WO1994005636A1

WO1994005636A1 - 2-arylhydrazono-3-ketonic acid piperidides as pest control agents

Info

Publication number: WO1994005636A1
Application number: PCT/EP1993/001963
Authority: WO
Inventors: Günther HEUBACH; Peter Braun; Burkhard Sachse
Original assignee: Hoechst Schering Agrevo Gmbh
Priority date: 1992-08-29
Filing date: 1993-07-23
Publication date: 1994-03-17
Also published as: AU4701893A; MX9305213A; ZA936308B; IL106819A0; DE4228793A1; TR27221A; CN1084512A

Abstract

Compounds have formula (I), in which R1 stands for hydrogen, an aliphatic or a cyclic residue: R2 stands for hydrogen, alkyl or acyl; R3 stands for alkyl; R4 stands for hydrogen, cyanethyl, benzyl, OH, O or alkoxycarbonyl; X stands for the substituents of an aromatic residue, Y O or NOH; R?4 and R5¿ stand for hydrogen, an aliphatic or an alicyclic residue; and n is an integer from 0 to 4. Also disclosed is a process for producing these compounds, agents containing the same and their use as pest control agents, in particular as fungicides.

Description

DESCRIPTION

2-ARYLHYDRAZ0N0-3-KETOIC ACID PIPERIDIDES AS A PEST CONTROL

The present invention relates to new amide derivatives of 2,2,6,6-tetraalkyl-4-aminopiperidine, processes for their preparation, compositions containing them and their use as pesticides, in particular fungicides.

Amides of 2,2,6,6-tetramethyl-4-aminopiperidine are already known as components in fungicidal compositions (cf. DE-A-39 01 246, DD-A-138 729). However, the effect of these amides is not always satisfactory, especially when the application rates are low.

New amides of 2,2,6,6-tetraalkyl-4-aminopiperidine have been found which have advantageous effects in combating a broad spectrum of phytopathogenic fungi, in particular in low doses.

The present invention therefore relates to compounds of the general formula I.

wherein R ^{1 is} hydrogen, (C, -C ₁₂ ) alkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl, alkyl, alkenyl and alkynyl optionally being up to 3 identical or various substituents from the series include halogen, (C, -C ₃ ) alkoxy, (C ₁ -C ₃ ) alkylthio, cyano, (C ₃ -C ₆ ) cycloalkyl, optionally substituted aryl and optionally substituted aryloxy or these three Residues, if not included in the above definition, are optionally partially or fully halogen-substituted, an optionally substituted 5- or 6-membered heterocycle residue with up to 3 identical or different heteroatoms from the series oxygen, sulfur and nitrogen, optionally substituted (C ₃ -C ₉ ) cycloalkyl or optionally substituted phenyl or naphthyl;

R ^{2 is} hydrogen, (C., - C ₄ ) alkyl. (CC ₃ ) alkanoyl or (C _r C ₃ ) -

Alkoxycarbonyl;

R ^{3 represents} (CC ₄ ) alkyl;

R ^{4 is} hydrogen, cyanoethyl, benzyl, OH; Represents O or COOR ³ ;

X for identical or different radicals from the halogen, cyano,

Nitro, thiocyanato, (CC ₆ ) -alkyl, (C ^ C ^ -alkoxy, (C ^ C ^ -alkylthio, where alkyl, alkoxy and alkylthio optionally carry up to three identical or different substituents from the series halogen and (C, -C ₃ ) - alkoxy or these three radicals, if not included in the above definition, are optionally partially or completely halogen-substituted, (C ₁ -C ₃ ) alkoxycarbonyl, aryl, aryloxy or aroyl, preferably phenyl, phenoxy or benzoyl, each can carry up to 5 identical or different substituents from the halogen or trifluoromethyl series, (C ₃ -C ₆ ) cycioalkyl or NR ⁵ R ⁶ , or for n> 2 two adjacent radicals X together with the phenyl ring bearing them a naphthalene or form a tetrahydronaphthalene radical and, in the case of n> 2, the other radicals X are as defined above;

Y represents O or NOH;

R ⁵ and R ^{6 are the} same or different and hydrogen, (C, -C ₄ ) alkyl or (C ₃ - C ₆ ) cycloalkyl, which is up to 3 times by the same or different

may be substituted, mean and n is an integer from 0 to 4, and their salts, preferably those which are compatible with plants

Acid addition salts of inorganic or organic acids.

