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WO2008027539A1 - Insecticidal n-substituted (2- sudstituted-1,3-thiazol) alkyl sulfoximines - Google Patents

Insecticidal n-substituted (2- sudstituted-1,3-thiazol) alkyl sulfoximines Download PDF

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Publication number
WO2008027539A1
WO2008027539A1 PCT/US2007/019176 US2007019176W WO2008027539A1 WO 2008027539 A1 WO2008027539 A1 WO 2008027539A1 US 2007019176 W US2007019176 W US 2007019176W WO 2008027539 A1 WO2008027539 A1 WO 2008027539A1
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WO
WIPO (PCT)
Prior art keywords
insecticides
methyl
alkyl
compounds
spp
Prior art date
Application number
PCT/US2007/019176
Other languages
French (fr)
Inventor
Michael R. Loso
Benjamin M. Nugent
Yuanming Zhu
Thomas L. Siddall
Francis E. Tisdell
Jim X. Huang
Zoltan L. Benko
Original Assignee
Dow Agrosciences Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Agrosciences Llc filed Critical Dow Agrosciences Llc
Priority to MX2009002302A priority Critical patent/MX2009002302A/en
Priority to CN2007800406155A priority patent/CN101541771B/en
Priority to ES07837600T priority patent/ES2389385T3/en
Priority to CA2661517A priority patent/CA2661517C/en
Priority to BRPI0719053A priority patent/BRPI0719053B1/en
Priority to EP07837600A priority patent/EP2057135B1/en
Priority to JP2009526741A priority patent/JP5248502B2/en
Priority to KR1020097004196A priority patent/KR101393850B1/en
Publication of WO2008027539A1 publication Critical patent/WO2008027539A1/en
Priority to HK10102881.6A priority patent/HK1134815A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D277/00Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/26Radicals substituted by sulfur atoms
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/781,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N51/00Biocides, 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
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00Antiparasitic agents
    • A61P33/10Anthelmintics
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00Antiparasitic agents
    • A61P33/14Ectoparasiticides, e.g. scabicides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P7/00Drugs for disorders of the blood or the extracellular fluid
    • A61P7/04Antihaemorrhagics; Procoagulants; Haemostatic agents; Antifibrinolytic agents
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D417/00Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention concerns novel N-substituted (2-substituted-l,3- thiazol)alkyl sulfoximines and their use in controlling insects, particularly aphids and other sucking insects, as well as certain other invertebrates.
  • This invention also includes new synthetic procedures for preparing the compounds, pesticide compositions containing the compounds, and methods of controlling insects using the compounds.
  • This invention concerns compounds useful for the control of insects, especially useful for the control of aphids and other sucking insects. More specifically, the invention concerns compounds of the formula (I)
  • X represents NO 2 , CN, COOR 4 or COR 5 ;
  • L represents either a single bond or -CH(CH 2 )IIi- where m is an integer from 1-3 in cases where R 1 , S and L taken together represent a 4-, 5-, or 6- membered ring;
  • n is an integer from 0-3;
  • Y represents C 1 -C4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, fluoro, bromo, iodo, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, CN, NO 2 or R 6 SO 2 where z is an integer from 0-2;.
  • R 1 represents Ci-C 4 alkyl, Cj-C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloakenyl, C 3 -Cg alkynyl, or -(CH 2 )- in cases where R 1 , S and L taken together represent a 4-, 5-, or 6-membered ring;
  • R 2 and R 3 independently represent hydrogen, methyl, ethyl, cyclopropyl, fluoro, chloro, bromo, or iodo;
  • R 4 represents Ci-C 4 alkyl, C 1 -C 4 haloalkyl, aryl, heteroaryl, arylalkyl or heteroarylalkyl;
  • R 5 represents hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, aryl, heteroaryl; arylalkyl or heteroarylalkyl; and
  • R 6 represents Ci-C 4 alkyl, Ci-C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloakenyl or C 3 -C 6 alkynyl.
  • Preferred compounds of formula (I) include the following classes:
  • the invention also provides new processes for preparing compounds of formula (I) as well as new compositions and methods of use, which will be described in detail hereinafter.
  • alkyl alkenyl and “alkynyl”, as well as derivative terms such as “alkoxy”, “acyl”, “alkylthio”, “arylalkyl”, “heteroarylalkyl” and “alkylsulfonyl”, as used herein, include within their scope straight chain, branched chain and cyclic moieties.
  • typical alkyl groups are methyl, ethyl, 1-methylethyl, propyl, 1,1-dimethylethyl, and cyclopropyl.
  • each may be unsubstituted or substituted with one or more substituents selected from but not limited to halogen, hydroxy, alkoxy, alkylthio, C t -C ⁇ acyl, formyl, cyano, aryloxy or aryl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied.
  • haloalkyl and haloalkenyl includes alkyl and alkenyl groups substituted with from one to the maximum possible number of halogen atoms, all combinations of halogens included.
  • halogen or “halo” includes fluorine, chlorine, bromine and iodine, with fluorine being preferred.
  • alkenyl and “alkynyl” are intended to include one or more unsaturated bonds.
  • aryl refers to a phenyl, indanyl or naphthyl group.
  • heteroaryl refers to a 5- or 6-membered aromatic ring containing one or more heteroatoms, viz., N, O or S; these heteroaromatic rings may be fused to other aromatic systems.
  • the aryl or heteroaryl s ⁇ bstituents may be unsubstituted or substituted with one or more substituents selected from halogen, hydroxy, nitro, cyano, aryloxy, formyl, Cj-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Q-C 6 alkoxy, halogenated Q-C 6 alkyl, halogenated Q-C 6 alkoxy, Q-C 6 acyl, Q-C 6 alkylthio, C 1 -C 6 alkylsulfinyl, Cj-C 6 alkylsulfonyl, aryl, Ci-C 6 OC(O)alkyl, Ci-C 6 NHC(O)al
  • the compounds of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include geometric isomers, diastereomers and enantiomers.
  • the compounds of the present invention include racemic mixtures, individual stereoisomers and optically active mixtures. It will be appreciated by those skilled in the art that one stereoisomer may be more active than the others. Individual stereoisomers and optically active mixtures may be obtained by selective synthetic procedures, by conventional synthetic procedures using resolved starting materials or by conventional resolution procedures.
  • step a of Scheme A sulfide of formula (A) is oxidized with meta- chloroperoxybenzoic acid (mCPBA) in a polar solvent below 0 C to provide sulfoxide of formula (B).
  • mCPBA meta- chloroperoxybenzoic acid
  • dichloromethane is the preferred solvent for oxidation.
  • step b of Scheme A sulfoxide (B) is iminated with sodium azide in the presence of concentrated sulfuric acid in an aprotic solvent under heating to provide sulfoximine of formula (C). In most cases, chloroform is the preferred solvent for this reaction.
  • the nitrogen of sulfoximine (C) can be either cyanated with cyanogen bromide in the presence of a base, or nitrated with nitric acid in the presence of acetic anhydride under mildly elevated temperature, or carboxylated with alkyl (R 4 ) chloroformate in the presence of base such as 4- dimethylaminopyridine (DMAP), or acylated with acyl halide in the presence of base such as 4-dimethylaminopyridine (DMAP) to provide ⁇ f-substituted sulfoximine (Ia).
  • Base is required for efficient cyanation, carboxylation or acylation and the preferred base is DMAP, whereas sulfuric acid is used as catalyst for efficient nitration reaction.
  • step a of Scheme B sulfide is oxidized with iodobenzene diacetate in the presence of cyanamide at 0 C to give sulfilimine (D).
  • the reaction can be carried out in a polar aprotic solvent like CH 2 Cl 2 .
  • step b of Scheme B the sulfilimine (D) is oxidized with mCPB A.
  • a base such as potassium carbonate is employed to neutralize the acidity of OTCPB A.
  • Protic polar solvents such as ethanol and water are used to increase the solubility of the sulfilimine starting material and the base employed.
  • KHMDS potassium hexamethyl- disilamide
  • step a of Scheme D which is similar to step b of Scheme A, sulfoxide is iminated with sodium azide in the presence of concentrated sulfuric acid or with 0-mesitylsulfonylhydroxylamine in a polar aprotic solvent to provide the corresponding N-unsubstituted sulfoximine.
  • Chloroform or dichloromethane are the preferred solvents.
  • the nitrogen of sulfoximine can be either cyanated with cyanogen bromide, or nitrated with nitric acid followed by treatment with acetic anhydride under refluxing conditions, or carboxylated with methyl chloroformate in the presence of base such as DMAP, or acylated with acyl halide in the presence of base such as 4-dimethylamino- pyridine (DMAP) to provide ⁇ f-substitued cyclic sulfoximine.
  • Base is required for efficient cyanation, carboxylation or acylation and the preferred base is DMAP, whereas sulfuric acid is used as catalyst for efficient nitration reaction.
  • the ⁇ -carbon of ⁇ f-substituted sulfoximine can be alkylated with a 1,3-thiazolyl methyl halide in the presence of a base such as KHMDS or butyl lithium (BuLi) to give the desired ,/V-substituted sulfoxi ⁇ nes.
  • a base such as KHMDS or butyl lithium (BuLi)
  • the preferred halide can be bromide, chloride or iodide.
