EP2300449A1 - Pesticidal compositions containing a pyrandione or a thiopyrandione or a cyclohexanetrione derivative - Google Patents

Pesticidal compositions containing a pyrandione or a thiopyrandione or a cyclohexanetrione derivative

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Publication number
EP2300449A1
EP2300449A1 EP09761658A EP09761658A EP2300449A1 EP 2300449 A1 EP2300449 A1 EP 2300449A1 EP 09761658 A EP09761658 A EP 09761658A EP 09761658 A EP09761658 A EP 09761658A EP 2300449 A1 EP2300449 A1 EP 2300449A1
Authority
EP
European Patent Office
Prior art keywords
hydrogen
methyl
formula
compound
alkyl
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP09761658A
Other languages
German (de)
French (fr)
Inventor
Christopher John Mathews
James Nicholas Scutt
Mangala Govenkar
Michel Muehlebach
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syngenta Participations AG
Syngenta Ltd
Original Assignee
Syngenta Participations AG
Syngenta Ltd
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
Priority claimed from GB0810817A external-priority patent/GB0810817D0/en
Priority claimed from GB0813689A external-priority patent/GB0813689D0/en
Application filed by Syngenta Participations AG, Syngenta Ltd filed Critical Syngenta Participations AG
Publication of EP2300449A1 publication Critical patent/EP2300449A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/32—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/02—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic 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
    • C07D417/02—Heterocyclic 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
    • C07D417/10—Heterocyclic 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 aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/10—Spiro-condensed systems

Definitions

  • the present invention relates to new pesticidal, in particular insecticidal, acaricidal, molluscicidal and nematicidal compositions and to methods of using them to combat and control pests such as insect, acarine, mollusc and nematode pests.
  • R 1 is halogen, d-C 4 alkyl, CrC 4 haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl,
  • R 2 is optionally substituted aryl or optionally substituted heteroaryl; r is O, 1 , 2 or 3;
  • R 3 if r is 1 is halogen, Ci.C 6 alkyl, Ci.C 6 haloalkyl, Ci.C 6 alkoxy, Ci.C 6 haloalkoxy, C 2-
  • Ci.C 6 alkoxy Ci.C 6 haloalkoxy
  • Ci.C 6 haloalkoxy C 2- C 6 alkenyl, C 2- C 6 alkynyl, Ci.C 6 alkylthio, Ci-
  • R 4 , R 5 , R 6 and R 7 independently of each other, are hydrogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl,
  • C 2 haloalkyl or halogen cyclobutyl or cyclobutyl substituted by d- or C 2 alkyl; oxetanyl or oxetanyl substituted by d- or C 2 alkyl; C 5 -C 7 cycloalkyl or C 5 -C 7 cycloalkyl substituted by d- or C 2 alkyl or d- or C 2 haloalkyl, where a methylene group of the cycloalkyl moiety is optionally replaced by an oxygen or sulfur atom or a sulfinyl or sulfonyl group; C 4 - dcycloalkenyl or C 4 -C 7 cycloalkenyl substituted by d- or C 2 alkyl or d- or C 2 haloalkyl, where a methylene group of the cycloalkenyl moiety is optionally replaced by an oxygen or sulfur atom or a sulfin
  • R 4 and R 5 , or R 6 and R 7 are joined to form a 5-7 membered saturated or unsaturated ring in which a methylene group is optionally replaced by an oxygen or sulfur atom, or a 5-7 membered saturated or unsaturated ring substituted by Cr or C 2 alkyl, where a methylene group of the ring is optionally replaced by an oxygen or sulfur atom; or R 4 and R 7 are joined to form a 5-7 membered saturated or unsaturated ring unsubstituted or substituted by d- or C 2 alkyl, d- or C 2 alkoxy, Ci-C 2 alkoxyCi-C 2 alkyl, hydroxy, halogen, phenyl or phenyl substituted by d-C 4 alkyl, d-C 4 alkoxy, Ci-C 4 haloalkyl, halogen, nitro, cyano, d-C 4 alkylthio, d-C 4 alkylsulfiny
  • R 8 is hydrogen, d-C 6 alkyl, C 3 -C 6 cycloalkyl, d-C 6 alkoxycarbonyl, tri(d-C 6 alkyl)silyl- ethyloxycarbonyl, d-C 6 haloalkoxycarbonyl, cyano, d-C 6 haloalkyl, d-C 6 hydroxyalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkenyl, d-C 6 alkylcarbonyl, d-C 6 haloalkylcarbonyl, Ci-C 6 cycloalkylcarbonyl, phenylcarbonyl or phenylcarbonyl substituted by R 9 ; benzylcarbonyl or benzylcarbonyl substituted by R 9 ; pyridylcarbonyl or pyridylcarbonyl substituted by R 9 ;
  • the compounds of the formula I are known as herbicides from International application No. PCT/EP2007/010848.
  • a preferred composition contains those compounds of the formula I, wherein R 1 is halogen, Ci-C 4 alkyl, C r C 4 haloalkyl, C 2 -C 4 alkenyl or C 2 -C 4 alkynyl.
  • R 2 in the compounds of the formula I is aryl or heteroaryl; or aryl or heteroaryl both substituted by halogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, Ci-C 4 alkoxy, Ci-C 4 haloalkoxy, phenoxy, Ci-C 4 alkylthio, d- C 4 alkylsulfinyl, Ci-C 4 alkylsulfonyl, Ci-C 4 haloalkylthio, Ci-C 4 haloalkylsulfinyl, d- C 4 haloalkylsulfonyl, C 3 -C 6 cycloalkyl, Ci-C 4 alkylsulfonyloxy, Ci-C 4 haloalkylsulfonyloxy, d- C
  • R 2 is phenyl, thienyl, furyl, pyrrolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, pyridazinyl, oxadiazolyl and thiadiazolyl, and N-oxides and salts thereof, where these rings are unsubstituted or substituted by halogen, d-C 4 alkyl, Ci-C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 - C 4 haloalkenyl, C 2 -C 4 alkynyl, Ci-C 4 alkoxy, Ci-C 4 haloalkoxy, Ci-C 4 alkylthio, d- C 4 alkylsul
  • R 2 is phenyl or pyridyl or phenyl or pyridyl both substituted by halogen, nitro, cyano, Ci-C 2 alkyl, Ci-C 2 haloalkyl, d-C 2 alkoxy or
  • Ci-C 2 haloalkoxy Ci-C 2 haloalkoxy
  • R 2 is phenyl substituted at the para-position by halogen (in particular chlorine) and is optionally further substituted by halogen, nitro, d-
  • Ci-C 2 haloalkyl Ci-C 2 alkoxy or Ci-C 2 haloalkoxy.
  • R 3 in the compounds of the formula I is hydrogen (r is 0), halogen or d-C 6 alkyl, especially hydrogen.
  • R 3 if r is 1 , is halogen or d-C 3 alkyl.
  • R 4 , R 5 , R 6 and R 7 in the compounds of the formula I are hydrogen, d-dalkyl, d-dhaloalkyl, d-C 4 alkoxyd-C 4 alkyl, d-dalkylthiod-dalkyl, d-dalkylsulfinyld-dalkyl, d-dalkylsulfonyld-dalkyl; C 5 - dcycloalkyl or C 5 -dcycloalkyl substituted by d- or C 2 alkyl or d- or C 2 haloalkyl and in which a methylene group is optionally replaced by an oxygen or sulfur atom or a sulfinyl or sulfonyl group; C 5 -dcycloalkylCi-C 5 alkyl or C 5 -dcycloalkylCi-C 5 alkyl substituted by d- C
  • R 4 , R 5 , R 6 and R 7 independently of each other, are hydrogen, d-C 2 alkyl, d-C 2 haloalkyl or d-C 2 alkoxyd-C 2 alkyl.
  • G in the compounds of the formula I is C(X a )-R a or C(X b )- X c -R b , and the meanings of X a , R a , X b , X c and R b are as defined above.
  • the latentiating group G is selected from the groups C(X a )-R a , C(X b )-X c -R b , wherein X a , X b and X c are oxygen, R a is d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl or d- dalkoxyd-dalkyl and R b is d-C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl or d- C 4 alkoxyCi-C 4 alkyl.
  • More important groups G comprise hydrogen, an alkali metal or alkaline earth metal cation as an agriculturally acceptable cation, where hydrogen is particularly preferred.
  • R 1 in the compounds of the formula I is CrC 4 alkyl
  • R 2 is phenyl or phenyl substituted by halogen or Ci-C 2 alkyl
  • R 3 is hydrogen
  • R 4 , R 5 , R 6 and R 7 independently of each other, are CrC 2 alkyl
  • Y is O
  • G is hydrogen.
  • the invention covers also compositions with salts of the compounds of the formula I with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.
  • alkali metal and alkaline earth metal hydroxides as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially the hydroxides of sodium and potassium.
  • the compounds of formula I according to the invention also include hydrates which may be formed during the salt formation.
  • amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary Ci-Ci 8 alkylamines, Ci-C 4 hydroxyalkylamines and C 2 -C 4 alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbuty
  • Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(R 3 R b R c Rd)]OH wherein R 3 , R b , R c and R d are each independently of the others CrC 4 alkyl.
  • Further suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.
  • substituents G R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 , compounds of formula I may exist in different isomeric forms.
  • G is hydrogen
  • compounds of formula I may exist in different tautomeric forms:
  • the compounds of formula I can be prepared by methods described in International application No. PCT/EP2007/010848.
  • compositions according to the invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants.
  • the active ingredients act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina.
  • the insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e.
  • compositions according to the invention can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and lsoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests.
  • insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and lsoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests.
  • pests Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as pests.
  • the pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies).
  • pest species which may be controlled by the inventive compositions include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs), Frankliniella occidentalis (thrip), Thrips spp.
  • the active ingredients can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
  • Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts,
  • crops is to be understood as including also crops that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors) as a result of conventional methods of breeding or genetic engineering.
  • herbicides like bromoxynil or classes of herbicides
  • ALS inhibitors for example primisulfuron, prosulfuron and trifloxysulfuron
  • EPSPS 5-enol-pyrovyl-shikimate-3-phosphate-synthase
  • GS glutamine synthetase
  • imazamox by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola).
  • crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.
  • the term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bi ) or Cry9c, or vegetative insecticidal proteins (VIP), e.g. VIP1 , VIP2, VIP3 or VIP3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins for example insecticidal proteins from Bacillus cereus or Bacillus popliae
  • Bacillus thuringiensis such as ⁇ -endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF(
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsine inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecd
  • ⁇ -endotoxins for example CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bi ) or Cry9c, or vegetative insecticidal proteins (VIP), for example VIP1 , VIP2, VIP3 or VIP3A, expressly also hybrid toxins, truncated toxins and modified toxins.
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ).
  • Truncated toxins for example a truncated CrylA(b), are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of CrylllA055, a cathepsin-D-recognition sequence is inserted into a CrylllA toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-O 374 753, WO 93/07278, WO 95/34656, EP-A-O 427 529, EP-A-451 878 and WO 03/052073.
  • Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-O 367 474, EP-A-O 401 979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bi ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bi ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) tox
  • transgenic crops are:
  • Bt1 1 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylA(b) toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect- resistant by transgenic expression of a modified CrylllA toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-D-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a CrylllB(bi ) toxin and has resistance to certain Coleoptera insects.
  • NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacte ⁇ um sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylA(b) toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-O 392 225).
  • PRPs pathogenesis-related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-O 392 225, WO 95/33818, and EP-A-O 353 191.
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A- 0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906).
  • ion channel blockers such as blockers for sodium and calcium channels
  • the viral KP1 , KP4 or KP6 toxins for example the viral KP1 , KP4 or KP6 toxins
  • stilbene synthases such as the viral K
  • compositions according to the invention are the protection of stored goods and storerooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.
  • compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas. Examples of such parasites are:
  • Anoplurida Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp..
  • Nematocerina and Brachycerina for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Glossina spp., Calliphora spp., Glossina spp., Call
  • Siphonaptrida for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp..
  • Heteropterida for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp..
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp.
  • compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
  • the invention therefore provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula I.
  • the compositions are preferably used against insects or acarines.
  • plant as used herein includes seedlings, bushes and trees.
  • inventively used compounds can be applied in unmodified form, as obtained in the synthesis, but they are generally formulated into herbicidal compositions in a variety of ways using formulation adjuvants, such as carriers, solvents and surface-active substances.
  • the formulations can be in various physical forms, for example in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil flowables, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known, for example, from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition,
  • the formulations can be prepared, for example, by mixing the active ingredient with formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, for example finely divided solids, mineral oils, vegetable oils, modified vegetable oils, organic solvents, water, surface-active substances or combinations thereof.
  • the active ingredients can also be contained in very fine microcapsules consisting of a polymer. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into their surroundings in controlled amounts (e.g. slow release). Microcapsules usually have a diameter of from 0.1 to 500 microns.
  • the active ingredients contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be present in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes comprise, for example, natural and synthetic gums, cellulose, styrene- butadiene copolymers, polyacrylonitrile, polyacrylate, polyester, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art in this connection.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylenes carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropy
  • Water is generally the carrier of choice for the dilution of the concentrates.
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montomorillonite, cottonseed husks, wheatmeal, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar materials, as described, for example, in CFR 180.1001. (c) & (d).
  • a large number of surface-active substances can advantageously be used both in solid and in liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface-active substances may be anionic, cationic, non-ionic or polymeric and they may be used as emulsifiying, wetting or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecyl- benzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonat.es, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride, polyethylene glycol est
  • Further adjuvants which can usually be used in pesticidal formulations include crystallisation inhibitors, viscosity-modifying substances, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing aids, anti-foams, complexing agents, neutralising or pH- modifying substances and buffers, corrosion-inhibitors, fragrances, wetting agents, absorption improvers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, anti-freezes, microbiocides, and also liquid and solid fertilisers.
  • the formulations may also comprise additional active substances, for example further herbicides, herbicide safeners, plant growth regulators, fungicides or insecticides.
  • compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives.
  • the amount of oil additive used in the composition according to the invention is generally from 0.01 to 10 %, based on the spray mixture.
  • the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® (Rh ⁇ ne-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • a preferred additive contains, for example, as active components essentially 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers.
  • Especially preferred oil additives comprise alkyl esters of C 8 -C 22 fatty acids, especially the methyl derivatives of Ci 2 -Ci 8 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being important.
  • Those esters are known as methyl laurate (CAS-1 1 1-82-0), methyl palmitate (CAS-1 12-39- 0) and methyl oleate (CAS-1 12-62-9).
  • a preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH).
  • Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000.
  • the application and action of the oil additives can be further improved by combining them with surface-active substances, such as non-ionic, anionic or cationic surfactants.
  • surface-active substances such as non-ionic, anionic or cationic surfactants.
  • suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485.
  • Preferred surface-active substances are anionic surfactants of the dodecyl- benzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C 12 -C 22 fatty alcohols having a degree of ethoxylation of from 5 to 40.
  • Examples of commercially available surfactants are the Genapol types (Clariant AG).
  • silicone surfactants especially polyalkyl-oxide-modified heptamethyltrisiloxanes, which are commercially available e.g. as Silwet L-77®, and also perfluorinated surfactants.
