WO2020035565A1 - Composés hétéroaromatiques bicycliques mésoioniques à action pesticide - Google Patents

Composés hétéroaromatiques bicycliques mésoioniques à action pesticide Download PDF

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WO2020035565A1
WO2020035565A1 PCT/EP2019/071934 EP2019071934W WO2020035565A1 WO 2020035565 A1 WO2020035565 A1 WO 2020035565A1 EP 2019071934 W EP2019071934 W EP 2019071934W WO 2020035565 A1 WO2020035565 A1 WO 2020035565A1
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spp
alkyl
methyl
ccn
formula
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PCT/EP2019/071934
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Jürgen Harry SCHAETZER
Aurelien BIGOT
Pierre Joseph Marcel Jung
André Stoller
Julien Daniel Henri GAGNEPAIN
Roger Graham Hall
Stefano RENDINE
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Syngenta Crop Protection Ag
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Publication of WO2020035565A1 publication Critical patent/WO2020035565A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • 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

Definitions

  • the present invention relates to pesticidally-active, in particular insecticidally-active, fused bicyclic heterocyclic compounds, to compositions comprising those compounds, and to their use for controlling animal pests (including arthropods and in particular insects or representatives of the order Lepidoptera and Hemiptera).
  • Insecticidally-active fused bicyclic heteroaromatic compounds are known, for example, from WO 2013/149903, WO 2007/1 15647, WO 2012/136751 , WO 2013/144088, WO 2013/1501 15, WO 2012/152741 and WO 2014/076272.
  • W is O or S
  • R 1 is Ci-C6alkyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or Ci-C6haloalkyl;
  • C2-C6alkenyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or C2-C6haloalkenyl;
  • C2-C6alkynyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or C2-C6haloalkynyl;
  • C3-C6cycloalkyl wherein the cycloalkyl moiety is optionally substituted by 1 or 2 substituents independently selected from Lh or a single substituent selected from U2;
  • U 2 is phenyl, heteroaryl wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3, or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur, or a 5- or 6-membered saturated or partially saturated heterocyclic ring wherein the heterocyclic ring comprises 1 to 3 heteroatoms selected from nitrogen, oxygen and sulfur, and wherein each phenyl, heteroaryl or heterocyclic ring is optionally substituted by: (i) 1 , 2, 3, 4 or 5 independently selected halogen groups, or (ii) 1 or 2 groups independently selected from LU and optionally a halogen group;
  • U4 is nitro, cyano, amino, hydroxyl, -SCN, -C0 2 H, Ci-C 4 alkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, C3-C6cycloalkyl-Ci-C 4 alkyl, C3-C6halocycloalkyl-Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, Ci-C 4 alkoxy- Ci-C 4 alkyl, Ci-C 4 alkoxy-Ci-C 4 alkoxy, cyano-Ci-C 4 alkyl, cyano-Ci-C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, Ci-C 4 haloalkoxy, Ci-C 4 haloal
  • C 4 haloalkoxycarbonyl (Ci-C 4 alkyl)NH-, (Ci-C 4 alkyl) 2 N-, (C3-C6cycloalkyl)NH-, (C3-C6cycloalkyl) 2 N-, C1- C 4 alkylcarbonylamino, C3-C6cycloalkylcarbonylamino, Ci-C 4 haloalkylcarbonylamino, C3- Cehalocycloalkylcarbonylamino, Ci-C 4 alkylaminocarbonyl, C3-C6cycloalkylaminocarbonyl, C1-
  • R 2 is independently selected from halogen, cyano, amino, hydroxyl, Ci-C 4 alkyl, Ci-C 4 haloalkyl, C1- C 4 haloalkoxy, Ci-C 4 alkoxy, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, C1- C 4 alkylsulfanyl, Ci-C 4 alkylsulfinyl, Ci-C 4 alkylsulfonyl, Ci-C 4 haloalkylsulfanyl, Ci-C 4 haloalkylsulfinyl, C1- C 4 haloalkylsulfonyl and cyclopropyl;
  • R 3a and R 3b are independently selected from hydrogen, halogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci- C 4 alkoxy, Ci-C 4 haloalkoxy and cyano;
  • R4 is selected from one of Y1 to Y7;
  • n 0, 1 , 2, or 3;
  • Z is hydrogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy or Ci-C 4 haloalkoxy;
  • U is independently selected from halogen, cyano, nitro, hydroxyl, amino, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, Ci-C 4 haloalkoxy, Ci-C 4 haloalkoxy-Ci-C 4 alkyl, Ci-C 4 alkoxy-Ci-C 4 alkyl, Ci-C 4 alkylsulfanyl, Ci-C 4 alkylsulfinyl, Ci-C 4 alkylsulfonyl, Ci-C 4 haloalkylsulfanyl, Ci-C 4 haloalkylsulfinyl, C1- C 4 haloalkylsulfonyl, formyl, cyclopropyl, Ci-C6alkylcarbonyl or C3-C6cycloalkylcarbonyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxid
  • novel compounds of Formula (I) have, for practical purposes, a very advantageous level of biological activity for protecting plants against insects.
  • an agrochemical composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined according to the invention.
  • a method of controlling insects, acarines, nematodes or molluscs which comprises applying an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined according to the invention, or a composition comprising this compound as active ingredient, to a pest, a locus of pest (preferably a plant), to a plant susceptible to attack by a pest or to plant a propagation material thereof (such as a seed).
  • the method may exclude methods for the treatment of the human or animal body by surgery or therapy.
  • a compound according to Formula (I) as an insecticide, acaricide, nematicide or molluscicide.
  • the use may exclude methods for the treatment of the human or animal body by surgery or therapy.
  • halogen refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.
  • cyano means a -CN group.
  • hydroxyl or“hydroxy” means an -OH group.
  • amino means an -NH2 group.
  • nitro means an -NO2 group.
  • formyl means a -C(0)H group.
  • Ci-C6alkyl refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to six carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • Ci-C 4 alkyl, Ci-C3alkyl and Ci-C2alkyl are to be construed accordingly.
  • Examples of Ci-C6alkyl include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (iso-propyl), n-butyl, and 1 , 1-dimethylethyl (f-butyl).
  • C1- C 4 alkylene refers to the corresponding definition of Ci-C 4 alkyl, except that such radical is attached to the rest of the molecule by two single bonds.
  • Ci-C6haloalkyl refers to a Ci-C6alkyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • Examples of Ci-C6haloalkyl include, but are not limited to fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl, and 3,3,3-trifluoropropyl.
  • Ci-C6alkoxy refers to a radical of the formula R a O- where R a is a C1- Cealkyl radical as generally defined above.
  • the term "Ci-C 4 alkoxy” should be construed accordingly. Examples of Ci-C6alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy, and t- butoxy.
  • Ci-C6haloalkoxy refers to a Ci-C6alkoxy group as defined above substituted by one or more of the same or different halogen atoms. Ci-C 4 haloalkoxy is to be construed accordingly. Examples of Ci-C6haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy, and trifluoroethoxy.
  • C2-C6alkenyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond that can be of either the (E)- or (Z)-configu ration, having from two to six carbon atoms, which is attached to the rest of the molecule by a single bond.
  • Examples of C2-C6alkenyl include, but are not limited to, prop-1-enyl, allyl (prop-2-enyl), and but-1-enyl.
  • C2-C6haloalkenyl refers to a C2-C6alkenyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C2-C6alkynyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two to six carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • Examples of C2-C6alkynyl include, but are not limited to, prop-1 -ynyl, propargyl (prop-2-ynyl), and but-1-ynyl.
  • C2-C6haloalkynyl refers to a C2-C6alkynyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C3-C6cycloalkyl refers to a stable, monocyclic ring radical which is saturated or partially unsaturated and contains 3 to 6 carbon atoms.
  • C3-C 4 cycloalkyl is to be construed accordingly.
  • Examples of C3-C6cycloalkyl include, but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclopenten-1-yl, cyclopenten-3-yl, and cyclohexen-3-yl.
  • C3-C6cycloalkylCi-C 4 alkyl refers to a C3-C6cycloalkyl ring as defined above attached to the rest of the molecule by a Ci-C 4 alkylene radical as defined above.
  • Examples of C3-C6cycloalkylCi-C 4 alkyl include, but are not limited to cyclopropyl-methyl, cyclobutyl-ethyl, and cyclopentyl-methyl.
  • C3-C6halocycloalkyl refers to a C3-C6cycloalkyl ring as defined above substituted by one or more of the same or different halogen atoms.
  • C3-C6halocycloalkylCi-C 4 alkyl refers to a C3-C6halocycloalkyl radical as defined above attached to the rest of the molecule by a Ci-C 4 alkylene radical as defined above.
  • Ci-C 4 alkoxyCi-C 4 alkyl refers to a radical of the formula Ry-O-Rx- where R y is a Ci-C 4 alkyl radical as generally defined above, and R x is a Ci-C 4 alkylene radical as generally defined above.
  • Ci-C 4 haloalkoxyCi-C 4 alkyl refers to a radical of the formula Ry-O-Rx- where R y is a Ci-C 4 alkyl radical as generally defined above substituted by one or more of the same or different halogen atoms, and R x is a Ci-C 4 alkylene radical as generally defined above.
  • Ci-C 4 alkoxyCi-C 4 alkoxy refers to radical of the formula Ry-O-Rx-O- where R y is a Ci-C 4 alkyl radical as generally defined above, and R x is a Ci-C 4 alkylene radical as generally defined above. Ci-C2alkoxyCi-C2alkoxy” should be construed accordingly.
  • cyanoCi-C 4 alkyl refers to a Ci-C 4 alkyl radical as generally defined above substituted by one or more cyano groups. CyanoCi-C2alkyl should be construed accordingly.
  • cyanoCi-C 4 haloalkyl refers to a Ci-C6haloalkyl radical as generally defined above substituted by one or more cyano groups.
