WO2013156433A1 - Dérivés de thiazole actifs en tant que pesticide - Google Patents

Dérivés de thiazole actifs en tant que pesticide Download PDF

Info

Publication number
WO2013156433A1
WO2013156433A1 PCT/EP2013/057784 EP2013057784W WO2013156433A1 WO 2013156433 A1 WO2013156433 A1 WO 2013156433A1 EP 2013057784 W EP2013057784 W EP 2013057784W WO 2013156433 A1 WO2013156433 A1 WO 2013156433A1
Authority
WO
WIPO (PCT)
Prior art keywords
crc
alkyl
mono
polysubstituted
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2013/057784
Other languages
English (en)
Inventor
Andrew Edmunds
Aurelien BIGOT
Roger Graham Hall
André Jeanguenat
Sebastian RENDLER
Peter Renold
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syngenta Participations AG
Original Assignee
Syngenta Participations AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Syngenta Participations AG filed Critical Syngenta Participations AG
Publication of WO2013156433A1 publication Critical patent/WO2013156433A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • the present invention relates to insecticidally active 2-(3-pyridyl)-thiazole derivatives, to processes for their preparation, to compositions comprising those compounds, and to their use for controlling insects or representatives of the order Acarina.
  • X is nitrogen or CR 7 ;
  • n 0 or 1 ;
  • Gi is a three- to four- membered ring which can be partially saturated or fully saturated and can contain one heteroatom selected form the group consisting of nitrogen, oxygen and sulphur; said three- to four- membered ring system can be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, CrC 6 alkyl, d- C 6 haloalkyl, CrC 6 alkoxy, CrC 6 alkylthio, Ci-C 6 alkylamino and Ci-C 6 di-alkylamino; or Gi is C 2 -C 6 alkenyl which can be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, CrC 6 alkyl and CrC 6 haloalkyl; with the proviso that if the double bond is not directly connected to the ring then the substituents on the carbon between the thiazole and the unsaturation are different from halogen; or
  • Gi is C 2 -C 6 alkynyl which can be substituted by substituents independently selected from the group consisting of halogen, CrC 6 alkyl and CrC 6 haloalkyl; with the proviso that if the triple bond is not directly connected to the ring then the substituents on the carbon between the thiazole and the unsaturation are different from halogen;
  • G 2 is a five- 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, said five- to ten- membered ring system can be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, CrC 6 alkyl, CrC 6 alkoxy, CrC 6 alkylthio, d- C 6 alkoxycarbonyl, Ci-C 6 alkylamino, Ci-C 6 di-alkylamino, Ci-C 6 alkoxycarbonylamino, pyrimidinyl, thiazolyl, pyridinyl, pyrazinyl, pyridazinyl, pyrazinyloxy, imidazolyl, dihydro- oxazo
  • Ri is hydrogen, CrC 6 alkyl, which can be mono- to polysubstituted by substituents selected from the group consisting of C 3 -C 6 cycloalkyl, CrC 6 alkylthio, CrC 6 haloalkyl, d- C 6 alkylsulfinyl, CrC 6 alkylsulfonyl, halogen, cyano, hydroxy, CrC 6 alkoxy, C 2 -C 6 alkenyl, C 2 - C 6 alkynyl, Ci-C 6 alkoxy-C3-C 6 alkynyl, oxolanyl, dioxolanyl, thienyl, thietanyl, thiethanyloxide, thiethanyldioxide, di-Ci-C 4 alkyl-phosphinoylmethyl, 1 -H-benzoimidazol-2-yl,
  • phenyl can be mono- to polysubstituted by substituents selected from the group consisting of hydroxy, halogen, CrC 6 alkoxy, CrC 6 haloalkoxy, pyrazolyl, piperidinyl, phenoxy and CrC 4 alkylsulfonyl;
  • R-i is CrC 6 alkyl, which is substituted by pyridyl, wherein said pyridyl can be mono- to polysubstituted by substituents selected from the group consisting of halogen and C
  • Ri is CrC 6 alkyl, which is substituted by phenoxy, wherein said phenoxy can be mono- to polysubstituted by substituents selected from the group consisting of halogen and CrC 4 alkyl; or Ri is CrC 6 alkyl, which is substituted by phenylcarbonyl, wherein said phenylcarbonyl can be mono- to polysubstituted by substituents selected from the group consisting of halogen and CrC 4 haloalkoxy;
  • Ri is CrC 6 alkyl, which is substituted by imidazolinyl, wherein said imidazolinyl can be mono- to polysubstituted by Ci-C 4 alkyl;
  • Ri is CrC 6 alkyl, which is substituted by isoxazolyl, wherein said isoxazolyl can be mono- to polysubstituted by halo-substituted phenyl;
  • Ri is pyridyl, which can be mono- to polysubstituted by substituents selected from the group consisting of Ci-C 4 alkyl, Ci-C 4 alkoxycarbonyl, phenyl and phenoxy;
  • Ri is pyrimidinyl, which can be mono- to polysubstituted by substituents selected from the group consisting of hydroxy, Ci-C 4 alkoxy and Ci-C 4 alkyl;
  • Ri is piperazinyl, which can be monosubstituted by benzyl;
  • Ri is piperidinyl, which can be mono- to polysubstituted by CrC 4 alkyl;
  • Ri is pyrazolyl, which can be mono- to polysubstituted by substituents selected from the group consisting of Ci-C 4 alkyl, cyano and phenyl;
  • Ri is thiethanyl, which can be substituted by CrC 4 alkyl;
  • Ri is dihydro-thiophene-2-one-3-yl
  • Ri is azetidinyl, which can be mono- to polysubstituted by substituents selected from the group consisting of Ci-C 4 haloalkyl and benzyl;
  • Ri is pyrrolidinyl which can be substituted by benzyl;
  • Ri is Ci-C 6 alkoxycarbonylamino
  • Ri is C 3 -C 6 cycloalkenyl which can be mono- to polysubstituted by CrC 6 alkoxycarbonyl; or Ri is phenyl, which can be mono- to polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkylthio, di(Ci-
  • R- ⁇ is quinolinyl, benzothiazolyl, oxolanyl or indazolyl;
  • Ri is benzothiophenyl, which can be monosubstituted by CrC 6 alkoxycarbonyl;
  • Ri is thiazolyl, which can be mono- to polysubstituted by substituents selected from the group consisting of Ci-C 4 alkyl, pyridyl, phenyl, pyrimidinyl and CrC 4 alkylcarbonyl; wherein said phenyl can be mono- to polysubstituted by CrC 4 alkyl and wherein said pyrimidinyl can be mono- to polysubstituted by Ci-C 4 alkoxy;
  • Ri is benzothiazolyl which can be mono- to polysubstituted by CrC 4 alkyl;
  • Ri is chromen-2-one which can be mono- to polysubstituted by CrC 4 alkyl;
  • Ri is isoxazolyl, which can be mono- to polysubstituted by substituents selected from the group consisting of Ci-C 4 alkyl and phenyl;
  • Ri is thiadiazolyl, which can be monosubstituted by substituents selected from the group consisting of CrC 4 alkyl and halo-substituted phenyl;
  • Ri is furyl which can be mono- to polysubstituted by substituents selected from the group consisting of cyano and phenyl;
  • Ri is pyrazolopyridinyl which can be mono- to polysubstituted by CrC 4 alkyl; or R-i is thienyl which can be mono- to polysubstituted by CrC 4 alkoxycarbonyl; or R-i is
  • Ri is isoxazolidin-3-one, which can be monosubstituted by substituents selected from d- C 4 alkyl and CrC 4 haloalkyl;
  • Ri and R 2 form together with the nitrogen atom to which they are bonded a 3- to 6- membered saturated ring which can be mono- to polysubstituted by substituents selected from the group consisting of CrC 4 alkyl, Ci-C 4 alkoxy and halogen; and further mono- to polysubstituted by substituents selected from the group consisting of
  • phenylcarbonyl, phenoxy-CrC 4 alkyl and phenoxy wherein said phenylcarbonyl, phenoxy-Cr C 4 alkyl and phenoxy can be mono- to polysubstituted by halogen; and said saturated ring can be additionally substituted by an ethylene chain;
  • R 2 is hydrogen, CrC 6 alkyl, CrC 6 haloalkyl or C 3 -C 6 cycloalkyl;
  • R 3 is oxygen, sulfur, NR 8 or NOR 8 ;
  • R 8 is hydrogen, cyano, Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 3 -Ci 0 cycloalkyl, C 3 -Ci 0 cycloalkenyl, a three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated, S(0) n Ci-C 6 alkyl or N(Ci-C 6 alkyl) 2 ; or
  • R 8 is CrC 6 alkyl, C 2 -C 6 alkenyl, C 3 -Ci 0 cycloalkyl, C 3 -Ci 0 cycloalkenyl or a three- to ten- membered, monocyclic or fused bicyclic ring system which can be aromatic, partially saturated or fully saturated; each mono- to polysubstituted by substituents independently selected from the group consisting of fluoro, chloro, bromo, iodo, cyano, nitro, CrC 6 alkyl, C 2 - C 6 alkenyl, Ci-C 6 haloalkyl, C 2 -C 6 haloalkenyl, CrC 6 haloalkoxy, C 2 -C 6 haloalkenyloxy, C 3 - Ciocycloalkyl, C 3 -Ci 0 cycloalkenyl, C 3 -Ci 0 halocycloalkyl, C 3 -Ci 0
  • n 0, 1 or 2; and agrochemically acceptable salts, enantiomers, tautomers and N-oxides of those compounds.
  • Compounds of formula I which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulphuric acid, nitric acid, nitrose acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as Ci-C 4 alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as CrC 4 alkane- or arylsulfonic acids which are
  • Compounds of formula I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower- alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
  • bases for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower- alkylamine, for example ethyl-, dieth
  • 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, nonyl, decyl 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 trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.