  • concentration of surface-active substances in relation to the total additive is generally from 1 to 30 % by weight.
  • oil additives that consist of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Syngenta AG, CH) and Actipron® (BP Oil UK Limited, GB).
  • the said surface-active substances may also be used in the formulations alone, that is to say without oil additives.
  • an organic solvent to the oil additive/surfactant mixture can contribute to a further enhancement of action.
  • Suitable solvents are, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation).
  • the concentration of such solvents can be from 10 to 80 % by weight of the total weight.
  • Such oil additives which may be in admixture with solvents, are described, for example, in US-A-4 834 908.
  • a commercially available oil additive disclosed therein is known by the name MERGE® (BASF Corporation).
  • a further oil additive that is preferred according to the invention is SCORE® (Syngenta Crop Protection Canada.)
  • alkylpyrrolidones e.g. Agrimax®
  • formulations of alkylpyrrolidones such as, for example, Agrimax®
  • synthetic latices such as, for example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g. Bond®, Courier® or Emerald®)
  • propionic acid for example Eurogkem Pen-e-trate®
  • the compositions comprise 0.1 to 99%, especially 0.1 to 95%, of active ingredient and 1 to 99.9%, especially 5 to 99.9%, of at least one solid or liquid adjuvant, it being possible as a rule for 0 to 25%, especially 0.1 to 20%, of the composition to be surfactants(% in each case meaning percent by weight).
  • the end consumer as a rule uses dilute compositions which have substantially lower concentrations of active ingredient.
  • Emulsifiable concentrates active ingredient: 1 to 95%, preferably 5 to 20% surfactant: 1 to 30%, preferably 10 to 20 % solvent: 5 to 98%, preferably 70 to 85%
  • Dusts active ingredient: 0.1 to 10%, preferably 0.1 to 1 % solid carrier: 99.9 to 90%, preferably 99.9 to 99%
  • Suspension concentrates active ingredient: 5 to 75%, preferably 10 to 50% water: 94 to 24%, preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30% Wettable powders: active ingredient: 0.5 to 90%, preferably 1 to 80% surfactant: 0.5 to 20%, preferably 1 to 15% solid carrier: 5 to 99%, preferably 15 to 98%
  • Granulates active ingredient: 0.5 to 30%, preferably 3 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%
  • compositions can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
  • auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators
  • compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • compositions that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention.
  • Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient.
  • the rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.
  • a preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question.
  • the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.
  • compositions according to the invention are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type.
  • the propagation material can be treated with the compositions prior to planting, for example seed can be treated prior to sowing.
  • the compositions can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling.
  • a compound of formula I is usually formulated into a composition which includes, in addition to the compound of formula I, a suitable inert diluent or carrier and, optionally, a formulation adjuvant in form of a surface active agent (SFA) as described herein or, for example, in EP- B-1062217.
  • SFA surface active agent
  • SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound of formula I.
  • the composition is generally used for the control of pests such that a compound of formula I is applied at a rate of from 0.1 g tol Okg per hectare, preferably from 1 g to 6kg per hectare, more preferably from 1 g to 1 kg per hectare.
  • a compound of formula I When used in a seed dressing, a compound of formula I is used at a rate of 0.0001 g to 10g (for example 0.001 g or 0.05g), preferably 0.005g to 10g, more preferably 0.005g to 4g, per kilogram of seed.
  • compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations.
  • the formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula I.
  • Dustable powders may be prepared by mixing a compound of formula I with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
  • solid diluents for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers
  • Soluble powders may be prepared by mixing a compound of formula I with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
  • water-soluble inorganic salts such as sodium bicarbonate, sodium carbonate or magnesium sulphate
  • water-soluble organic solids such as a polysaccharide
  • wetting agents such as sodium bicarbonate, sodium carbonate or magnesium sulphate
  • dispersing agents such as sodium bicarbonate, sodium carbonate or magnesium sulphate
  • SG water soluble granules
  • WP Wettable powders
  • WG Water dispersible granules
  • Granules may be formed either by granulating a mixture of a compound of formula I and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula I (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula I (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary.
  • a hard core material such as sands, silicates, mineral carbonates, sulphates or phosphates
  • Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils).
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters
  • sticking agents such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils.
  • One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
  • DC Dispersible Concentrates
  • a compound of formula I may be prepared by dissolving a compound of formula I in water or an organic solvent, such as a ketone, alcohol or glycol ether.
  • organic solvent such as a ketone, alcohol or glycol ether.
  • surface active agent for example to improve water dilution or prevent crystallisation in a spray tank.
  • Emulsifiable concentrates or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula I in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents).
  • Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as Cs-C-io fatty acid dimethylamide) and chlorinated hydrocarbons.
  • aromatic hydrocarbons such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark
  • ketones such as
  • An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.
  • Preparation of an EW involves obtaining a compound of formula I either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 7O 0 C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion.
  • Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
  • Microemulsions may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation.
  • a compound of formula I is present initially in either the water or the solvent/SFA blend.
  • Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs.
  • An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation.
  • An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
  • SC Suspension concentrates
  • SCs may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula I.
  • SCs may be prepared by ball or bead milling the solid compound of formula I in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound.
  • One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle.
  • a compound of formula I may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
  • Aerosol formulations comprise a compound of formula I and a suitable propellant (for example n-butane).
  • a compound of formula I may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
  • a compound of formula I may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.
  • Capsule suspensions may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula I and, optionally, a carrier or diluent therefor.
  • the polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure.
  • the compositions may provide for controlled release of the compound of formula I and they may be used for seed treatment.
  • a compound of formula I may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
  • a composition of the present invention may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula I).
  • additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula I).
  • a compound of formula I may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS).
  • DS powder for dry seed treatment
  • SS water soluble powder
  • WS water dispersible powder for slurry treatment
  • CS capsule suspension
  • the preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above.
  • Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
  • Wetting agents, dispersing agents and emulsifying agents may be surface active agents (SFAs) of the cationic, anionic, amphoteric or non-ionic type.
  • Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
  • Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di- /sopropyl- and tri-/sopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric
  • Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.
  • Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
  • alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof
  • fatty alcohols such as oleyl alcohol or cetyl alcohol
  • alkylphenols such as octylphenol, nonyl
  • Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
  • hydrophilic colloids such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose
  • swelling clays such as bentonite or attapulgite
  • a composition of the invention may be applied by any of the known means of applying pesticidal compositions. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment. It may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
  • compositions for use as aqueous preparations are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use.
  • These concentrates which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
  • Such aqueous preparations may contain varying amounts of a compound of formula I (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
  • a composition of the inventionl may contain mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers).
  • fertilisers for example nitrogen-, potassium- or phosphorus-containing fertilisers.
  • Suitable formulation types include granules of fertiliser.
  • the mixtures suitably contain up to 25% by weight of the compound of formula I.
  • the invention therefore also provides a fertiliser composition comprising a fertiliser and a compound of formula I.
  • compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.
  • the compound of formula I may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide (insect, acarine, mollusc and nematode pesticide), fungicide, synergist, herbicide or plant growth regulator where appropriate.
  • An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula I; or help to overcome or prevent the development of resistance to individual components.
  • the particular additional active ingredient will depend upon the intended utility of the composition.
  • Suitable pesticides include the following: a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or 5-benzyl-3-furylmethyl-(E_)-(1 R,3S)-2,2-dimethyl- 3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate; b) Organophosphates, such as, profenofos, sulprofos, acep
  • Chloronicotinyl compounds such as imidacloprid, thiacloprid, acetamiprid, nitenpyram or thiamethoxam; m) Diacylhydrazines, such as tebufenozide, chromafenozide or methoxyfenozide; n) Diphenyl ethers, such as diofenolan or pyriproxifen; o) Indoxacarb; p) Chlorfenapyr; or q) Pymetrozine.
  • other pesticides having particular targets may be employed in the composition, if appropriate for the intended utility of the composition.
  • selective insecticides for particular crops for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed.
  • insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).
  • fungicidal compounds which may be included in the composition of the invention are (£)- ⁇ /-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy- iminoacetamide (SSF-129), 4-bromo-2-cyano- ⁇ /, ⁇ /-dimethyl-6-trifluoromethylbenzimidazole- 1 -sulphonamide, ⁇ -[ ⁇ /-(3-chloro-2,6-xylyl)-2-methoxyacetamido]- ⁇ -butyrolactone, 4-chloro-2- cyano- ⁇ /, ⁇ /-dimethyl-5-p-tolylimidazole-1 -sulfonamide (IKF-916, cyamidazosulfamid), 3-5-dichloro- ⁇ /-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide (RH-7281 , zoxamide
  • the compounds of formula I may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
  • synergists for use in the compositions include piperonyl butoxide, sesamex, safroxan and dodecyl imidazole.
  • composition according to the invention can also be used in combination with one or more other herbicides.
  • the following mixtures of the compound of formula I are important: compound of formula I + acetochlor, compound of formula I + acifluorfen, compound of formula I + acifluorfen-sodium, compound of formula I + aclonifen, compound of formula I + acrolein, compound of formula I + alachlor, compound of formula I + alloxydim, compound of formula I + allyl alcohol, compound of formula I + ametryn, compound of formula I + amicarbazone, compound of formula I + amidosulfuron, compound of formula I + aminopyralid, compound of formula I + amitrole, compound of formula I + ammonium sulfamate, compound of formula I + anilofos, compound of formula I + asulam, compound of formula I + atraton, compound of formula I + atrazine, compound of formula I + azimsulfuron, compound of formula I + BCPC, compound of formula
  • the mixing partners of the compound of formula I may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 12th Edition (BCPC), 2000.
  • the compound of the formula I is preferably a compound of Tables 1 to 294, and more preferably, a compound of the following Tables A to D.
  • the mixing ratio of the compound of formula I to the mixing partner is preferably from 1 : 100 to 1000:1.
  • mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of compound of formula I with the mixing partner).
  • Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type.
  • other formulation types may be prepared.
  • one active ingredient is a water insoluble solid and the other a water insoluble liquid
  • the resultant composition is a suspoemulsion (SE) formulation.
  • R 1 is methyl
  • R 4 , R 5 , R 6 and R 7 are hydrogen
  • G is hydrogen
  • R 2 and R are as defined below:
  • Y is O
  • R 1 is methyl
  • R 4 and R 5 are methyl
  • R 6 and R 7 are hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 1.
  • Y is O
  • R 1 is chlorine
  • R 4 and R 5 are methyl
  • R 6 and R 7 are hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 1.
  • This table covers 378 compounds of the following type: wherein Y is O, R 1 is methyl, R 4 and R 6 are methyl, R 5 and R 7 are hydrogen, G is hydrogen and R 2 and R 3 are as defined in Table 1.
  • Y is O
  • R 1 is chlorine
  • R 4 and R 6 are methyl
  • R 5 and R 7 are hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 1.
  • This table covers 378 compounds of the following type: wherein Y is O, R 1 is ethyl, R 4 , R 5 , R 6 and R 7 are methyl, G is hydrogen and R 2 and R 3 are as defined in Table 1.
  • Y is S
  • R 1 is ethyl
  • R 4 , R 5 , R 6 and R 7 are hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 1.
  • Y is S, R 1 is ethyl, R 4 is methyl, R 5 , R 6 and R 7 are hydrogen, G is hydrogen and R 2 and R 3 are as defined in Table 1.
  • Y is S, R 1 is chlorine, R 4 and R 5 are methyl, R 6 and R 7 are hydrogen, G is hydrogen and R 2 and R 3 are as defined in Table 1.
  • This table covers 378 compounds of the following type: wherein Y is S, R 1 is methyl, R 4 and R 6 are methyl, R 5 and R 7 are hydrogen, G is hydrogen and R 2 and R 3 are as defined in Table 1.
  • Y is S, R 1 is chlorine, R 4 and R 6 are methyl, R 5 and R 7 are hydrogen, G is hydrogen and R 2 and R 3 are as defined in Table 1.
  • Y is S, R 1 is ethyl, R 4 , R 5 and R 6 are methyl, R 7 is hydrogen, G is hydrogen and R 2 and R 3 are as defined in Table 1.
  • This table covers 378 compounds of the following type: wherein Y is S, R 1 is ethyl, R 4 , R 5 , R 6 and R 7 are methyl, G is hydrogen and R 2 and R 3 are as defined in Table 1.
  • R 1 is chlorine
  • R 4 , R 5 , R 6 and R 7 are hydrogen
  • G is hydrogen and R 2 and
  • R 3 are as defined in Table 1.
  • R 2 and R 3 are as defined in Table 1.
  • R 1 is chlorine
  • R 4 and R 5 are methyl
  • R 6 and R 7 are hydrogen
  • G is hhyyddrrooggeenn
  • R 2 and R 3 are as defined in Table 1.
  • R 2 and R 3 are as defined in Table 1.
  • R 1 is methyl
  • R 4 , R 5 , R 6 and R 7 are hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 1.
  • R 1 is chlorine
  • R 4 is methyl
  • R 5 , R 6 and R 7 are hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 1.
  • R 1 is methyl
  • R 4 and R 5 are methyl
  • R 6 and R 7 are hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 1.
  • R 1 is ethyl
  • R 4 and R 5 are methyl
  • R 6 and R 7 are hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 1.
  • R 1 is methyl
  • R 4 and R 6 are methyl
  • R 5 and R 7 are hydrogen
  • G is hhyyddrrooggeenn
  • R 2 and R 3 are as defined in Table 1.
  • R 1 is ethyl
  • R 4 and R 6 are methyl
  • R 5 and R 7 are hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 1.
  • R 1 is chlorine
  • R 4 , R 5 and R 6 are methyl
  • R 7 is hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 1.
  • R 1 is methyl
  • R 4 and R 5 are methyl
  • R 6 and R 7 are hydrogen
  • G is hhyyddrrooggeenn
  • R 2 and R 3 are as defined in Table 1.
  • R 2 and R 3 are as defined in Table 1.
  • Table 81 :
  • R 1 is methyl
  • R 4 , R 5 , R 6 and R 7 are hydrogen
  • G is hydrogen
  • R 2 and R 3' are as defined below:
  • Y is O
  • R 1 is ethyl
  • R 4 and R 5 are methyl
  • R 6 and R 7 are hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 85.
  • R 2 and R 3 are as defined in Table 85.
  • R 2 and R 3 are as defined in Table 85.
  • Y is S
  • R 1 is ethyl
  • R 4 , R 5 , R 6 and R 7 are hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 85.
  • R 2 and R 3 are as defined in Table 85.
  • This table covers 126 compounds of the following type: wherein Y is S, R 1 is ethyl, R 4 is methyl, R 5 , R 6 and R 7 are hydrogen, G is hydrogen and R 2 and R 3 are as defined in Table 85.
  • Y is S, R 1 is ethyl, R 4 and R 5 are methyl, R 6 and R 7 are hydrogen, G is hydrogen and R 2 and R 3 are as defined in Table 85.
  • Y is S, R 1 is ethyl, R 4 and R 6 are methyl, R 5 and R 7 are hydrogen, G is hydrogen and R 2 and R 3 are as defined in Table 85.
