EP0176594A1 - Insecticides et produits intermediaires a base de cyclopropanecarboxylate de fluoropyridinylmethyle - Google Patents

Insecticides et produits intermediaires a base de cyclopropanecarboxylate de fluoropyridinylmethyle

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Publication number
EP0176594A1
EP0176594A1 EP85902259A EP85902259A EP0176594A1 EP 0176594 A1 EP0176594 A1 EP 0176594A1 EP 85902259 A EP85902259 A EP 85902259A EP 85902259 A EP85902259 A EP 85902259A EP 0176594 A1 EP0176594 A1 EP 0176594A1
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EP
European Patent Office
Prior art keywords
compound
dimethylcyclopropyl
hydrogen
chloro
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP85902259A
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German (de)
English (en)
Inventor
Richard Benton Phillips
Ernest Lockhart Plummer
John Francis Engel
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FMC Corp
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FMC Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C07D213/643—2-Phenoxypyridines; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C07D213/647—One oxygen atom attached in position 2 or 6 and having in the molecule an acyl radical containing a saturated three-membered ring, e.g. chrysanthemumic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/76—Nitrogen atoms to which a second hetero atom is attached
    • C07D213/77—Hydrazine radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84—Nitriles

Definitions

  • the present invention relates to cyclopropanecarboxylate insecticides. More particularly it relates to cyclopropanecarboxylate insecticides in which the alcohol component is a substituted fluoropyridinylmethyl group, to a process for making them, to insect icidal compositions thereof, and to novel intermediates useful in the preparation of such insecticidal compounds.
  • the insecticidal compounds of this invention are compounds of formula I:
  • X is hydrogen, halogen, particularly chlorine or fluorine, C 1-2 alkoxy, phenoxy, or di(C 1 _ 2 alkyl)amino;
  • R is 3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropyl;
  • R is hydrogen or a halogen, particularly chlorine or fluorine.
  • the invention includes compounds in which the carboxylate group is attached at position 2 or 4 of the pyridine ring, preferably position 4, or a mixture of compounds in which the carboxylate group is attached at positions 2 and 4.
  • insecticidal compounds have two asymmetric centers on the cyclopropane ring, thus providing the possibility for four isomers, two cis isomers and two trans isomers, and that various mixtures of these isomers, designated cis, trans also exist. It will also be apparent that some of the compounds also exist in the E and Z forms depending on the configuration about the vinyl group at the 3-position of the cyclopropane ring. Each of these isomers and configurations and all combinations of them are included in and form a part of the present invention.
  • tetrafluoropyridinyl-methanols which may be made by the method of Sket and Zupan, J. Heterocycl. Chem. , 15, 527 (1978). This method produces a mixture of 2-hydroxymethyl and 4-hydroxymethyl isomers of tetrafluoropyridine.
  • the mixture can be esterified without separation of isomers to produce the insecticidal compound of the invention having a corresponding mixture of isomers.
  • the 4-hydroxymethyl tetrafluoropyridine may also be separated from the mixture of isomers and used as the starting material for preparation of the 4-pyridinylmethyl esters of the invention.
  • X is hydrogen, halogen, C 1-2 -alkoxy, phenoxy, or di(C 1-2 -alkyl)amino or hydrazino;
  • R 1 is hydrogen or a halogen;
  • Q is a leaving group.
  • Suitable leaving groups, Q, in the aforesaid structural formula are known in the art today and include bromo, chloro, methylsulfonyl, and hydroxy. It is recognized that any leaving groups readily displaced by carboxylate anions are and will be functional equivalents for Q in the aforesaid formula.
  • the insecticidal compounds of the invention may be prepared from these novel intermediates by esterification techniques, for example by reacting an acid chloride of the formula RCOCl or a carboxylic acid or salt of the formula RCOOM, in which R is as defined above and M is hydrogen or a cation, with an appropriately substituted fluoropyridinyl intermediate.
  • esterification techniques for example by reacting an acid chloride of the formula RCOCl or a carboxylic acid or salt of the formula RCOOM, in which R is as defined above and M is hydrogen or a cation, with an appropriately substituted fluoropyridinyl intermediate.
  • EXAMPLE 1 SYNTHESIS OF A MIXTURE OF 2-HYDROXYMETHYL- 3,4,5,6-TETRAFLUOROPYRIDINE AND 4-HYDROXYMETHYL-2,3,5,6-TETRAFLUOROPYRIDINE AS AN INTERMEDIATE
  • the crude product was dissolved in 20 ml of dry diethyl ether, and to this solution was added 0.5 g (0.003 mole) of the mixture of 4-hydroxymethyl-2,3,5,6-tetrafluoropyridine and 2-hydroxymethyl-3,4,5,6-tetrafluoropyridine (from Example 1) followed by the addition of 1 ml of anhydrous triethylamine.
