WO1991017659A1 - Nitroethyelenes et nitroguanidines arthropodicides - Google Patents

Nitroethyelenes et nitroguanidines arthropodicides Download PDF

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Publication number
WO1991017659A1
WO1991017659A1 PCT/US1991/003118 US9103118W WO9117659A1 WO 1991017659 A1 WO1991017659 A1 WO 1991017659A1 US 9103118 W US9103118 W US 9103118W WO 9117659 A1 WO9117659 A1 WO 9117659A1
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Prior art keywords
alkyl
group
formula
compounds
haloalkyl
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PCT/US1991/003118
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English (en)
Inventor
James Mood Chapman
Willy Dietrich Kollmeyer
Joseph William Kosh
Stephen Frederick Mccann
Joseph Walter Sowell
Faith Blersch Zwick
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E.I. Du Pont De Nemours And Company
University Of South Carolina
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Application filed by E.I. Du Pont De Nemours And Company, University Of South Carolina filed Critical E.I. Du Pont De Nemours And Company
Priority to JP91509844A priority Critical patent/JPH05507088A/ja
Publication of WO1991017659A1 publication Critical patent/WO1991017659A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/06—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
    • 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
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/20—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with substituted hydrocarbon radicals, directly attached to ring carbon atoms

Definitions

  • This invention concerns nitroethylene and nitroguanidine compositions and a method for using the nitroethylene and
  • nitroguanidine compounds of Formula I to control arthropods in agronomic and nonagronomic environments.
  • Insecticidal nitroethylene compounds are disclosed in EPA 302,389 and EPA 302,833.
  • Insecticidal alkylenediamines are disclosed in U.S. 4,025,529 and U.S. 4,806,553.
  • Heterocyclic alkylenediamine insecticides are disclosed in EPA 254,859.
  • Insecticidal 1-nitro-2,2-diaminoethylenes are disclosed in AU 88/20510.
  • U.K. 1,483,633 discloses 2- (nitromethylene)-1,3-diazocycloalkanes as insecticides.
  • the invention pertains to use of compounds of Formula I, including all geometric and stereoisomers, agriculturally suitable salts thereof, and agricultural compositions containing them, for the control of
  • Z is selected from the group CHNO 2 and NNO 2 ;
  • X is selected from S(O) n ;
  • A is selected from the group C 1 -C 4 alkylene optionally
  • R 1 is selected from the group C 1 -C 4 alkyl, C 1 -C 4 haloalkyl,
  • n 0, 1 or 2;
  • R 2 and R 3 are independently selected from the group H, CH 2 CN, C 1 -C 4 alkyl, CHO, C 2 -C 4 alkylcarbonyl, C 2 -C 3
  • alkoxycarbonyl C 2 -C 4 alkoxyalkyl, C 3 -C 6 dialkoxyalkyl,
  • R 4 is selected from the group C 1 -C 4 alkyl, C 1 -C 4 haloalkyl,
  • R 2 and R 4 can be taken together as C 2 -C 3 alkylene or C 2 -C 3 alkenylene each optionally substituted with 1-4 C 1 -C 2 alkyl;
  • R 5 is selected from the group halogen, C 1 -C 2 alkyl, C 1 -C 2
  • haloalkyl C 1 -C 2 alkoxy, C 1 -C 2 thioalkyl, C 1 -C 2 halothioalkyl, C 1 -C 2 haloalkoxy, NO 2 and CN.
  • Preferred Method A for controlling plant and leaf hoppers comprises use of compounds of Formula I wherein Z is CHNO 2 .
  • Preferred Method B employs compounds of Formula I wherein Z is NNO 2 .
  • Preferred Method C employs compounds A wherein:
  • A is CH 2 CH 2 ;
  • R 1 is selected from the group C 1 -C 4 alkyl
  • R 2 and R 3 are independently selected from the group H, C 1 -C 4 alkyl, C 2 -C 3 alkoxycarbonyl and C 2 -C 4 alkylcarbonyl; and R 4 is selected from the group C 1 -C 4 alkyl.
  • Preferred Method D employs compounds A wherein:
  • R 2 and R 4 are taken together and independently selected from the group C 2 -C 3 alkylene and C 2 -C 3 alkenylene, each optionally substituted by 1-4 C 1 -C 4 alkyl.
