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WO1997005145A1 - Tetrahydropyrimidines arthropodicides - Google Patents

Tetrahydropyrimidines arthropodicides Download PDF

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Publication number
WO1997005145A1
WO1997005145A1 PCT/US1995/009704 US9509704W WO9705145A1 WO 1997005145 A1 WO1997005145 A1 WO 1997005145A1 US 9509704 W US9509704 W US 9509704W WO 9705145 A1 WO9705145 A1 WO 9705145A1
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WIPO (PCT)
Prior art keywords
group
independently selected
optionally substituted
alkyl
substituents independently
Prior art date
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PCT/US1995/009704
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English (en)
Inventor
Stephen Frederick Mccann
Original Assignee
E.I. Du Pont De Nemours And Company
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Priority to PCT/US1995/009704 priority Critical patent/WO1997005145A1/fr
Publication of WO1997005145A1 publication Critical patent/WO1997005145A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/30—Germanium compounds

Definitions

  • the present invention pertains to tetrahydropyrimidines which are useful as arthropodicides.
  • U.S. 4,831,036 discloses insecticidal tetrahydropyrimidines that do not suggest those of the instant invention.
  • 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:
  • X is selected from the group Si and Ge;
  • A is selected from the group C 1 -C 20 alkylene, C 2 -C 20 alkenylene, C 2 -C 20
  • alkynylene C 3 -C 8 cycloalkylene, C 7 -C 10 aralkylene and phenyiene, each group optionally substituted with 1-3 substituents independently selected from W; or A is a direct bond;
  • R 1 and R 3 are independently selected from the group H, C 1 -C 10 alkyl, C 2 -C 10 alkenyl or C 2 -C 10 alkynyl, each group optionally substituted with 1-2 substituents independently selected from the group halogen, CN, C(O)R 7 , C(S)R 7 , NO 2 , OH, SC(O)R 7 , SC(S)R 7 , OC(O)R 7 , OC(S)R 7 , NR 8 C(O)R 7 , NR 8 C(S)R 7 , SH, Si(R 8 )(R 9 )(R 10 ), C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino, C 3 -C 8 cycloalkyl and phenyl optionally substituted with 1-3 substituents independently
  • R 2 is selected from the group H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl,
  • R 2 and R 3 can be taken together as CH 2 CH 2 and CH 2 CH 2 CH 2 each group
  • R 4 is selected from the group H and C 3 -C 6 trialkylsilyl; or R 4 is selected from the group C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 1 -C 10 alkoxy, C 1 -C 10 alkylthio, phenyl, phenoxy, phenylthio and naphthyl, each group optionally substituted with 1-3 substituents independently selected from W 1 ;
  • R 5 and R 6 are independently selected from the group C 1 -C 10 alkyl, C 2 -C 10
  • R 7 is selected from the group H, NH 2 , OH, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino and phenyl optionally substituted with 1-3 substituents independently selected from W 1 ;
  • R 8 is H; or R 8 is selected from the group C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 1 -C 10 alkoxy, phenoxy, phenyl and naphthyl, each group optionally substituted with 1-3 substituents independently selected from W 1 ;
  • R 9 and R 10 are independently selected from the group C 1 -C 10 alkyl, C 2 -C 10
  • alkenyl C 2 -C 10 alkynyl, C 1 -C 10 alkoxy, phenoxy, phenyl and naphthyl, each group optionally substituted with 1-3 substituents independently selected from W 1 ; and OH;
  • R 1 - is selected from the group H, NH 2 , OH, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 2 alkylthio, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino and phenyl optionally substituted with 1-3 substituents independently selected from W 1 ;
  • W is selected from the group halogen, CN, NO 2 , OH, C 1 -C 6 alkyl, C 1 -C 6
  • W 1 is selected from the group halogen, CN, NO 2 , C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy, C 1 -C 2 haloalkoxy, C 1 -C 2 alkylthio, C 1 -C 2 haloalkylthio, C 1 -C 2 alkylsulfonyl, C 1 -C 2 haloalkylsulfonyl, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino and C 3 -C 6 trialkylsilyl;.
  • Preferred Compounds A are compounds of Formula I wherein
  • A is C 1 -C 6 alkylene
  • R 1 is C 1 -C 3 alkyl substituted with a 5- or 6-membered aromatic ring, attached through carbon or nitrogen, containing 1 to 4 heteroatoms independently selected from the group 0-4 nitrogen, 0-1 oxygen, and 0-1 sulfur, the ring optionally substituted with 1-3 substituents independently selected from W 1 ;
  • R 4 is selected from the group C 1 -C 10 alkyl and phenyl, each group
