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WO2007080131A2 - Anthranilamide derivatives and their use for the control of insects and acari - Google Patents

Anthranilamide derivatives and their use for the control of insects and acari Download PDF

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Publication number
WO2007080131A2
WO2007080131A2 PCT/EP2007/000302 EP2007000302W WO2007080131A2 WO 2007080131 A2 WO2007080131 A2 WO 2007080131A2 EP 2007000302 W EP2007000302 W EP 2007000302W WO 2007080131 A2 WO2007080131 A2 WO 2007080131A2
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alkyl
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formula
haloalkyl
cycloalkyl
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WO2007080131A3 (en
Inventor
Michel Muehlebach
André Jeanguenat
Roger Graham Hall
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Syngenta Participations AG
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Syngenta Participations AG
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Priority to BRPI0707882-0A priority Critical patent/BRPI0707882A2/en
Application filed by Syngenta Participations AG filed Critical Syngenta Participations AG
Priority to AU2007204417A priority patent/AU2007204417B2/en
Priority to JP2008549849A priority patent/JP5215190B2/en
Priority to CN2007800075913A priority patent/CN101394742B/en
Priority to US12/160,794 priority patent/US8084474B2/en
Priority to EP07711342A priority patent/EP1976385A2/en
Priority to CA2635827A priority patent/CA2635827C/en
Priority to NZ569504A priority patent/NZ569504A/en
Publication of WO2007080131A2 publication Critical patent/WO2007080131A2/en
Publication of WO2007080131A3 publication Critical patent/WO2007080131A3/en
Priority to IL192470A priority patent/IL192470A/en
Anticipated expiration legal-status Critical
Priority to KR1020087020082A priority patent/KR101342875B1/en
Priority to US13/314,564 priority patent/US8278464B2/en
Priority to IL219104A priority patent/IL219104A/en
Ceased legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D223/12—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D331/00—Heterocyclic compounds containing rings of less than five members, having one sulfur atom as the only ring hetero atom
    • C07D331/04—Four-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero 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
    • C07D409/12—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 chain containing hetero atoms as chain links
    • 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
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
    • C07F9/65681—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a (thio)phosphinic acid or ester thereof

Definitions

  • the present invention relates to novel anthranilamide derivatives, to processes for their preparation, to compositions comprising those compounds, and to their use for controlling insects or representatives of the order Acarina.
  • Anthranilamide derivatives with insecticidal properties are known and described, for example, in WO 03/015518 or WO 2006/055922.
  • novel anthranilamide derivatives with pesticidal properties especially for the control of insects and members of the order Acarina.
  • the novel compounds are characterised by a 4-membered, saturated heterocyclic ring attached to the aminocarbonyl substituent of the phenyl ring.
  • the present invention accordingly relates to compounds of formula I
  • D is phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl; or phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl mono-, di- or trisubstituted by Ci-C 6 alkyl, C 3 -C 6 cycloalkyl, d-Cehaloalkyl, halogen, cyano, C 1 -
  • R 4 , R 4 ', Rio, Ri7. and R 19 independently from each other, are hydrogen, CrC 6 alkyl, C 3 - C 6 cycloalkyl, Ci-C 6 haloalkyl, halogen, cyano, CrC 4 alkoxy, Ci-C 4 haloalkoxy, C 2 - C 4 alkoxycarbonyl, Ci-C 4 alkylthio, d-C 4 haloalkylthio, Ci-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, CrC 4 haloalkylsulfinyl or CrC 4 haloalkylsulfonyl;
  • R16 and Ri 8 independently from each other, are Ci-C 6 alkyl, or C 1 - C 6 atkyl mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, C 1 -C A aIkOXy, C 2 - C 4 alkoxycarbonyl, d-C 4 alkylthio, CrC 4 alkylsulfinyl, d-C 4 alkylsulfonyl, d-C 4 alkylamino, C 2 - C 4 dialkylamino or C 3 -C 6 cycloalkylamino; or are phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl; or are phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl mono-, di- or trisubstituted by Ci-C 6 alky
  • R 7 , R 9 , R 13 and R 14 independently from each other, are hydrogen, Ci-C 6 alkyl, C r C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 3 -C 6 alkenyl or C 3 -C 6 haloalkenyl; each R 1 independently is halogen, nitro, cyano, hydroxy, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 - C 6 alkynyl, C 3 -C 6 cycloalkyl, d-C ⁇ haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 - C 6 halocycloalkyl, d-C 4 alkoxy, d-C 4 haloalkoxy, CrC ⁇ lkylthio, CrC ⁇ aloalkylthio, C 1
  • each of E 1 and E 2 which may be the same or different, represents oxygen or sulfur;
  • R 33 is hydrogen, C r C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, d-C 6 haloalkyl, d-C 6 alkoxy, hydroxy, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl-d-C 6 alkyl, benzyl or phenyl; where phenyl and benzyl for their part may be mono- di- or trisubstituted by d-C 6 alkyl, d-C 6 haloalkyl, halogen, cyano or nitro; or R 33 is O Na + , O Li + or O K + ;
  • R 36 is hydrogen, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, d-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -
  • X is oxygen or sulfur; p is 0 or 1 ; t is 0 or 1 ; each of R 34 and R 35 , which may be the same or different, represents hydrogen, COOH, halogen, nitro, cyano, hydroxy, d-C 6 alkyl, d-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 2 -
  • R is hydrogen, Ci-C 6 alkyl, C r C 6 haloalkyl, drCecycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkylthio, d-Cehaloalkylthio, d-Cealkoxy-d-Cealkyl or d-C ⁇ haloalkoxy-d-Cealkyl; or
  • R is d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkylthio, d-Cehaloalkylthio, d-C 6 alkoxy-CrC 6 alkyl or d-Cehaloalkoxy-d-Cealkyl substituted by d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkoxy, or C r C 6 haloalkoxy; or R is cyano, nitro, -C(O)R 2 6, -C(O)OR 27 , -CONR 28 R 2 S, -SO 2 R 30 or -
  • Ro is hydrogen, d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, CrC 6 alkylthio, d-C 6 haloalkylthio, Ci -C B aIkOXy-C 1 -C 6 alkyl or CrC 6 haloalkoxy-Ci-C 6 alkyl; or R 0 is CrC 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C ⁇ alkylthio, d-C 6 haloalkylthio, CrC 6 alkoxy-Ci-C 6 alkyl or Ci -C 6 IIaIOaIkOXy-C 1 -C 6 alkyl substituted by d-C ⁇ alkyl, d-C 6 hal
  • R3o, R31, R32, R 0 27, R 0 2 ⁇ , R029, R O 3o, R ⁇ I and R 032 which may be the same or different, represents d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl; or d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl or CrC 6 halocycloalkyl substituted by d-C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C r C 6 alkoxy or d-C 6 haloalkoxy; with the proviso that E 1 or E 2 is sulfur if A is oxygen, sulfur or N-R 0 , wherein R 0 is hydrogen, d-C 3
  • Compounds of formula I which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrose acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as d-C 4 alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as d-C 4 alkane- or arylsulfonic acids which are unsubstituted or substituted,
  • Compounds I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower- alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
  • the corresponding internal salts can furthermore be formed.
  • agrochemically advantageous salts Preferred within the scope of the invention are agrochemically advantageous salts; however, the invention also encompasses salts which have disadvantage for agrochemical use, for example salts which are toxic to bees or fish, and which are employed, for example, for the isolation or purification of free compounds of formula I or agrochemically utilizable salts thereof.
  • the free compounds of formula I or their salts hereinabove and hereinbelow are respectively to be understood as including, where appropriate, the corresponding salts or the free compounds of formula I.
  • the free form is preferred in each case.
  • alkyl groups occurring in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso- butyl, tert-butyl, pentyl, hexyl, heptyl and octyl and their branched isomers.
  • Alkoxy, alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned.
  • the alkenyl and alkynyl groups can be mono- or polyunsaturated.
  • Halogen is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl or halophenyl.
  • Haloalkyl groups preferably have a chain length of from 1 to 6 carbon atoms.
  • Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 ,1 -difluoro- 2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferably trichloro- methyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.
  • Suitable haloalkenyl groups are alkenyl groups which are mono- or polysubstituted by halogen, halogen being fluorine, chlorine, bromine and iodine and in particular fluorine and chlorine, for example 2,2-difluoro-1 -methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluorobut-2-en- 1 -yl.
  • alkenyl groups which are mono-, di- or trisubstituted by halogen preference is given to those having a chain length of from 3 to 5 carbon atoms.
  • Suitable haloalkynyl groups are, for example, alkynyl groups which are mono- or polysubstituted by halogen, halogen being bromine, iodine and in particular fluorine and chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoro- propynyl and 4,4,4-trifluorobut-2-yn-1-yl.
  • alkynyl groups which are mono- or polysubstituted by halogen preference is given to those having a chain length of from 3 to 5 carbon atoms.
  • Alkoxy groups preferably have a preferred chain length of from 1 to 6 carbon atoms.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also the isomeric pentyloxy and hexyloxy radicals; preferably methoxy and ethoxy.
  • Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert- butoxycarbonyl; preferably methoxycarbonyl or ethoxycarbonyl.
  • Haloalkoxy groups preferably have a chain length of from 1 to 6 carbon atoms.
  • Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1 ,1 ,2,2- tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2- trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.
  • Alkylthio groups preferably have a chain length of from 1 to 6 carbon atoms.
  • Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert- butylthio, preferably methylthio and ethylthio.
  • Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl; preferably methylsulfinyl and ethylsulfinyl.
  • Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
  • Alkoxyalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms.
  • alkoxyalkoxy groups are: methoxymethoxy, methoxyethoxy, methoxypropoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy or butoxybutoxy.
  • Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the isomeric butylamines.
  • Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino and diisopropylamino.
  • Alkoxyalkyl groups preferably have a chain length of 1 to 6 carbon atoms.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
  • Alkylthioalkyl groups preferably have from 1 to 8 carbon atoms.
  • Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl.
  • the cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Phenyl also as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl, may be substituted.
  • the substituents can be in ortho, meta and/or para position.
  • the preferred substituent positions are the ortho and para positions to the ring attachment point.
  • E 1 and/or E 2 is preferably oxygen.
  • R 2 is hydrogen or C 1 -C 4 alkyl; and/or b) R 3 is hydrogen or d-C 4 alkyl; and/or c) D is a group D 1 and/or. d) E 2 is sulfur.
  • R 91 is C- ⁇ -C 4 alkyl or halogen, preferably chloro, bromo or methyl;
  • R 92 is halogen or cyano, preferably fluoro, chloro, bromo or cyano;
  • R 93 is halogen, Ci-C 4 haloalkyl or Ci-C 4 haloalkoxy
  • R 0 is C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, Ci-C 6 alkylthio, d-Cehaloalkylthio, d-Cealkoxy-d-Cealkyl or d-Cehaloalkoxy-d-Cealkyl; or R 0 is C 1 -C 6 SIkVl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, Ci-C 6 alkylthio, Ci-C 6 haloalkylthio, d-C 6 alkoxy-d-C 6 alkyl or Ci-C 6 haloalkoxy-d-C 6 alkyl substituted by C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkoxy, or Ci-C 6 haloal
  • R 0 is C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkylthio, Ci-C 6 haloalkylthio, C r C 6 alkoxy-d-C 6 alkyl or d-C 6 haloalkoxy-d-C 6 alkyl; or R 0 is d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, d-C 6 alkylthio, d-C 6 haloalkylthio, Ci-C 6 alkoxy-Ci-C 6 alkyl or CrC 6 haloalkoxy-Ci-C 6 alkyl substituted by C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, Ci-C 6 alkoxy, or Ci-C 6 halo
  • Me represents the methyl group.
  • R 26 is hydrogen, d-C 6 alkyl, d-C 6 haloalkyl or C 3 -C 6 cycloalkyl.
  • R 27 , R 28 , R 29 ,R3o , R 31 and R 32 independently of one another are d-C 6 alkyl or d-C 6 haloalkyl; or d-C 6 alkyl or d-C 6 haloalkyl substituted with d-C 6 alkyl or d-C 6 haloalkyl.
  • R 02 6 is hydrogen, d-C 6 alkyl, Ci-C 6 haloalkyl or C 3 -C 6 cycloalkyl.
  • R 027 , R 028 , R 02 9,R 030, R 031 and R 032 independently of one another are d-C 6 alkyl or d-C 6 haloalkyl; or d-C 6 alkyl or d-C 6 haloalkyl substituted with d-C 6 alkyl or d-C 6 haloalkyl.
  • the process according to the invention for preparing compounds of the formula I or, where appropriate, a tautomer and/or salt thereof is carried out analogously to known processes, for example those described in WO 01/70671 , WO 03/016284, WO 03/015518 and WO 04/033468.
  • the process for the preparation of a compound of the formula I, or, when appropriate, a tautomer thereof, in each case in free form or in salt form comprises, for example,
  • R 1 , n, and D have the meanings given for formula I, or, where appropriate, a tautomer and/or salt thereof with a compound of formula III
  • R 1 , R 2 , n, E 1 , E 2 and D have the meanings given for the formula I; and X 1 is a leaving group, or, where appropriate, a tautomer and/or salt thereof with a compound of formula III in which A, R 3 , R 34 , R 35 and m have the meanings given for formula I, or, where appropriate, with a tautomer and/or salt thereof or,
  • n, R 1 , R 2 , R 3 , E 2 , R 34 , R 35 , A and m have the meanings given for formula I, or, where appropriate, a tautomer and/or salt thereof with a compound of formula Vl
  • E 1 and D have the meanings given for formula I; and X 2 is a leaving group, or, where appropriate, with a tautomer and/or salt thereof and/or converting a compound of formula I or, where appropriate, a tautomer thereof, in each case in free form or in salt form, into another compound of formula I or, where appropriate, a tautomer thereof, separating an isomer mixture, which can be obtained in accordance with the process, and isolating the desired isomer and/or converting a free compound of formula I or, where appropriate, a tautomer thereof into a salt or a salt of a compound of formula I or, where appropriate, a tautomer thereof into the free compound of formula I or, where appropriate, a tautomer thereof or into another salt.
  • the compounds of formula Il are described in WO 04/111030.
  • the compounds of formula III and V are novel and especially developed for the preparation of the compounds of formula I and constitute therefore a further embodiment of the present invention.
  • the preferences for the substituents of formula I mentioned above are also valid for the compounds of formula III and V.
  • R 3 is hydrogen
  • R 34 is hydrogen or d-C 4 alkyl, preferably hydrogen or methyl
  • R 35 is hydrogen, halogen, cyano, CrC 4 alkyl, Ci-C 4 haloalkyl, CrC ⁇ alkoxycarbonyl, Ci-C 4 haloalkoxy-d-C 4 alkyl;
  • R 1 is Ci-C 4 alkyl, halogen, d-Cshaloalkyl, cyano, nitro, C 1 -C 4 BIkOXy, C 1 -C 4 -IIaIOaIkOXy, C 1 -
  • R 2 and R 3 are hydrogen
  • E 2 is oxygen or sulfur
  • R 34 is hydrogen or Ci-C 4 alkyl, preferably hydrogen or methyl
  • R 35 is hydrogen, halogen, cyano, C 1 -C 4 alkyl, Ci-C 4 haloalkyl, C r C 4 alkoxycarbonyl,
  • Table G Preferred compounds of formula V represented by formula Vb where E 2 is sulfur listing compounds G1 to G92 wherein R 91 , R 92 , A, R 34 and R 35 have the meanings given in Table D lines D1 to D92.
  • the compounds of formula Va can also be prepared by reacting a compound of formula Xl with a compound of formula III in the presence of a base and an inert solvent
  • n, R 1 , R 3 , E 2 , R 34 , R 35 , A and m have the meanings given in formula I; and X 1 is a leaving group (for example chlorine, bromine), or, where appropriate, a tautomer and/or salt thereof.
  • Suitable bases are for example N(C 2 H 5 ) 3 , DBU, DBN or imidazole.
  • Preferred solvents are tetrahydrofurane, dioxane, glyme, ethyl acetate or toluene.
  • the reaction is carried out at temperatures of from 0 0 C to 100 0 C, preferably at +15°C to +30 0 C in particular at ambient temperature.
  • a further process for the preparation of compounds of formula V is described in PCT/EP2006/003504.
  • R 9 - I is Ci-C 4 alkyl or halogen, preferably chloro, bromo or methyl;
  • R 92 is halogen or cyano, preferably fluoro, chloro, bromo or cyano
  • Amides of formula V/Va/Vb where E 2 is oxygen are readily converted to thioamides of formula V/Va/Vb where E 2 is sulfur by using commercially available thio transfer reagents such as phosphorus pentasulfide and Lawesson's reagent, for example in analogy to X. Fontrodona et al., Synthesis, 2001 , (13), 2021-27.
  • a compound of the formula Ib or, where appropriate, a tautomer and/or salt thereof, in each case in free form or in salt form, is prepared, for example, from a compound of the formula
  • n, R 1 , R 2 , R3, D, E 1 , E 2 , R ⁇ , R35 and m have the meanings given in formula I and q is 0 or 1 , according to known procedures (H. Okamura, C. BoIm, Org. Lett. 2004, 6, 1305; H. Okamura, C. BoIm, Chem. Lett. 2004, 33, 482; D. Leca, K. Song, M. Amatore, L. Novabank, E. Lac ⁇ te, M. Malacria, Chem. Eur. J. 2004, 10, 906) or as described below.
  • the compounds of formulae III, V and VIII are novel, especially developed for the preparation of the compounds of formula I and therefore constitute a further object of the present invention.
  • oxidation reagents are KMnO 4 , mCPBA, NaIOVRuO 2 , H 2 O 2 , oxone.
  • the reactions described hereinabove and hereinbelow are carried out in a manner known per se, for example in the absence or, normally, in the presence of a suitable solvent or diluent or of a mixture of these, the process being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range of from approximately -80 0 C to the boiling point of the reaction mixture, preferably from approximately -20 0 C to approximately +150 0 C, and, if required, in a sealed vessel, under reduced, normal or elevated pressure, in an inert gas atmosphere and/or under anhydrous conditions.
  • a suitable solvent or diluent or of a mixture of these the process being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range of from approximately -80 0 C to the boiling point of the reaction mixture, preferably from approximately -20 0 C to approximately +150 0 C, and, if required, in a sealed vessel, under reduced, normal or elevated pressure, in an in
  • the starting materials mentioned hereinabove and hereinbelow which are used for the preparation of the compounds of formula I or, where appropriate, the tautomers thereof, in each case in free form or in salt form, are known or can be prepared by methods known per se, for example in accordance with the information given below.
  • the reactants can be reacted in the presence of a base.
  • Suitable bases for facilitating the detachment of HX 2 are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N- alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
  • Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N- dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N- methylmorpholine, benzyltrimethylammonium hydroxide and 1 ,8-diazabicyclo[5.4.0]undec-7- ene (DBU).
  • the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N 1 N- diethylaniline, may also act as solvents or diluents.
  • the reaction is advantageously carried out in a temperature range from approximately -80 0 C to approximately +140 0 C, preferably from approximately -30 0 C to approximately +100 0 C, in many cases in the range between room temperature and approximately +80 0 C.
  • a compound of formula I can be converted in a manner known per se into another compound I by replacing one or more substituents of the starting compound of formula I in the customary manner by (an)other substituent(s) according to the invention.
  • Salts of compounds of formula I can be prepared in a manner known per se.
  • acid addition salts of compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula I can be converted in the customary manner into the free compounds of formula I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula I can be converted in a manner known per se into other salts of compounds of formula I, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the compounds of formula I which have salt-forming properties can be obtained in free form or in the form of salts.
  • the compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.
  • Diastereomer mixtures or racemate mixtures of compounds of formula I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
  • Enantiomer mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high- performance liquid chromatography (HPLC) on acetyl celulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is com- plexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities
  • Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereose- lective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.
  • the compounds according to the invention and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • the compounds 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 according to the invention 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.
  • Examples of the abovementioned animal pests are: from the order Acarina, for example,
  • Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order Coleoptera, for example,
  • Curculio spp. Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., Otiorhynchus spp.,
  • Aedes spp. Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp.,
  • Cimex spp. Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Lep- tocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotino- phara spp. and Triatoma spp.; from the order Homoptera, for example,
  • Vespa spp. from the order Isoptera, for example,
  • Reticulitermes spp. from the order Lepidoptera, for example,
  • Ostrinia nubilalis Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypi- ela, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scir- pophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp.,
  • Thaumetopoea spp. Tortrix spp., Trichoplusia ni and Yponomeuta spp.; from the order Mallophaga, for example,
  • Blatta spp. Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.; from the order Psocoptera, for example,
  • Liposcelis spp. from the order Siphonaptera, for example,
  • the active ingredients according to the invention 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,
  • the active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops.
  • the active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca(preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
  • 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®.
  • 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(a
  • 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 Cry ⁇ c, 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.
  • 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.
  • 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: 1. Bt11 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. Bt11 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
  • the compounds 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.
  • 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. and Laminosioptes spp..
