The present invention relates to halomethyl substituted dialkoxypyridine compounds, a fungicidal composition containing them, and a method for protecting plants from fungal disease organisms.

U.S. Patent No. 3,244,722 describes, among other related compounds, those corresponding to the formula:

wherein R is an alkyl group containing 1 to 18 carbon atoms or a lower alkenyl group.

Exemplary compounds listed in this patent include 2-chloro-4-methoxy-6-(trichloromethyl)pyridine, 2-chloro= 6-methoxy-4-(trichloromethyl)pyridine, 5-chloro-2-methoxy-4-(trichloromethyl)pyridine, and 3-chloro-2-methoxy-4-(trichloromethyl)pyridine. As disclosed in this patent specification, various of these compounds are useful as herbicides; various other compounds are useful in the control of pest fish and aquatic insects; and other compounds are taught to be useful as insecticides and anthelmintic a agents for warm-blooded animals.

U.S. Patent No. 4,062,962 discloses the use of a select group of the compounds disclosed in U.S. Patent No. 3,244,722 as fungicides for the control of soil-borne plant disease organisms which attack the roots of plants.

Accordingly, the present invention provides a halomethyl substituted dialkoxypyridine derivative having the general formula:

wherein X and Y represent an OR', trichloromethyl, trifluoromethyl, dichloromethyl, dichlorofluoromethyl or chlorodifluoromethyl group with the proviso that one of X or Y must be OR' and the other of X and Y is other than OR'; and R and R' each independently represent an alkyl group containing 1 to 12 carbon atoms or an alkenyl group containing 3 or 4 carbon atoms.

In the present specification and claims, the term "alkyl" designates a straight or branched chain saturated aliphatic hydrocarbon group containing from 1 to 12 carbon atoms, such as, for example, methyl, ethyl, propyl, isopropyl, butyl, secondary-butyl, tertiary-butyl, amyl, isoamyl, hexyl, secondary-hexyl, heptyl, octyl, nonyl, decyl, dodecyl, 4-methyldecyl, undecyl, 3-ethylnonyl, 2-ethylhexyl, or 3-propylheptyl. The term "alkenyl" designates straight or branched chain alkenyl groups of 3 or 4 carbon atoms, such as, for example, 2-propenyl, 2-butenyl, 3-butenyl, 2-isobutenyl, or 2-secondary butenyl.

The pyridine compounds of the present invention are crystalline solids or oils and generally are of low solubility in water and of moderate solubility in common organic solvents.

The pyridine compounds of the present invention and compositions containing said compounds have been found useful as agronomic fungicides, especially valuable for the control of soil-borne plant root disease organisms.

The compounds of the present invention can be prepared by the reaction of an appropriate halomethyl substituted halopyridine reactant with an appropriate alkali metal alkoxide or alkenoxide in the presence of a reaction medium. This reaction can be represented as follows:

In the above reaction representation, no attempt has been made to present a balanced equation. In addition, Y' and X' represent chloro, bromo, fluoro, trichloromethyl, trifluoromethyl, dichloromethyl, dichlorofluoromethyl or chlorodifluoromethyl with the proviso that one of Y' or X' must be chloro, bromo or fluoro and the other of Y' and X' must be other than chloro, bromo or fluoro; Y, X and R are as hereinbefore defined; Z represents chloro, fluoro, bromo or OR and M represents an alkali metal, i.e., sodium, potassium, lithium, or cesium.

In carrying out the above reaction, the halomethyl substituted halopyridine reactant is mixed with the alkali metal alkoxide or alkenoxide and the reaction medium and the mixture heated at a temperature of from about 50°C up to the reflux temperature of the mixture until the reaction is complete. The reaction is usually complete in from about 1 to about 163 hours, depending upon the specific reactant, solvent, and temperature employed.

