SK65896A3 - Derivatives of 2,3,5,6-tetrafluorobenzoic acid and their use in combating pests - 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

The present invention relates to 2,3,5,6-tetrafluorobenzoic acid derivatives, to a process for their preparation, and to their use for pest control.

SUMMARY OF THE INVENTION

The present invention relates to acid derivatives

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

0) in which

Y is an oxygen or sulfur atom; and

X is -O-N = CR ¹ R ² , -OR ³ , -OCHR ⁴ -CO-NR ⁵ R ^6, or

-NR ⁷ R ⁸ , wherein

R ¹ and R ² are each independently an optionally substituted alkyl, cycloalkyl and aryl group,

ABOUT

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

R ⁴ , R ⁵ and R ⁶ independently represent a hydrogen atom and an optionally substituted alkyl, aryl and aralkyl group, or

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

R and R ° are each independently hydrogen and optionally substituted alkyl, cycloalkyl, aryl, aralkyl, alkylheteroaryl and heteroaryl, or -CHR ⁴ -COOH and -CHR ⁴ -COOCH ₃ groups, wherein R ⁷ and R ^{8 are} not simultaneously 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.

It has further been found that the 2,3,5,6-tetrafluorobenzoic acid derivatives of the formula I are obtained by reacting 2,3,5,6-tetrafluorobenzoyl chloride or 2,3,5,6-tetrafluorobenzoic anhydride with the corresponding oxime, an alcohol or an amine, optionally in the presence of a solvent or a base.

Finally, it has been found that the novel 2,3,5,6-tetrafluorobenzoic acid derivatives of the formula I exhibit significant microbicidal activity, in particular against plants pathogenic microorganisms. In addition, the active compounds according to the invention have a marked resistance-inducing effect in plants against attack by unwanted microorganisms.

In the following, for the sake of simplicity, the compounds of the formula I are mentioned, although they are meant to mean both these pure compounds and mixtures with different proportions of isomeric, enantiomeric and diastereomeric compounds.

The 2,3,5,6-tetrafluorobenzoic acid derivatives of the present invention are defined by Formula I.

In formula I, preferably unless otherwise indicated, alkyl is singly or in related moieties

a straight or branched alkyl group having 1 to 8 carbon atoms, in particular 1 to 4 carbon atoms. By way of example and preferably, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl, cycloalkyl are mentioned.

- a 3- to 7-membered ring, in particular a ring having 3, 5 or 6 carbon atoms. By way of example and preferably, mention may be made of a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group, an aryl group which is unsubstituted or substituted by an aryl group having 6 to 10 carbon atoms. Examples which may be mentioned are, for example, unsubstituted or substituted phenyl and naphthyl, especially unsubstituted or substituted phenyl, unsubstituted or substituted aralkyl having 1 to 4 carbon atoms, in particular 1 to 2 carbon atoms in the straight or branched alkyl moiety and 6 to 10 carbon atoms in the aryl moiety, especially in the phenyl group. Examples which may be mentioned are benzyl, 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 9-membered ring, especially a 5- to 7-membered ring, which contains 1 to 4, preferably 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 especially pyridyl, and heteroarylalkyl.

a group in which the heteroaryl moiety is as defined above and in the preferred region and the alkyl moiety is straight or branched and contains 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms. Exemplary and preferably, mention may be made of heteroarylmethyl, 1,1-heteroarylethyl, 1,2-heteroaryl-ethyl, 1,1-heteroarylpropyl, 1,2-heteroarylpropyl,

A 1,3-heteroarylpropyl group and a 2,2-heteroarylpropyl group.