  • This table covers 126 compounds of the following type
  • Y is S, R 1 is ethyl, R 4 , R 5 and R 6 are methyl, R 7 is hydrogen, G is hydrogen and R 2 and R 3 are as defined in Table 85.
  • R 3 are as defined in Table 85.
  • R 2 and R 3 are as defined in Table 85.
  • R 2 and R 3 are as defined in Table 85.
  • R 1 is methyl
  • R 4 is methyl
  • R 5 , R 6 and R 7 are hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 85.
  • R 1 is methyl
  • R 4 and R 6 are methyl
  • R 5 and R 7 are hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 85.
  • R 1 is ethyl
  • R 4 , R 5 and R 6 are methyl
  • R 7 is hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 85.
  • R 1 is ethyl
  • R 4 , R 5 , R 6 and R 7 are methyl
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 85.
  • Y is O and R 1 and R 3a are methyl, R 4 , R 5 , R 6 and R 7 are methyl, R 3b is methyl, and
  • G is hydrogen and R 2 is as defined in Table 85.
  • Y is O and R 1 is ethyl and R 3a is methyl, R 4 , R 5 , R 6 and R 7 are methyl, R 3b is methyl, and G is hydrogen and R 2 is as defined in Table 85.
  • This table covers 126 compounds of the following type: wherein Y is O and R 1 and R 3a are ethyl, R 4 , R 5 , R 6 and R 7 are methyl, R 3b is methyl, and G is hydrogen and R 2 is as defined in Table 85.
  • G is hydrogen and R 2 is as defined in Table 85.
  • G is hydrogen and R 2 is as defined in Table 85.
  • R 2 and R 3 are as defined in Table 1.
  • Table 168 :
  • This table covers 126 compounds of the following type: wherein Y is O, R 1 is methyl, R 5 is hydrogen and R 6 is methyl, G is hydrogen and R 2 and R 3 are as defined in Table 85.
  • Y is O
  • R 1 and R 3a are ethyl
  • R 5 is hydrogen and R 6 is methyl
  • R 3b is methyl
  • G is hydrogen and R 2 is as defined in Table 85.
  • Y is S, R 1 is methyl, R 5 and R 6 are hydrogen, G is hydrogen and R 2 and R 3 are as defined in Table 1.
  • This table covers 126 compounds of the following type: wherein Y is S, R 1 is methyl, R 5 is hydrogen and R 6 is methyl, G is hydrogen and R 2 and R 3 are as defined in Table 85.
  • Y is S, R 1 and R 3a are methyl, R 5 and R 6 are hydrogen, R 3b is methyl, and G is hydrogen and R 2 is as defined in Table 85.
  • R 3 are as defined in Table 85.
  • G is hydrogen and R is as defined in Table 85.
  • Table 233 :
  • R 1 and R 3a are ethyl
  • R 5 and R 6 are hydrogen
  • R 3b is methyl
  • G is hydrogen and R 2 is as defined in Table 85.
  • R 1 is methyl
  • R 5 and R 6 are hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 1.
  • R 1 is ethyl
  • R 5 and R 6 are methyl
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 1.
  • R 1 is methyl
  • R 5 and R 6 are hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 85.
  • R 1 is ethyl
  • R 5 and R 6 are hydrogen
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 85.
  • R 1 is ethyl
  • R 5 and R 6 are methyl
  • G is hydrogen
  • R 2 and R 3 are as defined in Table 85.
  • R 1 and R 3a are ethyl
  • R 5 and R 6 are hydrogen
  • R 3b is methyl
  • G is hydrogen and R 2 is as defined in Table 85.
  • R 3 are as defined in Table 85.
  • G is hydrogen and R 2 is as defined in Table 85.
  • G is hydrogen and R is as defined in Table 85.
  • Example B1 Activity against Myzus persicae (green peach aphid,)
  • Sunflower leaf discs are placed on agar in a 24-well microtiter plate and sprayed with test solutions. After drying, the leaf discs are infested with an aphid population of mixed ages.
  • A-143, B-3, B-46 and D-33 show an activity of over 80% at a concentration of 400ppm.
  • Sunflower leaf discs are placed on agar in a 24-well microtiter plate and sprayed with test solutions. After drying, the leaf discs are infested with a thrips population of mixed ages.
  • A-1 17, A-123, A-125, A-126, A-128, A-131 , A-132, A-141 , A-149, B-4, B-12, B-15, B- 18, B-21 , B-23, B-29, B-31 , B-44, B-49, B-53, C-2, C-3, D-3, D-4, D-5, D-6 and D-33 show an activity of over 80% at a concentration of 400ppm.
  • Example B3 Activity against Tetranychus urticae (two-spotted spider mite)
  • Bean leaf discs on agar in 24-well microtiter plates are sprayed with test solutions. After drying, the leaf discs are infested with mite populations of mixed ages. 8 days later, discs are checked for egg mortality, larval mortality, and adult mortality.
  • B-4, B-18, B-22, B-23, B-52, D-3, D-4, D-5, D-6 and D-33 show an activity of over 80% at a concentration of 400ppm.
  • Example B4 Activity against Heliothis virescens (Tobacco budworm)
  • Eggs (0-24 h old) are placed in 24-well microtiter plate on artificial diet and treated with test solutions by pipetting. After an incubation period of 4 days, samples are checked for egg mortality, larval mortality, and growth regulation.
  • D-4 and D-5 show an activity of over 80% at a concentration of 400ppm.
  • Example B5 Activity against Plutella xylostella (Diamond back moth)
  • MTP 24-well microtiter plate
  • the MTP's are infested with larvae (L2)(10-15 per well). After an incubation period of 5 days, samples are checked for larval mortality, antifeedant and growth regulation. In this test, compounds listed in the Tables A, B, C and D above show good activity.
  • compounds A-1 , A-3, A-4, A-5, A-10, A-29, A-30, A-36, A-37, A-40, A-42, A-43, A- 45, A-47, A-48, A-49, A-50, A-51 , A-79, A-80, A-83, A-84, A-86, A-90, A-96, A-99, A-101 , A- 103, A-1 17, A-123, A-125, A-128, A-132, A-141 , A-142, A-144, A-149, B-4, B-15, B-17, B- 18, B-22, B-23, B-25, B-26, B-31 , B-34, B-36, B-39, B-42, B-43, B-46, B-47, B-51 , D-3, D-4, D-5, D-12, D-15 and D-33 show an activity of over 80% at a concentration of 400ppm.
  • Example B6 Activity against Diabrotica balteata (Corn root worm)
  • MTP 24-well microtiter plate
  • MTP's After drying, the MTP's are infested with larvae (L2)(6-10 per well). After an incubation period of 5 days, samples are checked for larval mortality, antifeedant and growth regulation.

Abstract

Pesticidal compositions containing pyrandione, thiopyrandione and cyclohexanetrione compounds and methods of using them to combat and control pests such as insect, acarine, mollusc and nematode pests.

Description

PESTiciDAL COMPOSITIONS CONTAINING A PYRANDIONE OR A THIOPYRANDIONE OR A
CYCLOHEXANETRIONE DERIVATIVE
The present invention relates to new pesticidal, in particular insecticidal, acaricidal, molluscicidal and nematicidal compositions and to methods of using them to combat and control pests such as insect, acarine, mollusc and nematode pests.
The present invention accordingly relates to a pesticidal composition comprising a pesticidal effective amount of at least one compound of formula I
wherein
R1 is halogen, d-C4alkyl, CrC4haloalkyl, C3-C6cycloalkyl, C2-C4alkenyl, C2-C4haloalkenyl,
C2-C4alkynyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, d-
C4alkylsulfonyl, nitro or cyano;
R2 is optionally substituted aryl or optionally substituted heteroaryl; r is O, 1 , 2 or 3;
R3 if r is 1 , is halogen, Ci.C6alkyl, Ci.C6haloalkyl, Ci.C6alkoxy, Ci.C6haloalkoxy, C2-
C6alkenyl, C2-C6alkynyl, Ci.C6alkylthio, Ci.C6alkylsulfinyl, Ci.C6alkylsulfonyl, cyano or nitro; or the substituents R3, if r is 2 or 3, independently of each other, are halogen, d.Cβalkyl, Ci-
C6haloalkyl, Ci.C6alkoxy, Ci.C6haloalkoxy, C2-C6alkenyl, C2-C6alkynyl, Ci.C6alkylthio, Ci-
C6alkylsulfinyl, Ci.C6alkylsulfonyl, cyano or nitro;
R4, R5, R6 and R7, independently of each other, are hydrogen, Ci-C4alkyl, Ci-C4haloalkyl,
Ci-C4alkoxyCi-C4alkyl, Ci-C4alkylthioCrC4alkyl, C1-C4alkylsulfinylC1-C4alkyl, d-
C4alkylsulfonylCi-C4alkyl, cyclopropyl or cyclopropyl substituted by d- or C2alkyl, d- or
C2haloalkyl or halogen; cyclobutyl or cyclobutyl substituted by d- or C2alkyl; oxetanyl or oxetanyl substituted by d- or C2alkyl; C5-C7cycloalkyl or C5-C7cycloalkyl substituted by d- or C2alkyl or d- or C2haloalkyl, where a methylene group of the cycloalkyl moiety is optionally replaced by an oxygen or sulfur atom or a sulfinyl or sulfonyl group; C4- dcycloalkenyl or C4-C7cycloalkenyl substituted by d- or C2alkyl or d- or C2haloalkyl, where a methylene group of the cycloalkenyl moiety is optionally replaced by an oxygen or sulfur atom or a sulfinyl or sulfonyl group; cyclopropylCi-C5alkyl or cyclopropylCi-C5alkyl substituted by d- or C2alkyl, d- or C2haloalkyl or halogen; cyclobutylCi-C5alkyl or cyclobutylCi-C5alkyl substituted by Ci-C2alkyl; oxetanylCi-C5alkyl or oxetanylCi-C5alkyl substituted by d- or C2alkyl; C5-C7 cycloalkylCi-C5alkyl or C5-C7cycloalkylCi-C5alkyl substituted by d-or C2alkyl or d- or C2haloalkyl, where a methylene group of the cycloalkyl moiety is optionally replaced by an oxygen or sulfur atom or a sulfinyl or sulfonyl group; C4- C7cycloalkenylCi-C5 alkyl or C4-C7cycloalkenylCi-C5alkyl which is substituted by d- or C2alkyl or d- or C2haloalkyl, where a methylene group of the cycloalkenyl moiety is optionally replaced by an oxygen or sulfur atom or a sulfinyl or sulfonyl group; phenyl or phenyl substituted by d-C4alkyl, d-C4alkoxy, Ci-C4haloalkyl, halogen, nitro, cyano, d- dalkylthio, d-C4alkylsulfinyl, d-C4alkylsulfonyl or Ci-C4alkylcarbonyl; benzyl or benzyl substituted by d-C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl, halogen, nitro, cyano, Ci-C4alkylthio, d-dalkylsulfinyl, Ci-C4alkylsulfonyl or Ci-C4alkylcarbonyl; heteroaryl or heteroaryl substituted by Ci-C4alkyl, d-C4alkoxy, Ci-C4haloalkyl, halogen, nitro, cyano, d-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl or Ci-C4alkylcarbonyl; or
R4 and R5, or R6 and R7, are joined to form a 5-7 membered saturated or unsaturated ring in which a methylene group is optionally replaced by an oxygen or sulfur atom, or a 5-7 membered saturated or unsaturated ring substituted by Cr or C2alkyl, where a methylene group of the ring is optionally replaced by an oxygen or sulfur atom; or R4 and R7 are joined to form a 5-7 membered saturated or unsaturated ring unsubstituted or substituted by d- or C2alkyl, d- or C2alkoxy, Ci-C2alkoxyCi-C2alkyl, hydroxy, halogen, phenyl or phenyl substituted by d-C4alkyl, d-C4alkoxy, Ci-C4haloalkyl, halogen, nitro, cyano, d-C4alkylthio, d-C4alkylsulfinyl, d-C4alkylsulfonyl or d-C4alkylcarbonyl; heteroaryl or heteroaryl substituted by d-C4alkyl, d-C4alkoxy, Ci-C4haloalkyl, halogen, nitro, cyano, d-dalkylthio, d-C4alkylsulfinyl, d-C4alkylsulfonyl or d-C4alkylcarbonyl; Y is O, C=O, S(O)m or S(O)nNR8; provided that when Y is C=O, R6 and R7 are different from hydrogen when either R4 or R5 is hydrogen, and R4 and R5 are different from hydrogen when either R6 or R7 is hydrogen; m is O or 1 or 2 and n is O or 1 ;
R8 is hydrogen, d-C6alkyl, C3-C6cycloalkyl, d-C6alkoxycarbonyl, tri(d-C6alkyl)silyl- ethyloxycarbonyl, d-C6haloalkoxycarbonyl, cyano, d-C6haloalkyl, d-C6hydroxyalkyl, C2-C6alkenyl, C2-C6alkynyl, C2-C6haloalkenyl, d-C6alkylcarbonyl, d-C6haloalkylcarbonyl, Ci-C6cycloalkylcarbonyl, phenylcarbonyl or phenylcarbonyl substituted by R9; benzylcarbonyl or benzylcarbonyl substituted by R9; pyridylcarbonyl or pyridylcarbonyl substituted by R9; phenoxycarbonyl or phenoxycarbonyl substituted by R9; benzyloxycarbonyl or benzyloxycarbonyl substituted by R9; R9 is CrC6haloalkyl, CrC6alkoxycarbonyl, nitro, cyano, formyl, carboxyl or halogen, and G is hydrogen, an agriculturally acceptable cation or a latentiating group.
The compounds of the formula I are known as herbicides from International application No. PCT/EP2007/010848.
A preferred composition contains those compounds of the formula I, wherein R1 is halogen, Ci-C4alkyl, CrC4haloalkyl, C2-C4alkenyl or C2-C4 alkynyl.
In another preferred composition, R2 in the compounds of the formula I is aryl or heteroaryl; or aryl or heteroaryl both substituted by halogen, Ci-C4alkyl, Ci-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, Ci-C4alkoxy, Ci-C4haloalkoxy, phenoxy, Ci-C4alkylthio, d- C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylthio, Ci-C4haloalkylsulfinyl, d- C4haloalkylsulfonyl, C3-C6cycloalkyl, Ci-C4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, d- C4alkoxyCi-C4alkyl, Ci-C4alkylthioCrC4alkyl, C1-C4alkylsulfinylC1-C4alkyl, d- C4alkylsulfonylCi-C4alkyl, nitro, cyano, thiocyanato, hydroxy, amino, Ci-C6alkylamino, d- C6dialkylamino, C3-C6cycloalkylamino, morpholino, thiomorpholino, d- C6alkylcarbonylamino, Ci-Cealkoxycarbonylamino, C3-C6 alkenyloxycarbonylamino, C3-C6 alkynyloxycarbonylamino, d-C6 alkylaminocarbonylamino, di(Ci-6alkyl)aminocarbonylamino, formyl, Ci-C6alkylcarbonyl, C2-C6alkenylcarbonyl, C2-C6alkynylcarbonyl, carboxy, d- C6alkoxycarbonyl, Cs-Cβalkenyloxycarbonyl, C3-C6alkynyloxycarbonyl, carboxamido, d- C6alkylaminocarbonyl, di(d-C6alkyl)aminocarbonyl, Ci-Cealkylcarbonyloxy, d- C6alkylaminocarbonyloxy, di(d-C6alkyl)aminocarbonyloxy or Ci-Cealkylthiocarbonylamino; Preferably, R2 in the compounds of formula I is aryl or heteroaryl; or aryl or heteroaryl both substituted by halogen, d-C4alkyl, Ci-C4haloalkyl, phenoxy, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, d- C4alkylsulfonyl, Ci-C4haloalkylthio, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, nitro or cyano.