  • Alkoxy groups preferably have a preferred chain length of from 1 to 6 carbon atoms.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also the isomeric pentyloxy and hexyloxy radicals; preferably methoxy and ethoxy.
  • Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert- butoxycarbonyl; preferably methoxycarbonyl or ethoxycarbonyl.
  • Haloalkoxy groups preferably have a chain length of from 1 to 6 carbon atoms.
  • Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1 ,1 ,2,2- tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2- trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.
  • Alkylthio groups preferably have a chain length of from 1 to 6 carbon atoms.
  • Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio and ethylthio.
  • Alkylsulphinyl is, for example, methylsulphinyl, ethylsulphinyl, propylsulphinyl, isopropylsulphinyl, n-butylsulphinyl, isobutylsulphinyl, sec-butylsulphinyl, tert-butylsulphinyl; preferably methylsulphinyl and ethylsulphinyl.
  • Alkylsulphonyl is, for example, methylsulphonyl, ethylsulphonyl, propylsulphonyl,
  • Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the isomeric butylamines.
  • Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino and diisopropylamino.
  • Preference is given to alkylamino groups having a chain length of from 1 to 4 carbon atoms.
  • Alkoxyalkyl groups preferably have a chain length of 1 to 6 carbon atoms.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n- propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
  • the cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, for example
  • 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.
  • mono- to polysubstituted in the definition of the substituents, means typically, depending on the chemical structure of the substituents, monosubstituted to seven-times substituted, preferably monosubstituted to five-times substituted, more preferably mono-, double- or triple-substituted.
  • halo-substituted phenyl in the definition of the substituents, means for example a phenyl group which is mono- to polysubstituted by substituents selected from the group consisting of fluoro, chloro, bromo and iodo.
  • halo-substituted phenyl is phenyl which is mono- di or tri-substituted by chloro, in particular mono-substituted by chloro.
  • five- 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 or 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 cyclopropi, cyclobutyl, oxetanyl, thietanyl,
  • cyclopentyl, cyclohexyl, where said cycloalkylgroups for their part may be preferably unsubstituted or substituted by CrC 6 alkyl 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-1 H-pyrazol-3-yl)-; (1 -propyl-1 H-pyrazol-3- yl)-; (1 H-pyrazol-3-yl)-; (1 ,5-d
  • each R 2 6 is methyl
  • each R 27 and each R 23 are independently hydrogen, CrC 3 alkyl, CrC 3 alkoxy, CrC 3 alkylthio or trifluoromethyl
  • Gi is a three- to four- membered ring which can be partially saturated or fully saturated and can contain one heteroatom selected form the group consisting of nitrogen, oxygen and sulphur; said three- to four- membered ring system can be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, methyl and trifluoromethyl; or
  • Gi is C 2 -C 6 alkenyl which can be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, methyl and trifluoromethyl; or
  • Gi is C 2 -C 6 alkynyl which can be substituted by substituents selected from the group consisting of halogen, methyl and trifluoromethyl;
  • G 2 is selected from the group consisting of J-1 to J-24
  • each group J-1 to J-24 is mono- di- or trisubstituted with Rx, wherein
  • Rx is halogen, CrC 6 alkyl, CrC 6 alkoxy, CrC 6 alkylthio, CrC 6 alkoxycarbonyl, d- C 6 alkylamino, Ci-C 6 di-alkylamino, Ci-C 6 alkoxycarbonylamino, pyrimidinyl, thiazolyl, pyridinyl, pyrazinyl, pyridazinyl, pyrazinyloxy, imidazolyl, dihydro-oxazolyl, oxazolyl, dioxolanyl, 1 ,3- dioxanyl and 5,6-dihydro-[1 ,4,2]dioxazinyl, wherein said pyrimidinyl, thiazolyl, pyridinyl, pyrazinyl, pyridazinyl, pyrazinyloxy, imidazolyl , dihydro-oxazolyl, oxazo
  • Ri is hydrogen, CrC 6 alkyl, which can be mono- to polysubstituted by substituents selected from the group consisting of C 3 -C 6 cycloalkyl, CrC 6 alkylthio, CrC 6 haloalkyl, d- C 6 alkylsulfinyl, CrC 6 alkylsulfonyl, halogen, cyano, hydroxy, CrC 6 alkoxy, C 2 -C 6 alkenyl, C 2 - C 6 alkynyl, Ci-C 6 alkoxy-C3-C 6 alkynyl, oxolanyl, dioxolanyl, thienyl, thietanyl,
  • Ri is CrC 6 alkyl, which is substituted by pyridyl, wherein said pyridyl can be mono- to polysubstituted by substituents selected from the group consisting of halogen and C
  • Ri is CrC 6 alkyl, which is substituted by phenoxy, wherein said phenoxy can be mono- to polysubstituted by substituents selected from the group consisting of halogen and CrC 4 alkyl; or Ri is CrC 6 alkyl, which is substituted by phenylcarbonyl, wherein said phenylcarbonyl can be mono- to polysubstituted by substituents selected from the group consisting of halogen and CrC 4 haloalkoxy;
  • Ri is CrC 6 alkyl, which is substituted by imidazolinyl, wherein said imidazolinyl can be mono- to polysubstituted by CrC 4 alkyl;
  • Ri is CrC 6 alkyl, which is substituted by isoxazolyl, wherein said isoxazolyl can be mono- to polysubstituted by halo-substituted phenyl;
  • Ri is pyridyl, which can be mono- to polysubstituted by substituents selected from the group consisting of CrC 4 alkyl, CrC 4 alkoxycarbonyl, phenyl and phenoxy;
  • Ri is pyrimidinyl which can be mono- to polysubstituted by substituents selected from the group consisting of hydroxy, CrC 4 alkoxy and CrC 4 alkyl;
  • Ri is piperazinyl, which can be monosubstituted by benzyl;
  • Ri is piperidinyl, which can be mono- to polysubstituted by CrC 4 alkyl;
  • Ri is pyrazolyl, which can be mono- to polysubstituted by substituents selected from the group consisting of CrC 4 alkyl, cyano and phenyl;
  • Ri is thiethanyl, which can be substituted by CrC 4 alkyl; or R- ⁇ is dihydro-thiophene-2-one-3-yl;
  • Ri is azetidinyl, which can be mono- to polysubstituted by substituents selected from the group consisting of Ci-C 4 haloalkyl and benzyl;
  • Ri is pyrrolidinyl which can be substituted by benzyl;
  • Ri is Ci-C 6 alkoxycarbonylamino
  • Ri is C 3 -C 6 cycloalkenyl which can be mono- to polysubstituted by CrC 6 alkoxycarbonyl; or Ri is phenyl, which can be mono- to polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkylthio, di(Ci-
  • Ri is quinolinyl, benzothiazolyl, oxolanyl or indazolyl;
  • Ri is benzothiophenyl, which can be monosubstituted by CrC 6 alkoxycarbonyl;
  • Ri is thiazolyl, which can be mono- to polysubstituted by substituents selected from the group consisting of CrC 4 alkyl, pyridyl, phenyl, pyrimidinyl and CrC 4 alkylcarbonyl; wherein said phenyl can be mono- to polysubstituted by CrC 4 alkyl and wherein said pyrimidinyl can be mono- to polysubstituted by Ci-C 4 alkoxy;
  • Ri is benzothiazolyl which can be mono- to polysubstituted by CrC 4 alkyl;
  • Ri is chromen-2-one which can be mono- to polysubstituted by CrC 4 alkyl;
  • Ri is isoxazolyl, which in can be mono- to polysubstituted by substituents selected from the group consisting of CrC 4 alkyl and phenyl;
  • Ri is thiadiazolyl, which can be monosubstituted by substituents selected from the group consisting of CrC 4 alkyl and halo-substituted phenyl;
  • Ri is furyl which can be mono- to polysubstituted by substituents selected from the group consisting of cyano and phenyl;
  • Ri is pyrazolopyridinyl which can be mono- to polysubstituted by CrC 4 alkyl; or R-i is thienyl which can be mono- to polysubstituted by CrC 4 alkoxycarbonyl; or R-i is
  • Ri is isoxazolidin-3-one, which can be monosubstituted by substituents selected from d- C 4 alkyl and CrC 4 haloalkyl;
  • Ri and R 2 form together with the nitrogen atom to which they are bonded a 3- to 6- membered saturated ring which can be mono- to polysubstituted by substituents selected from the group consisting of CrC 4 alkyl, Ci-C 4 alkoxy and halogen; and further mono- to polysubstituted by substituents selected from the group consisting of phenylcarbonyl, phenoxy-CrC 4 alkyl and phenoxy, wherein said phenylcarbonyl, phenoxy-CrC 4 alkyl and phenoxy can be mono- to polysubstituted by halogen; and said saturated ring can be additionally substituted by an ethylene chain;
  • R 2 is hydrogen, CrC 6 alkyl, CrC 6 haloalkyl or C 3 -C 6 cycloalkyl
  • R 3 is oxygen
  • n 0;
  • Gi is cyclopropyl, ethenyl or ethynyl
  • R 7 is hydrogen, fluoro, chloro, bromo or iodo
  • G 2 is J-1 , J-4 or J-16;
  • each J group is mono- di- or trisubstituted with Rx, wherein
  • Rx is halogen, CrC 6 alkoxycarbonyl, pyrimidinyl, dihydro-oxazolyl, dioxolanyl, 1 ,3-dioxanyl and 5,6-dihydro-[1 ,4,2]dioxazinyl, wherein said pyrimidinyl, pyridinyl, dihydro-oxazolyl, dioxolanyl, 1 ,3-dioxanyl and 5,6-dihydro-[1 ,4,2]dioxazinyl can be mono- to polysubstituted by
  • Ri is CrC 6 alkyl, which can be mono- to polysubstituted by substituents selected from the group consisting of CrC 6 alkylthio, CrC 6 haloalkyl, CrC 6 alkylsulfinyl, halogen, oxolanyl, thietanyl, thiethanyldioxide, pyrimidinyl and Ci-C 6 alkylcarbonylamino;