After the completion of the reaction, the reaction mixture is usually diluted with water and extracted with a solvent such as methylene chloride, petroleum ether, hexane, or toluene. The extract is thereafter usually washed with water, dried, filtered, and the solvent removed by evaporation or other conventional separatory procedures. The product is thereafter recovered and, if desired, can be purified by various conventional techniques such as crystallization and/or recrystallization from solvents such as, for example, methanol, methylene chloride, hexane, or toluene, or by distillation, depending upon whether the product is a solid or oil.

Since many 2- or 4-halomethyl-2 or 4-halo-6--alkoxy or alkenoxy pyridines are known as taught in U.S. Patent 3,244,722, it is within the scope of the present invention to employ such compounds as starting materials. In such procedures, this reactant is mixed with the desired MOR reactant as hereinabove set forth, and the reaction proceeds as outlined hereinbefore. By following this procedure, compounds can be prepared wherein both of the OR substituents are the same; wherein one R substituent is alkyl and the other R substituent is alkenyl or wherein one R substituent is alkyl or alkenyl of a given chain length and the other R substituent is alkyl or alkenyl of another chain length.

In addition to the above, it is also within the scope of the present invention to employ a 2,4-di- halo-6-(halomethyl)pyridine or 2,6-dihalo-4-(halomethyl)-pyridine as starting material and to react these materials with the desired MOR reactant as set forth hereinabove. In addition, by carefully controlling the reaction, compounds can be prepared wherein both of the R substituents are the same; or by carrying out the reaction in sequential steps employing different MOR reactants for each step thus obtaining products wherein one R substituent is alkyl and the other R substituent is alkenyl or wherein one R substituent is alkyl or alkenyl of a given chain length and the other R substituent is alkyl or alkenyl of another chain length.

In carrying out the above preparations, the amounts of the reactants employed are not critical as some of the desired product is formed with any amounts. However, equimolar proportions (1 molar equivalent of the alkali metal alkoxide or alkenoxide per halogen atom to be reacted) for the most part should be employed. However, it has been found that, when preparing compounds wherein both halogens are reacted or wherein the last halogen is being reacted, an increase in the yield of the desired product can be obtained by employing an excess of the alkali metal alkoxide or alkenoxide. Therefore, it is preferred to employ from about 1.5 to about 6 molar equivalents of the alkali metal alkoxide or alkenoxide per halogen atom to be reacted.

Representative reaction media useful for carrying out the above preparations include, for example, dimethylsulfoxide, alkanols and alkenols of the same carbon content as the alkali metal alkoxide or alkenoxide employed for the reaction, dimethoxyethane, and diglyme.

In some instances, it may be desirable to convert the halomethyl group of an existing product to a different halomethyl group. For example, a compound of the present invention containing a trichloromethyl group can be dehalogenated with a dehalogenation agent such as, for example, stannous chloride or zinc metal, in the presence of concentrated hydrochloric acid and a solvent, to the dichloromethyl analog under conventional conditions.

In such a procedure, a solution of the trichloromethyl substituted pyridine compound in a solvent, such as acetone or other conventional solvent for this reaction, is contacted and refluxed with a solution containing an excess of the dehalogenation agent dissolved in one of the above solvents. The reaction is usually complete in from about 1 to about 4 hours.

The following examples are given by way of illustration and should not be construed as limitations upon the overall scope of the same.

Example 1 - 2,6-Dimethoxy-4-(trichloromethyl)pyridine

A solution was prepared by refluxing 2.64 gram--moles of 2,6-dichloro-4-(trichloromethyl)pyridine in 2 liters of methanol. To this solution was added over about 2 hours a solution of 3 gram-moles of sodium methalate in 1.5 liters of methanol. The mixture was refluxed for 6 hours. The mixture was cooled and filtered to remove insoluble by-products. The methanol was thereafter removed, and the solid 2,6-dimethoxy--4-(trichloromethyl)pyridine product was recovered by filtration. The product melted at 70-73°C and was found to have carbon, hydrogen and nitrogen contents of 37.70, 2.80 and 5.40 percent, respectively, as compared to the theoretical contents of 37.46, 3.12 and 5.46 percent, respectively. The structure was also confirmed by nuclear magnetic resonance spectroscopy (NMR).

