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WO1998000015A1 - Sels insecticides de n-(arylmethyle substitue)-4-[bis(aryle substitue)hydroxymethyle]piperidinium - Google Patents

Sels insecticides de n-(arylmethyle substitue)-4-[bis(aryle substitue)hydroxymethyle]piperidinium

Info

Publication number
WO1998000015A1
WO1998000015A1 PCT/US1997/011077 US9711077W WO9800015A1 WO 1998000015 A1 WO1998000015 A1 WO 1998000015A1 US 9711077 W US9711077 W US 9711077W WO 9800015 A1 WO9800015 A1 WO 9800015A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
bis
hydroxymethyl
piperidinium
trifluoromethylphenyl
Prior art date
Application number
PCT/US1997/011077
Other languages
English (en)
Inventor
Steven W. Szczepanski
Original Assignee
Fmc Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US08/852,160 external-priority patent/US5795901A/en
Application filed by Fmc Corporation filed Critical Fmc Corporation
Priority to EP97931416A priority Critical patent/EP0912090A4/fr
Priority to BR9710108A priority patent/BR9710108A/pt
Priority to AU35051/97A priority patent/AU3505197A/en
Publication of WO1998000015A1 publication Critical patent/WO1998000015A1/fr

Links

Classifications

    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
    • C07D211/14—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with hydrocarbon or substituted hydrocarbon radicals attached to the ring nitrogen atom

