DE2734426A1 - COMPOSITION AND METHOD OF CONTROL OF FUNGI - Google Patents

Description

8UU0 MUNICH 5

Folder 24 312

ICI Case No. PP 28966/29176/29329 IMPERIAL CHEMICAL INDUSTRIES LIMITED, London / England Composition and method of combating fungi

Priority England No. 31649/76 of July 29, 1976, No. 47667/76 of November 16, 1976 and No. 5139/77 of February 8, 1977

The invention relates to fungicidal compositions and methods for controlling fungi. In particular, the invention relates to compositions and methods for treating plants and seeds.

There has long been a need to protect plants and seeds from the adverse effects of deciduous, seed and soil borne fungal diseases. A fungal attack on the seeds can often prevent them from germinating

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can. Such a fungal infestation can also lead to diseased seedling plants, whose survivability is therefore considerable has been decreased. Plants infected by fungi can often no longer produce good yields.

To mitigate these adverse effects, plants and seeds have been treated with chemicals for many years that have a have fungicidal activity and thus fight the piIz diseases.

However, many such chemicals are limited in the extent to which they can be used. A particular limitation to be considered is the tendency for some of these chemicals to cause undesirable side effects in plants result, at least to a certain extent, the beneficial effects of combating fungal diseases destroy again.

Examples of such undesirable side effects are e.g .:

a) prevention of the rhyming of the seed;

b) the stunted growth of plants and

c) phytotoxic effects of varying degrees.

It has now been found that these undesirable effects are caused by certain specific chemical substances such as those below are described and which are otherwise excellent fungicides, can be reduced so that these compounds in the With regard to any serious effects on plants and seeds, it is safer and without reduction in fungicidal activity can be used.

The invention therefore provides a composition for combating made available by mushrooms, which are characterized by

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net is that they (a) have a fungicidal chemical compound with the formula:

N-N

wherein R is the group -COX, -CH (OH) X or -C (R ³ ) (OH) X stent, where X is isopropyl or tert-butyl or phenyl, which is optionally substituted by one or more halogen atoms , R ^{3 stands} for alkyl with up to 4 carbon atoms, R ^{1 stands} for hydrogen, hydroxyl or alkyl with up to 4 carbon atoms, and R stands for phenyl, which is optionally substituted by one or more halogen atoms or nitro or haloalkyl groups, or contains a salt, an isomer or a metal complex thereof and (b) gibberellic acid or another gibberellin.

Preferred haloalkyl groups are trifluoromethyl groups.

R preferably represents the group -CH (OH) C (CH,) ,. R preferably represents hydrogen or methyl and in particular represents hydrogen. R ³ , if it does not mean hydrogen, preferably represents methyl. R preferably represents phenyl which is substituted by one or two chlorine or fluorine atoms, in particular chlorine atoms. R stands in particular for 4-chlorophenyl, 2-chlorophenyl or 2,4-dichlorophenyl.

Preferred compositions according to the invention are those in which the fungicidal chemical compound is combined with the above general formula the preferred substituent definition as stated in the previous paragraph.

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Particularly preferred compositions contain special substances indicated in Table I and in particular compound no. 1.

Table I.

Connection no.

Structural formula - -

N-N-

CH-CH (OH) C (CH ₃ )

Cl
Isomer A

Ν —Ν

H-CH (OH) C (CH ₃ )

Isomer B

(Isomer of Compound No. 1)

N-N-

CH-CH (OH) C (CH ₃ )

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Table I continued N -Ν CH-CH (OH) C (CH ₃ ) ₃

Cl

- N CH-CH (OH) C (CH ₃ ) ₃

N — Ν — CH-CH (OH) C (CH ₃ ) ₃ CH «,

ClK MCl

Ν — N CH-CH (OH) C (CH,),

Cl

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Table I continued

N-N CH-CH (OH) C (CH.

I CH "

Cl

Ν — N CH-CH (OK) C (CH ₃ )

CH,

N - N CH-CH (OHC (CH ₃ )

Ν — N CH-CH (OH) C (CH-,),

<y ^CH 2

NN CH-CH (OH) C (CH ₇ ),

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S6S0 / Z.08608

( ^E ED) D (BO) ED-H N-N

^Z ( ^C HD) D (EO) HD-BD — Ν — Ν

^C HD ID (HO) HD-HD-

—Ν — Ν

'HD

^€ ( ^e HD) D (EO) ED-HD NN

Stm2q.asq.a0j

44

Continued Table I.

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_N CH-CH (OH) C (CH, J,

ι 3 3

CH.

CF.

N-N CH-CH (OH) C

I.
CH-,

Cl

N-N CH-C (OH) C (CH, J,

/. j 3 3

. 2

Ν— Ν CH-C (OHJ

CH ₀

Cl

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Table I continued

Ν — N CH-CH (OH) CH (CE-),

I ^{3 2}

CH,

Cl

Ν - Ν - CH-CH (OH) CH (CH ₃ ) ₂

CH.

Ν — Ν CH-CO

CH-CH.

Ν-Ν CH-CO-C 'V P

I.
CH-CH.

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Table I continued

Ν —Ν CH-CO-C (CH,),

^{3 3}

These substances, their manufacture and their use, for example as fungicides and for regulating plant growth are described in GB-PA »en 31 650/76, 34 590/76, 42 667/76 and 5139/77.

The compounds of the general formula:

N - N-

: h-ch (oh) x

CH \

or their salts thereof can be prepared in such a way that a compound of the general formula II:

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wherein R _{1 is} optionally substituted benzyl and X is as defined above, or a salt thereof is reduced. Suitable reducing agents are, for example, sodium borohydride or lithium aluminum hydride. If desired, a catalytic hydrogenation can be carried out with a suitable metal catalyst. If the compound of general formula II is a sterically hindered ketone, then a Grignard reagent, for example a butyl magnesium halide (for example the bromide or iodide), can be used as the reducing agent.