Example 2 - 2,6-Dimethoxy-4-(trichloromethyl)pyridine

In another procedure, 2,6-dimethoxy-4-(trichloromethyl)pyridine was prepared by dissolving 4.6 grams (0.2 mole) of sodium metal in 200 milliliters (ml) of methanol. This solution was quickly added to a solution of 26.09 grams (0.1 mole) of 6-chloro-2-methoxy-4--(trichloromethyl)pyridine in 100 ml of dimethylsulfoxide. The mixture was refluxed at about 75°C for 12 hours and 25 ml of methanol was removed, resulting in a reflux temperature of 78°C. An additional 50 ml of dimethylsulfoxide was added and refluxing continued for 5.5 hours at 85°C. An additional 50 ml of methanol was removed, additional dimethylsulfoxide was added, and refluxing continued at 95°C for about 5 hours. The mixture was thereafter diluted with water and extracted with methylene chloride. The methylene chloride layer was washed thoroughly with water and dried over sodium sulfate. The oily product which remained was crystallized from methanol to give 11.2 grams (44 percent yield) of the desired 2,6--dimethoxy-4-(trichloromethyl)pyridine which melted at 71-73°C. The structure of the compound was confirmed by NMR.

Example 3 - 2,6-Diethoxy-4-(trichloromethyl)pyridine

A solution was prepared by dissolving 17.24 grams (0.75 mole) of sodium metal in 400 ml of ethanol. To this solution was rapidly added a solution prepared by dissolving 137.48 grams (0.5 mole) of 6-chloro-2--ethoxy-4-(trichloromethyl)pyridine in 300 ml of ethanol at 35°C. The mixture was heated to reflux at 72° for 42 hours. Thereafter, a solution of 8.62 grams of sodium metal dissolved in 200 ml of ethanol was added and the mixture refluxed for about an additional 5 hours. The mixture was diluted with 500 ml of water after first removing 500 ml of ethanol. The mixture was extracted twice with methylene chloride, and the methylene chloride layers were combined and washed with water. (An emulsion formed and ammonium chloride was added thereto and the mixture allowed to set 3 days for the emulsion to break.) The methylene chloride layer was dried over sodium sulfate, treated with activated charcoal, and filtered. The methylene chloride was removed by evaporation, and 150 ml of methanol was added thereto. The mixture was chilled, and the 2,6-diethoxy-4-(trichloromethyl)pyridine product which precipitated was separated. The product was recrystallized from 150 ml of methanol and dried over methylene chloride. The product melted at 45.5-47.0°C and was recovered in a yield of 46 grams (32 percent yield). The product was found by analysis to have carbon, hydrogen, and nitrogen contents of 42.12, 4.17 and 4.92 percent, respectively, as compared with the theoretical contents of 42.20, 4.25 and 4.92 percent, respectively. The structure of the compound was confirmed by NMR.

Example 4 - 2,6-Dimethoxy-4-(dichloromethyl)pyridine

A solution was prepared by dissolving 19.63 grams (0.087 mole) of stannous chloride dihydrate in 100 ml of acetone. To this mixture was added 7.3 ml of concentrated hydrochloric acid. The mixture was stirred for 10 minutes. To this mixture was added a solution prepared by dissolving 12.8 grams (0.05 mole) of 2,6-dimethoxy-4-(trichloromethyl)pyridine in 40 ml of acetone at 30°C. The mixture was heated to reflux (60°C) and refluxed for 3.5 hours. The reaction mixture was cooled to 15°C and the acetone was removed at this temperature. The residual material was mixed with 250 ml of water and raised to a pH of 12 with 20-30 ml of a 50 percent sodium hydroxide solution. The mixture was extracted twice with 250 ml portions of warm (60-100°C) petroleum ether and the petroleum ether extract washed twice with water. The petroleum ether extract was dried over sodium sulfate, filtered, and the ether removed by evaporation. The desired 2,6-dimethoxy-4-(dichloromethyl)-pyridine product was recovered from the residue by crystallization from hexane. The product melted at 59-62°C and was recovered in a yield of 7.3 grams (65.8 percent). Upon analysis, the product was found to have carbon, hydrogen, nitrogen and chlorine contents of 43.44, 4.08, 6.32 and 31.68 percent, respectively, as compared to the theoretical contents of 43.26, 4.08, 6.30 and 31.93 percent, respectively. The structure of the compounds was confirmed by NMR.

