WO2012143395A1 - 4,5-dihydro-isoxazole derivatives as fungicides - Google Patents

4,5-dihydro-isoxazole derivatives as fungicides Download PDF

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WO2012143395A1
WO2012143395A1 PCT/EP2012/057082 EP2012057082W WO2012143395A1 WO 2012143395 A1 WO2012143395 A1 WO 2012143395A1 EP 2012057082 W EP2012057082 W EP 2012057082W WO 2012143395 A1 WO2012143395 A1 WO 2012143395A1
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substituted
substituents
phenyl
alkyl
alkoxy
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PCT/EP2012/057082
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French (fr)
Inventor
Camilla Corsi
Ruud Titulaer
Jilali Kessabi
Alexander Bartovic
Carla Bobbio
Sebastian Volker Wendeborn
Stephane André Marie JEANMART
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Syngenta Participations Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • 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
    • A01N43/80—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 1,2
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the present invention relates to novel 4,5-dihydro-isoxazol moieties containing compounds, especially 3-aryl or heteroaryl substituted -5,5-disubstituted-4,5-dihydro-isoxazol-4-yl)- heteroaryl -3 -yl -methanol moieties containing compounds or 3- aryl or heteroaryl substituted - 5,5- disubstituted -4-methylene-4,5-dihydro-isoxazole moieties containing compounds their use in compositions and methods for the control and/or prevention of microbial infection, particularly fungal infection, in plants and to processes for the preparation of these compounds.
  • Fungicides are compounds, of natural or synthetic origin, which act to protect plants against damage caused by fungi.
  • Current methods of agriculture rely heavily on the use of fungicides. In fact, some crops cannot be grown usefully without the use of fungicides.
  • fungicidal compounds allow a grower to increase the yield of the crop and consequently, increase the value of the crop.
  • Numerous fungicidal agents have been developed.
  • the treatment of fungal infestations continues to be a major problem.
  • fungicide resistance has become a serious problem, rendering these agents ineffective for some agricultural uses. As such, a need exists for the development of new fungicidal compounds.
  • R 1 is aryl or heteroaryl, or substituted aryl or substituted heteroaryl each optionally substituted by one to five substituents R 8a , which may be the same or different;
  • R 2 andR 3 independently are H, aryl or Heterocyclyl, substituted aryl or substituted heteroaryl each optionally substituted by one to five substituents R 8 , which may be the same or different; Ci-C 8 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -Cecycloalkyl, Ci-Cehaloalkyl, C 2 - Cehaloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, Ci-C 6 alkoxy, Ci-C 6 alkoxy-Ci- C 6 alkyl, Ci-Cehaloalkoxy, Ci-Cealkylthio, Ci-Cehaloalkylthio, or substituted Ci-C 8 alkyl, substituted C 2 -C 6 alkenyl, substituted C 2 -C 6 alkynyl, substituted C 3 -Cecycl
  • R 2 and R 3 form together a 3 to 14 membered ring which may be monocyclic or polycyclic, preferably monocyclic, bicyclic or tricyclic, more preferably monocyclic or bicyclic, even more preferably monocyclic, and the ring formed by R 2 and R 3 together may be a alicyclic systems or heteroalicyclic systems wherein the carbocyclic ring structure which may comprise at least one endocyclic double bond or at least one endocyclic triple bond) wherein in the case of the heteroalicyclic systems optionally one or more of the carbon atoms are replaced by a heteroatom selected from O, N and S and wherein the alicyclic systems or heteroalicyclic systems are unsubstituted or substituted by one to five substituents R 9 ;
  • R 4 is heteroaryl, or substituted heteroaryl substituted by one to five substituents R 8 , which may be the same or different;
  • R 5 is H, OH; Ci-C 6 alkoxy or Ci-C 6 alkylcarbonyl, or substituted Ci-C 6 alkoxy or substituted Ci-C 6 alkylcarbonyl each substituted by one to five substituents R 9 , which may be the same or different;
  • R 6 is H or forms together with R 7 a bond
  • R 7 is H, OH, CN, halogen; Ci-C 8 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, Ci-C 6 alkoxy, Ci- C 6 alkoxy-Ci-C 6 alkyl, Ci-C 6 haloalkoxy, Ci-C 6 alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C 8 alkyl, substituted C 2 -C 6 alkenyl, substituted C 2 -C 6 alkynyl, substituted C 3 -Cecycloalkyl, substituted Ci-C 6 haloalkyl, substituted C 2 -C 6 haloalkenyl, substituted
  • each R is independently selected from cyano, amino, nitro, hydroxy, halogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, C 3 - C 6 cycloalkyl, C 3 -C6halocycloalkyl, Ci-C 3 alkoxy, Ci-C 3 haloalkoxy, Ci-C 3 alkylthio, Ci- C 3 haloalkylthio, Ci-C 3 alkylsulfinyl, Ci-C 3 haloalkylsulfinyl, Ci-C 3 alkylsulfonyl, Ci-C 3 hal
  • each R 8a is independently selected from cyano, amino, nitro, hydroxy, halogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, C 3 - C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, Ci-C 3 alkoxy, Ci-C 3 haloalkoxy, Ci-C 3 alkylthio, Ci-
  • Ci-C 3 alkylthio Ci-C 3 alkylsulfinyl, Ci-C 3 haloalkylsulfinyl, Ci-C 3 alkylsulfonyl, Ci-C 3 halo- alkylsulfonyl, Ci-C 4 alkylamino, di-(Ci-C 4 alkyl)amino, Ci-C 4 alkylcarbonyl,
  • each R 9 is independently halogen, cyano, nitro, hydroxy, Ci-C 8 alkoxy, Ci-C 8 haloalkoxy-, Ci-C 8 alkylthio-, Ci-C 8 haloalkylthio-, Ci-C 8 alkylsulfinyl-, Ci-C 8 haloalkylsulfinyl-, Ci- C 8 alkylsulfonyl-, Ci-C 8 haloalkylsulfonyl-, Ci-C 8 alkylcarbonyl-, Ci-C 8 alkoxycarbonyl-, aryl or aryl substituted by one to five R 9 , or heterocyclyl or heterocyclyl substituted by one to five R 8 ;
  • the invention covers all agronomically acceptable salts, isomers, structural isomers, stereoisomers, diastereoisomers, enantiomers, tautomers and N-oxides of those compounds.
  • Centres of tautomerisation may be present.
  • This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds. Also atropisomerism may occur as a result of a restricted rotation about a single bond and cationic compounds of formula (I).
  • Suitable salts of the compounds of formula (I) include acid addition salts such as those with an inorganic acid such as hydrochloric, hydrobromic, sulphuric, nitric or phosphoric acid, or an organic carboxylic acid such as oxalic, tartaric, lactic, butyric, toluic, hexanoic or phthalic acid, or a sulphonic acid such as methane, benzene or toluene sulphonic acid.
  • organic carboxylic acids include haloacids such as trifluoroacetic acid.
  • N-oxides are oxidised forms of tertiary amines or oxidised forms of nitrogen containing heteroaromatic compounds. They are described in many books for example in "Heterocyclic N-oxides" by Angelo Albini and Silvio Pietra, CRC Press, Boca Raton, Florida, 1991.
  • alkyl groups occurring in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, ⁇ -propyl, «-butyl, «-pentyl, «-hexyl, iso- propyl, «-butyl, sec-butyl, zso-butyl or tert-butyl.
  • Alkoxy, alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned.
  • the alkenyl and alkynyl groups can be mono- or di-unsaturated.
  • the cycloalkyl groups are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • Halogen is generally fluorine, chlorine, bromine or iodine, preferably fluorine, bromine or chlorine more preferably chlorine or fluorine. This also applies, correspondingly, to halogen in combination with other meanings, such as halogenalkyl or halogenalkoxy.
  • Haloalkyl groups preferably have a chain length of from 1 to 6 carbon atoms and comprise at least one halogen atom up to perhalogenated alkyle group.
  • Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl,
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n- butoxy, isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy and ethoxy.
  • Halogenalkoxy 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.
  • Thioalkyl is, for example, methylthio, ethylthio, propylthio, tert-butylthio, hexylthio.
  • Alkylamino is, for example, methylamino, ethylamino, propylamino, tert- butylamino, hexylamino as well as, for example dimethylamino, diethylamino,
  • the aryl groups are groups derived from monoyclic and polycyclic aromatic hydrocarbons by removal of a hydrogen atom from a ring carbon atom.
  • Heteroaryl means a mono-, bi- or tricyclic, aromatic hydrocarbon, containing 3 to 14, preferably 5 to 10, more preferably 6 to 8, ring-atoms, including 1 to 6, preferably 1 to 4, heteroatoms independently selected from nitrogen, oxygen and sulfur.
  • the aryl and heteroaryl groups are, for example, acridinyl, anthracenyl, benzimidazolyl, benzisoxazolyl, benzo[c]thiopheny, benzofuranyl, benzothiazolyl, benzothiophenyl, benzoxazolyl, cinnolinyl, furyl, imidazolyl, indazolyl, indolyl, isobenzofuranyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, naphthalenyl, naphthyl, oxadiazolyl, oxazolyl, phenyl, preferablythesgroupsareoptionallymono-, purinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, qui
  • Heterocyclyl are cyclic compounds having as ring members atoms of at least two different elements, e.g. quinoline, 1,2-thiazole, bicyclo[3.3.1]tetrasiloxane includes therefore heteroaryl preferably those containing from 3 to 10 ring-atoms up to 4 of which are heteroatoms selected from nitrogen, oxygen and sulfur, and in addition non aromatic heterocyclic compounds which may be a saturated or partially unsaturated cyclic
  • non- aromatic heterocyclyl groups are oxiranyl, azetidinyl, tetrahydrofuranyl, thiolanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, sulfolanyl, dioxolanyl, dihydropyranyl, tetrahydropyranyl, piperidinyl, pyrazolinyl, pyrazolidinyl, dioxanyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl, azepinyl, oxazepinyl, thiazepinyl, thiazolinyl and diazapanyl.
  • Heteroalkencyclyl includes non aromatic heterocyclic compounds which may be a saturated or partially unsaturated cyclic hydrocarbon containing from 3 to 10 ring- atoms up to 4 of which are heteroatoms selected from nitrogen, oxygen and sulfur, and may be optionally substituted by one or more groups independently selected from halogen, nitro, cyano, alkyl, alkoxy and may be optionally substituted by one or more groups independently selected from halogen, nitro, cyano, alkyl, alkoxy or as indicated in the claims or in the other parts of the description
  • R , R R R R , R°, R , R° and R' are, in any combination, as set out below.
  • R 1 is aryl or substituted aryl substituted by one to five
  • R 1 is phenyl or substituted aryl substituted by one to five substituents R 8a , which may be the same or different;
  • R 1 is 4-chloro-phenyl, 4-chloro-2-fluoro-phenyl, 2,4-difluoro-phenyl, 2,4-dichloro-phenyl, 2-fluoro-phenyl, 5-chloro-2-thiophenyl, 4-chloro-benzyl, cyclohexyl;
  • R 2 andR 3 independently are aryl or heterocyclyl, or substituted aryl or substituted heterocyclyl each substituted by one to five substituents R 8 , which may be the same or different; Ci-C 8 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C3-Cecycloalkyl, Ci- C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, Ci-C 6 alkoxy, Ci- C 6 alkoxy-Ci-C 6 alkyl, Ci-C 6 haloalkoxy, Ci-C 6 alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C 8 alkyl, substituted C 2 -C 6 alkenyl, substituted C 2 -C 6 alkynyl, substituted C 3 -
  • R 2 andR 3 form together a 5 to 14 membered ring which may be bicyclic or tricyclic, more preferably monocyclic or bicyclic, even more preferably monocyclic
  • the 5 to 8 membered ring may be a alicyclic systems or heteroalicyclic systems wherein in the case of the heteroalicyclic systems optionally one or more of the carbon atoms are replaced by a heteroatom selected from O, N and S and wherein the alicyclic systems or heteroalicyclic systems are optionally substituted by one to five substituents R 9 ;
  • R 2 andR 3 form together a 5 to 6 membered ring which may more preferably monocyclic or bicyclic, even more preferably monocyclic
  • the 5 to 8 membered ring may be a alicyclic systems or heteroalicyclic systems wherein the carbocyclic ring structure which may comprise at least one endocyclic double bond or at least one endocyclic triple bond wherein in the case of the heteroali
  • R 2 andR 3 independently H, Ci-C 8 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 Cycloalkyl, Ci-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 - Cehalocycloalkyl, Ci-C 6 alkoxy, Ci-Cealkoxy-Ci-Cealkyl, Ci-C 6 haloalkoxy, Ci-C 6 alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C 8 alkyl, substituted C 2 -C 6 alkenyl, substituted C 2 - C 6 alkynyl, substituted C 3 -Cecycloalkyl, substituted Ci-C 6 haloalkyl, substituted C 2 - C 6 haloalkenyl, substituted C 2 - C 6 halo
  • R 2 and R 3 independently Ci-C 8 alkyl, C 2 - C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, Ci-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 - C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, Ci-C 6 alkoxy, Ci-C 6 alkoxy-Ci-C 6 alkyl, Ci- C 6 haloalkoxy, Ci-C 6 alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C 8 alkyl, substituted C 2 - C 6 alkenyl, substituted C 2 -C 6 alkynyl, substituted C 3 -Cecycloalkyl, substituted Ci-C 6 haloalkyl, C 2 -C 6 haloalkenyl, substituted C 2 -C 6 haloal
  • R 4 is
  • R 4 is
  • R 4 is
  • R s which may be substituted by one to three substituents R s , which may be the same or different.
  • R 4 is pyrid-3-yl which may be substituted by one to three substituents R 8 , which may be the same or different
  • heteroaryl moieties of R 4 are not further substituted.
  • R 5 is H, OH; Ci-Cealkoxy or Ci-Cealkylcarbonyl, or substituded Ci-Cealkoxy or substituded Ci- C 6 alkylcarbonyl each substituted by one to five substituents R 9 , which may be the same or different; more preferably when R 6 are not forming together with R 7 a bond then R 5 is OH.
  • R 6 is H and R 7 is H, OH, halogen; Ci-C 8 alkyl, C 2 - C 6 alkenyl, C 2 -C 6 alkynyl, C3-Cecycloalkyl, Ci-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 - C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, Ci-C 6 alkoxy, Ci-C 6 alkoxy-Ci-C 6 alkyl, Ci- C 6 haloalkoxy, Ci-C 6 alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C 8 alkyl, substituted C 2 - C 6 alkenyl, substituted C 2 -C 6 alkynyl, substituted C 3 -Cecycloalkyl, substituted Ci-Cehaloalkyl, substituted C 2 -C 6 haloalken
  • R 6 forms together with R 7 a bond and R 7 forms together with R 6 a bond, respectively.
  • R 5 is H;
  • each R 8 is independently selected from cyano, amino, nitro, hydroxy, halogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 - C 4 alkynyl, C 2 -C 4 haloalkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, Ci-C 3 alkoxy, Ci- C 3 haloalkoxy;
  • each R 9 is independently halogen, cyano, nitro, hydroxy, Ci- C 3 alkoxy, or Ci-C 3 haloalkoxy, Ci-C 3 alkylthio, Ci-C 3 haloalkylthio, Ci-C 3 alkylsulfinyl, Ci- C 3 haloalkylsulfinyl, Ci-C 3 alkylsulfonyl, Ci-C 3 haloalkylsulfonyl, Ci-C 3 alkylcarbonyl,Ci-C 8 - Ci-C 3 alkoxycarbonyl, aryl or aryl substituted by one to five R 9 , or heterocyclyl or heterocyclyl substituted by one to five R 8 ; In a more preferred embodiment each R 9 is independently halogen, cyano, nitro, hydroxy, Ci-C 8 alkoxy-, Ci-C 8 haloalkoxy-, Ci- C 8 alkylcarbonyl-, Ci-
  • aryl signifies phenyl, naphthyl, anthracenyl, indenyl,
  • aryl groups may be substituted as mentioned above.
  • heteroaryl signifies a mono-, bi- or tricyclic, aromatic
  • hydrocarbon containing 5 to 14, preferably 5 to 10, more preferably 6 to 8, ring-atoms, including 1 to 6, preferably 1 to 4, heteroatoms independently selected from nitrogen, oxygen and sulfur; preferably a mono- or bicyclic, aromatic hydrocarbon, containing 5 to 14, preferably 5 to 10, more preferably 6 to 8, ring-atoms, including 1 to 6, preferably 1 to 4, heteroatoms independently selected from nitrogen, oxygen and sulfur; more preferably pyridyl, pyrimydyl or 1,2,4-triazolyl which may be substituted as mentioned above
  • heterocyclyl signifies heteroaryl, and in addition may be a saturated or partially unsaturated cyclic hydrocarbon containing from 3 to 10 ring-atoms up to 4 of which are heteroatoms selected from nitrogen, oxygen and sulfur, and may be optionally substituted
  • R 1 signifies phenyl or phenyl substituded by halogen.
  • R 2 signifies Me, Et, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, tert-butyl, sec-butyl, isoamyl, z ' so-propyl, CF 3 , 4-chloro-phenyl, 3-chloro-phenyl, 2-chloro-phenyl, 2,4- dichloro-phenyl, 2-thiophenyl, 5-chloro-2-thiophenyl, 5-bromo-2-thiophenyl, 4-fluoro- phenyl, 3-fluoro-phenyl, 2-fluoro-phenyl, 2,4-difluoro-phenyl, 2-fluoro-4-chloro-phenyl, 2- chloro-4-fluoro-phenyl, 4-trifluoromethyl-phenyl, 3-trifluoromethyl-phenyl, 2- trifluoromethyl-phenyl, 4-bromo-phenyl,
  • R 3 signifies H, Me Et.
  • El Embodiment
  • R 1 is aryl or aryl substituted by one to five substituents R 8a , which may be the same or different;
  • R 2 andR 3 independently are aryl or heterocyclyl, or substituted aryl or substituted heterocyclyl each optionally substituted by one to five substituents R 8
  • R 1 is phenyl or phenyl substituted by one to five substituents R 8a , which may be the same or different;
  • R 2 andR 3 independently are aryl or heterocycl, or substituted aryl or substituted heterocyclyl each substituted by one to five substituents R 8
  • R 1 is aryl or aryl substituted by one to four substituents R 8a , which may be the same or different;
  • R 2 andR 3 form together a 3 to 14 membered ring which may be polycyclic, more preferably monocyclic or bicyclic, even more preferably monocyclic, and the 5 to 8 membered ring may be a alicyclic systems or heteroalicyclic systems wherein in the case of the heteroalicyclic systems optionally one or more of the carbon atoms are replaced by a heteroatom selected from O, N and S and wherein the alicyclic systems or systems are optionally substituted by one to five substituents R 9 ;
  • E4 is further preferred Embodiment
  • R 1 is phenyl or penyl substituted by one to four substituents R 8a , which may be the same or different;
  • R 2 andR 3 form together a 3 to 14 membered ring which may be bicyclic, more preferably monocyclic or bicyclic, even more preferably monocyclic, and the 5 to 8 membered ring may be a alicyclic systems or heteroalicyclic systems wherein in the case of the heteroalicyclic systems optionally one or more of the carbon atoms are replaced by a heteroatom selected from O, N and S and wherein the alicyclic systems or heteroalicyclic systems are optionally substituted by one to four substituents R 9 ;
  • R 1 is aryl aryl substituted by one to four substituents R 8 , which may be the same or different;
  • R 2 andR 3 independently H, Ci-C 8 alkyl, C2-C 6 alkenyl, C2-C 6 alkynyl, C3-Cecycloalkyl, Ci- C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, Ci-C 6 alkoxy, Ci- C6alkoxy-Ci-C6alkyl, Ci-C 6 haloalkoxy, Ci-C 6 alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C 8 alkyl, substituted C2-C 6 alkenyl, substituted C 2 -C 6 alkynyl, substituted C 3 -C 6 Cycloalkyl, substituted Ci-C 6 haloalkyl,
  • R 1 is phenyl or phenyl substituted by one to four substituents R 8 , which may be the same or different;
  • R 2 andR 3 independently are H, Ci-C 8 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -Cecycloalkyl, Ci-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, Ci-C 6 alkoxy, Ci- C 6 alkoxy-Ci-C 6 alkyl, Ci-C 6 haloalkoxy, or substituted Ci-C 8 alkyl, substituted C 2 -C 6 alkenyl, substituted C 2 -C 6 alkynyl, substituted C 3 -Cecycloalkyl, substituted Ci-C 6 haloalkyl, substituted C 2 -C 6 haloalkenyl, substituted C 2 -C 6 haloalkynyl, substituted C 3 -C 6 halocyclo
  • R 4 is heteroaryl, or heteroaryl substituted by one to five substituents R 8 , which may be the same or different and the further substituents have the meaning given in the embodiment (El).
  • R 4 is heteroaryl, or heteroaryl substituted by one to five substituents R 8 , which may be the same or different and the further substituents have the meaning given in the embodiment (E2).
  • R 4 is heteroaryl, or heteroaryl substituted by one to five substituents R 8 , which may be the same or different and the further substituents have the meaning given in the embodiment (E3).
  • R 4 is heteroaryl, or heteroaryl substituted by one to five substituents R 8 , which may be the same or different and the further substituents have the meaning given in the embodiment (E4).
  • R 4 is heteroaryl, or heteroaryl substituted by one to five substituents R 8 , which may be the same or different and the further substituents have the meaning given in the embodiment (E5).
  • R 4 is heteroaryl, each optionally substituted by one to five substituents R 8 , which may be the same or different and the further substituents have the meaning given in the embodiment (E6).
  • R 4 is a monocyclic heteroaryl, or monocyclic heteroaryl substituted by one to five substituents R 8 , which may be the same or different, which may be the same or different and the further substituents have the meaning given in the embodiment (El).
  • R 5 is H, OH; Ci-Cealkoxy or Ci-Cealkylcarbonyl, or substituted Ci-Cealkoxy or substituted Ci-C 6 alkylcarbonyl each substituted by one to five substituents R 9 , which may be the same or different;
  • R 6 is H and R 7 is H, OH, halogen;
  • Cehalocycloalkyl Ci-C 6 alkoxy, Ci-Cealkoxy-Ci-Cealkyl, Ci-C 6 haloalkoxy, Ci-C 6 alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C 8 alkyl, substituted C 2 -C 6 alkenyl, substituted C 2 - C 6 alkynyl, substituted C 3 -C 6 cycloalkyl, substituted Ci-C 6 haloalkyl, substituted C 2 - C 6 haloalkenyl, substituted C 2 -C 6 haloalkynyl, substituted C 3 -C 6 halocycloalkyl, substituted Ci-C 6 alkoxy, substituted Ci-Cealkoxy-Ci-Cealkyl, substituted Ci-C 6 haloalkoxy, substituted Ci-C 6 alkylthio, substituted Ci-Cehaloalkylthio each substituted by one
  • the substituents have the meaning of the corresponding embodiments (El . A) to (E8.H) and when R 6 are not forming together with R 7 a bond then R 5 is OH; R 6 is H and R 7 is H, OH, halogen; Ci-C 8 alkyl, Ci-C 6 alkoxy, or substituted C 8 alkyl, substituted Ci-C 6 alkoxy each substituted by one to five substituents R 9 , which may be the same or different; more preferably preferably R 6 is H and R 7 is H, OH, Ci- C 2 alkyl, Ci-C 2 alkoxy, or substituted Ci-C 2 alkyl, substituted Ci-C 2 alkoxy each substituted by one substituent R 9 , which may be the same or different;
  • the substituents have the meaning of the corresponding embodiments (El . A) to (E8.H) and R 5 is H, OH; Ci-C 6 alkoxy or Ci- C 6 alkylcarbonyl, or Ci-C 6 alkoxy or Ci-C 6 alkylcarbonyl each substituted by one to five substituents R 9 , which may be the same or different; R 6 forms together with R 7 a bond and R 7 forms together with R 6 a bond, respectively; In a further preferred embodiment (E1.A.2) to (E8.H.2) the substituents have the meaning of the corresponding embodiments (El .
  • each R 8 and R 8a is independently selected from cyano, amino, nitro, hydroxy, halogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, C 2 -C 4 alkenyl,
  • each R 9 is independently halogen, cyano, nitro, hydroxy, Ci-C 8 alkoxy-, Ci-C 8 haloalkoxy-, Ci-C 8 alkylcarbonyl-, Ci-C 8 alkoxycarbonyl-, aryl or aryl substituted by one to five R 9 , or heterocyclyl or heterocyclyl substituted by one to five R 8 ;
  • each R 8 and R 8a is independently selected from cyano, amino, nitro, hydroxy, halogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, C 2 -C 4 alkenyl,
  • each R 9 is independently halogen, cyano, nitro, hydroxy, Ci-C 8 alkoxy-, Ci-C 8 haloalkoxy-, Ci-C 8 alkylcarbonyl-, Ci-C 8 alkoxycarbonyl- , aryl or aryl substituted by one to five R 9 , or heterocyclyl or heterocyclyl substituted by one to five R 8 ;
  • each R 8 and R 8a is independently selected from cyano, amino, nitro, hydroxy, halogen;
  • each R 9 is independently halogen, cyano, nitro, hydroxy
  • Compounds of formula (A) can be prepared by reacting compound of type (B) with a substrate R 4 H (triazole, imidazole, tetrazole, benzoimidazole, etc) in the presence of base such as potassium carbonate in a suitable solvent such as dimethylformamide at a temperature between 0°C and 50°C.