The reduction can be carried out in such a way that the starting materials in a solvent such as diethyl ether or Tetrahydrofuran (when reducing with lithium aluminum hydride) or with water (when reducing with sodium borohydride). The reaction temperature depends on the starting materials and the solvent. In general, the reaction mixture will heated to reflux. After the reaction, the product can be acidified by extraction into a suitable solvent be isolated with dilute mineral acid. After the solvent has been removed in vacuo, the product can be removed from a suitable Solvent are crystallized.

The compounds of the general formula I in which R 1 is alkyl, or the salts thereof, can be prepared in this manner that a compound of general formula II or a salt thereof is mixed with a suitable Grignard reagent, e.g. an alkyl magnesium halide such as methyl magnesium bromide or

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-iodide. This reaction can be carried out according to known methods be performed.

The starting compound of the general formula II can be prepared in such a way that 1,2,4-triazole or a salt of which with an oc-halo ketone of the general formula III:

0
R ₀ C-CH-X

^ ι

^R 1

in which X is halogen, preferably bromine or chlorine, and R ₁ and R _{2 have} the meanings given above. This process can be carried out by heating the starting materials together in the absence of a solvent or diluent. However, it is preferably carried out in the presence of a solvent.

Suitable solvents are solvents free of hydroxyl groups, such as acetonitrile, dimethylformamide, dimethyl sulfoxide, suIfolan and tetrahydrofuran. In certain cases, solvents with hydroxyl groups such as methanol and ethanol can also be used if the presence of the hydroxyl groups does not interfere with the reaction. The process can be carried out in the presence of a base, e.g. of sodium hydride, sodium ethoxide, excess triazole or an alkali metal carbonate (e.g. potassium carbonate) will. The reaction temperature depends on the selection of the starting materials, the solvent and the base. In general however, the reaction mixture is refluxed. The process generally consists of the starting materials dissolved in a solvent and then the product isolated by removing the reaction solvent in vacuo. Unreacted triazole can be removed by extracting the product with a suitable solvent, which then

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is washed with water. A crystallization or another Cleaning can be done if desired.

The α-haloketones can be prepared by known methods will.

The compound of the general formula II can also be prepared in such a way that a compound of the general formula IV:

Ν — N-CH, -C-X-

² Il ²

wherein X has the above meaning, alkenylated, alkynylated or aralkylated. Further details of this reaction can be found e.g. in DT-OS 2 610 022, to which reference is expressly made.

The preparation of compound no. 1 in Table I is to be described in more detail below as an example.

1-t-Butyl-2- (1,2,4-triazol-1-yl) -2-p -chlorobenzylethanol (compound 1):

Stage I: 1,2,4-triazole (33.4 g) and sodium ethoxide [from sodium (11.6 g) and ethanol (250 ml)] were refluxed for 1 hour. To this solution was added bromopinacolone (87 g) at reflux temperature and heating was continued for 2 hours. The mixture was then cooled to ambient temperature, filtered to remove the precipitated sodium bromide and the Solvent was removed in vacuo. The residue was extracted with chloroform (100 ml). The solvent was

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water (4 × 15 ml), dried (sodium sulfate) and filtered. Petroleum ether (50 ml; b.p. 60 to 80 ° C) was added and the solution was concentrated, whereby oc ~ 1,2,4-triazol-4-yl-pinacolon, Mp 176 ° C. Further concentration of the solution gave α-1,2,4-triazol-1-yl-pinacolone, melting point 63 to 65.degree.

Step II: a-1,2,4-triazol-1-yl-pinacolone (3.3 g) in dimethylformamide (20 ml) was added dropwise to a solution of sodium hydride (0.48 g; 100 #) in dimethylformamide (10 ml) at room temperature with stirring. After stirring for 2 hours, p-chlorobenzyl chloride (3.2 g) in dimethylformamide (2 to 3 ml) was added dropwise and the reaction mixture was kept at 5 to 10 ^° C. for 2 hours. The solvent was removed in vacuo and V / water was added to the residue. The aqueous solution was extracted with methylene chloride. The organic layer was washed with water and dried (magnesium sulfate). The solvent was removed. Crystallization of the yellow solid gave ap-chlorobenzyl-ai ^^ - triazol-i-yl-pinacolone, melting point 122 to 123 ° C., as a white crystalline solid.

Step III: A solution of the product (2.0 g) from Step II in methanol (20 ml) was added portionwise with sodium borohydride (0.26 g) treated. The reaction mixture was then refluxed for 1 hour. The solvent was removed in vacuo and hydrochloric acid (1N; 40 ml) was added to the residue. The white precipitate was filtered off, washed with water, dried and crystallized from aqueous ethanol, whereby the compound mentioned as a white crystalline solid, mp 162 to 164 ° C.

The fungicidal substances Nos. 23 and 24 and other compounds of this type can be prepared in the manner that one 1,2,4-triazole or a salt thereof with the corresponding cc-halo ketone implemented according to a known literature process. Consequently

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you can, for example, 1,2,4-triazole with an oc-halo ketone of the general Formula II:

Q-CH-COX

I.
CH

(ID

where Q is halogen (preferably bromine or chlorine) and X,

1 2
R and R have the above meanings.

This process can in some cases be carried out in such a way that only the starting materials are combined heated in the absence of a solvent or diluent. However, it is preferably in the presence of a solvent worked.

Suitable solvents are hydroxyl group-free solvents such as acetonitrile (which is preferred), dimethylformamide, dimethyl sulfoxide, SuIfolan and tetrahydrofuran. Containing hydroxyl groups Solvents (e.g. methanol and ethanol) can be used in certain cases when the presence of hydroxyl groups does not interfere with the progress of the reaction.