Salts according to the invention are e.g. Addition salts of chloric, bromic or iodine-hydrogen acid, sulfuric acid, phosphoric acid, phosphorous acid, nitric acid, acetic acid, propionic acid, maleic acid, fumaric acid, lactic acid, glycolic acid, oxalic acid, succinic acid, citric acid, para-toluenesulfonic acid, salicylic acid, or dodecylsulfonic acid.

Preferred among the compounds of the formula I are those in which

R ^{1 is} hydrogen, optionally substituted (C _, - C ₄ ) alkyl, optionally substituted phenyl, optionally substituted phenylmethyl or optionally substituted (C ₃ -C ₆ ) cycloalkyl;

R ^{2 represents} hydrogen, (C, -C ₄ ) alkanoyl or (C _ * - C ₃ ) alkoxycarbonyl;

R ^{3 represents} methyl;

R ^{4 represents} hydrogen;

X is the same or different and halogen, nitro, thiocyanato, cyano, (C., - C ₃ ) alkoxycarbonyl, (C ^ C ^ alkyl, (C ^ C ^ alkoxy, (C ₁ -C ₃ ) alkylthio , where alkyl, alkoxy and alkylthio can be substituted in whole or in part with identical or different halogen atoms, phenyl, phenoxy or benzoyl, which can each be substituted with halogen atoms one or more times and / or with trifluoromethyl

Y is 0 or NOH and n can be 0-3, and the salts thereof.

Those compounds of the general formula I in which R ^{1 is} methyl or cyclopropyl are particularly preferred; R ^{2 is} hydrogen, R ^{3 is} methyl, R ^{4 represents} hydrogen,

X is the same or different and means halogen, cyano, (C ^ C ^ alkyl, (C _-- C ₃ ) alkoxy or (C ^ C ^ alkylthio), wherein alkyl, alkoxy and alkylthio in whole or in part by the same or different Halogen atoms can be substituted;

Y is 0 or NOH and n can be 1-3, and their salts, in particular their acid addition salts of acids such as hydrochloric acid, para-toluenesulfonic acid or saccharin.

Unless otherwise defined in individual cases, alkyl, alkenyl and alkynyl can be straight-chain or branched; the same applies to residues derived therefrom, such as alkoxy, alkylthio or alkanoyl. Halogen means fluorine, chlorine, bromine or iodine.

"Aryl" means in particular a benzoid aromatic radical having 6 to 18 carbon atoms, such as phenyl, naphthyl, biphenylyl or indenyl; preferred is phenyl. The same applies to "aryloxy", where phenoxy is preferred, and to "aroyl", where benzoyl is preferred.

(C ₃ -C ₉ ) Cycloalkyl means, for example, cyclopentyl, cyclohexyl or cycloheptyl, with cyclohexyl being preferred.

Optionally substituted aryl, aryloxy or cycloalkyl can each carry up to 5, preferably up to 3 identical or different substituents, preferably from the series halogen, nitro, thiocyanato, cyano, (C * -C ₃ ) alkoxycarbonyl, (C _-- C ₃ ) -alkyl, (C ₁ -C ₃ ) -alkoxy, (C _r C ₃ ) -alkylthio, where alkyl, alkoxy and alkylthio can be wholly or partly substituted with identical or different halogen atoms, phenyl and phenoxy, both with halogen atoms can be substituted one or more times and / or with trifluoromethyl.

A "heterocycle residue" is preferably a heteroaryl residue or a partially or provisionally saturated residue derived therefrom. Under a "heteroaryl residue" is preferably understood to mean a phenyl radical in which at least one CH is replaced by N and / or in which at least two adjacent CH groups are jointly replaced by one NH, O and / or S each. Examples of such radicals are thienyl, furyl, benzofuryl, pyrrolyl, imidazolyl, pyryzolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, oxazolyl, isoxazolyl, thiazolyl, isothiazoyl and tetrazolyl.

Some of the compounds of the formula I have one or more asymmetric carbon atoms. Racemates and diastereomers can therefore occur. The invention encompasses both the pure isomers and their mixtures. The mixtures of diastereomers can be made by conventional methods, e.g. be separated into the components by selective crystallization from suitable solvents or by chromatography. Racemates can be separated into the enantiomers by conventional methods, e.g. by salt formation with an optically active acid, separation of the diastereomeric salts and release of the pure enantiomers using a base.

The new amides I can be prepared by the following methods:

a) implementation of compounds of general formula II

with diazonium salts of the general formula III

(+)

J & ¹ 'C l (-)

( IN THE ) in which the substituents have the meanings given above, according to the usual literature conditions for the reaction of methylene-active compounds with diazonium salts. This coupling is carried out optimally in water or alcohol-water mixtures in the pH range between 4 and 5, which can be achieved by adding a buffer such as sodium acetate or simultaneously adding a base such as sodium hydroxide solution under pH control.

