WO1986002075A1 - Pesticidal tricycloalkyl-(2-pyridylthio) tin n-oxides - Google Patents

Pesticidal tricycloalkyl-(2-pyridylthio) tin n-oxides Download PDF

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Publication number
WO1986002075A1
WO1986002075A1 PCT/US1985/001870 US8501870W WO8602075A1 WO 1986002075 A1 WO1986002075 A1 WO 1986002075A1 US 8501870 W US8501870 W US 8501870W WO 8602075 A1 WO8602075 A1 WO 8602075A1
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Prior art keywords
compound
effective amount
plants
compounds
inert carrier
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PCT/US1985/001870
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French (fr)
Inventor
William F. King
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Chevron Research Company
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
    • A01N55/04—Tin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • C07F7/226—Compounds with one or more Sn-S linkages

Definitions

  • the present invention relates to novel tricycloalkyl tin derivatives of 2-pyridyl N-oxide.
  • R, R' , and R" are independently selected alkyl and preferably lower alkyl, i.e., alkyl having 1-4 carbon atoms; and aryl having 6-10 carbon atoms, preferably phenyl; n and m independently are 0-1 and r is 1-2, with the proviso that n plus m plus r is three, which are useful as heat stabilizers for vinyl chloride resins.
  • R is cycloalkyl of 3 to 8 carbon atoms and show surprisingly good activity as miticides and insecticides, especially against lepidoptera. These compounds also exhibit good activity as a fungicide against a variety of fungi, particularly fungi which cause plant fungal diseases as well as an acaricide and insecticide.
  • the present invention is based on my finding that the present compounds exhibit surprisingly good activity against mites and lepidoptera, and against certain plant fungicidal diseases. Moreover, it is believed these compounds do not exhibit phyto- toxicity, unlike other trialkyl and triaryl tin deriva ⁇ tives of 2-pyridyl N-oxides. Thus, lack of phytotoxicity is a distinct advantage in agricultural applications, since the compound may be used to protect plant crops from insect, acarine, and various plant fungal bests without herbicidal effects or damage to the plant itself.
  • the present invention is also directed to fungicidal, insecticidal and acaricidal compositions containing and methods of using the compounds of the present invention. In addition, the present invention is directed to non- phytotoxic fungicidal, insecticidal and acaricidal compositions comprising these compounds which are not appreciably phytotoxic.
  • cycloalkyl refers to cyclic alkyl groups and includes, for example, cyclopropyl, cyclopentyl, cyclohexyl , cycloheptyl , and the like.
  • Preferred R groups include cyclopentyl, cyclohexyl, cycloheptyl, and the like.
  • Especially preferred R groups include cyclohexyl.
  • the compound of the present invention may be conveniently prepared according to the following reaction scheme:
  • Reaction (1) is a conventional preparation of the mercaptide salt of a mercaptan. Reaction (1) is conducted by combining II and III in solvent. It is preferred to use a slight excess of III relative to II, on the order of up to about 1.1 equivalents III per equivalent II. Suitable solvents include low molecular weight alcohols. Especially preferred are such alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, and the like. The reaction is conducted at a temperature of about 0°C to about 20°C preferably about 20°C, or, for convenience at ambient temperature. The reaction is generally complete within about 0.5 to about 1 hour.
  • the product mercaptide salt is isolated by conventional procedures, such as stripping, and the like, or, after removal of the solvent may be used in reaction (2) without further isolation.
  • Reaction (2) is conducted by combining approximately equimolar amounts of IV and V in solvent. Although the reactants may be combined in any order, it is preferred to add V to a stirred mixture of IV in solvent. Suitable solvents include inert organic solvents such as dimethoxyethane, and the like. The reaction is conducted at a temperature of about 0°C to about 80°C, preferably from about 20°C to about 80°C, or at reflux, and is generally complete within about 4 to about 8 hours.
  • the product, I is isolated by conventional procedures such as stripping, extraction, filtration, and the like. Utility
  • the compounds of the present invention are useful in controlling a wide variety of pests.
  • These compounds are active as a fungicide and are particularly effective in controlling a variety fungi which are deleterious to plants, including plant fungal infections. These compounds are particularly effective in controlling leaf blights caused by organisms such as Phytophthora infestans and Septoria apii. In addition, they are useful in controlling downy mildews caused by organisms such as Plasmopara viticola, early blights caused by organisms such as Alternaria solani, and powdery mildews such as that caused by Erisiphe polygoni .
  • These compounds are also effective as an insecticide and acaracide and may be used in controlling a variety of insect and arthropod pests. In particular, they are especially effective in controlling arachnids of the order Acarina such as mites, and in controlling
  • the compounds are not usually applied " full strength, but are generally incorporated with conventional biologically inert extenders or carriers normally employed for
  • the toxicants of this invention may be applied as sprays, dusts, or
  • ⁇ ⁇ granules to the insects, their environment or hostages susceptible to insect attack. It may be formulated as granules of large particle size, powdery dusts, wettable powders, emulsifiable concentrates, solutions, or as any of several other known types of formulations, depending on the desired mode of application.
  • Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants. These compositions normally contain from about 5% to 80% insecticide, and the rest inert material, 0 which includes dispersing agents, emulsifying agents and wetting agents.
  • the powder may be applied to the soil as a dry dust, or preferably as a suspension in water.
  • Typical carriers include fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wettable, 5 inorganic diluents.
