KR900000566B1 - Photoactive azole pesticides - Google Patents

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Description

Photoactive azole insecticide

The present invention belongs to the field of heterocyclic organic chemical compounds containing azole nuclei. More particularly, the present invention includes methods for controlling agricultural pests such as insects, mites and nematodes using particular oxazole and triazole compounds per se, agricultural compositions containing the novel compounds, and a broad class of such compounds.

There is increasing scientific evidence that light-induced toxicity mechanisms play an important role in the natural removal of certain insect populations. In the last few years, the concept of using a surfactant such as an insecticide has been advanced. Such photosensitizers typically exhibit pesticidal activity by catalyzing the conversion of electronic triplets of molecular oxygen into singlets. Here, the singlet oxygen acts as a peroxidant, which kills insects by destroying the contacted tortural tissue.

According to the invention, the oxazole / thiazole compounds of the general formula are not only photodynamic pesticides and acaricides, but also nematicides:

Wherein W is selected from oxygen and sulfur: R ₂ is selected from optionally substituted thienyl and optionally substituted phenyl, and R ₄ is hydrogen, halogen, lower alkyl, lower haloalkyl, thienyl, tri (lower alkyl) Is selected from silyl and optionally substituted phenyl, R ₅ is selected from hydrogen, lower alkyl, optionally substituted thienyl, or optionally substituted phenyl, provided that at least one of R ₂ and R ₅ is optionally substituted thienyl; R ₄ is not hydrogen when the other of R ₂ and R ₅ is unsubstituted phenyl.

Substituents which may be substituted by any phenyl include radicals independently selected from one or more of the following:

Hydrogen, halogen, lower alkyl, lower haloalkyl, lower alkoxy, lower haloaxoxy cyano, dialkylamino, phenyl, pyridyl, thienyl, lower alkylsulfonyloxy, thiobenzoyl, phenylsulfonyloxy, nitro Or -C ₄ H _4- , OC (X) ₂ O-, -OCF ₂ CF _2- , or -OC (CH ₃ ) ₂ CH _2- , -OCX ₂ CX ₂ O- that crosslinks adjacent ring positions. Where X is hydrogen, fluoro or methyl.

Thienyl may be optionally substituted with substituents independently selected from the following: hydrogen, halogen, lower alkyl, lower hydroxyalkyl, lower alkylthio, lower haloalkylthio, lower alkylsulfonyl, lower haloalkenylthio, thi Nil, tri (lower) alkylsilyl, or loweralkoxycarbonyl, more particularly the invention as defined above for W, where R ₂ is phenyl, naphthyl, 2,2-difluoro-1,3-benzodioxyl Phenyl substituted with at least a substituent with a substituent selected from halogen, lower alkyl, lower haloalkyl, cyano, lower alkoxy, lower haloaxoxy, di (lower) alkylamino, phenylthiocarbonyl or phenylsulfonyloxy: Thievo: and halogen, and substituted thienyl selected from lower alkyl and thienyl: R ₄ is selected from hydrogen, tri (lower) alkylsilyl, phenyl, halophenyl, and thienyl: R ₅ is hydrogen , Lower alkyl, phenyl, halogen, lower egg Phenyl substituted with at least one substituent selected from lower haloalkyl, lower alkoxy, phenyl or nit: thienyl: and lower alkyl, halogen, lower hydroxyalkyl, lower haloalkylthio, lower alkylsulfonyl, lower Is selected from thienyl substituted with a substituent selected from among lower alkenylthio, lower alkylsulfonyl, lower haloalkenylthio, lower alkoxycarbonyl or tri (lower) alkylsilyl: at least one of R ₂ and R ₅ is optionally substituted thienyl group, preferably an optionally substituted 2-thienyl group, R ₂ and R ₅ of the other is an unsubstituted thienyl, R ₂ and R ₅ of the other is R in the case of the unsubstituted phenyl ₄ Provides a pesticide compound of the above-described structural formula other than hydrogen.

The term "halogen" or "halogen" as used herein means fluorine, chlorine or bromine. The term “lower”, which modifies “alkyl”, “alkoxy”, etc., means a straight or branched hydrocarbon having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms: “halo” used with other terms, ＂Hydroxy＂ and the like means that one or more hydrogens are each replaced with halogen or hydroxy.

Of the foregoing compounds, thiazoles are preferred, and for most active compounds, R ₄ is hydrogen. Furthermore, it is preferred that R ₅ is a 5-substituted thienyl substituent.