  • Ri is CrC 6 alkyl, which is substituted by pyridyl, wherein said pyridyl can be mono- to polysubstituted by substituents selected from the group consisting of halogen and C
  • Ri is thiethanyl, which can be substituted by CrC 4 alkyl;
  • Ri is thietanyloxide, thiethanyldioxide or tetrahydrothienyl
  • R 2 is hydrogen or d-C 6 alkyl
  • G 2 is J-1 , J-4 or J-16;
  • each J group is mono- di- or trisubstituted with Rx, wherein preferably Rx is halogen, CrC 6 alkoxycarbonyl, pyrimidinyl, dihydro-oxazolyl, dioxolanyl, 1 ,3-dioxanyl and 5,6-dihydro-[1 ,4,2]dioxazinyl, wherein said pyrimidinyl, pyridinyl, dihydro-oxazolyl, dioxolanyl, 1 ,3-dioxanyl and 5,6-dihydro-[1 ,4,2]dioxazinyl can be mono- to polysubstituted by C C 6 alkyl.
  • n 0;
  • R 7 is hydrogen, fluoro, chloro, bromo or iodo.
  • G 2 is preferably
  • Ri is CrC 6 alkyl, which can be mono- to polysubstituted by substituents selected from the group consisting of CrC 6 alkylthio, CrC 6 haloalkyl, CrC 6 alkylsulfinyl, halogen, oxolanyl, thietanyl, thiethanyldioxide, pyrimidinyl and Ci-C 6 alkylcarbonylamino;
  • Ri is CrC 6 alkyl, which is substituted by pyridyl, wherein said pyridyl can be mono- to polysubstituted by substituents selected from the group consisting of halogen and C
  • Ri is thiethanyl, which can be substituted by CrC 4 alkyl;
  • Ri is oxolanyl
  • Ri is thietanyloxide, thiethanyldioxide or tetrahydrothienyl
  • R 2 is hydrogen or CrC 6 alkyl.
  • An outstanding group of compounds of formula I is represented by the compounds of formula
  • Rio is C 3 -C 4 cycloalkyl which can be substituted by CrC 4 haloalkyl, or is C 3 -C 6 cycloalkenyl which can be substituted by substituents selected from the group consisting of C
  • C 4 haloalkyl and halogen or is C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, or C 2 -C 6 alkynyl substituted by d- C 4 haloalkyl, or R 10 is a three- to four membered saturated ring which can contain one heteroatom selected from oxygen or nitro; and
  • Rii is pyrimidinyl, pyridyl substituted by pyrimidinyl, or is Ci-C 4 haloalkylaminocarbonyl.
  • R-I2 is C 3 -C 4 cycloalkyl which can contain a nitrogen atom, or is C 2 -C 6 alkynyl, C 2 -C 6 alkenyl, or C 2 -C 6 alkenyl substituted by halogen;
  • R-I3 is pyrimidinyl which can be substituted by pyrimidinyl, or is pyridyl which can be substituted by substituents selected from the group consisting of pyrimidinyl, d- C 4 alkoxyalkyl, dithianyl and dioxanyl, or is Ci-C 4 haloalkylaminocarbonyl or d- C 4 alkylsulfonylaminocarbonyl.
  • Examples of a suitable base are triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, ⁇ , ⁇ -diethylaniline, pyridine, 4-(N,N- dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1 ,5-Diazabicyclo(4.3.0)non-5- ene (DBN).
  • DBU 1-,8-diazabicyclo[5.4.0]undec-7-ene
  • DBN 1 ,5-Diazabicyclo(4.3.0)non-5- ene
  • bases which are employed in excess such as triethylamine, pyridine, N-methylmorpholine or ⁇ , ⁇ -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 -30°C to approximately +100°C, in many cases in the range between ambient temperature and approximately +80°C.
  • the compound of formula III is prepared from the compound of formula II under routine reaction conditions as described in March's Advanced Organic Chemistry, 6 th edition, Wiley, New York, 2007, p. 1440-1 .
  • the compound of formula II is prepared according to reaction scheme 1.
  • the known compound of formula IV is chlorinated to the compound of formula V, as described e.g. in WO 2008/083070 p. 63, which is deprotonated with a base such as LDA, LiHMDS,
  • G 2 is a 5- or 6-membered optionally substituted heterocycle; preferably G 2 is pyridyl or pyrimidyl, said pyridyl or pyrimidyl can be mono- to polysubstituted by substituents selected from the group consisting of pyrimidinyl, halogen and pyridyl, wherein said pyrimidinyl and pyridyl in turn can be mono- to polysubstituted by halogen, CrC 6 alkyl, d- C 6 haloalkyl, CrC 6 alkoxy; or is thiazolyl which can be substituted by substituents selected from the group consisting of halogen, di-Ci-C 4 alkyl-phosphinoylmethyl-aminocarbonyl and Ci-C 6 alkoxycarbonylamino; is [1 ,3,4]oxadiazole-2-yl, which can be substituted by pyridinyl which in turn can be substituted
  • X is chloro, bromo, iodo, OMesyl or trifluoromethanesulfonate (OTf), in a Suzuki reaction with a compound of formula G 2 - a, wherein G 2 is as described under formula lb above and Ra is B(OH) 2 , B(OMe) 2 , B(OiPr) 2 , BF 3 K or B(-OCMe 2 CMe20-).
  • Compounds of formula X, wherein X is chloro, bromo or iodo can be made from compounds of formula XI according to the reaction scheme 2. Halogenation reactions are known from literature, e.g. March's Advanced Organic Chemistry, 6 th edition, Wiley, New York, 2007.
  • the compound of formula X wherein X is chloro, bromo, iodo OMesyl or trifluoromethanesulfonate, is borylated under known condition to a compound of formula XII, which react with a compound of formula G 2 -X, wherein X is chloro, bromo, iodo, OMesyl or trifluoromethanesulfonate (OTf) in a Suzuki reaction to give a compound of formula lb.
  • the reactants can be reacted in the presence of a base.
  • suitable bases 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,
  • the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or ⁇ , ⁇ -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 -30°C to approximately +100°C, in many cases in the range between ambient temperature and approximately +80°C.
  • a compound of formula I can be converted in a manner known per se into another compound of formula I by replacing one or more substituents of the starting compound of formula I in the customary manner by (an)other substituent(s) according to the invention.
  • Salts of compounds of formula I can be prepared in a manner known per se.
  • acid addition salts of compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula I can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula I can be converted in a manner known per se into other salts of compounds of formula I, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the compounds of formula I which have salt-forming properties can be obtained in free form or in the form of salts.
  • the compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.
  • Diastereomer mixtures or racemate mixtures of compounds of formula I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
  • Enantiomer mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high- performance liquid chromatography (HPLC) on acetyl celulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is com- plexed, or by conversion into diastereomeric salts, for example by reacting a basic end-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 crystallization based on their differing so
  • 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.
  • N-oxides can be prepared by reacting a compound of the formula I with a suitable oxidizing agent, for example the H 2 0 2 /urea adduct in the presence of an acid anhydride, e.g.
  • the compounds of formula 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 of formula I according to the invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants.
  • the active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina.
  • the insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e.
  • Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order Coleoptera, for example,
  • Agriotes spp. Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis, Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp,
  • Sphenophorus spp Sphenophorus spp, Sternechus subsignatus, Tenebrio spp., Tribolium spp. and Trogoderma spp.;
  • Hemiptera for example, Acanthocoris scabrator, Acrosternum spp, Adelphocoris lineolatus, Amblypelta nitida, Bathycoelia thalassina, Blissus spp, Cimex spp., Clavigralla tomentosicollis, Creontiades spp, Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp, Euchistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Lep- tocorisa spp., Lygus spp, Margarodes spp, Murgantia histrionic, Neomegalotomus spp, Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus ins
  • Piezodorus spp Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp. , Thyanta spp , Triatoma spp., Vatiga illudens;
  • Acyrthosium pisum Adalges spp, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp, Brachycaudus spp,
  • Blatta spp. Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp. , Scapteriscus spp, and Schistocerca spp.;
  • Calliothrips phaseoli Frankliniella spp., Heliothrips spp, Hercinothrips spp., Parthenothrips spp, Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp; from the order Thysanura, for example, Lepisma saccharina.
  • the active ingredients according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on or- gans, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
  • Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts,
  • the active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops.
  • the active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca(preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
  • crops is to be understood as including also 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 popilliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g.