  • the compounds of formula (Ic) can be prepared by a first ⁇ - alkylation of sulfoxides to give ⁇ -substituted sulfoxides and then an imination of the sulfoxide followed by ⁇ f-substitution of the resulting sulfoximine by using the steps c , a and b respectively as described above for Scheme D.
  • base such as potassium terr-butoxide
  • a base like potassium-f-butoxide in a polar aprotic solvent such as THF.
  • a lower test concentration (50 ppm) was prepared by making sequential a 4X dilution from the 200 ppm solution with a diluent consisting 80 parts of 0.025% Tween 20 in H 2 O and 20 parts of acetone : methanol (1 : 1).
  • a hand-held Devilbiss sprayer was used to apply the spray solutions until runoff to both sides of the squash cotyledon leaves.
  • Four plants (4 replications) were used for each concentration of each compound.
  • Reference plants (solvent check) were sprayed with the diluent only.
  • Treated plants were held in a holding room for 3 days at approximately 23 0 C and 40% RH before the number of live aphids on each plant was recorded.
  • Insecticidal activity was measured by Corrected % Control using Abbott's correction formula and the values for the lower test concentrations are presented in Table 1:
  • CA 200 refers to % control at 200 ppm against cotton aphid in foliar spray tests
  • CA 50 refers to % control at 50 ppm against cotton aphid in foliar spray tests
  • Table 2 the rating scale is as follows:
  • the compounds of the invention are useful for the control of insects. Therefore, the present invention also is directed to a method for inhibiting an insect which comprises applying an insect-inhibiting amount of a compound of formula (I) to a locus of the insect, to the area to be protected, or directly on the insect to be controlled.
  • the compounds of the invention may also be used to control other invertebrate pests such as mites and ticks, and nematodes.
  • insects which eat, damage or contact edible, commodity, ornamental, turf or pasture plants can be controlled by applying the active compounds to the seed of the plant before planting, to the seedling, or cutting which is planted, the leaves, stems, fruits, grain, and/or roots, or to the soil or other growth medium before or after the crop is planted. Protection of these plants against virus, fungus or bacterium diseases may also be achieved indirectly through controlling sap-feeding pests such as whitefly, plant hopper, aphid and spider mite. Such plants include those which are bred through conventional approaches and which are genetically modified using modern biotechnology to gain insect-resistant, herbicide-resistant, nutrition-enhancement, or any other beneficial traits.
  • the compounds might also be useful to protect textiles, paper, stored grain, seeds and other foodstuffs, houses and other buildings which may be occupied by humans and/or companion, farm, ranch, zoo, or other animals, by applying an active compound to or near such objects.
  • domesticated animals, buildings or human beings might be protected with the compounds by controlling invertebrate and/or nematode pests that are parasitic or are capable of transmitting infectious diseases.
  • pests include, for example, chiggers, ticks, lice, mosquitoes, flies, fleas and heartworms.
  • Nonagronomic applications also include invertebrate pest control in forests, in yards, along road sides and railroad right of way.
  • insects which can be inhibited include, but are not limited to:
  • Lepidoptera Heliothis spp., Helicoverpa spp., Spodoptera spp., Mythimna unipuncta, Agrotis ipsilon, Earias spp., Euxoa auxiliaris, Trichoplusia ni, Anticarsia gemmatalis, Rachiplusia nu, Plutella xylostella, Chilo spp., Scirpophaga incertulas, Sesamia inferens, Cnaphalocrocis medinalis, Ostrinia nubilalis, Cydia pomonella, Carposina niponensis, ' Adoxophyes orana, Archips argyrospilus, Pandemis heparana, Epinotia aporema, Eupoecilia ambiguella, Lobesia botrana, Polychrosis viteana, Pectinophora gossypiell
  • Coleoptera Diabrotica spp., Leptinotarsa decemlineata, Oulema oryzae, Anthonomus grandis, Lissorhoptrus oryzophilus, Agriotes spp., Melanotics communis, Popillia japonica, Cyclocephala spp., Tribolium spp.
  • Hemiptera - Lygus spp. Eurygaster maura, Nezara viridula, Piezodorus guildingi, Leptocorisa varicornis
  • Thysanoptera Frankliniella occidentalis m Thrips spp., Scirtothrips dorsalis
  • Isoptera Reticulitermes flavipes, Coptotermes formosanus
  • Diptera Liriomyza spp., Musca domestica, Aedes spp., Culex spp., Anopheles spp.
  • Hymenoptera Iridomyrmex humilis, Solenopsis spp., Monomorium pharaonis, Atta spp., Pogonomyrmex spp., Camponotus spp.
  • Siphonaptera - Ctenophalides spp. Pulex irritans Acarina - Tetranychus spp., Panonychus spp., Eotetranychus carpini, Phyllocoptruta oleivora, Aculus pelekassi, Brevipalpus phoenicis, Boophilus spp., Dermacentor variabilis, Rhipicephalus sanguineus, Amblyomma americanum, Ixodes spp., Notoedres cati, Sarcoptes scabiei, Dermatophagoides spp.
  • Nematoda Dirofilaria immitis, Meloidogyne spp., Heterodera spp., Hoplolaimus columbus, Belonolaimus spp., Pratylenchus spp., Rotylenchus reniformis, Criconemella ornata, Ditylenchus spp., Aphelenchoides besseyi, Hirschmanniella spp.
  • compositions which are important embodiments of the invention, and which comprise a compound of this invention and a phytologically-acceptable inert carrier. Control of the pests is achieved by applying compounds of the invention in forms of sprays, topical treatment, gels, seed coatings, microcapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants aerosols, dusts and many others.
  • the compositions are either concentrated solid or liquid formulations which are dispersed in water for application, or are dust or granular formulations which are applied without further treatment.
  • the compositions are prepared according to procedures and formulae which are conventional in the agricultural chemical art, but which are novel and important because of the presence therein of the compounds of this invention. Some description of the formulation of the compositions will be given, however, to assure that agricultural chemists can readily prepare any desired composition.
  • the dispersions in which the compounds are applied are most often aqueous suspensions or emulsions prepared from concentrated formulations of the compounds.
  • Such water-soluble, water-suspendable or emulsifiable formulations are either solids, usually known as wettable powders, or liquids usually known as emulsifiable concentrates or aqueous suspensions.
  • Wettable powders which may be compacted to form water dispersible granules, comprise an intimate mixture of the active compound, an inert carrier, and surfactants.
  • the concentration of the active compound is usually from about 10% to about 90% by weight.
  • the inert carrier is usually chosen from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, or the purified silicates.
  • Effective surfactants comprising from about 0.5% to about 10% of the wettable powder, are found among the sulfonated lignins, the condensed naphthalenesulfonates, the naphthalenesulfonates, the alkylbenzenesulfonates, the alkyl sulfates, and nonionic surfactants such as ethylene oxide adducts of alkyl phenols.
  • Emulsifiable concentrates of the compounds comprise a convenient concentration of a compound, such as from about 50 to about 500 grams per liter of liquid, equivalent to about 10% to about 50%, dissolved in an inert carrier which is either a water miscible solvent or a mixture of water-immiscible organic solvent and emulsif ⁇ ers.
  • an inert carrier which is either a water miscible solvent or a mixture of water-immiscible organic solvent and emulsif ⁇ ers.
  • Useful organic solvents include aromatics, especially the xylenes, and the petroleum fractions, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha.
  • organic solvents may also be used, such as the terpenic solvents including rosin derivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol.
  • Suitable emulsifiers for emulsifiable concentrates are chosen from conventional nonionic surfactants, such as those discussed above.
  • Aqueous suspensions comprise suspensions of water-insoluble compounds of this invention, dispersed in an aqueous vehicle at a concentration in the range from about 5% to about 50% by weight.
  • Suspensions are prepared by finely grinding the compound, and vigorously mixing it into a vehicle comprised of water and surfactants chosen from the same types discussed above.
  • Inert ingredients such as inorganic salts and synthetic or natural gums, may also be added, to increase the density and viscosity of the aqueous vehicle. It is often most effective to grind and mix the compound at the same time by preparing the aqueous mixture, and homogenizing it in an implement such as a sand mill, ball mill, or piston-type homogenizer.
  • the compounds may also be applied as granular compositions, which are particularly useful for applications to the soil.
  • Granular compositions usually contain from about 0.5% to about 10% by weight of the compound, dispersed in an inert carrier which consists entirely or in large part of clay or a similar inexpensive substance.
  • Such compositions are usually prepared by dissolving the compound in a suitable solvent and applying it to a granular carrier which has been pre-formed to the appropriate particle size, in the range of from about 0.5 to 3 mm.
  • Such compositions may also be formulated by making a dough or paste of the carrier and compound and crushing and drying to obtain the desired granular particle size.
  • Dusts containing the compounds are prepared simply by intimately mixing the compound in powdered form with a suitable dusty agricultural carrier, such as kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1% to about 10% of the compound.
  • Insecticides and acaricides are generally applied in the form of a dispersion of the active ingredient in a liquid carrier. It is conventional to refer to application rates in terms of the concentration of active ingredient in the carrier.
  • the most widely used carrier is water.
  • the compounds of the invention can also be applied in the form of an aerosol composition. In such compositions the active compound is dissolved or dispersed in an inert carrier, which is a pressure-generating propellant mixture.
  • the aerosol composition is packaged in a container from which the mixture is dispensed through an atomizing valve.
