DD235174A5 - SCHAEDLINGSBEKAEMPFUNGSMITTEL - Google Patents

Abstract

The invention relates to pesticidal compositions containing new substituted pyrazolin-5-ones. The aim of the invention is the provision of new agents with a strong fungicidal and bactericidal action. According to the invention, substituted pyrazolin-5-ones of the general formula (I) in which R 1 is hydrogen or alkyl, R 2 is hydrogen, alkyl, alkenyl, alkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, hydroxycarbonylalkyl, alkoxycarbonylalkyl are used as the active ingredient in the novel agents or is in each case optionally substituted aralkyl or aryl and R 3 is alkyl, alkenyl, alkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, hydroxycarbonylalkyl, alkoxycarbonylalkyl, cycloalkyl, cycloalkylalkyl or in each case optionally substituted aralkyl, aryloxyalkyl or arylthioalkyl, but where R 3 is only Methyl or ethyl is when R1 and / or R2 are not simultaneously hydrogen or methyl. Formula (I)

Description

The invention relates to pesticides containing new substituted pyrazolin-5-ones _f and their use as pesticides in agriculture.

Characteristic of the known technical solutions

It is already known that organic nitrogen compounds, such as, for example, zinc ethylene-1,2-bis (dithiocarbamate), have fungicidal properties (cf., for example, R. VVegler "Chemie der Pflanzenschutz- und Schädlingsbekungsmittel", Springer Verlag Berlin , Heidelberg, New York 1970, Volume 2, p. 65 f).

However, the effect of these compounds is not always completely satisfactory in all applications, especially at low application rates and concentrations.

Object of the invention

The aim of the invention is the provision of new pesticides with more fungicidal and bactericidal action.

Explanation of the essence of the invention

The invention has for its object to find »new compounds with strong fungicidal and bactericidal action, which are useful as active ingredients in pesticides.

According to the invention as the active ingredient in the new pesticides new substituted pyrazolin-5-ones of the general formula (I)

applied

in which

R is hydrogen or alkyl,

R is hydrogen, alkyl, alkenyl, alkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, hydroxycarbonylalkyl, alkoxycarbonylalkyl, aminocarbonylalkyl, alkylaminocarbonylalkyl, dialkylamxnocarbonylalkyl or each optionally substituted oxiranylalkyl, aralkyl or aryl and

R is alkyl, alkenyl, alkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, hydroxycarbonylalkyl, alkoxycarbonylalkyl, cycloalkyl, cycloalkylalkyl or in each case optionally substituted aralkyl, aryloxyalkyl or arylthioalkyl,

however, R is methyl or ethyl only when

1 2

R and / or R are not simultaneously hydrogen or methyl,

found.

The compounds of the formula (I) can be present as geometric isomers or mixtures of isomers of different composition. Both the pure isomers and the isomer mixtures are claimed according to the invention.

Furthermore, it has been found that the novel substituted pyrazolin-5-ones of the general formula (I)

(D

R ²

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in which R is hydrogen or alkyl,

R is hydrogen, alkyl, alkenyl, alkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, hydroxycarbonylalkyl, alkoxycarbony1alkyl, aminocarbonylalkyl, alkylaminocarbonylalkyl, dialkylaminocarbonylalkyl or each optionally substituted oxiranylalkyl, aralkyl or aryl and

R is alkyl, alkenyl, alkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, hydroxycarbonylalkyl, alkoxycarbonylalkyl, cycloalkyl, cycloalkylalkyl or in each case optionally substituted aralkyl, aryloxyalkyl or arylthioalkyl,

however, R is methyl or ethyl only when

1 2

R and / or R are not simultaneously hydrogen or methyl,

if you get

(a) 4-oximino-pyrazolin-5-ones of the formula (II)

R ¹ NOA

in which

1 2

R and R have the abovementioned meaning and

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A is hydrogen or an alkali metal cation,

with alkylating agents of the formula (III)

R ³ -X (III)

in which R has the meaning given above and

X is an electron attracting leaving group,

if appropriate in the presence of a diluent, if appropriate in the presence of an acid binder and if appropriate in the presence of a catalyst, or if

(b) the 4-alkoximinopyrazolin-5-ones of the formula (Ia) obtainable by process (a)

NOR ³

(La)

in which

1 3 R and R have the abovementioned meaning,

with alkylating agents of the formula (IV)

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R ² '-Y (IV)

in which

2 '

R is alkyl, alkenyl, alkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, hydroxycarbonylalkyl, alkoxycarbonylalkyl or each optionally substituted aralkyl or aryl and

Y is an electron attracting leaving group,

if appropriate in the presence of a diluent, if appropriate in the presence of an acid binder and if appropriate in the presence of a catalyst.

Finally, it has been found that the novel substituted pyrazolin-5-ones of the formula (I) have fungicidal and bactericidal properties.

Surprisingly, the novel substituted pyrazolin-5-ones of the formula (I) show better fungicidal properties than the zinc ethylene-1,2-bis-dithiocarbamate known from the prior art, which is effectively an obvious compound.

The pyrazolin-5-ones according to the invention are generally defined by the formula (I). Preference is given to compounds of the formula (I) in which

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R is hydrogen or straight-chain or branched alkyl having 1 to 8 carbon atoms,

R is hydrogen, in each case straight-chain or branched alkyl, alkenyl, alkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, hydroxycarbonylalkyl, alkoxycarbonylalkyl, aminocarbonylalkyl, alkylaminocarbonylalkyl or dialkylaminocarbonylalkyl having in each case up to 8 carbon atoms in the individual alkyl or alkenyl or alkynyl moieties for oxiranylalkyl with 1 to 4 carbon atoms in the straight-chain or branched alkyl part for straight-chain or branched, optionally mono- or polysubstituted, identically or differently substituted aralkyl having 1 to 4 carbon atoms in the alkyl part and 6 to 10 carbon atoms in the aryl part or optionally monosubstituted or polysubstituted by identical or different substituents Aryl having 6 to 10 carbon atoms, wherein as substituents in question are each: halogen, cyano, nitro, hydroxy, in each case straight-chain or branched alkyl, alkoxy, dioxyalkylene, alkylcarbonyloxy or alkylthio each having up to 4 carbon atoms, straight branched or branched haloalkyl, haloalkoxy or haloalkylthio having in each case up to 4 carbon atoms and up to 9 identical or different halogen atoms or phenyl and

R is straight-chain or branched alkyl having 1 to 20 carbon atoms, in each case straight-chain or branched alkenyl, alkynyl, cyanoalkyl, hydroxyalkenyl

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kyl, alkoxyalkyl, hydroxycarbonylalkyl or alkoxycarbonylalkyl having in each case up to 8 carbon atoms in the individual alkyl or alkenyl or alkynyl moieties, cycloalkyl having 3 to 7 carbon atoms, cycloalkylalkyl having 3 to 6 carbon atoms in the cycloalkyl moiety and 1 or 2 carbon atoms in the alkyl moiety, or in each case optionally mono- or polysubstituted, identically or differently substituted arylalkyl, aryloxyalkyl or arylthioalkyl having in each case 1 to 4 carbon atoms in the individual alkyl moieties and 6 to 10 carbon atoms in the aryl moieties

2, wherein as substituents which are mentioned in R, but where R is methyl only

1 2

or ethyl is when R and R are not simultaneously

represent hydrogen or methyl.

