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WO2020120697A1 - Pesticidally-active cyanamide heterocyclic compounds - Google Patents

Pesticidally-active cyanamide heterocyclic compounds Download PDF

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Publication number
WO2020120697A1
WO2020120697A1 PCT/EP2019/084951 EP2019084951W WO2020120697A1 WO 2020120697 A1 WO2020120697 A1 WO 2020120697A1 EP 2019084951 W EP2019084951 W EP 2019084951W WO 2020120697 A1 WO2020120697 A1 WO 2020120697A1
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Prior art keywords
alkyl
spp
optionally substituted
cyano
independently selected
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PCT/EP2019/084951
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French (fr)
Inventor
Pierre Joseph Marcel Jung
Aurelien BIGOT
Julien Daniel Henri GAGNEPAIN
Stefano RENDINE
André Stoller
Nicola COMPAGNONE
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Syngenta Crop Protection AG Switzerland
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Syngenta Crop Protection AG Switzerland
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention relates to pesticidally active, in particular insecticidally active 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 imino-substituted N-heterocyclic compounds are known, for example, from EP 2 634 174, EP 0 259 738 or Journal of Agricultural and Food Chemistry (2017), 65(36), 7865-7873. It has now been found that further imino-substituted N-heterocyclic compounds have insecticidal properties.
  • A is a direct link, O, or S(0) P wherein p is selected from 0, 1 or 2;
  • 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 optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2;
  • C2-C6alkenyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or C2-C6haloalkenyl;
  • C 2 -C7alkynyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or C2-C6haloalkynyl;
  • 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 4- to 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 L4 and optionally a halogen group;
  • L is halogen, nitro, cyano, amino, hydroxyl, CO2H, Ci-C 4 alkyl, Ci-C 4 haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, 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 alky
  • U4 is nitro, cyano, amino, hydroxyl, -SCN, -CO2H, Ci-C 4 alkyl, C3-C6cycloalkyl, C3- Cehalocycloalkyl, 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
  • R 3a and R 3b are independently selected from hydrogen, halogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy and cyano;
  • R 4 is selected from one of Y1 to Y4;
  • n 0, 1 or 2;
  • 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
  • R 5 is hydrogen, Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, cyanoCi-Cealkyl, nitroCi-C 4 alkyl, Ci-C 4 alkoxyCi-C 4 alkyl, Ci- C 4 halolkoxyCi-C 4 alkyl, Ci-C 4 alkylsulfinylCi-C 4 alkyl, Ci-C 4 alkylsulfonylCi-C 4 alkyl, Ci- C 4 haloalkylsulfanylCi-C 4 alkyl, Ci-C 4 haloalkylsulfinylCi-C 4 alkyl, Ci-C 4 haloalkylsulfonylCi-C 4 alkyl and C3
  • R 5 is Ci-C 4 alkyl or Ci-C 4 haloalkyl substituted by phenyl or 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, and wherein each phenyl or heteroaryl ring is optionally substituted by 1 or 2 groups independently selected from halogen, cyano, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, Ci-C 4 haloalkoxy, Ci-C 4 alkylsulfanyl, Ci-C 4 alkylsulfinyl, Ci-C 4 alkylsulfonyl, Ci- C 4 haloalkylsulfanyl, Ci-C 4 haloalkylsulfinyl and Ci-C 4 haloalkylsulfonyl;
  • R 5 is Ci-C6alkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, 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 alkylsulfanyl, Ci-C 4 alkylsulfinyl, Ci-C 4 alkylsulfonyl, Ci-C 4 haloalkylsulfanyl, Ci-C 4 haloalkylsulfinyl, Ci- C 4 haloalkylsulfonyl, C3-C6cycloalkyl and phenyl or 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,
  • R 5 is Ci-C6haloalkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, 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 alkylsulfanyl, Ci-C 4 alkylsulfinyl, Ci-C 4 alkylsulfonyl, Ci-C 4 haloalkylsulfanyl, Ci-C 4 haloalkylsulfinyl, Ci-C 4 haloalkylsulfonyl, C3-C6cycloalkyl and phenyl or 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
  • R 5 is C3-C6cycloalkoxy
  • R 6 is hydrogen, Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, Ci-C6haloalkoxy;
  • R 7 is Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, Ci-C6haloalkoxy, or 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; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.
  • novel compounds of Formula (I) have, for practical purposes, a very advantageous level of biological activity for protecting plants against insects.
  • R 1 , R 2 , m, R 3a , R 3b and R 4 are as defined according to the compounds of Formula co
  • 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, acaracide, nematicide or molluscicide.
  • the use may exclude methods forthe treatment ofthe human or animal body by surgery or therapy.
  • the compounds of Formula (I) may exist as geometric isomers (or isomeric mixtures thereof (ie, (E) and/or (Z)) as defined by Formulae (la) and (lb) shown below, wherein A, R 1 , R 2 , m, R 3a , R 3b and R 4 are as defined for Formula (I) according to the invention, including any compound selected from a compound 1 .001 to 1 .051 listed in Table 1 (below) or a compound A1 to A137 listed in Table A (below), a compound C1 or C2 listed in Table C (below) or a compound E1 to E6 listed in Table E (below).
  • Both (E) and (Z) isomeric forms may exist and interconvert as a function of temperature or the environment. See for example: Journal of Organic Chemistry (1972), 37(19), 2969-79 or Chemische Berichte 1 16, 2668-2675.
  • the present invention is not limited to one specific isomer and may relate to the (E)-isomer or (Z)-isomer, or a mixture thereof.
  • Both isomeric forms (E) and (Z) are represented by a crossed bond in the reaction schemes herein and the transition from (E)-form to (Z)- form (or (Z)- form to (E)-form) could be represented, for example, by the following scheme.
  • 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 (isopropyl), n-butyl, and 1 ,1 -dimethylethyl (f-butyl).
  • Ci- 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 Ci- C6alkyl radical as generally defined above.
  • 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, difluoro methoxy, 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 ( ⁇ -configuration, 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.
  • C 2 -C7alkynyl 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 seven carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • Examples of C 2 -C7alkynyl 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.
  • Ci-C 4 alkoxyCi-C 4 alkyl refers to a radical of the formula Ry-O-R*- 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.
  • 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.
  • Ci-C6alkylsulfanyl refers to a radical of the formula RxS- wherein R x is a Ci-C6alkyl radical as generally defined above.
