CS214710B2 - Fungicide means - Google Patents

Abstract

1. Claims for the contracting states : BE, CH, LI, DE, FR, GB, IT, LU, NL, SE Carbinol ethers of the general formula (I) see diagramm : EP0019153,P10,F3 where R**1 denotes halogen or phenyl, R**2 denotes alkyl of 1 to 6 carbon atoms or unsubstituted or chlorine-substituted phenyl, R**3 denotes alkyl of 1 to 6 carbon atoms, vinyl, ethynyl or unsubstituted or chlorine-substituted benzyl, R**4 denotes alkyl of 1 to 4 carbon atoms, allyl, unsubstituted or chlorine-substituted benzyl, or 3,3-dimethylbutan-2-on-1-yl, and n denotes 0, 1 or 2, and salts and metal complex compounds thereof. 1. Claims for the contracting state : AT A fungicide containing a carbinolether of the general formula (I) see diagramm : EP0019153,P11,F1 where R**1 denotes halogen or phenyl, R**2 denotes alkyl of 1 to 6 carbon atoms or unsubstituted or chlorine-substituted phenyl, R**3 denotes alkyl of 1 to 6 carbon atoms, vinyl, ethynyl or unsubstituted or chlorine-substituted benzyl, R**4 denotes alkyl of 1 to 4 carbon atoms, allyl, unsubstituted or chlorine-substituted benzyl, or 3,3-dimethylbutan-2-on-1-yl, and n denotes 0, 1 or 2, and salts and metal complex compounds thereof.

Description

A fungicidal composition comprising a solid or liquid carrier and, as active ingredient, a carbinol ether of the formula I

in which

R 1 represents a halogen atom or an optionally halogenated or phenyl-substituted phenyl group,

R 2 represents a C 1 -C 4 alkyl group or an optionally substituted phenyl group,

R 3 represents a C 1 -C 4 alkyl group, a C 2 alkenyl group, a C 2 alkynyl group, a net or halogen-substituted benzyl group,

R 4 is C 1 -C 4 alkyl, C 3 alkenyl or optionally halogenated benzyl and n is 1 or 2.

The present invention relates to novel carbinol ethers, to a process for their preparation, to fungicidal compositions containing these active substances and to a method for combating harmful fungi using such substances.

It is already known that l- [2- (2 ^< ', 4' dichlorophenyl] -2 '- (2 "propenyloxy) Jethyl-imidazo-ol (see British Pat. No. 1,318,590), the fungicidally effective.

However, the effect of this substance, in particular against mildew and rust, is not sufficient. Thus, the compound is not very suitable for combating harmful fungi in plant protection.

It has now been found that the novel carbinol ethers of formula (I)

in which

R ¹ represents a halogen atom or an optionally halogenated or phenyl-substituted phenyl group,

R ² represents an alkyl group having 1 to 4 carbon atoms or optionally halogen substituted phenyl group,

R ³ represents a C 1 -C 4 alkyl group, a C 2 alkenyl group, a C 2 alkynyl group or an optionally halogenated benzyl group,

R ⁴ represents a C 1 -C 4 alkyl group, a C 3 alkenyl group or an optionally halogenated benzyl group, and n is 1 or 2 having excellent fungicidal activity.

In the general formula (I), R @ ¹ as halogen represents, for example, fluorine, chlorine or bromine, or furthermore, for example, a phenyl group, especially substituted in the 4-position by halogen, for example chlorine.

R @ ² is, for example alkyl having 1-4 carbon atoms which can be linear, such as methyl, ethyl, propyl or butyl, or branched, * such as isopropyl or tert-butyl. Further, R ² represents an unsubstituted or halogen such as chlorine, mono- or disubstituted phenyl radical.

R ³ is, for example unbranched alkyl group having 1-4 carbon atoms such as methyl, ethyl, propyl or butyl, and for example, branched alkyl having 3 or 4 carbon atoms such as isopropyl or isobutyl, e.g. alkenyl or alkynyl group having 2 carbon atoms, such as a vinyl or ethynyl group or, for example, a benzyl radical, optionally mono- or disubstituted by halogen, such as chlorine.