Optionally substituted radicals of the general formula can carry one or more, preferably one to three, in particular 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 a group, 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, ibutyloxy, sec-butyloxy and tert-butyloxy; 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 halogen atoms being the same or different, preferably halogen being fluorine , chloro or bromo, especially fluoro such as trifluoromethyl, difluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluorochloroethyl, trifluoroethyl, trifluoroethoxy, trifluoromethoxy, trifluoromethoxy, pentafluoroethoxy, tetrafluoroethoxy, tetrafluoroethoxy, tetrafluoroethoxy, tetrafluoroethoxy, tetrafluoroethoxy, tetrafluoroethoxy; OH; 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; carbonylaryl having 6 to 10 carbon atoms in the aryl moiety, such as benzoyl; 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; carboxylamine, carbonylaminoalkyl, carbonylaminodialkyl, aminocarbonyl ,. alkyloaminocarbonyl, arainocarbonylalkyl and alkylaminocarbonylalkyl having in each case 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms in the alkyl moieties; sulfonamido; sulfonylalkyl, sulfonylalkyl and sulfonylalkoxy having in each case 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, or phenyl or phenoxy, unsubstituted or substituted by halogens, in particular fluorine, chlorine and / or bromine.

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

Preferred are compounds of formula I wherein:

R 1 and R ² are the same or different and are unsubstituted or substituted C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl or phenyl,

R '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 7, R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, a phenylalkyl group having 1 to an alkyl moiety, wherein R ⁷ and a hydrogen atom , or a phenyl group or carbon atoms

R ⁸ do not simultaneously represent independently of one another additionally unsubstituted or 3 to 7 carbon heteroaryl, various non-heteroatoms such as oxygen, nitrogen and sulfur, or the corresponding 1 to 4 carbon heteroarylalkyl

substituted cycloalkyl group by atoms of five to nine members containing 1 to 4 identical or atoms in the alkyl moiety; or

R ^b 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 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 additionally may contain 1 or 2 identical or different heteroatoms such as oxygen, nitrogen and sulfur.

Particularly preferred are compounds of formula I wherein n is n

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,

R ^&lt; 2 ^&gt; is alkyl of 2 to 6 carbon atoms, substituted alkyl of 1 to 6 carbon atoms, unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl,

R ⁴ represents a hydrogen atom or a C 1 -C 4 alkyl group or an optionally substituted phenyl or benzyl group, c: 6

R and R are the same or different and are hydrogen, alkyl of 1 to 8 carbon atoms, or unsubstituted or substituted phenyl, preferably halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy and haloalkoxy; .

R⁷ and R⁸ they 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 groups, the substituents being preferably a halogen atom, an alkyl group, an alkoxy group, , haloalkyl, haloalkoxy, haloalkyl thio and dialkylamino, however,

P

R and R do not simultaneously represent a hydrogen atom

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

R and R 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 piperidine, morpholine, hexahydroazepine or piperazine ring, preferably alkyl and hydroxyalkyl being substituents.

Very particularly preferred are compounds of formula I wherein t

R ¹ is methyltriazolyl, optionally unsubstituted or halo substituted phenoxy, substituted butyl, pentyl, hexyl and heptyl, or optionally one to three times fluorine, chlorine, bromine, methyl, ethyl, methoxy, trifluoromethoxy, trifluoromethoxy, trifluoromethoxy, trifluoromethoxy, trifluoromethoxy, trifluoromethoxy, trifluoromethoxy, trifluoromethoxy, phenyl or cyclopropyl group,

R 6 represents ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl or dimethylamino, diethylamino, methoxycarbonyl or ethyl-substituted ethoxycarbonyl , n-propyl, i-propyl, n-butyl. i-butyl, sec-butyl and tert-butyl, or optionally fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy substituted phenyl, benzyl or cyclopropyl, cyclobutyl, cyclobutyl, cyclobutyl, cyclobutyl, cyclobutyl, cyclobutyl, cyclobutyl, cyclobutyl, cyclobutyl, cyclobutyl,

R ¹ 'represents a hydrogen atom, an n-propyl group, a group. i-butyl and tert-butyl

R 4 'represents a hydrogen atom, an n-propyl group, an i-butyl group and a tert-butyl group

R ⁶ represents a hydrogen atom, an n-propyl group, an i-butyl group and a tert-butyl group a methyl group, an ethyl group, an i-propyl group, a n-butyl group, a sec-butyl group a methyl group, an ethyl group, i -propyl, n -butyl, sec -butyl, methyl, ethyl, i -propyl, n -butyl, sec -butyl, or

R 0 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,

R ^c 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 mono- to trisubstituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy-substituted phenyl, benzyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or represents the group -CHR ⁴ -COOH or -CHR ⁴ -COOCHg, wherein

R ⁴ '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, a tert-butyl group, a phenyl group, a biphenyl group , hydroxyphenyl and benzyl, or

R 1 and R ⁸ together with the nitrogen atom to which they are attached optionally form once or twice a group, a hydroxymethyl group substituted with a methyl group, an ethyl group and a hydroxyethyl piperidine, morpholine, piperazine or pyrrolidine ring.