Implementation of compounds of general formula IV

wherein R ¹ and X _{n have} the meanings given above and R ^{5 can be} methyl or ethyl, with compounds of the general formula V

in R ² , R ³ and R ^{4 have} the meanings given above, at temperatures between 100 and 200 ° C, preferably at temperatures between 130 and 180 ° C with or without solvent. Examples of suitable organic solvents are: xylene, dichlorobenzene, dimethylformamide, dimethyl sulfoxide, diphenyl ether etc.

The compounds of the formula II are prepared by methods known from the literature by reacting β-ketoester VI ^• CH ₂ - C 00 R (VI)

wherein R ¹ and R ⁵ have the abovementioned meaning, with compounds of formula V or, in the case of R ¹ = CH _3, ^'l rteraturbekannte by reacting V with diketene.

The corresponding oximes of general formula I with Y = NOH can be prepared by methods known from the literature from the ketones of general formula I with Y = 0 by reaction with hydroxylamine.

The compounds of the formula I according to the invention are distinguished by an excellent protective and curative action. Fungal pathogens that have already penetrated into the plant tissue can therefore be successfully combated curatively. This is particularly important and advantageous in the case of those fungal diseases which can no longer be effectively combated with the usual fungicides after infection has occurred. The spectrum of activity of the claimed compounds encompasses a number of different economically important phytopathogenic fungi, such as e.g. Piasmopara viticola, Phytophthora infestans and Botrytis cinerea.

The compounds according to the invention are also suitable for use in technical fields, for example as wood preservatives, as preservatives in paints, in cooling lubricants for metalworking or as preservatives in drilling and cutting oils.

The invention also relates to compositions which contain the compounds of the formula I in addition to suitable formulation auxiliaries. The agents according to the invention generally contain the active ingredients of the formula I in an amount of 1 to 95% by weight. They can be formulated in different ways, depending on how it is specified by the biological and / or chemical-physical parameters. Possible formulation options are therefore: wettable powder (WP), emulsifiable concentrates (EC), aqueous dispersions based on oil or water (SC), suspoemulsions (SC), dusts (DP), mordants, granules in the form of water-dispersible granules (WG) , ULV formulations, microcapsules or waxes.

These individual types of formulation are known in principle and are described, for example, in:

Winnacker-Küchler, "Chemical Technology", Volume 7, C-Hauser Verlag Munich,

4th ed. 1986; van Falkenberg, "Pesticides Formulations", Marcel Dekker N.Y., 2nd

Ed. 1972-73; K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd.

London.

The necessary formulation aids such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in:

Watkins, "Handbook of Insecticide Dust Diluents and Carrier," 2nd Ed., Darland Books, Caldwell N.J .; H.v. Olphen, "Introduction to Clay Colloid Chemistry, 2nd Ed., J. Wiley & Sons, NY; Marschen," Solvents Guide ", 2nd Ed., Interscience, NY 1950; McCutcheon's" Detergents and Emulsifiers Annual ", MC Publ. Corp. , Ridgewood NJ; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., NY 1964; Schönfeldt, "interfacial ethylene oxide adducts", Scientific Publishing Company, Stuttgart 1976; Winnacker-Küchler, "Chemical Technology ", Volume 7, C. Hauser Verlag Munich, 4th edition 1986.

On the basis of these formulations, combinations with other pesticidally active substances, fertilizers and / or growth regulators can also be produced, for example in the form of a finished formulation or as a tank mix. Spray powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, contain not only a diluent or an inert substance, but also wetting agents, for example polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenol sulfonates and dispersants, for example sodium iignosulfonate, 2,2'-dinaphthylmethane-6, Contain 6'-disulfonic acid sodium, dibutylnaphthalene-sulfonic acid sodium or oleylmethyl tauric acid sodium. Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or even higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers. The following can be used as emulsifiers:

Alkylarylsulfonic acid calcium salts such as Ca-dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or polyoxethylene sorbitol esters.

Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. Talc, natural clays such as kaolin, bentonite, poryphillite or diatomaceous earth. Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g. Polyvinyl alcohol, sodium polyacrylic acid or mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.

The active ingredient concentration in wettable powders is, for example, about 10 to 90% by weight, the remainder to 100% by weight consists of customary formulation components. In the case of emulsifiable concentrates, the active substance concentration can be approximately 5 to 80% by weight. Dust-like formulations usually contain 5 to 20% by weight. In the case of granules, the active ingredient content depends in part on whether the active compound is liquid or solid and which compound is liquid or solid and which additives, fillers etc. are used.

