 carbon atoms or substituted alkyl having 1 to 6 carbon atoms, each unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl,

R ^{3 represents} alkyl having 2 to 6 carbon atoms, substituted alkyl having 1 to 6 carbon atoms, in each case unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl,

R ^{4 represents} hydrogen or alkyl having 1 to 4 carbon atoms or optionally phenyl or benzyl, R ⁵ and R ^{6 are the} same or different and are hydrogen,

Alkyl having 1 to 8 carbon atoms and unsubstituted or substituted phenyl are preferably substituted by halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy and haloalkylthio,

R ⁷ and R ^{8 are the} same or different and represent hydrogen, in each case unsubstituted or substituted alkyl having 1 to 6 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl and benzyl, the substituents being preferably halogen, alkyl, alkoxy, alkylthio, haloalkyl, Haloalkoxy, haloalkylthio and dialkylamino may be mentioned, but R ⁷ and R ⁸ do not simultaneously represent hydrogen, and

R ⁵ and R ⁶ together with the nitrogen atom to which they are attached form an unsubstituted or substituted piperidine, morpholine, hexahydroaze¬ pin or piperazine ring, alkyl and hydroxyalkyl preferably being mentioned as substituents, or

R ⁷ and R ⁸ together with the nitrogen atom to which they are attached form an unsubstituted or substituted piperidine, pyrrolidine, morpholine, hexahydroazepine or piperazine ring, alkyl and hydroxyalkyl preferably being mentioned as substituents.

Compounds of formula (I) according to claim 1, in which R ^{1 represents} methyltriazolyl,

R ² for optionally unsubstituted or halogen-substituted

Phenoxy-substituted butyl, pentyl, hexyl and heptyl, or in each case optionally phenyl or cyclopropyl which is substituted once to three times by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,

R ^{3 represents} ethyl, n- and i-propyl, n-, i-, s- and t-butyl, or for methyl, ethyl, n.- and i.-propyl substituted by dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n.-, i.-, s.- and t.-butyl, or each optionally by fluorine, chlorine, bromine,

Methyl, ethyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy substituted phenyl, benzyl or cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,

R ^{4 represents} hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t.-butyl,

R ^{5 represents} hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, L-, s.- and t.-butyl,

R ^{6 represents} hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, L-, s.- and t.-butyl, or

R ^{8 represents} methyl, ethyl, n.- and i.-propyl, n -, i.-, s.- and t.-butyl which is optionally substituted by dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, or is in each case optionally simple is phenyl, benzyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl which is substituted three times by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy,

or represents the groups -CHR ^{4 '} -COOH and -CHR ^' -COOCH ₃ , wherein

R ^{4 'represents} hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t.-butyl, phenyl, biphenyl and hydroxybiphenyl and benzyl, or

R ⁷ and R ⁸ together with the nitrogen atom to which they are attached form a piperidine, pyrrolidine, morpholine or piperazine ring which is optionally mono- or disubstituted by methyl, ethyl, hydroxymethyl and hydroxyethyl.

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

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

7. Process for the preparation of compounds of formula (I) according to

Claim 1, characterized in that 2,3,5,6-tetrafluorobenzoyl chloride or anhydride is reacted with a corresponding oxime, alcohol or amine, optionally in the presence of a diluent and / or a base.

8. Use of compounds of formula (I) according to claims 1 to 4 for controlling pests. Process for the preparation of pesticides, characterized in that compounds of the formula (I) according to Claims 1 to 4 are mixed with extenders and / or surface-active agents.