CA1222526A - Fungicidal 2,3-dichloro-3-methylsulfonyl and sulfinyl acrylanilides - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Compounds of the formula:

Description

1~22~i2~

FUNGICIDAL 2,3-DICHLORO-3-METHYLSULFONYL
AND SULFINYL ACRYLANILIDES

BACKGROUND OF THE INVENTION

This invention is drawn to novel compounds which are effective as fungicides.
Since the world is dependent on an ever-decreas-ing amount of cultivated land to produce crops to feed anever-increasing population, it is important to develop fungicides which protect crops from destruction by fungal pests.
U.S. Patent No. 4,021,482 to Schempp discloses

2-chloroacrylic acid amide compounds of the formulas o Rl S ( O ) X--CH = CCl-C--NEIR2 wherein Rl is Cl-C4 alkyl, R2 is Cl-C8 alkyl or a cyclo-alkyl bound directly or by way of an alkylene bridge mem-ber, or a benzyl or phenyl radical which is unsubstituted or at most tri-substituted in the aromatic nucleus, and X
is 1 or 2; which are effective agents for the control of various micro-organisms.
~ SUMMARY OF THE INVENTION
The compounds of this invention are represented by the formula:

y : H O

N-C-CCl-CCl-S(o)n-CH3. ~I) )=~
X
wherein n is 1 or 2, X is chloro or trifluoromethyl and one of Y or Z is hydrogen and the other is chloro.
Among other factors, the present invention is based on my surprising finding that the compounds of this invention are effective as anti-fungal agents, and are , , . ....

Ol -2-particularly effective in combatting plant fungal diseases. These compounds are especially effective in 05 preventing plant funyal diseases, such as Grape Downy Mildew and Celery Late Blight.
DETAILED DESCRIPTION OF TH~ INVENTION
The compounds o this invention are conveniently prepared according to the following reaction scheme:

\ O Cl Cl ~ o Z - ~ NH2 + Cl-C-C =C + b - > Z ~ N-C-CCl=C~

X X (l) II III IV V
Y

V + C~3SH + b - > Z ~ N-C-CCl=CCl-SCH3 (2) IV X
VI VII

"
Cl COO~ Y

VII + ~ > ~ ~ N-C-CCl=CCl~S(O)nCH3

(3) VIII

wherein n, X, Y and Z are as previously defined in connec-tion with Formula I, and b is a base.
Reaction (1) is conducted by combining approxi-mately equimolar amounts of II, III and IV in an iner~
organic solvent. Although the reactants may be combined in any order, it is preferred to add III to a mixture o II and IV in solvent. Suitable solvents include aprotic ~L2~:52~

01 ~3~

solvents, such as toluene, benzene, ethyl acetate, dimethoxyethane, ethyl ether, chlorinated hydrocarbons, 05 such as m~thylene chloride or chloroform, and the like.
The base, b, is preferably an organic base, such as tri-ethylamine or pyridine. The reaction is conducted at a temperature of about 20C to about 100C, preferably about 20C to about 50C. 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 V is isolated by conventional proce-dures, such as stripping, extraction, filtration, crystal-lization and the like.
~eaction (2) is conducted by combinin~ IV, V and VI in an inert organic solvent. It is preferred to add VI
to a mixture of IV and V in solventO 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 reac-tion is carried out at a temperature of about 20C to about 80C, preferably from about 20C to about 50C. For convenience, the reaction may be carried out at ambient temperature and pressure. The reaction is generally com-plete within about 1 to about 48 hours. The product VIIis 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 meta-chloroperoxybenzoic acid (MCPBA) is the preferred oxidi-zing agent, other suitable oxidizing agents may be employed and include other peroxy acids, such as pero~y-acetic acid, hydroyen peroxide in glacial acetic acid and the like. The ratio of MCPBA (VIII) to VII used deter-mines whether the sulfinyl or sulfonyl compound is formed.Thus, if the sulfinyl compound is desired, the ratio of MCPBA to VII used is about 1:1. However, ratios of MCPBA
(VIII) to VII of about 2 or greater will yield the sulfonyl compound. The reaction is carried out in the ~0 presence of a solvent or diluent inert to the reactants.