Specific preferred pesticides include the following compounds: 5- (5-methylthien-2-yl) -2- (4-trifluoro-methylphenyl) thiazole, 5- (5-methylthien-2-yl ) -2- [3,5-bis (trifluoromethyl) phenyl] thiazole, 2- (4-flufuo-phenyl) -5- (thien-2-yl) thiazole, 2- (4-chloro Phenyl) -5- (thien-2-yl) thiazole, 2- (4-trifluoromethylphenyl) -5- (thien-2-yl) thiazole, 5- (5-chlorophenyl-2-yl) -2- (4-fluorophenyl) thiazole, 2- (4-methylphenyl) -2- (5-methylphenyl-2-yl) thiazole, 2- (5-methylphenyl-2-yl) -5- ( Thien-2-yl) thiazole, 2,5-bis (5-chlorothien-2-yl) thiazole, 5- (5-methylthien-2-yl) -2- (thien-2-yl) thia Sol, 2- (5-chlorothien-2-yl) -5- (5-methylphenyl-2-yl) thiazole, and 2- (2,2-difluoro-1,3-benzodioxol-5 -Yl) -5- (5-methylphenyl-2-yl) thiazole.

The active compounds of the present invention can be prepared by basically modifying the synthetic techniques known in the art. See, US Pat. No. 4,024,156, J. Am. Chem. Soc., 71, 2473 (1949), Synth. Comm., 14, 1 (1984), and US Pat. No. 4,153,703.

Processes for preparing the oxazole / thiazole compounds of the present invention are described in the specific examples below. In general, compounds are characterized by melting point, elemental analysis and absorption spectrum.

5- (5-methylthien-2-yl) -2- (4-trifluoro-methylphenyl) thiazole

A warm solution of 5-methyl-2-acetylthiophene (20.1 g, 0.14 mol) in chloroform (100 ml) was stirred and refluxed with copper (II) bromide (48.0 g, 0.22 mol) in ethyl acetate (100 ml). To the mixture. After the addition is completed, the resulting mixture is heated to reflux for 2.5 hours. The mixture is cooled slightly and filtered. Additional 31.9 g (0.14 mol) of copper (II) bromide is added to the filtrate and the mixture is heated to reflux for 1.5 hours. Cool the mixture and filter. The filtrate is evaporated under reduced pressure to give 32.1 g of 2-bromo-1- (5-methylthien-2-yl) ethanone as a dark liquid.

A mixture of 2-bromo-1- (5-methylthien-2-yl) ethanone (30.0 g of the dark liquid described above) and hexamethylene tetramine (21.0 g, 0.15 mole) in chloroform (500 ml) was stirred at room temperature. Stir for 3 days. The solvent is evaporated under reduced pressure to remove from the reaction mixture, leaving a dark residue. This residue is stirred in warm methylene chloride. Diethyl ether is slowly added to the mixture and the solids are allowed to settle. After cooling for several hours, the solids are collected by filtration. The filler cake was washed with diethyl ether and dried under reduced pressure to yield 1- [2-oxo-2- (5-methylthienyl) ethyl] -3,5,7-triaza-1-azoniat 43.1 g of cyclo [3,3,1,1,3,7] decane bromide (melting point 141 ° C., decomposition) is obtained.

1- [2-oxo-2- (5-methylthienyl) ethyl] -3,5,7-triaza-1-azoniatricyclo [3,3,1,1,3 in ethanol (200 ml) , 7] a mixture of decanbromide (41.7 g, 0.12 mol) and concentrated hydrochloric acid (50 ml) is stirred at room temperature for approximately 18 hours and a precipitate is formed. This precipitate is collected by filtration and dried under reduced pressure to give 26.3 g of a solid. The filtrate is evaporated down to a volume of about 100 ml. Dietel ether is added and more precipitate is formed. The precipitate is collected by filtration and dried under reduced pressure to give 9.0 g of 2-amino-1- (5-methylthienyl) ethanone hydrochloride.

Stirred of 2-amino-1- (5-methylthienyl) ethanol hydrochloride (3.0 g of a mixture containing approximately 60% 2-amino-1- (5-methylthienyl) ethanol hydrochloride) in methylene chloride (100 ml) The suspension is cooled in an ice bath. To the cooled mixture, 4- (trifluoromethyl) benzoyl chloride (2.8 g, 0.013 mol) is added, followed by slowly adding 2N sodium hydroxide solution (9.4 ml). After the addition, the mixture is stirred for 3 days at room temperature. The mixture is first washed with 5% aqueous hydrochloric acid solution and then with water. The organic phase is dried over anhydrous magnesium sulfate and filtered. The filtrate is evaporated under pressure to afford 3.9 g of solid N- [2- (5-methylthienyl) -2-ogoethyl] -4-trifluoromethyl benzeneamide. Small amounts are recrystallized from ethanol for analysis. Melting point: 182-183 degreeC.