  • a substrate R 4 H triazole, imidazole, tetrazole, benzoimidazole, etc
  • base such as potassium carbonate
  • suitable solvent such as dimethylformamide
  • Compounds of formula (B) may be prepared by epoxidation of compounds of formula (C) in the presence of peracids like w-CPBA (weto-Chloroperoxybenzoic acid) in a suitable solvent such as dichl orom ethane at a temperature between 0°C and 100°C.
  • peracids like w-CPBA (weto-Chloroperoxybenzoic acid)
  • suitable solvent such as dichl orom ethane at a temperature between 0°C and 100°C.
  • Compounds of formula (C) may be prepared by treated compounds of formula (D) where R5 is a suitable leaving group like a mesylate with a suitable base like DBU (1,8- Diazabicyclo[5.4.0]undec-7-en) in a suitable solvent like dichl oromethane at a temperature between 0°C and 100°C:
  • R5 is a suitable leaving group like a mesylate with a suitable base like DBU (1,8- Diazabicyclo[5.4.0]undec-7-en) in a suitable solvent like dichl oromethane at a temperature between 0°C and 100°C:
  • Substrate (D) may undergo directly to nucleophilic substitution to generate L in the presence of an appropriate base like potassium carbonate in a suitable solvent like dimethylsulfoxide at a temperature between 0°C and 50°C.
  • the epoxide (B) can be reacted with ammonia to form (Al) that could then undergo to the Van Leusen synthesis by cycloaddition with aldehyde R 7 and tosylmethyl isocyanides (TosMIC) to give the desired product A2.
  • TosMIC tosylmethyl isocyanides
  • the reactions to give compounds of formula (I) are advantageously carried out in aprotic inert organic solvents.
  • solvents are hydrocarbons such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles such as acetonitrile or propionitrile, amides such as ⁇ , ⁇ -dimethylformamide, diethylformamide or N-methylpyrrolidinone.
  • reaction temperatures are advantageously between -20°C and +120°C.
  • the reactions are slightly exothermic and, as a rule, they can be carried out at ambient temperature.
  • the mixture may be heated briefly to the boiling point of the reaction mixture.
  • the reaction times can also be shortened by adding a few drops of base as reaction catalyst.
  • Suitable bases are, in particular, tertiary amines such as trimethylamine, triethylamine, quinuclidine, l,4-diazabicyclo[2.2.2]octane, l,5-diazabicyclo[4.3.0]non-5-ene or 1,8-diazabicyclo- [5.4.0]undec-7-ene.
  • inorganic bases such as hydrides, e.g. sodium hydride or calcium hydride, hydroxides, e.g. sodium hydroxide or potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, or hydrogen carbonates such as potassium hydrogen carbonate and sodium hydrogen carbonate may also be used as bases.
  • the bases can be used as such or else with catalytic amounts of a phase-transfer catalyst, for example a crown ether, in particular 18-crown-6, or a tetraalkylammonium salt.
  • a phase-transfer catalyst for example a crown ether, in particular 18-crown-6, or a tetraalkylammonium salt.
  • the compounds of formula (I) and, where appropriate, the tautomers thereof, 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 invention therefore also relates to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a compound of formula (I) is applied as active ingredient to the plants, to parts thereof or the locus thereof.
  • compounds of formula (I) according to the invention are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous useful plants.
  • the compounds of formula (I) can be used to inhibit or destroy the diseases that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.
  • compounds of formula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
  • the compounds of formula (I) according to the invention may be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage or in hygiene management.
  • the compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara). Furthermore, the novel compounds of formula (I) are effective against phytopathogenic bacteria and viruses (e.g. against
  • Xanthomonas spp Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus.
  • the compounds of formula (I) are also effective against Asian soybean rust (Phakopsora pachyrhizi).
  • useful plants to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucum- bers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or
  • useful plants is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, FIPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering.
  • herbicides like bromoxynil or classes of herbicides
  • EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors
  • GS glutamine synthetase
  • PPO protoporphyrinogen-oxidase
  • imazamox by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola).
  • crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® , Herculex I® and LibertyLink®.
  • Useful plants is to be understood as including also useful 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.
  • YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CryIF(a2) toxin and the enzyme
  • phosphinothricine N-acetyltransferase PAT
  • NuCOTN 33B® cotton variety that expresses a CrylA(c) toxin
  • Bollgard I® cotton variety that expresses a CrylA(c) toxin
  • Bollgard II® cotton variety that expresses a CrylA(c) and a CryllA(b) toxin
  • VIPCOT® cotton variety that expresses a VIP toxin
  • NewLeaf® potato variety that expresses a CrylllA toxin
  • NatureGard® Agrisure® GT Advantage GA21 glyphosate-tolerant trait
  • Agrisure® CB Advantage Btl 1 corn borer (CB) trait
  • Agrisure® RW corn rootworm trait
  • useful plants is to be understood as including also useful 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).
  • PRPs pathogenesis-related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-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.
  • locus of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil.
  • An example for such a locus is a field, on which crop plants are growing.
  • plant propagation material is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material” is understood to denote seeds.
  • the compounds of formula I can be used in unmodified form or, preferably, together with carriers and adjuvants conventionally employed in the art of formulation.
  • plant or “useful plants” as used herein includes seedlings, bushes and trees.
  • crops is to be understood as including also crop plants which have been so
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vipl, Vip2, Vip3 or
  • Vip3A or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3 -hydroxy steroidoxidas
  • ⁇ -endotoxins for example CrylAb, Cry 1 Ac, Cry IF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), for example Vipl, 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 butterflies (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available.
  • YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bbl toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bbl toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry lFa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry 1 Ac toxin); Bollgard I® (cotton variety that expresses a Cry 1 Ac toxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab to
  • transgenic crops are:
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de l'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-l 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bbl toxin and has resistance to certain Coleoptera insects.
  • NK603 x MON 810 Maize from Monsanto Europe S. A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties K603 and MON 810.
  • NK603 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 Cry 1 Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle).
  • Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds).
  • Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®.
  • Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events).
  • seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.
  • Crops are also to be understood as being those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
  • output traits e.g. improved storage stability, higher nutritional value and improved flavour.
  • a compound of formula (I) is usually formulated into a composition which includes, in addition to the compound of formula (I), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA).
  • SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting).
  • compositions both solid and liquid formulations
  • the composition is generally used for the control of pests such that a compound of formula (I) is applied at a rate of from O. lg tolOkg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to 1kg per hectare.
  • a compound of formula (I) When used in a seed dressing, a compound of formula (I) is used at a rate of O.OOOlg to lOg (for example O.OOlg or 0.05g), preferably 0.005g to lOg, more preferably 0.005g to 4g, per kilogram of seed.
  • the present invention provides an insecticidal, acaricidal, nematicidal or molluscicidal composition
  • an insecticidal, acaricidal, nematicidal or molluscicidal composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) and a suitable carrier or diluent therefor.
  • the composition is preferably an insecticidal, acaricidal, nematicidal or molluscicidal composition.
  • compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations.
  • the formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).
  • Dustable powders may be prepared by mixing a compound of formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
  • solid diluents for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, talc and other organic and inorganic solid carriers
  • Soluble powders may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
  • water-soluble inorganic salts such as sodium bicarbonate, sodium carbonate or magnesium sulfate
  • water-soluble organic solids such as a polysaccharide
  • WP Wettable powders
  • WG Water dispersible granules
  • Granules may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulfates or phosphates) and drying if necessary.
  • a hard core material such as sands, silicates, mineral carbonates, sulfates or phosphates
  • Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils).
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters
  • sticking agents such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils.
  • One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
  • DC Dispersible Concentrates
  • a compound of formula (I) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether.
  • organic solvent such as a ketone, alcohol or glycol ether.
  • surface active agent for example to improve water dilution or prevent crystallisation in a spray tank.
  • Emulsifiable concentrates or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents).
  • organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or
  • An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.
  • Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion.
  • Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
  • Microemulsions may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation.
  • a compound of formula (I) is present initially in either the water or the solvent/SFA blend.
  • Suitable solvents for use in MEs include those hereinbefore described for use in ECs or in EWs.
  • An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation.
  • An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
  • SC Suspension concentrates
  • SCs may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I).
  • SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound.
  • One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle.
  • a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
  • Aerosol formulations comprise a compound of formula (I) and a suitable propellant (for example w-butane).
  • a compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as «-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
  • a compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.
  • Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefore.
  • the polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure.
  • the compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment.
  • a compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
  • a composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)).
  • additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)).
  • a compound of formula (I) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS).
  • DS powder for dry seed treatment
  • SS water soluble powder
  • WS water dispersible powder for slurry treatment
  • CS capsule suspension
  • the preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above.
  • Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
  • Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type.
  • Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
  • Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (for example sodium lauryl sulfate), salts of sulfonated aromatic compounds (for example sodium dodecylbenzenesulfonate, calcium
  • tetraphosphoric acid additionally these products may be ethoxylated
  • sulfosuccinamates may be ethoxylated
  • paraffin or olefine sulfonates taurates and lignosulfonates.
  • Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.
  • Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
  • Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
  • hydrophilic colloids such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose
  • swelling clays such as bentonite or attapulgite
  • a compound of formula (I) may be applied by any of the known means of applying pesticidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or
  • composition such as a granular composition or a composition packed in a water-soluble bag
  • incorporation of a composition in soil or an aqueous environment.
  • the compounds of formula (I) or compositions, comprising a compound of formula (I) as active ingredient and an inert carrier can be applied to the locus of the plant or plant to be treated, simultaneously or in succession with further compounds.
  • further compounds can be e.g. fertilizers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
  • a preferred method of applying a compound of formula (I), or a composition, comprising a compound of formula (I) as active ingredient and an inert carrier is foliar application.
  • the frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen.
  • the compounds of formula (I) can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field.
  • the compounds of formula (I) may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
  • a formulation i.e. a composition comprising the compound of formula (I) and, if desired, a solid or liquid adjuvant, is prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface-active compounds (surfactants).
  • extenders for example solvents, solid carriers and, optionally, surface-active compounds (surfactants).
  • the agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula (I), 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.
  • a compound of formula (I) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
  • compositions for use as aqueous preparations are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use.
  • These concentrates which may include DCs, SCs, ECs, EWs, MEs, SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
  • Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
  • a compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers).
  • fertilisers for example nitrogen-, potassium- or phosphorus-containing fertilisers.
  • Suitable formulation types include granules of fertiliser.
  • the mixtures preferably contain up to 25% by weight of the compound of formula (I).
  • the invention therefore also provides a fertiliser composition comprising a fertiliser and a compound of formula (I).
  • compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.
  • the compounds of formula (I), or a pharmaceutical salt thereof, described above may also have an advantageous spectrum of activity for the treatment and/or prevention of microbial infection in an animal.
  • Animal can be any animal, for example, insect, mammal, reptile, fish, amphibian, preferably mammal, most preferably human.
  • Treatment means the use on an animal which has microbial infection in order to reduce or slow or stop the increase or spread of the infection, or to reduce the infection or to cure the infection.
  • prevention means the use on an animal which has no apparent signs of microbial infection in order to prevent any future infection, or to reduce or slow the increase or spread of any future infection.
  • a compound of formula (I) in the manufacture of a medicament for use in the treatment and/or prevention of microbial infection in an animal.
  • a compound of formula (I) as a pharmaceutical agent.
  • a compound of formula (I) as an antimicrobial agent in the treatment of an animal.
  • a pharmaceutical composition comprising as an active ingredient a compound of formula (I), or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable diluent or carrier. This composition can be used for the treatment and/or prevention of antimicrobial infection in an animal.
  • This pharmaceutical composition can be in a form suitable for oral administration, such as tablet, lozenges, hard capsules, aqueous suspensions, oily suspensions, emulsions dispersible powders, dispersible granules, syrups and elixirs.
  • this pharmaceutical composition can be in a form suitable for topical application, such as a spray, a cream or lotion.
  • this pharmaceutical composition can be in a form suitable for parenteral administration, for example injection.
  • this pharmaceutical composition can be in inhalable form, such as an aerosol spray.
  • the compounds of formula (I) may be effective against various microbial species able to cause a microbial infection in an animal.
  • microbial species are those causing brown rust such as Puccinia recondita, those that are causing leaf blotch such as Septoria tritici, those that are causing gray mould such as Botrytis cinerea, those causing Aspergillosis such as Aspergillus fumigatus, A. flavus, A. terrus, A. nidulans and niger; those causing Blastomycosis such as Blastomyces dermatitidis; those causing Candidiasis such as Candida albicans, C. glabrata, C. tropicalis, C. parapsilosis, C. krusei and C.
  • Fusarium Spp such as Fusarium oxysporum and Fusarium solani
  • Scedosporium Spp such as Scedosporium apiospermum and Scedosporium proliflcans.
  • Microsporum Spp Trichophyton Spp, Epidermophyton Spp, Mucor Spp, Sporothorix Spp, Phialophora Spp, Cladosporium Spp, Petriellidium spp, Paracoccidioides Spp and Histoplasma Spp.
  • the method of the invention comprises applying to the useful plants, the locus thereof or propagation material thereof in admixture or separately, a synergistically effective aggregate amount of a compound of formula (I) and a further, other compound or compositions (e.g. a further, other biocidally active ingredients or compositions).
  • Some of said combinations according to the invention have a systemic action and can be used as foliar, soil and seed treatment fungicides.
  • the combinations of the present invention are of particular interest for controlling a large number of fungi in various useful plants or their seeds, especially in field crops such as potatoes, tobacco and sugarbeets, and wheat, rye, barley, oats, rice, maize, lawns, cotton, soybeans, oil seed rape, pulse crops, sunflower, coffee, sugarcane, fruit and ornamentals in horticulture and viticulture, in vegetables such as cucumbers, beans and cucurbits.
  • field crops such as potatoes, tobacco and sugarbeets, and wheat, rye, barley, oats, rice, maize, lawns, cotton, soybeans, oil seed rape, pulse crops, sunflower, coffee, sugarcane, fruit and ornamentals in horticulture and viticulture, in vegetables such as cucumbers, beans and cucurbits.
  • field crops such as potatoes, tobacco and sugarbeets, and wheat, rye, barley, oats, rice, maize, lawns, cotton, soybeans, oil seed
  • compositions according to the invention have a systemic action and can be
  • the compound of formula I (herein after abbreviated by the term "TX” thus means a compound encompassed by the compounds of formula I, or preferably the term “TX” refers to a compound selected from the Tables 1 and 2 and Tables TA01.01 to TA09.11 and Tables TB01.01 to TB01.11) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide (insect, acarine, mollusc and nematode pesticide), fungicide, synergist, herbicide, safener or plant growth regulator where appropriate.
  • a pesticide insect, acarine, mollusc and nematode pesticide
  • fungicide synergist
  • herbicide herbicide
  • safener plant growth regulator
  • compositions according to the invention may thereby be broadened considerably and may have surprising advantages which can also be described, in a wider sense, as synergistic activity.
  • An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; provide a composition demonstrating better plant/crop tolerance by reducing phytotoxicity; provide a composition controlling insects in their different development stages; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the TX; or help to overcome or prevent the
  • pesticides include the following:
  • a) Pyrethroids such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or
  • Organophosphates such as, profenofos, sulprofos, acephate, methyl parathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl,
  • Carbamates including aryl carbamates, such as pirimicarb, triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur, methomyl or oxamyl;
  • Benzoyl ureas such as diflubenzuron, triflumuron, hexaflumuron, flufenoxuron or chlorfluazuron;
  • Organic tin compounds such as cyhexatin, fenbutatin oxide or azocyclotin;
  • Macrolides such as avermectins or milbemycins, for example abamectin, emamectin benzoate, ivermectin, milbemycin, or spinosad, spinetoram or azadirachtin;
  • Organochlorine compounds such as endosulfan, benzene hexachloride, DDT, chlordane or dieldrin;
  • Amidines such as chlordimeform or amitraz
  • Fumigant agents such as chloropicrin, dichloropropane, methyl bromide or metam
  • Neonicotinoid compounds such as imidacloprid, thiacloprid, acetamiprid, clothianidin, nitenpyram, dinotefuran or thiamethoxam;
  • Diacylhydrazines such as tebufenozide, chromafenozide or methoxyfenozide
  • Diphenyl ethers such as diofenolan or pyriproxifen
  • pesticides having particular targets may be employed in the composition, if appropriate for the intended utility of the composition.
  • selective insecticides for particular crops for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed.
  • insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).
  • acaricidal ovo-larvicides such as clofentezine, flubenzimine, hexythiazox or tetradifon
  • acaricidal motilicides such as dicofol or propargite
  • acaricides such as bromopropylate or chlorobenzilate
  • growth regulators such
  • TX refers to a compound covered by the compounds of formula I or preferably the term “TX” refers to a compound selected from the Tables 1 to 12, A, B and C and the following List shows specific examples of mixtures comprising thecomponent TX and the component (B):
  • 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 l,l-bis(4-chlorophenyl)-2- ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate
  • 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, vaniliprol
  • an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and
  • an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, cruf ornate (1011) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,
  • an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX,
  • a bactericide selected from the group of substances consisting of 1 -hydroxy- lH-pyridine-2- thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicin (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + T
  • 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 (IUPAC name) (542) and methyl bromide (537) + TX
  • a chemostenlant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [
  • an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-l-yl acetate with (£)-dec-5-en-l-ol (IUPAC name) (222) + TX, (£)-tridec-4-en-l-yl acetate (IUPAC name) (829) + TX, (£)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)- tetradeca-4, 10-dien-l-yl acetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-l-yl acetate (IUPAC name) (285) + TX, (Z)-hexadec-l 1-enal (IUPAC name) (436) + TX, (Z)-hexadec- 11-en-l-yl acetate (IUPAC name) (437) + TX, (Z)-hexadec-13-
  • an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,
  • an insecticide selected from the group of substances consisting of 1-dichloro-l-nitroethane (IUPAC/Chemical Abstracts name) (1058) + TX, l, l-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), + TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1- bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-l- (3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX, 2,2-dichlorovinyl 2- ethylsulphinylethyl methyl phosphate (IUPAC name) (1066) + TX, 2-(
  • milbemectin 557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naftalofos (alternative name) [CCN] + TX, naled (567) + TX, naphthalene (IUPAC/Chemical Abstracts name) (1303) + TX, NC-170 (development code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifluridide (1309) + TX, nitenpyram (579) + TX, nithiazine (1311) + TX, nitrilacarb (1313) + TX,
  • a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + T
  • a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, l,2-dibromo-3-chloropropane (IUPAC/Chemical Abstracts name) (1045) + TX, 1,2-dichloropropane (IUPAC/ Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4- dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstracts name) (1065) + TX, 3- (4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-l,3,5- thiadiazinan-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopur
  • 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- ⁇ -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-l,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91) + TX, bromethalin (9
  • a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(l,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX, an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX,
  • 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 [116255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [119446-68-3] + TX, diniconazole
  • the components (B) are known.
  • the references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number.
  • the above described mixing partners are known.
  • the active ingredients are included in "The Pesticide Manual” [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1).
  • the compound of the formula I is preferably a compound selected from the Tables 1 and 2 and Tables TA01.01 to TA09.11 and Tables TBOl .Ol to TB01.11; more preferably a compound selected from T1.14, T.124, Tl .
  • the mixing ratios can vary over a large range and are, preferably 100: 1 to 1 :6000, especially 50: 1 to 1 :50, more especially 20: 1 to 1 :20, even more especially 10: 1 to 1 : 10.
  • Those mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios.
  • the mixtures comprising a TX selected from Tables 1 and 2 and Tables TA01.01 to TA09.11 and Tables TBOl .Ol to TBOl . l l and one or more active ingredients as described above comprises a compound selected from table P 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
  • 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.
  • mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of TX with the mixing partner).
  • Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type.
  • other formulation types may be prepared.
  • one active ingredient is a water insoluble solid and the other a water insoluble liquid
  • the resultant composition is a suspoemulsion (SE) formulation.
  • the mixtures comprising a TX selected from Tables 1 and 2 and Tables TA01.01 to TA09.11 and Tables TB01.01 to TB01.11 and one or more active ingredients as described above can be applied, for example, in a single "ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the compounds of formula I selected from Tables 1 and 2 and Tables TA01.01 to TA09.11 and Tables TB01.01 to TB01.11 and the active ingredients as described above is not essential for working the present invention.
  • the Table TA01.01 discloses 232 compounds according to formula (II) (compound TAOl .01.001 to compound TAOl .01.232) wherein in the first 116 compounds R 7 signifies H, R 1 signifies 4-chloro-phenyl, X signifies CH and and R 2 and R 3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116
  • R 7 signifies OH
  • R 1 signifies 4-chloro-phenyl
  • X signifies CH
  • R 2 and R 3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116
  • the Table TA01.03 discloses 232 compounds according to formula (II) (compound TA01.03.001 to compound TA01.03.232) wherein in the first 116 compounds R 7 signifies OMe, R 1 signifies 4-chloro-phenyl, X signifies CH and and R 2 and R 3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116
  • the Table TA01.04 discloses 232 compounds according to formula (II) (compound TA01.04.001 to compound TA01.04.232) wherein in the first 116 compounds R 7 signifies Me, R 1 signifies 4-chloro-phenyl, X signifies CH and and R 2 and R 3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116
  • the Table TA01.05 discloses 232 compounds according to formula (II) (compound TA01.05.001 to compound TA01.05.232) wherein in the first 116 compounds R 7 signifies Et, R 1 signifies 4-chloro-phenyl, X signifies CH and and R 2 and R 3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116
  • the Table TA01.07 discloses 232 compounds according to formula (II) (compound TA01.07.001 to compound TA01.07.232) wherein in the first 116 compounds R 7 signifies CI, R 1 signifies 4-chloro-phenyl, X signifies CH and and R 2 and R 3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116 compounds but X signifies N instead of CH.
  • formula (II) compound TA01.07.001 to compound TA01.07.232
  • R 7 signifies CI
  • R 1 signifies 4-chloro-phenyl
  • X signifies CH
  • R 2 and R 3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116 compounds but X signifies N instead of CH.
  • the Table TA01.08 discloses 232 compounds according to formula (II) (compound TA01.08.001 to compound TA01.08.232) wherein in the first 116 compounds R 7 signifies Br, R 1 signifies 4-chloro-phenyl, X signifies CH and and R 2 and R 3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116 compounds but X signifies N instead of CH.
  • formula (II) compound TA01.08.001 to compound TA01.08.232
  • R 7 signifies Br
  • R 1 signifies 4-chloro-phenyl
  • X signifies CH
  • R 2 and R 3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116 compounds but X signifies N instead of CH.
  • the Table TA01.09 discloses 232 compounds according to formula (II) (compound TA01.09.001 to compound TA01.09.232) wherein in the first 116 compounds R 7 signifies CF 3 , R 1 signifies 4-chloro-phenyl, X signifies CH and and R 2 and R 3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116 compounds but X signifies N instead of CH.
  • the Table TA01.11 discloses 232 compounds according to formula (II) (compound TA01.11.001 to compound TA01.11.232) wherein in the first 116 compounds R 7 signifies OAc, R 1 signifies 4-chloro-phenyl, X signifies CH and and R 2 and R 3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116 compounds but X signifies N instead of CH.
  • formula (II) compound TA01.11.001 to compound TA01.11.232
  • R 7 signifies OAc
  • R 1 signifies 4-chloro-phenyl
  • X signifies CH
  • R 2 and R 3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116 compounds but X signifies N instead of CH.
  • Tables TA02.01 to TA02.11 disclose each 232 compounds (2552 compounds in total) according to formula (II) wherein the meaning of all substituents are as given in the Tables TA01.01 to TA01.11 exept that R 1 signifies 4-chloro-2-fluoro-phenyl instead of 4- chloro-phenyl.
  • Tables TA03.01 to TA03.11 disclose each 232 compounds (2552 compounds in total) according to formula (II) wherein the meaning of all substituents are as given in the Tables TA01.01 to T AO 1.11 exept that R 1 signifies 2,4-difluoro-phenyl instead of 4-chloro- phenyl.
  • Tables TA04.01 to TA04.11 disclose each 232 compounds (2552 compounds in total) according to formula (II) wherein the meaning of all substituents are as given in the Tables TA01.01 to TA01.11 exept that R 1 signifies 2,4-dichloro-phenyl instead of 4-chloro- phenyl.
  • Tables TA05.01 to TA05.11 disclose each 232 compounds (2552 compounds in total) according to formula (II) wherein the meaning of all substituents are as given in the Tables TA01.01 to TA01.11 exept that R 1 signifies 2-fluoro-phenyl instead of 4-chloro- phenyl.
  • Tables TA06.01 to TA06.11 disclose each 232 compounds (2552 compounds in total) according to formula (II) wherein the meaning of all substituents are as given in the Tables TA01.01 to TA01.11 exept that R 1 signifies 4-fluoro-phenyl instead of 4-chloro- phenyl.
  • Tables TA07.01 to TA07.11 disclose each 232 compounds (2552 compounds in total) according to formula (II) wherein the meaning of all substituents are as given in the Tables TA01.01 to TA01.11 exept that R 1 signifies 5-chloro-2-thiophenyl instead of 4- chloro-phenyl.
  • the Tables TA08.01 to TA08.11 disclose each 232 compounds (2552 compounds in total) according to formula (II) wherein the meaning of all substituents are as given in the Tables TA01.01 to TA01.11 exept that R 1 signifies 4-chloro-benzyl instead of 4-chloro- phenyl.