R ⁴ is, for example, an optionally substituted alkyl group, for example unbranched and containing from 1 to 4 carbon atoms, such as methyl, ethyl or n-propyl, or for example branched, containing 3 or 4 carbon atoms, such as isopropyl or 2-methyl- 1-propyl, further for example unbranched or branched alkenyl having 3 carbon atoms, such as 2-propen-1-yl, and further for example benzyl optionally substituted by halogen.

New karbinoilethery may contain two asymmetric centers, at the acetal carbon, and where R ² and R ³ are different, at the carbinol carbon. Individual diastereomers can be obtained using conventional resolution methods, which are also within the scope of the invention. Both the individual diastereomers and mixtures thereof, which usually resulitate during synthesis, can be used as fungicides.

Crbinols of formula II

in which

R @ ¹ , R @ ² , R @ ^3, and R @ ³ : as defined above, required as starting materials for the production of novel carbinol ethers, are known in part.

Thus, DOS No. 2,324,010 describes the preparation of 1- (4'-chlorophenoxy) -1- (1,2,2,4'-triazol-1'-yl) -2,3,3-trimethylbutan-2-ol By Grignard reaction, namely, by reaction of methylmagnesium iodide with 1- (4'-chlorophenoxy) -1- [1,2 ', 4'-triazol-1'-yl) -3,3-dimethylbutan-2-one. Correspondingly, other ketones, known for example from DOS Nos. 2 201 063 and 2 705 678, can be reacted with Grignard reagents of the general formula R ³ MgHal, where R ³ is as defined above and Hal represents chlorine, bromine or iodine, to formation of carbinols of the general formula II.

It has been found that the carbinols of the formula IV can be used

in which

R ¹ and n are as defined above and

R ⁵ represents a branched or unbranched alkyl group having 1 to 4 carbon atoms, obtained by the formation of esters of the general formula V (Q-O-C-OR ^{6 L} -N (V) in which

R ¹ and n are as defined above and

R ⁶ represents a C 1 -C 4 alkyl group, for example methyl, ethyl, propyl or butyl, reacted with the Grignard reagents of formula VI

R ⁵ MgHal (VI) in which

R ⁵ is as defined above and

Hal represents chlorine, bromine or iodine in the presence of an inert solvent.

Esters of formula V are known and their synthesis is described in DOS Nos. 2 720 654 and 2 846 127.

Solvents, preparation of Grignard reagents, reaction accelerators, reaction temperatures, as well as isolation of carbinols are all known in the literature (see Houben-Weyl, Methoden der O.organischen Chemie, Thieme-Verlag Stuttgart 1973, vol. 13/2 a, p. 47). and more).

Furthermore, it has been found that the compounds of the above formula I are obtained by the formation of carbinols of the general formula II, wherein ^{R 2} -U ³ -N in which:

R ¹ , R ² , R ³ and n are as defined above, or their alkali metal or quaternary ammonium salts thereof, reacted with an alkylating agent of formula III

L-R ⁴ (III) wherein

R ⁴ is as defined above and

L represents a micleophilic leaving group, optionally in the presence of a solvent or diluent, optionally in the presence of an inorganic or organic base and optionally in the presence of a reaction accelerator, at a temperature between 0 and 100 ° C.

Examples of the above-mentioned nucleophilically leaving groups L are halogen atoms such as chlorine, bromine or iodine, alkyl sulfate residues such as methyl sulfate, optionally substituted alkylsulfonyloxy groups such as methanesulfonyloxy or trifluoromethanesulfonyloxy groups such as aryloxy.