  • Preferred Method E employs compounds C wherein X is S.
  • Preferred Method F employs compounds D wherein X is S.
  • This invention also concerns novel arthropodicidal compositions comprising an effective amount of a compound of Formula I and a carrier therefor which is effective to deliver the compound to agronomic and nonagronomic arthropods, particularly planthoppers and leafhoppers, and their environment so that said arthropods are controlled.
  • 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, isopropyl or the different butyl isomers.
  • Alkoxy denotes methoxy, ethoxy, n-propyloxy and isopropyloxy.
  • Alkenyl denotes straight chain or branched alkenes such as vinyl, 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl isomers.
  • Alkynyl denotes straight or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl isomers.
  • Alkylthio denotes methylthio, ethylthio and the different propylthio and butylthio isomers. Alkylsulfonyl and alkylamino are defined analogously to the above examples. Cycloalkyl denotes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • haloalkyl denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl” said alkyl can be partially or fully substituted with halogen atoms, which can be the same or different. Examples of haloalkyl include CH 2 CHF 2 , CF 2 CF 3 and CH 2 CHFCI.
  • 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 6.
  • C 1 -C 3 alkylsufonyl designates methylsulfonyl through
  • propylsulfonyl designates OCH 2 CH 3 and C 3 alkoxy
  • C 2 alkylcarbonyl designates C(O)CH 3 and C 4 alkylcarbonyl designates C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 ;
  • C 3 alkoxyalkyl designates CH 2 OCH 2 CH 3 and
  • CH 2 CH 2 OCH 3 designates CH 2 OCH 2 CH 2 CH 3 ,
  • C 4 dialkoxyalkyl designates CH 2 OCH 2 CH 2 OCH 3 .
  • the compounds of Formula I can be prepared by the reaction of nitroethenes and nitroimines of Formula II with an amine of Formula III (Scheme 1).
  • compounds of Formula I can be prepared by the reaction of nitroethenes and nitroimines of Formula IV with amines of Formula V (Scheme 2) using procedures which are analogous to those used for reactions of compounds of Formula II with compounds of
  • Formula II with compounds of Formula III are described. Typical conditions involve combination of II with a stoichiometric excess of III in a suitable solvent or combination of solvents at temperatures generally in the range of about 0 to 100°C.
  • suitable solvents typically have sufficient polarity to effect solution of the Formula II compound and the Formula III amine and include, but are not limited to, alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; esters such as ethyl acetate; water; and polar and aprotic solvents such as dimethylformamide and dimethylacetamide.
  • Amine III can also be used as its hydrochloride salt and in these cases an
  • A, X, Z, R 1 , R 2 , R 3 , and R 4 are as previously defined.
  • Compounds of Formula I include both geometrical and optical isomers as well as Z and E isomers around the nitroethene or imine double bond. These isomers may vary in their biological activity. In some instances, it may be desirable to obtain compounds which are geometrically and/or optically pure or which are enriched in one or more of the possible isomers. All such isomers are included within the scope of the invention. They, as well as all salts, are included within the term "compound(s)".
  • the generic formula (Formula I) encompasses certain compounds that may have long term stability problems and/or are difficult to prepare.
  • haloalkylamines when R 4 is C 1 to C 4 haloalkyl are unstable when the halo substituent is directly adjacent to nitrogen. These generally decompose to the corresponding hydrogen halides and imine.
  • Formula I compounds where A is a C 1 haloalkyl would be expected to be hydrolytically unstable. These compounds, however, are relatively few; their identity would be obvious to one skilled in the art, and their excision from the scope would unduly compUcate and lengthen the description of the invention.