  • the compounds 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 also relates to pesticidal compositions such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise - at least - one of the active ingredients according to the invention and which are to be selected to suit the intended aims and the prevailing circumstances.
  • pesticidal compositions such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise - at least - one of the active ingredients according to the invention and which are to be selected to suit the intended aims and the prevailing circumstances.
  • the active ingredient is employed in pure form, a solid active ingredient for example in a specific particle size, or, preferably, together with - at least - one of the auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).
  • auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).
  • suitable solvents are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the fractions C 8 to Ci 2 of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-me- thylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils, such as unexpoi
  • Solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • highly disperse silicas or highly disperse absorbtive polymers are also possible to add highly disperse silicas or highly disperse absorbtive polymers.
  • Suitable particulate adsorptive carriers for granules are porous types, such as pumice, brick grit, sepiolite or bentonite, and suitable non-sorptive carrier materials are calcite or sand.
  • a large number of granulated materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.
  • Suitable surface-active compounds are, depending on the type of the active ingredient to be formulated, non-ionic, cationic and/or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties.
  • the surfactants mentioned below are only to be considered as examples; a large number of further surfactants which are conventionally used in the art of formulation and suitable according to the invention are described in the relevant literature.
  • Suitable non-ionic surfactants are, especially, polyglycol ether derivatives of aliphatic or cyc- loaliphatic alcohols, of saturated or unsaturated fatty acids or of alkyl phenols which may contain approximately 3 to approximately 30 glycol ether groups and approximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatic hydrocarbon radical or approximately 6 to approximately 18 carbon atoms in the alkyl moiety of the alkyl phenols.
  • water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopo- lypropylene glycol or alkyl polypropylene glycol having 1 to approximately 10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene glycol ether groups and approximately 10 to approximately 100 propylene glycol ether groups.
  • the abovementioned compounds contain 1 to approximately 5 ethylene glycol units per propylene glycol unit.
  • nonylphenoxypolyethoxyethanol examples which may be mentioned are nonylphenoxypolyethoxyethanol, castor oil polyglycol ether, polypropylene glycol/polyethylene oxide adducts, tributylpheno- xypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol.
  • fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate.
  • the cationic surfactants are, especially, quarternary ammonium salts which generally have at least one alkyl radical of approximately 8 to approximately 22 C atoms as substituents and as further substituents (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl radicals.
  • the salts are preferably in the form of halides, methylsulfates or ethylsulfates. Examples are stearyltrimethylammonium chloride and benzylbis(2-chloroethyl)ethyl- ammonium bromide.
  • Suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface-active compounds.
  • suitable soaps are the alkali, alkaline earth or (un- substituted or substituted) ammonium salts of fatty acids having approximately 10 to approximately 22 C atoms, such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which are obtainable for example from coconut or tall oil; mention must also be made of the fatty acid methyl taurates.
  • synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates.
  • the fatty sulfonates and fatty sulfates are present as alkali, alkaline earth or (substituted or unsubstituted) ammonium salts and they generally have an alkyl radical of approximately 8 to approximately 22 C atoms, alkyl also to be understood as including the alkyl moiety of acyl radicals; examples which may be mentioned are the sodium or calcium salts of lignosulfonic acid, of the dodecylsulfuhc ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and a fatty acid radical of approximately 8 to approximately 22 C atoms.
  • alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, of dibutyl- naphthalenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensate.
  • suitable phosphates such as salts of the phosphoric ester of a p- nonylphenol/(4-14)ethylene oxide adduct, or phospholipids.
  • 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, scatte- ring 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.
  • Step 1 Preparation of 2-methyl-2-nitro-1 ,3-propanediol ditosylate:
  • Step 4 Preparation of (2-(3-Chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carboxylic acid [4-chloro-2-methyl-6-(3-methyl-thietan-3-ylcarbamoyl)-phenyl]-amide):
  • 6-chloro-2-[1 -(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1 H-pyrazol-5-yl]-8- methyl-4/-/-3,1-benzoxazin-4-one (1 .13 g, 2.56 mmol) (prepared according to WO 02/48115, example 2D) in tetrahydrofuran (15 ml) is added 3-amino-3-methyl-thietane (the product of step 3) (0.66 g, 6.40 mmol), and the mixture is heated for 48 hours at 5O 0 C, then to reflux for 12 hours.
  • Step 5 Preparation of compound T13.1.2 (2-(3-Chloro-pyridin-2-yl)-5-trifluoromethyl-2H- pyrazole-3-carboxylic acid [4-chloro-2-methyl-6-(3-methyl-1 ,1-dioxo-1 ⁇ 6 -thietan-3- ylcarbamoyl)-phenyl]-amide):
  • Step 1 Preparation of 2-methyl-2-nitro-1 ,3-propanediol ditriflate:
  • Step 4 Preparation of compound T44.1.2 (2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H- pyrazole-3-carboxylic acid [4-chloro-2-methyl-6-(3-methyl-N-benzylazetidine-3-ylcarbamoyl)- phenyl]-amide):
  • Step 1 Preparation of N-(terf-butyloxycarbonyl)-3-thietanamine:
  • the ether filtrate is concentrated and the residue resubjected to the same reaction conditions and workup giving another 1.3 g of product.
  • the crude solid product (7.3 g, 89%) with a melting point of 186-190°C is used in the next step without further purification.
  • Step 3 Preparation of 2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carboxylic acid ⁇ -chloro ⁇ -methyl-e-Cthietan-S-ylcarbamoylJ-phenylJ-amide:
  • Step 4 Preparation of compound T9.1.1 (2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H- pyrazole-3-carboxylic acid [4-chloro-2-methyl-6-(1 -oxo-1 ⁇ 4 -thietan-3-ylcarbamoyl)-phenyl]-
  • the reaction mixture is treated with NaHCO 3 aq. sat. and extracted with dichioromethane, the combined organic layer washed with brine, dried (Na 2 SO 4 ), filtered, and concentrated.
  • the crude product is purified by flash chromatography (ethyl acetate) to afford 50 mg (24%) of the title compound T9.1.1 as a white solid, m.p. 241 -244°C (major diastereomer called T9.1.1 diastereomer A).
  • Step 1 Preparation of 1 ,1 -dioxo-3-methyl-3-thietanamine trifluoroacetic acid salt:
  • Step 3 Preparation of 2-amino-5-chloro-3-methyl-N-(3-methyl-1 ,1 -dioxo-1 ⁇ -thietan-3-yl)- benzamide
  • Step 4 Preparation of compound T13.1.22 (2-(3-chloro-pyr ⁇ d ⁇ n-2-yl)-5-(2,2,2-tr ⁇ fluoro- eetthhooxxyy))--22HH--ppyyrraazzoollee--33--ccaarrbbooxxyylic acid [4-chloro-2-methyl-6-(3-methyl-1 ,1 -d ⁇ oxo-1 ⁇ 6 -th ⁇ etan-
  • the crude product is purified by column chromatography on silica gel (gradient ethyl acetate/hexane 1 :4->1 :1 ) to afford the title bisamide compound T13.1 22 (279 mg, 41 %) as a white solid with a melting point >250°C.
  • Example P4 step 2 and Example P1 , step 3 giving a white solid with a melting point of 92-
  • the residue is poured into water, extracted with diethyl ether (2x), the pH of the aqueous phase adjusted to pH 11 with 30% sodium hydroxide and the product extracted with diethyl ether.
  • the combined organic layers are washed with brine, dried (Na 2 SO 4 ), filtered and concentrated.
  • the crude oily product (1.47 g, 16%) is used without further purification.
  • Table A Substituent designations for Tables 1 to 44:
  • Table 1 This table discloses the 465 compounds T1.1.1 to T1.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • the specific compound T1.1.23 is the compound of the formula T1 , in which each of the of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the line A.1.23 of the Table A.
  • all of the other 359 specific compounds disclosed in the Table 1 as well as all of the specific compounds disclosed in the Tables 2 to 44 are specified analogously.
  • Table 2 This table discloses the 465 compounds T2.1.1 to T2.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 3 This table discloses the 465 compounds T3.1.1 to T3.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 4 This table discloses the 465 compounds T4.1.1 to T4.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 5 This table discloses the 465 compounds T5.1.1 to T5.1 .465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1 .465, of the Table A.
  • Table 6 This table discloses the 465 compounds T6.1.1 to T6.1.465 of the formula
  • each of the variables Rc n , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 7 This table discloses the 465 compounds T7.1.1 to T7.1.465 of the formula
  • each of the variables R 91 , Rg 2 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 8 This table discloses the 465 compounds T8.1.1 to T8.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 9 This table discloses the 465 compounds T9.1.1 to T9.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 10 This table discloses the 465 compounds T10.1.1 to T10.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 11 This table discloses the 465 compounds T11.1.1 to T11.1.465 of the formula
  • each of the variables R 91 , Rg 2 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 12 This table discloses the 465 compounds T12.1.1 to T12.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 13 This table discloses the 465 compounds T13.1.1 to T13.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 14 This table discloses the 465 compounds T14.1.1 to T14.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 15 This table discloses the 465 compounds T15.1.1 to T15.1.465 of the formula
  • each of the variables R 91 , R 92 , Rg 3 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 16 This table discloses the 465 compounds T16.1.1 to T16.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 17 This table discloses the 465 compounds T17.1.1 to T17.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 18 This table discloses the 465 compounds T18.1.1 to T18.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 19 This table discloses the 465 compounds T19.1.1 to T19.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 20 This table discloses the 465 compounds T20.1.1 to T20.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 21 This table discloses the 465 compounds T21.1.1 to T21.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1 .1 to A.1 .465, of the Table A.
  • Table 22 This table discloses the 465 compounds T22.1 .1 to T22.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1 .1 to A.1 .465, of the Table A.
  • Table 23 This table discloses the 465 compounds T23.1 .1 to T23.1 .465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 24 This table discloses the 465 compounds T24.1.1 to T24.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 25 This table discloses the 465 compounds T25.1.1 to T25.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 26 This table discloses the 465 compounds T26.1.1 to T26.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1 .465, of the Table A.
  • Table 27 This table discloses the 465 compounds T27.1.1 to T27.1.465 of the formula
  • each of the variables R 9 i, R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 28 This table discloses the 465 compounds T28.1.1 to T28.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 29 This table discloses the 465 compounds T29.1.1 to T29.1.465 of the formula
  • each of the variables R 91 , Rg 2 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 30 This table discloses the 465 compounds T30.1.1 to T30.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1 .465, of the Table A.
  • Table 31 This table discloses the 465 compounds T31 .1.1 to T31.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 32 This table discloses the 465 compounds T32.1.1 to T32.1.465 of the formula
  • each of the variables R 91 , Rg 2 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 33 This table discloses the 465 compounds T33.1.1 to T33.1.465 of the formula
  • each of the variables R 91 , R 92 , Rg 3 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 34 This table discloses the 465 compounds T34.1.1 to T34.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1 .465, of the Table A.
  • Table 35 This table discloses the 465 compounds T35.1.1 to T35.1 .465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 36 This table discloses the 465 compounds T36.1.1 to T36.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 37 This table discloses the 465 compounds T37.1 .1 to T37.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 38 This table discloses the 465 compounds T38.1.1 to T38.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 39 This table discloses the 465 compounds T39.1.1 to T39.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 40 This table discloses the 465 compounds T40.1.1 to T40.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 41 This table discloses the 465 compounds T41.1.1 to T41.1.465 of the formula
  • each of the variables R 9 i, R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 42 This table discloses the 465 compounds T42.1.1 to T42.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 43 This table discloses the 465 compounds T43.1.1 to T43.1 .465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Table 44 This table discloses the 465 compounds T44.1.1 to T44.1.465 of the formula
  • each of the variables R 91 , R 92 , R 93 and R 35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
  • Example F1 Emulsion concentrates a) b) c)
  • Tributylphenoxypolyethylene glycol ether (30 mol of EO) - 12 % 4 %
  • Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
  • Example F2 Solutions a) b) c) d)
  • Active ingredient 80 10 % 5 % 95 % ⁇
  • Petroleum ether (boiling range: 160-190°) - - 94 %
  • the solutions are suitable for use in the form of microdrops.
  • Example F3 Granules a) b) c) d)
  • the active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier(s), and the solvent is subsequently evaporated in vacuo.
  • Example F4 Dusts a) b) Active ingredient 2 % 5 % Highly disperse silica 1 % 5 % Talc 97 % - Kaolin 90 %
  • Ready-to-use dusts are obtained by intimately mixing the carriers and the active ingredient.
  • Example F5 Wettable powders a) b) c)
  • Active ingredient 25 % 50 % 75 % Sodium lignosulfonate 5% 5% -
  • the active ingredient is mixed with the additives and the mixture is ground thoroughly in a suitable mill. This gives wettable powders, which can be diluted with water to give suspensions of any desired concentration.
  • Example F6 Extruder granules
  • the active ingredient is mixed with the additives, and the mixture is ground, moistened with water, extruded, granulated and dried in a stream of air.
  • Example F7 Coated granules
  • the finely ground active ingredient is applied uniformly to the kaolin, which has been moistened with the polyethylene glycol. This gives dust-free coated granules.
  • Nonylphenoxypolyethylene glycol ether (15 mol of EO) 6 %
  • Silicone oil (75 % aqueous emulsion) 0.8 %
  • the finely ground active ingredient is mixed intimately with the additives.
  • Suspensions of any desired concentration can be prepared from the thus resulting suspension concentrate by dilution with water.
  • the activity of the compounds according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally or acaricidally active ingredients.
  • Suitable additions to active ingredients are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridyl- methyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
  • TX means: "one compound selected from the group consisting of the compounds specifically described in tables T1 to T44 of the present invention":
  • Ra 5 is trifluoromethyl or difluoromethyl (WO2004/058723) + TX, the compound of formula F-2
  • Ra 6 is trifluoromethyl or difluoromethyl (WO2004/058723) + TX, the racemic compound of formula F-3 (syn)
  • Ra 7 is trifluoromethyl or difluoromethyl (W 02004/035589) + TX.
  • the compound of formula F-5 which is an epimeric mixture of racemic compounds of formulae F-3 (syn) and F-4 (anti), wherein the ratio from racemic compounds of formula F-3 (syn) to racemic cmpounds of formula F-4 (anti) is from 1000 : 1 to 1 : 1000 and wherein Ra 7 is trifluoromethyl or difluoromethyl (WO2004/035589) + TX, the compound of formula F-6
  • Ra 8 is trifluoromethyl or difluoromethyl (WO2004/035589) + TX, the racemic compound of formula F-7 (trans)
  • R 10 is trifluoromethyl or difluoromethyl (WO2004/058723) + TX, the racemic compound of formula F- 11 (trans) ),
  • the active ingredient mixture of the compounds of formula I selected from tables T1 to T43 with active ingredients described above comprises a compound selected from tables T1 to T43 and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1 :6000, especially from 50:1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10:1 to 1 :10, very especially from 5:1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1 :1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or
  • mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios.
  • the mixtures comprising a compound of formula I selected from tables T1 to T43 and one or more active ingredients as described above can be applied, for example, in a single "ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the compounds of formula I selected from tables T1 to T43 and the active ingredients as described above is not essential for working the present invention.
  • Example B1 Activity against Spodootera littoralis (Egyptian cotton leafworm): Cotton 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 5 L 1 larvae. The samples are checked for mortality, repellent effect, feeding behaviour, and growth regulation 3 days after treatment (DAT).
  • DAT growth regulation 3 days after treatment
  • Example B2 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.
  • T13.1.92 T13.1.361 , T13.1.391 , T13.1.91 , T13.1.6, T13.1.96, T44.1.2, T13.1.8, T13.1.23,
  • T13.1.93, T13.1.113, T13.1.21 , T13.1.111 have an activity of over 80% at 400ppm.
  • Example B3 Activity against Plutella xylostella (Diamond back moth): 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 above show good activity.
  • Example B4 Activity against Diabrotica balteata (Corn root worm): 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 above show good activity.
  • MTP microtiter plate
  • Example B5 Activity against Myzus persicae (Green peach aphid): (contact)
  • 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.
  • T13.1.2 (diastereomer A), T17.1.2 (diastereomer B), T13.1.92, T13.1.91 , T13.1.96, T13.1.21 have an activity of over 80% at 400ppm.
  • Example B6 Activity against Myz ⁇ s persicae (Green peach aphid): (systemic)
  • Roots of pea seedlings, infested with an aphid population of mixed ages, are placed directly in the test solutions. 6 days after introduction, samples are checked for mortality and special effects on the plant.
  • T13.1 .113, T13.1.21 have an activity of over 80% at 400ppm.
  • Example B7 Activity against Thrips tabaci (Onion Thrips):
  • 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.
  • T17.1 .2 (diastereomer A), T17.1.2 (diastereomer B), T16.1 .91 , T13.1 .92, T13.1.91 , T13.1.6, T13.1.96, T44.1.2, T13.1.93, T13.1.1 13, T13.1.21 , T13.1.111 have an activity of over 80% at 400ppm.
  • Example B8 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.
  • Example B9 Systemic Insecticide Test for Spodoptera littoralis (cotton leafworm): Four day old maize seedlings ⁇ Zea grass, variety Stoneville) are placed individual in vials containing 24ml water into which the chemical is diluted at 12.5 ppm. Seedlings are allowed to grow for six days. Subsequently leaves are cut and placed in a Petri dish (5 cm diameter), inoculated with twelve to fifteen 1st instar S. littoralis larvae and incubated for four days in a growth chamber (25°C, 50% r.h., 18:6 L:D photo period). Number of alive insects are counted and percentage of dead calculated. Tests were conducted with one replicate.
  • Example B10 Activity against Cvdia oomonella (codling moth):
  • Standard Cydia diet cubes (1.5 cm width) are pierced with a tooth-pick and are immersed in liquid paraffin (ca. 80 0 C). After the paraffin coat has hardened, an aqueous emulsion containing 400 ppm of active ingredient is applied using a De Vilbis sprayer (25 ml, 1 bar). After the spray coating has dried, the cubes are put into plastic containers which are then populated with two freshly hatched Cydia pomonella (1 st instar). The containers are then closed with a plastic cap. After 14 days incubation at 26 0 C and 40-60% relative humidity, the survival rate of the caterpillars as well as their growth regulation is determined. In this test, compounds listed in the Tables above show good activity. In particular compounds T9.1.2 (diastereomer A), T9.1.2 (diastereomer B), T17.1.2 (diastereomer A), T13.1.92 have an activity of over 80%.
  • Example B1 1 Comparison of the insecticidal activity of compounds according to the invention with the structurally most closely comparable compound from the state of the art (compound No. 296 described on page 108 of WO2003/015518):
  • Table B11 shows that compound No. T13.1.391 according to the invention exerts a substantially better insecticidal action on Spodoptera littoralis than the compound from the state of the art. Especially at an application rate of 3 ppm the compound according to the invention is far superior to the compound of the state of the art. This enhanced effect was not to be expected on the basis of the structural similarity of these compounds.

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Abstract

Compounds of formula (I) wherein the substituents are as defined in claim (1), and the agrochemically acceptable salts and all stereoisomers and tautomeric forms of the compounds of formula (I) can be used as agrochemical active ingredients and can be prepared in a manner known per se.

Description

Novel Insecticides
The present invention relates to novel anthranilamide derivatives, to processes for their preparation, to compositions comprising those compounds, and to their use for controlling insects or representatives of the order Acarina.
Anthranilamide derivatives with insecticidal properties are known and described, for example, in WO 03/015518 or WO 2006/055922. There have now been found novel anthranilamide derivatives with pesticidal properties, especially for the control of insects and members of the order Acarina. The novel compounds are characterised by a 4-membered, saturated heterocyclic ring attached to the aminocarbonyl substituent of the phenyl ring.