  • Typical wetting, dispersing or emulsifying agents include, for example: the aryl and alkylaryl sulfonates and their sodium salts; alkylamide sulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols and polyvinyl 0 alcohols; polyethylene oxides; sulfonated animal and vege ⁇ table oils; sulfonated petroleum oils; fatty acid esters
  • the surface-active agent when used, normally 1 Q comprises from 1% to 15% by weight of the insecticidal composition.
  • Dusts are freely flowing admixtures of the active insecticide with finely divided solids such as talc, natural clays, kieselguhr, pyrophyllite, chalk,
  • diatomaceous earths 15 diatomaceous earths, calcium phosphates, calcium and magnesium 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
  • a typical dust formulation useful herein contains 75% silica and 25% of toxicant.
  • Useful liquid concentrates include the emulsifiable concentrates, which are homogeneous liquid or paste compositions which are readily dispersed in water or 5 other dispersant, and may consist entirely of the insecti ⁇ cide with a liquid or solid emulsifying agent, or may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isophorone, and other nonvolatile organic solvents.
  • these concentrates are 0 dispersed in water or other liquid carrier, and are normally applied as a spray to the area to be treated.
  • compositions for insecticidal applications include simple solutions of the active insecticide in a dispersant in which it is completely 5 soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents.
  • Granular formulations, wherein the insecticide is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover-crop 0 canopy.
  • Pressurized sprays typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low-boiling dispersant solvent carrier, such as the Freons, may also be used. All of those techniques for formulating and applying insecticides are well known in the art.
  • the percentages by weight of the insecticide 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 insecticidal composition.
  • insecticidal compositions may be formulated and applied with other active ingredients, including nema- tocides, insecticides, fungicides, bactericides, plant- growth regulators, fertilizers, etc.
  • active ingredients including nema- tocides, insecticides, fungicides, bactericides, plant- growth regulators, fertilizers, etc.
  • an effective amount and concentration of the toxicant of this invention is, of course, employed.
  • insects refer to their broad and commonly understood usage rather than to those creatures which, in the strict bio ⁇ logical sense, are classified as insects.
  • insect is used not only to include small invertebrate animals belonging to the class "Insecta”, but also to other related classes of arthropods, whose members are segmented invertebrates having more or fewer than six legs, such as spiders, mites, ticks, centipedes, worms, and the like.
  • the compounds of the invention When used as a fungicide, 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.
  • 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.
  • the fungicide of this invention may be formulated and applied as granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.
  • Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants. These compositions normally contain from about 5% to 80% fungicide, and the rest inert material, which includes dispersing agents, emulsifying agents and wetting agents.
  • the powder may be applied to the soil as a dry dust, or preferably as a suspension in water.
  • Typical carriers include fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wettable, inorganic diluents.
  • Typical wetting, dispersing or emul ⁇ sifying agents include, for example: 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 vege ⁇ table oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition products of long-chain mercaptans and ethylene oxide.
  • Many 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 composition.
  • 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 carbonates, sulfur, lime, flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant.
  • finely divided solids have an average particle size of less than about 50 microns.
  • a typical dust formulation useful herein contains 75% silica and 25% of toxicant.
  • Useful liquid concentrates include the emulsifiable concentrates, which are homogeneous liquid or paste compositions which are readily dispersed in water or other dispersant, and may consist entirely of the fungi ⁇ cide with a liquid or solid emulsifying agent, or may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isophorone, and other nonvolatile organic sol ⁇ vents.
  • these concentrates are dispersed in water or other liquid carrier, and are normally applied as a spray to the area to be treated.
  • fungicidal applications include simple solutions of the active fungi ⁇ cide in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylatsd naphthalenes, xylene, or other organic solvents.
  • Granular formulations wherein the fungicide is carried on rela ⁇ tively 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 carrier, 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 fungicide 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.
  • ambient or “room temperature” refers to about 20°C to about 25°C.
  • percent refers to gram moles.
  • 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. Also, unless expressly stated to the contrary, geometric isomer and racemic mixtures are used as starting materials and correspondingly, isomer mixtures are obtained as products.
  • step (a) To a stirred mixture of 2.5 g (0.01966 mole) 2-mercaptopyridine-N-oxide in methanol which had been stirred for a few minutes at room temperature, 0.5 g- (0.022 mole) sodium metal was added slowly and stirred until all dissolved. The methanol was removed with reduced pressure and heat, using toluene to chase the methanol, yielding the sodium salt which was used in step (b) without further isolation.
  • step (b) Dimethoxyethane (about 100 ml) was added to the sodium salt from step (a). To that stirred mixture, 6 g (0.01339 mole) tricyclohexyl tin bromide was added in one portion with stirring. The reaction mixture was refluxed for 8 hours.
  • the dimethoxyethane was removed under reduced pressure and heat. Water (about 75 ml) and methylene chloride (about 125 ml) were added to the residue; the resulting mixture was stirred. The layers were phase separated. The methylene chloride layer was washed with water 2 times, dried with magnesium sulfate, filtered and stripped to give the crude product. The crude product was washed with hexane and ethyl ether, filtered and stripped to give about 4.8 g of the above- identified product as a liquid which upon standing gave an opaque solid.
  • Mycelial Inhibition Compounds were evaluated for in vitro fungicidal effectiveness by means of a mycelial inhibition test. This test is designed to measure the fungitoxic activity of fungicidal chemicals in terms of their degree of inhi ⁇ bition of mycelium growth. Fungi used were Pythium ultimum, Rhizoctonia solani, Fusarium moniloforme, Botrytis cinerea, Aspergillus niger and Ustilago hordeii. Each compound to be tested was dissolved in acetone to 500 ppm concentration. Paper strips were infused with the particular mycelium growth by covering the paper with a potato dextrose broth culture of mycelial suspension.
