PT93256B - PROCESS FOR THE PREPARATION OF MICROBICIDAL COMPOSITIONS CONTAINING 1,2,4-TRIAZOL DERIVATIVES - Google Patents

Abstract

The present invention relates to a process for the preparation of a combination of the plant microbicide 1- [2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-ylmethyl]- 1H-1,2,4-triazole (= propiconazole) with the plant microbicide 1-{2-[2-chloro-4-(4-chlorophenoxy)-phenyl]-4- methyl-1,3-dioxalan-2-ylmethyl}-1H-1,2,4-triazole, which combination results in increased activity in the control of plant diseases. The microbicidal compositions based on such combinations are especially suitable for the control of diseases in cereals. Said process normally involves including the aforesaid compounds in a weight ratio from 10:1 to 1:10 as active components in said combination.

Description

PROCESS FOR THE PREPARATION OF MICROBICIDE COMPOSITIONS CONTAINING 1,2,4-TRIAZOL DERIVATIVES

LUDWIG MITTERMEIER; WILHELM RUESS

Claim of the right of priority under Article 42 of the Paris Union Convention of 20 March 1883.

DESCRIPTIVE MEMORY

The present invention relates to a process for the preparation of a combination of the plant microbicide 1- / ^- 2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl7-1H-1, 2,4-triazole (= propiconazole), with plant microbicides 1- 2- / ~ 2-chloro-4- (4-chlorophenoxy) -phenyl7-4-methyl-1,3-dioxalan-2-ylmethylJj -1H -1,2,4-triazole, a combination that results in increased activity in the control of plant diseases.

resume

CIBA-GEIGY AG

PROCESS FOR THE PREPARATION OF MICROBICIDE COMPOSITIONS CONTAINING 1,2, 4-TRIAZOL DERIVATIVES

Microbicidal compositions, based on such combinations, are especially suitable for the control of diseases in cereals.

Said process normally consists of including in the said combination, as active components, the aforementioned compounds in a weight ratio of 10: 1 to 1:10.

The present invention relates to microbicidal mixtures, which have a synergistically enhanced activity against plant diseases, and processes for the use of such mixtures, especially in cereals.

The invention relates, in particular, to the control and prevention of diseases in the culture of channels.

A mixture that has been unpredictably favorable is a combination of component I) of the active ingredient l- / ^- 2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl7-1H- 1,2,4-triazole (= propiconazole) of formula I

Cl.C3H7

Ç1 --- ^zn \ V ⁴ Λ _z --C — ch ₂ -n _x (I), or a salt thereof, with component II) of the active ingredient 1- [2- / 2-chloro-4- ( 4-chlorophenoxy) -phenyl7-4-methyl-1,3-dioxolan-2-ylmethyl ^ -1H-1,2,4-triazole of formula II or a salt thereof.

The compound of formula I is described in British Patent No. 1,522,657.

compound of formula II is described, as a fungicidal active substance, in British Patent Application No. 2,098,607. The activity of these two triazole derivatives is based, especially, on the inhibition of biosynthesis, of ergosterol, on the development cycle of phytopathogenic fungi.

The mentioned salts of compounds I and II can be prepared by reacting the respective base with acids.

Of the acids, which are suitable, the following may be mentioned: hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodic acid, as well as sulfuric acid, phosphoric acid, nitric acid, and organic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid , oxalic acid, formic acid, tenzenesulfonic acid, ja-toluenesulfonic acid, methanesulfonic acid, salicylic acid, g-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid or 1,2 -naphthalenedisulfonic.

The term salts also includes the metal complexes of the basic components I or II. These complexes consist of the fundamental organic molecule and a salt of an inorganic or organic metal, for example,

halides, nitrates, sulfates, phosphates, acetates, trifluoracetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates, etc., of the elements of the second main group, such as calcium, magnesium, and the third and fourth main groups , such as aluminum, tin or lead, and from the first to the eighth subsidiary groups, such as chromium, manganese, iron, cobalt, nickel, copper, zzinc, etc. The members of the subsidiary group of the fourth period are preferred. Metals can be of any of several valences. The metal complexes can be mono- or poly-nuclear, that is, they can contain one or more organic molecular components, such as ligands.

Surprisingly, however, it was found that the combination of active ingredients I and II translates into a substantial, absolutely unpredictable increase in activity against fungi generated by seed, air and soil. The increase in activity, achieved by the combination according to the invention, is decisively higher than the activity to be predicted, adding, together, the activities of the two components, individually.

