DE2101789A1 - - Google Patents

Description

dr. W. Schalk dipl.-ing. P. Wirth dipl.-ing. G. Dannenberg DR. V. SCHMIED-KOWARZIK · DR. P. WEINHOLD · DR. D. G UDEL

6 FRANKFURT AM MAIN

CR. ESCHENHEIMER STRASSE 39 * SK / SK

- BA2608 / 70 -Fisons Limited

Harvest House

Felixstcnve / Suffolk (England)

Fungicide and method for its use

The present invention relates to the use of certain compounds as fungicides and to fungicidal preparations containing compounds.

It has been found that the tetracyanocyclohexenes identified in more detail below are extremely effective fungicides.

The present invention therefore relates to a method for the control of fungi in an infected or possibly infected location, which thereby is characterized by the fact that a cdlzbekämpfende amount of a ^ Compound of the formula:

R ⁶ R ⁵
\. •

R ¹ -C ^{/ V} C ^

η I CN
I / CN

12 3 4 5 6 applies, in which R ₁ R ₁ R ₁ R ₁ R and R, which are identical or different, each represent hydrogen, halogen (such as chlorine or bromine), alkyl (e.g.

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with 1-5 carbon atoms, such as methyl or isopropylJ, unsaturated alk / l (e.g. with 2-t carbon atoms, such as vinyl, allyl or propargyl), alkoxy (e.g. with 1-b carbon atoms, such as methoxy or isopropoxy), aryl (e.g. u. Phenyl or naphthyl) or acyl (for example alkanoyl with 1-6 carbon atoms, such as acetyl or benzpyl) or one or two pairs of the substituents R to R each form a bridge or a fused ring together with at least one material from the group of tyetzmittel, carriers and other physiologically active chemical compounds.

In one embodiment of the present invention, R to R, which are identical or different, each represent hydrogen or alkyl, or. or two. Pairs of the substituents R to R biloen each have a bridge or a fused ring, ie the compound (without the 4 indicated cyano groups) is a hydrocarbon. Each bridge or fused ring from the pairs of substituents R to R is expediently a methylene bridge, an o-benzeno bridge or a fused benzene ring.

1 2 In a further embodiment of the present invention, R ₁ R ₁ R and R each represent hydrogen and R and R together form a methylene bridge, ie the compound is a 4,4,5,5-tetracyano-3,6-methano- 1-cyclo ~ hexene of the formula:

^ CH CN
CH I ^ C

' ^{| N} CN

I ^CH 2 I, CN

CH I ^ C
^N CH CN

In a further embodiment of the present invention, R ¹ to R each represent hydrogen, ie the compound is 4,4,5,5-tetracyano-i- cyclohexene. . BATH ORIGINAL

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3 H.

3 In a further example c: tr varlie-jcndfin invention H and

5 12

R for i'.asserijtuff, R and H together form a condensed Genzolrinq unn μ and η fcilUc: n zuEar.mr-n an α-ßnzeno bridge, ie the compound is a 13,11,12,12-tetracyano-9,1ü -dihydra ~ 9, ICKithnnaanthracen of the formula:

CH

CH

CH

c I crj G

C-CN
CH

CH

CH

CH

The area to be treated against fungal attack can be plants, animals, soil, Be land or sea areas or materials. Any material can be treated susceptible to fungal attack, such as fabrics, textiles, paper and wood. The present invention is particularly useful for places containing plants, on the ground or on land, but especially for plants ..

The tetracyanocyclohexenes given above are extremely useful fungicides with a certain systemic effectiveness. They are particularly suitable for Combating Pxlz diseases in plants.

The tetracyanocyclchexenes, and especially A ^ jSj 1-cyclohexene, sfrtd particularly suitable for the treatment of Phytophthora infestans, .Plasraopara viticola and other cold weather, e.g. in rubber, tobacco and cocoa. The tracyanocyclohexenes are also useful in treating others Fungal diseases, such as Uromyces phaseoli.

t ORiGlNAL BATHROOM.

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The tetracyanocyclohexenes can be prepared by any suitable mixing method be incorporated into the fungicidal preparations. So you can get the tetracyc- cyclohexcn e.g. in aqueous organic solvent solutions with or without Dissolve or disperse wetting agents.

If necessary, the tetracyanocyclohexenes cannot be mixed with water miscible solvent, e.g. a high-boiling hydrocarbon, the expediently contained a lust emulsifier, in order to act as a self-emulsifiable oil after addition to water.