  • the reaction mixture was stirred at room temperature for twelve hours after which it was poured into 5% hydrochloric acid. This mixture was extracted three times with 35 ml of diethyl ether. The combined extracts were washed twice with 30 ml of water and once with 25 ml of a saturated aqueous sodium chloride solution.
  • the material collected was 90% (2,3,5,6-tetra fluoropyridin-4-yl)methyl cis-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethyl-cyclopropanecarboxylate and 10% (3,4,5,6-tetrafluoropyridin-2-yl)methyl cis-3-(2-chloro- 3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate, Compound No. 1 of the tables below.
  • This white solid was a mixture composed of 90% (2,3,5,6-tetrafluoropyridin-4-yl)methyl cis-3-(2,2-dichloroeth ⁇ enyl)-2,2-dimethylcyclopropanecarboxylate and 10%
  • Example 2 By the method of Example 2 , 0.5 g (0.002 mole) of 2-dimethylamino-4-hydroxymethyl-3,5,6-trifluoropyridine (from Example 13) was reacted with 0.6 g (0.002 mole) of cis-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethyIcyclo propanecarbonyl chloride to produce, after purification through a short silica gel column and the Chromatotron, 0.45 g of (2-methoxy-3,5,6- trifluoropyridin-4-yl) methyl cis-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethyIcyclo propanecarboxylate as an oil, Compound No. 20 of the tables below.
  • Step B Synthesis of 3 , 5-dichloro-2,6-difluoropyridine-4-carboxaldehyde
  • Example 15 By the method of Example 2 0.6 (0.002 mole) of 3,5-di ⁇ chloro2,6-difluoro-4-hydroxymethylpyridine (Example 15) was reacted with 0.61 g (0.002 mole) of cis-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarbonyl chloride to produce, after purification using the Chromatotron, 0.5 g of (3,5-dichloro-2,6-difluoropyridin-4-yl)methyl cis-3- (2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate as a clear, white liquid, compound 21 in the Tables below.
  • Example 2 By the method of Example 2,0.5 g (0.0019 mole) of cis-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclo propanecarbonyl chloride was reacted with 0.5 g (0.0020 mole) of 4-hydroxymethyl-1-phenoxy-3,5,6-trifluoropyridine to produce 0.6 g of ( 2-phenoxy-3,5,6-trifluoropyridin ⁇ -4-yl)methyl cis-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate as a colorless oil compound 23 in the Tables below.
  • the ir and nmr spectra were consistent with the proposed structure.
  • Fractions 2 and 3 were >96% pure 2-bromomethyl-6-fluoropyridine and were therefore combined.
  • Fraction 4 was composed of a 1:1 mixture of 2-bromomethyl-6-fluoropyridine and 2-dibromomethyl-6-fluoropyridine. The nmr spectra was consistent with the proposed structure for Fractions 2 and 3.
  • Example 22 By the method of Example 21, 0.970 g (0.004 mole) of cis-3- ( 2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylic acid and 0.75 g (0.004 mole) of 4-bromo ⁇ methyl-2-fluoropyridine (Example 22) were reacted in the presence of 0.609 g (0.004 mole) of 1,8-diazabicyclo[5.4.0]-undec-7-ene in 20 ml of acetonitrile to produce 1.09 g of (2-fluoropyridin-4-yl) methyl cis-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate, compound 28 in the Tables below.
  • the ir, proton nmr, and 19F nmr spectra were all consistent with the proposed structure.
  • the treated soil was allowed to stand uncovered in a hood for 0.5 hour to evaporate the acetone.
  • the soil was mixed thoroughly and two three-day-old corn sprouts were placed in the cup.
  • Ten early third-stage (9-10 days old) southern corn rootworm larvae (Diabratica undecimpunctita howardi Barber) were placed in the cup which was then covered with a plastic lid and placed in a closed plastic bag. After storage at 74-78°F for 48 hours, the mortality of the larvae was determined by removing the cup from the plastic bag, removing the cover, and placing the cup in a modified Berlese polyethylene funnel fitted with an 18-mesh screen. The funnels were placed over containers of an aqueous detergent solution.
  • Incandescent lights (100 watts) were placed 36 cm above the soil samples. The heat from these lights slowly dried the soil causing larvae that had not been affected by the test compound to emerge from the soil and drop into the detergent solution. The percent mortality was determined in this manner for each concentration. Duplicate tests were run at each concentration. The results of these tests, shown in Table 2, demonstrate outstanding initial activity against southern corn rootworm. Residual Southern Corn Rootworm Activity The residual activity of the test compounds was determined in the same manner as the initial activity except that treated soil was not infested with larvae until 7, 14, 28, and 42 days after treatment, the usual concentration of test compound being 4 ppm. Whenever the mortality dropped below 20% at 7 or 14 days, the remainder of the test was not run. Many of the compounds had excellent residual activity as shown by the results in Table 3. Foliar Insecticide Activity