Particular preference is given to compounds of the formula (I) in which

R is hydrogen, methyl, ethyl, η- or i-propyl and n-, i-, s- or t-butyl,

R is hydrogen, methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl, allyl, butenyl, propargyl, cyanomethyl, cyanoethyl, hydroxymethyl, hydroxyethyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, Hydroxycarbonylmethyl, hydroxycarbonylethyl, methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, aminocarbony1-methyl, methylaminocarbonylmethyl, ethylaminocarbonylmethyl, dimethylaminocarbonylmethyl, diethylamino

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carbonylmethyl, aminocarbonylethyl, oxiranylmethyl, oxiranylethyl or in each case optionally mono- to trisubstituted by identical or different substituents phenyl or benzyl, where possible substituents being: fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, methyl, ethyl, η- or i-propyl, η-, i-, s- or t-butyl, methoxy, ethoxy, dioxymethylene, dioxyethylene, methylthio, ethylthio, acetoxy or propionyloxy, chloromethyl, dichloromethyl, trichloromethyl, trifluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, trifluoromethoxy, trifluoromethylthio or Phenyl and

R is methyl, ethyl, n- or i-propyl, n- or i-butyl, n- or i-pentyl, n- or i-hexyl, n- or i-heptyl, n- or i-octyl, n- or i-nonyl, n- or i-decyl, n- or i-dodecyl, n- or i-hexadecyl, allyl, butenyl, propargyl, cyanomethyl, cyanoethyl, hydroxymethyl, hydroxyethyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, hydroxycarbonylmethyl, Hydroxycarbonylethyl, methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexylmethyl or an optionally mono- to trisubstituted by identical or different substituent of the formula Ar- (Z) _n , - (CH,) -, Ar- ( Z) -CH- or

IH£ * LL ill ·

CH ₃

Ar- (Z) -CH-, where m,

CN

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Each Ar is phenyl or naphthyl,

Z is in each case oxygen or sulfur,

m stands for 0 or 1 respectively and

η is 1, 2 or 3,

and being suitable as substituents mentioned in R, with the proviso that R only then

1 2 is methyl or ethyl, if R and R are not simultaneously hydrogen or methyl.

Specifically, the following compounds of the general formula (I) may be mentioned:

CH.

CH.

-C ₂ H ₅

-C ₂ H ₅

-C ₂ H ₅

CH.

CH.

CH.

CH.

-CH

Cl Cl

NC

CH ₂ -

CN

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CH.

CH,

NC

-C ₃ H ₇ -H -C ₄ H ₉ -H

CH.

CH.

CN Cl-

CH ₂ -

-n

CH.

NC

CH ₂ -

-C ₄ H ₉ -C ₂ H ₅

-C ₃ H ₇ -n

CH.

-CH ₂ -CN

-CH ₂ -CN

CH ₂ -

CN Cl

Cl

-CH ₂ -

-n

-CH ₂ -CN

CH.

CH.

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If, for example, 4-hydroximino-1,3-dimethyl-pyrazolin-5-one and 2,6-dichlorobenzyl chloride are used as starting materials, the course of the reaction of process (a) according to the invention can be represented by the following formula scheme:

Χί

* hA ⁺

CH-

CH ₂ -Cl

CH, (base) ^ 3

-HCl

CH.

If, for example, 4- (2-chlorobenzyloximino) -S-methyl-pyrazoline-S-on and chloroacetonitrile are used as starting materials, the course of the reaction of process (b) according to the invention can be represented by the following formula scheme:

Cl-CH ₂ -CN

(Base)

STILL

-HCl

CH ₂ -CN

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For carrying out the process (a) required as starting materials 4-oximino-pyrazolin-5-ones are generally defined by the formula (II).

1 2

In this formula (II), R and R preferably represent those radicals which have already been mentioned as preferred for these substituents in the description of the substances of the formula (I) according to the invention. A is preferably hydrogen or a sodium or potassium cation.

The 4-oximino-pyrazolin-5-ones of the formula (II) are partially known / cf. eg Ber. Dtsch., former Ges. 29 , 249 (1896); Coll. Czech. Chem. Commun. _2_5, 55 (1960); Arch. Pharm. 309 , 900 (1976); Liebigs Ann Chem. 1976 , 13807. They are obtained, for example, when β-ketoesters of the formula (V)

₉ (V)

in which R has the meaning given above and

4 R is lower alkyl, in particular methyl or

Ethyl, stands,

or ethoxymethylenemalon esters of the formula (V a)

/ ^CO 2 ^C 2 ^H 5 C ^

first in a 1st stage with hydrazines of the formula (VI)

R ² -NH-NH ₂ (VI)

in which Le A 23 089-foreign countries

R has the meaning given above,

optionally in the presence of a diluent such as ethanol, cyclized at temperatures between 0 ⁰ C and 100 ⁰ C, the resulting from the malonate of the formula (V a) resulting 4-ethoxycarbonylpyrazolin-5-ones of the formula (VII a),

CO CH ^(VIIa)

CO ₂ C ₂ H ₅

R ²

in which

R has the meaning given above,

in an intermediate step, saponified and decarboxylated by conventional methods, for example with aqueous hydrochloric acid at temperatures between 50 ⁰ C and 120 ⁰ C, and the thus obtainable pyrazolin-5-ones of the formula (VII)

(VII)

in which

1 2

R and R have the abovementioned meaning,

with a nitrosating agent, such as isopentyl nitrite or sodium nitrite, optionally in

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genwart a diluent, such as ethanol, water or aqueous hydrochloric acid, and optionally in the presence of a base such as sodium ethylate, at temperatures between -2O ⁰ C and + 50 ⁰ C reacted.