Preferred compounds are also acid addition products and derivatives thereof of the general formula I, in which the substituents R ¹ and R ^{8 have the} meanings indicated above as being preferred.

Acids which can be added preferably include hydrohalic 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 acetic acid, raleinic 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, salt and metal addition products II are also preferred. to IV. the main and I. and II., and IV. to VIII. the sub - group of the Periodic System of the Elements and their derivatives of formula (I),. in which the substituents R and R 0 have the meanings given above as being preferred.

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

The novel tetrafluorobenzoic acid derivatives of the formula I can be prepared by methods 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 methods known per se.

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 such as ethyl acetate and / or in the presence of acid binders such as potassium carbonate, triethylamine, pyridine,

N-methylpiperidine, potassium hydroxide or sodium hydroxide, at a temperature in the range of 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 an 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 forming salts with optically active acids, such as camphorsulfonic acid or dibenzoyltartaric acid, and further by selective crystallization or derivatization with suitable optically active reagents, separation of diastereomeric derivatives and reverse resolution or optically active resolution. column.

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

Fungicidal agents in plant protection are used for the proofing of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes,

Zygomycet, Ascomycet, Basidiomycet and Deuteromycet.

Examples of, but not limited to, some agents of fungal diseases that fall under the above.

Pythium species, such as Pythium ultimum.

Phytophzhora 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 Peronospora pisi or Peronospora brassicae.

Ervsiphe species, such as Erysiphe graminis.

Sphaerotheca species, such as 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: Helminthosportum).

Cochliobolus species, such as, for example, Cochliobolus sativus (conidia form: Drechslera, Synonym: Helminthosporium).

Uromyces species, such as Uromyces appendiculatus.

Puccinia species, such as Puccinia recondita.

Tilletia species, such as Tilletia caries.

Ustilago species, such as Ustilago nuda or Ustilago avenae.

Pellicularia species, such as Pellicularia sasakii.

Pyricularia species, such as Pyricularia oryzae.

Types Fusarium than is a for example Fusarium culmorum. Types Botrytis than is a for example Botrytis cinerea. Types Septoria, than is a for example Septoria nodorum.

Leptosphaeria species, such as Leptosphaeria nodorum.

Cercospora species, such as Cercospora canescens.

Alternative species, such as Alternaria brassicae.

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

The good acceptability of the active ingredients for plants at the concentrations necessary for the propagation of plant diseases permits the treatment of above-ground parts of plants, plant seedlings, seeds and soil.

The active compounds according to the invention can in this case be used with a particularly good success for the proofing of Pyricularia on rice.

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

Resistance-inducing substances in this context are understood to be those which, by acting directly on undesirable microorganisms, exhibit only slight activity but, on the other hand, are capable of stimulating the plant defense system so that the treated plants have a high resistance when subsequently inoculated with undesirable microorganisms. against these microorganisms.

The term undesirable microorganisms in this case refers to phytopathogenic 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.

Undesirable microorganisms in plant protection include fungi of the classes Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

The active substances can, depending on their physical and / or chemical properties, be converted into conventional preparations, such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, fine capsules in polymeric substances and encapsulating tips for axes. as well as cold and hot milling 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. emulsifying agents and / or dispersing agents 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, ac. is, for example, xylene, toluene and alkylnaphthalenes, fluorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins such as petroleum fractions, 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, strongly polar solvents such as dimethylformamide or δ; ethylsulfox i.d as well as water. Liquid diluents and both carriers are understood to be those liquids which are gaseous at normal temperature and pressure, for example aerosolized carrier gases such as butane, propane, nitrogen and carbon dioxide.