The process can also be carried out in the presence of a base, but is preferably carried out in the presence of excess Triazole worked to remove HX released from the reaction. Other suitable bases are, for example, sodium hydride (but not if a solvent containing hydroxyl groups or diluent is used), alkali metal

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bonates (such as potassium carbonate) and alkali metal hydroxides (such as potassium hydroxide). The reaction temperature depends on the selection of the starting materials, the solvent and the base. In general the reaction mixture is heated to reflux.

In the process one proceeds in general so that one dissolves the starting materials in a solvent and after taking place Reaction, the product is isolated by removing the reaction solvent in vacuo. Unreacted triazole will removed by extraction with a suitable solvent, which is then washed with water. A crystallization or other cleaning can then be performed if desired.

The α-haloketone starting material can be prepared according to known literature procedures getting produced.

The compounds can also be prepared in such a way that a corresponding compound of the general formula III:

NN-CH ₂ -COX

(III)

where X has the above meaning, aralkylates, for example, first with an alkali metal hydride (e.g. sodium hydride) in a suitable solvent (such as dimethylformamide or tetrahydrofuran) to the alkali metal salt, which then e.g. with an α-alkyl aralkyl halide, e.g. a bromide (das is preferred) or a chloride.

In this process, one proceeds in general in such a way that the compound of the general formula III is in the solvent dissolves and an equivalent amount of the alkali metal hydride

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puts. After the reaction has taken place, the cc-alkylaralkyl halide is added drop by drop. After implementation, the pro The product can be isolated by pouring the reaction mixture into water and recrystallizing the solid from a suitable solvent or by purifying the resulting oil by column chromatography or another suitable technique.

The fungicidal chemical contemplated according to the invention Compounds contain chiral centers. The compounds are generally obtained in the form of racemic mixtures or diastereoisomeric mixtures. However, if desired, these mixtures can be converted into the individual isomers by known methods be separated. The present invention is intended to encompass not only the racemic and the diastereolomeric mixtures, but also other mixtures of the isomers as well as the individual isolated isomers as fungicidal chemical compounds which are suitable for the compositions and methods according to the invention.

Suitable salts are the salts with inorganic or organic acids. For example, the salts with hydrochloric acid, nitric acid, sulfuric acid, acetic acid and oxalic acid can be used as fungicidal chemical compounds can be used in the compositions of the invention.

Suitable metal complexes are, for example, those containing copper, Contain zinc, manganese or iron. They preferably have the general formula:

R ¹ R ^Z

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where R, R ₁ and R _{2 have} the above meanings, M stands for a metal, A stands for an anion (for example a chloride, bromide, iodide, nitrate >> sulfate or phosphate anion), η den Is 2 or 4 and y is 0 or an integer from 1 to 12.

The salts and metal complexes of the compounds of the general Formula I can be prepared in a known manner. For example, the complexes can be prepared in such a way that the non-complexed compound with a metal salt in a suitable Reacts solvent.

The fungicidal chemical compounds used according to the invention are effective fungicides, especially against the following diseases:

Piricularia oryzae on rice,

Puccinia recondita, Puccinia striiformis and other rust diseases on wheat, Puccinia horde !, Puccinia striiformis and other rust diseases on barley and rust diseases on others Useful plants, e.g. coffee plants, apple trees, plants and ornamental plants,

Plasmopara viticola on vines

Erysiphe graminis (powdery mildew) on barley and wheat and other powdery mildew diseases on various crops, such as Sphaerotheca fuliginea on pumpkin plants (e.g. cucumbers), Podosphaera leucotricha on apple trees and Uncinula necator Vines,

Botrytis cinerea (gray mold) on tomato plants, strawberry plants, Vines and other useful plants, Phytophthora infestans (Brand) on tomato plants, Venturia inaequalis (scab) on apple trees, Rhynchosporium secalis.

The fungicidal substances also have a wide range of activity against fungi in vitro. They are also available as a sanen treatment

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agents against Fusarium spp., Septoria spp., Tilletia spp., Ustilago spp., Helminthosporium spp. and Pyrenophora spp. on Cereal crops active.

The fungicidal chemical compounds contemplated by the present invention also have plant growth regulators Activities.

The plant growth-regulating effects of the invention Considered substances show up e.g. as stunting or crippling effects on vegetative growth of monocotyledonous and dicotyledonous plants. Such stunting or crippling can occur, for example, in cereal crops, Soybean plants, be useful where a reduction in the growth of the stem reduces the risk of it being turned over. Substances, that induce stunting or crippling can also be useful to stimulate the growth of sugar in the cane sugar plants to wither during harvest. Stunting peanut plants can make harvesting easier. A decrease the growth of grasses can make the maintenance of grass lawns easier.

Other effects that regulate plant growth and are brought about by these substances are, for example, a change in the leaf angle and the promotion of the forcing of shoots in monocot plants. The first-mentioned effect can be useful, for example, to change the leaf orientation of, for example, potato plants, as a result of which more light can hit the useful plants and an increase in photosynthesis and the tuber weight is induced. By increasing the sprouting of the shoots of monocotyledonous crops (eg rice), the number of flowering shoots per unit area can be increased, whereby the total grain yield of such crops is increased. The treatment of the plants with the chemical

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Seeing compounds can cause the leaves to be darker green Develop color.

The above-described plant growth-regulating effects of the active fungicidal chemical compounds as desired, to the extent desired, controlled, e.g., compensated (i.e. reduced or modified) by using the compositions according to the invention or by the plant or seed treatment processes according to the invention are used according to the invention.