Example 5 - 2,6-Dimethoxy-4-(difluorochloromethyl)-pyridine

To a solution of 11.62 grams (0.05 mole) of 2,6-dichloro-4-(chlorodifluoromethyl)pyridine dissolved in 32 ml of dimethylsulfoxide was added a solution of 2.64 grams (0.115 mole) of sodium metal dissolved in 65 ml of methanol in five increments as follows: (1) 15 ml of the solution was added and the temperature rose to 38°C. The mixture was stirred 5 minutes, and (2) 10 ml of the solution was added, and the temperature rose to 42°C. The mixture was stirred for 5 minutes, cooled to 33°C, and (3) 10 ml of the solution was added, and the temperature rose to 40°C. The mixture was stirred for 5 minutes, cooled to 35°C, and (4) 20 ml of the solution was added. No exotherm occurred, and (5) 10 ml of the solution was added, and the mixture stirred for 5 minutes. The mixture was then heated at reflux temperature for 7 hours. The reaction mixture was cooled, diluted with 400 ml of water, and extracted twice with methylene chloride. The methylene chloride layer was washed with water, dried with sodium sulfate, and the methylene chloride removed by evaporation. The 2,6-dimethoxy-4--(difluorochloromethyl)pyridine product was dried over chloroform and was recovered in a yield of 9.5 grams (85 percent). The product had a refractive index of n2⁵ 1.4747, and upon analysis, was found to have carbon, hydrogen, nitrogen and chlorine contents of 42.84, 3.82, 6.28 and 16.02 percent, respectively, as compared with the theoretical contents of 42.97, 3.60, 6.26 and 15.80 percent, respectively. The structure of the compounds was confirmed by NMR.

Example 6 - 2,6-Dimethoxy-4-(trifluoromethyl)pyridine

To a solution of 10.80 grams (0.05 mole) of 2,6-dichloro-4-(trifluoromethyl)pyridine dissolved in 32 ml of dimethylsulfoxide was slowly added portionwise, with stirring, a solution of 2.64 grams (0.115 mole) of sodium metal dissolved in 65 ml of methanol. The mixture was heated to reflux (75°C) and maintained under reflux for 3.5 hours. After cooling, the mixture was diluted with 500 ml of water and extracted twice with 250 ml portions of methylene chloride. The solvent extract was washed with water, dried with sodium sulfate, and filtered. The methylene chloride was removed by evaporation, and the 2,6-dimethoxy-4-(trifluoromethyl)-pyridine product crystallized from methanol. The product was dried over carbon tetrachloride and recovered in a yield of 6 grams (58 percent), and melted at 26-27°C. The structure was confirmed by NMR, and upon analysis, the product was found to have carbon, hydrogen and nitrogen contents of 49.47, 5.30 and 6.24 percent, respectively, as compared with the theoretical contents of 46.38, 3.89 and 6.76 percent, respectively.