The present invention concerns not only mixtures of components I and II, but also the use of individual components I and II, formulated as microbicidal compositions, in direct succession.

The favorable mixing ratios of the two active ingredients are: from 10: 1 to 1:10, especially from 5: 1 to 1: 5, and more especially from 4: 1 to 1: 4. Other mixing ratios are: I: II = = 2: 3, 1: 3, 1: 2, 2: 5, 1: 1, 5: 2, 3: 1, 2: 1, 3: 2 and 2.8 :1.

The mixing ratio of

I: II from 3: 1 to 3: 2 is especially preferred. In this proportion, a particularly favorable interaction takes place between the two active ingredients, in total application proportions of 100 to 200 g / ha.

The combination of active components I and II, according to the invention under consideration, has a curative, protective and beneficial action on the organism, as well as a residual action, in the control of plant diseases generated by the seed and the soil. The combinations, according to the invention, destroy microorganisms within and on the plant, and protect developing plants from attack by microorganisms.

Compound I, propiconazole, is a fungicide known on the market, for the control of several cereal diseases, such as Erysiphe spp., Puccinia spp. , Pyrenophora spp. (= Helminthosporium spp.),

Rhynchosporium spp. and others.

Compound II is a broad spectrum fungicide for the control of powdery downy mildew species (Erysiphe spp.) From plant rust diseases (Puccinia spp., Hemileia etc), from leaf ecchymosis infestation (Septoria spp., Pyrenophora spp.) and others. Particularly persistent success is achieved in the control of black fungi, such as Alternaria spp. and Cladosporium spp., in addition to plant rust and leaf ecchymosis.

The combined use of the two compounds in cereals, either in the form of a mixture prepared from the foregoing or in the form of a reservoir mixture, provides an unpredictably durable increase in activity compared to the required degrees of application, if used. the compounds individually, for example in the control of Septoria spp., in leaves or ears. The same applies to the prevention of attack by Puccinia recondita, Pyrenophora spp., And Fusarium spp. The extremely extensive prevention of these cereal diseases results in higher yields per hectare, with distinctly improved crop quality.

The mixture of the two components of I and II, according to the invention, reaches not only preventive protection, but especially, also a curative protection, in all cases where the disease has already attacked the plant and the first signs of its spread become visible. This result is observed, especially, in the case of the attack of plant rust (Puccinia recondita), which, even at this stage, can still be fully controlled. This advantageous property is important, ·, all agricultural production systems that are based on forecasts of Ataq ^u> time - dependent, the tempera ture and epidemics. Such a mixture provides the user with a very flexible tool to prevent the spread of the disease, even if the attack has reached an advanced stage.

The inventive mixtures are active against phytopathogenic fungi, belonging to the following classes:

Ascomycetes (for example, the genera Mycosphaerella, Pyrenophora); Basidiomycetes (for example, the genera Tilletia, Rhizoctonia); imperfect Fungi (for example, the genera Fusarium, Septoria, Phoma, Alternaria).

Other species, which are difficult to control, but which can be well controlled, with surprise, by mixing, according to the invention, are Cercospora, Cercosporidium, Ascochyta, Ramularia, Venturia Guignardia and Colletotrichum. The combinations according to the invention are efficient, especially in the treatment of leaves and ears, but they are also suitable for the direct treatment of seeds and other parts of the plant (fruit, tubers and grains). They are well tolerated by plants and are, ecologically, harmless.

For its application, the mixture, according to the invention, is usually used in conjunction with adjuvants, used conventionally in the technique of compositions. The active components of formulas I and II are formulated in the known manner, for example, as emulsifiable concentrates, as coated pastes, as directly sprayable solutions or as directly dilutable solutions, as diluted emulsions, as wettable powders, as soluble powders, as dust, as granules and also as encapsulations in, for example, polymeric substances. The application processes, such as spraying, atomization, dusting, diffusion, coating or pouring and the composition modality are chosen according to the intended objectives and prevailing circumstances. Favorable degrees of application are, in general, from 50 grams to 700 grams of the total active ingredient, per hectare, with the proportion of I (propiconazole) staggered from 25 grams to 400 grams ai / hectare, and the proportion of II staggered, approximately, from 25 grams to 300 grams ai / hectare, for example from 75 to 150 grams of I with 40 to 125 grams of II, for example I: II = 125 grams: 50 grams, or I: II = 75 grams: 75 grams.

