HU184055B - Compositions containing 3-square bracket-n-btacket-chloro-acetyl-bracket closed-n-bracket-aril-amino-bracket closed-square bracket closed-gamma-buthyrolaktone againts peronosporaceae and phytophtoraceae - Google Patents

Abstract

The fungicidal composition according to the invention contains, as at least one active ingredient, a compound of the formula I <IMAGE> in which R denotes a hydrogen atom or a methyl group. The fungicidal composition according to the invention can be used for controlling downy mildew infections in plants, caused by the fungal family of the Peronosporaceae, and for the treatment of crown and root rot caused by soil fungi from the genus Phytophthora.

Description

FIELD OF THE INVENTION The present invention provides fungicidal compositions comprising 3- (N-chloroacetyl) -N-arylamino / gamma-butyrolactone derivatives, more particularly compounds of formula (I) wherein R is hydrogen or methyl; 3- (N-Chloroacetyl) -N- (2,6-dimethylphenyl) amino-gamma-butyrolactone or 3- (N-Chloroacetyl) -N- (2) , 6-dimethylphenyl) amino / -5-methyl-gamma-butyrolactone as active ingredients, which are very effective in preventing and eradicating phytophthora fungal diseases and plant diseases associated with phytophthora fungal rot and root rot.

A large group of 3-N-acyl-N-arylaminolactones and 3-N-acyl-N-arylammono-lactams, known from U.S. Patent Nos. 3,933,860 and 4,012,519, which has a protectant fungicidal effect. However, there is no indication in these patents that any of the compounds disclosed therein have curative or eradicant fungicidal activity.

British Patent Nos. 1,445,387 and U.S. Patents 4,015,648 have disclosed N-methoxycarbonylethyl / -N-haloacetyl anilines as preventive and curative fungicides. Comparative experiments have shown that the compounds of the present invention have a much more beneficial healing and fungicidal activity than the fungicidal active compounds described herein.

U.S. Patent Nos. 2,643,403 and 2,643,445 have disclosed N-alkylthiocarbonylethylacetanilides effective against fungi, especially those of the Phycomycetes family.

From Dutch Patent Publication No. 152,849/77 N-alkoxymethylacetanilides having a fungicidal action have become known.

It should be noted that, except for U.S. Patent Nos. 3,933,860 and 1,445,387, each of the aforementioned publications is available to the public after October 12, 1976.

Thus, it has been found that the fungicidal compositions containing the compound of formula (I) as an active ingredient are effective in the treatment of gray mold fungal diseases and of rotting diseases of the foliage crown and root system caused by Phytophthora fungi. The fungicidal compositions of the invention are effective as both protective fungicides (i.e., to prevent or protect against fungal infections) and as eradicating fungicides (i.e., to eliminate or cure existing or widespread infections). As will be explained later, the recognition of the killing effect of the fungicidal compositions of the present invention is particularly advantageous. The compositions of the present invention are particularly useful for controlling gray mold on grapes, since they have not been shown to inhibit the fermentation of grapes harvested from grape vines. It has also been found that the compositions of the present invention have surprisingly high efficacy in eradicating gray mold on the vine and in developing no resistance to the compositions of the invention in fungi causing this disease.

The present invention therefore relates to a fungicidal composition, characterized in that it contains as an active ingredient a compound of formula (I) wherein R is hydrogen or methyl, in a fungicidal effective amount, preferably in an amount of from 5 to 80% by weight with conventional carriers and / or surfactants.

The compounds of formula I are known from U.S. Patent No. 3,933,860.

Thus, the fungicidal compositions of the present invention are highly effective in the treatment of gray mold plant diseases caused by species of the genus Peronosporaceae, as well as rotting diseases on the crown and root of plants caused by living species of the Phytophthora genus.

Gray mold is an umbrella term for a relatively large group of diseases common to plants growing in cold and wet regions of the world. The disease group includes gray mold caused by Bremia lactucae species on lettuce, gray mold caused by Peronospora effusa species on spinach, gray mold caused by Peronospora destructor species on onion, gray mold caused by Peronospora manshurica urica species, gray mold, Peronospora parasítica ssp. gray mold caused by brassicae species, gray mold caused by Peronospora tabacina species on tobacco, gray mold caused by Peronospora trifoliorum species on alfalfa, gray mold caused by Peronospora schactii species on sugar beet, Phytophthora species by Phytophthora phase, Gray mold caused by Plasmopora viticola species on grapes, gray mold caused by Pseudoperonospora cubensis on watermelons, cucumbers, pumpkins and plants related to these plants and gray mold caused by Pseudoperonospora humuli on hops.

Phytophthora fungi in the soil cause rotting on the crown and root system of a large number of different plants. These fungi are extremely difficult to control with fungicidal agents given that they live in the soil. Soil treatment to destroy fungi is not always effective considering that many fungicidal agents are not uniformly distributed in the soil and / or the soil is detoxifying, i.e. eliminating the fungicidal action. Soil fungi can thus be controlled by so-called downward systemic fungicidal agents,

-2184 055, which migrate down to the root system after being applied to the foliage of the vegetation. However, most of the known fungicides for Phytophthora fungicide do not show such systemic effects. In contrast, the fungicidal agents of the present invention are systemic in their action from the root to the foliage and from the foliage to the root. The fungicidal active compounds of the present invention are not deactivated by the soil and are rapidly taken up by the roots of the vegetation. Thus, the fungicidal active compounds of the present invention are highly active against soil-borne Phytophthora fungi.