  • Propellant mixtures comprise either low- boiling halocarbons, which may be mixed with organic solvents, or aqueous suspensions pressurized with inert gases or gaseous hydrocarbons.
  • the actual amount of compound to be applied to loci of insects and mites is not critical and can readily be determined by those skilled in the art in view of the examples above. In general, concentrations from 10 ppm to 5000 ppm by weight of compound are expected to provide good control. With many of the compounds, concentrations from 100 to 1500 ppm will suffice.
  • the locus to which a compound is applied can be any locus inhabited by an insect or mite, for example, vegetable crops, fruit and nut trees, grape vines, ornamental plants, domesticated animals, the interior or exterior surfaces of buildings, and the soil around buildings.
  • Systemic movement of compounds of the invention in plants may be utilized to control pests on one portion of the plant by applying the compounds to a different portion of it.
  • control of foliar-feeding insects can be controlled by drip irrigation or furrow application, or by treating the seed before planting.
  • Seed treatment can be applied to all types of seeds, including those from which plants genetically transformed to express specialized traits will germinate.
  • Representative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis or other insecticidal toxins, or those expressing herbicide resistance, such as "Roundup Ready" seed.
  • An insecticidal bait composition consisting of compounds of the present invention and attractants and/or feeding stimulants may be used to increase efficacy of the insecticides against insect pest in a device such as trap, bait station, and the like.
  • the bait composition is usually a solid, semi-solid (including gel) or liquid bait matrix including the stimulants and one or more non- microencapsulated or microencapsulated insecticides in an amount effective to act as kill agents.
  • the compounds of the present invention are often applied in conjunction with one or more other insecticides or fungicides to obtain control of a wider variety of pests and diseases.
  • the presently claimed compounds can be formulated with the other insecticides or fungicides, tank mixed with the other insecticides or fungicides, or applied sequentially with the other insecticides or fungicides.
  • antibiotic insecticides such as all
  • lilacinus Photorhabdus luminescens, Spodoptera exigua NPV, trypsin modulating oostatic factor, Xenorhabdus nematophilus, and X. bovienii, plant incorporated protectant insecticides such as CrylAb, CrylAc, CrylF, CrylA.105, Cry2Ab2, Cry3A, mir Cry3A, Cry3Bbl, Cry34, Cry35, and VIP3A; botanical insecticides such as anabasine, azadirachtin, d-limonene, nicotine, pyrethrins, cinerins, cinerin I, cinerin II, jasmolin I, jasmolin ⁇ , pyrethrin I, pyrethrin II, quassia, rotenone, ryania and sabadilla; carbamate insecticides such as bendiocarb and carbaryl; benzofuranyl methylcarbamate insecticide

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Abstract

N-Substituted (2-substituted-1,3-thiazol)alkyl sulfoximines of formula (I) are effective at controlling insects.

Description

iNSECTiciDAL W-SUBSTΓΓUTED (2-SUBSTΓΓUTED-I,3-THIAZOL)ALKYL
SULFOXIMINES
Cross-Reference to Related Application
This application claims priority from provisional application 60/841,938 filed in the United States Patent Office on September 1, 2006.
Background of the Invention
The present invention concerns novel N-substituted (2-substituted-l,3- thiazol)alkyl sulfoximines and their use in controlling insects, particularly aphids and other sucking insects, as well as certain other invertebrates. This invention also includes new synthetic procedures for preparing the compounds, pesticide compositions containing the compounds, and methods of controlling insects using the compounds.
There is an acute need for new insecticides. Insects are developing resistance to the insecticides in current use. At least 400 species of arthropods are resistant to one or more insecticides. The development of resistance to some of the older insecticides, such as DDT, the carbamates, and the organophosphates, is well known. But resistance has even developed to some of the newer pyrethroid insecticides. Therefore a need exists for new insecticides, and particularly for compounds that have new or atypical modes of action.
U.S. Patent Application Publication 2005/0228027 Al describes certain sulfoximine compounds including some containing (2-chloro-l,3-thiazol)alkyl groups and their use in controlling insects. It will be demonstrated that certain (2- substituted-l,3-thiazol-4yl)alkyl sulfoximines and (2-substituted-l,3-thiazol-5- yl)alkyl sulfoximines will have comparable or even greatly improved activity. Summary of the Invention
This invention concerns compounds useful for the control of insects, especially useful for the control of aphids and other sucking insects. More specifically, the invention concerns compounds of the formula (I)
Figure imgf000003_0001
ω wherein
X represents NO2, CN, COOR4 or COR5;
L represents either a single bond or -CH(CH2)IIi- where m is an integer from 1-3 in cases where R1, S and L taken together represent a 4-, 5-, or 6- membered ring;
n is an integer from 0-3;
Y represents C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, fluoro, bromo, iodo, C1-C4 alkoxy, C1-C4 haloalkoxy, CN, NO2 or R6SO2 where z is an integer from 0-2;.
R1 represents Ci-C4 alkyl, Cj-C4 haloalkyl, C3-C6 alkenyl, C3-C6 haloakenyl, C3-Cg alkynyl, or -(CH2)- in cases where R1, S and L taken together represent a 4-, 5-, or 6-membered ring;
R2 and R3 independently represent hydrogen, methyl, ethyl, cyclopropyl, fluoro, chloro, bromo, or iodo; R4 represents Ci-C4 alkyl, C1-C4 haloalkyl, aryl, heteroaryl, arylalkyl or heteroarylalkyl;
R5 represents hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, aryl, heteroaryl; arylalkyl or heteroarylalkyl; and
R6 represents Ci-C4 alkyl, Ci-C4 haloalkyl, C3-C6 alkenyl, C3-C6 haloakenyl or C3-C6 alkynyl.
Preferred compounds of formula (I) include the following classes:
(1) Compounds of formula (I) wherein X is NO2 or CN, most preferably CN.
(2) Compounds of formula (I) wherein Y is Ci-C4 haloalkyl, fluoro, or bromo, most preferably CF3.
(3) Compounds of formula (I) wherein n is either 0 or 1 and R1, S and L taken together form a saturated 5-membered ring having the structure
Figure imgf000004_0001
(4) Compounds of formula (I) wherein L represents a single bond and n > 0 having the structure
Figure imgf000004_0002
It will be appreciated by those skilled in the art that the most preferred compounds are generally those which are comprised of combinations of the above preferred classes.
The invention also provides new processes for preparing compounds of formula (I) as well as new compositions and methods of use, which will be described in detail hereinafter.
Detailed Description of the Invention
Throughout this document, all temperatures are given in degrees Celsius, and all percentages are weight percentages unless otherwise stated.
The terms "alkyl", "alkenyl" and "alkynyl", as well as derivative terms such as "alkoxy", "acyl", "alkylthio", "arylalkyl", "heteroarylalkyl" and "alkylsulfonyl", as used herein, include within their scope straight chain, branched chain and cyclic moieties. Thus, typical alkyl groups are methyl, ethyl, 1-methylethyl, propyl, 1,1-dimethylethyl, and cyclopropyl. Unless specifically stated otherwise, each may be unsubstituted or substituted with one or more substituents selected from but not limited to halogen, hydroxy, alkoxy, alkylthio, Ct-Cδacyl, formyl, cyano, aryloxy or aryl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied. The term "haloalkyl" and "haloalkenyl" includes alkyl and alkenyl groups substituted with from one to the maximum possible number of halogen atoms, all combinations of halogens included. The term "halogen" or "halo" includes fluorine, chlorine, bromine and iodine, with fluorine being preferred. The terms "alkenyl" and "alkynyl" are intended to include one or more unsaturated bonds.
The term "aryl" refers to a phenyl, indanyl or naphthyl group. The term
"heteroaryl" refers to a 5- or 6-membered aromatic ring containing one or more heteroatoms, viz., N, O or S; these heteroaromatic rings may be fused to other aromatic systems. The aryl or heteroaryl sυbstituents may be unsubstituted or substituted with one or more substituents selected from halogen, hydroxy, nitro, cyano, aryloxy, formyl, Cj-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, Q-C6 alkoxy, halogenated Q-C6 alkyl, halogenated Q-C6 alkoxy, Q-C6 acyl, Q-C6 alkylthio, C1-C6 alkylsulfinyl, Cj-C6 alkylsulfonyl, aryl, Ci-C6 OC(O)alkyl, Ci-C6 NHC(O)alkyl, C(O)OH, C1-C6 C(O)Oalkyl, C(O)NH2, C1-C6 C(O)NHalkyl, or Q- C6 C(O)N(alkyl)2, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied.
The compounds of this invention can exist as one or more stereoisomers.
The various stereoisomers include geometric isomers, diastereomers and enantiomers. Thus the compounds of the present invention include racemic mixtures, individual stereoisomers and optically active mixtures. It will be appreciated by those skilled in the art that one stereoisomer may be more active than the others. Individual stereoisomers and optically active mixtures may be obtained by selective synthetic procedures, by conventional synthetic procedures using resolved starting materials or by conventional resolution procedures.