  • Ci-C 4 alkylsulfanyl refers to a radical of the formula R X S- wherein R x is a Ci-C 4 alkyl radical as generally defined above.
  • Ci-C 4 haloalkylsulfanyl refers to a Ci-C 4 alkylsulfanyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • Ci-C 4 alkylsulfinyl refers to a radical of the formula R x S(0)- wherein R x is a Ci-C 4 alkyl radical as generally defined above.
  • Ci-C 4 haloalkylsulfinyl refers to a Ci-C 4 alkylsulfinyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • Ci-C 4 alkylsulfonyl refers to a radical of the formula R X S(0) 2 - wherein R x is a Ci-C 4 alkyl radical as generally defined above.
  • Ci-C 4 haloalkylsulfonyl refers to a Ci-C 4 alkylsulfonyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • Ci-C 4 alkylcarbonyl refers to a radical of the formula R x C(0)- where R x is a Ci-C 4 alkyl radical as generally defined above.
  • Ci-C 4 haloalkylcarbonyl refers to a Ci-C 4 alkylcarbonyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • Ci-C 4 alkoxycarbonyl refers to a radical of the formula R x OC(0)- where R x is a Ci-C 4 alkyl radical as generally defined above.
  • Ci-C 4 haloalkoxycarbonyl refers to a Ci-C 4 alkoxycarbonyl as generally defined above substituted by one or more of the same or different halogen atoms.
  • Ci-C 4 alkylcarbonylamino refers to a radical of the formula R x C(0)N(H)- where R x is a Ci-C 4 alkyl radical as generally defined above.
  • Ci-C 4 haloalkylcarbonylamino refers to a Ci-C 4 alkylcarbonylamino radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C3-C6cycloalkylcarbonylamino refers to a radical of the formula RxC(0)N(H)- where R x is a C3-C6cycloalkyl radical as generally defined above.
  • C3-C6halocycloalkylcarbonylamino refers to a C3-
  • Ci-C 4 alkylaminocarbonyl refers to a radical of the formula RxNHC(O)- where R x is a Ci-C 4 alkyl radical as generally defined above.
  • Ci-C 4 haloalkylaminocarbonyl refers to a Ci-C 4 alkylaminocarbonyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C3-C6cycloalkylaminocarbonyl refers to a radical of the formula RxNHC(O)- where R x is a C3-C6cycloalkyl radical as generally defined above.
  • C3-C6halocycloalkylaminocarbonyl refers to a C3-
  • C3-C 4 cycloalkylcarbonyl refers to a radical of the formula R x C(0)- where R x is a C3-C 4 cycloalkyl radical as generally defined above.
  • C3-C6halocycloalkylcarbonyl refers to a C3-C6cycloalkylcarbonyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • heteroaryl generally refers to a 5- or 6-membered monocyclic aromatic ring radical which comprises 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur.
  • the heteroaryl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom.
  • heteroaryl may include pyridyl, pyrimidyl, pyrrolyl, pyrazolyl, furyl, thienyl, imidazolyl, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyrazinyl, pyridazinyl, triazinyl, pyranyl.
  • heterocyclyl or “heterocyclic” generally refers to a stable, saturated or partially saturated, 4- to 6-membered, non-aromatic monocyclic ring, which comprises 1 , 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur.
  • the heterocyclyl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom.
  • heterocyclyl examples include, but are not limited to, azetidinyl, oxetanyl, pyrrolidyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidinyl, piperazinyl, tetrahydropyranyl, dioxolanyl, and morpholinyl.
  • the compounds of formula (I) are mesoionic inner salts.
  • Inner salts also known in the art as “zwitterions”
  • zwitterions are electrically neutral molecules, but carry formal positive and negative charges on different atoms in each valence bond structure according to valence bond theory.
  • the molecular structure of the compounds of formula (I) can be represented by the four valence bond structures shown below, each placing the formal positive and negative charges on different atoms. Because of this resonance, the compounds of formula (I) are also described as "mesoionic".
  • the compounds of formula (I) according to the invention which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as Ci-C 4 alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxy carboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as Ci-C 4 -alkane- or arylsulfonic acids which are unsubstituted or substituted, for example
  • Compounds of formula (I) which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
  • bases for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts
  • salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, die
  • asymmetric carbon atoms in a compound of Formula (I) means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Also, atropisomers may occur as a result of restricted rotation about a single bond.
  • Formula (I) is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof for a compound of Formula (I).
  • Formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) where present. The present invention includes all possible tautomeric forms for a compound of Formula (I).
  • the compounds of Formula (I) according to the invention are in free form, in oxidized form as an N-oxide, in covalently hydrated form, or in salt form, e.g., an agronomically usable or agrochemically acceptable salt form.
  • N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
  • the compounds of formula (I) according to the invention also include hydrates, which may be formed during salt formation.
  • W is O or S.
  • W is O.
  • R 1 is Ci-C6alkyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or Ci-C6haloalkyl; or
  • R 1 is C2-C6alkenyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or C2-C6haloalkenyl; or
  • R 1 is C2-C6alkynyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or C2-C6haloalkynyl; or
  • R 1 is C3-C6cycloalkyl, wherein the cycloalkyl moiety is optionally substituted by 1 or 2 substituents independently selected from Lh or a single substituent selected from U2; or
  • R 1 is cyano
  • R 1 is Ci-C6alkyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or R 1 is Ci-C 4 haloalkyl; or
  • R 1 is C2-C6alkenyl or C 2 -C 4 haloalkenyl
  • R 1 is C2-C6alkynyl or C 2 -C 4 haloalkynyl
  • R 1 is cyano
  • R 1 is Ci-C 4 alkyl optionally substituted by: (i) a single substituent selected from Ui , wherein Ui is selected from cyano, Ci-C 4 alkylcarbonyl, Ci-C 4 alkoxycarbonyl, Ci-C 4 haloalkylcarbonyl, C1- C 4 haloalkoxycarbonyl, Ci-C 4 alkylaminocarbonyl or Ci-C 4 haloalkylaminocarbonyl, or (ii) a single substituent selected from U2, wherein U2 is selected from phenyl or pyridinyl optionally substituted by 1 or 2 independently selected halogen groups or a single U4 selected from methyl, ethyl, trifluoromethyl, cyclopropyl, methoxy; or
  • R 1 is Ci-C 4 haloalkyl
  • R 1 is C3-C 4 alkenyl; or R 1 is C3-C 4 alkynyl; or
  • R 1 is cyano
  • R 1 may be selected from:
  • R 1 is methyl or ethyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, eg, such that a methylene linker is present between the Ui or U2 group and the rest of the molecule.
  • R 1 is methyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, ie, such that a methylene linker is present between the Ui or U2 group and the rest of the molecule.
  • R 1 is Ci-C6haloalkyl, preferably, it is Ci-C 4 haloalkyl, and in particular, Ci-C2fluoroalkyl or C1- C2chloroalkyl.
  • Ui is cyano, C3-C6cycloalkyl, C3-C6halocycloalkyl, Ci-C 4 alkoxy, Ci-C 4 haloalkoxy, Ci- C2alkoxy-Ci-C2alkoxy, Ci-C 4 alkylsulfanyl, Ci-C 4 haloalkylsulfanyl, Ci-C 4 alkylcarbonyl, Ci- C 4 alkoxycarbonyl, Ci-C 4 haloalkylcarbonyl, Ci-C 4 haloalkoxycarbonyl, C3-C 4 cycloalkylcarbonyl, Ci- C 4 alkylaminocarbonyl or Ci-C 4 haloalkylaminocarbonyl.
  • Ui is cyano, C3-C 4 cycloalkyl, C3-C 4 fluorocycloalkyl, C3-C 4 chlorocycloalkyl, Ci-C3alkoxy, Ci-C2alkoxy-Ci-C2alkoxy, Ci-C3alkylsulfanyl, Ci-C3alkoxycarbonyl, Ci-C3alkylcarbonyl, Ci-C3alkoxycarbonyl, Ci-C3haloalkylcarbonyl, Ci- C3haloalkoxycarbonyl, C3-C 4 cycloalkylcarbonyl, Ci-C3alkylanninocarbonyl or Ci-
  • U2 is phenyl, heteroaryl wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3, or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur, or a 5- or 6-membered saturated or partially saturated heterocyclic ring wherein the heterocyclic ring comprises 1 to 3 heteroatoms selected from nitrogen, oxygen and sulfur, and wherein each phenyl, heteroaryl or heterocyclic ring is optionally substituted by: (i) 1 , 2, 3, 4 or 5 independently selected halogen groups, or (ii) 1 or 2 groups independently selected from LU and optionally a halogen group;
  • U2 is phenyl, thiazolyl, thienyl, isoxazolyl, pyrazolyl, pyridinyl, pyrimidinyl or pyrazinyl optionally substituted by: (i) 1 , 2, 3, 4 or 5 independently selected halogen groups, or (ii) 1 or 2 groups independently selected from LU and optionally a halogen group.
  • U2 is phenyl, thiazol- 5-yl, thien-2-yl, isoxazol-4-yl, pyrazol-3-yl, pyridin-2-yl, pyridin-3-yl, pyrimidin-5-yl or pyrazin-2-yl optionally substituted by: (i) 1 , 2, 3, 4 or 5 independently selected halogen groups, or (ii) 1 or 2 groups independently selected from LU and optionally a halogen group.
  • U2 is phenyl, or pyridin-3-yl optionally substituted by: (i) 1 , 2 or 3 independently selected fluoro or chloro groups, or (ii) 1 group selected from LU and optionally a fluoro or chloro group.