Example 7 - 2,4-Dimethoxy-6-(trichloromethyl)pyridine

To a solution of 13.27 grams (0.05 mole) of 2,4-dichloro-6-(trichloromethyl)pyridine dissolved in 32 ml of dimethylsulfoxide was slowly added over 30 minutes, with stirring, a solution of 2.64 grams (0.12 mole) of sodium metal dissolved in 65 ml of methanol. The mixture was heated at reflux (75°C) for 2 hours and allowed to sit overnight at room temperature. The mixture was diluted with 450 ml of water and extracted with methylene chloride. The extract was washed with water, dried with sodium sulfate, filtered, and evaporated to dryness. The crude 2,4-dimethoxy-6-trichloromethyl)pyridine product was recovered by crystallization from 25 ml of chilled methanol. The product was further refined by recrystallization from pentane followed by recrystallization from chilled methanol. The product melted at 47.5-49°C and the purest material was recovered in a yield of 3.3 grams (25 percent). The structure of the product was confirmed by NMR. Upon analysis, the compound was found to have carbon, hydrogen and nitrogen contents of 38.52, 3.49 and 5.28 percent, respectively, as compared with the theoretical contents of 37.45, 3.14 and 5.46 percent, respectively.

Example 8 - 2-Methoxy-6-ethoxy-4-(trichloromethyl)-pyridine

To a solution of 54.99 grams (0.20 mole) of 2-chloro-6-ethoxy-4-(trichloromethyl)pyridine dissolved in 100 ml of methanol at 60°C was rapidly added a solution of 6.90 grams (0.3 mole) of sodium metal dissolved in 150 ml of methanol. The mixture was heated at reflux for about 1 hour, then stirred at 62°C overnight, refluxed for 8 hours, stirred at 62°C overnight, and then refluxed for 1 hour. A solution of 3.45 grams of sodium metal dissolved in 75 ml of methanol was added and the mixture brought back to reflux. The methanol was removed by evaporation and the residue diluted with water and extracted with methylene chloride. The extract was washed with water, dried with sodium sulfate, and the methylene chloride removed by evaporation. The desired 2-methoxy-6-ethoxy-4-(trichloromethyl)pyridine product was recovered by crystallization from methanol followed by recrystallization from ethanol. The product was recovered in a yield of 8.5 grams and melted at 36-38°C. Upon analysis, the product was.found to have carbon, hydrogen, nitrogen and chlorine contents of 39.49, 3.54, 5.17 and 39.82 percent, respectively, as compared with the theoretical contents of 39.95, 3.72, 5.17 and 39.31 percent, respectively.

Example 9 - 2-Methoxy-6-butoxy-4-(trichloromethyl)-pyridine

To a solution of 52.19 grams (0.2 mole) of 2-chloro-6-methoxy-4-(trichloromethyl)pyridine dissolved in 100 ml of butanol was added over a 25-minute period a solution of 6.9 grams (0.3 mole) of sodium metal dissolved in 300 ml of butanol. The mixture was heated to 115°C and held there for 3 hours. Thereafter, the butanol was removed by evaporation, leaving an oily residue. The residue was taken up in methylene chloride, washed with water (the emulsion formed was dispersed by treatment with ammonium chloride), dried over sodium sulfate, and filtered. The methylene chloride was removed, leaving an oily material. The desired 2-methoxy-6-butoxy--4-(trichloromethyl)pyridine product was recovered by multiple distillation with the center cut yielding 6.9 grams (11 percent of theoretical) of the product. The product had a refractive index of D^{S -} 1.5226, and upon analysis, the product was found to have carbon, hydrogen and nitrogen contents of 54.27, 6.25 and 4.51 percent, respectively, as compared with the theoretical contents of 49.35, 5.92 and 4.11 percent, respectively.

By following the general procedures as set forth above and in the examples, the following compounds are prepared.

Preparation of Starting Materials

2,6-Dichloro-4-(dichloromethyl)pyridine

To a solution of 73 grams (0.275 mole) of 2,6-dichloro-4-(trichloromethyl)pyridine dissolved in 125 milliliters of acetone was added a solution of 108 grams (0.48 mole) of stannous chloride hydrate and 40 milliliters of concentrated hydrochloric acid in 500 milliliters of acetone. The mixture was refluxed for 2.0 hours. The solid which formed was separated by filtration, and three-fourths of the solvent was thereafter removed by evaporation. The remainder of the reaction mixture was diluted with water, and the oil phase which formed was removed by extraction with hexane. The 2,6--dichloro-4-(dichloromethyl)pyridine product was dried and recovered from the solvent by evaporation of the solvent. The product had a boiling point of 123-126°C at 1.6 mm. Hg.