More preferably, R2 is phenyl, thienyl, furyl, pyrrolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, pyridazinyl, oxadiazolyl and thiadiazolyl, and N-oxides and salts thereof, where these rings are unsubstituted or substituted by halogen, d-C4alkyl, Ci-C4haloalkyl, C2-C4alkenyl, C2- C4haloalkenyl, C2-C4alkynyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkylthio, d- C4alkylsulfinyl, Ci-C4alkylsulfonyl, d-C4haloalkylthio, Ci-C4haloalkylsulfinyl, d- C4haloalkylsulfonyl, nitro or cyano. - A -
In even more preferred compounds of the formula I, R2 is phenyl or pyridyl or phenyl or pyridyl both substituted by halogen, nitro, cyano, Ci-C2alkyl, Ci-C2haloalkyl, d-C2alkoxy or
Ci-C2haloalkoxy.
In an especially preferred group of compounds, R2 is phenyl substituted at the para-position by halogen (in particular chlorine) and is optionally further substituted by halogen, nitro, d-
C2alkyl, Ci-C2haloalkyl, Ci-C2alkoxy or Ci-C2haloalkoxy.
In another preferred composition, R3 in the compounds of the formula I is hydrogen (r is 0), halogen or d-C6alkyl, especially hydrogen. Preferably, R3, if r is 1 , is halogen or d-C3alkyl.
In another preferred composition, R4, R5, R6 and R7 in the compounds of the formula I, independently of each other, are hydrogen, d-dalkyl, d-dhaloalkyl, d-C4alkoxyd-C4 alkyl, d-dalkylthiod-dalkyl, d-dalkylsulfinyld-dalkyl, d-dalkylsulfonyld-dalkyl; C5- dcycloalkyl or C5-dcycloalkyl substituted by d- or C2alkyl or d- or C2haloalkyl and in which a methylene group is optionally replaced by an oxygen or sulfur atom or a sulfinyl or sulfonyl group; C5-dcycloalkylCi-C5alkyl or C5-dcycloalkylCi-C5alkyl substituted by d- C2alkyl or d- or C2haloalkyl and in which a methylene group is optionally replaced by an oxygen or sulfur atom or a sulfinyl or sulfonyl group.
More preferably, R4, R5, R6 and R7, independently of each other, are hydrogen, d-C2alkyl, d-C2haloalkyl or d-C2alkoxyd-C2alkyl.
In another preferred composition, Y in the compounds of the formula I is O, C=O and S. Y is O is especially preferred.
In another preferred composition, G in the compounds of the formula I is C(Xa)-Ra or C(Xb)- Xc-Rb, and the meanings of Xa, Ra, Xb, Xc and Rb are as defined above. Even more preferably, the latentiating group G is selected from the groups C(Xa)-Ra, C(Xb)-Xc-Rb, wherein Xa, Xb and Xc are oxygen, Ra is d-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl or d- dalkoxyd-dalkyl and Rb is d-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, C3-C6cycloalkyl or d- C4alkoxyCi-C4alkyl.
More important groups G comprise hydrogen, an alkali metal or alkaline earth metal cation as an agriculturally acceptable cation, where hydrogen is particularly preferred. In another preferred composition, R1 in the compounds of the formula I is CrC4alkyl, R2 is phenyl or phenyl substituted by halogen or Ci-C2alkyl, R3 is hydrogen, R4, R5, R6 and R7, independently of each other, are CrC2alkyl, Y is O and G is hydrogen.
The invention covers also compositions with salts of the compounds of the formula I with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the alkali metal and alkaline earth metal hydroxides as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially the hydroxides of sodium and potassium. The compounds of formula I according to the invention also include hydrates which may be formed during the salt formation.
Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary Ci-Ci8alkylamines, Ci-C4hydroxyalkylamines and C2-C4alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n- amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n- propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N- butylethanolamine, allylamine, n-but-2-enylamine, n-pent-2-enylamine, 2,3-dimethylbut-2- enylamine, dibut-2-enylamine, n-hex-2-enylamine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec- butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.
Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(R3 Rb Rc Rd)]OH wherein R3, Rb, Rc and Rd are each independently of the others CrC4alkyl. Further suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions. Depending on the nature of the substituents G, R1, R2, R3, R4, R5, R6, R7 and R8, compounds of formula I may exist in different isomeric forms. When G is hydrogen, for example, compounds of formula I may exist in different tautomeric forms:
Furthermore, when Y is C=O and R is hydrogen, further compounds of formula I may exist in different tautomeric forms:
Also, when substituents contain double bonds, cis- and trans-isomers can exist. This invention covers all such isomers and tautomers and mixtures thereof in all proportions. These isomers, too, are within the scope of the claimed compounds of the formula I.
The compounds of formula I can be prepared by methods described in International application No. PCT/EP2007/010848.
The compositions according to the invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. The active ingredients act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate, a good activity corresponding to a destruction rate (mortality) of at least 50 to 60%. The compositions according to the invention can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and lsoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests. Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as pests. The pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies).
Examples of pest species which may be controlled by the inventive compositions include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips), Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis (boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp. (white flies), Bemisia tabaci (white fly), Ostrinia nubilalis (European corn borer), Spodoptera littoralis (cotton leafworm), Heliothis virescens (tobacco budworm), Helicoverpa armigera (cotton bollworm), Helicoverpa zea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pieris brassicae (white butterfly), Plutella xylostella (diamond back moth), Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locusta migratoria (locust), Chortiocetes terminifera (locust), Diabrotica spp. (rootworms), Panonychus ulmi (European red mite), Panonychus citri (citrus red mite), Tetranychus urticae (two-spotted spider mite), Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (broad mite), Brevipalpus spp. (flat mites), Boophilus microplus (cattle tick), Dermacentor variabilis (American dog tick), Ctenocephalides felis (cat flea), Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti (mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp. (blowflies), Blattella germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis (cockroach), termites of the Mastotermitidae (for example Mastotermes spp.), the Kalotermitidae (for example Neotermes spp.), the Rhinotermitidae (for example Coptotermes formosanus, Reticulitermes flavipes, R. speratu, R. virginicus, R. hesperus, and R. santonensis) and the Termitidae (for example Globitermes sulphureus), Solenopsis geminata (fire ant), Monomorium pharaonis (pharaoh's ant), Damalinia spp. and Linognathus spp. (biting and sucking lice), and Deroceras reticulatum (slug).
The active ingredients can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines, hops, the plantain family, latex plants and ornamentals.
The term "crops" is to be understood as including also crops that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®. The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bi ) or Cry9c, or vegetative insecticidal proteins (VIP), e.g. VIP1 , VIP2, VIP3 or VIP3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsine inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
In the context of the present invention there are to be understood by δ-endotoxins, for example CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bi ) or Cry9c, or vegetative insecticidal proteins (VIP), for example VIP1 , VIP2, VIP3 or VIP3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ). Truncated toxins, for example a truncated CrylA(b), are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of CrylllA055, a cathepsin-D-recognition sequence is inserted into a CrylllA toxin (see WO 03/018810). Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-O 374 753, WO 93/07278, WO 95/34656, EP-A-O 427 529, EP-A-451 878 and WO 03/052073.
The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-O 367 474, EP-A-O 401 979 and WO 90/13651.
The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bi ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bi ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); Nature- Gard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt1 1 corn borer (CB) trait) and Protecta®.
Further examples of such transgenic crops are:
1. Bt1 1 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylA(b) toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylA(b) toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect- resistant by transgenic expression of a modified CrylllA toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-D-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a CrylllB(bi ) toxin and has resistance to certain Coleoptera insects.
5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/ES/96/02.
6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1 160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1 F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.
7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacteήum sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylA(b) toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
Transgenic crops of insect-resistant plants are also described in BATS (Zentrum fur Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003.
The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-O 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-O 392 225, WO 95/33818, and EP-A-O 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A- 0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906).
Further areas of use of the compositions according to the invention are the protection of stored goods and storerooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.
In the hygiene sector, the compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas. Examples of such parasites are:
Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp..
Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp..
Of the order Diptera and the suborders Nematocerina and Brachycerina, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp..
Of the order Siphonapterida, for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp..
Of the order Heteropterida, for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp..
Of the order Blattarida, for example Blatta orientalis, Periplaneta americana, Blattelagermanica and Supella spp..
Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata, for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp..
Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.. The compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
The invention therefore provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula I. The compositions are preferably used against insects or acarines.
The term "plant" as used herein includes seedlings, bushes and trees.
The inventively used compounds can be applied in unmodified form, as obtained in the synthesis, but they are generally formulated into herbicidal compositions in a variety of ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The formulations can be in various physical forms, for example in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil flowables, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known, for example, from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. Such formulations can either be used directly or are diluted prior to use. Diluted formulations can be prepared, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
The formulations can be prepared, for example, by mixing the active ingredient with formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, for example finely divided solids, mineral oils, vegetable oils, modified vegetable oils, organic solvents, water, surface-active substances or combinations thereof. The active ingredients can also be contained in very fine microcapsules consisting of a polymer. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into their surroundings in controlled amounts (e.g. slow release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be present in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes comprise, for example, natural and synthetic gums, cellulose, styrene- butadiene copolymers, polyacrylonitrile, polyacrylate, polyester, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art in this connection. Alternatively it is possible for very fine microcapsules to be formed wherein the active ingredient is present in the form of finely divided particles in a solid matrix of a base substance, but in that case the microcapsule is not encapsulated.
The formulation adjuvants suitable for the preparation of the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylenes carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethyl hexanol, ethylene carbonate, 1 ,1 ,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n- hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o- xylene, phenol, polyethylene glycol (PEG 400), propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and higher molecular weight alcohols, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like. Water is generally the carrier of choice for the dilution of the concentrates. Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montomorillonite, cottonseed husks, wheatmeal, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar materials, as described, for example, in CFR 180.1001. (c) & (d).
A large number of surface-active substances can advantageously be used both in solid and in liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they may be used as emulsifiying, wetting or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecyl- benzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonat.es, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkyl phosphate esters; and also further substances described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, 1981.
Further adjuvants which can usually be used in pesticidal formulations include crystallisation inhibitors, viscosity-modifying substances, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing aids, anti-foams, complexing agents, neutralising or pH- modifying substances and buffers, corrosion-inhibitors, fragrances, wetting agents, absorption improvers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, anti-freezes, microbiocides, and also liquid and solid fertilisers.
The formulations may also comprise additional active substances, for example further herbicides, herbicide safeners, plant growth regulators, fungicides or insecticides.
The compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive used in the composition according to the invention is generally from 0.01 to 10 %, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® (Rhόne-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. A preferred additive contains, for example, as active components essentially 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers. Especially preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of Ci2-Ci8 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being important. Those esters are known as methyl laurate (CAS-1 1 1-82-0), methyl palmitate (CAS-1 12-39- 0) and methyl oleate (CAS-1 12-62-9). A preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH). Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000.
The application and action of the oil additives can be further improved by combining them with surface-active substances, such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485. Preferred surface-active substances are anionic surfactants of the dodecyl- benzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C12-C22 fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available surfactants are the Genapol types (Clariant AG). Also preferred are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltrisiloxanes, which are commercially available e.g. as Silwet L-77®, and also perfluorinated surfactants. The concentration of surface-active substances in relation to the total additive is generally from 1 to 30 % by weight. Examples of oil additives that consist of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Syngenta AG, CH) and Actipron® (BP Oil UK Limited, GB).
The said surface-active substances may also be used in the formulations alone, that is to say without oil additives.
Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture can contribute to a further enhancement of action. Suitable solvents are, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation). The concentration of such solvents can be from 10 to 80 % by weight of the total weight. Such oil additives, which may be in admixture with solvents, are described, for example, in US-A-4 834 908. A commercially available oil additive disclosed therein is known by the name MERGE® (BASF Corporation). A further oil additive that is preferred according to the invention is SCORE® (Syngenta Crop Protection Canada.)
In addition to the oil additives listed above, in order to enhance the activity of the compositions according to the invention it is also possible for formulations of alkylpyrrolidones, (e.g. Agrimax®) to be added to the spray mixture. Formulations of synthetic latices, such as, for example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g. Bond®, Courier® or Emerald®) can also be used. Solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, can also be mixed into the spray mixture as activity-enhancing agents.
As a rule, the compositions comprise 0.1 to 99%, especially 0.1 to 95%, of active ingredient and 1 to 99.9%, especially 5 to 99.9%, of at least one solid or liquid adjuvant, it being possible as a rule for 0 to 25%, especially 0.1 to 20%, of the composition to be surfactants(% in each case meaning percent by weight). Whereas concentrated compositions tend to be preferred for commercial goods, the end consumer as a rule uses dilute compositions which have substantially lower concentrations of active ingredient. Preferred compositions are composed in particular as follows (% = percent by weight):
Emulsifiable concentrates: active ingredient: 1 to 95%, preferably 5 to 20% surfactant: 1 to 30%, preferably 10 to 20 % solvent: 5 to 98%, preferably 70 to 85%
Dusts: active ingredient: 0.1 to 10%, preferably 0.1 to 1 % solid carrier: 99.9 to 90%, preferably 99.9 to 99%
Suspension concentrates: active ingredient: 5 to 75%, preferably 10 to 50% water: 94 to 24%, preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30% Wettable powders: active ingredient: 0.5 to 90%, preferably 1 to 80% surfactant: 0.5 to 20%, preferably 1 to 15% solid carrier: 5 to 99%, preferably 15 to 98%
Granulates: active ingredient: 0.5 to 30%, preferably 3 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%
The compositions can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds I for the preparation of these compositions are also a subject of the invention.
The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.
A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.
The compositions according to the invention are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type. The propagation material can be treated with the compositions prior to planting, for example seed can be treated prior to sowing. Alternatively, the compositions can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention.
In order to apply a compound of formula I as an insecticide, acaricide, nematicide or molluscicide to a pest, a locus of pest, or to a plant susceptible to attack by a pest, a compound of formula I is usually formulated into a composition which includes, in addition to the compound of formula I, a suitable inert diluent or carrier and, optionally, a formulation adjuvant in form of a surface active agent (SFA) as described herein or, for example, in EP- B-1062217. SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound of formula I. The composition is generally used for the control of pests such that a compound of formula I is applied at a rate of from 0.1 g tol Okg per hectare, preferably from 1 g to 6kg per hectare, more preferably from 1 g to 1 kg per hectare. When used in a seed dressing, a compound of formula I is used at a rate of 0.0001 g to 10g (for example 0.001 g or 0.05g), preferably 0.005g to 10g, more preferably 0.005g to 4g, per kilogram of seed.
The compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula I.