  • Lh is halogen, nitro, cyano, amino, hydroxyl, CO2H, Ci-C 4 alkyl, Ci-C 4 haloalkyl, C3-C6cycloalkyl, C3- Cehalocycloalkyl, C3-C6halocycloalkyl-Ci-C 4 alkyl, C3-C6cycloalkyl-Ci-C 4 alkyl, Ci-C 4 alkoxy, Ci-C 4 alkoxy- Ci-C 4 alkyl, Ci-C 4 haloalkoxy, Ci-C 4 haloalkoxy-Ci-C 4 alkyl, cyano-Ci-C 4 alkyl, cyano-Ci-C 4 haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, Ci-C 4 alkylsulfanyl, Ci-C 4 alkyl
  • U3 is independently selected from halogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, C3-C6cycloalkyl, C1- C 4 alkoxy. More preferably, U3 is independently selected from chloro, fluoro, methyl, ethyl, trifluoromethyl, cyclopropyl, methoxy.
  • U4 is nitro, cyano, amino, hydroxyl, -SCN, -CO2H, Ci-C 4 alkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, C3-C6cycloalkyl-Ci-C 4 alkyl, C3-C6halocycloalkyl-Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, Ci-C 4 alkoxy- Ci-C 4 alkyl, Ci-C 4 alkoxy-Ci-C 4 alkoxy, cyano-Ci-C 4 alkyl, cyano-Ci-C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, Ci-C 4 haloalkoxy, Ci-C 4 haloalk
  • U4 is cyano, amino, hydroxyl, -SCN, -CO2H, C1- C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, or Ci-C 4 haloalkoxy. More preferably, U4 is cyano, Ci-C 4 alkyl, C1- C 4 fluoroalkyl, Ci-C 4 alkoxy or Ci-C 4 fluoroalkoxy. Still more preferably, U4 is cyano, methyl, trifluormethyl, methoxy or trifluoromethoxy.
  • m is 0, 1 or 2. In some embodiments of the invention, m is 0. In some embodiments of the invention, m is 1. In some embodiments of the invention, m is 2. Preferably, m is 0 or 1 , and more preferably, m is 0.
  • R 2 is independently selected from halogen, cyano, amino, hydroxyl, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci- C 4 haloalkoxy, Ci-C 4 alkoxy, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, Ci- C 4 alkylsulfanyl, Ci-C 4 alkylsulfinyl, Ci-C 4 alkylsulfonyl, Ci-C 4 haloalkylsulfanyl, Ci-C 4 haloalkylsulfinyl, Ci- C 4 haloalkylsulfonyl and cyclopropyl.
  • R 2 is independently selected from halogen, cyano, amino, hydroxyl, Ci-C 4 alkyl, Ci- C 4 fluoroalkyl, Ci-C 4 fluoroalkoxy, Ci-C 4 alkoxy, C 2 -C 4 alkenyl, C 2 -C 4 fluoroalkenyl, C 2 -C 4 alkynyl, and C 2 -C 4 fluoroalkynyl.
  • R 2 is independently selected from fluoro, chloro, methyl, ethyl, trifluoromethyl, trifluoromethoxy, methoxy or ethoxy. Still more preferably, R 2 is methyl.
  • R 3a and R 3b are independently selected from hydrogen, halogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci- C 4 alkoxy, Ci-C 4 haloalkoxy and cyano.
  • R 3a is hydrogen and R 3b is selected from hydrogen, chloro, fluoro, methyl, ethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, methoxy or ethoxy. More preferably, R 3a is hydrogen and R 3b is hydrogen or methyl. Most preferably, R 3a is hydrogen and R 3b is hydrogen.
  • R4 is selected from one of Y1 to Y7; wherein, n is 0, 1 , 2, or 3.
  • n is 0 or 1 .
  • Z is hydrogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy or Ci-C 4 haloalkoxy.
  • Z is hydrogen, methyl, ethyl or trifluoromethyl. More preferably, Z is hydrogen or methyl.
  • U is independently selected from halogen, cyano, nitro, hydroxyl, amino, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, Ci-C 4 haloalkoxy, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, Ci- C 4 haloalkoxy-Ci-C 4 alkyl, Ci-C 4 alkoxy-Ci-C 4 alkyl, Ci-C 4 alkylsulfanyl, Ci-C 4 alkylsulfinyl, Ci- C 4 alkylsulfonyl, Ci-C 4 haloalkylsulfanyl, Ci-C 4 haloalkylsulfinyl, Ci-C 4 haloalkylsulfonyl, formyl, cyclopropyl, Ci-C
  • U is independently selected from halogen, cyano, nitro, hydroxyl, amino, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C2alkoxy, Ci-C2haloalkoxy, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, Ci-C2haloalkoxy-Ci-C2alkyl, Ci- C2alkoxy-Ci-C2alkyl, Ci-C2alkylsulfanyl, Ci -C2al ky Isu If i ny I , Ci-C2alkylsulfonyl, Ci-C2haloalkylsulfanyl, Ci-C2haloalkylsulfinyl, Ci-C2haloalkylsulfonyl, formyl, cyclopropyl
  • U is independently selected from halogen, cyano, nitro, hydroxyl, amino, methyl, ethyl, trifluoromethyl, methoxy, formyl, cyclopropyl. Still more preferably, U is independently selected from halogen or trifluoromethyl, in particular when n is 1. Most preferably, U is fluoro, chloro or trifluoromethyl, in particular when n is 1.
  • R 4 is selected from one of Y2, Y3 or Y4.
  • R 4 is selected from one of:
  • R 4 is selected from one of:
  • R 4 is selected from one of:
  • the compound of Formula (I) is:
  • R 1 is defined in accordance with the present invention.
  • the compound of Formula (I) is:
  • R 1 is defined in accordance with the present invention.
  • the compound of Formula (I) is:
  • R 1 is defined in accordance with the present invention.
  • W is O or S
  • R 1 is Ci-C6alkyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or R 1 is Ci-C 4 haloalkyl; or R 1 is C2-C6alkenyl or C 2 -C 4 haloalkenyl; or R 1 is C2-C6alkynyl or C 2 -C 4 haloalkynyl; or R 1 is cyano;
  • n 0 or 1 ;
  • R 2 is fluoro, chloro, methyl, ethyl, trifluoromethyl, trifluoromethoxy, methoxy or ethoxy;
  • R 3a is hydrogen and R 3b is hydrogen or methyl
  • W is O
  • R 1 is Ci-C6alkyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or R 1 is Ci-C 4 haloalkyl; or R 1 is C2-C6alkenyl; or R 1 is C2-C6alkynyl; or R 1 is cyano;
  • n 0 or 1 ;
  • R 2 is fluoro, chloro or methyl
  • R 3a is hydrogen and R 3b is hydrogen or methyl
  • W is O
  • R 1 is Ci-C6alkyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or Ci-C 4 haloalkyl; or R 1 is C2-C6alkenyl; or R 1 is C2-C6alkynyl; or R 1 is cyano;
  • Ui is selected from cyano, Ci-C 4 alkylcarbonyl, Ci-C 4 alkoxycarbonyl, Ci-C 4 haloalkylcarbonyl, C1- C 4 haloalkoxycarbonyl, Ci-C 4 alkylaminocarbonyl, or Ci-C 4 haloalkylaminocarbonyl;
  • U2 is selected from phenyl or pyridinyl optionally substituted by 1 or 2 independently selected chloro or fluoro groups, or a single L4 selected from from methyl, ethyl, trifluoromethyl, cyclopropyl, methoxy;
  • n 0 or 1 ;
  • R 2 is fluoro, chloro or methyl
  • R 3a is hydrogen and R 3b is hydrogen or methyl
  • compounds of formula (I) can be prepared by treatment of compounds of formula (I la) with a compound of formula Ri- LG3 wherein LG3 is hydroxyl via activation of this hydroxyl using triphenyl phosphine and, for example di-isopropyl azodicarboxylate in an inert solvent such as THF at temperatures of 25 to 50°C.
  • a compound of formula Ri- LG3 wherein LG3 is hydroxyl via activation of this hydroxyl using triphenyl phosphine and, for example di-isopropyl azodicarboxylate in an inert solvent such as THF at temperatures of 25 to 50°C.
  • THF inert solvent
  • Compounds of formula (III) wherein R 1 , R 2 , R 3a , R 3b , R 4 and m are as described for the compounds of formula (I) may be prepared from the intermediates of formula (lib) by treatment with an electrophilic aminating agent, for example, with O-diphenylphosphorylhydroxyl amine (by analogy with procedures described in Bioorg. Med. Chem. 201 1 , 19, p. 5924) or O-mesitylenesulfonylhydroxylamine (by analogy with procedures described in Bioorg. Med. Chem. 2012, 20, p 1644).
  • the reaction can be performed in a solvent, for instance in dimethylformamide, dichloromethane or a mixture of both.
  • the reaction can be performed in a temperature range of -100 °C to the boiling point of the solvent, for example, between -10 to 20 °C.
  • the counter ion (anion) may depend on the electrophilic amination reagent (for example mesitylenesulfonate or diphenylphosphinate).
  • compounds of the formula (III) can lose the conjugated acid of the counter ion to leave the corresponding compounds of the formula (Ilia).
  • Compounds of formula (I), can be made by the reaction of compounds of formula (III) or compounds of formula (Ilia), wherein R 1 , R 2 , R 3a , R 3b , R 4 and m are as described for the compounds of formula (I) with compounds of formula (IVa) when W is O, or (IVb), when W is S.
  • LG1 and LG2 are independently from each other leaving groups, such as, for example halide, an aryloxy group or imidazolyl.
  • the reaction can be performed at 0°C to the boiling point of the solvent and preferably in the presence of a base, which could be, for example, pyridine, Hijnig’s base, triethylamine or sodium carbonate.
  • compounds of formula (I) where W is S may be prepared from compounds of formula (I), where W is O, as depicted in Scheme 1 , by treatment with a reagent such as Lawesson’s reagent or P 2 S5.
  • a reagent such as Lawesson’s reagent or P 2 S5.