The present invention accordingly relates to compounds of formula I
Figure imgf000002_0001
wherein
D is phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl; or phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl mono-, di- or trisubstituted by Ci-C6alkyl, C3-C6cycloalkyl, d-Cehaloalkyl, halogen, cyano, C1-
C4alkoxy, Ci-C4haloalkoxy, CrC^alkylthio, CrC4haloalkylthio, C1-C4alkylsulfinyl, C1-
C4alkylsulfonyl, CrGjhaloalkylsulfinyl or C1-C4haloalkylsulfonyl; or D is a group
Figure imgf000002_0002
Figure imgf000003_0001
R4, R4', Rio, Ri7. and R19 independently from each other, are hydrogen, CrC6alkyl, C3- C6cycloalkyl, Ci-C6haloalkyl, halogen, cyano, CrC4alkoxy, Ci-C4haloalkoxy, C2- C4alkoxycarbonyl, Ci-C4alkylthio, d-C4haloalkylthio, Ci-C4alkylsulfinyl, d-C4alkylsulfonyl, CrC4haloalkylsulfinyl or CrC4haloalkylsulfonyl;
R5, Rβ> Re, Rn, R12, R15. R16 and Ri8 independently from each other, are Ci-C6alkyl, or C1- C6atkyl mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, C1-CAaIkOXy, C2- C4alkoxycarbonyl, d-C4alkylthio, CrC4alkylsulfinyl, d-C4alkylsulfonyl, d-C4alkylamino, C2- C4dialkylamino or C3-C6cycloalkylamino; or are phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl; or are phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl mono-, di- or trisubstituted by Ci-C6alkyl, C3- C6cycloalkyl, d-C6haloalkyl, halogen, cyano, Ci-C4alkoxy, Ci-C4haloalkoxy, d-C4alkylthio, d-C4haloalkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, d-C4haloalkylsulfinyl Or C1- C4haloalkylsulfonyl;
R7, R9, R13 and R14 independently from each other, are hydrogen, Ci-C6alkyl, CrC6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C3-C6alkenyl or C3-C6haloalkenyl; each R1 independently is halogen, nitro, cyano, hydroxy, d-C6alkyl, C2-C6alkenyl, C2- C6alkynyl, C3-C6cycloalkyl, d-Cβhaloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3- C6halocycloalkyl, d-C4alkoxy, d-C4haloalkoxy, CrC^lkylthio, CrC^aloalkylthio, C1- C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, d-C4alkylsulfinyl, d-C4alkylsulfonyl, C1- C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, d-C6alkyl-C3-C6cycloalkylamino, C2- C4alkylcarbonyl, Cs-Cβalkoxycarbonyl, C2-C6alkylaminocarbonyl, Cs-Cedialkylaminocarbonyl, C2-C6alkoxycarbonyloxy, Ca-Cealkylaminocarbonyloxy, C3-C6dialkylaminocarbonyloxy or C3- C6trialkylsilyl, phenyl, benzyl or phenoxy, or phenyl, benzyl or phenoxy mono-, di- or trisubstituted by halogen, cyano, nitro, halogen, d-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, d-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, C1- C4alkoxy, d-C4haloalkoxy, d-C4alkylthio, CrC4haloalkylthio, CrC4alkylsulfinyl, C1- C4alkylsulfonyl, d-C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, d-C6alkyl-C3- C6cycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, C3- Cedialkylaminocarbonyl, C2-C6alkoxycarbonyloxy, C^Cealkylaminocarbonyloxy, C3- Cedialkylaminocarbonyloxy or C3-C6trialkylsilyl; n is O1 1 , 2 or 3; each of R2 and R3, which may be the same or different, represents hydrogen, CrC6alkyl, C2-
C6alkenyl, C2-C6alkynyl or C3-C8cycloalkyl; or CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl or C3-
C8cycloalkyl substituted by one or more substituents selected from halogen nitro, cyano, hydroxy, CrC4alkoxy, d-C4haloalkoxy, d-C4alkylthio, d-C4haloalkylthio, Ci-C4alkylsulfinyl, d-C4alkylsulfonyl, d-C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino and C1-
C6alkyl-C3-C6cycloalkylamino; each of E1 and E2, which may be the same or different, represents oxygen or sulfur;
A is oxygen, sulfur, SO, SO2, S(O)P=N-R, C=N-OR36, N-R0, C=O or P(X)1-R33;
R33 is hydrogen, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, d-C6haloalkyl, d-C6alkoxy, hydroxy, C3-C6cycloalkyl, C3-C6cycloalkyl-d-C6alkyl, benzyl or phenyl; where phenyl and benzyl for their part may be mono- di- or trisubstituted by d-C6alkyl, d-C6haloalkyl, halogen, cyano or nitro; or R33 is O Na+, O Li+ or O K+;
R36 is hydrogen, d-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, d-C6haloalkyl, C2-C6haloalkenyl, C2-
C6haloalkynyl, d-Cealkoxy-d-Cβalkyl, d-C6haloalkoxy-d-C6alkyl or benzyl;
X is oxygen or sulfur; p is 0 or 1 ; t is 0 or 1 ; each of R34 and R35, which may be the same or different, represents hydrogen, COOH, halogen, nitro, cyano, hydroxy, d-C6alkyl, d-C6haloalkyl, C2-C6alkenyl, C2-C6alkynyl, C2-
C6haloalkenyl, C2-C6haloalkynyl, d-C6alkylthio, d-C6alkylsulfinyl, d-C6alkylsulfonyl, d-C6haloalkylthio, d-C6haloalkylsulfinyl, d-C6haloalkylsulfonyl, d-C6alkoxycarbonyl, d-C6alkylcarbonyl, drCealkylaminocarbonyl, Cs-Cedialkylaminocarbonyl, d-Cealkoxy-C^Cealkyl, d-Cehaloalkoxy-d-Cealkyl, d-C6alkoxy, CrC6haloalkoxy, C1-
C6alkylamino, C2-C6dialkylamino, C3-C6trialkylsilyl, benzyl or phenyl; where phenyl and benzyl for their part may be mono- di- or trisubstituted by d-C6alkyl, d-C6haloalkyl, d-C6alkoxy, d-C6haloalkoxy, halogen, cyano, hydroxyl or nitro; m is O, 1 , 2, 3 or 4;
R is hydrogen, Ci-C6alkyl, CrC6haloalkyl, drCecycloalkyl, C3-C6halocycloalkyl, d-C6alkylthio, d-Cehaloalkylthio, d-Cealkoxy-d-Cealkyl or d-Cβhaloalkoxy-d-Cealkyl; or
R is d-C6alkyl, d-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, d-C6alkylthio, d-Cehaloalkylthio, d-C6alkoxy-CrC6alkyl or d-Cehaloalkoxy-d-Cealkyl substituted by d-C6alkyl, d-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, d-C6alkoxy, or CrC6haloalkoxy; or R is cyano, nitro, -C(O)R26, -C(O)OR27, -CONR28R2S, -SO2R30 or -
Figure imgf000005_0001
Ro is hydrogen, d-C6alkyl, d-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, CrC6alkylthio, d-C6haloalkylthio, Ci -CBaIkOXy-C1 -C6alkyl or CrC6haloalkoxy-Ci-C6alkyl; or R0 is CrC6alkyl, d-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, d-Cβalkylthio, d-C6haloalkylthio, CrC6alkoxy-Ci-C6alkyl or Ci -C6IIaIOaIkOXy-C1 -C6alkyl substituted by d-Cβalkyl, d-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, d-C6alkoxy, or CrCehaloalkoxy; or R0 is cyano, nitro, -C(O)R026, -C(O)OR027, -CONR028R029, -SO2R030 or -P(O)(OR031)(OR032); or R0 is phenyl or benzyl, or phenyl or benzyl mono-, di- or trisubstituted by substituents selected from d-C6alkyl, C3-C6cycloalkyl, d-C6haloalkyl, halogen, cyano, d-C4alkoxy, d-C4haloalkoxy, C1-C4alkylthio, d-C4haloalkylthio, C1- C4alkylsulfinyl, d-C4alkylsulfonyl, d-C4haloalkylsulfinyl and C1-C4haloalkylsulfonyl; each of R26 and R026, which may be the same or different, represents hydrogen, Ci-C6alkyl, d-Cehaloalkyl, C3-C6cycloalkyl, d-Cehalocycloalkyl, d-C6alkylthio, d-C6haloalkylthio, d-Cealkoxycarbonyl, CrC6alkylcarbonyl or d-C6alkoxy-d-C6alkyl; or d-C6alkyl, CrCehaloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, CrC6alkylthio, d-C6haloalkylthio, CrCβalkoxycarbonyl, CrC6alkylcarbonyl or CrC6alkoxy-CrC6alkyl substituted by d-C6alkyl, CrC6haloalkyl, C3-C6cycloalkyl, Cs-Cβhalocycloalkyl, d-C6alkoxy, or d-C6haloalkoxy; each of R27, R28, R29. R3o, R31, R32, R027, R02β, R029, RO3o, R∞I and R032 which may be the same or different, represents d-C6alkyl, d-C6haloalkyl, C3-C6cycloalkyl or C3-C6halocycloalkyl; or d-C6alkyl, d-C6haloalkyl, C3-C6cycloalkyl or CrC6halocycloalkyl substituted by d-C6alkyl, CrC6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, CrC6alkoxy or d-C6haloalkoxy; with the proviso that E1 or E2 is sulfur if A is oxygen, sulfur or N-R0, wherein R0 is hydrogen, d-C3alkyl, d-C3haloalkyl, C2-C4alkylcarbonyl, C2- C4haloalkylcarbonyl, C2-C4alkoxycarbonyl or d-C3alkylsulfonyl; and agronomically acceptable salts/isomers/diastereomers/enantiomers/tautomers/N-oxides of those compounds.
Compounds of formula I which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrose acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as d-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as d-C4alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p- toluenesulfonic acid. Compounds I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower- alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine. Where appropriate, the corresponding internal salts can furthermore be formed. Preferred within the scope of the invention are agrochemically advantageous salts; however, the invention also encompasses salts which have disadvantage for agrochemical use, for example salts which are toxic to bees or fish, and which are employed, for example, for the isolation or purification of free compounds of formula I or agrochemically utilizable salts thereof. Owing to the close relationship between the compounds of formula I in free form and in the form of their salts, for the purposes of the invention the free compounds of formula I or their salts hereinabove and hereinbelow are respectively to be understood as including, where appropriate, the corresponding salts or the free compounds of formula I. The same applies analogously to tautomers of compounds of formula I and salts thereof. In general, the free form is preferred in each case.
The alkyl groups occurring in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso- butyl, tert-butyl, pentyl, hexyl, heptyl and octyl and their branched isomers. Alkoxy, alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned. The alkenyl and alkynyl groups can be mono- or polyunsaturated.
Halogen is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl or halophenyl.
Haloalkyl groups preferably have a chain length of from 1 to 6 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 ,1 -difluoro- 2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferably trichloro- methyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.
Suitable haloalkenyl groups are alkenyl groups which are mono- or polysubstituted by halogen, halogen being fluorine, chlorine, bromine and iodine and in particular fluorine and chlorine, for example 2,2-difluoro-1 -methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluorobut-2-en- 1 -yl. Among the alkenyl groups which are mono-, di- or trisubstituted by halogen, preference is given to those having a chain length of from 3 to 5 carbon atoms.
Suitable haloalkynyl groups are, for example, alkynyl groups which are mono- or polysubstituted by halogen, halogen being bromine, iodine and in particular fluorine and chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoro- propynyl and 4,4,4-trifluorobut-2-yn-1-yl. Among the alkynyl groups which are mono- or polysubstituted by halogen, preference is given to those having a chain length of from 3 to 5 carbon atoms.
Alkoxy groups preferably have a preferred chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also the isomeric pentyloxy and hexyloxy radicals; preferably methoxy and ethoxy.
Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert- butoxycarbonyl; preferably methoxycarbonyl or ethoxycarbonyl. Haloalkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1 ,1 ,2,2- tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2- trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy. Alkylthio groups preferably have a chain length of from 1 to 6 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert- butylthio, preferably methylthio and ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl; preferably methylsulfinyl and ethylsulfinyl. Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl. Alkoxyalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms. Examples of alkoxyalkoxy groups are: methoxymethoxy, methoxyethoxy, methoxypropoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy or butoxybutoxy. Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the isomeric butylamines. Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino and diisopropylamino. Preference is given to alkylamino groups having a chain length of from 1 to 4 carbon atoms. Alkoxyalkyl groups preferably have a chain length of 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl. Alkylthioalkyl groups preferably have from 1 to 8 carbon atoms. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl. The cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Phenyl, also as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl, may be substituted. In this case, the substituents can be in ortho, meta and/or para position. The preferred substituent positions are the ortho and para positions to the ring attachment point.
E1 and/or E2 is preferably oxygen.
Preference is given to subgroups of compounds of formula I wherein a) R2 is hydrogen or C1-C4alkyl; and/or b) R3 is hydrogen or d-C4alkyl; and/or c) D is a group D1 and/or. d) E2 is sulfur.
Further compounds of formula I are preferred, wherein A is N-benzyl, SO or SO2, in particular SO or SO2.
A preferred subgroup of compounds of formula I is represented by the compounds of formula Ia
Figure imgf000009_0001
wherein
R91 is C-ι-C4alkyl or halogen, preferably chloro, bromo or methyl;
R92 is halogen or cyano, preferably fluoro, chloro, bromo or cyano;
R93 is halogen, Ci-C4haloalkyl or Ci-C4haloalkoxy; and
A, R34 and R35 and m have the meanings given under formula I.
In a preferred subgroup of compounds of formula I or of formula Ia, A is SO, SO2, S(O)P=N- R, C=N-OR36, C=O, P(X)t-R33 or N-R0; wherein p, t, X, R33 and R36 have the meanings given under formula I and
R0 is C3-C6cycloalkyl, C3-C6halocycloalkyl, Ci-C6alkylthio, d-Cehaloalkylthio, d-Cealkoxy-d-Cealkyl or d-Cehaloalkoxy-d-Cealkyl; or R0 is C1-C6SIkVl, d-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, Ci-C6alkylthio, Ci-C6haloalkylthio, d-C6alkoxy-d-C6alkyl or Ci-C6haloalkoxy-d-C6alkyl substituted by C3-C6cycloalkyl, C3-C6halocycloalkyl, d-C6alkoxy, or Ci-C6haloalkoxy; or R0 is cyano, nitro, -CONR028Ro29 or -P(O)(OR03i)(OR032) wherein R02S, R029, R031 and R032 have the meanings given under formula I, or R0 is phenyl or benzyl, or phenyl or benzyl mono-, di- or trisubstituted by substituents selected from Ci-C6alkyl, C3-C6cycloalkyl, Ci-C6haloalkyl, halogen, cyano, Ci- C4alkoxy, CrC4haloalkoxy, C1-C4alkylthio, CrC4haloalkylthio, d-C4alkylsulfinyl, Ci- C4alkylsulfonyl, d-C4haloalkylsulfinyl and Ci-C4haloalkylsulfonyl.
In a further preferred subgroup of compounds of formula I or of formula Ia, A is SO, SO2, S(O)p=N-R, C=N-OR36, C=O, P(X)t-R33 or N-R0; wherein p, t, X, R33 and R36 have the meanings given under formula I and
R0 is C3-C6cycloalkyl, C3-C6halocycloalkyl, d-C6alkylthio, Ci-C6haloalkylthio, CrC6alkoxy-d-C6alkyl or d-C6haloalkoxy-d-C6alkyl; or R0 is d-C6alkyl, d-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, d-C6alkylthio, d-C6haloalkylthio, Ci-C6alkoxy-Ci-C6alkyl or CrC6haloalkoxy-Ci-C6alkyl substituted by C3-C6cycloalkyl, C3-C6halocycloalkyl, Ci-C6alkoxy, or Ci-C6haloalkoxy; or R0 is cyano, nitro, -CONR028R029 or -P(0)(ORo3i)(ORo32) wherein R028. R029, R031 and R032 have the meanings given under formula I.
Special emphasis should also be given to compounds of formula I wherein e) R34 is hydrogen or C1-C4alkyl, preferably hydrogen or methyl; and/or f) R35 is hydrogen or d-C4alkyl, preferably hydrogen or methyl; and/or g) A is oxygen, sulfur, SO, SO2, S=NR or S(O)P=NR, preferably S, SO, SO2 or S(O)P=NR, wherein p is 1 ; most preferably oxygen or sulfur; and/or h) R is hydrogen, cyano, nitro, -C(O)R26, -C(O)OR27, -CONR28R29, -SO2R30 or - P(O)(OR31)(OR32), preferably hydrogen, cyano, -COOMe, -SO2Me or -C(O)CF3 and/or i) R0 is hydrogen, cyano, nitro, -C(O)R026, -C(O)OR027, -CONR028R029, -SO2R030 or -P(O)(OR031)(OR032), preferably hydrogen, cyano, -COOMe, -SO2Me or -C(O)CF3 and/or j) R4' is different from hydrogen.
"Me" represents the methyl group.
In preferred compounds of formula I, R26 is hydrogen, d-C6alkyl, d-C6haloalkyl or C3-C6cycloalkyl. In preferred compounds of formula I, R27, R28, R29,R3o, R31 and R32 independently of one another are d-C6alkyl or d-C6haloalkyl; or d-C6alkyl or d-C6haloalkyl substituted with d-C6alkyl or d-C6haloalkyl.
In preferred compounds of formula I, R026 is hydrogen, d-C6alkyl, Ci-C6haloalkyl or C3-C6cycloalkyl. In preferred compounds of formula I, R027, R028, R029,R030, R031 and R032 independently of one another are d-C6alkyl or d-C6haloalkyl; or d-C6alkyl or d-C6haloalkyl substituted with d-C6alkyl or d-C6haloalkyl.
The process according to the invention for preparing compounds of the formula I or, where appropriate, a tautomer and/or salt thereof, is carried out analogously to known processes, for example those described in WO 01/70671 , WO 03/016284, WO 03/015518 and WO 04/033468. The process for the preparation of a compound of the formula I, or, when appropriate, a tautomer thereof, in each case in free form or in salt form, comprises, for example,
a) to prepare a compound of formula I, in which R2 is hydrogen and E1 and E2 are oxygen, or, where appropriate, a tautomer and/or salt thereof, by reacting a compound of formula Il
Figure imgf000011_0001
in which R1, n, and D have the meanings given for formula I, or, where appropriate, a tautomer and/or salt thereof with a compound of formula III
Figure imgf000011_0002
in which A, R3, R34, R35 and m have the meanings given for the formula I, or, where appropriate, with a tautomer and/or salt thereof or,
b) to prepare a compound of formula I, or, where appropriate, a tautomer and/or salt thereof, reacting a compound of formula IV
in which R1, R2, n, E1, E2 and D have the meanings given for the formula I; and X1 is a leaving group, or, where appropriate, a tautomer and/or salt thereof with a compound of formula III
Figure imgf000012_0001
in which A, R3, R34, R35 and m have the meanings given for formula I, or, where appropriate, with a tautomer and/or salt thereof or,
c) to prepare a compound of formula I, or, where appropriate, a tautomer and/or salt thereof, by reacting a compound of formula V
Figure imgf000012_0002
in which n, R1, R2, R3, E2, R34, R35, A and m have the meanings given for formula I, or, where appropriate, a tautomer and/or salt thereof with a compound of formula Vl
X2Ct=E1)D (Vl),
in which E1 and D have the meanings given for formula I; and X2 is a leaving group, or, where appropriate, with a tautomer and/or salt thereof and/or converting a compound of formula I or, where appropriate, a tautomer thereof, in each case in free form or in salt form, into another compound of formula I or, where appropriate, a tautomer thereof, separating an isomer mixture, which can be obtained in accordance with the process, and isolating the desired isomer and/or converting a free compound of formula I or, where appropriate, a tautomer thereof into a salt or a salt of a compound of formula I or, where appropriate, a tautomer thereof into the free compound of formula I or, where appropriate, a tautomer thereof or into another salt. The compounds of formula Il are described in WO 04/111030. The compounds of formula III and V are novel and especially developed for the preparation of the compounds of formula I and constitute therefore a further embodiment of the present invention. The preferences for the substituents of formula I mentioned above are also valid for the compounds of formula III and V.
In especially preferred compounds of formula III
R3 is hydrogen;
R34 is hydrogen or d-C4alkyl, preferably hydrogen or methyl;
R35 is hydrogen, halogen, cyano, CrC4alkyl, Ci-C4haloalkyl, CrC^alkoxycarbonyl,
Figure imgf000013_0001
Ci-C4haloalkoxy-d-C4alkyl;
A is oxygen, sulfur, SO, SO2, S=NR or S(O)P=NR, preferably S, SO, SO2 or S(O)P=NR, wherein p is 1 and wherein R is hydrogen, cyano, nitro, -C(O)R2S, -C(O)OR27, -CONR28R29, -
SO2R30 or -P(O)(OR31)(OR32), preferably hydrogen, cyano, -COOMe, -SO2Me or -C(O)CF3; m is 0,1 ,2,3 or 4.
In especially preferred compounds of formula V
R1 is Ci-C4alkyl, halogen, d-Cshaloalkyl, cyano, nitro, C1-C4BIkOXy, C1-C4-IIaIOaIkOXy, C1-
C4alkylthio, d-dalkylsulfinyl, Ci-C4alkylsulfonyl, CrC^aloalkylthio, d-dhaloalkylsulfinyl or
CrC4haloalkylsulfonyl;
R2 and R3 are hydrogen;
E2 is oxygen or sulfur;
R34 is hydrogen or Ci-C4alkyl, preferably hydrogen or methyl;
R35 is hydrogen, halogen, cyano, C1-C4alkyl, Ci-C4haloalkyl, CrC4alkoxycarbonyl,
C1-C4HIkOXy-Ci -C4alkyl, d-Oihaloalkoxy-CrCealkyl;
A is oxygen, sulfur, SO, SO2, S=NR or S(O)P=NR, preferably S, SO, SO2 or S(O)P=NR, wherein p is 1 and wherein R is hydrogen, cyano, nitro, -C(O)R26, -C(O)OR27, -CONR28R29, -
SO2R30 or -P(O)(OR3i)(OR32), preferably hydrogen, cyano, -COOMe, -SO2Me or -C(O)CF3; m is O, 1 , 2, 3 or 4. n is 1 , 2 or 3.