  • the Tables TA09.01 to TA09.11 disclose each 232 compounds (2552 compounds in total) according to formula (II) wherein the meaning of all substituents are as given in the Tables TA01.01 to TAOl . l 1 exept that R 1 signifies Cyclohexyl instead of 4-chloro-phenyl.
  • the Table TB01.01 discloses 232 compounds according to formula (III) (compound TBOl .01.001 to compound TB01.01.232) wherein in the first 116 compounds R 1 signifies 4- chloro-phenyl, X signifies CH and and R 2 and R 3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116 compounds but X signifies N instead of CH.
  • Table TB01.02 discloses 232 compounds according to formula (III) wherein all the substituents have the meaning as given in Table TB01.01 but R 1 signifies 4-chloro-2- fluoro-phenyl instead of 4-chloro-phenyl.
  • Table TB01.03 discloses 232 compounds according to formula (III) wherein all the substituents have the meaning as given in Table TB01.01 but R 1 signifies 2,4-difluoro- phenyl instead of 4-chloro-phenyl.
  • Table TB01.04 discloses 232 compounds according to formula (III) wherein all the substituents have the meaning as given in Table TB01.01 but R 1 signifies 2,4-dichloro- phenyl instead of 4-chloro-phenyl
  • the Table TB01.05 discloses 232 compounds according to formula (III) wherein all the substituents have the meaning as given in Table TB01.01 but R 1 signifies 2-fluoro-phenyl instead of 4-chloro-phenyl.
  • the Table TB01.06 discloses 232 compounds according to formula (III) wherein all the substituents have the meaning as given in Table TB01.01 but R 1 signifies 5-chloro-2- thiophenyl instead of 4-chloro-phenyl.
  • Table TB01.07 discloses 232 compounds according to formula (III) wherein all the substituents have the meaning as given in Table TB01.01 but R 1 signifies 4-chloro- benzyl instead of 4-chloro-phenyl.
  • Table TB01.08 discloses 232 compounds according to formula (III) wherein all the substituents have the meaning as given in Table TB01.01 but R 1 signifies Cyclohexyl instead of 4-chloro-phenyl.
  • Botrytis cinerea (Gray mould): Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24 °C and the inhibition of growth was determined photometrically after 72 hrs.
  • Erysiphe graminis Barley leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with spores of the fungus. After appropriate incubation the activity of a compound is assessed 7 dpi (days after inoculation) as preventive fungicidal activity. The following compounds give at least 80% control of Erysiphe graminis at 200 ppm:
  • Septoria tritici (leaf blotch): Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24 C and the inhibition of growth was determined photometrically after 72 hrs.
  • Puccinia recondita (Brown rust): Wheat leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 8 dpi (days after inoculation) as preventive fungicidal activity.

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Abstract

Compounds of Formula (I), wherein the other substituents R1, R2, R3, R4, R5, R6 and R7 are as defined in claim 1, and their use as microbiocides.

Description

4 , 5 -DIHYDRO- ISOXAZOLE DERIVATIVES AS FUNGICIDES
The present invention relates to novel 4,5-dihydro-isoxazol moieties containing compounds, especially 3-aryl or heteroaryl substituted -5,5-disubstituted-4,5-dihydro-isoxazol-4-yl)- heteroaryl -3 -yl -methanol moieties containing compounds or 3- aryl or heteroaryl substituted - 5,5- disubstituted -4-methylene-4,5-dihydro-isoxazole moieties containing compounds their use in compositions and methods for the control and/or prevention of microbial infection, particularly fungal infection, in plants and to processes for the preparation of these compounds.
The incidence of serious microbial infections, particularly fungal infections, either systemic or topical, continues to increase for plants.
Fungicides are compounds, of natural or synthetic origin, which act to protect plants against damage caused by fungi. Current methods of agriculture rely heavily on the use of fungicides. In fact, some crops cannot be grown usefully without the use of fungicides.
Using fungicides allows a grower to increase the yield of the crop and consequently, increase the value of the crop. Numerous fungicidal agents have been developed. However, the treatment of fungal infestations continues to be a major problem. Furthermore, fungicide resistance has become a serious problem, rendering these agents ineffective for some agricultural uses. As such, a need exists for the development of new fungicidal compounds.
Accordingly, the present invention provides a compound of formula (I)
Figure imgf000003_0001
wherein
R1 is aryl or heteroaryl, or substituted aryl or substituted heteroaryl each optionally substituted by one to five substituents R8a, which may be the same or different;
R2 andR3 independently are H, aryl or Heterocyclyl, substituted aryl or substituted heteroaryl each optionally substituted by one to five substituents R8, which may be the same or different; Ci-C8alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-Cecycloalkyl, Ci-Cehaloalkyl, C2- Cehaloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, Ci-C6alkoxy, Ci-C6alkoxy-Ci- C6alkyl, Ci-Cehaloalkoxy, Ci-Cealkylthio, Ci-Cehaloalkylthio, or substituted Ci-C8alkyl, substituted C2-C6alkenyl, substituted C2-C6alkynyl, substituted C3-Cecycloalkyl, substituted Ci-C6haloalkyl, substituted C2-C6haloalkenyl, substituted C2-C6haloalkynyl, substituted C3- Cehalocycloalkyl, substituted Ci-C6alkoxy, substituted Ci-Cealkoxy-Ci-Cealkyl, substituted Ci-Cehaloalkoxy, substituted Ci-Cealkylthio, substituted Ci-Cehaloalkylthio each substituted by one to five substituents R9, which may be the same or different; provided that only one of the substituents R2 and R3 is H;
or R2 and R3 form together a 3 to 14 membered ring which may be monocyclic or polycyclic, preferably monocyclic, bicyclic or tricyclic, more preferably monocyclic or bicyclic, even more preferably monocyclic, and the ring formed by R2 and R3 together may be a alicyclic systems or heteroalicyclic systems wherein the carbocyclic ring structure which may comprise at least one endocyclic double bond or at least one endocyclic triple bond) wherein in the case of the heteroalicyclic systems optionally one or more of the carbon atoms are replaced by a heteroatom selected from O, N and S and wherein the alicyclic systems or heteroalicyclic systems are unsubstituted or substituted by one to five substituents R9;
R4 is heteroaryl, or substituted heteroaryl substituted by one to five substituents R8, which may be the same or different;
R5 is H, OH; Ci-C6alkoxy or Ci-C6alkylcarbonyl, or substituted Ci-C6alkoxy or substituted Ci-C6alkylcarbonyl each substituted by one to five substituents R9, which may be the same or different;
R6 is H or forms together with R7 a bond;
R7 is H, OH, CN, halogen; Ci-C8alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, Ci-C6alkoxy, Ci- C6alkoxy-Ci-C6alkyl, Ci-C6haloalkoxy, Ci-C6alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C8alkyl, substituted C2-C6alkenyl, substituted C2-C6alkynyl, substituted C3-Cecycloalkyl, substituted Ci-C6haloalkyl, substituted C2-C6haloalkenyl, substituted C2-C6haloalkynyl, substituted C3-C6halocycloalkyl, substituted Ci-C6alkoxy, substituted Ci-C6alkoxy-Ci- C6alkyl, substituted Ci-C6haloalkoxy, substituted Ci-C6alkylthio, substituted Ci-
C6haloalkylthio each substituted by one to five substituents R9, which may be the same or different; or forms together with R6 a bond; each R is independently selected from cyano, amino, nitro, hydroxy, halogen, Ci-C4alkyl, Ci-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, C3- C6cycloalkyl, C3-C6halocycloalkyl, Ci-C3alkoxy, Ci-C3haloalkoxy, Ci-C3alkylthio, Ci- C3haloalkylthio, Ci-C3alkylsulfinyl, Ci-C3haloalkylsulfinyl, Ci-C3alkylsulfonyl, Ci-C3halo- alkylsulfonyl, Ci-C4alkylamino, di-(Ci-C4alkyl)amino, Ci-C4alkylcarbonyl, Ci-C4alkyl- carbonyloxy, Ci-C4alkoxycarbonyl, Ci-C4alkylcarbonylamino and phenyl or phenyl substituted by one to five R8 but not phenyl or substituted phenyl;
each R8a is independently selected from cyano, amino, nitro, hydroxy, halogen, Ci-C4alkyl, Ci-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, C3- C6cycloalkyl, C3-C6halocycloalkyl, Ci-C3alkoxy, Ci-C3haloalkoxy, Ci-C3alkylthio, Ci-
C3haloalkylthio, Ci-C3alkylsulfinyl, Ci-C3haloalkylsulfinyl, Ci-C3alkylsulfonyl, Ci-C3halo- alkylsulfonyl, Ci-C4alkylamino, di-(Ci-C4alkyl)amino, Ci-C4alkylcarbonyl,
Figure imgf000005_0001
carbonyloxy, Ci-C4alkylcarbonylamino and phenyl or phenyl substituted by one to five R8 but not phenyl or substituted phenyl;
each R9 is independently halogen, cyano, nitro, hydroxy, Ci-C8alkoxy, Ci-C8haloalkoxy-, Ci-C8alkylthio-, Ci-C8haloalkylthio-, Ci-C8alkylsulfinyl-, Ci-C8haloalkylsulfinyl-, Ci- C8alkylsulfonyl-, Ci-C8haloalkylsulfonyl-, Ci-C8alkylcarbonyl-, Ci-C8alkoxycarbonyl-, aryl or aryl substituted by one to five R9, or heterocyclyl or heterocyclyl substituted by one to five R8;
or an agrochemically acceptable salt or N-oxides thereof.
The invention covers all agronomically acceptable salts, isomers, structural isomers, stereoisomers, diastereoisomers, enantiomers, tautomers and N-oxides of those compounds. The compounds of formula (I) may exist in different geometric or optical isomeric forms or in different tautomeric forms. One or more centres of chirality may be present, in which case compounds of the formula I may be present as pure enantiomers, mixtures of enantiomers, pure diastereomers or mixtures of diastereomers. There may be double bonds present in the molecule, such as C=C or C=N bonds, in which case compounds of formula I may exist as single isomers or mixtures of isomers. Centres of tautomerisation may be present. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds. Also atropisomerism may occur as a result of a restricted rotation about a single bond and cationic compounds of formula (I). Suitable salts of the compounds of formula (I) include acid addition salts such as those with an inorganic acid such as hydrochloric, hydrobromic, sulphuric, nitric or phosphoric acid, or an organic carboxylic acid such as oxalic, tartaric, lactic, butyric, toluic, hexanoic or phthalic acid, or a sulphonic acid such as methane, benzene or toluene sulphonic acid. Other examples of organic carboxylic acids include haloacids such as trifluoroacetic acid.
N-oxides are oxidised forms of tertiary amines or oxidised forms of nitrogen containing heteroaromatic compounds. They are described in many books for example in "Heterocyclic N-oxides" by Angelo Albini and Silvio Pietra, CRC Press, Boca Raton, Florida, 1991.
The alkyl groups occurring in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, ^-propyl, «-butyl, «-pentyl, «-hexyl, iso- propyl, «-butyl, sec-butyl, zso-butyl or tert-butyl. Alkoxy, alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned. The alkenyl and alkynyl groups can be mono- or di-unsaturated. The cycloalkyl groups are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Halogen is generally fluorine, chlorine, bromine or iodine, preferably fluorine, bromine or chlorine more preferably chlorine or fluorine. This also applies, correspondingly, to halogen in combination with other meanings, such as halogenalkyl or halogenalkoxy. Haloalkyl groups preferably have a chain length of from 1 to 6 carbon atoms and comprise at least one halogen atom up to perhalogenated alkyle group. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl,
trichlorom ethyl, 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
dichlorofluorom ethyl. Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n- butoxy, isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy and ethoxy.
Halogenalkoxy 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. Thioalkyl is, for example, methylthio, ethylthio, propylthio, tert-butylthio, hexylthio. Alkylamino is, for example, methylamino, ethylamino, propylamino, tert- butylamino, hexylamino as well as, for example dimethylamino, diethylamino,
dipropylamino, ditert-butylamino, dihexylamino or trimethylamino, triethylamino, tripropylamino, tri tert-butylamino, trihexylamino or 2- to 3-fold substituted amines with different alkyl groups.
The aryl groups are groups derived from monoyclic and polycyclic aromatic hydrocarbons by removal of a hydrogen atom from a ring carbon atom. The heterocyclyl groups are derived from heteroarenes by removal of a hydrogen atom from any ring atom and the heteroarenes are monoyclic and polycyclic aromatic hydrocarbons wherein one or more methine (-C=) and/or vinylene (-CH=CH-) groups by trivalent or divalent heteroatoms, respectively, in such a way as to maintain the continuous π-electron system characteristic of aromatic systems. Heteroaryl means a mono-, bi- or tricyclic, aromatic hydrocarbon, containing 3 to 14, preferably 5 to 10, more preferably 6 to 8, ring-atoms, including 1 to 6, preferably 1 to 4, heteroatoms independently selected from nitrogen, oxygen and sulfur. The aryl and heteroaryl groups are, for example, acridinyl, anthracenyl, benzimidazolyl, benzisoxazolyl, benzo[c]thiopheny, benzofuranyl, benzothiazolyl, benzothiophenyl, benzoxazolyl, cinnolinyl, furyl, imidazolyl, indazolyl, indolyl, isobenzofuranyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, naphthalenyl, naphthyl, oxadiazolyl, oxazolyl, phenyl, preferablythesgroupsareoptionallymono-, purinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl, thiadiazolyl, thiazoyl, thienyl, which can be optionally substituted, preferably these groups are optionally mono-, di- or tri substituted.
Heterocyclyl, as used herein, are cyclic compounds having as ring members atoms of at least two different elements, e.g. quinoline, 1,2-thiazole, bicyclo[3.3.1]tetrasiloxane includes therefore heteroaryl preferably those containing from 3 to 10 ring-atoms up to 4 of which are heteroatoms selected from nitrogen, oxygen and sulfur, and in addition non aromatic heterocyclic compounds which may be a saturated or partially unsaturated cyclic
hydrocarbon containing from 3 to 10 ring-atoms up to 4 of which are heteroatoms selected from nitrogen, oxygen and sulfur, and the heterocycly substituent may be optionally substituted by one or more groups independently selected from halogen, nitro, cyano, alkyl, alkoxy or as indicated in the claims or in the other parts of the description. Examples of non- aromatic heterocyclyl groups are oxiranyl, azetidinyl, tetrahydrofuranyl, thiolanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, sulfolanyl, dioxolanyl, dihydropyranyl, tetrahydropyranyl, piperidinyl, pyrazolinyl, pyrazolidinyl, dioxanyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl, azepinyl, oxazepinyl, thiazepinyl, thiazolinyl and diazapanyl.
Heteroalkencyclyl, as used herein, includes non aromatic heterocyclic compounds which may be a saturated or partially unsaturated cyclic hydrocarbon containing from 3 to 10 ring- atoms up to 4 of which are heteroatoms selected from nitrogen, oxygen and sulfur, and may be optionally substituted by one or more groups independently selected from halogen, nitro, cyano, alkyl, alkoxy and may be optionally substituted by one or more groups independently selected from halogen, nitro, cyano, alkyl, alkoxy or as indicated in the claims or in the other parts of the description
1 2 3 4 5 6 7 8 9
Preferred values of R , R R R R , R°, R , R° and R' are, in any combination, as set out below. In a preferred embodiment R1 is aryl or substituted aryl substituted by one to five
substituents R8a, which may be the same or different; More preferably R1 is phenyl or substituted aryl substituted by one to five substituents R8a, which may be the same or different; Preferably R1 is 4-chloro-phenyl, 4-chloro-2-fluoro-phenyl, 2,4-difluoro-phenyl, 2,4-dichloro-phenyl, 2-fluoro-phenyl, 5-chloro-2-thiophenyl, 4-chloro-benzyl, cyclohexyl;
In a preferred embodiment R2 andR3 independently are aryl or heterocyclyl, or substituted aryl or substituted heterocyclyl each substituted by one to five substituents R8, which may be the same or different; Ci-C8alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-Cecycloalkyl, Ci- C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, Ci-C6alkoxy, Ci- C6alkoxy-Ci-C6alkyl, Ci-C6haloalkoxy, Ci-C6alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C8alkyl, substituted C2-C6alkenyl, substituted C2-C6alkynyl, substituted C3-C6Cycloalkyl, substituted Ci-C6haloalkyl, substituted C2-C6haloalkenyl, substituted C2-C6haloalkynyl, substituted C3-C6halocycloalkyl, substituted Ci-C6alkoxy, substituted Ci-C6alkoxy-Ci- C6alkyl, substituted Ci-C6haloalkoxy, substituted Ci-C6alkylthio, substituted Ci- C6haloalkylthio each substituted by one to five substituents R9, which may be the same or different; Preferably R2 and R3 independently are aryl or heterocyclyl, or substituted aryl or sunbstituted heterocyclyl each substituted by one to five substituents R8, which may be the same or different; Ci-C8alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, Ci-C6alkoxy, Ci-C6alkoxy-Ci- C6alkyl, Ci-Cehaloalkoxy, Ci-Cealkylthio, Ci-Cehaloalkylthio, or substituted Ci-C8alkyl, substituted C2-C6alkenyl, substituted C2-C6alkynyl, substituted C3-Cecycloalkyl, substituted Ci-Cehaloalkyl, substituted C2-C6haloalkenyl, substituted C2-C6haloalkynyl, substituted C3- C6halocycloalkyl, substituted Ci-C6alkoxy, substituted Ci-C6alkoxy-Ci-C6alkyl, substituted Ci-Cehaloalkoxy, substituted Ci-Cealkylthio, substituted Ci-Cehaloalkylthio each substituted by one to five sub stituents R9,
In a preferred embodiment wherein R2 andR3 form together a 5 to 14 membered ring which may be bicyclic or tricyclic, more preferably monocyclic or bicyclic, even more preferably monocyclic, and the 5 to 8 membered ring may be a alicyclic systems or heteroalicyclic systems wherein in the case of the heteroalicyclic systems optionally one or more of the carbon atoms are replaced by a heteroatom selected from O, N and S and wherein the alicyclic systems or heteroalicyclic systems are optionally substituted by one to five substituents R9 ; more preferred wherein R2 andR3 form together a 5 to 6 membered ring which may more preferably monocyclic or bicyclic, even more preferably monocyclic, and the 5 to 8 membered ring may be a alicyclic systems or heteroalicyclic systems wherein the carbocyclic ring structure which may comprise at least one endocyclic double bond or at least one endocyclic triple bond wherein in the case of the heteroalicyclic systems optionally one or more of the carbon atoms are replaced by a heteroatom selected from O, N and S and wherein the alicyclic systems or heteroalicyclic systems are optionally substituted by one to five substituents R9 ;
In a preferred embodiment wherein R2 andR3 independently H, Ci-C8alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6Cycloalkyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3- Cehalocycloalkyl, Ci-C6alkoxy, Ci-Cealkoxy-Ci-Cealkyl, Ci-C6haloalkoxy, Ci-C6alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C8alkyl, substituted C2-C6alkenyl, substituted C2- C6alkynyl, substituted C3-Cecycloalkyl, substituted Ci-C6haloalkyl, substituted C2- C6haloalkenyl, substituted C2-C6haloalkynyl, substituted C3-C6halocycloalkyl, substituted Ci-C6alkoxy, substituted Ci-Cealkoxy-Ci-Cealkyl, substituted Ci-C6haloalkoxy, substituted Ci-C6alkylthio, substituted Ci-Cehaloalkylthio, each substituted by one to five substituents R9, provided that only one of the substituents R2 andR3 is H; more preferred wherein R2 and R3 independently are H, Ci-C8alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, Ci- Cehaloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, Ci-C6alkoxy, Ci- C6alkoxy-Ci-C6alkyl, Ci-Cehaloalkoxy, or substituted Ci-C8alkyl, substituted C2-C6alkenyl, substituted C2-C6alkynyl, substituted C3-Cecycloalkyl, substituted Ci-Cehaloalkyl, substituted C2-C6haloalkenyl, substituted C2-Cehaloalkynyl, substituted C3-C6halocycloalkyl, substituted Ci-C6alkoxy, substituted Ci-C6alkoxy-Ci-C6alkyl, substituted Ci-C6haloalkoxy each substituted by one to five substituents R9, provided that only one of the substituents R2 and R3 is H;
In an even more preferred embodiment wherein R2 and R3 independently Ci-C8alkyl, C2- C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2- C6haloalkynyl, C3-C6halocycloalkyl, Ci-C6alkoxy, Ci-C6alkoxy-Ci-C6alkyl, Ci- C6haloalkoxy, Ci-C6alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C8alkyl, substituted C2- C6alkenyl, substituted C2-C6alkynyl, substituted C3-Cecycloalkyl, substituted Ci-C6haloalkyl, C2-C6haloalkenyl, substituted C2-C6haloalkynyl, substituted C3-C6halocycloalkyl, substituted Ci-C6alkoxy, substituted Ci-C6alkoxy-Ci-C6alkyl, substituted Ci-C6haloalkoxy, substituted Ci-C6alkylthio, substituted Ci-Cehaloalkylthio each substituted by one to five substituents R9; more preferred wherein R2 and R3 independently are H, Ci-C8alkyl, C2-C6alkenyl, C2- C6alkynyl, C3-Cecycloalkyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3- Cehalocycloalkyl, Ci-C6alkoxy, Ci-Cealkoxy-Ci-Cealkyl, Ci-C6haloalkoxy, or substituted Ci-C8alkyl, substituted C2-C6alkenyl, substituted C2-C6alkynyl, substituted C3-C6cycloalkyl, substituted Ci-C6haloalkyl, substituted C2-C6haloalkenyl, substituted C2-C6haloalkynyl, substituted C3-C6halocycloalkyl, substituted Ci-C6alkoxy, substituted Ci-C6alkoxy-Ci- C6alkyl, substituted Ci-C6haloalkoxy each substituted by one to five substituents R9; In a preferred embodiment R4 is a monocyclic heteroaryl, or a substituted monocyclic heteroaryl substituted by one to five substituents R8, which may be the same or different; more preferably R4 is a monocyclic 5 to 6 membered heteroaryl comprising one to three heteroatoms seleced from S, N more preferably the one to three heteroatoms are seleced from N, which may be unsubstituted or substituted by one to five substituents R8, which may be the same or different; most preferably R4 is
Figure imgf000010_0001
wherein X has the meaning of C-H or N each may be substituted by one substituent R ; In a further preferred embodiment R4 is
Figure imgf000011_0001
which may be substituted by one to three substituents R8, which may be the same or different.
In a further preferred embodiment R4 is
Figure imgf000011_0002
which may be substituted by one to three substituents R , which may be the same or different.
In a further preferred embodiment R4 is
Figure imgf000011_0003
which may be substituted by one to four substituents R8, which may be the same or different. In a further preferred embodiment R4 is
Figure imgf000011_0004
which may be substituted by one to three substituents Rs, which may be the same or different.
In a further preferred embodiment R4 is pyrid-3-yl which may be substituted by one to three substituents R8, which may be the same or different
Preferably the heteroaryl moieties of R4 and are not further substituted.
In a preferred embodiment when R6 are not forming together with R7 a bond then R5 is H, OH; Ci-Cealkoxy or Ci-Cealkylcarbonyl, or substituded Ci-Cealkoxy or substituded Ci- C6alkylcarbonyl each substituted by one to five substituents R9, which may be the same or different; more preferably when R6 are not forming together with R7 a bond then R5 is OH. In a further preferred embodiment R6 is H and R7 is H, OH, halogen; Ci-C8alkyl, C2- C6alkenyl, C2-C6alkynyl, C3-Cecycloalkyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2- C6haloalkynyl, C3-C6halocycloalkyl, Ci-C6alkoxy, Ci-C6alkoxy-Ci-C6alkyl, Ci- C6haloalkoxy, Ci-C6alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C8alkyl, substituted C2- C6alkenyl, substituted C2-C6alkynyl, substituted C3-Cecycloalkyl, substituted Ci-Cehaloalkyl, substituted C2-C6haloalkenyl, substituted C2-Cehaloalkynyl, substituted C3-C6halocycloalkyl, substituted Ci-C6alkoxy, substituted Ci-Cealkoxy-Ci-Cealkyl, substituted Ci-Cehaloalkoxy, Ci-Cealkylthio, substituted Ci-Cehaloalkylthio each substituted by one to five substituents R9, which may be the same or different; preferably R6 is H and R7 is H, OH, halogen; Ci- C8alkyl, Ci-C6alkoxy, or substituted Ci-C8alkyl, substituted Ci-C6alkoxy each substituted by one to five substituents R9, which may be the same or different; more preferably preferably R6 is H and R7 is H, OH, Ci-C2alkyl, Ci-C2alkoxy, or substituted Ci-C2alkyl, substituted Ci- C2alkoxy each substituted by one substituent R9, which may be the same or different; Even more preferably R7 is H, OH, OMe, Me, Et, F, CI, Br, CF3, CN, OAc
In a further preferred embodiment R6 forms together with R7 a bond and R7 forms together with R6 a bond, respectively. Preferably if R6 forms together with R7 a bond then R5 is H; In a preferred embodiment each R8 is independently selected from cyano, amino, nitro, hydroxy, halogen, Ci-C4alkyl, Ci-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2- C4alkynyl, C2-C4haloalkynyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, Ci-C3alkoxy, Ci- C3haloalkoxy;
In a preferred embodiment each R9 is independently halogen, cyano, nitro, hydroxy, Ci- C3alkoxy, or Ci-C3haloalkoxy, Ci-C3alkylthio, Ci-C3haloalkylthio, Ci-C3alkylsulfinyl, Ci- C3haloalkylsulfinyl, Ci-C3alkylsulfonyl, Ci-C3haloalkylsulfonyl, Ci-C3alkylcarbonyl,Ci-C8- Ci-C3 alkoxycarbonyl, aryl or aryl substituted by one to five R9, or heterocyclyl or heterocyclyl substituted by one to five R8; In a more preferred embodiment each R9 is independently halogen, cyano, nitro, hydroxy, Ci-C8alkoxy-, Ci-C8haloalkoxy-, Ci- C8alkylcarbonyl-, Ci-C8alkoxycarbonyl-, aryl or aryl substituted by one to five R9, or heterocyclyl or heterocyclyl substituted by one to five R8;
In a preferred embodiment aryl signifies phenyl, naphthyl, anthracenyl, indenyl,
anphenanthrenyl, with phenyl being preferred. The aryl groups may be substituted as mentioned above.