  • Compounds of Formula II where Z is CHNO 2 can be prepared using processes known in the art involving reaction of nitroethene VI with an amine of Formula V (Scheme 3).
  • Compounds of Formula IV where Z is CHNO 2 can be prepared by procedures which are analogous to those for compounds of Formula II; therefore, for brevity, only the compounds of Formula II are described. Typical conditions involve the combination of equimolar amounts of V and VI in a suitable solvent or solvent mixture at temperatures in the range of about 0 to 100°C.
  • Suitable solvents typically have sufficient polarity to effect solution of V and VI and include, but are not limited to, alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydroniran and dioxane; esters such as ethyl acetate; polar aprotic solvents such as dimethylformamide and dimethylacetamide; water as well as mixtures of solvents.
  • Amines of Formula V can be prepared by reaction of an alkylating agent of Formula VII with an amine of Formula VIII (Scheme 4). Typical conditions involve combination of VII with a stoichiometric excess of VIII in a suitable solvent or combination of solvents at temperatures in the range of about 0 to 100°C. Suitable solvents or solvent mixtures typically have sufficient polarity to effect solution of the Formula VIII amine and the Formula V product and include, but are not limited to, alcohols such as methanol, ethanol and isopropanol; ethers such as tetrahydrofuran and dioxane; water and acetonitrile. Amine VIII can also be used as its hydrochloride salt and in these cases an equivalent amount of a base (such as potassium hydroxide) is added to the reaction mixture.
  • Y is a leaving group
  • A, X, R 1 and R 2 are as previously defined.
  • B is C 2 -C 3 alkylene or C 2 -C 3 alkenylene each optionally substituted with 1-4 C 1 -C 2 alkyl;
  • Y is a leaving group
  • A, X, R 1 , R 3 , and Z are as previously defined.
  • Reactions such as those shown in Scheme 5 are typically carried out by treatment of a solution of Formula IX and VII compounds in a suitable solvent with a proton acceptor such as, but not limited to, sodium hydride at a temperature of about 0 to 100°C.
  • a proton acceptor such as, but not limited to, sodium hydride at a temperature of about 0 to 100°C.
  • Suitable solvents include, but are not limited to, dimethylformamide and THF.
  • Scheme 7 illustrates the formation of Formula IX compounds. Procedures for this transformation are analogous to those previously described for Scheme 5.
  • Formula XI compounds may exist as the amino-imidazole tautomer, XII.
  • Scheme 8 illustrates the formation of Formula IX nitroguanidines using the precursors of Formula XII.
  • Scheme 9 illustrates the formation of Formula I compounds where Z is NNO 2 and B is an optionally
  • R 6 and R 7 are H, or C 1 -C 2 alkyl.
  • Formula XII nitroaminoimidazoles can be formed by the reaction of S-methyl-N-nitro-isothiourea with amino-acetals of Formula X II I.
  • Typical reaction conditions involve the treatment of a mixture of XIII and S-methyl-N-nitroisothiourea in a suitable solvent with 0 to 5 equivalents of an acid catalyst such as hydrochloric acid at a temperature of 0°C to the reflux temperature of the solvent.
  • Typical solvents include, but are not limited to, methanol, ethanol and isopropanol. Scheme 10 illustrates this transformation. SCHEME 10
  • R 8 is an alkyl or aryl group
  • R 6 and R 7 are as previously defined.
  • Compounds of Formula XI where B is an optionally substituted C 2 -C 3 alkylene and Z is CHNO 2 can be prepared by the reactions of diamines of Formula XIV with V in a suitable solvent at temperatures in the range of about 0 to 100°C.
  • suitable solvents include, but are not limited to, alcohols such as methanol, ethanol and isopropanol, and water, as well as other polar solvents. Typical reactions involve the use of equimolar amounts of V and XIV. Scheme 11 illustrates this transformation.
