WO2006040113A2 - Heterocyclic diamide insecticidal agents - Google Patents

Heterocyclic diamide insecticidal agents Download PDF

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Publication number
WO2006040113A2
WO2006040113A2 PCT/EP2005/010891 EP2005010891W WO2006040113A2 WO 2006040113 A2 WO2006040113 A2 WO 2006040113A2 EP 2005010891 W EP2005010891 W EP 2005010891W WO 2006040113 A2 WO2006040113 A2 WO 2006040113A2
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Prior art keywords
crc
halogen
alkyl
alkylthio
cyano
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PCT/EP2005/010891
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French (fr)
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WO2006040113A3 (en
Inventor
Anthony Cornelius O'sullivan
David John Hughes
André Jeanguenat
Michel Muehlebach
Olivier Loiseleur
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Syngenta Participations Ag
Syngenta Limited
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Priority to MX2007003908A priority Critical patent/MX2007003908A/en
Priority to NZ553939A priority patent/NZ553939A/en
Priority to JP2007535114A priority patent/JP4955562B2/en
Priority to CN2005800396826A priority patent/CN101061110B/en
Priority to EP05800574A priority patent/EP1802611A2/en
Priority to BRPI0518301-4A priority patent/BRPI0518301B1/en
Application filed by Syngenta Participations Ag, Syngenta Limited filed Critical Syngenta Participations Ag
Priority to CA002580419A priority patent/CA2580419A1/en
Priority to US11/576,950 priority patent/US8106075B2/en
Priority to AU2005293801A priority patent/AU2005293801B2/en
Publication of WO2006040113A2 publication Critical patent/WO2006040113A2/en
Publication of WO2006040113A3 publication Critical patent/WO2006040113A3/en
Priority to IL181949A priority patent/IL181949A0/en

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    • 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
    • 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
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D231/38—Nitrogen atoms
    • C07D231/40—Acylated on said nitrogen atom
    • 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
    • C07D401/04—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 directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D405/08—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 carbon chain containing alicyclic 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
    • C07D409/14—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

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 01/70671 , WO 03/016284, WO 03/015518, WO 03/024222 and WO 04/033468. There have now been found novel anthranilamide derivatives with pesticidal properties, especially for the control of insects and members of the order Acarina.
  • the present invention accordingly relates to compounds of formula I
  • each of E and Z which may be the same or different, represents oxygen or sulfur
  • A is CrC ⁇ alkylene, C 2 -C 6 alkenylene, C 2 -C 6 alkynylene, or a bivalent three- to ten-membered monocyclic or fused bicyclic ring system which can be partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms; and it being possible for the three- to ten-membered ring system itself and also for the C 1 -
  • Y is CrCealkylene, C 2 -C 6 alkenylene, C 2 -C 6 alkynylene, or a bivalent three- to ten-membered monocyclic or fused bicyclic ring system which can be partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms; and it being possible for the three- to ten-membered ring system itself and also for the C 1 - C 6 alkylene, C 2 -C 6 alkenylene and C 2 -C 6 alkynylene groups to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, C r C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 5 - C 7
  • B is a three- to four-membered ring system which is fully or partially saturated and can contain a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, and it being possible for the three- to four-membered ring system itself to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, C r C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 - C 6 cycloalkyl, C 5 -C 7 cycloalkenyl, C 5 -C 8 cycloalkynyl, C ⁇ Cehaloalkyl, C 2 -C 6 haloalkenyl, C 2 - C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, Cs-C T -halocycloalkenyl, C 5 -C 8 halocycloalkynyl, C 1 -
  • 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, CrC 6 haloalkyl, halogen, cyano, C 1 - C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C r C 4 haloalkylthio, Ci-C 4 alkylsulfinyl, C 1 - C 4 alkylsulfonyl, C r C 4 haloalkylsulfinyl or C r C 4 haloalkylsulfonyl; or D is a group
  • R 4 , R 4 ', Rio, Ri 7 , and R 19 independently from each other, are hydrogen, C ⁇ Cealkyl, C 3 - C 6 cycloalkyl, CVCehaloalkyl, halogen, cyano, C r C 4 alkoxy, C r C 4 haloalkoxy, C 2 - C 4 alkoxycarbonyl, Ci-C 4 alkylthio, CrC 4 haloalkylthio, CrC 4 alkylsulfinyl, C r C 4 alkylsulfonyl, Ci-C 4 haloalkylsulfinyl or C r C 4 haloalkylsulfonyl;
  • R5, Re, Rs, Rn, R 12 , Ri5, R 1 6 and R 18 independently from each other, are C ⁇ Cealkyl or C 1 - C 6 alkyl mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, CrC ⁇ lkoxy, C 2 - C 4 alkoxycarbonyl, CrC 4 alkylthio, CrC 4 alkylsulfinyl, CrC ⁇ lkylsulfonyl, C 1 -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 CrC 6 alkyl, C 3 - C 6 cycloalkyl, Cr
  • R 7 , R 9 , R 13 and R 14 independently from each other, are hydrogen, CrC ⁇ alkyl, CrCehaloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 3 -C 6 alkenyl or C 3 -C 6 haloalkenyl and agronomically acceptable salts/isomers/enantiomers/tautomers/N-oxides of those compounds, with the exception of the compound 2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3- carboxylic acid [2-methyl-6-(oxiranylmethyl-carbamoyl)-phenyl]-amide.
  • Compounds 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 C 1 -C 4 alkanecarboxylic acids which are unsubstitu- ted 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 orga ⁇ nic sulfonic acids, such as C r C 4 alkane- or arylsulfonic acids which are unsubstit
  • Com ⁇ pounds 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 mor- pholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, die ⁇ thyl-, 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 disadvan ⁇ tage 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 I or agrochemically utilizable salts thereof.
  • the free compounds I or their salts hereinabove and hereinbelow are respectively to be understood as including, where appropriate, the corresponding salts or the free compounds 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-i-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluorobut-2-en- 1-yl.
  • halogen being fluorine, chlorine, bromine and iodine and in particular fluorine and chlorine, for example 2,2-difluoro-i-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluorobut
  • 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 (C 2 -alkoxycarbonyl), ethoxy carbony I (C 3 - alkoxycarbonyl), 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 methylsulfiny! 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.
  • Alkylamino groups having a chain length of from 1 to 4 carbon atoms.
  • Alkylaminocarbonyl is, for example, methylaminocarbonyl (C 2 -alkylaminocarbonyl) or ethylaminocarbonyl (C 3 -aminocarbonyl).
  • 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.
  • Examples for B as a optionally substituted three- to four-membered ring system which is fully or partially saturated and can contain a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, are cyclopropyl, methyl-cyclopropyl, cyclopropenyl, cyclobutyl,
  • a three- to ten-membered, monocyclic or fused bicyclic ring system which may be partially saturated or fully saturated is, depending of the number of ring members, for example, selected from the group consisting of
  • each R 26 is methyl
  • each R 27 and each R 28 are independently hydrogen, C r C 3 alkyl, CrC 3 alkoxy, CrCsalkylthio or trifluoromethyl
  • the second valence for the bivalent ring system of substituent A or Y can be located at any suitable position of the ring.
  • a three- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated is, depending of the number of ring members, for example, selected from the group consisting of
  • each R 2 ⁇ is methyl
  • each R 27 and each R 28 are independently hydrogen, C r C 3 alkyl, CrC 3 alkoxy, CrCsalkylthio or trifluoromethyl
  • R 4 ' is hydrogen and each R 1 independently is halogen, nitro, hydroxy, C r C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 - C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, Cs-Cehalocycloalkyl, C 1 -C -I aIkOXy, C 1 - C 4 haloalkoxy, C 1 -C 4 alkylthio, C r C 4 haIoalkylthio, CrC ⁇ aloalkylsulfinyl, C 1 - C 4 haloalkylsulfonyl, CrC 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C r C
  • B is a three- to four-membered ring system which is fully or partially saturated, and it being possible for the three- to four-membered ring system itself to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, CrC 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 5 -C 7 cycloalkenyl, C 5 -C 8 cycloalkynyl, CrCehaloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 - C 6 halocycloalkyl, C 5 -C 7 halocycloalkenyl, C 5 -C 8 halocycloalkynyl, CrC 4 alkoxy, C 1 - C 4 haloalkoxy, CrC 4 alkylthi
  • X is preferably oxygen, NH; NMe or NEt.
  • Y is preferably C r C 4 alkylene, C 2 -C 6 alkenylene or C 3 -C 6 alkinylene or, C 1 -C 4 alkylene, C 2 - C 6 alkenylene or C 3 -C 6 alkinylene substituted by halogen, C 3 -C 6 cycloalkyl, ⁇ alkylsulfonyl or C 1 -C 4 BIkOXy.
  • R 1 is selected from CrC 4 alkyl, halogen, CrCshaloalkyl, nitro, C r C 4 alkoxy, Ci-C 4 -haloalkoxy, C 1 -C 4 alkylthio, C 1 - C 4 alkylsulfinyl, C r C 4 alkylsulfonyl, C r C 4 haloalkylthio, CrC ⁇ haloalkylsulfinyl and C 1 - C 4 haloalkylsulfonyl, in particular from halogen and CrC ⁇ alkyl, preferably selected from methyl and halogen, most preferably selected from methyl and chloro, and n is 1 or 2, preferably 2.
  • Preferred position of R 1 is meta to the group -C(Z)-N(R 3 )-A-(X)p-(Y)q-B.
  • An outstanding group of compounds of formula I comprises those compounds wherein A is C r C 6 alkylene which may be substituted by C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, cyano, C 1 - C 4 alkylthio, C r C 4 alkylsulfonyl, C r C 4 alkoxy, halogen or C r C 6 haloalkyI; or A is C 3 - C 6 cycloalkylene.
  • A is CrCealkylene or cyclopropylene, most preferably methylene or cyclopropylene.
  • B is cyclopropyl or cyclobutyl, preferably cyclopropyl.
  • D is a group D 1 , wherein R 5 is 2-pyridyl which can be substituted by halogen, preferably which is monosubstituted by chloro at the 3-position of the pyridine ring, R 4 ' is hydrogen or halogen, preferably hydrogen and R 4 is halogen preferably chloro and bromo, C ⁇ Cehaloalkyl preferably trifluoromethyl, C r C 4 haloaIkoxy, preferably 2,2,2-trifluoroethoxy.
  • R 5 is 2-pyridyl which can be substituted by halogen, preferably which is monosubstituted by chloro at the 3-position of the pyridine ring
  • R 4 ' is hydrogen or halogen, preferably hydrogen and R 4 is halogen preferably chloro and bromo, C ⁇ Cehaloalkyl preferably trifluoromethyl, C r C 4 haloaIkoxy, preferably 2,2,2-trifluoroethoxy.
  • B is cyclopropyl or cyclobutyl which may be mono- di-, or trisubstituted by halogen, C-rC 4 aIkyl, hydroxy, cyano, C 1 - C 4 alkoxy or C r C 4 alkylthio; or B is CH(CH 2 O), CH(CHMeO), CH-(CMe 2 O), CH(CH 2 S), CH(CH 2 OCH 2 ), CH(CHMeOCH 2 ), CH(CMe 2 OCH 2 ), CH(CH 2 S-(O) 2 CH 2 ), CH(CHMeS(O) 2 CH 2 ), CH(CMe 2 S(O) 2 CH 2 ), C(Me)-(CH 2 O), C(Me)(CHMeO), C(Me)-(CMe 2 O), C(Me)-(CH 2 S), C(Me)-(CH 2 S), C(Me)-(CH 2 OCH 2 ), C(Me)(CHMe
  • n is 2 and one R 1 is CrC 4 alkyl, preferably methyl, or halogen, preferably chloro, the other R 1 is halogen preferably chloro or bromo; wherein most preferably one R 1 with the meaning C 1 -
  • C 4 alkyl occupies the ortho position with regard to the group -N(R 2 )-C(E)-D.
  • D is a group D 1 , wherein R 4 ' is hydrogen, R 4 is halogen preferably chloro and bromo, C 1 -
  • Cehaloalkyl preferably trifluoromethyl, C r C 4 haloalkoxy, preferably 2,2,2-trtifluoroethoxy and
  • R 5 is 2-pyridyl monosubstituted by halogen, preferably by 3-chloro;
  • R 2 and R 3 are hydrogen
  • A is CrC 6 alkylene or a fully saturated bivalent 3-to 6-membered moncyclic ring system, preferably methylene, cyclopropylene or cyclobutylene, most preferably a fully saturated bivalent 3-to 6-membered moncyclic ring system, in particular cyclopropylene or cyclobutylene; p and q are O;
  • E and Z are oxygen; and B is cyclopropyl or cyclobutyl, preferably cyclopropyl.
  • the process according to the invention for preparing compounds of formula I 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 formula I or, where appropriate, a tautomer thereof, in each case in free form or in salt form comprises a) for the preparation of a compound of formula I, in which R 2 is hydrogen and E and Z are oxygen, or, where appropriate, a tautomer and/or salt thereof, reacting a compound of formula Il
  • R 1 , n, and D have the meanings given for formula I in claim 1, or, where appropriate, a tautomer and/or salt thereof with a compound of formula III
  • R 3 , A, X, Y, p, q and B have the meanings given for formula I, or, where appropriate, with a tautomer and/or salt thereof or,
  • R 1 , R 2 , n, Z and D have the meanings given for the formula I in claim 1 ; and X 1 is a leaving group, or, where appropriate, a tautomer and/or salt thereof with a compound of formula III
  • D has the meaning given for formula I in claim 1 ; 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 formulae III and V are novel and especially developped 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 formulae III and V. In especially preferred compounds of formula III
  • R 3 is hydrogen
  • A is CrC 6 alkylene which may be substituted by C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, cyano, C 1 -
  • X is oxygen, NH; NCH 3 or NC 2 H 5 ;
  • Y is CrC 4 alkylene, C 2 -C 6 alkenylene or C 3 -C 6 alkinylene or, C 2 -C 6 alkenylene or C 3 -C 6 alkinylene substituted by halogen, C 3 -C 6 cycloalkyl, CrCialkylsulfonyl or C r C 4 alkoxy;
  • B is cyclopropyl or cyclobutyl which may be mono- di-, or trisubstituted by halogen, C 1 - C 4 alkyl, hydroxy, cyano, C r C 4 alkoxy or C r C 4 alkylthio; or B is CH(CH 2 O), CH(CHMeO), CH- (CMe 2 O), CH(CH 2 S), CH(CH 2 OCH 2 ), CH(CHMeOCH 2 ), CH(CMe 2 OCH 2 ), CH(CH 2 S-(O) 2 CH 2 ), CH(CHMeS(O) 2 CH
  • R 1 is C r C 4 alkyl, halogen, CrC 5 haloalkyl, nitro, C 1 -C ⁇ IkOXy, C 1 -C 4 -IIaIOaIkOXy, C 1 -
  • R 2 and R 3 are hydrogen
  • A is CrCealkylene which may be substituted by C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, cyano, C 1 -
  • X is oxygen, NH; NCH 3 or NC 2 H 5 ;
  • Y is C r C 4 alkylene, C 2 -C 6 alkenylene or C 3 -C 6 alkinylene or, C ⁇ dalkylene, C 2 -C 6 alkenylene or C 3 -C 6 alkinylene substituted by halogen, C 3 -C 6 cycloalkyl, C r C 4 alkylsulfonyl or CrC 4 aIkoxy;
  • B is cyclopropyl or cyclobutyl which may be mono- di-, or trisubstituted by halogen, C 1 - C 4 alkyl, hydroxy, cyano, C r C 4 alkoxy or C r C 4 alkylthio; or B is CH(CH 2 O), CH(CHMeO), CH- (CMe 2 O), CH(CH 2 S), CH(CH 2 OCH 2 ), CH(CHMeOCH 2 ), CH(CMe 2 OCH 2 ), CH(CH 2 S-(O) 2 CH 2 ),
  • 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 di ⁇ luent 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 -8O 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 di ⁇ luent 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 -8O 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
  • the reactants can be reacted with each other as such, i. e. without addition of a solvent or diluent, for example in the melt. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these.
  • solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halohydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromo- benzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetra- chloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters such as ethyl acetate; ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethyleneglycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dime
  • the reaction is advantageously carried out in a temperature range from approximately -80 0 C to approximately +140 0 C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between room temperature and approximately +80°C.
  • Examples of suitable leaving groups X 1 in the compounds IV are hydroxy, CrC ⁇ alkoxy, halo- C r C 8 alkoxy, CrCsalkanoyloxy, mercapto, C r C 8 alkylthio, halo-CrCsalkylthio, CrCsalkylsul- fonyloxy, halo-CrCsalkylsulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and halogen, such as chlorine.
  • Preferred are hydroxy, C r C 8 alkoxy and chlorine.
  • the reactants can be reacted with each other as such, i.e. without adding a solvent or dilu ⁇ ent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. Examples of suitable solvents or diluents are of the type described under variant a).
  • the reaction is advantageously carried out in a temperature range from approximately -80°C to approximately +14O 0 C, preferably from approximately -20°C to approximately +100 0 C, in many cases in the range between room temperature and the reflux temperature of the reaction mixture.
  • Examples of suitable leaving groups X 2 in the compounds Vl are hydroxy, CrCsalkoxy, halo- C r C 8 alkoxy, CrC ⁇ alkanoyloxy, mercapto, C r C 8 alkylthio, halo-C r C 8 alkylthio, C r C 8 alkylsul- fonyloxy, halo-CrCsalkylsulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and halogen, such as chlorine.
  • Preferred are hydroxy and chlorine.
  • 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 dilu ⁇ ent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. Examples of suitable solvents or diluents are of the type described under variant a). 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,N-diethylaniline, may also act as solvents or diluents.
  • the reaction is advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -3O 0 C to approximately +100 0 C, in many cases in the range between room temperature and approximately +80 0 C.
  • a compound I can be converted in a manner known per se into another compound I by replacing one or more substituents of the starting compound I in the customary manner by (an)other substituent(s) according to the invention.
  • R 2 which is different from hydrogen; or - in compounds I, in which R 3 is hydrogen, this hydrogen R 3 can be replaced by a substituent R 3 , which is different from hydrogen.
  • Salts of compounds I can be prepared in a manner known per se.
  • acid addition salts of compounds 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 I can be converted in the customary manner into the free compounds 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 I can be converted in a manner known per se into other salts of compounds 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 I which have salt- forming properties can be obtained in free form or in the form of salts.
  • the compounds 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 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 mi ⁇ croorganisms, 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-pro ⁇ duct 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 cry ⁇ stallization based
  • 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 biologically more effective iso ⁇ mer for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological ac ⁇ tivity.
  • the compounds I 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 I according to the invention are preventively and/or curatively valuable ac ⁇ tive 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 in ⁇ gredients 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.,
  • 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., Stor
  • 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 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.,
  • Myzus spp. Nephotettix spp., Nilaparvata spp., Parlatoria spp., Pemphigus spp., Planococ- cus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla 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,
  • 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., Pluteila 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, especi ⁇ ally on useful plants and ornamentals in agriculture, in horticulture and in forests, or on or ⁇ gans, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some ca ⁇ ses 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, to ⁇ matoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and
  • 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® , Herculex I® 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
  • VIP vegetative insecticidal proteins
  • 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 CrylMA055, 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.
  • 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-acetyitransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin);
  • transgenic crops are:
  • 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-1150 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-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacte ⁇ um sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylA(b) toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-O 392 225).
  • PRPs pathogenesis-related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-O 392 225, WO 95/33818, and EP-A-O 353 191.
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A- 0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906).
  • ion channel blockers such as blockers for sodium and calcium channels
  • the viral KP1 , KP4 or KP6 toxins for example the viral KP1 , KP4 or KP6 toxins
  • stilbene synthases such as the viral K
  • compositions according to the invention are the protection of stored goods and storerooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.
  • compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • 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., Omithocheyletia 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..
  • compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
  • compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec.,Tryptodendron spec, Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec, and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus
  • the invention therefore also relates to pesticidal compositions such as emulsifiable concen ⁇ trates, 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 concen ⁇ trates, 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 ingredi ⁇ ent 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 sol ⁇ vents or solid carriers, or such as surface-active compounds (surfactants).
  • auxiliaries conventionally used in the art of formulation, such as extenders, for example sol ⁇ vents or solid carriers, or such as surface-active compounds (surfactants).
  • Suitable solvents are: unhydrogenated or partially hydrogenated aromatic hy ⁇ drocarbons, preferably the fractions C 8 to Ci 2 of alkylbenzenes, such as xylene mixtures, al ⁇ kylated 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 ep
  • 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 dis- perse absorbtive polymers are also possible to add highly disperse silicas or highly dis- perse 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 conven ⁇ tionally 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 propy ⁇ lene 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.
  • soaps are the alkali, alkaline earth or (un- substituted or substituted) ammonium salts of fatty acids having approximately 10 to appro ⁇ ximately 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 pre ⁇ sent as alkali, alkaline earth or (substituted or unsubstituted) ammonium salts and they ge ⁇ nerally 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 dodecylsulfuric 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 circum- stances - 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 pro ⁇ pagation 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.
  • Example H1 Preparation of ⁇ /-(4-chloro-2-methyl-6-r(roxetan-2- ylmethvnamino)carbonv ⁇ phenyl)-1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1fV-pyrazole-5- carboxamide (compound P25):
  • Me means the methyl group.
  • Et means the ethyl group.
  • tBu is tert- butyl. If no definition for substituent X is given, then p is 0, if X is a substituent, then p is 1. If no definition for substituent Y is given, then q is 0, if Y is a substituent, then q is 1.
  • Example F1 Emulsion concentrates a) b) c)
  • 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)
  • 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)
  • 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 %
  • 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.
  • compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally 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, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
  • TX means "one compound selected from the group consisting of the compounds specifically described in tables P, P' and A of the present invention":
  • trichloronat (1452) + TX, trifenofos (1455) + TX, triflumuron (835) + TX, trimethacarb (840) + TX, triprene (1459) + TX, vamidothion (847) + TX, vaniliprole [CCN] + TX, veratridine (alternative name) (725) + TX, veratrine (alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302 (compound code) + TX 1 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(tribut
  • Ra 6 is trifluoromethyl or difluoromethyl (WO2004/058723) + TX,; the racemic compound of formula F-3 (syn)
  • Ra 9 is trifluoromethyl or difluoromethyl (WO03/074491) + TX, the compound of formula F-9
  • R 10 is trifluoromethyl or difluoromethyl (WO2004/058723) + TX, the racemic compound of formula F- 11 (trans)
  • R 11 is trifluoromethyl or difluoromethyl (WO03/074491) + TX, the racemic compound of formula F-12 (cis)
  • R 11 is trifluoromethyl or difluoromethyl (WO03/074491) + TX
  • the compound of formula F-13 which is a racemic mixture of formulae F-11 (trans) and F-12 (cis)
  • R 11 is trifluoromethyl or difluoromethyl (WO 03/074491) + TX
  • the compound of formula F-14 is trifluoromethyl or difluoromethyl (WO 03/074491) + TX
  • the mixtures comprising a compound of formula I 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 also 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 components (I) and active ingredients as described above is not essential for working the present invention.
  • Example B1 Activity against Aphis craccivora
  • Pea seedlings are infected with Aphis craccivora, subsequently sprayed with a spray mixture comprising 400 ppm of active ingredient and then incubated at 20°. 3 and 6 days later, the percentage reduction in the population (% activity) is determined by comparing the number of dead aphids between the treated and untreated plants.
  • Example B2 Activity a ⁇ ainst Diabrotica balteata
  • Maize seedlings are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient and, after the spray coating has dried on, populated with 10 larvae (2nd instar) of Diabrotica balteata and introduced into a plastic container. 6 days later, the percentage reduction in the population (% activity) is determined by comparing the number of dead larvae between the treated and untreated plants.
  • P22, P14, P21 , P11 P67, P68 have an activity of over 80%.
  • Example B3 Activity against Heliothis virescens (foliar application)
  • Young soya plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient and, after the spray coating has dried on, populated with 10 caterpillars (1st instar) of Heliothis virescens and introduced into a plastic container. 6 days later, the percentage reduction in the population and in the feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage between the treated and untreated plants.
  • P66, P9, P8, P67, P68, P23, P21 , P10, P11 , P47, P52, P53 have an activity of over 80%.
  • Example B4 Activity against Heliothis virescens (application to eggs)
  • Heliothis virescens eggs which have been deposited on cotton, are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. After 8 days, the percentage hatching rate of the eggs and the survival rate of the caterpillars (% activity) are evaluated in comparison with untreated control batches.
  • Example B5 Activity against Mvzus persicae (foliar application)
  • Pea seedlings are infected with Myzus persicae, subsequently sprayed with a spray mixture comprising 400 ppm of active ingredient and then incubated at 20°. 3 and 6 days later, the percentage reduction in the population (% activity) is determined by comparing the number of dead aphids between the treated and untreated plants.
  • Example B6 Activity against Mvzus persicae (systemic application)
  • Pea seedlings are infected with Myzus persicae, and their roots are subsequently placed into a spray mixture comprising 400 ppm of active ingredient. The seedlings are then incubated at 20°. 3 and 6 days later, the percentage reduction in the population (% activity) is determined by comparing the number of dead aphids between the treated and untreated plants.
  • Example B7 Activity against Plutella xylostella
  • Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient and, after the spray coating has dried on, populated with 10 caterpillars (3rd instar) of Plutella xylostella and introduced into a plastic container. 3 days later, the percentage reduction in the population and in the feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage between the treated and untreated plants.
  • compounds listed in the Tables above show good activity.
  • compounds P1 , P2, P6, P39, P3, P41 , P7, P10, P15, P24, P29, P31 , P25, P8, P9, P32, P30, P12, P13, P23, P22, P63, P62, P61, P60, P64, P63, P14, P46, P48, P50, P51, P17, P65, P66, P21 , P18, P10, P67, P68, P16, P11, P35, P52, P53, P38, P40, P70 have an activity of over 80%.
  • Young soya plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient and, after the spray coating has dried on, populated with 10 caterpillars (1st instar) of Spodoptera littoralis and introduced into a plastic container. 3 days later, the percentage reduction in the population and in the feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage between the treated and untreated plants.
  • Standard Cydia diet cubes (1.5 cm width) are pierced with a tooth-pick and are immersed in liquid paraffin (ca. 8O 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.
  • Example B10 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. 566 described on page 122 of WO03/024222):
  • Table B10a Systemic Insecticide Test for Spodoptera littoralis
  • Table B10a shows that compound No. P41 according to the invention exerts a substantially better insecticidal action on Spodoptera littoralis than the compound from the state of the art. Especially at low application rates (3 and 0.8 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.
  • Table B10b shows that compound No. P41 according to the invention exerts a substantially better insecticidal action on Heliothis virescens than the compound from the state of the art. Especially at low application rates (3, 0.8 and 0.2 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.
  • Table B10c shows that compound No. P41 according to the invention exerts a substantially better insecticidal action on Plutella xylostella than the compound from the state of the art. Especially at low application rates (3 and 0.8 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 01/70671 , WO 03/016284, WO 03/015518, WO 03/024222 and WO 04/033468. There have now been found novel anthranilamide derivatives with pesticidal properties, especially for the control of insects and members of the order Acarina.