  • Example B Tomato Late Blight Compounds 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 incubated at 66°F to 68°F and 100% relative humidity for at least 16 hours. Following the incubation, the plants were maintained in a greenhouse for approximately 7 days. The percent disease control provided by a given test compound was based on the percent disease reduction relative to untreated check plants. The results are tabulated in Table I.
  • Example C Rice Blast Compounds of this invention were tested for control of the Rice Blast organism Piricularia oryzae, using 10- to 14-day-old rice plant seedlings (Calrose M-9 variety). Seedling plants were sprayed with a 625-ppm solution of the test compound in acetone, water and a non- ionic emulsifier (ORTHO X-77 spreader). The sprayed plants were inoculated 1 day later with the organism in an environmental chamber. After inoculation, the plants were kept in an environmental chamber for about 48 hours under conditions of about 72°F to 75°F and about 100% relative humidity. Following the incubation period, the plants were placed in a greenhouse with a temperature of about 72°F and maintained with bottom watering for about 12 to
  • the percent disease control provided by a given test compound is based on a comparison of the percentage disease relative to the percent disease development on the untreated check plants: (% disease in treated plants)
  • Example D Tomato Early Blight Compounds were tested for the control of the Tomato Early Blight organism Alternaria solani.
  • 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 emulsi ⁇ fier.
  • the sprayed plants were inoculated 1 day later with the organism, placed in the environmental chamber and incubated at 66°F to 68°F and 100% relative humidity for 24 hours. Following the incubation, the plants were main ⁇ tained in a greenhouse for about 12 days. Percent disease control was based on the percent disease development on untreated check plants. The results are tabulated in Table I.
  • Example E Celery Late Blight
  • the Celery Late Blight tests were conducted using celery (Utah) plants 11 weeks old.
  • the Celery Late Blight organism was Septoria apii.
  • the celery plants were sprayed with 200-ppm solutions 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 66°F to 68°F in 100% relative humidity for an extended period of time (approximately 48 hours). Following the incubation, the plants were allowed to dry and then were maintained in a greenhouse for approximately 14 days.
  • the percent disease control provided by a given test compound is based on the percent disease reduction relative to untreated check plants. The results are reported in Table I.
  • Bean Powdery Mildew organism Erysiphe 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 inoculated 1 day later with the organism. The plants were maintained for 10 days at temperatures of 68°F at night with daytime temperatures of 72°F to 80°F; relative humidity was maintained at 40% to 60%. The percent disease control provided by a given test compound was based on the percent disease reduction rela ⁇ tive to the untreated check plants. The results as percent control are tabulated in Table I.
  • Example G Bean Rust Compounds were evaluated for their ability to eradicate Bean Rust caused by Uromyces phaseoli typica on pinto beans.
  • Pinto bean plants, variety Idaho 1-11, 16 (summer) or 19 (winter) days old were inoculated with a 50-ppm suspension of uredospores in water containing a small amount of nonionic 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 66-68°F 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 nonionic surfactant.
  • One or two replicate pots (each containing two plants) were used for each compound.
  • one or two replicate pots were sprayed with the 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 compound was based on the percent disease reduction relative to the untreated Checks. The results are reported in Table I.
  • Example H Example H
  • the compounds of this invention were tested for their insecticidal activity against cotton aphids (Aphis gossypii Glover) .
  • An acetone solution of the test com- pound containing a small amount of nonionic emulsifier was diluted with water to give a concentration of 40 ppm.
  • Example I Aphid Systemic Evaluation This procedure is used to assess the ability of a candidate insecticide to be absorbed through the plant root system and translocate to the foliage and thus to show insecticidal activity against the cotton aphid (Aphis gossypii Glover) .
  • Two cucumber plants planted in a 4-inch fiber r pot with a soil surface area of 80 cm'' are used. Forty ml of an 80-ppm solution of the candidate insecticide is poured around the plants in each pot. (This corresponds to 40 of actual toxicant.) The plants are maintained throughout in a greenhouse at 75-85°F.
  • the treated plants are infested with aphids by placing well-colonized leaves over the treated leaves so as to allow the aphids to migrate easily from the inoculated leaf to the treated leaf. Three days after infestation, mortality readings were taken. The results are tabulated in Table II in terms of percent control.
  • Example J Mite Adult Compounds of this invention were tested for their insecticidal activity against parathion-resistant Two-spotted Spider Mite [Tetranychus urticae Koch] .
  • An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 40 ppm.
  • Lima bean leaves which were infested with mites were dipped in the toxicant solution.
  • the results are tabulated in Table II in terms of percent control.
  • Example K Mite Egg Control Compounds of this invention were tested for their ovicidal activity against eggs of the two-spotted spider mite [Tetranychus urticae Koch] .
  • Housefly Compounds of this invention were tested for their insecticidal activity against the Housefly (Musca domestica Linnaeus) .
  • a 500-ppm acetone solution of the candidate toxicant was placed in a micro sprayer
  • Example M American Cockroach Compounds of this invention were tested for their insecticidal activity against Chlorodane-resistant American Cockroaches (Periplaneta americana Linnaeus).
  • a 500-ppm acetone solution of the candidate toxicant was placed in a micro sprayer (atomizer) .