The substances which can be used as component (b) of the compositions according to the invention are the substances which are generally known as gibberellic acid and gibberellins. These compounds are well known for promoting plant growth. There is a detailed documentation and description about this. Some of these compounds are listed in the Merck Index (9th edition) under the headings "Gibberellic acid ' ¹ and" Gibberellins "(see pages 4250 and 4251 of the 9th edition) GA, is known) and the other particularly useful and commercially available gibberellins GA ^ and GA ~ (the latter are usually commercially available as a mixture) are indicated below. It should be noted that the compositions of the invention are a salt or a derivative of gibberellic acid or another gibberellin Mixtures of gibberellins are also considered as constituents of the compositions according to the invention.

Gibberellic acid:

CH ₃ COOH 809807/0595

IQ

(GB-PS 783 611)

(Gibberellic acid is also known as Gibberellin A, or GA ^),

Gibberellin A ₇ (GA ₇ ) (7-deoxygibberellic acid):

CH ₃ COOH

(GB-PS 914 893)

Gibberellin A ^ (GA ^)

-CH.

CH ₃ COOH

The compositions of the invention can vary in proportions of the active fungicidal compound and the gibberellic acid or the other gibberellin, but will a weight ratio of 1: 5 to 1: 50 gibberellic acid or other gibberellin to fungicidal compound preferred. A ratio of 1: 5 v / δ is very particularly preferred.

The compositions of the invention can in addition to the common excipients and fillers used for pesticides Compositions have been developed containing an inorganic or organic acid to increase the activity of the gibberellin

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acid or the other gibberellin. Suitable acids are, for example, phosphoric acid and hydrochloric acid, as well as various Sulfonic, hydroxy, carboxylic and dicarboxylic acids. citric acid and tartaric acid are preferred organic acids. The amount by weight of acid in the compositions can be up to 10 times Be the amount by weight of the fungicidal chemical compound.

The compositions can also contain alkali metal, alkaline earth metal, Metal or ammonium salts contain the phytotoxicity or the growth-regulating effects of the fungicidal chemical compound to reduce and / or the effect of gibberellic acid or the other gibberellin (or the derivative or salt thereof). Zinc chloride and alkali metal, Alkaline earth metal or ammonium salts of mineral acids, especially the nitrates, phosphates, sulfates, chlorides and carbonates of sodium, potassium, ammonium, magnesium and calcium are preferred.

The compositions of the invention can be in the form of dustable Powders are present in which the active ingredients are mixed with a solid diluent or carrier. Suitable Diluents or carriers are e.g. kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesium oxide, Puller's earth, plaster of paris, Hewitt's earth, diatoaene and china clay. Compositions for treating seeds can e.g. contain an agent that helps the composition adhere to the seed, e.g., a mineral oil.

The compositions can also be in the form of dispersible Powders or granules are present which, in addition to the active ingredient, contain a wetting agent in order to facilitate the dispersion of powder or granules in liquids. Such powders or granules can also contain fillers and suspending agents and the like included.

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The compositions can also be in the form of liquid preparations that contain the active ingredients. Such liquid preparations for the purposes of the invention are generally Solutions, aqueous dispersions or emulsions containing the active ingredients in the presence of one or more wetting agents, i.e. surfactants, dispersants, emulsifiers or suspending agents. The amount of weight such surfactants can contain up to 10 times the amount by weight of the fungicidal chemical compound in the compositions according to the invention.

Humectants, dispersants and emulsifiers can be of the cationic, anionic or nonionic types be. Suitable agents of the cationic type are, for example, quaternary ammonium compounds such as cetyltrimethylammonium bromide. Suitable agents of the anionic type are, for example, soaps, salts of aliphatic monoesters or sulfuric acid, e.g. Sodium lauryl sulfate, salts of sulfonated aromatic compounds, such as sodium dodecylbenzenesulfonate, sodium, calcium or ammonium lignosulfonates, butylnaphthalene sulfonate and mixtures from the sodium salts of diisopropyl and triisopropyl naphthalene and, for example, condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkylphenols such as octylphenol, nonylphenol and Octylcresol.

Other suitable non-ionic agents are the half esters derived from long chain fatty acids and hexitanhydrides, the condensation products of these half esters with ethylene oxide and the lecithins. Suitable suspending agents are, for example, hydrophilic Colloids, such as polyvinylpyrrolidone and sodium carboxymethyl cellulose, and vegetable gums such as acacia and tragacanth gum.

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The aqueous solutions, dispersions or enulsions can be prepared in such a way that the active ingredients in one organic solvents, which may contain one or more moisturizing, dispersing or emulsifying agents, dissolves, dispersed or emulsified. Suitable organic solvents are dimethylformamide, ethylene dichloride, isopropyl alcohol, propylene glycol and other glycols, diacetone alcohol, toluene, kerosene, Methylnaphthalene, xylenes and trichlorethylene, N-methyl-2-pyrrolidone and tetrahydrofurfuryl alcohol (THFA).

The compositions used as spray preparations should, can also be in the form of aerosols, the preparation in a container under pressure in the presence a propellant such as fluorotrichloromethane or dichlorodifluoromethane, is held.

By adding suitable additives, for example to improve the distribution, adhesion and rain resistance of the treated To improve surfaces, the different compositions can adapt to the different purposes for which they are intended to be better adapted.

The compositions can also be mixed with fertilizers be formulated. A preferred composition of this type contains granules of a fertilizer which contain one according to the invention contemplated connection included. The fertilizer material may, for example, contain nitrogen or phosphate Be substance.

The compositions to be used in the form of aqueous dispersions or emulsions are generally used in Supplied in the form of a concentrate, which contains a high proportion of the active ingredients. The concentrate is then pre-mixed with water diluted after use.

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The concentrates often have to be storage-stable over extended periods of time be. After such storage, they should be able to be diluted with water in order to obtain aqueous preparations to form that remain homogeneous over a sufficient period of time that they are applied by conventional spraying equipment can be.

The concentrates may suitably contain up to 50 and generally 10 to 20 % by weight of active ingredient.

