GB2137620A - Fungicidal acrylanilide derivatives - Google Patents

Abstract

Acrylanilide derivatives having fungicidal activity are represented by the general formula: <IMAGE> wherein n is 1 or 2, X is chloro or trifluoromethyl, and one of Y and Z is hydrogen and the other is chloro.

Description

SPECIFICATION Fungicidal acrylanilide derivatives This invention relates to 2,3-dichloro-3-methylsulfonyl and sulfinyl acrylanilides which are effective as fungicides.

Sincetheworid is dependent on an ever-decreas ing amount of cultivated land to produce cropsto feed an ever-increasing population,itis importantto develop fungicides which protect crops from destruction byfungal pests.

The compounds ofthis invention are represented by the general formula:

wherein n is 1 or 2, is chloro ortrifluoromethyl, and one of Y and Z is hydrogen and the other is Dichloro.

The present invention is based on the surprising finding thatthe compounds ofthis invention are effective as anti-fungal agents, and are particularly effective in combatting plantfungal diseases. These compounds are especially effective in preventing plantfungal diseases, such as Grape Downy Mildew and Celery Late Blight.

The compounds ofthis invention are conveniently prepared according to the following reaction scheme:

wherein n, X, Y and Z are as previously defined in connection with Formula I, and b is a base.

Reaction (1) is conducted by combining approx imately equimolaramounts of Ill and IV in an inert organic solvent. Although the reactants may be combined in any order, it is preferred to add Ill to a mixture of II and IV in solvent. Suitable solvents include aprotic solvents, such as toiuene, benzene, ethyl acetate, dimethoxyethane, ethyl ether, chlorinated hydrocarbons, such as methylene chloride or chloroform, and the like. The base, b, is preferably an organic base, such as triethylamine or pyridine. The reaction is conducted at a temperature of about 20"C to about 100 C, preferably about 20 Cto about 50 C.

For convenience, the reaction may be carried out at ambienttemperature and pressure. The reaction is generally complete within about 1 to about48 hours.

The productVis isolated by conventional procedures, such as stripping, extraction,filtration, crystallization and the like.

Reaction (2) is conducted by combining IV, V and VI in an inert organic solvent. It is preferred to add VI to a mixture of IV and V in solvent. Suitable solvents include methanol, methylene chloride, dimethoxyethane and the like. The base, b, is preferably an organic base, such as triethylamine, pyridine and the like. The reaction is carried out at a temperature of about 20"C to about 80"C, preferably from about 20"C to about 50"C. For convenience, the reaction may be carried out at ambient temperature and pressure. The reaction is generally complete within about 1 to about 48 hours. The product Vll is isolated by conventional procedures, such as stripping, extraction, filtration, crystallization and the like.

Reaction (3) is a conventional oxidation of a sulfide to give the sulfoxide or sulfone. Although metachlor- operoxybenzoic acid (MCPBA) is the preferred oxidizing agent, other suitable oxidizing agents may be employed and include other peroxy acids, such as peroxyacetic acid, hydrogen peroxide in glacial acetic acid and the like. The ratio of MCPBA (VIII) to VII used determineswhetherthesulfinyl orsulfonyl compound is formed. Thus, if the sulfinyl compound is desired, the ratio of MCPBAto VII used is about 1:1.

However, ratios of MCPBA (VIII) to VII of about 2 or greaterwill yield the sulfonyl compound. The reaction is carried out in the presence of a solvent or diluentinerttothe reactants. Suitable solvents include methylene chloride, chloroform and the like.

The reaction is carried out at a temperature of about 20"C to about 1 00 C, preferably about 30"C to about 50"C and is generally complete within about 1 to about 48 hours. For convenience the reaction may be carried out at ambient temperature and pressure.

Utility The compounds of the invention are effective in controlling fungal infections. Some ofthe compounds ofthis invention are particularly effective in controlling powdery mildewfungal infections caused by the organism Ersyiphe polygoni, Some of the compounds ofthis invention are also useful for controlling leaf blights caused by organisms such as Phytophthora infestans conidia, Alternaria solani conidia, and Septoria apii. Some of the compounds of this invention are also useful forcontrolling fungal infections caused by Uromyces phaseoli tipica, Plasmopara viticola, and Piricularia oryzae. However, somefungicidal compounds of this invention may be more fungicidally active than others against particu- larfungi.