  • R 5 and R 6 are independently selected from the group C 1 -C 10 alkyl and phenyl, each group optionally substituted with 1-3 substituents independently selected from W 1 ;
  • W 1 is selected from the group halogen and C 1 -C 2 haloalkyl.
  • Preferred Compounds B are compounds of Preferred A wherein
  • X is Si
  • R 1 is CH 2 substituted with pyridyl, thiazole or isoxazole, the ring
  • R 2 and R 3 are taken together as CH 2 CH 2 or CH 2 CH 2 CH 2 , each group optionally substituted with 1-2 CH 3 ;
  • R 4 , R 5 and R 6 are independently selected from C 1 -C 3 alkyl, C 1 -C 3 alkoxy and phenyl.
  • Preferred Compounds C are compounds of Preferred A wherein
  • X is Si
  • R 1 is CH 2 substituted with pyridyl, thiazole or isoxazole, the ring
  • R 2 is selected from the group H and C 1 -C 3 alkyl
  • R 4 , R 5 and R 6 are independently selected from C 1 -C 3 alkyl, C 1 -C 3 alkoxy and phenyl.
  • Compound D of Preferred B which is:
  • Compound E of Preferred B 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.
  • 5- or 6-membered aromatic ring is defined as those rings which satisfy the H ⁇ ckel rule; examples include 5- or 6-membered monocyclic aromatic rings containing 0 to 4 heteroatoms such as phenyl, furyl, furazanyl, thienyl, pyrrolyl, pyrazolyl, oxazolyl, oxadiazolyl, imidazolyl, isoxazolyl, thiazolyl, thiadiazolyl isothiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl and triazinyl with said ring attached through any available carbon or nitrogen.
  • the aromatic ring when the aromatic ring is furyl, it can be 2-furyl or 3-furyl, for pyrrolyl, the aromatic ring is 1 -pyrrolyl, 2-pyrrolyl or 3-pyrrolyl, for pyridyl, the aromatic ring is 2-pyridyl, 3-pyridyl or 4-pyridyl and similarly for other monocyclic aromatic rings.
  • 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 isomers through C 10 -
  • alkylene examples include CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 and the different isomers through C 20 .
  • alkenyl denotes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different isomers through C 10 .
  • Alkynyl denotes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 3-propynyl and the different isomers through C 10 .
  • alkynylene examples include C ⁇ C, CH 2 G ⁇ C, C ⁇ CCH 2 and the different isomers through C 20 .
  • Alkoxy denotes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different isomers through C 10 .
  • Alkylthio denotes straight-chain or branched alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylsulfonyl denotes CH 3 S(O) 2 and CH 3 CH 2 S(O) 2 .
  • Alkylamino denotes methylamino, ethylamino, n-propylamino, isopropylamino and the different butylamino isomers.
  • Dialkylamino denotes nitrogen substituted with two alkyl groups, which may be different.
  • Examples include N,N-dimethylamino and N-ethyl-N-methylamino.
  • Cycloalkyl denotes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl and the different C 6 and C 7 isomers bonded to straight-chain or branched alkyl groups.
  • halogen either alone or in compound words such as "haloalkyl”, denotes fluorine, chlorine, bromine or iodine.
  • alkyl 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.
  • haloalkyl include F 3 C, ClCH 2 , CF 3 CH 2 and CF 3 CCl 2 .
  • haloalkynyl include HC ⁇ CCHCl, CF 3 C ⁇ C, CCl 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, CF 2 HCH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio examples include CCl 3 S, CF 3 S, and CCl 3 CH 2 S.
  • haloalkylsulfonyl examples include CF 3 SO 2 , CCl 3 SO 2 , CF 3 CH 2 SO 2 and CF 3 CF 2 SO 2 .
  • 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 20.
  • C 1 -C 20 alkylene designates methylene, ethylene, and propylene through dodecylene isomers
  • C 2 alkoxy designates CH 3 CH 2 O-
  • C 3 alkoxy designates CH 3 CH 2 CH 2 O- or
  • the compounds of Formula I can be prepared by the reaction of Formula II compounds with one or more equivalents of an amine of Formula III and at least two molar equivalents of formaldehyde in a suitable solvent as depicted in Scheme 1. These reactions are typically carried out at temperatures ranging from 0 °C to the reflux temperature of the solvent, with 0 °C-25 °C being preferred. Scheme 1 reactions are typically complete within one day, however, certain Scheme 1 reactions may require longer reaction times (up to 5 days).
  • Suitable solvents include alcohols such as methanol and ethanol, water, and polar aprotic solvents such as tetrahydrofuran and dimethylformamide.
  • Formaldehyde can be used in amounts of about 2-10 molar equivalents.
  • Either solid paraformaldehyde or aqueous solutions of formaldehyde can be used.
  • a strong, non-oxidizing acid such as hydrochloric acid
  • a hydrohalide or a hydrosulfonic acid salt of amine III can be used.