Suitable solid carriers are, for example, natural powdery rocks such as kaolin, clay, talc, chalk, quartz, and pulp, montmorillonite or diatomaceous earth and synthetic flours such as highly disperse silica, alumina and silicates. Suitable solid carriers for granulates are, for example, crushed and fractionated natural rocks such as calcite, marble, popaz, sepiolite, dolomite, as well as synthetic granules of inorganic and organic flours and granules of organic materials such as sawdust, coconut shells, corn bars and tobacco stems.

Suitable emulsifiers and / or foaming agents are, for example, non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters and polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, and alkylsulfates, arylsulfonates, as well as protein sulfonates. Suitable dispersing agents are, for example, lignosulphite leachates and methylcellulose.

Adhesion enhancers such as carboxymethylcellulose, natural and synthetic, β, clinker, granular or latex polymers such as acacia, p.

n, for example, polyvinyl acetate cephalins, as well as natural phospholipids, and lecithins and synthetic phospholipids. Other ingredients may be mineral and vegetable oils.

Dyes such as inorganic pigments, such as iron oxides, titanium dioxide, ferrocyanate blue and organic colorants such as alizarin dyes, azo dyes metal phthalocyanine dyes and trace nutrients such as iron, nangan, boron, copper, cobalt, molybdenum and zinc.

The formulations generally contain from 0.1 to 95% by weight of the active substance. preferably 0.5 to 90% by weight.

The active ingredients of the present invention may be present in the formulations in admixture with other known active ingredients such as xigicides, insecticides, acaracids, nematicides and herbicides, such as. Mixtures with fertilizers 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.

The components of these mixtures include:

'<·' I.-igicides:

2-Aminobutane 2-anilino-4-methyl-6-cyclopropyl-pyrimidine, 2 ', 6'-dihydro-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3- thiazole

- carboxanil, 2,6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide, (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide, 8-hydroxyquinoline sulphate, methyl - (E) -2- {2- [6- (2-cyanophenoxy) -pyrimidin-4-yloxy] -phenyl-3-methoxyacrylate, methyl (E) -methoxyimino- [α- (o-tolyl) oxy] -o-tol / 1 Acetate, 2-phenylphenol (OPP),

AJ.dimorph, Amoropylfos, Anilazine, Azaconazole,

Eiiaiaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Betertanol, nl isticidin: ·, Bromuconazole, Bupirimate, Buthiobate, ··. : .ciumpoly: i ·; ··!; .fid, Captafol, Captan, Cardendazim, Carboxin,

C.;, .Nomethiona- (Quinomethionat), Chloroneb, Chloropicrin,

Ch i.orothaloni L, Chlozolinate, Cufraneb, Cymaxanil, Cyproconazole, Cyprofuran,

D i .--. Hlorophen .. Diclobutrazole, Diclof luanide, Diclomezin, Dicloran,

Dlethofencar :? Difenocanazole, Dimethirimol, Dimethomorph, D.I.niconazole, Dinocap, Diphenylamine, Dipyrithion, Ditalimfos, Dithianon, Dedine, Drazoxolone,

Ed .fenpho

Im cf \ arimol, npropidine. rbam, F iquincona /

Flutriafol).

F. lalaxyl, i'i

TJ

t .; Λ

Fpoxyconazole, enbuconazole,

Fenpropimorph, rimzone, Fluazinam,

Le, Flusilazole, Folpet, Fosetyl-Aluminum, rmecyclox,

Ethirimol, Etridiazole,

Fenfuram, Fenitropan, Fenpiclonil, Fentinacetate, Fentrinhydroxyd, Fluoromide, Flutolanil, Fuberidazole,

fludioxonil

flusulfamide.

Fthalide.

guazatine;

Heachlorobenzole, Hexaconazole, Hymexazole,

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

Tsoprot-hiolan.