  • a random mixture of anesthetized male and female roaches was placed in a con- tainer and 55 mg of the above-described solution was sprayed on them.
  • a lid was placed on the container.
  • a mortality reading was made after 24 hours. The results are tabulated in Table II in terms of percent control.
  • Example N Alfalfa Weevil The compounds of this invention were tested for their insecticidal activity against Alfalfa Weevil [Hypera brunneipennis (Boheman)].
  • a 500-ppm acetone solution of the candidate toxicant was placed in a micro sprayer (atomizer).
  • a random mixture of male and female weevils was placed in a container and 55 mg of the above-described acetone solution was sprayed on them.
  • a lid was placed on the container.
  • a mortality reading was made after
  • Example O Cabbage Looper Control The compounds of this invention were tested for their insecticidal activity against Cabbage Looper [Trichoplusia ni (Hubner)]. An acetone solution of the - candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to give a concentration of 500 ppm. Excised cucumber leaves were dipped in the toxicant solution and allowed to dry. The leaves were then infested with Cabbage Looper larvae. Mortality readings were taken after 24 hours. The results are tabulated in Table II in terms of percent control. Examples P and O
  • Example P The compound was respectively tested for pre-emergent and post-emergent activity against a variety of grasses and broad-leaf plants including one grain crop and one broad-leaf crop.
  • Example P The compound was respectively tested for pre-emergent and post-emergent activity against a variety of grasses and broad-leaf plants including one grain crop and one broad-leaf crop.
  • An acetone solution of the test compound was prepared by mixing 750 mg of the test compound, 220 mg of a nonionic surfactant and 25 ml of acetone. This solution was added to approximately 125 ml of water containing 156 mg of surfactant.
  • Seeds of the test vegetation were planted in a pot of soil and the test compound solution was sprayed uniformly onto the soil surface at a dose of 27.5 micro- grams/cm .
  • the pot was watered and placed in a green- house.
  • the pot was watered intermittently and was observed for seedling emergence, health of the emerging seedlings, etc., for a 3-week period.
  • the herbicidal effectiveness of the test compound was rated based on the physiological observations.
  • a O-to-100-scale was used, 0 representing no phytotoxicity and 100 representing complete kill. The results of these tests are summarized in Table III, hereinbelow.
  • Example 0 Post-Emergent Test The test compound was formulated in the same manner as described above for the pre-emergent test. The concentration of the test compound in this formulation was 5000 ppm. This formulation was uniformly sprayed on 2 similar pots of 24-day-old plants (approximately 15 to 25 plants per pot) at a dose of 27.5 micrograms/cm 2 .

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Abstract

Compounds of formula (I), wherein R is cycloalkyl of 3 to 8 carbon atoms and show good activity as a fungicide, acaricide and insecticide without appreciable phytotoxicity.

Description

PESTICIDAL TRICYCLOALKYL- (2-PYRIDYLTHIO) TIN N-OXIDES
BACKGROUND OF THE INVENTION The present invention relates to novel tricycloalkyl tin derivatives of 2-pyridyl N-oxide.
U.S. Patent No. 3,533,993 discloses organo-tin derivatives of 2-mercaptopyridine-l-oxide of the formula:
Figure imgf000003_0001
wherein R, R' , and R" are independently selected alkyl and preferably lower alkyl, i.e., alkyl having 1-4 carbon atoms; and aryl having 6-10 carbon atoms, preferably phenyl; n and m independently are 0-1 and r is 1-2, with the proviso that n plus m plus r is three, which are useful as heat stabilizers for vinyl chloride resins.
SUMMARY OF THE INVENTION
The compounds of my invention have the following formula:
Figure imgf000003_0002
wherein R is cycloalkyl of 3 to 8 carbon atoms and show surprisingly good activity as miticides and insecticides, especially against lepidoptera. These compounds also exhibit good activity as a fungicide against a variety of fungi, particularly fungi which cause plant fungal diseases as well as an acaricide and insecticide.
Among other factors, the present invention is based on my finding that the present compounds exhibit surprisingly good activity against mites and lepidoptera, and against certain plant fungicidal diseases. Moreover, it is believed these compounds do not exhibit phyto- toxicity, unlike other trialkyl and triaryl tin deriva¬ tives of 2-pyridyl N-oxides. Thus, lack of phytotoxicity is a distinct advantage in agricultural applications, since the compound may be used to protect plant crops from insect, acarine, and various plant fungal bests without herbicidal effects or damage to the plant itself. The present invention is also directed to fungicidal, insecticidal and acaricidal compositions containing and methods of using the compounds of the present invention. In addition, the present invention is directed to non- phytotoxic fungicidal, insecticidal and acaricidal compositions comprising these compounds which are not appreciably phytotoxic.
The term "cycloalkyl" refers to cyclic alkyl groups and includes, for example, cyclopropyl, cyclopentyl, cyclohexyl , cycloheptyl , and the like.
Preferred R groups include cyclopentyl, cyclohexyl, cycloheptyl, and the like.
Especially preferred R groups include cyclohexyl.
DETAILED DESCRIPTION OF THE INVENTION
The compound of the present invention may be conveniently prepared according to the following reaction scheme:
Figure imgf000004_0001
II III IV
Figure imgf000004_0002
V wherein R is as previously defined, in conjunction with formula I, M is a group IA [alkali] metal and X is halogen. Reaction (1) is a conventional preparation of the mercaptide salt of a mercaptan. Reaction (1) is conducted by combining II and III in solvent. It is preferred to use a slight excess of III relative to II, on the order of up to about 1.1 equivalents III per equivalent II. Suitable solvents include low molecular weight alcohols. Especially preferred are such alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, and the like. The reaction is conducted at a temperature of about 0°C to about 20°C preferably about 20°C, or, for convenience at ambient temperature. The reaction is generally complete within about 0.5 to about 1 hour. The product mercaptide salt is isolated by conventional procedures, such as stripping, and the like, or, after removal of the solvent may be used in reaction (2) without further isolation.