Dustable powders (DP) may be prepared by mixing a compound of formula I with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
Soluble powders (SP) may be prepared by mixing a compound of formula I with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
Wettable powders (WP) may be prepared by mixing a compound of formula I with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG). Granules (GR) may be formed either by granulating a mixture of a compound of formula I and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula I (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula I (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
Dispersible Concentrates (DC) may be prepared by dissolving a compound of formula I in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).
Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula I in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as Cs-C-io fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of formula I either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 7O0C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of formula I is present initially in either the water or the solvent/SFA blend. Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs. An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula I. SCs may be prepared by ball or bead milling the solid compound of formula I in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, a compound of formula I may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
Aerosol formulations comprise a compound of formula I and a suitable propellant (for example n-butane). A compound of formula I may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
A compound of formula I may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.
Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula I and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of formula I and they may be used for seed treatment. A compound of formula I may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
A composition of the present invention may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula I). Such additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula I).
A compound of formula I may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS). The preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above. Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
Wetting agents, dispersing agents and emulsifying agents may be surface active agents (SFAs) of the cationic, anionic, amphoteric or non-ionic type.
Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di- /sopropyl- and tri-/sopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated), sulphosuccinamates, paraffin or define sulphonates, taurates and lignosulphonates.
Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.
Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
A composition of the invention may be applied by any of the known means of applying pesticidal compositions. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment. It may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use. These concentrates, which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Such aqueous preparations may contain varying amounts of a compound of formula I (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
A composition of the inventionl may contain mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers). Suitable formulation types include granules of fertiliser. The mixtures suitably contain up to 25% by weight of the compound of formula I.
The invention therefore also provides a fertiliser composition comprising a fertiliser and a compound of formula I.
The compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.
The compound of formula I may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide (insect, acarine, mollusc and nematode pesticide), fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula I; or help to overcome or prevent the development of resistance to individual components. The particular additional active ingredient will depend upon the intended utility of the composition. Examples of suitable pesticides include the following: a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or 5-benzyl-3-furylmethyl-(E_)-(1 R,3S)-2,2-dimethyl- 3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate; b) Organophosphates, such as, profenofos, sulprofos, acephate, methyl parathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl, pirimiphos-ethyl, fenitrothion, fosthiazate or diazinon; c) Carbamates (including aryl carbamates), such as pirimicarb, triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur, methomyl or oxamyl; d) Benzoyl ureas, such as diflubenzuron, triflumuron, hexaflumuron, flufenoxuron or chlorfluazuron; e) Organic tin compounds, such as cyhexatin, fenbutatin oxide or azocyclotin; f) Pyrazoles, such as tebufenpyrad and fenpyroximate; g) Macrolides, such as avermectins or milbemycins, for example abamectin, emamectin benzoate, ivermectin, milbemycin, spinosad or azadirachtin; h) Hormones or pheromones; i) Organochlorine compounds such as endosulfan, benzene hexachloride, DDT, chlordane or dieldrin; j) Amidines, such as chlordimeform or amitraz; k) Fumigant agents, such as chloropicrin, dichloropropane, methyl bromide or metam;
I) Chloronicotinyl compounds such as imidacloprid, thiacloprid, acetamiprid, nitenpyram or thiamethoxam; m) Diacylhydrazines, such as tebufenozide, chromafenozide or methoxyfenozide; n) Diphenyl ethers, such as diofenolan or pyriproxifen; o) Indoxacarb; p) Chlorfenapyr; or q) Pymetrozine. In addition to the major chemical classes of pesticide listed above, other pesticides having particular targets may be employed in the composition, if appropriate for the intended utility of the composition. For instance, selective insecticides for particular crops, for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed. Alternatively insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).
Examples of fungicidal compounds which may be included in the composition of the invention are (£)-Λ/-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy- iminoacetamide (SSF-129), 4-bromo-2-cyano-Λ/,Λ/-dimethyl-6-trifluoromethylbenzimidazole- 1 -sulphonamide, α-[Λ/-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-γ-butyrolactone, 4-chloro-2- cyano-Λ/,Λ/-dimethyl-5-p-tolylimidazole-1 -sulfonamide (IKF-916, cyamidazosulfamid), 3-5-dichloro-Λ/-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide (RH-7281 , zoxamide), Λ/-allyl-4,5,-dimethyl-2-trimethylsilylthiophene-3-carboxamide (MON65500), N- (1 -cyano-1 ,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide (AC382042), Λ/-(2-methoxy-5-pyridyl)-cyclopropane carboxamide, acibenzolar, alanycarb, aldimorph, anilazine, azaconazole, azoxystrobin, benalaxyl, benomyl, biloxazol, bitertanol, blasticidin S, bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA41396, CGA41397, chinomethionate, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper oxyquinolate, copper sulphate, copper tallate and Bordeaux mixture, cymoxanil, cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulphide 1 ,1 '-dioxide, dichlofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O,O-di-/so-propyl-S-benzyl thiophosphate, dimefluazole, dimetconazole, dimethomorph, dimethirimol, diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethirimol, ethyl(Z)-Λ/-benzyl-/V- ([methyl(methyl-thioethylideneaminooxycarbonyl)amino]thio)-β-alaninate, etridiazole, famoxadone, fenamidone (RPA407213), fenarimol, fenbuconazole, fenfuram, fenhexamid (KBR2738), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, fluoroimide, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, hydroxyisoxazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine triacetate, ipconazole, iprobenfos, iprodione, iprovalicarb (SZX0722), isopropanyl butyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054, LY21 1795, LY248908, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil, metalaxyl, metconazole, metiram, metiram-zinc, metominostrobin, myclobutanil, neoasozin, nickel dimethyldithiocarbamate, nitrothal-Zsopropyl, nuarimol, ofurace, organomercury compounds, oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-AI, phosphorus acids, phthalide, picoxystrobin (ZA1963), polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, prop- iconazole, propineb, propionic acid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyr- oxyfur, pyrrolnitrin, quaternary ammonium compounds, quinomethionate, quinoxyfen, quintozene, sipconazole (F-155), sodium pentachlorophenate, spiroxamine, streptomycin, sulphur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamid, 2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl, thiram, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triforine, triflumizole, triticonazole, validamycin A, vapam, vinclo- zolin, zineb and ziram.
The compounds of formula I may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
Examples of suitable synergists for use in the compositions include piperonyl butoxide, sesamex, safroxan and dodecyl imidazole.
The composition according to the invention can also be used in combination with one or more other herbicides. In particular, the following mixtures of the compound of formula I are important: compound of formula I + acetochlor, compound of formula I + acifluorfen, compound of formula I + acifluorfen-sodium, compound of formula I + aclonifen, compound of formula I + acrolein, compound of formula I + alachlor, compound of formula I + alloxydim, compound of formula I + allyl alcohol, compound of formula I + ametryn, compound of formula I + amicarbazone, compound of formula I + amidosulfuron, compound of formula I + aminopyralid, compound of formula I + amitrole, compound of formula I + ammonium sulfamate, compound of formula I + anilofos, compound of formula I + asulam, compound of formula I + atraton, compound of formula I + atrazine, compound of formula I + azimsulfuron, compound of formula I + BCPC, compound of formula I + beflubutamid, compound of formula I + benazolin, compound of formula I + benfluralin, compound of formula I + benfuresate, compound of formula I + bensulfuron, compound of formula I + bensulfuron-methyl, compound of formula I + bensulide, compound of formula I + bentazone, compound of formula I + benzfendizone, compound of formula I + benzobicyclon, compound of formula I + benzofenap, compound of formula I + bifenox, compound of formula I + bilanafos, compound of formula I + bispyribac, compound of formula I + bispyribac-sodium, compound of formula I + borax, compound of formula I + bromacil, compound of formula I + bromobutide, compound of formula I + bromoxynil, compound of formula I + butachlor, compound of formula I + butafenacil, compound of formula I + butamifos, compound of formula I + butralin, compound of formula I + butroxydim, compound of formula I + butylate, compound of formula I + cacodylic acid, compound of formula I + calcium chlorate, compound of formula I + cafenstrole, compound of formula I + carbetamide, compound of formula I + carfentrazone, compound of formula I + carfentrazone-ethyl, compound of formula I + CDEA, compound of formula I + CEPC, compound of formula I + chlorflurenol, compound of formula I + chlorflurenol-methyl, compound of formula I + chloridazon, compound of formula I + chlorimuron, compound of formula I + chlorimuron-ethyl, compound of formula I + chloroacetic acid, compound of formula I + chlorotoluron, compound of formula I + chlorpropham, compound of formula I + chlorsulfuron, compound of formula I + chlorthal, compound of formula I + chlorthal- dimethyl, compound of formula I + cinidon-ethyl, compound of formula I + cinmethylin, compound of formula I + cinosulfuron, compound of formula I + cisanilide, compound of formula I + clethodim, compound of formula I + clodinafop, compound of formula I + clodinafop-propargyl, compound of formula I + clomazone, compound of formula I + clomeprop, compound of formula I + clopyralid, compound of formula I + cloransulam, compound of formula I + cloransulam-methyl, compound of formula I + CMA, compound of formula I + 4-CPB, compound of formula I + CPMF, compound of formula I + 4-CPP, compound of formula I + CPPC, compound of formula I + cresol, compound of formula I + cumyluron, compound of formula I + cyanamide, compound of formula I + cyanazine, compound of formula I + cycloate, compound of formula I + cyclosulfamuron, compound of formula I + cycloxydim, compound of formula I + cyhalofop, compound of formula I + cyhalofop-butyl, compound of formula I + 2,4-D, compound of formula I + 3,4-DA, compound of formula I + daimuron, compound of formula I + dalapon, compound of formula I + dazomet, compound of formula I + 2,4-DB, compound of formula I + 3,4-DB, compound of formula I + 2,4-DEB, compound of formula I + desmedipham, compound of formula I + dicamba, compound of formula I + dichlobenil, compound of formula I + ortho- dichlorobenzene, compound of formula I + para-dichlorobenzene, compound of formula I + dichlorprop, compound of formula I + dichlorprop-P, compound of formula I + diclofop, compound of formula I + diclofop-methyl, compound of formula I + diclosulam, compound of formula I + difenzoquat, compound of formula I + difenzoquat metilsulfate, compound of formula I + diflufenican, compound of formula I + diflufenzopyr, compound of formula I + dimefuron, compound of formula I + dimepiperate, compound of formula I + dimethachlor, compound of formula I + dimethametryn, compound of formula I + dimethenamid, compound of formula I + dimethenamid-P, compound of formula I + dimethipin, compound of formula I + dimethylarsinic acid, compound of formula I + dinitramine, compound of formula I + dinoterb, compound of formula I + diphenamid, compound of formula I + diquat, compound of formula I + diquat dibromide, compound of formula I + dithiopyr, compound of formula I + diuron, compound of formula I + DNOC, compound of formula I + 3,4-DP, compound of formula I + DSMA, compound of formula I + EBEP, compound of formula I + endothal, compound of formula I + EPTC, compound of formula I + esprocarb, compound of formula I + ethalfluralin, compound of formula I + ethametsulfuron, compound of formula I + ethametsulfuron-methyl, compound of formula I + ethofumesate, compound of formula I + ethoxyfen, compound of formula I + ethoxysulfuron, compound of formula I + etobenzanid, compound of formula I + fenoxaprop-P, compound of formula I + fenoxaprop-P-ethyl, compound of formula I + fentrazamide, compound of formula I + ferrous sulfate, compound of formula I + flamprop-M, compound of formula I + flazasulfuron, compound of formula I + florasulam, compound of formula I + fluazifop, compound of formula I + fluazifop-butyl, compound of formula I + fluazifop-P, compound of formula I + fluazifop-P-butyl, compound of formula I + flucarbazone, compound of formula I + flucarbazone-sodium, compound of formula I + flucetosulfuron, compound of formula I + fluchloralin, compound of formula I + flufenacet, compound of formula I + flufenpyr, compound of formula I + flufenpyr-ethyl, compound of formula I + flumetsulam, compound of formula I + flumiclorac, compound of formula I + flumiclorac-pentyl, compound of formula I + flumioxazin, compound of formula I + fluometuron, compound of formula I + fluoroglycofen, compound of formula I + fluoroglycofen-ethyl, compound of formula I + flupropanate, compound of formula I + flupyrsulfuron, compound of formula I + flupyrsulfuron-methyl-sodium, compound of formula I + flurenol, compound of formula I + fluridone, compound of formula I + flurochloridone, compound of formula I + fluroxypyr, compound of formula I + flurtamone, compound of formula I + fluthiacet, compound of formula I + fluthiacet-methyl, compound of formula I + fomesafen, compound of formula I + foramsulfuron, compound of formula I + fosamine, compound of formula I + glufosinate, compound of formula I + glufosinate-ammonium, compound of formula I + glyphosate, compound of formula I + halosulfuron, compound of formula I + halosulfuron-methyl, compound of formula I + haloxyfop, compound of formula I + haloxyfop-P, compound of formula I + HC-252, compound of formula I + hexazinone, compound of formula I + imazamethabenz, compound of formula I + imazamethabenz- methyl, compound of formula I + imazamox, compound of formula I + imazapic, compound of formula I + imazapyr, compound of formula I + imazaquin, compound of formula I + imazethapyr, compound of formula I + imazosulfuron, compound of formula I + indanofan, compound of formula I + iodomethane, compound of formula I + iodosulfuron, compound of formula I + iodosulfuron-methyl-sodium, compound of formula I + ioxynil, compound of formula I + isoproturon, compound of formula I + isouron, compound of formula I + isoxaben, compound of formula I + isoxachlortole, compound of formula I + isoxaflutole, compound of formula I + karbutilate, compound of formula I + lactofen, compound of formula I + lenacil, compound of formula I + linuron, compound of formula I + MAA, compound of formula I + MAMA, compound of formula I + MCPA, compound of formula I + MCPA-thioethyl, compound of formula I + MCPB, compound of formula I + mecoprop, compound of formula I + mecoprop-P, compound of formula I + mefenacet, compound of formula I + mefluidide, compound of formula I + mesosulfuron, compound of formula I + mesosulfuron-methyl, compound of formula I + mesotrione, compound of formula I + metam, compound of formula I + metamifop, compound of formula I + metamitron, compound of formula I + metazachlor, compound of formula I + methabenzthiazuron, compound of formula I + methylarsonic acid, compound of formula I + methyldymron, compound of formula I + methyl isothiocyanate, compound of formula I + metobenzuron, compound of formula I + metolachlor, compound of formula I + S-metolachlor, compound of formula I + metosulam, compound of formula I + metoxuron, compound of formula I + metribuzin, compound of formula I + metsulfuron, compound of formula I + metsulfuron- methyl, compound of formula I + MK-616, compound of formula I + molinate, compound of formula I + monolinuron, compound of formula I + MSMA, compound of formula I + naproanilide, compound of formula I + napropamide, compound of formula I + naptalam, compound of formula I + neburon, compound of formula I + nicosulfuron, compound of formula I + nonanoic acid, compound of formula I + norflurazon, compound of formula I + oleic acid (fatty acids), compound of formula I + orbencarb, compound of formula I + orthosulfamuron, compound of formula I + oryzalin, compound of formula I + oxadiargyl, compound of formula I + oxadiazon, compound of formula I + oxasulfuron, compound of formula I + oxaziclomefone, compound of formula I + oxyfluorfen, compound of formula I + paraquat, compound of formula I + paraquat dichloride, compound of formula I + pebulate, compound of formula I + pendimethalin, compound of formula I + penoxsulam, compound of formula I + pentachlorophenol, compound of formula I + pentanochlor, compound of formula I + pentoxazone, compound of formula I + pethoxamid, compound of formula I + petrolium oils, compound of formula I + phenmedipham, compound of formula I + phenmedipham-ethyl, compound of formula I + picloram, compound of formula I + picolinafen, compound of formula I + pinoxaden, compound of formula I + piperophos, compound of formula I + potassium arsenite, compound of formula I + potassium azide, compound of formula I + pretilachlor, compound of formula I + primisulfuron, compound of formula I + primisulfuron-methyl, compound of formula I + prodiamine, compound of formula I + profluazol, compound of formula I + profoxydim, compound of formula I + prometon, compound of formula I + prometryn, compound of formula I + propachlor, compound of formula I + propanil, compound of formula I + propaquizafop, compound of formula I + propazine, compound of formula I + propham, compound of formula I + propisochlor, compound of formula I + propoxycarbazone, compound of formula I + propoxycarbazone- sodium, compound of formula I + propyzamide, compound of formula I + prosulfocarb, compound of formula I + prosulfuron, compound of formula I + pyraclonil, compound of formula I + pyraflufen, compound of formula I + pyraflufen-ethyl, compound of formula I + pyrazolynate, compound of formula I + pyrazosulfuron, compound of formula I + pyrazosulfuron-ethyl, compound of formula I + pyrazoxyfen, compound of formula I + pyribenzoxim, compound of formula I + pyributicarb, compound of formula I + pyridafol, compound of formula I + pyridate, compound of formula I + pyriftalid, compound of formula I + pyriminobac, compound of formula I + pyriminobac-methyl, compound of formula I + pyrimisulfan, compound of formula I + pyrithiobac, compound of formula I + pyrithiobac- sodium, compound of formula I + quinclorac, compound of formula I + quinmerac, compound of formula I + quinoclamine, compound of formula I + quizalofop, compound of formula I + quizalofop-P, compound of formula I + rimsulfuron, compound of formula I + sethoxydim, compound of formula I + siduron, compound of formula I + simazine, compound of formula I + simetryn, compound of formula I + SMA, compound of formula I + sodium arsenite, compound of formula I + sodium azide, compound of formula I + sodium chlorate, compound of formula I + sulcotrione, compound of formula I + sulfentrazone, compound of formula I + sulfometuron, compound of formula I + sulfometuron-methyl, compound of formula I + sulfosate, compound of formula I + sulfosulfuron, compound of formula I + sulfuric acid, compound of formula I + tar oils, compound of formula I + 2,3,6- TBA, compound of formula I + TCA, compound of formula I + TCA-sodium, compound of formula I + tebuthiuron, compound of formula I + tepraloxydim, compound of formula I + terbacil, compound of formula I + terbumeton, compound of formula I + terbuthylazine, compound of formula I + terbutryn, compound of formula I + thenylchlor, compound of formula I + thiazopyr, compound of formula I + thifensulfuron, compound of formula I + thifensulfuron-methyl, compound of formula I + thiobencarb, compound of formula I + tiocarbazil, compound of formula I + topramezone, compound of formula I + tralkoxydim, compound of formula I + tri-allate, compound of formula I + triasulfuron, compound of formula I + triaziflam, compound of formula I + tribenuron, compound of formula I + tribenuron-methyl, compound of formula I + tricamba, compound of formula I + triclopyr, compound of formula I + trietazine, compound of formula I + trifloxysulfuron, compound of formula I + trifloxysulfuron-sodium, compound of formula I + trifluralin, compound of formula I + triflusulfuron, compound of formula I + triflusulfuron-methyl, compound of formula I + trihydroxytriazine, compound of formula I + tritosulfuron, compound of formula I + [3-[2- chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1 ,2,3,4-tetrahydropyrimidin-3- yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester (CAS RN 353292-31-6), compound of formula I + 4-[(4,5-dihydro-3-methoxy-4-methyl-5-oxo)-1 H-1 ,2,4-triazol-1- ylcarbonylsulfamoylJ-δ-methylthiophene-S-carboxylic acid (BAY636), compound of formula I + BAY747 (CAS RN 335104-84-2), compound of formula I + topramezone (CAS RN 210631-68-8), compound of formula I + 4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6- (trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one (CAS RN 352010-68-5), and compound of formula I + 4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3- pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one.