  • compounds of Formula II can be prepared by the reaction of Formula VI compounds with amines of Formula VII as depicted in Scheme 3 using conditions that are completely analogous to those described in Scheme 2.
  • Suitable solvents typically have sufficient polarity to effect solution of compounds of Formulas VII and VIII, and include alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; esters such as ethyl acetate; polar aprotic solvents such as dimethylformamide and dimethylacetamide; and water, as well as mixtures of solvents.
  • compounds of Formula I can be prepared by the reaction of tetrahydropyrimidines of Formula IX with amines of Formula VII as depicted in
  • compounds of Formula I (where R 1 is other than H) can be prepared by the reaction of compounds of Formula I (where R 1 is H) with an alkylating agent of Formula X in the presence of a proton acceptor in a suitable solvent.
  • Typical proton acceptors include NaH, KH, K 2 CO 3 , NaHCO 3 , andCs 2 CO 3
  • suitable solvents include DMF, THF, acetonitrile and water.
  • Scheme 7 reactions are carried out under phase transfer conditions using solvents that include toluene, dichloromethane, dichloroethane, ether, hexanes, benzene and the like and an aqueous base, including NaOH, KOH, NaHCO 3 , Na 2 CO 3 , K 2 CO 3 , among others.
  • phase transfer catalysts include tetrasubstituted ammonium halide salts, such as tetrabutylammonium iodide, benzyl triethyl ammonium bromide and the like. Reactions are typically carried out at temperatures ranging from 20-150 °C and are completed in 1 h to 3 days; however, 6 to 24 h is usually preferred. Scheme 7
  • Suitable solvents typically have sufficient polarity to effect solution of Formula XII and VIII compounds and include alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; esters such as ethyl acetate; polar aprotic solvents such as dimethylformamide and dimethylacetamide; and water, as well as mixtures of solvents.
  • Diamines of Formula XII can be formed by reaction of Formula X compounds wth a stoichiometric excess of amines of Formula XIII as depicted in Scheme 11. Typical reactions involve the use of 1.5-10 equivalents of Formula XIII compounds in solvents such as methanol, ethanol, isopropanol, THF, water or acetonitrile, among others.
  • Scheme 11 reactions are sometimes carried out in the absence of solvent. Typical reaction times for Scheme 11 reactions range from 30 min to several days, with 6 to 24 h being generally preferred.
  • Formula XII diamines where B is an optionally substituted CH 2 CH 2 group can be prepared by the two-step procedure depicted in Scheme 12.
  • Step i of Scheme 12 amines of Formula XIV are treated with potassium cyanide and compounds of Formula XV in the presence of zero to three equivalents of acid to form aminonitriles of Formula XVI.
  • compounds of Formula XV can be formaldehyde, acetaldehyde or acetone.
  • Other cyanide salts as well as HCN can be used in the procedure as well as hydrohalide and other acid salts of Formula XIV.
  • Suitable solvents include methanol, ethanol, isopropanol and water, as well as combinations of solvents.
  • Scheme 12 reactions are usually complete with 24 h.
  • Step ii of Scheme 12 aminonitriles of Formula XVI are reduced to form diamines of Formula XII.
  • This reduction can usually be achieved using lithium aluminum hydride or borane in amounts ranging from 0.75 to 3 molar equivalents, in a solvent such as diethyl ether or THF. Reactions are carried out at temperatures ranging from -20 °C to the reflux temperature of the solvent for times ranging from 0.5 h to 2 days.
  • Formula XII can be achieved using catalytic hydrogenation over a catalyst such as palladium on carbon or Raney nickel.
  • a catalyst such as palladium on carbon or Raney nickel.
  • ammonia to the hydrogenation reaction is sometimes useful to maximize the yield of diamines of Formula XII.
  • amino amides of Formula XVII are treated with 1 to 2 molar equivalents of acid chlorides of Formula XVIII in the presence of 1 to 3 molar equivalents of a base such as NaOH, KOH, K 2 CO 3 , NaHCO 3 , pyridine or triethylamine.
  • a base such as NaOH, KOH, K 2 CO 3 , NaHCO 3 , pyridine or triethylamine.
  • Suitable solvents include THF, CH 2 Cl 2 , water or pyridine.
  • the products (compounds of Formula XIX) can be isolated by extraction or, more conveniently, by removal of solvent, and are usually suitable for use in Step ii of Scheme 13 in crude form.
  • Amides of Formula XVII can be used either in neutral form as depicted or as the salt form (typically as the HCl or CF 3 CO 2 H salt, among others). When the salt form of XVII is used, an additional one equivalent of base is used in Step i