If they have been diluted to form aqueous preparations, then such preparations can contain varying amounts of the active ingredient depending on the intended use. For example, aqueous preparations can be used which contain 0.002 to 0.2% by weight, preferably 0.01 to 0.05% by weight , of active ingredient.

It should be noted that the compositions according to the invention in addition to one or more active compounds according to the invention, one or more substances with a biological one Activity, e.g., an insecticidal, fungicidal or bactericidal activity.

In particular, if seeds are to be treated, then it can be equivalent or even more beneficial to use the fungicidal Substance either before, but preferably after, the application of the gibberellic acid or the other gibberellin to the seed to raise. Also a simultaneous application to the seeds of both substances in the form of a composition according to the invention may happen. A seed treatment process and a device suitable for this can therefore be used, wherein in successive stages or simultaneously the aforementioned substances on the seeds as "treatment" or impregnation be applied. The substances can either

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individually or together with a solid or liquid carrier, suitable for this purpose can be mixed. Water or polar liquids of organic character are preferred liquid carriers, in particular dimethylformamide, N-methyl-2-pyrrolidone, Tetrahydrofurfuryl alcohols and glycols for their ability to penetrate the seed. Non-aromatic Hydrocarbons such as isoparaffins can also be used, but low boiling dichloromethane can also be used and acetone can be used. Encapsulated preparations in which one substance or both substances are encapsulated Shape can also be used.

The invention also provides a method for controlling fungal diseases of plants and seeds (in particular of Powder meltau) made available, which is characterized in that the plants or seeds (especially cereal plants) treated with a composition as defined above or that components (a) and (b) of such Composition sequentially applies in any order.

The invention is illustrated in the examples. Percentages are based on weight. Describe examples 1, 2 and 3 Compositions according to the invention and their use for combating fungal diseases. Describe Examples 4-16 compositions according to the invention.

example 1

Barley seeds of the "Proctor" variety were germinated in soil that had been sprayed with a liquid preparation which 250 or 500 ppm of the fungicidal compound # 25 of Table I contained. At the same time the earth became 1.5 and 10 ppm gibberellic acid treated. The plants appeared three

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Days after sowing the seed. After four more days it was their height measured in mm.

The emerged plants were grown in a green room in which the daytime temperature was 23.9 ° C and the relative Humidity was kept at 6O? 6 and the night temperature held at 19.4 ° C and the relative humidity at 95% became. The day length was 16 hours.

The measured values given in the table below for the Height represent the mean of 24 plants (3 repeated pots per treatment, with 8 plants growing in each pot The plant growth reported for the sown seed was practically $ 1005.

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Table II

Fungicidal compound-
(see Table I regarding
of identification. Application rate of the
fungicidal compound
ppm. . Height of the plants in mm per up
rate of delivery of gibberellin
acid inpp.m 5 1 0 D. 500
250 10 62
83 47
64.5 50
62.5 Gibberellic acid (alone - 65
79 150 124 - Water (alone) 144 ; 129
139 in the greenhouse
untreated sand bed - : - - 129 -

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Example 2

Compounds No. 1 and 26 of Table I were nit one Concentration of 25% in powdered seed treatment preparations incorporated (these contained talc as filler and 255 Oodecylbenzene as a glue to support the adhesion to the seeds) .

Powdered preparations containing 10% and 25 # gibberellin and a mixture of gibberellin A ^ and gibberellin Ay were also made (these also contained talc and dodecylbenzene).

At the same time, 50 g quantities of wheat sans (Maris variety Butler) and barley seeds (Proctor variety) in glass jars with a Capacity of 120 ml weighed out to form individual batches of the sanen.

In these vessels (with the exception of those that were not treated at all or to which only fungicides No. 1 and 26 were given) the corresponding weights of the fungicidal preparation and the gibberellin preparation (GA, or GA ^ / ") given that concentrations of 250 or 500 ppm of the fungicidal compound and 10, 50 and 100 ppa gibberellin were obtained. The bottles were then shaken vigorously and then rotated mechanically for 20 minutes.

Two centimeters by ^five of each batch of seed was then shaken onto the surface of compost in 60 meter square plastic pots that had been filled to 60% capacity with John Innes # 1 pot compost. The surface of the Koapost had been strengthened and leveled. The sane was then covered with a layer of the same compost to a depth of 2 cm.

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covers. The surface was strengthened again by pressure. There were three repetitions per treatment and per crop carried out.

The pots were lightly watered from above and placed in a glass house at 16 ° C. Every 14 days they were given liquid fertilizer offset. The plants were grown 10 days after sowing the seed is inoculated by shaking spore-infested plants over the grouped pots.

The disease for barley was Erysiphe graminis f. Sp. hordei. The disease for wheat was Erysiphe graminis f. Sp. tritici.

The heights of the emerged plants were in cm 11, 16 and Measured 36 days after sowing. The average heights per pot were calculated. The results of this experiment are in given in the tables below. The values represent the mean values of three repetitions.

The disease was assessed using a scale of 0, 1, 2, 3 and 4 with the following meaning:

0 means the presence of 61 to 100% disease

1 means the presence of 26 to 60% disease

2 means the presence of 6 to 25% disease

3 means the presence of 0 to 5% disease

4 means no disease.