Reaction (2) is conducted by combining approximately equimolar amounts of IV and V in solvent. Although the reactants may be combined in any order, it is preferred to add V to a stirred mixture of IV in solvent. Suitable solvents include inert organic solvents such as dimethoxyethane, and the like. The reaction is conducted at a temperature of about 0°C to about 80°C, preferably from about 20°C to about 80°C, or at reflux, and is generally complete within about 4 to about 8 hours. The product, I, is isolated by conventional procedures such as stripping, extraction, filtration, and the like. Utility
The compounds of the present invention are useful in controlling a wide variety of pests.
These compounds are active as a fungicide and are particularly effective in controlling a variety fungi which are deleterious to plants, including plant fungal infections. These compounds are particularly effective in controlling leaf blights caused by organisms such as Phytophthora infestans and Septoria apii. In addition, they are useful in controlling downy mildews caused by organisms such as Plasmopara viticola, early blights caused by organisms such as Alternaria solani, and powdery mildews such as that caused by Erisiphe polygoni .
05 These compounds are also effective as an insecticide and acaracide and may be used in controlling a variety of insect and arthropod pests. In particular, they are especially effective in controlling arachnids of the order Acarina such as mites, and in controlling
10 insects of the order Lepidoptera.
Like most insecticides and acaricides, the compounds are not usually applied"full strength, but are generally incorporated with conventional biologically inert extenders or carriers normally employed for
*■ facilitating dispersion of active ingredients for agricultural chemical application, recognizing the accepted fact that the formulation and mode of application may affect the activity of a material. The toxicants of this invention may be applied as sprays, dusts, or
^ϋ granules to the insects, their environment or hostages susceptible to insect attack. It may be formulated as granules of large particle size, powdery dusts, wettable powders, emulsifiable concentrates, solutions, or as any of several other known types of formulations, depending on the desired mode of application.
Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants. These compositions normally contain from about 5% to 80% insecticide, and the rest inert material, 0 which includes dispersing agents, emulsifying agents and wetting agents. The powder may be applied to the soil as a dry dust, or preferably as a suspension in water.
Typical carriers include fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wettable, 5 inorganic diluents. Typical wetting, dispersing or emulsifying agents include, for example: the aryl and alkylaryl sulfonates and their sodium salts; alkylamide sulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols and polyvinyl 0 alcohols; polyethylene oxides; sulfonated animal and vege¬ table oils; sulfonated petroleum oils; fatty acid esters
Q5 of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition products of long-chain mercaptans and ethylene oxide. Many other types of useful surface-active agents are available in commerce. The surface-active agent, when used, normally 1Q comprises from 1% to 15% by weight of the insecticidal composition.
Dusts are freely flowing admixtures of the active insecticide with finely divided solids such as talc, natural clays, kieselguhr, pyrophyllite, chalk,
15 diatomaceous earths, calcium phosphates, calcium and magnesium 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
20 50 microns. A typical dust formulation useful herein contains 75% silica and 25% of toxicant.
Useful liquid concentrates include the emulsifiable concentrates, which are homogeneous liquid or paste compositions which are readily dispersed in water or 5 other dispersant, and may consist entirely of the insecti¬ cide with a liquid or solid emulsifying agent, or may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isophorone, and other nonvolatile organic solvents. For application, these concentrates are 0 dispersed in water or other liquid carrier, and are normally applied as a spray to the area to be treated.
Other useful formulations for insecticidal applications include simple solutions of the active insecticide in a dispersant in which it is completely 5 soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents. Granular formulations, wherein the insecticide is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover-crop 0 canopy. Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low-boiling dispersant solvent carrier, such as the Freons, may also be used. All of those techniques for formulating and applying insecticides are well known in the art.
The percentages by weight of the insecticide 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 insecticidal composition.
The insecticidal compositions may be formulated and applied with other active ingredients, including nema- tocides, insecticides, fungicides, bactericides, plant- growth regulators, fertilizers, etc. In applying the chemical, an effective amount and concentration of the toxicant of this invention is, of course, employed.
The terms "insecticide" and "insect" as used herein refer to their broad and commonly understood usage rather than to those creatures which, in the strict bio¬ logical sense, are classified as insects. Thus, the term "insect" is used not only to include small invertebrate animals belonging to the class "Insecta", but also to other related classes of arthropods, whose members are segmented invertebrates having more or fewer than six legs, such as spiders, mites, ticks, centipedes, worms, and the like.
When used as a fungicide, 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 fungicide of this invention may be formulated and applied as granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.
Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants. These compositions normally contain from about 5% to 80% fungicide, and the rest inert material, which includes dispersing agents, emulsifying agents and wetting agents. The powder may be applied to the soil as a dry dust, or preferably as a suspension in water.
Typical carriers include fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wettable, inorganic diluents. Typical wetting, dispersing or emul¬ sifying agents include, for example: 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 vege¬ table oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition products of long-chain mercaptans and ethylene oxide. Many 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 composition.