  • the reaction can be performed in a non-participating solvent, such as for example THF or toluene, preferably at a temperature between 0°C and the boiling temperature of the solvent.
  • compounds of formula (lib) wherein R 1 , R 2 , R 3a , R 3b , R 4 and m are as described for formula (I) may also be prepared from compounds of formula (lla) in a three-step process by performing the following synthetic sequence: a) forming compounds of formula (lie), wherein R 2 , R 3a , R 3b , R 4 and m are as described for the compounds of formula (I) and ActG is an activating group, such as for example t-buyloxycarbonyl (BOC) by ways that are well known to the person skilled in the art, followed by,
  • compounds of formula (lid) can be prepared by treatment of compounds of formula (lie) with a compound of formula R1-LG3 wherein LG3 is hydroxyl via activation of this hydroxyl using triphenyl phosphine and, for example di-isopropyl azodicarboxylate in an inert solvent such as THF at temperatures of 25 to 50°C.
  • an inert solvent such as THF at temperatures of 25 to 50°C.
  • Compounds of formula (I) may be prepared from compounds of formula (IV) by treatment with a compound of formula R 1 -LG3 wherein LG3 is a leaving group such as for example chloride, iodide or a sulfonate in the presence of a base such as cesium carbonate or sodium hydride in an appropriate solvent, such as acetonitrile or dimethylformamide.
  • a base such as cesium carbonate or sodium hydride
  • an appropriate solvent such as acetonitrile or dimethylformamide.
  • Such alkylation is well known from the literature, however, two compounds may be obtained through an N-alkylation or O-alkylation. Here only the N- alkylation is desired and some control on the selectivity of the reaction could be obtained, by analogy as described, see, for example in European Journal of Organic Chemistry 2002, (1 1 ), p. 1763-1769.
  • compounds of formula (I) can be prepared by treatment of compounds of formula (IV) with a compound of formula R 1 -LG wherein LG is hydroxyl via activation of hydroxyl using triphenyl phosphine and, for example, di-isopropyl azodicarboxylate in an inert solvent such as THF at temperatures between 25 to 50°C.
  • an inert solvent such as THF
  • the reaction may be catalyzed by a palladium based catalyst, such as for example, (1 ,T-bis(diphenylphosphino)-ferrocene) dichloropalladium (Pd(dppf)Cl2) or bis(triphenylphosphine)palladium(ll) dichloride, optionally in the presence of phosphine additives (such as, for example, 2-dicyclohexyl-phosphino-2',6'-dimethoxy-biphenyl (S-PHOS)), in a solvent, such as, for example, 1 ,2-dimethoxyethane, dioxane, toluene, or tetrahydrofuran, preferably under an inert atmosphere.
  • the reaction temperature may preferentially be in the range from ambient temperature to the boiling point of the reaction mixture.
  • Compounds of formula (V) and compounds of formula (VI) are known to those skilled in the art or can be prepared by analogy to literature
  • the reaction is commonly performed in the presence or not of a base, such as potassium carbonate or sodium hydride, in a solvent, such as, for example, 1-methyl-2-pyrrolidinone, ethanol, water, dioxane or DMSO at a temperature between 50 to 210°C via a classical heating system or via microwaves.
  • a base such as potassium carbonate or sodium hydride
  • solvent such as, for example, 1-methyl-2-pyrrolidinone, ethanol, water, dioxane or DMSO at a temperature between 50 to 210°C via a classical heating system or via microwaves.
  • Example of these reactions are well known to those skilled in the art, see for example US 2010/0160303 or WO 2012/117059.
  • compounds of formula (lla') are a selection of compounds of formula (I la) wherein R 2 , R 4 and m are as described for the compounds of formula (I) and R 3a is hydrogen, Ci- C 4 alkyl or Ci-C 4 haloalkyl and R 3b is hydrogen.
  • Many compounds of formula (VII), wherein R 2 and m are as described for the compounds of formula (I) and X 2 is a halogen (preferably, X 2 is bromine), and susceptible to undergoing halogen-metal exchange by treatment with an organometallic reagent (eg, with butyllithium) are known in the literature and are even commercially available.
  • This group can be conveniently formed by reacting a compound of formula (VII) with hexane-2,5- dione in presence of a catalytic amount of a strong acid, such as para-toluenesulfonic acid, in refluxing toluene under azeotropic removal of water.
  • a strong acid such as para-toluenesulfonic acid
  • Compounds of formula (XI) may also be converted into compounds of formula (XII) via a radical reduction reaction, for example, after conversion of the hydroxyl group into a group susceptible to be cleaved in a radical reaction, such as a xanthate derivative or an iodide, in the presence of a radical initiator, such as azoisobutyronitrile, in refluxing acetonitrile or toluene and in the presence of a reagent that readily transfers hydrogen radicals (such as, trialkyltin hydride).
  • a radical reduction reaction for example, after conversion of the hydroxyl group into a group susceptible to be cleaved in a radical reaction, such as a xanthate derivative or an iodide, in the presence of a radical initiator, such as azoisobutyronitrile, in refluxing acetonitrile or toluene and in the presence of a reagent that readily transfers hydrogen radicals (such as, trial
  • this reaction can be performed under aqueous acidic conditions, for example, with an excess of hydrochloric acid in a solvent such as ethanol, preferably at a temperature between 0°C and 200 °C, most preferably in a closed reactor, for example, under microwave irradiation.
  • a solvent such as ethanol
  • the compounds of formula (lla') prepared as described in Scheme 5 are a subset of compounds of formula (lla) and can be used as starting materials in the synthetic sequences described in Schemes 1 to 4 to prepare a subset of compounds of formula (I), wherein R 1 , R 2 , R 4 and m are as described for formula (I) and R 3a is hydrogen, Ci-C 4 alkyl or Ci-C 4 haloalkyl and R 3b is hydrogen.
  • Suitable bases include pyridine, triethylamine, 4-(dimethylamino)- pyridine ("DMAP") or diisopropylethylamine (Hunig's base).
  • Solvents are, for example, tetrahydrofuran, dichloromethane or toluene.
  • the reaction is carried out at a temperature of from 0 °C to 100 °C, preferably from 15 °C to 30 °C, in particular at ambient temperature. Such reactions may be carried out under well-established methods and a variety of conditions used.
  • the resulting solution is generally used without purification in the next step.
  • Compounds of formula (I) can be made by the reaction of compounds of formula (XII) wherein R 1 , R 2 , R 3a , R 3b , R 4 and m are as described for formula (I) with an azide salt, such as sodium azide, in the presence of a solvent, such as dimethylformamide (DMF).
  • an azide salt such as sodium azide
  • a solvent such as dimethylformamide (DMF).
  • the reaction is typically carried out at a temperature of from 0 °C to 160 °C, preferably from 50 °C to 160 °C.
  • examples of suitable bases may include alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
  • Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N- diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
  • DBU ,8-diazabicyclo[5.4.0]undec-7-ene
  • the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also act as solvents or diluents.
  • Reactions are advantageously carried out in a temperature range from approximately -80 °C to approximately 140 °C, preferably from approximately -30 °C to approximately 100 °C, in many cases in the range between ambient temperature and approximately 80 °C.
  • a compound of formula (I) can be converted in a manner known per se into another compound of formula (I) by replacing one or more substituents of the starting compound of formula (I) in the customary manner by (an)other substituent(s) according to the invention.
  • Salts of compounds of formula (I) can be prepared in a manner known per se.
  • acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in the customary manner into the free compounds (I), acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • an acid for example with silver acetate
  • an inorganic salt which forms, for example silver chloride is insoluble and thus precipitates from the reaction mixture.
  • the compounds of formula (I) which have salt-forming properties, can be obtained in free form or in the form of salts.
  • the compounds of formula (I) and, where appropriate, the tautomer’s thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule, the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and herein below, even when stereochemical details are not mentioned specifically in each case.
  • Diastereomeric mixtures or racemic mixtures of compounds of formula (I), in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
  • Enantiomeric mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the di
  • Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.
  • the compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • the compounds of formula (I) according to the invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and may be well-tolerated by warm-blooded species, fish and plants.
  • the compounds of formula (I) may have a beneficial safety profile towards non-target species, such as bees, and accordingly a good toxicity profile.
  • the active ingredients according to the invention may act against all or individual developmental stages of normally sensitive, but also resistant pests, such as insects or representatives of the order Acarina.
  • the insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate.
  • Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp., from the order Coleoptera, for example,
  • Agriotes spp. Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromacu latus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Conoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp., Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemLineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Mala
  • Thyanta spp. Triatoma spp., Vatiga illudens, Acyrthosium pisum, Adalges spp., Agalliana ensigera, Agonoscena targionii, Aleurodicus spp., Aleurocanthus spp., Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp., Brachycaudus spp., Brevicoryne brassicae, Cacopsylla spp., Cavariella aegopodii Scop., Ceroplaster spp., Chrysom
  • Coptotermes spp. Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp., Solenopsis geminate
  • Thysanoptera for example
  • Thysanura for example, Lepisma saccharina.
  • the active ingredients according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
  • Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum, beet, such as sugar or fodder beet, fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries, leguminous crops, such as beans, lentils, peas or soya, oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts, cucurbits, such as pumpkins, cucumbers or melons, fibre plants, such as cotton, flax, hemp or jute, citrus fruit, such as oranges, lemons, grapefruit or tangerines, vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers, Lauraceae, such as avocado, Cinnamonium or camphor, and also tobacco, nuts,
  • the active ingredients according to the invention may especially be suitable for controlling Aphis craccivora, Diabrotica balteata, Thrips tabaci, Euschistus heros, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops.