Suitable inorganic or organic bases which can also be used as acid binding agents for this reaction are, for example, alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal carbonates such as potassium carbonate or carbonate sodium, alkali metal hydrides such as sodium hydride, alkali metal or alkaline earth metal alkoxides such as sodium methoxide, magnesium methoxide or sodium isopropoxide, tertiary amines such as trimethylamine, itriethylamine, Ν, Ν-dimethylaniline, N, N-dimethylcyclohexylamine, N-methylpiperidine or; pyridine. However, other conventional bases may also be used for this purpose.

By treatment with suitable bases, such as alkali metal hydrides such as sodium hydride, or alkyl lithium compounds such as butyllithium, or alkali metal or alkaline earth metal alkoxides such as sodium methoxide, the alcohols of the formula II can also be converted to the corresponding alkoxides prior to the reaction; then only undergo its own reaction.

Suitable diluents or solvents include, for example, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane or chlorobenzene, aliphatic or aromatic hydrocarbons such as cyclohexane, petroleum ether, benzene, toluene or xylenes, esters such as ethyl acetate, amides such as dimethylformamide, nitriles such as acetonitrile, sulfoxides such as dimethylsulfoxide, ketones such as acetone or methyl ethyl ketone, ethers such as diethyl ether, tetrahydrofuran or dioxane, or mixtures of these solvents.

Suitable reaction accelerators are, for example, metal halides such as potassium iodide, crown ethers, quaternary ammonium compounds such as tetrabutylammonium iodide, acids or mixtures of these accelerators. The reaction of the invention is generally carried out at a temperature between 0 and 150 ° C, for a period of from 1 to 60 hours at normal or elevated pressure, continuously or discontinuously.

The compounds of the invention are isolated from the reaction mixture in a conventional manner. The products thus obtained generally do not require any further purification, but can be further purified by methods known per se, such as recrystallization, extraction, distillation or chromatography.

If desired, the carbinol ethers of formula (I) can be converted into plant-compatible salts or metal complexes in a manner known per se. Salts include, for example, hydrochlorides, hydrobromides, sulfates, nitrates, phosphates, oxalates or dodecylbenzenesulfonates.

Metal complexes include complex compounds of carbinol ethers with heavy metal salts, such as zinc chloride, copper chloride, copper sulfate, manganese chloride, ferrous chloride. or nickel bromide.

The preparation of the novel compounds of formula (I) is illustrated by the following non-limiting examples.

Example la d'l

1.25 g of sodium hydride are added to 80 ml of absolute tetrahydrofuran under nitrogen, and a solution of 12.8 g of 1- (1 ', 2', 4'-triazol-1'-) is added with stirring. yl] -1- (4'-chloro-phenoxy) -2-iodo-3,3-chloro-1,2,3,4-triazol-2-ol in 80 ml of absolute tetrahydrofuran. 6.8 g of methyl iodide are added dropwise at room temperature (20 DEG C.) and the reaction mixture is stirred for 12 hours, then the excess of sodium hydride is quenched with water, after adding 300 ml of ether, the organic phase is washed twice with water and dried. of a residue of 13.4 g crystallized after trituration with petroleum ether 9.7 g of 1- (1 ', 2', 4'-triazol-1'-yl) -1- (4'-chlorophenoxy) -2-vinyl-3 3-dimethylbutyl-2-methyl ether, m.p. 96-98 ° C (# 1).

Analysis:

calculated: C: 60.8%, H: 6.6%, N: 12.5%, Cl: 10.6%;

found: C: 60.7%, H: 6.5%, N: 12.8%, Cl: 10.5%. ^{1 *}

1- (1,2 ', 4'-Triazol-1'-yl) -1- (4'-chlorophenoxy) -2-vinyl-3,3-dimethylbutan-2-ol, used as starting material, was prepared as follows: as follows:

To a solution of 0.22 mol of vinylmagnesium chloride in 140 ml of absolute tetrahydrofuran at 20-35 ° C is added dropwise, with stirring, a solution of 29.4 g (0.1 mol of 1- (1 ', 2', 4'-triazole). 4'-1'-yl) -1- (4'-chlorophenoxy) -3,3-dimethylbutan-2-one in 100 ml of absolute tetrahydrofuran, stirred at 40-45 ° C for a further 5 hours then The reaction mixture was quenched with 150 ml of water and the precipitate was dissolved in 200 ml of 20% aqueous ammonium chloride solution, the organic phase was separated, washed twice with water and evaporated, and the oily residue was recrystallized from cyclohexane with little ethyl acetate. There was obtained 10 g of 1- (1,2 ', 4'-trlazol-1'-yl) -1- (4'-chlorophenoxy) -2-vinyl-3,3-dimethylbutan-2-ol, m.p. Mp 152-153 ° C.