The target crops in the field of action of this invention are, for example, the following species of plants: cereals (wheat, barley, rye, oats, rice, sorghum, corn and related crops); beet (sugar beet, fodder beet); leguminous plants (beans, lentils, soybeans, peas); oily plants (rapeseed, mustard, poppy, peanut, olive, sunflower); cucumber plants (cucumber, pumpkin, melon); fibrous plants (cotton, flax); vegetables (cabbage, spinach, carrots, onions, garlic, tomatoes, betata, paprika), ornamental plants (tulips, daffodils, dahlias, chrysanthemums and other flowers); tea, coffee, cocoa, and mango; condiment plants and their seeds; pomos (apple, pear), drupes (cherries, plums, peaches, bald peaches); came; grass.

A preferred method of applying the inventive mixture comprises spraying or moistening the plant elements with a liquid composition, or treating the plant elements with a solid composition of the active ingredient.

The active ingredients of formulas I and II, according to the invention, are applied in the form of compositions, and can be applied, if desired, in conjunction with other vehicles, surfactants or other adjuvants, which promote the application, usually employed , in the technique of compositions.

Suitable vehicles and suitable adjuvants can be solid or liquid and correspond to the substances commonly used in the technique of compositions, for example, natural substances, or regenerated mineral substances, solvents, dispersants, wetting agents,

viscosity, thickening agents, binding agents or fertilizers.

A preferred method of applying a mixture of the active ingredients of formulas I and II, or a chemical (agro) composition containing these active ingredients, is the application to the leaves or the application to the ears, if the plant is a cereal. The number of applications and the degree of application depend on the risk of attack by the corresponding pathogen (fungus species). The mixture of the active ingredient can, non-offending, also penetrate the plant, through the roots, through the soil (action of the organism), if the plant site is impregnated with a liquid composition, or if the substances were applied in the form of solids , to the soil, for example in the granular mode (application to the soil). The mixture of the compounds of formulas I and II can, according to an especially preferred process, be applied (coating) to the seeds, tubers, fruit or other elements of the plant to be protected, either by impregnating the elements with a composition liquid of the active ingredients, or coating the elements with a solid composition. In special cases, other types of application are also possible, for example, the selective treatment of plant stems or plant buds.

The compounds of formula I and II are used in an unmodified form, or, preferably, together with adjuvants conventionally employed in the technique of compositions, and are therefore formulated in a known manner, for example, in emulsifiable concentrates, in coated pastes, in directly sprayable or dilutable solutions, in diluted emulsions, in wettable powders, in soluble powders, in dust, in granules and also in encapsulations in, for example,

polymer substances. As with the nature of the compositions, the application processes, such as spraying, atomizing, dusting, dispersing, coating or pouring, are chosen according to the intended objectives and the prevailing circumstances.

Formulations, that is, compositions, preparations or mixtures containing the active ingredients of formulas I and II and, where appropriate, a solid or liquid adjuvant, are prepared in a known manner, for example, by homogeneously mixing and / or grinding active ingredients with extenders, for example, with solvents, with solid vehicles and, where appropriate, with surface active compounds (surfactants).

Suitable solvents are:

hydrocarbons, preferably portions containing 8 to 12 carbon atoms, for example mixtures of xylene or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffin, alcohols and glycols and their ethers and esters, such as monomethyl ethylene glycol ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone dimethyl sulfoxide, dimethylformamide, as well as vegetable oils or epoxidized vegetable oils, or soy oil; or water.

The solid vehicles used, for example, for dust and dispersible powders, are calcite, talc, kaolin, montimorilonite or atapulgite, very dispersed silicic acid or absorbent polymers. Suitable granular absorbent vehicles are powder, broken brick, sepiolite or bentonite, and suitable non-absorbent vehicles are, for example, calcite.

-12 or dolomite.

Depending on the nature of the active ingredients of formulas I and II, the active compounds with suitable surfaces to be formulated are non-ionic, cationic and / or anionic surfactants, with good wetting, dispersing and emulsifying properties. The term surfactants is to be understood as encompassing mixtures of surfactants.