~L2~;25:26 01 ~4~

Suitable solvents include methylene chloride, chloroform and the like. The reaction is carried out at a tempera-05 tur~ of about 20C to about 100C, preferably about 30C
to about 50C 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 of the compounds of this invention are particularly effective in controlling powdery mildew fungal infections caused by the organism Erysiphe pol~oni. Some of the compounds of this inven-tion 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 for control-ling fungal infections caused by Uromyces phaseoli tipica, Plasmopara viticola, and Piricularia ory2ae. However, some fungicidal compounds of this in~ention may be more fungicidally active than others against particular fungi.
When used as fungicides, the compounds of the invention are applied in fungicidally effective amounts to fungi and/or their 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 of fungus, and the particular compound of the invention. As with most pesticidal compounds, the fungicides of the invention are not usually applied full strength, but are generally incorporated with conven-tional, biologically inert extenders or carriers normally employed for facilitating dispersion of active fungicidal compounds, recognizing that the formulation and mode of application may affect the activity of the fungicide.
Thus, the fungicides of the invention may be formulated and applied as granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of se~eral other known types of formulations, depend-ing on the desired mode of application.

01 ~5~

Wettable powders are in the form of finely divided particles which disperse readily in water or other oS 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 pre~erably 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 ernul-sifying agents include, for e~ample: the aryl and alkyl-aryl sulfonates and their sodium salts; alkylamide sulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols and polyvinyl alcohols; polyethylene oxides; sulfonated animal and vegetable oils; suifonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addi-tion products of such esters; and the addition products oflong-chain mercaptans and ethylene oxide. Many other ; types of useful surface-active agents are available in commerce~ The surface-active agent, when used, normally comprises from 1% to 15~ by weight of the fungicidal com-~5 position.
Dusts are freely flowing admixtures of the active fungicide with finely divided solids such as talc, natural clays, kieselguhr, pyrophyllite, chalk, diatoma-ceous earths, calcium phosphates, calcium and magnesium 3~ carbonates, sulfur, lime, flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant.~ These finely divided solids have an average particle size of less than about S0 microns. A typical dust formulation useful herein contains 75% silica and 25 35~ of toxicant.
Useful liquid concentrates include the emulsifi-able concentrates, which are homogeneous liquid or paste compositions which are readily dispersed in water or other dispersant, and may consist entirely of the fungicide with a liquid or solid emulsifying agent, or may also contain a - - ;

~L~2;~5~

liquid carrier such as xylene, heavy aromatic naphthas, isophorone, and other nonvolatile organic solvents. For 05 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 formulations for fungicidal appli-cations include simple solutions of the active fungicide in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naphtha-lenes, xylene, or other organic solvents. Granular formu-lations, wherein the fungicide is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of 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 car-rier, such as the Freons, may also be used. All of those techniques for formulating and applying fungicides are well known in the art.
The percentages by weight of the funyicide may vary according to the manner in which the composition is to be applied and the particular type of formulation, but in general comprise 0.5% to 95% of the toxicant by weight of the fungicidal composition.
The fungicidal compositions may be formulated and applied with other active ingredients, including other fungicides, insecticides, nematocides, bactericides, plant-growth regulators, fertilizers, etc.
A further understanding of the invention can be had in the followiny non-limiting Examples. Wherein, unless expressly stated to the contxary, all temperature ranyes refer to the Centigrade system and the term "ambient" or "room temperature" refers to about 20C to 25C. The term "percent" refers to gram moles. The term "equivalent" refers to a quantity of reagent equal in moles, to the moles of the preceding or succeeding reagent recited in that example in terms of finite moles or finite weight or volume. ~lso, unless expressly stated to the * Trade Mark 3L~2252i~