The alkylating agents which are furthermore required as starting materials for carrying out the process (a) according to the invention are generally defined by the formula (III). In this formula (III), R preferably represents those radicals which have already been mentioned as preferred for these substituents in the description of the substances of the formula (I) according to the invention. X is preferably halogen, in particular chlorine, bromine or iodine, or optionally substituted alkylsulfonyloxy, alkoxysulfonyloxy or arylsulfonyloxy, for example methanesulfonyloxy, methoxysulfonyloxy, trifluoromethanesulfonyloxy or p-toluenesulfonyloxy.

The alkylating agents of the formula (III) are generally known compounds of organic chemistry.

The β-keto esters of the formula (V) or of the ethoxymethylenemalon esters of the formula (V a) are likewise generally known.

The 4-Alkoximinopyrazolin-5-ones required as starting materials for carrying out the process (b) according to the invention are generally defined by the formula (Ia). In this formula (Ia), R and R preferably represent those radicals which have already been mentioned as preferred for these substituents in the description of the substances of the formula (I) according to the invention.

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The 4-alkoximinopyrazolin-5-ones of the formula (Ia) are compounds according to the invention and can be obtained by means of process (a) according to the invention.

The alkylating agents which are furthermore required as starting materials for carrying out the process (b) according to the invention are generally defined by the formula (IV). In

2 'of this formula (IV) R preferably represents those radicals which have already been described in the description of the substances of the formula (I) according to the invention as being preferred for the sub-

R substituents were called, with the exception of the hydrogen radical. Y preferably represents those leaving groups which have already been mentioned as preferred for the substituent X in the description of the alkylating agents of the formula (III).

The alkylating agents of the formula (IV) are likewise generally known compounds of organic chemistry.

Suitable diluents for carrying out processes (a) and (b) according to the invention are inert organic solvents or aqueous systems.

These include in particular aliphatic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones, such as acetone or butanone; Nitriles, such as acetonitrile or propionitrile; Amides, such as dimethyl

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formamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters, such as ethyl acetate; Sulfoxides, such as dimethyl sulfoxide, or water or aqueous-organic two-phase mixtures, such as dichloromethane-water or toluene-water.

The processes (a) and (b) according to the invention are optionally carried out in the presence of an acid binder.

As such, all customary inorganic or organic bases are suitable. These include, for example, alkali metal hydroxides, amides, alcoholates or hydrides, such as sodium hydroxide or potassium hydroxide, sodium methoxide or potassium t-butylate, sodium hydride or sodium amide, alkali metal carbonates, such as sodium carbonate, potassium carbonate or sodium bicarbonate, and tertiary amines, such as triethylamine, N, N Dimethylaniline, pyridine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can be varied within a substantial range when carrying out the processes (a) and (b) according to the invention. In general, one works at temperatures between -2O ⁰ C and +200 ⁰ C, preferably at temperatures between 0 ⁰ C and +150 ⁰ C.

When carrying out the processes (a) and (b) according to the invention, in general 1.0 to 3.0 mol, preferably 1, are employed per mole of 4-oximino-pyrazolin-5-one of the formulas (II) or (Ia) , 0 to 1.5 mol, of alkylating agent

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of formulas (III) and (IV) and optionally 1.0 to 3.0 mol, preferably 1.0 to 1.5 mol, of acid binder.

If the reaction is carried out in an organo-aqueous two-phase system, it is optionally possible to work in the presence of from 0.1 to 1 mol of a suitable phase transfer catalyst, for example a quaternary ammonium or phosphonium compound. Examples which may be mentioned are triethylbenzylammonium chloride and benzyldodecyl-dimethylammonium chloride.

The work-up and isolation of the reaction products of the formula (I) is carried out by customary methods.

The active compounds according to the invention have a strong microbicidal action and can be used practically for controlling unwanted microorganisms. The active substances are suitable for use as pesticides.

Crop protection fungicides are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Bactericidal agents are used in crop protection for controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

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By way of example but not limitation, some pathogens of fungal and bacterial diseases, which fall under the above-enumerated generic terms, are named:

Botrytis species, such as Botrytis cinerea; Plasmopara species, such as Plasmopara viticola; Uromyces species, such as Uranyces appendiculatus; Sphaerotheca species, such as Sphaerotheca fuliginea; Venturia species, such as Venturia inaequalis;

Podosphaera species, such as Podosphaera leucotricha; Phytophthora species, such as Phytophthora infestans; Erysiphe species, such as Erysiphe graminis;

Puccinia species, such as Puccinia recondita;

Fusarium species such as Fusarium culmorum; Ustilago species such as Utilago nuda or üstilago avenae;

Septoria species such as Septoria nodorum; Tilletia species, such as Tilletia caries; Xanthcmonas species, such as Xanthomonas oryzae; Pseudomonas species, such as Pseudcmonas lachrymans; Pyricularia species, such as Pyricularia oryzae; Pellicularia species such as Pellicularia sasakii and Pyrenophora species such as Pyrenophora teres. (Conidia form: Drechslera, Syn: Helminthosporium); Leptosphaeria species, such as Leptosphaeria nodorum; Cochliobolus species, such as Cochliobolus sativus (conidia form: Drechslera, Syn: Helminthosporium) and Cercospora species, such as Cercospora canescens.

The good plant tolerance of the active ingredients in the necessary concentrations for controlling plant diseases allows treatment of aboveground plant parts, of plant and seed, and the soil.

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In this case, the active compounds according to the invention can be used to combat cereal diseases, such as Cochliobolus sativus, Leptosphaeria nodorum, Fusarium species or Pyrenophora teres, against pathogens, against mildew pathogens, for combating vegetable diseases, such as, for example, against the pathogen of the tomato brown rot ( Phytophthora infestans) or against the pathogen of the bean gray mold (Botrytiscinerea) or for controlling rice diseases, such as against the causative agent of rice blast disease (Pyricularia oryzae). The active compounds according to the invention also show systemic properties in addition to protective activity.

The active compounds according to the invention, in addition to outstanding protective effectiveness, also show very good systemic properties. They are characterized by broad in vitro fungicidal activity and by additional bactericidal properties.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates, seed powders, active substance-impregnated natural and synthetic substances, very fine encapsulations in polymers Substances and in encapsulants for seed, and also in formulations with fuel packs, such as smoked cartridges, doses, spirals and others as well as ULV KaIt and warm mist formulations.