  • Vip vegetative insecticidal proteins
  • Vip e.g. Vip1 , Vip2, Vip3 or Vip3A
  • insecticidal proteins of bacteria colonising nematodes for example Photorhabdus spp.
  • 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 trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • 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.
  • ⁇ -endotoxins for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins.
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ).
  • Truncated toxins for example a truncated CrylAb, 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 Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths
  • 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.
  • YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1 Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a CrylAc toxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab tox
  • transgenic crops are:
  • 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 Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
  • NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb 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-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such
  • PRPs pathogenesis-related proteins
  • antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191 .
  • 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).
  • PRPs pathogenesis-related proteins
  • 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).
  • 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.
  • 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.
  • 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.. Of the order Blattarida, for example Blatta orientalis, Periplaneta americana,
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp.
  • compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
  • 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 concentrates, suspension concentrates, microemulsions, oil dispersibles, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise - at least - one of the active ingredients according to the invention and which are to be selected to suit the intended aims and the prevailing circumstances.
  • pesticidal compositions such as emulsifiable concentrates, suspension concentrates, microemulsions, oil dispersibles, 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
  • the active ingredient is employed in pure form, a solid active ingredient for example in a specific particle size, or, preferably, together with - at least - one of the auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).
  • auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).
  • suitable solvents are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the fractions C 8 to Ci 2 of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-me- thylpyrrolid-2-one, dimethyl sulfoxide or ⁇ , ⁇ -dimethylformamide, water, unepoxidized or epoxidized vegetable oils, such as un
  • Solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • highly disperse silicas or highly disperse absorbtive polymers are Suitable adsorptive carriers for granules.
  • porous types such as pumice, brick grit, sepiolite or bentonite
  • suitable non-sorptive carrier materials are calcite or sand.
  • a large number of granulated materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.
  • Suitable surface-active compounds are, depending on the type of the active ingredient to be formulated, non-ionic, cationic and/or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties.
  • the surfactants mentioned below are only to be considered as examples; a large number of further surfactants which are conventionally used in the art of formulation and suitable according to the invention are described in the relevant literature.
  • Suitable non-ionic surfactants are, especially, polyglycol ether derivatives of aliphatic or cyc- loaliphatic alcohols, of saturated or unsaturated fatty acids or of alkyl phenols which may contain approximately 3 to approximately 30 glycol ether groups and approximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatic hydrocarbon radical or approximately 6 to approximately 18 carbon atoms in the alkyl moiety of the alkyl phenols.
  • water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopo- lypropylene glycol or alkyl polypropylene glycol having 1 to approximately 10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene glycol ether groups and approximately 10 to approximately 100 propylene glycol ether groups.
  • the abovementioned compounds contain 1 to approximately 5 ethylene glycol units per propylene glycol unit.
  • nonylphenoxypolyethoxyethanol castor oil polyglycol ether, polypropylene glycol/polyethylene oxide adducts, tributylpheno- xypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol.
  • fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate.
  • the cationic surfactants are, especially, quarternary ammonium salts which generally have at least one alkyl radical of approximately 8 to approximately 22 C atoms as substituents and as further substituents (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl radicals.
  • the salts are preferably in the form of halides, methylsulfates or ethylsulfates. Examples are stearyltrimethylammonium chloride and benzylbis(2-chloroethyl)ethyl- ammonium bromide.
  • Suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface-active compounds.
  • suitable soaps are the alkali, alkaline earth or (un- substituted or substituted) ammonium salts of fatty acids having approximately 10 to approximately 22 C atoms, such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which are obtainable for example from coconut or tall oil; mention must also be made of the fatty acid methyl taurates.
  • synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates.
  • the fatty sulfonates and fatty sulfates are present as alkali, alkaline earth or (substituted or unsubstituted) ammonium salts and they generally have an alkyi radical of approximately 8 to approximately 22 C atoms, alkyi also to be understood as including the alkyi moiety of acyl radicals; examples which may be mentioned are the sodium or calcium salts of lignosulfonic acid, of the dodecylsulphuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulphuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain 2 sulphonyl 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 are:
  • active ingredient 1 to 95%, preferably 5 to 20%
  • surfactant 1 to 30%, preferably 10 to 20 %
  • active ingredient 0.1 to 10%, preferably 0.1 to 1 %
  • active ingredient 5 to 75%, preferably 10 to 50%
  • 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%
  • Example P2 Preparation of 2,4-dichloro-thiazole-5-carboxylic acid: Diisopropylamine (42 ml, 297 mmol) was dissolved in 1000 ml THF and cooled to -70°C. 181 .2 ml nBuLi (1.6M in hexane, 290 mmol) was added. The temperature was briefly raised to 0°C and the reaction mixture was again cooled down to -70°C. 2,4-Dichlorothiazole (40.8 g, 265 mmol) in 200 ml THF was slowly added at -70°C.
  • benzyltriethylammonium chloride 2.62 g (18.5 mmol) K 2 C0 3 , 82.9 mg (0.369 mmol) Pd(OAc) 2 and 3.7 mL (3.69 mmol) of a 1.0 M solution of tri-tert-butylphosphine in toluene were added under an argon atmosphere and the reaction was stirred at room temperature for 18 hours. The mixture was subsequently diluted with ethyl acetate, washed with water, the water phase was extracted twice with ethyl acetate, the combined organic phases were washed with brine, dried over sodium sulphate and evaporated.
  • the reaction mixture was diluted in water and ethyl acetate, the water phase was extracted twice with ethyl acetate, the organic phases were washed with brine, dried over MgS0 4 and evaporated.
  • the residue was purified by column chromatography on silica gel with cyclohexane/ethyl acetate followed by CH 2 Cl 2 /MeOH to afford 31 mg (0.08 mmol) of 4- cyclopropyl-2-(3-pyridyl)-5-(6-pyrimidin-2-yl-2-pyridyl)thiazole as light yellow crystal.
  • Example P1 1 Preparation of 2-(3-pyridyl)-5-(6-pyrimidin-2-yl-2-pyridyl)-4-vinyl-thiazole:
  • the reaction mixture was diluted with water and ethyl acetate then filtered, the water phase was extracted twice with ethyl acetate, the organic phases were washed with brine, dried over MgS0 4 and evaporated.
  • the residue was purified by column chromatography on silica gel with cyclohexane/ethyl acetate followed by CH 2 Cl2/MeOH to afford 126 mg (0.36 mmol) of 2-(3-pyridyl)-5-(6-pyrimidin-2-yl-2-pyridyl)-4- vinyl-thiazole as amorphous yellow crystal.
  • Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 350°C, Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector.
  • Spectra were recorded on a ZQ Mass Spectrometer from Waters (Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 100°C, Desolvation Temperature: 250°C, Cone Gas Flow: 50 L/Hr, Desolvation Gas Flow: 400 L/Hr, Mass range: 100 to 900 Da) and an Agilent 1 100 LC (Solvent degasser, binary pump, heated column compartment and diode-array detector.