Analysis:

calculated: C: 59.7%, H: 6.3%, N: 13.1%, Cl: 11.0%;

Found: C: 59.8%, H: 6.1%, N: 13.3%, Cl: 10.8%.

Example 2

A solution of 21.4 g of 1- (1 ', 2', 4'-triazol-1'-yl) -1- (4 ') is added dropwise at room temperature (20 ° C) to a suspension of 4 g of sodium hydride in 100 ml of tetrahydrofuran. (chlorophenoxy) -2-methylpropan-2-ol in 200 ml tetrahydrofuran and stirred for 4 hours. After addition of 15.9 g of methyl iodide, the resulting mixture was stirred overnight (12 hours), then the excess sodium hydride was quenched with water, neutralized with sulfuric acid and evaporated. The residue was dissolved in 500 ml of methylene chloride and the solution was washed twice with water. The organic phase was separated and evaporated to dryness. 18 g of 1- (1 ', 2', 4'-triazol-1'-yl) -1- (4'-chlorophenoxy) -2-methylpropyl-2-methyl ether are obtained. (No 2) in the form of an oil with a refractive index Ho ²⁰ - · 1,5251.

Analysis:

calculated: C: 55.4%, H: 5.7%, N: 14.9%, Cl: 12.5%;

found: C: 55.2%, H: 5.6%, N: 14.5%,

Cl: 12.5%.

1- (r, 2 ', 4'-triazol-1'-yl) -1- (4'-chlorophenoxy) -2-methylpropan-2-ol is prepared as follows:

To a solution of 1 mol of methylmagnesium iodide in 100 ml of diethyl ether (methylmagnesium iodide prepared from 24 g magnesium shavings and 142 g methyl iodide) was slowly added dropwise 56.3 g of methyl 2- (1 ', 2', 4'-triazol-1'-yl) After stirring for one hour at 40 ° C, the reaction mixture is allowed to stand overnight, after addition of 150 ml of saturated ammonium chloride solution, the ether phase is separated off, the aqueous phase is separated. Shake twice with ether, dry and evaporate the combined organic phases, and 22 g of 1- (1 ', 2', 4'-triazol-1'-yl) -1- (4'-chlorophenioxy) -2-methylpropane-2 crystallize from diisopropyl ether. m.p. 99-100 ° C.

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The following compounds of the general formula I, characterized by IR and NMR spectroscopy, as well as by elemental analysis, were prepared in an analogous manner:

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The novel compounds of the invention and their salts and metal complexes are distinguished by excellent activity against a wide range of phytopathogenic fungi, in particular from the class of Ascomycetes and Basidiomycetes. The disclosed compounds are partially systemically active and can be used as foliar and soil fungicides.

Of particular interest is the usefulness of the fungicidally active compounds for controlling numerous fungi on various crop plants or their seeds.

In this context, crop plants include, in particular, wheat, rye, barley, oats, rice, maize, cotton, soybean, sugarcane, fruit and ornamental plants in garden architecture, as well as vegetables such as cucumbers, beans, beans and cucurbits.