The present invention accordingly relates to compounds of formula I
Figure imgf000003_0001
wherein each of E and Z, which may be the same or different, represents oxygen or sulfur;
A is CrCδalkylene, C2-C6alkenylene, C2-C6alkynylene, or a bivalent three- to ten-membered monocyclic or fused bicyclic ring system which can be partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms; and it being possible for the three- to ten-membered ring system itself and also for the C1-
C6alkylene, C2-C6alkenylene and C2-C6alkynylene groups to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C5-
C7cycloalkenyl, C5-C8cycloalkynyl, CrC6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-
C6halocycloalkyl, Cs-C^alocycloalkenyl, C5-C8halocycloalkynyl, CrC4alkoxy, C1-
C4haloalkoxy, CrC4alkylthio, C1-C4haloalkylthio, CrC4alkylsulfinyl, C1-C4alkylsulfonyl, C1- C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, CrC6alkyl-C3-C6cycloalkylamino, C2- C4alkylcarbonyl, C2-C6alkoxycarbonyl) C2-C6alkylaminocarbonyl, Ca-Cedialkylaminocarbonyl, C2-C6alkoxycarbonyloxy, C^Cealkylaminocarbonyloxy, Ca-Cβdialkylaminocarbonyloxy or G3- Cetrialkylsilyl, or by a three- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic, partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms, and it being possible for the three- to ten-membered ring system itself to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C5- C7cycloalkenyl, C5-C8cycloalkynyl, CrCβhaloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3- C6halocycloalkyl, C5-C7halocycloalkenyl, C5-C8halocycloalkynyl, CrC4alkoxy, Cr C4haloalkoxy, C^C^lkylthio, CrC4haloalkylthio, C1-C4alkylsulfinyl, Cr^alkylsulfonyl, C1- C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, CrC6alkyl-C3-C6cycloalkylamino, C2- C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, Cs-Cβdialkylaminocarbonyl, C2-C6alkoxycarbonyloxy,
Figure imgf000004_0001
Cs-Cedialkylaminocarbonyloxy, C3- C6trialkylsilyl or phenyl, it being possible for the phenyl group in turn to be substituted by hydroxy, CrC6alkyl, CrC6haloalkyl, CrC6alkylthio, CrC6halσalkylthio, C3-C6alkenylthio, C3- C6haloalkenylthio, C3-C6alkynylthio, CrCsalkoxy-CrCsalkylthio, C2-C4alkylcarbonyl-Cr C3alkylthio, C^-C^lkoxycarbonyl-CrCsalkylthio, cyano-CrC∑jalkylthio, CrCealkylsulfinyl, C1- C6haloalkylsulfinyl, CrC6alkylsulfonyl, CrC6haloalkylsulfonyl, aminosulfonyl, C1- C2alkylaminosulfonyl, N,N-di(CrC2alkyl)aminosulfonyl, di(CrC4alkyl)amino, halogen, cyano or nitro; and substituents at nitrogen atoms in the ring systems being other than halogen; X is oxygen, NH or CτC4alkyl-N;
Y is CrCealkylene, C2-C6alkenylene, C2-C6alkynylene, or a bivalent three- to ten-membered monocyclic or fused bicyclic ring system which can be partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms; and it being possible for the three- to ten-membered ring system itself and also for the C1- C6alkylene, C2-C6alkenylene and C2-C6alkynylene groups to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C5- C7cycloalkenyl, C5-C8cycloalkynyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3- C6halocycloalkyl, Cs-CT-halocycloalkenyl, C5-C8halocycloalkynyl, CrC4alkoxy, C1- C4haloalkoxy, CrC4alkylthio, C1-C4haloalkylthio, CrC4alkylsulfinyl, C1-C4BlRyISuIfOnYl, C1- C4alkylamino, C2-C4clialkylamino, C3-C6cycloalkylamino, C-rCealkyl-Cs-Cecycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl,
Figure imgf000005_0001
C3- Cedialkylaminocarbonyl, Ca-Cealkoxycarbonyloxy, C2-C6alkylaminocarbonyloxy, C3- C6dialkylaminocarbonyloxy or C3-C6trialkylsilyl, or by a three- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic, partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms, and it being possible for the three- to ten-membered ring system itself to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, CrC6alkyl, C2- C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C5-C7cycloalkenyl, C5-C8cycloalkynyl, C1- C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, Cs-Cβhalocycloalkyl, C5-C7halocycloalkenyl, C5-C8halocycloalkynyl, CrC4alkoxy, C1-C4haloalkoxy, Ci-C4alkylthio, Ci-C4haloalkylthio, C1- C4alkylsulfinyl, CrGjalkylsulfonyl, CrC^lkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, CrCβalkyl-Cs-Cecycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2- C6alkylaminocarbonyl, Cs-Cedialkylaminocarbonyl, C2-C6alkoxycarbonyloxy, C2- C6alkylaminocarbonyloxy, CrCedialkylaminocarbonyloxy, C3-C6trialkylsilyl or phenyl, it being possible for the phenyl group in turn to be substituted by hydroxy, Ci-C6alkyl, CrC6haloalkyl, CrCealkylthio, CrCehaloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, CrCsalkoxy-CrCsalkylthio, C2-C4alkylcarbonyl-CrC3alkylthio, C2-C4alkoxycarbonyl-CrC3- alkylthio, CyBnO-C1 -C3alkylthio, CrC6alkylsulfinyl, CrC6haloalkylsulfinyl, CrC6alkylsulfonyl, CrCehaloalkylsulfonyl, aminosulfonyl, CrC^lkylaminosulfonyl, N.N-di^rCaalkyOamino- sulfonyl, di(CrC4alkyl)amino, halogen, cyano or nitro; and substituents at nitrogen atoms in the ring systems being other than halogen; p is 0 or 1; q is O or 1;
B is a three- to four-membered ring system which is fully or partially saturated and can contain a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, and it being possible for the three- to four-membered ring system itself to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, C5-C7cycloalkenyl, C5-C8cycloalkynyl, C^Cehaloalkyl, C2-C6haloalkenyl, C2- C6haloalkynyl, C3-C6halocycloalkyl, Cs-CT-halocycloalkenyl, C5-C8halocycloalkynyl, C1- C4alkoxy, CrC4haloalkoxy, CrC4alkylthio, CrC4haloalkylthio, C1^aIkYlSuIfJnYl, C1- C4alkylsulfonyl, CrC4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, CrC6alkyl-C3- - A -
Cecycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, Ca-Cδalkylaminocarbonyl, C3- Cedialkylaminocarbonyl, C2-C6alkoxycarbonyloxy, C2-C6alkylaminocarbonyloxy, C3- Cedialkylaminocarbonyloxy, QrCetrialkylsilyl, or by a three- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic, partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms, and it being possible for the three- to ten-membered ring system itself to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, CrC6alkyl, C2- C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C5-C7cycloalkenyl, C5-C8cycloalkynyl, C1- C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, C5-C7halocycloalkenyl, C5-C8halocycloalkynyl, CrC4alkoxy, C1-C4IIaIOaIkOXy1 CrC4alkylthio, CrC4haloalkylthio, C1- C4alkylsulfinyl, d^alkylsulfonyl, C-ι-C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, CrCealkyl-CrCecycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2- C6alkylaminocarbonyl, QrCedialkylaminocarbonyl, C2-C6alkoxycarbonyloxy, C2- C6alkylaminocarbonyloxy, Cs-Cβdialkylaminocarbonyloxy, C3-C6trialkylsilyl or phenyl, it being possible for the phenyl group in turn to be substituted by hydroxy, C^Cealkyl, C1- C6haloalkyl,CrC6alkylthio, CrC6haIoalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3- C6alkynylthio, CrCsalkoxy-CrCsalkylthio, CrC^lkylcarbonyl-CrCsalkylthio, C2- C^lkoxycarbonyl-CrCsalkylthio, cyano-CrCsalkylthio, d-Cealkylsulfinyl, CrC6halo- alkylsulfinyl, CrCealkylsulfonyl, CrCβhaloalkylsulfonyl, aminosulfonyl, CrC2alkylamino- sulfonyl, N^-di^rC^lkyOaminosulfonyl, di(CrC4alkyl)amino, halogen, cyano or nitro; and substituents at nitrogen atoms in the ring systems being other than halogen; each R1 independently is halogen, nitro, hydroxy, Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, CrC6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, C1- C4alkoxy, CrC4haloalkoxy, C1-C4alkylthio, C1-C4haloalkylthio, CrC4haloalkylsulfinyl, C1- C4haloalkylsulfonyl,
Figure imgf000006_0001
C2- C4dialkylamino, C3-C6cycloalkylamino, CrCβalkyl-Cs-Cecycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, Cs-Cedialkylaminocarbonyl, C2- C6alkoxycarbonyloxy, C2-C6alkylaminocarbonyloxy, Cs-Cedialkylaminocarbonyloxy or C3- C6trialkylsilyl, phenyl, benzyl or phenoxy, or phenyl, benzyl or phenoxy mono-, di- or trisubstituted by halogen, cyano, nitro, halogen, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, CrCβhaloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, C1- C4alkoxy, CrC4haloalkoxy, CrC^lkylthio, CrC4haloalkylthio, CrC4alkylsulfinyl, C1- C4alkylsulfonyl, CrC4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, CrC6alkyl-C3- Cecycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, C^Cealkylaminocarbonyl, C3- C6dialkylaminocarbonyl, C2-C6alkoxycarbonyloxy, C2-C5alkylaminocarbonyloxy, C3- C6dialkylaminocarbonyloxy or C3-C6trialkylsilyl; or each R1 independently is amino, formyl, C2-C6cyanoalkenyl, C2-C6alkylcarbonylamino, phenylcarbonyiamino which can be mono-, di- or trisubstituted by halogen, cyano, nitro, halogen, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, CrC6haIoalkyl, C2- C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, CrC4alkoxy, CrC4haloalkoxy, C1- C4alkylthio, C1-C4haloalkylthio, CrC4alkylsulfinyl, CrC4alkylsulfonyl, Cr^alkylamino, C2- C4dialkylamino, C3-C6cycloalkylamino, CrCβalkyl-Cs-Cecycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C3alkylaminocarbonyl, Cs-Cβdialkylaminocarbonyl, C2- C6alkoxycarbonyloxy, C^Cealkylaminocarbonyloxy, Cs-Cβdialkylaminocarbonyloxy or C3- Cetrialkylsilyl; or each R1 independently is 2-,3- or 4-pyridylcarbonylamino which can be mono-, di- or trisubstituted by halogen, cyano, nitro, halogen, Ci-Cealkyl, C2-C6alkenyl, C2- C6alkynyl, C3-C6cycloalkyl, CrC6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3- C6halocycloalkyl, C1-C4alkoxy, C-,-C4haloalkoxy, CrC4alkylthio, CrC4haloalkylthio, C1- C4alkylsulfinyl, Cr^alkylsulfonyl, CrC4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, CrCβalkyl-Cs-Cecycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2- C6alkylaminocarbonyl, Ca-Cβdialkylaminocarbonyl,
Figure imgf000007_0001
C2- C6alkylaminocarbonyioxy, Cs-Cβdialkylaminocarbonyloxy or C3-C6trialkylsilyl; or each R1 independently is C2-C6alkoxycarbonylamino,
Figure imgf000007_0002
C3- C6dialkylaminocarbonylamino, C2-C6haloalkylcarbonyl or is a group RxON=C(Ry)-, wherein Rx and Ry independently are hydrogen or CrC6alkyl; n is O, 1 , 2, 3 or 4; 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, C1-C^IkOXy, CrC4haloalkoxy, CrC4alkylthio, CrC4haloalkylthio, C1-C4alkylsulfinyl, CrC4alkylsulfonyl, C-ι-C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino and C1- C6alkyl-C3-C6cycloalkylamino;
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, CrC6haloalkyl, halogen, cyano, C1- C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, CrC4haloalkylthio, Ci-C4alkylsulfinyl, C1- C4alkylsulfonyl, CrC4haloalkylsulfinyl or CrC4haloalkylsulfonyl; or D is a group
Figure imgf000008_0001
Figure imgf000008_0002
R4, R4', Rio, Ri7, and R19 independently from each other, are hydrogen, C^Cealkyl, C3- C6cycloalkyl, CVCehaloalkyl, halogen, cyano, CrC4alkoxy, CrC4haloalkoxy, C2- C4alkoxycarbonyl, Ci-C4alkylthio, CrC4haloalkylthio, CrC4alkylsulfinyl, CrC4alkylsulfonyl, Ci-C4haloalkylsulfinyl or CrC4haloalkylsulfonyl;
R5, Re, Rs, Rn, R12, Ri5, R16 and R18 independently from each other, are C^Cealkyl or C1- C6alkyl mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, CrC^lkoxy, C2- C4alkoxycarbonyl, CrC4alkylthio, CrC4alkylsulfinyl, CrC^lkylsulfonyl, C1-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, CrCehaloalkyl, halogen, cyano, CrC4alkoxy, d-C^aloalkoxy, CrC4alkylthio, CrC4haloalkylthio, CrC^lkylsulfinyl, CrC^lkylsulfonyl, Cr^haloalkylsulfinyl or C1- C4haloalkylsulfonyl;
R7, R9, R13 and R14 independently from each other, are hydrogen, CrCβalkyl, CrCehaloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C3-C6alkenyl or C3-C6haloalkenyl and agronomically acceptable salts/isomers/enantiomers/tautomers/N-oxides of those compounds, with the exception of the compound 2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3- carboxylic acid [2-methyl-6-(oxiranylmethyl-carbamoyl)-phenyl]-amide.
Compounds 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 C1-C4alkanecarboxylic acids which are unsubstitu- ted 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 orga¬ nic sulfonic acids, such as CrC4alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. Com¬ pounds 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 mor- pholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, die¬ thyl-, 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 disadvan¬ tage 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 I or agrochemically utilizable salts thereof. Owing to the close relationship between the compounds I in free form and in the form of their salts, for the purposes of the invention the free compounds I or their salts hereinabove and hereinbelow are respectively to be understood as including, where appropriate, the corresponding salts or the free compounds I. The same applies analogously to tautomers of compounds 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-i-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 C3-C2oalkenyl 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 (C2-alkoxycarbonyl), ethoxy carbony I (C3- alkoxycarbonyl), 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 methylsulfiny! 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. Alkylaminocarbonyl is, for example, methylaminocarbonyl (C2-alkylaminocarbonyl) or ethylaminocarbonyl (C3-aminocarbonyl). 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.
Examples for B as a optionally substituted three- to four-membered ring system which is fully or partially saturated and can contain a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, are cyclopropyl, methyl-cyclopropyl, cyclopropenyl, cyclobutyl,
Figure imgf000011_0001
cyclobutenyl, or According to the present invention, a three- to ten-membered, monocyclic or fused bicyclic ring system which may be partially saturated or fully saturated is, depending of the number of ring members, for example, selected from the group consisting of
Figure imgf000012_0001
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, where said cycloalkylgroups for their part may be preferably unsubstituted or substituted by CrC6alkyl or halogen, or is
Figure imgf000012_0002
Figure imgf000013_0001
wherein each R26 is methyl, each R27 and each R28 are independently hydrogen, CrC3alkyl, CrC3alkoxy, CrCsalkylthio or trifluoromethyl, X4 is oxygen or sulfur and r = 1 , 2, 3 or 4.
CH
Where no free valency is indicated in those definitions, for example as in ° , the linkage
site is located at the carbon atom labelled "CH" or in a case such as, for example,
Figure imgf000013_0002
at the bonding site indicated at the bottom left. The second valence for the bivalent ring system of substituent A or Y can be located at any suitable position of the ring.
