CZ147396A3 - Derivatives of 2,3,5,6-tetrafluorobenzoic acid and their use for pest fighting - Google Patents

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<1>R<2>, -OR<3>, -OCHR<4>-CO-NR<5>R<6> or -NR<7>R<8> as well as a process for manufacturing the said substance and uses thereof in combating pests.

Description

Technical field

OJSO

The present invention relates to 2,3,5,6-tetrafluoro-benzoic acid derivatives, processes for their preparation and their use for controlling pests. i-f-3

The essence of the invention

The present invention relates to acid derivatives

2,3,5,6-tetrafluorobenzoic compounds of formula I

in which

Y begins with an oxygen or sulfur atom and

X Get Started skupiu -0-N = CR ^T R ^2, -OR ^3, -OCHR ⁴ -CO-NR ⁵ R ⁶ or

-NR ^of r8, wherein r! and R ² are independently optionally substituted alkyl, cycloalkyl and aryl.

R p represents an alkyl group with at least two carbon atoms, a substituted alkyl group and an optionally substituted cycloalkyl. aryl and aralkyl groups,

R ⁴ _and R ^ are independently hydrogen aa optionally substituted alkyl, aryl and aralkyl groups, or R5 and R6 represent together with the nitrogen atom to which they are attached optionally substituted ring, or

R ^7a denotes, independently of one another, a hydrogen atom and an optionally substituted alkyl, cycloalkyl, aryl, aralkyl, alkylheteroaryl and heteroaryl group, or -CHR ⁴ -C00H and -CHR ⁴ -COOCH ³ groups, wherein R ⁷ and R ^{8 do} not simultaneously represent a hydrogen atom, 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 2,3,5,6-tetrafluorobenzoic acid derivatives of the general formula I are obtained by:

2.3.5.6-Tetrafluorobenzoyl chloride or acid anhydride

2.3.5.6-Tetrafluorobenzoic acid is reacted with the corresponding oxime, alcohol or amine, optionally in the presence of a solvent and / or a base.

Finally, it has been found that new acid derivatives

The 2,3,5,6-tetrafluorobenzoic compounds of the formula I possess significant microbicidal activity, in particular against plant pathogenic microorganisms. In addition, the active compounds according to the invention have a marked resistance-inducing effect in plants against attack by unwanted microorganisms.

For the sake of simplicity, the following compounds of formula (I) are referred to below, although both pure compounds and mixtures with different proportions of isomeric, enantiomeric and diastereomeric compounds are meant.

The 2,3,5, -tetrafluorobenzoic acid derivatives of the present invention are defined by formula (I).

In formula I preferably, unless otherwise indicated, an alkyl group, singly or in related moieties, denotes a straight or branched alkyl group having 1 to 8 carbon atoms, in particular 1 to 4 carbon atoms. Exemplary and preferably, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl;

a cycloalkyl group of a 3- to 7-membered ring, in particular a ring of 3,5 or 6 carbon atoms. Exemplary and preferably, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl;

aryl is unsubstituted or unsubstituted aryl of 6 to 10 carbon atoms. Exemplary and preferably unsubstituted or substituted phenyl and naphthyl groups, especially unsubstituted or substituted phenyl groups;

aralkyl group unsubstituted or substituted aralkyl group having 1 to 4 carbon atoms, in particular 1 to 2 carbon atoms in a straight or branched alkyl moiety and having 6 to 10 carbon atoms in an aryl moiety, especially in a phenyl group 1,1-phenethyl, 1,2-phenethyl, 1,1-phenylpropyl, 1,2-phenylpropyl, 1,3-phenylpropyl and 2,2-phenylpropyl;

a heteroaryl group, an unsubstituted or substituted 5- to 7-membered ring, in particular a 5- to 7-membered ring, containing from 1 to 4, preferably from 1 to 3, identical or different heteroatoms. The heteroatoms are preferably oxygen, sulfur and nitrogen. Examples which may be mentioned are pyrimidinyl, pyrrolyl, isothiazolyl, oxazolyl, thienyl, furyl, pyridazinyl, pyrazinyl, isoxazolyl, thiazolyl, and in particular pyridyl; and a heteroarylalkyl group a group in which the heteroaryl moiety is as defined above and the preferred regions and the alkyl moiety is straight or branched and contains 1 to 4 carbon atoms, especially 1 or 2 carbon atoms. Exemplary and preferably, heteroarylmethyl, 1,1-heteroarylethyl, 1,2-heteroarylethyl, 1,1-heteroarylpropyl, 1,2-heteroarylpropyl, 1,3-heteroarylpropyl, and 2,2-heteroarylpropyl may be mentioned. group.