In a preferred embodiment heteroaryl signifies a mono-, bi- or tricyclic, aromatic
hydrocarbon, containing 5 to 14, preferably 5 to 10, more preferably 6 to 8, ring-atoms, including 1 to 6, preferably 1 to 4, heteroatoms independently selected from nitrogen, oxygen and sulfur; preferably a mono- or bicyclic, aromatic hydrocarbon, containing 5 to 14, preferably 5 to 10, more preferably 6 to 8, ring-atoms, including 1 to 6, preferably 1 to 4, heteroatoms independently selected from nitrogen, oxygen and sulfur; more preferably pyridyl, pyrimydyl or 1,2,4-triazolyl which may be substituted as mentioned above
In a preferred embodiment heterocyclyl signifies heteroaryl, and in addition may be a saturated or partially unsaturated cyclic hydrocarbon containing from 3 to 10 ring-atoms up to 4 of which are heteroatoms selected from nitrogen, oxygen and sulfur, and may be optionally substituted
Preferably R1 signifies phenyl or phenyl substituded by halogen.
Preferably R2 signifies Me, Et, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, tert-butyl, sec-butyl, isoamyl, z'so-propyl, CF3, 4-chloro-phenyl, 3-chloro-phenyl, 2-chloro-phenyl, 2,4- dichloro-phenyl, 2-thiophenyl, 5-chloro-2-thiophenyl, 5-bromo-2-thiophenyl, 4-fluoro- phenyl, 3-fluoro-phenyl, 2-fluoro-phenyl, 2,4-difluoro-phenyl, 2-fluoro-4-chloro-phenyl, 2- chloro-4-fluoro-phenyl, 4-trifluoromethyl-phenyl, 3-trifluoromethyl-phenyl, 2- trifluoromethyl-phenyl, 4-bromo-phenyl, phenyl, 4-chloro-benzyl, or if R2 and R3 together form cycle the cycle formed is selected from cyclohexyl, cyclopentyl, cyclobutyl,
Figure imgf000013_0001
cyclopropyl,
Figure imgf000013_0002
*- *U *-*U -*P -*P -*P' - *P*°
Figure imgf000014_0001
Preferably R3 signifies H, Me Et. In an preferred Embodiment (El)
R1 is aryl or aryl substituted by one to five substituents R8a, which may be the same or different;
R2 andR3 independently are aryl or heterocyclyl, or substituted aryl or substituted heterocyclyl each optionally substituted by one to five substituents R8
In an further preferred Embodiment (E2)
R1 is phenyl or phenyl substituted by one to five substituents R8a, which may be the same or different;
R2 andR3 independently are aryl or heterocycl, or substituted aryl or substituted heterocyclyl each substituted by one to five substituents R8
In an further preferred Embodiment (E3)
R1 is aryl or aryl substituted by one to four substituents R8a, which may be the same or different;
R2 andR3 form together a 3 to 14 membered ring which may be polycyclic, more preferably monocyclic or bicyclic, even more preferably monocyclic, and the 5 to 8 membered ring may be a alicyclic systems or heteroalicyclic systems wherein in the case of the heteroalicyclic systems optionally one or more of the carbon atoms are replaced by a heteroatom selected from O, N and S and wherein the alicyclic systems or systems are optionally substituted by one to five substituents R9; In an further preferred Embodiment (E4)
R1 is phenyl or penyl substituted by one to four substituents R8a, which may be the same or different;
R2 andR3 form together a 3 to 14 membered ring which may be bicyclic, more preferably monocyclic or bicyclic, even more preferably monocyclic, and the 5 to 8 membered ring may be a alicyclic systems or heteroalicyclic systems wherein in the case of the heteroalicyclic systems optionally one or more of the carbon atoms are replaced by a heteroatom selected from O, N and S and wherein the alicyclic systems or heteroalicyclic systems are optionally substituted by one to four substituents R9;
In an further preferred Embodiment (E5)
R1 is aryl aryl substituted by one to four substituents R8, which may be the same or different; R2 andR3 independently H, Ci-C8alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-Cecycloalkyl, Ci- C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, Ci-C6alkoxy, Ci- C6alkoxy-Ci-C6alkyl, Ci-C6haloalkoxy, Ci-C6alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C8alkyl, substituted C2-C6alkenyl, substituted C2-C6alkynyl, substituted C3-C6Cycloalkyl, substituted Ci-C6haloalkyl, substituted C2-C6haloalkenyl, substituted C2-C6haloalkynyl, substituted C3-C6halocycloalkyl, substituted Ci-C6alkoxy, substituted Ci-C6alkoxy-Ci- C6alkyl, substituted Ci-C6haloalkoxy, substituted Ci-C6alkylthio, substituted Ci-
C6haloalkylthio each substituted by one to five substituents R9, provided that only one of the substituents R2 andR3 is H;
In an further preferred Embodiment (E6)
R1 is phenyl or phenyl substituted by one to four substituents R8, which may be the same or different;
R2 andR3 independently are H, Ci-C8alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-Cecycloalkyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, Ci-C6alkoxy, Ci- C6alkoxy-Ci-C6alkyl, Ci-C6haloalkoxy, or substituted Ci-C8alkyl, substituted C2-C6alkenyl, substituted C2-C6alkynyl, substituted C3-Cecycloalkyl, substituted Ci-C6haloalkyl, substituted C2-C6haloalkenyl, substituted C2-C6haloalkynyl, substituted C3-C6halocycloalkyl, substituted Ci-C6alkoxy, substituted Ci-Cealkoxy-Ci-Cealkyl, substituted Ci-C6haloalkoxy each substituted by one to five substituents R9, provided that only one of the substituents R2 andR3 is H:
In a preferred embodiment (El . A) R4 is heteroaryl, or heteroaryl substituted by one to five substituents R8, which may be the same or different and the further substituents have the meaning given in the embodiment (El).
In a preferred embodiment (E2. A) R4 is heteroaryl, or heteroaryl substituted by one to five substituents R8, which may be the same or different and the further substituents have the meaning given in the embodiment (E2).
In a preferred embodiment (E3.A) R4 is heteroaryl, or heteroaryl substituted by one to five substituents R8, which may be the same or different and the further substituents have the meaning given in the embodiment (E3).
In a preferred embodiment (E4. A) R4 is heteroaryl, or heteroaryl substituted by one to five substituents R8, which may be the same or different and the further substituents have the meaning given in the embodiment (E4).
In a preferred embodiment (E5.A) R4 is heteroaryl, or heteroaryl substituted by one to five substituents R8, which may be the same or different and the further substituents have the meaning given in the embodiment (E5).
In a preferred embodiment (E6. A) R4 is heteroaryl, each optionally substituted by one to five substituents R8, which may be the same or different and the further substituents have the meaning given in the embodiment (E6).
In a preferred embodiments (El .B) R4 is a monocyclic heteroaryl, or monocyclic heteroaryl substituted by one to five substituents R8, which may be the same or different, which may be the same or different and the further substituents have the meaning given in the embodiment (El).
In a preferred embodiment (E2.B) the substituents are as given in (El .B) but the meaning of the substituents given in (El) have the meaning of (E2).
In a preferred embodiment (E3.B) the substituents are as given in (El .B) but the meaning of the substituents given in (El) have the meaning of (E3).
In a preferred embodiment (E4.B) the substituents are as given in (El .B) but the meaning of the substituents given in (El) have the meaning of (E4). In a preferred embodiment (E5.B) the substituents are as given in (El .B) but the meaning of the substituents given in (El) have the meaning of (E5).
In a preferred embodiment (E6.B) the substituents are as given in (El .B) but the meaning of the substituents given in (El) have the meaning of (E6).
In a preferred embodiment (E7.B) the substituents are as given in (El B) but the meaning of the substituents given in (El) have the meaning of (E7).
In a preferred embodiment (E8.B) the substituents are as given in (El .B) but the meaning of the substituents given in (El) have the meaning of (E8). In the embodiment (El .C) to (E8.C) have the same meaning as in the corresponding embodiments (El .B) to (E8.B) but R4 is
Figure imgf000017_0001
wherein X has the meaning of C-H or N each may be substituted substituted by one substituent R8
In the embodiment (El .D) to (E8.D) have the same meaning as in the corresponding embodiments (El .B) to (E8.B) but R4 is
Figure imgf000017_0002
In the embodiment (El .E) to (E8.E) have the same meaning as in the corresponding embodiments (El .B) to (E8.B) but R4 is
Figure imgf000017_0003
In the embodiment (El .F) to (E8.F) have the same meaning as in the corresponding embodiments (El .B) to (E8.B) but R4 is
Figure imgf000017_0004
In the embodiment (El .G) to (E8.G) have the same meaning as in the corresponding embodiments (El .B) to (E8.B) but R4 is
Figure imgf000018_0001
In the embodiment (El .H) to (E8.H) have the same meaning as in the corresponding embodiments (El .B) to (E8.B) but R4 is pyrid-3-yl In a further preferred embodiment (El .A.1) to (E8.H.1) the substituents have the meaning of the corresponding embodiments (El . A) to (E8.H) and when R6 are not forming together with R7 a bond then R5 is H, OH; Ci-Cealkoxy or Ci-Cealkylcarbonyl, or substituted Ci-Cealkoxy or substituted Ci-C6alkylcarbonyl each substituted by one to five substituents R9, which may be the same or different; R6 is H and R7 is H, OH, halogen; Ci-C8alkyl, C2-C6alkenyl, C2- C6alkynyl, C3-Cecycloalkyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-
Cehalocycloalkyl, Ci-C6alkoxy, Ci-Cealkoxy-Ci-Cealkyl, Ci-C6haloalkoxy, Ci-C6alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C8alkyl, substituted C2-C6alkenyl, substituted C2- C6alkynyl, substituted C3-C6cycloalkyl, substituted Ci-C6haloalkyl, substituted C2- C6haloalkenyl, substituted C2-C6haloalkynyl, substituted C3-C6halocycloalkyl, substituted Ci-C6alkoxy, substituted Ci-Cealkoxy-Ci-Cealkyl, substituted Ci-C6haloalkoxy, substituted Ci-C6alkylthio, substituted Ci-Cehaloalkylthio each substituted by one to five substituents R9, which may be the same or different;
In a further preferred embodiment (E1.A.2) to (E8.H.2) the substituents have the meaning of the corresponding embodiments (El . A) to (E8.H) and when R6 are not forming together with R7 a bond then R5 is OH; R6 is H and R7 is H, OH, halogen; Ci-C8alkyl, Ci-C6alkoxy, or substituted C8alkyl, substituted Ci-C6alkoxy each substituted by one to five substituents R9, which may be the same or different; more preferably preferably R6 is H and R7 is H, OH, Ci- C2alkyl, Ci-C2alkoxy, or substituted Ci-C2alkyl, substituted Ci-C2alkoxy each substituted by one substituent R9, which may be the same or different;
In a further preferred embodiment (El .A. l) to (E8.H.1) the substituents have the meaning of the corresponding embodiments (El . A) to (E8.H) and R5 is H, OH; Ci-C6alkoxy or Ci- C6alkylcarbonyl, or Ci-C6alkoxy or Ci-C6alkylcarbonyl each substituted by one to five substituents R9, which may be the same or different; R6 forms together with R7 a bond and R7 forms together with R6 a bond, respectively; In a further preferred embodiment (E1.A.2) to (E8.H.2) the substituents have the meaning of the corresponding embodiments (El . A) to (E8.H) and R5 is H, OH; R6 forms together with R7 a bond and R7 forms together with R6 a bond, respectively; In a preferred embodiment (El) to (E8.H.2) each R8 and R8a is independently selected from cyano, amino, nitro, hydroxy, halogen, Ci-C4alkyl, Ci-C4haloalkyl, C2-C4alkenyl,
C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, C3-Cecycloalkyl, C3-C6halocycloalkyl, Ci-C3alkoxy, Ci-C3haloalkoxy;
In a preferred embodiment (El) to (E8.H.2) each R9 is independently halogen, cyano, nitro, hydroxy, Ci-C8alkoxy-, Ci-C8haloalkoxy-, Ci-C8alkylcarbonyl-, Ci-C8alkoxycarbonyl-, aryl or aryl substituted by one to five R9, or heterocyclyl or heterocyclyl substituted by one to five R8;
In a more preferred embodiment (El) to (E8.H.2) each R8 and R8a is independently selected from cyano, amino, nitro, hydroxy, halogen, Ci-C4alkyl, Ci-C4haloalkyl, C2-C4alkenyl,
C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, C3-Cecycloalkyl, C3-C6halocycloalkyl, Ci-C3alkoxy, Ci-C3haloalkoxy;
In a more preferred embodiment (El) to (E8.H.2) each R9 is independently halogen, cyano, nitro, hydroxy, Ci-C8alkoxy-, Ci-C8haloalkoxy-, Ci-C8alkylcarbonyl-, Ci-C8alkoxycarbonyl- , aryl or aryl substituted by one to five R9, or heterocyclyl or heterocyclyl substituted by one to five R8;
In a most preferred embodiment (El) to (E8.H.2) each R8 and R8a is independently selected from cyano, amino, nitro, hydroxy, halogen;
In a most preferred embodiment (El) to (E8.H.2) each R9 is independently halogen, cyano, nitro, hydroxy;
Compounds of formula (I) may be prepared as shown in the following schemes.
Compounds of formula (A) can be prepared by reacting compound of type (B) with a substrate R4H (triazole, imidazole, tetrazole, benzoimidazole, etc) in the presence of base such as potassium carbonate in a suitable solvent such as dimethylformamide at a temperature between 0°C and 50°C. For example of analogous methods see: DE 94- 4425949, WO2007107556, WO2008124922.
Figure imgf000020_0001
B A
Compounds of formula (B) may be prepared by epoxidation of compounds of formula (C) in the presence of peracids like w-CPBA (weto-Chloroperoxybenzoic acid) in a suitable solvent such as dichl orom ethane at a temperature between 0°C and 100°C. For example of analogous method see D. Swern Organic Peroxides, 2, 355, Interscience Publishers, NY, 1971; D. I. Metelitsa ita Chem. Rev.1972, 41, 807; D. Swern Org. React.1953, 7, 378.
Figure imgf000020_0002
Compounds of formula (C) may be prepared by treated compounds of formula (D) where R5 is a suitable leaving group like a mesylate with a suitable base like DBU (1,8- Diazabicyclo[5.4.0]undec-7-en) in a suitable solvent like dichl oromethane at a temperature between 0°C and 100°C:
Figure imgf000020_0003
D C
Compounds of formula (D) are known, or may be made from known compounds by known methods (Wada et al. Tet. Lett.1992, 33, 1357; Hon et al. JACS 1994, 116, 2324). A typical sequence for the preparation of (D) will involve the preparation of the intermediate alcohol E through a cycloaddition step involving the chloro oxime (F) with appropriate alkene (H) in the presence of a base in an inert solvent at the temperature between -10°C and 100°C. Alternatively, E can be prepared by reduction of the ester I in the presence of an appropriate reducing agent like lithium aluminium hydride in a suitable solvent like THF at the temperature between -10°C and 100°C. Compounds of formula (I) may be prepared by cycloaddition between the chloro oxime (F) and alkene (G) as depicted in the scheme below.
Figure imgf000021_0001
Substrate (D) may undergo directly to nucleophilic substitution to generate L in the presence of an appropriate base like potassium carbonate in a suitable solvent like dimethylsulfoxide at a temperature between 0°C and 50°C.
Figure imgf000021_0002
In a further approach, compound of type (A) when R4= Imidazole, could be prepared by using the following scheme. The epoxide (B) can be reacted with ammonia to form (Al) that could then undergo to the Van Leusen synthesis by cycloaddition with aldehyde R7 and tosylmethyl isocyanides (TosMIC) to give the desired product A2. For example of analogous methods see: Van Leusen et al. JOC 1977, 42, 1153; Olsen et al. JOC 2000, 65, 1516;
Gracias et al. Org. Lett. 2005, 7, 3183.
Figure imgf000022_0001
Figure imgf000022_0002
The reactions to give compounds of formula (I) are advantageously carried out in aprotic inert organic solvents. Such solvents are hydrocarbons such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles such as acetonitrile or propionitrile, amides such as Ν,Ν-dimethylformamide, diethylformamide or N-methylpyrrolidinone. The reaction temperatures are advantageously between -20°C and +120°C. In general, the reactions are slightly exothermic and, as a rule, they can be carried out at ambient temperature. To shorten the reaction time, or else to start the reaction, the mixture may be heated briefly to the boiling point of the reaction mixture. The reaction times can also be shortened by adding a few drops of base as reaction catalyst. Suitable bases are, in particular, tertiary amines such as trimethylamine, triethylamine, quinuclidine, l,4-diazabicyclo[2.2.2]octane, l,5-diazabicyclo[4.3.0]non-5-ene or 1,8-diazabicyclo- [5.4.0]undec-7-ene. However, inorganic bases such as hydrides, e.g. sodium hydride or calcium hydride, hydroxides, e.g. sodium hydroxide or potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, or hydrogen carbonates such as potassium hydrogen carbonate and sodium hydrogen carbonate may also be used as bases. The bases can be used as such or else with catalytic amounts of a phase-transfer catalyst, for example a crown ether, in particular 18-crown-6, or a tetraalkylammonium salt. The compounds of formula (I) and, where appropriate, the tautomers thereof, 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.
It has now been found that the compounds of formula (I) according to the invention have, for practical purposes, a very advantageous spectrum of activities for protecting useful plants against diseases that are caused by phytopathogenic microorganisams, such as fungi, bacteria or viruses.
The invention therefore also relates to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a compound of formula (I) is applied as active ingredient to the plants, to parts thereof or the locus thereof. The
compounds of formula (I) according to the invention are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous useful plants. The compounds of formula (I) can be used to inhibit or destroy the diseases that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.
It is also possible to use compounds of formula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
Furthermore, the compounds of formula (I) according to the invention may be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage or in hygiene management.
The compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara). Furthermore, the novel compounds of formula (I) are effective against phytopathogenic bacteria and viruses (e.g. against
Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus). The compounds of formula (I) are also effective against Asian soybean rust (Phakopsora pachyrhizi).
Within the scope of the invention, useful plants to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucum- bers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.
The term "useful plants" is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, FIPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® , Herculex I® and LibertyLink®. The term "useful plants" is to be understood as including also useful 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.
Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CryIF(a2) toxin and the enzyme
phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); NatureGard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Btl 1 corn borer (CB) trait), Agrisure® RW (corn rootworm trait) and Protecta®.
The term "useful plants" is to be understood as including also useful 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 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.
The term "locus" of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil. An example for such a locus is a field, on which crop plants are growing.
The term "plant propagation material" is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material" is understood to denote seeds.
The compounds of formula I can be used in unmodified form or, preferably, together with carriers and adjuvants conventionally employed in the art of formulation.
The term "plant" or "useful plants" as used herein includes seedlings, bushes and trees. The term "crops" is to be understood as including also crop plants which have been so
transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vipl, Vip2, Vip3 or
Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3 -hydroxy steroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG- COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases. In the context of the present invention there are to be understood by δ-endotoxins, for example CrylAb, Cry 1 Ac, Cry IF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), for example Vipl, 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. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of 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 processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl- type deoxyribonucleic acids and their preparation are known, for example, from WO
95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available.
Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bbl toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bbl toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry lFa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry 1 Ac toxin); Bollgard I® (cotton variety that expresses a Cry 1 Ac toxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a Cry 1 Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard ®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Btl 1 corn borer (CB) trait) and Protecta®.
Further examples of such transgenic crops are:
1 Btll Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer {Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry 1 Ab toxin. Btl 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
2. Btl76 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer {Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a Cry 1 Ab toxin. Btl76 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'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.
4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-l 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bbl toxin and has resistance to certain Coleoptera insects.
5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-l 150 Brussels, Belgium, registration number C/ES/96/02. 6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry IF for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.
7. NK603 x MON 810 Maize from Monsanto Europe S. A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties K603 and MON 810. NK603 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 Cry 1 Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®.
Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.
Crops are also to be understood as being those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
In order to apply a compound of formula (I) as an insecticide, acaricide, nematicide or molluscicide to a pest, a locus of pest, or to a plant susceptible to attack by a pest, a compound of formula (I) is usually formulated into a composition which includes, in addition to the compound of formula (I), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA). SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%), of a compound of formula (I). The composition is generally used for the control of pests such that a compound of formula (I) is applied at a rate of from O. lg tolOkg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to 1kg per hectare.
When used in a seed dressing, a compound of formula (I) is used at a rate of O.OOOlg to lOg (for example O.OOlg or 0.05g), preferably 0.005g to lOg, more preferably 0.005g to 4g, per kilogram of seed.
In another aspect the present invention provides an insecticidal, acaricidal, nematicidal or molluscicidal composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) and a suitable carrier or diluent therefor. The composition is preferably an insecticidal, acaricidal, nematicidal or molluscicidal composition.
The compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).
Dustable powders (DP) may be prepared by mixing a compound of formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
Soluble powders (SP) may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
Wettable powders (WP) may be prepared by mixing a compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).
Granules (GR) may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulfates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
Dispersible Concentrates (DC) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).
Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or
methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C8-Ci0 fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of formula (I) is present initially in either the water or the solvent/SFA blend. Suitable solvents for use in MEs include those hereinbefore described for use in ECs or in EWs. An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
Aerosol formulations comprise a compound of formula (I) and a suitable propellant (for example w-butane). A compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as «-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
A compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound. Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefore. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment. A compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
A composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)). Such additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)).
A compound of formula (I) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS). The preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above. Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type.
Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (for example sodium lauryl sulfate), salts of sulfonated aromatic compounds (for example sodium dodecylbenzenesulfonate, calcium
dodecylbenzenesulfonate, butylnaphthalene sulfonate and mixtures of sodium di- z'sopropyl- and tri-z'sopropyl-naphthalene sulfonates), ether sulfates, alcohol ether sulfates (for example sodium laureth-3 -sulfate), ether carboxylates (for example sodium laureth-3- carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide
(predominately di-esters), for example the reaction between lauryl alcohol and
tetraphosphoric acid; additionally these products may be ethoxylated), sulfosuccinamates, paraffin or olefine sulfonates, taurates and lignosulfonates.
Suitable SFAs of the amphoteric type include betaines, propionates and glycinates. Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
A compound of formula (I) may be applied by any of the known means of applying pesticidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or
incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.
The compounds of formula (I) or compositions, comprising a compound of formula (I) as active ingredient and an inert carrier, can be applied to the locus of the plant or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation. A preferred method of applying a compound of formula (I), or a composition, comprising a compound of formula (I) as active ingredient and an inert carrier, is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen. However, the compounds of formula (I) can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula (I) may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
A formulation, i.e. a composition comprising the compound of formula (I) and, if desired, a solid or liquid adjuvant, is prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface-active compounds (surfactants).
The agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula (I), 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.
Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.
Advantageous rates of application are normally from 5g to 2kg of active ingredient
(a.i.) per hectare (ha), preferably from lOg to 1kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient rates of application are from lOmg to lg of active substance per kg of seeds. The rate of application for the desired action can be determined by experiments. It depends for example on the type of action, the developmental stage of the useful plant, and on the application (location, timing, application method) and can, owing to these parameters, vary within wide limits. A compound of formula (I) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use. These concentrates, which may include DCs, SCs, ECs, EWs, MEs, SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
A compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers). Suitable formulation types include granules of fertiliser. The mixtures preferably contain up to 25% by weight of the compound of formula (I).
The invention therefore also provides a fertiliser composition comprising a fertiliser and a compound of formula (I).
The compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.
The compounds of formula (I), or a pharmaceutical salt thereof, described above may also have an advantageous spectrum of activity for the treatment and/or prevention of microbial infection in an animal. "Animal" can be any animal, for example, insect, mammal, reptile, fish, amphibian, preferably mammal, most preferably human. "Treatment" means the use on an animal which has microbial infection in order to reduce or slow or stop the increase or spread of the infection, or to reduce the infection or to cure the infection. "Prevention" means the use on an animal which has no apparent signs of microbial infection in order to prevent any future infection, or to reduce or slow the increase or spread of any future infection.
