WO1995006631A1 - Arthropodicides polycycliques - Google Patents

Arthropodicides polycycliques Download PDF

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Publication number
WO1995006631A1
WO1995006631A1 PCT/US1994/009524 US9409524W WO9506631A1 WO 1995006631 A1 WO1995006631 A1 WO 1995006631A1 US 9409524 W US9409524 W US 9409524W WO 9506631 A1 WO9506631 A1 WO 9506631A1
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group
alkyl
halogen
alkoxy
optionally substituted
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PCT/US1994/009524
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English (en)
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Caleb William Holyoke, Jr.
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E.I. Du Pont De Nemours And Company
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Priority to AU76731/94A priority Critical patent/AU7673194A/en
Publication of WO1995006631A1 publication Critical patent/WO1995006631A1/fr

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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
    • A01N45/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds having three or more carbocyclic rings condensed among themselves, at least one ring not being a six-membered ring
    • A01N45/02—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds having three or more carbocyclic rings condensed among themselves, at least one ring not being a six-membered ring having three carbocyclic 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
    • A01N45/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds having three or more carbocyclic rings condensed among themselves, at least one ring not being a six-membered 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/45—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C255/47—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of rings being part of condensed ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
    • C07C255/51—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings containing at least two cyano groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/46—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by amide or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/30—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/10—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms two oxygen atoms and one sulfur atom, e.g. cyclic sulfates
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4018—Esters of cycloaliphatic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
    • C07C2603/62—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing three- or four-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
    • C07C2603/62—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing three- or four-membered rings
    • C07C2603/64—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing three- or four-membered rings having a tricyclo[2.2.1.0(2,6)]heptstructure
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/86—Ring systems containing bridged rings containing four rings