In addition, the active ingredient formulations mentioned may contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, solvents, fillers or carriers.

For use, the concentrates, which are commercially available, are diluted in the customary manner, e.g. for wettable powders, emulsifiable concentrates, dispersions and sometimes also for microgranules using water. Dust-like and granulated preparations as well as sprayable solutions are usually no longer diluted with other inert substances before use.

With the external conditions such as temperature, humidity, etc. the required application rate varies. It can fluctuate within wide limits, e.g. between 0.05 and 10.0 kg / ha or more of active substance, but is preferably between 0.01 and 5 kg / ha.

The active compounds according to the invention can be used in their commercially available formulations either alone or in combination with other fungicides known from the literature.

Examples of fungicides known from the literature which can be combined according to the invention with the compounds of the formula I include the following products: aldimorph, andoprim, anilazines, BAS 480F, BAS 490F, benalaxyl, benodanil, benomyl, binapacryl, bitertanol, bromuconazole, buthiobate, captafol , Captan, Carbendazim, Carboxin, CGA 173506, Chlobenzthiazone, Chlorthalonil, Cymoxanil, Cyproconazole, Cyprofuram, Dichlofluanid, Dichlomezin, Diclobutrazol, Diethofencarb, Difconconodol, Difluconimodonol, Difluconimodonol, Dimethiromimodolone, Dimethiromimazodol, Dimethiromimodolole, Dimethiromimodolone, Dimethiromimodolone, Dimethiromimodolole, Dimethiromimodolole, Dimethiromimodolone, Dimethiromimodolone, Dimethiromimodolone, Dimethiromimodolone, Dimethiromimodolone, Dimethiromimidone, Dimethiromimidone, Dimethiromimidone, Dimethiromimidone, Dimethiromimodole Edifenfos, Ethirimol, Etridiazol, Fenarimol, Fenfuram, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetate, Fentinhydroxide, Ferimzone (TF 164), Fluazinam, Fluobenzimine, Fluorimide, Fluquinconazole, Flusilazole, Flutolafolanil, Flutriafolanil, Flutriafanil Fosetylaluminium, Fuberidazole, Fulsufamid (MT-F 651), Furalaxyl, Furconazol, Furmecyclox, Guazatine, Hexaconazole, ICI A 5504, Imazalil, Imiben-Conazol, Iprobefos, Iprodione, Isoprothiolane, KNF 317, copper compounds such as Cu-oxy , Cu-oxide, Mancozeb, Maneb, Mepanipyrim (KIF 3535), Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, MON 24000, Myclobutanil, Nabam, Nitrothalidopropyl, Nuarimol, Ofurace, Oxadixyl, Oxycarboxin, Pox9azolonolole, Powderconazol , Propineb, Prochloraz, Procymidon, Propamocarb, Propiconazol, Prothiocarb, Pyracarbolid, Pyrifenox, Pyrimethanil, Pyroquilon, Rabenzazole, RH 7592, Fenbuconazol, Sulfur, Tebuconazole, TF 167, Thiabendazole, Thicyofen, Thiofamidadylclim , Triadimenol, tricyclazole, tridemorph, triflumizole, triforine, validamycin, vinchlozolin, XRD 563, zineb, sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium C13 / C15 alcohol ether sulfonate, sodium cetos tearylphosphate ester, dioctyl sodium sulfosuccinate, sodium isopropyl naphthalene sulfonate, sodium methylene bisnaphthalene sulfonate, cetyl trimethyl ammonium chloride, salts of long-chain primary, secondary or tertiary amines, alkyl propylene amines, lauryl pyrimidinium bromide, dimethyl aminomethylchloride, ethoxilyl aminomethylchloride, ethoxilaminoethyl aminomethylchloride, ethoxilaminoethyl aminomethylchloride 1-hydroxyethyl-2-alkyl imidazoline.

The above-mentioned combination partners are known active ingredients, which are largely in CH.R Worthing, U.S.B. Walker, The Pesticide Manual, 7th edition (1983), British Crop Protection Council.