Optionally substituted radicals of the formula can carry one or more, preferably one to three, especially one or two, identical or different substituents. These substituents include, by way of example and preferably, an alkyl group, preferably having 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl i-butyl, sec-butyl and tert-butyl; alkoxy having preferably 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, such as methoxy, ethoxy, n-propyloxy, i-propyloxy, n-butyloxy, i-butyloxy, sec-butyloxy and tert-butoxy; alkylthio having preferably 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, such as methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, sec-butylthio and tert-butylthio; a haloalkyl, haloalkoxy and haloalkylthio group having preferably 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms and 1 to 9, especially 1 to 5 halogen atoms, the Jialogen atoms being the same or different, the halogen atoms being preferably fluoro, chloro or bromo, especially fluoro such as trifluoromethyl, difluoroethyl, pentafluoroethyl, tetrafluoroethyl, trifluoromethyl, trifluoroethyl, trifluoroethoxy, difluoromethoxy, pentafluoroethoxy, tetrafluoroethoxy, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoroethyl; hydroxy; a halogen atom, preferably fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine; cyano; nitro; dialkylamino having preferably 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms in each alkyl group, such as dimethylamino and diethylamino; carboxy; (C 1 -C 4) alkylalkoxy, in particular 1 or 2 carbon atoms in each alkyl moiety; carbonylalkoxy having 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms in the alkyl moiety, such as carbonylmethoxy and carbonylethoxy; carbonylalkyl having 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms in the alkyl moiety, such as acetyl and propionyl; a formyl group; carbonylaryloxy of 5 to 10 carbon atoms in the aryl moiety, such as carbonylphenoxy; a (C 6 -C 10) carbonylaryl group such as a benzoyl group; oxycarbonylalkyl having 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms in the alkyl moiety, such as acetoxy; a (C 6 -C 10) oxycarbonylaryl group such as a benzoyloxy group; carboxylamino, carbonylaminoalkyl, carbonylaminodialkyl, aminocarbonyl, alkylaminocarbonyl, aminocarbonylalkyl and alkylaminocarbonylalkyl having in each case 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms in the alkyl moieties; sulfonamido; a sulfonalkyl, sulfonylalkyl and sulfonylalkoxy group each having 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms; or a phenyl or phenoxy group, unsubstituted or substituted by halogens, in particular fluorine, chlorine and / or bromine.

The definitions provided herein also apply accordingly to the definitions in the following preferred residue combinations.

Preferred are compounds of formula (I) wherein:

2

R and R are the same or different and are unsubstituted or substituted alkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 7 carbon atoms, or phenyl,

R ³ represents an alkyl group having 2 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 7 carbon atoms, a phenyl group or a phenylalkyl group having 1 to 4 carbon atoms in the alkyl moiety,

R ⁴ , R ⁵ , R ⁶ , R? and R (R) are the same or different and represent a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, a phenyl group or a phenylalkyl group having 1 to 4 carbon atoms in the alkyl moiety;

R and R do not simultaneously represent a hydrogen atom, or _and r8 --------- independently of each other additionally represents an unsubstituted or substituted cycloalkyl group having 3 to 7 carbon atoms, a 5- to 9-membered heteroaryl group containing from 1 to 4 of the same or various heteroatoms such as oxygen, nitrogen and sulfur, or a corresponding heteroarylalkyl group having 1 to 4 carbon atoms in the alkyl moiety, or

R ⁸ is -CHR ⁴ -COOH and -CHR ⁴ -COOCH ₃ , or

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

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

Particularly preferred are compounds of formula I wherein:

2

R and R are the same or different and are unsubstituted branched alkyl of 4 to 6 carbon atoms, substituted alkyl of 1 to 6 carbon atoms, unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl; 2 to 6 carbon atoms, a substituted alkyl group having 1 to 6 carbon atoms, unsubstituted or substituted cyclopropyl, cycloburyl, cyclopentyl, cyclohexyl, phenyl or benzyl,

R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or an optionally substituted phenyl or benzyl group,

R 6 and R 6 are the same or different and are hydrogen, C 1 -C 8 alkyl or unsubstituted or substituted phenyl, the substituents being preferably halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy and haloalkylthio,

8 ·

R and R are the same or different and represent a hydrogen atom, a substituted or unsubstituted C 1 -C 6 alkyl group, a cyclopropyl, cycloburyl, cyclopentyl, cyclohexyl, phenyl and benzyl group, the substituents being preferably halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio and diakylamino, wherein R and R are not simultaneously hydrogen, R 8 is -CHR ⁴ -C00H and -CHR ⁴ COOCH ⁴ , or

R 6 and R 6 together with the nitrogen atom to which they are attached form an unsubstituted or substituted piperidine, morpholine, hexahydroazepine or piperazine ring, the substituents being preferably an alkyl group and a hydroxyalkyl group, or

R? and R ® together with the nitrogen atom to which they are attached form an unsubstituted or substituted piperidino, morpholine, hexahydroazepine or piperazine ring, preferably alkyl and hydroxyalkyl being substituents.