When used as fungicides, the compounds ofthe invention are applied in fungicidally effective amounts to fungi andlortheir habitats, such as vegetative hosts and non-vegetative hosts, e.g., animal products. The amount used will, of course, depend on several factors such as the host, the type offungus, and the particular compound of the invention.As with most pesticidal compounds,the fungicides of the invention are not usuallyappliedfull strength, but are generally incorporated with conventional, biologically inert extenders or carriers normal ly employed for facilitating dispersion of active fungicidal compounds, recognizing thattheformula- tion and mode of application may affect the activity of the fungicide. Thus, the fung icides ofthe invention may be formulated and applied as granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.

Wettable powders are in the form offinely divided particles which disperse readily in water or other dispersants. These compositions normally contain from about 5% to 80% fungicide, and the rest inert material, which includes dispersing agents, emulsifying agents and wetting agents. The powder may be applied to the soil as a dry dust, or preferably as a suspension in water. Typical carriers include fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wettable, inorganic diluents.Typical wetting, dispersing or emulsifying agents include, for example: the acryl and alkylaryl sulfonates and their sodium salts; alkylamide sulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sul fated higher alcohols and polyvinyl alcohols; polyethylene oxides; sulfonated animal and veget able oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition products of long-chain mercaptans and ethylene oxide. Many othertypes of useful surface-active agents are available in commerce. The surface-active agent, when used, normally comprises from 1% to 15% byweightofthefungicidal composition.

Dusts are freely flowing admixtures of the active fungicidewith finely divided solids such as talc, natural clays, kieselguhr, pyrophyllite, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, and other organic and inorganic solids which act as disperants and carriers for the toxicant. These finely divided solids have an average particle size of less than about 50 microns. Atypical dust formulation useful herein contains 75% silica and 25% oftoxicant.

Useful liquid concentrates include the emulsifiabie concentrates, which are homogeneous liquid or paste compositions which are readily dispersed in waterorotherdispersant, and may consist entirely of thefungicidewith a liquid or solid emulsifying agent, or may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isophorone, and other nonvolatileorganicsolvents. For application, these concentrates are dispersed in water or other liquid carrier, and are normally applied as a spray to the area to be treated.

Other useful formulationsforfungicidal applications include simple solutions of the activefungicide in a dispersant in which it is completely soluble atthe desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents.

Granularformulations, wherein the fungicide is carried on relatively coarse particles, are of particular utilityforaerialdistribution orforpenetrationof cover-crop canopy. Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low-boiling dispersant solvent carrier, such as the Freons, may also be used. All ofthose techniques for formulating and applying fungicides are well known intheart.

The percentages byweight ofthefungicide may vary according to the manner in which the composition isto be applied and the particulartype of formulation, but in general comprise 0.5% to 95% of the toxicant by weight ofthe fungicidal composition.

Thefungicidal compositions may be formulated and applied with other active ingredients, inciuding otherfungicides, insecticides, nematocides, bactericides, plant-growth regulators or fertilizers.

Afurtherunderstanding ofthe invention can be had fromthefollowing non-limiting Examples wherein, unless expressly stated to the contrary, all temperature ranges referto the Centigrade system and the term "ambient" or "room temperature" refersto about 20"C to 25"C. The term "percent" refers to gram moles. The term "equivalent" refers to a quantity of reagent equal in moles, to the moles ofthe preceding orsucceeding reagent recited in that example in terms of finite moles orfinite weight orvolume. Also, unless expressly stated to the contrary, geometric isomer and racemic mixtures are used as starting materials and correspondingly, isomer mixtures are obtained as products.