Phytophthora species that cause foliage and root rot include Phytophthora cactorum (root rot of walnut, root rot of clove and root rot of alligator pears) , Phytophthora capsici (causes pepper root rot), Phytophthora cinnamoni (causes rotten pineapple and root rot), Phytophthora (alligator and citrus), root rot, Phytophthora citrophthora (root cause of citrus tree root rot), Phytophthora cryptogea (root rot of tomato, safflower and tobacco on canopy and root), Ph. ytophthora dreschleri (root rot of safflower root), Phytophthora erythrosytica (root cause of potato pink rot), Phytophthora fragariae (red stele of strawberry) , walnut and peach root rot), Phytophthora nicotianae (pathogen of tobacco stalk), Phytophthora palmivora (root rot of citrus fruits, coconut root rot and. black rot), Phytophthora parasitica (watermelon and citrus root rot), and Phytophthora syringae (citrus root rot).

The fungicidal compositions of the present invention are particularly useful as fungicidal agents, since they are also useful in the treatment of advanced fungal infections. This feature makes them extremely economical because they do not need to be applied to the vegetation until fungal infection is detected. In other words, there is no need for preventive application of these fungicidal compositions.

There is generally a significant difference between the mechanism of action of so-called protective or preventive fungicidal agents and the so-called elimination or curative fungicidal agents. While the former generally inhibit fungal infection by preventing spore formation and / or infection, the latter cure 4 fungal infections after infection of the host. Therefore, it should be surprisingly found that the fungicidal agents of the present invention have both preventive and curative properties.

The fungicidal compositions of the present invention can be applied in fungicidally effective amounts to fungi and / or their environment, such as growing host plants and the environment of the latter. Of course, the amount of active ingredient used in each case will depend on a number of factors, such as the nature of the host, the particular fungal species, and the composition of the particular formulation used. In addition to the active ingredient, the compositions of the present invention will usually contain conventional, biologically inert carriers and / or diluents and / or surfactants, which excipients are intended to facilitate proper dispersion of the active ingredient. When selecting these excipients, it should always be borne in mind that the formulation and mode of application may influence the action of the fungicidal agent. The compositions of the invention may be formulated, for example, as particulate compositions, dustable formulations, wettable powder formulations, emulsifiable concentrates, or solutions, depending on the intended use.

Wettable powder formulations consist of finely divided particles which are readily dispersible in water or other decorative dispersants. These formulations usually contain from about 5% to about 80% of the fungicidal active ingredient and, in the amount required, 100% of the inert excipients, such as dispersants, emulsifiers and wetting agents. The wettable powder composition may be applied to the soil in a dry state or preferably suspended in water. Typical carriers for wettable powder formulations include fuller earth, kaolin-containing materials, silicates, and other high-absorbency wettable inorganic diluents. Typical wetting, dispersing or emulsifying agents that may be used include, but are not limited to, aryl and alkyl aryl sulfonates and their sodium salts, alkyl amide sulfonates (including fatty acid methyl taurides), alkyl aryl polyether alcohols, fatty acid esters of ethyl alcohol and polyvinyl alcohols, polyethylene oxides, sulfonated animal and vegetable oils, sulfonated mineral oils, fatty acid esters of polyhydric alcohols, ethylene oxide addition products thereof and long chain thiols ethylene oxide addition products. However, many other types of surfactants that are well utilized are commercially available. When used, the surfactant may comprise from 1 to 15% by weight of the fungicidal composition of the invention.

Dustable compositions are free-flowing mixtures of the fungicidal active ingredient which are finely divided solids such as talc, natural substances, diatomaceous earth, pyrophyllite, limestone, diatomaceous earth, calcium phosphate, calcium 055 Contains sodium, sulfur, slaked lime, finely ground other mineral powders and other organic or inorganic substances. These finely divided solids have an average particle size of less than about 50 microns. A typical dustable composition contains 25% active ingredient and 75% silica.

Useful liquid concentrates include emulsifiable concentrates which are homogeneous liquid or paste-like formulations which are readily dispersible in water or other dispersants. These concentrates may be comprised of the fungicidal active ingredient itself and a liquid or solid emulsifier, or may also contain a liquid carrier such as xylene, higher carbon aromatic gasoline, isophorone or other non-volatile organic solvent. When used, these concentrates are dispersed in water or other liquid carrier and are usually applied as a spray to the area to be treated.

A ready-to-use formulation is a simple solution which is a solution of the fungicidal active ingredient in a dispersant in which the fungicidal active ingredient is completely soluble in the desired concentration. Acetone, alkylated naphthalenes, xylene or other organic solvents may be used as the solvent. Granular formulations, in which the fungicidal active ingredient is contained in relatively coarse granules, are of particular importance in the case of aerosol application or where the crop to be treated is already densely covered by a crop.

Pressurized compositions, typically aerosols, in which the active ingredient is dispersed in a finely divided form by evaporation of a low boiling solvent as carrier, such as freon, may also be used.

The methods of use and application described above are known in the art without exception.

The amount of active ingredient in the compositions of the invention may vary depending on the form of preparation and use, but in most cases will be between 0.5% and 95% by weight of the total composition.

The compositions of the invention may contain or be co-applied with other biologically active substances such as other fungicides, insecticides, nematocides, bactericides, plant growth regulators, fertilizers, and the like. together.

The following examples illustrate the invention.

Example 1

Preparation of 3- (N-chloroacetyl) -N- (2,6-dimethylphenyl) amino / gamma-butyrolactone (hereinafter "Compound A")

3-N- (2,6-Dimethylphenyl) amino-gamma-butyrolactone (m.p. 85-86.5 ° C) (410 g, 2 moles) and pyridine 2 (197.5 g, 2.5 moles). of benzene (reflux) and chloroacetyl chloride (260 g, 2.3 mol) was added dropwise over 40 minutes while refluxing. The reaction mixture was refluxed for a further 20 minutes, cooled and filtered to remove the pyridine hydrochloride precipitate. The filtrate was then washed with water, dried over magnesium sulfate and concentrated under reduced pressure to give a colorless to white precipitate. This is slurried with isopropanol and the resulting suspension is filtered and the filtered solid is dried. 501 g of the title compound are obtained in the form of a colorless precipitate, m.p. 145.5-147 ° C.