According to the present invention, a three- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated is, depending of the number of ring members, for example, selected from the group consisting of
Figure imgf000013_0003
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, where said cycloalkylgroups for their part may be preferably unsubstituted or substituted by CVCealkyl or halogen, or is phenyl, benzyl, naphthyl or the following heterocyclic groups: pyrrolyl; pyridyl; pyrazolyl; pyrimidyl; pyrazinyl; imidazolyl; thiadiazolyl; quinazolinyl; furyl; oxadiazolyl; indolizinyl; pyranyl; isobenzofuranyl; thienyl; naphthyridinyl; (1-methyl-1 H-pyrazol-3-yl)-; (1-ethyl-1H-pyrazol-3- yl)-; (1-propyl-1H-pyrazol-3-yl)-; (1 H-pyrazol-3-yl)-; (1 ,5-dimethyI-1 H-pyrazόl-3-yl)-; (4-chloro- 1-methyl-1H-pyrazol-3-yl)-; (1H-pyrazol-1-yl)-; (3-methyl-1 H-pyrazol-1-yl)-; (3,5-dimethyl-1 H- pyrazol-1-yl)-; (3-isoxazolyl)-; (5-methyl-3-isoxazolyl)-; (3-methyl-5-isoxazolyl)-; (5-isox- azolyl)-; (1 H-pyrrol-2-yl)-; (1-methyl-1H-pyrrol-2-yl)-; (1 H-pyrrol-1-yl)-; (1-methyl-1H-pyrrol-3- yl)-; (2-furanyl)-; (5-methyl-2-furany!)-; (3-furanyl)-; (5-methyl-2-thienyl)-; (2-thienyI)-; (3- thienyl)-; (1-methyl-1H-imidazol-2-yl)-; (1 H-imidazol-2-yl)-; (1-methyl-1H- imidazol-4-yl)-; (1- methyl-1 H-imidazol-5-yl)-; (4-methyl-2-oxazolyl)~; (5-methyl-2-oxazolyl)-; (2-oxazolyl)-; (2- methyl-5-oxazolyl)-; (2-methyl-4-oxazolyl)-; (4-methyl-2-thiazolyl)-; (5-methyl-2-thiazolyl)-; (2- thiazolyl)-; (2-methyl-5-thiazolyl)-; (2-methyl-4-thiazolyl)-; (3-methyl-4-isothiazolyl)-; (3- methyl-5-isothiazolyl)-; (5-methyl-3-isothiazolyl)-; (1-methyl-1 H-1 ,2,3-triazol-4-yl)-; (2-methyl- 2H-1 ,2,3-triazol-4-yl)-; (4-methyl-2H-1 ,2,3-triazol-2-yl)-; (1-methyl-1 H-1 ,2,4-triazol-3-yl)-; (1 ,5- dimethyl-1 H-1 ,2,4-triazol-3-yl)-; (3-methyl-1 H-1 ,2,4-triazol-1 -yl)-; (5-methyl-1 H-1 ,2,4-triazoI- 1-yl)-; (4,5-dimethyl-4H-1 ,2,4-triazol-3-yl)-; (4-methyl-4H-1 ,2,4-triazol-3-yl)-; (4H-1 ,2,4-triazol- 4-yl)-; (5-methyl-1 ,2,3-oxadiazol-4-yl)-; (1 ,2,3-oxadiazol-4-yl)-; (3-methyl-1 ,2,4-oxadiazol-5- yl)-; (5-methyl-1 ,2,4-oxadiazol-3-yl)-; (4-methyl-3-furazanyl)-; (3-furazanyl)-; (5-methyl-1 ,2,4- oxadiazol-2-yl)-; (5-methyl-1 ,2,3-thiadiazol-4-yl)-; (1 ,2,3-thiadiazol-4-yl)-; (3-methyl-1 ,2,4- thiadiazol-5-yl)-; (5-methyl-1 ,2,4-thiadiazol-3-yl)-; (4-methyl-1 ,2,5-thiadiazol-3-yl)-; (5-methyl- 1 ,3,4-thiadiazol-2-yl)-; (1-methyl-1 H-tetrazol-5-yl)-; (1 H-tetrazol-5-yl)-; (5-methyl-1 H-tetrazol- 1 -yl)-; (2-methyl-2H-tetrazol-5-yl)-; (2-ethyl-2H-tetrazol-5-yl)-; (5-methyl-2H-tetrazol-2-yl)-; (2H-tetrazol-2-yl)-; (2-pyridyl)-; (6-methyl-2-pyridyl)-; (4-pyridyl)-; (3-pyridyl)-; (6-methyl-3- pyridazinyl)-; (5-methyl-3-pyridazinyl)-; (3-pyridazinyl)-; (4,6-dimethyl-2-pyrimidinyl)-; (4- methyl-2-pyrimidinyl)-; (2-pyrimidinyl)-; (2-methyl-4-pyrimidinyl)-; (2-chloro-4-pyrimidinyl)-; (2,6-dimethyl-4-pyrimidinyl)-; (4-pyrimidinyl)-; (2-methyl-5-pyrimidinyI)-; (6-methyl-2-pyr- azinyl)-; (2-pyrazinyl)-; (4,6-dimethyl-1 ,3,5-triazin-2-yl)-; (4,6-dichloro-1 ,3,5-triazin-2-yl)-; (1 ,3,5-triazin-2-yl)-; (4-methyl-1 ,3,5-triazin-2-yl)-; (3-methyl-1 ,2,4-triazin-5-yl)-; (3-methyl- 1,2,4-triazin-6-yl)-;
Figure imgf000014_0001
Figure imgf000015_0001
wherein each R2β is methyl, each R27 and each R28 are independently hydrogen, CrC3alkyl, CrC3alkoxy, CrCsalkylthio or trifluoromethyl, X4 is oxygen or sulfur and r = 1 , 2, 3 or 4.
Where no free valency is indicated in those definitions, for example as in ° , the linkage
site is located at the carbon atom labelled "CH" " o orr i inn a a c caassee s suucchh a ass,, f foorr e exxaammppllee,,
Figure imgf000015_0002
' at the bonding site indicated at the bottom left.
Compounds of formula I are preferred, wherein R4' is hydrogen and each R1 independently is halogen, nitro, hydroxy, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C1- C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, Cs-Cehalocycloalkyl, C1-C-IaIkOXy, C1- C4haloalkoxy, C1-C4alkylthio, CrC4haIoalkylthio, CrC^aloalkylsulfinyl, C1- C4haloalkylsulfonyl, CrC4alkylsulfinyl, C1-C4alkylsulfonyl, CrC4alkylamino, C2- C4dialkylamino, C3-C6cycloalkylamino, C-i-Cealkyl-Cs-Cecycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, Cs-Cedialkylaminocarbonyl, C2- C6alkoxycarbonyloxy, C2-C6alkylaminocarbonyloxy, Cs-Cδdialkylaminocarbonyloxy 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, CrCehaloalkyl, C2-C6haloalkenyl, C2-Cβhaloalkynyl, C3-C6halocycloalkyl, C1- C4alkoxy, CrC4haloalkoxy, CrC4alkylthio, CrC4haloalkylthio, CrC4alkylsulfinyl, C1- C4alkylsulfonyl, C1-C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, CrC6alkyl-C3- Cβcycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, C3- C6dialkylaminocarbonyl, Ca-Cβalkoxycarbonyloxy, C2-C6alkylaminocarbonyloxy, C3- C6dialkylaminocarbonyloxy or C3-C6trialkylsilyl.
In especially preferred compounds of formula I,
B is a three- to four-membered ring system which is fully or partially saturated, and it being possible for the three- to four-membered ring system itself to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C5-C7cycloalkenyl, C5-C8cycloalkynyl, CrCehaloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3- C6halocycloalkyl, C5-C7halocycloalkenyl, C5-C8halocycloalkynyl, CrC4alkoxy, C1- C4haloalkoxy, CrC4alkylthio, CrC4haloaIkylthio, CrC4alkylsulfinyl, CrC4alkylsulfonyl, C1- C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, CrC6alkyl-C3-C6cycloalkylamino, C2- C4alkylcarbonyl, Ca-Cealkoxycarbonyl, C2-C6alkylaminocarbonyl, Cs-Cedialkylaminocarbonyl, C2-C6alkoxycarbonyloxy, C2-C6alkylaminocarbonyloxy, Cs-Cedialkylaminocarbonyloxy, C3- C6trialkylsilyl, or by a three- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic, partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms, and it being possible for the three- to ten-membered ring system itself to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, C5-C7cycloalkenyl, C5-C8cycloalkynyl, CrCehaloalkyl, C2-C6haloalkenyl, C2- C6haloa!kynyl, Cs-Cehalocycloalkyl, C5-C7halocycloalkenyl, C5-C8halocycloalkynyl, C1- C4alkoxy, CrC4haloalkoxy, CrC4alkylthio, CrC4haloalkylthio, CrC4alkylsulfinyl, C1- C4alkylsulfonyl, CrC4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, CrC6alkyl-C3- C6cycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, C3- C6dialkylaminocarbonyl, Ca-Cβalkoxycarbonyloxy, C2-C6alkylaminocarbonyloxy, C3- Cedialkylaminocarbonyloxy, C3-C6trialkylsilyl or phenyl, it being possible for the phenyl group in turn to be substituted by hydroxy, CrC6alkyl, CrC6haloalkyl,CrC6alkylthio, C1- C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, CrC3alkoxy-Cr C3alkylthio, C2-C4alkylcarbonyl-CrC3alkylthio, C2-C4alkoxycarbonyl-CrC3alkylthio, cyano-Cr C3alkylthio, CrC6alkylsulfinyl, CrCehaloalkylsulfinyl, CrC6alkylsulfonyl, C1- C6haloalkylsulfonyl, aminosulfonyl, Cr^alkylaminosulfonyl, N,N-di(CrC2alkyl)aminosuIfonyl, di(C1-C4alkyl)amino, halogen, cyano or nitro; and substituents at nitrogen atoms in the ring systems being other than halogen.
Preference is given to subgroups of compounds of formula I wherein a) p and/or q is 0; b) E and/or Z is oxygen; and/or c) R2 and/or R3 is hydrogen.
X is preferably oxygen, NH; NMe or NEt.
Y is preferably CrC4alkylene, C2-C6alkenylene or C3-C6alkinylene or, C1-C4alkylene, C2- C6alkenylene or C3-C6alkinylene substituted by halogen, C3-C6cycloalkyl, ^^alkylsulfonyl or C1-C4BIkOXy.
Special mention should be made of compounds of formula I wherein R1 is selected from CrC4alkyl, halogen, CrCshaloalkyl, nitro, CrC4alkoxy, Ci-C4-haloalkoxy, C1-C4alkylthio, C1- C4alkylsulfinyl, CrC4alkylsulfonyl, CrC4haloalkylthio, CrC^haloalkylsulfinyl and C1- C4haloalkylsulfonyl, in particular from halogen and CrCβalkyl, preferably selected from methyl and halogen, most preferably selected from methyl and chloro, and n is 1 or 2, preferably 2. Preferred position of R1 is meta to the group -C(Z)-N(R3)-A-(X)p-(Y)q-B.
An outstanding group of compounds of formula I comprises those compounds wherein A is CrC6alkylene which may be substituted by C3-C6cycloalkyl, C2-C6alkenyl, cyano, C1- C4alkylthio, CrC4alkylsulfonyl, CrC4alkoxy, halogen or CrC6haloalkyI; or A is C3- C6cycloalkylene. Preferably A is CrCealkylene or cyclopropylene, most preferably methylene or cyclopropylene.
In further preferred compounds of formula I, B is cyclopropyl or cyclobutyl, preferably cyclopropyl.
Special emphasis should also be given to compounds of formula I wherein D is a group D1, wherein R5 is 2-pyridyl which can be substituted by halogen, preferably which is monosubstituted by chloro at the 3-position of the pyridine ring, R4' is hydrogen or halogen, preferably hydrogen and R4 is halogen preferably chloro and bromo, C^Cehaloalkyl preferably trifluoromethyl, CrC4haloaIkoxy, preferably 2,2,2-trifluoroethoxy.
Preference is also given to compounds of formula I wherein B is cyclopropyl or cyclobutyl which may be mono- di-, or trisubstituted by halogen, C-rC4aIkyl, hydroxy, cyano, C1- C4alkoxy or CrC4alkylthio; or B is CH(CH2O), CH(CHMeO), CH-(CMe2O), CH(CH2S), CH(CH2OCH2), CH(CHMeOCH2), CH(CMe2OCH2), CH(CH2S-(O)2CH2), CH(CHMeS(O)2CH2), CH(CMe2S(O)2CH2), C(Me)-(CH2O), C(Me)(CHMeO), C(Me)-(CMe2O), C(Me)-(CH2S), C(Me)-(CH2OCH2), C(Me)(CHMeOCH2), C(Me)-(CMe2OCH2), C(Me)- (CH2S(O)2CH2), C(Me)-(CHMe-S(O)2CH2) or C(Me)-(CMe2-S(O)2CH2). In especially preferred compounds of formula I B is cyclopropyl or cyclobutyl which may be substituted by halogen or methyl, in particular by chloro, bromo and methyl; preferably B is cyclopropyl.
In an outstanding group of compounds of formula I the substituents have the following meanings: n is 2 and one R1 is CrC4alkyl, preferably methyl, or halogen, preferably chloro, the other R1 is halogen preferably chloro or bromo; wherein most preferably one R1 with the meaning C1-
C4alkyl occupies the ortho position with regard to the group -N(R2)-C(E)-D.
D is a group D1, wherein R4' is hydrogen, R4 is halogen preferably chloro and bromo, C1-
Cehaloalkyl preferably trifluoromethyl, CrC4haloalkoxy, preferably 2,2,2-trtifluoroethoxy and
R5 is 2-pyridyl monosubstituted by halogen, preferably by 3-chloro;
R2 and R3 are hydrogen;
A is CrC6alkylene or a fully saturated bivalent 3-to 6-membered moncyclic ring system, preferably methylene, cyclopropylene or cyclobutylene, most preferably a fully saturated bivalent 3-to 6-membered moncyclic ring system, in particular cyclopropylene or cyclobutylene; p and q are O;
E and Z are oxygen; and B is cyclopropyl or cyclobutyl, preferably cyclopropyl.
The process according to the invention for preparing compounds of formula I 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 formula I or, where appropriate, a tautomer thereof, in each case in free form or in salt form, comprises a) for the preparation of a compound of formula I, in which R2 is hydrogen and E and Z are oxygen, or, where appropriate, a tautomer and/or salt thereof, reacting a compound of formula Il
Figure imgf000019_0001
in which R1, n, and D have the meanings given for formula I in claim 1, or, where appropriate, a tautomer and/or salt thereof with a compound of formula III
HN(R3)-A-(X)p-(Y)q-B (III),
in which R3, A, X, Y, p, q and B have the meanings given for formula I, or, where appropriate, with a tautomer and/or salt thereof or,
b) for the preparation of a compound of formula I, or, where appropriate, a tautomer and/or salt thereof, reacting a compound of formula IV
Figure imgf000019_0002
in which R1, R2, n, Z and D have the meanings given for the formula I in claim 1 ; and X1 is a leaving group, or, where appropriate, a tautomer and/or salt thereof with a compound of formula III
HN(Rg)-A-(X)P-OOq-B (III), in which R3, A, X, Y, p, q and B have the meanings given for formula I, or, where appropriate, with a tautomer and/or salt thereof or,
c) for the preparation of a compound of formula I1 or, where appropriate, a tautomer and/or salt thereof, reacting a compound of formula V
Figure imgf000020_0001
in which R1, R2, R3, n, A, X, Y, Z and B have the meanings given for the formula I in claim 1 , or, where appropriate, a tautomer and/or salt thereof with a compound of formula Vl
X2C(=O)D (Vl),
in which D has the meaning given for formula I in claim 1 ; 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 formulae III and V are novel and especially developped 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 formulae III and V. In especially preferred compounds of formula III
R3 is hydrogen;
A is CrC6alkylene which may be substituted by C3-C6cycloalkyl, C2-C6alkenyl, cyano, C1-
C4alkylthio, C^alkylsulfonyl, CrC4alkoxy, halogen or CrC6haloalkyl; or A is C3-
C6cycloalkylene; p and q are, independently from each other, 0 or 1 ;
X is oxygen, NH; NCH3 or NC2H5;
Y is CrC4alkylene, C2-C6alkenylene or C3-C6alkinylene or,
Figure imgf000021_0001
C2-C6alkenylene or C3-C6alkinylene substituted by halogen, C3-C6cycloalkyl, CrCialkylsulfonyl or CrC4alkoxy; B is cyclopropyl or cyclobutyl which may be mono- di-, or trisubstituted by halogen, C1- C4alkyl, hydroxy, cyano, CrC4alkoxy or CrC4alkylthio; or B is CH(CH2O), CH(CHMeO), CH- (CMe2O), CH(CH2S), CH(CH2OCH2), CH(CHMeOCH2), CH(CMe2OCH2), CH(CH2S-(O)2CH2), CH(CHMeS(O)2CH2), CH(CMe2S(O)2CH2), C(Me)-(CH2O), C(Me)(CHMeO), C(Me)-(CMe2O), C(Me)-(CH2S), C(Me)-(CH2OCH2), C(Me)(CHMeOCH2), C(Me)-(CMe2OCH2), C(Me)- (CH2S(O)2CH2), C(Me)-(CHMe-S(O)2CH2) or C(Me)-(CMe2-S(O)2CH2), preferably B is cyclopropyl or cyclobutyl which may be mono- di-, or trisubstituted by halogen, CrC^lkyl, hydroxy, cyano, Ci-C4alkoxy or C|-C4alkylthio.