Compounds which were prepared in accordance with Examples 1 through 10 below are found in Table EXAMPLES Example 1 Preparation of 2,3,3-Trichloro-3',4'-dichloroacrylanilide

To a stirred mixture of 10 g (0.0617 moles) 3,4-dichloroaniline and 8.6 ml (0.0617 moles) triethylamine in 150 ml methylene chloride, 7.3 ml [11.96 g (0.0617 moles)j trichloroacryloyl chloride were added dropwise. The addition reaction was exothermic, with reflux occurring during the addition. The reaction mixture was then stirred overnight at room temperature. The mixture was washed with water and then dried over magnesium sulfate. Thesolvent was stripped to give 18.9 g of a yellow solid which was then recrystallized from methylene chloride to give 13.0 g of the product, a light yellow solid, m.p.

123-128"C.

Example 2 Preparation of 2,3 - Dichloro - 3 - methylthio - 3',4' dichloroacrylanilide

To a mixture of 13 g (0.041 moles) of 2,3,3-trichioro- 3',4'-dichloroacrylanilide (the product of Example 1) and 6.3 ml (0.0451 moles)triethylamine in 100 ml methanol, 28 ml of a 2.18M solution of methanethiol in methanol (0.061 mole) were added dropwise with stirring. The addition was mildly exothermic. The reaction mixture was stirred an additional hour after the addition was complete. To the reaction mixture, 300 ml I of ofwaterwere added which caused the product to precipitate. The precipitate was filtered and airdried overnightto give 14.0 g of a white solid. The solid was dissolved in methylene chloride and the resulting mixture cooled with dry ice to give 5.8 g of white crystals.Hexane was added to the mother liquor and the mixture cooled again with dry ice, yielding another crop of 3.6 g, to give a total yield of 9.4 g of product.

Example 3 Preparation of 2,3 - Dichloro - 3 - methylsulfonyl - 3',4' dichloroacrylanilide

To a stirred mixture of 4.0 g (0.0121 moles) of 2,3 dichloro -3 - methylthio - 3',4' - dichloroacrylanilide (the product of Example 2) in 100 ml chloroform, 4.6 g (0.0277 moles) of 85% m-chloroperoxybenzoic acid (MCPBA) were added in portions. The reaction mixture was then stirred at room temperature overnight and the next day (about 36 hours). The reaction mixture was then washed with a saturated sodium carbonate solution, and dried over magnesium sulfate. The solventwas partly stripped and the resulting mixture allowed to stand overnight at which point a crop of crystals formed. Collection ofthe crystals by filtration gave 2.5 g of the product, melting point 187-190"C.

Elemental analysisforC10H7CI4NO3S showed: calculated %C 33.08, %H 1.94 and %N 3.86; found %C33.71,%H2.11,and%N4.17.

Example 4 Preparation of Z,3,3-Trichloro-3',5'-dichloroacrylanilide

To a stirred mixture of 15 g (0.0926 mole) 3,5 dichioroaniline and 12.9 ml (0.0926 mole) triethylamine in 150 ml methylene chloride, 17.95g [10.9 ml (0.0926 mole)j trichioroacryloyl chloride were added dropwise. The resulting mixture was stirred overnight at room temperature. The reaction mixture was then washed with dilute hydrochloric acid which caused a large amount of solid to precipitate.

Filtration of the mixture and recrystallization of the solid from methylene chloride gave 10.5g of an off-white solid, melting point 131-135"C.

Example 5 Preparation of 2,3- Dichloro - 3 - methylthio - 3' - 5' - dichloroacrylanilide

To a stirred mixture of 10.5 g (0.033 mole) of 2,3,3 Trichioro - 3',5' - dichloroacrylanilide (the product of Example 5) and 5 ml (0.036 mole) triethylamine in 100 ml methanol, 23 ml of a 2.18M solution of methanethiol in methanol (0.050 mole) were added dropwise. The resulting mixture was stirred overnight at room temperature. Then, 300 ml water were added to the reaction mixture, causing the crude product to precipitate. The mixture was filtered to give a white gummy solid. The solid was dissolved in methylene chloride and the small amount of aqueous phase removed by separation. The methylene chloride phase was dried over magnesium sulfate. Hexane was added to the mixture.The hexane-methylene chloride mixture was cooled with dry ice, at which point 3.5 g white crystals (melting point 105-107 C) were obtained. Additional concentration of the mother liquor, followed by cooling, yielded an additional 1.3 g of crystals.