Table C: Preferred compounds of formula III represented by the formula Ilia:
Figure imgf000014_0001
Figure imgf000014_0002
Figure imgf000015_0001
Figure imgf000016_0002
Table D: Preferred compounds of formula V represented by formula Vb where E2 is oxygen
Figure imgf000016_0001
Figure imgf000016_0003
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Table G: Preferred compounds of formula V represented by formula Vb where E2 is sulfur listing compounds G1 to G92 wherein R91, R92, A, R34 and R35 have the meanings given in Table D lines D1 to D92.
Physical data for compounds of formula Ilia and Vb according to Tables C, D and G:
Figure imgf000021_0002
Figure imgf000022_0003
Compounds of formula Va, a subgroup of compounds of formula V where R2 is hydrogen, can be prepared for example in analogy to methods described in W 02001/070671.
Figure imgf000022_0001
The compounds of formula Va can also be prepared by reacting a compound of formula Xl with a compound of formula III in the presence of a base and an inert solvent
Figure imgf000022_0002
in which n, R1, R3, E2, R34, R35, A and m have the meanings given in formula I; and X1 is a leaving group (for example chlorine, bromine), or, where appropriate, a tautomer and/or salt thereof.
Suitable bases are for example N(C2H5)3, DBU, DBN or imidazole. Preferred solvents are tetrahydrofurane, dioxane, glyme, ethyl acetate or toluene. The reaction is carried out at temperatures of from 00C to 1000C, preferably at +15°C to +300C in particular at ambient temperature. A further process for the preparation of compounds of formula V is described in PCT/EP2006/003504.
Special emphasis should also be given to a subgroup of compounds of formula V represented by the compounds of formula Vb
Figure imgf000023_0001
wherein
R9-I is Ci-C4alkyl or halogen, preferably chloro, bromo or methyl;
R92 is halogen or cyano, preferably fluoro, chloro, bromo or cyano; and
E2, A, R34, R35 and m have the meanings given under formula I.
Amides of formula V/Va/Vb where E2 is oxygen are readily converted to thioamides of formula V/Va/Vb where E2 is sulfur by using commercially available thio transfer reagents such as phosphorus pentasulfide and Lawesson's reagent, for example in analogy to X. Fontrodona et al., Synthesis, 2001 , (13), 2021-27.
Compounds of formula Xl, in particular those compounds of formula Xl where X1 is chlorine, can be prepared for example in analogy to J. Garin et al., Tetrahedron Letters, 1991 , 32, 3263-64.
Compounds of formula III are either known in the literature or can be prepared in analogy according to known methods.
Figure imgf000024_0001
acidic treatment
(R3 344)/m
Figure imgf000024_0002
(Ilia)
Compounds of formula Ilia, a subgroup of compounds of formula III where R3 is hydrogen, can be prepared for example as described above via reduction, or via reductive amination, or via acidic treatment, or in further analogy according to known methods
A subgroup of compounds of formula I represented by the compounds of formula Ib
Figure imgf000024_0003
in which n, R1, R2, R3, D, E1, E2, R34, R35, m and R have the meanings given in formula I, is prepared, for example, under similar conditions as described for a compound of formula in variants a), b) or c), wherein the group A of formula I, III and V in variants a), b) or c) is replaced by the group S(O)P=NR, wherein p is 1
Alternatively, a compound of the formula Ib, or, where appropriate, a tautomer and/or salt thereof, in each case in free form or in salt form, is prepared, for example, from a compound of the formula
Figure imgf000025_0001
in which n, R1, R2, R3, D, E1, E2, R^, R35 and m have the meanings given in formula I and q is 0 or 1 , according to known procedures (H. Okamura, C. BoIm, Org. Lett. 2004, 6, 1305; H. Okamura, C. BoIm, Chem. Lett. 2004, 33, 482; D. Leca, K. Song, M. Amatore, L. Fensterbank, E. Lacόte, M. Malacria, Chem. Eur. J. 2004, 10, 906) or as described below.
A compound of formula I or a compound of formula III, where the group A of formula I and is replaced by the group S(O)P=NR, wherein p is 1 , are prepared, for example, from a compound of formula VIl
Figure imgf000025_0002
in which n, R1, R2, R3, D, E1, E2, R34, R35 and m have the meanings given in formula I and q is 0 or 1 , respectively from a compound of formula VIII
Figure imgf000026_0001
in which R3, R34, R35 and m have the meanings given in the formula I and q is 0 or 1 , according to known procedures (scheme 1 : q = 0: step A and then B; q = 1 : step B, see e.g. M. Reggelin, C. Zur, Synthesis, 2000, 1 ). The compounds of formulae III, V and VIII are novel, especially developed for the preparation of the compounds of formula I and therefore constitute a further object of the present invention.
Scheme 1
O Step B p
I ^S ~ f N-R sulfoxide sulf oximine
Step A Step A1
Step B'
^S N-R
I S
I sulfide sulfilimine
Alternatively, a compound of formula I or a compound of formula III, where the group A of formula I and III is replaced by the group S(O)P=NR, wherein p is 1 , are prepared, for example, from a compound of formula IX
Figure imgf000027_0001
in which n, R1, R2, R3, D1 E1, E2, R34, R35, m and R have the meanings given in formula I, respectively from a compound of formula X
Figure imgf000027_0002
in which R3, R34, R35, m and R have the meanings given in the formula I, according to known methods (scheme 1 , step A'), wherein a compound of formula IX or a compound of formula X are prepared, for example, from a compound of formula VII (q = 0) respectively from a compound of formula VIII (q = 0) according to known methods, as described in scheme 1 , step B'.
For the transformation of a sulfide to a sulfoxide or a sulfilimine to a sulfoximine (scheme 1 , step A or A'), classical oxidation reagents are KMnO4, mCPBA, NaIOVRuO2, H2O2, oxone. For the transformation of a sulfoxide to a sulfoximine or a sulfide to a sulfilimine (scheme 1 , step B or B'), typical reagents are NaN3ZH2SO4, O-mesitylenesulfonylhydroxylamine (MSH), or metal-catalyzed methods such as RN3ZFeCI2, Phl=N-R/CuOTf, Phl=N-R/Cu(OTf)2, PhI=N- RZCuPF6, PHI(OAc)2ZR-NH2Z MgOZRu2(OAc)4 or oxaziridines (e.g. 3-(4-cyano-phenyl)- oxaziridine-2-carboxylic acid tert-butyl ester). Detailed preparation conditions useful for the synthesis of compounds of formula Ib (preparation of sulfoximines) are given in WO2006/061200.
What has been said above for tautomers and/or salts of compounds of formula I applies analogously to starting materials mentioned hereinabove and hereinbelow with regard to the tautomers and/or salts thereof.
The reactions described hereinabove and hereinbelow are carried out in a manner known per se, for example in the absence or, normally, in the presence of a suitable solvent or diluent or of a mixture of these, the process being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range of from approximately -800C to the boiling point of the reaction mixture, preferably from approximately -200C to approximately +1500C, and, if required, in a sealed vessel, under reduced, normal or elevated pressure, in an inert gas atmosphere and/or under anhydrous conditions. Especially advantageous reaction conditions can be seen from the examples.
Unless otherwise specified, the starting materials mentioned hereinabove and hereinbelow, which are used for the preparation of the compounds of formula I or, where appropriate, the tautomers thereof, in each case in free form or in salt form, are known or can be prepared by methods known per se, for example in accordance with the information given below. The reactants can be reacted in the presence of a base. Examples of suitable bases for facilitating the detachment of HX2 are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N- alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N- dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N- methylmorpholine, benzyltrimethylammonium hydroxide and 1 ,8-diazabicyclo[5.4.0]undec-7- ene (DBU).
The reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N1N- diethylaniline, may also act as solvents or diluents.
The reaction is advantageously carried out in a temperature range from approximately -800C to approximately +1400C, preferably from approximately -300C to approximately +1000C, in many cases in the range between room temperature and approximately +800C.
A compound of formula I can be converted in a manner known per se into another compound I by replacing one or more substituents of the starting compound of formula I in the customary manner by (an)other substituent(s) according to the invention.
Depending on the choice of the reaction conditions and starting materials which are suitable in each case, it is possible, for example, in one reaction step only to replace one substituent by another substituent according to the invention, or a plurality of substituents can be replaced by other substituents according to the invention in the same reaction step.
Salts of compounds of formula I can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
Salts of compounds of formula I can be converted in the customary manner into the free compounds of formula I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
Salts of compounds of formula I can be converted in a manner known per se into other salts of compounds of formula I, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
Depending on the procedure or the reaction conditions, the compounds of formula I, which have salt-forming properties can be obtained in free form or in the form of salts.
The compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.
Diastereomer mixtures or racemate mixtures of compounds of formula I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
Enantiomer mixtures, such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high- performance liquid chromatography (HPLC) on acetyl celulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is com- plexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the diastereomers, from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents.
Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereose- lective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.
It is advantageous to isolate or synthesize in each case the biologically more effective isomer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological activity.
The compounds according to the invention and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
The compounds 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 according to the invention 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%.
Examples of the abovementioned animal pests are: from the order Acarina, for example,
Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophi- lus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Derma- nyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Oly- gonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polypha- gotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.; from the order Anoplura, for example,
Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order Coleoptera, for example,
Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp.,
Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., Otiorhynchus spp.,
Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.; from the order Diptera, for example,
Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp.,
Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp.,
Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit,
Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp.,
Tabanus spp., Tannia spp. and Tipula spp.;
from the order Heteroptera, for example,
Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Lep- tocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotino- phara spp. and Triatoma spp.; from the order Homoptera, for example,
Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspi- diotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Parlatoria spp., Pemphigus spp., Planococ- cus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylta spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri; from the order Hymenoptera, for example, Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplo- campa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and
Vespa spp.; from the order Isoptera, for example,
Reticulitermes spp.; from the order Lepidoptera, for example,
Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambi- guella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Gra- pholita spp., Hedya nubiferana, Heliothis spp., HeIIuIa undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Ly- onetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp.,
Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypi- ela, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scir- pophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp.,
Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.; from the order Mallophaga, for example,
Damalinea spp. and Trichodectes spp.; from the order Orthoptera, for example,
Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.; from the order Psocoptera, for example,
Liposcelis spp.; from the order Siphonaptera, for example,
Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis; from the order Thysanoptera, for example,
Frankliniella spp., Hercinothrips spp., Scirtothrips aurantii, Taeniothrips spp., Thrips palmi and Thrips tabaci; and from the order Thysanura, for example,
Lepisma saccharina. The active ingredients according to the invention 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 active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops. The active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca(preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
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 Cryθc, 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. Bt11 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. Bt11 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 com 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-1150 Brussels, Belgium, registration number C/ES/96/02.
6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 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, (http://bats.ch).
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 compounds 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 compounds 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., Wemeckiella 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 compounds 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 also relates to pesticidal compositions such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise - at least - one of the active ingredients according to the invention and which are to be selected to suit the intended aims and the prevailing circumstances.
In these compositions, the active ingredient is employed in pure form, a solid active ingredient for example in a specific particle size, or, preferably, together with - at least - one of the auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).
Examples of suitable solvents are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the fractions C8 to Ci2 of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-me- thylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils, such as unexpodized or epoxidized rapeseed, castor, coconut or soya oil, and silicone oils. Solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly disperse silicas or highly disperse absorbtive polymers. Suitable particulate adsorptive carriers for granules are porous types, such as pumice, brick grit, sepiolite or bentonite, and suitable non-sorptive carrier materials are calcite or sand. In addition, a large number of granulated materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.
Suitable surface-active compounds are, depending on the type of the active ingredient to be formulated, non-ionic, cationic and/or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties. The surfactants mentioned below are only to be considered as examples; a large number of further surfactants which are conventionally used in the art of formulation and suitable according to the invention are described in the relevant literature.
Suitable non-ionic surfactants are, especially, polyglycol ether derivatives of aliphatic or cyc- loaliphatic alcohols, of saturated or unsaturated fatty acids or of alkyl phenols which may contain approximately 3 to approximately 30 glycol ether groups and approximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatic hydrocarbon radical or approximately 6 to approximately 18 carbon atoms in the alkyl moiety of the alkyl phenols. Also suitable are water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopo- lypropylene glycol or alkyl polypropylene glycol having 1 to approximately 10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene glycol ether groups and approximately 10 to approximately 100 propylene glycol ether groups. Normally, the abovementioned compounds contain 1 to approximately 5 ethylene glycol units per propylene glycol unit. Examples which may be mentioned are nonylphenoxypolyethoxyethanol, castor oil polyglycol ether, polypropylene glycol/polyethylene oxide adducts, tributylpheno- xypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.
The cationic surfactants are, especially, quarternary ammonium salts which generally have at least one alkyl radical of approximately 8 to approximately 22 C atoms as substituents and as further substituents (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates. Examples are stearyltrimethylammonium chloride and benzylbis(2-chloroethyl)ethyl- ammonium bromide.
Examples of suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface-active compounds. Examples of suitable soaps are the alkali, alkaline earth or (un- substituted or substituted) ammonium salts of fatty acids having approximately 10 to approximately 22 C atoms, such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which are obtainable for example from coconut or tall oil; mention must also be made of the fatty acid methyl taurates. However, synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates. As a rule, the fatty sulfonates and fatty sulfates are present as alkali, alkaline earth or (substituted or unsubstituted) ammonium salts and they generally have an alkyl radical of approximately 8 to approximately 22 C atoms, alkyl also to be understood as including the alkyl moiety of acyl radicals; examples which may be mentioned are the sodium or calcium salts of lignosulfonic acid, of the dodecylsulfuhc ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and a fatty acid radical of approximately 8 to approximately 22 C atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, of dibutyl- naphthalenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensate. Also possible are, furthermore, suitable phosphates, such as salts of the phosphoric ester of a p- nonylphenol/(4-14)ethylene oxide adduct, or phospholipids.
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, scatte- ring 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.
Preparation examples
The examples which follow are intended to illustrate the invention and show preferred compounds of formula I. Free valences represent the methyl group.
Example P1 : Preparation of compound T13.1.2:
Step 1 : Preparation of 2-methyl-2-nitro-1 ,3-propanediol ditosylate:
Figure imgf000045_0001
In analogy to F.I. Carroll, J. Org. Chem. 1969, 34, 466-8:
To a solution of 2-methyl-2-nitro-1 ,3-propanediol (80 g, 0.592 mol) and triethylamine (131.8 g, 1.303 mol) in diethyl ether (250 ml) is added a solution of tosyl chloride (225.7 g, 1.184 mol) in diethyl ether (800 ml) between -15° and -200C. The resulting suspension is stirred at 00C for 1 hour, then 18 hours at ambient temperature. The reaction mixture is filtered, the solid residue is taken up twice in ethyl acetate and stirred, the suspension being filtered again. The combined ethyl acetate layers are evaporated to dryness giving a first crop of crude product (175.8 g). The ether filtrate is washed with water (2x) and brine, dried (Na2SO4), filtered, and partly concentrated. The suspension is filtered giving another 15.0 g of product. The crude solid product (190.8 g, 73%) is used in the next step without further purification.
Step 2: Preparation of 3-methyl-3-nitro-thietane:
Figure imgf000045_0002
In analogy to K.K. Andersen et al., J. Org. Chem. 1978, 43, 3827-34: A solution of 2-methyl-2-nitro-1 ,3-propanediol ditosylate (the product of step 1 ) (17 g, 38.3 mmol) in DMSO (130 ml) is treated with sodium sulfide (Na2S^xH2O 32-38%, 1 1.92 g, -53.5 mmol) and the mixture is stirred at a temperature of 900C (bath 1 100C) for 2 hours. The cooled reaction mixture is poured into water, extracted with Et2O, the combined organic layers washed with water (2x) and brine, dried (Na2SO4), filtered, and concentrated. The crude liquid product (3.52 g, 69%) is used in the next step without further purification.
Step 3: Preparation of 3-amino-3-methyl-thietane:
Figure imgf000046_0001
To a solution of 3-methyl-3-nitro-thietane (the product of step 2) (3.52 g, 26.4 mmol) in ethanol (100 ml) and water (50 ml) is added ammonium chloride (1.55 g, 29.0 mmol), followed by iron powder (14.0 g, 250.7 mmol) and the mixture is heated to reflux for 1 hour. The cooled reaction mixture is filtered through Hyflo, the residue washed with diethyl ether and dichloromethane, and the combined filtrate is concentrated carefully under reduced pressure. The product, a yellowish liquid (0.66 g, 24%), is used in the next step without further purification. 1H-NMR (CDCI3): 3.25 (d, J=9.3 Hz, 2H), 3.04 (d, J=9.8 Hz, 2H), 1.78 (s, 2H), 1.53 (s, 3H).
Step 4: Preparation of (2-(3-Chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carboxylic acid [4-chloro-2-methyl-6-(3-methyl-thietan-3-ylcarbamoyl)-phenyl]-amide):
Figure imgf000046_0002
To a solution of 6-chloro-2-[1 -(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1 H-pyrazol-5-yl]-8- methyl-4/-/-3,1-benzoxazin-4-one (1 .13 g, 2.56 mmol) (prepared according to WO 02/48115, example 2D) in tetrahydrofuran (15 ml) is added 3-amino-3-methyl-thietane (the product of step 3) (0.66 g, 6.40 mmol), and the mixture is heated for 48 hours at 5O0C, then to reflux for 12 hours. The cooled reaction mixture is poured into water, extracted with ethyl acetate, the combined organic layers washed with water and brine, dried (Na2SO4), filtered, and concentrated. The crude product is purified by flash chromatography (ethyl acetate/hexane 1 :2) to afford 560 mg (40%) of the title compound as a white solid, m.p. 238-2410C. 1H-NMR (CDCI3): 10.19 (s, 1 H), 8.46 (d, 1 H), 7.88 (d, 1 H), 7.69 (s, 1 H), 7.41 (dd, 1 H), 7.10 (s, 2H), 6.39 (s, 1 H)1 3.63 (d, 2H), 2.98 (d, 2H), 2.09 (s, 3H), 1.68 (s, 3H); MS (electrospray ES+): 544, 546 (M+H)+.
Step 5: Preparation of compound T13.1.2 (2-(3-Chloro-pyridin-2-yl)-5-trifluoromethyl-2H- pyrazole-3-carboxylic acid [4-chloro-2-methyl-6-(3-methyl-1 ,1-dioxo-1λ6-thietan-3- ylcarbamoyl)-phenyl]-amide):
Figure imgf000047_0001
To a solution of 2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carboxylic acid [4- chloro-2-methyl-6-(3-methyl-thietan-3-ylcarbamoyl)-phenyl]-amide (the product of step 4, 150 mg, 0.275 mmol) in dichloromethane (10 ml) is added m-chloroperbenzoic acid (143 mg, 0.579 mmol), and the mixture is stirred at room temperature for 1 hour. The reaction mixture is partly concentrated, taken up in ethyl acetate, the organic layer washed with Na2CO3 aq. sat. (3x) and brine, dried (Na2SO4), filtered, and concentrated. The crude product is purified by flash chromatography (ethyl acetate) to afford 78 mg (49%) of the title compound T13.1.2 as a white solid, m.p. 168-1710C.
1H-NMR (CDCI3): 9.61 (s, 1 H), 8.48 (d, 1 H), 7.90 (d, 1 H), 7.42 (dd, 1 H), 7.33 (s, 1 H), 7.25- 7.22 (2xs, 2H), 6.72 (s, 1 H), 4.38 (d, 2H), 4.09 (d, 2H), 2.14 (s, 3H), 1.75 (s, 3H); MS (electrospray ES+): 576, 578 (M+H)+.
Example P2: Preparation of compound T44.1.2:
Step 1 : Preparation of 2-methyl-2-nitro-1 ,3-propanediol ditriflate:
Figure imgf000048_0001
To a solution of triflic anhydride (16.5 ml, 0.1 mol) in chloroform (50 ml) is added a solution of 2-methyl-2-nitro-1 ,3-propanediol (6.75 g, 0.05 mol) and pyridine (8.85 ml, 0.11 mol) in chloroform (50 ml) with external cooling to ensure a temperature of between 0° and 5°C during the addition. After the addition the cooling bath is removed and the reaction stirred for 18 hours at ambient temperature. The reaction mixture is transferred to a separating funnel and washed with water. The organic layer is dried (Na2SO4), filtered and evaporated to dryness. The crude product is purified by chromatography using a 4:1 mixture of Hexane: Ethyl acetate as eluant; the product is obtained as a solid with melting point 50-520C.