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These formulations are prepared in a known manner, e.g. by mixing the active compounds with extenders, that is to say liquid solvents, liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender, e.g. also organic solvents can be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water. By liquefied gaseous diluents or carriers are meant those liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: e.g. ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates. Suitable solid carriers for granules are: e.g. broken and fractional

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natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours, as well as granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. Suitable emulsifying and / or foam-forming agents are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates. Suitable dispersants are: e.g. Lignin sulphite waste liquors and methylene chloride.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

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

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

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

In the treatment of parts of plants, the drug concentrations can be varied in the use forms in a wider range. They are generally between 1 and 0.0001 wt .-%, preferably between 0.5 and 0.001%.

In the seed treatment, in general, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, needed.

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

Off fQhrungsbeispiel

The invention will be explained in more detail below with reference to some examples.

Preparation Examples

example 1 • • C] a) H-. .NO-CH _n CH ₃ (Method

To 10 g (0.071 mol) of 1,3-dimethyl-4-hydroxy-pyrazolin-5-one and 7.2 g (0.071 mol) of triethylamine in 50 ml of absolute dimethylformamide is added dropwise while stirring at room temperature 13.9 g (0.071 Mol) 2,6-DichlorbenzylChlorid in 3 0 ml of absolute dimethylformamide and stirred for a further 24 hours at room temperature.

For workup, the mixture is poured into 3 00 ml of water and extracted four times with 70 ml of chloroform. The combined organic phases are washed five times with 200 ml of water, dried over magnesium sulfate and concentrated in vacuo. The crystalline residue is triturated with a little ether and filtered with suction. This gives 9 g (42% of theory) of l, 3-dimethyl-4- (2,6-dichlorobenzyloximino) -pyrazolin-5-one of melting point 132 ° C,

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CH-Ji-OH

CH ₃

To 175 g (1.56 mol) of 1,3-dimethyl-pyrazolin-5-one and 84.4 g (1.56 mol) of sodium in 1 1 absolute ethanol is added dropwise with stirring and ice cooling 183 g (1.56 Mol) isopentyl nitrite, so that the internal temperature does not exceed 25 ° C to 30 ⁰ C. After completion of the addition, the mixture is stirred for a further 24 hours at room temperature and sucks the precipitated sodium salt of l, 3-dimethyl-4-hydroximino-pyrazolin-5-one from. The crystalline product is dissolved in 1 liter of water and acidified with glacial acetic acid. For complete precipitation is cooled to O ⁰ C for several hours and then sucks the product. This gives 162 g (74% of theory) of 1,3-dimethyl-4-hydroximino-pyrazolin-5-one of melting point 93 ⁰ C,

Example 2:

CH ₂ -CN

To 1.6 g (0.053 mol) of sodium hydride (80% suspension in mineral oil) in 30 ml of absolute dimethylformamide

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10 g (0.04 mol) of 4- (2-chlorobenzyloximino) -3-methylpyrazolin-5-one are added dropwise at 0 ^° C. with stirring and simultaneous passing of a stream of dry nitrogen into 50 ml of absolute dimethylformamide and the mixture is stirred for a further hour after the end of the addition at ^{0 0} C. Thereafter added dropwise at 0 ⁰ C 3.6 g (0.048 mol) of chloroacetonitrile, stirred for a further 3 hours at 0 ⁰ C and then overnight at room temperature.

For working up, excess sodium hydride is destroyed by careful addition of water and then extracted four times with 80 ml of chloroform each time. The combined organic phases are washed five times with 200 ml of water, dried over magnesium sulfate and concentrated in vacuo.

The residual oil is purified by column chromatography (silica gel / dichloromethane-ether 1: 1) and the oil thus obtained is crystallized by trituration with ether and filtered with suction. This gives 3.7 g (32% of theory) of 4- (2-Chlorbenzyloximino) -l-cyanomethyl-S-methyl-pyrazolin-S-one of melting point 118-125 ⁰ C.

The following compounds of the general formula (I) are obtained in a corresponding manner and according to the general preparation data:

(I)

k ²

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C ε * ftf ε * I cb Z ou N You I You rh ro ro C O) O) e "Β * -P ro O Q IQ Π W > 1

CU to

S3

VO o ro ppm Ό "O ppm * ppm ppm ppm fa σι Τ * fa fa ro J " ro in T- in VO CtJ 1 OS Z «CtS i «I U I fa I as t I I

S U

S3 U

(N

X U

Il

as u

CS

as u

as u

as ro as U as LO] ro as ro ro U U as a: U Il as I U as as as Il as CM U U ro CM U U U V as CS fO as CM U as as co O ro as ro ro U as I as U as as I υ U ro ro U U as as U U ro as ro U as U

ro

in

vo

CM

ro

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> d cn

Expl R ¹ Phys. dates

/ F = melting point in ^o c7

14 15

16 17 18 19 20 21 22 23

CH.

CH.

CH.

CH.

CH.

CH.

CH.

CH.

CH.

CH.

CH.

-CH ₂ -OC ₂ H ₅

CH.

CH.

CH.

CH.

CH.

CH.

CH.

CH

CN

Cl

CH ₂ -

CH ₂ -

CH ₂ -

Cl

CH.

NO,

CH ₂ -C = CH

F

¹ H-NMR * 5.0 and 5.6 ppm

F 98

¹ H-NMR * ⁾ 5.5 ppm F 98

¹ H-NMR * '5.4 ppm F

¹ H NMR ** 4.7 ppm F 110 F 95

ο υ co

(0 Il Alfa

ck

VO

in

TJ in

ps

S3

e e α Cu α

in

(N

FAPI

ε ζ

S3

VO

co

in

S3

U * r-

cn CM S3 CM in CM S3 cn U S3 S3 33 U S3 U CM U s CM U S3 B X U O U CM , S3 CM U S3 V S3 I CJ U CM I I S3 U I

CM

X U

CM

X O

CM

co co η cn X S X S U υ U U U

S3 U

η X U

cn

S U

X U

cn cn co cn cn S S as X 93 U U U U U

CM

in VO Γ " CO CM O cn CM CM CM CM CM s cn

Le A 23 089-foreign countries

ο οο οο

Expl R Phys. dates

/ F = melting point in ^o c7

33 34 35 36 37 38

39 40

41 42

CH.

CH.

CH.

CH-

CH.

CH.

CH.

CH.

CH.