In especially preferred compounds of formula V
R1 is CrC4alkyl, halogen, CrC5haloalkyl, nitro, C1-C^IkOXy, C1-C4-IIaIOaIkOXy, C1-
C4alkylthio, Ci-C4alkylsulfinyl, d-C4alkylsulfonyl, CrC4haloalkylthio, CrC4haloalkylsulfinyl or
C1-C4haloalkylsulfonyl;
R2 and R3 are hydrogen;
A is CrCealkylene which may be substituted by C3-C6cycloalkyl, C2-C6alkenyl, cyano, C1-
C4alkylthio, CτC4alkylsulfonyl, CrC4alkoxy, halogen or Ct-C6haloalkyl; or A is C3-
C6cycloalkylene; p and q are, independently from each other, O or 1 ;
X is oxygen, NH; NCH3 or NC2H5;
Y is CrC4alkylene, C2-C6alkenylene or C3-C6alkinylene or, C^dalkylene, C2-C6alkenylene or C3-C6alkinylene substituted by halogen, C3-C6cycloalkyl, CrC4alkylsulfonyl or CrC4aIkoxy; B is cyclopropyl or cyclobutyl which may be mono- di-, or trisubstituted by halogen, C1- C4alkyl, hydroxy, cyano, CrC4alkoxy or CrC4alkylthio; or B is CH(CH2O), CH(CHMeO), CH- (CMe2O), CH(CH2S), CH(CH2OCH2), CH(CHMeOCH2), CH(CMe2OCH2), CH(CH2S-(O)2CH2), CH(CHMeS(O)2CH2), CH(CMe2S(O)2CH2), C(Me)-(CH2O), C(Me)(CHMeO), C(Me)-(CMe2O), C(Me)-(CH2S), C(Me)-(CH2OCH2), C(Me)(CHMeOCH2), C(Me)-(CMe2OCH2), C(Me)- (CH2S(O)2CH2), C(Me)-(CHMe-S(O)2CH2) or C(Me)-(CMe2-S(O)2CH2), preferably B is cyclopropyl or cyclobutyl which may be mono- di-, or trisubstituted by halogen, CrC4alkyl, hydroxy, cyano, C1-C-^IkOXy or CrC4aIkylthio.
Table B: Preferred compounds of formula III represented by the formula Ilia:
HN(H)-A-(X)p-(Y)q-B (Ilia),
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0002
Table D: Preferred compounds of formula V represented by formula Va:
Figure imgf000024_0001
Figure imgf000024_0003
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Physical data for compounds of formula Va according to Table D:
Figure imgf000028_0001
What has been said above for tautomers and/or salts of compounds 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 di¬ luent 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 -8O0C 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 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.
Variant a)
The reactants can be reacted with each other as such, i. e. without addition of a solvent or diluent, for example in the melt. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. Examples of such solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halohydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromo- benzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetra- chloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters such as ethyl acetate; ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethyleneglycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides such as N,N-di- methylformamide, N,N-diethylformamide, N.N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide.
The reaction is advantageously carried out in a temperature range from approximately -800C to approximately +1400C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between room temperature and approximately +80°C.
Variant b)
Examples of suitable leaving groups X1 in the compounds IV are hydroxy, CrCβalkoxy, halo- CrC8alkoxy, CrCsalkanoyloxy, mercapto, CrC8alkylthio, halo-CrCsalkylthio, CrCsalkylsul- fonyloxy, halo-CrCsalkylsulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and halogen, such as chlorine. Preferred are hydroxy, CrC8alkoxy and chlorine.
The reactants can be reacted with each other as such, i.e. without adding a solvent or dilu¬ ent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. Examples of suitable solvents or diluents are of the type described under variant a).
The reaction is advantageously carried out in a temperature range from approximately -80°C to approximately +14O0C, preferably from approximately -20°C to approximately +1000C, in many cases in the range between room temperature and the reflux temperature of the reaction mixture.
Variant c)
Examples of suitable leaving groups X2 in the compounds Vl are hydroxy, CrCsalkoxy, halo- CrC8alkoxy, CrCβalkanoyloxy, mercapto, CrC8alkylthio, halo-CrC8alkylthio, CrC8alkylsul- fonyloxy, halo-CrCsalkylsulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and halogen, such as chlorine. Preferred are hydroxy and chlorine. 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 dilu¬ ent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. Examples of suitable solvents or diluents are of the type described under variant a). 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,N-diethylaniline, may also act as solvents or diluents.
The reaction is advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -3O0C to approximately +1000C, in many cases in the range between room temperature and approximately +800C.
A compound I can be converted in a manner known per se into another compound I by replacing one or more substituents of the starting compound I in the customary manner by (an)other substituent(s) according to the invention.
For example,
- in compounds I, in which R2 is hydrogen, this hydrogen R2 can be replaced by a substituent
R2, which is different from hydrogen; or - in compounds I, in which R3 is hydrogen, this hydrogen R3 can be replaced by a substituent R3, which is different from hydrogen.
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 re¬ placed by other substituents according to the invention in the same reaction step.
Salts of compounds I can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds 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 I can be converted in the customary manner into the free compounds 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 I can be converted in a manner known per se into other salts of compounds 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 I, which have salt- forming properties can be obtained in free form or in the form of salts.
The compounds 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 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 mi¬ croorganisms, 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-pro¬ duct 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 cry¬ stallization based on their differing solubilities, to give the diastereomers, from which the de¬ sired 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 iso¬ mer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological ac¬ tivity. The compounds I 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 I according to the invention are preventively and/or curatively valuable ac¬ tive 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 in¬ gredients 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 exam¬ ple 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., Psylla 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., Pluteila 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, especi¬ ally on useful plants and ornamentals in agriculture, in horticulture and in forests, or on or¬ gans, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some ca¬ ses 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, to¬ matoes, 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® , Herculex I® 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 CrylMA055, 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-acetyitransferase (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 (Bt11 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 corn borer (Ostrinia nuhilalis 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-1150 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/NIJ00/10. 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-1150 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 compositions according to the invention are the protection of stored goods and storerooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.
In the hygiene sector, the compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
Examples of such parasites are:
Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp..
Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp..
Of the order Diptera and the suborders Nematocerina and Brachycerina, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma s ~~p"p\, 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., Omithocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp..
The compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
The compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec.,Tryptodendron spec, Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec, and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur, and termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus, and bristletails such as Lepisma saccharina.
The invention therefore also relates to pesticidal compositions such as emulsifiable concen¬ trates, 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 ingredi¬ ent 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 sol¬ vents or solid carriers, or such as surface-active compounds (surfactants).
Examples of suitable solvents are: unhydrogenated or partially hydrogenated aromatic hy¬ drocarbons, preferably the fractions C8 to Ci2 of alkylbenzenes, such as xylene mixtures, al¬ kylated 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 im¬ prove the physical properties, it is also possible to add highly disperse silicas or highly dis- perse 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 conven¬ tionally 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 propy¬ lene 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 appro¬ ximately 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 pre¬ sent as alkali, alkaline earth or (substituted or unsubstituted) ammonium salts and they ge¬ nerally 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 dodecylsulfuric 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 circum- stances - 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 pro¬ pagation 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
Example H1: Preparation of Λ/-(4-chloro-2-methyl-6-r(roxetan-2- ylmethvnamino)carbonvπphenyl)-1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1fV-pyrazole-5- carboxamide (compound P25):
Step 1 : Preparation of 2-(phtalimidomethyl)oxetane:
Figure imgf000047_0001
A solution of 2-(tosyioxymethyI)oxetane (27g, 111.4 mmol) (prepared according to A.O. Fitton et al., Synthesis 1987, (12), 1140-2) and potassium phtalimide (20.64g, 111.4 mmol) in DMF (200ml) is stirred at a temperature of 12O0C for 18hours, then evaporated in vacuo. The residue is taken up in ethyl acetate, the organic layer washed with water and brine, dried (Na2SO4), filtered, and evaporated to dryness. The crude solid product (19.8 g, 82%) is used in the next step without further purification.
Step 2: Preparation of 2-aminomethyloxetane:
Figure imgf000047_0002
To a solution of 2-(phtalimidomethyl)oxetane (the product of step 1) (19 g, 87.5 mmol) in ethanol (250 ml) is added hydrazine hydrate (6.56 g, 131.2 mmol) and the reaction mixture is heated to reflux for 30 minutes. The resulting precipitates are filtered off, a small amount of Raney Ni (W-2) added to the filtrate, and the mixture further refluxed for 1.5 hours. The inorganic materials are filtered off, and the filtrate was concentrated carefully under reduced pressure. The residue is distilled in vacuo to give a colorless liquid (3.63 g, ~47%), b.p. 55- 60°C/30 mbar. Contaminated with ethanol and DMF, the product is used in the next step without further purification.
Step 3: Preparation of compound P25:
Figure imgf000048_0001
To a solution of 6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl]-8- methyl-4f/-3,1-benzoxazin-4-one (200 mg, 0.45 mmol) (prepared according to WO 02/48115, example 2D) in tetrahydrofurane (4 ml), is added 2-aminomethyloxetane (the product of step 2) (79 mg, 0.91 mmol), and the mixture is heated to reflux for 30 minutes. The solution is allowed to cool to ambient temperature and the solvent evaporated in vacuo. The residue is purified by prep. HPLC (hexane/ethyl acetate gradient on LiChrospher Si 60, Merck NW25 column) to afford 180 mg (71%) of the title compound as a white solid. [1H- NMR (CDCI3): 10.21 (s, 1H), 8.48 (d, 1H), 7.88 (d, 1H), 7.41 (m, 1H), 7.32 (s, 1 H), 7.29 (m, 2H)1 6.63 (m, 1H), 4.98 (m, 1H), 4.68 (m, 1H), 4.48 (m, 1H), 3.71 (m, 1H), 3.59 (m, 1H), 2.68 (m, 1H), 2.43 (m, 1H), 2.19 (s, 3H); MS (electrospray ES+): 528, 530 ((M+H)+)].
Preparation of the intermediate bicyclopropyMylamine:
Figure imgf000048_0002
93.2 ml ( 328 mmol) Ti(OiPr)4 is added to a solution of 20 g (298 mmol) cyclopropane carbo- nitrile in 300 ml ether. The solution is cooled down to a temperature of -780C and 199 ml (596 mmol) ethylmagnesium bromide solution (3 M in ether) is slowly added. After 10 min at -780C, the slurry is allowed to warm up to ambient temperature and stirred for 1 hour. 84.6 g (595 mmol) BF3OEt2 is added and the mixture is stirred at ambient temperature for 18 hours. To this mixture, 600 ml NaOH 2N is slowly added at a temperature of O0C. The organic phase is separated and extracted with 600 ml HCI 2N. The water phase is evaporated and the residue is triturated in ether to afford 30.9 g (78%) of the title compound as an hydrochloride salt. The compounds listed in the following Tables P, P' and A can be prepared analogous to the procedures described above (m.p. = melting point in 0C): If no definition for substituent X is given, then p is 0, if X is a substituent, then p is 1. If no definition for substituent Y is given, then q is 0, if Y is a substituent, then q is 1. The group C(CH2CH2) for the substituent A means cyclopropyl with two free valences:
Figure imgf000049_0001
Designations for substituent B like CH(CH2O), CH(CHMeO), CH-(CMe2O), CH(CH2S), CH(CH2OCH2), CH(CHMeOCH2), CH(CMe2OCH2), CH(CH2S-(O)2CH2), CH(CHMeS(O)2CH2), CH(CMe2S(O)2CH2), C(Me)-(CH2O), C(Me)-(CHMeO), C(Me)- (CMe2O), C(Me)-(CH2S), C(Me)-(CH2OCH2), C(Me)-(CH-MeOCH2), C(Me)-(CMe2OCH2), C(Me)-(CH2S(O)2CH2), C(Me)-(CHMe-S(O)2CH2) or C(Me)-(CMe2-S(O)2CH2) define cyclic
rings. For example, CH(CH2O) is
Figure imgf000049_0002
, C(Me)-(CH-MeO) is , and
C(Me)-(CHMe-S(O)2CH2) is
Figure imgf000049_0003
Table P: Compounds of formula Ia:
Figure imgf000049_0004
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0002
Table P': Compounds of formula Ia':
Figure imgf000054_0001
Figure imgf000055_0002
The examples which follow are intended to illustrate the invention and show preferred compounds of formula I. Me means the methyl group. Et means the ethyl group. tBu is tert- butyl. If no definition for substituent X is given, then p is 0, if X is a substituent, then p is 1. If no definition for substituent Y is given, then q is 0, if Y is a substituent, then q is 1.