According to the present invention there is provided the use of a compound of formula (I) in the manufacture of a medicament for use in the treatment and/or prevention of microbial infection in an animal. There is also provided the use of a compound of formula (I) as a pharmaceutical agent. There is also provided the use of a compound of formula (I) as an antimicrobial agent in the treatment of an animal. According to the present invention there is also provided a pharmaceutical composition comprising as an active ingredient a compound of formula (I), or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable diluent or carrier. This composition can be used for the treatment and/or prevention of antimicrobial infection in an animal. This pharmaceutical composition can be in a form suitable for oral administration, such as tablet, lozenges, hard capsules, aqueous suspensions, oily suspensions, emulsions dispersible powders, dispersible granules, syrups and elixirs. Alternatively this pharmaceutical composition can be in a form suitable for topical application, such as a spray, a cream or lotion. Alternatively this pharmaceutical composition can be in a form suitable for parenteral administration, for example injection. Alternatively this pharmaceutical composition can be in inhalable form, such as an aerosol spray.
The compounds of formula (I) may be effective against various microbial species able to cause a microbial infection in an animal. Examples of such microbial species are those causing brown rust such as Puccinia recondita, those that are causing leaf blotch such as Septoria tritici, those that are causing gray mould such as Botrytis cinerea, those causing Aspergillosis such as Aspergillus fumigatus, A. flavus, A. terrus, A. nidulans and niger; those causing Blastomycosis such as Blastomyces dermatitidis; those causing Candidiasis such as Candida albicans, C. glabrata, C. tropicalis, C. parapsilosis, C. krusei and C.
lusitaniae; those causing Coccidioidomycosis such as Coccidioides immitis; those causing Cryptococcosis such as Cryptococcus neoformans; those causing Histoplasmosis such as Histoplasma capsulatum and those causing Zygomycosis such as Absidia corymbifera, Rhizomucor pusillus and Rhizopus arrhizus. Further examples are Fusarium Spp such as Fusarium oxysporum and Fusarium solani and Scedosporium Spp such as Scedosporium apiospermum and Scedosporium proliflcans. Still further examples are Microsporum Spp, Trichophyton Spp, Epidermophyton Spp, Mucor Spp, Sporothorix Spp, Phialophora Spp, Cladosporium Spp, Petriellidium spp, Paracoccidioides Spp and Histoplasma Spp.
It has been found that the use of a further, other compound or compositions (e.g. a further, other biocidally active ingredients or compositions) in combination with the compound of formula (I) surprisingly and substantially enhance the effectiveness of the latter against fungi, and vice versa. Additionally, the method of the invention is effective against a wider spectrum of such fungi that can be combated with the active ingredients of this method, when used solely.
The method of the invention comprises applying to the useful plants, the locus thereof or propagation material thereof in admixture or separately, a synergistically effective aggregate amount of a compound of formula (I) and a further, other compound or compositions (e.g. a further, other biocidally active ingredients or compositions).
Some of said combinations according to the invention have a systemic action and can be used as foliar, soil and seed treatment fungicides.
With the combinations according to the invention it is possible to inhibit or destroy the phytopathogenic microorganisms which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different useful plants, while at the same time the parts of plants which grow later are also protected from attack by phytopathogenic microorganisms.
The combinations of the present invention are of particular interest for controlling a large number of fungi in various useful plants or their seeds, especially in field crops such as potatoes, tobacco and sugarbeets, and wheat, rye, barley, oats, rice, maize, lawns, cotton, soybeans, oil seed rape, pulse crops, sunflower, coffee, sugarcane, fruit and ornamentals in horticulture and viticulture, in vegetables such as cucumbers, beans and cucurbits. However, besides the actual synergistic action with respect to fungicidal activity, the compositions according to the invention can also have further surprising advantageous properties. Examples of such advantageous properties that may be mentioned are: more advantageuos degradability; improved toxicological and/or ecotoxicological behaviour; or improved characteristics of the useful plants including: emergence, crop yields, more developed root system, tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf colour, less fertilizers needed, less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, improved plant vigor, and early germination. Some compositions according to the invention have a systemic action and can be
used as foliar, soil and seed treatment fungicides. The compound of formula I (herein after abbreviated by the term "TX" thus means a compound encompassed by the compounds of formula I, or preferably the term "TX" refers to a compound selected from the Tables 1 and 2 and Tables TA01.01 to TA09.11 and Tables TB01.01 to TB01.11) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide (insect, acarine, mollusc and nematode pesticide), fungicide, synergist, herbicide, safener or plant growth regulator where appropriate. The activity of the compositions according to the invention may thereby be broadened considerably and may have surprising advantages which can also be described, in a wider sense, as synergistic activity. An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; provide a composition demonstrating better plant/crop tolerance by reducing phytotoxicity; provide a composition controlling insects in their different development stages; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the TX; or help to overcome or prevent the
development of resistance to individual components. The particular additional active ingredient will depend upon the intended utility of the composition. Examples of suitable pesticides include the following:
a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or
5-benzyl-3-furylmethyl-(E)-(lR,3S)-2,2-dimethyl- 3-(2-oxothiolan-3-ylidenemethyl)cyclopr opane carboxylate;
b) Organophosphates, such as, profenofos, sulprofos, acephate, methyl parathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl,
pirimiphos-ethyl, fenitrothion, fosthiazate or diazinon; c) Carbamates (including aryl carbamates), such as pirimicarb, triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur, methomyl or oxamyl;
d) Benzoyl ureas, such as diflubenzuron, triflumuron, hexaflumuron, flufenoxuron or chlorfluazuron;
e) Organic tin compounds, such as cyhexatin, fenbutatin oxide or azocyclotin;
f) Pyrazoles, such as tebufenpyrad and fenpyroximate;
g) Macrolides, such as avermectins or milbemycins, for example abamectin, emamectin benzoate, ivermectin, milbemycin, or spinosad, spinetoram or azadirachtin;
h) Hormones or pheromones;
i) Organochlorine compounds such as endosulfan, benzene hexachloride, DDT, chlordane or dieldrin;
j) Amidines, such as chlordimeform or amitraz;
k) Fumigant agents, such as chloropicrin, dichloropropane, methyl bromide or metam;
1) Neonicotinoid compounds such as imidacloprid, thiacloprid, acetamiprid, clothianidin, nitenpyram, dinotefuran or thiamethoxam;
m) Diacylhydrazines, such as tebufenozide, chromafenozide or methoxyfenozide;
n) Diphenyl ethers, such as diofenolan or pyriproxifen;
o) Indoxacarb;
p) Chlorfenapyr;
q) Pymetrozine or pyrifluquinazon;
r) Spirotetramat, spirodiclofen or spiromesifen;
s) Flubendiamide, chloranthraliniprole, or cyanthraniliprole;
t) Cyenopyrafen or cyflumetofen; or
u) Sulfoxaflor.
In addition to the major chemical classes of pesticide listed above, other pesticides having particular targets may be employed in the composition, if appropriate for the intended utility of the composition. For instance, selective insecticides for particular crops, for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed. Alternatively insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron). The following mixtures of the compounds of formula I with active ingredients are preferred, wherein, preferably, the term "TX" refers to a compound covered by the compounds of formula I or preferably the term "TX" refers to a compound selected from the Tables 1 to 12, A, B and C and the following List shows specific examples of mixtures comprising thecomponent TX and the component (B):
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 l,l-bis(4-chlorophenyl)-2- ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate
(IUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro-N-methyl-N-l-naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981) + TX, abamectin (1) + TX, acequinocyl (3) + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidithion (870) + TX, amidoflumet [CCN] + TX, amidothioate (872) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, aramite (881) + TX, arsenous oxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos- ethyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (IUPAC name) (888) + TX, azocyclotin (46) + TX, azothoate (889) + TX, benomyl (62) + TX, benoxafos (alternative name) [CCN] + TX, benzoximate (71) + TX, benzyl benzoate (IUPAC name) [CCN] + TX, bifenazate (74) + TX, bifenthrin (76) + TX, binapacryl (907) + TX, brofenvalerate
(alternative name) + TX, bromocyclen (918) + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bromopropylate (94) + TX, buprofezin (99) + TX, butocarboxim (103) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, calcium poly sulfide (IUPAC name) (111) + TX, camphechlor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbophenothion (947) + TX, CGA 50'439
(development code) (125) + TX, chinomethionat (126) + TX, chlorbenside (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorfenethol (968) + TX, chlorfenson (970) + TX, chlorfensulphide (971) + TX, chlorfenvinphos (131) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, cinerin I (696) + TX, cinerin 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. No. : 400882-07-7) + TX, cyhalothrin (196) + TX, cyhexatin (199) + TX, cypermethrin (201) + TX, DCPM (1032) + TX, DDT (219) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton- methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton- S-methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diazinon (227) + TX, dichlofluanid (230) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicofol (242) + TX, dicrotophos (243) + TX, dienochlor (1071) + TX, dimefox (1081) + TX, dimethoate (262) + TX, dinactin (alternative name) (653) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinobuton (269) + TX, dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinocton (1090) + TX, dinopenton (1092) + TX, dinosulfon (1097) + TX, dinoterbon (1098) + TX, dioxathion (1102) + TX, diphenyl sulfone (IUPAC name) (1103) + TX, disulfiram (alternative name) [CCN] + TX, disulfoton (278) + TX, DNOC (282) + TX, dofenapyn (1113) + TX, doramectin (alternative name) [CCN] + TX, endosulfan (294) + TX, endothion (1121) + TX, EPN (297) + TX, eprinomectin (alternative name) [CCN] + TX, ethion (309) + TX, ethoate-methyl (1134) + TX, etoxazole (320) + TX, etrimfos (1142) + TX, fenazaflor (1 147) + TX, fenazaquin (328) + TX, fenbutatin oxide (330) + TX, fenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fen- pyroximate (345) + TX, fenson (1157) + TX, fentrifanil (1161) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacrypyrim (360) + TX, fluazuron (1166) + TX, flubenzimine (1167) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1174) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1192) + TX, formparanate (1193) + TX, gamma-HCH (430) + TX, glyodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecyl cyclopropanecarboxylate (IUPAC/Chemical Abstracts name) (1216) + TX, hexythiazox (441) + TX, iodomethane (IUPAC name) (542) + TX, isocarbophos (alternative name) (473) + TX, isopropyl 0-(methoxyaminothiophosphoiyl)salicylate (IUPAC 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, methomyl (531) + TX, methyl bromide (537) + TX, metolcarb (550) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naled (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, nifluridide (1309) + TX, nikkomycins (alternative name) [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb 1 : 1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, phenkapton (1330) + TX, phenthoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosphamidon (639) + TX, phoxim (642) + TX, pirimiphos-methyl (652) + TX, polychloroterpenes (traditional name) (1347) + TX, polynactins (alternative name) (653) + TX, proclonol (1350) + TX, profenofos (662) + TX, promacyl (1354) + TX, propargite (671) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridaphenthion (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinalphos (711) + TX, quintiofos (1381) + TX, R-1492 (development code) (1382) + TX, RA-17 (development code) (1383) + TX, rotenone (722) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, sophamide (1402) + TX, spirodiclofen (738) + TX, spiromesifen (739) + TX, SSI- 121 (development code) (1404) + TX, sulfiram (alternative name) [CCN] + TX, sulfluramid (750) + TX, sulfotep (753) + TX, 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, vaniliprole [CCN] and YI-5302 (compound code) + TX,
an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and
triphenyltin hydroxide (IUPAC name) (347) + TX,
an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, cruf ornate (1011) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,
an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX,
a bactericide selected from the group of substances consisting of 1 -hydroxy- lH-pyridine-2- thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicin (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxy quinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal (alternative name) [CCN] + TX,
a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis
(alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide
(scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla cornea (alternative name) (151) + TX, Cryptolaemus montrouzieri (alternative name) (178) + TX, Cydia pomonella GV (alternative name) (191) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (alternative name) (300) + TX, Helicoverpa zea NPV (alternative name) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433) + TX, Hippodamia convergens (alternative name) (442) + TX, Leptomastix dactylopii (alternative name) (488) + TX, Macrolophus caliginosus (alternative name) (491) + TX, Mamestra brassicae NPV (alternative name) (494) + TX, Metaphycus helvolus (alternative name) (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575) + TX, Orius spp. (alternative name) (596) + TX, Paecilomyces fumosoroseus (alternative name) (613) + TX, Phytoseiulus persimilis (alternative name) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis (alternative name) (742) + TX, Steinernema carpocapsae (alternative name) (742) + TX, Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX,
Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX,
a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX, a chemostenlant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and uredepa (alternative name) [CCN] + TX,
an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-l-yl acetate with (£)-dec-5-en-l-ol (IUPAC name) (222) + TX, (£)-tridec-4-en-l-yl acetate (IUPAC name) (829) + TX, (£)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)- tetradeca-4, 10-dien-l-yl acetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-l-yl acetate (IUPAC name) (285) + TX, (Z)-hexadec-l 1-enal (IUPAC name) (436) + TX, (Z)-hexadec- 11-en-l-yl acetate (IUPAC name) (437) + TX, (Z)-hexadec-13-en-l 1-yn-l-yl acetate
(IUPAC name) (438) + TX, (Z)-icos-13-en-10-one (IUPAC name) (448) + TX, (Z)-tetradec- 7-en-l-al (IUPAC name) (782) + TX, (Z)-tetradec-9-en-l-ol (IUPAC name) (783) + TX, (Z)- tetradec-9-en-l-yl acetate (IUPAC name) (784) + TX, (7£,9Z)-dodeca-7,9-dien-l-yl acetate (IUPAC name) (283) + TX, (9Z,1 l£)-tetradeca-9, 11-dien-l-yl acetate (IUPAC name) (780) + TX, (9Z, 12£)-tetradeca-9, 12-dien-l-yl acetate (IUPAC name) (781) + TX, 14- methyloctadec-l-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol with 4-methylnonan- 5-one (IUPAC name) (544) + TX, alpha-multistriatin (alternative name) [CCN] + TX, brevicomin (alternative name) [CCN] + TX, codlelure (alternative name) [CCN] + TX, codlemone (alternative name) (167) + TX, cuelure (alternative name) (179) + TX, disparlure (277) + TX, dodec-8-en-l-yl acetate (IUPAC name) (286) + TX, dodec-9-en-l-yl acetate (IUPAC name) (287) + TX, dodeca-8 + TX, 10-dien-l-yl acetate (IUPAC name) (284) + TX, dominicalure (alternative name) [CCN] + TX, ethyl 4-methyloctanoate (IUPAC name) (317) + TX, eugenol (alternative name) [CCN] + TX, frontalin (alternative name) [CCN] + TX, gossyplure (alternative name) (420) + TX, grandlure (421) + TX, grandlure I (alternative name) (421) + TX, grandlure II (alternative name) (421) + TX, grandlure III (alternative name) (421) + TX, grandlure IV (alternative name) (421) + TX, hexalure [CCN] + TX, ipsdienol (alternative name) [CCN] + TX, ipsenol (alternative name) [CCN] + TX, japonilure (alternative name) (481) + TX, lineatin (alternative name) [CCN] + TX, litlure (alternative name) [CCN] + TX, looplure (alternative name) [CCN] + TX, medlure [CCN] + TX, megatomoic acid (alternative name) [CCN] + TX, methyl eugenol (alternative name) (540) + TX, muscalure (563) + TX, octadeca-2, 13-dien-l-yl acetate (IUPAC name) (588) + TX, octadeca-3, 13-dien-l-yl acetate (IUPAC name) (589) + TX, orfralure (alternative name) [CCN] + TX, oryctalure (alternative name) (317) + TX, ostramone (alternative name) [CCN] + TX, siglure [CCN] + TX, sordidin (alternative name) (736) + TX, sulcatol (alternative name) [CCN] + TX, tetradec-11-en-l-yl acetate (IUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure Bi (alternative name) (839) + TX, trimedlure B2 (alternative name) (839) + TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN] + TX,
an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,
an insecticide selected from the group of substances consisting of 1-dichloro-l-nitroethane (IUPAC/Chemical Abstracts name) (1058) + TX, l, l-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), + TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1- bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-l- (3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX, 2,2-dichlorovinyl 2- ethylsulphinylethyl methyl phosphate (IUPAC name) (1066) + TX, 2-(l,3-dithiolan-2- yl)phenyl dimethylcarbamate (IUPAC/ Chemical Abstracts name) (1109) + TX, 2-(2- butoxyethoxy)ethyl thiocyanate (IUPAC/Chemical Abstracts name) (935) + TX, 2-(4,5- dimethyl-l,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/ Chemical Abstracts name) (1084) + TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984) + TX, 2-imidazolidone (IUPAC name) (1225) + TX, 2-isovalerylindan-l,3-dione (IUPAC name) (1246) + TX, 2-methyl(prop-2- ynyl)aminophenyl methylcarbamate (IUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-l-chloroprop-l-ene (IUPAC name) (917) + TX, 3- methyl-l-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283) + TX, 4- methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name) (1285) + TX, 5,5- dimethyl-3-oxocyclohex-l-enyl dimethylcarbamate (IUPAC name) (1085) + TX, abamectin (1) + TX, acephate (2) + TX, acetamiprid (4) + TX, acethion (alternative name) [CCN] + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, acrylonitrile (IUPAC name) (861) + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, aldrin (864) + TX, allethrin (17) + TX, allosamidin (alternative name) [CCN] + TX, allyxycarb (866) + TX, alpha-cypermethrin (202) + TX, alpha-ecdysone (alternative name) [CCN] + TX, aluminium phosphide (640) + TX, amidithion (870) + TX, amidothioate (872) + TX, aminocarb (873) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, anabasine (877) + TX, athidathion (883) + TX, AVI 382 (compound code) + TX, AZ 60541
(compound code) + TX, azadirachtin (alternative name) (41) + TX, azamethiphos (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azothoate (889) + TX, Bacillus thuringiensis delta endotoxins (alternative name) (52) + TX, barium hexafluorosilicate (alternative name) [CCN] + TX, barium polysulfide (IUPAC/Chemical Abstracts name) (892) + TX, barthrin [CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bendiocarb (58) + TX, benfuracarb (60) + TX, bensultap (66) + TX, beta-cyfluthrin (194) + TX, beta-cypermethrin (203) + TX, bifenthrin (76) + TX, bioallethrin (78) + TX, bioallethrin ^-cyclopentenyl isomer (alternative name) (79) + TX, bioethanomethrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX, bis(2-chloroethyl) ether (IUPAC name) (909) + TX, bistrifluron (83) + TX, borax (86) + TX, brofenvalerate (alternative name) + TX, bromfenvinfos (914) + TX, bromocyclen (918) + TX, bromo-DDT (alternative name) [CCN] + TX, bromophos (920) + TX, bromophos- ethyl (921) + TX, bufencarb (924) + TX, buprofezin (99) + TX, butacarb (926) + TX, butathiofos (927) + TX, butocarboxim (103) + TX, butonate (932) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (IUPAC name) (111) + TX, camphechlor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbon disulfide (IUPAC/Chemical Abstracts name) (945) + TX, carbon tetrachloride (IUPAC name) (946) + TX, carbophenothion (947) + TX, carbosulfan (119) + TX, cartap (123) + TX, cartap hydrochloride (123) + TX, cevadine (alternative name) (725) + TX, chlorbicyclen (960) + TX, chlordane (128) + TX, chlordecone (963) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorethoxyfos (129) + TX, chlorfenapyr (130) + TX, chlorfenvinphos (131) + TX, chlorfluazuron (132) + TX, chlormephos (136) + TX, chloroform [CCN] + TX, chloropicrin (141) + TX, chlorphoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos- methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, cis-resmethrin (alternative name) + TX, cismethrin (80) + TX, clocythrin (alternative name) + TX, cloethocarb (999) + TX, closantel (alternative name) [CCN] + TX, clothianidin (165) + TX, copper acetoarsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, coumithoate (1006) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, crufomate (1011) + TX, cryolite (alternative name) (177) + TX, CS 708 (development code) (1012) + TX, cyanofenphos (1019) + TX, cyanophos (184) + TX, cyanthoate (1020) + TX, cyclethrin [CCN] + TX, cycloprothrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201) + TX, cyphenothrin (206) + TX, cyromazine (209) + TX, cythioate (alternative name) [CCN] + TX, <i-limonene (alternative name) [CCN] + TX, d- tetramethrin (alternative name) (788) + TX, DAEP (1031) + TX, dazomet (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, deltamethrin (223) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton- methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton- S-methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diamidafos (1044) + TX, diazinon (227) + TX, dicapthon (1050) + TX, dichlofenthion (1051) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicresyl (alternative name) [CCN] + TX, dicrotophos (243) + TX, dicyclanil (244) + TX, dieldrin (1070) + TX, diethyl 5-methylpyrazol-3-yl phosphate
(IUPAC name) (1076) + TX, diflubenzuron (250) + TX, dilor (alternative name) [CCN] + TX, dimefluthrin [CCN] + TX, dimefox (1081) + TX, dimetan (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinphos (265) + TX, dimetilan (1086) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinoprop (1093) + TX, dinosam (1094) + TX, dinoseb (1095) + TX, dinotefuran (271) + TX, diofenolan (1099) + TX, dioxabenzofos (1100) + TX, dioxacarb (1101) + TX, dioxathion (1102) + TX, disulfoton (278) + TX, dithicrofos (1108) + TX, DNOC (282) + TX, doramectin (alternative name) [CCN] + TX, DSP (1115) + TX, ecdysterone (alternative name) [CCN] + TX, EI 1642 (development code) (1118) + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, EMPC (1120) + TX, empenthrin (292) + TX, endosulfan (294) + TX, endothion (1121) + TX, endrin (1122) + TX, EPBP (1123) + TX, EPN (297) + TX, epofenonane (1124) + TX, eprinomectin