  • Formula XIV diamines with nitroguanidine using procedures completely analogous to those described for Scheme 11 and, for the sake of brevity, will not be discussed further.
  • Formula XIV compounds are 1,2- and 1,3-diamines whose preparations are known in the art.
  • Compounds of Formula II where Z is NNO 2 can be prepared by the reaction of N-nitroimines of Formula XV with an alkylating agent of Formula VII in a suitable solvent in the presence of a proton acceptor (Scheme 12).
  • Typical proton acceptors are metal hydrides such as sodium hydride, metal alkoxides such as sodium methoxide or potassium tbutoxide and carbonates such as cesium carbonate.
  • Suitable solvents for reactions using metal hydride include DMF and THF.
  • Suitable solvents for reactions using metal alkoxides include alcohols such as methanol, ethanol and t-butanol and THF.
  • Suitable solvents for reactions using carbonate bases include methanol, ethanol and acetonitrile.
  • the reactions are typically run at temperatures that range from 0 to 100°C. Typical reactions involve the use of equimolar amounts of VII and XV.
  • R 2 is as previously defined.
  • Compounds of Formula XV can be prepared by the reaction of an alkylating agent of Formula XVIII with S-methyl-N-nitroisothiourea (Scheme 14) using procedures that are analogous to those described for Scheme 12.
  • Compounds of Formula XVI can be prepared by the reaction of an alkylating agent of Formula X with S-methyl-N-nitroisothiourea (Scheme 15) using procedures that are analogous to those described for Scheme 12.
  • R 2 , R 3 , R 4 and Y are as previously defined.
  • Compounds of Formula I where X is SO can be obtained by reaction of the corresponding compound of Formula I where X is S with a variety of oxidants including, but not limited to, peracids, periodates and hydroperoxides in a suitable solvent.
  • Compounds of Formula I where X is SO 2 can be obtained using analogous reaction conditions wherein the amount of oxidant used is greater than or equal to two oxidizing equivalents.
  • Step A N-Methyl-2-( methylthio)ethanamine
  • step B Methyl N-methyl-N-[2-(methylthio)ethyl]-2-nitro- ethanimidothioate
  • Step C N,N'-Dimethyl-N-[2-(methylthio)ethyl]-2-mtro-1,1- ethenediamine
  • Aqueous sodium hydroxide (50%, 0.5 mL, 9.0 mmoles) was added to a solution of the product of Step B (0.4 g, 1.8 mmoles), methylamine hydrochloride (0.6 g, 9 mmoles), ethanol (5 mL), tetrahydrofuran (2 mL) and water (1 mL).
  • the resulting solution was stirred for 20 hours at room temperature and then silica gel (2 g) was added and the solvent was removed. Flash chromatography of the residue on silica gel using 5% ethanol in methylene chloride gave 0.36 g (98%) of the title compound as a yellow oil.
  • Step B 1-[2-(Methylthio)ethyl]-2-(nitroethylene)imidazolidine
  • Step A The product from Step A (2.0 g, 0.016 moles) was added to a suspension of 60% sodium hydride (0.7 g, 0.017 moles) and 31 mL of DMF at room temperature. The resulting mixture was stirred for 10 min and then 1.5 mL (0.016 moles) of 2-chloroethyl methyl sulfide was added. Resulting mixture was heated at 100°C for 12 h and then cooled to room temperature. Ethanol, 20 ml, was added and the reaction was
  • the compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent or an organic solvent.
  • Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like. Many of these can be applied directly.
  • Sprayable formulations can be extended in suitable media and used at spray volumes of from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation.
  • the formulations broadly, contain from less than about 1% to 99% by weight of active ingredient(s) and at least one of a) about 0.1% to 20% surfactant(s) and b) about 5% to 99% solid or liquid diluent(s). More specifically, they will contain effective amounts of these ingredients in the following
  • Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts.
  • Typical liquid diluents and solvents are described in Marsden, “Solvents Guide,” 2nd Ed., Intersdence, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C. "McCutcheon's Detergents and
  • All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc.
  • ingredients should be approved by the U.S. Environmental Protection Agency for the use intended.
  • Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill.
  • 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 J. E. Browning, "Agglomeration",
  • the ingredients are combined and stirred with gentle warming to speed solution.
  • a fine screen filter is included in packaging operation to insure the absence of any extraneous undissolved material in the product.
  • Example C The active ingredient is mixed with the inert materials in a blender. After grinding in a hammermill, the material is re-blended and sifted through a 50 mesh screen.
  • the wettable powder and the pyrophyllite diluent are thoroughly blended and then packaged.
  • the product is suitable for use as a dust.
  • the active ingredient is dissolved in a volatile solvent such as acetone and sprayed upon dedusted and pre-warmed attapulgite granules in a double cone blender.
  • a volatile solvent such as acetone
  • the acetone is then driven off by heating.
  • the granules are then allowed to cool and are packaged.
  • the ingredients are blended in a rotating mixer and water sprayed on to accomplish granulation. When most of the material has reached the desired range of 0.1 to 0.42 mm (U.S.S. No. 18 to 40 sieves), the granules are removed, dried, and screened. Oversize material is crushed to produce additional material in the desired range. These granules contain 4.5% active ingredient.
  • Example G The ingredients are combined and stirred to produce a solution suitable for direct, low volume application.
  • Example G The ingredients are combined and stirred to produce a solution suitable for direct, low volume application.
  • the ingredients are thoroughly blended and pulverized to make a driftless dust.
  • the material can then be packaged.
  • the ingredients are combined and ground together in a sand mill to produce particles substantially all below 5 microns.
  • the product can be used directly, extended with oils, or emulsified in water.
  • the active ingredient and surfactant blend are dissolved in a suitable solvent such as acetone and sprayed onto the ground corn cobs.
  • a suitable solvent such as acetone
  • the granules are then dried and packaged.
  • Compounds of Formula I can also be mixed with one or more other insectiddes, fungicides, nematoddes, bactericides, acariddes, or other biologically active compounds to form a multi-component pestidde giving an even broader spectrum of effective agricultural protection.
  • Other agricultural protectants with which compounds of this invention can be formulated are: Insecticides:
  • Additional insectiddes are listed hereafter by their common names: triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fonophos,
  • the compounds of this invention exhibit activity in agricultural and non-agricultural environments against a wide spectrum of foliar and soil-inhabiting arthropods 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.
  • arthropods 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.
  • the compounds are particularly useful against
  • brown planthopper including brown planthopper, small brown planthopper, green leafhopper and other rice plant and leafhoppers, other leafhoppers (Cicadellidae) and planthoppers (Superfamily Ful goroidea espedally Cixiidae,
  • Thysanoptera adults and immatures of the order Thysanoptera including onion thrips and other foliar feeding thrips;
  • Insect pests of the order Hymenoptera including carpenter ants, bees, hornets and wasps;