Table A: Compounds of formula Ia:
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
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 imgf000075_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_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000100_0001
Figure imgf000101_0001
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%
Ethylene glycol monomethyl ether 20 % -
Polyethylene glycol MW 400 70 %
N-Methylpyrrolid-2-one - - 20 %
Epoxidized coconut oil - - 1 % 5 %
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%
Attapulgite - 90% - 18%
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 %
Ethylene glycol 10 %
Nonylphenoxypolyethylene glycol ether (15 mol of EO) 6 %
Sodium lignosulfonate 10 %
Carboxymethylcellulose 1 %
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 compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally 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, pyridylmethyleneamino 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 P, P' and A 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) + TX1 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) + TX, 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) (111) + TX, camphechlor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbophenothion (947) + TX1 CGA 50'439 (development code) (125) + TX, chinomethionat (126) + TX, chlorbenside (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX1 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-0 (1037) + TX1 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-methyi (224) + TX, demeton-S- methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diazinon (227) + TX, dichlofluanid (230) + TX1 dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicofol (242) + TX, dicrotophos (243) + TX1 dienochlor (1071) + TX1 dimefox (1081) + TX, dimethoate (262) + TX1 dinactin (alternative name) (653) + TX1 dinex (1089) + TX, dinex-diclexine (1089) + TX, dinobuton (269) + TX, dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinocton (1090) + TX1 dinopenton (1092) + TX, dinosulfon (1097) + TX, dinoterbon (1098) + TX1 dioxathion (1102) + TX, diphenyl sulfone (IUPAC name) (1103) + TX1 disulfiram (alternative name) [CCN] + TX, disulfoton (278) + TX, DNOC (282) + TX, dofenapyn (1113) + TX1 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) + TX1 etoxazole (320) + TX1 etrimfos (1142) + 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 (1157) + TX, fentrifanil (1161) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacrypyrim (360) + TX, fluazuron (1166) + TX, flubenzimine (1167) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1174) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1192) + TX, formparanate (1193) + TX, gamma-HCH (430) + TX, glyqdin (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) + TX1 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 (711) + TX, quintiofos (1381) + TX, R-1492 (development code) (1382) + TX1 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) + TX1 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) + TX, 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, etnamectin (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-1H- pyridine-2-thione (IUPAC name) (1222) + TX, 4~(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoIine sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX1 dipyrithione (1105) + TX, dodicin (1112) + TX, fenaminosulf (1144) + TX1 formaldehyde (404) + TX1 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 (611) + 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) + TX1 Heterorhabditis bacteriophora and H. megidis (alternative name) (433) + TX, Hippodamia 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, Steinemema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinemema 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] + TX, 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, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829) + TX, (£)-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, (7 E + 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) + TX1 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 + TX, 13-dien-1-yl acetate (IUPAC name) (588) + TX, octadeca-3 + TX, 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-11-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 (1137) + 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 + TX1 1-dichloro- 1-nitroethane (lUPAC/Chemical Abstracts name) (1058) + TX, 1 + TX, 1-dichloro-2 + TX, 2-bis(4-ethylphenyl)ethane (IUPAC name) (1056) + TX, 1 + TX, 2-dichloropropane (lUPAC/Chemical Abstracts name) (1062) + TX, 1 + TX, 2-dichloropropane with 1 + TX, 3-dichloropropene (IUPAC name) (1063) + TX, 1-bromo-2-chloroethane (lUPAC/Chemical Abstracts name) (916) + TX, 2 + TX, 2 + TX, 2-trichloro-1-(3 + TX, 4-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX, 2 + TX, 2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate (IUPAC name) (1066) + TX, 2-(1 + TX, 3-dithiolan-2-yl)phenyl dimethylcarbamate (IUPAC/ Chemical Abstracts name) (1109) + TX, 2-(2- butoxyethoxy)ethyl thiocyanate (lUPAC/Chemical Abstracts name) (935) + TX, 2-(4 + TX, 5-dimethyl-1 + TX, 3-dioxolan-2-yI)phenyl methylcarbamate (IUPAC/ Chemical Abstracts name) (1084) + TX, 2-(4-chIoro-3 + TX, 5-xylyloxy)ethanol (IUPAC name) (986) + TX, 2- chlorovinyl diethyl phosphate (IUPAC name) (984) + TX, 2-imidazolidone (IUPAC name) (1225) + TX, 2-isovalerylindan-1 + TX, 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 + TX, 5-xylyl methylcarbamate (IUPAC name) (1285) + TX, 5 + TX, 5-dimethyl-3-oxocyclohex-1-enyi 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, aidoxycarb (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) + TX1 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) (111) + TX, camphechlor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbon disulfide (lUPAC/Chemica! 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, cyfluthrin (193) + TX1 cyhalothrin (196) + TX, cypermethrin (201) + TX, cyphenothrin (206) + TX, cyromazine (209) + TX, cythioate (alternative name) [CCN] + TX, d-limonene (alternative name) [CCN] + TX, cf-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) + TX1 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] + TX1 dimefluthrin [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) + TX1 diofenolan (1099) + TX1 dioxabenzofos (1100) + TX, dioxacarb (1101 ) + TX1 dioxathion (1102) + TX, disulfoton (278) + TX, dithicrofos (1108) + TX, DNOC (282) + TX, doramectin (alternative name) [CCN] + TX, DSP (1115) + TX, ecdysterone (alternative name) [CCN] + TX, EM 642 (development code) (1118) + TX, emamectin (291) + TX, emamectin benzoate (291 ) + TX, EMPC (1120) + TX, empenthrin (292) + TX, endosulfan (294) + TX, endothion (1121) + TX, endrin (1122) + TX, EPBP (1123) + TX, EPN (297) + TX, epofenonane (1124) + TX, eprinomectin (alternative name) [CCN] + TX, esfenvalerate (302) + TX, etaphos (alternative name) [CCN] + TX, ethiofencarb (308) + TX, 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) + TX, ethylene oxide [CCN] + TX, etofenprox (319) + TX, etrimfos (1142) + 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, flucofuron (1168) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1169) + TX, flufenerim [CCN] + TX, flufenoxuron (370) + TX, flufenprox (1171) + TX, flumethrin (372) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, fonofos (1191 ) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1192) + TX, formparanate (1193) + TX, fosmethilan (1194) + TX, fospirate (1195) + TX, fosthiazate (408) + TX, fosthietan (1196) + TX, 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] + TX1 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 0-(methoxyaminothiophosphoιγl)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, ieptophos (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) + TX1 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 (1311) + 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, 0-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate (IUPAC name) (1057) + TX, 0,0-diethyl O-4-methyl-2-oxo-2H- chromen-7-yl phosphorothioate (IUPAC name) (1074) + TX, 0,0-diethyl O-6-methyl-2- propylpyrimidin-4-yl phosphorothioate (IUPAC name) (1075) + TX, O,O,O',O'-tetrapropyl 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) + TX1 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 (711) + 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) + TX, selamectin (alternative name) [CCN] + TX, SI- 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) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenoxide (623) + TX, 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) + TX, 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, veratridine (alternative name) (725) + TX, veratrine (alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302 (compound code) + TX1 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 + TX, 2-dibromo-3-chloropropane (lUPAC/Chemical Abstracts name) (1045) + TX, 1 + TX, 2-dichloropropane (IUPAC/ Chemical Abstracts name) (1062) + TX, 1 + TX, 2-dichloropropane with 1 + TX, 3-dichloropropene (IUPAC name) (1063) + TX, 1 + TX, 3-dichloropropene (233) + TX, 3 + TX, 4-dichlorotetrahydrothiophene 1 + TX, 1 -dioxide (lUPAC/Chemical Abstracts name) (1065) + TX, 3-(4-chlorophenyI)-5- methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1 + TX, 3 + TX, 5- thiadiazinan-3-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) + TX1 chloropicrin (141) + TX, chlorpyrifos (145) + TX, cloethocarb (999) + TX, cytokines (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 (1196) + 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) + TX, 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) + TX1 thionazin (1434) + TX1 triazophos (820) + TX, triazuron (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternative name) (210) + TX1 a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX1 a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX1 probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX, a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1 + TX, 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, coumafuryl (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 (1183) + 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 + TX, 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, and a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX, the compound of formula A-1
Figure imgf000119_0001
the formula A-2
Figure imgf000119_0002
the formula A-3
Figure imgf000119_0003
the formula A-4
Figure imgf000120_0001
H CH, the formula A-5
Figure imgf000120_0002
the formula A-6
Figure imgf000120_0003
the formula A-7
(A-7) + TX,
Figure imgf000120_0004
the formula A-8
Figure imgf000121_0001
the formula A-9
Figure imgf000121_0002
the formula A-10
Figure imgf000121_0003
the formula A-11
Figure imgf000122_0001
the formula A-12
Figure imgf000122_0002
the formula A-13
Figure imgf000122_0003
the formula A- 14
Figure imgf000122_0004
H CH, the formula A-15
Figure imgf000123_0001
the formula A-16
Figure imgf000123_0002
the formula A-17
Figure imgf000123_0003
the formula A-18
Figure imgf000124_0001
the formula A-19
Figure imgf000124_0002
the formula A-20
Figure imgf000124_0003
the formula A-21
Figure imgf000125_0001
the formula A-22
Figure imgf000125_0002
the formula A-23
Figure imgf000125_0003
the formula A-24
Figure imgf000126_0001
the formula A-25
Figure imgf000126_0002
the formula A-26
Figure imgf000126_0003
and Azaconazole (60207-31-0] + TX, Bitertanol [70585-36-3] + TX, Bromuconazole [116255-48-2] + TX, Cyproconazole [94361 -06-5] + TX, Difenoconazole [119446-68-3] + 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] + TX1 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 [118134-30-8] + 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] + TX, 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, Procymi- done [32809-16-8] + TX1 Vinclozoline [50471-44-8] + TX1 Boscalid [188425-85-6] + TX1 Carboxin [5234-68-4] + TX1 Fenfuram [24691-80-3] + TX, Flutolanil [66332-96-5] + TX, Mepronil [55814-41-0] + TX, Oxycarboxin [5259-88-1] + TX1 Penthiopyrad [183675-82-3] + TX1 Thifluzamide [130000-40-7] + TX1 Guazatine [108173-90-6] + TX, Dodine [2439-10-3] [112-65-2] (freie Base) + TX1 lminoctadine [13516-27-3] + TX, Azoxystrobin [131860-33-8] + TX, Dimoxystrobiπ [149961-52-4] + TX, Enestroburin {Proc. BCPC + TX, Int. Congr. + TX, Glasgow + TX1 2003 + TX, 1 + TX1 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, Tolylfluanid [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] + TX1 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] + TX, Famoxadone [131807-57-3] + TX, Fenamldone [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 imgf000129_0001
wherein Ra5 is trifluoromethyl or difluoromethyl (WO2004/058723) + TX, ; the compound of formula F-2
Figure imgf000129_0002
wherein Ra6 is trifluoromethyl or difluoromethyl (WO2004/058723) + TX,; the racemic compound of formula F-3 (syn)
Figure imgf000129_0003
wherein Ra7 is trifluoromethyl or difluoromethyl (WO2004/035589) + TX, the racemic mixture of formula F-4 (anti)
Figure imgf000130_0001
wherein Ra7 is trifluoromethyl or difluoromethyl (WO2004/035589) + TX.the compound of formula F-5
Figure imgf000130_0002
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_0003
wherein Ra8 is trifluoromethyl or difluoromethyl (WO2004/035589) + TX, the racemic compound of formula F-7 (trans)
Figure imgf000131_0001
wherein Ra9 Is trifluoromethyl or difluoromethyl (WO03/074491) + TX, the racemic compound of formula F-8 (cis)
Figure imgf000131_0002
wherein Ra9 is trifluoromethyl or difluoromethyl (WO03/074491) + TX, the compound of formula F-9
Figure imgf000131_0003
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 (WO03/074491) + TX, the compound of formula F-10
Figure imgf000132_0001
wherein R10 is trifluoromethyl or difluoromethyl (WO2004/058723) + TX, the racemic compound of formula F- 11 (trans)
Figure imgf000132_0002
wherein R11 is trifluoromethyl or difluoromethyl (WO03/074491) + TX, the racemic compound of formula F-12 (cis)
Figure imgf000132_0003
wherein R11 is trifluoromethyl or difluoromethyl (WO03/074491) + TX, the compound of formula F-13
Figure imgf000133_0001
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, and the compound of formula F-14
Figure imgf000133_0002
(WO2004/058723) + TX, and the compound of formula F-15
Figure imgf000133_0003
+ TX.
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.
The mixtures comprising a compound of formula I 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 also 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 components (I) and active ingredients as described above is not essential for working the present invention.
Biological Examples (% = per cent by weight, unless otherwise specified)
Example B1: Activity against Aphis craccivora
Pea seedlings are infected with Aphis craccivora, subsequently sprayed with a spray mixture comprising 400 ppm of active ingredient and then incubated at 20°. 3 and 6 days later, the percentage reduction in the population (% activity) is determined by comparing the number of dead aphids between the treated and untreated plants.
In this test, compounds listed in the Tables above show good activity. Example B2: Activity aαainst Diabrotica balteata
Maize seedlings are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient and, after the spray coating has dried on, populated with 10 larvae (2nd instar) of Diabrotica balteata and introduced into a plastic container. 6 days later, the percentage reduction in the population (% activity) is determined by comparing the number of dead larvae between the treated and untreated plants.
In this test, compounds listed in the Tables above show good activity. In particular compounds P1 , P2, P6, P7, P24, P29, P25, P60, P62, P63, P48, P46, P50, P23, P8, P66,
P22, P14, P21 , P11 P67, P68 have an activity of over 80%.
Example B3: Activity against Heliothis virescens (foliar application)
Young soya plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient and, after the spray coating has dried on, populated with 10 caterpillars (1st instar) of Heliothis virescens and introduced into a plastic container. 6 days later, the percentage reduction in the population and in the feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage between the treated and untreated plants.
In this test, compounds listed in the Tables above show good activity. In particular compounds P1 , P2, P6, P10, P3, P7, P15, P24, P51, P50, P63, P62, P61 , P60, P12, P65,
P66, P9, P8, P67, P68, P23, P21 , P10, P11 , P47, P52, P53 have an activity of over 80%.
Example B4: Activity against Heliothis virescens (application to eggs)
Heliothis virescens eggs, which have been deposited on cotton, are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. After 8 days, the percentage hatching rate of the eggs and the survival rate of the caterpillars (% activity) are evaluated in comparison with untreated control batches.
In this test, compounds listed in the Tables above show good activity. In particular compound
PI, P2, P6, P7, P39, P3, P10, P24, P46, P48, P50, P51 , P29, P31, P25, P67, P63, P62,
P61 , P60, P64, P68, P10, P8, P32, P9, P30, P23, P14, P21 , P11, P40, P69, P70, P71 , P72 have an activity of over 80%. Example B5: Activity against Mvzus persicae (foliar application)
Pea seedlings are infected with Myzus persicae, subsequently sprayed with a spray mixture comprising 400 ppm of active ingredient and then incubated at 20°. 3 and 6 days later, the percentage reduction in the population (% activity) is determined by comparing the number of dead aphids between the treated and untreated plants.
In this test, compounds listed in the Tables above show good activity.
Example B6: Activity against Mvzus persicae (systemic application)
Pea seedlings are infected with Myzus persicae, and their roots are subsequently placed into a spray mixture comprising 400 ppm of active ingredient. The seedlings are then incubated at 20°. 3 and 6 days later, the percentage reduction in the population (% activity) is determined by comparing the number of dead aphids between the treated and untreated plants.