The novel compounds described are particularly suitable for combating the following plant diseases:

Erysiiphe gramtais (powdery mildew) on cereals

Erysiphe cichoracearum (Powdery mildew) on cucurbits

Podosphaera leucotricha [apple powdery mildew] on apple trees

Uncinula necator (powdery mildew) on grapevine

Erysiphe polygoni (powdery mildew) on beans and beans

Sphaerotheca pannosa (powdery mildew) on roses Puccinia species (rust) on cereals

Rhizumerotaia solaini (cotton potato) on cotton Helminthosporium species (helminthosporosis) on cereals Ustilago species (dusty smut) on cereals and sugar cane

Rhynchosporium secale (rhynchosporium spots) on cereals

Ventur-ia inaequalis

Mycosphaerella musicola (septeriosis) on bananas

Piricularia oryzae on rice

Pellicularia sasakii on rice

Botrytis cinerea (gray mold) on vines and strawberries.

The compounds of the invention are applied by spraying or dusting the plants with the active compounds or by treating the seeds of the plants with the active compounds. Application is carried out before or after infection of the plants or seeds by the fungus.

The active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The dosage forms depend entirely on the intended use, but in any case are intended to ensure a fine and uniform distribution of the active ingredient. These compositions are prepared in a manner known per se, for example by mixing the active ingredient with solvents and / or carriers, optionally with emulsifiers and dispersants, where organic solvents can also be used as co-solvents when water is used as a diluent. Suitable carriers and auxiliaries are, in particular, solvents: aromatics (e.g. xylene or benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol or butanol), amines (e.g. ethanolamine) dimethylformamide and water; carriers such as natural stone meal (for example kaolins, alumina, talc or chalk) and synthetic stone meal (for example silicates); emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin, sulfite waste liquors and methylcellulose.

The concentrates generally contain between 0.1 and 95 wt. % of active ingredient, preferably 0.5 to 90 wt. % active substance.

Depending on the type of effect desired, the active substance consumption is between 0.1 and 3 kg or more of active substance per hectare.

The novel active substances can also be used for the protection of materials, inter alia for combating wood-destroying fungi such as Coniophora puteana and Polystictus venicolor. In the present case, the application is carried out by treating the wood with such means, for example impregnating or painting.

The concentrates, or compositions which can be prepared therefrom, such as solutions, emulsions, suspensions, powders, dusts, pastes or granules, are applied in a known manner, for example by spraying, fogging, dusting, pickling or dressing.

The following preparations are exemplified by the above compositions:

AND.

parts by weight of the compound of Example 1 are mixed with 10 parts by weight of N-methyl-1-pyrrolidone to give a solution which is suitable for application as small droplets.

II.

parts by weight of the compound of the example are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide per mole of N-mono-ethanolamide oleic acid, 5 parts by weight of calcium dodecylbenzenesulfonic acid; 5 parts by weight of the addition product of 40 ^{l of} ethylene oxide per mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

III.

parts by weight of the compound of Example 1 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of an adduct of 7 moles of ethylene oxide per mole of isooctylphenol and 10 parts by weight of an adduct of 40 moles of ethylene oxide per mole of castor. oils. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

IV.

parts by weight of the compound of Example 1 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point of 210 to 280 and 10 parts by weight of an adduct of 40 moles of ethylene oxide per mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

IN.

parts by weight of the active compound of Example 1 are mixed well with 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 17 parts by weight of ligninsulphonic acid sodium salt from waste sulphite lyes and 60 parts by weight of powdered silica gel and milled in a hammer mill. By finely distributing it in 20 parts by weight of water, a spray suspension is obtained which contains 0.1% by weight of active ingredient.

VI.

parts by weight of the compound of Example 1 are intimately mixed with 97 parts by weight of finely divided kaolin. In this way, a dust is obtained which contains 3% by weight of active ingredient.

VII.

parts by weight of the compound of Example 1 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of the silica gel. In this way, an effective formulation of good adhesion is obtained.

VIII.

parts by weight of the active compound of Example 1 are intimately mixed with 10 parts of sodium salt of the condensation product of phenolsulfonic acid, urea and formaldehyde, 2 parts of silica gel and 48 parts of water to obtain a stable aqueous dispersion. By diluting this dispersion with 100,000 parts by weight of water, an aqueous dispersion containing 0.04% by weight of the active ingredient is prepared.