To a stirred suspension of Lawesson's reagent (2.3 g, 0.0057 moles) in approximately 40 ml toluene, N- [2- (5-methylthienyl) -2-oxoethyl] -4- in toluene (35 ml) A mixture of trifluoromethyl benzeneamide (3.0 g, 0.011 mol) is added. After the addition the reaction mixture is heated to reflux for approximately 4 hours, then cooled to room temperature and stirred for 2 days. The solvent is evaporated under reduced pressure to remove from the reaction mixture, leaving oil. The oil was dissolved in a small amount of methylene chloride and eluted with methylene chloride, purified by column chromatography on silica gel, then solid 5- (5-methylthien-2-yl) -2- (4-trifluoro-methylphenyl ) 1.0 g of thiazole is obtained. Melting point: 150-152 degreeC.

Example 2

5- (5-methylthien-2-yl) -2- [3,5-bis (trifluoromethyl) phenyl] thiazole

In a similar manner to Example 1, 2-amino-1- (5-methylthienyl) ethanol hydrochloride (2.6 g, 0.014 mol) in methylene chloride (75 ml) was added to 3,5-bis (trifluoromethyl) benzoyl chloride. (3.8g, 0.014mol) and 2N sodium hydroxide solution (13.7ml) to give solid N- [2- (5-methylthienyl) -2-oxoethyl] -3,5-bis (trifluoromethyl 4.6 g of benzamide is obtained.

In a similar manner to Example 1, N- [2- (5-methylthienyl) -2-oxoethyl] -3,5-bis (trifluoromethyl) benzamide (4.0 g, 0.01 in toluene (100 ml) Mole) was reacted with a suspension of Laweson's reagent (2.0 g, 0.005 mole) in toluene (100 ml) to give solid 5- (5-methylthien-2-yl) -2- [3,5-bis (triflo) 1.0 g of oromethyl) phenyl] thiazole is obtained. Melting point: 119.5 to 121 ° C.

Example 11

2- (4-methylphenyl) -5- (thien-2-yl) thiazole

Into a stirred mixture of 4-methyl-N- [2- (thien-2-yl) -2-oxoethyl] benzamide (3.01 g, 0.0116 mol) in approximately 200 ml pyridine (5.16 g, 0.0116 mol) Add. After the addition is completed, the mixture is heated to reflux for 2.5 hours. The hot mixture is poured into ice water and a precipitate is formed. The precipitate is collected by filtration. The melter cake is dissolved in methylene chloride and eluted with methylene chloride and column chromatography on silica gel to give a yellow solid. This solid is recrystallized from ethanol to give 0.96 g of 2- (4-methylphenyl) -5- (thien-2-yl) thiazole. Melting Point: 85.5-86.5 ℃

Example 31

2- (4-methylphenyl) -5- (5-ketylthienyl-2-yl) thiazole

Under anhydrous nitrogen atmosphere, the solution of 2- (4-methylphenyl) -5- (thien-2-yl) thiazole 90.17 g, 0.00066 mol) in anhydrous tetrahydrofuran (15 ml) is cooled to -78 ° C. To this solution is added n-butyllithium (0.40 ml of 1.3 M solution in hexane). After the addition is complete the reaction mixture is stirred at −78 ° C. for approximately 1 hour. Methyl iodide (0.1 g, 0.0007 moles) is added followed by dimethyl sulfate (0.027 g, 0.00021 moles). The resulting mixture is stirred and slowly warmed to room temperature. To this was added saturated aqueous ammonium chloride solution. After brief stirring the mixture is extracted with methylene chloride. The extract is dried over anhydrous magnesium sulfate and filtered. The filtrate is evaporated under reduced pressure to yield 0.22 g of a yellow solid. Melting point; 108 to 110 ° C. NMR analysis showed that the yellow solid had 85% 2- (4-methylphenyl) -5- (5-ketylthienyl-2-yl) thiazole and 15% 2- (4-methylphenyl) -5- (thiene-2 A mixture containing -yl) thiazole was suggested.

