HU191843B - Fungicide composition containing n-/2-methyl-5-chlorophenyl/-n-/methoxy-acetyl/-3-amino-1,3-oxazolidin-2-one as active agent - Google Patents

Abstract

N-(2-methyl-5-chlorophenyl)-N- methoxyacetyl-3-amino-1,3-oxazolydin- 2-one having the formula: <IMAGE> exhibits decidedly superior fungicidal activity than other compounds of its class. The compound has both preventative and curative action and may be applied in conventional formulations.

Description

FIELD OF THE INVENTION This invention relates to antifungal compositions containing N- (2-methyl-5-chlorophenyl) -N- (methoxyacetyl) -3-amino-1,3-oxazolidin-2-one.

The authors of the present invention, in Belgian Patent 885,117, describe the preparation of fungicidal compounds belonging to the group N-aryl-N-acyl-3-amino-1,3-oxazolidin-2-one, wherein the compounds of formula (I) compounds are also included. In formula I, R, R ¹ and R ² may be the same or different and are hydrogen, halogen, or C 1-4 alkyl or alkoxy.

The compounds of the above-mentioned Belgian patent, in particular the compounds of general formula (I), have shown that the position of the substituents R, R ¹ and R ^{2 on} the aromatic ring is particularly important. Surprisingly, it has been found that among the compounds of formula I having good fungicidal activity, wherein at least one ortho position is unsubstituted, N- (2-methyl-5-chlorophenyl) of the formula II is undoubtedly N-methoxyacetyl-3-amino-1,3-oxazolidin-2-one has the strongest fungicidal action.

This compound has an extremely strong fungicidal action and can be used in the form of a composition or a suitable mixture composition for combating fungi.

The compound of formula (II) is prepared by the reactions described in Belgian Patent No. 885,117. Using 2-methyl-5-chlorophenylhydrazine as the starting material, the above-described patent compound gave the compound of formula II in good yield as a dense oil with a refractive index of λ = 1.5375 at 50 ° C.

Crystallization from ethyl acetate in naphtha gave a white crystalline solid, m.p. 69-70 ° C.

The most characteristic absorption bands in the infrared spectrum (cm ^-1 ): 2930,

1775, 1710, 1490, 1410, 1130 and 1035.

As mentioned above, the compound of formula (II) has a significant fungicidal activity, which is particularly useful against fungi of the Phycomicetes class.

It will be appreciated from the examples that the fungicidal activity of the compound of formula (II) is undoubtedly greater than that of the compounds of formula (I) in which at least one ortho position of the aromatic ring is unsubstituted.

The compositions of the invention containing the compound of formula II are well tolerated by the plants to be protected against attacks by phytopathogenic fungi and exhibit less phytotoxicity than the compositions containing the compounds mentioned in the above-mentioned Belgian patent.

The composition of the invention has both curative and prophylactic properties and has excellent general properties.

Due to all these properties, the formulations containing the compound of formula II can be used to prevent and treat diseases caused by phytopathogenic fungi of crop plants, in particular Peronospora, Phytophtora, Plasmopara, Pseudoperonospora and Pythium, and to treat diseases caused by such fungi.

The extremely high activity of the compound in stone 15 proves to be very low, depending on the crop to be protected, the type and degree of fungal infection that may or may not exist, and the climatic and environmental factors.

Can be 1 + 100 g / ha.

In accordance with standard formulation practice, formulations obtainable with the compound of formula (II) as the active ingredient may be liquid concentrates, emulsifiable concentrates, dry or wettable powders.

Said mixtures may contain, in addition to the compound of formula II, inactive liquids or solid carriers and optionally other additives such as emulsifiers, surfactants, wetting agents and suspending agents.

Optionally, it is possible to add to the fungicidal mixtures other ingredients which are useful for agriculture and are compatible with the compound of formula II, e.g. herbicides, fertilizers, biostimulants, other fungicides, etc.

For special practical purposes, it is particularly suitable for the preparation of other so-called "compound II" compositions. .covering with fungicides.

These fungicides include, for example, alkylene bis-dithiocarbamates, copper salts or oxides, N45-haloalkylthioimides.

The following examples are intended to further illustrate the invention.

Example 1

Healing effect against Plasmopara viticola on sol.

General method:

The lower half of the leaves of Dolcetto grapes grown in pots at 25 ° C and 60% relative humidity were sprayed with an aqueous suspension of Plasmopara viticola conidia (Béri et de Toni; 200,000 conidium / ml).

After 24 hours of thermostating at <RTIgt; C, </RTI> the plants were divided into three groups. After that, the individual

On both sides of leaves of plants belonging to Groups 2191843 were sprayed with a solution of test compound in aqueous acetone (20% v / v acetone), the first group on the first day after infection, the second on the second day and the third on the third day. At the end of the incubation period (7 days), the extent of infection was estimated on a scale from 100 to healthy (free of infection) and O to fully infected plant 10.