  • Ci-C6alkylsulfonyl refers to a radical of the formula RxS(0) 2 - wherein R x is a Ci-C6alkyl radical as generally defined above.
  • Ci-C6alkylcarbonyl refers to a radical of the formula RxC(O)- where R x is a Ci-C6alkyl radical as generally defined above.
  • Ci-C6alkoxycarbonyl refers to a radical of the formula RxOC(O)- where Rx is a Ci-C6alkyl radical as generally defined above.
  • C3-C6cycloalkylcarbonyl refers to a radical of the formula RxC(O)- where R x is a C3-C6cycloalkyl 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 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 examples include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl, pyridyl, and indolyl.
  • heterocyclyl refers to a stable 5- or 6-membered non-aromatic monocyclic ring radical, 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 include, but are not limited to, pyrrolinyl, pyrrolidyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidyl, piperazinyl, tetrahydropyranyl, dioxolanyl, morpholinyl.
  • 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 hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as Ci-C 4 -alkane- or arylsulfonic acids which are unsubstituted or substituted, for
  • 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.
  • A is a direct link (between R 1 and the rest of the molecule), -0-, or -S(0) P - wherein p is selected from 0, 1 or 2.
  • A is selected from a direct link, O or S (ie, p is 0).
  • A is a direct link.
  • A is -O-.
  • A is -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; or C2-C6alkenyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or C2-C6haloalkenyl; or C2-C6alkynyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or C2-C6haloalkynyl; or C3-C6cycloalkyl, wherein the cycloalkyl moiety is optionally substituted by 1 or 2 substituents independently selected from U3 or a single substituent selected from U2; or cyano, halogen, C(0)R 5 or C(0)NR6R7.
  • R 1 is selected from cyano, Ci-C6alkyl, Ci-C6haloalkyl, cyanoCi-Cealkyl, Ci-C 4 alkoxyCi- C 4 alkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, -C(0)0(Ci-C 4 alkyl), or C3- C6cycloalkyl, -C(0)0(C3-C6cycloalkyl), -CH 2 (C3-C6cycloalkyl), -OHSRI ⁇ , -CH2(pyridinyl) or -CH2(furanyl), wherein each cycloalkyl, phenyl, pyridinyl or furanyl group is optionally substituted by 1 , 2 or 3 independently selected halogen groups.
  • R 1 is selected from cyano, Ci-C 4 alkyl, Ci-C 4 haloalkyl, cyanoCi-C 4 alkyl, Ci- -C(0)0(Ci- (pyridinyl) or -ChhCfuranyl), wherein each cycloalkyl, phenyl, pyridinyl or furanyl group is optionally substituted by a single chloro or fluoro group.
  • R 1 is selected from cyano, Ci-C 4 alkyl, Ci-C 4 fluoroalkyl, cyanoCi-C 4 alkyl, Ci- C2alkoxyCi-C2alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, -C(0)0(Ci-C 4 alkyl), or C3-C 4 cycloalkyl, -C(0)0(C3- C 4 cycloalkyl), -CH 2 (C3-C 4 cycloalkyl), -ChhPh, -CH2(pyridinyl), -CH2(furanyl), wherein each cycloalkyl, phenyl, pyridinyl or furanyl group is optionally substituted by a single chloro or fluoro group.
  • R 1 is selected from cyano, methyl, ethyl, propyl, iso-propyl, butyl (including n- butyl, s-butyl, i-butyl, t-butyl), methoxymethyl, -C(0)CH3 (acetyl), propenyl (including allyl), propynyl (including propargyl), difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, cyclopropyl, cyclobutyl, -C(0)0(cyclopropyl), benzyl, -CH 2 (2-chloro-pyridin-5-yl), -CH 2 (furan-2-yl), -CH 2 (pyridin-2-yl).
  • R 1 is methyl or ethyl each optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or R 1 is Ci- C 4 haloalkyl.
  • R 1 is methyl or ethyl each optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or R 1 is Ci-C 4 fluoroalkyl.
  • R 1 is ethynyl (-CHoCH) or propynyl (-CHECChh) each optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or R 1 is C 2 -C 4 fluoroalkenyl.
  • R 1 is ethynyl (-CHoCH) or propynyl (- CHoCCH3) each optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or R 1 is C 2 -C 4 fluoroalkynyl.
  • R 1 may be ethynyl (-CHoCH) optionally substituted by a single substituent selected from Ui or a single substituent selected from U2,
  • Ui is cyano, amino, hydroxy, methoxy, ethoxy, n-propoxy, methoxymethoxy, methoxyethoxy, methylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, t- butoxycarbonyl, cyclopropyl,
  • 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 L4 and optionally a halogen group.
  • U2 is phenyl, furanyl, pyridinyl, imidazolyl, oxetanyl, thienyl, pyrazolyl, cyclohexyl, N-morpholinyl, pyrrolidinyl, piperidinyl or tetrazolyl, wherein each ring is optionally substituted by 1 , 2 or 3 independently selected halogen, methyl or ethyl groups, or a single trifluoromethyl group. More preferably, U2 is phenyl, furanyl or pyridinyl, each optionally substituted by (i) a single fluoro, chloro or bromo group.
  • L 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 alkyls
  • U3 is selected from halogen, Ci-C 4 alkyl or Ci-C 4 haloalkyl. More preferably, U3 is selected from fluoro, chloro, bromo, methyl, ethyl, trifluoromethyl.
  • 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
  • C 4 haloalkoxycarbonyl (Ci-C 4 alkyl)NH-, (Ci-C 4 alkyl) 2 N-, (C3-C6cycloalkyl)NH-, (C3-C6cycloalkyl) 2 N-, Ci- C 4 alkylcarbonylamino, C3-C6cycloalkylcarbonylamino, Ci-C 4 haloalkylcarbonylamino, C3- Cehalocycloalkylcarbonylamino, Ci-C 4 alkylaminocarbonyl, C3-C6cycloalkylaminocarbonyl, Ci- C 4 haloalkylaminocarbonyl, C3-C6halocycloalkylaminocarbonyl, C3-C6cycloalkylcarbonyl, C3-C6 halocycloalkylcarbonyl, -SFs or -C(0)NH2.
  • n 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, C1-C4 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 fluoro, chloro, methyl, ethyl, trifluoromethyl, trifluoromethoxy, methoxy or ethoxy. Still more preferably, R 2 is fluoro or methyl, in particular, when m is 1 .