Definitions

  • the present invention relates to methods for controlling insects.
  • it relates to control by the application of certain novel N-(substituted arylmethyl)-4-[bis(substituted phenyl or pyridyl)hydroxymethyl]piperfdinium salts and to the locus where insect control is needed.
  • U is -(CH2)rr. where n is 1 ;
  • V, W, Y f and Z are each hydrogen
  • X is alkoxy, cycloalkylalkoxy, alkoxycarbonyl, alkoxycarbonylamino, or a five- or six-membered heteroaryl or heteroaryloxy, each heteroaryl optionally substituted with halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, or haloalkoxyalkyl;
  • R 1 and R 2 are independently selected from haloalkyl; phenyl substituted with halogen, halothio, haloalkyl, or haloalkoxy; or a five- or six-membered heteroaryl substituted with halogen or haloalkyl;
  • R is alkyl, haloalkyl, hydroxyalkyl, alkoxyalkyl, dialkylaminoalkyl, alkylaminocarbonyloxyalkyl, alkylthioalkyl, alkylsulfon
  • the compounds of the invention differ from the piperidine compounds from which they are derived in chemical and physical properties, they can be formulated in ways not possible or practicable for the parent compounds. These differences can also be expected to affect the manner in which the target insects metabolize the compounds. Preferred are those compounds in which
  • X is alkoxy, cycloalkylalkoxy, alkoxycarbonyl, alkoxycarbonylamino, or a five- or six-membered heteroaryl or heteroaryloxy; each heteroaryl selected from 1 ,2,4-oxadiazolyl, oxazolinyl, pyridazinyl, pyrazinyl, pyridyl, pyrimidinyl, pyrolyl, 2H-t ⁇ trazol-5-yl, 1 ,2,3-thiadiazolyl, 1 ,3,5-triazinyl, and 1 ,2,4-triazolyl, each optionally substituted with halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, or haloalkoxyalkyl;
  • R 1 and R 2 are independently selected from p-trifluoromethoxyphenyl, p- trifluoromethylphenyl, 5-trifluoromethylpyrid-2-yl, and 5-trifluoromethoxypyrid- 2-yl; 5-trifluoromethylpyrimidin-2-yl, and 5-trifluoromethoxypyrimidin-2-yl;
  • R 3 is alkyl, haloalkyl, hydroxyalkyl, alkoxyalkyl, dialkylaminoalkyl, alkylaminocarbonyloxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, alkylcarbonyioxyalkyl, alkoxycarbonylalkyl, carboxyalkyl, carboxyarylalkyl, or arylcarbonyl; and a separate anion is chloride, bromide, or iodide; with the proviso that halogen means chlorine or fluorine, and R 3 may contain up to
  • X is a n-propyloxy, cyclopropylmethoxy, methoxycarbonylamino, i-pro- poxycarbonylamino, or a heteroaryl selected from 1 ,2,4-oxadiazol-5-yl, oxazolin-2-yl, pyrid-2-yl, pyrimidin-2-yl, pyrol-3-yl, 2H-tetrazol-5yl, 1 ,2,3-thia- diazol-4-yt, 1 ,2,4-triazol-3-yl, each optionally substituted with halogen, cyano, C ( i. 3) alkyl, C ( i- 3 )haloalkyl, or C ( ⁇ -4)alkoxyalkyl;
  • R 3 is alkyl, C ( i_ 4 )haloalkyl, C ( ⁇ _ 4 )hydroxyalkyl, C ( ⁇ _ ) alkoxyalkyl, C ( ⁇ . 4 )dialkyl- aminoalkyl, bonyioxyalkyl, C ( ⁇ -4)alkoxycarbonylalkyl, carboxyC(i-4)alkyl, benzylcarboxy, or benzoyl.
  • the compounds of the present invention were prepared by methods known to one skilled in the art.
  • ethyl piperidin-4-ylcarboxylate was reacted with an appropriately substituted phenylalkyl halide, for example, 4-propoxyphenylmethyl chloride, affording the corresponding ethyl N-substituted alky!piperidin-4-ytcarboxylate (A).
  • phenylalkyl halide for example, 4-propoxyphenylmethyl chloride
  • the so-prepared ethyl carboxylate (A) was then treated with a two to three molar excess of the Grignard reagent of an appropriately substituted halide, for example, 4-trifluoromethylphenyl magnesium bromide, yielding the intermediate N-(substituted alkyl)-4-[bis(substituted)hydroxy-methyl]piperidine Q).
  • an appropriately substituted halide for example, 4-trifluoromethylphenyl magnesium bromide
  • the N-oxides (IA) were prepared by treating (I) with an oxidizing agent, such as 30% aqueous hydrogen peroxide or 50% 3-chloroperoxybenzoic acid in an appropriate solvent, yielding the corresponding N-oxide, for example, N-(4- propoxyphenylmethyl)-4-[bis(trifluoromethylphenyl)hydroxy-methyl]piperidine N-oxide.
  • the N-oxide (IA) was then reacted with an appropriate halide such as ethyl iodide or 3-bromopropionic acid, or a sulfate or sulfonate, as shown in Schema 3, yielding the targeted salts.
  • ethyl piperidin-4-ylcarboxylate was reacted with trimethylsilyl chloride, yielding ethyl N-trimethylsilylpiperidin-4-ylcarboxylate (B).
  • Intermediate (B) was then reacted with a two to three molar excess of the Grignard reagent of an appropriately substituted halide, as described above, affording a 4-[bis(substrtuted)hydroxymethyl]piperidine (C), for example 4-[bis(4-trifluoromethylphenyl)hydroxymethyl]piperidine.
  • Schemata 1-3 depict the general methods used to prepare these compounds. Examples 1 and 2 provide the details for these methods of preparation.
  • reaction mixture was maintained at 10 °C.
  • reaction mixture was stirred for one hour and poured into a solution of 350 mL of water containing 100 mL of an aqueous solution saturated with ammonium chloride.
  • the organic layer was washed with two 250 mL portions of an aqueous solution saturated with sodium bicarbonate, and dried with magnesium chloride.
  • the mixture was filtered, and the filtrate was concentrated under reduced pressure, yielding 56.4 grams of material.
  • the material was distilled under reduced pressure, yielding 52.5 grams of 4- propoxyphenylmethyl chloride, bp 92 °C/0.3 mm Hg.
  • Step B Synthesis of ethyl N-(4-propoxyphenylmethyl)piperidin-4-yl carboxyiate as an intermediate
  • the reaction caused the reaction mixture temperature to rise to about 35 °C.