In addition, the active ingredient according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active ingredients, such as insecticides, attractants, sterilants, acaricides, nematicides or herbicides. The insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, formamidines, tin compounds, substances produced by microorganisms, etc. Preferred mixing partners are: 1. From the group of phosphorus compounds

Acephate, Azamethiphos, Azinphos-ethyl, Azinphosmethyl, Bromophos, Bromophos-ethyl, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyπfos-methyl, Demeton, Demeton-S-methyl, Demeton-S-methylsulfphone, Dialifos, Diazinon, Dichlorophos, 0, Dicrotophos 0-1,2,2,2- tetrachloroethylphosphorthioate (SD) 208 304), Dimethoate, Disutfoton, EPN, Ethion, Ethoprophos, Etrimfos, Famphur, Fenamiphos, Fenitriothion, Fensulfothion, Fenthion, Fonofos, Formothion, Heptenophos, Isozophos, Isothio Isoxathion, Malathion, Methacrifos, Methamidophos, Methidation, Salithion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosfolan, Phosmet, Phosphamidon, Phoxim, Pirimiphos methyl, Profenofos, Propaphos, Proetamphos, Prothiofos, Pyraclofos, Pyridapenthion, Quinalphos, Sulprofos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Trichlorphon, Vamidothion.

2. From the group of carbamates

Aldicaarb, 2-sec-butylphenylmethylcarbamate (BPMC), carbaryl, carbofuran, carbosulfan, cloethocarb, benfuracarb, ethiofencarb, furathiocarb, isoprocarb, methomyl, 5-methyl-m-cu-menylbutyryl (methyl) carbamate, oxamyl, pirimicarburic , Thiodicarb, thiofanox, ethyl 4,6,9-triaza-4-benzyl-6,10-dimethyl8-oxa-7-oxo-5,11-dithia-9-dodecenoate (OK 135), 1-methylthio (ethylideneamino) -N-methyl-N- (morpholinothio) carbamate (UC 51717).

3. From the group of carboxylic acid esters

Allethrin, alphametrin, 5-benzyl-3-furylmethyl- (E) - (1 R) -cis2,2-dimethyl-3- (2-oxothiolan-3-ylidenemethyl) cyclopropane-carboxylate, bioallethrin, bioallethrin ((p ) -cyclopentyl isomer), bioresmethrin, biphenates, (RS) -l-cyano- 1- (6-phenoxy-2-pyridyl) -methyl- (1R) -trans-3- (4-tert.butylphenyl) -2.2 -dimethylcyclopropanecarboxylate (NCI 85193), cycloprothrin, cyhalothrin, cypermethrin, cyphenothrin, deltamethrin, empenthrin, Esfenvalerate, Fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumenthrin, fluvalinate (D-isomer), permethrin, pheothrin ((R) -isomer), d-pralethrin, pyrethrins (natural products), resmethrin, tefluthrin, tetramethrin, tralomethrin.

4. From the group of the amides Amitraz, chlorodime form

5. From the group of tin compounds cyhexatin, fenbutatin oxide

6. Other

Abamectin, Bacillus thuringiensis, Bensultap, Binapacryl, Bromopropylate, Buprofezin ,, Camphechlor, Cartap, Chlorobenzilate, Chlorfluazuron, 2- (4- (Chlorphenyl) -4,5-diphenylthiophene (UBI-T 930), Chlorfentezine, Cyclopropanecarboxylic acid- (2- naphthylmethyl) ester (Ro12-0470), cyromazine, N- (3,5-dichloro-4- (1,1,2,3,3,3-hexafluoro-1-propyloxy) phenyl) carbamoyl) -2-chloro ethyl benzcarboximidate, DDT, dicofol, N- (N- (3,5-dichloro-4- (1, 1,2,2-tetrafluoroethoxy) phenylamino) carbonyl) -2,6-difluorobenzamide (XRD 473), diflubenzuron, N- (2,3-dihydro-3-methyl-1,3-thiazol-2-ylidenes) -2,4-xylidines, dinobutone, dinocap, endosulfan, ethofenprox, (4-ethoyphenyl) (dimethyl) (3- (3- phenoxyphenyl) propyl) silane, (4-ethoxyphenyl) (3- (4-fluoro-3-phenoxyphenyl) propyl) dimethylsilane, fenoxycarb, 2-fluoro-5- (4- (4-ethoxyphenyl-4-methyl-1-pentyl) ) diphenyl ether (MTI 800), granular and nuclear polyhedron viruses, fenthiocarb, flubenzimine, flucycloxuron, flufenoxuron, gamma-HCH, hexythiazox, hydramechyinone (AC 217300), ivermectin, 2-nitromethyl-4,5-dihydro-6H-thiazine (SD 52618), 2-nitromethyl-3,4-dihydrothiazole (SD 35651), 2-nitromethylene-1,2-thiazinan-3-ylcarbamaldehydes (WL 108477), Propargite, teflubenzuron, tetradifon, tetrasul, thiocyclam, triflumuron.