  • Formula I are prepared as described for Scheme 1 reactions using enantiomerically enriched forms of compounds of Formula II, the compounds of Formula I are obtained in enantiomerically enriched form.
  • diamines of Formula XII can be obtained in enantiomerically enriched forms by resolution with enantiomeric acids, such as tartaric acid.
  • resolutions are well-known to one skilled in the art (see e.g., Synthesis, (1991), 789 for a related example).
  • Amines of Formula III can be prepared by the reaction of a silyl halide or germanyl halide of Formula XX with an excess of ammonia as shown in Scheme 14. These transformations typically involve the addition of compounds of Formula XX to anhydrous, liquid ammonia (2 to 100 equivalents) at temperatures ranging from -78 to 100 °C. In cases where temperatures greater than -33 °C are required, the reactions are carried out in a sealed, high pressure apparatus. Usually no solvent is required; however, solvents such as THF or diethyl ether are sometimes used. Reactions generally require
  • Silanes and germanes of Formula XX can be prepared by the reaction of organolithium or Grignard reagents of Formula XXI with chlorosilanes or
  • Chlorosilanes and chlorogremanes of Formula XXII can be prepared by treatment of dichlorides of Formula XXIII with one molar equivalent of an organometallic reagent of Formula XXIV as depicted in Scheme 16.
  • Conditions for Scheme 16 reactions are analogous to those described for Scheme 15 reactions.
  • the preparation of compounds of Formula XX where R 4 is equal to R 5 can be achieved by the use of two equivalents of compounds of Formula XXIV in procedures depicted in Scheme 16.
  • Silanes and germanes of Formula XX where R 4 and R 5 are alkoxy or phenoxy can be prepared by the reaction of dichlorides of Formula XXIII with two equivalents of alcohols of Formula XXVI in the presence of a base using procedures analogous to those described for Scheme 18 reactions.
  • compounds of Formula XX where R 4 , R 5 and R 6 are alkoxy or phenoxy can be prepared by the reaction of trichlorosilanes or trichlorogermanes of Formula XXV with three equivalents of an alcohol of
  • protection/deprotection 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.
  • Step C N 2 -[(6-chloro-3-pyridinyl)-methyI]-1,2-propanediamine
  • Step D 2-Chloro-5-[[5-methyl-2-(nitromethylene)-1-imidazolidinyl]methyl]pyridine
  • a suspension of 2.5 g (0.013 mol) of the product from Step C, 1.6 g (0.009 mol) of 1,1-bis(methylthio)-2-nitroethylene and 63 mL of anhydrous EtOH was heated at reflux for 3 h and was then allowed to stand at 24°C for 72 h.
  • the resulting mixture was concentrated and chromatographed on silica gel using 15:1:0.1 CH 2 Cl 2 -EtOH-30% NH 4 OH to give 0.70 g of the title compound as a yellow solid; m.p. 127-131°C.
  • Step E 1-[(6-Chloro-3-pyridinyl)methyl]-1,2,3,5,6,7-hexahydro-2-methyl-8-nitro-6- [(trimethylsilyl)methyl]imidazo[1,2-c]pyrimidine (Compound 1)
  • Step B 1,2,3,5,6,7-Hexahydro-8-nitro-6-[(trimethylsilyl)methyl]imidazo[1,2-c]pyrimidine
  • Step C 1-[(6-Chloro-3-pyridinyl)methyl]-1,2,3,5,6,7-hexahydro-8-nitro-6- [(trimethylsilyl)methyl]-imidazo[1,2-c]pyrimidine
  • Tables 1-16 and Index Tables A-E can be prepared.
  • the compounds of Table 1, line 1 can be referred to as 1-1, 1-2, 1-3 and 1-4 (as designated by line and column). All the other specific compounds covered in these Tables can be designated in an analogous fashion.
  • Tables 1-16 and Index Tables A-E the following notations have been used:
  • 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 100 weight percent.
  • 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.
  • 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
  • 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 army worm (Spodoptera frugiperda), black bean aphid (Aphis fabae), green peach aphid (Myzus persica), cotton aphid (Aphis gossypi ⁇ ), Russian wheat aphid (Diuraphis noxia), English grain aphid (Sitobion avenae), tobacco budworm (Heliothis virescens), rice water weevil (Lissorhoptrus oryzophilus), rice leaf beetle (Oulema oryzae), whitebacked planthopper (Sogatellafurcifera), green leafhopper (Nephotettix cincticeps), 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 californicus and Brevipalpus obovatus; Eriophyida
  • Compounds of this invention can also be mixed with one or more other 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,
  • 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, myclobutanil, tebuconazole, difenoconazole, diniconazole, fluquinconazole, ipconazole, metconazole, penconazole, propiconazole, uniconzole, flutriafol, prochloraz, pyrifenox, fenarimol, triadimenol, diclobutrazol, copper oxychloride, furala