  • an electrospray source Polyity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 100°C, Desolvation Temperature: 250°C, Cone Gas Flow: 50 L/Hr, Desolvation Gas Flow: 400 L/Hr, Mass range: 100 to 900
  • Example F1 Emulsion concentrates a) b) c)
  • glycol ether (36 mol of EO) 5 % -
  • 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)
  • 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)
  • Example F5 Wettable powders a) b) c)
  • 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
  • Example F8 Suspension concentrate
  • Nonylphenoxypolyethylene glycol ether (15 mol of EO) 6 %
  • Carboxymethylcellulose 1 % 37 % aqueous formaldehyde solution 0.2 %
  • Silicone oil (75 % aqueous emulsion) 0.8 %
  • the finely ground active ingredient is mixed intimately with the additives.
  • Suspensions of any desired concentration can be prepared from the thus resulting suspension concentrate by dilution with water.
  • compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients.
  • mixtures of the compounds of formula I with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use.
  • Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridyl- methyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
  • TX means "one compound selected from the group consisting of the compounds No. 1 .001 to No. 1.021 described in Table 1 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-chlorophenyl)-2- ethoxyethanol (lUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate
  • 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 II (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.
  • TX isopropyl 0-(methoxyaminothiophosphoryl)salicylate (lUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (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, methomy
  • 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 II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridaphenthion (701 ) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinalphos (71 1 ) + TX, quintiofos (1381 ) + TX,
  • spirodiclofen (738) + TX, spiromesifen (739) + TX, SSI-121 (development code) (1404) + TX, sulfiram (alternative name) [CCN] + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulphur (754) + TX, SZI-121 (development code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbam (alternative name) + TX,
  • tetrachlorvinphos (777) + TX, tetradifon (786) + TX, tetranactin (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
  • an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (lUPAC 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 (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX,
  • an anthelmintic selected from the group of substances consisting of abamectin (1 ) + TX, crufomate (101 1 ) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,
  • an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1 122) + TX, fenthion (346) + TX, pyridin-4-amine (lUPAC name) (23) and strychnine (745) + TX,
  • a bactericide selected from the group of substances consisting of 1 -hydroxy-1 /-/-pyridine-2- thione (lUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (lUPAC name) (170) + TX, copper hydroxide (lUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1 105) + TX, dodicin (1 1 12) + TX, fenaminosulf (1 144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride
  • 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
  • a soil sterilant selected from the group of substances consisting of iodomethane (lUPAC 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,
  • an insect pheromone selected from the group of substances consisting of (£)-dec-5-en-1 -yl acetate with (£)-dec-5-en-1 -ol (lUPAC name) (222) + TX, (£)-tridec-4-en-1 -yl acetate (lUPAC name) (829) + TX, (£)-6-methylhept-2-en-4-ol (lUPAC name) (541 ) + TX, (£,Z)- tetradeca-4,10-dien-1 -yl acetate (lUPAC name) (779) + TX, (Z)-dodec-7-en-1 -yl acetate (lUPAC name) (285) + TX, (Z)-hexadec-l 1 -enal (lUPAC name) (436) + TX, (Z)-hexadec- 1 1 -en-1 -yl acetate (lUPAC name) (437) + T
  • an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (lUPAC name) (591 ) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (lUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (lUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate
  • an insecticide selected from the group of substances consisting of 1 -dichloro-1 -nitroethane (lUPAC/Chemical Abstracts name) (1058) + TX, 1 ,1 -dichloro-2,2-bis(4-ethylphenyl)ethane (lUPAC name) (1056), + TX, 1 ,2-dichloropropane (lUPAC/Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1 -bromo- 2-chloroethane (lUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-1 -(3,4- dichlorophenyl)ethyl acetate (lUPAC name) (1451 ) + TX, 2,2-dichlorovinyl 2- ethylsulphinylethyl methyl
  • 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] +
  • development code (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
  • a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (lUPAC 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 (lUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb
  • a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1 ,2-dibromo-3-chloropropane (lUPAC/Chemical Abstracts name) (1045) + TX, 1 ,2-dichloropropane (lUPAC/ Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1 ,3-dichloropropene (233) + TX, 3,4- dichlorotetrahydrothiophene 1 ,1 -dioxide (lUPAC/Chemical Abstracts name) (1065) + TX, 3- (4-chlorophenyl)-5-methylrhodanine (lUPAC name) (980) + TX, 5-methyl-6-thioxo-1 ,3,5- thiadiazinan-3-ylacetic acid (lUPAC name
  • a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,
  • a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX,
  • a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1 ,3-dione (lUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC 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
  • a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (lUPAC name) (934) + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (lUPAC 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
  • 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, pyridin-4-amine
  • a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX,
  • a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX, and biologically active compounds selected from the group consisting of azaconazole (60207-31 -0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [1 16255-48-2] + TX, cyproconazole [94361 -06-5] + TX, difenoconazole [1 19446-68-3] + TX, diniconazole
  • the active ingredient mixture of the compounds of formula I selected from Table 1 with active ingredients described above comprises a compound selected from Table 1 and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1 :6000, especially from 50:1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10:1 to 1 :10, very especially from 5:1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1 :1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 :150, or 1
  • the mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
  • the mixtures comprising a compound of formula I selected from Table 1 and one or more active ingredients as described above can be applied, for example, in a single "ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the compounds of formula I selected from Table 1 and the active ingredients as described above is not essential for working the present invention.
  • compositions can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
  • auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators
  • compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • compositions that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing 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 propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type.
  • the propagation material can be treated with the compositions prior to planting, for example seed can be treated prior to sowing.
  • the compositions can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling.
  • Example B1 Activity against Myzus persicae (green peach aphid)
  • Cotton leaf discs are placed on agar in a 24-well microtiter plate and sprayed with test solutions. After drying, the leaf discs are infested with 12 to 18 adults. After an incubation period of 6 days after infestation, samples are checked for mortality and special effects (e.g. phytotoxicity).
  • Example B3 Activity against Thrips tabaci (Onion Thrips):
  • Sunflower leaf discs are placed on agar in a 24-well microtiter plate and sprayed with test solutions. After drying, the leaf discs are infested with a thrips population of mixed ages. After an incubation period of 7 days after infestation, samples are checked for mortality and special effects (e.g. phytotoxicity).
  • compound 1.019 showed an activity of over 80% at a concentration of 200 ppm.
  • Example B4 Activity against Aphis craccivora (Black bean aphid):
  • Example B5 Activity against Aonidiella aurantii (Citrus red scale)
  • Potato tubers are infested with about 50 crawlers. After a 2 week settling period, the N 2 nymphs are treated through dipping the tubers in the test solution. 4-6 weeks after treatment, samples are checked for number of crawlers from the next generation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