Example 40

2- (4-Flufluorophenyl) -5- (5-methylsulfonylthien-2-yl) thiazole

To a stirred solution of 2- (4-flufuophenyl) -5- (5-methylsulfonylthien-2-yl) thiazole (1.07 g, 0.0035 moles) in methylene chloride (50 ml) in methylene chloride (25 ml) A solution of m-chloroperbenzoic acid (1.7 g, 0.0084 mol) is added dropwise. After the addition is complete the mixture is stirred at room temperature for approximately 18 hours. Approximately 100 ml of 10% aqueous sodium sulfate solution is added and the mixture is stirred for about 15 minutes. The mixture is washed successively with saturated aqueous sodium bicarbonate solution, water and saturated aqueous sodium chloride solution. Thin layer chromatography of the organic phase showed that the starting material remained. The washed organic phase is therefore diluted with methylene chloride and additional 1.7 g of m-chlorobenzoic acid are added. The mixture is stirred and heated to reflux until only one point appears on thin layer chromatography. Approximately 100 dml 10% aqueous sodium sulfate solution is added and the mixture is stirred for about 15 minutes. The mixture is washed successively with saturated aqueous sodium bicarbonate solution, water and saturated aqueous sodium chloride solution. The washed organic phase is evaporated under reduced pressure leaving a solid residue. It is eluted with methylene chloride and purified by column chromatography on silica gel to give 0.59 g of solid 2- (4-flufuophenyl) -5- (5-methylsulfonylthien-2-yl) thiazole. . Melting point: 183 to 184 ° C.

Example 50

4-phenyl-2- (thien-2-yl) thiazole

To a stirred solution of 2-thiophenthiocarboxamide (1.56 g, 0.0109 mol) in ethanol (50 ml) is added 2-broacethetophenone (2.19 g, 0.0110 mol). After the addition is complete the mixture is heated to reflux for 2 hours, then cooled to room temperature and stirred for approximately 18 hours. The solvent is evaporated under reduced pressure to remove from the reaction mixture, leaving behind an oil which solidifies. This solid is suspended in water and extracted twice with methylene chloride. The extracts are combined and dried over anhydrous magnesium sulfate and filtered. The filtrate is evaporated under reduced pressure to yield 2.48 g of solid 4-phenyl-2- (thien-2-yl) thiazole. Melting point: 51-53 degreeC.

Example 63

4- (4-chlorophenyl) -2- (5-chlorothien-2-yl) -5- (4-methylphenyl) thiazole

Under anhydrous nitrogen atmosphere, 2-bromo-2- (4-methylphenyl) -1- (4-chlorophenyl) ethanone (4.5 g, 0.014 mol) and 5-chloro-2-thiophenthiocarboxamide (2.5 g, 0.014 mol) is heated at 110 ° C. for 2.5 hours. The mixture is cooled, eluted with diethyl ether: n-hexane (5: 95), and column chromatography on silica gel leaves a solid. This solid is recrystallized from ethanol to give 0.68 g of 4- (4-chlorophenyl) -2- (5-chlorothien-2-yl) -5- (4-methylphenyl) thiazole. Melting point: 103.35 to 104.5 ° C.

Example 92

2,5-di (thien-2-yl) oxazole

A stirred mixture of N- [2-oxoethyl-2- (thien-2-yl)]-2-thiogen carboxamide (2.02 g, 0.0080 moles) and phosphorus oxychloride (30 ml) was added for approximately 18 hours. Heat to reflux. Cool the mixture and slowly pour into ice water. After the addition the aqueous mixture is stirred to destroy all remaining phosphorus oxychloride and then extracted twice with methylene chloride. The extracts are combined and dried over anhydrous magnesium sulfate and filtered. The filtrate is evaporated under reduced pressure, leaving a solid residue. This solid is eluted with methylene chloride: n-hexane (50: 40) and purified by chromatography to give 1.42 g of 2,5-bis (thien-2-yl) oxazole. Melting point: 64.5 to 66 ° C.

Still other azole compounds that fall within the scope of the present invention are prepared by similar techniques and are shown in Table 1.

In the normal use of the pesticidal azole compounds of the present invention, the active compounds are usually not usable without mixing or dilution, but are usually suitably formulated for the application method and are suitably formulated containing a pesticide, acaricide or nematicidal dose of the active compound. Will be used in the formulated composition. The active compounds of the present invention, such as most pesticides, are aware of the fact that the formulation and application of the pesticides may affect the activity of the substance and are an agriculturally acceptable interface normally used to facilitate dispersion of the active ingredient. Can be mixed with the active agent and the carrier. The active compounds can be applied, for example, as sprays, powders, or granules, by varying the application depending on the insect and the environment in the area where insect control is desired. Accordingly, the active compounds of the present invention can be formulated as granules, dispersants, lubricating agents, emulsion concentrates, liquids and the like in particle size.