  • the reaction mixture was stirred for 30 minutes, warmed to 40 °C, and then allowed to cool to ambient temperature.
  • reaction mixture was poured into 500 mL of aqueous 10% ammonium chloride.
  • the mixture was extracted with three 250 mL portions of diethyl ether, and the combined extracts were washed with two 250 mL portions of an aqueous solution saturated with ammonium chloride, one 250 mL portion of water, and one 250 mL portion of an aqueous solution saturated with sodium chloride.
  • the organic layer was dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, yielding 80.0 grams of ethyl N-(4- propoxyphenylmethyl)-piperidin-4-ylcarboxylate.
  • the NMR spectrum was consistent with the proposed structure.
  • reaction mixture was heated at reflux for an additional one hour, then cooled to ambient temperature and poured into an aqueous solution saturated with ammonium chloride.
  • the mixture was extracted with ethyl acetate, and the extract was dried with magnesium sulfate.
  • the mixture was filtered, and the filtrate was concentrated under reduced pressure, yielding a crude product that was subjected to column chromatography on silica gel with 1 :1 ethyl acetate : heptane as the eluant.
  • the product-containing fractions were combined and concentrated under reduced pressure, yielding 1.4 grams of N-(4-propoxyphenylmethyl)-4-[bis-(trifluoromethylphenyl)hydroxy- methyl]piperidine.
  • the NMR spectrum was consistent with the proposed structure.
  • Step D Synthesis of N-(4-propoxyphenylmethyl)-4-[bis(4-trifluoro methylphenyl)-hydroxymethyl]piperidine N-oxide as an intermediate
  • TLC thin layer chromatography
  • Step B Synthesis of 4-[bis(4-trifluoromethylphenyl)hydroxymethyl] piperidine as an intermediate
  • This compound was prepared in the manner of Step C of Example 1 , with 30 grams (0.131 mole) of ethyl N-trimethylsilylpiperidin-4-ylcarboxylate, 70.6 grams (0.314 mole) of 4-trifluoromethylphenyl bromide, and 7.8 grams (0.320 gram-atom) of magnesium turnings in about 400 mL of tetrahydro- furan as reagents.
  • the yield of 4-[bis(4-trifluoromethytphenyl)hydroxy- methyljpiperidine was 33.0 grams of powdery solid.
  • the NMR spectrum was consistent with the proposed structure.
  • Step C Synthesis of N-[4-(cyclopropylmethoxy)phenylmethyl]-4-[bis(4- trifluoromethylphenyl)hydroxymethyl]piperidine as an intermediate
  • the reaction mixture was then poured into an aqueous solution saturated with sodium bicarbonate.
  • the mixture was extracted with two portions of ethyl acetate, and the extracts combined.
  • the combination was dried with sodium sulfate and filtered.
  • the filtrate was concentrated under reduced pressure to a residue, which was subjected to column chromatography on silica gel with 50% heptane in methylene chloride to 50% acetone in methylene chloride.
  • the product-containing fractions were combined and concentrated under reduced pressure, yielding 22.0 grams of N-[4-(cyclopropylmethoxy)- phenylmethyl]-4-[bis(4-trifluoromethylphenyl)hydroxymethyl]piperidine.
  • the NMR spectrum was consistent with the proposed structure.
  • Step E Synthesis of N-[4-(cyclopropylmethoxy)phenylmethyl]-N- ethoxy-4-[bis(4-trifluoromethylphenyl)hydroxymethyl] piperidinium iodide (Compound 1 1 )
  • Candidate insecticides were incorporated into an artificial diet for evaluation of insecticidal activity against the tobacco budworm (Heliothis viresc ⁇ ns [Fabricius]) in the following manner.
  • One hundred microliters of each of the stock solutions was manually stirred into 50 mL of a molten (65-70°C) wheat germ-based artificial diet.
  • the 50 mL of molten diet containing the test chemical was poured evenly into twenty wells in the outer two rows on each side of a twenty-five well, five row plastic tray.
  • the negative log of the concentration of the test _ chemical that provided 50% growth inhibition (plso) was determined by linear regression, when possible, for each test chemical. Also, where possible, the negative log of the concentration of the test chemical that provided 50% mortality (pLCso) was determined.
  • Candidate insecticides with high plso values from the diet test were tested for insecticidal activity in foliar evaluations against tobacco budworm, beet armyworm (Spodoptera exig ⁇ a [Hubner]), and cabbage looper (Trichoplusia n/ ' [Hubner]).
  • the four chick pea plants for each replicate treated with test chemical as described above were removed from their pots by cutting the stems just above the soil line.
  • the excised leaves and stems from the four plants in each replicate were placed in individual 8-ounce paper cups, each containing a moistened filter paper.
  • Five second-instar (6 days old) tobacco budworms or beet armyworms (7-8 days old) were counted into each cup, taking care not to cause injury.
  • An opaque plastic lid was placed on each cup, which was then held in a growth chamber for a 96 hour exposure period at 25°C and 50% relative humidity. At the end of the 96 hour exposure period the cups were opened, and the numbers of dead, moribund, and live insects were counted.
  • test plants were also observed for phytotoxicity and for reduction of feeding damage as compared to an untreated control.
  • Foliar tests with cabbage looper were conducted in the same manner as described above, the difference being that pinto bean plants ⁇ Phaseolus vulgaris) were used in place of chick pea plants.
  • the compounds of the present invention were active in the diet test against the tobacco budworm.
  • Table 3 gives the insecticidal activity data for compounds tested in the diet test.