L'invention concerne des composés de formule (I), dans laquelle les substituants sont tels que définis dans la revendication 1, et des sels agrochimiquement acceptables et toutes les formes stéréo-isomères et tautomères des composés de formule (I), pouvant être utilisés comme ingrédients actifs agrochimiques et pouvant être préparés de manière connue en soi.
PCT/EP2013/057784 2012-04-17 2013-04-15 Dérivés de thiazole actifs en tant que pesticide Ceased WO2013156433A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP12164415.7 2012-04-17
EP12164415 2012-04-17

Publications (1)

Publication Number Publication Date
WO2013156433A1 true WO2013156433A1 (fr) 2013-10-24

Family

ID=48087603

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2013/057784 Ceased WO2013156433A1 (fr) 2012-04-17 2013-04-15 Dérivés de thiazole actifs en tant que pesticide

Country Status (1)

Country Link
WO (1) WO2013156433A1 (fr)

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8815271B2 (en) 2010-11-03 2014-08-26 Dow Agrosciences, Llc. Pesticidal compositions and processes related thereto
US8901153B2 (en) 2012-04-27 2014-12-02 Dow Agrosciences, Llc. Pesticidal compositions and processes related thereto
US9024031B1 (en) 2014-08-19 2015-05-05 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9029555B1 (en) 2014-07-31 2015-05-12 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9029556B1 (en) 2014-07-31 2015-05-12 Dow Argosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9029554B1 (en) 2013-10-17 2015-05-12 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9044017B2 (en) 2013-10-17 2015-06-02 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9085564B2 (en) 2013-10-17 2015-07-21 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9085552B1 (en) 2014-09-12 2015-07-21 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9102655B2 (en) 2013-10-17 2015-08-11 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9102654B2 (en) 2013-10-17 2015-08-11 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9108946B2 (en) 2013-10-17 2015-08-18 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9137998B2 (en) 2013-10-22 2015-09-22 Dow Agrosciences Llc Pesticidal compositions and related methods
US9144241B2 (en) 2013-10-22 2015-09-29 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9149040B2 (en) 2013-10-22 2015-10-06 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9155304B2 (en) 2013-10-22 2015-10-13 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9174962B2 (en) 2013-10-17 2015-11-03 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9199964B1 (en) 2014-07-31 2015-12-01 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9282739B2 (en) 2012-04-27 2016-03-15 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
US9282740B2 (en) 2013-10-22 2016-03-15 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9295260B2 (en) 2013-10-22 2016-03-29 Dow Agrosciences Llc Pesticidal compositions and related methods
US9295258B2 (en) 2013-10-22 2016-03-29 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9445597B2 (en) 2013-10-22 2016-09-20 Dow Agrosciences Llc Pesticidal compositions and related methods
US9474276B2 (en) 2013-10-22 2016-10-25 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9491944B2 (en) 2013-10-22 2016-11-15 Dow Agrosciences Llc Pesticidal compositions and related methods
US9497966B2 (en) 2013-10-22 2016-11-22 Dow Agrosciences Llc Pesticidal compositions and related methods
US9549560B2 (en) 2013-10-22 2017-01-24 Dow Agrosciences Llc Pesticidal compositions and related methods
US9655365B2 (en) 2011-10-26 2017-05-23 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
US9708288B2 (en) 2012-04-27 2017-07-18 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
US9788546B2 (en) 2013-10-22 2017-10-17 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9788545B2 (en) 2013-10-22 2017-10-17 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9801376B2 (en) 2013-10-22 2017-10-31 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9801383B2 (en) 2013-10-22 2017-10-31 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9808008B2 (en) 2013-10-22 2017-11-07 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US10100033B2 (en) 2016-12-29 2018-10-16 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US10233155B2 (en) 2016-12-29 2019-03-19 Dow Agrosciences Llc Processes for the preparation of pesticide compounds
US10273221B2 (en) 2015-03-27 2019-04-30 Syngenta Participations Ag Microbiocidal heterobicyclic derivatives
WO2025155603A1 (fr) * 2024-01-19 2025-07-24 Corteva Agriscience Llc Mélanges inhibiteurs de nitrification
WO2025155791A1 (fr) * 2024-01-19 2025-07-24 Corteva Agriscience Llc Compositions comprenant des inhibiteurs de nitrification

Citations (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4080457A (en) 1971-05-05 1978-03-21 Harrison William A Thiazoles and their use in controlling insects and pests
EP0353191A2 (fr) 1988-07-29 1990-01-31 Ciba-Geigy Ag Séquences d'ADN codant des polypeptides avec activité béta-1,3-glucanase
EP0367474A1 (fr) 1988-11-01 1990-05-09 Mycogen Corporation Souche de bacillus thuringiensis appelée b.t. ps81gg, active contre les lépidoptères nuisibles et gène codant une toxine active contre les lépidoptères.
EP0374753A2 (fr) 1988-12-19 1990-06-27 American Cyanamid Company Toxines insecticides, gènes les codant, anticorps les liant, ainsi que cellules végétales et plantes transgéniques exprimant ces toxines
EP0392225A2 (fr) 1989-03-24 1990-10-17 Ciba-Geigy Ag Plantes transgéniques résistantes aux maladies
WO1990013651A1 (fr) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Genes bacteriens
EP0401979A2 (fr) 1989-05-18 1990-12-12 Mycogen Corporation Souches de bacillus thuringiensis actives contre les lépidoptères nuisibles, et gènes codant pour des toxines actives contre les lépidoptères
EP0427529A1 (fr) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Lectines larvicides, et résistance induite des plantes aux insectes
EP0451878A1 (fr) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modification de plantes par techniques de génie génétique pour combattre ou contrôler les insectes
WO1993007278A1 (fr) 1991-10-04 1993-04-15 Ciba-Geigy Ag Sequence d'adn synthetique ayant une action insecticide accrue dans le mais
WO1995033818A2 (fr) 1994-06-08 1995-12-14 Ciba-Geigy Ag Genes pour la synthese des substances antipathogenes
WO1995034656A1 (fr) 1994-06-10 1995-12-21 Ciba-Geigy Ag Nouveaux genes du bacillus thuringiensis codant pour des toxines actives contre les lepidopteres
WO2000015615A1 (fr) 1998-09-15 2000-03-23 Syngenta Participations Ag Pyridinecetones utilises comme herbicides
WO2002015701A2 (fr) 2000-08-25 2002-02-28 Syngenta Participations Ag Nouvelles toxines insecticides derivees de proteines cristallines insecticides de $i(bacillus thuringiensis)
WO2003000906A2 (fr) 2001-06-22 2003-01-03 Syngenta Participations Ag Genes de resistance aux maladies chez les plantes
WO2003018810A2 (fr) 2001-08-31 2003-03-06 Syngenta Participations Ag Toxines cry3a modifiees et sequences d'acides nucleiques les codant
WO2003052073A2 (fr) 2001-12-17 2003-06-26 Syngenta Participations Ag Nouvel evenement du mais
WO2006087343A1 (fr) 2005-02-16 2006-08-24 Basf Aktiengesellschaft Anilides d'acide carboxylique pyrazole, procedes de production associes et agents les contenant pour la lutte antifongique
WO2007048556A1 (fr) 2005-10-25 2007-05-03 Syngenta Participations Ag Dérivés d'amides hétérocycliques utiles en tant que microbiocides
WO2008083070A1 (fr) 2006-12-29 2008-07-10 Neurogen Corporation Ligands des récepteurs du crf1 comprenant des groupes fonctionnels hétéroaryle bicycliques
WO2009149858A1 (fr) 2008-06-13 2009-12-17 Bayer Cropscience Ag Nouveaux amides et thioamides utilisés comme agents de lutte contre les parasites
WO2010006713A2 (fr) 2008-07-17 2010-01-21 Bayer Cropscience Ag Composés hétérocycliques utilisés comme pesticides
WO2010129497A1 (fr) 2009-05-05 2010-11-11 Dow Agrosciences Llc Compositions pesticides
WO2011138285A1 (fr) 2010-05-05 2011-11-10 Bayer Cropscience Ag Dérivés thiazole en tant qu'agents de lutte contre les nuisibles
WO2012000896A2 (fr) 2010-06-28 2012-01-05 Bayer Cropscience Ag Composés hétérocycliques utilisés en tant qu'agents de lutte contre les parasites
WO2013010946A2 (fr) 2011-07-15 2013-01-24 Basf Se Méthodes pesticides utilisant des composés 3-pyridyl thiazole substitués et dérivés pour combattre les parasites animaux de type i

