Classifications

• • 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;
• 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.
• R 6 and R 7 are H, or C 1 -C 2 alkyl.
• 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
• 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.
• 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 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.
• 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.
• 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:
• 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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