Example 6 Preparation of 2,3 - Dichloro - 3 - methylsulfinyl - 3',5' - dichloroacrylanilide

A mixture of 24 g (0.0072 mole) of 2,3 - dichloro - 3 methylthio - 3',5' - dichloroacrylanilide (the product of Example 5), and 1.5 g (0.0074 mole) of 85% meta ch loroperoxybenzoic acid in chloroform was stirred overtheweekend (about 72 hours) at room temperature. The reaction mixture was then washed with a saturated sodium bicarbonate solution and then dried over magnesium sulfate. The chloroform mixturewas partially stripped and then 2 parts hexane were added to the mixture. The product began to crystallize at room temperature. The mixture was cooled slightly and filtered to give 1.7 g of white solid.

Chromatography on silica gel, eluting firstwith methylene chloride and then with ethyl acetate gave 1.3 g ofthe product, a white solid, melting point 175-182"C.

Elemental analysis for CfoH7C14NO2S showed: calculated %C 34.50, %H 1.72, and %N 4.02; found %C34.91, %H2.38,and %N3.94.

Example 7 Preparation of 2,3 - Dichloro - 3 - methylsulfonyl - 3',5' - dich loroacrylan llide

To a mixture of 2.4 g (0.0072 mole) of 2,3 - dichloro 3 - methylthio - 3',5' - dichloroacrylanilide (the product of Example 5) in 100 ml chloroform, 3.0 g (0.015 mole) of 85% meta-chloroperoxybenzoic acid were added in portions. The resulting mixture was then stirred two days at room tem peratu re. The chloroform mixture was washed with a saturated sodium bicarbonate solution. The solventwasstrip- ped, and the residue was chromatographed on silica gel, eluting with methylene chloride, to give 2.4 g of the product, a white solid, melting point 172-174"C.

Elemental analysis for C10H7Cl4NO3S showed: Calculated %C32.99, %H 2.21, and %N 3.85; found %C 32.88, %H 1.95, and % N 4.07.

Example 8 Preparation of 2,3,3 - Trichloro - 3' - trifluromethyl- 4' chloroacrylanilide

To a mixtureof 10 9 (0.051 mole) 3-trifluromethyl-4- chloroaniline and 4.0 g (4.1 ml [0.051 mole]) pyridine in about 10 ml methylene chloride, 9.9 g (6.05 ml) [0.051 molel) trichloroacryloyl chloride in a small amount methylene chloride were added dropwise.

The reaction mixture was stirred fortwo hours after the addition was complete. The reaction mixture was washed three times with 5% HCI, dried over magne sium sulfate, and stripped to give 19.3 g of a red oil.

The red oil was passed through a short silica gel column (elutingwith methylene chloride) to remove the red color, yielding 18 g ofthe product, a pink oil.

Elemental analysis for C10H4C14F3NO showed: calculated %C34.02, %H 1.14, and %N 3.97; found %C35.12, %H 1.3, and %N 4.62.

Example 9 Preparation of 2,3 - Dichloro - 3 - methylthio - 3'- trifluoromethyl - 4'- chloroacrylanilide

To a mixture of 15.5 g (0.044 mole) of 2,3,3 trichloro-3' -trifluoromethyl - 4' - chloroacrylanilide (the product of Example 8) and 6.4 ml (0.046 mole) triethylamine in 150 ml methanol, 24 ml of a 2.18M solution of methanethiol in methanol (0.052 mole) were added dropwise. The reaction mixture was stirred at room temperature for several days. About 200 ml waterwere added to the mixture, which caused a voluminous white precipitate to form.The gummywhite solid was collected by filtration and recrystallized from methylene chloride/hexane, yielding a first crop of g white crystals (melting point 117-120 C). A second crop of 3.8 g crystals (melting point 120-123 C) was obtained from the mother liquor. The two crops combined gave7.6 g of the product.

Elemental analysisfor C11H7C13F3NOS showed: calculated %C 36.23, %H 1.94, and %N 3.84, found %C36.3, %H2.02,and %N4.29.