In this test, compounds listed in the Tables above show good activity.
Example B7: Activity against Plutella xylostella
Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient and, after the spray coating has dried on, populated with 10 caterpillars (3rd instar) of Plutella xylostella and introduced into a plastic container. 3 days later, the percentage reduction in the population and in the feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage between the treated and untreated plants.
In this test, compounds listed in the Tables above show good activity. In particular compounds P1 , P2, P6, P39, P3, P41 , P7, P10, P15, P24, P29, P31 , P25, P8, P9, P32, P30, P12, P13, P23, P22, P63, P62, P61, P60, P64, P63, P14, P46, P48, P50, P51, P17, P65, P66, P21 , P18, P10, P67, P68, P16, P11, P35, P52, P53, P38, P40, P70 have an activity of over 80%.
Example B8: Activity against Spodoptera littoralis
Young soya plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient and, after the spray coating has dried on, populated with 10 caterpillars (1st instar) of Spodoptera littoralis and introduced into a plastic container. 3 days later, the percentage reduction in the population and in the feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage between the treated and untreated plants.
In this test, compounds listed in the Tables above show good activity. In particular compounds P1, P2, P3, P6, P39, P41, P10, P63, P62, P61, P60, P64, P24, P7, P10, P67, P68, P29, P31 , P25, P8, P32, P30, P9, P23, P14, P65, P66, P21 , P11 , P35, P34, P33, P38, P40, P69, P52, P53, P70 have an activity of over 80%.
Example B9: Activity against Cvdia
Standard Cydia diet cubes (1.5 cm width) are pierced with a tooth-pick and are immersed in liquid paraffin (ca. 8O0C). 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 P22, P6, P11 , P65, P66, P17, P63, P62, P61 , P60, P2, P3, P14, P67, P68, P15, P7, P21, P10, P24, P8, P13, P9, P23, P12 have an activity of over 80%.
Example B10: 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. 566 described on page 122 of WO03/024222):
(Compound No. P41 according to this invention)
Figure imgf000137_0001
(Cpd No. 566 according to the state of the art)
Figure imgf000138_0001
B10 a: 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 the prescribed concentrations (12.5, 3 and O.δppm). 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 LD photo period). Number of alive insects are counted and percentage of dead calculated. Tests were conducted with one replicate. Results are shown in Table B10a:
Table B10a: Systemic Insecticide Test for Spodoptera littoralis
Figure imgf000138_0002
Table B10a shows that compound No. P41 according to the invention exerts a substantially better insecticidal action on Spodoptera littoralis than the compound from the state of the art. Especially at low application rates (3 and 0.8 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.
B10 b; Insecticide Test for Heliothis virescens (tobacco budworm):
50-60 newly laid H. virescens eggs were placed on artificial diet in Petri dishes (5 cm diameter) and topically treated with 0.8ml solution of compounds at the following rates: 3, 0.8, 0.2, 0.05. Petri dishes are maintained at 26 ± 2°C, 50 ± 10% r.h. in a dark room and assessment conducted one week after application (two replicates/treatment). Larvae mortality and effects on larvae growth were compared to the control. Results are shown in Table B10b:
Table B10 b: Insecticide Test for Heliothis virescens
Figure imgf000139_0001
Table B10b shows that compound No. P41 according to the invention exerts a substantially better insecticidal action on Heliothis virescens than the compound from the state of the art. Especially at low application rates (3, 0.8 and 0.2 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.
B10 c: Insecticide Test for Plutella xylostella (diamond back moth):
Chinese cabbage plants were sprayed with insecticide at 3, 0.8, 0.2 and O.Oδppm. Five cm diameter leaf disks were cut and placed in a Petri dish containing 6ml agar (0.8%). Five P. xylostella larvae L3 were introduced into Petri dishes and kept at 26 ± 2°C, 50 ± 10% r.h. in a dark room (two replicates per treatment). Number of alive insects were counted and percentage of dead calculated after three days. Results are shown in Table B10c:
Table B10 c: Insecticide Test for Plutella xylostella
Figure imgf000140_0001
Table B10c shows that compound No. P41 according to the invention exerts a substantially better insecticidal action on Plutella xylostella than the compound from the state of the art. Especially at low application rates (3 and 0.8 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 imgf000141_0001
wherein each of E and Z, which may be the same or different, represents oxygen or sulfur;
A is CrC6alkylene, C2-C6alkenylene, C2-C6alkynylene, or a bivalent three- to ten-membered monocyclic or fused bicyclic ring system which can be partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms; and it being possible for the three- to ten-membered ring system itself and also for the C1-
C6alkylene, C2-C6alkenylene and C2-C6alkynylene groups to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6Cy cloalky I, C5-
Cycycloalkenyl, C5-C8cycloalkynyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-
C6halocycloalkyl, Cβ-Cyhalocycloalkenyl, C5-C8halocycloalkynyl, CrC4alkoxy, C1-
C4haloalkoxy, Ci-C4alkylthio, CrC4haloalkylthio, CrC4alkylsulfinyl, Ci-C4alkylsulfonyl, C1-
C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, C-ι-C6alkyl-C3-C6cycloalkylamino, C2-
C4alkylcarbonyl, C2-C6alkoxycarbonyl, CrCβalkylaminocarbonyl, Cs-Cedialkylaminocarbonyl,
C2-C6alkoxycarbonyloxy, C2-C6alkylaminocarbonyloxy, Cs-Cβdialkylaminocarbonyloxy or C3-
C6trialkylsilyl, or by a three- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic, partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms, and it being possible for the three- to ten-membered ring system itself to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, CVCβalkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C5- C7cycloalkenyl, C5-C8cycloalkynyl, CrC6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3- Cehalocycloalkyl, C5-C7halocycloalkenyl, C5-C8halocycloalkynyl, CrC4alkoxy, C1- C4haloalkoxy, CrC4alkylthio, CrC4haloalkylthio, CrC4alkylsulfinyl, CrC4alkylsulfonyl, C1- C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, CrCealkyl-Cs-Cecycloalkylamino, C2- C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, Cs-Cβdialkylaminocarbonyl, C2-C6alkoxycarbonyloxy, Ca-Cealkylaminocarbonyloxy, CrCedialkylaminocarbonyloxy, C3- Cetrialkylsilyl or phenyl, it being possible for the phenyl group in turn to be substituted by hydroxy, Ci-C6alkyl, CrC6haloalkyl, CrCealkylthio, CrC6haloalkylthio, C3-C6alkeny!th!θ, C3- C6haloalkenylthio, C3-C6alkynylthio, CrC3alkoxy-CrC3alkylthio, C2-C4alkylcarbonyl-C1- C3alkylthio, QrCtalkoxycarbonyl-CrCsalkylthio, cyano-CrCsalkylthio, C-ι-C6alkylsulfinyl, C1- C6haloalkylsulfinyl, CrCβalkylsulfonyl, CrC6haloaIkylsulfonyl, aminosulfonyl, C1- C2alkylaminosulfonyl, N,N-di(CrC2alkyl)aminosulfonyl, di(CrC4alkyl)amino, halogen, cyano or nitro; and substituents at nitrogen atoms in the ring systems being other than halogen; X is oxygen, NH or CrC4alkyl-N;
Y is CrCealkylene, C2-C6alkenylene, C2-C6alkynylene, or a bivalent three- to ten-membered monocyclic or fused bicyclic ring system which can be partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms; and it being possible for the three- to ten-membered ring system itself and also for the C1- C6alkylene, C2-C6alkenylene and C2-C6alkynylene groups to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C5- C7cycloalkenyl, C5-C8cycloalkynyl, CrC6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3- C6halocycloalkyl, Cs-CT-halocycloalkenyl, C5-C8halocycloalkynyl, CrC4alkoxy, C1- C4haloalkoxy, CrC4alkylthio, CrC4haloalkylthio, CrC4alkylsulfinyl, CrC4alkylsulfonyl, C1- C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, CrC6alkyl-C3-C6cycloalkylamino, C2- C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, QrCedialkylaminocarbonyl, Ca-Cβalkoxycarbonyloxy, C2-C6alkylaminocarbonyloxy, Cs-Cβdialkylaminocarbonyloxy or C3- C6trialkylsilyl, or by a three- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic, partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms, and it being possible for the three- to ten-membered ring system itself to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, C5-C7cycloalkenyl, C5-C8cycloalkynyl, CrCehaloalkyl, C2-C6haloalkenyl, C2- C6haloalkynyl, C3-C6halocycloalkyl, Cs-C/halocycloalkenyl, C5-C8halocycloalkynyl, C1- C4alkoxy, Ci-C4haloalkoxy, CrC4alkylthio, CrC4haloalkylthio, CrC4alkylsulfinyl, C1- C4alkylsulfonyl, C-ι-C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, Ci-C6alkyl-C3- C6cycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, C3- C6dialkylaminocarbonyl, C2-C6alkoxycarbonyloxy, C∑-Cealkylaminocarbonyloxy, C3- C6dialkylaminocarbonyloxy, C3-C6trialkylsilyl or phenyl, it being possible for the phenyl group in turn to be substituted by hydroxy, CrC6alkyl, C^Gehaloalkyl, CrCealkylthio, C1- C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, CrCsalkoxy-C,- C3alkylthio, C2-C4alkylcarbonyl-CrC3alkylthio, C2-C4alkoxycarbonyl-CrC3alkylthio, cyano-Cr C3alkylthio, CrC6alkylsulfinyl, CrC6haloalkylsulfinyl, CrC6alkylsulfonyl, C1- C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, N,N-di(CrC2alkyl)aminosulfonyl, di(C1-C4alkyl)amino, halogen, cyano or nitro; and substituents at nitrogen atoms in the ring systems being other than halogen; p is 0 or 1 ; q is 0 or 1 ;
B is a three- to four-membered ring system which is fully or partially saturated and can contain a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, and it being possible for the three- to four-membered ring system itself to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, C5-C7cycloalkenyl, C5-C8cycloalkynyl, CrCshaloalkyl, C2-C6haloalkenyl, C2- C6haloalkynyl, C3-C6halocycloalkyl, C5-C7halocycloalkenyl, C5-C8halocycloalkynyl, C1- C4alkoxy, CrCthaloalkoxy, CrC4alkylthio, CrC4haloalkylthio, CrC4alkylsulfinyl, C1- C4alkylsulfonyl, CrC4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, CrC6alkyl-C3- C6cycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, CrCβalkylaminocarbonyl, C3- C6dialkylaminocarbonyl,
Figure imgf000143_0001
CrCβalkylaminocarbonyloxy, C3- C6dialkylaminocarbonyloxy, C3-C6trialkylsilyl, or by a three- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic, partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms, and it being possible for the three- to ten-membered ring system itself to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, CrC6alkyl, C2- C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C5-C7cycloalkenyl, C5-C8cycloalkynyl, C1- C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyi, C3-C6halocycloalkyl, Cs-Cyhalocycloalkenyl, C5-C8halocycloalkynyl, CrC4alkoxy, CrC4haloalkoxy, CrC4alkylthio, CrC4haloalkylthio, C1- C4alkylsulfinyl, CrC4alkylsulfonyl, C1-C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, CrCealkyl-Cs-Cecycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2- C6alkylaminocarbonyl, QrCedialkylaminocarbonyl, C2-C6alkoxycarbonyloxy, C2- C6alkylaminocarbonyloxy, Cs-Cedialkylaminocarbonyloxy, C3-C6trialkylsilyl or phenyl, it being possible for the phenyl group in turn to be substituted by hydroxy, CrCealkyl, C1- Cehaloalkyl.CrCealkylthio, CrC6haIoalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3- C6alkynylthio, CrCsalkoxy-CrCsalkylthio, C2-C4alkylcarbonyl-CrC3alkylthio, C2- C4alkoxycarbonyl-C1-C3alkylthio, cyano-CrCsalkylthio, CrC6alkylsulfinyl, C1-C6IIaIo- alkylsulfinyl, CrC6alkylsulfonyl, CrC6haloalkylsulfonyl, aminosulfonyl, CrC2alkylamino- sulfonyl, N,N-di(CrC2aIkyl)aminosulfonyl, di(CrC4alkyl)amino, halogen, cyano or nitro; and substituents at nitrogen atoms in the ring systems being other than halogen; each R1 independently is halogen, nitro, hydroxy, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, CrC6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, C1- C4alkoxy, C1-C4haloalkoxy, CrC4alkylthio, C1-C4haloalkylthio,
Figure imgf000144_0001
C1- C4haloalkylsulfonyl, CrC4alkylsulfinyl, CrC4alkylsulfonyl, CrC4alkylamino, C2- C4dialkylamino, Cs-Cecycloalkylamino, CrCealkyl-Cs-Cecycloalkylamino, C2-C4alkylcarbonyl, Ca-Cβalkoxycarbonyl, C2-C6alkylaminocarbonyl, Cs-Cedialkylaminocarbonyl, C2- C6alkoxycarbonyloxy, CrCealkylaminocarbonyloxy, Cs-Cβdialkylaminocarbonyloxy or C3- C6trialkylsilyl, phenyl, benzyl or phenoxy, or phenyl, benzyl or phenoxy mono-, di- or trisubstituted by halogen, cyano, nitro, halogen, CrCealkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, CrC6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, C1- C4alkoxy, CrC4haloalkoxy, CrC4alkylthio, CrC4haloalkylthio, CrC4alkylsulfinyl, C1- C4alkylsulfonyl, CrC4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, CrC6alkyl-C3- C6cycloalkylamino, C2-C4alkylcarbonyl, Ca-Cealkoxycarbonyl, C2-C6alkylaminocarbonyl, Cs- Cedialkylaminocarbonyl, C2-C6alkoxycarbonyloxy, C^Cealkylaminocarbonyloxy, C3- C6dialkylaminocarbonyloxy or C3-C6trialkylsilyl; or each R1 independently is amino, formyl, C2-C6cyanoalkenyl, C2-C6alkylcarbonylamino, phenylcarbonylamino which can be mono-, di- or trisubstituted by halogen, cyano, nitro, halogen, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, CrC6haloalkyl, C2- C6haloalkenyl, C2-C6haloalkynyl, Cs-Cehalocycloalkyl, CrC4alkoxy, CrC4haloalkoxy, C1- C4alkylthio, CrC4haloalkylthio, CrC4alkylsulfinyl, CrC4alkylsulfonyl, CrC4aikylamino, C2- C4dialkylamino, C3-C6cycloalkylamino, CrCealkyl-CjrCeCycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, Ca-Cβalkylaminocarbonyl, Cs-Cedialkylaminocarbonyl, C2- C6alkoxycarbonyloxy, C2-C6alkylaminocarbonyloxy, Cs-Cedialkylaminocarbonyloxy or C3- C6trialkylsilyl; or each R1 independently is 2-,3- or 4-pyridylcarbonylamino which can be mono-, di- or trisubstituted by halogen, cyano, nitro, halogen, CτC6alkyl, C2-C6alkenyl, C2- C6alkynyl, C3-C6cycloalkyl, CrCehaloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3- C6halocycloalkyl, CrC4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, C1-C4haloalkylthio, C1- C4alkylsulfinyl, CrC4alkylsulfonyl, C.|-C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, CrCealkyl-Cs-Cecycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2- C6alkylaminocarbonyl, Cs-Cedialkylaminocarbonyl, C^Cealkoxycarbonyloxy, C2- C6alkylaminocarbonyloxy, Cs-Cedialkylaminocarbonyloxy or C3-C6trialkylsilyl; or each R1 independently is C2-C6alkoxycarbonylamino, C^Cealkylaminocarbonylamino, C3- C6dialkylaminocarbonylamino, C2-C6haloalkylcarbonyl or is a group RxON=C(Ry)-, wherein Rx and Ry independently are hydrogen or C-ι-C6aIkyl; n is O, 1, 2, 3 or 4; 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- Cscycloalkyl substituted by one or more substituents selected from halogen nitro, cyano, hydroxy, CrC4alkoxy, C1-C4haloalkoxy, CrC4alkylthio, C1-C4haloalkylthio, C1-C4alkylsulfinyl, CrC4alkylsulfonyl, CrC^lkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino or Ci-C6alkyl- C3-C6cycloalkylamino;
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, CrC6haIoalkyl, halogen, cyano, C1- C4alkoxy, CrC4haloalkoxy, CrC4aIkylthio, CrC4haloalkylthio, C1-C4BIkVlSuIfJnVl, C1- C4alkylsulfonyl, CrC4haloalkylsulfinyl or CrC4haloalkylsulfonyl; or D is a group
Figure imgf000145_0001
(D7) or (D8),
Figure imgf000146_0001
Figure imgf000146_0002
R4, R4', R10, Ri7) and R19 independently from each other, are hydrogen, CrC6alkyl, C3- C6cycloalkyl, CrC6haloalkyl, halogen, cyano, CrC4alkoxy, CrC4haloalkoxy, C2- C4alkoxycarbonyl, CrC4alkylthio, CrC4haloalkylthio, CrC4alkylsulfinyl, Crdalkylsulfonyl, CrC4haloalkylsulfinyl or CrC4haloalkylsulfonyl;
R5, Re, Rs, Rii, Ri2, Ri5, Ri6 and R18 independently from each other, are CrC6alkyl or C1- C6alkyl mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, CrC4alkoxy, C2- C4alkoxycarbonyl, CrC4aIkylthio, CrC4alkylsulfinyl, CrC^alkylsulfonyl, CrC4alkylamino, 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, CrCehaloalkyl, halogen, cyano, CrC4alkoxy, CrC4haloalkoxy, CrC4alkylthio, CrC4haloalkylthio, CrC4alkylsuIfinyl, CrC4alkylsulfonyl, CrC4haloalkylsulfinyl or C1- C4haloalkylsulfonyl;
R7, R9, Ri3 and R14 independently from each other, are hydrogen, CrCealkyl, CrCehaloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C3-C6alkenyl or C3-C6haloalkenyl; and agronomically acceptable salts/isomers/enantiomers/tautomers/N-oxides of those compounds with the exception of the compound 2-(3-chloro-pyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3- carboxylic acid β-methyl-δ-Coxiranylmethyl-carbamoyO-phenyri-arnide.