The compounds of formula (Ia), wherein R1, R2, R3, R4, R5, n, X, and Y are as previously defined and L is a single bond, can be prepared by the methods illustrated in Scheme A:
Scheme A 0
R-s- -fVv - R-sL(CR2R3)n_£VY ^→
(A) (B)
Figure imgf000006_0001
In step a of Scheme A, sulfide of formula (A) is oxidized with meta- chloroperoxybenzoic acid (mCPBA) in a polar solvent below 0 C to provide sulfoxide of formula (B). In most cases, dichloromethane is the preferred solvent for oxidation.
In step b of Scheme A, sulfoxide (B) is iminated with sodium azide in the presence of concentrated sulfuric acid in an aprotic solvent under heating to provide sulfoximine of formula (C). In most cases, chloroform is the preferred solvent for this reaction.
In step c of Scheme A, the nitrogen of sulfoximine (C) can be either cyanated with cyanogen bromide in the presence of a base, or nitrated with nitric acid in the presence of acetic anhydride under mildly elevated temperature, or carboxylated with alkyl (R4) chloroformate in the presence of base such as 4- dimethylaminopyridine (DMAP), or acylated with acyl halide in the presence of base such as 4-dimethylaminopyridine (DMAP) to provide Λf-substituted sulfoximine (Ia). Base is required for efficient cyanation, carboxylation or acylation and the preferred base is DMAP, whereas sulfuric acid is used as catalyst for efficient nitration reaction.
The compounds of formula (Ia), wherein X represents CN can be prepared by the mild and efficient method illustrated in Scheme B.
Scheme B
Figure imgf000007_0001
mCPBA, K2CO3
Figure imgf000007_0002
In step a of Scheme B, sulfide is oxidized with iodobenzene diacetate in the presence of cyanamide at 0 C to give sulfilimine (D). The reaction can be carried out in a polar aprotic solvent like CH2Cl2.
In step b of Scheme B, the sulfilimine (D) is oxidized with mCPB A. A base such as potassium carbonate is employed to neutralize the acidity of OTCPB A. Protic polar solvents such as ethanol and water are used to increase the solubility of the sulfilimine starting material and the base employed.
The α-carbon of the TV-substituted sulfoximine of formula (Ia), i.e., n = 1, R3 = H in the (CR2R3) group adjacent to the sulfoximine function can be further alkylated or halogenated in the presence of a base such as potassium hexamethyl- disilamide (KHMDS) to give sulfoximines of formula (Ib), wherein R1, R2, X, L and Y are as previously defined and Z is an appropriate leaving group, as depicted in Scheme C. Preferred leaving groups are iodide (R6 = alkyl), benzenesulfon- imide (R6 = F), tetrachloroethene (R6= Cl), and tetrafluoroethene (R6= Br).
Scheme C
Figure imgf000008_0001
Sulfoximine compounds of formula (Ic) wherein R1, S and L taken together form a saturated 4-, 5- or 6-membered ring and n=l can be prepared by the methods illustrated in Scheme D wherein X and Y are as previously defined and m is O, I, or 2. Scheme D
O] NaNj. H2SO4 or MSH
Figure imgf000009_0002
Figure imgf000009_0001
In step a of Scheme D, which is similar to step b of Scheme A, sulfoxide is iminated with sodium azide in the presence of concentrated sulfuric acid or with 0-mesitylsulfonylhydroxylamine in a polar aprotic solvent to provide the corresponding N-unsubstituted sulfoximine. Chloroform or dichloromethane are the preferred solvents.
In step b of Scheme D, similar to step c of Scheme A, the nitrogen of sulfoximine can be either cyanated with cyanogen bromide, or nitrated with nitric acid followed by treatment with acetic anhydride under refluxing conditions, or carboxylated with methyl chloroformate in the presence of base such as DMAP, or acylated with acyl halide in the presence of base such as 4-dimethylamino- pyridine (DMAP) to provide Λf-substitued cyclic sulfoximine. Base is required for efficient cyanation, carboxylation or acylation and the preferred base is DMAP, whereas sulfuric acid is used as catalyst for efficient nitration reaction.
In step c of Scheme D, the α-carbon of Λf-substituted sulfoximine can be alkylated with a 1,3-thiazolyl methyl halide in the presence of a base such as KHMDS or butyl lithium (BuLi) to give the desired ,/V-substituted sulfoxiπύnes. The preferred halide can be bromide, chloride or iodide. Alternatively, the compounds of formula (Ic) can be prepared by a first α- alkylation of sulfoxides to give α-substituted sulfoxides and then an imination of the sulfoxide followed by Λf-substitution of the resulting sulfoximine by using the steps c , a and b respectively as described above for Scheme D.
The starting sulfides (A) in Scheme A can be prepared in different ways as illustrated in Schemes E, F G, and H.
In Scheme E, the sulfide of formula (Ai), wherein R1, R2 and Y are as previously defined, n=l, and R3 = H, can be prepared from 1,3-thiazolyl methyl halides of formula (E) by nucleophilic substitution with the sodium salt of an alkyl thiol.
Scheme E
Figure imgf000010_0001
In Scheme F, the sulfide of formula (A2), wherein R1, R2 and Y are as previously defined, n=3, and R3 = H, can be prepared from halides of formula (E) by reacting with a 2-mono substituted methyl malonate in the presence of base such as potassium terr-butoxide to provide 2,2-disubstitued malonate, hydrolysis under basic conditions to form a diacid, decarboxylation of the diacid by heating to give a monoacid, reduction of the monoacid with borane-tetrahyrofuran complex to provide an alcohol, tosylation of the alcohol with toluenesulfonyl chloride (tosyl chloride) in the presence of a base like pyridine to give a tosylate and replacement of the tosylate with the sodium salt of the desired thiol. Scheme F
Figure imgf000011_0001
In Scheme G, the sulfide of formula (A3), wherein R1, R2 and Y are as previously defined, n=2, and R3 = H, can be prepared from the nitrile of formula (F) by deprotonatioπ with a strong base and alkylation with an alkyl iodide to give α-alkylated nitrile, hydrolysis of the α-alkylated nitrile in the presence of a strong acid like HCl to give an acid, reduction of the acid with borane-tetrahyrofuran complex to provide an alcohol, tosylation of the alcohol with tosyl chloride in the presence of a base like pyridine to give a tosylate and replacement of the tosylate with the sodium salt of the desired thiol.
Scheme G
n base R2 R*
NC ^N NC 7 S/ HC. H<v/ 1V BH3THF
(F)
Figure imgf000011_0002
In Scheme H, the sulfide of formula (A4), wherein R1, S and L taken together represents a 4-, 5- or 6-membered ring (m = 0, 1 , or 2) and n is 0 can be prepared from 1,3-thiazolyl methyl halides (E) by treatment with thiourea, hydrolysis and subsequent alkylation with the appropriate bromo chloroalkane (m = 0, 1, or 2) under aqueous base conditions, and cyclization in the presence of a base like potassium-f-butoxide in a polar aprotic solvent such as THF.
Scheme H
Figure imgf000012_0001
where n = 0. 1, 2
1 ,3-thiazolyl methyl halides (E) can be prepared according to literature procedures. For example, the preparation of 5-bromomethyl-2-trifluoromethyl- 1,3-thiazole (Ei) is described in US patent 5,324,837.
-O^ Br
Y
(E1)
Another procedure, illustrated in Scheme I, is useful for preparing certain
4-chloromethyl 2-substituted-l,3-thiazoles (E2) where Y = Cj-C4 (halo)alkyl, or C2-C4 (halo)alkenyl or alkynyl. In this scheme, amides which bear the appropriate Y group are converted to thioamides with phosphorous pentasulfide and then treated ethyl bromopyruvate to provide the corresponding 4-carboethoxy-l,3- thiadiazole (G). Subsequent reduction with lithium aluminum hydride and conversion of the resultant alcohol to the chloride with thionyl chloride provides desired 2-substituted-l,3-thiazol-4-yl methyl chlorides (E2). Scheme I
Figure imgf000013_0001
(E1)
ExamDles
These examples are provided to further illustrate this invention. They are not meant to be construed as limiting the invention.
Example I Methyl(oxido) { [2-(trifluoromethyl)- 1 ,3-thiazol-5-yl]methyl } -λ4- sulfanylidenecyanamide (1)
Figure imgf000013_0002
(D
(A)
Figure imgf000013_0003
(A)
A solution of 5-(bromomethyl)-2-(trifluoromethyl)-l,3-thiazole [prepared in accordance with U.S. patent 5,338,856] (170 mg, 069 mmol) in 5 mL of ethanol was treated sodium methylthiolate (60 mg, 0.86 mmol) at room temperature. The reaction was complete in 10 min and so the solvent was carefully removed under reduced pressure (40 mmHg) without heating. The residue was partitioned between dichloromethane and dilute hydrochloric acid, washed with saturated brine and dried over sodium sulfate. The solvent was again carefully removed under reduced pressure (40 mmHg) without heating to yield 5- [(methylthio)methyl]-2-(trifluoromethyl)-l,3-thiazole (140 mg; 96%) as a pale orange liquid: IH NMR (CDCl3) δ 7.75 (s, IH), 3.90 (s, 2H), 2.10 (s, 3H); GCMS (FID) m/z 213 (M+).