  • R 2 is not chloro when m is
  • R 3a and R 3b are independently selected from hydrogen, halogen, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci- C 4 alkoxy 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.
  • R 4 is selected from one of Y1 to Y4;
  • n 0, 1 or 2;
  • 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 not methyl when n is
  • R 4 is selected from one of Y2 or Y3. In one embodiment of the invention, R 4 is Y2. In another embodiment of the invention, R 4 is Y3.
  • R 4 is:
  • R 4 is:
  • R 5 is hydrogen, Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, cyanoCi-Cealkyl, nitroCi-C 4 alkyl, Ci-C 4 alkoxyCi-C 4 alkyl, Ci- C 4 halolkoxyCi-C 4 alkyl, Ci-C 4 alkylsulfinylCi-C 4 alkyl, Ci-C 4 alkylsulfonylCi-C 4 alkyl, Ci- C 4 haloalkylsulfanylCi-C 4 alkyl, Ci-C 4 haloalkylsulfinylCi-C 4 alkyl, Ci-C 4 haloalkylsulfonylCi-C 4 alkyl and C3
  • R 5 is Ci-C6alkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, 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 alkylsulfanyl, Ci-C 4 alkylsulfinyl, Ci-C 4 alkylsulfonyl, Ci-C 4 haloalkylsulfanyl, Ci-C 4 haloalkylsulfinyl, Ci- C 4 haloalkylsulfonyl, C3-C6cycloalkyl and phenyl or 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,
  • R 5 is Ci-C6haloalkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, 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 alkylsulfanyl, Ci-C 4 alkylsulfinyl, Ci-C 4 alkylsulfonyl, Ci-C 4 haloalkylsulfanyl, Ci-C 4 haloalkylsulfinyl, Ci-C 4 haloalkylsulfonyl, C3-C6cycloalkyl and phenyl or 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
  • R 5 is Ci-C6alkyl, C3-C6cycloalkyl, or C3-C6cycloalkoxy. More preferably, R 5 is Ci-C4alkyl, cyclopropyl or cyclopropoxy. Even more preferably, R 5 is methyl, ethyl, cyclopropyl or cyclopropoxy.
  • R 6 is hydrogen, Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, Ci-C6haloalkoxy.
  • R 6 is hydrogen, methyl or ethyl. More preferably, R 6 is hydrogen.
  • R 7 is Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, Ci-C6haloalkoxy, or 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.
  • R 1 is:
  • Ci-C6alkyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U 2 , or Ci-C6haloalkyl optionally substituted by a single substituent selected from Ui; or
  • C 2 -C6alkenyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U 2 , or C 2 -C6haloalkenyl;
  • C2-C7alkynyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U 2 , or C 2 -C6haloalkynyl;
  • Ui is nitro, cyano, amino, hydroxyl, CO 2 H, C3-C6cycloalkyl, C3-C6halocycloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C 2 alkoxy-Ci-C 2 alkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, Ci-C4alkylcarbonyl, Ci- C 4 alkoxycarbonyl, -OSi(Ci-C 4 alkyl) 3 , (Ci-C 4 alkyl)NH-, (Ci-C 4 alkyl) 2 N-, (PhCH 2 )NH-, (PhCH 2 )(Ci-
  • U3 IS halogen, Ci-C4alkyl, Ci-C4haloalkyl or Ci-C4alkoxy;
  • R 5 is hydrogen, Ci-C6alkyl, Ci-C4haloalkyl or Ci-C4haloalkoxy, or Ci-C6alkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, C2-C4alkenyl, C2-C4alkynyl, Ci- C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C3-C6cycloalkyl, phenyl, pyridinyl, furanyl or thiazolyl wherein each ring is optionally substituted by 1 or 2 groups independently selected from halogen, methyl, ethyl, methoxy, ethoxy or trifluromethyl;
  • R 6 is hydrogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy;
  • R 7 is Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy.
  • R 1 is:
  • Ci-C 4 alkyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or Ci-C 4 fluorooalkyl optionally substituted by a single substituent selected from Ui ; or
  • C 2 -C 4 alkynyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or C 2 -C 4 fluoroalkynyl;
  • Ui is nitro, cyano, amino, hydroxyl, CO2H, C3-C6cycloalkyl, C3-C6fluorocycloalkyl, Ci-C 4 alkoxy, Ci-C 4 fluoroalkoxy, Ci-C2alkoxy-Ci-C2alkoxy, Ci-C 4 alkylsulfanyl, Ci-C 4 alkylsulfinyl, Ci-C 4 alkylsulfonyl, Ci-C 4 fluoroalkylsulfanyl, Ci-C 4 fluoroalkylsulfinyl, Ci-C 4 fluoroalkylsulfonyl, Ci-C 4 alkylcarbonyl, Ci- C 4 alkoxycarbonyl, -OSi(Ci-C 4 alkyl) 3 , (Ci-C 4 alkyl)NH-, (Ci-C 4 alkyl) 2 N-, (PhCH 2 )NH-, (PhCH 2
  • U3 IS halogen, Ci-C4alkyl, Ci-C4fluoroalkyl or Ci-C4alkoxy;
  • R 5 is hydrogen, Ci-C6alkyl, Ci-C4fluoroalkyl or Ci-C4fluoroalkoxy, or Ci-C6alkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, C2-C4alkenyl, C2-C4alkynyl, Ci- C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C3-C6cycloalkyl, phenyl, pyridinyl, furanyl or thiazolyl wherein each ring is optionally substituted by 1 or 2 groups independently selected from halogen, methyl, ethyl, methoxy, ethoxy or trifluromethyl.
  • R 6 is hydrogen, Ci-C4alkyl, Ci-C4fluoroalkyl, Ci-C4alkoxy, Ci-C4fluoroalkoxy;
  • R 7 is Ci-C4alkyl, Ci-C4fluoroalkyl, Ci-C4alkoxy.