Kasugamycin. copper preparations such as copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxin-copper and Bordeaux-blend, bancopper, ilancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Meeconazole, le thysox ocarb, Methfuroxam Metiram, Metsulfovax,

Mycobutanil, rekel-dimethyl rdithiocarbamat, Nitrothyl-isopropyl, Naurimol,

Irradiation, Oxadixyl, Oxamocarb, Oxycarboxin,

Peturazoate, Penconazole, Pencycuron, Phosdiphen, Phthalid, P.i.maricin, Fiperalin, Polycarbamate, Polyoxin, Probenazole, Prochloraz, Procymidone, Propamocarb, Propiconazole, Propineb, Pyrazophos, Žyrifenox, Pyrimethynil, Pyroquilon,

Quintozene (PCNB), sulfur and sulfur preparations,

T-buconazole, Tecloftalam, Tacnazen, Tetraconazole, Thiabendazole, Ti: Lcyofen, Thiophanate-methyl, Thiram, Tolclophos-methylTolylfluanid, Triadimefon, Triadimenol, Triazoxide, Trichlamide, Tricylamide, Triforol, Triforol, Triforol, Triforol, Triforol, α1 idamycin A Vinclozolin.

Zrneb, Ziram

B. Z. tericides i <:> nopol, Dichlorophen, Nitrapyrin, Nickel-Dimethyldithio-bamat, Kasugamycin, Octhilinone, furancarboxylic acid, tetracyclic, Probenazole, Streptomycin, Tecloftalam, sulphate

I '. ^- ·· Phosphate and d'cJ. ecticides /.->: <aricides / Nematicides

AB.imectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, and. Amitraz, Avermectin AZ 60541, Azadirachtin, Azi.nphos A, A? inphos M, Azocyclotin,

Bacilus tturingiensis, Bendiocarb, Benfuracarb, Bensultap, Beaacyluthrin · Bifentrin, BPMC, Brofenprox, Bromophos A, Eufencarb, Buprofezin, Butocarboxin, Butylpyridaben,

Cadusafos, Carbaryl, Carbofuran,

C: ta p, CGA 157 419, CGA 184699

C 'i lorfenviphcs, Chlorfl.uazuron,

Carbophenothion, Carbosulfan, Chloethocarb, Chorethoxyfos, Chlorormephos, Chlorpyrifos,

C ··, i.orpyrif axis M,

Cis-Resmethrin, Clocythrin, Clofentezin, b / anophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin,

'jermethrin. cyromazine,

D ?, lethethrin. Demeton M, Demeton S, Demeton-S-methyl, ... ifenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, .rotophos. Biethion, Diflubenzuron, Dimethoat, Dimethylvinphos,

D. oxathion, Disulfoton,

EBifenphos. Emamectin, Esfenvalerat, Ethiofencarb, Ethion, ' ) of enprox Ethoprophos, Etrimphos, F ^ iamiphos, ’Anazaquin, Fenbutatin oxide, Fenitrothion, Fenobucarb,

FenothiocarbFenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, r'Aiithion, lerate can, Fipronil, Fluazinam, Flucycloxuron, l'ixythrinat. Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, salmion, Fosthiazat, Fubfenprox, Furathiocarb,

H., Heptosios, Hexaf lumuron, Hexythiazox,

Idacloprid, Ibrobenfos, Isazophos, Isofenphos, Isoprocarb,. > -> xathion, ve.rmectin, Lambda-cyhalothrin, Lufenuron,

1 '.athion, Iecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Alacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, ii ·· rolcarb, Milbemectin, Monocrotophos, Moxidectin,

Ed .ed, NC 182, NI 25, Nitenpyram, ithoat, Oxamyl, Oxydemethone M, Oxydeprofos,

· Athion A, Parathion M, Permethrin, Phenthoat, Phorat, 'saloon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos 1; Pirimipho s A, Profenofos, Promecarb, Propaphos, Propoxur, -athiophos, Prothoat, Pymetrozine, Pyrachlophos, Pyradaphenthion, P. · esmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Q · inalphos, λ ·. 5992,

3 · ·. ..ithion, Sebufos, Silafluofen, Sulfotep, Sulfprofos, ··. rufenozide, Tebufenpyrad, Tebupirimphos, Teflubenzuron,, ^; luthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Th.afenox, Thiodicarb, Thiofanox, Thiomethon, Thionazine, Th iringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron, <chlorphon, Triflumuron, Trimethacarb,

v.aiidothion.

i. · ': Xylylcarb

5301/5303,.! '.Amethrin.