(B)
Figure imgf000014_0001
(B)
A solution of 5-[(methylthio)methyl]-2-(trifluoromethyl)-l,3-thiazole (140 mg, 0.62 mmol) and cyanamide (35 mg, 0.83 mmol) in 6 mL of dichloromethane was cooled to 0° C and treated with iodobenzene diacetate (860 mg, 2.59 mmol). A clear yellow solution was obtained. The mixture was allowed to warm to room temperature over an hour and then the solvent removed under reduced pressure and the residue further purified by flash column chromatography on silica gel using a 50% mixture of acetone and petroleum ether as the eluant. The solvents were removed under reduced pressure to yield 130 mg (83%) of (lE)-methyl{[2- (trifluoromethyl)- 1 ,3-thiazol-5-yl]methyl } -λ4-sulfanylidenecyanamide as a pale yellow syrup: IH NMR (CDCl3) δ 8.00 (s, IH), 4.60 (s, 2H), 2.85 (s, 3H); LCMS (ESI) m/z 254 (M+H).
(Q
RuCI3ZNaIO4
Figure imgf000014_0003
Figure imgf000014_0002
(C) A rapidly stirring solution of (lE)-methyl{[2-(trifluoromethyl)-l,3- thiazol-5-yl]methyl}-λ4-sulfanylidenecyanamide (86 mg, 0.34 mmol) in 10 mL of dichloromethane was first treated with ruthenium(III) chloride hydrate (8 mg, 0.04 mmol) and then a solution of sodium periodate (146 mg, 0.68 mmol) in 5 mL of water. The dark mixture was stirred for 45 min at room temperature at which point all starting material was consumed. The dark mixture was then passed through a plug of alumina followed by an acetone wash. The combined filtrates were partitioned between dichloromethane and water, washed with brine, and the organic layer dried over sodium sulfate. The solvent was removed under reduced pressure to yield 70 mg (76%) of methyl(oxido){[2-(trifluoromethyl)-l,3-thiazol- 5-yl]methyl}-λ4-sulfanylidenecyanamide as a white solid: mp 123-124° C; IH NMR (CDCl3) δ 8.00 (s, IH), 4.95 (s, 2H), 3.10 (s, 3H); LCMS (ESI) m/z 268 (M-H).
Examples II Methyl(oxido) { 1 -methyl- 1 -[2-(trifluoromethyl)- 1 ,3-thiazol-5- yl]ethyl}-λ4-sulfanylidenecyanamide (2) and Methyl(oxido){ l-[2- (trifluoromethyl)-l,3-thiazol-5-yl]ethyl}-λ4-sulfanylidenecyanamide (3).
Figure imgf000015_0001
(2) W
A solution of methyl(oxido){[2-(trifluoromethyl)-l,3-thiazol-5- yl]methyl}-λ4-sulfanylidenecyanamide (124 mg, 0.46 mmol) in 8 mL of tetrahydrofuran was cooled to -78° C under a nitrogen atmosphere and treated with 1.10 mL of a 0.5 M solution of potassium hexamethyldisilazide in toluene and hexamethylphosphroamide (0.04 mL, 0.23 mmol). After 20 minutes, iodomethane (0.3 mL, 4.8 mmol) was added and the mixture allowed to warm to 0° C over 2 hours. The reaction was quenched with IM hydrochloric acid and the mixture partitioned between dilute hydrochloric acid and dichloromethane. The organic layer was dried over sodium sulfate and the solvent removed under reduced pressure to yield 180 mg of a yellow syrup. The products and remaining starting material were separated by flash column chromatography on silica gel using a 1% solution of ethanol in dichloromethane. The less polar dimethylated product (50 mg, 39%) was obtained as a pale yellow syrup: IH NMR (CDCI3) δ 8.05 (s, IH), 3.05 (s, 3H), 2.08 (s, 6H); LCMS (ESI) m/z 296 (M-H).
The diastereomeric mixture of monomethylated products (45 mg, 31%) was obtained as a colorless syrup: IH NMR (CDCl3) δ 8.03 (d, J = 4 Hz, IH), 5.02 (q, J = 8 Hz, IH), 3.08 (d, J = 6 Hz, 3H) 2.05 (d, J = 8 Hz, 3H); LCMS (ESI) m/z 282 (M-H).
Example m 1 -Oxo-2-(2-trifluoromethyl-thiazol-5-ylmethyl)-tetrahydro- 1 -λ6- thiophen- 1-ylidene-cyan amide.
Figure imgf000016_0001
(4)
A solution of 1-Oxo-tetrahydro-l- λff"thiophen-l-ylidene-cyanamide [prepare in accordance with U.S. patent application 2005228027] (200 mg, 1.39 mmol) in 8 mL of tetrahydrofuran was cooled to -78° C under a nitrogen atmosphere and treated with 0.60 mL of a 2.5 M solution of n-butyllithium in hexanes. After 15 minutes, 5-(bromomethyl)-2-(trifluoromethyl)-l,3-thiazole (340 mg, 1.39 mmol) dissolved in 1 mL of tetrahydrofuran was added all at once to the mixture. After 90 minutes, the mixture was allowed to warm to -40° C and quenched with IM hydrochloric acid. The reaction mixture was partitioned between dilute hydrochloric acid and dichloromethane. The organic layer was dried over sodium sulfate and the solvent removed under reduced pressure to yield 430 mg of a yellow syrup. The mixture was further purified by reverse phase HPLC using an acetonitrile and water mixture as eluant. The diastereomeric mixture of products (71 mg, 17%) was obtained as a pale yellow syrup: IH NMR (CDCl3) δ 7.90 (s, IH), 3.4-3.8 (m, 3H), 3.2-3.4 (m, 2H) 1.9-2.7 (m, 4H); LCMS (ESI) m/z 310 (M+H).
Example IV Methyl(oxido) { [2-(trifluoromethyl)- 1 ,3-thiazol-4-yl]methyl } -λ4- sulfanylidenecyanamide (5)
Figure imgf000017_0001
(5)
(A)
Figure imgf000017_0002
(A)
2-(Trifluoromethyl)4-thiazolemethanol (EP 402246; 1.5g, 8.3mmol) was dissolved in 15ml chloroform, treated with thionyl chloride( 1.8ml, 2.4g, 21mmol) and heated to reflux. After Ih, the mixture was cooled and volatiles were removed under vacuum. The residue was taken up in 25ml ethyl acetate and washed with 10ml sat. NaHCO3, 10ml sat. NaCl, dried(Na2Sθ4) and evaporated. The residue was taken up in 5ml ethanol and treated in portions with sodium thiomethoxide (800mg, 12mmol) and stirred for Ih at 25°C. The mixture was poured into 15ml water and extracted 2X 15ml ethyl acetate. The combined extracts were washed with sat. NaCl, dried(Na2SC«4) and evaporated to obtain 1.3g of 2-(Trifluoro- methyl)-4(methylthio)methyl thiazole (A).
(B)
Figure imgf000017_0003
<5> 2-(Trifluoromethyl)-4(methylthio)methyl thiazole(1.3g, ό.lmmol) was dissolved in 10ml dichloromethane, treated with cyanamide(520mg, 12mmol), cooled to 0-50C and treated with iodobenzene diacetate(2. Ig, 6.7mmol) in one portion. After 3h, the solvent was removed by evaporation and the residue was chromatographed on silica eluting with 5% methanol/ 25% ethyl acetate/ 70% dichloromethane to give 680mg of the intermediate sulfilimine. This material was dissolved in 7ml dichloromethane and poured into a stirred mixture of sodium periodate (l.lg, 5.4mmol) and ruthenium trichloride hydrate (30mg, 0.14mmol) in 7ml water. The mixture was stirred for 2h at 25°C, the dichloromethane phase was separated and the aqueous phase was extracted once with 10ml dichloromethane. The combined extracts were dried(Na2SO4), evaporated and the residue was chromatographed on silica eluting with 1% methanol/ 25% acetone/ 75% hexane to give 335mg of methyl(oxido){ [2-(trifluoromethyl)- 1,3 -thiazol-4-yl] methyl }-λ4- sulfanylidenecyanamide (5). MP 66-680C. Electrospray MS M+ = 246.
Example V Insecticidal Testing
The compounds identified in the foregoing examples (compounds 1-5) and in Table 1 (compounds 6-18) were tested against cotton aphid using procedures described hereinafter.
Insecticidal test for cotton aphid (Aphis gossypii) in foliar spray assay
Squash with fully expanded cotyledon leaves were trimmed to one cotyledon per plant and infested with cotton aphid (wingless adult and nymph) 1 day prior to chemical application. Each plant was examined before chemical application to ensure proper infestation (ca. 30-70 aphids per plant). Compounds (2 mg) were dissolved in 2 ml of acetone : methanol (1 : 1) solvent, forming stock solutions of 1000 ppm. The stock solutions were diluted 5X with 0.025% Tween 20 in H2O to obtain the highest test solution at 200 ppm. A lower test concentration (50 ppm) was prepared by making sequential a 4X dilution from the 200 ppm solution with a diluent consisting 80 parts of 0.025% Tween 20 in H2O and 20 parts of acetone : methanol (1 : 1). A hand-held Devilbiss sprayer was used to apply the spray solutions until runoff to both sides of the squash cotyledon leaves. Four plants (4 replications) were used for each concentration of each compound. Reference plants (solvent check) were sprayed with the diluent only. Treated plants were held in a holding room for 3 days at approximately 23 0C and 40% RH before the number of live aphids on each plant was recorded. Insecticidal activity was measured by Corrected % Control using Abbott's correction formula and the values for the lower test concentrations are presented in Table 1:
Corrected % Control = 100 * (X - Y) / X
where X = No. of live aphids on solvent check plants
Y = No. of live aphids on treated plants
Table 1
Figure imgf000019_0001
CA 200 refers to % control at 200 ppm against cotton aphid in foliar spray tests, CA 50 refers to % control at 50 ppm against cotton aphid in foliar spray tests, In each case of Table 2 the rating scale is as follows:
Figure imgf000020_0001
Insecticide Utility
The compounds of the invention are useful for the control of insects. Therefore, the present invention also is directed to a method for inhibiting an insect which comprises applying an insect-inhibiting amount of a compound of formula (I) to a locus of the insect, to the area to be protected, or directly on the insect to be controlled. The compounds of the invention may also be used to control other invertebrate pests such as mites and ticks, and nematodes.