The product has an oral LD ₅₀ value greater than 1000 mg / kg in rats and a dermal LD ₅₀ value in rats also greater than 2000 mg / kg.

Example 2

Preparation of 3- (N-Chloroacetyl) -N- (2,6-dimethylphenyl) amino / -5- / methyl gamma-butyrolactone (hereinafter "Compound B")

Into a 500 mL round bottom flask equipped with a two-hole glass stopper was charged 24.2 g (0.2 mole) of 2,6-dimethylaniline and 19.0 g (0.106 mole) of alpha-bromo-gamma-valerolactone. The flask was then evacuated to 26.7 mbar and then slowly heated to 100 ° C while occasionally evacuating the flask with a water jet pump to maintain a vacuum of about 22.7 to 53.3 mbar. After heating the reaction mixture at about 100 ° C and under a vacuum of about 22.7-53.3 mbar for 22 hours, it was cooled and diluted with 300 mL of diethyl ether. The solid precipitated 2,6-dimethylaniline hydrobromide was filtered off and the filtrate was washed with 5% aqueous hydrochloric acid, water, dried over magnesium sulfate and concentrated under reduced pressure to give 19.2 g of a viscous oil. N- (2,6-Dimethyl-phenyl) -amino / -5-methyl-gamma-butyrolactone is obtained.

Chloroacetyl chloride (10.9 g, 0.096 mol) was added slowly to a solution of the compound (19.2 g, 0.088 mol) and pyridine (7.6 g, 0.096 mol) in ethyl acetate (250 ml). An exothermic reaction occurs and a precipitate forms. After stirring for 16 hours at about 20 ° C, the precipitated mixture was washed first with a saturated aqueous sodium bicarbonate solution, then with water, dried over magnesium sulfate and concentrated under reduced pressure to give a thick oil which crystallized from diethyl ether to give a yellow precipitate. ad. This precipitate was then washed with a cold mixture of diethyl ether and petroleum ether and air-dried to give 15.8 g of the title compound, mp 128-131 ° C.

Example 5 - Wettable Powder Formulation A wettable powder formulation containing by weight active ingredient is prepared by mixing 52.1 parts by weight of Compound A (96% purity), 42.9 parts by weight of attapulgite and 5 parts by weight of a mixture of anionic surfactant5

It consists of -4184 055 g, lignosulfonates and sodium stearate.

Example 4 - An aqueous liquid preparation

A liquid formulation containing 0.41 kg of active ingredient per liter is prepared by mixing 44.22 parts by weight of Compound A (96% purity), 43.43 parts by weight of water, polyvinyl acetate and polyvinyl 1.42 parts by weight, 9.73 parts by weight of propylene glycol, 0.2 parts by weight of a polysaccharide thickener and 1 part by weight of a nonionic surfactant.

Example 5 - Prevention of gray mold on grapes

Compounds A and B, as well as a number of related compounds, are tested for their ability to prevent gray mold caused by Plasmopora viticola on the vine. Seven-week-old leaves of a Vitis vinifera Emperor variety of 70 mm to 85 mm in diameter are used as the host. The leaves were sprayed with acetone solutions of the test compounds, dried, inoculated with a spore suspension of the test fungus, then placed in a climate chamber and incubated at 18-22 ° C and about 100% relative humidity. 7-9 after inoculation. At day 3, the degree of disease control is determined. The percentage control provided by a particular test compound is the percentage reduction seen with untreated control plants. The test compounds, experimental concentrations and results are summarized in Table I below.

Example 6 - Treatment for the elimination of gray mold on grapes

Compounds A and B and a number of related compounds are tested for their ability to eliminate the gray mold caused by Plasmopora viticola on grapes. Again, the leaflets mentioned in Example 5 are utilized as host plants. The leaves were inoculated with the experimental fungus and placed in a climate chamber and incubated at 18-22 ° C and 100% relative humidity for 2 days. The leaves are then sprayed with a solution of the test compounds in acetone, and the sprayed leaves are again kept at 18-22 ° C and about 100% relative humidity. 7-9 days after vaccination, the percentage of disease control is established. The percentage control provided by a particular test compound is the percentage reduction seen with untreated control plants. The experimental compounds, experimental concentrations and results are summarized in Table I below.

Example 7 - Prevention of gray mold on grapes

An experiment was conducted with Compound A and two commercially available fungicides, namely folpet (N-trichloromethylthiophthalimide) and captafol (cis-N- / 1,1,2,2-tetrachloro-). ethylthio / 4-cyclohexene-1,2-dicarboxy [mid]). The experiment is carried out as follows:

The host plant is the cut leaves of 3-month-old Cabernet Sauvignon grape seedlings. Four letters are used in each experiment. The leaves were sprayed with a solution of 1% acetone in 99% water containing 40 ppm nonionic surfactant in addition to the test compound. After spraying, the leaves are dried and then inoculated from a spore suspension of the test fungus (which is an aqueous suspension containing about 400,000 conidia per milliliter). The percentage control provided by a particular test compound is the percentage reduction seen with untreated control plants. Test compounds, experimental concentrations and results are reported in Table II. are summarized in Table.