Definitions

  • U.S. 4,647,581 discloses certain polycyclic compounds useful as arthropodicides.
  • Diss. Abstr. Int. B, (1986), 57 (6), 2434 discloses certain polycyclic cyclobutanes, with no disclosure of any biological utility.
  • J. Am. Chem. Soc. (1972), 94, 787 discloses certain polycyclic cyclobutanes, also with no disclosure of any biological utility.
  • This invention pertains to compounds of Formula I, including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use to control arthropods in both agronomic and nonagronomic environments.
  • the compounds are:
  • A is selected from the group H, CN, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl and halogen;
  • E is selected from the group H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, halogen, CH 2 (C 1 -C 3 alkoxy), CH(C 1 -C 3 alkoxy) 2 , CH(C 1 -C 3 alkoxy)(C 3 -C 5 alkenyl), C 2 -C 6 alkoxycarbonyl, C 3 -C 7 alkoxycarbonylalkyl, P(X)(C 1 -C 3 alkoxy) 2 , P(X)(C 1 -C 3 alkyl) 2 , P(X)(C 1 -C 3 alkoxy)(C 1 -C 3 alkyl), and phenyl optionally substituted with 1-3 substituents independently selected from the group halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 hal
  • a and E are taken together and selected from the group C 2 -C 3 alkylene and
  • L is selected from the group H, CN, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 6
  • G is selected from the group O, S, S(O), S(O) 2 and ;
  • U is selected from the group halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, OH, OR 4 , C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkylthio, C 1 -C 3 haloalkylthio, C 1 -C 3 alkylsulfinyl, C 1 -C 3 haloalkylsulfinyl, C 1 -C 3 alkylsulfonyl, C 1 -C 3 haloalkylsulfonyl, C 2 -C 4 alkylcarbonyl, C 2 -C 4 haloalkylcarbonyl, C 2 -C 4 alkoxycarbonyl, C(O)NR 2 R 3 , S(O) 2 NR 2 R 3 , Si(C 1 -C 4 alkyl) 3 , C 2 -C 4 alkenyl and phenyl
  • W is selected from the group halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, OR 4 , C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkylthio, C 1 -C 3 haloalkylthio, C 1 -C 3 alkylsulfinyl, C 1 -C 3 haloalkylsulfinyl, C 1 -C 3 alkylsulfonyl, C 1 -C 3
  • haloalkylsulfonyl C 2 -C 4 alkylcarbonyl, C 2 -C 4 haloalkylcarbonyl, C 2 -C 4 alkoxycarbonyl, C(O)NR 2 R 3 , S(O) 2 NR 2 R 3 , Si(C 1 -C 4 alkyl) 3 , C 2 -C 4 alkenyl and phenyl optionally substituted with 1-2 substituents independently selected from the group halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 2 -C 4 alkylcarbonyl, C 2 -C 4 alkoxycarbonyl, CN and NO 2 ;
  • X is selected from the group O and S;
  • Y is selected from the group O and CH 2 optionally substituted with 1-2
  • Z is selected from the group CH 2 and CH 2 CH 2 each optionally substituted with 1-2 substituents independently selected from R; or Z is O;
  • R is selected from the group C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, OH, OR 4 , C 1 -C 4 alkoxy, C 1 -C 3 haloalkoxy, C 2 -C 4 alkoxycarbonyl, halogen, CN and phenyl optionally suostituted with 1-2 substituents independently selected from the group halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 2 -C 4 alkylcarbonyl, C 2 -C 4 alkoxycarbonyl, CN and NO 2 ;
  • R 1 is selected from the group halogen, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 2 -C 4 alkoxycarbonyl, CN and phenyl;
  • R 2 is selected from the group H and C 1 -C 3 alkyl
  • R 3 is selected from the group C 1 -C 3 alkyl and C 1 -C 3 alkoxy;
  • R 4 is selected from the group C 2 -C 4 alkylcarbonyl and C 2 -C 4 haloalkylcarbonyl; m is 0, 1 or 2;
  • n 1 or 2;
  • Preferred Compounds A are compounds of Formula I wherein
  • A is selected from the group H, CN, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl and halogen;
  • E is selected from the group H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl and halogen; or
  • a and E are taken together as C 2 -C 3 alkylene optionally substituted with
  • L is selected from the group CN, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl and halogen; or
  • L and E are taken together as C 2 -C 5 alkylene optionally substituted with
  • Preferred Compounds B are compounds of Preferred A wherein
  • Preferred Compounds C are compounds of Preferred B wherein
  • A is CN;
  • L is selected from the group C 1 -C 4 alkyl, C 1 -C 3 haloalkyl, F, Cl and Br; and
  • Z is CH 2 .
  • Preferred Compounds D are compounds of Preferred B wherein
  • A is selected from the group H, C 1 -C 4 alkyl, C 1 -C 3 haloalkyl, F, Cl and
  • a and E are taken together as C 2 -C 3 alkylene optionally substituted with
  • Z is CH 2 .