The "locus" of insects or other pests is a term used herein to refer to the environment in which the insects or other pests live or where their eggs are present, including the air surrounding them, the food they eat, or objects which they contact. For example, insects which eat, damage or contact edible, commodity, ornamental, turf or pasture plants can be controlled by applying the active compounds to the seed of the plant before planting, to the seedling, or cutting which is planted, the leaves, stems, fruits, grain, and/or roots, or to the soil or other growth medium before or after the crop is planted. Protection of these plants against virus, fungus or bacterium diseases may also be achieved indirectly through controlling sap-feeding pests such as whitefly, plant hopper, aphid and spider mite. Such plants include those which are bred through conventional approaches and which are genetically modified using modern biotechnology to gain insect-resistant, herbicide-resistant, nutrition-enhancement, or any other beneficial traits.
It is contemplated that the compounds might also be useful to protect textiles, paper, stored grain, seeds and other foodstuffs, houses and other buildings which may be occupied by humans and/or companion, farm, ranch, zoo, or other animals, by applying an active compound to or near such objects. Domesticated animals, buildings or human beings might be protected with the compounds by controlling invertebrate and/or nematode pests that are parasitic or are capable of transmitting infectious diseases. Such pests include, for example, chiggers, ticks, lice, mosquitoes, flies, fleas and heartworms. Nonagronomic applications also include invertebrate pest control in forests, in yards, along road sides and railroad right of way.
The term "inhibiting an insect" refers to a decrease in the numbers of living insects, or a decrease in the number of viable insect eggs. The extent of reduction accomplished by a compound depends, of course, upon the application rate of the compound, the particular compound used, and the target insect species. At least an inactivating amount should be used. The term "insect-inactivating amount" is used to describe the amount, which is sufficient to cause a measurable reduction in the treated insect population. Generally an amount in the range from about 1 to about 1000 ppm by weight active compound is used. For example, insects which can be inhibited include, but are not limited to:
Lepidoptera — Heliothis spp., Helicoverpa spp., Spodoptera spp., Mythimna unipuncta, Agrotis ipsilon, Earias spp., Euxoa auxiliaris, Trichoplusia ni, Anticarsia gemmatalis, Rachiplusia nu, Plutella xylostella, Chilo spp., Scirpophaga incertulas, Sesamia inferens, Cnaphalocrocis medinalis, Ostrinia nubilalis, Cydia pomonella, Carposina niponensis,' Adoxophyes orana, Archips argyrospilus, Pandemis heparana, Epinotia aporema, Eupoecilia ambiguella, Lobesia botrana, Polychrosis viteana, Pectinophora gossypiella, Pieris rapae, Phyllonorycter spp., Leucoptera malifoliella, Phyllocnisitis citrella
Coleoptera — Diabrotica spp., Leptinotarsa decemlineata, Oulema oryzae, Anthonomus grandis, Lissorhoptrus oryzophilus, Agriotes spp., Melanotics communis, Popillia japonica, Cyclocephala spp., Tribolium spp.
Homoptera - Aphis spp., Myzus persicae, Rhopalosiphum spp., Dysaphis plantaginea, Toxoptera spp., Macrosiphum euphorbiae, Aulacorthum solani, Sitobion avenae, Metopolophium dirhodum, Schizaphis graminum, Brachycolus noxius, Nephotettix spp., Nilaparvata lugens, Sogatellafurcifera, Laodelphax striatellus, Bemisia tabaci, Trialeurodes vaporariorum, Aleurodes proletella, Aleurothrixus floccosus, Quadraspidiotus perniciosus, Unaspis yanonensis, Ceroplastes rubens, Aonidiella aurantii
Hemiptera - Lygus spp., Eurygaster maura, Nezara viridula, Piezodorus guildingi, Leptocorisa varicornis
Thysanoptera — Frankliniella occidentalism Thrips spp., Scirtothrips dorsalis
Isoptera — Reticulitermes flavipes, Coptotermes formosanus
Orthoptera - Blattella germanica, Blatta orientalis, Gryllotalpa spp.
Diptera — Liriomyza spp., Musca domestica, Aedes spp., Culex spp., Anopheles spp.
Hymenoptera — Iridomyrmex humilis, Solenopsis spp., Monomorium pharaonis, Atta spp., Pogonomyrmex spp., Camponotus spp.
Siphonaptera - Ctenophalides spp., Pulex irritans Acarina - Tetranychus spp., Panonychus spp., Eotetranychus carpini, Phyllocoptruta oleivora, Aculus pelekassi, Brevipalpus phoenicis, Boophilus spp., Dermacentor variabilis, Rhipicephalus sanguineus, Amblyomma americanum, Ixodes spp., Notoedres cati, Sarcoptes scabiei, Dermatophagoides spp.
Nematoda — Dirofilaria immitis, Meloidogyne spp., Heterodera spp., Hoplolaimus columbus, Belonolaimus spp., Pratylenchus spp., Rotylenchus reniformis, Criconemella ornata, Ditylenchus spp., Aphelenchoides besseyi, Hirschmanniella spp.
Compositions
The compounds of this invention are applied in the form of compositions which are important embodiments of the invention, and which comprise a compound of this invention and a phytologically-acceptable inert carrier. Control of the pests is achieved by applying compounds of the invention in forms of sprays, topical treatment, gels, seed coatings, microcapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants aerosols, dusts and many others. The compositions are either concentrated solid or liquid formulations which are dispersed in water for application, or are dust or granular formulations which are applied without further treatment. The compositions are prepared according to procedures and formulae which are conventional in the agricultural chemical art, but which are novel and important because of the presence therein of the compounds of this invention. Some description of the formulation of the compositions will be given, however, to assure that agricultural chemists can readily prepare any desired composition.
The dispersions in which the compounds are applied are most often aqueous suspensions or emulsions prepared from concentrated formulations of the compounds. Such water-soluble, water-suspendable or emulsifiable formulations are either solids, usually known as wettable powders, or liquids usually known as emulsifiable concentrates or aqueous suspensions. Wettable powders, which may be compacted to form water dispersible granules, comprise an intimate mixture of the active compound, an inert carrier, and surfactants. The concentration of the active compound is usually from about 10% to about 90% by weight. The inert carrier is usually chosen from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, or the purified silicates. Effective surfactants, comprising from about 0.5% to about 10% of the wettable powder, are found among the sulfonated lignins, the condensed naphthalenesulfonates, the naphthalenesulfonates, the alkylbenzenesulfonates, the alkyl sulfates, and nonionic surfactants such as ethylene oxide adducts of alkyl phenols.
Emulsifiable concentrates of the compounds comprise a convenient concentration of a compound, such as from about 50 to about 500 grams per liter of liquid, equivalent to about 10% to about 50%, dissolved in an inert carrier which is either a water miscible solvent or a mixture of water-immiscible organic solvent and emulsifϊers. Useful organic solvents include aromatics, especially the xylenes, and the petroleum fractions, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, such as the terpenic solvents including rosin derivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable concentrates are chosen from conventional nonionic surfactants, such as those discussed above.
Aqueous suspensions comprise suspensions of water-insoluble compounds of this invention, dispersed in an aqueous vehicle at a concentration in the range from about 5% to about 50% by weight. Suspensions are prepared by finely grinding the compound, and vigorously mixing it into a vehicle comprised of water and surfactants chosen from the same types discussed above. Inert ingredients, such as inorganic salts and synthetic or natural gums, may also be added, to increase the density and viscosity of the aqueous vehicle. It is often most effective to grind and mix the compound at the same time by preparing the aqueous mixture, and homogenizing it in an implement such as a sand mill, ball mill, or piston-type homogenizer.
The compounds may also be applied as granular compositions, which are particularly useful for applications to the soil. Granular compositions usually contain from about 0.5% to about 10% by weight of the compound, dispersed in an inert carrier which consists entirely or in large part of clay or a similar inexpensive substance. Such compositions are usually prepared by dissolving the compound in a suitable solvent and applying it to a granular carrier which has been pre-formed to the appropriate particle size, in the range of from about 0.5 to 3 mm. Such compositions may also be formulated by making a dough or paste of the carrier and compound and crushing and drying to obtain the desired granular particle size.
Dusts containing the compounds are prepared simply by intimately mixing the compound in powdered form with a suitable dusty agricultural carrier, such as kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1% to about 10% of the compound.
It is equally practical, when desirable for any reason, to apply the compound in the form of a solution in an appropriate organic solvent, usually a bland petroleum oil, such as the spray oils, which are widely used in agricultural chemistry.