Mixtures with other known active substances such as iobicides or with fertilizers and growth regulators are also possible.

The active ingredients can be used as such, in the form of their formulations, or from their application forms, such as solution solutions, suspensions, spray powders, pastes, soluble powders, sprays and granules. The application is carried out by conventional means, for example by watering, spraying, spraying, spraying, foaming, coating and the like. It is also possible to use the Ultra-Low-Volume method. bias the pro-drug of the active substance or the active substance itself into;. Plant seed may also be processed.

Concentrations can be effective in controlling plant parts

..year in application forms to move in a wide range.

\: generally ’j-? this concentration is from 1 to 0.0001% by weight, i.e. 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: 000 to 1% by weight, preferably 0.0001 to 0.02%, are required.

In .. •• on site.

When used as resistance inducers, the concentrations of the plant substance treatment agent can vary widely in application forms. They are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

Examples The preparation and use of compounds of the present invention, the _<f: ;; simultaneously pojwcou following examples.

Production examples

prik

F

F

55 g (0.26 mol) of 5,6-tetrafluorobenzoyl chloride are added dropwise with stirring at 20 DEG C. to a solution of 42.4 g (0.27 mol) of. 5,6,7-hexahydroazepine and 27 g (0.27 mol) of t-ethylamine; in 500 mL of methylene chloride over 30 minutes. After stirring overnight, the reaction mixture is treated with water and the dichloromethane is separated and the organic phase is concentrated in vacuo. It is obtained as follows:. an oily liquid which soon crystallizes.

Yield: 67.3 g (77.9% of theory). : 6 4 to 6 ⁰ C. Example 2 Y F F in/ 1 CH, 1 ^z M -CO-NH-CH-COOH

To a solution of 8.08 g (49 mmol) of L-phenylalanine in 25 ml of 2N sodium hydroxide was added dropwise simultaneously with ice-cooling 10.6 g. 2.3,5,6-tetrafluorobenzoyl chloride and 25 ml of 2N hydroxide with another. After stirring overnight, the pH was adjusted to 2 with dilute hydrochloric acid and the crystallizate formed was filtered off with suction.

Yield: 15 µg (93.4% of theory): 146-147 ° C.

The following compounds of general formula (I) are prepared accordingly

F F

Example X Y 1.1. (° C) 3 -O-CH ₂ -CO-N (C 3 H ₇ -i) ₂ 0 72 4 -O-CH ₂ -CO-N (C ₂ H 5) ₂ 0 88 5 -0-CH ₂ - 0 54 6 -O-CH NCqHj). 0 ng ⁰ = 1.4598 7 -O-CH-COOC ₂ H _S 0 n ²⁰ = 1.4473 8 -Ο-ΟΗο- ^ Ηγ-ί 0 ηβ ° = 1.4430 9 CH, -O 0 60-64 10 MpHy / ⁰¹ --Of 0 118-20

Example X Y 1.1. CC) 11 i-CÄ / ^CF '-M 0 132 12 iC ₃ H ₇ ^-N -2 H 2 ^-CH 3 0 122 13 CH ₃ CK 0 102 14 J 0 158 15 C NH ( 1 F / _r 0 102 l 16 -ΝΗ-εΗ, εΗ, -Νίσ, ΗΛ, 0 76 17 -NH-CH, CH, -N (C, 1H), x HCl 0 148 18 -NH-N.-COOH 0 138 19 CH, 1 — NH-CH-COOH 0 157 20 CH (CH ₃₎ C ₂ H _5, -NH-CH-COOH 0 178

Example X Y t i. (° C) 21 * - ^C 3 ^H 7 1 —NH-CH-COOH 0 137 22 -NH-CH ₂ - £) 0 120 23 -N 0 110 24 -ABOUT 0 72 25 . -about 0 67 26 CH- ch ₃ 0 114 27 -N - N - CH - CH - OH ² 0 81 28 COOF h ~ ^N \ and 0 4 ° = 1.4952 29 1 ------------------------------------------------- ------------- CH, / - (--NMCH3 ₎ 0 84