The mixing partners of the compound of formula I may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 12th Edition (BCPC), 2000. In the above list, the compound of the formula I is preferably a compound of Tables 1 to 294, and more preferably, a compound of the following Tables A to D.
The mixing ratio of the compound of formula I to the mixing partner is preferably from 1 : 100 to 1000:1.
The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of formula I with the mixing partner).
Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.
The invention is illustrated by the following Examples:
The compounds in the following Table A were prepared by procedures known from International application No. PCT/EP2007/010848, from appropriate starting materials. It should be noted that certain of the inventively used compounds exist as a mixture of atropisomers, or other isomers noted above, under the conditions used to obtain the 1H nmr data. Where this has occurred, the characterising data are reported for individual isomers, isomer A and isomer B, which together represent the mixture of atropisomers, or other isomers, present at ambient temperature in the specified solvent.
Table A (m, 1.62 (d,
(m, A or d, A or
B), (m,
2H), 6H).
(d, 1.63
br. d,
6H, (s, (t,
(app.
A and (app.
5.44 1.17
5.45 1.14
(s, (t,
(dd, 2.55-
(s, 2.45
(m, 6H), (br. s, 1.61
(m,
1H), s,
1H), (br.
1H), s,
2H), s,
(s,
1H), (br. 1H),
1H), s,
1H), s,
1 H), d,
1H),
1H),
(d, 1 H), s,
1H), 3H),
Additional compounds in Tables B, C and D for use in the pesticidal compositions according to the invention were prepared by analogues procedures, from appropriate starting materials.
Table B
1 H),
7.02 3H), (s, 5.9 6H).
6H).
(d,
(s,
(d, 1.55
1 H), (m,
2H), (s, (d, 1H), (br. 6H),
3H),.
2H),
7.29 3H),
7.18
7.32 1H), (s,
7.3 6H), 6.0
5.87
7.22 1H), (s,
7.34 6H),
7.5 1H),
7.3 6H),
1H), 1H),
1H),
(t,
(m, 2.58-
(m, (d,
1H),
3H).
7.22
1 H), (m, 1.56 3H). (m,
7.49 3H),
7.02
(s,
(d,
3H), 7.32 1H), (s,
7.27
7.49
1H),
1.55
7.31 6H),
7.61 1H),
Table C
The compounds of the following Tables 1 to 294 may be obtained in an analogous manner.
Table 1 :
This table covers 378 compounds of the following type:
wherein Y is O, R1 is methyl, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R are as defined below:
Table 2:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is ethyl, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 3:
This table covers 378 compounds of the following type: wherein Y is O, R1 is chlorine, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 4:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is methyl, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen and RR22 aanndd R R3 are as defined in Table 1. Table 5:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is ethyl, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 6:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is chlorine, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen and RR22 aanndd R R3 are as defined in Table 1. Table 7:
This table covers 378 compounds of the following type:
Wherein Y is O, R1 is methyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 8:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is ethyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen aanndd RR22 aand R3 are as defined in Table 1. Table 9:
This table covers 378 compounds of the following type:
Wherein Y is O, R1 is chlorine, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 10:
This table covers 378 compounds of the following type: wherein Y is O, R1 is methyl, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 1 1 :
This table covers 378 compounds of the following type:
wherein Y is O, R1 is ethyl, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen aanndd RR22 aannd R3 are as defined in Table 1. Table 12:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is chlorine, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 13:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is methyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and RR22 aanndd RR33 are as defined in Table 1. Table 14:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is ethyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 15:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is chlorine, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and RR22 aanndd RR33 are as defined in Table 1. Table 16:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is methyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 17:
This table covers 378 compounds of the following type: wherein Y is O, R1 is ethyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 18:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is chlorine, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 19:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is methyl, R4, R5 and R6 are methyl, R7 is methoxymethyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 20:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is ethyl, R4, R5 and R6 are methyl, R7 is methoxymethyl, G is hydrogen aanndd RR22 aannd R3 are as defined in Table 1. Table 21 : nds of the following type:
wherein Y is O, R1 is chlorine, R4, R5 and R6 are methyl, R7 is methoxymethyl, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 22:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is methyl, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 23: nds of the following type:
wherein Y is S, R1 is ethyl, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 24:
This table covers 378 compounds of the following type: wherein Y is S, R1 is chlorine, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 25:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is methyl, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen and RR22 aanndd RR33 are as defined in Table 1. Table 26:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is ethyl, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 27:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is chlorine, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen and RR22 aanndd RR33 are as defined in Table 1. Table 28:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is methyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 29:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is ethyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen aanndd RR22 aannd R3 are as defined in Table 1. Table 30:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is chlorine, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 31 :
This table covers 378 compounds of the following type: wherein Y is S, R1 is methyl, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 32:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is ethyl, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen aanndd RR22 aannd R3 are as defined in Table 1. Table 33:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is chlorine, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 34:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is methyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and R2 aanndd RR33 aarcre as defined in Table 1. Table 35:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is ethyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 36:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is chlorine, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and RR22 aanndd RR33 are as defined in Table 1. Table 37:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is methyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 38:
This table covers 378 compounds of the following type: wherein Y is S, R1 is ethyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 39:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is chlorine, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 40:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is methyl, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 41 :
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is ethyl, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 42:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is chlorine, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and
R3 are as defined in Table 1.
Table 43:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is methyl, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen aanndd RR22 aannd R3 are as defined in Table 1. Table 44:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is ethyl, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen and
R2 and R3 are as defined in Table 1.
Table 45:
This table covers 378 compounds of the following type: wherein Y is S=O, R1 is chlorine, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 46:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is methyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 47:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is ethyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 48:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is chlorine, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hhyyddrrooggeenn and R2 and R3 are as defined in Table 1.
Table 49:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is methyl, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 50:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is ethyl, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen aanndd RR22 aannd R3 are as defined in Table 1. Table 51 :
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is chlorine, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 52:
This table covers 378 compounds of the following type: wherein Y is S=O, R1 is methyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and
R2 and R3 are as defined in Table 1.
Table 53:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is ethyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and RR22 aanndd RR33 are as defined in Table 1. Table 54:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is chlorine, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 55:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is methyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 56:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is ethyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 57:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is chlorine, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 58:
This table covers 378 compounds of the following type:
wherein Y is S(=0)2, R1 is methyl, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 59:
This table covers 378 compounds of the following type: wherein Y is S(=O)2, R1 is ethyl, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and RR33 aarree aass defined in Table 1. Table 60:
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is chlorine, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 aanndd RR33 aarcre as defined in Table 1. Table 61 :
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is methyl, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 62:
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen aanndd RR22 aannd R3 are as defined in Table 1. Table 63:
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is chlorine, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 64:
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is methyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 65:
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 66:
This table covers 378 compounds of the following type: wherein Y is S(=O)2, R1 is chlorine, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 67:
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is methyl, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hhyyddrrooggeenn and R2 and R3 are as defined in Table 1.
Table 68:
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 69:
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is chlorine, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hhyyddrrooggeenn i and R2 and R3 are as defined in Table 1. Table 70::
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is methyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 71 :
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen aanndd RR22 aannd R3 are as defined in Table 1. Table 72:
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is chlorine, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 73:
This table covers 378 compounds of the following type: wherein Y is S(=O)2, R1 is methyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and RR33 aarree aass defined in Table 1. Table 74:
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 75:
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is chlorine, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and RR33 aarree aass defined in Table 1. Table 76:
This table covers 378 compounds of the following type:
Wherein Y is C=O, R1 is methyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hhyyddrrooggeenn and R2 and R3 are as defined in Table 1.
Table 77:
This table covers 378 compounds of the following type:
wherein Y is C=O, R1 is ethyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 78:
This table covers 378 compounds of the following type:
wherein Y is C=O, R1 is ethyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen aanndd RR22 aannd R3 are as defined in Table 1. Table 79:
This table covers 378 compounds of the following type:
wherein Y is C=O, R1 is methyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 80:
This table covers 378 compounds of the following type: wherein Y is C=O, R1 is ethyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and
R2 and R3 are as defined in Table 1. Table 81 :
This table covers 378 compounds of the following type:
wherein Y is C=O, R1 is chlorine, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen aanndd RR22 aannd R3 are as defined in Table 1. Table 82:
This table covers 378 compounds of the following type:
wherein Y is C=O, R1 is methyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 83:
This table covers 378 compounds of the following type:
wherein Y is C=O, R1 is ethyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 84:
This table covers 378 compounds of the following type:
wherein Y is C=O, R1 is chlorine, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 85:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is methyl, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3' are as defined below:
Table 86:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is ethyl, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 87:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is methyl, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen and RR22 aanndd RR33 are as defined in Table 85. Table 88:
This table covers 126 compounds of the following type: wherein Y is O, R1 is ethyl, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85. Table 89:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is methyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen aanndd RR22 aannd R3 are as defined in Table 85. Table 90:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is ethyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 91 :
This table covers 126 compounds of the following type:
wherein Y is O, R1 is methyl, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen aanndd RR22 aannd R3 are as defined in Table 85. Table 92:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is ethyl, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen aanndd RR22 aannd R3 are as defined in Table 85. Table 93:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is methyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and
R2 and R3 are as defined in Table 85.
Table 94:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is ethyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 95:
This table covers 126 compounds of the following type: wherein Y is O, R1 is methyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 85. Table 96:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is ethyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 97:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is methyl, R4, R5, R6 are methyl, R7 is methoxymethyl, G is hydrogen and
R2 and R3 are as defined in Table 85.
Table 98:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is ethyl, R4, R5, R6 are methyl, R7 is methoxymethyl, G is hydrogen and RR22 aanndd RR33 are as defined in Table 85. Table 99:
This table covers 126 compounds of the following type:
wherein Y is S, R1 is methyl, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and Ra are as defined in Table 85.
Table 100:
This table covers 126 compounds of the following type:
wherein Y is S, R1 is ethyl, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 101 :
This table covers 126 compounds of the following type:
wherein Y is S, R1 is methyl, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen and
R2 and R3 are as defined in Table 85.
Table 102:
This table covers 126 compounds of the following type: wherein Y is S, R1 is ethyl, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85. Table 103:
This table covers 126 compounds of the following type:
wherein Y is S, R1 is methyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen aanndd RR22 aanndd R3 are as defined in Table 85. Table 104:
This table covers 126 compounds of the following type:
wherein Y is S, R1 is ethyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 105:
This table covers 126 compounds of the following type:
wherein Y is S, R1 is methyl, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen aanndd RR22 aanndd R3 are as defined in Table 85. Table 106:
This table covers 126 compounds of the following type:
wherein Y is S, R1 is ethyl, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 107:
This table covers 126 compounds of the following type:
wherein Y is S, R1 is methyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and R2 and R are as defined in Table 85.