To form a wettable powder, the tetracyanocyclahexene can be mixed with a Wetting agents can be mixed with or without a solid carrier. The powder is then soluble or dispersible in water. Or the tetracyanocyclohexene can be used to Formation of a fixed, z.H. powdery product mixed with a solid carrier.

Solid carriers into which the tetracyanocyclohexene can be incorporated include clays, sands, talc, mica, peat and fertilizers. Ils can dust and larger particle size materials are used. Possibly For example, the tetracyanocyclahexene can be used for impregnating or coating preformed grains, e.g. peat granules.

The wetting agents that can be used include anionic compounds, such as, for example, soaps, fatty sulfate esters, such as dodecyl sodium sulfate, aromatic fatty sulfonates, such as alkylbenzenesulfonates or butylnaphthalene sulfonates, more complex fatty sulfonates, such as the amide condensation product of oleic acid and [J-methyl succinic acid succinic sulfonate or sodium sulfonate.

BATH ORIGINAL

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The wetting agents further comprise non-ionic wetting agents, such as the Κ cation products of fatty acids, fatty alcohols or fat-substituted phenols with ethylene oxide, or fatty esters of sugars or polyhydric alcohols, or those obtained from the latter by condensation with ethylene oxide Products as well as those as block copolymers from i-.thylenoxyd ura Propylene oxide known products. The wetting agents also include cationic agents Agents such as cetyltrimethylammonium bromide, etc.

The fungicidal preparations according to the invention can be used in addition to the Tetracyanocyclc— hexen other fungicides, such as copper compounds, dithiocarbamates, e.g. "Maneta" and "Zineb" contain crotonates such as "Dinocap" and "Einapacryl". Furthermore, the preparation can contain other physiologically active materials, such as insecticides such as DDT, carbamate insecticides, e.g. carbaryl, or organophosphoric insecticides, such as dimethoate, and nematocides such as i ^ -dibromo-Ci-chloropropane.

The tetracyanocyclohexenes are used in amounts of 70 mg to 4.4 kg per hectare of active ingredient according to the particular plant species and the Disease used. For the treatment of Phytophthora infestans are 560 d: j Particularly suitable up to 2.2 kg per hectare. The concentration of the active ingredient in the preparation for storage and transport is not decisive and is expediently between 10-50

The dilution of the preparation for application is also not decisive. and when spraying as an aqueous spray material, 114-2275 liters per hectare are suitable.

j.

The following examples illustrate the present invention without it to restrict.

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-G-

Example 1_

Aqueous acetone solutions with 2000, £ ΰθ, 125 and 31 parts per mill. 4,4,5,5-Tetracyano-SjS-methano-i-cyclohexene, LCO ₁ 125 and 31 Ttdlün per million 4,4,5,5-Tetracyana-i-cyclohexene and 500 parts 11,11,12,12 -Tetracyt dihydro-9,10-äthancnnthracGn together with 125 parts per million, the tion product of nonylphenol with, ethylene oxide as wetting agent were sprayed onto the foliage of young potato plants with 7 fully expanded leaves. After 24 hours, the treated plants were infected with an aqueous Gporcngia solution of the organism responsible for Phytüphthora infestans. The plants were left to stand in an atmosphere saturated with water for 24 hours and then kept for 5 days in a room with a regulated environment (temperature = 16 ° C., relative humidity = 60-90 ^c / ₃ ) . After this time, the protection against the disease was determined by comparison with control plants which had only been treated with a solution of the wetting agent. The results were as follows:

Connection applied lienge ^ i protection

Partly per million

4,4,5,5 — Tetracyano — 3, ß-methano— 1-cyclohexene

4,4,5,5-tetracyano-i-cyclohexene

1,1,12,12-tetracyano-g, 10-dihydro 9,10-ethanoanthracene

2000 100 500 98 125 95 31 70 500 93 125 80 31 65

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H Gi s ρ i rl 2

Aqueous acetone solutions with 20%, 500, 125 and 31 parts per million 4,4,5,5-tctracyano-3, ti-metikina-1-cyclohexene and 500 and 125 parts per mill, 4,4,5,5-tetracyano-1-cyclohfixene together with 125 parts per mill, of the condensation product from monylphenol with methylene oxide as a wetting agent were applied to the Ulattv.ert juncjrr red plants (Phaseolus vulgaris) with 2 fully expanded Leaves sprayed. ! »The treated plants were tuned with a aqueous leakage of spores of the disease organism of Uromyces phasno- Ii infected. The plants were grown for 24 hours in a water saturated with water Maintained atmosphere and then 14 doughs in a room controlled environment (Temperature = 16 C, relative humidity = OC-90 ■>) left standing.