Very particularly preferred are the compounds of formula I in which

R ¹ represents a methyltriazolyl group,

R 'represents an optionally unsubstituted or halo-substituted phenoxy substituted butyl, pentyl, hexyl and heptyl group, or optionally one to three times fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy substituted phenyl, denotes ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl, or dimethylamino, diethylamino, methoxycarbonyl, or ethoxycarbonyl substituted ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl, or optionally ---- fluoro, chloro, bromo, methyl, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or trifluorometho xyl substituted by phenyl, benzyl or cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, denotes hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl, denotes hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl, r6 represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group and a tert-butyl group, or

R 2 and R 2 together with the nitrogen atom to which they are attached form a piperidine, morpholine, hexahydroase pin or piperazine ring,

R ⁷ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group and a tert-butyl group,

O

R is optionally dimethylamino, diethylamino-12, methoxycarbonyl, or exoxycarbonyl substituted by methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl, or optionally once up to three times fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy substituted phenyl, benzyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or denotes -CHR 1 -COOH and -CHR 1 -COOH wherein R 4 denotes hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, phenyl, biphenyl a hydroxyphenyl group and a benzyl group; or

R ⁷ and R ⁸ together with the nitrogen atom to which they are attached optionally form one or two methyl, ethyl, hydroxymethyl, and hydroxyethyl substituted piperidine, morpholine, piperazine or pyrrolidine rings.

Preferred compounds are also acid addition products and derivatives thereof having the general formula (I) in which the substituents R ³ to R 6 have the meanings indicated above as being preferred.

Acids which may be added preferably include hydrohalogenic acids such as hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, monofunctional, difunctional and trifunctional carboxylic and hydroxycarboxylic acids, such as e.g. 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 1,1'-naphthalenedisulfonic acid, as well as saccharin or thiosaccharin.

In addition, preferred compounds are also salt and metal addition products II. to IV. Major and I. and II. as well as IV. to VIII. the side groups of the Periodic Table of the Elements and their derivatives of the general formula I, in which the substituents R to R have the meanings indicated above as being preferred.

The salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred. Suitable anions of these salts are those derived from those acids which lead to environmentally acceptable additive products. Particularly preferred acids in this context are hydrohalic acids such as hydrochloric acid and hydrobromic acid, or nitric acid and sulfuric acid.

The novel tetrafluorobenzoic acid derivatives of the formula I can be prepared by processes analogous to those known in the art. 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 reaction of the starting compounds is preferably carried out in inert, water-immiscible diluents such as aromatic, non-aromatic or halogenated hydrocarbons such as chlorinated hydrocarbons such as dichloromethane and trichloromethane, aromatics such as toluene or cyclohexane, or mixtures thereof, or esters, for example ethyl acetate, and / or in the presence of acid binders, for example potassium carbonate, triethylamine, pyridine, N-methylpiperidine, potassium hydroxide or sodium hydroxide, at a temperature ranging from 0 ° C to 100 ° C, preferably 20 ° C to 40 ° C and under normal pressure. The reaction with the amino acids is carried out in aqueous solution, preferably with sodium hydroxide as auxiliary base, at a temperature in the range of 0 ° C to 20 ° C.

The present invention includes both pure isomers and mixtures. These mixtures can be separated into their components using suitable methods, for example by selective crystallization from suitable solvents or by chromatography on silica gel or alumina. The racemates can be separated into the individual enantiomers by conventional methods, for example by formation of salts with optically active acids such as charafersulfonic acid or dibenzoyltartaric acid, and further by selective crystallization or derivatisation with suitable optically active reagents, separation of diastereomeric derivatives and resolving or optically resolving material column.

The active compounds according to the invention of the general formula I show a strong action against pests and can be used practically for controlling harmful organisms. These active compounds are suitable for use as plant protection agents, in particular as fungicides.

Fungicidal plant protection agents are used to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteroraycetes.