(alternative name) [CCN] + TX, esfenvalerate (302) + TX, etaphos (alternative name) [CCN] + TX, ethiofencarb (308) + TX, ethion (309) + TX, ethiprole (310) + TX, ethoate-methyl (1134) + TX, ethoprophos (312) + TX, ethyl formate (IUPAC name) [CCN] + TX, ethyl- DDD (alternative name) (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1136) + TX, ethylene oxide [CCN] + TX, etofenprox (319) + TX, etrimfos (1142) + TX, EXD (1143) + TX, famphur (323) + TX, fenamiphos (326) + TX, fenazaflor (1147) + TX, fenchlorphos (1148) + TX, fenethacarb (1149) + TX, fenfluthrin (1150) + TX, fenitrothion (335) + TX, fenobucarb (336) + TX, fenoxacrim (1153) + TX, fenoxycarb (340) + TX, fenpirithrin (1155) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fensulfothion (1158) + TX, fenthion (346) + TX, fenthion-ethyl [CCN] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonicamid (358) + TX, flubendiamide (CAS. Reg. No.: 272451-65-7) + TX, flucofuron (1168) + TX, flucycloxuron (366) + TX, flucythnnate (367) + TX, fluenetil (1169) + TX, flufenerim [CCN] + TX, flufenoxuron (370) + TX, flufenprox (1171) + TX, flumethrin (372) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, fonofos (1191) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1192) + TX, formparanate (1193) + TX, fosmethilan (1194) + TX, fospirate (1195) + TX, fosthiazate (408) + TX, fosthietan (1196) + TX, furathiocarb (412) + TX, furethrin (1200) + TX, gamma-cyhalothrin (197) + TX, gamma-HCH (430) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, GY-81 (development code) (423) + TX, halfenprox (424) + TX, halofenozide (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptachlor (1211) + TX, heptenophos (432) + TX, heterophos [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydramethylnon (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX, hyquincarb (1223) + TX, imidacloprid (458) + TX, imiprothrin (460) + TX, indoxacarb (465) + TX, iodom ethane (IUPAC name) (542) + TX, IPSP (1229) + TX, isazofos (1231) + TX, isobenzan (1232) + TX, isocarbophos (alternative name) (473) + TX, isodrin (1235) + TX, isofenphos (1236) + TX, isolane (1237) + TX, isoprocarb (472) + TX, isopropyl O-(methoxy- aminothiophosphoryl)salicylate (IUPAC name) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxathion (480) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, juvenile hormone I (alternative name) [CCN] + TX, juvenile hormone II (alternative name) [CCN] + TX, juvenile hormone III (alternative name) [CCN] + TX, kelevan (1249) + TX, kinoprene (484) + TX, lambda-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin (CCN) + TX, leptophos (1250) + TX, lindane (430) + TX, lirimfos (1251) + TX, lufenuron (490) + TX, lythidathion (1253) + TX, w-cumenyl methylcarbamate (IUPAC name) (1014) + TX, magnesium phosphide (IUPAC name) (640) + TX, malathion (492) + TX, malonoben (1254) + TX, mazidox (1255) + TX, mecarbam (502) + TX, mecarphon (1258) + TX, menazon (1260) + TX, mephosfolan (1261) + TX, mercurous chloride (513) + TX, mesulfenfos (1263) + TX, metaflumizone (CCN) + TX, metam (519) + TX, metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methanesulphonyl fluoride (IUPAC/Chemical Abstracts name) (1268) + TX, methidathion (529) + TX, methiocarb (530) + TX, methocrotophos (1273) + TX, methomyl (531) + TX, methoprene (532) + TX, methoquin-butyl (1276) + TX, methothrin (alternative name) (533) + TX, methoxychlor (534) + TX, methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methylchloroform (alternative name) [CCN] + TX, methylene chloride [CCN] + TX, metofluthrin [CCN] + TX, metolcarb (550) + TX, metoxadiazone (1288) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX,
milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naftalofos (alternative name) [CCN] + TX, naled (567) + TX, naphthalene (IUPAC/Chemical Abstracts name) (1303) + TX, NC-170 (development code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifluridide (1309) + TX, nitenpyram (579) + TX, nithiazine (1311) + TX, nitrilacarb (1313) + TX, nitrilacarb 1 : 1 zinc chloride complex (1313) + TX, NI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nornicotine
(traditional name) (1319) + TX, novaluron (585) + TX, noviflumuron (586) + TX, 0-5- dichloro-4-iodophenyl O-ethyl ethylphosphonothioate (IUPAC name) (1057) + TX, Ο,Ο- di ethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name) (1074) + TX, 0,0-di ethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate (IUPAC name) (1075) + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate (IUPAC name) (1424) + TX, oleic acid (IUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydemeton-methyl (609) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, para-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-m ethyl (616) + TX, penfluron (alternative name) [CCN] + TX, pentachlorophenol (623) + TX,
pentachlorophenyl laurate (IUPAC name) (623) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, PH 60-38 (development code) (1328) + TX, phenkapton (1330) + TX, phenothrin (630) + TX, phenthoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosnichlor (1339) + TX, phosphamidon (639) + TX, phosphine (IUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, pirimetaphos (1344) + TX, pirimicarb (651) + TX, pirimiphos- ethyl (1345) + TX, pirimiphos-methyl (652) + TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346) + TX, polychloroterpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, prallethrin (655) + TX, precocene I (alternative name) [CCN] + TX, precocene II (alternative name) [CCN] + TX, precocene III (alternative name) [CCN] + TX, primidophos (1349) + TX, profenofos (662) + TX, profluthrin [CCN] + TX, promacyl (1354) + TX, promecarb (1355) + TX, propaphos (1356) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothiofos (686) + TX, prothoate (1362) + TX, protrifenbute [CCN] + TX, pymetrozine (688) + TX, pyraclofos (689) + TX, pyrazophos (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridalyl (700) + TX, pyridaphenthion (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, pyriproxyfen (708) + TX, quassia (alternative name) [CCN] + TX, quinalphos (711) + TX, quinalphos-methyl (1376) + TX, quinothion (1380) + TX, quintiofos (1381) + TX, R-1492 (development code) (1382) + TX, rafoxanide (alternative name) [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (development code) (723) + TX, RU 25475 (development code) (1386) + TX, ryania (alternative name) (1387) + TX, ryanodine (traditional name) (1387) + TX, sabadilla (alternative name) (725) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenoxide (623) + TX, sodium selenate (IUPAC name) (1401) + TX, sodium thiocyanate [CCN] + TX, sophamide (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spirotetrmat (CCN) + TX, sulcofuron (746) + TX, sulcofuron- sodium (746) + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulphuryl fluoride (756) + TX, sulprofos (1408) + TX, tar oils (alternative name) (758) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, tebupirimfos (764) + TX, teflubenzuron (768) + TX, tefluthrin (769) + TX, temephos (770) + TX, TEPP (1417) + TX, terallethrin (1418) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachloroethane [CCN] + TX, tetrachlorvinphos (777) + TX, tetramethrin (787) + TX, theta-cypermethrin (204) + TX, thiacloprid (791) + TX, thiafenox (alternative name) + TX, thiamethoxam (792) + TX, thicrofos (1428) + TX, thiocarboxime (1431) + TX, thiocyclam (798) + TX, thiocyclam hydrogen oxalate (798) + TX, thiodicarb (799) + TX, thiofanox (800) + TX, thiometon (801) + TX, thionazin (1434) + TX, thiosultap (803) + TX, thiosultap-sodium (803) + TX, thuringiensin (alternative name) [CCN] + TX, tolfenpyrad (809) + TX, tralomethrin (812) + TX, transfluthrin (813) + TX, transpermethrin (1440) + TX, triamiphos (1441) + TX, triazamate (818) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trichlormetaphos-3 (alternative name) [CCN] + TX, trichloronat (1452) + TX, trifenofos (1455) + TX, triflumuron (835) + TX, trimethacarb (840) + TX, triprene (1459) + TX, vamidothion (847) + TX, vaniliprole [CCN] + TX, veratridine (alternative name) (725) + TX, veratrine
(alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302
(compound code) + TX, zeta-cypermethrin (205) + TX, zetamethrin (alternative name) + TX, zinc phosphide (640) + TX, zolaprofos (1469) and ZXI 8901 (development code) (858) + TX, cyantraniliprole [736994-63-19] + TX, chlorantraniliprole [500008-45-7] + TX, cyenopyrafen [560121-52-0] + TX, cyflumetofen [400882-07-7] + TX, pyrifluquinazon [337458-27-2] + TX, spinetoram [187166-40-1 + 187166-15-0] + TX, spirotetramat
[203313-25-1] + TX, sulfoxaflor [946578-00-3] + TX, flufiprole [704886-18-0] + TX, meperfluthrin [915288-13-0] + TX, tetramethylfluthrin [84937-88-2] + TX,
a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, trifenmorph (1454) + TX, trimethacarb (840) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, pyriprole [394730-71-3] + TX,
a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, l,2-dibromo-3-chloropropane (IUPAC/Chemical Abstracts name) (1045) + TX, 1,2-dichloropropane (IUPAC/ Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4- dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstracts name) (1065) + TX, 3- (4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-l,3,5- thiadiazinan-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine
(alternative name) (210) + TX, abamectin (1) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, cloethocarb (999) + TX, cytokinins (alternative name) (210) + TX, dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dichlofenthion (1051) + TX, dicliphos (alternative name) + TX, dimethoate (262) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alternative name) + TX, fensulfothion (1158) + TX, fosthiazate (408) + TX, fosthietan (1196) + TX, furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidofos (1230) + TX, isazofos (1231) + TX, ivermectin (alternative name) [CCN] + TX, kinetin (alternative name) (210) + TX, mecarphon (1258) + TX, metam (519) + TX, metam- potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, Myrothecium verrucaria composition
(alternative name) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphocarb [CCN] + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachlorothiophene (IUPAC/ Chemical Abstracts name) (1422) + TX, thiafenox (alternative name) + TX, thionazin (1434) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternative name) (210) + TX, fluensulfone [318290-98-1] + TX,
a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,
a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-^-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-l,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumachlor (1004) + TX, coumafuryl (1005) + TX, coumatetralyl (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, difethialone (249) + TX, diphacinone (273) + TX, ergocalciferol (301) + TX, flocoumafen (357) + TX, fluoroacetamide (379) + TX, flupropadine (1183) + TX, flupropadine hydrochloride (1183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, norbormide (1318) + TX, phosacetim (1336) + TX, phosphine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371) + TX, scilliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and zinc phosphide (640) + TX,
a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(l,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX, an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX,
a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX,
a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX, and biologically active compounds selected from the group consisting of azaconazole (60207-31-0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [116255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [119446-68-3] + TX, diniconazole
[83657-24-3] + TX, epoxiconazole [106325-08-0] + TX, fenbuconazole [114369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674- 21-0] + TX, hexaconazole [79983-71-4] + TX, imazalil [35554-44-0] + TX, imibenconazole [86598-92-7] + TX, ipconazole [125225-28-7] + TX, metconazole [125116-23-6] + TX, myclobutanil [88671-89-0] + TX, pefurazoate [101903-30-4] + TX, penconazole [66246-88- 6] + TX, prothioconazole [178928-70-6] + TX, pyrifenox [88283-41-4] + TX, prochloraz [67747-09-5] + TX, propiconazole [60207-90-1] + TX, simeconazole [149508-90-7] + TX, tebuconazole [107534-96-3] + TX, tetraconazole [112281-77-3] + TX, triadimefon [43121- 43-3] + TX, triadimenol [55219-65-3] + TX, triflumizole [99387-89-0] + TX, triticonazole [131983-72-7] + TX, ancymidol [12771-68-5] + TX, fenarimol [60168-88-9] + TX, nuarimol [63284-71-9] + TX, bupirimate [41483-43-6] + TX, dimethirimol [5221-53-4] + TX, ethinmol [23947-60-6] + TX, dodemorph [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564-91-4] + TX, spiroxamine [118134-30-8] + TX, tridemorph [81412-43-3] + TX, cyprodinil [121552-61-2] + TX, mepanipyrim [110235-47-7] + TX, pyrimethanil [53112-28-0] + TX, fenpiclonil [74738-17-3] + TX, fludioxonil [131341-86-1] + TX, benalaxyl [71626-11-4] + TX, furalaxyl [57646-30-7] + TX, metalaxyl [57837-19-1] + TX, R-metalaxyl [70630-17-0] + TX, ofurace [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21-7] + TX, debacarb [62732-91- 6] + TX, fuberidazole [3878-19-1] + TX, thiabendazole [148-79-8] + TX, chlozolinate
[84332-86-5] + TX, dichlozoline [24201-58-9] + TX, iprodione [36734-19-7] + TX, myclozoline [54864-61-8] + TX, procymidone [32809-16-8] + TX, vinclozoline [50471-44- 8] + TX, boscalid [188425-85-6] + TX, carboxin [5234-68-4] + TX, fenfuram [24691-80-3] + TX, flutolanil [66332-96-5] + TX, mepronil [55814-41-0] + TX, oxycarboxin [5259-88-1] + TX, penthiopyrad [183675-82-3] + TX, thifluzamide [130000-40-7] + TX, guazatine
[108173-90-6] + TX, dodine [2439-10-3] [112-65-2] (free base) + TX, iminoctadine [13516- 27-3] + TX, azoxystrobin [131860-33-8] + TX, dimoxystrobin [149961-52-4] + TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1, 93 } + TX, fluoxastrobin [361377- 29-9] + TX, kresoxim-methyl [143390-89-0] + TX, metominostrobin [133408-50-1] + TX, trifloxystrobin [141517-21-7] + TX, orysastrobin [248593-16-0] + TX, picoxystrobin
[117428-22-5] + TX, pyraclostrobin [175013-18-0] + TX, ferbam [14484-64-1] + TX, mancozeb [8018-01-7] + TX, maneb [12427-38-2] + TX, metiram [9006-42-2] + TX, propineb [12071-83-9] + TX, thiram [137-26-8] + TX, zineb [12122-67-7] + TX, ziram
[137-30-4] + TX, captafol [2425-06-1] + TX, captan [133-06-2] + TX, dichlofluanid [1085- 98-9] + TX, fluoroimide [41205-21-4] + TX, folpet [133-07-3 ] + TX, tolylfluanid [731-27- 1] + TX, bordeaux mixture [8011-63-0] + TX, copperhydroxid [20427-59-2] + TX, copperoxychlorid [1332-40-7] + TX, coppersulfat [7758-98-7] + TX, copperoxid [1317-39- 1] + TX, mancopper [53988-93-5] + TX, oxine-copper [10380-28-6] + TX, dinocap [131-72- 6] + TX, nitrothal-isopropyl [10552-74-6] + TX, edifenphos [17109-49-8] + TX,
iprobenphos [26087-47-8] + TX, isoprothiolane [50512-35-1] + TX, phosdiphen [36519-00- 3] + TX, pyrazophos [13457-18-6] + TX, tolclofos-methyl [57018-04-9] + TX, acibenzolar- S-methyl [135158-54-2] + TX, anilazine [101-05-3] + TX, benthiavalicarb [413615-35-7] + TX, blasticidin-S [2079-00-7] + TX, chinomethionat [2439-01-2] + TX, chloroneb [2675-77- 6] + TX, chlorothalonil [1897-45-6] + TX, cyflufenamid [180409-60-3] + TX, cymoxanil [57966-95-7] + TX, dichlone [117-80-6] + TX, diclocymet [139920-32-4] + TX, diclomezine [62865-36-5] + TX, dicloran [99-30-9] + TX, diethofencarb [87130-20-9] + TX, dimethomorph [110488-70-5] + TX, SYP-LI90 (Flumorph) [211867-47-9] + TX, dithianon [3347-22-6] + TX, ethaboxam [162650-77-3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX, fenamidone [161326-34-7] + TX, fenoxanil [115852- 48-7] + TX, fentin [668-34-8] + TX, ferimzone [89269-64-7] + TX, fluazinam [79622-59-6] + TX, fluopicolide [239110-15-7] + TX, flusulfamide [106917-52-6] + TX, fenhexamid
[126833-17-8] + TX, fosetyl-aluminium [39148-24-8] + TX, hymexazol [10004-44-1] + TX, iprovalicarb [140923-17-7] + TX, D F-916 (Cyazofamid) [120116-88-3] + TX,
kasugamycin [6980-18-3] + TX, methasulfocarb [66952-49-6] + TX, metrafenone [220899- 03-6] + TX, pencycuron [66063-05-6] + TX, phthalide [27355-22-2] + TX, polyoxins
[11113-80-7] + TX, probenazole [27605-76-1] + TX, propamocarb [25606-41-1] + TX, proquinazid [189278-12-4] + TX, pyroquilon [57369-32-1] + TX, quinoxyfen [124495-18-7] + TX, quintozene [82-68-8] + TX, sulphur [7704-34-9] + TX, tiadinil [223580-51-6] + TX, triazoxide [72459-58-6] + TX, tricyclazole [41814-78-2] + TX, triforine [26644-46-2] + TX, validamycin [37248-47-8] + TX, zoxamide (RH7281) [156052-68-5] + TX, mandipropamid [374726-62-2] + TX, isopyrazam [881685-58-1] + TX, sedaxane [874967-67-6] + TX, 3- difluorom ethyl- 1 -methyl- lH-pyrazole-4-carboxylic acid (9-dichlorom ethylene- 1 ,2,3,4- tetrahydro-l,4-methano-naphthalen-5-yl)-amide (dislosed in WO 2007/048556) + TX, 3- diflu orom ethyl- 1 -methyl- lH-pyrazole-4-carboxylic acid [2-(2,4-dichlorophenyl)-2-methoxy- l-methyl-ethyl]-amide (disclosed in WO 2008/148570) + TX, l-[4-[4-[(5S)5-(2,6- difluorophenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2-yl]piperidin-l-yl]-2-[5-methyl-3- (trifluoromethyl)-lH-pyrazol-l-yl]ethanone + TX, l-[4-[4-[5-(2,6-difluorophenyl)-4,5- dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2-yl]piperidin-l-yl]-2-[5-methyl-3-(trifluoromethyl)- lH-pyrazol-l-yl]ethanone [1003318-67-9], both disclosed in WO 2010/123791, WO
2008/013925, WO 2008/013622 and WO 2011/051243 page 20) +TX, 5)-[3-(4-Chloro-2- fluoro-phenyl)-5 -(2,4-difluoro-phenyl)-isoxazol-4-y l]-pyridin-3-yl-methanol + TX, 3-(4- Chloro-2-fluoro-phenyl)-5 -(2,4-difluoro-phenyl)-isoxazol-4-y l]-pyridin-3-yl-methanol + TX, 3-difluoromethyl-l-methyl-lH-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2- yl)-amide (disclosed in WO 2006/087343) + TX, 3-(difluoromethyl)-N-methoxy-l-methyl- N-[l-methyl-2-(2,4,6-trichlorophenyl)ethyl]-lH-Pyrazole-4-carboxamide + TX, 4-[(55)-5- (3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(thietan-3- yl)benzamide (WO2011/104089) + TX, 4-[(5R)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)- 4H-isoxazol-3-yl]-2-methyl-N-(thietan-3-yl)benzamide (WO2011/104089) + TX, 4-[(55)-5- (3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(cis-l-oxo-thietan- 3-yl)benzamide (WO2011/104089) + TX, 4-[(5R)-5-(3,5-dichlorophenyl)-5- (trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(cis-l-oxo-thietan-3-yl)benzamide
(WO2011/104089) + TX, 4-[(55)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3- yl]-2-methyl-N-(trans-l-oxo-thietan-3-yl)benzamide (WO2011/104089) + TX, 4-[(5R)-5- (3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(trans-l-oxo- thietan-3-yl)benzamide (WO2011/104089) + TX, 4-[(55)-5-(3,5-dichlorophenyl)-5- (trifluoromethyl)-4H-isoxazol-3-yl]-N-(l,l-dioxothietan-3-yl)-2-methyl-benzamide
(WO2011/104089) + TX, 4-[(5R)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3- yl]-N-(l,l-dioxothietan-3-yl)-2-methyl-benzamide (WO2011/104089) + TX, 4-[(55)-5-(3,5- dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-[2-oxo-2-(2,2,2- trifluoroethylamino)ethyl]benzamide (WO2011/104089) + TX, 4-[(5R)-5-(3,5- dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-[2-oxo-2-(2,2,2- trifluoroethylamino)ethyl]benzamide (WO2011/104089) + TX, Penflufen [494793-67-8] and TX, 5-[(5S)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-(l,2,4-triazol-l- yl)benzonitrile (WO2007/075459) + TX, 5-[(5R)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)- 4H-isoxazol-3-yl]-2-(l,2,4-triazol-l-yl)benzonitrile (WO2007/075459) + TX. The components (B) are known. The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet under the internet address http://www.alanwood.net/pesticides/ [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2012]; or preferably one of the further pesticides listed below.
In the above different lists of active ingredients to be mixed with a TX, the compound of the formula I is preferably a compound selected from the Tables 1 and 2 and Tables TA01.01 to TA09.11 and Tables TBOl .Ol to TB01.11; more preferably a compound selected from T1.14, T.124, Tl . l, T1.13, T1.14, T1.15, T1.16, T1.17, T1.2, T1.20, T1.22, T1.23, T1.24, T1.25, T1.28, T1.3, T1.35, T1.42, T1.43, T1.5, T1.6, T1.8, T1.9, T2.1, T2.10, T2.9 In the above-mentioned mixtures of compounds of formula I, in particular a compound selected from said Tables 1 and 2 and Tables TA01.01 to TA09.11 and Tables TBOl .Ol to TBOl . l l, with other insecticides, fungicides, herbicides, safeners, adjuvants and the like, the mixing ratios can vary over a large range and are, preferably 100: 1 to 1 :6000, especially 50: 1 to 1 :50, more especially 20: 1 to 1 :20, even more especially 10: 1 to 1 : 10. Those mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios.
The mixtures comprising a TX selected from Tables 1 and 2 and Tables TA01.01 to TA09.11 and Tables TBOl .Ol to TBOl . l l and one or more active ingredients as described above comprises a compound selected from table P and an active ingredient as described above preferably in a mixing ratio of from 100: 1 to 1 :6000, especially from 50: 1 to 1 :50, more especially in a ratio of from 20: 1 to 1 :20, even more especially from 10: 1 to 1 : 10, very especially from 5: 1 and 1 :5, special preference being given to a ratio of from 2: 1 to 1 :2, and a ratio of from 4: 1 to 2: 1 being likewise preferred, above all in a ratio of 1 : 1, or 5: 1, or 5:2, or 5:3, or 5:4, or 4: 1, or 4:2, or 4:3, or 3 : 1, or 3 :2, or 2: 1, or 1 :5, or 2:5, or 3 :5, or 4:5, or 1 :4, or 2:4, or 3 :4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 : 150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 : 1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750. Those mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios.
The mixtures 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 can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of TX with the mixing partner).
Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.
The mixtures comprising a TX selected from Tables 1 and 2 and Tables TA01.01 to TA09.11 and Tables TB01.01 to TB01.11 and one or more active ingredients as described above can be applied, for example, in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula I selected from Tables 1 and 2 and Tables TA01.01 to TA09.11 and Tables TB01.01 to TB01.11 and the active ingredients as described above is not essential for working the present invention.
The following non-limiting examples illustrate the above-described invention in greater detail without limiting it.
Preparatory examples:
Preparation of ethyl 3-(4-chlorophenyl)-l-oxa-2-azaspiro[4.5]dec-2-ene-4-carboxylate
Figure imgf000061_0001
A solution of (7^-4-chloro-N-hydroxybenzimidoyl chloride (7.60 g; 40 mmol) and ethyl 2- cyclohexylideneacetate (20.19 g; 120 mmol) in z'-PrOH (100 ml) was treated with sodium carbonate (6.72 g; 80 mmol) and the resulting mixture was heated at 60°C for 16 h.
The mixture was quenched with water (100 ml) and diluted with DCM (75 ml). The aqueous layer was extracted with DCM (3x75 ml) and the combined organic layers were dried over Na2S04. The drying agent was filtered off and after concentration, the residue was purified by column chromatography (heptane/ AcOEt = 9/1) to give 9 g of the desired product as a colorless oil (58%).
Preparation of 2-(4-chlorophenyl)-4-oxa-3-azaspiro[4.5]dec-2-en-l-yl]methanol
Figure imgf000062_0001
A solution of ethyl 3-(4-chlorophenyl)-l-oxa-2-azaspiro[4.5]dec-2-ene-4-carboxylate (7.5 g; 23.31 mmol) in dry THF (35 ml) was cooled to 0°C. A THF solution of lithium aluminum hydride (2.4 M; 23.28 mmol; 9.7 ml) was added dropwise over a 15 min. period. The resulting mixture was stirred for 30 min. at 0°C and then quenched with water (3.6 ml) and 2N NaOH (1.2 ml).
After filtration over a plug of Na2S04, the organic layer was concentrated and the residue was purified by column chromatography (heptane/ AcOEt = 4/1) to afford 1.55 g (23%) of 2- (4-chlorophenyl)-4-oxa-3-azaspiro[4.5]dec-2-en-l-yl]methanol.
Preparation of [2-(4-chlorophenyl)-4-oxa-3-azaspiro[4.5]dec-2-en-l-yl]methyl methanesulfonate
Figure imgf000062_0002
To a solution of (3-(4-chlorophenyl)-l-oxa-2-azaspiro[4.5]dec-2-en-4-yl)methanol (1.54 g; 5.5 mmol) and triethylamine (2.3 ml; 16.51 mmol) in dry DCM (25 ml) was added a solution of methanesulfonyl chloride (0.70 g; 6.1 mmol) in dry DCM (5 ml). The mixture was stirred at room temperature for 1 h, diluted with DCM and then successively washed with 0.5N HCl, sat. NaHC03, brine and dried over Na2S04. After filtration and concentration under reduced pressure, the desired product was obtained as a pale yellow solid (1.91 g, 97%). Preparation of 2-(4-chlorophenyl)-l-(l,2,4-triazol-l-ylmethyl)-4-oxa-3- azaspiro[4.5]dec-2-ene and 2-(4-chlorophenyl)-l-methylene-4-oxa-3-azaspiro[4.5]dec-2- ene
Figure imgf000063_0001
To a solution of [2-(4-chlorophenyl)-4-oxa-3-azaspiro[4.5]dec-2-en-l-yl]methyl
methanesulfonate (1.91 g; 5.34 mmol) in DMSO (15 ml) were added lH-l,2,4-triazole (442 mg; 6.40 mmol) and powdered potassium carbonate (1.11 g; 8.01 mmol). The mixture was stirred at room temperature overnight and then diluted with water (125 ml) and extracted with AcOEt (150 ml). The organic layer was washed with brine (2x125 ml), dried over Na2S04, filtered and concentrated in vacuo. The residue was purified by flash column chromatography (heptane/ AcOEt = 8/2). 2-(4-chlorophenyl)-l-(l,2,4-triazol-l-ylmethyl)-4- oxa-3-azaspiro[4.5]dec-2-ene was obtained as white solid (367 mg, 20%, LCMS: [MET^ = 331/333, mp: 113-114°C) together with a major amount of 2-(4-chlorophenyl)-l-methylene- 4-oxa-3-azaspiro[4.5]dec-2-ene (903 mg, 65%).
Preparation of 12-(4-chlorophenyl)-2,10-dioxa-ll-azadispiro[2.0.5A4.3A3]dodec-ll-ene
Figure imgf000063_0002
To a solution of 2-(4-chlorophenyl)-l-methylene-4-oxa-3-azaspiro[4.5]dec-2-ene (0.85 g; 3.25 mmol) in DCM (10 ml) was added w-CPBA (70% in water; 1.20 g; 4.87 mmol) and the mixture was stirred at room temperature for 3 days. The reaction mixture was diluted with DCM (15 ml), washed with sat. NaHC03 (3x25 ml), brine (25 ml), dried over Na2S04, filtered and concentrated under reduced pressure. The residue was purified by flash column chromatography using a mixture of heptane/ AcOEt (95/5). The desired product was obtained as white crystalline solid (652 mg, 72%, LCMS [MH+] = 278/280)
Preparation of 4-((lH-l,2,4-triazol-l-yl)methyl)-3-(4-chlorophenyl)-l-oxa-2- azaspiro [4.5] dec-2-en-4-ol
Figure imgf000064_0001
To an ice-cooled solution of lH-l,2,4-triazole (138 mg; 2.0 mmol) in dry DMF (3 ml) under nitrogen was added NaH (60% in mineral oil; 80 mg; 2.0 mmol) and the mixture was stirred for 15 min. at 0°C. To this mixture, a solution of 12-(4-chlorophenyl)-2, 10-dioxa-l 1- azadispiro[2.0.5A4.3A3]dodec-l 1-ene (278 mg; 1.0 mmol) in dry DMF (1 ml) was added dropwise and the stirring was continued at room temperature for 2 h. The reaction mixture was quenched with water (30 ml) and AcOEt (30 ml). After separation, the organic layer was washed with water (30 ml), brine (30 ml), dried over Na2S04, filtered and concentrated in vacuo. The residue was purified by column chromatography (heptane/ AcOEt = 1/1). The desired product was obtained as a white solid (50 mg, 14%, LCMS [MH+] = 347/349, mp: 220 -22FC). Preparation of [3-(4-chlorophenyl)-5,5-dimethyl-4H-isoxazol-4-yl] methanol
Figure imgf000065_0001
To a solution of 4-chloro-N-hydroxybenzimidoyl chloride (41.2 g; 217 mmol) and 3- methylbut-2-en-l-ol (110 ml; 1.08 mol) in z'-PrOH (650 ml) was added sodium bicarbonate (36.4 g; 433 mmol) and the mixture was heated at 65°C for 6 h. The reaction mixture was concentrated and partitioned between AcOEt (1000 ml) and water (1000 ml). After separation, the organic layers were washed with brine (1000 ml), dried over Na2S04, filtered and concentrated under reduced pressure. The residue was purified by column
chromatography (heptane/ AcOEt = 8/2) affording 23.8 g (46%) of the desired compound as white crystalline solid.