Step 2: Preparation of 3-methyl-3-nitro-N-benzylazetidine:
Figure imgf000048_0002
A solution of 2-methyl-2-nitro-1 ,3-propanediol ditriflate [the product of step 1 ] (4.Og, 10 mmol) in acetonitrile (70 ml) is cooled to O0C - 50C and N-ethyl-diisopropylamine (3.23 g, 25 mmol) is added, followed by benzylamine (1 .60 g, 15 mmol) and the mixture is stirred at a temperature of 800C for 12 hours. The cooled reaction mixture concentrated under reduced pressure, dissolved in ethyl acetate and transferred to a separating funnel. This is then washed with water (2x) and brine, dried (Na2SO4), filtered, and concentrated. The crude liquid product is used in the next step without further purification. The crude product is purified by chromatography using a 3:1 mixture of Hexane: Ethyl acetate as eluant; the product is obtained as an oil. 1H-NMR (CDCI3): 7.3 (m, 5H), 3.75 (d, 2H), 3.68 (s, 2H), 3.42 (d, 2H), 1.88 (s, 3H). Preparation of 3-amino-3-methyl-N-benzylazetidine:
Figure imgf000049_0001
A solution of 3-methyl-3-nitro-N-benzylazetidine [the product of step 2] (3.9 g, 18.9 mmol) in ethyl acetate (370 ml) and 5% acetic acid (370 ml) is heated to reflux. Iron powder (5.25 g, 94.1 mmol) is added portion-wise every 5 minutes. After the addition is complete the reaction mixture is heated at reflux for 6 hours. The cooled reaction mixture is filtered through Hyflo, and the residue washed with ethyl acetate. The filtrate is transferred to a separating funnel and the organic layer separated and discarded. The aqueous layer is treated with 30% NaOH solution with ice cooling to give a pH of ca. 11. Dichloromethane is then added and the mixture vigorously stirred at ambient temperature for 10 minutes. This mixture is filtered through Hyfol, the filtrate transferred to a separating funnel and the organic layer is separated, dried (Na2SO4), filtered, and concentrated. The crude oily product (2.30 g, 69%) is used in the next step without further purification. 1H-NMR (CDCI3): 7.2 (m, 5H), 3.62 (s, 2H), 3.27 (d, 2H), 2.88 (d, 2H), 1.68 (bs, 2H), 1.4 (s, 3H).
Step 4: Preparation of compound T44.1.2 (2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H- pyrazole-3-carboxylic acid [4-chloro-2-methyl-6-(3-methyl-N-benzylazetidine-3-ylcarbamoyl)- phenyl]-amide):
Figure imgf000049_0002
To a solution of 6-chloro-2-[1 -(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1 H-pyrazol-5-yl]-8- methyl-4H-3,1 -benzoxazin-4-one (353 mg, 0.8 mmol) [prepared according to WO 02/48115, example 2D] in tetrahydrofuran (10 ml) is added 3-amino-3-methyl-N-benzylazetidine [the product of step 3] (176 mg, 0.8 mmol), and the mixture is stirred at ambient temperature for 18 hours. The reaction mixture is concentrated and the crude product is purified by flash chromatography (ethyl acetate) to afford 250 mg (45%) of the title compound T44.1.2 as a white solid, m.p. 127-1300C.
1H-NMR (CDCI3): 10.4 (s, 1 H), 8.4 (d, 1 H), 7.85 (d, 1 H), 7.75 (s, 1 H), 7.4 (dd, 1 H), 7.26 (m, 5H), 7.1 (d, 2H), 6.5 (s, 1 H), 3.5 (s, 2H), 3.35 (d, 2H), 3.07 (d, 2H), 2.1 (s, 3H)1 1.57 (s, 3H).
Example P3: Preparation of compound T9.1.1 :
Step 1 : Preparation of N-(terf-butyloxycarbonyl)-3-thietanamine:
Figure imgf000050_0001
A solution of N-(terf-butyloxycarbonyl)-2-amino-1 ,3-propanediol dimesylate [prepared according to E. Benoist et al., Synthesis 1998, (8), 1 1 13-1 118] (25 g, 72.0 mmol) in ethanol (375 ml) is treated with sodium sulfide (Na2S^xH2O 32-38%, 16.82 g, -75.4 mmol) and the mixture is stirred at a temperature of 500C (bath 600C) for 45 minutes. The cooled reaction mixture is concentrated under reduced pressure and the solid residue poured into water, extracted with Et2O, the combined organic layers washed with brine, dried (Na2SO4), filtered, and concentrated. The crude solid product (12.6 g, 92%) is used in the next step without further purification.
Step 2: Preparation of 3-thietanamine hydrobromide salt:
Figure imgf000050_0002
A 5.7M solution of HBr in acetic acid (1 1.0 ml, 62.7 mmol) is added dropewise to a solution of N-(tert-butyloxycarbonyl)-3-thietanamine [the product of step 1 ] (9.17 g, 48.5 mmol) in diethyl ether (250 ml) cooled at -200C and the mixture is stirred at -200C for 10 minutes. The cooling bath is removed and the reaction stirred for 3 hours at ambient temperature. The resulting white suspension is filtered and the residue washed with diethyl ether yielding a first crop of product (6.0 g). The ether filtrate is concentrated and the residue resubjected to the same reaction conditions and workup giving another 1.3 g of product. The crude solid product (7.3 g, 89%) with a melting point of 186-190°C is used in the next step without further purification.
1H-NMR (d6-DMSO): 8.23 (br s, 3H), 4.52 (m, 1 H), 3.47 (m, 2H)1 3.18 (m, 2H).
Step 3: Preparation of 2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carboxylic acid ^-chloro^-methyl-e-Cthietan-S-ylcarbamoylJ-phenylJ-amide:
Figure imgf000051_0001
To a solution of 6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1 H-pyrazol-5-yl]-8- methyl-4H-3,1 -benzoxazin-4-one (500 mg, 1.13 mmol) [prepared according to WO 02/48115, example 2D] in tetrahydrofuran (10 ml) is added triethylamine (0.4 ml, 2.87 mmol) and 3-thietanamine hydrobromide salt [the product of step 2] (250 mg, 1.47 mmol), and the mixture is heated to reflux overnight. The cooled reaction mixture is poured into water, extracted with ethyl acetate, the combined organic layers washed with water and brine, dried (Na2SO4), filtered, and concentrated. The crude product is purified by flash chromatography (ethyl acetate/hexane 1 :2) to afford 250 mg (41 %) of the title compound as a white solid. 1H-NMR (CDCI3): 9.94 (s, 1 H), 8.48 (d, 1 H), 7.88 (d, 1 H), 7.42 (dd, 1 H)1 7.29 (s, 2H), 7.24 (s, 1 H), 6.53 (d, 1 H), 5.31 (m, 1 H), 3.41 (m, 2H), 3.33 (m, 2H), 2.18 (s, 3H); MS (electrospray ES+): 530, 532 (M+H)+.
Step 4: Preparation of compound T9.1.1 (2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H- pyrazole-3-carboxylic acid [4-chloro-2-methyl-6-(1 -oxo-1 λ4-thietan-3-ylcarbamoyl)-phenyl]-
amide):
Figure imgf000052_0001
To a solution of 2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carboxylic acid [4- chloro-2-methyl-6-(thietan-3-ylcarbamoyl)-phenyl]-amide [the product of step 3] (200 mg, 0.377 mmol) in dichioromethane (10 ml) at 00C is added m-chloro-perbenzoic acid (93 mg, 0. 377 mmol) in dichioromethane (2 ml) dropewise. Another 10 mg of m-chloro-perbenzoic acid is needed to complete the reaction after stirring at 00C for 40 minutes. The reaction mixture is treated with NaHCO3 aq. sat. and extracted with dichioromethane, the combined organic layer washed with brine, dried (Na2SO4), filtered, and concentrated. The crude product is purified by flash chromatography (ethyl acetate) to afford 50 mg (24%) of the title compound T9.1.1 as a white solid, m.p. 241 -244°C (major diastereomer called T9.1.1 diastereomer A).
1H-NMR (de-DMSO): 10.38 (s, 1 H), 8.91 (d, 1 H)1 8.54 (d, 1 H), 8.23 (d, 1 H), 7.75 (s, 1 H), 7.67 (dd, 1 H), 7.52 (s, 1 H), 7.42 (s, 1 H), 4.22 (m, 1 H), 3.95 (m, 2H), 3.16 (m, 2H), 2.20 (s, 3H); MS (electrospray ES+): 546, 548 (M+H)+.
Example P4: Preparation of compound T13.1.22:
Step 1 : Preparation of 1 ,1 -dioxo-3-methyl-3-thietanamine trifluoroacetic acid salt:
Figure imgf000052_0002
A solution of N-(fert-butyloxycarbonyl)-1 ,1 -dioxo-3-methyl-3-thietanamine [prepared in analogy to Example P3, step 1 and Example P1 , step 5 ] (1 .7 g, 7.2 mmol) in dichioromethane (20 ml) at 00C is treated with trifluoroacetic acid (13 ml) and the reaction mixture stirred overnight at ambient temperature. The mixture is concentrated under reduced pressure, the solid residue suspended in diethyl ether, stirred, filtered and dried. The crude solid product (1.4 g, 78%) with a melting point of 208-2100C is used in the next step without further purification. 1H-NMR Cd6-DMSO): 8.82 (br s, 3H), 4.56 (d, 2H), 4.29 (d, 2H), 1.68 (s, 3H).
Step 2: Preparation of 5-chloro-3-methyl-2-sulfinylaminobenzoyl chloride
Figure imgf000053_0001
In analogy to J. Garin et al., Tetrahedron Lett. 1991 , 32, 3263-3264:
To a suspension of 2-amino-5-chloro-3-methyl-benzoic acid (18.5 g, 100 mmol) in toluene
(200 ml) is added thionyl chloride (36 ml, 500 mmol) and the mixture is heated to reflux and stirred at that temperature until the rapid gas evolution slowed down. The resulting solution is concentrated under reduced pressure to give a solid residue which is dried under high vacuum. The crude solid product (23.7 g, 95%) is used in the next step without further purification.
1H-NMR (CDCI3): 8.07 (d, 1 H), 7.56 (d, 1 H), 2.30 (s, 3H).
Step 3: Preparation of 2-amino-5-chloro-3-methyl-N-(3-methyl-1 ,1 -dioxo-1 λ -thietan-3-yl)- benzamide
Figure imgf000053_0002
To a solution of 1 ,1 -dioxo-3-methyl-3-thietanamine trifluoroacetic acid salt [the product of step 1] (598 mg, 2.40 mmol) and triethylamine (0.836 ml, 6.00 mmol) in tetrahydrofuran (6 ml) cooled at 0-50C is added a solution of 5-chloro-3-methyl-2-sulfinylaminobenzoyl chloride [the product of step 2] (600 mg, 2.4 mmol) in tetrahydrofuran (4 ml). The reaction mixture is stirred at room temperature overnight, and then poured into water. After extraction with ethyl acetate, the combined organic layers are washed with brine, dried (Na2SO4), filtered and concentrated. The crude product is purified by column chromatography on silica gel (ethyl acetate/hexane 1 :4) to afford the title benzamide [compound D54 from Table D] (410 mg, 56%) as a white solid with a melting point of 79-82°C.
1H-NMR (CDCI3): 7.20 (s, 1 H), 7.12 (s, 1 H), 6.52 (s, 1 H), 5.58 (br s, 2H), 4.64 (d, 2H), 4.15 (d, 2H), 2.13 (s, 3H), 1.87 (s, 3H); MS (electrospray ES+): 303, 305 ((M+H)+).
Step 4: Preparation of compound T13.1.22 (2-(3-chloro-pyrιdιn-2-yl)-5-(2,2,2-trιfluoro- eetthhooxxyy))--22HH--ppyyrraazzoollee--33--ccaarrbbooxxyylic acid [4-chloro-2-methyl-6-(3-methyl-1 ,1 -dιoxo-1 λ6-thιetan-
3-ylcarbamoyl)-phenyl]-amιde)
Figure imgf000054_0001
To a solution of 2-amιno-5-chloro-3-methyl-N-(3-methyl-1 ,1 -dioxo-1 λ6-thιetan-3-yl)- benzamide [the product of step 3] (340 mg, 1.12 mmol) in tetrahydrofuran (6 ml) cooled at 0- 5°C is added a solution of 2-(3-chloro-pyrιdιn-2-yl)- 5-(2,2,2-tπfluoro-ethoxy)-2H-pyrazole-3- carbonyl chloride (1.12 mmol, 1 eq.) in tetrahydrofuran (4 ml) The reaction mixture is stirred at room temperature overnight, and the solvent evaporated in vacuo. The crude product is purified by column chromatography on silica gel (gradient ethyl acetate/hexane 1 :4->1 :1 ) to afford the title bisamide compound T13.1 22 (279 mg, 41 %) as a white solid with a melting point >250°C.
1H-NMR (CDCI3): 10.05 (s, 1 H), 8.83 (s, 1 H), 8.45 (d, 1 H), 7.85 (d, 1 H), 7.42 (s, 1 H), 7.38 (dd, 1 H), 7.29 (s, 1 H), 6.67 (s, 1 H), 4.69 (q, 2H), 4.54 (d, 2H), 4.08 (d, 2H), 2.22 (s, 3H), 1 .76 (s, 3H); MS (electrospray ES+): 606, 608 ((M+H)+). Example P5: Preparation of compound D14 from Table D: (2-amino-5-chloro-3-methyl-N- (3-methyl-thietan-3-yl)-benzamide)
Figure imgf000055_0001
This benzamide is prepared in analogy to Example P4, step 3 from the starting materials
Example P4, step 2 and Example P1 , step 3 giving a white solid with a melting point of 92-
94°C.
1H-NMR (CDCI3): 7.14 (s, 1 H), 7.10 (s, 1 H), 6.09 (s, 1 H), 5.57 (br s, 2H), 3.90 (d, 2H), 3.03
(d, 2H), 2.14 (s, 3H), 1.83 (s, 3H); MS (electrospray ES+): 271 , 273 ((M+H)+).
Example P6: Preparation of compound C13 from Table C: (2,2-dimethyl-thietan-3-ylamine)
Figure imgf000055_0002
C13 from Table C
To a solution of 2,2-dimethyl-thietan-3-one [prepared according to W. Luettke et al., Chemische Berichte 1977, 110, 1421 -31] (8.9 g, 76.6 mmol) in methanol (200 ml) is added ammonium acetate (59 g, 765 mmol) and sodium cyanoborohydride (7.8 g, 118.7 mmol) and the reaction mixture is heated to reflux for 2 hours. The cooled reaction mixture is flushed with nitrogen, acidified to pH 2 with concentrated hydrochloric acid (maintaining the temperature under 100C), and concentrated under reduced pressure. The residue is poured into water, extracted with diethyl ether (2x), the pH of the aqueous phase adjusted to pH 11 with 30% sodium hydroxide and the product extracted with diethyl ether. The combined organic layers are washed with brine, dried (Na2SO4), filtered and concentrated. The crude oily product (1.47 g, 16%) is used without further purification.
1H-NMR (CDCI3): 3.83 (dd, 1 H), 3.19 (t, 1 H), 2.95 (t, 1 H), 1.63 (br S, 2H), 1 .50 (s, 3H), 1.42 (s, 3H). The compounds listed in the following Table P can be prepared analogous to the procedures described above (m.p. = melting point in 0C).
Table P: Compounds of formula I:
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
The examples which follow are intended to illustrate the invention and show further preferred compounds of formula I. They do not limit the invention. "Me" is the methyl group.
Table A: Substituent designations for Tables 1 to 44:
Figure imgf000063_0002
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0002
Table 1 : This table discloses the 465 compounds T1.1.1 to T1.1.465 of the formula
Figure imgf000084_0001
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A. For example, the specific compound T1.1.23 is the compound of the formula T1 , in which each of the of the variables R91, R92, R93 and R35 has the specific meaning given in the line A.1.23 of the Table A. According to the same system, also all of the other 359 specific compounds disclosed in the Table 1 as well as all of the specific compounds disclosed in the Tables 2 to 44 are specified analogously.
Table 2: This table discloses the 465 compounds T2.1.1 to T2.1.465 of the formula
Figure imgf000085_0001
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 3: This table discloses the 465 compounds T3.1.1 to T3.1.465 of the formula
Figure imgf000085_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 4: This table discloses the 465 compounds T4.1.1 to T4.1.465 of the formula
Figure imgf000086_0001
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 5: This table discloses the 465 compounds T5.1.1 to T5.1 .465 of the formula
Figure imgf000086_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1 .465, of the Table A.
Table 6: This table discloses the 465 compounds T6.1.1 to T6.1.465 of the formula
Figure imgf000086_0003
in which, for each of these 465 specific compounds, each of the variables Rcn, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 7: This table discloses the 465 compounds T7.1.1 to T7.1.465 of the formula
Figure imgf000087_0001
in which, for each of these 465 specific compounds, each of the variables R91, Rg2, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 8: This table discloses the 465 compounds T8.1.1 to T8.1.465 of the formula
Figure imgf000087_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 9: This table discloses the 465 compounds T9.1.1 to T9.1.465 of the formula
Figure imgf000088_0001
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 10: This table discloses the 465 compounds T10.1.1 to T10.1.465 of the formula
Figure imgf000088_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 11 : This table discloses the 465 compounds T11.1.1 to T11.1.465 of the formula
Figure imgf000089_0001
in which, for each of these 465 specific compounds, each of the variables R91, Rg2, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 12: This table discloses the 465 compounds T12.1.1 to T12.1.465 of the formula
Figure imgf000089_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 13: This table discloses the 465 compounds T13.1.1 to T13.1.465 of the formula
Figure imgf000090_0001
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 14: This table discloses the 465 compounds T14.1.1 to T14.1.465 of the formula
Figure imgf000090_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 15: This table discloses the 465 compounds T15.1.1 to T15.1.465 of the formula
Figure imgf000091_0001
in which, for each of these 465 specific compounds, each of the variables R91, R92, Rg3 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 16: This table discloses the 465 compounds T16.1.1 to T16.1.465 of the formula
Figure imgf000091_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 17: This table discloses the 465 compounds T17.1.1 to T17.1.465 of the formula
Figure imgf000092_0001
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 18: This table discloses the 465 compounds T18.1.1 to T18.1.465 of the formula
Figure imgf000092_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 19: This table discloses the 465 compounds T19.1.1 to T19.1.465 of the formula
Figure imgf000093_0001
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 20: This table discloses the 465 compounds T20.1.1 to T20.1.465 of the formula
Figure imgf000093_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 21 : This table discloses the 465 compounds T21.1.1 to T21.1.465 of the formula
Figure imgf000094_0001
in which, for each of these 465 specific compounds, each of the variables R91 , R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1 .1 to A.1 .465, of the Table A.
Table 22: This table discloses the 465 compounds T22.1 .1 to T22.1.465 of the formula
Figure imgf000094_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1 .1 to A.1 .465, of the Table A.
Table 23: This table discloses the 465 compounds T23.1 .1 to T23.1 .465 of the formula
Figure imgf000095_0001
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 24: This table discloses the 465 compounds T24.1.1 to T24.1.465 of the formula
Figure imgf000095_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 25: This table discloses the 465 compounds T25.1.1 to T25.1.465 of the formula
Figure imgf000096_0001
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 26: This table discloses the 465 compounds T26.1.1 to T26.1.465 of the formula
Figure imgf000096_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1 .465, of the Table A.
Table 27: This table discloses the 465 compounds T27.1.1 to T27.1.465 of the formula
Figure imgf000097_0001
in which, for each of these 465 specific compounds, each of the variables R9i, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 28: This table discloses the 465 compounds T28.1.1 to T28.1.465 of the formula
Figure imgf000097_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 29: This table discloses the 465 compounds T29.1.1 to T29.1.465 of the formula
Figure imgf000098_0001
in which, for each of these 465 specific compounds, each of the variables R91, Rg2, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 30: This table discloses the 465 compounds T30.1.1 to T30.1.465 of the formula
Figure imgf000098_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1 .465, of the Table A.
Table 31 : This table discloses the 465 compounds T31 .1.1 to T31.1.465 of the formula
Figure imgf000099_0001
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 32: This table discloses the 465 compounds T32.1.1 to T32.1.465 of the formula
Figure imgf000099_0002
in which, for each of these 465 specific compounds, each of the variables R91, Rg2, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 33: This table discloses the 465 compounds T33.1.1 to T33.1.465 of the formula
Figure imgf000100_0001
in which, for each of these 465 specific compounds, each of the variables R91, R92, Rg3 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 34: This table discloses the 465 compounds T34.1.1 to T34.1.465 of the formula
Figure imgf000100_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1 .465, of the Table A.
Table 35: This table discloses the 465 compounds T35.1.1 to T35.1 .465 of the formula
Figure imgf000101_0001
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 36: This table discloses the 465 compounds T36.1.1 to T36.1.465 of the formula
Figure imgf000101_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 37: This table discloses the 465 compounds T37.1 .1 to T37.1.465 of the formula
Figure imgf000102_0001
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 38: This table discloses the 465 compounds T38.1.1 to T38.1.465 of the formula
Figure imgf000102_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 39: This table discloses the 465 compounds T39.1.1 to T39.1.465 of the formula
Figure imgf000103_0001
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 40: This table discloses the 465 compounds T40.1.1 to T40.1.465 of the formula
Figure imgf000103_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 41 : This table discloses the 465 compounds T41.1.1 to T41.1.465 of the formula
Figure imgf000104_0001
in which, for each of these 465 specific compounds, each of the variables R9i, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 42: This table discloses the 465 compounds T42.1.1 to T42.1.465 of the formula
Figure imgf000104_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 43: This table discloses the 465 compounds T43.1.1 to T43.1 .465 of the formula
Figure imgf000105_0001
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Table 44: This table discloses the 465 compounds T44.1.1 to T44.1.465 of the formula
Figure imgf000105_0002
in which, for each of these 465 specific compounds, each of the variables R91, R92, R93 and R35 has the specific meaning given in the corresponding line, appropriately selected from the 465 lines A.1.1 to A.1.465, of the Table A.