-¾

By way of example, but not by way of limitation, some of the agents of fungal diseases which fall under the above may be mentioned:

Pythium species, such as Pythium ultimum;

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

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

Plasraopara species, such as, for example, Plasmopara viticola;

Peronospora species, such as, for example, Peronospora spp. Or Peronospora brassicae;

Erysiphe species, such as Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

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

Venturia species, such as Venturia inaequalis;

Pyrenophora species, such as Pyrenophora teres or Pyrenophora graminea (conidia form. Drechslera, Synonym: Helminxhosporium);

Cochliobolus species, such as, for example, Cochliobolus sarivus (conidia form: Drechselera, Synonym: Helminxhosporium);

Uromyces species, such as Uromyces appendiculaxus; Puccinia species, such as Puccinia recondita; Tillexia species, such as Tellexia caries; Usxilago species, lago avenae; such as Usxilago Boredom or Usti

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

Pyricularia species, such as Pyricularia oryzae;

Fusarium species, such as Fusarium colmorum; Boxryxis species, such as Botrytis cinerea; Sepxoria species, such as Sepxoria nodorum;

Lepxosphaeria species, such as Lepxosphaeria nodorum;

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

Alternaria species, such as Alternaria brassicae;

Pserdocercosporella species, such as, for example, Pserdocercospo rella herpotrichoides.

The good acceptability of the active ingredients for plants at the concentrations necessary to combat plant diseases allows the treatment of aboveground parts of plants, plant seedlings, seeds and soil.

The active compounds according to the invention can be used with particular success for combating Pyricularia on rice.

Furthermore, the active compounds according to the invention have a strong resistance-inducing effect in plants. They are therefore suitable for growing resistance in plants against attack by unwanted microorganisms.

Resistance-inducing substances in this context are those which, on the one hand, have little activity on direct action on undesirable microorganisms, but on the other hand are capable of stimulating the plant defense system so that treated plants have a high resistance when inoculated with undesirable microorganisms. against these microorganisms.

Unwanted microorganisms in this case refer to phyxopathogenic fungi, bacteria and viruses. Thus, the compounds of the present invention can be used so that the plants acquire resistance to attack by said causative agents over a period of time after treatment.

The time period during which resistance is achieved is generally 1 to 10 days, preferably 1 to 7 days, after treatment of the plants with the active substances.

Unwanted microorganisms in plant protection include Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Depending on their physical and / or chemical properties, the active substances can be converted into the customary preparations such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, fine capsules in polymeric substances and seed encapsulants as well as cold and hot misting preparations (ULV preparations).

These preparations are prepared by known methods, for example by mixing the active ingredient with a filler, i.e. a liquid solvent, under pressure with a liquefied gas and / or a solid carrier, optionally using surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents. If water is used as a diluent, for example, organic solvents can also be used as solubilizers.

Basically suitable liquid solvents are: aromatics such as xylene, toluene and alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins such as petroleum fractions, furthermore alcohols such as butyl alcohol or glycols as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethylformamide or dimethylsulfoxide as well as water.

Liquefied gaseous diluents or carriers are understood to be liquids which are gaseous at normal temperature and pressure, for example aerosol carrier gases such as butane, propane, nitrogen and carbon dioxide.

Suitable solid carriers are, for example, natural pulverulent rocks such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic flours such as highly disperse silicic acid, alumina and silicates. Suitable solid carriers for granulates are, for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sephiolite, dolomite, as well as synthetic granules of inorganic and organic flours and granules of organic materials such as sawdust, coconut shells, corn cobs and tobacco stems.

Suitable emulsifiers and / or foaming agents are, for example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters and polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates. Suitable dispersing agents are, for example, ligninsulphite leachates and methylcellulose.

Adhesion promoters such as carboxymethylcellulose, natural and synthetic, powdered, granular or latex polymers such as acacia, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins and synthetic phospholipids may also be used in the compositions. Other additives may be mineral and vegetable oils.

Dyes such as inorganic pigments such as iron oxides, titanium dioxide, ferrocyanate blue and organic dyes such as alizarin dyes, azo dyes and metallic phthalocyanine dyes and trace nutrients such as iron, manganese, boron, media, cobalt, molybdenum and zinc.

The formulations generally contain 0.1 to 95% by weight of active ingredient, preferably 0.5 to 90% by weight.

The active compounds according to the invention can be present in the formulations in admixture with other known active compounds, such as fungicides, insecticides, acaracides, nematicides and herbicides, as well as in a mixture with fertilizer and growth regulators.

The active compounds according to the invention can also be used in their formulations in admixture with known fungicides, bactericides, insecticides, acaracides, nematicides and herbicides in order to broaden their spectrum of action or to prevent resistance. In many cases, a synergistic effect is achieved, i.e. the effect of the mixture is higher than that of the individual components.