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 I.
EXAMPLES
Example 1 Preparation of 2,3,3-Trichloro-3',4_'-d_chloroacrylanilide O Cl r~-~ H " ¦ ~Cl Cl ~/ \ ~ N C C = C ~
~ Cl Cl 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)]
trichloroacryloyl chloride were added dropwise. The addi-tion reaction was exothermic, with reflux occurring during the addition. The reaction mixture was then stirred over-night at room temperature. The mixture was washed with water and then dried over magnesium sulfate. The solvent was stripped to give 18.9 9 of a yellow solid which was then recrystallized from methylene chloride to give 13.0 g of the product, a light yellow solid, mOp. 123-128C.
Example 2 Preparation of 2,3-Dichloro-3-methylthio-3',4'-dichloroacrylanilide Cl ~ N C CCl=CCl-SCH3 ~ O
Cl To a mixture of 13 g (0.041 moles) of 2,3,3-trichloro-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 ~222S26 stirring. The addition was mildly exothermicO The reac-~ tion mixture was stirred an additional hour after the 05 addition was complete. To the reaction mixture, 300 ml of water were added which caused the product to precipitate.
The precipitate was filtered and air-dried overnight to give 14.0 g of a white solid. The solid was dissolved in methylene chloride and the resulting mixture cooled with 1~ 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 9, to give a total yield of 9.4 9 of product.
Example 3 Preparation of 2,3-Dichloro-3-methylsulfonyl-3',4'-dichloroacrylanilide Cl ~ N C CCl=CCl-SO2CH3 ~0 ~ O
Cl 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 9 (0.0277 moles) of 85% m-chloroperoxyben~oic acid (MCPBA) were added in portions. The reaction mixture was thsn stirred at room temperature overnight and the next day ~about 36 hours). The reaction mixture was then washed with a satu-rated sodium carbonate solution, and dried over magnesium sulfate. The solvent was partly stripped and the result-ing mixture allowed to stand overnight at which point a crop of crystals formed. Collection of the crystals by filtration gave 2.5 y of the product, melting point 187-1~0C.
Elemental analysis for CloH7C14NO3S showed:
calculated %C 33008, %H 1.94 and %N 3.86; found ~C 33.71, %H 2.11, and %N 4.17O

.

:L~Z~S26 Example 4 preparation of 05 2,3,3-Trichloro-3',5'-dichloroacr~anilide O
N C-CCl= C\
~ Cl Cl To a stirred mixture of 15 g (0.0926 mole) 3,5-dichloroaniline and 12.9 ml (0.092G mole) triethylamine in 150 ml methylene chloride, 17.95 g [10.9 ml (0.0926 mole)~
trichlorGacryloyl chloride were added dropwise. The lS resulting mixture was stirred overnight at room tempera-tureO The reaction mixture was then washed with dilute hydrochloric acid which caused a large amount of 50lid to precipitate. Filtration of the mixture and recrystalliza-tion of the solid from methylene chloride gave 10.5 g of an off-white solid, melting point 131-135C.
Example 5 Preparation of 2,3-Dichloro-3-methylthio-3'-5'-dichloroacrylanilide Cl ~ N C-CCl-CCl-SCH

Cl To a stirred mixture of 10.5 g (0.033 mole) of 2,3,3-Trichloro-3',5'-dichloroacrylanilide (the product of Example 5) and S ml (0.036 mole~ triethylamine in 100 ml methanol, 23 ml of a 2.18~ 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 dis-solved in methylene chloride and She small amount of aqueous phase removed by separation. The methylene chloride phase was dried over magnesium sulfate. Hexane ; ~ .

:
::

2~Z6 was added to the mixture. The hexane-methylene chloride mixture was cooled with dry ice, at which point 3.5 g 05 white crystals (melting point 105-107C) were obtained.
Additional concentration of the mother liquor, followed by cooling, yielded an additional 1.3 9 of crystals.
Example 6 Preparation of 2,3-Dichloro-3-methylsulfinyl-3',5'-dichlo acrylanilide Cl ~ N-C-CCl = CCl-SOCH3 Cl 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-chloro-peroxybenzoic acid in chloroform was stirred over the weekend (about 72 hours) at room temperature. The reac-tion mixture was then washed with a saturated sodium bicarbonate solution and then dried over magnesium sulfate. The chloro~orm mixture was 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 first with methylene chloride and then with ethyl acetate gave 1.3 9 of the product, a white solid, melting point 175-182C.
Elemental analysis for CloH7C14NO2S showed:
calculated %C~34.50, %H 1.72, and %N 4.02; found %C 34.91, %H 2.38, and %N 3.94.

.

..... . .... .. .

3L22;~;2~

Example 7 Preparation of 05 2,3-Dichloro-3-methylsulfonyl-3',5'-dichloroacrylanilide .