Formulation examples (% = percent by weight)
Example F1 : Emulsion concentrates a) b) c)
Active ingredient 25 % 40 % 50 %
Calcium dodecylbenzenesulfonate 5 % 8 % 6 %
Castor oil polyethylene glycol ether (36 mol of EO) 5 % - -
Tributylphenoxypolyethylene glycol ether (30 mol of EO) - 12 % 4 %
Cyclohexanone 15 % 20 % Xylene mixture 65 % 25 % 20 %
Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
Example F2: Solutions a) b) c) d)
Active ingredient 80 % 10 % 5 % 95 % Ό
Ethylene glycol monomethyl ether 20 %
Polyethylene glycol MW 400 - 70 %
N-Methylpyrrolid-2-one - 20 %
Epoxidized coconut oil - - 1 % 5 % ■o
Petroleum ether (boiling range: 160-190°) - - 94 %
The solutions are suitable for use in the form of microdrops.
Example F3: Granules a) b) c) d)
Active ingredient 5 % 10 % 8 % 21 %
Kaolin 94 % - 79 % 54 " %
Highly disperse silica 1 % - 13 % 7 7c
Attapulgite 90 % 18 ' Vo
The active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier(s), and the solvent is subsequently evaporated in vacuo.
Example F4: Dusts a) b) Active ingredient 2 % 5 % Highly disperse silica 1 % 5 % Talc 97 % - Kaolin 90 %
Ready-to-use dusts are obtained by intimately mixing the carriers and the active ingredient.
Example F5: Wettable powders a) b) c)
Active ingredient 25 % 50 % 75 % Sodium lignosulfonate 5% 5% -
Sodium lauryl sulfate 3% - 5%
Sodium diisobutylnaphthalenesulfonate - 6% 10%
Octylphenoxypolyethylene glycol ether (7-8 mol of EO) 2% _
Highly disperse silica 5% 10% 10%
Kaolin 62% 27%
The active ingredient is mixed with the additives and the mixture is ground thoroughly in a suitable mill. This gives wettable powders, which can be diluted with water to give suspensions of any desired concentration.
Example F6: Extruder granules
Active ingredient 10 %
Sodium lignosulfonate 2 %
Carboxymethylcellulose 1 %
Kaolin 87 %
The active ingredient is mixed with the additives, and the mixture is ground, moistened with water, extruded, granulated and dried in a stream of air.
Example F7: Coated granules
Active ingredient 3 %
Polyethylene glycol (MW 200) 3 %
Kaolin 94 %
In a mixer, the finely ground active ingredient is applied uniformly to the kaolin, which has been moistened with the polyethylene glycol. This gives dust-free coated granules.
Example F8: Suspension concentrate
Active ingredient 40 % Ό
Ethylene glycol 10 % Ό
Nonylphenoxypolyethylene glycol ether (15 mol of EO) 6 %
Sodium lignosulfonate 10 % o
Carboxymethylcellulose 1 % O 37 % aqueous formaldehyde solution 0.2 %
Silicone oil (75 % aqueous emulsion) 0.8 %
Water 32 %
The finely ground active ingredient is mixed intimately with the additives. Suspensions of any desired concentration can be prepared from the thus resulting suspension concentrate by dilution with water.
The activity of the compounds according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally or acaricidally active ingredients. Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridyl- methyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
The following mixtures of the compounds of formula I with active ingredients are preferred (the abbreviation "TX" means: "one compound selected from the group consisting of the compounds specifically described in tables T1 to T44 of the present invention"):
an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX, an acaricide selected from the group of substances consisting of 1 ,1 -bis(4-chloro- phenyl)-2-ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate (lUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro-Λ/-methyl-Λ/-1 -naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981 ) + TX, abamectin (1 ) + TX, acequinocyl (3) + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidithion (870) + TX, amidoflumet [CCN] + TX, amidothioate (872) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, aramite (881 ) + TX, arsenous oxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (IUPAC name) (888) + TX, azocyclotin (46) + TX, azothoate (889) + TX, benomyl (62) + TX, benoxafos (alternative name) [CCN] + TX, benzoximate (71 ) + TX, benzyl benzoate (IUPAC name) [CCN] + TX, bifenazate (74) + TX, bifenthrin (76) + TX, binapacryl (907) + TX1 brofenvalerate (alternative name) + TX, bromocyclen (918) + TX, bromophos (920) + TX, bromophos-ethyl (921 ) + TX, bromopropylate (94) + TX, buprofezin (99) + TX, butocarboxim (103) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, calcium polysulfide (IUPAC name) (1 11 ) + TX, camphechlor (941 ) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbof uran (1 18) + TX, carbophenothion (947) + TX, CGA 50'439 (development code) (125) + TX, chinomethionat (126) + TX, chlorbenside (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorfenethol (968) + TX, chlorfenson (970) + TX, chlorfensulphide (971 ) + TX, chlorfenvinphos (131 ) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, cinerin I (696) + TX, cinerin Il (696) + TX, cinerins (696) + TX, clofentezine (158) + TX, closantel (alternative name) [CCN] + TX, coumaphos (174) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, cufraneb (1013) + TX, cyanthoate (1020) + TX, cyflumetofen (CAS Reg. No.: 400882-07-7) + TX, cyhalothrin (196) + TX, cyhexatin (199) + TX, cypermethrin (201 ) + TX, DCPM (1032) + TX, DDT (219) + TX, demephion (1037) + TX, demephion-O (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton-S- methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diazinon (227) + TX, dichlofluanid (230) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicofol (242) + TX, dicrotophos (243) + TX, dienochlor (1071 ) + TX, dimefox (1081 ) + TX, dimethoate (262) + TX, dinactin (alternative name) (653) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinobuton (269) + TX, dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinocton (1090) + TX, dinopenton (1092) + TX, dinosulfon (1097) + TX, dinoterbon (1098) + TX, dioxathion (1102) + TX, diphenyl sulfone (IUPAC name) (1103) + TX, disulfiram (alternative name) [CCN] + TX, disulfoton (278) + TX, DNOC (282) + TX, dofenapyn (1 1 13) + TX, doramectin (alternative name) [CCN] + TX, endosulfan (294) + TX, endothion (1121 ) + TX1 EPN (297) + TX, eprinomectin (alternative name) [CCN] + TX, ethion (309) + TX, ethoate-methyl (1134) + TX, etoxazole (320) + TX, etrimfos (1 142) + TX, fenazaflor (1147) + TX, fenazaquin (328) + TX, fenbutatin oxide (330) + TX, fenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fenpyroximate (345) + TX, fenson (1 157) + TX, fentrifanil (1161 ) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacrypyrim (360) + TX, fluazuron (1 166) + TX, flubenzimine (1 167) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1 169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1 174) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1 185) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1192) + TX, formparanate (1 193) + TX, gamma-HCH (430) + TX, glyodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecyl cyclopropanecarboxylate (lUPAC/Chemical Abstracts name) (1216) + TX, hexythiazox (441 ) + TX, iodomethane (IUPAC name) (542) + TX, isocarbophos (alternative name) (473) + TX, isopropyl O- (methoxyaminothiophosphoryl)salicylate (IUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin Il (696) + TX, jodfenphos (1248) + TX, lindane (430) + TX, lufenuron (490) + TX, malathion (492) + TX, malonoben (1254) + TX, mecarbam (502) + TX, mephosfolan (1261 ) + TX, mesulfen (alternative name) [CCN] + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methidathion (529) + TX, methiocarb (530) + TX, methomyl (531 ) + TX, methyl bromide (537) + TX, metolcarb (550) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561 ) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naled (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, nifluridide (1309) + TX, nikkomycins (alternative name) [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb 1 :1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, phenkapton (1330) + TX, phenthoate (631 ) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosphamidon (639) + TX, phoxim (642) + TX, pirimiphos-methyl (652) + TX, polychloroterpenes (traditional name) (1347) + TX, polynactins (alternative name) (653) + TX, proclonol (1350) + TX, profenofos (662) + TX, promacyl (1354) + TX, propargite (671 ) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin Il (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridaphenthion (701 ) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinalphos (71 1 ) + TX, quintiofos (1381 ) + TX, R-1492 (development code) (1382) + TX, RA-17 (development code) (1383) + TX, rotenone (722) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, sophamide (1402) + TX, spirodiclofen (738) + TX, spiromesifen (739) + TX, SSI-121 (development code) (1404) + TX, sulfiram (alternative name) [CCN] + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulfur (754) + TX, SZI-121 (development code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbam (alternative name) + TX, tetrachlorvinphos (777) + TX, tetradifon (786) + TX, tetranectin (alternative name) (653) + TX, tetrasul (1425) + TX, thiafenox (alternative name) + TX, thiocarboxime (1431) + TX, thiofanox (800) + TX, thiometon (801 ) + TX, thioquinox (1436) + TX, thuringiensin (alternative name) [CCN] + TX, triamiphos (1441 ) + TX, triarathene (1443) + TX, triazophos (820) + TX1 triazuron (alternative name) + TX, trichlorfon (824) + TX, trifenofos (1455) + TX, trinactin (alternative name) (653) + TX, vamidothion (847) + TX, vaniliprole [CCN] and YI-5302 (compound code) + TX, an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, an anthelmintic selected from the group of substances consisting of abamectin (1 ) + TX, crufomate (1011 ) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX, an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX, a bactericide selected from the group of substances consisting of 1 -hydroxy-1 H- pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicin (1 1 12) + TX, fenaminosulf (1 144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (61 1 ) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal (alternative name) [CCN] + TX, a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51 ) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla carnea (alternative name) (151 ) + TX, Cryptolaemus montrouzieri (alternative name) (178) + TX, Cydia pomonella GV (alternative name) (191 ) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (alternative name) (300) + TX, Helicoverpa zea NPV (alternative name) (431 ) + TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433) + TX, Hippσdamia convergens (alternative name) (442) + TX, Leptomastix dactylopii (alternative name) (488) + TX, Macrolophus caliginosus (alternative name) (491 ) + TX, Mamestra brassicae NPV (alternative name) (494) + TX, Metaphycus helvolus (alternative name) (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575) + TX, Orius spp. (alternative name) (596) + TX, Paecilomyces fumosoroseus (alternative name) (613) + TX, Phytoseiulus persimilis (alternative name) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741 ) + TX, Steinernema bibionis (alternative name) (742) + TX, Steinernema carpocapsae (alternative name) (742) + TX, Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX, a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX, a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX1 bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and uredepa (alternative name) [CCN] + TX, an insect pheromone selected from the group of substances consisting of (E)-dec-5- en-1 -yl acetate with (£)-dec-5-en-1-ol (IUPAC name) (222) + TX, (£)-tridec-4-en-1-yl acetate (IUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541 ) + TX, (E + TX, Z)-tetradeca-4 + TX, 10-dien-1 -yl acetate (IUPAC name) (779) + TX, (Z)-dodec- 7-en-1-yl acetate (IUPAC name) (285) + TX, (Z)-hexadec-11 -enal (IUPAC name) (436) + TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name) (437) + TX, (Z)-hexadec-13-en-11-yn- 1 -yl acetate (IUPAC name) (438) + TX, (Z)-icos-13-en-10-one (IUPAC name) (448) + TX, (Z)-tetradec-7-en-1 -al (IUPAC name) (782) + TX, (Z)-tetradec-9-en-1 -ol (IUPAC name) (783) + TX, (Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784) + TX, (7E+ TX, 9Z)- dodeca-7 + TX, 9-dien-1-yl acetate (IUPAC name) (283) + TX, (9Z+ TX, 11 £)-tetradeca-9 + TX, 11 -dien-1 -yl acetate (IUPAC name) (780) + TX, (9Z + TX, 12£)-tetradeca-9 + TX, 12-dien-1 -yl acetate (IUPAC name) (781 ) + TX, 14-methyloctadec-i -ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one (IUPAC name) (544) + TX, alpha-multistriatin (alternative name) [CCN] + TX, brevicomin (alternative name) [CCN] + TX, codlelure (alternative name) [CCN] + TX, codlemone (alternative name) (167) + TX, cuelure (alternative name) (179) + TX, disparlure (277) + TX, dodec-8-en-1-yl acetate (IUPAC name) (286) + TX, dodec-9-en-1 -yl acetate (IUPAC name) (287) + TX, dodeca-8 + TX, 10-dien-1 -yl acetate (IUPAC name) (284) + TX, dominicalure (alternative name) [CCN] + TX, ethyl 4-methyloctanoate (IUPAC name) (317) + TX, eugenol (alternative name) [CCN] + TX, frontalin (alternative name) [CCN] + TX, gossyplure (alternative name) (420) + TX, grandlure (421 ) + TX, grandlure I (alternative name) (421 ) + TX, grandlure Il (alternative name) (421 ) + TX, grandlure III (alternative name) (421 ) + TX, grandlure IV (alternative name) (421 ) + TX, hexalure [CCN] + TX, ipsdienol (alternative name) [CCN] + TX, ipsenol (alternative name) [CCN] + TX, japonilure (alternative name) (481 ) + TX, lineatin (alternative name) [CCN] + TX, litlure (alternative name) [CCN] + TX, looplure (alternative name) [CCN] + TX, medlure [CCN] + TX, megatomoic acid (alternative name) [CCN] + TX, methyl eugenol (alternative name) (540) + TX, muscalure (563) + TX, octadeca-2,13-dien-1 -yl acetate (IUPAC name) (588) + TX, octadeca-3,13-dien-1 -yl acetate (IUPAC name) (589) + TX, orfralure (alternative name) [CCN] + TX, oryctalure (alternative name) (317) + TX, ostramone (alternative name) [CCN] + TX, siglure [CCN] + TX, sordidin (alternative name) (736) + TX, sulcatol (alternative name) [CCN] + TX, tetradec- 1 1 -en-1 -yl acetate (IUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure B1 (alternative name) (839) + TX, trimedlure B2 (alternative name) (839) + TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN] + TX, an insect repellent selected from the group of substances consisting of 2-(octylthio)- ethanol (IUPAC name) (591 ) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1 137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX, an insecticide selected from the group of substances consisting of 1 -dichloro-1 - nitroethane (lUPAC/Chemical Abstracts name) (1058) + TX, 1 ,1 -dichloro-2,2-bis(4- ethylphenyl)ethane (IUPAC name) (1056), + TX, 1 ,2-dichloropropane (lUPAC/Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (IUPAC name) (1063) + TX, 1 -bromo-2-chloroethane (lUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451 ) + TX, 2,2- dichlorovinyl 2-ethylsulfinylethyl methyl phosphate (IUPAC name) (1066) + TX, 2-(1 ,3- dithiolan-2-yl)phenyl dimethylcarbamate (IUPAC/ Chemical Abstracts name) (1 109) + TX, 2-(2-butoxyethoxy)ethyi thiocyanate (lUPAC/Chemical Abstracts name) (935) + TX, 2-(4,5- dimethyl-1 ,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/ Chemical Abstracts name) (1084) + TX1 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984) + TX, 2-imidazolidone (IUPAC name) (1225) + TX, 2-isovalerylindan-1 ,3-dione (IUPAC name) (1246) + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (IUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-1 -chloroprop-1 -ene (IUPAC name) (917) + TX, 3-methyl-1 - phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283) + TX, 4-methyl(prop-2- ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name) (1285) + TX, 5,5-dimethyl-3- oxocyclohex-1-enyl dimethylcarbamate (IUPAC name) (1085) + TX, abamectin (1 ) + TX, acephate (2) + TX, acetamiprid (4) + TX, acethion (alternative name) [CCN] + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, acrylonitrile (IUPAC name) (861 ) + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, aldrin (864) + TX, allethrin (17) + TX, allosamidin (alternative name) [CCN] + TX, allyxycarb (866) + TX, alpha-cypermethrin (202) + TX, alpha-ecdysone (alternative name) [CCN] + TX, aluminium phosphide (640) + TX, amidithion (870) + TX, amidothioate (872) + TX, aminocarb (873) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, anabasine (877) + TX, athidathion (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (alternative name) (41 ) + TX, azamethiphos (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azothoate (889) + TX, Bacillus thuringiensis delta endotoxins (alternative name) (52) + TX, barium hexafluorosilicate (alternative name) [CCN] + TX, barium polysulfide (lUPAC/Chemical Abstracts name) (892) + TX, barthrin [CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bendiocarb (58) + TX, benfuracarb (60) + TX, bensultap (66) + TX, beta-cyfluthrin (194) + TX, beta- cypermethrin (203) + TX, bifenthrin (76) + TX, bioallethrin (78) + TX, bioallethrin S- cyclopentenyl isomer (alternative name) (79) + TX, bioethanomethrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX, bis(2-chloroethyl) ether (IUPAC name) (909) + TX, bistrifluron (83) + TX, borax (86) + TX, brofenvalerate (alternative name) + TX, bromfenvinfos (914) + TX, bromocyclen (918) + TX, bromo-DDT (alternative name) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921 ) + TX, bufencarb (924) + TX, buprofezin (99) + TX, butacarb (926) + TX, butathiofos (927) + TX, butocarboxim (103) + TX, butonate (932) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (IUPAC name) (11 1 ) + TX, camphechlor (941 ) + TX, carbanolate (943) + TX, carbaryl (1 15) + TX, carbof uran (1 18) + TX, carbon disulfide (lUPAC/Chemical Abstracts name) (945) + TX, carbon tetrachloride (IUPAC name) (946) + TX, carbophenothion (947) + TX, carbosulfan (119) + TX, cartap (123) + TX, cartap hydrochloride (123) + TX, cevadine (alternative name) (725) + TX, chlorbicyclen (960) + TX, chlordane (128) + TX, chlordecone (963) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorethoxyfos (129) + TX, chlorfenapyr (130) + TX, chlorfenvinphos (131 ) + TX, chlorfluazuron (132) + TX, chlormephos (136) + TX, chloroform [CCN] + TX, chloropicrin (141 ) + TX, chlorphoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin Il (696) + TX, cinerins (696) + TX, cis-resmethrin (alternative name) + TX, cismethrin (80) + TX, clocythrin (alternative name) + TX, cloethocarb (999) + TX, closantel (alternative name) [CCN] + TX, clothianidin (165) + TX, copper acetoarsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, coumithoate (1006) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, crufomate (1011 ) + TX, cryolite (alternative name) (177) + TX, CS 708 (development code) (1012) + TX, cyanofenphos (1019) + TX, cyanophos (184) + TX, cyanthoate (1020) + TX, cyclethrin [CCN] + TX, cycloprothrin (188) + TX, cyf luthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201 ) + TX, cyphenothrin (206) + TX, cyromazine (209) + TX, cythioate (alternative name) [CCN] + TX, d-limonene (alternative name) [CCN] + TX, d-tetramethrin (alternative name) (788) + TX, DAEP (1031 ) + TX, dazomet (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, deltamethrin (223) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton- methyl (224) + TX, demeton-O (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton-S-methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diamidafos (1044) + TX, diazinon (227) + TX, dicapthon (1050) + TX, dichlofenthion (1051 ) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicresyl (alternative name) [CCN] + TX, dicrotophos (243) + TX, dicyclanil (244) + TX, dieldrin (1070) + TX, diethyl 5-methylpyrazol-3-yl phosphate (IUPAC name) (1076) + TX, diflubenzuron (250) + TX, dilor (alternative name) [CCN] + TX, dimef luthrin [CCN] + TX, dimefox (1081 ) + TX, dimetan (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinphos (265) + TX, dimetilan (1086) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinoprop (1093) + TX, dinosam (1094) + TX, dinoseb (1095) + TX, dinotefuran (271 ) + TX, diofenolan (1099) + TX, dioxabenzofos (1100) + TX, dioxacarb (1101 ) + TX, dioxathion (1 102) + TX, disulfoton (278) + TX1 dithicrofos (1 108) + TX, DNOC (282) + TX, doramectin (alternative name) [CCN] + TX, DSP (1 115) + TX, ecdysterone (alternative name) [CCN] + TX, El 1642 (development code) (1 118) + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, EMPC (1120) + TX, empenthrin (292) + TX, endosulfan (294) + TX, endothion (1121 ) + TX, endrin (1122) + TX1 EPBP (1 123) + TX, EPN (297) + TX, epofenonane (1124) + TX, eprinomectin (alternative