Insecticides and acaricides are generally applied in the form of a dispersion of the active ingredient in a liquid carrier. It is conventional to refer to application rates in terms of the concentration of active ingredient in the carrier. The most widely used carrier is water. The compounds of the invention can also be applied in the form of an aerosol composition. In such compositions the active compound is dissolved or dispersed in an inert carrier, which is a pressure-generating propellant mixture. The aerosol composition is packaged in a container from which the mixture is dispensed through an atomizing valve. Propellant mixtures comprise either low- boiling halocarbons, which may be mixed with organic solvents, or aqueous suspensions pressurized with inert gases or gaseous hydrocarbons.
The actual amount of compound to be applied to loci of insects and mites is not critical and can readily be determined by those skilled in the art in view of the examples above. In general, concentrations from 10 ppm to 5000 ppm by weight of compound are expected to provide good control. With many of the compounds, concentrations from 100 to 1500 ppm will suffice.
The locus to which a compound is applied can be any locus inhabited by an insect or mite, for example, vegetable crops, fruit and nut trees, grape vines, ornamental plants, domesticated animals, the interior or exterior surfaces of buildings, and the soil around buildings.
Because of the unique ability of insect eggs to resist toxicant action, repeated applications may be desirable to control newly emerged larvae, as is true of other known insecticides and acaricides.
Systemic movement of compounds of the invention in plants may be utilized to control pests on one portion of the plant by applying the compounds to a different portion of it. For example, control of foliar-feeding insects can be controlled by drip irrigation or furrow application, or by treating the seed before planting. Seed treatment can be applied to all types of seeds, including those from which plants genetically transformed to express specialized traits will germinate. Representative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis or other insecticidal toxins, or those expressing herbicide resistance, such as "Roundup Ready" seed.
An insecticidal bait composition consisting of compounds of the present invention and attractants and/or feeding stimulants may be used to increase efficacy of the insecticides against insect pest in a device such as trap, bait station, and the like. The bait composition is usually a solid, semi-solid (including gel) or liquid bait matrix including the stimulants and one or more non- microencapsulated or microencapsulated insecticides in an amount effective to act as kill agents.
The compounds of the present invention (Formula I) are often applied in conjunction with one or more other insecticides or fungicides to obtain control of a wider variety of pests and diseases. When used in conjunction with other insecticides or fungicides, the presently claimed compounds can be formulated with the other insecticides or fungicides, tank mixed with the other insecticides or fungicides, or applied sequentially with the other insecticides or fungicides.
Some of the insecticides that can be employed beneficially in combination with the compounds of the present invention include: antibiotic insecticides such as allosamidin and thuringiensin; macrocyclic lactone insecticides such as spinosad, DE-175, and other spinosyns including the 21-butenyl spinosyns and their derivatives; avermectin insecticides such as abamectin, doramectin, emamectin, eprinomectin, ivermectin and selamectin; milbemycin insecticides such as lepimectin, milbemectin, milbemycin oxime and moxidectin; arsenical insecticides such as calcium arsenate, copper acetoarsenite, copper arsenate, lead arsenate, potassium arsenite and sodium arsenite; biological insecticides such as Bacillus popilliae, B. sphaericus, B. thuringiensis subsp. aizawai, B. thuringiensis subsp. kurstaki, B. thuringiensis subsp. tenebrionis, Beauveria bassiana, Cydia pomonella granulosis virus, Douglas fir tussock moth NPV, gypsy moth NPV, Helicoverpa zea NPV, Indian meal moth granulosis virus, Metarhizium anisopliae, Nosema locustae, Paecilomyces fumosoroseus, P. lilacinus, Photorhabdus luminescens, Spodoptera exigua NPV, trypsin modulating oostatic factor, Xenorhabdus nematophilus, and X. bovienii, plant incorporated protectant insecticides such as CrylAb, CrylAc, CrylF, CrylA.105, Cry2Ab2, Cry3A, mir Cry3A, Cry3Bbl, Cry34, Cry35, and VIP3A; botanical insecticides such as anabasine, azadirachtin, d-limonene, nicotine, pyrethrins, cinerins, cinerin I, cinerin II, jasmolin I, jasmolin π, pyrethrin I, pyrethrin II, quassia, rotenone, ryania and sabadilla; carbamate insecticides such as bendiocarb and carbaryl; benzofuranyl methylcarbamate insecticides such as benfuracarb, carbofuran, carbosulfan, decarbofuran and furathiocarb; dimethylcarbamate insecticides dimitan, dimetilan, hyquincarb and pirimicarb; oxime carbamate insecticides such as alanycarb, aldicarb, aldoxycarb, butocarboxim, butoxycarboxim, methomyl, nitrilacarb, oxamyl, tazimcarb, thiocarboxime, thiodicarb and thiofanox; phenyl methylcarbamate insecticides such as allyxycarb, aminocarb, bufencarb, butacarb, carbanolate, cloethocarb, dicresyl, dioxacarb, EMPC, ethiofencarb, fenethacarb, fenobucarb, isoprocarb, methiocarb, metolcarb, mexacarbate, promacyl, promecarb, propoxur, trimethacarb, XMC and xylylcarb; dinitrophenol insecticides such as dinex, dinoprop, dinosam and DNOC; fluorine insecticides such as barium hexafluorosilicate, cryolite, sodium fluoride, sodium hexafluorosilicate and suifiummid; formamidine insecticides such as amitraz, chlordimeform, formetanate and formparanate; /αmigα/i/ insecticides such as acrylonitrile, carbon disulfide, carbon tetrachloride, chloroform, chloropicrin, para-dichlorobenzene, 1,2-dichloropropane, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, hydrogen cyanide, iodomethane, methyl bromide, methylchloroform, methylene chloride, naphthalene, phosphine, sulfuryl fluoride and tetrachloroethane; inorganic insecticides such as borax, calcium polysulfide, copper oleate, mercurous chloride, potassium thiocyanate and sodium thiocyanate; chitin synthesis inhibitors such as bistrifluron, buprofezin, chlorfluazuron, cyromazine, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron and triflumuron; juvenile hormone mimics such as epofenonane, fenoxycarb, hydroprene, kinoprene, methoprene, pyriproxyfen and triprene; juvenile hormones such as juvenile hormone I, juvenile hormone II and juvenile hormone HI; moulting hormone agonists such as chromafenozide, halofenozide, methoxyfenozide and tebufenozide; moulting hormones such as α-ecdysone and ecdysterone; moulting inhibitors such as diofenolan; precocenes such as precocene I, precocene π and precocene HI; unclassified insect growth regulators such as dicyclanil; nereistoxin analogue insecticides such as bensultap, cartap, thiocyclam and thiosultap; nicotinoid insecticides such as flonicamid; nitroguanidine insecticides such as clothianidin, dinotefuran, imidacloprid and thiamethoxam; nitromethylene insecticides such as nitenpyram and nithiazine; pyridylmethylamine insecticides such as acetamiprid, imidacloprid, nitenpyram and thiacloprid; organochlorine insecticides such as bromo-DDT, camphechlor, DDT, pp'-DDT, ethyl-DDD, HCH, gamma-HCH, lindane, methoxychlor, pentachlorophenol and TDE; cyclodiene insecticides such as aldrin, bromocyclen, chlorbicyclen, chlordane, chlordecone, dieldrin, dilor, endosulfan, endrin, HEOD, heptachlor, HHDN, isobenzan, isodrin, kelevan and mirex; organophosphate insecticides such as bromfenvinfos, chlorfenvinphos, crotoxyphos, dichlorvos, dicrotophos, dimethylvinphos, fospirate, heptenophos, methocrotophos, mevinphos, monocrotophos, naled, naftalofos, phosphamidon, propaphos, TEPP and tetrachlorvinphos; organothiophosphate insecticides such as dioxabenzofos, fosmethilan and phenthoate; aliphatic organothiophosphate insecticides such as acethion, amiton, cadusafos, chlorethoxyfos, chlormephos, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-S, demeton-methyl, demeton-O-methyl, demeton-S-methyl, demeton-S-methylsulphon, disulfoton, ethion, ethoprophos, IPSP, isothioate, malathion, methacrifos, oxydemeton- methyl, oxydeprofos, oxydisulfoton, phorate, sulfotep, terbufos and thiometon; aliphatic amide organothiophosphate insecticides such as amidithion, cyanthoate, dimethoate, ethoate-methyl, formothion, mecarbam, omethoate, prothoate, sophamide and vamidothion; oxime organothiophosphate insecticides such as chlorphoxim, phoxim and phoxim-methyl; heterocyclic organothiophosphate insecticides such as azamethiphos, coumaphos, coumithoate, dioxathion, endothion, menazon, morphothion, phosalone, pyraclofos, pyridaphenthion and quinothion; benzothiopyran organothiophosphate insecticides such as dithicrofos and thicrofos; benzotriazine organothiophosphate insecticides such as azinphos- ethyl and azinphos-methyl; isoindole organothiophosphate insecticides such as dialifos and phosmet; isoxazole organothiophosphate insecticides such as isoxathion and zolaprofos; pyrazolopyrimidine organothiophosphate insecticides such as chlorprazophos and