~N--C-CCl=CCl-S02CH3 Cl To a mixture of 2.4 9 (0.0072 mole) of 2,3-di-chloro-3-methylthio-3',5'-dichloroacrylanilide (the prod-uct of Example 5) in 100 ml chloroform, 3.0 y (0.015 mole) of 85% meta-chloroperoxybenzoic acid were added in por-tions. The resulting mixture was then stirred two days at room temperature. The chloroform mixture was washed with a saturated sodium bicarbonate solution. The solvent was stripped, 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 172-174C.
Elemental analysis for CloH7C14 NO3S showed.
calculated ~C 32.99, %H 2.21, and %N 3.85; found %C 32188, ~H 1.95, and %N 4.07.
Example 8 Preparation of 2,3,3-Tr_chloro-3'-trifluromethyl-4'-chloroacrylanilide O
Cl ~ N C-CCl= C

To à mixture of 10 9 (0.051 mole) 3-trifluro-methyl-4-~hloroaniline and 4.0 g (4.1 ml 10.051 molel) pyridine in about 10 ml methylene chloride, 9.9 9 (6.05 ml [0.051 mole]) trichloroacryloyl chloride in a small amount methylene chloride were added dropwise. The reaction mix-ture was stirred for two hours after the addition was complete. The reaction mixture was washed three times with 5% HCl, dried over magnesium sulfate, and stripped to Z~i2~

give lg.3 g of a red oil. The red oil was passed through a short silica gel column (eluting with methylene chlo-05 ride) to remove the red color, yielding 18 g of theproduct, a pink oil.
Elemental analysis for CloH4C14F3NO showed:
calculated %C 34.02, %H 1.14, and %N 3.97; found ~C 35.12, %H 1.3, and %N 4.62.
Example 9 Preparation of 2,3-Dichloro-3-methylthio-3'-trifluoromethyl-

4'-chloroacrylanilide o lS Cl ~ N C-CCl=CCl-SCH3 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) triethyl-amine 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 water were added to the mix-ture, which caused a voluminous white precipitate to form.
The gummy white solid was collected by filtration and recrystallized from methylene chloride/hexane, yielding a first crop of 3.8 g white crystals (melting point 117-120C)~ A second crop of 3.8 g crystals (melting point 120-123C) was obtained from the mother liquor. The two crops combined yave 7.6 g of the product.
Elemental analysis for CllH7C13F3NOS showed:
calculated ~C 36.23, %H 1.94, and %N 3.84, found %C 36.3, %H 2.02, and %N 4.29.

4~

252~

Example 10 Preparation of 2,3-Dichloro-3-methylsulfonyl-3'-05 trifluoromethyl-4'-chloroacrylanilide Cl ~ N-C-CCl =CCl-SO2CH3 To a stirred mixture of 3O0 g (0.0082 mole) of 2,3-dichloro-3-methylthio-3'-trifluoromethyl-4'-chloro-acrylanilide (the product of Example 9) in 75 ml chloro-form, 3.4 g (0.017 mole) of 85% meta-chloroperoxybenzoic acid were added. The reaction mixture was stirred several days at room temperature. At that point there were some solids in the chloroform solution. The m-chlorobenzoic ; acid formed during the reaction was dissolved by stirring the reaction mixture with 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 of the product as a tan solid, melting point 153-155C.
Elemental analysis for CllH7C13F3NO3S showed:
calculated %C 33.31, %H 1.78, and %N 3.53; found ~C 33.62, %H 1.8 and ~N 3.83.
Example A
Bean Powdery Mildew The compounds of the invention were tested for the control of the Bean Powdery Mildew organism ~
polygoni. seedling bean plants were sprayed with a 250-ppm solution of the test compound in acetone, water and a nonionic emulsifier. The sprayed plants were then inocu-lated 1 day later with the organism. The plants were maintainecl for 10 days at temperatures of 68F at night with daytime temperatures of 72F to 80QF; relative humid-ity was maintained at 40~ to 60%. The percent disease control provided by a given test compound was based on the percent disease reduction relative to the untreated check ~2Z2~