  • Test compounds were dissolved in a mixture containing 10% acetone, 0.25% octylphenoxypolyethoxyethanol, and 89.75% water to give a solution containing 1000 ppm of the compound. This solution was sprayed on the upper and lower surfaces of the leaves of the green test plants to run-off. After spraying, the plants were allowed to dry. Two replicates of each com pound were run for each species.
  • Insecticidal activity against the pea aphid was tested by placing a broad bean plant which had been sprayed and had dried into a 1400 ml cup. Each plant was infested with ten aphids, and the cups were then capped. Mortality was determined 48 hours after treatment. Pinto bean plants were used for tests against the Mexican bean beetle (Epilachna varivestis) and the southern armyworm (Spodoptera eridania). For both species treated leaves were removed from the plants and placed in paper cups. Ten individuals of one species were placed in a cup and the cup was then capped. Mortality was recorded 48 hours after treatment.
  • the twospotted spider mite (Tetranychus urticae) was also tested on pinto beans.
  • the plants were infested by placing a section of a leaf taken from an infested plant onto the test plant to be infested. Approximately 75 mites were used.
  • the test plants were sprayed after infestation and were placed on a shelf at ambient conditions for 48 hours. Mortality was determined at the conclusion of this period.
  • the compounds are generally not applied full strength but are typically applied as formulations which may be applied as such or further diluted for application.
  • Typical formulations include compositions of the active ingredient in combination with one or more agriculturally acceptable adjuvants, carriers or diluents, preferably with a surface active agent, and optionally with other active ingredients.
  • Suitable formulations include solid compositions such as dusts, wettable powders, and granules or liquid compositions such as solutions, dispersions, suspensions, and emulsifiable concentrates, the choice varying with the type of pest and environmental factors present at the particular locus of infestation.
  • a typical formulation may vary widely in concentration of active ingredient and other ingredients depending upon the particular agent used, the additives and carriers used, other active ingredients, the desired mode of application, and numerous other factors well known to those skilled in formulating compositions for use in agriculture.
  • the active ingredient of a typical formulation may, for example, comprise 0.01 percent to 1 percent by weight up to about 95 percent by weight, preferably 1 per cent up to 90 or 95 percent by weight, of the formulation.
  • Agriculturally acceptable carriers, diluents, adjuvants, surface active agents, and optionally other suitable active ingredients comprise the balance of the formulation.
  • a typical formulation may contain from 0.01 to 95 (preferably 1 to 95) percent by weight active ingredient, from 0 to 30 percent by weight surface active agent, and from 5 to 99.99 (preferably 5 to 99) percent by weight of an inert agriculturally acceptable carrier or diluent.
  • an inert agriculturally acceptable carrier or diluent Provided below is a general description of exemplary types of formulations which may be employed for application of the compounds of the present invention.
  • Dry formulations are mixtures of a liquid or solid active ingredient with a solid carrier to form a particulate product comprising discrete solid particles of various sizes.
  • Solid or dry compositions may take the form of dusts, wettable powders and granules having average particle sizes varying from about 5 microns to about 5000 microns. These compositions employ solid or dry carriers and/or diluents which may be selected from one or more of the following: 1. Attapulgite Clay: Characterized as hydrated aluminum-magnesium silicate, with or without free water, and possessing sorptive capacity of at least 35% w/w.
  • Kaolin or Kaolinite Clay Characterized as hydrated aluminum silicate, and including the species dickite, nakrite, and halloysite, and further characterized by having low values for cation exchange capacity.
  • Montmorillonite Characterized as hydrous aluminum silicate derived by natural modification of mica and pyrophyllite, and further sub-divided into swelling (sodium form) and non-swelling (calcium form).
  • Pyrophyllite Characterized as hydrous magnesium or aluminum silicate and having neutral to basic pH, and further characterized by low to moderate sorptive capacity.
  • Diatomite Class of opaline silica skeletal remains of aquatic species which includes diatomaceous earth, tripolite, kieselguhr, and fossil flour, characterized by high (85-93%) silica content, and having high absorptive and low adsorptive capacity.
  • Silica Diverse origin materials characterized by very high (98-100%) silica content and high (75-100%) sorptive capacity (synthetic), or low sorptive capacity, such as sand. 7.
  • Botanicals Any material of plant origin capable of being processed into particles of the desired size, including nut shell flours, wood and cellulose flours, corncobs, and the like. 8. Calcium Carbonate