The granulation may consist of porous or nonporous particles, such as, for example, attapulgire clay or sand, which acts as a carrier for the active compound. The particles of the granules are relatively large and typically have a diameter of about 400 to 2500 microns. The particles are saturated with the active compound from the solution or covered with the active compound, and an adhesive is sometimes used. Granules generally contain an insecticidal effective amount of from 0.05 to 10%, preferably from 0.5 to 5%.

Powders are finely divided solids and pesticides, acaricides, or fleshs such as talc, attapulgite clay, kieselguhr pyrophyllite, chalk, calcium phosphate, calcium carbonate and magnesium carbonate, sulfur, powder Mixtures of other organic and inorganic solids and active compounds which serve as carriers for nematodes. The finely divided solids have an average particle size of about 50 microns or less. Typical powder forms useful for controlling insects, mites, or nematodes include 1 part active compound such as 5- (5-methylthien-2-yl) -2- (4-trifluoromethylphenyl) thiazole, and 99 parts talc It contains.

The active compounds of the present invention can be prepared as liquid thickeners by dissolving or emulsifying in suitable liquids and mixed with other known solid carriers used in the field of talc, clays and pesticides to prepare solid concentrates. Thickeners are compositions containing about 5-50% active compound and 95-50% inert material, including surfactant dispersants, emulsifiers, and wetting agents, with a pesticide effective amount, although Can be used experimentally. The thickener is diluted with water or another liquid for practical use as a nebulizer or with another solid carrier for use as a powder.

A typical 50% wet powder type is 50.0% (wt / wt) of 5- (5-methylthien-2-yl) -2- [3,5-bis (trifluoromethyl) phenyl] thiazole, 22.0% Attapulgite diluent, 22.0% kaolin diluent, and 6.0% sodium salt of sulfonated kraft lignin emulsifier.

Typical carriers for solid concentrates (also called wet powders) include clay, clay, silica, and other superabsorbents, easily wetted inorganic diluents. Solid concentrates useful for controlling insects, mites, or nematodes are 1.5 parts of sodium lignosulfonate and sodium laurylsulfate, respectively, as a wetting agent, 5- (5-methylthien-2-yl) -2- [3,5- 25 parts of bis (trifluoromethyl) phenyl] thiazole and 72 parts of attapulgite clay.

Commercialized thickeners are useful for the shipment of low melting point products of the present invention. A low melting solid product can be melted with at least 1% of a solvent to produce a thickener that does not solidify upon cooling to or below the freezing point of the pure product.

Useful liquid thickeners include emulsifying thickeners, which are homogeneous liquid or paste compositions which are readily dispersed in water or other liquid carriers. They consist entirely of the active compound together with liquid or solid emulsifiers, or they also include liquid carriers such as xylene, heavy aromatic naphtha, isophorone and other relatively nonvolatile organic solvents. For application, the thickener is normally applied as a spray to the area to be treated by dispersing it in water or other liquid carrier.

A typical 50g per liter of emulsifier concentrate is an emulsifier (1.80% mixture of nonionic 6-mol ethylene oxide condensation product of calcium salt of dodecylbenzene sulfonate and nonylphenol, calcium salt of dodecylbenzene sulfonate and nonionic of nonylphenol 5- (5-methylthien-2-yl) -2 (4-trifluoromethylphenyl) thiathiane as a mixture of 30-mol ethylene oxide condensation product 2.7%, 1.50% nonionic paste of polyalkylene glycol ether) Sol 5.90% (wt / wt) and 88.10% purified xylene solvent.

Typical interfacial-active wetting agents, dispersants, and emulsifiers used in insecticide form include, for example, alkyl and alkylaryl sulfonates and sulfates and their sodium salts: alkylamide sulfonates (including fatty methyl taurides): alkylaryl polys Ether alcohols, sulfurized higher alcohols, polyvinyl alcohols: polyethylene oxides: sulfonated animal and vegetable fibers: sulfonated petroleum oils: fatty acid esters of polyhydric alcohols and ethylene oxide adducts of such esters: and long-chain mercaps Adducts of carbon and ethylene oxide. Many other forms of useful surfactants are commercially available. When used, surfactants normally contain from about 1 to 15% by weight of the pesticide, plant, or nematicide composition. Other useful formulations include simple solutions of the active ingredient that dissolve completely at the desired concentration in a solvent, such as acetone or other organic solvent.