Components of these mixtures include:

Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;

^r, D ';^{-dibromo-2-methyl-4'}trifluoromethoxy-4'-trifluoro-methyl-l,3-thiazole-5-carboxanilide;

2,6-Dichloro-N- (4-trifluoromethylbenzyl) -benzamide;

(E) -2-Methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-Hydroxyquinoline sulfate; Methyl (E) -2- (2- (6- (2-cyanophenoxy) pyrimidin-4-yloxy) phenyl) -3-methoxyacrylate;

Methyl (E) -methoximino- [α- (o-tolyloxy) -o-tolyl] acetate;

2-Phenylphenol (0PP)

Aldimorph, Ampropylfos, Snilazine, Azaconazole,

Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl,

Betertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,

Calciumpolysulfide, Captafol, Captan, Carbendazim, Carboxin, Chinomethionat (Quinomethionat), Chloroneb, Chloropicrin, Chlorothalonil, Chlozolinate, Cufraneb, Cymaxanil, Cyproconazole, Cyprofuram,

Dichlorophen, Diclobutrazole, Diclofluanid, Diclomezin, Dicloran Diethofencarb, Difenocanazole, Dimethirimol, Dimethomorph, Diniconazole, Dinocap, Diphenylamine, Pipyrithion, Ditalimfos, Dithianon, Dodine, Drazoxolon, Epoxyconid, Epoxyconid, Edifenphosol

Fenarimol, Fenbuconazole, Fenfuram, Fenitropane, Fenpiclonil, Fenpropidine, Fenpropimorph, Fentinacetate, Fentrinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusilazole, Flusilazole, Flusilazole, Flusilazole, Flusilazole

Fuberidazole, Furalaxyl, Furmecyclox,

Guazatine,

Heachlorobenzole, Hexaconazole, Hymexazole,

Imazalil, Imibenconazole, Iminoctadine, Iprobenphos (IBP), Iprodion, Isoprothiolane,

Casugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux-mixture,

Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil,

Mexalaxyl, Metconazole, Methysulfocarb, Methfuroxam, Metiram Metsulfovax, Myclobutanil,

Nickel-dimexhyldixhiocarbamat, Nixroxyl-isopropyl,

Nuarimol,

Ofuration, Oxadixyl, Oxamocarb, Oxycarboxin,

Pefurazoate, Penconazole, Pencycuron, Phosdiphen, Phxhalid, Pimaricin, Piperaline, Polycarbamaxe, Polyoxin, Probenazole, Prochloraz, Procyraidone, Propamocarb, Propiconazole, Propineb, Pyrazophos, Pyrifenox, Pyrimexhynil, Quinozil, PCN

Tebuconazole, Teclofxalam, Tacnazen, Texraconazole,

Thiabendazole, Thicyofen, Thiophanax-mexhyl, Thiram,

Tolclophos-mexhyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxide, Trichlamide, Tricyclazole, Tridemorph, Triflumizole Triforin, Trixiconazole,

Validamycin A, Vinclozolin,

Zineb, I look,

BaJcxericidy

Bronopol, Dichlorophen, Nixrapyrin,

Nickel-Dimexhyldixhiocarbamax, Kasugamycin, Ocxhilinone, furancarboxylic acid, Oxyxexracycline, Probenazole, Sxrepxomycin, Teclofxalam, Copper sulphate and other copper preparations,

Insecxicides / Acaricides / Nematicides:

Abamecxin, AC 303 630, Acephat, Acrinathrin, Alanycarb,

Aldicarb, Alphamethrin, Amitraz, Avermecin AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,

Bacilus xhuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyluthrine, Bifentrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben, Cadusafos, Carbaryl, Carbofuran, Carbophosulfol, Carbophenothion, Carbophenothion 41 Chlorphen.viph.os, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmerhrin, Clocyxhrin, Clofenxezine, Cyanophos, Cycloproxhrin, Cyflu.xh.rin, Cyhaloxhrin, Cyhexaxin, Demamonin, Cypermethin, Cypermexin Demexon-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,

Edifenphos, Emamectin, Esfenvalerate, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos,

Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flufenocinxat, Flufenthinat

HCH, Heptenophos, Hexaflumuron, Hexythiazox,

Imidacloprid, Iprobenphos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda-cyhalothrin, Lufenuron, Malathion, Mecarbam, Mervinphos, Mesulfenphos, Methyldehyd, Methacrifos, Methamidophos, Methidbath, Methidathion, Methidathion, Methidathion NC 182, Ni 25, Nitenpyram

Omethoat, Oxamyl, Oxydemethone M, Oxydeprofos,

Parathion A, Parathion M, Permethrin, Phenchoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, P rimicarb,

Pirimiphos M, Pirimiphos A, Profenofos, Promecarb ,.