plants. The results as percent control are tabulated in Table II.
oS Example B
Tomato Late Blight Compounds of the invention were tested for the preventative control of the Tomato Late Blight organism Phytophthora infestans. Five- to six-week-old tomato (cultivar Bonny Best) seedlings were used. The tomato plants were sprayed with a 200-ppm suspension of the test compound in acetone, water and a nonionic emulsifier.
The sprayed plants were then inoculated 1 day later with the organism, placed in an environmental chamber and incu-bated at 66F to 68F 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 com-pound was based on the percent disease reduction relative to untreated check plants. The results as percent control are tabulated in Table II.
Example C
Celery Late Blight The Celery Late Blight tests were conducted ~5 using celery tUtah) plants 11 weeks old. The Celery Late Blight organism was Septoria apii. The celery plants were sprayed with 200-ppm solutions of the 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 66F to 68F
in 100% relative humidity for an extended period of time (approximatel~ 48 hoursj. Following the incubation, the plants were allowed to dry and then were maintained in a greenhouse for approximately 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.

~22;~:5~6 Example D
Tomato Early Blight 05 Compounds of the invention were tested for the control of the Tomato Early Blight organism Alternaria solani conidia. 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 66F to 68F and 100~ relative humidity for 24 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 II.
Example E
Grape Downy_Mildew The compounds of this invention were tested for the control of the Grape Downy Mildew organism, Plasmopara viticola. Seedlings of Vitis vini~era 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 green-house at a temperature of about 68F to about 72F (rela-tive humidify~varied between about 30 and about 99%) for 4 days. The plants were then placed in an environmental chamber at 100% relative humidity to induce sporulation.
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.

, ~L2~ 6 Exam~
Bean Rust 05 The compounds of this invention wer~ evaluated for their ability to eradicate Bean Rust caused by Uromyces phaseoli tipica on pinto beans, Pinto bean plants, variety Idaho l-11, 16 (summer) or 19 (winter) days old were inoculated with a 50-ppm suspension of uredospores in water containing a small amount of non-ionic surfactant. The inoculated plants were placed in an environmental chamber immediately after inoculation and incubated 20 hours. Following the incubation period, the plants were removed from the cham-ber and placed in a greenhouse maintained at 66-68F and 60-80~ relative humidity. Two days after inoculation, the plants were treated by spraying with a 200-ppm solution of test compound in an acetone and water carrier formulation 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 or two replicate pots were sprayed with ~he same carrier formulation (without a test compound) as a control (hereinafter "untreated Checks"). The plants were kept in the greenhouse until evaluated. The plants were evaluated for disease control when disease symptoms were well developed on the untreated Checks, normally about 14 days after treatment. The per-centage disease control (or eradication) provided by a test co~pound was based on the percent disease reduction relative to the untreated Checks. The results are reported in Table II.
Example G
Rice Blast Compounds of this invention were tested for control of the Rice Blast organism Piricularia oryzae r using 10- to 14-day-old rice plant seedlings (Calrose M-9 variety). SeedIing plants were sprayed with a 625-ppm solution of the test compound in acetone, water and a non-ionic emulsi~ier (ORTHO X-77 spreader). The sprayed plants were inoculated l day later with the organism in an ~L2Z;2~i~6 environmental chamber. After inoculation, the plants were kept in an environmental chamber for about 48 hours under 05 conditions of about 72F to 75~ and about 100% relative humidity. Followiny the incubation period, the plants were placed in a greenhouse with a temperat~lre of about 72F and maintained with bottom watering for about 12 to 16 days. The percent disease control provided by a given test compound is based on a comparison of the percentage disease relative to the percent disease ~evelopment on the untreated check plants:

~ disease in treated ~lants) ~ Control =100 - 100 x ( % disease in check The results as percent control are tabulated in Table II.
Example H
Mycelial Inhibition A number of the compounds of the present inven-tion were evaluated for in v_ ro funyicidal effectiveness by means of a mycelial inhibition test. This test is designed to measure the fungitoxic activity of fungicidal chamicals in terms of their degree of inhibition of mycelium growth. Fungi used were Phythium ultimum, Rhizoctonia solani, Fusarium monilofroma, Botrytis cinerea and Aspergillus ni~erO Each compound to be tested was dissolved in acetone to 500 ppm concentration. Paper strips were infusad with the particular mycelium growth by covering the paper with 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 25C and the data is taken after 24 hoursO Fungicidal activities are measured by a zone of inhibited mycelial grow-th from the center of the paper strip in terms of mg/cm2 needed for 99% control of the fungus (EDg9). The effectiveness of the compounds tested for fungicidal activity is reported in Table II in 52~;