  • Preferred Compounds E are compounds of Preferred C wherein
  • Preferred Compounds F are compounds of Preferred D wherein
  • a and E are taken together as C 2 -C 3 alkylene optionally substituted with 1-6 substituents independently selected from the group F and Cl.
  • 1-6 substituents independently selected from the group F and Cl.
  • Compound G of Preferred E which is:
  • Stereoisomers of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate said stereoisomers. Accordingly, the present invention comprises racemic mixtures, individual stereoisomers, and optically active mixtures of compounds of Formula I as well as agriculturally suitable salts thereof.
  • optically active compound(s) includes individual stereoisomers, mixtures of stereoisomers enriched in one
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” denotes straight-chain or branched alkyl such as methyl, ethyl, n-propyl, i-propyl, or the different butyl isomers.
  • alkenyl denotes straight or branched chain alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl isomers.
  • Alkoxy denotes methoxy, ethoxy, n-propyloxy, and i- propyloxy isomers.
  • alkylthio denotes methylthio, ethylthio, /7-propylthio, and /-propylthio analogs.
  • alkylsulfinyl and “alkylsulfonyl” are defined analogously to the above examples.
  • halogen either alone or in compound words such as “haloalkyl”, denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F 3 C, ClCH 2 , CF 3 CH 2 and CF 3 CCl 2 .
  • C i -C j The total number of carbon atoms in a substituent group is indicated by the "C i -C j " prefix where i and j are numbers from 1 to 7.
  • C 1 -C 3 alkyl designates methyl through propyl
  • C 2 alkoxy designates CH 3 CH 2 O
  • C 3 alkoxy designates
  • C 2 -C 4 alkoxycarbonyl designates CH 3 OC(O), CH 3 CH 2 OC(O), CH 3 CH 2 CH 2 OC(O) and (CH 3 ) 2 CHOC(O).
  • C 2 -C 5 alkylene designates CH 2 CH 2, CH 2 CH 2 CH 2 and the different C 4 and C 5 isomers.
  • the cycloadditions can be performed in the presence or absence of inert solvents or in the presence or absence of additives.
  • Suitable solvents include petroleum ether, cyclic and acyclic alkyl ethers and halogenated solvents.
  • Suitable additives include lithium perchlorate and lithium tetrafluoroborate. The reactions can be performed at
  • Compounds of Formula II can be prepared by irradiation of the corresponding [2.2.1]-bicyclohepta-2,5-diene as described in Org. Syn. (1971) 51, 133.
  • additional compounds of the invention can be prepared by techniques such as alkylation, acylation, hydration, epoxidation, and halogenation of the compounds of Formula I (see for example March, J., Advanced Organic Chemistry, John Wiley & Sons, New York, 3rd ed. (1985) 657-779).
  • Compounds of Formula I can also be prepared by transition metal catalyzed cycloaddition as shown in Scheme ⁇ .
  • Appropriate solvents include benzene, toluene and the dienophilic reactant of Formula in.
  • Examples of appropriate catalysts include complexes of nickel and ruthenium. This method is similar to procedures described in the art J. C. S., Chem. Commun. (1976) 722.
  • Step 1 is based on forming optionally protected cyanohydrins of the carbonyl followed by dehydration as described in Chem. Lett. (1979) 1427 and Org. Syn. (1972) 52, 96. Procedures for Step 2 (hydrocyanation) are well known in the art (see for example Org. React. (1977) 25, 255). Step 3 can be performed by halogenation/dehydrohalogenation in a manner similar to that described in Helv. Chim. Acta. (1973) 56, 3004 or by oxidative dehydrogenation as described for example in U. S. Patent 4,146,552.
  • Formula III compounds where either A or L is CN can be prepared by displacements involving other compounds of Formula III in which the displaced substituent is halogen or alkylthio. See for example Russ. J. Gen. Chem. (1963) 62, 2530.
  • nucleophiles could be used and that differing conditions would be required for different nucleophiles.
  • the intermediate compounds of Formula IV which include compounds such as norbornene, benzonorbornadiene, [2,2,2]bicyclooctadienes, and the like are well documented in the chemical literature as are procedures for their preparation ⁇ Rodd's Chemistry of Carbon Compounds, 2nd Ed., S. Coffey (Ed) Vol II. Part C, pp 89-116, Elsevier, Amsterdam, (1969)). Selected examples of Formula IV are available commercially as well.
  • the intermediate compounds of Formula V which include derivatives such as maleic anhydride, are well-known in the literature and many are commercially available.