Example . X Y 1.1. CC) 30 ~~ ^N d / ⁰ 0 60 31 Cl · ^ —O ~ N = C — Br CH ¹² (\ N U 0 ng ° = 1.5498 32 CH ₃ -ON = C-Br CH, N ¹² N S f f Stereosomer A 'U 0 140 33 CK -ON = C? A-Br CH, ¹² rf StereoCome B 'U 0 116 34 ^c = -O-N = C-CH, 1 ² .N. Y N Stereotsomef A 'U 0 150 35 ^c — —O — N = C — N. XN Stereoomer: 0 V 0 126

Example X Y 1.1. (° C) 36 CH, - O - N = C - C - CH 2 O - C y - Cl CH, CH, A ^< 0 87 37 CI-ON = CH 2 CH ² O ² 0 88 38 -ON = C-C (CH ₃₎ CH _3, (\ ^N U 0 98 39 Τ '-ON = C - C-CH CHjCHjO-, JL ^<N Yu 0 n D ° = 1.5276 40 COOH -NH-CH 0 170 41 COOH - NH - CH - CH - 0 152-55

Example X Y mp , (»C) 42 1 0 WITH 138-40 43 - WITH 104-06 44 CH, -p CH / WITH 124-27 45 _COOCH3 NH-CH CH ₂ - 0 120 46 COOCHj -NH-CH-- 0 158-60 47 COOCH, —NH -CH-- 0 log P: 2.68

Examples of use

Example A

Pyricularia (rice) / systemic test

Solvent: 12.5 parts by weight of acetone emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether to

To make a suitable active ingredient preparation, 1 part by weight of the active ingredient is mixed with the stated amount of solvent and the concentrate is diluted with water and the said amount of emulsifier to the desired concentration.

To test the systemic properties, 40 ml of the active ingredient preparation is poured onto the unit soil in which the young rice plants were. 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 show a 100% degree of action at an application rate of 100 mg of active ingredient per 100 cm ³ .

Claims (2)