The active substance content of those prepared from the commercially available formulations Forms of use can vary within wide ranges, the active substance concentration of the forms of use can be from 0.0001 to 95% by weight of active substance, preferably between 0.001 and 1% by weight. The application takes place in a customary manner adapted to the application forms.

The following examples serve to explain the invention, without this being restricted thereto.

A. Examples of formulation

a) A dusting agent is obtained by mixing 10 parts by weight of active ingredient and 90 parts by weight of talc as an inert substance and comminuting them in a hammer mill.

b) A wettable powder which is readily dispersible in water is obtained by adding 25 parts by weight of active compound, 65 parts by weight of kaolin-containing quartz as inert substance, 10 parts by weight of lignosulfonic acid potassium and 1 part by weight of oleoylmethyl tauric acid sodium as the wetting agent. and dispersant mixes and grinds in a pin mill.

c) A dispersion concentrate which is readily dispersible in water is prepared by mixing 40 parts by weight of active compound with 7 parts by weight of a sulfosuccinic acid half-ester, 2 parts by weight of a lignosulfonic acid sodium salt and 51 parts by weight of water and in a attritor ground to a fineness of less than 5 microns.

d) An emulsifiable concentrate can be prepared from 15 parts by weight of active ingredient, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonylphenol (10 AeO) as emulsifier.

e) Granules can be produced from 2 to 15 parts by weight of active ingredient and an inert granule carrier material such as attapulgite, pumice granules and / or quartz sand. A suspension of the is expediently used Wettable powder from Example b) with a solids content of 30% and sprayed this onto the surface of an attapulgite granulate, dried and mixed intimately. The proportion by weight of the wettable powder is approximately 5% and that of the inert carrier material approximately 95% of the finished granulate.

B. Chemical examples

example 1

2- (4-chlorophenylhydrazono) acetoacetic acid- (2,2,6,6-tetramethyl-piperidin-4-yl) amide-

Hydrochloride

0.02 mol of 4-chloroaniline (2.55 g) are dissolved in a mixture of 20 ml of water and 9 ml of concentrated hydrochloric acid and at 0 ° C with a solution of 0.02 mol of sodium nitrite (1.38 g) in 10 ml Water diazotized.

After stirring for 10 minutes at 0 ° C., this diazonium salt solution becomes a vigorously stirred mixture of 0.02 mol of acetoacetic acid (2,2,6,6-tetramethylpiperidin-4-yl) amide (4.8 g) in 30 ml Water, 10 ml of methanol and 8 g of sodium acetate were added dropwise at 0 ° C. to + 3 ° C. After stirring for 2 hours at room temperature, the product is filtered off with suction, the residue is washed with water and boiled in acetone. 6.5 g of cream-colored crystals which melt above 260 ° C. are obtained.

NMR data (CDCI ₃ , £ values, TMS as internal standard) 4-chlorophenyl: m; 7.15-4H

CH ₃ -CO: s; 2.5-3H

remaining piperidine hydrogens: m; 1.38-2.15

Example 2 2- (4-Chlorophenylhydrazono) acetoacetic acid- (2,2,6,6-tetramethyl-piperidin-4-yl) amide

0.01 mol of amide from Example No. 1 (4.15 g) was suspended in a mixture of 30 ml of water and 15 ml of methanol and 5N NaOH was added dropwise to pH 10.

Then it was completely precipitated with excess water. Light orange crystals (3.6 g) of mp: 164-165 are obtained

NMR data

4-chlorophenyl: m; 7.3-4H

remaining piperidine hydrogens: m; 1.0-1.42 and 1, 82-2.06-17H

Example 64

2- (4-chlorophenylhydrazono) acetoacetic acid- (2,2,6,6-tetramethylpiperidine-4 -) - amide oxime hydrochloride

0.03 mol of hydroxylammonium chloride (2.08 g) in 30 ml of methanol was neutralized with 0.03 mol of sodium hydroxide solution (1.2 g) in 15 ml of ice-cold water and this hydroxylamine solution to a solution of 0.03 mol of 2- (4- Chlorphenylhydrazono) - acetoacetic acid (2,2,6,6-tetramethylpiperidin-4-yl) amide hydrochloride (12.5 g, from Example 1) added dropwise in 150 ml of DMF. After stirring for 5 hours at room temperature, the mixture was cooled to 0 ° C., filtered off with suction from the precipitated crystals and washed with water and ice-cold methanol. 9.3 g of ocher-colored crystals are obtained which melt at 260 ° C.

C ₁₉ H ₂₉ CI ₂ N ₅ 0 ₂ (430.38)

manufactured.