2. A compound according to claim 1 , wherein R4' is hydrogen and each R1 independently is halogen, nitro, hydroxy, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C1- C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, C1-C4BIkOXy, C1- C4haloalkoxy, CrC4alkylthio, CrC4haloalkylthio, CrC4haloalkylsulfinyl, C1- C4haloalkylsulfonyl, CrC4alkylsulfinyl, CrC4alkylsulfonyl, CrC4alkylamino, C2- C4dialkylamino, C3-C6cycloalkylamino, CrCealkyl-Cs-Cecycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, Ca-Cealkylaminocarbonyl, Cjj-Cedialkylaminocarbonyl, C2- C6alkoxycarbonyloxy, Ca-Cealkylaminocarbonyloxy, Cs-Cedialkylaminocarbonyloxy or C3- C6trialkylsilyl, phenyl, benzyl or phenoxy, or phenyl, benzyl or phenoxy mono-, di- or trisubstituted by halogen, cyano, nitro, halogen, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, CrC6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, C1- C4alkoxy, C1-C4IIaIOaIkOXy, CrC4alkylthio, C1-C4haloalkylthio, CrC4alkylsulfinyl, C1- C4alkylsulfonyl, C1-C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, Ci-C6alkyl-C3- Cecycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, C3- C6dialkylaminocarbonyl, C2-C6alkoxycarbonyloxy, CrCβalkylaminocarbonyloxy, C3- C6dialkylaminocarbonyloxy or C3-C6trialkylsilyl;
3. A compound according to claim 1 , wherein
B is a three- to four-membered ring system which is fully or partially saturated, and it being possible for the three- to four-membered ring system itself to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C5-C7cycloalkenyl, C5-C8cycloalkynyl, CrCδhaloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3- C6halocycloalkyl, C5-C7halocycloalkenyl, C5-C8halocycloalkynyl, C1-C4BIkOXy, C1- C4haloalkoxy, C1-C4alkylthio, Ci-C4haloalkylthio, CrC4alkylsulfinyl, CrC4alkylsulfonyl, C1- C4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, C-ι-C6alkyl-C3-C6cycloalkylamino, C2- C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, Cs-Cβdialkylaminocarbonyl, C2-C6alkoxycarbonyloxy, C2-C6alkylaminocarbonyloxy, Cs-Cβdialkylaminocarbonyloxy, C3- Cetrialkylsilyl, or by a three- to ten-membered monocyclic or fused bicyclic ring system which can be aromatic, partially saturated or fully saturated and can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms, and it being possible for the three- to ten-membered ring system itself to be mono-, di- or trisubstituted by halogen, cyano, nitro, hydroxy, CrCβalkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl, C5-C7cycloalkenyl, C5-C8cycloalkynyl, C-i-Cβhaloalkyl, C2-C6haloalkenyl, C2- C6haloalkynyl, C3-C6halocycloalkyl, Cs-CT-halocycloalkenyl, C5-C8halocycloalkynyl, C1- C4alkoxy, CrC4haloalkoxy, CrC4alkylthio, C1-C4haloalkylthio, CrC4alkylsuIfinyl, C1- C4alkylsulfonyl, CrC4alkylamino, C2-C4dialkylamino, C3-C6cycloalkylamino, CrCealkyl-Cs- C6cycloalkylamino, C2-C4alkylcarbonyl, C2-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, C3- Cedialkylaminocarbonyl, C2-C6alkoxycarbonyloxy, C2-C6alkylaminocarbonyloxy, C3- Cedialkylaminocarbonyloxy, C3-C6trialkylsilyl or phenyl, it being possible for the phenyl group in turn to be substituted by hydroxy, CrCealkyl, CrCehaloalkyl.CrCealkylthio, C1- C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, CrCsalkoxy-Cr C3alkylthio, C2-C4alkylcarbonyl-C1-C3alkylthio, C2-C4alkoxycarbonyl-C1-C3alkylthio, cyano-Cr C3alkylthio, CrCealkylsulfinyl, CrC6haIoalkylsulfinyl, CrC6aIkylsulfonyl, C1- C6haloalkylsulfonyl, aminosulfonyl, CrC^lkylaminosulfonyl, N.N-dKCrQjalkyOaminosulfonyl, di(CrC4alkyl)amino, halogen, cyano or nitro; and substituents at nitrogen atoms in the ring systems being other than halogen.
4. A compound according to claim 1 , wherein A is Ci-C6alkylene which may be substituted by C3-C6cycloalkyl, C2-C6alkenyi, cyano, C-rC4alkylthio, d-C4alkyIsulfonyl, CrC4alkoxy, halogen or CrC6haloalkyl; or A is Cs-Cecycloalkylene.
5. A compound according to claim 1, wherein B is cyclopropyl or cyclobutyl which may be mono- di-, or trisubstituted by halogen, CrC4alkyl, hydroxy, cyano, CrC4alkoxy or C1- C4alkylthio.
6. A compound according to claim 1 , wherein D is the group D1.
7. A pesticidal composition, which comprises at least one compound according to claim 1 of 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.
8. A composition according to claim 7 for controlling insects or representatives of the order Acarina.
9. A method for controlling pests, which comprises applying a composition according to claim 6 to the pests or their environment.
10. A method according to claim 9 for controlling insects or representatives of the order Acarina.
11. A method according to claim 9 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.
12. Plant propagation material treated in accordance with the method described in claim 11.
13. A process for the preparation of a compound of formula I according to claim 1 or, where appropriate, a tautomer thereof, in each case in free form or in salt form, which comprises a) for the preparation of a compound of formula I, in which R2 is hydrogen and E and Z are oxygen, or, where appropriate, a tautomer and/or salt thereof, reacting a compound of formula Il
Figure imgf000149_0001
in which R1, n, and D have the meanings given for formula I in claim 1 , or, where appropriate, a tautomer and/or salt thereof with a compound of formula III
HN(R3)-A-(X)p-(Y)q-B (III),
in which R3, A, X, Y, p, q and B have the meanings given for formula I, or, where appropriate, with a tautomer and/or salt thereof or,
b) for the preparation of a compound of formula I, or, where appropriate, a tautomer and/or salt thereof, reacting a compound of formula IV
Figure imgf000149_0002
in which R1, R2, n, Z and D have the meanings given for the formula I in claim 1 ; and X1 is a leaving group.or, where appropriate, a tautomer and/or salt thereof with a compound of formula III
HN(R3)-A-(X)p-(Y)q-B (III), in which R3, A, X, Y, p, q and B have the meanings given for formula I, or, where appropriate, with a tautomer and/or salt thereof or,
c) for the preparation of a compound of formula I, or, where appropriate, a tautomer and/or salt thereof, reacting a compound of formula V
Figure imgf000150_0001
in which R1, R2, R3, n, A, X, Y, Z and B have the meanings given for the formula I in claim 1, or, where appropriate, a tautomer and/or salt thereof with a compound of formula Vl
X2C(=O)D (Vl),
in which D has the meaning given for formula I in claim 1 ; and X2 is a leaving group, or, where appropriate, with a tautomer and/or salt thereof.
14. A compound of formula V
Figure imgf000150_0002
wherein R1, R2, R3, n, A, X, Y, Z and B have the meanings given for formula I in claim 1.
15. A compound according to claim 14, wherein Ri is Ci-C4alkyl, halogen, d-Cshaloalkyl, nitro, C1-C4BIkOXy, C1-C4-IIaIOaIkOXy, C1-
C4alkylthio, CrC4alkylsulfinyl, C1-C4alkylsulfonyl, CrC4haloalkylthio, C-ι-C4haloalkylsulfinyl or
CrC4haloalkylsulfonyl;
R2 and R3 are hydrogen;
A is CrC6alkylene which may be substituted by C3-C6cycloalkyl, C2-C6alkenyl, cyano, C1-
C4alkylthio, Crdalkylsulfonyl, C-i-C4alkoxy, halogen or CrCβhaloalkyl; or A is C3-
C6cycloalkylene; p and q are, independently from each other, 0 or 1 ;
X is oxygen, NH; NCH3 or NC2H5;
Y is CrC4alkylene, C2-C6alkenylene or C3-C6alkinylene or, CrC4alkylene, C2-C6alkenylene or C3-C6alkinylene substituted by halogen, C3-C6cycloalkyl, CrC4alkylsulfonyl or CrC4alkoxy;
B is cyclopropyl or cyclobutyl which may be mono- di-, or trisubstituted by halogen, Cr
C4alkyl, hydroxy, cyano, d-C4alkoxy or CrC4alkylthio; or B is CH(CH2O), CH(CHMeO), CH-
(CMe2O), CH(CH2S), CH(CH2OCH2), CH(CHMeOCH2), CH(CMe2OCH2), CH(CH2S-(O)2CH2),
CH(CHMeS(O)2CH2), CH(CMe2S(O)2CH2), C(Me)-(CH2O), C(Me)(CHMeO), C(Me)-(CMe2O),
C(Me)-(CH2S), C(Me)-(CH2OCH2), C(Me)(CHMeOCH2), C(Me)-(CMe2OCH2), C(Me)-
(CH2S(O)2CH2), C(Me)-(CHMe-S(O)2CH2) or C(Me)-(CMe2-S(O)2CH2).
16. A compound according to claim 15, wherein
B is cyclopropyl or cydobutyl which may be mono- di-, or trisubstituted by halogen, C1- C4alkyl, hydroxy, cyano, d-C4alkoxy or CrC4alkylthio.
17. A compound of formula III
HN(Ra)-A-(XV(Y)C-B (III),
in which R3, A, X, Y, p, q and B have the meanings given for formula I in claim 1.
18. A compound according to claim 17, wherein R3 is hydrogen;
A is CrC6alkylene which may be substituted by C3-C6cycloalkyl, C2-C6alkenyl, cyano, C1-
C4alkylthio, C1-C4alkylsulfonyl, C1-C^IkOXy, halogen or CrC6haloalkyl; or A is C3-
C6cycloalkylene; p and q are, independently from each other, O or 1 ; X is oxygen, NH; NCH3 or NC2H5;
Y is CrC4alkylene, C2-C6alkenylene or C3-C6alkinylene or, CrC4alkylene, C2-C6alkenylene or C3-C6alkinylene substituted by halogen, C3-C6cycloalkyl, CrC4alkylsulfonyl or CrC4alkoxy; B is cyclopropyl or cyclobutyl which may be mono- di-, or trisubstituted by halogen, C1- C4alkyl, hydroxy, cyano, CrC4alkoxy or CrC4alkylthio; or B is CH(CH2O), CH(CHMeO), CH- (CMe2O), CH(CH2S), CH(CH2OCH2), CH(CHMeOCH2), CH(CMe2OCH2), CH(CH2S-(O)2CH2), CH(CHMeS(O)2CH2), CH(CMe2S(O)2CH2), C(Me)-(CH2O), C(Me)(CHMeO), C(Me)-(CMe2O), C(Me)-(CH2S)1 C(Me)-(CH2OCH2), C(Me)(CHMeOCH2), C(Me)-(CMe2OCH2), C(Me)- (CH2S(O)2CH2), C(Me)-(CHMe-S(O)2CH2) or C(Me)-(CMe2-S(O)2CH2).
19. A compound according to claim 18, wherein
B is cyclopropyl or cyclobutyl which may be mono- di-, or trisubstituted by halogen, d-
C4alkyl, hydroxy, cyano, C1-C-^IkOXy or Crdalkylthio.
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