IX

parts of the active ingredient of Example 1 are intimately mixed with 2 parts of calcium dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium phenol-sulfonic acid, urea and formaldehyde condensation product, and 68 parts of paraffinic mineral oil fraction to obtain stable oil dispersion.

The active compounds according to the invention may be present in these compositions, together with other active substances, such as, for example, herbicides, insecticides, growth regulators and fungicides, or they can also be mixed with fertilizers and applied in this form. When mixed with fungicides, in many cases the efficacy spectrum is expanded.

The following list of fungicides with which the compounds of the present invention may be combined illustrates, but is not limited to, these combination possibilities.

Fungicides with which the compounds of the invention may be combined are, for example:

dithiocarbamates and their derivatives, such as: ferric dimethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese ethylenebis-dithiocarbamate, manganatosin ethylenediamine-bis-dithiocarbamate, ethylenebis-dithiocarbamate zinc di-thiocarbamate, zinc di-thiocarbamate, zinc bis-dithiocarbamate and N, N'-polyethylene-bis- (thiocarbamoyl) disulfide,

Zinc, Ν-pollyeithylein-bis- (thlokarbamoyl) disulfonammonium complex of N, N‘-propylene-bis-dithiocarbamate and

N, N'-polypropylene-bis- (thiocarbamoyl) disulfide;

nitroderivatives such as:

dinitro- (1-methylheptyl) phenyl crotonate, s-sec-butyl-4, 6-dimtrophenyl-3,3-dimethyl acrylate,

16

2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate;

heterocyclic compounds such as:

N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthio-phthalimide, 2-heptadecyl-2-imidazoline acetate,

2,4-dichloro-6- (o-chlorotamino) -s-triazine, 0,0-diethylphthalimidophosphonothloate, 5-amino-1- [bis- (dimethylamino) phosphinyl] -3-

-phenyl-1,2,4-triazole,

5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole,

2,3- dicyano-4-dithionathrachinon, 2-thio-l, 3-dithla [4,5-b] quinoxaline ^and CIII, l-methyl-2-butylkarbam'Oyl benzimida- zolkarbamové acid

2-methoxycarbonylaminobenzimidazole, 2-thiocyanatomethylthiobenzthiazole,

4- (2-chlorophenylhydrazone) -3-methyl-5-isoxazolone, pyridine-2-thiol-1-oxide,

8-hydroxycillinoline or its copper salt,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiamine-4-dioxide;

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin,

2- (2-furyl) benzimidazole, piperazijl-1,4-diyl-bis- [1- (2,2,2-trichloroethyl ethyloramide)],

2- (4-thiazolyl) benzimidazole,

5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis- (p-chlorophenyl) pyridine methanol,

1,2-bis- (3-ethoxycarbonyl-2-thioureido) benzene,

1,2-bis- (3-methoxycarbonyl-1-thioureido) benzene;

and various fungicides such as:

dodecylguanidine acetate,

3- (3- (3,5-Dimethyl-2-hydroxycyclohexyl) -2-hydroxyethyl) glutarimide, hexachlorobenzene, N-dichloro-trifluoromethylthio-N, N'-diethyl-N-phenyldiamide sulfuric acid,

2,5-dimethylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxylic acid cyclohexylamide, 2-methylbenzoic anilide, 2-iodobenzoic anilide, 1- (3,4-dichloroanilino] -1-formylamino-2, 2,2-trichloroethane,

2,6-dimethyl-N-tridecylimorpholine and its salts,

2,6-dimethyl-N-cyclododecylmorpholine, and its salts, D, L-methyl-N- (2,6-dimethylphenyl) -N.-2-uroylalaninate, methyl ester D, LN- (2,6- dimethylphenyl) -N- (2'-methoxyacetyl Jalanine, 5-nitrosoftalic acid diisopropyl ester, 1- (1 ', 2', 4'-triazol-1'-yl) - (1- (4'-chlorophenoxy)) -3 3-dimethylbutan-2-one