Propaphos, Propoxur, Prothiophos, Prothoat, Pymetrozine, Pyrachlophos, Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,

Quinalphos,

RH 5992,

Salixhion, Sebufos, Silafluofen, Sulfoxep, Sulprofos, Tebufenozide, Tebuf eripyrad, Tebupirimphos, Tef lubenzuron, Tefluxhrin, Temephos, Terbam, Terbufos, Texrachlorvinphos, Thiafenox, Thiodinarb, Thiinanox, Thiinano Trichlorfon, Triflumuron, Trimexhacarb, Vamidoxhion,

XMC, Xylylcarb,

Yl 5301/5302,

Zexamexhrin.

Mixtures with other known active ingredients such as herbicides or with fertilizer and growth regulators are also possible.

The active compounds can be used as such, in the form of their preparations or in dosage forms prepared therefrom, such as application solutions, suspensions, spray powders, pastes, soluble powders, sprayings and granules. Application is effected by conventional means, for example by pouring, spraying, spraying, dusting, spraying, foaming, painting and the like. It is also possible to use the Ultra-Low-Volume procedure or inject the active substance preparation or the active substance itself into the soil. Plant seed may also be processed.

When treating parts of plants, the concentrations of the active compounds in the use forms can be varied within a wide range. In general, this concentration is 1 to 0.0001% by weight, preferably 0.5 to 0.001% by weight.

In the treatment of seed, amounts of active compound of from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

In soil treatment, active compound concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action.

When used as resistance inducers, the concentrations of the active ingredient for the treatment of plant parts can be varied within a wide range of dosage forms. It is generally in the range of 1 to 0.0001% by weight, preferably 0.5 to 0.001% by weight.

DETAILED DESCRIPTION OF THE INVENTION

The manufacture and use of the compounds of the present invention is illustrated by the following examples.

Manufacturing examples

Example 1

F

F

F

F

55 g (0.26 mol) of 2,3,5,6-tetrafluorobenzoyl chloride are added dropwise with stirring at 20 DEG C. to a solution of 42.4 g (0.27 mol) of 1-hydroxyacetyl-2,3,4,5, 6,7-hexahydroazepine and 27 g (0.27 mol) of triethylamine in 500 ml of methylene chloride over 30 minutes. After stirring overnight, the reaction mixture was treated with water and dichloromethane and the organic phase separated and concentrated in vacuo. A viscous oil is obtained, a liquid which soon crystallizes.

Yield: 67.5 g (77.9% of theory)

m.p. : 64-66 ° C.

Example 2

F F

To a solution of 8.08 g (49 mmol) of L-phenylalanine in 25 ml of 2N sodium hydroxide was added dropwise, while cooling with ice, 10.6 g (50 mmol) of 2,3,5,6-tetrafluorobenzoyl chloride and 25 ml of 2N sodium hydroxide. After stirring overnight, the pH was adjusted to 2 with dilute hydrochloric acid and the crystallisate formed was filtered off with suction.

Yield: 15.6 g (93.4% of theory)

m.p. : 146-147 ° C.

The following compounds of formula I are prepared accordingly

Example X Y m.p. CC) 3 -O-CH _r -CO-N (C 3 H _r i) ₂ 0 72 4 -O-CE ₂ -CO-N (C, H 5) ₂ 0 83 5 -o-ch ₂ - 0 54 6 -Ο-Οί, ΟΗ, Νζ ^), 0 Hq ° = 1.4598 7 CH, -O-CH-COOC ₂ H _s 0 n ° = 1.4473 WITH -0-CH ₂ and _R -CjH 0 ηβ ° = 1.4430 1 9 CH, 0 60-64 1 10 i-c ₃ h _t i-i 0 118-20

Example X Y m.p. (° C) 11 i * CH CF ₃ - “A 0 132 12 -n <> _OCH3 0 122 13 CH, -C _N ^ J> 0 102 14 / ^Cl- i-ZVci 0 153 15 Dec Cl F fax —NH — j-J CH, 0 102 16 -NK-CH, CH, -N * (C, H <), 0 76 17 -NH-CK, CH, -N (C, H), x HCl 0 143 13 -NH-CH, -COOH 0 133 19 Dec CH, -NH-CH-COOH 0 157 20 May CH (CH ₃ ) C ₂ H _s -NH-CH-COOH 0 173