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Table III

Barley seedling plants

Connection no . 26 at 250 ppm 36 valuation
the
illness Compound No. 1 at 250 ppm 16 after valuation
the sick
Ness Concentration of
GAj (ppm) Height (cm) according to
Days 10.6 4th Height (cm)
Days 7.5 36 4th 10 11 16 12.6 4th 11 9.5 6.3 4th 50 5.6 8.3 ' 14.6 4th 4.9 12.5 10.0 4th 100 6.8 10.5 10.3 4th 6.3 5.5 12.0 4th fungicide only 8.2 11.7 24.3 1 7.0 13.5 5.0 1 untreated. 3.9 5.8 3.3 24.3 9.3 13.5 9.3

Table IV

Barley seedling plants

en α> σι

Compound No. 1 at 500 ppm 36 valuation
the
illness GA 16 2 alone valuation
the
Illness Concentration of
GA ^ (ppm) Height (cm) according to
Days 7.0 4th Height (cm)
Days 15.7 after O 10 11 16 7.3 4th 11 15.3 36 0 50 4.1 7.0 12.0 4th 9.3 19.5 23 O 100 5.1 9.3 4.3 4th 9.6 - 24.3 - fungicide only 7.7 12.5 24.3 1 11.7 13.5 23 1 untreated 3.1 4.8 - - 9.3 13.5 9.3 24.3

TDbol3 ο V

Connection no 36 at 2!) 0 ppm valuation
the sick
Ness Connection N L «, 1 böi 2 ') 0 i> i> m valuation
the
Cranes it Concentration of
GA ₃ (ppm) - - Ilöho (cm)
Days after - 10 Height (cm) according to
Days - - 11 16 36 4th 50 11 16 13th 4th 3.1 9.0 - 4th 100 3.7 7.5 6th 4th 4.9 13.0 13.83 4th fungicide only 4.9 9.7 27 66 0 5.7 15.6 18.66 0 untreated 5.5 11.3 83 1.5 4.7 9.18 1.8 6.3 33 7.7 16.5 27.33 7.7 16.5

K) CjO

- Jk " -

Table VI

Wheat seedling plants

Link ] 16 \ $ t. 1 at 500 ppm valuation
the sick
Ness height GA ₃ alone valuation
the
Illness: Concentration of
GA ₃ (ppm) Height (cn)
Days 6.5 after - 11 (cm)
Days after O 10 il 8.6 36 - 9.5 16 36 O 50 2.1 11.0 - 4th 9.8 19.0 31.0 O 100 3.7 3.5
16.5 - 4th
O 10.6 19.0 31.33 O fungicide only
untreated 4.7 12.3 7.7 19.2 30.66 1.1
7.7 5.6
27.33 16.5 27.33

-Jl * -

Table VII

Barley seedlings

ta a »

cn cn

Connection no. 26 at 250 ppm 36 valuation
the sick
Ness link number 1 36 at 250 ppm Concentration of
GA3 / 7 (ppm) Height (cm) according to
Days 11 4th Height (cm) according to
Days - valuation
the sick
Ness 10 11 16 10.6 4th 11 16 9.0 - 50 5.7 10 14.0 4th 4.1 7.7 11.0 4th 100 4.9 7.8 10.3 4th 6.0 10.5 5.0 4th fungicide only 7.0 12.0 24.3 1 8.0 12.3 24.3 4th untreated 3.9 5.8 3.3 5.5 1 9.3 13.5 9.3 13.5

K) OJ

ho

CD

Table VIII

Barley seedling plants

Compound No. 1 at 500 ppm valuation
the
illness ^GA 4/7 ^alone valuation
the
Illness Concentration of
GA ₂ ^ ₇ (ppm)> Height (cm) according to
Days 4th
4th
4th
1 Height (cm) according to
Days - 1
1
1
1 IO
50
100
fungicide only
untreated. 11 16 36 11 16 36 3.7 6.3
5.8 9.2 7
6.0 9.8 9
3.1 4.8 4.3
9.3 13.5 24.3 8.6 14.5 22.3
9.3 15.8 23.3
11.5 16.5 22.3
9.3 13.5 24.3

Table IX

Wheat seedling plants

Connection no. 36 valuation
the sick
Ness Compound No. 1 at 250 ppm (cm) after 11 16 36 valuation
the sick
Ness . 26 at 250 ppm - - height
Ti, 5.1 11.2 12.0 4th Concentration'
from GA ^ ₇ (ppm) Height (cm) according to 12.33 4th 7.1 13.8 17.33 4th 10 lay 14.66 4th 7.8 15.3 17.0 4th 50 11 16 6.83 4th 1.5 4.7 9.18 4th 100 3.6 8.8 27.33 O 7.7 16.5 27.33 O fungicide only 4.1 9.0 unbohanddlt 4.6 12.5 1.8 6.3 7.7 16.5

Table X

Wheat seedling plants

CD O CD OO O

Compound No. 1 at 500 ppm 36 valuation
the sick
Ness ^GA 4/7 alone Height (cm) according to
.Days 36 valuation
the sick
Ness Concentration of
^GA 4/7 (PP ^m ) Height (cm) according to
Days - - 11 16 30.66 O 10 11 16 13.5 4th 8.6 17.0 31.0 O 50 3.9 8.8 13.83 4th 9.4 18.7 31.0 O 100 4.6 11.2 5.6 4th 9.8 18.7 - - fungicide only 5.8 11.3 27.33 O - 27.33 O untreated 1.1 3.5 7.7 16.5 7.7 16.5

273U26

Example 3

A. In this experiment, various preparations of the fungicidal compounds of Table I were made and with an active ingredient rate of 250, 100 and 50 ppm on wheat seeds (Maris Butler variety) and applied to barley sans (Ilidas variety). In each case, it was previously confirmed that the seed had a germination rate of 90%.

The exact nature of the individual treatments is summarized in the table below.