name) [CCN] + TX, esfenvalerate (302) + TX, etaphos (alternative name) [CCN] + TX, ethiofencarb (308) + TX1 ethion (309) + TX, ethiprole (310) + TX, ethoate-methyl (1134) + TX, ethoprophos (312) + TX, ethyl formate (IUPAC name) [CCN] + TX, ethyl-DDD (alternative name) (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1136) + TX1 ethylene oxide [CCN] + TX, etofenprox (319) + TX, etrimfos (1 142) + TX, EXD (1143) + TX, famphur (323) + TX, fenamiphos (326) + TX, fenazaflor (1147) + TX, fenchlorphos (1148) + TX, fenethacarb (1149) + TX, fenfluthrin (1150) + TX, fenitrothion (335) + TX, fenobucarb (336) + TX, fenoxacrim (1153) + TX, fenoxycarb (340) + TX, fenpirithrin (1155) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fensulfothion (1158) + TX, fenthion (346) + TX, fenthion-ethyl [CCN] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonicamid (358) + TX, flubendiamide (CAS. Reg. No.: 272451 -65-7) + TX, f lucofuron (1168) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1 169) + TX, flufenerim [CCN] + TX, flufenoxuron (370) + TX, flufenprox (1 171 ) + TX, flumethrin (372) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, fonofos (1191 ) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1 192) + TX, formparanate (1193) + TX, fosmethilan (1194) + TX, fospirate (1 195) + TX, fosthiazate (408) + TX, fosthietan (1196) + TX1 furathiocarb (412) + TX, furethrin (1200) + TX, gamma-cyhalothrin (197) + TX, gamma-HCH (430) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, GY-81 (development code) (423) + TX, halfenprox (424) + TX, halofenozide (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptachlor (1211 ) + TX, heptenophos (432) + TX, heterophos [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydramethylnon (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX, hyquincarb (1223) + TX, imidacloprid (458) + TX, imiprothrin (460) + TX, indoxacarb (465) + TX, iodomethane (IUPAC name) (542) + TX, IPSP (1229) + TX, isazofos (1231 ) + TX, isobenzan (1232) + TX, isocarbophos (alternative name) (473) + TX, isodrin (1235) + TX, isofenphos (1236) + TX, isolane (1237) + TX, isoprocarb (472) + TX, isopropyl O(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxathion (480) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin Il (696) + TX, jodfenphos (1248) + TX, juvenile hormone I (alternative name) [CCN] + TX, juvenile hormone Il (alternative name) [CCN] + TX, juvenile hormone III (alternative name) [CCN] + TX, kelevan (1249) + TX, kinoprene (484) + TX, lambda-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin (CCN) + TX, leptophos (1250) + TX, lindane (430) + TX, lirimfos (1251 ) + TX, lufenuron (490) + TX, lythidathion (1253) + TX, m-cumenyl methylcarbamate (IUPAC name) (1014) + TX, magnesium phosphide (IUPAC name) (640) + TX, malathion (492) + TX, malonoben (1254) + TX, mazidox (1255) + TX, mecarbam (502) + TX, mecarphon (1258) + TX, menazon (1260) + TX, mephosfolan (1261 ) + TX, mercurous chloride (513) + TX, mesulfenfos (1263) + TX, metaflumizone (CCN) + TX, metam (519) + TX, metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methanesulfonyl fluoride (lUPAC/Chemical Abstracts name) (1268) + TX, methidathion (529) + TX, methiocarb (530) + TX, methocrotophos (1273) + TX, methomyl (531 ) + TX, methoprene (532) + TX, methoquin-butyl (1276) + TX, methothrin (alternative name) (533) + TX, methoxychlor (534) + TX, methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methylchloroform (alternative name) [CCN] + TX, methylene chloride [CCN] + TX, metofluthrin [CCN] + TX, metolcarb (550) + TX, metoxadiazone (1288) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561 ) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naftalofos (alternative name) [CCN] + TX, naled (567) + TX, naphthalene (lUPAC/Chemical Abstracts name) (1303) + TX, NC-170 (development code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifluridide (1309) + TX, nitenpyram (579) + TX, nithiazine (131 1 ) + TX, nitrilacarb (1313) + TX, nitrilacarb 1 :1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nomicotine (traditional name) (1319) + TX, novaluron (585) + TX, noviflumuron (586) + TX, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate (IUPAC name) (1057) + TX, O,O-diethyl O-4-methyl-2-oxo-2H- chromen-7-yl phosphorothioate (IUPAC name) (1074) + TX, O,O-diethyl O-6-methyl-2- propylpyrimidin-4-yl phosphorothioate (IUPAC name) (1075) + TX, O^CCMetrapropyl dithiopyrophosphate (IUPAC name) (1424) + TX, oleic acid (IUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydemeton-methyl (609) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, para-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-methyl (616) + TX, penfluron (alternative name) [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (IUPAC name) (623) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, PH 60-38 (development code) (1328) + TX, phenkapton (1330) + TX, phenothrin (630) + TX, phenthoate (631 ) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosnichlor (1339) + TX, phosphamidon (639) + TX, phosphine (IUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, pirimetaphos (1344) + TX, pirimicarb (651 ) + TX, pirimiphos-ethyl (1345) + TX, pirimiphos-methyl (652) + TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346) + TX, polychloroterpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, prallethrin (655) + TX, precocene I (alternative name) [CCN] + TX, precocene Il (alternative name) [CCN] + TX, precocene III (alternative name) [CCN] + TX, primidophos (1349) + TX, profenofos (662) + TX, profluthrin [CCN] + TX, promacyl (1354) + TX, promecarb (1355) + TX, propaphos (1356) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothiofos (686) + TX, prothoate (1362) + TX, protrifenbute [CCN] + TX, pymetrozine (688) + TX, pyraclofos (689) + TX, pyrazophos (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin Il (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridalyl (700) + TX, pyridaphenthion (701 ) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, pyriproxyfen (708) + TX, quassia (alternative name) [CCN] + TX, quinalphos (71 1 ) + TX, quinalphos- methyl (1376) + TX, quinothion (1380) + TX, quintiofos (1381 ) + TX, R-1492 (development code) (1382) + TX, rafoxanide (alternative name) [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (development code) (723) + TX, RU 25475 (development code) (1386) + TX, ryania (alternative name) (1387) + TX, ryanodine (traditional name) (1387) + TX, sabadilla (alternative name) (725) + TX, schradan (1389) + TX, sebufos (alternative name) + TX1 selamectin (alternative name) [CCN] + TX, Sl- 0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (lUPAC/Chemical Abstracts name) (1399) + TX1 sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenoxide (623) + TX1 sodium selenate (IUPAC name) (1401 ) + TX, sodium thiocyanate [CCN] + TX, sophamide (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spirotetrmat (CCN) + TX, sulcofuron (746) + TX, sulcofuron- sodium (746) + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulfuryl fluoride (756) + TX1 sulprofos (1408) + TX, tar oils (alternative name) (758) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, tebupirimfos (764) + TX, teflubenzuron (768) + TX, tefluthrin (769) + TX, temephos (770) + TX, TEPP (1417) + TX, terallethrin (1418) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachloroethane [CCN] + TX, tetrachlorvinphos (777) + TX, tetramethrin (787) + TX, theta-cypermethrin (204) + TX, thiacloprid (791 ) + TX, thiafenox (alternative name) + TX, thiamethoxam (792) + TX, thicrofos (1428) + TX, thiocarboxime (1431 ) + TX, thiocyclam (798) + TX, thiocyclam hydrogen oxalate (798) + TX, thiodicarb (799) + TX, thiofanox (800) + TX, thiometon (801 ) + TX, thionazin (1434) + TX, thiosultap (803) + TX, thiosultap-sodium (803) + TX, thuringiensin (alternative name) [CCN] + TX, tolfenpyrad (809) + TX, tralomethrin (812) + TX, transfluthrin (813) + TX, transpermethrin (1440) + TX, triamiphos (1441 ) + TX, triazamate (818) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trichlormetaphos-3 (alternative name) [CCN] + TX, trichloronat (1452) + TX, trifenofos (1455) + TX, triflumuron (835) + TX, trimethacarb (840) + TX, triprene (1459) + TX, vamidothion (847) + TX, vaniliprole [CCN] + TX, verathdine (alternative name) (725) + TX, veratrine (alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302 (compound code) + TX, zeta-cypermethrin (205) + TX, zetamethrin (alternative name) + TX, zinc phosphide (640) + TX, zolaprofos (1469) and ZXI 8901 (development code) (858) + TX, a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, trifenmorph (1454) + TX, trimethacarb (840) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1 ,2-dibromo-3-chloropropane (lUPAC/Chemical Abstracts name) (1045) + TX, 1 ,2-dichloropropane (IUPAC/ Chemical Abstracts name) (1062) + TX, 1 ,2- dichloropropane with 1 ,3-dichloropropene (IUPAC name) (1063) + TX, 1 ,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1 ,1 -dioxide (lUPAC/Chemical Abstracts name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX1 5-methyl-6- thioxo-1.S.δ-thiadiazinan-S-ylacetic acid (IUPAC name) (1286) + TX, 6- isopentenylaminopurine (alternative name) (210) + TX, abamectin (1) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141 ) + TX, chlorpyrifos (145) + TX, cloethocarb (999) + TX, cytokinins (alternative name) (210) + TX, dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dichlofenthion (1051 ) + TX, dicliphos (alternative name) + TX, dimethoate (262) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, eprinomectin (alternative name) [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alternative name) + TX, fensulfothion (1158) + TX, fosthiazate (408) + TX, fosthietan (1 196) + TX, furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidofos (1230) + TX, isazofos (1231 ) + TX, ivermectin (alternative name) [CCN] + TX, kinetin (alternative name) (210) + TX, mecarphon (1258) + TX, metam (519) + TX1 metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, Myrothecium verrucaria composition (alternative name) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphocarb [CCN] + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachlorothiophene (IUPAC/ Chemical Abstracts name) (1422) + TX, thiafenox (alternative name) + TX, thionazin (1434) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternative name) (210) + TX, a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX, a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX, a rodenticide selected from the group of substances consisting of 2-isovalerylindan- 1 ,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891 ) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91 ) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumachlor (1004) + TX, coumafury! (1005) + TX, coumatetralyl (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, difethialone (249) + TX, diphacinone (273) + TX, ergocalciferol (301 ) + TX, flocoumafen (357) + TX, fluoroacetamide (379) + TX, flupropadine (1 183) + TX, flupropadine hydrochloride (1183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, norbormide (1318) + TX, phosacetim (1336) + TX, phosphine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341 ) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371 ) + TX, scilliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851 ) and zinc phosphide (640) + TX, a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)- ethyl piperonylate (IUPAC name) (934) + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2- enone (IUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX, an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171 ) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridine- amine (IUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX, a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX, a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX, an insecticide selected from the group consisting of the compound of formula A-1
(A-1) + TX, the formula (A-2) + TX,
Figure imgf000123_0001
Figure imgf000123_0002
the formula A-3
(A-3) + TX, the formula A-4 (A-4) + TX,
Figure imgf000123_0003
Figure imgf000123_0004
the formula A-5
(A-5) + TX, the formula A-6
Figure imgf000123_0005
Figure imgf000123_0006
the formula A-7
(A-7) + TX1 the formula A-8 (A-8) + TX,
Figure imgf000123_0007
Figure imgf000123_0008
the formula A-9
(A-9) + TX, the formula A-1 (A-IO) + TX,
Figure imgf000124_0001
Figure imgf000124_0002
the formula A-1 1
-i ) + TXj the formula A-12 (A-12) + TX,
Figure imgf000124_0003
Figure imgf000124_0004
the formula A-13
Figure imgf000124_0005
the formula A-15 (A-15) + TX, the formula A-16 (A-16) + TX,
Figure imgf000125_0002
Figure imgf000125_0001
the formula A-17
(A-17) + TX, the formula A-18 8) + TX,
Figure imgf000125_0004
Figure imgf000125_0003
the formula A-19
(A-20) + TX,
Figure imgf000125_0005
the formula A-21
(A-21 ) + TX, the formula A-22 (A-22) + TX,
Figure imgf000125_0006
Figure imgf000125_0007
the formula A-23 (A-23) + TX, the formula (A-24) + TX,
Figure imgf000126_0002
Figure imgf000126_0001
the formula A-25
(A-25) + TX, and the formula A-26 (A-26) + TX,
Figure imgf000126_0004
Figure imgf000126_0003
and biologically active compounds selected from the group consisting of Azaconazole (60207-31 -0] + TX, Bitertanol [70585-36-3] + TX, Bromuconazole [1 16255-48-2] + TX, Cyproconazole [94361-06-5] + TX, Difenoconazole [1 19446-68-3] + TX, Diniconazole [83657-24-3] + TX, Epoxiconazole [106325-08-0] + TX, Fenbuconazole [114369-43-6] + TX, Fluquinconazole [136426-54-5] + TX, Flusilazole [85509-19-9] + TX, Flutriafol [76674-21-0] + TX, Hexaconazole [79983-71 -4] + TX, Imazalil [35554-44-0] + TX, Imibenconazole [86598-92-7] + TX, Ipconazole [125225-28-7] + TX, Metconazole [125116-23-6] + TX, Myclobutanil [88671 -89-0] + TX, Pefurazoate [101903-30-4] + TX, Penconazole [66246-88-6] + TX, Prothioconazole [178928-70-6] + TX, Pyrifenox [88283-41-4] + TX, Prochloraz [67747-09-5] + TX, Propiconazole [60207-90-1 ] + TX, Simeconazole [149508-90-7] + TX, Tebuconazole [107534-96-3] + TX, Tetraconazole [112281 -77-3] + TX, Triadimefon [43121 -43-3] + TX, Triadimenol [55219-65-3] + TX, Triflumizole [99387-89-0] + TX, Triticonazole [131983-72-7] + TX, Ancymidol [12771 - 68-5] + TX, Fenarimol [60168-88-9] + TX, Nuarimol [63284-71 -9] + TX, Bupirimate [41483-43-6] + TX, Dimethirimol [5221 -53-4] + TX, Ethirimol [23947-60-6] + TX, Dodemorph [1593-77-7] + TX, Fenpropidine [67306-00-7] + TX, Fenpropimorph [67564-91-4] + TX, Spiroxamine [1 18134-30-8] + TX, Tridemorph [81412-43-3] + TX, Cyprodinil [121552-61 -2] + TX, Mepanipyrim [110235-47-7] + TX, Pyrimethanil [53112- 28-0] + TX, Fenpiclonil [74738-17-3] + TX, Fludioxonil [131341 -86-1 ] + TX, Benalaxyl [71626-11 -4] + TX, Furalaxyl [57646-30-7] + TX, Metalaxyl [57837-19-1 ] + TX, R-Metalaxyl [70630-17-0] + TX, Ofurace [58810-48-3] + TX, Oxadixyl [77732-09-3] + TX, Benomyl [17804-35-2] + TX, Carbendazim [10605-21 -7] + TX, Debacarb [62732- 91-6] + TX, Fuberidazole [3878-19-1] + TX1 Thiabendazole [148-79-8] + TX, Chlozolinate [84332-86-5] + TX, Dichlozoline [24201 -58-9] + TX, lprodione [36734-19- 7] + TX, Myclozoline [54864-61 -8] + TX, Procymidone [32809-16-8] + TX, Vinclozoline [50471 -44-8] + TX, Boscalid [188425-85-6] + TX, Carboxin [5234-68-4] + TX, Fenfuram [24691 -80-3] + TX, Flutolanil [66332-96-5] + TX, Mepronil [55814-41 -0] + TX, Oxycarboxin [5259-88-1 ] + TX, Penthiopyrad [183675-82-3] + TX, Thifluzamide [130000-40-7] + TX, Guazatine [108173-90-6] + TX, Dodine [2439-10-3] [112-65-2] (freie Base) + TX, lminoctadine [13516-27-3] + TX, Azoxystrobin [131860-33-8] + TX5 Dimoxystrobin [149961-52-4] + TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1 , 93} + TX, Fluoxastrobin [361377-29-9] + TX, Kresoxim-methyl [143390-89-0] + TX, Metominostrobin [133408-50-1] + TX, Trifloxystrobin [141517-21- 7] + TX, Orysastrobin [248593-16-0] + TX, Picoxystrobin [117428-22-5] + TX, Pyraclostrobin [175013-18-0] + TX, Ferbam [14484-64-1] + TX, Mancozeb [8018-01 -7] + TX, Maneb [12427-38-2] + TX, Metiram [9006-42-2] + TX, Propineb [12071-83-9] + TX, Thiram [137-26-8] + TX, Zineb [12122-67-7] + TX, Ziram [137-30-4] + TX, Captafol [2425-06-1 ] + TX, Captan [133-06-2] + TX, Dichlofluanid [1085-98-9] + TX, Fluoroimide [41205-21 -4] + TX, Folpet [133-07-3 ] + TX, ToIyIf luanid [731 -27-1 ] + TX, Bordeaux Mixture [8011 -63-0] + TX, Copperhydroxid [20427-59-2] + TX, Copperoxychlorid [1332-40-7] + TX, Coppersulfat [7758-98-7] + TX, Copperoxid [1317- 39-1] + TX, Mancopper [53988-93-5] + TX, Oxine-copper [10380-28-6] + TX, Dinocap [131-72-6] + TX, Nitrothal-isopropyl [10552-74-6] + TX, Edifenphos [17109-49-8] + TX, lprobenphos [26087-47-8] + TX, lsoprothiolane [50512-35-1 ] + TX, Phosdiphen [36519- 00-3] + TX, Pyrazophos [13457-18-6] + TX, Tolclofos-methyl [57018-04-9] + TX, Acibenzolar-S-methyl [135158-54-2] + TX, Anilazine [101 -05-3] + TX, Benthiavalicarb [413615-35-7] + TX, Blasticidin-S [2079-00-7] + TX, Chinomethionat [2439-01 -2] + TX, Chloroneb [2675-77-6] + TX, Chlorothalonil [1897-45-6] + TX, Cyflufenamid [180409- 60-3] + TX, Cymoxanil [57966-95-7] + TX, Dichlone [117-80-6] + TX, Diclocymet [139920-32-4] + TX, Diclomezine [62865-36-5] + TX, Dicloran [99-30-9] + TX, Diethofencarb [87130-20-9] + TX, Dimethomorph [110488-70-5] + TX, SYP-LI90 (Flumorph) [211867-47-9] + TX, Dithianon [3347-22-6] + TX, Ethaboxam [162650-77- 3] + TX, Etridiazole [2593- 15-9] + TX1 Famoxadone [131807-57-3] + TX, Fenamidone [161326-34-7] + TX, Fenoxanil [115852-48-7] + TX, Fentin [668-34-8] + TX, Ferimzone [89269-64-7] + TX, Fluazinam [79622-59-6] + TX, Fluopicolide [239110-15- 7] + TX, Flusulfamide [106917-52-6] + TX, Fenhexamid [126833-17-8] + TX, Fosetyl- aluminium [39148-24-8] + TX, Hymexazol [10004-44-1 ] + TX, Iprovalicarb [140923-17-7] + TX, IKF-916 (Cyazofamid) [120116-88-3] + TX, Kasugamycin [6980-18-3] + TX, Methasulfocarb [66952-49-6] + TX, Metrafenone [220899-03-6] + TX, Pencycuron [66063-05-6] + TX, Phthalide [27355-22-2] + TX, Polyoxins [11113-80-7] + TX, Probenazole [27605-76-1] + TX, Propamocarb [25606-41-1] + TX, Proquinazid [189278-12-4] + TX, Pyroquilon [57369-32-1] + TX, Quinoxyfen [124495-18-7] + TX, Quintozene [82-68-8] + TX, Schwefel [7704-34-9] + TX, Tiadinil [223580-51-6] + TX, Triazoxide [72459-58-6] + TX, Tricyclazole [41814-78-2] + TX, Triforine [26644-46-2] + TX, Validamycin [37248-47-8] + TX, Zoxamide (RH7281 ) [156052-68-5] + TX, Mandipropamid [374726-62-2] + TX, the compound of formula F- 1
Figure imgf000128_0001
wherein Ra5 is trifluoromethyl or difluoromethyl (WO2004/058723) + TX, the compound of formula F-2
Figure imgf000129_0001
wherein Ra6 is trifluoromethyl or difluoromethyl (WO2004/058723) + TX, the racemic compound of formula F-3 (syn)
Figure imgf000129_0002
CK wherein Ra7 is trifluoromethyl or difluoromethyl (WO2004/035589) + TX, the racemic mixture of formula F-4 (anti)
Figure imgf000129_0003
wherein Ra7 is trifluoromethyl or difluoromethyl (W 02004/035589) + TX.the compound of formula F-5
Figure imgf000130_0001
which is an epimeric mixture of racemic compounds of formulae F-3 (syn) and F-4 (anti), wherein the ratio from racemic compounds of formula F-3 (syn) to racemic cmpounds of formula F-4 (anti) is from 1000 : 1 to 1 : 1000 and wherein Ra7 is trifluoromethyl or difluoromethyl (WO2004/035589) + TX, the compound of formula F-6
Figure imgf000130_0002
wherein Ra8 is trifluoromethyl or difluoromethyl (WO2004/035589) + TX, the racemic compound of formula F-7 (trans)
Figure imgf000130_0003
wherein Ra9 is trifluoromethyl or difluoromethyl (W 003/074491 ) + TX, the racemic compound of formula F-8 (cis)
Figure imgf000131_0001
wherein Ra9 is trifluoromethyl or difluoromethyl (WO03/074491 ) + TX, the compound of formula F-9
Figure imgf000131_0002
which is a mixture of the racemic compounds of formulae F-7 (trans) and F-8 (cis), wherein the ratio of the racemic compound of formula F-7 (trans) to the racemic compound of formula F-8 (cis) is 2 : 1 to 100 : 1 ; and wherein Ra9 is trifluoromethyl or difluoromethyl (W 003/074491 ) + TX, the compound of formula F-10
Figure imgf000131_0003
wherein R10 is trifluoromethyl or difluoromethyl (WO2004/058723) + TX, the racemic compound of formula F- 11 (trans) ),
Figure imgf000132_0001
wherein R11 is trifluoromethyl or difluoromethyl (W 003/074491 ) + TX, the racemic compound of formula F-12 (cis)
Figure imgf000132_0002
wherein R11 is trifluoromethyl or difluoromethyl (W 003/074491) + TX, the compound of formula F-13
Figure imgf000132_0003
which is a racemic mixture of formulae F- 11 (trans) and F-12 (cis), and wherein R11 is trifluoromethyl or difluoromethyl (WO 03/074491 ) + TX, the compound of formula F-14
(WO2004/058723) + TX, and the compound of formula F-15
Figure imgf000133_0002
+ TX.