  • the active compounds are formulated into insecticidal compositions by admixture in insecticidally effective amount with adjuvants and carriers normally employed in the art for facilitating the dispersion of active ingredients for the particular utility desired, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the material in a given application.
  • the present insecticidal compounds may be formulated as granules of relatively large particle size, as water-soluble or water-dispersible granules, as powdery dusts, as wettabie powders, as e ulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.
  • insecticidal compositions may be applied either as water-diluted sprays, or dusts, or granules to the areas in which insect control is desired. These formulations may contain as little as 0.1%, 0.2% or 0.5% to as much as 95% or more by weight of active ingredient.
  • Dusts are free flowing admixtures of the active ingredients with finely divided solids such as talc, natural clays, kieselguhr, flours such as walnut shell and cottonseed 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 is one containing 1.0 part or less of the insecticidal compound and 99.0 parts of talc.
  • Wettabie powders are in the form of finely divided particles which disperse readily in water or other dispersant.
  • the wettabie powder is ultimately applied to the locus where insect control is desired either as a dry dust or as an emulsion in water or other liquid.
  • Typical carriers for wettabie powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet, inorganic diluents. Wettabie powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a wetting, dispersing, or emulsifying agent to facilitate dispersion.
  • a useful wettabie powder formulation contains 80.8 parts of the insecticidal compound, 17.9 parts of Palmetto clay, and 1.0 part of sodium lignosuifonate and 0.3 part of suifonated aliphatic polyester as wetting agents.
  • ECs emulsifiable concentrates
  • ECs emulsifiable concentrates
  • ECs emulsifiable concentrates
  • these concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated.
  • the percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the insecticidal composition.
  • Flowable formulations are similar to ECs except that the active ingredient is suspended in a liquid carrier, generally water.
  • Flowables like ECs, may include a small amount of a surfactant, and contain active ingredient in the range of 0.5 to 95%, frequently from 10 to 50%, by weight of the composition.
  • flowables may be diluted in water or other liquid vehicle, and are normally applied as a spray to the area to be treated.
  • Typical wetting, dispersing, or emulsifying agents used in agricultural formulations include, but are not limited to, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkylaryl poly ether alcohols; sulfated higher alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition product of long-chain mercaptans and ethylene oxide.
  • the surface-active agents when used, normally comprise from 1 to 15% by weight of the composition.
  • compositions include suspensions of the active ingredient in a relatively non-volatile solvent such as water, com oil, kerosene, propylene glycol, or other suitable solvents.
  • Still other useful formulations for insecticidal applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents.
  • Granular formulations, wherein the toxicant is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover crop canopy.
  • Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as carbon dioxide, propane, or butane, may also be used.
  • Water-soluble or water-dispersible granules are also useful formulations for insecticidal application of the present compounds.
  • Such granular formulations are free-flowing, non-dusty, and readily water-soluble or water- miscible.
  • the soluble or dispersible granular formulations described in U.S. patent No. 3,920,442 are useful herein with the present insecticidal compounds.
  • the granular formulations, emulsifiable concentrates, flowable concentrates, solutions, etc. may be diluted with water to give a concentration of active ingredient in the range of say 0.1% or 0.2% to 1.5% or 2%.
  • the active insecticidal compounds of this invention may be formulated and/or applied with other insecticides, fungicides, nematicides, plant growth regulators, fertilizers, or other agricultural chemicals.
  • an effective amount and concentration of the active compound is applied to the locus where control is desired.
  • the locus may be, e.g., the insects themselves, plants upon which the insects feed, or the insect habitat.
  • the composition of the active compound may be applied to and optionally incorporated into the soil.
  • the effective amount may be as low as, e.g. about 10 to 500 g/ha, preferably about 100 to 250 g/ha.
  • V, W, Y, and Z are hydrogen
  • R 1 and R 2 are selected from:
  • the rate of application is expressed as the negative log of the molar concentration of the test compound in the diet.
  • Percent growth inhibition is derived from the total weight of the insects (IW) at each rate of application in the test relative to the total weight of the insects in an untreated control: c r r , _ [lW(contror)- IW(test)]
  • 3 plso is the negative log of the concentration of the test chemical that provides 50% growth inhibition in the test species.
  • Percent mortality is derived from the number of dead insects (TD) relative to the number of insects (Tl) used in the test.
  • 5 pLCso is the negative log of the concentration of the test chemical that provides 50% mortality of the test insects.