Patent Citations (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4080457A (en) 1971-05-05 1978-03-21 Harrison William A Thiazoles and their use in controlling insects and pests
US4260765A (en) 1971-05-05 1981-04-07 Uniroyal, Inc. 2-(3-Pyridyl)-5-thiazolecarboxamides
EP0451878A1 (fr) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modification de plantes par techniques de génie génétique pour combattre ou contrôler les insectes
EP0353191A2 (fr) 1988-07-29 1990-01-31 Ciba-Geigy Ag Séquences d'ADN codant des polypeptides avec activité béta-1,3-glucanase
EP0367474A1 (fr) 1988-11-01 1990-05-09 Mycogen Corporation Souche de bacillus thuringiensis appelée b.t. ps81gg, active contre les lépidoptères nuisibles et gène codant une toxine active contre les lépidoptères.
EP0374753A2 (fr) 1988-12-19 1990-06-27 American Cyanamid Company Toxines insecticides, gènes les codant, anticorps les liant, ainsi que cellules végétales et plantes transgéniques exprimant ces toxines
EP0392225A2 (fr) 1989-03-24 1990-10-17 Ciba-Geigy Ag Plantes transgéniques résistantes aux maladies
WO1990013651A1 (fr) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Genes bacteriens
EP0401979A2 (fr) 1989-05-18 1990-12-12 Mycogen Corporation Souches de bacillus thuringiensis actives contre les lépidoptères nuisibles, et gènes codant pour des toxines actives contre les lépidoptères
EP0427529A1 (fr) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Lectines larvicides, et résistance induite des plantes aux insectes
WO1993007278A1 (fr) 1991-10-04 1993-04-15 Ciba-Geigy Ag Sequence d'adn synthetique ayant une action insecticide accrue dans le mais
WO1995033818A2 (fr) 1994-06-08 1995-12-14 Ciba-Geigy Ag Genes pour la synthese des substances antipathogenes
WO1995034656A1 (fr) 1994-06-10 1995-12-21 Ciba-Geigy Ag Nouveaux genes du bacillus thuringiensis codant pour des toxines actives contre les lepidopteres
WO2000015615A1 (fr) 1998-09-15 2000-03-23 Syngenta Participations Ag Pyridinecetones utilises comme herbicides
WO2002015701A2 (fr) 2000-08-25 2002-02-28 Syngenta Participations Ag Nouvelles toxines insecticides derivees de proteines cristallines insecticides de $i(bacillus thuringiensis)
WO2003000906A2 (fr) 2001-06-22 2003-01-03 Syngenta Participations Ag Genes de resistance aux maladies chez les plantes
WO2003018810A2 (fr) 2001-08-31 2003-03-06 Syngenta Participations Ag Toxines cry3a modifiees et sequences d'acides nucleiques les codant
WO2003052073A2 (fr) 2001-12-17 2003-06-26 Syngenta Participations Ag Nouvel evenement du mais
WO2006087343A1 (fr) 2005-02-16 2006-08-24 Basf Aktiengesellschaft Anilides d'acide carboxylique pyrazole, procedes de production associes et agents les contenant pour la lutte antifongique
WO2007048556A1 (fr) 2005-10-25 2007-05-03 Syngenta Participations Ag Dérivés d'amides hétérocycliques utiles en tant que microbiocides
WO2008083070A1 (fr) 2006-12-29 2008-07-10 Neurogen Corporation Ligands des récepteurs du crf1 comprenant des groupes fonctionnels hétéroaryle bicycliques
WO2009149858A1 (fr) 2008-06-13 2009-12-17 Bayer Cropscience Ag Nouveaux amides et thioamides utilisés comme agents de lutte contre les parasites
WO2010006713A2 (fr) 2008-07-17 2010-01-21 Bayer Cropscience Ag Composés hétérocycliques utilisés comme pesticides
WO2010129497A1 (fr) 2009-05-05 2010-11-11 Dow Agrosciences Llc Compositions pesticides
WO2011138285A1 (fr) 2010-05-05 2011-11-10 Bayer Cropscience Ag Dérivés thiazole en tant qu'agents de lutte contre les nuisibles
WO2012000896A2 (fr) 2010-06-28 2012-01-05 Bayer Cropscience Ag Composés hétérocycliques utilisés en tant qu'agents de lutte contre les parasites
WO2013010946A2 (fr) 2011-07-15 2013-01-24 Basf Se Méthodes pesticides utilisant des composés 3-pyridyl thiazole substitués et dérivés pour combattre les parasites animaux de type i

Non-Patent Citations (13)

* Cited by examiner, † Cited by third party
Title
"March's Advanced Organic Chemistry, 6th edition,", 2007, WILEY
"March's Advanced Organic Chemistry, 6th edition,", 2007, WILEY, pages: 1440 - 1
A. WOOD, COMPENDIUM OF PESTICIDE COMMON NAMES, 2004
ALDRICH CHEMFILES, vol. 7, no. 2, 2007, Retrieved from the Internet <URL:url: http://www.sigmaaldrich.com/etc/medialib/docs/Aldrich/Brochure/al_chemfile_v7_n2.Par.000 1.File.tmp/al_chemfile_v7_n2.pdf>
C. A. G. N. MONTALBETTI; V. FALQUE, TETRAHEDRON, vol. 61, 2005, pages 10827
C. D. S. TOMLIN: "The Pesticide Manual Thirteenth Edition", THE BRITISH CROP PROTECTION COUNCIL
DATABASE REGISTRY [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 11 April 2011 (2011-04-11), XP002684407, retrieved from STN Database accession no. 1052543-31-3 *
J. CHEM. SOC. PERKIN TRANS., 1992, pages 215
J. MED. CHEM., vol. 32, no. 12, 1989, pages 2561 - 73
J. P. WOLFE; J. S. NAKHLA: "The Suzuki Reaction in Name Reactions for Homologations", 2009, JOHN WILEY & SONS, INC., pages: 163
J. Q. YU, Z. SHI: "Topics in Current Chemistry", vol. 292, 2010, SPRINGER
L. ACKERMANN ET AL., ANGEW. CHEM. INT ED., vol. 48, 2009, pages 9792
RONKIN S M ET AL: "Discovery of pyrazolthiazoles as novel and potent inhibitors of bacterial gyrase", BIOORGANIC & MEDICINAL CHEMISTRY LETTERS, PERGAMON, ELSEVIER SCIENCE, GB, vol. 20, no. 9, 1 May 2010 (2010-05-01), pages 2828 - 2831, XP027012843, ISSN: 0960-894X, [retrieved on 20100315] *