Surfactants, habitual in the formulation technique, are described in the publications, which follow, among others:

McCutcheon ¹ s Detergents and Emulsifiers Annual MC Publishing Corp., Ridgewood New Jersey 1980, Sisley and Wood,

Encyclopedia of Surfacs Active Agents Chemical Publishing Co., Inc. New York, 1980.

Agrochemical compositions generally contain from 0.1 to 95% of the total active ingredient, from 99.9 to 5% of a solid or liquid adjuvant, and from 0 to 25%, especially from 0.1 to 25 %, of a surfactant.

Although commercial products are preferably formulated as concentrates, the user ultimately uses diluted compositions.

The invention under consideration concerns such (agro) chemical compositions.

The following examples are intended to make the invention clear, the active ingredient being a mixture of propiconazole I and compound II, in a specific mixing ratio of 10: 1 to 1:10.

Wettable powders: The) B) ç ) Active ingredient (I: II = = 10: 1, 5: 2, 1: 3) 25% 50% 75% Sodium lignosulfonate 5% 5% - Sodium lauryl sulfate 3% - 5% Diisobutylnaphthalenesulfonate sodium - 6% 10% Octylphenol polyethylene glycol ether (7 to Θ moles of oxide ethylene) 2% Very dispersed silicic acid 5% 10% 10% Kaolin 62% 2 7%

-140 active ingredient is meticulously mixed with the adjuvants, and the mixture is meticulously crushed in a suitable mill, providing moisturable powders, which can be diluted with water, to give suspensions of the desired concentration.

Emulsifiable concentrate:

Active ingredient (I: II = 4: 1) 10% polyethylene glycol ether and octylphenol (4 to 5 moles of ethylene oxide) 3% calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether (35 moles of ethylene oxide) 4% cyclohexanone 30% mixture of xylenes 50%

Emulsions, of any concentration required, can be obtained from this concentrate by dilution with water.

Dust

Active ingredient (I: II 1: 1) kaolin talc a) b) = 3: 2 and

5% 8%

95%

92%

Dusts, ready for use, are obtained by mixing the active ingredient with the vehicle, and grinding the mixture in a suitable mill.

Extruder granulate:

Active ingredient (I: II = 5: 2) 10%

2% sodium lignosulfonate

Carboxymethylcellulose 1%

Kaolin

87%

-160 active ingredient is mixed and crushed with the adjuvants, and the mixture is subsequently moistened with water. The mixture is subjected to extrusion, and then it is dried in an air stream.

Coated granulate:

Active ingredient (I: II = 3: 2) 3%

Polyethylene glycol (molecular weight 200) 3%

Kaolin 94% (MW is the molecular weight)

The active ingredient, finely ground, is applied evenly, in a mixer, to the kaolin, moistened with polyethylene glycol. Coated, non-dusty granules are obtained in this way.

Biological Examples:

Example 1: Action against Puccinia graminis on wheat

a) Residual protective action

The wheat plants are sprayed, 6 days after being sown, with a spray mixture (6 parts per million active ingredient) prepared from a wet powder composition of the two active ingredients (I: II = 5: 2) . After 24 hours, the treated plants are infected with a suspension of fungal uredospores. Infected plants are incubated for 48 hours at 95 to 100% relative humidity and about 20 ° C, and then are kept in a greenhouse at about 22 ° C. The evaluation of the development of the rust pustule is made 12 days after infection.

b / Action on the organism

A spray mixture (2 parts per million of the active ingredient, based on the volume of the soil), prepared from a wet powder composition of the active ingredient, is poured onto the wheat plants, 5 days after being sown. After 48 hours, the treated plants are infected with a suspension of fungal uredospores. The infected plants are then incubated for 48 hours at a

-18 relative humidity of 95 to 100%, and at about 20 ° C, and then are kept in an oven at about 22 ° C. The evaluation of the development of the rust pustule is done days after the infection.

The spread of the disease was completely prevented (= 100% action) in both experiments a) and b).

EXAMPLE 2:

Action against Erysiphe graminis on barley

a) Residual protective action

The barley plants, about 8 cm high, are sprayed with a spray mixture (6 parts per million active ingredient), prepared from a wet powder composition of the two active ingredients (I: II = 3 :1). The treated plants are stoned with the fungus conidia after 3 to 4 hours. The infected barley plants are kept in a greenhouse, at about 229C, and the fungi attack is evaluated after 10 days.

b) Action on the organism

A spray mixture (2 parts per million of the active ingredient, based on the volume of the soil), prepared from a wet powder composition of the active ingredient, is poured over the barley plants, about 8 cm high. Care was taken that the spray mixture could not come into contact with the plant parts above the ground. The treated plants are dusty, 48 hours later, with the fungus conidia. The infected barley plants are kept in a greenhouse, at about 22 ° C, and the assessment of fungal attack is done after 10 days.