PATENT CLAIMS 1. 2,3,5,6-Tetrafluorobenzoic acid derivatives of general formula I Torom is an oxygen or sulfur atom; and is -O-N = CR ¹ R ² , -OR ³ , -OCHR ⁴ -CO-NR ⁵ R ⁶ or -NR ⁷ R ⁸ , wherein R 12 and R ⁶ are independently optionally substituted alkyl, cycloalkyl and aryl, R represents an alkyl group with at least two carbon atoms, a substituted alkyl group and an optionally substituted cycloalkyl, aryl and aralkyl group, R ⁴ , R ⁵ and R ⁶ independently represent a hydrogen atom and an optionally substituted alkyl, aryl and aralkyl group, or K (Z,, R @ 2 and R @ 2 together with the nitrogen atom to which they are attached represent an optionally substituted ring or R ⁷ and R ⁸ are each independently hydrogen and optionally substituted alkyl, cycloalkyl, aryl, aralkyl, alkylheteroaryl and heteroaryl, or -CHR ⁴ -COOH and -CHR ⁴ -COOCH ₃ groups, wherein R ⁷ and R ^{8 are} not simultaneously a hydrogen atom, or R 1 and R 2 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 Ί 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 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,. . 5 r 'P R 'in R, R, R' and R are the same or different and represent a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, a phenylalkyl group having 1 to an alkyl moiety, wherein R a is a hydrogen atom or a phenyl group or 4 carbon atoms ABOUT R do not mean simultaneously R ² and R ⁸ independently of each other additionally also represent an unsubstituted or substituted cycloalkyl group having 3 to 7 carbon atoms, a 5- to 9-membered heteroaryl group containing 1 to 4 identical or different heteroatoms such as oxygen, nitrogen and sulfur, or the corresponding heteroarylalkyl a (1-4C) alkyl group; or R c is -CHR ⁴ -COOH and -CHR 4 -COOCH 4, or Pr 1 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 R ² and R ⁸ 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. 2,3,5,6-Tetrafluorobenzoic acid derivatives according to claim 1, in which R ¹ and R ² are the same or different and represent an unsubstituted branched alkyl group having 4 to 6 carbon atoms, a substituted alkyl group having 1 to 6 carbon atoms, an unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl group, R 'represents an alkyl group having 2 to 6 carbon atoms, a substituted alkyl group having 1 to 6 carbon atoms, an unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl group, R ' ¹ represents a hydrogen atom or a C 1 -C 4 alkyl group or an optionally substituted phenyl or benzyl group, L and R ⁶ are identical or different and denote hydrogen, alkyl group having up to 8 carbon atoms, or an unsubstituted or substituted phenyl, substituents include preferably a halogen atom, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, and haloalkylthio, R ⁷ and R ⁷⁸ are the same or different and represent a hydrogen atom, a substituted or unsubstituted C 1 -C 6 alkyl group, a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl and benzyl group, preferably halogen atoms, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkyloxy and dialkylamino, but R and R do not simultaneously represent a hydrogen atom R 'is -CHR ⁴ -COOH and -CHR ⁴ -COOCH ₃ , or R 1 and R 0 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, 7 β R and R ° together with the nitrogen atom to which they are attached form an unsubstituted or substituted piperidine, morpholine, hexahydroazepine or piperazine ring, preferably alkyl and hydroxyalkyl being substituents. 2,3,5,6-Tetrafluorobenzoic acid derivatives according to claim 1, in which h is methyltriazolyl, optionally unsubstituted or halo-substituted phenoxy-substituted butyl, pentyl, hexyl and heptyl, or optionally one to three times fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy or trifluoromethyl or trifluoromethyl or trifluoromethyl or trifluoromethyl or trifluoromethyl or trifluoromethyl; group R 6 represents ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl or dimethylamino, diethylamino, methoxycarbonyl or ethyl-substituted ethoxycarbonyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl, or optionally fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy, substituted phenyl benzyl or cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl means hydrogen, n-propyl, i-butyl methyl, ethyl, i-propyl, n-butyl, sec-butyl and tert-butyl is hydrogen, n-propyl, i-butyl methyl, ethyl, ip is selected from hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl and n-butyl; i-butyl,; t-butyl or sec-butyl R ⁵ and ¹ 's; olefins with the nitrogen atom to which they are attached form a piperidine, morpholine, hexahydroazepine or piperazine ring, meaning a hydrogen atom, a n-propyl group, a group, an i-butyl methyl group, an ethyl group, an i-propyl group, n-butyl, sec-butyl, t-butyl, R ⁸ is optionally dimethylamino, diethylamino, methoxycarbonyl or ethoxycarbonyl-substituted methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and t-butyl, or optionally mono- to trisubstituted fluorine, chlorine, bromine, methyl, ethyl, full-length, ethoxy, trifluoromethyl or trifluoromethoxy substituted phenyl, ben; is a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl group, or is -CHR ⁴ '-COOH or -CHR ⁴ ' -COOCH ₃ , wherein: R 'represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an i-butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group, a phenyl group, a biphenyl group, hydroxyphenyl and benzyl, or R and R ° together with the nitrogen atom to which they are attached optionally form one or two methyl groups, an ethyl tiperazine or a pyrrolidine ring. A pest control agent comprising at least one 2,3,5,6-tetrafluorobenzic acid derivative according to claim 1 of the general formula (I). Method for the control of pests, characterized in that acid derivatives and / or their habitat are treated with acid derivatives: ί 2. 3,5,6-tetrafluorobenzoate according to claim 1 of the general formula. r A process for the preparation of 2,3,5,6-tetrafluorobenzoic acid derivatives of the formula I according to claim 1, characterized by reacting 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. . Use of 2,3,5,6-tetrafluorobenzoic acid derivatives of the general formula I according to claims 1 to 4 for pest control. *. Process for the preparation of pest control agents, characterized in that the 2,3,5,6-tetra-fluorobenzoic acid derivatives of the formula I according to claims 1 to 4 are mixed with fillers and / or surfactants.