  • Insect pests of the order Diptera including house flies, stable flies, face flies, horn flies, blow flies, and other muscoid fly pests, horse flies, deer flies and other Bradiycera. mosquitoes, black flies, biting midges, sand flies, sdarids, and other Nematocera;
  • Insect pests of the order Orthoptera including cockroaches and crickets;
  • Insect pests of the order Mallophnga and Anoplura induding the head louse, body louse, chicken head louse and other sucking and chewing parasitic lice that attack man and animals;
  • Insect pests of the order Siphonoptera including the cat flea, dog flea and other fleas.
  • a more preferred spectrum of activity for the compounds of this invention are foliar and soil-inhabiting arthropods which are pests of agronomic crops, as well as greenhouse, ornamental, nursery and fruit crops.
  • the compounds of this invention display activity against
  • the specific spedes for which control is exemplified are: aster leafhopper (Macrosteles fascifrons), rice planthopper (Sogatodes orzicola), black been aphid (Aphis fahae), and southern corn rootworm (Diabrotica undecimpunctata).
  • aster leafhopper Macrosteles fascifrons
  • rice planthopper Sogatodes orzicola
  • black been aphid Aphis fahae
  • southern corn rootworm Diabrotica undecimpunctata
  • Arthropod pests are controlled by applying one or more of the Formula I compounds of this invention, in an effective amount, to the locus of infestation, to the area to be protected, or directly on the pests to be controlled. Because of the diversity of habitat and behavior of these arthropod pest spedes, many different methods of application are employed. A preferred method of application is by spraying with equipment that directs the compo ⁇ md to the environment of the pests, on the foliage, in the soil or paddy, to the plant part that is infested or needs to be protected. Alternatively, granular formulations of these compounds can be applied to or incorporated into the soil, paddy or nursery box.
  • 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 in a carrier that may include diluents and/or
  • Preferred methods of application involve spraying a water dispersion, refined oil solution or dust containing the compound.
  • the rate of application of the Formula I compounds required for effective control will depend on such factors and the species of arthropod to be controlled, the pest's life cycle, life stage, location, time of year, host crop, feeding and mating behavior, ambient moisture and temperature, and the like. In general, application rates of 0.55-0.055 kg of active ingredient per hectare are suffident to provide large-scale effective control of pests in agronomic ecosystems under normal circumstances. Application rates as low as about 0.1 mg/sq meter or less up to about 150 mg/sq meter or more can be employed on arthropods in a nonagronomic environment such as the household or other building or nonagronomic locus.
  • Test units were prepared from a series of 12 oz. (350 ml) cups, each containing oat (Avena satavia) seedlings in a 1-inch layer of sterilized soil. Solutions of test compounds were prepared in a 75 acetone:25 water solvent and applied to the seedlings with a hydraulic sprayer by passing three sets of cups on a conveyor belt, beneath a flat-fan nozzle calibrated to deliver 0.055 kg/HA at 30 psi (207 kPa). Approximately 1 hour after treatment, a thin layer of sand was placed over the soil in each cup, the units capped and 10-20 adult aster leafhoppers (Macrosteles fascifrons) each aspirated into the cups. The units were held at 27°C, 50% RH and 14L:10D for 48 hours, after which time mortality readings were taken. The following table lists the activity of the compounds against aster leafhopper.
  • Example 3 The test procedure of Example 3 was repeated for efficacy against adults of the rice planthopper (Sogatodes orzicola) except four sets of cups containing rice (Oryza satavia) seedlings were treated.
  • the sprayer was calibrated to deliver 0.055 kg/HA. The results are tabulated below.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