Preparation of 3-(4-chlorophenyl)-5,5-dimethyl-4-methylene-isoxazole
Figure imgf000065_0002
A solution of [3-(4-chlorophenyl)-5,5-dimethyl-4H-isoxazol-4-yl]methanol (45.0 g; 188 mmol) and triethylamine (79 ml; 563 mmol) in dry DCM (700 ml) was cooled at 0°C under nitrogen. To this mixture, a solution of mesyl chloride (23.7 g; 207 mmol) in dry DCM (200 ml) was added drop-wise. After complete addition, the stirring was continued at 0°C for 30 min. before addition of DBU (141 ml; 939 mmol). The resulting mixture was stirred at room temperature overnight and then slowly quenched with 2N HC1 (700 ml). After separation, the organic layer was washed with water (750 ml), sat. aq. NaHC03 (750 ml), brine (750 ml), dried over Na2S04 and filtered. After concentration, the desired compound was obtained as a pale yellow solid (40 g, 97%). Preparation of 4-(4-chlorophenyl)-7,7-dimethyl-2,6-dioxa-5-azaspiro [2.4] hept-4-ene
Figure imgf000066_0001
3-(4-chlorophenyl)-5,5-dimethyl-4-methylene-isoxazole (82.1 g; 0.37 mol) was dissolved in DCM (1000 ml) and w-CPBA (140 g; 0.57 mol) was added portion wise. The mixture was stirred for 4 days at room temperature. The precipitate was filtered off and washed with DCM and the filtrate was cooled in ice and carefully quenched with 0.5 M sodium
metabisulfite (1000 ml). DCM (1000 ml) and water (1000 ml) were added and after separation, the organic layer was washed successively with sat. aq. NaHC03 (2x2000 ml), 0.25 M sodium metabisulfite (2000 ml), brine (2000 ml), dried over Na2S04, filtered and then concentrated in vacuo. The residue was recrystallised from heptane obtaining 71.6 g (81%) of the desired product as white crystals.
Preparation of 3-(4-chlorophenyl)-5,5-dimethyl-4-(l,2,4-triazol-l-ylmethyl)isoxazol-4-ol
Figure imgf000066_0002
4-(4-chlorophenyl)-7,7-dimethyl-2,6-dioxa-5-azaspiro[2.4]hept-4-ene (36.3 g; 153 mmol) was dissolved in dry DMF (450 ml) and to this solution, lH-l,2,4-triazole (13.7 g; 0.20 mol) and potassium carbonate (27.4 g; 0.20 mmol) were added. The mixture was stirred overnight at room temperature.
DMF was removed in vacuo and the residue was then dissolved in AcOEt (1000 ml) and water (1000 ml). After separation, the organic layer was washed with brine (2x 750 ml), dried over Na2S04, filtered and concentrated in vacuo. The residue was purified by column chromatography (heptane/ AcOEt = 1/1). After recrystallisation from heptane, the product was obtained as a white solid (35.4 g, 75%, LCMS [MH+] = 307/309, mp: 177-178°C)
Preparation of 2-(4-chloro-2-fluoro-phenyl)-l-(l,2,4-triazol-l-ylmethyl)-4-oxa-3- azaspiro[4.5]dec-2-en-l-ol
Figure imgf000067_0001
12-(4-chloro-2-fluoro-phenyl)-2, 10-dioxa-l l-azadispiro[2.0.5.3]dodec-l l-ene (296 mg; 1 mmol), lH-l,2,4-triazole (83 mg; 1.2 mmol) and ethyltriphenyl phosphonium bromide (18 mg; 0.05 mmol) were dissolved in dry acetonitrile (0.5 ml). The reaction mixture was stirred at 90°C for 3 h. The reaction was then allowed to reach room temperature and the formation of a white crystalline product was observed. The solid was filtered off, washed with acetonitrile and dried to afford the title compound as white crystals (197 mg, 54 %, mp: 198- 199°C).
Preparation of 2-(4-chloro-2-fluoro-phenyl)-l-fluoro-l-(l,2,4-triazol-l-ylmethyl)-4-oxa- 3-azaspiro[4.5]dec-2-ene and (Z)-2-(4-chloro-2-fluoro-phenyl)-l-(l,2,4-triazol-l- ylmethylene)-4-oxa-3-azaspiro[4.5]dec-2-ene
Figure imgf000067_0002
2-(4-chloro-2-fluoro-phenyl)- 1 -(1 ,2,4-triazol- 1 -ylmethyl)-4-oxa-3 -azaspiro[4.5]dec-2-en- 1 - ol (110 mg; 0.3 mmol) was dissolved in DCM (2 ml) and the resulting solution was cooled to -40°C under inert atmosphere. (Diethylamino)sulfur trifluoride (DAST) (48 mg; 0.3 mmol) was added dropwise with a syringe to the solution. After addition, the mixture was allowed to warm up to room temperature during 2 h. The reaction was quenched with a mixture of ice-water (5 ml) and the organic layer was then washed with water, brine and dried over Na2S04. The solvent was evaporated and the residue was separated by column
chromatography (hexane/AcOEt = 1/1). Two compounds were isolated: (Z)-2-(4-chloro-2- fluoro-phenyl)-l-(l,2,4-triazol-l-ylmethylene)-4-oxa-3-azaspiro[4.5]dec-2-ene (19 mg, 18 %, mp: 139-143°C) and 2-(4-chloro-2-fluoro-phenyl)-l-fluoro-l-(l,2,4-triazol-l-ylmethyl)- 4-oxa-3-azaspiro[4.5]dec-2-ene (62 mg, 56 %, amorphous).
Preparation of 2-(4-chloro-2-fluoro-phenyl)-l-methoxy-l-(l,2,4-triazol-l-ylmethyl)-4- oxa-3-azaspiro [4.5] dec-2-ene
Figure imgf000068_0001
To a solution of 2-(4-chloro-2-fluoro-phenyl)-l-(l,2,4-triazol-l-ylmethyl)-4-oxa-3- azaspiro[4.5]dec-2-en-l-ol (120 mg; 3.3 mmol) in dry THF (10 ml) at -10°C was added NaH ( 60 % in mineral oil, 15.8 mg; 3.9 mmol). The mixture was stirred at this temperature for 20 min. before the addition of methyl iodide (55.3 mg; 3.9 mmol). The reaction was allowed to reach room temperature and then stirred overnight. The solution was poured into water (20 ml) and extracted with AcOEt (3x10 ml). The combined organic layers were washed with water, brine, dried over Na2S04 and filtered. After evaporation, the residue was purified by column chromatography (hexane/ AcOEt = 1/1) to afford 52 mg (41%) of desired compound as amorphous material. Preparation of 2-(4-chloro-2-fluoro-phenyl)-l-(imidazol-l-ylmethyl)-4- azaspiro [4.5] dec-2-en-l-ol
Figure imgf000069_0001
A mixture of 12-(4-chloro-2-fluoro-phenyl)-2, 10-dioxa-l l-azadispiro[2.0.5.3]dodec-l 1-ene (592 mg; 2 mmol), imidazole (150 mg; 2.2 mmol) and ethyltriphenyl phosphonium bromide (37 mg; 0.1 mmol) were dissolved in dry acetonitrile (1.5 ml). The reaction mixture was heated at 90°C for 1 h. After cooling, the precipitation of a white crystalline solid was observed and was filtered off, washed with acetonitrile and dried. The desired compound was isolated as a crystalline material (450 mg, 62 %, mp: 221-222°C).
Preparation of 2-(4-chloro-2-fluoro-phenyl)-l-fluoro-l-(imidazol-l-ylmethyl)-4-oxa-3- azaspiro[4.5]dec-2-ene, (Z)-2-(4-chloro-2-fluoro-phenyl)-l-(imidazol-l-ylmethylene)-4- oxa-3-azaspiro[4.5]dec-2-ene and (E)-2-(4-chloro-2-fluoro-phenyl)-l-(imidazol-l- ylmethylene)-4-oxa-3-azaspiro[4.5]dec-2-ene
Figure imgf000069_0002
II (Z-isomer) III (E-isomer) To a solution of 2-(4-chloro-2-fluoro-phenyl)-l-(imidazol-l-ylmethyl)-4-oxa-3- azaspiro[4.5]dec-2-en-l-ol (500 mg; 1.37 mmol) in DCM (10 ml) under inert atmosphere at -40°C was added (diethylamino)sulfur trifluoride (DAST) (331 mg; 2.05 mmol ) followed by triethylamine (416 mg; 4.11 mmol). The mixture was stirred at 2 h at this temperature and then allowed to warm up to room temperature over 4 h. The clear solution was poured into ice-water (10 ml) and extracted with DCM (3x10 ml). After separation, the combined organic layers were washed with water, brine, dried over Na2S04, filtered and concentrated in vacuo. The crude residue was separated by column chromatography (hexane/AcOEt = 1/2) isolating three compounds:
I (50 mg, 10 %, mp: 185-188°C)
II (220 mg, 46.4 %, mp: 106-110°C)
III (32 mg, 6.7 %, mp: 153-155°C)
Preparation of 2-(4-chloro-2-fluoro-phenyl)-l-[(4-methylimidazol-l-yl)methyl]-4-oxa-3- azaspiro[4.5]dec-2-en-l-ol
Figure imgf000070_0001
To a solution of 12-(4-chloro-2-fluoro-phenyl)-2, 10-dioxa-l l-azadispiro[2.0.5.3]dodec-l l- ene (200 mg; 0.676 mmol) and 4-methyl-imidazole (83 mg; 1.01 mmol) in N-methyl-2- pyrrolidone (1.5 ml) was added ethyltriphenyl phosphonium bromide (12 mg; 0.034 mmol). The reaction mixture was submitted to microwave irradiation at 80°C over 105 min. Water (5 ml) was then added to the solution, followed by AcOEt (10 ml). After separation, the organic layer was washed with brine, dried over Na2S04, filtered and concentrated m vacuo. The residue was purified by column chromatography (AcOEt/MeOH = 99/1) to furnish the title product as a crystalline material (58 mg, 24 %, mp: 214-216°C). Preparation of 2-(4-chloro-2-fluoro-phenyl)-l-[(2-methylimidazol-l-yl)methyl]-4-oxa-3- azaspiro[4.5]dec-2-en-l-ol
Figure imgf000071_0001
To the solution of 12-(4-chloro-2-fluoro-phenyl)-2, 10-dioxa-l l-azadispiro[2.0.5.3]dodec-l 1- ene (200 mg; 0.676 mmol) and 2-methyl-imidazole (83 mg; 1.01 mmol) in dry acetonitrile (3 ml) was added ethyltriphenyl phosphonium bromide (12 mg; 0.034 mmol). The reaction mixture was submitted to microwave irradiation at 100°C over 75 min. The solvent was evaporated and the residue was dissolved in AcOEt (10 ml), washed with water (10 ml), brine (10 ml) and dried over Na2S04. After filtration and evaporation, the residue was purified by column chromatography (hexane/ AcOEt = 1/2) to furnish the title compound as a crystalline material (85 mg, 33 %, mp: 182-184°C).
Preparation 3-[[3-(4-chlorophenyl)-4-hydroxy-5,5-dimethyl-isoxazol-4- yl]methyl]imidazole-4-carbaldehyde
Figure imgf000071_0002
To a solution of 4-(4-chlorophenyl)-7,7-dimethyl-2,6-dioxa-5-azaspiro[2.4]hept-4-ene (5 g, 21.04 mmol) in DMF (50 ml) was added potassium carbonate (3.8 g, 27.35 mmol) and IH- imidazole-4-carbaldehyde (2.63 g, 27.35 mmol). The resulting mixture was stirred overnight at room temperature and then quenched by addition of water (300 ml) followed by AcOEt (300 ml). After separation, the organic layer was washed with brine, dried over Na2S04, filtered and concentrated m vacuo. The residue was purified by reverse phase
chromatography (20 to 40% Acetonitrile in water) obtaining 3-[[3-(4-chlorophenyl)-4- hydroxy-5,5-dimethyl-isoxazol-4-yl]methyl]imidazole-4-carbaldehyde (2 g, 28.5%, mp: 162- 164°C) and l-[[3-(4-chlorophenyl)-4-hydroxy-5,5-dimethyl-isoxazol-4-yl]methyl]imidazole- 4-carbaldehyde (3.6 g, 51.3%, mp: 181-183°C) as crystalline materials. Preparation of 3-[[3-(4-chlorophenyl)-4-methoxy-5,5-dimethyl-isoxazol-4- yl]methyl]imidazole-4-carbaldehyde
Figure imgf000072_0001
To a solution of 3-[[3-(4-chlorophenyl)-4-hydroxy-5,5-dimethyl-isoxazol-4- yl]methyl]imidazole-4-carbaldehyde (300 mg, 0.9 mmol) and methyl iodide (640 mg, 4.5 mmol) in THF (6 ml) at 0-5°C was added NaH (60% in mineral oil; 50 mg; 1.1 mmol) and the resulting mixture was stirred at room temperature for 30 min. Water (5 ml) was added followed by AcOEt (10 ml). After separation, the organic layer was washed with brine, dried over Na2S04, filtered and concentrated in vacuo. The residue was purified by column chromatography (AcOEt) to furnish the title compound as amorphous solid (40 mg, 13%).
Preparation of (4)-3-[[3-(4-chlorophenyl)-4-methoxy-5,5-dimethyl-isoxazol-4- yl]methyl]imidazole-4-carbaldehyde oxime
Figure imgf000072_0002
A mixture of 3-[[3-(4-chlorophenyl)-4-methoxy-5,5-dimethyl-isoxazol-4- yl]methyl]imidazole-4-carbaldehyde (40 mg, 0.1 mmol), hydroxylamine hydrochloride (16 mg, 0.2 mmol), sodium bicarbonate (19.3 mg, 0.2 mmol) in THF/water (1/0.2 ml) was stirred at room temperature for 5 h. After this time, a second amount of hydroxylamine
hydrochloride (16 mg, 0.2 mmol), and sodium bicarbonate (19.3 mg, 0.2 mmol) were added and the reaction was stirred overnight. The reaction was quenched with water (5 ml) and diluted with AcOEt (10 ml). After separation, the organic layer was washed with brine, dried over Na2S04, filtered and concentrated in vacuo. The desired compound was obtained as a crystalline material (40 mg, 96%).
Preparation of 3-[[3-(4-chlorophenyl)-4-methoxy-5,5-dimethyl-isoxazol-4- yl] methyl] imidazole-4-carbonitrile
Figure imgf000073_0001
(4)-3-[[3-(4-chlorophenyl)-4-methoxy-5,5-dimethyl-isoxazol-4-yl]methyl]imidazole-4 carbaldehyde oxime (30 mg, 0.1 mmol) was refluxed in acetic anhydride (2.5 ml) for 18 h. The reaction mixture was poured over ice and the pH was adjusted to 8 with sodium carbonate followed by extraction with AcOEt (10 ml). The organic layer was washed with brine (5 ml), dried over Na2S04, filtered and concentrated m vacuo. The residue was purified by column chromatography (AcOEt) to furnish the title compound as amorphous solid (11 mg, 39%).
Pre aration of 3-(4-chlorophenyl)-5,5-dimethyl-4H-isoxazole-4-carbaldehyde
Figure imgf000073_0002
Under nitrogen, oxalyl chloride (0.105 ml; 1.2 mmol) was dissolved in DCM (2.5 ml) and cooled to -78°C before addition of DMSO (0.149 ml; 2.1 mmol; 2.1 eq) in DCM (3 ml). After stirring at -78°C for 15 min, a solution of [3-(4-chlorophenyl)-5,5-dimethyl-4H- isoxazol-4-yl]methanol (240 mg; 1.0 mmol) in DCM (3 ml) was added and stirring was continued at
-78°C for 20 min. Triethylamine (0.70 ml; 5.0 mmol) was then added drop-wise and stirring was continued at -78°C for 30 min. The cooling bath was removed and the reaction was allowed to stir at room temperature for 1 h. The reaction mixture was diluted with DCM (10 ml) and then IN HC1 (10 ml) was added. After separation, the organic layer was dried over Na2S04, filtered and concentrated in vacuo. The residue was purified by column
chromatography (heptane/AcOEt = 9/1) to obtain the title compound as a white solid (137 mg, 57%).
Preparation of [3-(4-chlorophenyl)-5,5-dimethyl-4H-isoxazol-4-yl]-(3-pyridyl)methanol
Figure imgf000074_0001
A solution of 3-bromopyridine (207 mg; 1.31 mmol) in dry diethyl ether (5 ml) was cooled to -78°C and «-BuLi (1.6 M in hexanes; 0.76 ml; 1.21 mmol) was added drop-wise. After stirring for 30 min at this temperature, a solution of 3-(4-chlorophenyl)-5,5-dimethyl-4H- isoxazole-4-carbaldehyde (240 mg; 1.00 mmol) in dry THF (4 ml) was added drop-wise. After further 30 min at -78°C, the reaction mixture was quenched with water (10 ml) followed by AcOEt (10 ml). After separation, the organic layer was dried over Na2S04, filtered and concentrated in vacuo. The residue was purified by column chromatography (DCM/MeOH = 98/2). The product was obtained as a white solid (129 mg, 40%, mp: 142- 148°C).
Preparation of (4Z)-3-(4-chlorophenyl)-5,5-dimethyl-4-(3-pyridylmethylene)isoxazole
Figure imgf000075_0001
To a solution of [3-(4-chlorophenyl)-5,5-dimethyl-4H-isoxazol-4-yl]-(3-pyridyl)methanol (174 mg; 0.55 mmol) and triethylamine (0.23 ml; 1.65 mmol) in DCM (2 ml) was added drop-wise mesyl chloride (92 mg; 0.71 mmol). The mixture was stirred at room temperature for 1 h. DBU (0.41 ml; 2.75 mmol) was then added and the reaction mixture was stirred overnight at room temperature. The reaction mixture was concentrated and purified by column chromatography (hexane/AcOEt = 1/1). The product was isolated as an oil containing a cisltrans mixture (1 : 1) (30 mg, 19%, mp: 71-73°C).
Additional compounds in Table Tl and Table T2 are prepared by similar methods using appropriate starting materials.
Table Tl
Comp Name Structure [MH+] Mp ound
(rit. time ) (°C)
Tl.l 3-(4-chlorophenyl)-5,5- 104- dimethyl-4-( 1 ,2,4-triazol- 1 - 105 ylmethyl)-4H-isoxazole
T1.2 3-(4-chlorophenyl)-5,5- 177- dimethyl-4-( 1 ,2,4-triazol- 1 - 178 ylmethyl)isoxazol-4-ol HHO v
T1.3 3 -(4-chlorophenyl)-4, 5,5- [305/307]
trimethyl-4-(l ,2,4-triazol- 1 - (3.18 min) ylmethyl)isoxazole
Figure imgf000075_0002
T1.4 2-(4-chlorophenyl)- 1 -( 1 ,2,4- 220- triazol- 1 -ylmethyl)-4-oxa-3 - 221 azaspiro[4.5 ] dec-2-en- 1 -ol
Figure imgf000076_0001
T1.5 2-(4-chlorophenyl)- 1 -( 1 ,2,4- 113- triazol- 1 -ylmethyl)-4-oxa-3 - 114 azaspiro[4.5]dec-2-ene
T1.6 3-(4-chlorophenyl)-4- 138- methoxy-5,5-dimethyl-4- / "A 139 (1,2,4-triazol-l- ylmethyl)isoxazole
T1.7 3-(4-chloro-2-fluoro-phenyl)- 155- 5,5-dimethyl-4-(l,2,4-triazol- 156 1 -ylmethyl)isoxazol-4-ol
T1.8 2-(2,4-dichlorophenyl)- 1 - 215- ( 1 ,2,4-triazol- 1 -ylmethyl)-4- 219 oxa-3 -azaspiro[4.5 ] dec-2-en- l-ol
T1.9 2-(4-chloro-2-fluoro-phenyl)- 94-95
1 -(1 ,2,4-triazol- 1 -ylmethyl)- 4,9,12-trioxa-3- azadispiro[4.2.4A8.2A5]tetrad
ec-2-en-l-ol
T1.10 2-(4-chloro-2-fluoro-phenyl)- 198- 1 -(1 ,2,4-triazol- 1 -ylmethyl)- 199 4-oxa-3-azaspiro[4.5]dec-2- ( " χ J
en-l-ol
Tl.ll 2-(4-chloro-2-fluoro-phenyl)- [367/369]
1 -fluoro- 1 -( 1 ,2,4-triazol- 1 - (1.81 min) ylmethyl)-4-oxa-3 - azaspiro[4.5]dec-2-ene A? Λ vJ,
T1.12 2-(2,4-dichlorophenyl)- 1 - 124- fluoro- l-(l,2,4-tri azol-1- 126 ylmethyl)-4-oxa-3 - azaspiro[4.5]dec-2-ene
Figure imgf000077_0001
T1.23 3- cyclopropyl-5,5-dimethyl- 106-
4- (l,2,4-triazol-l- 108 ylmethyl)isoxazol-4-ol
T1.24 2-(4-chlorophenyl)- 1 -( 1 ,2,4- 113- triazol- 1 -ylmethyl)-4-oxa-3 - 114 azaspiro[4.5]dec-2-ene
T1.25 3- (4-chloro-2-fluoro-phenyl)- 186-
4- (imidazol-l-ylmethyl)-5,5- 187 dimethyl-isoxazol-4-ol
T1.26 2-(4-chloro-2-fluoro-phenyl)- 221- 1 -(imidazol- 1 -ylmethyl)-4- 222 oxa-3 -azaspiro[4.5 ] dec-2-en- l-ol
T1.27 2-(2,4-dichlorophenyl)- 1 - 220- (imidazol- l-ylmethyl)-4-oxa- 224 3 -azaspiro[4.5 ] dec-2-en- 1 -ol
T1.28 2-(4-chloro-2-fluoro-phenyl)- 185- 1 -fluoro- 1 -(imidazol- 1 - 188 ylmethyl)-4-oxa-3 - azaspiro[4.5]dec-2-ene
T1.29 2-(2,4-dichlorophenyl)-l-[(4- 124- methylimidazol- 1 - 127 yl)methyl]-4-oxa-3- azaspiro[4.5 ] dec-2-en- 1 -ol
Figure imgf000078_0001
T1.30 2-(4-chloro-2-fluoro-phenyl)- 214- 1 -[(4-methylimidazol- 1 - 216 yl)methyl]-4-oxa-3- azaspiro[4.5 ] dec-2-en- 1 -ol
T1.31 methyl l-[[2-(4-chloro-2- 147- fluoro-phenyl)- 1 -hy droxy-4- 149 oxa-3 -azaspiro[4.5 ] dec-2-en- 1 -yl]methyl]imidazole-4- carboxylate
T1.32 2-(4-chloro-2-fluoro-phenyl)- 182- 1 -[(2-methylimidazol- 1 - 184 yl)methyl]-4-oxa-3- azaspiro[4.5 ] dec-2-en- 1 -ol T1.33 2-(2,4-dichlorophenyl)- 1 - 1 18- fluoro- 1 -(imidazol- 1 - 121 ylmethyl)-4-oxa-3 - azaspiro[4.5]dec-2-ene
T1.34 3-(4-chlorophenyl)-4-[[4- [358/360]
(difluoromethyl)imidazol- 1 - (1.76 min) yl]methyl]-4-fruoro-5,5- dimethyl-isoxazole
Figure imgf000079_0001
T1.35 3-(4-chlorophenyl)-4-[[5- [370/372]
(difluoromethyl)imidazol- 1 - (1.72 min) yl]methyl]-4-methoxy-5,5- dimethyl-isoxazole
T1.36 3-(4-chlorophenyl)-4-[[4- [356/358]
(difluoromethyl)imidazol- 1 - (1.55 min) yl]methyl]-5,5-dimethyl- isoxazol-4-ol
T1.37 3-(4-chlorophenyl)-4-[[4- [370/372]
(difluoromethyl)imidazol- 1 - (1.79 min) yl]methyl]-4-methoxy-5,5- dimethyl-isoxazole
T1.38 3-[[3-(4-chlorophenyl)-4- 162- hy droxy-5, S-dimethyl- 164 isoxazoM- yl]methyl]imidazole-4- carbaldehyde
T1.39 l-[[3-(4-chlorophenyl)-4- 181- hy droxy-5 , 5 -dimethyl- 183 isoxazol-4- yl]methyl]imidazole-4- carbaldehyde
T1.40 3-(4-chlorophenyl)-5,5- 217- dimethyl-4-[(4- 219 nitroimidazol-1- yl)methyl]isoxazol-4-ol Λ
T1.41 3-(4-chlorophenyl)-4-[[5- 1 12- (hydroxymethyl)imidazol- 1 - 1 14 yl]methyl]-5,5-dimethyl- isoxazol-4-ol
T1.42 3-[[3-(4-chlorophenyl)-4- "Γ°Υ-~ [363/365]
methoxy-5 , 5 -dimethyl- (1.16 min) isoxazol-4- yl]methyl]imidazole-4- carbaldehyde oxime
Figure imgf000080_0001
Table T2
Compound Name Structure [MH+] Mp
(rit. time ) (°C)
T2.1 3-(4-chlorophenyl)-5,5- 71-73 dimethyl-4-(3- py ri dy Imethy 1 ene)i soxazol e
T2.2 2-(4-chloro-2-fluoro-phenyl)- 139- l-(l,2,4-triazol-l- 142 ylmethylene)-4-oxa-3- azaspiro[4.5]dec-2-ene
Figure imgf000080_0002
T2.3 2-(2,4-dichlorophenyl)- 1 - 132- (1,2,4-triazol-l- 136 ylmethylene)-4-oxa-3- azaspiro[4.5]dec-2-ene
T2.4 3-(4-chlorophenyl)-5,5- [289/291]
dimethyl-4-( 1 ,2,4-triazol- 1 - (1.74 min) ylmethylene)isoxazole
T2.5 2-(4-chloro-2-fluoro-phenyl)- [346/348]
1 -(imidazol- 1 -ylmethylene)- (1.60 min) 4-oxa-3-azaspiro[4.5]dec-2- ene
T2.6 2-(2,4-dichlorophenyl)- 1 - [362/364]
(imidazol- 1 -ylmethylene)-4- (1.62 min) oxa-3 -azaspiro[4.5 ] dec-2-ene
Figure imgf000080_0003
T2.7 (lZ)-2-(4-chloro-2-fluoro- 106- phenyl)- 1 -(imidazol- 1 - 110 ylmethylene)-4-oxa-3- azaspiro[4.5]dec-2-ene T2.8 (lE)-2-(4-chloro-2-fluoro- 153- phenyl)- 1 -(imidazol- 1 - 155 ylmethylene)-4-oxa-3- azaspiro[4.5]dec-2-ene
T2.9 (lZ)-2-(2,4-dichlorophenyl)- [362/364]
1 -(imidazol- 1 -ylmethylene)- (1.62 min) 4-oxa-3-azaspiro[4.5]dec-2- ene
a
T2.10 (lE)-2-(2,4-dichlorophenyl)- [362/364]
1 -(imidazol- 1 -ylmethylene)- (1.40 min) 4-oxa-3-azaspiro[4.5]dec-2- ene
T2.ll 3-(4-chlorophenyl)-4-[[4- [338/340]
(difluoromethyl)imidazol- 1 - (1.79 min) yl]methylene]-5,5-dimethyl- isoxazole ~r
The compounds of the following Tables TA01.01 to TA09.11 and Tables TB01.01 to
TB01.08 can be obtained in an analogous manner.