Example 10 Preparation of 2,3 - Dichloro - 3 - methylsulfonyl - 3' - trifluoromethyl - 4' - chioroacrylanilide

To a stirred mixture of 3.0 g (0.0082 mole) of 2,3 dichloro-3- methylthio - 3'-trifluoromethyl - 4' - chloro - acrylanilide (the product of Example 9) in 75 ml chloroform,3.4g (0.017 mole) of 85% meta chloroperoxybenzoic acid were added. The reaction mixture was stirred several days at room tempera ture. At that pointthere were some solids in the chloroform solution. The m-chlorobenzoic acid formed during the reaction was dissolved by stirring the reaction mixturewith a saturated aqueous sodium carbonate solution.The insoluble solids (containing the product) were filtered and dried in a vacuum oven to give 1.4 g ofthe product as a tan solid, melting point 153-155 C.

Elemental analysisforC11H7Cl3F3NO3S showed: calculated %C 33.31, %H 1.78, and %N 3.53; found %C33.62, %H 1.8 and %N 3.83.

Example A Bean Powdery Mildew The compounds ofthe invention were tested for the control ofthe Bean Powdery Mildeworganism Erysiphe polygoni. Seedling bean plants were sprayed with a 250-ppm solution ofthetest com pound in acetone, water and a nonionicemulsifier.

The sprayed plants were then inoculated 1 day later with the organism. The plantswere maintainedfor 10 days attemperatures of 68 F (20 C) at nightwith daytime temperatures of 72 F to 80 F (22.2-26.7 C); relative humidity was maintained at40% to 60%.The percent disease control provided by a given test compound was based on the percent disease reduc tion relative to the untreated check plants. The results as percent control aretabulated in Table II.

Example B Tomato Late Blight Compounds of the invention were tested for the preventative control oftheTomato Late Blight organism Phytophthora infestans. Five-to six-week old tomato (cultivar Bonny Best) seedlings were used. Thetomato plants were sprayed with a 200-ppm suspension ofthe test compound in acetone, water and a nonionic emulsifier. The sprayed plants were then inocluated 1 day later with the organism, placed in an environmental chamber and incubated at 66 Fto 68"F (18.9-20"C) and 100% relative humidity for at least 16 hours. Following the incubation,the plants were maintained in a greenhouse for approximately 7 days.The percent disease control provided by a given test compound was based on the percent disease reduction relative to untreated check plants. The results as percent control aretabulated in Table II.

Example C Celery Late Blight The Celery Late Blight tests were conducted using celery (Utah) plants 11 weeks old. The Celery Late Blight organism was Septoria apii. The celery plants were sprayed with 200-ppm solutions ofthe candidate toxicant mixed with acetone, water and a nonionic emulsifier. The plants were then inoculated with the organism and placed in an environmental chamber and incubated at 660Fto 68"F (18.9-20"C) in 100% relative humidity for an extended period of time (approximately 48 hours). Following the incubation, the plants were allowed to dry and then were maintained in a greenhouseforapproximately 14 days. The percent disease control provided by a given candidate toxicant is based on the percent disease reduction relative to untreated check plants.The results as percent control are reported in Table II.

Example D Tomato Early Blight Compounds of the invention were tested for the control of the Tomato EarlyBlightorganismAlternar- ia solaniconidia. Tomato (variety Bonny Best) seedlings of 6-to 7-weeks old were used. The tomato plants were sprayed with a 200-ppm solution of the test compound in an acetone-and-water solution containing a small amount of a nonionic emulsifier.

The sprayed plants were inoculated 1 day later with the organism, placed in the environmental chamber and incubated at 66"F to 68"F (18.9-20 C) and 100% relative humidityfor24 hours. Following the incubation,the plants were maintained in a greenhouse for about 12 days. Percent disease control was based on the percent disease development on untreated check plants. The compounds tested and the results as percent control are tabulated in Table ll.

Example E Grape Downy Mildew The compounds ofthis invention were tested for the control ofthe Grape Downy Mildew organism, Plasmopara viticola. Seedlings of Vitis vinifera var.

Emperor (7+ weeks old) were used as hosts. The plants were sprayed with a 200 ppm solution of the test compound in an acetone and water solution containing a small amount of non-ionic emulsifier.