  • protection/deprotectio sequences into the synthesis will aid in obtaining the desired products.
  • the use and choice of the protecting group will be apparent to one skilled in chemical synthesis and numerous examples are found in Greene, T. W., Protective Groups in Organic Synthesis, John Wiley & Sons, Inc., U.S.A., 2nd Ed., (1981).
  • 1,8-diazabicydo[5.4.0]undec-7-ene was added and the reaction mixture was refluxed 2.5 h.
  • the reaction was cooled and the orange solution decanted from a viscous oil on the flask wall.
  • the benzene solution was combined with 10 g of Raney cobalt, refluxed for 2 h, filtered and the benzene distilled off leaving a crude oil of about 70% purity.
  • the crude oil was dissolved in 1 : 1 ethyl acetate:hexanes, filtered through silica gel and concentrated under vacuum to afford 2.67 g of an oil with unchanged purity.
  • -H NMR (CDCl 3 ) ⁇ 2.82 (t,4H), 2.17 (quint.,2H).
  • Step E (3a ⁇ ,3b ⁇ ,4 ⁇ ,7 ⁇ ,7a ⁇ ,7b ⁇ )-2,3,3b,4,7,7a-hexahydro-4,7-methano-1H- cyclopenta[3,4]cyclobuta[1,2]benzene-3a,7b-dicarbonitrile
  • Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent.
  • Useful formulations include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
  • Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation.
  • the formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 weight percent. Active
  • Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill.
  • Water-dispersible granules can be produced by agglomerating a fine powder
  • composition see for example, Cross et al., Pesticide Formulations, Washington, D.C., (1988), pp 251-259.
  • Suspensions are prepared by wet-milling; see, for example, U.S. 3,060,084.
  • Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning,
  • the compounds of this invention exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, stem or root feeding, seed-feeding, aquatic and
  • arthropods includes insects, mites and nematodes which are pests of growing and stored agronomic crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. Those skilled in the art will appreciate that not all compounds are equally effective against all growth stages of all pests.
  • all of the compounds of this invention display activity against pests that include: eggs, larvae and adults of the Order Lepidoptera; eggs, foliar-feeding, fruit-feeding, root-feeding, seed-feeding larvae and adults of the Order Coleoptera; eggs, immatures and adults of the Orders Hemiptera and Homoptera; eggs, larvae, nymphs and adults of the Order Acari; eggs, immatures and adults of the Orders Thysanoptera, Orthoptera and Dermaptera; eggs, immatures and adults of the Order Diptera; and eggs, juveniles and adults of the Phylum Nematoda.
  • the compounds of this invention are also active against pests of the Orders Hymenoptera, Isoptera, Siphonaptera, Blattaria, Thysanura and Psocoptera; pests belonging to the Class Arachnida and Phylum Platyhelminthes.
  • the compounds are active against southern corn rootworm (Diabrotica undecimpunctata howardi), aster leafhopper (Mascrosteles fascifrons), boll weevil (Anthonomus grandis), two-spotted spider mite (Tetranychus urticae), fall armyworm (Spodopterafrugiperda), black bean aphid (Aphis fabae), tobacco budworm (Heliothis virescens), rice water weevil (Lissorhoptrus oryzophilus), rice leaf beetle (Oulema oryzae), whitebacked planthopper (Sogatellafurcifera), green leafhopper (Nephotettix cincticeps), brown planthopper (Nilaparvata lugens), small brown planthopper
  • Tetranychidae including Tetranychus urticae, Tetranychus cinnabarinus, Tetranychus mcdanieli, Tetranychus pacificus, Tetranychus turkestani, Byrobia rubrioculus, Panonychus ulmi, Panonychus citri, Eotetranychus carpini borealis, Eotetranychus, hicoriae, Eotetranychus sexmaculatus, Eotetranychus yumensis, Eotetranychus banksi and Oligonychus pratensis; Tenuipalpidae including Brevipalpus lewisi, Brevipalpus phoenicis, Brevipalpus calif ornicus and Brevipalpus obovatus; Eriophyid
  • insecticides fungicides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellants, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection.
  • insecticides such as avermectin B, monocrotophos, carbofuran, tetrachlorvinphos, malathion, parathion-methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate, esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fipronil, flufenprox, fonophos, isofenphos, methidathion, metha-midophos, phosmet,
  • fungicides such as carbendazim, thiuram, dodine, maneb, chloroneb, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimefon, captan, thiophanate-methyl, thiabendazole, phosethyl-Al, chlorothalonil, dichloran, metalaxyl, captafol, iprodione, oxadixyl, vinclozolin, kasugamycin