The effective amount of the pesticide, acaricide or nematode active compound in the pesticide, acaricide or nematicide composition diluted for application is qualitatively from about 0.001% to about 8% by weight. The spray and powder compositions known in the art can be varied by substituting the active compounds of the invention with compositions known or apparent in the art.

The insecticide, plant, or nematicide composition of the present invention may be formulated with other active ingredients, including other pesticides, nematicides, acaricides, fungicides, plant growth regulators, fertilizers and the like. In using the composition to control insects, mites, or nematodes, it is only necessary to apply an effective amount of an azole compound of worms, arachnids or nematodes to the area in which it is to be controlled. Such areas may be, for example, insects themselves, plants that insects feed, or insect habitats. If the site is a soil, for example an agricultural crop or soil to be grown, the active compound may be applied and optionally incorporated into the soil. For most applications, the worms, acaricide or nematode effective amount will be about 50 to 750 g per hectare, preferably 150 g to 500 g per hectare. The pesticidal activity of the active compounds described above for the preparation method is evaluated as follows:

The azole compounds are tested for pesticidal and acaricide activity under light in the vicinity of ultraviolet light (wavelengths 320 to 400 nanometers) at an intensity of 1600 to 2400 microwatts / cm 2 using test methods that employ various microorganisms during the test. Without distinction of microorganisms, the foliage of the whole plant or the foliage removed from the whole plant is sprayed for outflow with 10% acetone-0.25% octylphenoxypolyethoxyethanol-aqueous solution containing 200 ppm or less of the test compound.

Mature advantage The leaves infected with spider mite (Tetrany chusurticae) are removed from the culture plants and cut into fragments containing 50 to 75 female mites. Each fragment is placed on the entire leaf surface of the Phaseolus vulgaris plant. The mites are transferred below the surface of the leaves, then the fragments of the leaves used for infection are removed and each plant is sprayed with the test compound described above. After the plants are dried, the whole plant and cargo are placed in metal steps in a hood. Inflate the plant by watering the stage. The test is carried out for tolerance and low phosphate toughness.

In tests using Mexican bean beetles (Epila chna varivestis) or Cabbage worms (Trichoplusia ni), stained bean test plants are sprayed with test compounds and dried as described above. Each test plant is cut from the soil line and the stem is pushed through a small diameter hole drilled into the bottom of an 8 oz. Wax container. First, the larvae of the ten larvae Mexican bean beetles are counted in each container. Each container is covered with a glass petri dish and placed on a support shelf, with the stem of the plant protruding from the bottom, allowing the stem to remain in water during the discharge period.

The test results are collected and recorded at the end of the 24 or 48 hour release period. The data is presented in Table 2. In contrast to the results presented in Table 2, in the absence of ultraviolet radiation, when applied at a rate of 100 ppm, the compounds generally do not kill the insect order mites.

The azole compound is assessed for nematode activity against the rootworm nematode (Meloidogyme incognita) using an acetone aqueous solution or a 5% by weight powder formulation prepared as follows and powdered into fine powder:

Azole compound (100% activity basis) 5 parts

95 parts of materials

96% -Aterpulzite Clay

2% -highly purified sodium lignosulfonate (100%)

2% -powdered sodium alkylnaphthalenesalfonate (75%)

The formulations are tested for activity against the root-knot nematodes as follows.

Samples of the root-knot nematode spawning were subjected to the powder-sugar suspension extraction technique of caveness and Jensen [Caveness, F.E. and J Dundu, H.J., ＂Modification of the Centrifugal Flotation Technique for the Isolation and Concentration of Nematodes and their Eggs from soil and Plant Tissue＂, Proc. Helm. soc., Washington, 22, 87-89 (1955)] for nematodes and mixed with another stem-sterilized sandy soil, containing one container of soil (3 inches in diameter, each containing approximately 300 g of soil). Include 600-800 root-knot nematodes and eggs per egg. Depending on the total nematode infecting the required soil, mix for 5 minutes using a cement mixer or 60 seconds using a V-type rotary mixer.

Infected soil as above is used for soil-incorporated nematode studies during the two-day manufacturing period. Infected soil is treated with the formulation to test nematode activity by mixing 25 ppm or less of the formulation in soil (appropriate in mg for weight active compound soils in liters). Young tomato or cucumber plants are treated as above in a 3-inch pot and grown in infected soil. Control plants are grown in the same manner, but using untreated, infected soil. Without the active ingredient, the formulation base is added to the infected soil, respectively, and the tomato plants are grown there, if desired, to detect the effect of the compounds in the formulation base.