  • Dust formulations are finely divided solid compositions of active ingredient in admixture with a solid carrier. In most cases dust formulations have an average particle size of less than about 50 microns, typically 5 to 40 microns, an active ingredient content of 1 to 30 percent by weight, and from 70 to 99 percent by weight of one or more of the solid diluents or carriers described above. Since dust formulations are generally applied as such or mixed with other solids for application, they generally do not require a surface active agent or other adjuvants. The following exemplify typical dust formulations: 1% Dust % W/W
  • Wettable powders are finely divided solid compositions which disperse readily in water or other liquid vehicles.
  • the wettable powder may be applied as a dry dust or as a dispersion in water or other liquid.
  • wettable powders are essentially a dust or powder formulation containing a surface active agent in addition to the active ingredient and solid carrier normally employed in dusts.
  • a wettable powder may thus typically contain from 1 to 95 percent by weight active ingredient, from 1 to 15 percent surface active agent, and from 4 to 98 percent by weight of one or more of the inert solid or dry carriers or diluents described above.
  • Suitable surface active agents may be selected from the following:
  • Salts or esters of ethylene oxide condensates of sulfated or sulfonated fatty acids.
  • Salts of amine derivatives of various resin and fatty acids including, but not restricted to, palmitic and myristic acids, tall oils, and taurine.
  • Salts of alkylarylsulfonates including alkylnapthalenesulfonates and dialkylnaphthalenesulfonates.
  • Ethylene oxide condensates of linear or branched chain glycols, secondary alcohols, or alkylaryl alcohols.
  • Ethylene oxide condensates with fatty acid esters of sorbitan.
  • Active Ingredient 90.0 Sodium dibutylnaphthalenesulfonate 0.5
  • Granules are solid or dry compositions of active ingredient deposited on or in a large particle. Granules usually have an average particle size in the range of 150 to 5000 microns, typically 425 to 850 microns. Granular formulations generally contain from 1 to 50 percent by weight of active ingredient, from 1 to 15 percent by weight of one or more of the surface active agents described above, and from 50 to 98 percent by weight of one or more of the inert solid or dry carriers or diluents described above. Granular formulations may be of several types.
  • Impregnated granules are those in which the active ingredient is applied, normally as a solution, to large particles of an absorbent diluent or carrier such as attapulgite or kaolin clay, corncobs or expanded mica.
  • Surface coated granules are granules produced by adhering an active ingredient in finely divided form on the surface of a generally non-absorbent particle or by applying a solution of active ingredient to the surface of such a carrier.
  • the carrier or core may be water soluble, such as prilled fertilizer or urea, or insoluble, such as sand, marble chips, corncobs, or coarse talc, as described above.
  • Granules wherein a wettable powder is adhered as a surface coating to a sand or other insoluble particle, so that the wettable powder may be dispersed on contact of the granule with moisture.
  • Granules may also be produced by agglomeration of dusts or powders, by compaction, by extrusion through a die, or by use of a granulation disk. The following are typical granular formulations: 1% Granule % W/W
  • the granules above may be prepared by dissolving the active ingredient in a volatile solvent such as methylene chloride, coating large particles of attapulgite clay with the solution, then allowing the solvent to evaporate.
  • a volatile solvent such as methylene chloride
  • granules may also be adhered to a nonabsorbent core material.
  • a nonabsorbent core material As indicated above, granules may also be adhered to a nonabsorbent core material.
  • sand-core granules may be prepared by incorporating the active compound into the base, then adhering the base to sand, utilizing an adhesive such as polyvinylacetate to assure adhesion.
  • LIQUID AND SEMI-LIQUID FORMULATIONS Liquid formulations are those which contain the active ingredient dissolved or dispersed in one or more inert liquid carriers or diluents, containing from 0.01 to about 95% active ingredient.
  • Carriers suitable for use in liquid formulations may be selected from the following:
  • Aliphatic petroleum solvents including kerosene, light refined mineral oils, and diesel oils.
  • Aromatic petroleum solvents including coal tar fractions yielding xylene, toluene, and benzene; light, medium, and heavy aromatic naphthas; and alkylated mixed naphthenics.
  • Alcohols such as ethanol and isopropyl alcohol.
  • Esters including dibutyl phthalate, di-2-ethylhexyl phthalate, and ethyl acetate.
  • Ketones including cyclohexanone, methyl isobutyl ketone, acetone, diacetone, and isophorone.