The active ingredient mixture of the compounds of formula I selected from tables T1 to T43 with active ingredients described above comprises a compound selected from tables T1 to T43 and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1 :6000, especially from 50:1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10:1 to 1 :10, very especially from 5:1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1 :1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 :150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 :1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750. Those mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios. The mixtures comprising a compound of formula I selected from tables T1 to T43 and one or more active ingredients as described above can be applied, for example, in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula I selected from tables T1 to T43 and the active ingredients as described above is not essential for working the present invention.
The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The compouds of formulae A-1 to A-26 are described in WO 03/015518 or in WO 04/067528. The above described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. Tomlin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1 ). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names. Copyright © 1995-2004]; for example, the compound "acetoprole" is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html.
Most of the active ingredients described above are referred to hereinabove by a so-called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the lUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "develoment code" is used or, if neither one of those designations nor a "common name" is used, an "alternative name" is employed. "CAS Reg. No" means the Chemical Abstracts Registry Number.
Biological Examples (% = per cent by weight, unless otherwise specified) Example B1 : Activity against Spodootera littoralis (Egyptian cotton leafworm): Cotton 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 5 L1 larvae. The samples are checked for mortality, repellent effect, feeding behaviour, and growth regulation 3 days after treatment (DAT).
In this test, compounds listed in the Tables above show good activity. In particular compounds T13.1.2, T15.1.1 , T15.1.91 , T13.1.1 , T9.1.2 (diastereomer A), T9.1.2 (diastereomer B), T16.1.1 , T17.1.2 (diastereomer A), T17.1.2 (diastereomer B), T16.1.91 , T13.1.92, T13.1.361 , T13.1.391 , T13.1.91 , T13.1.6, T13.1.96, T44.1.2, T13.1.8, T13.1.23, T13.1.93, T13.1.113, T13.1.21 , T13.1.111 have an activity of over 80% at 400ppm.
Example B2: 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.
In this test, compounds listed in the Tables above show good activity. In particular compounds T13.1.2, T15.1.1 , T15.1.91 , T13.1.1 , T9.1.2 (diastereomer A), T9.1.2
(diastereomer B), T16.1.1 , T17.1.2 (diastereomer A), T17.1.2 (diastereomer B), T16.1.91 ,
T13.1.92, T13.1.361 , T13.1.391 , T13.1.91 , T13.1.6, T13.1.96, T44.1.2, T13.1.8, T13.1.23,
T13.1.93, T13.1.113, T13.1.21 , T13.1.111 have an activity of over 80% at 400ppm.
Example B3: Activity against Plutella xylostella (Diamond back moth): 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 above show good activity. In particular compounds T13.1.2, T15.1.1 , T15.1.91 , T13.1.1 , T9.1.2 (diastereomer A), T9.1.2 (diastereomer B), T16.1.1 , T17.1.2 (diastereomer A), T17.1.2 (diastereomer B), T16.1.91 , T13.1.92, T13.1.361 , T13.1.391 , T13.1.91 , T13.1.6, T13.1.96, T44.1.2, T13.1.8, T13.1.23, T13.1.93, T13.1.113, T13.1.21 , T13.1.1 1 1 have an activity of over 80% at 400ppm.
Example B4: Activity against Diabrotica balteata (Corn root worm): 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 above show good activity. In particular compounds T13.1.2, T15.1.1 , T15.1 .91 , T13.1.1 , T9.1.2 (diastereomer A), T9.1.2 (diastereomer B), T17.1.2 (diastereomer A), T17.1.2 (diastereomer B), T16.1 .91 , T13.1.92, 113.1.91 , 113.1.6, 113.1.96, 144.1.2, 113.1.8, 113.1.23, 113.1.1 13, 113.1 .21 , 113.1.11 1 have an activity of over 80% at 400ppm.
Example B5: Activity against Myzus persicae (Green peach aphid): (contact)
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 DAT, samples are checked for mortality and special effects
(e.g. phytotoxicity).
In this test, compounds listed in the Tables above show good activity. In particular compounds T13.1.2, T15.1.91 , T9.1.2 (diastereomer A), T9.1.2 (diastereomer B), T17.1.2
(diastereomer A), T17.1.2 (diastereomer B), T13.1.92, T13.1.91 , T13.1.96, T13.1.21 have an activity of over 80% at 400ppm.
Example B6: Activity against Myzυs persicae (Green peach aphid): (systemic)
Roots of pea seedlings, infested with an aphid population of mixed ages, are placed directly in the test solutions. 6 days after introduction, samples are checked for mortality and special effects on the plant.
In this test, compounds listed in the Tables above show good activity. In particular compounds T13.1.2, T13.1.1 , T9.1.2 (diastereomer A), T9.1.2 (diastereomer B), T17.1.2
(diastereomer A), T17.1.2 (diastereomer B), T13.1.92, T13.1.6, T13.1.96, T13.1.93,
T13.1 .113, T13.1.21 have an activity of over 80% at 400ppm.
Example B7: Activity against Thrips tabaci (Onion Thrips):
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 above show good activity. In particular compounds T13.1.2, T15.1.91 , T13.1.1 , T9.1.2 (diastereomer A), T9.1 .2 (diastereomer B),
T17.1 .2 (diastereomer A), T17.1.2 (diastereomer B), T16.1 .91 , T13.1 .92, T13.1.91 , T13.1.6, T13.1.96, T44.1.2, T13.1.93, T13.1.1 13, T13.1.21 , T13.1.111 have an activity of over 80% at 400ppm.
Example B8: 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.
In this test, compounds listed in the Tables above show good activity. In particular compounds T9.1.2 (diastereomer A), T17.1.2 (diastereomer B), T13.1.21 have an activity of over 80% at 400ppm.
Example B9: Systemic Insecticide Test for Spodoptera littoralis (cotton leafworm): Four day old maize seedlings {Zea mais, variety Stoneville) are placed individual in vials containing 24ml water into which the chemical is diluted at 12.5 ppm. Seedlings are allowed to grow for six days. Subsequently leaves are cut and placed in a Petri dish (5 cm diameter), inoculated with twelve to fifteen 1st instar S. littoralis larvae and incubated for four days in a growth chamber (25°C, 50% r.h., 18:6 L:D photo period). Number of alive insects are counted and percentage of dead calculated. Tests were conducted with one replicate. In this test, compounds listed in the Tables above show good activity. In particular compounds T13.1.2, T15.1.1 , T13.1.1 , T9.1.2 (diastereomer A), T9.1.2 (diastereomer B)1 T17.1.2 (diastereomer A), T17.1.2 (diastereomer B), T13.1.92, T13.1.361 , T13.1.391 , T13.1 .91. T13.1.6, T13.1.96, T44.1.2, T13.1.8, T13.1.23, Tϊ 3.1.113 have an activity of over 80%.
Example B10: Activity against Cvdia oomonella (codling moth):
Standard Cydia diet cubes (1.5 cm width) are pierced with a tooth-pick and are immersed in liquid paraffin (ca. 800C). After the paraffin coat has hardened, an aqueous emulsion containing 400 ppm of active ingredient is applied using a De Vilbis sprayer (25 ml, 1 bar). After the spray coating has dried, the cubes are put into plastic containers which are then populated with two freshly hatched Cydia pomonella (1st instar). The containers are then closed with a plastic cap. After 14 days incubation at 260C and 40-60% relative humidity, the survival rate of the caterpillars as well as their growth regulation is determined. In this test, compounds listed in the Tables above show good activity. In particular compounds T9.1.2 (diastereomer A), T9.1.2 (diastereomer B), T17.1.2 (diastereomer A), T13.1.92 have an activity of over 80%.
Example B1 1 : Comparison of the insecticidal activity of compounds according to the invention with the structurally most closely comparable compound from the state of the art (compound No. 296 described on page 108 of WO2003/015518):
(Compound No. T13.1.391 according to the invention)
Figure imgf000138_0001
(Compound No. 296 according to state of the art)
Figure imgf000138_0002
Four day old maize seedlings (Zea mais, variety Stoneville) are placed individual in vials containing 24ml water into which the chemical is diluted at the prescribed concentrations (3 and O.δppm). Seedlings are allowed to grow for six days. Subsequently leaves are cut and placed in a Petri dish (3.5 cm diameter), inoculated with twelve to fifteen 1 st instar S. littoralis larvae and incubated for four days in a growth chamber (25°C, 50% r.h., 18:6 LD photo period). Number of alive insects are counted and percentage of dead calculated. Effects on larvae growth were compared to the control and percentage of larvae growth reduction calculated. Tests were conducted with one replicate. Results are shown in Table B1 1 : Table B11 : Systemic Insecticide Test for Spodootera littoralis (Lepidoptera:Noctuidae):
Figure imgf000139_0001
Table B11 shows that compound No. T13.1.391 according to the invention exerts a substantially better insecticidal action on Spodoptera littoralis than the compound from the state of the art. Especially at an application rate of 3 ppm the compound according to the invention is far superior to the compound of the state of the art. This enhanced effect was not to be expected on the basis of the structural similarity of these compounds.

Claims

What is claimed is:
1. A compound of formula I
Figure imgf000140_0001
wherein
D is phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl; or phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl mono-, di- or trisubstituted by Ci-C6alkyl, C3-C6cycloalkyl, d-C6haloalkyl, halogen, cyano, C1-
C4alkoxy, d-d,haloalkoxy, C1-C4alkylthio, d-C4haloalkylthio, CrC4alkylsulfinyl, d-
C4alkylsulfonyl, Ci-C4haloalkylsulfinyl or d-C4haloalkylsulfonyl; or D is a group
Figure imgf000140_0002
(D7) or (D8),
Figure imgf000140_0003
Figure imgf000140_0004
R4, R4', R10. Ri7> and R19 independently from each other, are hydrogen, d-C6alkyl, C3- C6cycloalkyl, Ci-C6haloalkyl, halogen, cyano, CrC4alkoxy, C1-C4haloalkoxy, C2- C4alkoxycarbonyl, C1-C4alkylthio, d-C4haloalkylthio, d-C4alkylsulfinyl, d-C4alkylsulfonyl, d-C4haloalkylsulfinyl or Crdhaloalkylsulfonyl; Rs. Re. Rs. Rii, Ri2> Ri5. Ri6 and Ri8 independently from each other, are Ci-C6alkyl, or C1- C6alkyl mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, d-C4alkoxy, C2- C4alkoxycarbonyl, d-C4alkylthio, Ci-C4alkylsulfinyl, C1-C4alkylsulfonyl, Ci-C4alkylamino, C2- C4dialkylamino or C3-C6cycloalkylamino; or are phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl; or are phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl mono-, di- or trisubstituted by CrC6alkyl, C3- C6cycloalkyl, d-C6haloalkyl, halogen, cyano, C1-C4alkoxy, Ci-C4haloalkoxy, CrC4alkylthio, Ci-C4haloalkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfinyl or C1- C4haloalkylsulfonyl;
R7, R9, R13 and R14 independently from each other, are hydrogen, Ci-C6alkyl, Ci-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C3-C6alkenyl or C3-C6haloalkenyl; each R1 independently is halogen, nitro, cyano, hydroxy, CrC6alkyl, C2-C6alkenyl, C2- C6alkynyl, C3-C6cycloalkyl, CrC6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3- C6halocycloalkyl, d-C4alkoxy, C1-C4haloalkoxy, Ci-C4alkylthio, C1-C4haloalkylthio, C1- C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, Ci-C4alkylsulfinyl, d-C4alkylsulfonyl, C1- C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, d-Cealkyl-Ca-Cecycloalkylamino, C2- C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, Cs-Cβdialkylaminocarbonyl, C2-C6alkoxycarbonyloxy,
Figure imgf000141_0001
QrCedialkylaminocarbonyloxy or C3- C6trialkylsilyl, phenyl, benzyl or phenoxy, or phenyl, benzyl or phenoxy mono-, di- or trisubstituted by halogen, cyano, nitro, halogen, d-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, d-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, Cs-Cehalocycloalkyl, C1- C4alkoxy, d-C4haloalkoxy, d-C4alkylthio, CrC4haloalkylthio, d-C4alkylsulfinyl, C1- C4alkylsulfonyl, d-C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, d-C6alkyl-C3- C6cycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, C3- C6dialkylaminocarbonyl, C2-C6alkoxycarbonyloxy, Cz-Cβalkylaminocarbonyloxy, C3- C6dialkylaminocarbonyloxy or C3-C6trialkylsilyl; n is 0, 1 , 2 or 3; each of R2 and R3, which may be the same or different, represents hydrogen, d-C6alkyl, C2- C6alkenyl, C2-C6alkynyl or C3-C8cycloalkyl; or d-C6alkyl, C2-C6alkenyl, C2-C6alkynyl or C3- C8cycloalkyl substituted by one or more substituents selected from halogen nitro, cyano, hydroxy, d-C4alkoxy, d-C4haloalkoxy, d-C4alkylthio, d-C4haloalkylthio, C1-C4alkylsulfinyl, CrC4alkylsulfonyl, C1-C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino and C1- C6alkyl-C3-C6cycloalkylamino; each of E1 and E2, which may be the same or different, represents oxygen or sulfur; A is oxygen, sulfur, SO, SO2, S(O)P=N-R, C=N-OR36, N-R0, C=O or P(X)4-R33; R33 is hydrogen, d-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, CrC6haloalkyl, CrC6alkoxy, hydroxy, C3-C6cycloalkyl, C3-C6cycloalkyl-Ci-C6alkyl, benzyl or phenyl; where phenyl and benzyl for their part may be mono- di- or trisubstituted by Ci-C6alkyl, d-C6haloalkyl, halogen, cyano or nitro; or R33 is O Na+, O Li+ or O K+;
R36 is hydrogen, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, d-C6haloalkyl, C2-C6haloalkenyl, C2- C6haloalkynyl, d-C6alkoxy-d-C6alkyl, d-C6haloalkoxy-d-C6alkyl or benzyl; X is oxygen or sulfur; p is 0 or 1 ; t is 0 or 1 ; each of R34 and R35, which may be the same or different, represents hydrogen, COOH, halogen, nitro, cyano, hydroxy, d-C6alkyl, d-C6haloalkyl, C2-C6alkenyl, C2-C6alkynyl, C2- C6haloalkenyl, C2-C6haloalkynyl, Ci-C6alkylthio, d-C6alkylsulfinyl, d-C6alkylsulfonyl, Ci-C6haloalkylthio, d-C6haloalkylsulfinyl, d-C6haloalkylsulfonyl, d-C6alkoxycarbonyl, CrC6alkylcarbonyl, Cs-Cβalkylaminocarbonyl, Cs-Cedialkylaminocarbonyl, Ci-C6alkoxy-d-C6alkyl, CrC6haloalkoxy-Ci-C6alkyl, d-C6alkoxy, d-C6haloalkoxy, C1- C6alkylamino, C2-C6dialkylamino, C3-C6trialkylsilyl, benzyl or phenyl; where phenyl and benzyl for their part may be mono- di- or trisubstituted by CrC6alkyl, d-C6haloalkyl, Ci-C6alkoxy, d-C6haloalkoxy, halogen, cyano, hydroxyl or nitro; m is O, 1 , 2, 3 or 4;
R is hydrogen, d-C6alkyl, d-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, Ci-C6alkylthio, d-C6haloalkylthio, Ci -C6BIkOXy-C1 -C6alkyl or d-C6haloalkoxy-d-C6alkyl; or R is d-C6alkyl, d-C6haloalkyl, C3-C6cycloalkyl, Ca-Cehalocycloalkyl, d-C6alkylthio, d-C6haloalkylthio, d-C6alkoxy-Ci-C6alkyl or d-Cβhaloalkoxy-d-Cβalkyl substituted by d-C6alkyl, d-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, d-C6alkoxy, or d-C6haloalkoxy; or R is cyano, nitro, -C(O)R26, -C(O)OR27, -CONR28R29, -SO2R30 or - P(O)(OR31)(OR32);
R0 is hydrogen, d-C6alkyl, d-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, d-C6alkylthio, d-C6haloalkylthio, d-C6alkoxy-d-C6alkyl or d-C6haloalkoxy-d-C6alkyl; or R0 is d-C6alkyl, CrC6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, d-C6alkylthio, CrC6haloalkylthio, d-Cealkoxy-d-Cεalkyl or d-Cβhaloalkoxy-d-Cealkyl substituted by d-C6alkyl, d-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, d-C6alkoxy, or d-C6haloalkoxy; or R0 is cyano, nitro, -C(O)R026, -C(O)OR027, -CONR028R029, -SO2R030 or -P(O)(OR031)(OR032); or R0 is phenyl or benzyl, or phenyl or benzyl mono-, di- or trisubstituted by substituents selected from d-C6alkyl, C3-C6cycloalkyl, d-C6haloalkyl, halogen, cyano, C1-C4BIkOXy, C1-C4IIaIOaIkOXy, d-C4alkylthio, d-C4haloalkylthio, C1- C4alkylsulfinyl, d-C4alkylsulfonyl, d-C4haloalkylsulfinyl and d-C4haloalkylsulfonyl; each of R26 and R026. which may be the same or different, represents hydrogen, CrC6alkyl, d-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, d-C6alkylthio, d-Cehaloalkylthio, d-C6alkoxycarbonyl, d-C6alkylcarbonyl or CrCealkoxy-d-Cβalkyl; or d-C6alkyl, d-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, d-C6alkylthio, d-C6haloalkylthio, CrCealkoxycarbonyl, d-C6alkylcarbonyl or C1 -C6alkoxy-d -C6alkyl substituted by d-C6alkyl, Ci-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, d-Cβalkoxy, or d-C6haloalkoxy; each of R27, R28. R29, R30, R31. R32, R027. R028, R029. R030, R031 and R032 which may be the same or different, represents d-C6alkyl, d-C6haloalkyl, C3-C6cycloalkyl or C3-C6halocycloalkyl; or d-C6alkyl, d-C6haloalkyl, C3-C6cycloalkyl or C3-C6halocycloalkyl substituted by d-C6alkyl, d-C6haloalkyl, C3-C6cycloalkyl, Cs-Cβhalocycloalkyl, d-C6alkoxy or d-C6haloalkoxy; with the proviso that E1 or E2 is sulfur if A is oxygen, sulfur or N-R0, wherein R0 is hydrogen, d-C3alkyl, d-C3haloalkyl, C2-C4alkylcarbonyl, C2- C4haloalkylcarbonyl, C2-C4alkoxycarbonyl or CrC3alkylsulfonyl; and agronomically acceptable salts/isomers/diastereomers/enantiomers/tautomers/N-oxides of those compounds.
2. A compound of formula III
Figure imgf000143_0001
in which A, R3, R34, R35 and m have the meanings given for formula I in claim 1.
3. A compound of formula V
Figure imgf000143_0002
in which n, R1, R2, R3, E2, R34, R35, A and m have the meanings given for formula I in claim 1.
4. A compound of formula VIII
Figure imgf000144_0001
in which R3, R34, R35 and m have the meanings given in the formula I in claim 1 and q is 0 or 1.
5. A pesticidal composition, which comprises at least one compound according to claim 1 of the formula I or, where appropriate, a tautomer thereof, in each case in free form or in agrochemically utilizable salt form, as active ingredient and at least one auxiliary.
6. A composition according to claim 5 for controlling insects or representatives of the order Acarina.
7. A method for controlling pests, which comprises applying a composition according to claim 5 to the pests or their environment.
8. A method according to claim 7 for controlling insects or representatives of the order Acarina.
9. A method according to claim 7 for the protection of plant propagation material from the attack by pests, which comprises treating the propagation material or the site, where the propagation material is planted.
10. Plant propagation material treated in accordance with the method described in claim 9.
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