  • 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.
  • Other methods of application include direct and residual sprays, aerial sprays, seed coats, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others.
  • the compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like.
  • 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.
  • Control efficacy represents inhibition of arthropod development (including mortality) that causes significantly reduced feeding.
  • the pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-F for compound descriptions.
  • Test units each consisting of a H.I.S. (high impact styrene) tray with 16 cells were prepared. Wet filter paper and approximately 8 cm 2 of lima bean leaf was placed into twelve of the cells. A 0.5 cm layer of wheat germ diet was placed into the four remaining cells. Fifteen to twenty third-instar larvae of fall armyworm (Spodoptera frugiperda) were placed into a 230 mL (8 ounce) plastic cup. Solutions of each of the test compounds in 75/25 acetone/distilled water solvent were sprayed into the tray and cup.
  • H.I.S. high impact styrene
  • 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 0.14 kg of active ingredient per hectare (about 0.13 pounds per acre) at 207 kPa (30 p.s.i.).
  • the insects were transferred from the 230 mL cup to the H.I.S. tray (one insect per cell).
  • the trays were covered and held at 27°C and 50% relative humidity for 48 h, after which time readings were taken on the twelve cells with lima bean leaves.
  • Test units each consisting of a 230 mL (8 ounce) plastic cup containing a 2.54 cm 2 plug (1 square inch) of a wheatgerm diet, were prepared. The test units were sprayed as described in TEST A 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 held at 27°C and 50% relative humidity for 48 h, after which time mortality readings were taken.
  • Test units were prepared from a series of 350 mL (12 ounce) cups, each containing oat (Avena sativa) seedlings in a 2.54 cm (1 inch) layer of sterilized soil. The test units were sprayed as described in TEST A with individual solutions of the test compounds. After the oats had dried from the spraying, 10 to 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 h, after which time mortality readings were taken.
  • Test units consisting of 260 mL (9 ounce) cups containing five adult boll weevils (Anthonomus grandis grandis) were prepared. The test units were sprayed as described in TEST A 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 h, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 2*, 3*, 4*, 5*, 6*, 7*, 10*, 20 and 52.
  • the treated cups were held in a vented enclosure to dry for about 2 h. After drying, the cups were placed into conical shaped test units and the surface of the soil covered with 2 to 3 mm of quartz sand. Eight to ten 3rd-instar nymphs of the green leafhopper (Nephotettix cincticeps) were transferred into the test units using an aspirator. The test units were held at 27°C and 65% relative humidity. Counts of the number of live and dead nymphs were taken at 24 and 48 h post-infestation. Insects which cannot walk are classified as dead. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 h at an application rate equivalent to 0.05 kilograms per hectare: 1, 2, 3 4, 5, 6, 7, 8, 13, 40, 41, 42, 43, 44 and 45.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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Abstract

Composés et compositions arthropodicides, et utilisation de composés de formule (I), dans laquelle X, A, R?1, R2, R3, R4, R5 et R6¿sont tels que définis dans le texte.
PCT/US1995/009704 1995-08-01 1995-08-01 Tetrahydropyrimidines arthropodicides WO1997005145A1 (fr)

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PCT/US1995/009704 WO1997005145A1 (fr) 1995-08-01 1995-08-01 Tetrahydropyrimidines arthropodicides

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012050141A1 (fr) * 2010-10-14 2012-04-19 住友化学株式会社 Composé à noyau hétéroaromatique et son utilisation pour la lutte contre les organismes nuisibles

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4831036A (en) * 1986-05-30 1989-05-16 Bayer Aktiengesellschaft 1,2,3,6-tetrahydro-5-nitro-pyrimidine derivatives

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4831036A (en) * 1986-05-30 1989-05-16 Bayer Aktiengesellschaft 1,2,3,6-tetrahydro-5-nitro-pyrimidine derivatives

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012050141A1 (fr) * 2010-10-14 2012-04-19 住友化学株式会社 Composé à noyau hétéroaromatique et son utilisation pour la lutte contre les organismes nuisibles

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