  • R 1 is: methyl or ethyl each optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or Ci-C2fluorooalkyl optionally substituted by a single substituent selected from Ui;
  • C 2 -C3alkynyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or C 2 -C 4 fluoroalkynyl;
  • Ui is nitro, cyano, amino, hydroxyl, CO2H, C3-C6cycloalkyl, C3-C6fluorocycloalkyl, Ci-C 4 alkoxy, Ci-C 4 fluoroalkoxy, Ci-C2alkoxy-Ci-C2alkoxy, Ci-C 4 alkylsulfanyl, Ci-C 4 alkylsulfinyl, Ci-C 4 alkylsulfonyl, Ci-C 4 fluoroalkylsulfanyl, Ci-C 4 fluoroalkylsulfinyl, Ci-C 4 fluoroalkylsulfonyl, Ci-C 4 alkylcarbonyl, Ci- C 4 alkoxycarbonyl, -OSi(Ci-C 4 alkyl) 3 , (Ci-C 4 alkyl)NH-, (Ci-C 4 alkyl) 2 N-, (PhCH 2 )NH-, (PhCH 2
  • U3 IS chloro, fluoro, methyl, ethyl, trifluoromethyl, methoxy, ethoxy;
  • R 5 is hydrogen, Ci-C6alkyl, Ci-C 4 fluoroalkyl or Ci-C 4 fluoroalkoxy, or Ci-C6alkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, Ci- C 4 alkylsulfanyl, Ci-C 4 alkylsulfinyl, Ci-C 4 alkylsulfonyl, C3-C6cycloalkyl, phenyl, pyridinyl, furanyl or thiazolyl wherein each ring is optionally substituted by 1 or 2 groups independently selected from halogen, methyl, ethyl, methoxy, ethoxy or trifluromethyl.
  • R 6 is hydrogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy
  • R 7 is methyl, ethyl, trifluoromethyl, methoxy, ethoxy.
  • the compound of Formula (I) is:
  • R 1 is defined in accordance with the present invention, and A is O; or A is S; or A is a direct link.
  • the compound of Formula (I) is:
  • R 1 is defined in accordance with the present invention, and A is O, or A is S, or A is a direct link.
  • the compound according to Formula (I) is selected from a compound 1 .001 to 1 .051 listed in Table 1 (below) or a compound A1 to A137 listed in Table A (below), a compound C1 or C2 listed in Table C (below) or a compound E1 to E6 listed in Table E (below).
  • the compound according to Formula (II) is selected from a compound B1 to B93 listed in Table B (below), a compound D1 or D2 listed in Table D (below) or a compound F1 to F6 listed in Table F (below).
  • compounds of formula (I) wherein R 1 , R 2 , R 3a , R 3b , R 4 and A are as described herein for the compounds of formula (I), can be prepared from compounds of formula (II) via reaction with a compound of formula X-CN, wherein X is a halogen, such as bromine.
  • the reaction occurs in the presence or not of a base (such as triethylamine or sodium hydride), in the presence or not of a catalyst such as 4-dimethylaminopyridine (DMAP) in an appropriate solvent (eg, N,N- dimethylformamide, N,N-dimethylacetamide or acetonitrile (ACN)) or in the absence of a solvent, at temperatures between -78°C and 150°C, and preferably between 0°C and 150°C.
  • a base such as triethylamine or sodium hydride
  • a catalyst such as 4-dimethylaminopyridine (DMAP)
  • an appropriate solvent eg, N,N- dimethylformamide, N,N-dimethylacetamide or acetonitrile (ACN)
  • ACN acetonitrile
  • compounds of formula (II), wherein R 1 , R 2 , R 3a , R 3b , R 4 and A are as described herein for the compounds of formula (I), can be prepared from the compounds of formula (III) via alkylation with a compound of formula (IV) with (R 3a )(R 3b )(R 4 )C-Xi_G, wherein XLG is a leaving group (such as a halogen, preferably iodide, bromide or chloride) in the presence or not of a base (such as potassium carbonate or sodium hydride) in a appropriate solvent (eg, tetrahydrofuran, N,N- dimethylformamide (DMF), N,N-dimethylacetamide or acetonitrile) or in the absence of a solvent, at temperatures between -78°C and 150°C, and preferably between 0°C and 150°C.
  • a base such as potassium carbonate or sodium hydride
  • a catalyst could be used in this reaction such as sodium iodine or tetrabutylammonium iodide, principally if XLG is different to iodide.
  • Such reactions are well known, for example, see Russian Chemical Bulletin 2018, 67(1), 168- 171 ; EP 2 628 389 or WO 2001/1 1572.
  • Compounds of formula (III) wherein R 1 , R 2 , R 3a , R 3b , R 4 and A are as described herein for the compounds of formula (I), can exist under salt form.
  • compounds of formula (I) wherein R 1 , R 2 , R 3a , R 3b , R 4 and A are as described herein for the compounds of formula (I) can be prepared from compounds of formula (V) via alkylation with a compound of formula (IV) with ((R 3a )(R 3b )(R 4 )C-Xi_G), wherein XLG is a leaving group (such as a halogen, preferably iodide, bromide or chloride) and using the same conditions described for scheme 2.
  • XLG is a leaving group (such as a halogen, preferably iodide, bromide or chloride)
  • R 1 is as described herein for the compounds of formula (I) and A is O or S (ii) reduction of the nitro group of compounds of formula (VII).
  • Condition for the reactions of step (i) are well known to those skilled in the art and are described in, eg, in ARKIVOC (Gainesville, FL, United States), (16), 73-82; 2007 or WO 2014028669.
  • compounds of formula (VII) wherein R 1 and R 2 are as described herein for the compounds of formula (I) and A is O or S can be prepared from compounds of formula (VI) with reaction of compounds of formula R 1 -AH in the presence or not of a base (such as potassium carbonate or sodium hydride) in an appropriate solvent (eg, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide or acetonitrile) or in the absence of solvent, at temperatures between -78°C and 150°C, and preferably between 0°C and 100°C.
  • a base such as potassium carbonate or sodium hydride
  • an appropriate solvent eg, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide or acetonitrile
  • step (ii) is well known by those skilled in the art and are described, eg, in Synthetic Organic Methodology : Comprehensive Organic Transformations. A Guide to Functional Group Preparations, Larock, R. C. 1989 p 41 1 .
  • compounds of formula (VII) could be commercially available or or can be prepared by those skilled in the art (others examples are give in Scheme 6).