II. spreadsheet

Preventive effect of grape-gray mold

Experimental compound Percentage control 40 ppm 16 ppm 6.4 ppm Compound A 100 100 100 folpet 97.7 98.8 80.1 captafol 96.5 98.8 95.3

Example 8 - Fermentation experiment

An in vitro experiment was conducted to determine the effect of Compound A on fungi causing alcoholic fermentation of grapes. The experiment is performed as follows:

500 cm ³ Erlenmeyer flasks are filled with 200-200 ml of must (density 1.07 g / cm ³ ) from the bunches of Madeleine Angevine grape, and the test compound is added and the fermentation is determined by measuring cumulative weight loss due to carbon dioxide depletion, for comparison purposes, with an untreated control and a commercially available fungicidal agent. The results of the first 8 days of fermentation and the concentrations of the test compounds are shown in Table III. are summarized in Table.

Example 9 - Treatment for gray matter

We investigate the effects of Compound A and a number of commercially available fungicides on vine leaves to eliminate gray mold caused by Plasmopora viticola. Trade Traffic-5184,055

Table I Activity of the compounds of formula II against grape gray mold

Preventive effect

R _x R ¹ R ² Y% (ppm) ED _s0y90 *% (ppm) ^ED soa

"THE" 2,6- (CH ₃ ) ₂ ch ₂ ci H 0 97 (6.4) 1.2 / 4.4 99 (6.4) 1/3 "B" 2,6- (CH ₃ ) ₂ ch ₂ ci ch ₃ 0 80 (100) 8/100 99 (100) 95 (40) 7/28 1 3,4-Cl ₂ ch ₂ ch ₃ H 0 0 (100) 5 (40) 2 2,6- (CH ₃ ) ₂ 3,4-C1 ₂ -U H 0 - - 29 (100) - 3 2 — CH ₃ 0 ch ₂ ci H 0 0 (100) - 12 (100) - 4 2.6- (CH ₃ ) ₂ ch ₂ ci H nch ₃ - - 3 (100) - 5 H ch ₂ ci H 0 - - 0 (100) - 6 2.6- <C ₂ H ₅ ) ₂ ch ₂ ci H 0 0 (100) - 39 (100) - 7 2-iC ₃ H ₇ ch ₂ ci H 0 3 (100) - 17 (16) - 8 CA-2 ch ₂ ci H 0 0 (100) - 0 (100) - 9 2,6-Cl ₂ CH ₂ Cl H 0 0 (100) - 95 (100) 67 (40) 35/70 10 3,4-Cl ₂ ch ₂ ci H 0 89 (100) 66/107 39 (100) - 11 3,5-CL ₂ ch ₂ ci H 0 45 (100) - 54 (100) - 12 2.6- (C ₂ H _s ) ₂ ch ₂ ci ^CH 3 0 - - 87 (100) 38/100 13 2-CH ₃ -6-C ₂ H ₅ ch ₂ ci H 0 0 (100) - 87 (100) - 14 2-CH ₃ -6-C ₂ H _s ch ₂ ci ^CH 3 0 - - 29 (100) - 15 2,6- (CH ₃ ) ₂ CH ₂ Br H 0 - - 54 (100) 84 / - 16 2,6- (CH ₃ O) ₂ ch ₂ ci H 0 - - 67 (100) - 17 2,6- (CH ₃ ) ₂ CH ₂ CH _o C 1 H 0 - - 50 (100) 117 / - 18 2,6- (CH ₃ ) ₂ ch ₂ ci H NCH (CH ₃ ) ₂ 15 (100) - 37 (100) - 19 2,6- (CH ₃ ) ₂ cci = cci ₂ H 0 - - 15 (100) - 20 2,6- (CH ₃ ) ₂ ch ₂ ci H nch ₂ ch = ch ₂ - - 0 (100) - 21 2.6- (CH ₃ ) ₂ ch ₂ ci H NH - - 0 (100) - 22 2,6- (CH ₃ ) ₂ ch ₂ ci H N (3-CH ₃ 4 -C 1-) - - 32 (100) - 23 2,6- (CH ₃ ) ₂ 4-C1 H nch ₃ - - 0 (100) - 24 2,4,6- (CH ₃ ) ₃ ch ₂ ci H 0 - - 0 (100) - 25 2-CH ₃ -6-tC ₄ H ₉ ch ₂ ci H 0 - - 0 (100) - 26 3,4- (CH ₃ ) ₂ ch ₂ ci H 0 12 (100) - 87 (100) - 27 open-chain ester ** 78 (100) 32/152 96 (100) 5/10 28 captafol *** 84 (40) 22/54 74 (200) 100/310 100 (40) 2/13 100 (40) 5/19 29 burgundy juice (contains water as solvent) 92 (16) 86 (16)

* ED _S0 (50% control spray in ppm)

FD o (spray for 90% control in ppm) = phenyl group ** N- (1-methoxycarbonylethyl) -N- (chloroacetyl) -2,6-dimethylaniline (1,445,387) (c) N-cis-N- (1,2,2-tetrachloroethylthio) 4-cyclohexene-1,2-dicarboximide.

-6184.05

III. spreadsheet

Fermentation experiment

Experimental compound Concentration p.p.m. One day Weight loss in g due to CO ₂ removal 8 days 2 days 3 days 4 days after 7 days Compound A 1 0.9 5.0 10.5 11.3 14.2 14.5 2 0.8 5.2 10.4 11.1 13.4 13.7 4 1.0 5.2 10.4 11.1 13.1 13.3 8 1.0 5.4 11.0 11.8 14.5 15.2 Trade 1 0.4 0.5 2.8 3.6 8.9 10.1 fungicidal 2 0.2 0.4 1.3 1.8 4.7 5.6 4 0.4 0.4 0.7 0.8 2.1 3.1 8 0.3 0.4 0.7 0.7 1.2 1.5 - - 0.9 5.4 11.1 11.6 14.2 14.5

The fungicidal active ingredient already available is captafol, fentin acetate (triphenyltin acetate), chlorothalonil (2,4,5,6-tetrachloroisophthalonitrile) and copper (II) sulfate. We use the cut leaves of Carignane and Emperor grapes as host plants. The leaves were inoculated with the 25 experimental organisms and then incubated for 1 to 3 days (1-2 days for Emperor leaves and 2 days for Carignane leaves) in a climate chamber maintained at 18-22 ° C and approximately 100% relative humidity. . The leaves were subsequently the test compounds in acetone oldata- 30 with sprayed, and the sprayed leaves are stored at or near 100% RH _and 18-22 compliance. 8 to 9 days after inoculation, the extent of the disease is determined. The percentage reduction in disease provided by a particular test compound is a percentage reduction relative to untreated control plants. IV. Table I shows the test compounds, the type of vine leaves, the duration of treatment with the test compound (in days after inoculation) and the results in ED _S0 40 and ED _go (as defined in Table I).