Table 108:
This table covers 126 compounds of the following type
wherein Y is S, R1 is ethyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 109:
This table covers 126 compounds of the following type: wherein Y is S, R1 is methyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 85. Table 1 10:
This table covers 126 compounds of the following type:
wherein Y is S, R1 is ethyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 1 1 1 :
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is methyl, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and
R3 are as defined in Table 85.
Table 1 12:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is ethyl, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85. Table 1 13:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is methyl, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 1 14:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is ethyl, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen and
R2 and R3 are as defined in Table 85.
Table 1 15:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is methyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 1 16:
This table covers 126 compounds of the following type: wherein Y is S=O, R1 is ethyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85. Table 1 17:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is methyl, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 1 18:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is ethyl, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 1 19:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is methyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and RR22 aanndd RR33 ε are as defined in Table 85. Table 120:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is ethyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and
R2 and R3 are as defined in Table 85.
Table 121 :
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is methyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 122:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is ethyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 123:
This table covers 126 compounds of the following type: wherein Y is S(=O)2, R1 is methyl, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85. Table 124:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl, R4, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and RR33 aarree aass ddefined in Table 85. Table 125:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is methyl, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 126:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl, R4 is methyl, R5, R6 and R7 are hydrogen, G is hydrogen aanndd RR22 aanndd R3 are as defined in Table 85. Table 127:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is methyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85. Table 128:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hhyyddrrooggeenn aand R2 and R3 are as defined in Table 85. Table 129:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is methyl, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 130:
This table covers 126 compounds of the following type: wherein Y is S(=O)2, R1 is ethyl, R4 and R6 are methyl, R5 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 131 :
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is methyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen aanndd RR22 aanndd R3 are as defined in Table 85. Table 132:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 133:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is methyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and RR33 aarree aass ddefined in Table 85. Table 134:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 135:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 is methyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hhyyddrrooggeenn aand R2 and R3 are as defined in Table 85. Table 136:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 is ethyl, R4 and R5 are methyl, R6 and R7 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 137:
This table covers 126 compounds of the following type: wherein Y is C=O, R1 is methyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85. Table 138:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 is ethyl, R4, R5 and R6 are methyl, R7 is hydrogen, G is hydrogen and RR22 aanndd RR33 ε are as defined in Table 85. Table 139:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 is methyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 140:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 is ethyl, R4, R5, R6 and R7 are methyl, G is hydrogen and R2 and Ra are as defined in Table 85. Table 141.
This table covers 126 compounds of the following type:
wherein Y is O and R1 and R3a are methyl, R4, R5, R6 and R7 are methyl, R3b is methyl, and
G is hydrogen and R2 is as defined in Table 85.
Table 142:
This table covers 126 compounds of the following type:
wherein Y is S and R1 and R3a are methyl, R4, R5, R6 and R7 are methyl, R3b is methyl, and G
-,2 is hydrogen and R is as defined in the Table 85.
Table 143:
This table covers 126 compounds of the following type:
wherein Y is S=O and R1 and R3a are methyl, R4, R5, R6 and R7 are methyl, R3b is methyl, and G is hydrogen and R2 is as defined in the Table 85.
Table 144:
This table covers 126 compounds of the following type: wherein Y is S(=O)2 and R1 and R3a are methyl, R4, R5, R6 and R7 are methyl, R3b is methyl, and G is hydrogen and R2 is as defined in the Table 85.
Table 145:
This table covers 126 compounds of the following type:
wherein Y is C=O and R1 and R3a are methyl, R4, R5, R6 and R7 are methyl, R3b is methyl, and G is hydrogen and R2 is as defined in the Table 85.
Table 146:
This table covers 126 compounds of the following type:
wherein Y is O and R1 is ethyl and R3a is methyl, R4, R5, R6 and R7 are methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85.
Table 147:
This table covers 126 compounds of the following type:
wherein Y is S and R1 is ethyl and R3a is methyl, R4, R5, R6 and R7 are methyl, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 148:
This table covers 126 compounds of the following type:
wherein Y is S=O and R1 is ethyl and R3a is methyl, R4, R5, R6 and R7 are methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85.
Table 149:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2 and R1 is ethyl and R3a is methyl, R4, R5, R6 and R7 are methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85.
Table 150:
This table covers 126 compounds of the following type:
wherein Y is C=O and R1 is ethyl and R3a is methyl, R4, R5, R6 and R7 are methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85.
Table 151 :
This table covers 126 compounds of the following type: wherein Y is O and R1 and R3a are ethyl, R4, R5, R6 and R7 are methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85.
Table 152:
This table covers 126 compounds of the following type:
wherein Y is S and R1 and R3a are ethyl, R4, R5, R6 and R7 are methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 153:
This table covers 126 compounds of the following type:
wherein Y is S=O and R1 and R3a are ethyl, R4, R5, R6 and R7 are methyl, R3b is methyl, and
G is hydrogen and R2 is as defined in Table 85.
Table 154:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2 and R1 and R3a are ethyl, R4, R5, R6 and R7 are methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 155:
This table covers 126 compounds of the following type:
wherein Y is C=O and R1 and R3a are ethyl, R4, R5, R6 and R7 are methyl, R3b is methyl, and
G is hydrogen and R2 is as defined in Table 85.
Table 156:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is methyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 157
This table covers 378 compounds of the following type:
wherein Y is O, R1 is ethyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 158
This table covers 378 compounds of the following type: wherein Y is O, R1 is chlorine, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 159:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is methyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 160:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is ethyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 161 :
This table covers 378 compounds of the following type:
wherein Y is O, R1 is chlorine, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and RR33 aarree aass ddefined in Table 1. Table 162:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is methyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 163:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is ethyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 164:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is chlorine, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 165:
This table covers 378 compounds of the following type: wherein Y is O, R1 is methyl, R5 is hydrogen and R6 is methoxymethyl, G is hydrogen and R2 aanndd RR33 aarree as defined in Table 1. Table 166:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is ethyl, R5 is hydrogen and R6 is methoxymethyl, G is hydrogen and R2 aanndd RR33 aarree as defined in Table 1. Table 167:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is chlorine, R5 is hydrogen and R6 is methoxymethyl, G is hydrogen and
R2 and R3 are as defined in Table 1. Table 168:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is methyl, R5 is hydrogen and R6 is ethoxymethyl, G is hydrogen and R2 aanndd RR33 aarree as defined in Table 1. Table 169:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is ethyl, R5 is hydrogen and R6 is ethoxymethyl, G is hydrogen and R2 aanndd RR33 aarree as defined in Table 1. Table 170:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is chlorine, R5 is hydrogen and R6 is ethoxymethyl, G is hydrogen and R2 aanndd RR33 aarree as defined in Table 1. Table 171 :
This table covers 378 compounds of the following type:
wherein Y is O, R1 is methyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 172:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is ethyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 173:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is chlorine, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 174:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is methyl, R5 is methyl, R6 is hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 175:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is ethyl, R5 is methyl, R6 is hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 176:
This table covers 378 compounds of the following type:
wherein Y is O, R1 is chlorine, R5 is methyl, R6 is hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 177:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is methyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85. Table 178:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is ethyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 179:
This table covers 126 compounds of the following type: wherein Y is O, R1 is methyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 180:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is ethyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 181 :
This table covers 126 compounds of the following type:
wherein Y is O, R1 is methyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 182:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is ethyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 85. Table 183:
This table covers 126 compounds of the following type:
wherein Y is O, R1 and R3a are methyl, R5 and R6 are hydrogen, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85.
Table 184:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is ethyl and R3a is methyl, R5 and R6 are hydrogen, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 185:
This table covers 126 compounds of the following type:
wherein Y is O, R1 and R3a are ethyl, R5 and R6 are hydrogen, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 186: This table covers 126 compounds of the following type:
wherein Y is O, R1 and R3a are methyl, R5 is hydrogen and R6 is methyl, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 187:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is ethyl and R3a is methyl, R5 is hydrogen and R6 is methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 188:
This table covers 126 compounds of the following type:
wherein Y is O, R1 and R3a are ethyl, R5 is hydrogen and R6 is methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85.
Table 189:
This table covers 126 compounds of the following type:
wherein Y is O, R1 and R3a are methyl, R5 are R6 are methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 190:
This table covers 126 compounds of the following type:
wherein Y is O, R1 is ethyl and R3a is methyl, R5 are R6 are methyl, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 191 :
This table covers 126 compounds of the following type:
wherein Y is O, R1 and R3a are ethyl, R5 are R6 are methyl, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 192:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is methyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 193:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is ethyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 194:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is chlorine, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 195:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is methyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 196:
This table covers 378 compounds of the following type: wherein Y is S, R1 is ethyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 197:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is chlorine, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 198:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is methyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 199:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is ethyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 200:
This table covers 378 compounds of the following type:
wherein Y is S, R1 is chlorine, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 201 :
This table covers 126 compounds of the following type:
wherein Y is S, R1 is methyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85. Table 202:
This table covers 126 compounds of the following type:
wherein Y is S, R1 is ethyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 203:
This table covers 126 compounds of the following type: wherein Y is S, R1 is methyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 204:
This table covers 126 compounds of the following type:
wherein Y is S, R1 is ethyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 205:
This table covers 126 compounds of the following type:
wherein Y is S, R1 is methyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 85. Table 206:
This table covers 126 compounds of the following type:
wherein Y is S, R1 is ethyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 85. Table 207:
This table covers 126 compounds of the following type:
wherein Y is S, R1 and R3a are methyl, R5 and R6 are hydrogen, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85.
Table 208:
This table covers 126 compounds of the following type:
wherein Y is S, R1 is ethyl and R3a is methyl, R5 and R6 are hydrogen, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 209:
This table covers 126 compounds of the following type:
wherein Y is S, R1 and R3a are ethyl, R5 and R6 are hydrogen, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 210: This table covers 126 compounds of the following type:
wherein Y is S, R1 and R3a are methyl, R5 is hydrogen and R6 is methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 21 1 :
This table covers 126 compounds of the following type:
wherein Y is S, R1 is ethyl and R3a is methyl, R5 is hydrogen and R6 is methyl, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 212:
This table covers 126 compounds of the following type:
wherein Y is S, R1 and R3a are ethyl, R5 is hydrogen and R6 is methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 213:
This table covers 126 compounds of the following type:
wherein Y is S, R1 and R3a are methyl, R5 are R6 are methyl, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 214:
This table covers 126 compounds of the following type:
wherein Y is S, R1 is ethyl and R3a is methyl, R5 are R6 are methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 215:
This table covers 126 compounds of the following type:
wherein Y is S, R1 and R3a are ethyl, R5 are R6 are methyl, R3b is methyl, and G is hydrogen aanndd RR22 iiss aa;s defined in Table 85. Table 216:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is methyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 217:
This table covers 378 compounds of the following type: wherein Y is S=O, R1 is ethyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 218:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is chlorine, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 219:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is methyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and RR33 aarree aass ddefined in Table 1. Table 220:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is ethyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 221 :
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is chlorine, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and RR33 aarree aass ddefined in Table 1. Table 222:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is methyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 223:
This table covers 378 compounds of the following type:
wherein Y is S=O, R1 is ethyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 224:
This table covers 378 compounds of the following type: wherein Y is S=O, R1 is chlorine, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 225:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is methyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 226:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is ethyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 227:
This table covers 126 compounds of the following type: wherein Y is S=O, R1 is methyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and
R3 are as defined in Table 85.
Table 228:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is ethyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 229:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is methyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 85. Table 230:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is ethyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 85. Table 231 :
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 and R3a are methyl, R5 and R6 are hydrogen, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85.
Table 232:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is ethyl and R3a is methyl, R5 and R6 are hydrogen, R3b is methyl, and
G is hydrogen and R is as defined in Table 85. Table 233:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 and R3a are ethyl, R5 and R6 are hydrogen, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85.
Table 234:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 and R3a are methyl, R5 is hydrogen and R6 is methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 235:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is ethyl and R3a is methyl, R5 is hydrogen and R6 is methyl, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 236:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 and R3a are ethyl, R5 is hydrogen and R6 is methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 237:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 and R3a are methyl, R5 are R6 are methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 238:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 is ethyl and R3a is methyl, R5 are R6 are methyl, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 239:
This table covers 126 compounds of the following type:
wherein Y is S=O, R1 and R3a are ethyl, R5 are R6 are methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 240:
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is methyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 241 :
This table covers 378 compounds of the following type: wherein Y is S(=O)2, R1 is ethyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 242:
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is chlorine, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 243
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is methyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 aanndd RR33 aarree as defined in Table 1. Table 244:
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and RR33 aarree aass ddefined in Table 1. Table 245:
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is chlorine, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 aanndd RR33 aarree as defined in Table 1. Table 246:
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is methyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 247:
This table covers 378 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 248:
This table covers 378 compounds of the following type: wherein Y is S(=O)2, R1 is chlorine, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 249:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is methyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 250:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 251 :
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is methyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 aanndd RR33 aarree as defined in Table 85. Table 252:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and R3 are as defined in Table 85. Table 253:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is methyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 85. Table 254:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 255:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 and R3a are methyl, R5 and R6 are hydrogen, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 256:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl and R3a is methyl, R5 and R6 are hydrogen, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 257:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 and R3a are ethyl, R5 and R6 are hydrogen, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85.
Table 258:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 and R3a are methyl, R5 is hydrogen and R6 is methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 259:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl and R3a is methyl, R5 is hydrogen and R6 is methyl, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 260:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 and R3a are ethyl, R5 is hydrogen and R6 is methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 261 :
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 and R3a are methyl, R5 are R6 are methyl, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 262:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 is ethyl and R3a is methyl, R5 are R6 are methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 263:
This table covers 126 compounds of the following type:
wherein Y is S(=O)2, R1 and R3a are ethyl, R5 are R6 are methyl, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 264:
This table covers 378 compounds of the following type:
wherein Y is C=O, R1 is methyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 265:
This table covers 378 compounds of the following type: wherein Y is C=O, R1 is ethyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 266:
This table covers 378 compounds of the following type:
wherein Y is C=O, R1 is chlorine, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 267:
This table covers 378 compounds of the following type:
wherein Y is C=O, R1 is methyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and RR33 aarree aass ddefined in Table 1. Table 268:
This table covers 378 compounds of the following type:
wherein Y is C=O, R1 is ethyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 269:
This table covers 378 compounds of the following type:
wherein Y is C=O, R1 is chlorine, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 aanndd RR33 aarree as defined in Table 1. Table 270:
This table covers 378 compounds of the following type:
wherein Y is C=O, R1 is methyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 271 :
This table covers 378 compounds of the following type:
wherein Y is C=O, R1 is ethyl, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 272:
This table covers 378 compounds of the following type: wherein Y is C=O, R1 is chlorine, R5 and R6 are methyl, G is hydrogen and R2 and R3 are as defined in Table 1. Table 273:
This table covers 378 compounds of the following type:
wherein Y is C=O, R1 is methyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 274:
This table covers 378 compounds of the following type:
wherein Y is C=O, R1 is ethyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1. Table 275:
This table covers 378 compounds of the following type:
wherein Y is C=O, R1 is chlorine, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 1.