  • compounds of formula (III) wherein R 1 , R 2 , R 3a , R 3b , R 4 and A are as described herein for the compounds of formula (I) can be prepared from compounds of formula (Ilia) wherein R 1 , R 2 , R 3a , R 3b , R 4 and A are as described herein for the compounds of formula (I) and XLG could be a leaving group such as fluoride or chloride using substitution of XLG with a compound of formula R 1 -AH wherein R 1 is as described herein for the compounds of formula (I) and A is O or S in the presence or not of a base (such as potassium carbonate or sodium hydride) in an appropriate solvent (eg, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide or acetonitrile) or in the absence of solvent, at temperatures between -78°C and 150°C, and preferably between 0°C and 100°
  • a base such
  • Compounds of formula (II) wherein R 1 , R 2 , R 3a , R 3b , R 4 and A are as described herein for the compounds of formula (I), can be prepared from compounds of formula (lla) wherein R 1 , R 2 , R 3a , R 3b , R 4 and A are as described herein for the compounds of formula (I) and XLG could be a leaving group such iodide or bromide via“metal catalyst”: For example with in HA-Ri wherein A is O or S and using palladium coupling, see Chemistry - A European Journal 2012 18(9), 2498-2502, S2498/1 - S2498/31 ; and cited references; Journal of the American Chemical Society 2010 132(33), 1 1592-1 1598; or Organic Letters 2014 16(4), 1212-1215.
  • the reaction can be catalyzed by a palladium-based catalyst, for example palladium acetate, in the presence of a base, like cesium carbonate or sodium tert-butoxide, in a solvent or a solvent mixture, like, for example toluene, preferably under inert atmosphere and in the presence of chelating phosphine.
  • the reaction temperature can preferentially range from ambient temperature to the boiling point of the reaction mixture.
  • the metal used for the catalysis could be copper derivative, see for example, Tetrahedron 2013 69(16), 3415-3418; or Journal of Organic Chemistry 2009 74(14), 5075-5078; or Organic & Biomolecular Chemistry 2012 10(13), 2562-2568;.
  • the reaction is commonly performed with one to two equivalents of a base, like potassium phosphate, in presence of a copper catalyst, like for example copper (I) iodide and under an oxygen-containing atmosphere.
  • a base like potassium phosphate
  • a copper catalyst like for example copper (I) iodide
  • the reaction can be run in an inert solvent, like dioxane or toluene, usually at temperature between 50 to 150°C and in presence or not of a additional ligand such as for example diamine ligands (e.g. frans-cyclohexyldiamine.) or, for example, 1 ,10-phenanthroline.
  • compounds of formula (II) wherein R 1 , R 2 , R 3a , R 3b , R 4 and A are as described herein for the compounds of formula (I) can be prepared from compounds of formula (lla) wherein R 1 , R 2 , R 3a , R 3b , R 4 and A are as described herein for the compounds of formula (I) and XLG could be a leaving group such iodide or bromide via“metal catalyst”.
  • XLG could be a leaving group such iodide or bromide via“metal catalyst”.
  • the reaction can be catalyzed by a palladium-based catalyst, for example tetrakis(triphenylphosphine)-palladium(0), bis(triphenyl-phosphine) palladium(ll) dichloride or (1 ,Tbis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane (1 :1 complex), in presence of a base, like sodium carbonate or cesium fluoride, in a solvent (such as 1 ,2-dimethoxyethane, tetrahydrofuran or dioxane) or a solvent mixture, like, for example a mixture of 1 ,2-dimethoxyethane and water, or of dioxane and water, preferably under an inert atmosphere.
  • a palladium-based catalyst for example tetrakis(triphenylphosphine)-palladium(0), bis(triphenyl-phosphine) palladium
  • the reaction temperature can preferentially range from ambient temperature to the boiling point of the reaction mixture, or alternatively heating may be performed under microwave irradiation.
  • tin derivatives for example RiSnBu3
  • Such Stille reactions are usually carried out in the presence of a palladium catalyst, for example fefra/ «s(triphenylphosphine)palladium(0), or (1 ,Tbis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane (1 :1 complex), in an inert solvent such as DMF, acetonitrile, or dioxane, optionally in the presence of an additive, such as cesium fluoride, or lithium chloride, and optionally in the presence of a further catalyst, for example copper (I) iodide.
  • a palladium catalyst for example fefra/ «s(triphenylphosphine)palladium(0), or (1 ,Tbis(diphenyl
  • Stille couplings are also well known to those skilled in the art, and have been described in for example J. Org. Chem., 2005, 70, 8601 -8604, J. Org. Chem., 2009, 74, 5599-5602, Angew. Chem. Int. Ed., 2004, 43, 1 132-1 136 and Kurti, Laszlo; Czako, Barbara; (Editors) Strategic Applications of Named Reactions in Organic Synthesis (2005) p 438.
  • others well-known reactions could be used.
  • reaction such as Sonogashira cross-coupling (e.g.
  • compounds of formula (III) wherein R 1 , R 2 and A are as described herein for the compounds of formula (I) can be prepared from compounds of formula (Ilia) wherein R 2 is as described herein for the compounds of formula (I) and A is O or S, by reaction with a alkylating agent such as R-X, wherein R is alkyl optionally substituted and X is a leaving group such as, for example bromide or iodide.
  • a alkylating agent such as R-X, wherein R is alkyl optionally substituted and X is a leaving group such as, for example bromide or iodide.
  • reaction temperature can preferentially range from ambient temperature to the boiling point of the reaction mixture, or alternatively heating may be performed under microwave irradiation.
  • compounds of formula (III) wherein R 1 , R 2 and A are as described herein for the compounds of formula (I) can be prepared from compounds of formula (Vila) wherein R 2 is as described herein for the compounds of formula (I) and A is O or S, by reaction with an alkylating agent such as R-X wherein R is alkyl optionally substituted and X is a leaving group such as, for example bromide or iodide.
  • R-X alkylating agent
  • Mitsunobu types of reaction are very well known by those skilled in the art, see conditions used and described in Kurti, Laszlo; Czako, Barbara; (Editors) Strategic Applications of Named Reactions in Organic Synthesis (2005) p 295. More specifically, examples on substrate type compounds of formula (Vila) using a alcohol of type R 1 -OH are described in literature: see, for example, Journal of Medicinal Chemistry 2011 , 54(18), 6342-6363 or ACS Medicinal Chemistry Letters 2013, 4(8), 806-810. Conversion of compounds of formula (VII) to compounds of formula (III) are identical to the conditions described in scheme 4.
  • compounds of formula (lb) can be prepared from compounds of formula (VIII) by deplacement of -OLG group with an nucleophilic group such as alkoxy in presence of a base, like sodium hydride or lithium diisopropylamide, in a presence of a solvent (such as dimethyl formanide, tetrahydrofuran or dioxane) or not (e.g. in the case of use of alcohol as nucleophile, the alcohol used could be the solvent).