Example χ γ t.t. f> Q 21 n-c ₃ h ₇ —NH-CH-COOH 0 137 22nd -NH-CH ₂ -? 0 120 23 —Ν 0 110 24 Ό 0 72 25 . -ο 0 67 26 ch ₅ ν> CH 0 114 Λ / VJ-CH3OH 0 81 23 COOb > -] -Ν \ _ 1 0 ie ⁰ = 1.4952 29 CH, -Ν 0 CK ₃ 0 84

Example. X IN * m.p. ro 30 —1 /? 10 0 60 31 CH ₃ -ON = C-Br CH, one ^of .N. <N u 0 G 5 ° = 1.5493 32 -O-N = C — C V “3y ^ N. S N Steraoisotner A IN 0 140 JJ ch ₃ _ —0 — N = C — 3r | h ₂ 'N. <jq Slereoisomer 3 N— * 0 116 34 ^C > \ -ON = C — CH CH CH, .N. with [\ J Stereoisomef A • 0 150 35 -on = c - ₂ N XN Slereoisomer: 3 N - 0 126

'Example x Y m.p., TO 36 -O- _N , c — Γ-ΗΗ, ο-O-α CH, CH, .N. < ^N Ny 0 87 37 Cl-ON = C- <1 ² _X N. < ^N u 0 83 33 -ON = C-C (CH3) ₃ CH1 ^s .N. <N Ν-Ϊ 0 98 39 Γ —Q — N = CC-CH3CH3O — CH, CH, N, < ^N N— 0 nj '= 1.5276 40 COOH - NH —CH— 0 170 41 COOH —NH - CH-CH3 - 0 152-55

Example X Y mp, (’C) 42 -3 WITH 133-40 43 ^—Ν \ Ξ WITH 104-06 44 ch ₃ -p CH / WITH 124-27 45 COOCH ₃ - NH - CH - CH ₂ - 0 120 46 COOCH ^ —NH — CH- 0 153-60 47 CCCCHj —NH —CH4-OH 0 log P: 2.63

.Examples of Use -------- Example A

Pyricularia (rice) / systemic test

Absorption: 12.5 parts by weight of acetone emulsifier: 0.3 parts by weight of alkyl aryl polyglycol ether.

For the preparation of an effective preparation of active compound, 1 part by weight of active compound is mixed with the indicated amount of solvent and the concentrate is diluted with water and said amount of emulsifier to the desired concentration.

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

Assessment of disease infestation is performed 4 days after inoculation.

The compounds according to Production Examples 1, 2, 3 and 37 exhibit, at an application rate of 100 mg of active ingredient for 100 cra ≥ 100% degree of effect.

Claims (7)