Table T3
Compounds R2 R3
T3.1 Me H
T3.2 Et H
T3.3 cyclohexyl H
T3.4 cyclopentyl H
T3.5 cyclobutyl H
T3.6 cyclopropyl H
T3.7 tert-butyl H
T3.8 sec-butyl H
T3.9 isoamyl H
T3.10 z'so-propyl H
T3. l l CF3 H
T3.12 4-chloro-phenyl H
T3.13 3-chloro-phenyl H
T3.14 2-chloro-phenyl H
T3.15 2,4-dichloro-phenyl H
T3.16 2-thiophenyl H
T3.17 5-chloro-2-thiophenyl H
T3.18 5-bromo-2-thiophenyl H
T3.19 4-fluoro-phenyl H T3.20 3-fluoro-phenyl H
T3.21 2-fluoro-phenyl H
T3.22 2,4-difluoro-phenyl H
T3.23 2-fluoro-4-chloro-phenyl H
T3.24 2-chloro-4-fluoro-phenyl H
T3.25 4-trifluoromethyl-phenyl H
T3.26 3 -trifluoromethyl-phenyl H
T3.27 2-trifluoromethyl-phenyl H
T3.28 4-bromo-phenyl H
T3.29 phenyl H
T3.30 4-chloro-benzyl H
T3.31 Me Me
T3.32 Et Me
T3.33 cyclohexyl Me
T3.34 cyclopentyl Me
T3.35 cyclobutyl Me
T3.36 cyclopropyl Me
T3.37 tert-butyl Me
T3.38 sec-butyl Me
T3.39 isoamyl Me
T3.40 z'so-propyl Me
T3.41 CF3 Me
T3.42 4-chloro-phenyl Me
T3.43 3-chloro-phenyl Me
T3.44 2-chloro-phenyl Me
T3.45 2,4-dichloro-phenyl Me
T3.46 2-thiophenyl Me
T3.47 5-chloro-2-thiophenyl Me
T3.48 5-bromo-2-thiophenyl Me
T3.49 4-fluoro-phenyl Me
T3.50 3-fluoro-phenyl Me
T3.51 2-fluoro-phenyl Me
T3.52 2,4-difluoro-phenyl Me
T3.53 2-fluoro-4-chloro-phenyl Me
T3.54 2-chloro-4-fluoro-phenyl Me
T3.55 4-trifluoromethyl-phenyl Me
T3.56 3 -trifluoromethyl-phenyl Me
T3.57 2-trifluoromethyl-phenyl Me
T3.58 4-bromo-phenyl Me
T3.59 phenyl Me
T3.60 4-chloro-benzyl Me
T3.61 Me Et
T3.62 Et Et
T3.63 cyclohexyl Et
T3.64 cyclopentyl Et
T3.65 cyclobutyl Et
T3.66 cyclopropyl Et T3.67 tert-butyl Et
T3.68 sec-butyl Et
T3.69 isoamyl Et
T3.70 z'so-propyl Et
T3.71 CF3 Et
T3.72 4-chloro-phenyl Et
T3.73 3-chloro-phenyl Et
T3.74 2-chloro-phenyl Et
T3.75 2,4-dichloro-phenyl Et
T3.76 2-thiophenyl Et
T3.77 5-chloro-2-thiophenyl Et
T3.78 5-bromo-2-thiophenyl Et
T3.79 4-fluoro-phenyl Et
T3.80 3-fluoro-phenyl Et
T3.81 2-fluoro-phenyl Et
T3.82 2,4-difluoro-phenyl Et
T3.83 2-fluoro-4-chloro-phenyl Et
T3.84 2-chloro-4-fluoro-phenyl Et
T3.85 4-trifluoromethyl-phenyl Et
T3.86 3 -trifluoromethyl-phenyl Et
T3.87 2-trifluoromethyl-phenyl Et
T3.88 4-bromo-phenyl Et
T3.89 phenyl Et
T3.90 4-chloro-benzyl Et
Table 4
R2 and R3 together form cycle as described in Table 4 below:
Compounds Cycle formed by R2 and R3
T4.1 cyclohexyl
T4.2 cyclopentyl
T4.3 cyclobutyl
T4.4 cyclopropyl
T4.5
*
T4.6
*
o
T4.7
*
Figure imgf000084_0001
Figure imgf000085_0001
The following Tables disclose compounds according to the formula (II) in the Tables TA01.01 to TA09.11
Figure imgf000085_0002
wherein the subtituents have the meaning as given in the Tables TA01.01 to TA09.11 (99 Tables with 252648 compounds in total):
The Table TA01.01 discloses 232 compounds according to formula (II) (compound TAOl .01.001 to compound TAOl .01.232) wherein in the first 116 compounds R7 signifies H, R1 signifies 4-chloro-phenyl, X signifies CH and and R2 and R3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116
compounds but X signifies N instead of CH.
The Table TA01.02 discloses 232 compounds according to formula (II) (compound
TA01.021.001 to compound TA01.02.232) wherein in the first 116 compounds R7 signifies OH, R1 signifies 4-chloro-phenyl, X signifies CH and and R2 and R3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116
compounds but X signifies N instead of CH.
The Table TA01.03 discloses 232 compounds according to formula (II) (compound TA01.03.001 to compound TA01.03.232) wherein in the first 116 compounds R7 signifies OMe, R1 signifies 4-chloro-phenyl, X signifies CH and and R2 and R3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116
compounds but X signifies N instead of CH.
The Table TA01.04 discloses 232 compounds according to formula (II) (compound TA01.04.001 to compound TA01.04.232) wherein in the first 116 compounds R7 signifies Me, R1 signifies 4-chloro-phenyl, X signifies CH and and R2 and R3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116
compounds but X signifies N instead of CH.
The Table TA01.05 discloses 232 compounds according to formula (II) (compound TA01.05.001 to compound TA01.05.232) wherein in the first 116 compounds R7 signifies Et, R1 signifies 4-chloro-phenyl, X signifies CH and and R2 and R3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116
compounds but X signifies N instead of CH. The Table TA01.06 discloses 232 compounds according to formula (II) (compound TAOl .06.001 to compound TAOl .06.232) wherein in the first 116 compounds R7 signifies F, R1 signifies 4-fluoro-phenyl, X signifies CH and and R2 and R3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116 compounds but X signifies N instead of CH.
The Table TA01.07 discloses 232 compounds according to formula (II) (compound TA01.07.001 to compound TA01.07.232) wherein in the first 116 compounds R7 signifies CI, R1 signifies 4-chloro-phenyl, X signifies CH and and R2 and R3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116 compounds but X signifies N instead of CH.
The Table TA01.08 discloses 232 compounds according to formula (II) (compound TA01.08.001 to compound TA01.08.232) wherein in the first 116 compounds R7 signifies Br, R1 signifies 4-chloro-phenyl, X signifies CH and and R2 and R3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116 compounds but X signifies N instead of CH.
The Table TA01.09 discloses 232 compounds according to formula (II) (compound TA01.09.001 to compound TA01.09.232) wherein in the first 116 compounds R7 signifies CF3, R1 signifies 4-chloro-phenyl, X signifies CH and and R2 and R3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116 compounds but X signifies N instead of CH.
The Table TA01.10 discloses 232 compounds according to formula (II) (compound
TAOl .10.001 to compound TA01.10.232) wherein in the first 116 compounds R71 signifies CN, R1 signifies 4-chloro-phenyl, X signifies CH and and R2 and R3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116 compounds but X signifies N instead of CH.
The Table TA01.11 discloses 232 compounds according to formula (II) (compound TA01.11.001 to compound TA01.11.232) wherein in the first 116 compounds R7 signifies OAc, R1 signifies 4-chloro-phenyl, X signifies CH and and R2 and R3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116 compounds but X signifies N instead of CH.
The Tables TA02.01 to TA02.11 disclose each 232 compounds (2552 compounds in total) according to formula (II) wherein the meaning of all substituents are as given in the Tables TA01.01 to TA01.11 exept that R1 signifies 4-chloro-2-fluoro-phenyl instead of 4- chloro-phenyl.
The Tables TA03.01 to TA03.11 disclose each 232 compounds (2552 compounds in total) according to formula (II) wherein the meaning of all substituents are as given in the Tables TA01.01 to T AO 1.11 exept that R1 signifies 2,4-difluoro-phenyl instead of 4-chloro- phenyl.
The Tables TA04.01 to TA04.11 disclose each 232 compounds (2552 compounds in total) according to formula (II) wherein the meaning of all substituents are as given in the Tables TA01.01 to TA01.11 exept that R1 signifies 2,4-dichloro-phenyl instead of 4-chloro- phenyl.
The Tables TA05.01 to TA05.11 disclose each 232 compounds (2552 compounds in total) according to formula (II) wherein the meaning of all substituents are as given in the Tables TA01.01 to TA01.11 exept that R1 signifies 2-fluoro-phenyl instead of 4-chloro- phenyl.
The Tables TA06.01 to TA06.11 disclose each 232 compounds (2552 compounds in total) according to formula (II) wherein the meaning of all substituents are as given in the Tables TA01.01 to TA01.11 exept that R1 signifies 4-fluoro-phenyl instead of 4-chloro- phenyl.
The Tables TA07.01 to TA07.11 disclose each 232 compounds (2552 compounds in total) according to formula (II) wherein the meaning of all substituents are as given in the Tables TA01.01 to TA01.11 exept that R1 signifies 5-chloro-2-thiophenyl instead of 4- chloro-phenyl.
The Tables TA08.01 to TA08.11 disclose each 232 compounds (2552 compounds in total) according to formula (II) wherein the meaning of all substituents are as given in the Tables TA01.01 to TA01.11 exept that R1 signifies 4-chloro-benzyl instead of 4-chloro- phenyl. The Tables TA09.01 to TA09.11 disclose each 232 compounds (2552 compounds in total) according to formula (II) wherein the meaning of all substituents are as given in the Tables TA01.01 to TAOl . l 1 exept that R1 signifies Cyclohexyl instead of 4-chloro-phenyl.
The following Tables disclose compounds according to the formula (III) in the Tables TB01.01 to TB01.08
Figure imgf000089_0001
wherein the subtituents have the meaning as given in the Tables TB01.01 to TB01.11 (additional 8 Tables (Tables TB01.01 to TB01.08) with additional 1856 compounds in total).
The Table TB01.01 discloses 232 compounds according to formula (III) (compound TBOl .01.001 to compound TB01.01.232) wherein in the first 116 compounds R1 signifies 4- chloro-phenyl, X signifies CH and and R2 and R3 have the meaning as given in the Table 3 lines T3.1 to T3.90 and in Table 4 lines T4.1 to T4.26 and 116 further compounds wherein the meaning of the substituents is the same as in the first 116 compounds but X signifies N instead of CH.
The Table TB01.02 discloses 232 compounds according to formula (III) wherein all the substituents have the meaning as given in Table TB01.01 but R1 signifies 4-chloro-2- fluoro-phenyl instead of 4-chloro-phenyl.
The Table TB01.03 discloses 232 compounds according to formula (III) wherein all the substituents have the meaning as given in Table TB01.01 but R1 signifies 2,4-difluoro- phenyl instead of 4-chloro-phenyl.
The Table TB01.04 discloses 232 compounds according to formula (III) wherein all the substituents have the meaning as given in Table TB01.01 but R1 signifies 2,4-dichloro- phenyl instead of 4-chloro-phenyl
The Table TB01.05 discloses 232 compounds according to formula (III) wherein all the substituents have the meaning as given in Table TB01.01 but R1 signifies 2-fluoro-phenyl instead of 4-chloro-phenyl. The Table TB01.06 discloses 232 compounds according to formula (III) wherein all the substituents have the meaning as given in Table TB01.01 but R1 signifies 5-chloro-2- thiophenyl instead of 4-chloro-phenyl.
The Table TB01.07 discloses 232 compounds according to formula (III) wherein all the substituents have the meaning as given in Table TB01.01 but R1 signifies 4-chloro- benzyl instead of 4-chloro-phenyl.
The Table TB01.08 discloses 232 compounds according to formula (III) wherein all the substituents have the meaning as given in Table TB01.01 but R1 signifies Cyclohexyl instead of 4-chloro-phenyl.
For exam le the compound TA08.04.62 is a compound according the following formula
Figure imgf000090_0001
while the compound TA01.11.227 Discloses the following compound:
Figure imgf000090_0002
Biological examples:
These examples illustrate the fungicidal properties of the compounds described in table Tl and T2.
Description of the methods: Botrytis cinerea (Gray mould): Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24 °C and the inhibition of growth was determined photometrically after 72 hrs.
The following compounds give at least 80% control of Botrytis cinerea at 200 ppm:
T1.14, T1.15, T1.28, T1.35 Erysiphe graminis (Wheat powdery mildew): Barley leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with spores of the fungus. After appropriate incubation the activity of a compound is assessed 7 dpi (days after inoculation) as preventive fungicidal activity. The following compounds give at least 80% control of Erysiphe graminis at 200 ppm:
Tl . l, T1.2, T1.3, T1.5, T1.16, T1.17, T1.20, T.124, T1.42
Septoria tritici (leaf blotch): Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24 C and the inhibition of growth was determined photometrically after 72 hrs.
The following compounds give at least 80% control of Septoria tritici at 200 ppm:
T1.6, T1.8, T1.14, T1.42, T1.43, T2.1, T2.9, T2.10
Puccinia recondita (Brown rust): Wheat leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 8 dpi (days after inoculation) as preventive fungicidal activity.
The following compounds give at least 80% control of Puccinia recondita at 200 ppm: T1.5, T1.9, T1.13, T1.22, T1.23, T1.24, T1.25

Claims

1. A compound of formula (I)
Figure imgf000092_0001
wherein
R1 is aryl or heteroaryl, or substituted aryl or substituted heteroaryl each optionally substituted by one to five substituents R8a, which may be the same or different;
R2 andR3 independently are H, aryl or heterocycl, substituted aryl or substituted heteroaryl each optionally substituted by one to five substituents R8, which may be the same or different; Ci-C8alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-Cecycloalkyl, Ci-C6haloalkyl, C2- C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, Ci-C6alkoxy, Ci-C6alkoxy-Ci- C6alkyl, Ci-C6haloalkoxy, Ci-C6alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C8alkyl, substituted C2-C6alkenyl, substituted C2-C6alkynyl, substituted C3-C6cycloalkyl, substituted Ci-C6haloalkyl, substituted C2-C6haloalkenyl, substituted C2-C6haloalkynyl, substituted C3- Cehalocycloalkyl, substituted Ci-C6alkoxy, substituted Ci-Cealkoxy-Ci-Cealkyl, substituted Ci-C6haloalkoxy, substituted Ci-C6alkylthio, substituted Ci-Cehaloalkylthio each substituted by one to five substituents R9, which may be the same or different; provided that only one of the substituents R2 andR3 is H;
or R2 andR3 form together a 3 to 14 membered ring which may be monocyclic or polycyclic, preferably monocyclic, bicyclic or tricyclic, more preferably monocyclic or bicyclic, even more preferably monocyclic, and the ring formed by R2 andR3 together may be a alicyclic systems or heteroalicyclic systems wherein the carbocyclic ring structure which may comprise at least one endocyclic double bond or at least one endocyclic triple bond) wherein in the case of the heteroalicyclic systems optionally one or more of the carbon atoms are replaced by a heteroatom selected from O, N and S and wherein the alicyclic systems or heteroalicyclic systems are unsubstituted or substituted by one to five substituents R9;
R4 is heteroaryl, or substituted heteroaryl substituted by one to five substituents R8, which may be the same or different; R5 is H, OH; Ci-Cealkoxy or Ci-Cealkylcarbonyl, or substituted Ci-C6alkoxy or substituted Ci-C6alkylcarbonyl each substituted by one to five substituents R9, which may be the same or different;
R6 is H or forms together with R7 a bond;
R7 is H, OH, CN, halogen; Ci-C8alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, Ci-C6alkoxy, Ci- C6alkoxy-Ci-C6alkyl, Ci-C6haloalkoxy, Ci-C6alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C8alkyl, substituted C2-C6alkenyl, substituted C2-C6alkynyl, substituted C3-Cecycloalkyl, substituted Ci-C6haloalkyl, substituted C2-C6haloalkenyl, substituted C2-C6haloalkynyl, substituted C3-C6halocycloalkyl, substituted Ci-C6alkoxy, substituted Ci-C6alkoxy-Ci- C6alkyl, substituted Ci-C6haloalkoxy, substituted Ci-C6alkylthio, substituted Ci- C6haloalkylthio each substituted by one to five substituents R9, which may be the same or different; or forms together with R6 a bond;
each R8 is independently selected from cyano, amino, nitro, hydroxy, halogen, Ci-C4alkyl, Ci-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C alkynyl, C2-C haloalkynyl, C3- C6cycloalkyl, C3-C6halocycloalkyl, Ci-C3alkoxy, Ci-C3haloalkoxy, Ci-C3alkylthio, Ci- C3haloalkylthio, Ci-C3alkylsulfinyl, Ci-C3haloalkylsulfinyl, Ci-C3alkylsulfonyl, Ci-C3halo- alkylsulfonyl, Ci-C4alkylamino, di-(Ci-C4alkyl)amino, Ci-C4alkylcarbonyl, Ci-C4alkyl- carbonyloxy, Ci-C4alkoxycarbonyl, Ci-C4alkylcarbonylamino and phenyl or phenyl substituted by one to five R8 but not phenyl or substituted phenyl;
each R8a is independently selected from cyano, amino, nitro, hydroxy, halogen, Ci-C4alkyl, Ci-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, C3- C6cycloalkyl, C3-C6halocycloalkyl, Ci-C3alkoxy, Ci-C3haloalkoxy, Ci-C3alkylthio, Ci- C3haloalkylthio, Ci-C3alkylsulfinyl, Ci-C3haloalkylsulfinyl, Ci-C3alkylsulfonyl, Ci-C3halo- alkylsulfonyl, Ci-C4alkylamino, di-(Ci-C4alkyl)amino, Ci-C4alkylcarbonyl, Ci-C4alkyl- carbonyloxy, Ci-C4alkylcarbonylamino and phenyl or phenyl substituted by one to five R8 but not phenyl or substituted phenyl;
each R9 is independently halogen, cyano, nitro, hydroxy, Ci-C8alkoxy, Ci-C8haloalkoxy-, Ci-C8alkylthio-, Ci-C8haloalkylthio-, Ci-C8alkylsulfinyl-, Ci-C8haloalkylsulfinyl-, Ci- C8alkylsulfonyl-, Ci-C8haloalkylsulfonyl-, Ci-C8alkylcarbonyl-, Ci-C8alkoxycarbonyl-, aryl or aryl substituted by one to five R9, or heterocyclyl or heterocyclyl substituted by one to five R8;
or an agrochemically acceptable salt or N-oxides thereof.
2. A compound according to claim 1, characterized in that R4 is monocyclic heteroaryl or monocyclic heteroaryl substituted by one to five substituents R8, which may be the same or different.
3. A compound according to claim 1, characterized in that R1 is aryl or aryl substituted by one to four substituents R8a, which may be the same or different.
4. A compound according to claim 3, characterized in that R2 and R3 independently are aryl or heterocyclyl, or substituted aryl or substituted heterocyclyl each substituted by one to four substituents R8, which may be the same or different; Ci-C8alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6Cycloalkyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, Ci-C6alkoxy, Ci-Cealkoxy-Ci-Cealkyl, Ci-C6haloalkoxy, Ci-C6alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C8alkyl, substituted C2-C6alkenyl, substituted C2-C6alkynyl, substituted C3- C6cycloalkyl, substituted Ci-C6haloalkyl, substituted C2-C6haloalkenyl, substituted C2- C6haloalkynyl, substituted C3-C6halocycloalkyl, substituted Ci-C6alkoxy, substituted Ci- C6alkoxy-Ci-C6alkyl, substituted Ci-C6haloalkoxy, substituted Ci-C6alkylthio, substituted Ci-Cehaloalkylthio each substituted by one to five substituents R9, which may be the same or different.
5. A compound according to claim 3, characterized in that R2 and R3 form together a 5 to 14 membered ring which may be monocyclic or bicyclic or tricyclic, and the ring formed by R2 and R3 together may be a alicyclic systems or heteroalicyclic systems wherein in the case of the heteroalicyclic systems optionally one or more of the carbon atoms are replaced by a heteroatom selected from O, N and S and wherein the alicyclic systems or heteroalicyclic systems are optionally substituted by one to four substituents R9.
6. A compound according to claim 3, characterized in that R2 and R3 independently H, Ci- C8alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, Ci-C6alkoxy, Ci-Cealkoxy-Ci-Cealkyl, Ci-
C6haloalkoxy, Ci-C6alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C8alkyl, substituted C2- C6alkenyl, substituted C2-C6alkynyl, substituted C3-Cecycloalkyl, substituted Ci-C6haloalkyl, substituted C2-C6haloalkenyl, substituted C2-C6haloalkynyl, substituted C3-C6halocycloalkyl, substituted Ci-Cealkoxy, substituted Ci-Cealkoxy-Ci-Cealkyl, substituted Ci-Cehaloalkoxy, substituted Ci-Cealkylthio, substituted Ci-Cehaloalkylthio each substituted by one to five substituents R9, provided that only one of the substituents R2 andR3 is H.
7. A compound according to claim 6, characterized in that R2 andR3 independently Ci- C8alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-Cecycloalkyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, Ci-C6alkoxy, Ci-Cealkoxy-Ci-Cealkyl, Ci- C6haloalkoxy, Ci-C6alkylthio, Ci-Cehaloalkylthio, or substituted Ci-C8alkyl, substituted C2- C6alkenyl, substituted C2-C6alkynyl, substituted C3-C6cycloalkyl, substituted Ci-C6haloalkyl, substituted C2-C6haloalkenyl, substituted C2-C6haloalkynyl, substituted C3-C6halocycloalkyl, substituted Ci-C6alkoxy, substituted Ci-C6alkoxy-Ci-C6alkyl, substituted Ci-C6haloalkoxy, substituted Ci-C6alkylthio, substituted Ci-Cehaloalkylthio each substituted by one to five substituents R9
8. A compound according to claim 1, characterized in that R4 is a monocyclic 5 to 6 membered heteroaryl comprising one to three heteroatoms seleced from S, N more preferably the one to three heteroatoms are seleced from N,
9. A compound according to claim 8, characterized in that most referably R4 is
Figure imgf000095_0001
wherein X has the meaning of C-H or N each may be substituted by one substituent R
10. A method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a compound of formula (I) according to claim 1 or a composition, comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
11. A composition for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula I according to claim 1 and at least one auxiliary.
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