  • the reaction temperature can preferentially range from ambient temperature to the boiling point of the reaction mixture, or alternatively heating may be performed under microwave irradiation. Example of conditions for this reaction are described in ChemistrySelect 2019, 4(1), 175-180 or Journal of Organic Chemistry 2008, 73(18), 7096-7101.
  • 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
  • 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 atromaculatus, 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., Maladera
  • Coptotermes spp. Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp., Solenopsis geminate
  • Orthoptera for example, Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscus spp., and Schistocerca spp.,
  • 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 .051 listed in Table 1 (below) or a compound A1 to A137 listed in Table A (below), a compound C1 or C2 listed in Table C (below) or a compound E1 to E6 listed in Table E (below)) to a neonicotinoid-resistant insect.
  • a compound of Formula (I) eg, a single compound selected from compounds 1 .001 to 1 .051 listed in Table 1 (below) or a compound A1 to A137 listed in Table A (below), a compound C1 or C2 listed in Table
  • 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 .051 listed in Table 1 (below) or a compound A1 to A137 listed in Table A (below), a compound C1 or C2 listed in Table C (below) or a compound E1 to E6 listed in Table E (below) as an insecticide against neonicotinoid-resistant insects.
  • a compound of Formula (I) eg, a single compound selected from compounds 1 .001 to 1 .051 listed in Table 1 (below) or a compound A1 to A137 listed in Table A (below), a compound C1 or C2 listed in Table C (below) or a compound E1 to E6 listed in Table E (below) as an insecticide against neonicotinoid-resistant insects.
  • Such neonicotinoid-resistant insects may include insects from the order Lepidoptera or Hemiptera, in particular from the family Aphidida
  • 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
  • Metabolic resistance such as enhanced oxidative detoxification of neonicotinoids due to overexpression of monooxygenases
  • 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 modification of the active site of nicotinic acetylcholine receptor confers the resistance to nicotinoids.
  • modification of the active site of nicotinic acetylcholine receptor confers the resistance to nicotinoids.
  • 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 5-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 5-endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry
  • 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
  • 5-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
  • Vip vegetative insecticidal proteins
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ).
  • Truncated toxins for example a truncated 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 Cry1 Ab 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
  • transgenic crops are:
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
  • NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 c 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 Cry1 Ab 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.
  • it is contemplated to apply such 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.
  • 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.
  • 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. spretulus
  • Maladera spp. e.g. Asiatic garden beetle, M.
  • 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 Sphenophorus spp. , 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.,
  • Blattarida for example Blatta orientalis, Periplaneta americana, Blattelagermanica and Supella spp.
  • the orders Meta- and Meso-stigmata for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp.
  • 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. and Laminosioptes spp..
  • compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
  • compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec.,Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus
  • the 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.
  • the active ingredients 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:
  • 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 %
  • solid carrier 99.9 to 90 %, preferably 99.9 to 99 %
  • 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 waterto 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.
  • To this emulsion 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/orfungicidally 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 .051 listed in Table 1 (below) or a compound A1 to A137 listed in Table A (below), a compound C1 or C2 listed in Table C (below) or a compound E1 to E6 listed in Table E (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 (lUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate (lUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro-A/-methyl-A/-1 -naphthylacetamide (lUPAC name) (1295) +
  • an adjuvant selected from the group of substances consisting of petroleum oils (628) + TX
  • an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (lUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX,
  • an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, doramectin [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin [CCN] + TX, ivermectin [CCN] + TX, milbemycin oxime [CCN] + TX, moxidectin [CCN] + TX, piperazine [CCN] + TX, selamectin [CCN] + TX, spinosad (737) and thiophanate (1435) + TX, an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (lUPAC name) (23) and strychnine
  • a bactericide selected from the group of substances consisting of 1 -hydroxy-1 H-pyridine-2-thione (lUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (lUPAC name) (170) + TX, copper hydroxide (lUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicin (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargaphen [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(
  • 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 Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp.
  • a soil sterilant selected from the group of substances consisting of iodomethane (lUPAC name) (542) and methyl bromide (537) + TX,
  • a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir [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 (lUPAC name) (222) + TX, (E)-tridec-4-en-1 -yl acetate (lUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (lUPAC name) (541) + TX, (E,Z)-tetradeca-4,10-dien-1 -yl acetate (lUPAC name) (779) + TX, (Z)-dodec-7-en-1 -yl acetate (lUPAC name) (285) + TX, (Z)-hexadec-1 1 - enal (lUPAC name) (436) + TX, (Z)-hexadec-1 1 -en-1 -yl acetate (lUPAC name) (437) + TX, (
  • an insecticide selected from the group of substances consisting of 1 -dichloro-1 -nitroethane (lUPAC/Chemical Abstracts name) (1058) + TX, 1 ,1 -dichloro-2,2-bis(4-ethylphenyl)ethane (lUPAC name) (1056), + TX, 1 ,2-dichloropropane (lUPAC/Chemical Abstracts name) (1062) + TX, 1 ,2- dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1 -bromo-2-chloroethane (lUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-1 -(3,4-dichlorophenyl)ethyl acetate (lUPAC name) (1451) + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphat
  • a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (lUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (lUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913)
  • a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1 ,2-dibromo-3-chloropropane (lUPAC/Chemical Abstracts name) (1045) + TX, 1 ,2-dichloropropane (lUPAC/ Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1 ,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1 ,1-dioxide (lUPAC/Chemical Abstracts name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (lUPAC name) (980) + TX, 5-methyl-6-thioxo-1 ,3,5-thiadiazinan-3-ylacetic acid (lUPAC name
  • a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,
  • a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutha sachalinensis extract (720) + TX
  • a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1 ,3-dione (lUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91) + TX, bromethalin (92) + TX
  • a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (lUPAC name) (934) + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (lUPAC name) (903) + TX, farnesol with nerolidol (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 (lUPAC 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
  • 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
  • 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 rufUabris + 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 fiavipes + 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
  • the ratio (by weight) of active ingredient mixture of the compounds of formula (I) selected from a compound 1 .001 to 1 .051 listed in Table 1 (below) or a compound A1 to A137 listed in Table A (below), a compound C1 or C2 listed in Table C (below) or a compound E1 to E6 listed in Table E (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
  • 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 .051 listed in Table 1 (below) or a compound A1 to A137 listed in Table A (below), a compound C1 or C2 listed in Table C (below) or a compound E1 to E6 listed in Table E (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 afterthe other with a reasonably short period, such as a few hours or days.