Analogously to Examples 1 and 2, the compounds Example No. 3-63a and 68-102 in Tables 1, 3 and 4 and analogously to Example No. 64, the compounds No. 65-67 in Table 2 were prepared. Salts other than hydrochloride were prepared by adding aquimolar amounts of acid to the free amides (prepared according to Example 2) in methanolic solution.

Table 1

Mp: 68-70 ° C

x HCI mp:> 260 ° C

o l mp: 164-165 ° C

Table 2

Table 3

Table 4

C. Biological examples

Example 1: Plasmopara viticola

Wine seedlings of the "Riesling / Ehrenfelder" varieties were treated to runoff with aqueous suspensions of the claimed compounds about 6 weeks after sowing. After the spray coating had dried on, the plants were inoculated with a zoosporangia suspension of Plasmopara viticola and placed in a climatic chamber at 23.degree. C. and 80-90% relative atmospheric humidity until they were dripping wet.

After an incubation period of 7 days in the greenhouse, the plants were again placed in the climatic chamber overnight in order to stimulate the sporulation of the fungus. The infestation was then assessed. The degree of infestation was expressed in% infected leaf area in comparison to the untreated, 100% infected control plants.

At 500 mg active ingredient / I spray liquor, the following substances show complete suppression of infestation:

Compounds of Examples 1, 2, 3, 4, 5, 6, 11, 64, 65, 66 and 67.

Example 2: Phytophthora infestans

Tomato plants of the "Rheinlands Ruhm" variety were evenly dripping wet in the 3-4 leaf stage with aqueous suspensions of the claimed compounds. After drying, the plants were inoculated with a Zoosporangien¬ suspension of Phytophthora infestans and kept in a climatic chamber for 2 days under optimal infection conditions. The plants were then cultivated further in the greenhouse until the symptoms developed. The infection was assessed approximately 1 week after inoculation. The degree of infestation of the plants was expressed in% infected leaf area in comparison to the untreated, 100% infected control plants.

At 500 mg active ingredient / I spray mixture, the following substances show one Complete infection suppression:

Compounds of Examples 1, 2, 3, 4, 5, 6, 7, 12, 13, 15, 20, 21, 23, 64, 65, 66 and

67.

Example 3: Botrytis cinerea

Approximately 14 day old broad beans of the Ηerz-Freya or "Frank's Ackeφerle" varieties were treated to runoff with aqueous suspensions of the claimed compounds. After the spray coating had dried on, the plants were inoculated with a spore suspension (1.5 million spores / ml) of Botrytis cinerea. The plants were cultivated further in a climatic chamber at 20-22 ° C. and about 99% relative atmospheric humidity The infection of the plants manifests itself in the formation of black spots on leaves and stems The evaluation of the tests took place about 1 week after inoculation The degree of infestation of the plants was rated as a percentage of untreated, 100% infected control plants.

At 500 mg active ingredient / I spray mixture, the following compounds show complete suppression of infestation:

Compounds of Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 23, 24, 25, 64, 65 , 66 and 67.

Claims

PATENT CLAIMS:

1. Compound of the general formula I

in which

R ^{1 is} hydrogen, (C ¹ -C ₄ -alkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl, alkyl, alkenyl and alkynyl optionally carrying up to 3 identical or different substituents from the series Halogen, (C, -C ₃ ) alkoxy, (C, -C ₃ ) alkylthio, cyano, (C ₃ -C ₆ ) cycloalkyl, optionally substituted aryl and optionally substituted aryloxy or these three radicals, if any of the above Definition does not include, optionally partially or completely halogen-substituted, an optionally substituted 5- or 6-membered heterocycle residue with up to 3 identical or different heteroatoms from the series oxygen, sulfur and nitrogen, optionally substituted (C ₃ -C ₈ ) - Means cycloalkyl or optionally substituted phenyl or naphthyl;

R ^{2 is} hydrogen, (C ^ C ^ alkyl, (CC ₃ ) alkanoyl or (CC ₃ ) alkoxycarbonyl;

R ^{3 represents} (C _r C ₄ ) alkyl;

R ^{4 represents} hydrogen, cyanoethyl, benzyl, OH, O or COOR ³ ;