PATENT CLAIMS 1. 2,3,5,6-Tetrafluorobenzoic acid derivatives of the general formula I Y II c-x (I) *. ! - Λ i J: Ί i $ 7 'Λ ₍ > ΓΪ 3 Λ l ¹ : JJ i ₍ avy .3 in which Y begins with an oxygen or sulfur atom and 9 S. A 1 Z 1, J 1 = O 1; e ¹ ' ^- f'3 X starts with -ON = CR ¹ R ² , -OR ³ , -OCHR ⁴ -CO-NR ⁵ R ⁶ or -nr ⁷ r ⁸ while r! and R ² are independently optionally substituted alkyl, cycloalkyl and aryl, R ³ represents alkyl having at least two carbon atoms, substituted alkyl and optionally substituted cycloalkyl, aryl and aralkyl groups, R ⁴ , R ³ and R ³ independently represent a hydrogen atom and an optionally substituted alkyl, aryl and aralkyl group, or and together with the nitrogen atom to which they are attached an optionally substituted ring, or 7 8 R and R are independently hydrogen and optionally substituted alkyl, cycloalkyl, aryl, aralkyl, alkylheteroaryl, and heteroaryl, or skvpiny -CHR ⁴ -CHR ⁴ -C00H and -COOCH _3, where R ⁷ and R ⁸ do not simultaneously hydrogen or 7 8 R and R 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. 2,3,5,6-Tetrafluorobenzoic acid derivatives according to claim 1, in which 12 ·. " R and R are the same or different and are unsubstituted or substituted alkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 7 carbon atoms, or phenyl, R &lt; 4 &gt; is alkyl of 2 to 8 carbon atoms, substituted alkyl of 1 to 8 carbon atoms, unsubstituted or substituted cycloalkyl of 3 to 7 carbon atoms, phenyl or phenylalkyl of 1 to 4 carbon atoms in the alkyl moiety , R ⁴ , R ⁶ , R ⁶ , R ⁶ and R ^{7 8} are the same or different and denote a hydrogen atom, an unsubstituted or substituted C 1 -C 8 alkyl group, a phenyl group or a C 1 -C 4 phenylalkyl group in the alkyl moiety, whereas O R and R do not represent a hydrogen atom, or R @ 3 and R @ 3 independently of one another also represent unsubstituted or substituted cycloalkyl having 3 to 7 carbon atoms, 5- to 9-membered heteroaryl containing from 1 to 4 identical or different heteroatoms such as oxygen, nitrogen and sulfur, or the corresponding heteroarylalkyl 1-4 carbon atoms in the alkyl moiety; or R ⁸ is -CHR ⁴ -COOH and -CHR ⁴ -COOCH ₃ , or R 6 and r 6 together with the nitrogen atom to which they are attached form an unsubstituted or substituted 5- to 7-membered ring which may additionally contain 1 or 2 identical or different heteroatoms such as oxygen, nitrogen and sulfur, or 7 8 R and R together with the nitrogen atom to which they are attached form an unsubstituted or substituted 5- to 7-membered ring, which additionally may contain 1 or 2 identical or different heteroatoms such as oxygen, nitrogen and sulfur. 2,3,5,6-Tetrafluorobenzoic acid derivatives according to claim 1, in which 1 2 R and R are the same or different and are unsubstituted branched alkyl having 4 to 6 carbon atoms, unsubstituted alkyl having 1 to 6 carbon atoms, unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl, R is an alkyl group having 2 to 6 carbon atoms, a substituted alkyl group having 1 to 6 carbon atoms, unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl, R ⁴ denotes a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or an optionally substituted phenyl or benzyl group, and r 6 are the same or different and denotes a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an unsubstituted or substituted phenyl group, substituents which may be mentioned are preferably halogen atoms, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy and haloalkylthio, 7 8 R and R are the same or different and represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, cyclopropyl. cyclobutyl, cyclopentyl, cyclohexyl, phenyl and benzyl, the preferred substituents being halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio and dialkylamino, but not R and R are both R and R, but R and R are both R and H; R 8 additionally denotes -CHR 4 -COOH and -CHR 4 -COOCH 4, or and R 6 together with the nitrogen atom to which they are attached form an unsubstituted or substituted piperidine, morpholine, hexahydroazepine or piperazine ring, the substituents being: preferably an alkyl group and a hydroxyalkyl group, or R and R together with the nitrogen atom to which they are attached form an unsubstituted or substituted piperidino, morpholine, hexahydroazepine or piperazine ring, the substituents being preferably an alkyl group and a hydroxyalkyl group. The 2,3,5,6-tetrafluorobenzoic acid derivatives according to claim 1, in which R ³ represents methyltriazolylovou · radical, R 'denotes optionally unsubstituted or halogen-substituted39-substituted phenoxy substituted butyl, pentyl, hexyl and heptyl, or optionally one to three times fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxyphenyl or a cyclopropyl group, and R is ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl, pin, or diraethylamino, diethylamino, methoxycarbonyl, or ethoxycarbonyl substituted by ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl, or optionally fluorine, chlorine, bromine, methyl, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or tri fluoromethoxy substituted phenyl, benzyl or cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, R ⁴ represents hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl, R @ 6 denotes hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl, and R @ 6 denotes hydrogen, methyl a group, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl, or R 6 and R 6 together with the nitrogen atom to which they are attached form a piperidine, morpholine, hexahydroazepine or piperazine ring, R 'represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group and a tert-butyl group, Q R is optionally dimethylamino, diethylamino, methoxycarbonyl, or ethoxycarbonyl substituted by methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl, or optionally one to three times fluoro, chloro, bromo, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy substituted phenyl, benzyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or denotes -CHR 1 -COOH and -CHR 1 -COOCH 2, wherein R 4 is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, phenyl, biphenyl , hydroxyphenyl and benzyl, or 7 8 R 1 and R 2 together with the nitrogen atom to which they are attached optionally form one or two methyl, ethyl, hydroxymethyl and hydroxyethyl substituted piperidine, morpholine, piperazine or pyrrolidine rings. A pest control composition comprising at least one 2,3,5,6-tetrafluorobenzoic acid derivative according to claim 1 of the general formula I. A method of controlling pests, characterized in that the pests and / or their habitat are treated with the 2,3,5,6-tetrafluorobenzoic acid derivatives according to claim 1 of the general formula I. Process for the preparation of 2,3,5,6-tetrafluorobenzoic acid derivatives of the general formula I according to claim 1, characterized in that it is reacted 2,3,5,6-tetrafluorobenzoyl chloride or 2,3,5,6-tetrafluorobenzoyl anhydride with the corresponding oxime, alcohol or amine, optionally in the presence of a diluent and / or a base.