On élimine les arthropodes dans des environnements agronomiques et non agronomiques en mettant en contact lesdits arthropodes ou leur environnement avec une dose efficace de la formule (I), dans laquelle R1 à R4, X, A et Z sont définis dans le texte, comprenant des compositions arthropodicides contenant ledit ou lesdits composé(s).
PCT/US1991/003118 1990-05-17 1991-05-10 Nitroethyelenes et nitroguanidines arthropodicides WO1991017659A1 (fr)

Priority Applications (1)

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JP91509844A JPH05507088A (ja) 1990-05-17 1991-05-10 殺節足動物性ニトロエチレン及びニトログアニジン

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US52473890A 1990-05-17 1990-05-17
US524,738 1990-05-17

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WO1991017659A1 true WO1991017659A1 (fr) 1991-11-28

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EP (1) EP0530259A1 (fr)
JP (1) JPH05507088A (fr)
CN (1) CN1057833A (fr)
WO (1) WO1991017659A1 (fr)

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* Cited by examiner, † Cited by third party
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WO1993021161A1 (fr) * 1992-04-13 1993-10-28 E.I. Du Pont De Nemours And Company Nitroguanidines et nitroethylenes arthropodicides
US5504081A (en) * 1992-09-29 1996-04-02 Bayer Aktiengesellschaft Combating fish parasites
US5547965A (en) * 1994-04-27 1996-08-20 Bayer Aktiengesellschaft Use of substituted amines for the treatment of brain function disorders
US6114362A (en) * 1994-07-28 2000-09-05 Bayer Aktiengesellschaft Compositions for the control of plant pests
US6149913A (en) * 1998-11-16 2000-11-21 Rhone-Poulenc Ag Company, Inc. Compositions and methods for controlling insects
US6156703A (en) * 1999-05-21 2000-12-05 Ijo Products, Llc Method of inhibiting fruit set on fruit producing plants using an aqueous emulsion of eicosenyl eicosenoate and docosenyl eicosenoate
US6232309B1 (en) 1989-03-09 2001-05-15 Nihon Bayer Agrochem K.K. Insecticidal heterocyclic compounds
US6232328B1 (en) 1994-05-20 2001-05-15 Bayer Aktiengesellschaft Non-systemic control of parasites
US6344453B1 (en) 1989-03-09 2002-02-05 Kozo Shiokawa Insecticidal heterocyclic compounds
US6369054B1 (en) 1998-02-23 2002-04-09 Bayer Ag Aqueous agents for combating parasitic insects and acarina in human beings
WO2002043494A2 (fr) 2000-11-30 2002-06-06 Bayer Healthcare Llc Compositions destinees a produire une activite acaricide amelioree
US6528079B2 (en) 1996-06-04 2003-03-04 Bayer Aktiengesellschaft Shaped bodies which release agrochemical active substances
US6534529B2 (en) 1995-12-27 2003-03-18 Bayer Aktiengesellschaft Synergistic insecticide mixtures
US6716874B1 (en) 1999-03-24 2004-04-06 Bayer Aktiengesellschaft Synergistic insecticide mixtures
US6893651B1 (en) 1999-10-07 2005-05-17 Bayer Aktiengesellschaft Active ingredient combinations having insecticidal and acaricidal properties
US7001903B2 (en) 1998-05-26 2006-02-21 Bayer Aktiengesellschaft Synergistic insecticidal mixtures
US7659228B2 (en) 1995-12-27 2010-02-09 Bayer Aktiengesellschaft Synergistic insecticide mixtures
US7728011B2 (en) 2001-04-09 2010-06-01 Bayer Animal Health Gmbh Dermally applicable liquid formulations for controlling parasitic insects on animals
US8232261B2 (en) 2003-07-18 2012-07-31 Bayer Cropscience Lp Method of minimizing herbicidal injury
US8268750B2 (en) 2003-11-14 2012-09-18 Bayer Cropscience Ag Combination of active substances with insecticidal properties
US9919979B2 (en) 2005-01-21 2018-03-20 Bayer Cropscience Lp Fertilizer-compatible composition

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EP0254859A2 (fr) * 1986-07-01 1988-02-03 Nihon Tokushu Noyaku Seizo K.K. Alkylènediamines
EP0381130A2 (fr) * 1989-01-31 1990-08-08 Takeda Chemical Industries, Ltd. Préparation d'amines alpha-insaturées
EP0302389B1 (fr) * 1987-08-01 1993-12-22 Takeda Chemical Industries, Ltd. Amines alpha-insaturées, leur préparation et utilisation

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GB1483633A (en) * 1973-11-01 1977-08-24 Shell Int Research 2-(nitromethylene)-1,3-diazacycloalkanes insecticidal compositions containing them and their use for controlling unwanted insects
FR2322849A1 (fr) * 1975-09-08 1977-04-01 Shell Int Research Preparation d'aminals et leur utilisation comme pesticides
EP0254859A2 (fr) * 1986-07-01 1988-02-03 Nihon Tokushu Noyaku Seizo K.K. Alkylènediamines
EP0302389B1 (fr) * 1987-08-01 1993-12-22 Takeda Chemical Industries, Ltd. Amines alpha-insaturées, leur préparation et utilisation
EP0381130A2 (fr) * 1989-01-31 1990-08-08 Takeda Chemical Industries, Ltd. Préparation d'amines alpha-insaturées