After two weeks the roots of all plants are observed and the results evaluated when compared to untreated control plants. The test results are expressed in terms of% removal and are shown in Table 3.

The azole compounds of the invention have also been found to be effective against and tested against southern corn root worms (Diabrotice nudecimpuntata howardi) and free-living nematodes (Caenorhabditis elegans). Activity against the latter suggests pesticidal activity.

Table 1

[Table 2]

CL = cabbage insect

MBB = Mexican Bean Beetle

TSM-R = Advantage Spider Mite-resistance

TSM-S = Benefit Spider-Allow

Table 3

Claims (10)

Compound of the following general formula.

Wherein W is selected from oxygen and sulfur and R ₂ is phenyl, naphthyl, 2,2-difluoro-1,3-benzodioxyl: halogen, lower alkyl, lower haloalkyl, cyano, lower Phenyl substituted with at least one substituent selected from alkoxy, lower haloalkoxy, di (lower) alkylamino, phenylthiocarbonyl or phenylsulfonyloxy: thienyl: halogen and substituted with substituents selected from lower alkyl and thienyl Thienyl is selected from: R ₄ is selected from hydrogen, tri (lower) alkylsilyl, phenyl, haloperin, and thienyl: R ₅ is selected from hydrogen, lower alkyl, phenyl: halogen, lower alkyl, lower haloalkyl, Phenyl substituted with at least one substituent selected from lower alkoxy, phenyl or nitro: thienyl: and lower alkyl, halogen, lower hydroxyalkyl, lower haloalkylthio, lower alkylsulfonyl, lower haloalkenylthio, lower alkoxy Carbonyl or tree (low ) Alkylsilyl is selected from thienyl substituted with a substituent selected among: R ₂ and R ₅ in that at least one is an optionally substituted thienyl group: R ₂ and R is at least one of the _five is unsubstituted thienyl, R ₂ And R ₄ is not hydrogen when the other of R ₅ is unsubstituted phenyl. The compound of claim 1, wherein 5- (5-methylthien-2-yl) -2- (4-trifluoro-methylphenyl) thiazole: 5- (5-methylthien-2-yl) -2- [3 , 5-bis (trifluoromethyl) phenyl] thiazole: 2- (4-fluoro-phenyl) -5- (thien-2-yl) thiazole: 2- (4-chlorophenyl) -5- ( Thien-2-yl) thiazole: 2- (4-trifluoromethylphenyl) -5- (thien-2-yl) thiazole: 5- (5-chlorothien-2-yl) -2- (4- Fluorophenyl) thiazole: 2- (4-methylphenyl) -5- (5-methylthien-2-yl) thiazole: 2- (5-methylthien-2-yl) -5- (thien-2- Yl) thiazole: 2,5-bis (5-chlorothien-2-yl) thiazole: 5- (5-methylthien-2-yl) -2- (thien-2-yl) thiazole: 2- (5-Chlorothien-2-yl) -5- (5-methylthien-2-yl) thiazole: and 2- (2,2-difluoro-1,3-benzodiox TF-5-yl) -5- (5-methylthien-2-yl) thiazole. The compound of claim 1, wherein R ₄ is hydrogen. The compound of claim 3, wherein R _{5 is} substituted thienyl. The compound of claim 4 which is 5- (5-methylthien-2-yl) -2- (4-trifluoro-methylphenyl) thiazole. The compound of claim 4, which is 5- (5-methylthien-2-yl) -2- [3,5-bis (trifluoromethyl) phenyl] thiazole. An insecticidal, acaricidal, or nematicid composition comprising an effective amount of an insecticidal, acaricidal or nematicidal compound of at least one compound of the following general formula in an admixture with an agriculturally acceptable carrier.