  • nematocides such as aldoxycarb, fenamiphos and fosthietan
  • bactericides such as oxytetracy ⁇ ne, streptomycin and tribasic copper sulfate
  • acaricides such as binapacryl, oxythioquinox, chlorobenzilate, dicofol, dienochlor, cyhexatin, hexythiazox, amitraz, propargite, tebufenpyrad and fenbutatin oxide
  • biological agents such as
  • Arthropod pests are controlled and protection of agronomic, horticultural and specialty crops, animal and human health is achieved by applying one or more of the compounds of this invention, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
  • the present invention further comprises a method for the control of foliar and soil inhabiting arthropods and nematode pests and protection of agronomic and/or nonagronomic crops, comprising applying one or more of the compounds of Formula I, or compositions containing at least one such compound, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
  • a preferred method of application is by spraying.
  • granular formulations of these compounds can be applied to the plant foliage or the soil.
  • the compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use.
  • a preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, and synergists and other solvents such as piperonyl butoxide often enhance compound efficacy.
  • the rate of application required for effective control will depend on such factors as the species of arthropod to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.001 kg/hectare may be sufficient or as much as 8 kg hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required.
  • TESTS demonstrate the control efficacy of compounds of this invention on specific pests.
  • the pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A, B, C and D for compound descriptions.
  • Test units each consisting of a H.I.S. (high impact styrene) tray with 16 cells were prepared.
  • Wet filter paper was placed in 12 cells with approximately 8 cm 2 of lima bean leaf. In the other four cells, was placed a 0.5 cm thick layer of wheat germ diet.
  • 75/25 acetone/distilled water solvent were sprayed into the tray and cup. Spraying was accomplished by passing the tray and cup, on a conveyer belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.5 pounds of active ingredient per acre (about 0.55 kg/ha or 1000 ppm) at 30 p.s.i. (207 kPa). The insects were transferred from the 8 ounce cup to the H.I.S tray (one insect per cell). The trays were then covered and held at 27°C and 50% relative humidity for 48 h, after which time readings were taken on the 12 cells with lima bean leaves. The 4 remaining cells were read at 6-8 days for a delayed toxicity reading. Of the compounds tested, the following resulted in greater than or equal to 80% mortality and/or development activity: 11, 13, 27, 28, 31, 36, 62, and 63.
  • Test units each consisting of an 8 ounce (230 mL) plastic cup containing a one-inch square (2.54 cm 2 ) of a wheatgerm diet, were prepared. The test units were sprayed as described in TEST A and using the same rate with individual solutions of the test compounds. After the spray on the cups had dried, five second-instar larvae of the southern corn rootworm (Diabrotica undecimpunctata howardi) were placed into each cup. The cups were then held at 27°C and 50% relative humidity for 48 h, after which time mortality readings were taken. The same units were read again at 6-8 days.
  • Test units were prepared from a series of 12 ounce (350 mL) cups, each containing oat (Avena sativa) seedlings in a 1 inch (2.54 cm) layer of sterilized soil.
  • the test units were sprayed as described in TEST A and using the same rate with individual solutions of the test compounds. After the oats had dried from the spraying, between 10 and 15 adult aster leafhoppers (Mascrosteles fascifrons) were aspirated into each of the cups.
  • the cups were covered with vented lids and held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 7, 8, 9, 11, 14, 20, 21, 22, 23, 26, 27, 28, 30, 31, 32, 34, 35, 36, 42, 54, 62, 63, and 64.
  • Test units consisting of 9 ounce (260 mL) cups containing five adult boll weevils (Anthonomus grandis grandis) were prepared. The test units were sprayed as described in TEST A and using the same rate with individual solutions of the test compounds. Each cup was covered with a vented lid and held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 1, 6*, 7, 10, 11, 13, 17, 28, 35, 36, 54, 62, and 63.