ARC. Table 45

Grape-gray soothing effect

Test compound Emperor leaves Cariqnane- letters 3 days One day 2 days Compound A 9.3 / 58 27/99 20.7 / 113 captafol 55/145 64/168 206/670 fentin 47/171 88/219 254/562 chlorothalonil 128/293 410/1000 313/992 copper (II) sulfate * 118/289 204/445 380/610

It contains water as solvent.

Example 10 - Gray mold removal effect

The wettable powder composition of the wettable powder composition containing Compound A with attapulgite clay was tested on vine leaves. The host plant used is a three-month, single-shoots cabernet Sauvignon variety with 6-10 leaves grown on coarse sand. The backs of the leaves were sprayed with an aqueous spore suspension of Plasmopora viticola at 510,000 conidium / ml, and the inoculated cuttings were then placed in a steam-saturated chamber. An aqueous suspension of the test compound at 62.5 ppm was then sprayed onto the cuttings at a rate of close to 3.5 ml / 100 cm ² leaf area four times after inoculation. The degree of disease control is determined 10-11 days after vaccination. The percentage reduction in disease provided by a given compound is the percentage reduction relative to an untreated control plant. The results are shown in Table V.

Table V.

Duration between inoculation and treatment in days fungicidal concentration metabolize (Ppm) Percent infected levélfelü- being Percent disease- inspector- ing 1 0 21 1 62.5 0.51 97.6 2 0 14.3 - 2 62.5 0.55 96.2 3 0 27,14 - 3 61.5 4.15 84.7 5 0 29.84 91.6 5 62.5 2.5 -

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Example 77 - Residual activity against grape gray mold

To test for the effect indicated in the title, a wettable powder formulation containing Compound A on Attapulgite Clay was experimented with on vine leaves. The host plant is a three-month cuttings of unicorn Cabemet Sauvignon cultivated on rough sand with 5-8 leaves. The cuttings were sprayed with an aqueous suspension of the test compound at a concentration of 160 ppm at a leaf area of approximately 4 ml / 100 cm ² . The cuttings are then placed in a 90-95% relative humidity climatic chamber and the back of the leaves is sprayed with a spore suspension of Plasmopora viticola 3 days after treatment with the active ingredient. The inoculated cuttings are then stored in a steam-saturated chamber and then inoculated 8-10. days, determine the extent of disease control. The percentage of disease control provided by a particular test compound is the percentage reduction relative to untreated control plugs. The results obtained are shown in Table VI. Table.

VI. spreadsheet

Residual effect against grape-gray mold

Inoculation and manual fungicidal Percent Percent between concentration infected disease- period established by them levélfelü- inspector- days (Ppm) being ing 3 0 12.81 3 160 0.03 99.8

Example 12 - Prevention of Foliage Gray Fungal Infection by Root Treatment

The title effect was investigated with a wettable powder formulation of Attapulgite containing 50% Compound A as active ingredient. The host plant used is a three-month, single-shoots, 9-12 leaf Cabernet Sauvignon cuttings grown on coarse sand. The roots of the cuttings are immersed for 6 hours in an aqueous suspension containing 50 ppm of the test compound. The cuttings are then replanted on coarse sand and placed in a steam-saturated chamber. The backs of the leaves are treated with a spore suspension of Plasmopora viticola at four different times after root treatment. The inoculated cuttings are then repeatedly placed in a steam-saturated chamber to aid in the development of the disease. The degree of disease control is determined 10-12 days after vaccination. The percentage of disease control provided by a particular test compound is the percentage reduction relative to untreated control plugs. The results obtained are shown in Table VII. table.

VII. spreadsheet

Treatment of grape-gray mold by absorption through the root system

Period between root treatment and inoculation per day fungicidal concentration metabolize (Ppm) Percent infected levélfe- site on Percent disease- inspector- ing 1 0 10.92 _ 1 50 6.26 33.5 5 0 17.51 5 50 0.32 98 9 0 10.11 - 9 160 0.19 99 16 0 39.35 - 16 160 22.43 43 Example 13 - Checking for lettuce gray mold It contains the active 50% Compound A containing attapulgit clay made wettable porkészít-

to determine if it is capable of controlling the gray mold caused by Bremia lactucae in lettuce.

Seeds of Marty's lettuce are sown in plastic bowls containing a mixture of two-thirds compost and one-third sandy soil. The plates are then kept in a greenhouse at 17-24 ° C. Six days after planting, the cotyledonous seedlings are sprayed with an aqueous suspension containing different concentrations of the test compound (one dish is used to test one concentration). One day after application of the fungicidal agent, the seedlings are sprayed with an aqueous spore suspension of said fungus containing 140,000 conidia per milliliter. The seedlings were then placed in a humid chamber providing 12-14 ° C and 12 hours of artificial light per day. Eight days after inoculation, the degree of disease control is determined by counting the number of viable seedlings per bowl. The results for the test compound, two commercially available fungicides and the untreated control are shown in Table VIII. are summarized in Table.