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 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 50 microns. A typical dust formulation useful herein contains 75% silica and 25% of toxicant. Useful liquid concentrates include the emulsifiable concentrates, which are homogeneous liquid or paste compositions which are readily dispersed in water or other dispersant, and may consist entirely of the fungi¬ cide with a liquid or solid emulsifying agent, or may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isophorone, and other nonvolatile organic sol¬ vents. For application, these concentrates are dispersed in water or other liquid carrier, and are normally applied as a spray to the area to be treated. Other useful formulations for fungicidal applications include simple solutions of the active fungi¬ cide in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylatsd naphthalenes, xylene, or other organic solvents. Granular formulations, wherein the fungicide is carried on rela¬ tively 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 carrier, 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 fungicide 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 following non-limiting Examples. Wherein, unless expressly stated to the contrary, all temperature ranges refer to the Centigrade system and the term
"ambient" or "room temperature" refers to about 20°C to about 25°C. 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. Also, unless expressly stated to the contrary, geometric isomer and racemic mixtures are used as starting materials and correspondingly, isomer mixtures are obtained as products.
EXAMPLES
Example 1 Preparation of Tricyclohexyl
(2-pyridylthio) tin N-oxide
Figure imgf000011_0001
(a) To a stirred mixture of 2.5 g (0.01966 mole) 2-mercaptopyridine-N-oxide in methanol which had been stirred for a few minutes at room temperature, 0.5 g- (0.022 mole) sodium metal was added slowly and stirred until all dissolved. The methanol was removed with reduced pressure and heat, using toluene to chase the methanol, yielding the sodium salt which was used in step (b) without further isolation. (b) Dimethoxyethane (about 100 ml) was added to the sodium salt from step (a). To that stirred mixture, 6 g (0.01339 mole) tricyclohexyl tin bromide was added in one portion with stirring. The reaction mixture was refluxed for 8 hours. The dimethoxyethane was removed under reduced pressure and heat. Water (about 75 ml) and methylene chloride (about 125 ml) were added to the residue; the resulting mixture was stirred. The layers were phase separated. The methylene chloride layer was washed with water 2 times, dried with magnesium sulfate, filtered and stripped to give the crude product. The crude product was washed with hexane and ethyl ether, filtered and stripped to give about 4.8 g of the above- identified product as a liquid which upon standing gave an opaque solid.
Elemental analysis for C23H36 SSn showed: calculated %C 55.9, %H 7.36, and %N 2.84; found %C 56.62, %H 8.5, and %N 2.75. Example A
Mycelial Inhibition Compounds were evaluated for in vitro fungicidal effectiveness by means of a mycelial inhibition test. This test is designed to measure the fungitoxic activity of fungicidal chemicals in terms of their degree of inhi¬ bition of mycelium growth. Fungi used were Pythium ultimum, Rhizoctonia solani, Fusarium moniloforme, Botrytis cinerea, Aspergillus niger and Ustilago hordeii. Each compound to be tested was dissolved in acetone to 500 ppm concentration. Paper strips were infused 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 micro sprayer with the fungicidal solution. The treated paper strips were incubated at 25°C and the data is taken after 24 hours. Fungicidal activi¬ ties are measured by a zone of inhibited mycelial growth from the center of the paper strip in terms of mg/cm needed for 991/2 control of the fungus (EDgg). The effectiveness of the compounds for fungicidal activity are reported in Table I in terms of the percent of the EDgg of the test compound of the EDgg of the standard Difolatan®.
Example B Tomato Late Blight Compounds 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 incubated at 66°F to 68°F and 100% relative humidity for at least 16 hours. Following the incubation, the plants were maintained in a greenhouse for approximately 7 days. The percent disease control provided by a given test compound was based on the percent disease reduction relative to untreated check plants. The results are tabulated in Table I.
Example C Rice Blast Compounds of this invention were tested for control of the Rice Blast organism Piricularia oryzae, using 10- to 14-day-old rice plant seedlings (Calrose M-9 variety). Seedling plants were sprayed with a 625-ppm solution of the test compound in acetone, water and a non- ionic emulsifier (ORTHO X-77 spreader). The sprayed plants were inoculated 1 day later with the organism in an environmental chamber. After inoculation, the plants were kept in an environmental chamber for about 48 hours under conditions of about 72°F to 75°F and about 100% relative humidity. Following the incubation period, the plants were placed in a greenhouse with a temperature of about 72°F 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 development on the untreated check plants: (% disease in treated plants)
% Control = 100 - 100 x ( % disease in check )
The results are tabulated in Table I.
Example D Tomato Early Blight Compounds were tested for the control of the Tomato Early Blight organism Alternaria solani. 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 emulsi¬ fier. The sprayed plants were inoculated 1 day later with the organism, placed in the environmental chamber and incubated at 66°F to 68°F and 100% relative humidity for 24 hours. Following the incubation, the plants were main¬ tained in a greenhouse for about 12 days. Percent disease control was based on the percent disease development on untreated check plants. The results are tabulated in Table I.
Example E Celery Late Blight The Celery Late Blight tests were conducted using celery (Utah) plants 11 weeks old. The Celery Late Blight organism was Septoria apii. The celery plants were sprayed with 200-ppm solutions 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 66°F to 68°F in 100% relative humidity for an extended period of time (approximately 48 hours). Following the incubation, the plants were allowed to dry and then were maintained in a greenhouse for approximately 14 days. The percent disease control provided by a given test compound is based on the percent disease reduction relative to untreated check plants. The results are reported in Table I.