809807/0595

Table XI

treatment
No.
j * Application rate of the
fungicidal compound Components of the preparation 1
2
3 250
100
50 Compound No. 1 (10? S) of Table I.
GA ₃ (2%)
Dodecylbenz ol
Talk 4th
5
6th 250
100
50 v / ie for treatments 1 to 3,
but citric acid (40? 7th
θ
9 250
100
50 like bo1 den Dohandlun ^ en 1 am 3,
but also tartaric acid (hO%)

-X-

Table XI continued

10
11
12th 250
100
50 as with treatments 1 to 3,
but also EDTA disodium
salt
(EDTA = ethylenediaminetetraacetic
acid) 13th
14th
15th 250
100
50 as with treatments 1 to 3 »
but also succinic acid
(Where) 16
17th
18th 250
100
50 as with treatments 1 to 3,
but in addition filler and
additionally Cirrasol ALNWF
(2%)

Continuation of Table XI

CO OO O

19th
20th
21 250 /
100
50 as with treatments 1 to 3,
however, in addition to filler and too
also Cirrasol ALNWF
(4%) 22nd
23
24 250
100
50 as with treatments 1 to 3,
However, in addition to filler and too
also Cirrasol ALNWF
(1O%) 25th
26th
27 250
100
50 Compound No. -1 (20%) of Table I.
GA ₃ (All
Triton XlOO (2%)
Propylol glycol

OO O co co

Table XI continued

250 Jfer binding no.11 (20%) from Table.e_I 28 100 GA ₃ (4%) 29 50 Dimethylformamide _ 30th 250 Compound # 11 (20%) from Table I. 31 1OO GA ₃ (-4% * .32 50 Triton XlOO (2%) 33 Propylene glycol 250 Compound "No. _1 of Table I as ! 34 100 para-toluene sulfonate salt i 35 50 Dodecylbjahzbl j 36 TaBc ^s - '^ ^r

Table XI continued

oo σ

ο cn «ο σι

37 mm untreated control plants that
by mass inoculation with the
Disease had been infected 38 untreated control plants that
were naturally infected *

* i.e. plants that have been exposed to ambient meltau in the greenhouse

CO K)

Each formulation was applied to 50 g samples of clean seeds at rates yielding 250, 100 and 50 ppm fungicide, respectively. This was achieved by weighing the appropriate amount of the preparation and adding it to 50 g seeds was placed in a 227 g jar. This was immediately followed by rapid shaking for 1 minute and then on a mechanical rotator for 20 minutes moved.

12 seeds were placed equally spaced in three pots with a diameter of 14 cm per treatment. The pots were kept in a greenhouse at 15 to 20 ° C and watered from above. 7 days after the sowing, the eiEOor came Plants counted. The height of the bracts of all the seedlings was determined 12 days after sowing. The pots were after full development of the bracts randomly arranged on the bench.

The barley plants were mass inoculated by placing spore infected plants over the pots 16 arranged in groups Days after sowing were shaken at a point where the control samples had one bract and 2 fully expanded leaves had. Plant height was measured 18 days after sowing.

The wheat plants were mass inoculated 18 days after sowing (the control plants had one bract and two fully expanded leaves). The heights were 20 days after sowing certainly.

The diseases with which the barley and the wheat were infected were the same as in Example 2.

Meltau was determined on the wheat plants in such a way that leaves from the third lower leaf from the youngest leaf,

809807/0595

which showed a level of 7 * were taken as a sample. 10 such sheets are taken as a sample per treatment. The percentage coverage of the adaxial surface by meltau was determined.

Not much actively growing and sporulating HeItau appeared on the barley, despite its inoculation of hatred on two occasions and continuous exposure to ambient melt dew in the greenhouse. After 5 weeks, however, a meltau attack could be detected (see Results section for details).

* on the Feekes scale

809807/0595

Table XII

Wheat seedling plants - coming up

0 » (O

action no. percentage
Come up Treatment no. percentage
Come up 1 38.0 13th 44.1 2 67.4 14th 40.5 3 66.8 15th 61.4 4th 69.5 16 47.1 5 78.2 17th 46.6 6th 66.8 18th . 49.4 7th 72.8 19th 59.0 8th 73.4 20th 67.1 9 66.8 21 53.7 10 43.8 22nd 47.1 11 73.4 23 86.4 12th 64.1 24 83.9

K) U)

Continuation of Table XII

oo o <o CP O

e w «0 cn

25th 80.7 32 66.8 26th 92.3 33 76.5 27 69.7 34 41.7 28 67.5 35 46.9 29 72.6 36 36.5 30th 77.0 37 94.5 31 58.7 38 99.1

K) CO

.C-

■ P- CD

Barley seedling plants - coming up

2734A26

None of treatments 1 through 36 significantly decreased the rise.

Table XIII

Examination after days 14th 28 Treatment ur. 7th 167 40 39 4th 617 140 40 113 715 88 41 103 684 144 42 161 363 72 43 193 5 2 44 - 25th 10 45 - 65 30th 46 -

The above experiments show the effectiveness of the invention Compositions for controlling plant diseases and protecting plants from serious attack, reducing the degree of stunting caused by the special fungicidally active chemical compounds, which they contain is reduced. The results also show that the effects of gibberellin increase through incorporation the acid surprisingly due to the presence of the fun-

809807/0595

gicidal chemical compounds and the other formulation auxiliaries is not attacked or is not diminished. The benefits of incorporating the surfactant "Cirrasol" ALNWF in the compositions according to the invention also evident.

Example 4

This example describes an atomizable powder that can be applied directly to plants or other surfaces. It contains 5 wt -.% Of Compound No. 1 of Table I, 1 wt .- # Gibberella eil ynoic acid and 94 wt .- 4 Talk.?.

Example 5

The ingredients listed below are ground in the specified proportions, creating a powdery mixture is obtained which is easily dispersible in liquids.

Wt%

Compound No. 1 of Table I 45

Gibberellic acid 5

Dispersol T (Dispersol is a trademark) 5 China clay 45

100%

Example 6

A composition in the form of granules that was easily dispersible in a liquid (e.g. v / ater) became prepared in such a way that first the first four of the components listed below with one another in the presence of water were ground and that then sodium acetate was mixed in.

809807/0596

The Geaisch was dried and passed through a sieve with a clear Mesh size of about 0.3 to 0.15 now driven, whereby the desired size of the grains was obtained.