  • Chlorinated hydrocarbons including ethylene dichloride, methylene chloride, chlorobenzene, chlorinated toluene, and chlorinated xylene.
  • Vegetable oils including cottonseed, soybean, pine, sesame, and palm oils.
  • Aqueous solutions of natural origin such as liquors obtained in processing natural sugar products, and fermentation broths.
  • Solutions are liquid compositions containing from about 0.01 to 95 percent by weight active ingredient and from 1 to 99.99 percent by weight of one or more of the inert liquid diluents or carriers described above. These may be applied as such or further diluted for application.
  • Suspensions or dispersions also sometimes called flowable formulations
  • Suspension or dispersion is frequently facilitated by incorporating from 1 to 30 percent by weight of one or more surface active agents described above, alone or together with a thickner or suspending agent. Like solutions, dispersions may be used as such or further diluted with a liquid carrier for application.
  • Active ingredient 25.0 polyoxyethylene sorbitol hexaeleate 5.0 aliphatic hydrocarbon oil 70.0
  • Aqueous Suspension Active ingredient 40. 0 Polyacrylic acid thickener 0. 3 Dodecylphenol polyethylene glycol ether 0. 5 Disodium phosphate 1. 0
  • Emulsifiable concentrates are homogeneous liquid compositions, containing the active ingredient dissolved in a liquid carrier.
  • Commonly used liquid carriers include xylene , heavy aromatic naphthas , isophorone, and other nonvolatile or slightly volatile organic solvents.
  • EC's are dispersed in water, or other liquid vehicle, forming an emulsion, and are normally applied as a spray to the area to be treated.
  • the concentration of the essential active ingredient in EC's may vary according to the manner in which the composition is to be applied, but, in general, is in the range of 0.01 to 95 percent by weight of active ingredient.
  • Also included in the composition are from 1 to 30 percent by weight surface active agent and from 4 to 97.99 percent of one or more of the inert liquid carriers described above.
  • Nonionic polyethoxylated nonylphenol Mol. Wt. 450-500
  • Nonionic polyethoxylated nonylphenol Mol. Wt. 1400-1600
  • 1.1 Nonionic paste of 100% polyalkalene glycol ether 0.4
  • compositions include simple solutions of the active ingredient in a relatively non-volatile solvent such as corn oil, kerosene, propylene glycol, or other organic solvents. This type of formulation is particularly useful for ultra low volume application.
  • concentration of the active ingredient in use dilution is normally in the range of about 2% to about 0.1%.
  • spraying, dusting, and controlled or slow release compositions in the art may be used by substituting or adding a compound of this invention into compositions known or apparent to the art.
  • compositions may be formulated and applied with other suitable active ingredients, including nematicides, insecticides, acaricides, fungicides, plant regulators, herbicides, fertilizers, etc.
  • an effective insect controlling amount of active ingredient must be applied, sometimes referred to herein as an insectici dal amount. While the application rate will vary widely depending on the choice of compound, the formulation and mode of application, the plant species being protected and the planting density, a suitable use rate may be in the range of 0.10 to 0.50 kg per hectare, preferably 0.25 to about 1.5 kg/hectare.
  • the compounds of this invention may be applied by incorporating or applying a formulation thereof to a food source for the insects to be controlled, i.e. the locus where control is required, including application to the above ground portions of plants on which the insects feed, to the soil in which plants are or are about to be planted in order to provide control of soil-borne insects, or in a bait-type formulation for application to surfaces on which insects normally do not feed.
  • the compounds When applying the compounds to the soil, the compounds may be broadcast broadly over the planted area or the area to be planted or by limiting the application to a small area or band in the root zone where plants are or are to be planted.
  • sufficient compound must be applied to provide an insect controlling concentration of the compound in the soil in the root zone. For the present a suitable concentration is about 0.2 to about 50 parts by weight of compound per million parts of soil.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pyridine Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Composés insecticides de formule (I), leur formulation, leur utilisation dans la lutte contre les parasites du feuillage ou dans le sol, leur procédé de préparation, ainsi que certains nouveaux intermédiaires pour leur préparation.
EP85902259A 1984-04-13 1985-04-10 Insecticides et produits intermediaires a base de cyclopropanecarboxylate de fluoropyridinylmethyle Withdrawn EP0176594A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US59985284A 1984-04-13 1984-04-13
US599852 1984-04-13