Example F Bean Powdery Mildew Compounds were tested for the control of the
Bean Powdery Mildew organism Erysiphe 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 inoculated 1 day later with the organism. The plants were maintained for 10 days at temperatures of 68°F at night with daytime temperatures of 72°F to 80°F; relative humidity was maintained at 40% to 60%. The percent disease control provided by a given test compound was based on the percent disease reduction rela¬ tive to the untreated check plants. The results as percent control are tabulated in Table I.
Example G Bean Rust Compounds were evaluated for their ability to eradicate Bean Rust caused by Uromyces phaseoli typica on pinto beans.
Pinto bean plants, variety Idaho 1-11, 16 (summer) or 19 (winter) days old were inoculated with a 50-ppm suspension of uredospores in water containing a small amount of nonionic 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 66-68°F 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 nonionic 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 the 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 compound was based on the percent disease reduction relative to the untreated Checks. The results are reported in Table I. Example H
Aphid Control The compounds of this invention were tested for their insecticidal activity against cotton aphids (Aphis gossypii Glover) . An acetone solution of the test com- pound containing a small amount of nonionic emulsifier was diluted with water to give a concentration of 40 ppm.
Cucumber leaves infested with cotton aphids were dipped in the test compound solution. Mortality readings were taken after 24 hours. The results are tabulated in Table II in terms of percent control.
Example I Aphid Systemic Evaluation This procedure is used to assess the ability of a candidate insecticide to be absorbed through the plant root system and translocate to the foliage and thus to show insecticidal activity against the cotton aphid (Aphis gossypii Glover) . Two cucumber plants planted in a 4-inch fiber r pot with a soil surface area of 80 cm'' are used. Forty ml of an 80-ppm solution of the candidate insecticide is poured around the plants in each pot. (This corresponds to 40
Figure imgf000016_0001
of actual toxicant.) The plants are maintained throughout in a greenhouse at 75-85°F.
Forty-eight hours after the drenching, the treated plants are infested with aphids by placing well-colonized leaves over the treated leaves so as to allow the aphids to migrate easily from the inoculated leaf to the treated leaf. Three days after infestation, mortality readings were taken. The results are tabulated in Table II in terms of percent control.
Example J Mite Adult Compounds of this invention were tested for their insecticidal activity against parathion-resistant Two-spotted Spider Mite [Tetranychus urticae Koch] . An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 40 ppm. Lima bean leaves which were infested with mites were dipped in the toxicant solution. The results are tabulated in Table II in terms of percent control. Example K Mite Egg Control Compounds of this invention were tested for their ovicidal activity against eggs of the two-spotted spider mite [Tetranychus urticae Koch] . An acetone solution of the test toxicant containing a small amount of nonionic emulsifier was diluted with water to give a concentration of 40 ppm. Two days before testing, 2-week old lima bean plants were infested with spider mites. Two days after infestation, leaves from the infested plants are dipped in the toxicant solution, placed in a petridish with filter paper and allowed to dry in the open dish at room temperature. The treated leaves were then held in covered dishes at about 31°C to 33°C for seven days. On the eighth day egg mortality readings are taken. The results, expressed as percent control, are tabulated in Table II. Example L
Housefly Compounds of this invention were tested for their insecticidal activity against the Housefly (Musca domestica Linnaeus) . A 500-ppm acetone solution of the candidate toxicant was placed in a micro sprayer
(atomizer). A random mixture of anesthetized male and female flies was placed in a container and 55 mg of the above-described acetone solution was sprayed on them. A lid was placed on the container. A mortality reading was made after 24 hours. The results are tabulated in Table II in terms of percent control.
Example M American Cockroach Compounds of this invention were tested for their insecticidal activity against Chlorodane-resistant American Cockroaches (Periplaneta americana Linnaeus). A 500-ppm acetone solution of the candidate toxicant was placed in a micro sprayer (atomizer) . A random mixture of anesthetized male and female roaches was placed in a con- tainer and 55 mg of the above-described solution was sprayed on them. A lid was placed on the container. A mortality reading was made after 24 hours. The results are tabulated in Table II in terms of percent control.
Example N Alfalfa Weevil The compounds of this invention were tested for their insecticidal activity against Alfalfa Weevil [Hypera brunneipennis (Boheman)]. A 500-ppm acetone solution of the candidate toxicant was placed in a micro sprayer (atomizer). A random mixture of male and female weevils was placed in a container and 55 mg of the above-described acetone solution was sprayed on them. A lid was placed on the container. A mortality reading was made after
24 hours. The results are tabulated in Table II in terms of percent control.
Example O Cabbage Looper Control The compounds of this invention were tested for their insecticidal activity against Cabbage Looper [Trichoplusia ni (Hubner)]. An acetone solution of the - candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to give a concentration of 500 ppm. Excised cucumber leaves were dipped in the toxicant solution and allowed to dry. The leaves were then infested with Cabbage Looper larvae. Mortality readings were taken after 24 hours. The results are tabulated in Table II in terms of percent control. Examples P and O
The compound was respectively tested for pre-emergent and post-emergent activity against a variety of grasses and broad-leaf plants including one grain crop and one broad-leaf crop. Example P
Pre-Emergent Herbicide Test Pre-emergence herbicidal activity was determined in the following manner.
An acetone solution of the test compound was prepared by mixing 750 mg of the test compound, 220 mg of a nonionic surfactant and 25 ml of acetone. This solution was added to approximately 125 ml of water containing 156 mg of surfactant.