CH (CH ₃ J ₂

egg

-CH

0th

2 HO

¹ H-NMR ⁺ * 4.5 ppm F 146-151

¹ H-NMR ** 4.5 ppm

¹ H-NMR ** 4.5 ppm F 92

F 77-80

F 100 F 137

F 65 - 68 F 77

r.

C O 3 σ " α C ν O) + J (O α ϋ CO to H > 1

CO

fa

04

ID

as

in * S (N VD * ε O in 2; 00 I 00 S3 ¹ OO

ro ro ro ro ro ro ro ro S3 as as as as as as as U U U rj U U U

 » ro as U ro as U Chg Chg Chg Chg ro U Chg .-No. Ex. ro in VO r- OO O in

Le A 23 089 -Outland

- 62 -

ρ ε

to JZ

α υ co

η ηri

(H

01

a co tn

VO

: Ο

I CN I ΪΝ s a U U U ι I U U 2

η s in VO s CN s s CN CN CN

(N

K O

O U

in

CN

r en

CN

Le A 23 089-foreign countries

- 61 -

ο α) Ρ E <β λ α υ

ta ιι 5η XI

CU

CQ

ο o

CO

in <η ro ο ιη γ T η ιη

αο

O PO CM m CM ro (N "Ν

Le A 23 089-foreign countries

tr * (D

Expl R R

R * Phys. dates

/ F g melting point in ^o c7

223 H

HO-CH ₂ -CH ₂

Cl

CH, Cl F 90

224 H

225 H

HO-CH ₂ -CH ₂ -

CN

NC-CH ₂ -CH ₂ -

Cl ^{01 1} H-NMR **

ppm

Oil ¹ H-NMR ** 5.4 ppm

226 H

NC-CH ₂ -CH ₂ -

Cl Cl

-CH, Cl

118-119

227 H

NC-CH ₂ -CH ₂ - Cl- ^ QVo-CH ₂ -

VlV

W H (U

Expl R

217 H

218 H

219 H

220 h

NC-CH ₂ -CH ₂ - Br

HO-CH ₂ -CH ₂ -

CH.

Cl

Phys. dates

/ F = melting point in ^o c7

F 112-1,14

Oil ¹ H-NMR ** 5.4 ppm

F 118

Oil ¹ H-NMR ** 5.45 ppm '

221 H

HO-CH ₂ -CH ₂ -

Oil ¹ H-NMR ** 5.45 ppm

222 H

HO-CH ₂ -CH ₂ -

75

- 58 -

3 Q

CH O) φ-PE «β Λ Q υ

Ol Il> ι CI

OS

U Z

to

CQ

O O

OO

I CN

CM

S3

CN

CN

Cu in in

S3

: ο

CM

S3 U

CN

33

CN

8th.

VO

in

: ο

CN

CN

S3

co ο

in o

CN

S3 U

CN

S3 CJ

S3

CN

in

CN

in

CJ

33

f-l

:O

S3 U

CN

33 U

S3

vo

CN

Le A 23 089-foreign countries

> Example no. R

Phys. dates

/ F = melting point in ° c7

207 H

Cl

NC-CH ₂ -CH ₂ -

F 116-119

208 H

NC-CH ₂ -CH ₂ -

-CH ₂ -Cl F 118-120

209 H CH.

-CH "oil ¹ H-NMR ** 5.45 ppm

210 H

NC-CH ₂ -CH ₂ -

Ol ¹ H-NMR ** 5.6 ppm

211 H

NC-CH ₂ -CH ₂ - NC-M) V-CH ₂ -

Oil ¹ H-NMR ** 5.5 ppm

- 56 -

α) α> -ρ ε

CA (Q Il

XII

S5

ο. ηOQ

ιΛ

: ο

Ο <

ΙΛ

Ο "

ιη

ca

: ο

s η s ta ta S O O U

C4 s *! * in V £> O ο O O O (M CM CN CM

Le A 23 089-foreign countries

- 55 -

C • Η

* X

N CH

οι α) +> ε <β χ:

ο υco

W Il

AI

ro

CN

55

Ο · to CQ

ε ο «

OO

σ \ S ι

ro

a υ

cn

CN

CN

U U

co in

CN

O U

co cn Ο cn cn O τ- CN

Le A 23 089-foreign countries

- 54 -

ο Ή

O) Cj) + J E (0 £

ο υ η

01 OQ

CN

as

ro

νο r »

οο

ro o

co S3 O

CN

ro

in

a \

Le A 23 089-foreign countries

- 53 -

3 0 N

CH O) 0) E

ο υ

CQ Il

XI

οο

VO 00

if)

»• ^ k

I-i-l

:O

oooo oo

cn oo

ε ο *

if)

Oi S Z

:O

I CN CN I CM cn cn a a a B B U U O U O I I cn O O O a U O U U I a CN CN 55 ^^ I a m B U cn a cn O S U

ο cn

Le A 23 089-foreign countries

- 52 -

O N

O) α) • υ ε (O C

α co

W Il> ι CI

Oltnta

CM

"ΓΙ

00

If "

ve

00

VO

ir "

VO

cn

a

<Ι

CM U a a υ υ

ro a m m a a ο a B ο υ U O

00

CM 00

00

"J * oo

in co

Le A 23 089-foreign countries

- 51 -

C • Η

-P M

ω α) Ρ E η3 Λ Q υCO

η η

CU

in Γ *

If)

33

if "

cn οο

vo

ιη

Ο.

If)

:O

ON

Γ "

CNJ

ι CN CJ U I CN r-l in 1 CN I pH η va CJ CC Sat. r-i CJ υ CN U CJ CN U U CJ ι S CJ I U U U CN CJ "CN S3 O  Μ U "I I CN ac CJ I CJ ro I CJ va CJ SJ O K cc U ι cn O O CJ I K O O U in co I co U SC ! S 33 CNJ U U O CJ I in T * CNJ co U S3 cn CJ va CJ

O OO

Le A 23 089-foreign countries

- 5o -

C 3

CH CU <ΰ -ρ ε

Q U CQ

cn ii

• Clfa CU

CM

ck

ΙΛ

: ο

CU ιη

: ο

co

co

(N I CM I CM I CM CM • cm Np * CN co X U CN T * S CJ S ►K U CJ I O U I CJ I U U I I SC I I CJ O O O O S Il n / A e K CJ CM χ

(6 co K CJ co X CJ co S CJ co CJ co S3 CJ co CJ -No. • Cb approx cn VO O r » CM co rf P- η ^ " * "" * "" * ~