Publications (1)

Publication Number Publication Date
EP0176594A1 true EP0176594A1 (fr) 1986-04-09

Family

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Application Number Title Priority Date Filing Date
EP85902259A Withdrawn EP0176594A1 (fr) 1984-04-13 1985-04-10 Insecticides et produits intermediaires a base de cyclopropanecarboxylate de fluoropyridinylmethyle

Country Status (5)

Country Link
EP (1) EP0176594A1 (fr)
AU (1) AU4232985A (fr)
CA (1) CA1269387A (fr)
IL (1) IL74868A0 (fr)
WO (1) WO1985004553A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2587589B1 (fr) * 1985-09-23 1990-05-11 Roussel Uclaf Nouvelles compositions pesticides renfermant du (1r cis,e) 2,2-dimethyl 3/2-fluoro 3-oxo 3-methoxy 1-propenyl/cyclopropane carboxylate de pentafluoro phenyl methyl

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Publication number Priority date Publication date Assignee Title
US3737542A (en) * 1966-11-16 1973-06-05 Lars Anders Fritz Carlsson Lowering excessive serum lipid concentrations and preparations containing fluoro-pyridine derivatives
BE790563A (fr) * 1971-10-27 1973-04-26 Ciba Geigy Derives de la pyridine utilisables comme matieres actives de produits phytopharmaceutiques
US3829430A (en) * 1973-01-11 1974-08-13 Dow Chemical Co Method for the preparation of tetra-halo-4-(alkylsulfonyl)pyridines
US3974166A (en) * 1973-07-10 1976-08-10 Ciba-Geigy Corporation Process for the manufacture of bromopyridines
US3947457A (en) * 1974-12-27 1976-03-30 The Dow Chemical Company Method for preparing 2,5-dihalo- and 2,5,6-trihalopyridines
US4163787A (en) * 1977-03-14 1979-08-07 The Dow Chemical Company Substituted pyridine methyl esters of cyclopropane carboxylic acids and their use as insecticides
DE2861000D1 (en) * 1977-07-20 1981-11-26 Ciba Geigy Ag Phenyl acetates of 2-oxypyridyl, process for their preparation and their use as pesticides
US4191831A (en) * 1978-10-25 1980-03-04 E. R. Squibb & Sons, Inc. Imidazolylethoxy derivatives of pyridin-5-methanols
US4221799A (en) * 1979-07-30 1980-09-09 The Dow Chemical Substituted pyridine methyl esters of tetramethyl cyclopropane carboxylic acids and their use as insecticides
US4390543A (en) * 1979-07-30 1983-06-28 Malhotra Sudarshan K Substituted pyridine methyl esters of 2-isopropyl-2-(4-chlorophenyl) acetic acid and their use as insecticides
US4338326A (en) * 1979-11-27 1982-07-06 Union Carbide Corporation Phenoxypyridinemethyl esters of 4-alkenoic acids
FR2486078A1 (fr) * 1980-07-04 1982-01-08 Roussel Uclaf Nouveaux esters de l'acide cyclopropane carboxylique, leur procede de preparation et leur application a la lutte contre les parasites
US4426524A (en) * 1980-09-02 1984-01-17 Fmc Corporation Heterocyclic substituted benzyl alcohol, insecticidal ester derivatives, and intermediates
US4323574A (en) * 1980-11-24 1982-04-06 Zoecon Corporation Cis and trans isomers of α-methyl(6-phenoxy-2-pyridyl)methyl-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylates and derivatives thereof
US4357336A (en) * 1981-12-21 1982-11-02 Stauffer Chemical Company Certain 2,2-dimethyl-3-(ethenyl or propenyl)-cyclopropane carboxylic acid esters of the pyridyl-lower alkyl series having insect repelling properties
US4423222A (en) * 1982-05-21 1983-12-27 The Dow Chemical Company Pyridinyl fungicides and herbicides

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Title
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Also Published As

Publication number Publication date
CA1269387C (fr) 1990-05-22
IL74868A0 (en) 1985-07-31
CA1269387A (fr) 1990-05-22
AU4232985A (en) 1985-11-01
WO1985004553A1 (fr) 1985-10-24

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