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6344453B1 (en) 1989-03-09 2002-02-05 Kozo Shiokawa Insecticidal heterocyclic compounds
US6232309B1 (en) 1989-03-09 2001-05-15 Nihon Bayer Agrochem K.K. Insecticidal heterocyclic compounds
WO1993021161A1 (fr) * 1992-04-13 1993-10-28 E.I. Du Pont De Nemours And Company Nitroguanidines et nitroethylenes arthropodicides
CN1061213C (zh) * 1992-09-29 2001-01-31 拜尔公司 防治鱼类寄生虫的方法
US5504081A (en) * 1992-09-29 1996-04-02 Bayer Aktiengesellschaft Combating fish parasites
US5547965A (en) * 1994-04-27 1996-08-20 Bayer Aktiengesellschaft Use of substituted amines for the treatment of brain function disorders
US6232328B1 (en) 1994-05-20 2001-05-15 Bayer Aktiengesellschaft Non-systemic control of parasites
US6896891B2 (en) 1994-05-20 2005-05-24 Bayer Aktiengesellschaft Non-systemic control of parasites
US6329374B1 (en) 1994-05-20 2001-12-11 Bayer Aktiengesellschaft Non-systemic control of parasites
US8728507B2 (en) 1994-05-20 2014-05-20 Bayer Intellectual Property Gmbh Non-systemic control of parasites
US7517535B2 (en) 1994-05-20 2009-04-14 Bayer Animal Health Gmbh Non-systemic control of parasites
US6429206B2 (en) 1994-05-20 2002-08-06 Bayer Aktiengesellschaft Non-systemic control of parasites
US6495573B2 (en) 1994-05-20 2002-12-17 Bayer Aktiengesellschaft Non-systemic control of parasites
US6613783B2 (en) 1994-05-20 2003-09-02 Bayer Aktiengesellschaft Non-systemic control of parasites
US7884049B2 (en) 1994-07-28 2011-02-08 Bayer Cropscience Ag Compositions for the control of plant pests
US7008903B2 (en) 1994-07-28 2006-03-07 Bayer Aktiengesellschaft Pesticide
US6114362A (en) * 1994-07-28 2000-09-05 Bayer Aktiengesellschaft Compositions for the control of plant pests
US7659228B2 (en) 1995-12-27 2010-02-09 Bayer Aktiengesellschaft Synergistic insecticide mixtures
US6534529B2 (en) 1995-12-27 2003-03-18 Bayer Aktiengesellschaft Synergistic insecticide mixtures
US6680065B2 (en) 1996-06-04 2004-01-20 Bayer Aktiengesellschaft Shaped bodies which release agrochemical active substances
US6528079B2 (en) 1996-06-04 2003-03-04 Bayer Aktiengesellschaft Shaped bodies which release agrochemical active substances
US6369054B1 (en) 1998-02-23 2002-04-09 Bayer Ag Aqueous agents for combating parasitic insects and acarina in human beings
CN100403903C (zh) * 1998-05-26 2008-07-23 拜尔公司 增效杀虫混合物
US7001903B2 (en) 1998-05-26 2006-02-21 Bayer Aktiengesellschaft Synergistic insecticidal mixtures
US6149913A (en) * 1998-11-16 2000-11-21 Rhone-Poulenc Ag Company, Inc. Compositions and methods for controlling insects
US6716874B1 (en) 1999-03-24 2004-04-06 Bayer Aktiengesellschaft Synergistic insecticide mixtures
US6156703A (en) * 1999-05-21 2000-12-05 Ijo Products, Llc Method of inhibiting fruit set on fruit producing plants using an aqueous emulsion of eicosenyl eicosenoate and docosenyl eicosenoate
US6893651B1 (en) 1999-10-07 2005-05-17 Bayer Aktiengesellschaft Active ingredient combinations having insecticidal and acaricidal properties
US8841294B2 (en) 1999-10-07 2014-09-23 Bayer Cropscience Ag Active ingredient combinations having insecticidal and acaricidal properties
WO2002043494A2 (fr) 2000-11-30 2002-06-06 Bayer Healthcare Llc Compositions destinees a produire une activite acaricide amelioree
US7728011B2 (en) 2001-04-09 2010-06-01 Bayer Animal Health Gmbh Dermally applicable liquid formulations for controlling parasitic insects on animals
US8232261B2 (en) 2003-07-18 2012-07-31 Bayer Cropscience Lp Method of minimizing herbicidal injury
US8426339B2 (en) 2003-07-18 2013-04-23 Bayer Cropscience Lp Method of minimizing herbicidal injury
US8268750B2 (en) 2003-11-14 2012-09-18 Bayer Cropscience Ag Combination of active substances with insecticidal properties
US8993483B2 (en) 2003-11-14 2015-03-31 Bayer Intellectual Property Gmbh Combination of active substances with insecticidal properties
US9919979B2 (en) 2005-01-21 2018-03-20 Bayer Cropscience Lp Fertilizer-compatible composition

Also Published As

Publication number Publication date
JPH05507088A (ja) 1993-10-14
CN1057833A (zh) 1992-01-15
EP0530259A1 (fr) 1993-03-10

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