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

Abstract

Composés utiles en tant qu'insecticides et représentés par la formule suivante: [anion] dans laquelle Q représente hydroxy; U représente -(CH2)n-, dans laquelle n est 1; R est représenté par la formule dans laquelle V, W, Y et Z représentent chacun hydrogène; X représente alcoxy, cycloalkylalcoxy, alcoxycarbonyle, alcoxycarbonylamino ou un hétéroaryle à cinq ou six éléments ou hétéroaryloxy, chaque hétéroaryle étant éventuellement substitué par halogène, cyano, alkyle, haloalkyle, alcoxy, haloalcoxy, alcoxyalkyle ou haloalcoxyalkyle; R1 et R2 sont indépendamment sélectionnés dans haloalkyle; phényle substitué par halogène, halothio, haloalkyle ou haloalcoxy; ou un hétéroaryle à cinq ou six élément substitué par halogène ou haloalkyle; R3 représente, alkyle, haloalkyle, hydroxyalkyle, alcoxyalkyle, dialkylaminoalkyle, alkylaminocarbonyloxyalkyle, alkylthioalkyle, alkylsufonylalkyle, alkylcarbonyloxyalkyle,alcoxycarbonylalkyle, carboxyalkyle, carboxyarylalkyle, arylcarbonyle, sulfonato ou aulfonatoalkyle et peut éventuellement porter une charge négative permettant d'obtenir un sel intérieur; un anion séparé représente chlorure, bromure, iodure ou un sulfate ou sulfonate de phényle ou d'alkyle; à condition qu'au moins un de R1 et R2 soit substitué par phényle à la position para ou par pyrid-2-yle ou pyrimidin-2-yle, chacun substitué à la position 5; chaque fraction aliphatique ne contient pas plus de 4 atomes de carbone, sauf que R3 peut contenir jusqu'à dix-huit atomes de carbone; halogène signifie brome, chlore ou fluor; chaque hétéroaryle contient de 1 à 4 atomes d'azote ou 1 ou 2 atomes d'oxygène ou de soufre ou 1 ou 2 atomes d'azote et un atome d'oxygène ou de soufre.
PCT/US1997/011077 1996-07-02 1997-06-25 Sels insecticides de n-(arylmethyle substitue)-4-[bis(aryle substitue)hydroxymethyle]piperidinium WO1998000015A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP97931416A EP0912090A4 (fr) 1996-07-02 1997-06-25 Sels insecticides de n-(arylmethyle substitue)-4- bis(aryle substitue)hydroxymethyle]piperidinium
BR9710108A BR9710108A (pt) 1996-07-02 1997-06-25 Composto composição inseticida e método para controlar insetos
AU35051/97A AU3505197A (en) 1996-07-02 1997-06-25 Insecticidal n-(substituted arylmethyl)-4-{bis(substituted aryl) hydroxymethyl}piperidinium salts

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US2113996P 1996-07-02 1996-07-02
US60/021,139 1996-07-02
US08/852,160 US5795901A (en) 1996-07-02 1997-05-06 Insecticidal N-(substituted arylmethyl)-4- bis(substituted aryl)hydroxymethyl!piperidinium salts
US08/852,160 1997-05-06

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WO1998000015A1 true WO1998000015A1 (fr) 1998-01-08

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EP (1) EP0912090A4 (fr)
AU (1) AU3505197A (fr)
BR (1) BR9710108A (fr)
WO (1) WO1998000015A1 (fr)

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WO2000031034A1 (fr) * 1998-11-20 2000-06-02 Fmc Corporation Derives de sels acides photostables insecticides de n-benzyl-4-benzhydrolpiperidines
WO2003022808A1 (fr) * 2001-09-12 2003-03-20 Bayer Cropscience S. A. Derives d'azetidine, leur procede de preparation et leur utilisation comme produit phytosanitaire
US6638940B1 (en) 1999-09-03 2003-10-28 Syngenta Crop Protection, Inc. Tetrahydropyridines as pesticides

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US5569664A (en) * 1995-02-16 1996-10-29 Fmc Corporation Insecticidal n-(substituted arylmethyl)-4-[bis(substituted phenyl) methyl]pi

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Publication number Priority date Publication date Assignee Title
US5639763A (en) * 1994-03-01 1997-06-17 Fmc Corporation Insecticidal N-(substituted arylmethyl)-4-[bis(substituted phenyl)methyl]piperidines

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Publication number Priority date Publication date Assignee Title
WO2000031034A1 (fr) * 1998-11-20 2000-06-02 Fmc Corporation Derives de sels acides photostables insecticides de n-benzyl-4-benzhydrolpiperidines
US6638940B1 (en) 1999-09-03 2003-10-28 Syngenta Crop Protection, Inc. Tetrahydropyridines as pesticides
WO2003022808A1 (fr) * 2001-09-12 2003-03-20 Bayer Cropscience S. A. Derives d'azetidine, leur procede de preparation et leur utilisation comme produit phytosanitaire

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AU3505197A (en) 1998-01-21
BR9710108A (pt) 1999-08-10
EP0912090A1 (fr) 1999-05-06
EP0912090A4 (fr) 2000-05-17

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