X for identical or different radicals from the series halogen, cyano, nitro, thiocyanato, (CC ₆ ) alkyl, (C ₁ -C ₆ ) alkoxy, (CC ₆ ) alkylthio, where alkyl, alkoxy and alkylthio optionally up to three identical or different substituents from the series carry halogen and (C 1 -C 4 -alkoxy or these three radicals, if not included in the above definition, if appropriate are partially or completely halogen-substituted, (C _, - C ₃ ) -alkoxycarbonyl, aryl, aryloxy or aroyl, where these three radicals can each carry up to 5 identical or different substituents from the halogen or trifluoromethyl series, (C ₃ -C ₆ ) -Cycloalkyl or NR ⁵ R ⁶ , or for n ≥ 2 two adjacent radicals X together with the phenyl ring bearing them form a naphthalene or a tetrahydronaphthalene radical and, in the case of n> 2, the other radicals X are as defined above;

Y represents O or NOH;

R ⁵ and R ^{6 are the} same or different and are hydrogen, (C -C ^ alkyl or

(C ₃ -C ₆ ) cycloalkyl, which can be substituted up to 3 times by the same or different (C ^ C ₃ ) alkyl, mean and n is an integer from 0-4, or their salt.

2. A compound of formula I according to claim 1, in which

R is hydrogen, optionally substituted (C ₁ -C ₄ ) alkyl, optionally substituted phenyl, optionally substituted phenylmethyl or optionally substituted (C ₃ -C ₆ ) cycloalkyl;

R ^{2 represents} hydrogen, (C, -C ₄ ) alkanoyl or (C, -C ₃ ) alkoxycarbonyl;

R ^{3 represents} methyl;

R ^{4 represents} hydrogen;

X is identical or different and halogen, nitro, thiocyanato, cyano, (C, - C ₃ ) alkoxycarbonyl, (CC ₃ ) alkyl, (C ₁ -C ₃ ) alkoxy, (C ^ C ^ alkylthio, where Alkyl, alkoxy and alkylthio can be wholly or partly substituted by identical or different halogen atoms, phenyl, phenoxy or benzoyl, where these three radicals can each be substituted by halogen atoms one or more times and / or by trifluoromethyl;

Y is 0 or NOH and n can be 0-3, or their salt.

3. A compound of general formula I according to claim 1 or 2, in which

R ^{1 represents} methyl or cyclopropyl;

R ^{2 represents} hydrogen,

R ³ means methyl,

R ^{4 represents} hydrogen,

X is the same or different and means halogen, cyano, (C ₁ -C ₃ ) alkyl, (C _j -Cg) alkoxy or (C _j -CgJ alkylthio), alkyl, alkoxy and alkylthio being wholly or partly by the same or different halogen atoms can be substituted;

Y is 0 or NOH and n can be 1-3, or their salt.

4. A process for the preparation of compounds of formula I according to any one of claims 1 to 3, characterized in that a) compounds of general formula II

reacted with diazonium salts of the general formula III

wherein the substituents have the meanings given in claim 1, or b) compounds of the general formula IV

wherein R ¹ and X _{n have} the meanings given above and R ^{5 can be} methyl or ethyl, reacted with compounds of the general formula V.

wherein R ² , R ³ and R ^{4 have} the meanings given above, and the compounds of the formula I thus obtained are optionally converted into their salts.

5. Agent containing at least one compound according to one of claims 1 to 3 and at least one formulation agent.

6. Fungicidal compositions according to claim 5, containing a fungicidally effective amount of at least one compound according to one of claims 1 to 3 together with the additives or auxiliaries customary for their use.

7. Plant protection products containing a fungicidally effective amount of at least one compound according to one of claims 1 to 3 and at least one further active ingredient, preferably from the series of fungicides, insecticides, attractants, sterilants, acaricides, nematicides and herbicides together with those customary for this application Auxiliaries and additives.

8. Agents for use in wood preservation or as preservatives in paints, in cooling lubricants for metalworking or in drilling and cutting oils, containing an effective amount of at least one compound according to one of claims 1 to 3 together with the auxiliaries and additives customary for these applications .

9. A process for the preparation of an agent according to any one of claims 5 to 8, characterized in that the active ingredient and the other additives are added together and brought into a suitable form of use.

10. Use of a compound according to one of claims 1 to 3 or an agent according to one of claims 5 to 8 as a fungicide.

11. Use of a compound of formula I according to any one of claims 1 to 3 or an agent according to one of claims 5, 6 and 8 as a wood protection agent or as a preservative in paints, in cooling lubricants for metalworking or in drilling and cutting oils.

12. A method for combating phytopathogenic fungi, characterized in that a fungicidally effective amount of a compound according to any one of claims 1 to 3 or an agent according to any one of claims 5 is placed on these or the plants, areas or substrates or on infested by them or on seeds applied to 7.

13. Seed treated with a compound according to one of claims 1 to 3 or an agent according to one of claims 5 to 7.