  • the active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
  • the invention may also relate to a method of controlling damage to plant and parts thereof by plant parasitic nematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasitic nematodes), especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species, cyst-forming nematodes, Globodera rostochiensis and other Globodera species, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species, Seed gall nematodes, Anguina species, Stem and foliar nematodes, Aphelenchoides species, Sting nematodes, Belonolai
  • the compounds of the invention may also have activity against the molluscs.
  • Examples of which include, for example, Ampullariidae, Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus), Bradybaenidae (Bradybaena fruticum), Cepaea (C. hortensis, C. Nemoralis), ochlodina, Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum), Discus (D. rotundatus), Euomphalia, Galba (G. trunculata), Helicelia (H. itala, H.
  • H. aperta Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus), Lymnaea, Milax (M. gagates, M. marginatus, M. sowerbyi), Opeas, Pomacea (P. canaticulata), Vallonia and Zanitoides.
  • Compounds according to Formula (I) may find utility in controlling resistant populations of insects previously sensitive to the neonicotinoid class of pesticidal (insecticidal) agents (the “neonicotinoids”). Accordingly, the present invention may relate to a method of controlling insects which are resistant to a neonicotinoid insecticide comprising applying a compound of Formula (I) (eg, a single compound selected from compounds 1.001 to 1.045 listed in Table 1 (below) or a compound A1 to A29 listed in Table A (below)) to a neonicotinoid-resistant insect.
  • a compound of Formula (I) eg, a single compound selected from compounds 1.001 to 1.045 listed in Table 1 (below) or a compound A1 to A29 listed in Table A (below)
  • the present invention may relate to the use of a compound of Formula (I) (eg, a single compound selected from compounds 1.001 to 1.045 listed in Table 1 (below) or a compound A1 to A29 listed in Table A (below)) as an insecticide against neonicotinoid-resistant insects.
  • a compound of Formula (I) eg, a single compound selected from compounds 1.001 to 1.045 listed in Table 1 (below) or a compound A1 to A29 listed in Table A (below)
  • neonicotinoid-resistant insects may include insects from the order Lepidoptera or Hemiptera, in particular from the family Aphididae.
  • the neonicotinoids represent a well-known class of insecticides introduced to the market since the commercialization of pyrethroids (Nauen & Denholm, 2005: Archives of Insect Biochemistry and Physiology 58:200-215) and are extremely valuable insect control agents, not least because they had exhibited little or no cross-resistance to older insecticide classes, which suffer markedly from resistance problems.
  • reports of insect resistance to the neonicotinoid class of insecticides are on the increase.
  • Resistance may be defined as“a heritable change in the sensitivity of a pest population that is reflected in the repeated failure of a product containing an insecticidal active ingredient to achieve the expected level of control when used according to the label recommendation for that pest species” (IRAC).
  • Cross-resistance occurs when resistance to one insecticide confers resistance to another insecticide via the same biochemical mechanism. This can happen within insecticide chemical groups or between insecticide chemical groups. Cross-resistance may occur even if the resistant insect has never been exposed to one of the chemical classes of insecticide.
  • Target site resistance whereby resistance is associated with replacement of one or more amino acids in the insecticide target protein (i.e. the nicotinic acetylcholine receptor); and
  • the cytochrome P450 monooxygenases are an important metabolic system involved in the detoxification/activation of xenobiotics. As such, P450 monooxygenases play an important role in insecticide resistance. P450 monooxygenases have such a phenomenal array of metabolisable substrates because of the presence of numerous P450s (60-1 1 1 ) in each species, as well as the broad substrate specificity of some P450s. Studies of monooxygenase-mediated resistance have indicated that resistance can be due to increased expression of one P450 (via increased transcription) involved in detoxification of the insecticide and might also be due to a change in the structural gene itself. As such, metabolic cross-resistance mechanisms affect not only insecticides from the given class (e.g.
  • Target site resistance of nicotinoids is well studied and it has been shown that the modification of the active site of the nicotinic acetylcholine receptor confers resistance to nicotinoids.
  • Bass et al BMC Neuroscience 201 1 ), 12, p 51 , Pest Management Science (2016), 74(6), 1297- 1301 .
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae, or insecticidal proteins from Bacillus thuringiensis, such as d-endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A, or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins for example insecticidal proteins from Bacillus cereus or Bacillus popilliae
  • Bacillus thuringiensis such as d-endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2
  • 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-hydroxysteroidoxidase, ecdysteroid-UDP- glycosyl-transferase, cholesterol oxidases, ecd
  • d-endotoxins for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins.
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ).
  • Truncated toxins for example a truncated CrylAb, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • amino acid replacements preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G- recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • 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.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (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 Cry3Bb1 toxin), YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bb1 toxin), Starlink® (maize variety that expresses a Cry9C toxin), Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium), NuCOTN 33B® (cotton variety that expresses a CrylAc toxin), Bollgard I® (cotton variety that expresses a
  • transgenic crops are:
  • Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer ( Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
  • BPI76 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer ( Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylAb toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
  • NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 * MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225).
  • 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.
  • Crops may also be modified for enhanced resistance to fungal (for example Fusarium, Anthracnose, or Phytophthora), bacterial (for example Pseudomonas) or viral (for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens.
  • fungal for example Fusarium, Anthracnose, or Phytophthora
  • bacterial for example Pseudomonas
  • viral for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus
  • Crops also include those that have enhanced resistance to nematodes, such as the soybean cyst nematode.
  • Crops that are tolerance to abiotic stress include those that have enhanced tolerance to drought, high salt, high temperature, chill, frost, or light radiation, for example through expression of NF-YB or other proteins known in the art.
  • Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins, stilbene synthases, bibenzyl synthases, chitinases, glucanases, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225), antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906).
  • ion channel blockers such as blockers for sodium and calcium channels
  • the viral KP1 , KP4 or KP6 toxins stilbene synthases, bibenzyl synthases, chitinases, glucanases, the so-called
  • compositions according to the invention are the protection of stored goods and store ambients and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.
  • the present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors, see also http://www.who.int/malaria/vector_control/irs/en/).
  • the method for controlling pests comprises applying the compositions of the invention to the target pests, to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping.
  • an IRS indoor residual spraying
  • a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention.
  • compositions to a substrate such as non-woven or a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.
  • a substrate selected from nonwoven and fabric material comprising a composition which contains a compound of formula I.
  • the method for controlling such pests comprises applying a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention.
  • an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface.
  • compositions for residual control of pests on a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.
  • a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.
  • Substrates including non-woven, fabrics or netting to be treated may be made of natural fibres such as cotton, raffia, jute, flax, sisal, hessian, or wool, or synthetic fibres such as polyamide, polyester, polypropylene, polyacrylonitrile or the like.
  • the polyesters are particularly suitable.
  • the methods of textile treatment are known, e.g. WO 2008/151984, WO 03/034823, US 5631072, WO 2005/64072, WO 2006/128870, EP 1724392, WO 20051 13886 or WO 2007/090739.
  • compositions according to the invention are the field of tree injection/trunk treatment for all ornamental trees as well all sort of fruit and nut trees.
  • the compounds according to the present invention are especially suitable against wood-boring insects from the order Lepidoptera as mentioned above and from the order Coleoptera, especially against woodborers listed in the following Table:
  • the present invention may be also used to control any insect pests that may be present in turfgrass, including for example beetles, caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites, mole crickets, scales, mealybugs ticks, spittlebugs, southern chinch bugs and white grubs.
  • the present invention may be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.
  • the present invention may be used to control insect pests that feed on the roots of turfgrass including white grubs (such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green June beetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica), Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. (e.g. Black turfgrass ataenius, A.
  • white grubs such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp
  • Maladera spp. e.g. Asiatic garden beetle, M. castanea
  • Tomarus spp. ground pearls
  • Margarodes spp. mole crickets (tawny, southern, and short-winged, Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.).
  • the present invention may also be used to control insect pests of turfgrass that are thatch dwelling, including armyworms (such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta), cutworms, billbugs ( Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).
  • armyworms such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta
  • cutworms such as S. venatus verstitus and S. parvulus
  • sod webworms such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis.
  • the present invention may also be used to control insect pests of turfgrass that live above the ground and feed on the turfgrass leaves, including chinch bugs (such as southern chinch bugs, Blissus insularis), Bermudagrass mite ( Eriophyes cynodoniensis) , rhodesgrass mealybug ( Antonina graminis), two-lined spittlebug ( Propsapia bicincta), leafhoppers, cutworms ( Noctuidae family), and greenbugs.
  • chinch bugs such as southern chinch bugs, Blissus insularis
  • Bermudagrass mite Eriophyes cynodoniensis
  • rhodesgrass mealybug Antonina graminis
  • two-lined spittlebug Propsapia bicincta
  • leafhoppers Tricotuidae family
  • cutworms Noctuidae family
  • the present invention may also be used to control other pests of turfgrass such as red imported fire ants ( Solenopsis invicta) that create ant mounds in turf.
  • red imported fire ants Solenopsis invicta
  • compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • Anoplurida Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp.,
  • Nematocerina and Brachycerina for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysom
  • Heteropterida for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.,
  • Argas spp. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp.
  • Acarapis spp. for example Acarapis spp., Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp.
  • compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
  • compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec.,Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus
  • the compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants or addditives, such as carriers, solvents and surface-active substances.
  • formulation adjuvants or addditives such as carriers, solvents and surface-active substances.
  • the formulations can be in various physical forms, e.g.
  • Such formulations can either be used directly or diluted prior to use.
  • the dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
  • the active ingredients can also be contained in very fine microcapsules.
  • Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release).
  • Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art.
  • very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p- diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, A/,A/-dimethylformamide, dimethyl sulfoxide, 1 ,4- dioxane, di
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
  • a large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface- active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate, salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate, alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate, alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate, soaps, such as sodium stearate, salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate, dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate, sorbitol esters, such as sorbitol oleate, quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of
  • Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.
  • compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives.
  • the amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied.
  • the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively).
  • Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
  • inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.
  • the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Preferred formulations can have the following compositions (weight %):
  • Emulsifiable concentrates are:
  • active ingredient 1 to 95 %, preferably 60 to 90 %
  • surface-active agent 1 to 30 %, preferably 5 to 20 %
  • liquid carrier 1 to 80 %, preferably 1 to 35 %
  • active ingredient 0.1 to 10 %, preferably 0.1 to 5 %
  • active ingredient 5 to 75 %, preferably 10 to 50 %
  • surface-active agent 1 to 40 %, preferably 2 to 30 %
  • active ingredient 0.5 to 90 %, preferably 1 to 80 %
  • surface-active agent 0.5 to 20 %, preferably 1 to 15 %
  • solid carrier 5 to 95 %, preferably 15 to 90 %
  • active ingredient 0.1 to 30 %, preferably 0.1 to 15 %
  • solid carrier 99.5 to 70 %, preferably 97 to 85 %
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsions of any required dilution which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
  • the combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • the finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol.
  • Non-dusty coated granules are obtained in this manner.
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8: 1 ).
  • This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved.
  • a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added.
  • the mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
  • EC emulsion concentrate
  • SC suspension concentrate
  • SE suspo- emulsion
  • CS capsule suspension
  • WG water dispersible granule
  • the present invention makes available a pesticidal composition
  • a pesticidal composition comprising a compound of the first aspect, one or more formulation additives and a carrier.
  • compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients.
  • mixtures of the compounds of formula (I) with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use.
  • Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
  • TX means“one compound selected from the group consisting of a compound 1.001 to 1.045 listed in Table 1 (below) or a compound A1 to A29 listed in Table A (below)”: an adjuvant selected from the group of substances consisting of petroleum oils (628) + TX, an acaricide selected from the group of substances consisting of 1 , 1-bis(4-chlorophenyl)-2- ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate (lUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro-A/-methyl-A/-1-naphthylacetamide (IUPAC name) (1295) + TX, 4- chlorophenyl phenyl sulfone (IUPAC name) (981 ) + TX, abamectin (1 ) + T
  • an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, an anthelmintic selected from the group of substances consisting of abamectin (1 ) + TX, crufomate (101 1 ) + TX, dorame
  • a bactericide selected from the group of substances consisting of 1-hydroxy-1 /-/-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 (1 105) + TX, dodicin (1 1 12) + TX, fenaminosulf (1 144) + TX, formaldehyde (404) + TX, hydrargaphen [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(di
  • a biological agent selected from the group of substances consisting of Adoxophyes orana GV (12) + TX, Agrobacterium radiobacter (13) + TX, Amblyseius spp. (19) + TX, Anagrapha falcifera NPV (28) + TX, Anagrus atomus (29) + TX, Aphelinus abdominalis (33) + TX, Aphidius colemani (34) + TX, Aphidoletes aphidimyza (35) + TX, Autographa californica NPV (38) + TX, Bacillus firmus (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Kirk (scientific name) (51 ) + TX, Bacillus thuringiensis subsp.
  • a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX,
  • a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir [CCN] + TX, busulfan [CCN] + TX, diflubenzuron (250) + TX, dimatif [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron [CCN] + TX, tepa [CCN] + TX, thiohempa [CCN] + TX, thiotepa [CCN] + TX, tretamine [CCN] and uredepa [CCN] + TX,
  • an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541 ) + TX, (E,Z)-tetradeca-4, 10-dien-1-yl acetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, (Z)-hexadec-l 1- enal (IUPAC name) (436) + TX, (Z)-hexadec-l 1-en-1-yl acetate (IUPAC name) (437) + TX, (Z)- hexadec-13-en-1 1
  • an insecticide selected from the group of substances consisting of 1-dichloro-1-nitroethane (lUPAC/Chemical Abstracts name) (1058) + TX, 1 ,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), + TX, 1 ,2-dichloropropane (lUPAC/Chemical Abstracts name) (1062) + TX, 1 ,2- dichloropropane with 1 ,3-dichloropropene (IUPAC name) (1063) + TX, 1-bromo-2-chloroethane (lUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451 ) + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate (IUPAC name) (1066
  • 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, 1 ,2-dibromo-3-chloropropane (lUPAC/Chemical Abstracts name) (1045) + TX, 1 ,2-dichloropropane (IUPAC/ Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (IUPAC name) (1063) + TX, 1 ,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1 , 1-dioxide (lUPAC/Chemical Abstracts name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1 ,3,5-thiadiazinan-3-ylacetic acid (IUPAC name) (1286) +
  • a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (720) + TX
  • a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1 ,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891 ) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91 ) + TX, bromethalin (92) + T
  • a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (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 [CCN] and ribavirin [CCN] + TX,
  • a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX, and biologically active compounds selected from the group consisting of azaconazole (60207-31-0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [1 16255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [1 19446-68-3] + TX, diniconazole [83657-24-3] + TX, epoxiconazole [106325- 08-0] + TX, fenbuconazole [1 14369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674-21-0] + T
  • Acinetobacter Iwoffii + TX Acremonium alternatum + TX + TX, Acremonium cephalosporium + TX + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®) + TX, Agrobacterium radiobacter strain K84 (Galltrol-A®) + TX, Alternaria alternate + TX, Alternaria cassia + TX, Alternaria destruens (Smolder®) + TX, Ampelomyces quisqualis (AQ10®) + TX, Aspergillus flavus AF36 (AF36®) + TX, Aspergillus flavus NRRL 21882 (Aflaguard®) + TX, Aspergillus spp.
  • AdoxGV Adoxophyes orana granulovirus
  • Bacillus subtilis strain AQ178 + TX Bacillus subtilis strain QST 713 (CEASE® + TX, Serenade® + TX, Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain AQ153 + TX, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis var.
  • amyloliquefaciens strain FZB24 (Taegro® + TX, Rhizopro®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1 Ab + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis israelensis (BMP123® + TX, Aquabac® + TX, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin® + TX, Deliver® + TX, CryMax® + TX, Bonide® + TX, Scutella WP® + TX, Turilav WP ® + TX, Astuto® + TX, Dipel WP® + TX, Biobit® + TX, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone
  • aizawai (XenTari® + TX, DiPel®) + TX, bacteria spp. (GROWMEND® + TX, GROWSWEET® + TX, Shootup®) + TX, bacteriophage of Clavipacter michiganensis (AgriPhage®) + TX, Bakflor® + TX, Beauveria bassiana (Beaugenic® + TX, Brocaril WP®) + TX, Beauveria bassiana GHA (Mycotrol ES® + TX, Mycotrol O® + TX, BotaniGuard®) + TX, Beauveria brongniartii (Engerlingspilz® + TX, Schweizer Beauveria® + TX, Melocont®) + TX, Beauveria spp.
  • TX Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Bacillus thuringiensis tenebrionis (Novodor®) + TX, BtBooster + TX, Burkholderia cepacia (Deny® + TX, Intercept® + TX, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp.
  • TX Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reuêtii + TX, Candida saitoana (Bio-Coat® + TX, Biocure®) + TX, Candida sake + TX, Candida spp.
  • TX Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp.
  • TX Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean® / Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop® + TX, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp.
  • TX Halomonas subglaciescola + TX, Halovibrio variabilis + TX, Hanseniaspora uvarum + TX, Helicoverpa armigera nucleopolyhedrovirus (Helicovex®) + TX, Helicoverpa zea nuclear polyhedrosis virus (Gemstar®) + TX, Isoflavone - formononetin (Myconate®) + TX, Kioeckera apiculata + TX, Kioeckera spp.
  • Pasteuria spp. Econem® + TX, Pasteuria nishizawae + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart® + TX, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp.
  • TX Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Ps
  • Rhodosporidium diobovatum + TX Rhodosporidium toruloides + TX, Rhodotorula spp.
  • Trichoderma asperellum T34 Biocontrol®
  • Trichoderma gamsii TX
  • Trichoderma atroviride Plantmate®
  • Trichoderma harzianum rifai Mycostar®
  • Trichoderma harzianum T-22 Trianum-P® + TX, PlantShield HC® + TX, RootShield® + TX, Trianum-G®) + TX, Trichoderma harzianum T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma spp.
  • LC 52 (Sentinel®) + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma taxi + TX, Trichoderma virens + TX, Trichoderma virens (formerly Gliocladium virens GL-21 ) (SoilGuard®) + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium spp.
  • TX Trichothecium roseum + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplementary micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Verticillium lecanii (Mycotal® + TX, Vertalec®) + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhab
  • Plant extracts including: pine oil (Retenol®) + TX, azadirachtin (Plasma Neem Oil® + TX, AzaGuard® + TX, MeemAzal® + TX, Molt-X® + TX, Botanical IGR (Neemazad®, Neemix®) + TX, canola oil (Lilly Miller Vegol®) + TX, Chenopodium ambrosioides near ambrosioides (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, extract of neem oil (Trilogy®) + TX, essentials oils of Labiatae (Botania®) + TX, extracts of clove rosemary peppermint and thyme oil (Garden insect killer®) + TX, Glycinebetaine (Greenstim®) + TX, garlic + TX, lemongrass oil (GreenMatch®) + TX, neem oil + TX,
  • pheromones including: blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, Codling Moth Pheromone (Paramount dispenser-(CM)/ Isomate C-Plus®) + TX, Grape Berry Moth Pheromone (3M MEC-GBM Sprayable Pheromone®) + TX, Leafroller pheromone (3M MEC - LR Sprayable Pheromone®) + TX, Muscamone (Snip7 Fly Bait® + TX, Starbar Premium Fly Bait®) + TX, Oriental Fruit Moth Pheromone (3M oriental fruit moth sprayable pheromone®) + TX, Peachtree Borer Pheromone (Isomate-P®) + TX, Tomato Pinworm Pheromone (3M Sprayable pheromone®) + TX, Entostat powder (extract from palm tree) (Exosex CM®) + TX, Tetradecatrienyl a
  • Macrobials including: Aphelinus abdominalis + TX, Aphidius ervi (Aphelinus-System®) + TX, Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia®) + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius andersoni (Anderline® + TX, Andersoni-System®) + TX, Amblyseius californicus (Amblyline® + TX, Spical®) + TX, Amblyseius cucumeris (Thripex® + TX, Bugline cucumeris®) + TX, Amblyseius fallacis (Fallacis®) + TX, Amblyseius swirskii (Bugline
  • TX Bombus terrestris (Natupol Beehive®) + TX, Bombus terrestris (Beeline® + TX, T ripol®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperla carnea (Chrysoline®) + TX, Chrysoperla carnea (Chrysopa®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus spp.