2,6-Dichloro-4-(dichlorofluoromethyl)pyridine

A mixture containing 138.5 grams (0.522 mole) of 2,6-dichloro-4-(trichloromethyl)pyridine and 34 grams (0.187 mole) of antimony trifluoride was heated to 80-84°C and maintained under agitation for 23 minutes. During this step, a slow stream of chlorine gas was passed over the surface of the reaction mixture. The reaction mixture was steam distilled, and the crude 2,6-dichloro-4-(dichlorofluoromethyl)pyridine was purified by fractionation. The product had a boiling point of 74-76°C at 1.0 mm. Hg.

The 2,4-dichloro-6-(dichloromethyl)pyridine and the 2,4-dichloro-6-(dichlorofluoromethyl)pyridine reactants can be prepared by following the above procedure, employing 2,4-dichloro-6-(trichloromethyl)pyridine as the starting material.

The 2,4- and 2,6-dibromo or difluoro counterparts of the above dichloro compounds can be prepared by conventional halogen exchange. They can also be prepared by employing the 2,4- or 2,5-dibromo(or difluoro)-6--(or 4)(trichloromethyl)pyridine as the starting material in the above procedure.

The compounds employed as starting materials which contain a trifluoromethyl, dichlorofluoromethyl, or difluoromethyl group can be prepared employing the procedures taught by McBee et al., 2nd Eng. Chem. 39, pages 389-391 (1947) (see Chem. Abstracts, Vol. 41, page 3461d). In this procedure an appropriate 2,4- or 2,6--halogenated 4- or 6-(trichloromethyl)pyridine is treated with HF in an autoclave at temperatures up to 300°C.

The compounds of the present invention and formulations containing them have been found to be useful as plant fungicides especially valuable for the control of soil-borne plant root disease organisms which attack the roots of plants. In accordance with the present invention, a method for protecting plants, which are in soil containing soil-borne plant root disease organisms, from attack by said organisms is provided which comprises contacting plants or plant parts with at least one of the compounds set forth hereinabove or with a composition containing at least one of the compounds.

The mode of action of the compounds of the present invention is not fully understood. However, it has been found that, while the compounds employed at high dosage rates can kill fungal disease organisms, the use of high dosage rates may be phytotoxic to the plants being treated. It has also been found that the compounds are effective in eliminating plant root diseases from plants which are infected at the time of treatment and that non-infected plants can be protected from attack. It appears that the pathogencity of the disease organism is suppressed or inhibited, or the organism is in some way reduced to a level insufficient for disease expression, which permits normal plant growth.

The present method also offers a practical advantage in that there is no need to employ the additional time and labor required by conventional pre-plant sterilization with soil fumigants.

A further practical advantage of the present method is that the active compounds are used in much smaller amounts than conventional soil fumigants.

The term "plant part" is employed to designate all parts of a plant, and includes seeds, the underground portion (bulbs, stolons, tubers, rhizomes, ratoons, corms, root system), and the above-ground portion (the crown, stalk, stem, foliage, fruit or flower).

The term "systemic" refers to translocation of the active compounds employed in the present method through the plant whereby they selectively accumulate principally in the underground portions of the plant.

Compositions containing one or more of the active compounds of the present invention have been found to be very effective in the control of plant root disease in plants either before or after the plant has been attacked by soil-borne plant root disease organisms.

Representative soil-borne plant root disease organisms which attack the root system and which are controlled by the present method include Rhizoctonia, Phytophthora, Pythium, and Aphanomyces.

Generally in the actual practice of the method of the present invention, the active compounds can be applied to the plant or plant part by a variety of convenient procedures. Such procedures include soil incorporation, above-ground applications, drenching onto the soil surface, and seed treatment.

The exact dosage of the active compound employed can be varied depending upon the specific plant, its stage of development, hardiness, the mode of application, and the growth media. Generally, the active ingredient should be present in an amount equivalent to from about 50 micrograms to about 140 grams per plant. Translating this into conventional application rates, this amount is equivalent to from about 0.0005 to about 10 pounds of the active ingredient on a per acre (0.00056-11.2 kg/hectare).