  • 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 discloses the 51 compounds of the formula (I) having either the (£)- or (Z)- isomeric form, or a mixture of the (E)- or (Z)- isomeric forms:
  • R 3a and R 3b are hydrogen, and A, 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, 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)-.
  • Capillary 3.00 kV, Cone range: 30 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 350°C, Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650 l/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment, diode-array detector and ELSD detector.
  • HPLC Shimadzu LC-20A. Column: Dikma, DiamonsilC18(2) (5 pm,150*4.6mm). Mobile phase A:H 2 0(add 0.1 %TFA) and mobile phase B: CAN (add 0.1 %TFA). Flow: 1 .0mL/min. Detection:UV@254nm. Oven Temperature: 40°C. The mobile phase gradient:
  • Example 1 Preparation of (E) and/or (Z)-[1 -[(6-chloro-3-pyridyl)methyl]-3-(difluoromethoxy)-2- pyridylidene] cyanamide (compound A5).
  • Step 1 Preparation of 1 -[(6-chloro-3-pyridyl)methyl]-3-(difluoromethoxy)pyridin-2-imine.
  • 2-chloro-5- (chloromethyl)pyridine (2 g, 1 1.97 mmol)
  • 3-(difluoromethoxy)pyridin-2-amine (1 equiv., 11 .9740mmol)
  • sodium iodide (1 equiv., 11.974 mmol) in acetone (1.8 ml/mmol).
  • the resulting mixture was stirred overnight at reflux.
  • Step 2 Preparation of (E) and/or (Z)-[1-[(6-chloro-3-pyridyl)methyl]-3-(difluoromethoxy)-2-pyridylidene] cyanamide_(compound A5).
  • Example 2 Preparation of (E) and/or (Z)-[1-[(6-chloro-3-pyridyl)methyl]-3-(methoxymethyl)-2- pyridylidene]cyanamide (compound A7).
  • Step 1 Preparation of 1 -[(6-chloro-3-pyridyl)methyl]-3-(methoxymethyl)pyridin-2-imine (compound B7).
  • reaction mixture was then cooled to 20°C and filtered through a short path of Hyflo, which was rinsed with acetone.
  • the filtrate was evaporated under reduced pressure and the residue dissolved in DMSO (0.5 ml) and purified by reverse phase chromatography, eluting with a gradient of 20% to 60% of acetonitrile in water. The evaporation of the selected fractions yielded the title compound as a bright yellow oil.
  • Step 2 Preparation of (E) and/or (Z)-[1 -[(6-chloro-3-pyridyl)methyl]-3-(methoxymethyl)-2- pyridylidene]cyanamide (compound A7).
  • the vial was sealed and the red brown solution was stirred at 20 °C for 7.5 hours, after which time, the reaction mixture was treated with aqueous saturated ammonium chloride. The mixture was extracted twice with ethyl acetate. After drying over anhydrous magnesium sulfate, the solvent was removed under reduced pressure and the residue was dissolved in DMSO (0.5 ml) and submitted to reverse phase column chromatography, eluting with a gradient of 20% to 60% of acetonitrile in water. The evaporation of the selected fractions yielded the title compound as a solid.
  • Step 1 Preparation of 1 -[(6-chloro-3-pyridyl)methyl]-3-(methoxymethyl)pyridin-2-imine (compound B25)
  • Step A Synthesis of 3-bromo-1 -[(6-chloro-3-pyridyl)methyl]pyridin-2-imine.
  • Step B Synthesis of (E and/or Z)-[3-bromo-1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]cyanamide
  • Step 2 Preparation of intermediate phenyl (2E)-1 -[(6-chloro-3-pyridyl)methyl]-2-cyanoimino-pyridine-3- carboxylate.
  • General method A general method B or a classical method such as described in example 1 or 2 could be used to synthesize these type of derivatives.
  • Step 1 Preparation of 1-[1-(6-chloro-3-pyridyl)ethyl]-3-(trifluoromethyl)pyridin-2-imine (intermediate compound D1).
  • Example 6 Preparation of (E) and/or (Z)-f1-f(6-chloro-3-pyridyl)methyll-3-f(E)-2-ethoxyvinyll-2- pyridylidenel cvanamide (compound A28).
  • Example 7 Preparation of (E) and/or (Z)-[1-[(6-chloro-3-pyridyl)methyl1-3-(tetrazol-1-ylmethyl)-2- pyridylidenelcvanamide (compound A29).
  • Step 1 Preparation of 3-(tetrazol-1-ylmethyl)pyridin-2-amine.
  • Step 2 Preparation of 1 -[(6-chloro-3-pyridyl)methyl]-3-(tetrazol-1 -ylmethyl)pyridin-2-imine;hydroiodide
  • Step 3 Preparation of (E) and/or (Z)-[1 -[(6-chloro-3-pyridyl)methyl]-3-(tetrazol-1 -ylmethyl)-2- pyridylidenejcyanamide (compound A29).
  • the reaction mixture was concentrated under reduced pressure.
  • the crude material was purified twice by flash chromatography over silica gel (first ethyl acetate in cyclohexane, then methanol in dichloromethane).
  • the resulting residue was diluted with water and extracted twice with ethyl acetate.
  • the combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure to afford the desired product as a yellow solid (56 mg, 0.18 mmol).
  • Step 1 Preparation of 2-amino-N-methyl-N-(2,2,2-trifluoroethyl)pyridine-3-carboxamide 3.
  • Step 2 Preparation of 1 -[(6-chloro-3-pyridyl)methyl]-2-imino-N-methyl-N-(2,2,2-trifluoroethyl)pyridine- 3-carboxamide B27.
  • Step 3 Preparation of (2Z and/or 2E)-1 -[(6-chloro-3-pyridyl)methyl]-2-cyanoimino-N-methyl-N-(2,2,2- trifluoroethyl)pyridine-3-carboxamide A31.
  • Step 1 Preparation of (2-amino-3-pyridyl)-(2-pyridyl)methanol 3.
  • Step 2 Preparation of (2-amino-3-pyridyl)-(2-pyridyl) methanone 4.
  • Step 3 Preparation of 3-(2-pyridylmethyl)pyridin-2-amine 5.
  • (2-amino-3-pyridyl)-(2-pyridyl)methanone 4 (1.59 g, 8 mmol) in ethylene glycol (50 ml) was added N2H4.H2O (2.4g, 40mmol) and KOH (2.24 g, 40 mmol)at 25 °C.