Cited By (81)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9422278B2 (en) 2010-11-03 2016-08-23 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
US8815271B2 (en) 2010-11-03 2014-08-26 Dow Agrosciences, Llc. Pesticidal compositions and processes related thereto
US9655365B2 (en) 2011-10-26 2017-05-23 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
US9708288B2 (en) 2012-04-27 2017-07-18 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
US8901153B2 (en) 2012-04-27 2014-12-02 Dow Agrosciences, Llc. Pesticidal compositions and processes related thereto
US9282739B2 (en) 2012-04-27 2016-03-15 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
US9591857B2 (en) 2012-04-27 2017-03-14 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
US9102655B2 (en) 2013-10-17 2015-08-11 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9044017B2 (en) 2013-10-17 2015-06-02 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9433215B2 (en) 2013-10-17 2016-09-06 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9102654B2 (en) 2013-10-17 2015-08-11 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9108946B2 (en) 2013-10-17 2015-08-18 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9862702B2 (en) 2013-10-17 2018-01-09 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9126974B2 (en) 2013-10-17 2015-09-08 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9796682B2 (en) 2013-10-17 2017-10-24 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9723839B2 (en) 2013-10-17 2017-08-08 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9085564B2 (en) 2013-10-17 2015-07-21 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9670178B2 (en) 2013-10-17 2017-06-06 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9670164B2 (en) 2013-10-17 2017-06-06 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9174962B2 (en) 2013-10-17 2015-11-03 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9199942B2 (en) 2013-10-17 2015-12-01 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9661849B2 (en) 2013-10-17 2017-05-30 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9901095B2 (en) 2013-10-17 2018-02-27 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9029554B1 (en) 2013-10-17 2015-05-12 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9255083B2 (en) 2013-10-17 2016-02-09 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9255082B2 (en) 2013-10-17 2016-02-09 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9260396B2 (en) 2013-10-17 2016-02-16 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9908864B2 (en) 2013-10-17 2018-03-06 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9580405B2 (en) 2013-10-17 2017-02-28 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9550751B2 (en) 2013-10-17 2017-01-24 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9540342B2 (en) 2013-10-17 2017-01-10 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9988356B2 (en) 2013-10-17 2018-06-05 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9414594B2 (en) 2013-10-17 2016-08-16 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US10315999B2 (en) 2013-10-17 2019-06-11 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9447048B2 (en) 2013-10-17 2016-09-20 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9434712B2 (en) 2013-10-17 2016-09-06 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US9491944B2 (en) 2013-10-22 2016-11-15 Dow Agrosciences Llc Pesticidal compositions and related methods
US9788546B2 (en) 2013-10-22 2017-10-17 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9445597B2 (en) 2013-10-22 2016-09-20 Dow Agrosciences Llc Pesticidal compositions and related methods
US9474276B2 (en) 2013-10-22 2016-10-25 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
USRE48057E1 (en) 2013-10-22 2020-06-23 Dow Agrosciences Llc Pesticidal compositions and related methods
US9497967B2 (en) 2013-10-22 2016-11-22 Doe AgroSciences LLC Synergistic pesticidal compositions and related methods
US9497966B2 (en) 2013-10-22 2016-11-22 Dow Agrosciences Llc Pesticidal compositions and related methods
US9808008B2 (en) 2013-10-22 2017-11-07 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9295258B2 (en) 2013-10-22 2016-03-29 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9549560B2 (en) 2013-10-22 2017-01-24 Dow Agrosciences Llc Pesticidal compositions and related methods
US9295260B2 (en) 2013-10-22 2016-03-29 Dow Agrosciences Llc Pesticidal compositions and related methods
US9801383B2 (en) 2013-10-22 2017-10-31 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9282740B2 (en) 2013-10-22 2016-03-15 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9801376B2 (en) 2013-10-22 2017-10-31 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9137998B2 (en) 2013-10-22 2015-09-22 Dow Agrosciences Llc Pesticidal compositions and related methods
US9788545B2 (en) 2013-10-22 2017-10-17 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9144241B2 (en) 2013-10-22 2015-09-29 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9149040B2 (en) 2013-10-22 2015-10-06 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US9155304B2 (en) 2013-10-22 2015-10-13 Dow Agrosciences Llc Synergistic pesticidal compositions and related methods
US10035786B2 (en) 2014-07-31 2018-07-31 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1h-pyrazol-1-yl)pyridine
US9840490B2 (en) 2014-07-31 2017-12-12 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9371310B2 (en) 2014-07-31 2016-06-21 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9249122B1 (en) 2014-07-31 2016-02-02 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9029555B1 (en) 2014-07-31 2015-05-12 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9611247B2 (en) 2014-07-31 2017-04-04 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9255081B1 (en) 2014-07-31 2016-02-09 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9580403B2 (en) 2014-07-31 2017-02-28 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9573931B2 (en) 2014-07-31 2017-02-21 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9029556B1 (en) 2014-07-31 2015-05-12 Dow Argosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9199964B1 (en) 2014-07-31 2015-12-01 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9024031B1 (en) 2014-08-19 2015-05-05 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US10005758B2 (en) 2014-08-19 2018-06-26 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9115115B1 (en) 2014-08-19 2015-08-25 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9522900B2 (en) 2014-08-19 2016-12-20 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9809570B2 (en) 2014-08-19 2017-11-07 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9085552B1 (en) 2014-09-12 2015-07-21 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9422265B2 (en) 2014-09-12 2016-08-23 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9156813B1 (en) 2014-09-12 2015-10-13 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US9896430B2 (en) 2014-09-12 2018-02-20 Dow Agrosciences Llc Process for the preparation of 3-(3-CHLORO-1H-pyrazol-1-yl)pyridine
US9663489B2 (en) 2014-09-12 2017-05-30 Dow Agrosciences Llc Process for the preparation of 3-(3-chloro-1H-pyrazol-1-yl)pyridine
US10273221B2 (en) 2015-03-27 2019-04-30 Syngenta Participations Ag Microbiocidal heterobicyclic derivatives
US10100033B2 (en) 2016-12-29 2018-10-16 Dow Agrosciences Llc Processes for the preparation of pesticidal compounds
US10233155B2 (en) 2016-12-29 2019-03-19 Dow Agrosciences Llc Processes for the preparation of pesticide compounds
WO2025155603A1 (fr) * 2024-01-19 2025-07-24 Corteva Agriscience Llc Mélanges inhibiteurs de nitrification
WO2025155791A1 (fr) * 2024-01-19 2025-07-24 Corteva Agriscience Llc Compositions comprenant des inhibiteurs de nitrification

Similar Documents

Publication Publication Date Title
US9756858B2 (en) Insecticides
EP2726481B1 (fr) Pyridyl-thiazole actif à titre d&#39;insecticide et ses dérivés
EP3194394B1 (fr) Dérivés tétracycliques actifs sur le plan pesticide avec des substituants contenant du soufre
WO2013156433A1 (fr) Dérivés de thiazole actifs en tant que pesticide
WO2013156431A1 (fr) Dérivés de thiazole et de thiadiazole substitués par pyridyle et pyrimidyle, actifs en tant que pesticides
WO2016116338A1 (fr) Dérivés polycycliques à activité pesticide comportant des substituants contenant du soufre
US11365187B2 (en) Pesticidally active pyrazole derivatives
WO2015144826A1 (fr) Dérivés hétérocycliques à action pesticide comportant des substituants contenant du soufre
EP3353173A1 (fr) Dérivés polycycliques à activité pesticide comportant des systèmes cycliques hétérocycliques contenant du soufre, à 5 chaînons
US9133218B2 (en) Pesticidally active pyridyl- and pyrimidyl-substituted thiazole derivatives
EP2925758A1 (fr) Dérivés tricycliques de pyridyle à activité pesticide
US9403845B2 (en) Pesticidally active pyridyl- and pyrimidyl- substituted pyrazole derivatives
EP3665166A1 (fr) Dérivés de pyrazole actifs sur le plan pesticide
WO2016055605A1 (fr) Composés hétéroaromatiques bicycliques à activité pesticide
WO2016016131A1 (fr) Énaminones cycliques à activité pesticide
WO2020030754A1 (fr) Composés hétéroaromatiques bicycliques mésoioniques à action pesticide
EP3692038A1 (fr) Dérivés de pyrrole actifs sur le plan pesticide
WO2019030355A1 (fr) Dérivés de pyrazole actifs sur le plan pesticide
WO2020164994A1 (fr) Dérivés de pyrazole à action pesticide
WO2020035565A1 (fr) Composés hétéroaromatiques bicycliques mésoioniques à action pesticide
IT et al. 4058 Basel (CH)

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13715704

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13715704

Country of ref document: EP

Kind code of ref document: A1