Table 276:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 is methyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 277:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 is ethyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 278:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 is methyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and
R3 are as defined in Table 85.
Table 279:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 is ethyl, R5 is hydrogen and R6 is methyl, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 280:
This table covers 126 compounds of the following type:
,1 wherein Y is C=O, R is methyl, R and R are methyl, G is hydrogen and R and R are as defined in Table 85.
Table 281 :
This table covers 126 compounds of the following type:
,1 wherein Y is C=O, R is ethyl, R and R are methyl, G is hydrogen and R and R are as defined in Table 85.
Table 282:
This table covers 126 compounds of the following type: wherein Y is C=O, R1 is methyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85.
Table 283:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 is ethyl, R5 and R6 are hydrogen, G is hydrogen and R2 and R3 are as defined in Table 85. Table 284:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 and R3a are methyl, R5 and R6 are hydrogen, R3b is methyl, and G is
-,2 hydrogen and R is as defined in Table 85.
Table 285:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 is ethyl and R3a is methyl, R5 and R6 are hydrogen, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 286:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 and R3a are ethyl, R5 and R6 are hydrogen, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 287:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 and R3a are methyl, R5 is hydrogen and R6 is methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 288:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 is ethyl and R3a is methyl, R5 is hydrogen and R6 is methyl, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 289:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 and R3a are ethyl, R5 is hydrogen and R6 is methyl, R3b is methyl, and
G is hydrogen and R2 is as defined in Table 85.
Table 290:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 and R3a are methyl, R5 are R6 are methyl, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 291 :
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 is ethyl and R3a is methyl, R5 are R6 are methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85.
Table 292:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 and R3a are ethyl, R5 are R6 are methyl, R3b is methyl, and G is hydrogen and R2 is as defined in Table 85. Table 293:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 and R3a are methyl, R5 and R6 are hydrogen, R3b is methyl, and G is hydrogen and R is as defined in Table 85. Table 294:
This table covers 126 compounds of the following type:
wherein Y is C=O, R1 is ethyl and R3a is methyl, R5 and R6 are hydrogen, R3b is methyl, and
G is hydrogen and R is as defined in Table 85.
Table D
Biological Examples
These Examples illustrate the pesticidal/insecticidal properties of compounds of formula I.
Example B1 : Activity against Myzus persicae (green peach aphid,)
(mixed population, feeding/residual contact activity, preventive)
Sunflower leaf discs are placed on agar in a 24-well microtiter plate and sprayed with test solutions. After drying, the leaf discs are infested with an aphid population of mixed ages.
After an incubation period of 6 days, samples are checked for mortality and special effects
(e.g. phytotoxicity).
In this test, compounds listed in the Tables A, B, C and D above show good activity. In particular compounds A-5, A-20, A-30, A-38, A-40, A-41 , A-50, A-89, A-92, A-97, A-135, A-
141 , A-143, B-3, B-46 and D-33 show an activity of over 80% at a concentration of 400ppm.
Example B2: Activity against Thrips tabaci (onion Thrips)
(mixed population, feeding/residual contact activity, preventive)
Sunflower leaf discs are placed on agar in a 24-well microtiter plate and sprayed with test solutions. After drying, the leaf discs are infested with a thrips population of mixed ages.
After an incubation period of 6 days, samples are checked for mortality and special effects
(e.g. phytotoxicity).
In this test, compounds listed in the Tables A, B, C and D above show good activity. In particular compounds A-1 , A-2, A-3, A-4, A-5, A-15, A-20, A-29, A-30, A-37, A-38, A-40, A-
47, A-48, A-50, A-66, A-69, A-74, A-75, A-80, A-83, A-90, A-96, A-100, A-101 , A-103, A-
1 14, A-1 17, A-123, A-125, A-126, A-128, A-131 , A-132, A-141 , A-149, B-4, B-12, B-15, B- 18, B-21 , B-23, B-29, B-31 , B-44, B-49, B-53, C-2, C-3, D-3, D-4, D-5, D-6 and D-33 show an activity of over 80% at a concentration of 400ppm.
Example B3: Activity against Tetranychus urticae (two-spotted spider mite)
(mixed population, feeding/residual contact activity, preventive)
Bean leaf discs on agar in 24-well microtiter plates are sprayed with test solutions. After drying, the leaf discs are infested with mite populations of mixed ages. 8 days later, discs are checked for egg mortality, larval mortality, and adult mortality.
In this test, compounds listed in the Tables A, B, C and D above show good activity. In particular compounds A-2, A-3, A-4, A-5, A-10, A-36, A-40, A-42, A-43, A-44, A-51 , A-72, A-
80, A-83, A-90, A-96, A-99, A-106, A-125, A-128, A-135, A-138, A-141 , A-142, A-149, B-1 ,
B-4, B-18, B-22, B-23, B-52, D-3, D-4, D-5, D-6 and D-33 show an activity of over 80% at a concentration of 400ppm.
Example B4: Activity against Heliothis virescens (Tobacco budworm)
(ovo-larvicide, feeding/contact activity, curative)
Eggs (0-24 h old) are placed in 24-well microtiter plate on artificial diet and treated with test solutions by pipetting. After an incubation period of 4 days, samples are checked for egg mortality, larval mortality, and growth regulation.
In this test, compounds listed in the Tables A, B, C and D above show good activity. In particular compounds A-5, A-49, A-92, A-97, A-102, A-103, A-1 17, A-123, A-124, A-141 , D-
3, D-4 and D-5 show an activity of over 80% at a concentration of 400ppm.
Example B5: Activity against Plutella xylostella (Diamond back moth)
(larvicide, feeding/residual contact activity, preventive)
24-well microtiter plate (MTP) with artificial diet is treated with test solutions by pipetting.
After drying, the MTP's are infested with larvae (L2)(10-15 per well). After an incubation period of 5 days, samples are checked for larval mortality, antifeedant and growth regulation. In this test, compounds listed in the Tables A, B, C and D above show good activity. In particular compounds A-1 , A-3, A-4, A-5, A-10, A-29, A-30, A-36, A-37, A-40, A-42, A-43, A- 45, A-47, A-48, A-49, A-50, A-51 , A-79, A-80, A-83, A-84, A-86, A-90, A-96, A-99, A-101 , A- 103, A-1 17, A-123, A-125, A-128, A-132, A-141 , A-142, A-144, A-149, B-4, B-15, B-17, B- 18, B-22, B-23, B-25, B-26, B-31 , B-34, B-36, B-39, B-42, B-43, B-46, B-47, B-51 , D-3, D-4, D-5, D-12, D-15 and D-33 show an activity of over 80% at a concentration of 400ppm.
Example B6: Activity against Diabrotica balteata (Corn root worm)
(larvicide, feeding/residual contact activity, preventive)
24-well microtiter plate (MTP) with artificial diet is treated with test solutions by pipetting.
After drying, the MTP's are infested with larvae (L2)(6-10 per well). After an incubation period of 5 days, samples are checked for larval mortality, antifeedant and growth regulation.
In this test, compounds listed in the Tables A, B, C and D above show good activity. In particular compounds A-1 , A-3, A-5, A-15, A-28, A-43, A-69, A-97 and B-23 show an activity of over 80% at a concentration of 400ppm.

Claims

What is claimed is:
1. A pesticidal composition comprising a pesticidal effective amount of at least one compound of formula I
wherein
R1 is halogen, CrC4alkyl, CrC4haloalkyl, C3-C6cycloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, d- C4alkylsulfonyl, nitro or cyano;
R2 is optionally substituted aryl or optionally substituted heteroaryl; r is 0, 1 , 2 or 3;
R3 if r is 1 , is halogen, Ci.C6alkyl, Ci.C6haloalkyl, Ci.C6alkoxy, Ci.C6haloalkoxy, C2- C6alkenyl, C2-C6alkynyl, Ci.C6alkylthio, Ci.C6alkylsulfinyl, Ci.C6alkylsulfonyl, cyano or nitro; or the substituents R3, if r is 2 or 3, independently of each other, are halogen, Ci.C6alkyl, Ci- C6haloalkyl, Ci.C6alkoxy, Ci.C6haloalkoxy, C2-C6alkenyl, C2-C6alkynyl, Ci.C6alkylthio, Ci- C6alkylsulfinyl, Ci.C6alkylsulfonyl, cyano or nitro;
R4, R5, R6 and R7, independently of each other, are hydrogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxyCi-C4alkyl, Ci-C4alkylthioCrC4alkyl, C1-C4alkylsulfinylC1-C4alkyl, d- C4alkylsulfonylCi-C4alkyl, cyclopropyl or cyclopropyl substituted by d- or C2alkyl, d- or C2haloalkyl or halogen; cyclobutyl or cyclobutyl substituted by d- or C2alkyl; oxetanyl or oxetanyl substituted by d- or C2alkyl; C5-C7cycloalkyl or C5-C7cycloalkyl substituted by d- or C2alkyl or d- or C2haloalkyl, where a methylene group of the cycloalkyl moiety is optionally replaced by an oxygen or sulfur atom or a sulfinyl or sulfonyl group; C4- dcycloalkenyl or C4-C7cycloalkenyl substituted by d- or C2alkyl or d- or C2haloalkyl, where a methylene group of the cycloalkenyl moiety is optionally replaced by an oxygen or sulfur atom or a sulfinyl or sulfonyl group; cyclopropylCi-C5alkyl or cyclopropylCi-C5alkyl substituted by d- or C2alkyl, d- or C2haloalkyl or halogen; cyclobutylCi-C5alkyl or cyclobutylCi-C5alkyl substituted by Ci-C2alkyl; oxetanylCi-C5alkyl or oxetanylCi-C5alkyl substituted by d- or C2alkyl; C5-C7 cycloalkylCi-C5alkyl or C5-C7cycloalkylCi-C5alkyl substituted by d-or C2alkyl or d- or C2haloalkyl, where a methylene group of the cycloalkyl moiety is optionally replaced by an oxygen or sulfur atom or a sulfinyl or sulfonyl group; C4- C7cycloalkenylCrC5 alkyl or C4-C7cycloalkenylCi-C5alkyl which is substituted by d- or C2alkyl or d- or C2haloalkyl, where a methylene group of the cycloalkenyl moiety is optionally replaced by an oxygen or sulfur atom or a sulfinyl or sulfonyl group; phenyl or phenyl substituted by d-C4alkyl, d-C4alkoxy, Ci-C4haloalkyl, halogen, nitro, cyano, d- dalkylthio, d-C4alkylsulfinyl, d-C4alkylsulfonyl or Ci-C4alkylcarbonyl; benzyl or benzyl substituted by d-C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl, halogen, nitro, cyano, Ci-C4alkylthio, d-dalkylsulfinyl, Ci-C4alkylsulfonyl or Ci-C4alkylcarbonyl; heteroaryl or heteroaryl substituted by Ci-C4alkyl, d-C4alkoxy, Ci-C4haloalkyl, halogen, nitro, cyano, d-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl or Ci-C4alkylcarbonyl; or
R4 and R5, or R6 and R7, are joined to form a 5-7 membered saturated or unsaturated ring in which a methylene group is optionally replaced by an oxygen or sulfur atom, or a 5-7 membered saturated or unsaturated ring substituted by Cr or C2alkyl, where a methylene group of the ring is optionally replaced by an oxygen or sulfur atom; or R4 and R7 are joined to form a 5-7 membered saturated or unsaturated ring unsubstituted or substituted by d- or C2alkyl, d- or C2alkoxy, Ci-C2alkoxyCi-C2alkyl, hydroxy, halogen, phenyl or phenyl substituted by d-C4alkyl, d-C4alkoxy, Ci-C4haloalkyl, halogen, nitro, cyano, d-C4alkylthio, d-C4alkylsulfinyl, d-C4alkylsulfonyl or d-C4alkylcarbonyl; heteroaryl or heteroaryl substituted by d-C4alkyl, d-C4alkoxy, Ci-C4haloalkyl, halogen, nitro, cyano, d-dalkylthio, d-C4alkylsulfinyl, d-C4alkylsulfonyl or d-C4alkylcarbonyl; Y is O, C=O, S(O)m or S(O)nNR8; provided that when Y is C=O, R6 and R7 are different from hydrogen when either R4 or R5 is hydrogen, and R4 and R5 are different from hydrogen when either R6 or R7 is hydrogen; m is 0 or 1 or 2 and n is 0 or 1 ;
R8 is hydrogen, d-C6alkyl, C3-C6cycloalkyl, d-C6alkoxycarbonyl, tri(d-C6alkyl)silyl- ethyloxycarbonyl, d-C6haloalkoxycarbonyl, cyano, d-C6haloalkyl, d-C6hydroxyalkyl, C2-C6alkenyl, C2-C6alkynyl, C2-C6haloalkenyl, d-C6alkylcarbonyl, d-C6haloalkylcarbonyl, Ci-C6cycloalkylcarbonyl, phenylcarbonyl or phenylcarbonyl substituted by R9; benzylcarbonyl or benzylcarbonyl substituted by R9; pyridylcarbonyl or pyridylcarbonyl substituted by R9; phenoxycarbonyl or phenoxycarbonyl substituted by R9; benzyloxycarbonyl or benzyloxycarbonyl substituted by R9;
R9 is Ci-C6haloalkyl, d-C6alkoxycarbonyl, nitro, cyano, formyl, carboxyl or halogen, and G is hydrogen, an agriculturally acceptable cation or a latentiating group.
2. A pesticidal composition according to claim 1 , which, in addition to comprising the compound of formula I, comprises formulation adjuvants.
3. A pesticidal composition according to claim 1 , which, in addition to comprising the compound of formula I, comprises at least one additional insecticide, acaricide, nemacitide or molluscicide.
4. A pesticidal composition according to claim 1 , which, in addition to comprising the compound of formula I, comprises at least one additional fungicide, herbicide or plant growth regulator.
5. A pesticidal composition according to claim 1 comprising an effective amount of at least one insecticidally, acaricidally, nemacitidally or molluscicidally effective amount of a compound according to claim 1.
6. A method of combating and controlling pests which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest a pesticidally effective amount of a compound of formula I.
7. A method according to claim 6 for the protection of plant propagation material from the attack by pests, which comprises applying to the propagation material or the site, where the propagation material is planted, a pesticidally effective amount of a compound of formula I.
8. A method according to claim 6 of combating and controlling insects, acarines, nematodes or molluscs, which comprises applying to the pest, to a locus of the pest, or to a plant susceptible to attack by the pest an insecticidally, acaricidally, nemacitidally or molluscicidally effective amount of a compound according to claim 1.
EP09761658A 2008-06-12 2009-06-04 Pesticidal compositions containing a pyrandione or a thiopyrandione or a cyclohexanetrione derivative Withdrawn EP2300449A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB0810817A GB0810817D0 (en) 2008-06-12 2008-06-12 Pesticidal composition
GB0813689A GB0813689D0 (en) 2008-07-25 2008-07-25 Pesticidal compositions
PCT/EP2009/056881 WO2009150095A1 (en) 2008-06-12 2009-06-04 Pesticidal compositions containing a pyrandione or a thiopyrandione or a cyclohexanetrione derivative

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WO2015198859A1 (en) * 2014-06-26 2015-12-30 住友化学株式会社 Condensed heterocyclic compound

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