The treated plants were inoculated one day later by spraying them with a spore suspension of the organism. The treated plants were then held in a greenhouse at a temperature of about 68"F (20"C) to about 72'F (22.2"C) (relative humidify varied between about 30 and about 99%) for4 days. The plants were then placed in an environmental chamber at 100% relativityto inducesporulation. On removal from the chamber and after drying, the plants were evaluated for disease development. The percent disease control provided by a given test compound was based on the percent disease reduction relative to untreated check plants. The results as percent control are reported in Table II.

Example F Bean Rust The compounds ofthis invention were evaluated for their ability to eradicate Bean Rust caused by Uromyces phaseoli tipica on pinto beans.

Pinto bean plants, variety Idaho 1 -11,16 (summer) or 19 (winter) days old were inoculated with a 50-ppm suspension of uredospores in watercontaining a small amount of non-ionic surfactant. The inocluated plants were placed in an environmental chamber immediately after inoculation and incubated 20 hours. Following the incubation period, the plants were removed from the chamber and placed in a greenhouse maintained at 66-68 F (18.9-20 C) and 60-80% relatvie humidity. Two days after inoculation, the plants were treated by spraying with a 200-ppm solution of test compound in an acetone and water carrierformulation containing a small amount of non-ionic surfactant. One or two replicate pots (each containing two plants) were used for each compound.In addition one ortwo replicate pots were sprayed with the same carrierformulation (without a test compound) as a control (hereinafter"untreated Checks"). The plants were kept in the greenhouse until evaluated.The plantswere evaluated for disease control when disease symptoms were well developed on the untreated Checks, normally about 14 days after treatment. The percentage disease control (or eradication) provided by a test compound was based on the percent disease reduction relative to the untreated Checks. The results are reported in Table II.

Example G Rice Blast Compounds ofthis invention were tested for control of the Rice Blast organism piricularia oryzae, using 10-to 14-day-old rice plant seedlings (Cal rose M-9 variety). Seedling plants were sprayed with a 625-ppm solution of the test com pound in acetone, water and a non-ionic emulsifier (ORTHO X-77 spreader). The sprayed plants were inoculated 1 day later with the organism in an environmental chamber. Afterinocluation, the plants were kept in an environmental chamberforabout48 hoursunderconditionsofabout720Fto750F (22.2- 23.9"C) and about 100% relative humidity. Following the incubation period, the plants were placed in a greenhouse with a temperature of about 72"F (22.2"C) and maintained with bottom watering for about 12 to 16 days. The percent disease control provided buy a given test compound is based on a comparison ofthe percentage disease relative to the percent disease development on the untreated checkplants: (-% disease in treated plants) % Control = 100 - 100 x ~~~~~~~~~~~~~~~~~~~~~~~~~~~ % % disease in check The results as percent control are tabulated in Table Il.

Example H Mycelial Inhibition A number of the compounds ofthe present invention were evaluated for in vitro fungicidal effectiveness by means of a mycelial inhibition test.

This test is designed to measurethefungitoxic activity offungicidal chemicals in terms oftheir degree of inhibition of mycelium growth. Fungi used were Phythium ultimum, Rhizoctonia solani, Fusarium monilofroma, Botrytis cinerea and Aspergillus niger. Each compound to be tested was dissolved in acetoneto500ppmconcentration. Paperstripswere infused with the particular mycelium growth by covering the paper witch a potato dextrose broth culture of mycelial suspension. The papers were then placed on potato dextrose agar plates and sprayed by means of a microsprayer with the fungicidal solution.

The treated paper strips were incubated at 25"C and the data is taken after 24 hours. Fungicidal activities are measured by a zone of inhibited mycelial growth from the center of the paper strip in terms of mg/cm2 needed for 99% control ofthefungus (ED99).The effectiveness of the compounds tested forfungicidal activity is reported in Table II in terms of the percent of the ED99 of the test compound oftheED99ofthe standard Difolatan&commat;.

Example I Grape Downy Mildew Preventative Activity The compounds ofthis invention were tested for control ofthe Grape Downy Mildew organism, Plasmopara viticoa over a range of concentrations.