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VIII. spreadsheet

Effect against lettuce gray mold

fungicidal q active ingredient per fish the seedlings would close together per bowl perished seedlings percent The proportion percent control , Λ ” 25 689 5.9 75.8 Compound A 50 780 1.1 90.6 Compound A 100 780 2.3 95.5 captafol 160 614 3.6 85.2 maneb * 160 422 14.5 40.6 untreated contaminated control _ 363 1.9 untreated contaminated control - 427 24.4 -

* private ethylene bis (dithiocarbamate).

Example 14 - Preventive and curative action against cabbage greenspread A wettable powder formulation of Attapulgite Clay containing% Compound A as an active ingredient was tested for its ability to control Peronospora parasitica ssp. brassicae caused by gray cabbage.

(a) Preventive effect

Milanese hatif d'Aubervilliers cabbage seeds are planted in plastic bowls containing a mixture of three parts compost and one part sand. The plates were then kept in a humidified 35-air greenhouse, and 7 days after planting, the cabbage seedlings were sprayed to a damp soil with an aqueous suspension of the test compound in various concentrations. Two days after the application of the fungicidal agent, the dishes containing the cabbage seedlings are sprayed with an aqueous spore suspension of said fungus containing nearly 300,000 conidia per milliliter.

11 days after inoculation, the disease control rate was determined by counting the number of diseased seedlings of unicellular 45-state white mycelium. The results obtained with Compound A and a commercially available comparative fungicide and untreated control are shown in Table IX. table.

(b) Termination effect

The seeds referred to in part a) are sown in the soil of the composition also described in part a), and after being kept in a humid environment, 3 to 3 bowls are sprayed with the spore suspension mentioned in part a) 9 days after sowing. Four days after inoculation, the seedlings in the bowls were sprayed with drip wet with aqueous suspensions of the test compound in various concentrations. Seven days after application of the fungicidal agent, the degree of disease control is determined by counting the number of seedlings of unicellular white mycelium. The results obtained with Compound A, a commercially available comparative fungicide and untreated control are shown in Table IX. table.

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IX. spreadsheet

Check for cabbage gray mold

Preventive effect

fungicidal q active ingredient per hl the seedlings would close together per bowl perished seedlings percent The proportion ¹⁷ percent control Compound A 80 231 1.5 98.5 Compound A 40 138 2.2 97.7 Compound A 20 171 1.8 98.2 captafol 160 161 59.6 38.9 inoculated control - 175 97.6 - unvaccinated controls 177 1.7

Withdrawal effect

fungicidal q active ingredient per hl the seedlings would close together per bowl perished seedlings percent The proportion percent control Compound A 80 155 0.6 99.4 Compound A 40 203 1.0 99.0 Compound A 20 165 1.8 98.2 captafol 160 148 65.5 32.9 inoculated control - - - - unvaccinated controls - - - -

¹⁷ reduction of disease compared to a control plate not treated with a fungicidal agent.

Example 15 - Control of cucumber gray mold by foliage treatment

Compound A is an experiment using foliar spray to determine its ability to control 40 cucumber gray molds caused by Pseudoperonospora cubensis.

A 3-week cucumber plant of the Marker variety is sprayed with a suspension of the test compound in a mixture of 1% acetane and 99% water containing a non-ionic surfactant at a concentration of 40 ppm. Four leaves are then cut off and dried and sprayed with a spore suspension of said fungus. After inoculation, the leaves are kept in a humid climate at 20-25 ° C. After 6 days, the infection rate was determined. The percentage reduction in disease provided by a particular test compound is the percentage reduction compared to untreated control leaves. The test compounds, their concentrations and the percent control results obtained are given in Table X.

Inspection of cucumber gray mold by foliar spraying

Test compound Concentration (Ppm) Percent control Compound A 100 100 Compound A 40 88 Compound A 16 63 maneb 100 98.3 maneb 40 90 maneb 16 80

Example 16 - Action against foliage and root rot in sepsis

Compound A is tested to determine whether it is effective against phytophthora cryptogea in sycamore (rootstocks of Antirrhinum species)

-10184 055 In the suppression of warfare, however, we also investigate kappa and mancozeb for comparison purposes.

(a) Soil test

From pots containing young plants, the plants were transplanted into pots containing 13 cm of soil soil contaminated with the said fungus, and 40 ml of an aqueous solution containing the test compound at 100 ppm was poured into each pot. The plants are then placed in a greenhouse to help the disease develop. Five days after treatment, the plants are examined for leaf necrosis, opacities, and coronary anthrax. The percentage disease control provided by the test compound is the percentage reduction in disease relative to the untreated control plant. The results obtained are shown in Table XI. table.

(b) Foliage spraying experiment

As described in part a), young plants are transplanted into infected soil, covered with plastic in the pots and sprayed on the foliage of the plants with an aqueous suspension of the test compound at 100 ppm. The plants are then placed in a greenhouse to aid in the development of the disease and examined 5 days after treatment for leaf necrosis, decay, and coronary anthrax. The percentage disease control provided by the test compound is the percentage reduction in disease relative to the untreated control plant. The results obtained are also shown in Table XI. Table.

XI. spreadsheet

Effect of cranberry and root rot on sepals

Percentage control

Test compound talajázta- OTING lombozatper- metezés Compound A 100 97 captafol 0 0 mancozeb * 0 0

* a mixture of manganese and zinc ethylene bis (dithiocarbamate)

Example 17 - Systematic foliage management of safflower crown and root rot

Compound A is tested for systemic efficacy in foliar treatment for the treatment of foliage and root rot caused by Phytophthora cryptogea.