Seed treatment of small seeded plant species, such as grasses or carrots, will require much smaller amounts than 50 micrograms per plant. Generally, rates in the range of 1/32 to about 8 ounces per 100 pounds of seeds (0.002-0.5 percent by weight of active compound based on weight of seeds) will be optimum for seed treatment. For practices such as conventional tobacco transplant treatment or in-furrow soil treatment of plants such as soybeans at seeding or the like, an amount of active compound approximately equal to 8 to about 32 milligrams would be utilized on a per plant basis.

Larger amounts of the active ingredient may advantageously be applied when treatments are employed which distribute the material throughout the soil. For example, when the active ingredient is applied as an at--plant row treatment or as an early or mid-season post--plant side dress treatment, those amounts of chemical not proximal to plant roots are essentially unavailable to the plant and therefore not effective as set forth hereinabove. In such practices, the amount of the active ingredient employed needs to be increased to rates as high as about 20 pounds per acre (22.4 kg/hectare) to assure that the requisite effective quantity of active ingredient is made available to the plants.

The present invention can be carried out by employing the pyridine compounds directly, either singly or in combination. However, the present invention also embraces the employment of liquids, dusts, wettable powders, granules or encapsulated compositions containing at least one of said compounds as active ingredient. In such usage, the compound or compounds can be modified with one or more of a plurality of additaments or adjuvants including inert solvents, inert liquid carriers and/or surface active dispersing agents and coarsely or finely divided inert solids. The augmented compositions are also adapted to be employed as concentrates and subsequently diluted with additional inert carrier to produce other compositions in the form of dusts, sprays, granules, washes or drenches. In compositions where the adjuvant is a coarsely or finely divided solid, a surface active agent or the combination of a surface active agent and a liquid additament, the adjuvant cooperates with the active component so as to facilitate the invention. Whether the composition is employed in liquid, wettable powder, gel, wax, jelly, dust, granule, or encapsulated form, the active compound will normally be present in an amount of from 2 to 98 percent by weight of the total composition.

In the preparation of dust or wettable powder compositions, the active compounds can be compounded with any of the finely divided solids, such as pyro- phyllite, talc, chalk, gypsum, fuller's earth, bentonite, attapulgite, modified clays, starch, casein, or gluten. In such operations, the finely divided carrier is ground or mixed with the compound or wet with a solution of the compound in a volatile organic solvent. Also, such compositions when employed as concentrates can be dispersed in water, with or without the aid of dispersing agents to form spray mixtures.

Granular formulations are usually prepared by impregnating a solution of the compound in a volatile organic solvent onto a bed of coarsely divided attapulgite, bentonite, diatomite, or organic carrier such as ground corn cobs or walnut hulls.

Similarly, the active compounds can be compounded with a suitable water-immiscible inert organic liquid and a surface active dispersing agent to produce an emulsifiable concentrate which can be further diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions. In such compositions, the carrier comprises an aqueous emulsion, i.e., a mixture of inert water-immiscible solvent, emulsifying agent, and water. Preferred dispersing agents which can be employed in these compositions, are oil-soluble materials, including non-ionic emulsifiers such as the condensation products of alkylene oxides with the inorganic acids, polyoxyethylene derivatives or sorbitan esters, complex ether alcohols, or alkyl phenols. Also, oil-soluble ionic emulsifying agents such as mahogany soaps can be used. Suitable inert organic liquids which can be employed in the compositions include petroleum oils and distillates, toluene, liquid halohydrocarbons, synthetic organic oils, and vegetable oils. The surface--active dispersing agents are usually employed in liquid compositions and in the amount of from 0.1 to 20 percent by weight of the combined weight of the dispersing agent and active compound.