After this time, the protection against disease was compared with Control plants determined that only treated with a solution of the wetting agent had been. The results were as follows:

Connection Applied Amount ^c / ₀ Protection

Parts per million

4,4,5,5-Tetracyana-3,6-methano-jnnn 9fl

1-cyclDhexene

500 91 125 BO 31 50 500 97 125 50

4,4,5,5-tetracyano-i-cyclohsxen

Example 3

Aqueous acetone solutions with 500, 125 and 31 parts per million 4,4,5,5-tetracyana-3,6-methano-1-cyclohexene and 4 _{tons of} 4,5,5-tetracyano-1-cyclohexene together with 125 parts per Will, the condensation product of ftonylphenol with ethylene oxide as a wetting agent, was filled with 5 on the foliage of young vines

BATH ORIGINAL

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expanded leaves sprayed. After 24 hours the treated plants were with an aqueous Gporangia suspension of the person responsible for Plasmopara viticola Organism infected. Then the plants were kept in an atmosphere saturated with water for 5 days and after this time on protection Before the disease was examined, a comparison with control plants which had only been sprayed with a solution of the wetting agent, the results were as follows: ;

Connection Applied Amount ⁰ Jo Protection

Parts per million.

4,4,5,5-tetracyane D-3, b-fnethanc-1-
cyclohexene SCO " 99 125 91 31 70 4,4,5,5-tetracycline-i-cyclohexene 500 99 125 96 31 6Θ

example

Milling in a vortex energy device became the following Ingredients of a wettable powder formulation 4,4,5, S-Tetracyanc-Sjü-methano-i-cyclohexene 50%

Sodium N-methyl-N-oleoyltauride (33%, with _ ^

Sodium chloride and sodium sulphate) > °

Sodium salt of the condensate from sulfonated ».

Cresol and formamide *

Kaolin 42%

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Claims (1)

Claims
1.- Fungicide, consisting of or containing a compound of the formula: ^S CN CN
R ^ -C _n ^ C _n • ■ R ^{3 / C} V ^CN in which R ₁ R ₁ R ₁ R ₁ R and R, which are identical or different, each represent hydrogen, halogen, alkyl, unsaturated alkyl, alkoxy, aryl or 1 ß acyl or one or two pairs of the substituents R 'to R are a bridge or form a condensed ring. 1 Ft 2. Fungicide according to claim 1, characterized in that R to R, which are identical or different, each represent hydrogen or alkyl or one or two pairs of the substituents R to R form a bridge or a fused ring. 3. Fungicide according to claim 1 and 2, characterized in that each bridge A CZ or each fused ring made up of pairs of the substituents R to Fl one Methylene bridge, an o-benzene bridge or a fused-on benzene ring is. 4, - Fungicide according to claim 1 to 3, characterized in that it is 4,4,5,5-tetracyano-Bje-methano-i-cyclohexene, A ^ Sjö-Tetracyano-l-cyclohexene or 11,11,12,12-tetracycline-9,1ü-dihydro-9,10-ethanoanthracene. 5, - Fungicide according to claim I to 4, characterized in that there is another Contains wetting agents, a carrier or another phyiolocjiKch active chemical compound. BATH ORIGINAL 109831/2123 6. Fungicide according to claim j to 5, characterized in that it contains an agent . 1 to
7. Fungicide according to claim 1, characterized in that it also contains a solid carrier, preferably sand, talc, mica, peat or a fertilizer. 8, - Fungicide according to claim 1 to 7, characterized in that it is still eir = other, physiologically active chemical compound from the group of fungicides, Nematocides, drganophophorin insecticides and carbainatin insecticides contains. 9.- A method for combating fungus, characterized in that one Fungicide according to claim 1 to B used. 10.- The method according to claim 9, characterized in that the fungicide on a plant, preferably potatoes, vines, rubber trees, tobacco balances, Cocoa bushes or bean plants, containing place used. The patent attorney: 10 9 8 31/2123