  • TX Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug® + TX, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica + TX, Dacnusa sibirica (Minusa®) + TX, Diglyphus isaea (Diminex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis
  • TX Steinernematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator, and other biologicals including: abscisic acid + TX, bioSea® + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Colletotrichum gloeosporio
  • the ratio (by weight) of active ingredient mixture of the compounds of formula (I) selected from a compound 1.001 to 1.045 listed in Table 1 (below) or a compound A1 to A29 listed in Table A (below) with active ingredients described above is 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,
  • the mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
  • the mixtures comprising a compound of formula (I) selected from a compound 1.001 to 1.045 listed in Table 1 (below) or a compound A1 to A29 listed in Table A (below) 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 a compound 1.001 to 1.045 listed in Table 1 (below) or a compound A1 to A29 listed in Table A (below) and the active ingredients as described above is not essential for working the present invention.
  • the present invention provides a combination of active ingredients comprising a compound defined in the first aspect, and one or more further active ingredients (whether chemical or biological).
  • compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
  • auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides
  • compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • compositions that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention.
  • Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient.
  • the rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.
  • a preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question.
  • the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.
  • the compounds of the invention and compositions thereof are also be suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type.
  • the propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing.
  • the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling.
  • These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention.
  • Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.
  • seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
  • the present invention also comprises seeds coated or treated with or containing a compound of formula (I).
  • coated or treated with and/or containing generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application.
  • the seed product When the said seed product is (re)planted, it may absorb the active ingredient.
  • the present invention makes available a plant propagation material adhered thereto with a compound of formula (I). Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula (I).
  • Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
  • the seed treatment application of the compound formula (I) can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.
  • a further aspect is a plant propagation material comprising by way of treatment or coating one or more compounds of formula (I) according to the invention, optionally also comprising a colour pigment.
  • Table 1 This table discloses 45 compounds of the formula (1-1 ):
  • R 3a and R 3b are hydrogen, and R 1 and R 4 are as defined in the below Table.
  • the compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 20 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm, or lower application rates, such as 300, 200 or 100 mg of Al per m 2 .
  • Compounds of Formula (I) may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physicochemical properties, or increased biodegradability).
  • LC/MS means Liquid Chromatography Mass Spectrometry and the description of the apparatus and the method A is outlined below.
  • the characteristic LC/MS values obtained for each compound were the retention time (“Rt”, recorded in minutes (min)) and the measured molecular ion (M+H) + and/or (M- H)-.
  • 1 H NMR measurements were recorded on Brucker 400 MHz or 300 MHz spectrometers, chemical shifts (d) are given in ppm relevant to a TMS standard. Spectra are measured in deuterated solvents (eg, dimethyl sulfoxide (DMSO)) as indicated.
  • DMSO dimethyl sulfoxide
  • Example P1 Preparation of 2-[2-[(6-chloro-3-pyridyl)methyl]-8-oxo-7-aza-1-azonia-9-azanida- bicyclo[4.3.0]nona-1 ,3,5-trien-7-yl]acetonitrile (compound A1 ).
  • the reaction mixture was diluted with ethyl acetate and washed with water, then saturated aqueous solution of ammonium chloride.
  • the organic phase was dried over magnesium sulfate.
  • the crude product was submitted to flash chromatography over silica gel, eluting with a gradient from 0% to 100% of ethyl acetate in cyclohexane. After evaporation of the selected fractions, the title compound was isolated as a solid.
  • Example P2 Preparation of 2-[(6-chloro-3-pyridyl)methyl]-7-(difluoromethyl)-7-aza-1-azonia-9- azanidabicyclo[4.3.0]nona-1 ,3,5-trien-8-one (compound A2).
  • Step P2-A Synthesis of 6-[(6-chloro-3-pyridyl)methyl]-N-methyl-pyridin-2-amine.
  • Step P2-B Synthesis of 6-[(6-chloro-3-pyridyl)methyl]-N2-methyl-pyridin-1-ium-1 ,2-diamine:2, 4,6- trimethyl benzenesulfonate.
  • Step P2-C Synthesis of 2-[(6-chloro-3-pyridvDnnethvn-7-(difluoronnethvD-7-aza-1-azonia-9-azanida- bicvclo[4.3.0lnona-1 ,3.5-trien-8-one (compound A2V
  • the reaction mixture was then diluted with dichloromethane, washed with saturated aqueous solution of sodium bicarbonate, dried over sodium sulfate and evaporated.
  • the crude compound was submitted to flash chromatography over silica gel, eluting with 5% methanol in dichloromethane. The evaporation of the selected fractions left the title compound as an off-white solid.
  • Example P3 Preparation of 2-[(6-chloro-3-pyridyl)methyl]-7-(2,2-difluoroethyl)-7-aza-1-azonia-9- azanidabicyclo[4.3.0]nona-1 ,3,5-trien-8-one (compound A3).
  • Step P3-A Synthesis of tert-butyl N-[6-[(6-chloro-3-pyridyl)methyl]-2-pyridyl]carbamate.
  • Step P3-B Synthesis of tert-butyl N-[6-[(6-chloro-3-pyridyl)methyl]-2-pyridyl]-N-(2,2-difluoroethyl)- carbamate.
  • Step P3-C Synthesis of 6-[(6-chloro-3-pyridyl)methyl]-N-(2,2-difluoroethyl)pyridin-2-amine.
  • Step P3-D and Step P3-E Synthesis of 2-[(6-chloro-3-pyridyl)methyl]-7-(2,2-difluoroethyl)-7-aza-1- azonia-9-azanidabicyclo[4.3.0]nona-1 ,3,5-trien-8-one (compound A3)
  • Example P5 Preparation of 2-[(6-chloro-3-pyridyl)methyl]-7-ethyl-7-aza-1-azonia-9-azanidabicyclo [4.3.0]nona-1 ,3,5-trien-8-one (compound A5).
  • Step P5-A Synthesis of 6-[(6-chloro-3-pyridvnmethyll-N-ethyl-pyridin-2-amine.
  • Step P5-B and Step P5-C Preparation of 2-[(6-chloro-3-pyridyl)methyl]-7-ethyl-7-aza-1-azonia-9- azanidabicyclo[4.3.0]nona-1 ,3,5-trien-8-one (compound A5).
  • Example P6 Preparation of methyl 2-[2-[(6-chloro-3-pyridyl)methyl]-8-oxo-7-aza-1-azonia-9- azanidabicyclo[4.3.0]nona-1 ,3,5-trien-7-yl]acetate (compound A6).
  • reaction mixture was evaporated under reduced pressure and the residue was partitioned between water and ethyl acetate.
  • the aqueous phase was extracted with ethyl acetate.
  • the crude product was purified by flash chromatography over silica gel, eluting with a gradient from 0% to 100% of ethyl acetate in cyclohexane. After evaporation of the selected fractions, the title compound was isolated as a solid.
  • Example P7 Preparation of 2-[2-[(6-chloro-3-pyridyl)methyl]-8-oxo-7-aza-1-azonia-9-azanidabicyclo [4.3.0]nona-1 ,3,5-trien-7-yl]-N-methyl-acetannide (compound A7).
  • Step P7-A Synthesis of tert-butyl N-[6-[(6-chloro-3-pyridyl)methyl]-2-pyridyl]carbamate (compound A7.)
  • Methylamine hydrochloride (0.259 mmol) was added, followed by HATU (1-[bis(dimethylamino)methylene]-1 H-1 ,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate) (0.207 mmol) and triethylamine (0.518 mmol). The mixture was stirred at 20°C overnight. The reaction mixture was then evaporated under reduced pressure and the residue was chromatographed over silica gel. The selected fractions were evaporated to prepare the title compound as a colorless solid.
  • Step P8-A Synthesis of (2-chlorothiazol-5-yl)-[6-(2,5-dimethylpyrrol-1-yl)-2-pyridyl]methanol
  • Step P8-B Synthesis of 2-chloro-5-[[6-(2,5-dimethylpyrrol-1-yl)-2-pyridyl]methyl]thiazole.
  • the aqueous phase was extracted twice with ethyl acetate and the combined organic extracts washed with 1 M sodium hydroxide, dried over magnesium sulfate and evaporated to yield the crude title compound as a dark brown oil that was used without further purification.
  • Step P8-C Synthesis of 6-[(2-chlorothiazol-5-yl)methyl]pyridin-2-annine.
  • Step P8-D Synthesis of 6-[(2-chlorothiazol-5-yl)methyl]-N-prop-2-ynyl-pyridin-2-amine.
  • Step P8-E Synthesis of 2-[(2-chlorothiazol-5-yl)methyl]-6-prop-2-ynylimino-pyridin-1 -amine.
  • Step P8-F Synthesis of 5-[(2-chlorothiazol-5-yl)methyl]-1-prop-2-ynyl-[1 ,2,4]triazolo[1 ,5-a]pyridin-4- ium-2-olate (compound A12).