Wherein W is selected from oxygen and sulfur and R ₂ is phenyl, naphthyl, 2,2-difluoro-1,3-benzodioxyl: halogen, lower alkyl, lower haloalkyl, cyano, lower Phenyl substituted with at least one substituent selected from alkoxy, lower haloalkoxy, di (lower) alkylamino, phenylthiocarbonyl or phenylsulfonyloxy: thienyl: and substituents selected from halogen and lower alkyl and thienyl Selected from thienyl: R ₄ is selected from hydrogen, tri (lower) alkylsilyl, phenyl, haloperin, and thienyl: R ₅ is selected from hydrogen, lower alkyl, phenyl: halogen, lower alkyl, lower haloalkyl Phenyl substituted with at least one substituent selected from lower alkoxy, phenyl or nitro: thienyl: and lower alkyl, halogen, lower hydroxyalkyl, lower haloalkylthio, lower alkylsulfonyl, lower haloalkenylthio, lower Alkylsulfonyl, lower halo Alkenyl alkylthio, lower alkoxycarbonyl, or tri (lower) alkylsilyl is selected from thienyl substituted with a substituent selected among: R ₂ and R ₅ in that at least one is an optionally substituted thienyl group: R ₂ and R ₅ of at least One is unsubstituted thienyl and R | R ₄ is not hydrogen when the other of ₂ and R ₅ is unsubstituted phenyl. The compound of claim 7, wherein the compound is 5- (5-methylthien-2-yl) -2- (4-trifluoro-methylphenyl) thiazole: 5- (5-methylthien-2-yl) -2- [3,5-bis (trifluoromethyl) phenyl] thiazole: 2- (4-fluoro-phenyl) -5- (thien-2-yl) thiazole: 2- (4-chlorophenyl) -5 -(Thien-2-yl) thiazole: 2- (4-trifluoromethylphenyl) -5- (thien-2-yl) thiazole: 5- (5-chlorothien-2-yl) -2- ( 4-fluorophenyl) thiazole: 2- (4-methylphenyl) -5- (5-methylthien-2-yl) thiazole: 2- (5-methylthien-2-yl) -5- (thiene- 2-yl) thiazole: 2,5-bis (5-chlorothien-2-yl) thiazole: 5- (5-methylthien-2-yl) -2- (thien-2-yl) thiazole: 2- (5-chlorothien-2-yl) -5- (5-methylthien-2-yl) thiazole: and 2- (2,2-difluoro-1,3-benzodiox TF-5- Il) -5- (5-methylthien-2-yl) thiazole. A method for controlling insects, mites or nematodes, characterized by applying at least one compound of the general formula

Wherein W is selected from oxygen and sulfur and R ₂ is phenyl, naphthyl, 2,2-difluoro-1,3-benzodioxyl: halogen, lower alkyl, lower haloalkyl, cyano, lower Phenyl substituted with at least one substituent selected from alkoxy, lower haloalkoxy, di (lower) alkylamino, phenylthiocarbonyl or phenylsulfonyloxy: thienyl: and substituents selected from halogen and lower alkyl and thienyl Selected from thienyl: R ₄ is selected from hydrogen, tri (lower) alkylsilyl, phenyl, haloperin, and thienyl: R ₅ is selected from hydrogen, lower alkyl, phenyl: halogen, lower alkyl, lower haloalkyl Phenyl substituted with at least one substituent selected from lower alkoxy, phenyl or nitro: thienyl: and lower alkyl, halogen, lower hydroxyalkyl, lower haloalkylthio, lower alkylsulfonyl, lower haloalkenylthio, lower Alkylsulfonyl, lower halo Alkenyl alkylthio, lower alkoxycarbonyl, or tri (lower) alkylsilyl is selected from thienyl substituted with a substituent selected among: R ₂ and R, _5, at least one is an optionally substituted thienyl group of, R ₂ and R ₅ either When is unsubstituted phenyl R ₄ is not hydrogen. The compound according to claim 9, wherein the compound used is 5- (5-methylthien-2-yl) -2- (4-trifluoro-methylphenyl) thiazole: 5- (5-methylthien-2-yl)- 2- [3,5-bis (trifluoromethyl) phenyl] thiazole: 2- (4-fluoro-phenyl) -5- (thien-2-yl) thiazole: 2- (4-chlorophenyl) -5- (thien-2-yl) thiazole: 2- (4-trifluoromethylphenyl) -5- (thien-2-yl) thiazole: 5- (5-chlorothien-2-yl) -2 -(4-fluorophenyl) thiazole: 2- (4-methylphenyl) -5- (5-methylthien-2-yl) thiazole: 2- (5-methylthien-2-yl) -5- ( Thien-2-yl) thiazole: 2,5-bis (5-chlorothien-2-yl) thiazole: 5- (5-methylthien-2-yl) -2- (thien-2-yl) thia Sol: 2- (5-chlorothien-2-yl) -5- (5-methylthien-2-yl) thiazole: and 2- (2,2-difluoro-1,3-benzodiox TF- 5-yl) -5- (5-methylthien-2-yl) thiazole.