Le A 23 089-foreign countries

- 49 -

ft in in

oo

αο

it

as

CN

as υ

CN

X U

cn

CQ

VO

'CVJ

U U

as υ

in

VO

ro

CN I CN as as U υ as U U Il CN as U

'CN

as υ

s

as υ

as υ

vo

co

VO

Le A 23 089-foreign countries

CU

4J E

(β £

Q U CQ

(O Il

OO

S!

te υ

(O

in

IN

(N

ro U

σ »in

CN

IN

υ ι

CN

S U

cn

a

σ »σ»

(N

K O

ro

a · o

(N

VO

Cu OK

in

(H

S,

i-l

:O

(N

a ο

(N

a

ro

a

ro

VO

Le A 23 089-foreign countries

Expl R ¹ R Phys. dates

/ F = melting point in ^o c7

153 CH ₃ NC-CH ₂ -

-CH ₂ -

br

116

154 CH ₃ NC-CH ₂ -

Oil ¹ H-NMR ⁺ * 5.5 ppm

br

155 CH ₃ H

F 72

156 CH.

F 94

157 CH.

, 115

- 46 -

O N

fi-H O) <ΰ

 ρ e

Π3 =

D U

W Il

Q * m

en CC U

OO

ε α.

s ι

:O

ίΝ

a υ

U Il U

CN

σ \

S,

S3

:O

CN

CC U

in

in in

cn

in

CN I CN CC CC O O I cc O U B Hey Il U CN CC

cn

CC U

CN

in

Le A 23 089-foreign countries

> ti cn

Expl R ¹ R ² Phys. dates

/ F = melting point in ° c7

143

144

CH., NC-CH "-

NC-CH ₀ -

NC

 Cn ""

Oil ¹ H-NMR ** 5.65 ppm ¹ H-NMR ** 5.5 ppm

145 CH ₃ NC-CH ₂ -

NC-fl> -CH _o -

F 122

146

CH ₃ H ₂ C = CH-CH ₂ -

CN

F 83

147

CH ₃ H

-CH ₂ -

br

F 126

Expl R ¹ R

R '

Phys. dates

/ F = melting point in ° c7

138 CH _n H

F 169

139 CH.

NC-CH ₂ -

Cl Cl

140 CH.

HC = C-CH ₂ -

Cl

141 CH.

H ₂ C = CH-CH ₂ -

Cl

-CH ₂ -

Cl

¹ H-NMR ** 5.8 ppm

Oil ¹ HNMR ** 5.75 ppm ^F 80

142 CH ₃ NC-CH ₂ -

CH.

Oil ¹ H-NMR * ^J 5.5 ppm

- 43 -

-μ XL

C -I <ΰ ΰ +> EΠ5 JSQ UCO

to II

Οι

OO

(N

ro ro

ro U

ro ro ro S3 K U U U

ro

VD

ro

r-

ro

Le A 23 089-foreign countries

- 42 -

C H

Q) V

4J E

"Ä

α υ

cn π

05

0}

OQ

in in

Oi S 2 I

:O

in

ci

:O

Cι CU

in

Oi

S 2

:O

Cu o in

K U

I U

CM

K U

U 2

CN

th

O I

CJ

CN

CN

SG U

m U

CN

ta ο

S3 O

00 CN

cn η

(Τι CN

33 U

co

CN

S3 O

co

33 U

co

co To O

co

co

CN CO

Le A 23 089-foreign countries

Expl R Phys. dates

/ F = melting point in ° c7

122 CH ₃ - (CH ₂ J ₃ -

123 CH.

CH.

-CH ₂ -

, 93

¹ H-NMR ** 4.3 ppm

124 CH ₃ - (CH ₂ ) ₃ - NC-CH ₂ -. Cl

Cl

Oil ¹ H-NMR ** 5.35; 4.6 ppm

125 CH ₃ - (CH ₂ ) ₃ - NC-CH ₂ -

-CH _n , -

F 55

126 C ₁ H ₁

NC-CH ₀ -

CH ^ -

Oil ¹ H-NMR ** 5.6; 4.6 ppm

- 40 -

• Ρ M

3 Q

c tu α) • ρ ε ta £

Q U CO

cn ii

CU

ta

CQ

ro

ro

(N CJ

ro

EC CJ

CD

(N

ro

E U

ro

SC U

ro

ro ο

OO Γ »

in

CN O

O CN

CN CN

E U

ro E O

CN

Le A 23 089-foreign countries

- 39 -

X C

OO LD

OO

ιη

CJ

ιη

CN

CN

ΐΗ U

co CN cn I CN η η in S CN as CN ATS e S CJ U U U U U CN U I . I I

Le A 23 089-foreign countries

tr · (D

Expl R

108 CH ₃ CH ₃

109 C ₂ H ₅ CH ₃

110 CH ₃ CH ₃

111 CH ₃ CH ₃

R ³ .

-CH

Phys. dates

/ F = melting point in ° c7

F 125

¹ H-NMR * ¹ 5.5 ppm

¹ H-NMR ** 5.45 ppm

F 130

112 CH ₃ -MCH ₂ ) ₂ - · - CH ₃

CH ₂ -

113 CH ₃ - (CH ₂ ) ₃ - H

Cl

-CH ₂ -

Cl

112

- 37 -

C γ-Ι Q) V JJ (O

Q u w

Ol Il

in

ΛΟ

Pu in

Oi

CN

00 00

σι

CM

CM

(N

S U

(N

ro

as υ

ro

X Ό

K U

S U

as υ

S U

ro ro f SS X X U U U

PO ro ns th U U

O O

CN

• «3 · O

I DO

VO O

Le A 23 089 "abroad

- 36 -

04 N

C rH Φ 0) Ρ Ε

ta s

Q Ό W

• W Il

ro o

O Pm

(N in * I in in i OO VO in

Cu

eu

ro ro ro ro ro ro ro ro K X 33 S as pi X S U U U U U U

OS ro as U ro as O Chg Chg Chg Chg Chg ^CH 3 -No. Ex. cn ro cn σ " in VO σι σ " OO σ \ σ> 23 089 "Foreign countries Le A

- 35 -

ο υ co

e αin in

Ό C 3

νο

8th.