Table I shows the curative activity of the compound of formula (II) against P. viticola compared to the value of seven compounds (A-G) of formula (I). 15

From the data in Table I it is evident that the fungicidal activity of the compound of formula II is superior to that of the comparator compounds.

Moreover, the fungicidal activity of the compound of formula (II) is so high in absolute terms that it still exhibits complete activity at extremely low doses (0.0005% by weight) (complete elimination of fungal infection).

Table I

The table shows the curative effect against Plasmopara viticola on the grapes at the indicated doses as a percentage of the reduction in fungal infection.

Table I

agent R R ¹ R ² 0.01 Dose (% by weight) 0.0005 0,005 0,001 (Π) of formula. 2-CH3 5-C1 H 100 100 100 100 THE 2-CH3 H H 100 - 7 - B 3-C1 H H 100 85 74 - C H H H 100 100 23 - D 3-C1 5-C1 H 100 - 20 - E 3-CH H H 100 - 52 - F 3-F H H 100 - 15 - G 2-C1 5-C1 H 100 90 70 -

Example 2 35

Healing effect of Peronospora tabacina on tobacco.

General method:

Under conditioned conditions, the lower half of the leaves of Burley tobacco grown in pots were sprayed with an aqueous suspension of conidia of Peronospora tabacina Adam (45,000 conidia / ml).

After six hours of storage in a saturated humidity space, the tobacco plants were divided into two groups and at 20 ° C with 70%. placed in a humid environment to stimulate fungi. Each side of the leaves of the plants in each group was sprayed with a solution of the test compound in aqueous acetone (20% v / v acetone), the first group 24 and the second group 48 hours after infection. At the end of the incubation period (6 days), the degree of infection was estimated on a scale of 100 for healthy plants and 0 for fully infected plants.

II. Table II shows comparative data of the therapeutic activity against P. tabacina obtained with the compound of the formula XI and the seven compounds of the formula (A-G) I.

II. It is clear from the data in Table II that the fungicidal activity of the compound of formula II is undoubtedly higher than that of the comparator compounds and that this fungicidal activity is extremely high in absolute terms, so that even at very low concentration (0.0005 vol%) it is fully active.

(100% reduction in fungal infection).

II. spreadsheet:

Healing effect against Peronospora tabacina at the indicated doses, expressed as a percentage reduction in fungal infection.

II. -table

Compound R R> R ² 0.01 Dose (% by weight) 0.005 0.001 0.0005 (II) 2-CH3 5-C1 H 100 100 100 100

-3191843

Compound R R ¹ R2 0.01 Dose (% by weight) 0,005 0,001 0.0005 THE 2-CH3 H H 100 100 47 - B 3-C1 H H 100 100 92 68 C H H H 100 74 0 - D 3-C1 5-Cl H 100 - 30 - E 3-CH3 H H 100 - 60 - F 3-F H H 100 - 30 - G 2-Cl 5-Cl H 100 100 75 -

Example 3 20

Preventive effect of Plasmopara viticola on grapes.

General method:

The surface of the leaves of Dolcetto grapes grown in a conditioned environment was sprayed with a solution of the test product in aqueous acetone (20% v / v acetone). 30

The plants were then placed in a conditioned space.

The plants were divided into two groups. The lower half of the leaves were sprayed with an aqueous suspension (200,000 conidia / ml) of conidia of Plasmopara viticola, the first group one day, the second group seven days after treatment.

After 24 hours storage in a saturated humidity space, the plants were returned to a conditioned environment. At the end of the incubation period (7 days), the extent of infection was estimated on a scale of 100 (healthy plant) to 0 (fully infected plant).

The compound of formula (II) has a greater preventive effect than the comparator compounds in Table I (see Example 1).

The preventive effect of the compound of formula II against Plasmopara viticola is also extremely high in absolute terms because it was able to completely (100%) prevent the fungal infection at very low concentrations (0.0005% by weight). the artificial infection occurred on the first or 55th day after treatment.

Example 4

Preventive effect of tobacco against Prenospora tabacina.

General method:

Both sides of Burley tobacco plants grown in a conditioned environment were sprayed with a solution of the test product in aqueous acetone (20% v / v acetone). The plants were divided into two groups. One was infected one day and the other group infected 7 days by spraying the lower half of the leaves with an aqueous suspension of Peronoepora tabacina Adam conidia. After six hours of incubation in a saturated humidity chamber, the plants were incubated at 20 ° C with 70%. placed in a humid space for propagation of fungi.