The spread of the disease was completely prevented (= 100% action) in both experiments a) and b).

EXAMPLE 3: Action against Helminthosporium sativum on wheat

Winter wheat, naturally infected with Helminthosporium sativem, was treated, in a mixer calender, with the experiment fungicide with a concentration of 60 parts per million a.i. (based on the weight of the seeds).

The active ingredient was a 1: 3 mixture of components I and II.

The infected and treated wheat was sown in October outdoors, with a sower, in 2 meter long plots, containing 3 rows of seeds, with 3 reproductions.

Experimental plants are grown under normal field conditions, until the attack is evaluated.

To determine the activity of the active ingredient, the plants that appear are evaluated. Less than 5% of the plants were infected.

-21EXAMPLE 4: Action against Fusarium on rye

Rye of the Tetrahell variety naturally infected with the Fusarium of snow, is treated in a mixer calender, with the experiment fungicide, the following concentrations being applied: 20, or 60, parts per million a.i. (based on the weight of the seeds). A.i. is a 1: 4 mixture of components I and II.

Rye, infected and treated, is sown in October, outdoors, with a seeder, in plots measuring 3 meters in length, containing 6 rows of seeds, with 3 reproductions per concentration.

Experiment plants are grown under normal field conditions (preferably in a region with continuous snow cover during the winter months), until the attack is assessed.

In order to assess phytotoxicity in autumn, the appearance of seeds and in spring the density of crops / number of plants per unit area are evaluated.

To determine the activity of the active ingredients, the percentage of plants attacked by Fusariwas ”is counted in the spring, immediately after the snow has melted. The number of infected plants, in the case under consideration, was less than 5%. The emerging plants had a healthy appearance.

EXAMPLE 5: Action against Septoria nodorum on wheat

Wheat plants are sprayed, over the 3-leaf period, with a spray mixture (60 parts per million a.i.) prepared from a powder composition of the active ingredients (2.8: 1).

hours later, the treated plants are infected with a conidia suspension of the fungi. The plants are then incubated for 2 days at a relative humidity of 90 to 100% and kept in a greenhouse for another 10 days at 20 to 24 ° C. Fungal attack is evaluated 13 days after infection. They did not exhibit any attack less than 1% of the wheat plants.

Claims (7)

R Ε I V INDICATIONS: there. - Process for the preparation of a microbicidal plant composition, characterized in that said composition includes at least two components of active ingredients, where one component I) is 1- / 2- (2,4-dichlorophenyl) -4 -propyl-1,3-dioxolan-2-ylmethyl7H-1,2,4-triazole, of formula I or a salt thereof, and the other component II) is l-γ 2- / 2-chloro-4- (4 -chlorophenoxy) phenyl7-4-methyl-1,3-dioxolan-2-ylmethylJ-1H-1,2,4-triazole, of formula II (II), or a salt thereof, together with suitable vehicles. 2nd. Process according to claim 1, characterized in that the weight ratio of I: II is 10: 1 to 1:10. 3rd. Process according to claim 2, characterized in that the weight ratio of I: II is 5: 1 to 1: 5. 4th. Process according to claim 2, characterized in that the weight ratio of I: II is 4: to 1: 4. 5th. Process according to claim 2, characterized in that the weight ratio of I: II is from 3: 1 to 3: 2. 6th. - Process to control or prevent plant diseases, characterized by understanding the treatment of the plant site, which is already infected, or is subject to being infected, in any sequence, or simultaneously, with at least one ingredient active formula I and an active ingredient of formula II, in a weight ratio of I: II from 10: 1 to 1:10. 7th. Process according to claim 6, characterized in that it is a cereal. -258θ. Process according to claim 6, characterized in that it is vegetables, potatoes and sugar beet. Lisbon, February 23, 1990 J. PEREIRA DA CRUZ A§cntí Cfiskrf from PrepnoJssJc lií «ustriai RUA VICTOR ΟΟΛΟΦΝ, 10-A. V 1200 LISBON