In addition, other liquid compositions containing the desired amount of effective agent can be prepared by dissolving the active compound in an inert organic liquid such as acetone, methylene chloride, chlorobenzene, or petroleum distillate. The preferred inert organic solvent carriers are those which are adapted to accomplish the penetration and impregnation of the soil with the active compounds and are of such volatility as to leave little permanent residue thereon. Particularly desirable carriers are the petroleum distillates boiling almost entirely under 400°F (204°C) at atmospheric pressure and having a flash point above 80°F (27°C). Also desirable are those petroleum fractions with higher boiling points which can leave residues due to low vapor pressures, provided they are low in aromatic content, such as paraffinic or isoparaffinic oils that are of low phytotoxicity. The proportion of the compounds of this invention employed in a suitable solvent may vary from about 2 to about 50 percent. Additionally, the active components can be compounded with water or petroleum jellies to prepare viscous or semi-solid treating compositions.

The following examples are given to illustrate the manner by which the method can be practiced but should not be construed as limitations upon the overall scope of the same.

Example 10

Acetone dilutions were prepared by admixing one of the hereinafter set forth compounds with acetone.

Soil infected with the soybean root rot disease organism Phytophthora megasperma was uniformly mixed and used to fill 3-inch (7.5 cm.) pots. Five soybean seeds were planted in each pot with 4 pots being used per test mixture. The pots were treated by spraying one cubic centimeter (cc) of one of the test dilutions directly onto the soil surface in the pots to give dosages equivalent to 0.125, 0.25, and 0.5 pound per acre (0.14, 0.27, and 0.55 kg./hectare) in-furrow, based upon treating a 1" (2.5 cm.) band of a crop with a 36" (1 m.) row spacing. After the acetone had evaporated, the soil in the pots was capped with a layer of sterile soil. Additional pots were also prepared as above and sprayed with acetone containing no toxicant to serve as controls. The pots were thereafter maintained under conditions conducive to both plant growth and disease development. Two weeks after treatment, the pots were examined to determine the percent of disease control. The results of this examination are set forth below in Table II.

Example 11

Acetone dilutions were prepared by admixing one of the hereinafter set forth compounds with acetone.

Soil infected with the pea root rot disease organism Aphanomyces euteiches was uniformly mixed and used to fill 3-inch (7.5 cm.) pots. Five pea seeds were planted in each pot with 4 pots being used per test mixture. The pots were treated by spraying one cc. of one of the test dilutions directly onto the soil surface in the pots to give dosages equivalent to 0.25, 0.5 and 1.0 pounds per acre (0.27, 0.56, and 1.12 kg./hectare) in-furrow, based upon treating a 1" (2.5 cm.) band of a crop with a 36" (1 m.) row spacing. After the acetone had evaporated, the soil in the pots was capped with a layer of sterile soil. Additional pots were also prepared as above and sprayed with acetone alone to serve as controls. The pots were thereafter maintained under conditions conducive to both plant growth and disease development. Two weeks after treatment, the pots were examined to determine the amount of disease control, as evidenced by the number of plants surviving. The results of this examination are set forth below in Table III.

Example 12

Soil infected with the tobacco black shank pathogen Phytophthora parasitica var. nicotianeae was uniformly mixed and placed in 2-inch (5 cm.) pots. To said pots were transplanted four week old tobacco seedlings which had been grown in pathogen free soil. Test dispersions of the compounds were prepared by dissolving the chemicals in acetone and thereafter diluting the solution with water and a surfactant to prepare dispersions containing 100, 33, and 11 parts by weight of each of the compounds per million (1,000,000) parts of the ultimate dispersion (ppm). Thereafter, the various test dispersions were employed to treat separate pots containing the seedlings by pouring 50 cubic centimeters of each of the dispersions onto the soil, assuring root contact with sufficient chemical. Additional pots were treated with an aqueous acetone solution containing no toxicant to serve as controls. After treatments, the plants were maintained under conditions conducive for good plant growth and disease development. Five days, 8 days, and 13 days after treatment, the plants were examined for disease control. The results of these examinations are set forth below in Table IV.