Oil

ιη

ιη • α

VO

04

ο "

ιη

Ό C

νο

ο. ιη ιη • α

3 νο

00

Γ-

VO

ί'ΓΟ VO

em

CNJ CN CN CN CN a a a a a U U U U U I I I I

CN CN a a U U I

CS 2 CM 2 CM U CN co co ro ro ζ_) S U a U a I a a a a a I U I u I u O U U U U

ro ro co ro ro ro co ro a a a a a a a a U U U U U U U U

oo

in co

VO

co

οο

OO

σι

σ>

Le A 23 089-foreign countries

- 34 -

e * S U O. Z ο Q. C "** ιη  Ρ KA • σ C C 3 3 α N VO C <Η Q) Q) "he +> ε (β-C Q U CO 0) Il

ιη ιη

ac

in in in in Ό and

νο

OO

ιη

O CN

νο ο

CM

a υ

α υ

CM

CM

S I

Z U

CM

S U

CM

CM

CM

S O

CM

CM

Z U

CM

S U I CM

U I

PB approx CH ₃ ro a U ro X Ό Chg ro S U ro S U ro o ro U • Example VO co ΟΛ O ω r-oo CM CO ro 00 23 089 -Foreign countries Le A

ο οο οο

Expl R

Phys. dates

/ F = melting point in ° c7

68

70

CH.

69 CH.

CH.

CH.

CF.

Cl

¹ H-NMR ** 5.5 ppm ¹ H-NMR ** 5.5 ppm ¹ H-NMR * ⁾ 5.4 ppm

71 CH ₃ H

72 CH ₃ H

Cl

CH ₂ - (IJ) -Br

F 133

^1- NMR * '5.5 ppm

73 CH ₃ H

CH.

¹ H-NMR ** 5.5 ppm

74 CH ₃ -CH ₂ -CN

¹ H-NMR * ^ 4.6 and 5.5 ppm

75 CH ₃ H

F 115 - 120

- 32 -

Q U CO

0) Il

οι ιη

Oil

ck

in

CS

VO

οι σι

σ>

th

O O U

rs U

ro U

S U

ro co co co ta as as υ U U U

co

O VD

VO

rs

voPO VO

VO

in vo

vo vo

Le A 23 089 -Outland

Expl R

Phys. dates

/ F = melting point in ^o c7

CH.

CH.

F 119

52

CH.

CH.

^C 2 ^H 5

CH.

CH

¹ H-NMR ** 5.6 ppm

¹ H-NMR * '5.4 ppm

54 55 56 57

CH.

CH.

CH.

CH.

CH.

CH.

CH.

CH

- (CH

¹ H-NMR * '4.5 ppm ¹ H-NMR *' 4.5 ppm ¹ H-NMR * '4.5 ppm

F 28

CH.

CH.

NC

F 126

59

CH.

CH.

CN

F 126

U ε  κ Οι ε • κ S ο CU Ξ Z CU CU S3 C CU • Η ιη ιη • 4J CO • ιη M ιη S α N CH • ρ ε ο υ

14

CU U) CQ

:O

co

CM

cn

CM

CM

CU CU

VO

in

:O

CM

CJ

 sr νο

CM

O U

in

CM

ιη ο

co

CM

ac u

CM

CM CO CM CM

Le A 23 089-foreign countries

Expl R

Phys. dates

/ F = melting point in ^o c7

244

245

C ₂ H ₅ -O-CO-CH ₂ -

Cl

Cl

F 131

The H-NMR spectra were recorded in CDCl ₃ with tetramethylsilane as the internal standard. The chemical shifts are usually given as ο values for the grouping

Application examples;

In the following application examples, the compounds listed below were used as comparative substances

CH ₂ -NH-CS-S.

CH ₂ -NH-CS-S "

Zn (A)

Zinc ethylene-1,2-bis- (dithiocarbamate)

CH ₃ ) 2N-

(B)

N, N-dimethyl-N ¹ - (fluorodichloromethyl) -capto) -N'-phenylsulfamide.

Le A 23 089-foreign countries

Example A

Phytophthora test (tomato) / protective Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of the active ingredient until dripping wet. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Phytophthora infestans.

The plants are placed in an incubation cabin with 100% relative humidity and about 20 ⁰ C.

3 days after the inoculation the evaluation takes place.

Clear superiority in efficacy over the prior art is demonstrated in this test, e.g. the compound according to the preparation example: 9.

Le A 23 089-foreign countries

Example B

Pyricularia test (rice) / protective Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

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

To test for protective activity, young rice plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. Subsequently, the plants in a greenhouse at 100% rel. Humidity and 25 ° C set up.

4 days after the inoculation, the evaluation of the disease infestation takes place.

Clear superiority in efficacy over the prior art is demonstrated in this test, e.g. the compounds according to the preparation examples: 1, 12, 14, 163, 192, 193, 200, 201, 206, 212, 213, 214 and 215.

Le A 23 089-foreign countries

Example C

Pyricularia test (rice) / systemic Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

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

To test for systemic properties, 40 ml of the active compound preparation are poured on unit soil, in which young rice plants were grown. 7 days after treatment, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. Thereafter, the plants remain in a greenhouse at a temperature of 25 ⁰ C and a rel. Humidity of 100% until evaluation.

4 days after the inoculation, the evaluation of the disease infestation takes place.

Clear superiority in efficacy over the prior art is demonstrated in this test, e.g. the compounds according to the preparation examples: 2, 11 and 16.

Le A 23 089 -Outland

Example E

Botrytis test (bean) / protective Solvent: 4.7 parts by weight of ACSTON

Emulsifier: 0.3 part by weight of ALKYL-ARYL-POLYGLYCOLETHER

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of the active ingredient until dripping wet. After the spray coating has dried, 2 small pieces of agar covered with Botrytis cinerea are placed on each leaf. The inoculated plants are placed in a darkened, moist chamber at 20 ^° C. 3 days after the inoculation, the size of the infestation spots on the leaves is evaluated.

A clear superiority in effectiveness over the prior art show in this test z. Example, the compounds according to the preparation examples: 191, 192, 193, 194, 197, 201, 203, 204, 205, 206th

Le A 23 089-foreign countries

- 69 -

Example D

Cochliobolus sativus test (barley) / protective

Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 part by weight of alkylarylpolyglycol

ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound in a dewy manner. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Cochliobolus sativus. The plants remain 48 hours at 2O ⁰ C and 100% rel. Humidity in an incubation cabin.

The plants are placed in a greenhouse at a temperature of about 20 ⁰ C and a relative humidity of about 80%.

7 days after the inoculation the evaluation takes place.

Significant superiority in efficacy over the prior art is demonstrated in this assay, e.g. the compounds according to the preparation examples: 1, 2, 9, 15, 16, 17, 18, 19 and 21.