terms of the percent of the EDg9 of the test compound of the EDg9 of the standard Difolatan~.
oS Example I
Grape Downy Mildew Preventative Activity The compounds of this invention were tested for control of the Grape Downy Mildew organism, Plasmopara viticola over a range of concentrations. Seedlings of Vitis vinifera var. Emperor ~7~ weeks old) were used as -hosts. The plants were sprayed with a solution of test compound in an acetone and water carrier formulation con-taining 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 3~ 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 of freshly-hatcned zoospores of Plasmopara viticola. The inoculated ; plants were kept in an snvironmental chamber for two 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 to about 72F
(relative humidity about 30 to about 99~) and held there for 4 days. The plants were then placed in an environmen~
tal chamber at 100% relative humidity for 24 hours to induce sporulation. 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 III.
Example J
Celery Late Blight Preventative Activit~
The compounds of this invention were tested for control of the Celery Late Blight organism, Septoria a~ii ~ ~ over a ranye of concentrations using celery (var. Utah) ; 40 plants 11-12 weeks old. Four replicate plants were used 3L2~ 5~i at each concentration for each test compound. The concen-trations of test compound used were 200 ppm, 80 ppm, and 05 32 ppm. The plants were sprayed with a solution of test compound in an acetone and water carrier formulation con~
taining a small amount of non-ionic emulsifier. In addi-tion, four replicate plants were sprayed with the same carrier formulation (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 inoculated with a freshly-prepared pycnidial suspension.
After inoculation, the plants were placed in an environ-mental control chamber at 66 to 68F temperature and at 100~ relative humidity for one to two days. The plants were then removed from the environmental control chamber, allowed to dry, and placed in a greenhouse at 68F night and 72F day temperature for about 13 to 16 days. The plants were evaluated for disease development when the disease symptoms were well developed in the untreated Checks (about 14 to 17 days after inoculation). The per-centage 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.

~ ~ o a~
o er Z .
u ~r D ~ L~ 00 ~ CO D
-1 O ~ 3 ) ~D 11')d ' N
~a u~ ~ er ~ ~r ~ ~ ~ er U~
U~
~ ~ ~ ~ ~ a~ o co ~D
Z O
~C ~ ~ _~
~ d~ -E~ u ~ er ~ ~ ~ co _I o c~
;~
~) C~ _~ ~ ~ ~ ~ ~ ~
~D 1` a~ ~ 1` ~D ~9 00 ~ . . . . . . U~
~ O ~
d~ ~0 Ul .. ~ ~D O u~ O 1 _l ~ ~ d'~`'~ d' H ID r-l ~1 ~~1 s _I o ~ v~ u ~ n o ~ U U~ U
t~ ~ ~ U u? ~ O ~ ~ a ~ 3 'ol 1~) 3 ~D .~ o ~ o ,, (~ a~ o ~ u~ un o ~ .-t d' E~ U? ~~ ~n ~ o ~ o ~ --I I ~ ~ ~ o ,~ ,, Q~~ t U~ I a) o as I 'I I U~
~ ~ I o O.,~
o ~ a) o o ~ 5: ~ .c Q. ~ ~ ~ ~ J~ ~ S ~
8 ~C o ~ ~ u~ ~ 3 k 3 E~
U C I ~ ~

3 1 u u C~ u u u lu~
3 ~1 ~1 r-l ~1 ~1 C ) ~2 U ~.) U U C~ U U
0: U
m z ~ ~ u u c~
~ 1 $ $ c~ u c ~ 3 c X ~ I ,1 ,1 ,-1 ~ E4~ r'~
I u u u u c~ u u u . ~ ~ ~ ~ ~ ~ ~ ~ ~ co o ~ ~ ~
Co~ ~ I~ I` 00 CO ~D ~O
3~ ~ ~, ," ,, ~, ~r ~
U ~ ~ ~.. , ~" "., ~g ~U C~
:: ~ ~

~1 In o ut o u~
O O --I ~1 N t~

~2~:5~6 ~ er ~ ~
O ~r o. ~ Ln dP
O u~
~ o CO
u~ ~ ~
CO
~i ~ ~r ~ ~ ~o o ~ E-~

_l .