Safflower plants are used as host plants for two weeks. Pots containing these plants are sprayed with aqueous solutions containing the test compound in various concentrations. One day after the treatment, the fungus mesh obtained by cultivating said fungus in a mixture of oatmeal, burghole dextrose and soil was poured onto the soil in the pots. The inoculated plants are then stored in a greenhouse at 20-25 ° C during the day and 15-20 ° C at night. 3-4 weeks after inoculation, the roots and foliage of the plants are examined to determine the extent of the disease. The percentage disease control provided by the test compound is the percentage reduction in disease relative to the untreated control plant. The results obtained are shown in Table XII. table.

XII. spreadsheet

In the case of safflower, anti-rusting is achieved by foliar spraying

Test compound Concentration ppm Percent control , Compound A 100 100 2,6-Dimethyl-N - (chloro) 40 97 -acetyl) -N - (1-methoxy- 16 92 carbonyl) -aniline 100 10 40 0 16 0 5-ethoxy-3- (trichloro- 100 61 methyl) -1,2,4-tiadia- 40 1 zol ^{1 z} 16 0

^lz Nos. ^{3,260,588 and 3,260,725} . a compound known from U.S. Patents.

Example 18 - Systematic treatment of safflower foliage and root rot by soaking

To test for the effect indicated in the title, compound A was tested using the fungi Phytophthora cryptogea and Phytophthora parasitica.

Two weeks old safflower seedlings are used as hosts. The pots containing these seedlings were then poured into an aqueous suspension of the test compound in various concentrations (using four pots to test one concentration) and the fungal yarn obtained as in Example 17 was poured onto the soil surface of the pots 1 day after treatment. The inoculated seedlings are then kept in a greenhouse under the same conditions as in Example 17 and evaluated for the degree of disease 3-4 weeks after inoculation. Percentage disease control provided by experimental compound 11184,055 is provided by the percentage reduction in disease relative to the untreated control plant. The results obtained are shown in Table XIII. table.

XIII. spreadsheet

In safflower, anti-rusting is achieved by soaking the soil

Test compound concentration rationality ppm Percentage control P.cryp- toqea P.parasiti- ca Compound A 100 * 100 100 40 97 99 16 92 94 (5-ethoxy-3-trik- 100 78 80 chloropyridine-methyl-1,2,4- 40 12 21 -diazol 16 0 0

* 100 ppm = 50 micrograms / cm ²

Example 19 - Systemic Soil Treatment to Prevent Tobacco Crown and Root Rot

To test the effect mentioned in the title, compound "A" was tested using Phytophthora parasitica and Phytophthora cryptogea fungi as experimental organisms.

The host plant is 10-week old Glurk-type tobacco seedlings. The soil of the pots containing these seedlings was treated with aqueous solutions containing the test compound at various concentrations (four pots per assay), and the fungus fabric prepared as described in Example 17 was applied to the pots one day after the treatment. The seedlings thus inoculated are then stored in a greenhouse under the conditions described in Example 17. Three to four weeks after inoculation, the crowns and roots of the seedlings are examined to determine the extent of the disease. The percentage disease control provided by the test compound is the percentage reduction in disease relative to the untreated control plant. The results obtained are shown in Table XIV. table.

XIV. spreadsheet

Soil treatment against tobacco crown and root rot

Test compound concentration rationality ppm Percentage control P.crypto- qea P.parasi- tica Compound A 100 * 100 100 Compound A 40 99.8 99.8 Compound A 16 96 96 5-ethoxy-3- (trik- 100 80 52 chloromethyl) -1,2,4- 40 48 30 -diazol 16 9 0

* 100 ppm = 50 micrograms / cm ²

Example 20 - An anti-rotting effect on sweet peppers with a wettable powder composition containing Attapulgite Clay containing% 4% of the compound, is carried out on a so-called Phytophthora effect on the sweet pepper caused by Phytophthora capsici in soil.

Doux de Valence four-leaf pepper seedlings are planted in pots filled with sterilized mixture of half compost and half sandy soil. The pots were then inoculated with the test organism by spreading a layer of oat seeds (infected with Phytophthora capsici) on the soil surface and covering this layer with 1 cm thick sterilized soil. The seedlings were then sprayed to seed damp with aqueous suspensions containing the test compound in various concentrations (12 pots were used to test a single concentration). The degree of disease control is determined by counting the number of dead plants. The percentage disease control provided by the test compound is the percentage reduction in disease relative to the untreated control plant. The results obtained are shown in Table XV. table.

-12184.05

XV. spreadsheet

Inhibition of Phytophthora rotting in tobacco

fungicidal concentration established by them * Percentage of live seedlings percent inspector- ing impaired leaf area %-in 100 50 25 0 200 100 100 1.3 400 100 100 1.63 0 33.3 - 0

* Ppm

Example 21 An emulsifiable concentrate containing 3- (N- (chloroacetyl) -N- (2,6-dimethylphenyl) amino) gamma-butyrolactone by weight was prepared so that 10.2 g of said lactone was prepared. (99% purity) was mixed with 949.8 g of xylene and an emulsifier containing 20 g of calcium alkylbenzene sulfonate and 20 g of octylphenol ethoxylate [two products under the trade names Atlox 3403F and Atlox 3404F under the trademark ICI Americas (Wilmington, Delaware, United States).

Example 22 An emulsifiable concentrate containing 3- (N- (chloroacetyl) -N- (2,6-dimethylphenyl) amino) gamma-butyrolactone by weight was prepared by preparing 51 g of said lactone. 994% purity) was mixed with 884g xylene, 25g cyclohexanone and 40g of the emulsifier composition of Example 21.