  • Example P9 Preparation of 1-allyl-5-[(6-chloro-3-pyridyl)methyl]-[1 ,2,4]triazolo[1 ,5-a]pyridin-4-ium-2- olate (compound A13).
  • Example P10 Preparation of 1-[(6-chloro-3-pyridyl)methyl]-5-[(2-chlorothiazol-5-yl)methyl]-[1 ,2,4]- triazolo[1 ,5-a]pyridin-4-ium-2-olate (compound A14).
  • Step P10-A Synthesis of N-[(6-chloro-3-pyridyl)methyl]-6-[(2-chlorothiazol-5-yl)methyl]pyridin-2-annine.
  • 6-[(2-chlorothiazol-5-yl)methyl]pyridin-2-amine (preparation described above) (0.150 g, 0.67 mmol) in methanol (3.32 ml_), in a vial with a magnetic stirring bar, were added 6- chloropyridine-3-carbaldehyde (0.125 g, 0.86 mmol) and acetic acid (0.048 g, 0.80 mmol), followed by sodium cyanoborohydride (0.066 g, 1.0 mmol). The mixture was stirred at 20°C.
  • Step P10-B Synthesis of 2-[(6-chloro-3-pyridyl)methylimino]-6-[(2-chlorothiazol-5-yl)methyl]pyridin-1- amine.
  • Step P10-C Synthesis of 1-[(6-chloro-3-pyridyl)methyl]-5-[(2-chlorothiazol-5-yl)methyl]-[1 ,2,4]triazolo [1 ,5-a]pyridin-4-ium-2-olate.
  • the reaction mixture was then diluted with water, extracted twice with ethyl acetate and the organic phase was washed with water and saturated aqueous ammonium chloride solution. The organic phase was dried over magnesium sulfate and dried.
  • the crude compound was dissolved in dimethyl sulfoxide (0.5 ml_) and purified by reverse phase chromatography, eluting with a gradient of 20% to 60% acetonitrile in water. The selected fractions yielded the title compound.
  • Example P11 Preparation of 2-[(6-chloro-3-pyridyl)methyl]-7-cyclopropyl-7-aza-1-azonia-9- azanidabicyclo[4.3.0]nona-1 ,3,5-trien-8-one (compound A17).
  • Step A Synthesis of 2-bromo-6-[(6-chloro-3-pyridvDnnethvnpyhdine.
  • Step B Synthesis of tert-butyl N-[6-[(6-chloro-3-pyridvnmethyll-2-pyridyll-N-cvclopropyl-carbamate
  • Step D Synthesis of N-[6-[(6-chloro-3-pyridvnmethyll-2-pyridyll-N-cvclopropyl-carbamoyl chloride.
  • Step E Synthesis of 2-[(6-chloro-3-pyridvDnnethvn-7-cvclopropyl-7-aza-1-azonia-9-azanidabicvclo [4.3.0lnona-1 ,3.5-trien-8-one (Compound A17V
  • Example P12 Preparation of 2-[(6-chloro-3-pyridyl)methyl]-7-[(1-methylpyrazol-4-yl)methyl]-7-aza-1- azonia-9-azanidabicyclo[4.3.0]nona-1 ,3,5-trien-8-one (Compound A24).
  • Step A Synthesis of 2-chloro-5-[(6-fluoro-2-pyridvnmethyllpyridine.
  • reaction mixture was heated to 50°C for 3.5 hours.
  • the reaction mixture was allowed to cool down to room temperature and was extracted between ethyl acetate (2x), water and sat. aq. ammonium chloride.
  • the combined organics were dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • the crude was purified by chromatography over silica gel to afford 2-chloro-5- [(6-fluoro-2-pyridyl)methyl]pyridine (1 1.3 g, 85 %) as a bright yellow solid.
  • Step B Synthesis of 6-[(6-chloro-3-pyridvnmethyll-N-[(1-methylpyrazol-4-vnmethyllpyridin-2-amine.
  • Step C Synthesis of N-[6-[(6-chlorc>-3-pyridvDnnethyll-2-pyridyll-N-[(1-nnethylpyrazol-4-vDmethyll carbamoyl chloride
  • Step D Synthesis of 2-[(6-chloro-3-pyridvnmethyll-7-[(1-methylpyrazol-4-vnmethyll-7-aza-1-azonia-9- azanidabicvclo[4.3.0lnona-1 ,3.5-trien-8-one (Compound A24V
  • Example P13 Preparation of 2-[(6-chloro-3-pyridyl)methyl]-7-(2-methylsulfanylethyl)-7-aza-1-azonia-9- azanidabicyclo[4.3.0]nona-1 ,3,5-trien-8-one (compound A29), 2-[(6-chloro-3-pyridyl)methyl]-7-(2- methylsulfonylethyl)-7-aza-1-azonia-9-azanidabicyclo[4.3.0]nona-1 ,3,5-trien-8-one (Compound A25) and 2-[(6-chloro-3-pyridyl)methyl]-7-(2-methylsulfinylethyl)-7-aza-1-azonia-9-azanidabicyclo [4.3.0] nona-1 ,3,5-trien-8-one (Compound A26).
  • Step A Synthesis of 6-[(6-chloro-3-pyridvDnnethyl1-N-(2-nnethylsulfanylethvDpyridin-2-annine
  • Step B Synthesis of N-[6-[(6-chloro-3-pyridvDnnethyll-2-pyridyll-N-(2-methylsulfanylethyl)carbamoyl chloride.
  • Step C Synthesis of 2-[(6-chloro-3-pyridvDnnethvn-7-(2-methylsulfanylethvD-7-aza-1-azonia-9- azanidabicvclo[4.3.0lnona-1 ,3.5-trien-8-one (compound A29V
  • Step D Synthesis of 2-[(6-chloro-3-pyridvDnnethvn-7-(2-nnethylsulfonylethvD-7-aza-1-azonia-9- azanidabicvclo[4.3.0lnona-1 ,3.5-trien-8-one (Compound A25) and 2-[(6-chloro-3-pyridvDnnethyll-7-(2- methylsulfinylethylV7-aza-1-azonia-9-azanidabicvclo[4.3.0lnona-1.3.5-trien-8-one (Compound A26V
  • Table A This Table discloses compounds of the formula (1-1 )
  • R 3a and R 3b are hydrogen, and R 1 and R 4 are as defined in the below Table.
  • Bemisia tabaci (Cotton white fly): Feeding/contact activity.
  • Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying, the leaf discs were infested with adult white flies. The samples were checked for mortality 6 days after incubation.
  • Myzus persicae Green peach aphid:Feeding/Contact activity.
  • Sunflower leaf discs were placed onto agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. The samples were assessed for mortality 6 days after infestation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm:
  • Roots of pea seedlings infested with an aphid population of mixed ages were placed directly into aqueous test solutions prepared from 10,000 DMSO stock solutions. The samples were assessed for mortality 6 days after placing seedlings into test solutions.
  • Test compounds prepared from 10,000 ppm DMSO stock solutions were applied by pipette into 24-well microtiter plates and mixed with sucrose solution. The plates were closed with a stretched Parafilm. A plastic stencil with 24 holes was placed onto the plate and infested pea seedlings were placed directly on the Parafilm. The infested plate was closed with a gel blotting paper and another plastic stencil and then turned upside down. The samples were assessed for mortality 5 days after infestation.
  • Nilaparvata lugens (Brown plant hopper - metabolic neonicotinoid-resistant), larvicide, feeding/contact Rice plants were treated with the diluted test solutions in a spray chamber. After drying, the plants were infested with ⁇ 20 N3 nymphs. 7 days after the treatment, samples were assessed for mortality and growth regulation.
  • A3, A4, A5, A1 Myzus persicae (Green peach aphid - neonicotinoid-resistant), mixed population, contact.
  • Pea seedlings infested with a mixed-aged neonicotinoid-resistant Myzus persicae population were treated with diluted test solutions in a spray chamber and checked for mortality 5 days after treatment.
  • the following compounds gave at least 80% control of the neonicotinoid-resistant strain of Myzus persicae at 200 ppm:
  • RF(50) LC(50) of resistant strain/LC(50) of susceptible strain, wherein the LC(50) is the lethal concentration where 50% of the population is controlled.

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Abstract

Un composé de formule (I) dans laquelle les substituants sont tels que définis dans la revendication 1, et les sels, stéréoisomères, énantiomères, tautomères et N-oxydes agrochimiquement acceptables de ces composés peuvent être utilisés en tant qu'insecticides.
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WO2005113886A1 (fr) 2004-05-12 2005-12-01 Basf Aktiengesellschaft Procede de traitement de substrats flexibles
WO2006087343A1 (fr) 2005-02-16 2006-08-24 Basf Aktiengesellschaft Anilides d'acide carboxylique pyrazole, procedes de production associes et agents les contenant pour la lutte antifongique
EP1724392A2 (fr) 2005-05-04 2006-11-22 Fritz Blanke Gmbh & Co. Kg Procédé d'apprêtage anti-microbien de surfaces textiles
WO2006128870A2 (fr) 2005-06-03 2006-12-07 Basf Aktiengesellschaft Composition pour impregnation de fibres, tissus et filets a action protectrice contre les ravageurs
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WO2008151984A1 (fr) 2007-06-12 2008-12-18 Basf Se Formulation aqueuse et processus d'imprégnation de matières non vivantes exerçant une action protectrice contre les parasites
WO2010027500A1 (fr) 2008-09-08 2010-03-11 Signal Pharmaceuticals, Llc Aminotriazolopyridines et leur utilisation comme inhibiteurs de kinase
US20100160303A1 (en) 2008-12-19 2010-06-24 Bristol-Myers Squibb Company Carbazole carboxamide compounds useful as kinase inhibitors
WO2012092115A1 (fr) 2010-12-29 2012-07-05 E. I. Du Pont De Nemours And Company Pesticides à base pyrido[1,2-a]pyrimidines mésoioniques
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