1- (1‘, 2 2, 4‘-triazol-1‘-yl) - (1- (4‘-chlorophenoxy) -3,3-dimethylbutan-2-ol),

N- (2,6-dimethylphenyl) -N-chloroacetyl 1D, L-2 _; -aminobutyrolactone,

N- (n-propyl) -N- (2,6-trichlorophenoxyethyl) -N‘-imidazolylurea, sulfur,

N- (1,1,2,2-tetrachloroethylthio) tetrahydrophthalimide,

2-Cyano-N- (ethylaminocarbonyl) -2- (methoxyimino) acetamide.

In the following bioassays, 1- [2'- (2 ", 4" -dichlorophenyl) -2'- (2'-propenyloxy] ethyl-1H-imidazole, known from British Pat. 1,318,590.

Testi

Effect against powdery mildew (Erysiphe graminis var. Tritici)

The potted leaves of germinated wheat plants (Jubilar species) are sprayed with aqueous emulsions containing 80% by weight of the active ingredient and 20% emulsifier in the dry matter, and after spray coating has dried, they are dusted with spores (oidiemi) of Erysiphe graminis var. tritici (powdery mildew). The test plants are then kept in a greenhouse at 20 to 212 degrees Celsius and 75 to 80% relative humidity.

The results are summarized in the following table, with values from 0 to 5, where 0 means no fungus occurrence and 5 represents a complete fungal infestation of lislt.

infestation of leaves after spraying with active substance concentration (%)

0.025 0.012 0.006

Table active substance (example no)

1 0 0 0 3 0 0 0 4 0 0 0 5 0 0 0 6 0 0 0 7 0 0 0 8 0 0 0 9 0 0 0 12 0 0 0 13 0 0 0 15 Dec 0 0 0 16 0 0 0 17 0 0 1 18 '0 0 0 19 Dec O. 0 0 22nd 0 0 0 25 0 0 0 26 1 0 2 28 0 2 2 30 0 0 0 35 0 0 1 38 0 0 1 A (known) 3 3 4 control (untreated) 5

Test 2

Effect against Puccinia recondita

The leaves of potted wheat (Caribo) plants grown in pots are dusted with spores of Puccinia recondita (wheat rust). The pots are then stored at 20-22 ° C for 24 hours in a high humidity chamber (90-95%). During this time the spores germinate and their germs penetrate the leaf tissue. The infected plants are then sprayed with water at 0.025, 0.012 and 0.006% w / w containing 80% of active ingredient and 20% of lignin sulphonate in the dry state. After the spray coating has dried, the test plants are placed in a greenhouse at 20 to 22 ° C and 65 to 70% relative humidity. After 8 days, the rust attack of the leaves was evaluated.

The results obtained are summarized in the following overview, expressed on a scale of 0 to 5, where 0 means no fungal growth and 5 represents complete leaf infestation.

Table active ingredient infestation of leaves after spraying with a composition of (example.) Active ingredient concentration (%)

0.025 0.012 0.006

1 0 0 1 3 0 0 0 4 0 0 0 6 0 1 2 8 0 0 1 9 0 1 2—3 15 Dec 0 0 0 16 0 1 2 18 1 1 3 26 0 0 - 28 0 0 - 30 0 ï 3 38 1 2 3 A (known) 4 5 5 control (untreated) 5

Claims (1)

An unicidal composition comprising a solid or liquid carrier and, as active ingredient, a carbinol ether of the formula I OF THE INVENTION in which R ¹ represents a halogen atom or an optionally halogenated or phenyl-substituted phenyl group, R ² represents an alkyl group having 1 to 4 carbon atoms or optionally halogen substituted phenyl group, R ³ represents a C 1 -C 4 alkyl group, a C 2 alkenyl group, a C 2 alkynyl group or an optionally halogenated benzyl group, R ⁴ represents a C 1 -C 4 alkyl group, a C 3 alkenyl group or an optionally halogenated benzyl group and n is 1 or 2.