O ~ ~ I` ~
C~ E4 ~P

~ 0 ~D CO ~O
C~ ~

'O ~ ~ O '1 5 0 U J~ O--i O ~ O ~ O ~
U7 ~ ~ o ~ oo ..
~
3 El ~ ~i 3 c ~
_ I ~1 I
S

~
C~
o ~ ~ ~ o~
_, ~ o o ~ o~ ~o cn o O ~ ~r ~ er ~ 8 ~
c~ ~

, ~ o Ul o Ln o o ~ , t~

Z~i26 m o ~ o o o o o a~ ~
o o o o O o o o O o o o~ o ~ o o er o o ~ ~ o o ,~ ~ ~ ~ ~ ~ u~
o _~ ~ o o m I
2~ o o o o o o E~ I ~ I co ~1 C~ L~7 0 0 0 0 0 ~D O O O O

ml *
~o o ~ D O ~O ~ O ~ V 3 E~ ~ ~ ~ ~ ~ 3 s rl ~: O O O ~I` ~ ~: m m ~ I o o o o a~ ~ :~ '1 c~ ~ ~ _I I I --' I I ~ ~ ~ ~ v a~

o o o o o o o o o o o ~ a~ o m o ~
o o ~ ~ ~ c ca ~S ~ ~ ~ ~-v ~:
11 ll ll o ~ o o o o o o ~ o o o o o ~ 3 ~ ~
.~ O ~D O
~ m : s .
C h ~n oooooo IIooo ~ E4 0 O . .,1 h t~ a~

C) N I` o o o a~ ~r 't' d' O O ~ E~ t:: O C~
,~ ~ 1~ ~a r-l h ~1 v o E o c c c cr~ ~ o o o ~ ~ o o _~ C ~ ~ ,~
~c u~ 7 0 ~ ~ . ~ ~
S~ ~ N O
.rl ~4 ~rl ~
oO 00 00 OD O O ~ ~ ~ S S
oo ~ 1~ 0 ~ O a o er ~ ~ r ~ C 11 11 g c) N ta c~ ~ ~ ~ ~ n ~ ~ ~ ~ ~ u~ ~D S S ~ O U~
~ ,~ ~ * ~ P:; Ec. m _~ O u~ o u-~: .

~22;~S~6 TABLE III

05Grape Downy_Ml ew Preventative Activity % Control at Compound 200 ppm 80 p ~ 32 ppm 1 41~010 24 5 llC 4168799 85 73 TABLE IV

Celery Late Blight Preventative Activity % Control at Compound 200 ppm80 ppm ~ ED 50/90 6 4188~ : 77 67 48 34/---: 30 llC 41687 81 46 40 63/3~5 12C 41688 ~ 85 52 50 48/288

Claims (14)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound of the formula:

wherein n is 1 or 2, X is chloro or trifluoromethyl and one of Y or Z is H and the other is chloro.

2. A compound according to Claim 1 wherein X and z are chloro and Y is hydrogen.

3. A compound according to Claim 2 wherein n is 2.

4. A compound according to Claim 2 wherein n is 1.

5. A compound according to Claim 1 wherein X is trifluoromethyl, Y is hydrogen, Z i chloro and n is 2.

6. A compound according to Claim 1 wherein X is chloro, Y is chloro, and Z is hydrogen.

7. A compound according to Claim 6 wherein n is 1.

8. A method of controlling fungi which comprises contacting said fungi or their growth environment with a fungicidally effective amount of a compound of Claim 1.

9. A method of controlling fungi which comprises contacting said fungi or their growth environment with a fungicidally effective amount of a compound of Claim 2.

10. A method of controlling fungi which comprises contacting said fungi or their growth environment with a fungicidally effective amount of a compound of Claim 3.

11. A method of controlling fungi which comprises contacting said fungi or their growth environment with a fungicidally effective amount of a compound of Claim 4.

12. A method of controlling fungi which comprises contacting said fungi or their growth environment with a fungicidally effective amount of a compound of Claim 5.

13. A method of controlling fungi which comprises contacting said fungi or their growth environment with a fungicidally effective amount of a compound of Claim 6.

14. A method of controlling fungi which comprises contacting said fungi or their growth environment with a fungicidally effective amount of a compound of Claim 7.