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Abstract

Composés arthropodicides, compositions et utilisation de composés possédant la formule (I), dans laquelle A est sélectionné à partir du groupe H, CN, alkyle C1-C6, haloalkyle C1-C6 et halogène; E est sélectionné à partir du groupe H, alkyle C1-C6, haloalkyle C1-C6, alkényle C2-C6, halogène, CH2(alcoxy C1-C3), CH(alcoxy C1-C3), CH(alcoxy C1-C3)(alkényle C3-C5), alcoxycarbonyle C2-C6, alcoxycarbonylalkyle C3-C7, P(X)(alcoxy C1-C3)2, P(X)(alkyle C1-C3)2, P(X)(alcoxy C1-C3)(alkyle C1-C3) et phényle éventuellement substitué par 1-3 substituants sélectionnés indépendamment à partir du groupe halogène, alkyle C1-C3, haloalkyle C1-C3, alcoxy C1-C3, haloalcoxy C1-C3, CN et NO2; E étant différent de H quand A représente H, M représente CH2CH2 ou CH=CH et 2 représente CH2 ou CH2CH2, ou A et E sont pris ensemble et sélectionnés à partir du groupe alkylène C2-C3 et CH2C(O)CH2, chaque groupe étant éventuellement substitué par 1-6 substituants sélectionnés indépendamment à partir du groupe alkyle C1-C3, alcoxy C1-C3, alkylthio C1-C3 et halogène; L est sélectionné à partir du groupe H, CN, alkyle C1-C4, haloalkyle C1-C4, alcoxycarbonyle C2-C6, alcoxycarbonylalkyle C3-C7 et halogène; au moins un de A ou L étant CN; ou L et E sont pris ensemble et sélectionnés à partir du groupe alkylène C2-C5, =CH2 et CH2CH2GCH2CH2, chaque groupe étant éventuellement substitué par 1-6 substituants sélectionnés indépendamment à partir du groupe alkyle C1-C3, alcoxy C1-C3, alkylthio C1-C3, alkylthio et halogène; M est sélectionné à partir du groupe CH2CH2 éventuellement substitué par 1-2 substituants sélectionnés indépendamment à partir de U; CH=CH éventuellement substitué par 1-2 substituants sélectionnés indépendamment à partir de W; ou M est (a); Y est sélectionné à partir du groupe O et CH2 éventuellement substitué par 1-2 substituants sélectionnés indépendamment à partir de R1; Z est sélectionné à partir du groupe CH¿2? et CH2CH2 chacun éventuellement substitué par 1-2 substituants sélectionnés indépendamment à partir de R; ou Z représent O.
PCT/US1994/009524 1993-08-31 1994-08-30 Arthropodicides polycycliques WO1995006631A1 (fr)

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AU76731/94A AU7673194A (en) 1993-08-31 1994-08-30 Polycyclic arthropodicides

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US11527593A 1993-08-31 1993-08-31
US08/115,275 1993-08-31

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013102634A1 (fr) 2012-01-06 2013-07-11 Lonza Ltd Procédé de préparation de octahydrocyclopenta[c]pyrrole

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DE2022357A1 (de) * 1969-05-12 1970-11-19 Montedison Spa Neue polycyclische ungesaettigte Kohlenwasserstoffe und Verfahren zur Herstellung derselben
EP0084600A1 (fr) * 1981-10-16 1983-08-03 Bayer Ag Dérivés bicycliques substitués et leur emploi comme pesticide
WO1990004921A1 (fr) * 1988-11-04 1990-05-17 Frederick Coulston Pesticides non bioaccumulables

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2022357A1 (de) * 1969-05-12 1970-11-19 Montedison Spa Neue polycyclische ungesaettigte Kohlenwasserstoffe und Verfahren zur Herstellung derselben
EP0084600A1 (fr) * 1981-10-16 1983-08-03 Bayer Ag Dérivés bicycliques substitués et leur emploi comme pesticide
US4647581A (en) * 1981-10-16 1987-03-03 Bayer Aktiengesellschaft Bicyclic pesticidal agents
WO1990004921A1 (fr) * 1988-11-04 1990-05-17 Frederick Coulston Pesticides non bioaccumulables

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CHEMICAL ABSTRACTS, vol. 106, no. 17, 27 April 1987, Columbus, Ohio, US; abstract no. 137748b, DELUCA page 627; *
DISS. ABSTR. IND. B, vol. 47, no. 6, 1986, pages 2434 *
H. TAKAYA ET AL: "Nickel(0) Catalyzed [2+2] Cross-addition of Bicyclo[2.2.1]heptene Derivatives with Electon-deficient Olefins", BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, vol. 55, no. 3, 1982, TOKYO JP, pages 852 - 858 *
I. TABUSHI ET AL.: "Regio- and Stereospecific [2.pi.+2.sigma.+2.sigma.]Cycloaddition Reaction of Quadricyclane", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 94, 1972, WASHINGTON, DC US *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013102634A1 (fr) 2012-01-06 2013-07-11 Lonza Ltd Procédé de préparation de octahydrocyclopenta[c]pyrrole
US9126930B2 (en) 2012-01-06 2015-09-08 Lonza Ltd. Method for preparation of octahydrocyclopenta[c]pyrrole

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