pyrazophos; pyridine organothiophosphate insecticides such as chlorpyrifos and chlorpyrifos-methyl; pyrimidine organothiophosphate insecticides such as butathiofos, diazinon, etrimfos, lirimfos, pirimiphos-ethyl, pirimiphos-methyl, primidophos, pyrimitate and tebupirimfos; quinoxaline organothiophosphate insecticides such as quinalphos and quinalphos-methyl; thiadiazole organothiophosphate insecticides such as athidathion, lythidathion, methidathion and prothidathion; triazole organothiophosphate insecticides such as isazofos and triazophos; phenyl organothiophosphate insecticides such as azothoate, bromophos, bromophos- ethyl, carbophenothion, chlorthiophos, cyanophos, cythioate, dicapthon, dichlofenthion, etaphos, famphur, fenchlorphos, fenitrothion fensulfothion, fenthion, fenthion-ethyl, heterophos, jodfenphos, mesulfenfos, parathion, parathion-methyl, phenkapton, phosnichlor, profenofos, prothiofos, sulprofos, temephos, trichlormetaphos-3 and trifenofos; phosphonate insecticides such as butonate and trichlorfon; phosphonothioate insecticides such as mecarphon; phenyl ethylphosphonothioate insecticides such as fonofos and trichloronat; phenyl phenylphosphonothioate insecticides such as cyanofenphos, EPN and leptophos; phosphoramidate insecticides such as crufomate, fenamiphos, fosthietan, mephosfolan.phosfolan and pirimetaphos; phosphoramidothioate insecticides such as acephate, isocarbophos, isofenphos, methamidophos and propetamphos; phosphorodiamide insecticides such as dimefox, mazidox, mipafox and schradan; oxadiazine insecticides such as indoxacarb; phthalimide insecticides such as dialifos, phosmet and tetramethrin; pyrazole insecticides such as acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole, tebufenpyrad, tolfenpyrad and vaniliprole; pyrethroid ester insecticides such as acrinathrin, allethrin, bioallethrin, barthrin, bifenthrin, bioethanomethrin, cyclethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypeπnethrin, alpha-cypermethrin, beta-cypermethrin, theta- cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, dimefluthrin, dimethrin, empenthrin, fenfluthrin, fenpirithrin, fenpropathrin, fenvalerate, esfenvalerate, flucythrinate, fluvalinate, tau-fluvalinate, furethrin, imiprothrin, metofluthrin, permethrin, biopermethrin, transpermethrin, phenothrin, prallethrin, profluthrin, pyresmethrin, resmethrin, bioresmethrin, cismethrin, tefluthrin, terallethrin, tetramethrin, tralomethrin and transfluthrin; pyrethroid ether insecticides such as etofenprox, flufenprox, halfenprox, protrifenbute and silafluofen; pyrimidinamine insecticides such as flufenerim and pyrimidifen; pyrrole insecticides such as chiorfenapyr; tetronic acid insecticides such as spirodiclofen, spiromesifen and spirotetramat; thiourea insecticides such as diafenthiuron; urea insecticides such as flucofuron and sulcofuron; and unclassified insecticides such as AKD-3088, closantel, crotamiton, cyflumetofen, E2Y45, EXD, fenazaflor, fenazaquin, fenoxacrim, fenpyroximate, FKI- 1033, flubendiamide, HGW86, hydramethylnon, IKI-2002, isoprothiolane, malonoben, metaflumizone, metoxadiazone, nifluridide, NNI-9850, NNI-0101, pymetrozine, pyridaben, pyridalyl, Qcide, rafoxanide, rynaxypyr, SYJ- 159, triarathene and triazamate and any combinations thereof. Some of the fungicides that can be employed beneficially in combination with the compounds of the present invention include: 2-(thiocyanatomethylthio)- benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, Ampelomyces, quisqualis, azaconazole, azoxystrobin, Bacillus subtilis, benalaxyl, benomyl, benthiavalicarb-isopropyl, benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl, bismerthiazol, bitertanol, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, calcium polysulfide, captafol, captan, carbendazim, carboxin, caφropamid, carvone, chloroneb, chlorothalonil, chlozolinate, Coniothyrium mini tans, copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprous oxide, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, diammonium ethylenebis-(dithiocarbamate), dichlofluanid, dichlorophen, diclocymet, diclomezine, dichloran, diethofencarb, difenoconazole, difenzoquat ion, diflumetorim, dimethomorph, dimoxystrobin, diniconazole, diniconazole- M.dinobuton, dinocap, diphenylamine, dithianon, dodemoφh, dodemoφh acetate, dodine, dodine free base, edifenphos, epoxiconazole, ethaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimoφh, fentin, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorph, fluopicolide, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, formaldehyde, fosetyl, fosetyl- aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, guazatine acetates, GY-81, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate), ipconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane, kasugamycin, kasugamycin hydrochloride hydrate, kresoxim-methyl, mancopper, mancozeb, maneb, mepanipyrim, mepronil, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, mefenoxam, metalaxyl-M, metam, metam- ammonium, metam-potassium, metam-sodium, metconazole, methasulfocarb, methyl iodide, methyl isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fatty acids), orysastrobin, oxadixyl, oxine-copper, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercury acetate, phosphonic acid, phthalide, picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassium hydroxyquinoline sulfate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pyrazophos, pyributicarb, pyrifenox, pyrimethanil, pyroquilon, quinoclamine, quinoxyfen, quintozene, Reynoutria sachalinensis extract, silthiofam, simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z071, tar oils, tebuconazole, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate- methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, vinclozolin, zineb, ziram, zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp., Phlebiopsis gigantean, Streptomyces griseoviridis, Trichoderma spp., (RS)-N-(3,5-dichlorophenyl)-2- (methoxymethyl)-succinimide, 1,2-dichloropropane, l,3-dichloro-l,l,3,3- tetrafluoroacetone hydrate, l-chloro-2,4-dinitronaphthalene, l-chloro-2- nitropropane, 2-(2-heptadecyl-2-imidazolin- l-yl)ethanol, 2,3-dihydro-5-phenyl- 1,4-dithi-ine 1,1,4,4-tetraoxide, 2-methoxyethylmercury acetate, 2- methoxyethylmercury chloride, 2-methoxyethylmercury silicate, 3-(4- chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop-l-enyl)phenyl thiocyanateme: ampropylfos, anilazine, azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox, bentaluron, benzamacril; benzamacril-isobutyl, benzamorf, binapacryl, bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone, chloraniformethan, chlorfenazole, chlorquinox, climbazole, copper bis(3- phenylsalicylate), copper zinc chromate, cufraneb, cupric hydrazinium sulfate, cuprobam, cyclafuramid, cypendazole, cyprofuram, decafentin, dichlone, dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, ESBP, etaconazole, etem, ethirim, fenaminosulf, fenapanil, fenitropan, fluotrimazole, furcarbanil, furconazole, fiirconazole-cis, furmecyclox, fiirophanate, glyodine, griseofulvin, halacrinate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, methfiiroxam, methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride, myclozolin, N-3,5- dichlorophenyl-succinimide, N-3-nitrophenylitaconimide, natamycin, N- ethylmercurio-4-toluenesulfonanilide, nickel bis(dimethyldithiocarbamate), OCH, phenylmercury dimethyldithiocarbamate, phenyl mercury nitrate, phosdiphen, prothiocarb; prothiocarb hydrochloride, pyracarbolid, pyridinitril, pyroxychlor, pyroxyfur, quinacetol; quinacetol sulfate, quinazamid, quinconazole, rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trichlamide, urbacid, XRD-563, and zarilamid, and any combinations thereof.

Claims

We claim
1. A compound of the formula (I)
Figure imgf000035_0001
(I)
wherein
X represents NO2, CN, COOR* or COR 5J.;
L represents either a single bond or -CH(CH2)m- where m is an integer from 1-3 in cases where R1, S and L taken together represent a A-, 5-, or 6- membered ring;
n is an integer from 0-3;
Y represents Ci-C4 alkyl, Ci-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, fluoro, bromo, iodo, Q-C4 alkoxy, Ci-C4 haloalkoxy, CN, NO2 or R6SOZ where z is an integer from 0-2;.
R1 represents Q-C4 alkyl, C1-C4 haloalkyl, C3-C6 alkenyl, C3-C6 haloakenyl, C3-C6 alkynyl, or -(CH2)- in cases where R1, S and L taken together represent a 4-, 5-, or 6-membered ring;
R2 and R3 independently represent hydrogen, methyl, ethyl, cyclopropyl, fluoro, chloro, bromo, or iodo;
R4 represents Ci-C4 alkyl, Ci-C4 haloalkyl, aryl, heteroaryl, arylalkyl or heteroarylalkyl; R5 represents hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, aryl, heteroaryl; arylalkyl or heteroarylalkyl; and
R6 represents Ci-C4 alkyl, CrC4 haloalkyl, C3-C6 alkenyl, C3-C6 haloakenyl or C3-C6 alkynyl.
2. A composition for controlling insects which comprises a compound of any Claim 1 in combination with a phytologically-acceptable carrier.
3. A method of controlling insects which comprises applying to a locus where control is desired an insect-inactivating amount of a compound of Claim 1.
PCT/US2007/019176 2006-09-01 2007-08-30 Insecticidal n-substituted (2- sudstituted-1,3-thiazol) alkyl sulfoximines WO2008027539A1 (en)

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