Wt%

Connection ^IJ r. 1 of Table I Gibberellic Acid Dispersol T Calcium Lignosulfonate Ilatriumdodecylbenzenesulfonat Jlatr iumac e tat

Example 7

A composition useful as a seed treatment agent was prepared in such a way that all three ingredients indicated below in the indicated proportions were mixed.

Compound No. 1 of Table I 75

Gibberellic acid 5

Mineral oil 2

China clay 18

10095

Example 9

The following ingredients were mixed together to make a powdered one Seed treatment preparation was obtained.

809807/0595

link No. 1 of the table Gibberellin ^A 3 (GA ₃ ) Talk Example 10

4% 76%.

The substances given below were used in the given proportions mixed, whereby a liquid seed treatment preparation was obtained.

Compound No. 1 of Table I. 20% Gibberellin A ₃ (GA ₃ ) Dimethylformamide 100% Example 11

The following substances are mixed, producing a pulsed modified seed treatment preparation was obtained.

Compound No. 1 of Table I.

Gibberellin A ₃ (GA ₃ ) 2%

Tartaric acid 40%

Filler (talc) 48%.

Example 12

The following substances were mixed with each other in the specified proportions, whereby a liquid composition which was useful as a seed treatment agent.

Compound No. 1 of Table I.

Gibberellin A ₃ (GA ₃ ) 2%

Tartaric acid $ 20

Dimethylformamide $ 485.

809807/0595

273U26

Example 13

The following ingredients Λ / Mixing proportions together, whereby a powdery composition (a) and a liquid preparation (b) are obtained became.

Compound No. 1 of Table I.

Cirrasol ALN-WF 10%

Talc filler Compound no. 1 of Table I <iu> 3

GA ₃ V / i

Cirrasol ALN-W 2C $ Dimethylformamide 595ο Example 14

The following substances were mixed in the specified proportions, whereby a liquid preparation was obtained .

Compound No. 1 of Table I zinc chloride

Dimethylformamide 66/5.

Example 15

A powdery preparation was made by following the given Substances were mixed with one another in the specified amounts.

809807/0595

273U26

Compound No. 1 of Table I zinc chloride

Talc (filler) 2055
1055

6655.

In the following, compositions or substances are explained in more detail, which were defined in the above examples using Viaren names or trademarks:

Dispersol T is a mixture of sodium sulfate and a condensate of formaldehyde with the sodium salt of naphthalenesulfonic acid.

Cirrasol ALN-WX is a non-ionic surfactant that is a condensate of 1 mole of a long-chain (C ₁ / - to C ₁₈ ) aliphatic alcohol with 17 moles of ethylene oxide.

Triton X100 is a surfactant that is the isooctylphenyl ether of Polyethylene Glyko1 is.

809807/0595

Claims (12)

Claims 1. Composition for combating fungi, thereby characterized as being (a) a fungicidal chemical compound having the formula: Ν — Ν CH-R, CH , JP ^R , wherein R stands for the group -COX, -CH (OH) X or -C (R ³ ) (OH) X, where X stands for isopropyl or tert-butyl or phenyl, which is optionally substituted by one or more halogen atoms , R ^{3 stands} for alkyl with up to 4 carbon atoms, R for hydrogen, hydroxyl or alkyl with up to 4 carbon atoms atoms, and R is phenyl, which is optionally substituted by one or more halogen atoms or nitro or haloalkyl groups, or a salt, an isomer or a metal complex thereof and (b) gibberellic acid or another gibberellin. 2. Composition according to claim 1, characterized in that the weight ratio of the substance (a) to substance (b) is 50: 1 to 5: 1. 3. Composition according to claim 1, characterized in that the fungicidal chemical compound is a Compound of the general formula: Ν-Ν CH-CH (OH) C (CH ₃ ) ₃ 809807/0595 2734424 4 · -. ι ρ Άβ-ί »- _— - where Z stands for a chlorine or fluorine atom and η has the value 1 or 2, or a salt, an isomer or a metal complex of which is. 4. Composition according to claim 1 or 2, characterized in that the fungicidal chemical compound a compound of the formula: NN CH-CH (OH) C (CH ₃ ) or a salt, an isomer or a metal complex thereof. 5. Composition according to one of the preceding claims, characterized in that it contains an acidic substance in an amount capable of producing the v / growth-promoting properties of gibberellic acid or des reinforce other gibberellins. 6. Composition according to any one of the preceding claims, characterized in that it is a surface-active Contains agent that is capable of the growth-promoting properties of gibberellic acid or the other Amplify Gibberellins. 7. Composition according to any one of the preceding claims, characterized in that it has a sufficient Amount of a metal salt of a mineral acid that the 809607/0595 growth-promoting effect of gibberellic acid or gibberellin is increased and / or the phytotoxicity und.die plant growth effects The fungicidal chemical compound of the composition can be reduced. 8. Composition according to any one of the preceding claims, characterized in that it is a solid contains inert carrier substance and optionally a mineral oil. 9. Composition according to one of the preceding claims, characterized in that it contains up to 20% by weight of the fungicidal chemical compound. 10. Composition according to one of claims 3 to 6, characterized in that the amounts by weight the acidic substance and the surface active agent up to 10 times the amount by weight of the fungicidal chemical compound are. 11. The composition according to any one of claims 1 to 7 or 9 and 10, characterized in that it dimethylformamide, N-methyl-2-pyrrolidone containing tetrahydrofurfuryl or a ^G lykol or a combination of these compounds as the carrier liquid. 12. Methods of combating fungal diseases, in particular of powder meltau, characterized in that the plants or the seeds, especially grain seeds, with a composition according to one of the preceding claims or with components (a) and (b) of such Composition that are applied sequentially in any order treated. 809807 / 059B