Seeds of the test vegetation were planted in a pot of soil and the test compound solution was sprayed uniformly onto the soil surface at a dose of 27.5 micro- grams/cm . The pot was watered and placed in a green- house. The pot was watered intermittently and was observed for seedling emergence, health of the emerging seedlings, etc., for a 3-week period. At the end of this period the herbicidal effectiveness of the test compound was rated based on the physiological observations. A O-to-100-scale was used, 0 representing no phytotoxicity and 100 representing complete kill. The results of these tests are summarized in Table III, hereinbelow.
Example 0 Post-Emergent Test The test compound was formulated in the same manner as described above for the pre-emergent test. The concentration of the test compound in this formulation was 5000 ppm. This formulation was uniformly sprayed on 2 similar pots of 24-day-old plants (approximately 15 to 25 plants per pot) at a dose of 27.5 micrograms/cm2.
After the plants had dried, they were placed in a green¬ house and then watered intermittently at their bases, as needed. The plants were observed periodically for phytotoxic effects and physiological and morphological responses to the treatment. After 3 weeks, the herbicidal effectiveness of the compound was rated based on these observations. A -to-100-scale was used, 0 representing no phytotoxicity and 100 representing complete kill. The results of these tests are summarized in Table III. TABLE I
FUNGICIDAL ACTIVITY
Mycelial Inhibition
Pyth. Rhiz. Fusar. Botry. Asper. Ustil . TLB RB TEB CLB BPM BR
Compound of Example 1 0 0 91 0 100 30 97 88 42 98 100 0
Figure imgf000020_0001
) 3 40 40 120 25 117 100 31 75 97 100 0
Figure imgf000020_0002
Pyth. Phthium ultimum GDM = Grape Downy Mildew Rhiz . Rhizoctonia solani TLB = Tomato Late Blight Fusar. Fusarium moniloforme RB = Rice Blast Botry. Botrytis cmerea TEB = Tomato Early Blight Asper. Aspergillus niger CLB = Celery Late Blight Ustil . Ustilago hordeii BPM = Bean Powdery Mildew
= Test Failed BR = Bean Rust
TABLE II
INSECTICIDAL AND MITICIDAL ACTIVITY
Compound AR AW HF MA ME Aph, AS CL 5-CL
Compound of Example 1 0 100 100 100 100 )
Figure imgf000021_0001
n- CH2CH2CH2CH3)3 50 80 100 100 20 80 100
Figure imgf000021_0002
Figure imgf000021_0003
AR = American Cockroach Aph. = Aphid
AW = Alfalfa Weevil AS = Aphid Systemic
HF = Housefly CL = Cabbage Looper
MA = Mite Adult 5-CL = 5-Day Reading of Cabbage Looper
ME = Mite Egg Mortality
TABLE III
HERBICIDAL ACTIVITY (Phytotoxicity)
Pre-Emergence Post-Emergence
LO MUS PGW BG CG WO SB R LQ MUS PGW BG CG WO SB R
Compound of Example 1 0 0 0 0 0 0 0 0
)3 10 40 60 100 100 100 90 30 40 45
Figure imgf000022_0001
Figure imgf000022_0002
LO = Lambsquarter CG = Crabgrass
MUS = Mustard O = Wild Oat
PGW = Pigweed SB = Soybean
BG = Barnyard Grass R = Rice

Claims

WHAT IS CLAIMED IS:
i. A compound of the formula:
Figure imgf000023_0001
wherein R is cycloalkyl of 3 to 8 carbon atoms.
2. A compound according to Claim 1 wherein R is cyclopentyl, cyclohexyl or cycloheptyl.
3. A compound according to Claim 2 wherein R is cyclohexyl .
4. 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.
5. 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.
6. A fungicidal composition which comprises a biologically inert carrier and a fungicidally effective amount of a compound of Claim 1.
7. A fungicidal composition which comprises a biologically inert carrier and a fungicidally effective amount of a compound of Claim 3.
8. A method of killing insects which comprises contacting said insect or its environment with an insecticidally effective amount of a compound of Claim 1.
9. A method of killing insects which comprises contacting said insect or its environment with an insecticidally effective amount of a compound of Claim 3.
10. An insecticidal composition comprising a biologically inert carrier and an insecticidally effective amount of a compound of Claim 1.
11. An insecticidal composition comprising a biologically inert carrier and an insecticidally effective amount of a compound of Claim 3.
12. A method of killing acarines which comprises contacting said acarine or its environment with an acaricidally effective amount of a compound of Claim 1.
13. A method of killing acarines which comprises contacting said acarine or its environment with an acaricidally effective amount of a compound of Claim 3.
14. An acaricidal composition which comprises a biologically inert carrier and an acaricidally effective amount of a compound of Claim 1.
15. An acaricidal composition which comprises a biologically inert carrier and an acaricidally effective amount of a compound of Claim 3.
PCT/US1985/001870 1984-09-27 1985-09-26 Pesticidal tricycloalkyl-(2-pyridylthio) tin n-oxides WO1986002075A1 (en)

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Citations (10)

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CA501851A (en) * 1954-04-27 C. Ladd Elbert Fungicide containing pyridine-2-thiols or derivatives
US2809971A (en) * 1955-11-22 1957-10-15 Olin Mathieson Heavy-metal derivatives of 1-hydroxy-2-pyridinethiones and method of preparing same
US3027371A (en) * 1959-05-04 1962-03-27 Olin Mathieson Molybdenum-containing derivatives of 1-hydroxy-2-pyridinethiones and method of preparing same
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