At the end of the incubation period (6 days), the degree of infection was estimated on a scale of 100 for the healthy plant and 0 for the fully infected plant.

The compound of formula (II) also exhibited significantly higher fungicidal activity in this experiment than the comparative compounds described in Table I (see Example 1).

The preventive activity of the compound (II) against Peronospora tabacina is extremely high in absolute terms, so much that it can completely prevent fungal infection (100% reduction) when used at very low doses (e.g. 0005% w / w), regardless of whether at-4191843 is the first or seventh day after the treatment for artificial infection.

The following are examples of fungicidal mixtures containing the compound of formula (II) as an active ingredient.

The following abbreviations are used in these examples:

DMF xylene

Ca-DBS

COH-ETO

SO-ETO

NF-ETO

Na-DSS

Na-LS

A commercially available mixture of N, N-dimethylformamide xylene isomers is calcium dodecylbenzene sulfonate e.g. by Rol-Montedison .Emulson

Product sold under the trade name AG / CaL '.

polyoxyethylated hydrogenated castor oil e.g. .Emulson is a RolMontedison product marketed under the trade name COH '.

polyoxyethylated sorbitan oleate e.g. a Rol-Montedison .Emulson

20-OM ', sold as polyoxyethylated nonylphenol e.g. a product of Rol-Montedison .Emulson 10B ', sodium dialkylsulfosuccinate e.g. product sold by Rol-Montedison under the trade name .Madeol V40.

sodium lignin sulfonate pL is a product of Borregard .Ultrazina NA 'and Cartiere di Tolmezzo .Bretax'. Na-NS = sodium alkyl naphthalene sulfonate e.g. Rol-Montedison .Madeol W90 'and .Madeol 934'.

Example 5

Emulsifiable Concentrates (EC)

Components (% by weight)

5-40% of compound of formula II

B - solvent 40-90% c - surfactant 5-20%

Suitable solvents (B) = aromatic and alkyl-aromatic hydrocarbons, ketones, esters, DMF and mixtures thereof.

Suitable surfactants (C) = polyoxyethylated nonylphenol, polyoxyethylated triglycerides, polyoxyethylated fatty acids, Na, Ca or triethanolammonium dodecylbenzene sulfonate and mixtures thereof.

The mixtures are prepared by dissolving the compound of formula (II) in the solvent and then adding the surfactant.

Examples of mixtures in emulsifiable concentrate ^{30 are shown in} Table III. Table.

III. spreadsheet

Mixtures in emulsifiable concentrate (expressed as a percentage by weight of the components).

components mixtures 1 2 3 4 5 A / II compound 20 5 15 30 40 B / xylene 63 90 70 40 40 B / cyclohexanone 7 - - 10 - B / DMF - - 3 - 10 C / Ca-DBS 3 1 2.5 4 3 C / COH-ETO 3.5 - - 6 - C / SO-ETO - 4 4.5 - 3 C / NF-ETO 3.5 - 5 10 4

Example 6 Wettable Powder Mixtures (WP) Ingredients (% by Weight)

5-50% of compound A - II

B - wetting agent 0.5-5%

C - Suspending Thousand 1-5%

D - carrier 40-93.5% suitable wetting agents (B) = polyoxyethylated nonylphenol, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate and mixtures thereof.

Suitable suspending agents (C) = lignin sulfonate of sodium, calcium or aluminum, sodium alkylnaphthalenesulfonate condensed with formaldehyde, maleic anhydride diisobutylene copolymers and mixtures thereof.

Suitable carriers (D) = diatomaceous earth, kaolin, CaCO3, SiO2 and mixtures thereof.

To prepare wettable powder blends, the blend of ingredients is ground in a suitable mill to a desired particle size of 5.

The IV. Examples of wettable powder blends are given in Table.

ARC. spreadsheet

Wettable powder mixtures (% by weight of components).

components 1 mixtures 2 3 4 5 6 A / II compound 25 5 15 30 40 50 B / Na-DSS 2 - - 1 2 - B / Na-NS - 1 4 - 2 - B / NF-ETO - - - - - 5 C / Na-LS 3 2 1 3 2 5 D / kaolin 70 92 60 61 - 10 D / kovafOld - - 20 - 44 - D / SiOI - - - 5 10 30

Patent Claim Point

Claims (1)

Patent Claim Point Fungicidal composition, characterized in that the active ingredient is 0.0005-60% by weight of N- (2-methyl-5-chlorophenyl) -N- (methoxyacetyl) -3-amino-1,3-oxazolidine-2- g., in the presence of glazes, liquid and / or solid carriers, preferably organic solvents and / or natural or artificial rock fragments, and surfactants, preferably anionic, cationic or nonionic emulsifiers or dispersants.