Example 23

An aqueous base liquid concentrate containing 35.5% by weight of 3- (N- (chloroacetyl) -N- (2,6-dimethylphenyl) amino) gamma-butyrolactone is prepared by preparing 375% of said lactone. 2 g (95% purity) are mixed with 490.7 g water, 196 g polyvinyl alcohol, 14.3 g silicone antifoam (under the trademark "Antifoam C", Dow Corning Company Midland, Michigan), 98 g propylene glycol, 2 g sodium citrate, 2 g xanthan gum, 18 g octylphenol ethoxylate (see Example 21) and 2 g of an antioxidant mixture. , a mixture of hydroxytoluene and hydroxyanisole esterified with butyl alcohol (sold under the tradename "Tenox 6" by Eastman Chemicals Co., Kingsport, Tennessee, United States),

Example 24 A wettable powder composition containing 3- (N- (chloroacetyl) -N- (2,6-dimethylphenyl) amino) gamma-butyrolactone by weight is prepared so that 808 g (99%) of said lactone14 are prepared. % purity) is mixed with 142 g of attapulgite and 50 g of a dispersant marketed in the United States of America by Witco Chemical Company (Houston, Texas) under the trade name of lignosulfonate, tauride and sulfosuccinate.

Example 25 A wettable powder composition containing 3- (N- (chloroacetyl) -N- (2,6-dimethylphenyl) amino) gamma-butyrolactone by weight is prepared by 657 g of said lactone. 99% purity) was mixed with 293 g of attapulgite and 50 g of the dispersant mentioned in Example 24.

Example 26 A wettable powder composition containing 3-% of N- (chloroacetyl) -N- (2,6-dimethylphenyl) amino-gamma-butyrolactone by weight is prepared so that 521 g of said lactone is obtained. 96% pure), mixed with 379 g of talc, 50 g of synthetic silica and 50 g of the dispersant mentioned in Example 24.

Example 27 Weight = A wettable powder formulation containing 3- (N- (chloroacetyl) -N- (2,6-dimethylphenyl) amino) gamma-butyrolactone is prepared by 206 g of said lactone. 97% pure), mixed with 734 g of powdered calcium carbonate and 50 g of the dispersant mentioned in Example 24.

Example 28 A wettable powder composition containing by weight (3- (N- (chloroacetyl) -N- (2,6-dimethylphenyl) amino) gamma-butyrolactone) is prepared by 103 g of said lactone. mixed with 847 g of kaolin and 50 g of the dispersant mentioned in Example 24.

Example 29 A powder containing 3- (N- (chloroacetyl) -N- (2,6-dimethylphenyl) amino) gamma-butyrolactone by weight was prepared so that 909 g (99%) of said lactone was prepared. % purity) is mixed with 91 g of finely powdered kaolin.

Example 30 A powder containing 3- (N- (chloroacetyl) -N- (2,6-dimethylphenyl) amino (gamma) -butyrolactone by weight is prepared by mixing 253 g of said lactone with g of finely powdered kaolin.

Example 31

An aerosol is prepared by first 40.8 g of 3- (N-13184,055)

- (chloroacetyl) -N- (2,6-dimethylphenyl) amino) gamma-butyrolactone (99% purity) was mixed with 969.7 g of very fine particle size kaolin. To the mixture thus obtained is added a pressurized gas mixture (2000 g) consisting of 30% by weight of propane and 70% by weight of isobutane. The resulting mixture is then filled under pressure into containers capable of delivering spray. When operating the container, an aerosol powder containing 4% by weight of said lactone leaves the container. Apart from the weight of the propellant gas, the composition contains 1.3% by weight of active ingredient.

EXAMPLE 32 A particulate preparation containing 3- (N- (chloroacetyl) -N- (2,6-dimethylphenyl) amino-gamma-butyrolactone (w / w) was prepared by weight of 786 g of said lactone. is mixed with 286 g of pine resin of natural origin and 10 g of hydroxytoluene butyl ester as an antioxidant.

Example 33 A particulate preparation of 3- (N- (chloroacetyl) -N- (2,6-dimethylphenyl) amino (gamma) butyrolactone is prepared by weight, from which 102 g of said lactone is obtained. (98% purity) with 738 g of particulate diatomaceous earth and 160 g of N-methylpyrrolidone.

Example 34 A granular composition containing 30% by weight of 3- (N-chloroacetyl / -N- / 2,6-dimethylphenyl / amino) gamma-butyrolactone was prepared by making 102 g of said lactone ( (98% purity) was mixed with 718 g of particulate diatomaceous earth, 160 g of dimethylformamide and 20 g of octylphenol ethoxylate (see Example 21).

Example 35% by weight of 3- (N- (chloroacetyl) -N- (2,6-dimethylphenyl) amino) gamma-butyrolactone was prepared so that 50.5 g (99%) of said lactone was prepared. % purity) is mixed with 949.5 g of granular diatomaceous earth.

Claims (2)

Patent claims CLAIMS 1. A fungicidal composition against gray mold on plants caused by Peronosporaceae fungi, characterized in that the active ingredient is 0.5 to 95% by weight of a 3- (N- / chloroacetyl) -N- / 2,6-dimethyl compound of formula (I) -phenylamino-gamma-butyrolactone, wherein R is hydrogen or methyl, containing from 5 to 99.5% by weight of an excipient, preferably a solid or liquid inert carrier, preferably water, an organic solvent or a clay. optionally together with an anionic or nonionic surfactant, preferably an emulsifier or dispersant. (Priority: October 12, 1976) 2. A fungicidal composition against rot in the canopy and root system of soil-dwelling phytophthora fungi, characterized in that the active ingredient is 0.5 to 95% by weight of a 3- (N- / chloroacetyl / -N- / Containing 2,6-dimethylphenyl (amino) gamma-butyrolactone, wherein R is hydrogen or methyl, containing from 5 to 99.5% by weight of an excipient, preferably a solid or liquid inert carrier, preferably water, an organic solvent. or a clay formulation and optionally an anionic or nonionic surfactant, preferably an emulsifier or dispersant. (Priority: September 29, 1977)