Le A 23 089-foreign countries

Example F

Leptosphaeria nodorum test (wheat) / protective

Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 part by weight of alkylarylpolyglycol

ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound in a dewy manner. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Leptosphaeria nodorum. The plants remain 48 hours at 20 ⁰ C and 100% relative humidity in an incubation cabin.

The plants are placed in a greenhouse at a temperature of about 15 ⁰ C and a relative humidity of about 80%.

10 days after the inoculation the evaluation takes place.

A clear superiority in the effectiveness over the prior art show in this test z. B. the compounds according to the preparation examples: 190, 191, 192, 193.

Le A 23 089 -Outland

Claims (5)

Claim R is hydrogen, alkyl, alkenyl, alkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, hydroxycarbonylalkyl, alkoxycarbonylalkyl, aminocarbonylalkyl, alkylaminocarbonylalkyl, dialkylaminocarbonylalkyl or each optionally substituted oxiranylalkyl, aralkyl or aryl and R is alkyl, alkenyl, alkynyl, cyanoalkyl, hydroxyalkyl, Alkoxyalkyl, hydroxycarbonylalkyl, alkoxycarbonylalkyl, cycloalkyl, cycloalkylalkyl or in each case optionally substituted Aralkyly aryloxyalkyl or arylthioalkyl, but R is methyl or ethyl only if R and / or R are not simultaneously hydrogen or methyl in addition to extenders and / or surfactants, 1 2 is methyl or ethyl, if R and R are not simultaneously hydrogen or methyl, 2 »means according to item 1, characterized in that in the substituted pyrazolin-5-ones of the formula (I) R is hydrogen or straight-chain or branched alkyl having 1 to 8 carbon atoms. R is hydrogen, in each case straight-chain or branched alkyl, alkenyl, alkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, hydroxycarbonylalkyl, alkoxycarbonylalkyl, aminocarbonylalkyl, alkylaminocarbonylalkyl or dialkylaminocarbonylalkyl having in each case up to 8 carbon atoms in the individual alkyl or alkenyl or alkynyl moieties, for oxiranylalkyl with 1 to 4 carbon atoms in a straight-chain or branched alkyl part, straight-chain or branched, optionally mono- or polysubstituted, identically or differently, substituted aralkyl having 1 to 4 carbon atoms in the alkyl part and 6 to 10 carbon atoms in the aryl part or optionally mono- or polysubstituted, equal to or without. the differently substituted aryl having 6 to 10 carbon atoms, wherein as substituents in question are each: halogen, cyano, nitro, hydroxy, in each case straight-chain or branched alkyl, alkoxy, dioxyalkylene, alkylcarbonyloxy or alkylthio having in each case up to 4 carbon atoms, ger adkettiges or branched halogenoalkyl, haloalkoxy or haloalkylthio each having up to 4 carbon atoms and up to 9 identical or different halogen atoms or phenyl and -ιί- R represents straight-chain or branched alkyl having from 1 to 20 carbon atoms, in each case straight-chain or branched alkenyl, alkynyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, hydroxycarbonylalkyl or alkoxycarbonylalkyl having in each case up to 8 carbon atoms in the individual alkyl or alkenyl or alkynyl moieties, for cycloalkyl with 3 to 7 carbon atoms, cycloalkylalkyl having 3 to 6 carbon atoms in the cyeloalkyl part and 1 or carbon atoms in the alkyl part or for each optionally mono- or polysubstituted, identically or differently substituted arylalkyl, aryloxyalkyl or arylthioalkyl having 1 to 4 carbon atoms in the individual alkyl parts and 6 to 10 Carbon atoms in the aryl moieties, where as substituents mentioned in R, but where R is methyl or ethyl only when R and / or R are not simultaneously hydrogen or methyl. 3. Composition according to item 1, characterized in that in the substituted pyrazolin-5-ones of the formula (I) R is hydrogen, methyl, ethyl, η- or i-propyl and n-, i-, s- or t-butyl, R is hydrogen, methyl, ethyl, n- or i-propyl, n-i, s or t-butyl, allyl, butenyl, propargyl, cyanomethylr; Cyanoethyl, hydroxymethylv hydroxy "ethyl! Methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, hydroxycarboxylic -TS- is carbonylmethyl, hydroxycarbonylethyl, methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, aminocarbonylmethyl, methylaminocarbonylmethyl, ethylaminocarbonylethyl, ethylaminocarbonylmethyl, dimethyl aminocarbony lme thy 1, diethylaminocarbonylmethyl, aminocarbonylethyl, oxiranylmethyl, oxiranylethyl or in each case optionally monosubstituted to trisubstituted by identical or different substituents, phenyl or benzyl , being possible substituents: fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, methyl, ethyl, η- or i-propyl, η-, i-, s- or t-butyl, methoxy, ethoxy, Dioxymethylene, dioxyethylene, methylthio, ethylthio, acetoxy or propionyloxy, chloromethyl, dichloromethyl, trichloromethyl, trifluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, trifluoromethoxy, trifluoromethylthio or phenyl and R is methyl, ethyl, n- or i-propyl, n- or i-butyl, n- or i-pentyl, n- or i-hexyl, n- or i-heptyl, n- or i-octyl, n- or i-nonyl, n- or i-decyl, n- or i-dodecyl, n- or i-hexadecyl, allyl, butenyl, propargyl, cyanomethyl, cyanoethyl, hydroxymethyl, hydroxyethyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, hydroxycarbonylmethyl, Hydroxycarbonylethyl, methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexylmethyl or for Le A 23 089 -Outland an optionally mono- to trisubstituted by identical or different substituent of the formula Ar- (Z) _1n - (CH ₂ ) ,, -. Ar- (Z) _n -CH- or ^CH 3 Ar- (Z) -CH-, where m ι CN Each Ar is phenyl or naphthyl *, Z is in each case oxygen or sulfur, each m is O or 1 and η is 1 * 2 or 3, and wherein as substituents those mentioned in R in Come question, with the restriction that R only then Use of substituted pyrazolin-5-ones of the formula (I) according to item 1, characterized in that they are used for controlling pests. Method for controlling pests, characterized in that substituted pyrazolin-5-ones of the formula (I) according to Item 1 are allowed to act on pests and / or their habitat. Process for the preparation of pesticides, characterized in that substituted pyrazolin-5-ones of the formula (I) according to item 1 are mixed with extenders and / or surface-active agents. «