Seedlings of Vitis viniferavar. Emperor (7+ weeks old) were used as hosts. The plants were sprayed with a solution oftest compound in an acetone and water carrier formulation containing a small amount of non-ionic emulsifier. Four replicate plants were used at each concentration for each compound. The concentrations used were 200 ppm, 80 ppm and 32 ppm. In addition, four replicate plants were sprayed with the same carrier formulation (without a test compound) as a control (hereinafter "untreated Checks"). The plants were then randomized and watered. The plants are inoculated one day later with an inoculum offreshly-hatched zoospores of Plasmopara viticola. The inoculated plants were kept in an environmental chamberfortwo days after inoculation to prevent drying of the zoospores before they germinate.The plants were then placed in a greenhouse at a temperature of about 68"F (20"C) to about 72"F (22.2"C) (relative humidity about 30 to about 99%) and held therefor4 days. The plants were then placed in an environmental chamber at 100% relative humidityfor24hoursto inducesporulation. On removal from the chamber and after drying,the plants were evaluated for disease development. The percentage disease control provided by a test compound at a particular concentration was based on the percent disease reduction relative to the untreated checks. The results are reported in Table Ill.

Example J Celery Late Blight Preventative Activity The compounds ofthis invention were tested for control ofthe Celery Late Blight organism, Septoria apifovera range of concentrations using celery (var.

Utah) plants 11-12 weeks old. Four replicate plants were used at each concentration for each test compound. The concentrations of test compound used were 200 ppm, 80 ppm, and 32 ppm. The plants were sprayed with a solution oftest compound in an acetone and water carrierformulation containing a small amount of non-ionic emulsifier. In addition, four replicate plantswere sprayed with the same carrierformulation (without a test compound) as a control (hereinafter "untreated Checks"). The plants were inoculated with the celery late blight organism one day following spraying.Two hours before inoculation,the plants were randomized and watered. The plants were inocluated with a freshlyprepared pycnidial suspension.After inoculation, the plants were placed in an environmental control chamber at 66to 680F (18.9 to 200C) temperature and at 100% relative humidityfor one to two days. The plants were then removed from the environmental controlchamber,allowedtodry,and placed in a greenhouse at 680F (200C) night and 720F (22.20C) day temperature for about 13to 16 days. The plants were evaluated for disease development when the disease symptoms were well developed in the untreated Checks (about 14to 17 days after inoculation). The percentage disease control provided by a test compound at a particular concentration was based on the percent disease reduction relative to the untreated Checks. The results are reported in Table IV.

TABLE I Compounds of the Formula:

ELEMENTAL ANALYSIS Physical %C %H %N Compound X Y Z W W' n State Calc. Found Calc. Found Calc. Found 1 41801 Ci H C1 C1 C1 1 Off-white solid, 34.6 32.6 2.03 1.95 4.04 3.87 decomposed at 200 C 2 27226 C1 H C1 C1 C1 2 Solid, 33.08 33.71 1.94 2.11 3.86 4.17 mp 187-190 C 3 41713 Cl Cl H Cl Cl 1 White solid, 34.5 34.9 1.72 2.38 4.02 3.94 mp 175-182'C 4 41712 Cl Cl H Cl Cl 2 white solid, 33.0 32.9 2.21 1.95 3.85 4.07 mp 172-174'C 5 41883 CF3 H C1 C1 C1 1 Lt. yellow solid, 34.7 35.7 1.85 2.05 3.68 3.95 mp. 206-210 C 6 41884 CF3 N Cl Cl Cl 2 Lt. tan solid, 33.3 33.6 1.78 1.8 3.53 3.83 mp 153-155'C llC 41687 C1 H C1 C1 H 1 Lt. yellow solid, 38.4 38.6 2.58 2.61 4.48 4.72 mp 132-136'C 12C 41688 Cl H Cl Cl H 2 White solid, 36.55 3.58 2.45 2.88 4.26 4.29 mp 137-140 C Table I (Cont'd) ELEMENTAL ANALYSIS Physical ZC ZH ZN ~~~~~~~~~~~~~ ComPound X Y Z W W' n State Calc. Found Calc. Found Calc.Found 13C 41803 CF3 H Cl Cl H 1 white solid, 38.2 39.5 2.33 2.48 4.05 4.44 mp 152-157 C 14C 41802 CF H Cl Cl H 2 White solid, 36.5 37.1 2.23 2.33 3.87 4.09 mp 160-162 C 15C 41949 Cl H Cl H Cl 1 White solid, 38.4 37.5 2.58 2.72 4.48 4.61 mp 159-166 C 16C 42051 CI H Cl H Cl 2 White solid, 36.6 38.8 2.45 2.68 4.26 4.5 mp 168-171 C TABLE II Mycelial Inhibition ComPound Phyt. Rhiz. Fusar. Botry.Asper. GDM TLB RCB TEB CLB BPM BR 1 41801 59 27 0 0 0 - 71 25 0 18 0 0 2 27226 - 0 0 0 0 100* 99* - - - 0* 23* 3 41713 73 0 0 0 0 100 88 80 50 94 0 0 4 41712 0 0 0 0 0 100 0 0 - 0 0 0 5 41883 40 179 0 0 0 - 14 0 80 0 0 0 6 41884 20 54 0 0 0 - 86 20 0 94 0 0 llC 41687 43 44 - 67 100 100 96 90 - 31 0 0 12C 41688 64 64 - 100 100 93 80 96 - 46 0 0 13C 41803 0 0 0 0 0 - 86 50 0 73 0 0 14C 41802 - 0 0 0 0 - 93 50 0 36 0 0 15C 41949 0 0 0 0 0 7 0 0 - 0 20 0 16C 42057 31 34 - 0 33 86 97 90 - 50 50 0 * Concentration 250 ppm Phyt = Phythium ultimum GDM = Grape Downy Mildew Rhiz = Rhizoctonia solani TLB = Tomato Late Blight Fusar. = Fusarium monilofroma RCB = Rice Blast Botry. = Botrytis cinerea TEB = Tomato Early Blight Asper. = Aspergillus niger CLB = Celery Late Blight BPM = Bean Powdery Mildew BR = Bean Rust TABLE III Grape Downy Mildew Preventative Activity 8 Control at Compound 200 ppm 80 ppm 32 ppm 1 41801 0 24 5 2 27226 73 51 41 3 41713 85 78 84 4 41712 89 83 76 6 41884 93 89 85 llC 41687 99 85 73 12C 41688 98 85 72 13C 41803 100 98 80 14C 41802 66 82 51 TABLE IV Celery Late Blight Preventative Activity 8 Control at Compound 200 ppm 80 ppm 32 porn ED 50/90 1 41801 50 31 19 206/-- 2 27226 63 44 40 85/-- 3 41713 73 83 56 37/200 4 41712 81 67 54 26/533 6 41884 77 67 48 34/-- lIC 41687 81 46 40 63/365 12C 41688 85 52 50 48/288 13C 41803 85 56 50 43/307 14C 41802 79 38 21 89/357

Claims (10)

1. Compounds represented bythegeneralformula:

wherein n is 1 or2, Xis chloro ortrifluoromethyl, and one of Yand Z is H and the other is chloro.

2. Compounds as claimed in Claim 1, wherein X and Z are chloro and Y is hydrogen.

3. 2,3 - Dichloro - 3 - methylsulfonyl - 3',4' dichloroacrylanilide.

4. 2,3 - Dichloro - 3 - methylsulfinyl - 3',4' dichloroacryoanilide.

5. 2,3 - Dichloro - 3 - methylsulfonyl - 3' trifluoromethyl -4' - chloroacrylanilide.

6. Compounds as claimed in Claim 1, wherein Xis chloro,Yis chloro, and Z is hydrogen.

7. 2,3 - Dichloro - 3 - methylsulfinyl - 3',5' dichloroacrylanilide.

8. A method ofcontrolling fungi which comprises contactingsaidfungiortheirgrowth environment with a fungicidally effective amount of a compound as claimed in any one of Claims 1 to 7.

9. Afungicidal composition which comprises an inert carrier and a fungicidally effective amount a compound as claimed in any one of Claims 1 to 7.

10. Aprocessforpreparing acompoundas claimed in Claim 1, substantially as described in the foregoing Example 3,6,7 or 10.