  • the reaction mixture was stirred at 190 °C for 4 h.
  • the reaction mixture was quenched into saturated aqueous NaHCC>3 (100 mL) and extracted with ethyl acetate (2 x 100 ml_).
  • Step 4 Preparation of 1 -[(6-chloro-3-pyridyl)methyl]-3-(2-pyridylmethyl)pyridin-2-imine hydrochloride
  • Step 5 Preparation of (Z) or (E) -[1 -[(6-chloro-3-pyridyl) methyl]-3-(2-pyridylmethyl)-2-pyridylidene] cyanamide A32.
  • Example 1 1 Preparation of library of compounds according to Fornula (P A33 to A59 and A124 to A130.
  • Example 12 Preparation of (Z) or (EH3-[2-[tert-butyl(dimethvDsilyl1oxy-3.3.3-trifluoro-propoxy1-1-[(6- chloro-3-pyridvDmethyl1-2-pyridylidene1cvanamide (compound A137) and (Z) or (E) [1-[(6-chloro-3- pyridvDmethvn-3-(3.3.3-trifluoro-2-hvdroxy-propoxy)-2-pyridylidenelcvanamide (compound A136).
  • Step 1 Preparation of 1 ,1 ,1-trifluoro-3-[(2-chloro-3-pyridyl)oxy]propan-2-ol.
  • Step 2 Preparation of fe/f-butyl-[1 -[(2-chloro-3-pyridyl)oxymethyl]-2,2,2-trifluoro-ethoxy]-dimethyl- silane.
  • a 10 mL flask was charged with 1 ,1 ,1 -trifluoro-3-[(2-chloro-3-pyridyl)oxy]propan-2-ol (208 mg, 0.86 mmol), dichloromethane (3.4 mL), 2,6-dimethylpyridine (0.4 mL, 3.44 mmol), is cooled at 0 °C and [tert-butyl(dimethyl)silyl] trifluoromethanesulfonate (0.59 mL, 2.58 mmol) is slowly added.
  • Step 5 Preparation of [3-[2-[tert-butyl(dimethyl)silyl]oxy-3,3,3-trifluoro-propoxy]-1 -[(6-chloro-3- pyridyl)methyl]-2-pyridylidene]cyanamide (compound A137).
  • the resulting mixture was stirred at 80 °C for two hours and quenched with water (1 mL).
  • the aqueous phase was extracted with ethyl acetate (2 x 2 mL), the combined organic phases were then washed with water (3 x 3 mL), brine (3 mL), dried with sodium sulfate, filtered and then evaporated.
  • Table A discloses 137 compounds of the formula (I) having either the (£)- or (Z)- isomeric form, or a mixture of the (E)- or (Z)- isomeric forms.
  • Table B This table discloses 93 intermediate compounds of the formula (II):
  • R 3a and R 3b are hydrogen, and A, R 1 and R 4 are as defined in the following
  • Table C This table discloses 2 compounds of the formula (I) having either the (E)- or (Z)- isomeric form, or a mixture of the (E)- or (Z)- isomeric forms.
  • Table D This table discloses 2 intermediate compounds of the formula (II):
  • R 3a is hydrogen
  • R 3b is methyl
  • A, R 1 and R 4 are as defined in the following Table.
  • Table E This table discloses 6 compounds of the formula (I) having either the (E)- or (Z)- isomeric form, or a mixture of the (E)- or (Z)- isomeric forms.
  • Table F This table discloses 6 intermediate compounds of the formula (lie):
  • R 3a and R 3b are hydrogen
  • R 4 is 2-chloropyrid-5-yl
  • A, R 1 and R 2a , R 2b and R 2c are as defined in the following Table.
  • 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.
  • Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying, the leaves were infested with N2 nymphs. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation.
  • the following compounds from Table A gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:
  • 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.
  • 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.
  • Mvzus persicae neonicotinoid-resistant, Green peach aphid
  • Pepper plants were infested with mixed aged neonicotinoid-resistant aphid population and were treated 1 day after infestation in a spray chamber with diluted aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. 5 days after treatment, samples were assessed for mortality.
  • A2 A4, A5, A7, A13, A14, A23, A24, A26, A30, A75, A89, A91 , A93, A132.
  • Nilaparvata lugens Brown plant hopper - metabolic neonicotinoid-resistant.
  • Rice plants were treated with the diluted aqueous test solutions prepared from a 10,000 ppm DMSO stock solution 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.
  • Bemisia tabaci (neonicotinoid-resistant, Cotton whitefly), adult, contact.
  • RF50 resistance factor 50

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Abstract

A compound of formula (I) wherein the substituents are as defined in claim 1, and the agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, can be used as insecticides.

Description

PESTICIDALLY-ACTIVE CYANAMIDE HETEROCYCLIC COMPOUNDS
The present invention relates to pesticidally active, in particular insecticidally active 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 imino-substituted N-heterocyclic compounds are known, for example, from EP 2 634 174, EP 0 259 738 or Journal of Agricultural and Food Chemistry (2017), 65(36), 7865-7873. It has now been found that further imino-substituted N-heterocyclic compounds have insecticidal properties.
According to the present invention, there is provided a compound of Formula (I):
Figure imgf000002_0001
wherein:
A is a direct link, O, or S(0)P wherein p is selected from 0, 1 or 2;
R1 is Ci-C6alkyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or Ci-C6haloalkyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2;
or
C2-C6alkenyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or C2-C6haloalkenyl;
or
C2-C7alkynyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or C2-C6haloalkynyl;
or
C3-C6cycloalkyl, wherein the cycloalkyl moiety is optionally substituted by 1 or 2 substituents independently selected from U3 or a single substituent selected from U2;
or
cyano, nitro, halogen, C(0)R5, -C(0)NR6R7 or -C(R6)=NOR6;
Ui is nitro, cyano, amino, hydroxyl, CO2H, C3-C6cycloalkyl, C3-C6halocycloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C2alkoxy-Ci-C2alkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, Ci-C4alkylcarbonyl, Ci- C4alkoxycarbonyl, Ci-C4haloalkylcarbonyl, Ci-C4haloalkoxycarbonyl, C3-C4cycloalkylcarbonyl, =N- 0(Ci-C4alkyl), =N-0(Ci-C4haloaikyl), -Si(Ci-C4alkyl)3, -OSi(Ci-C4alkyl)3, (C1-C4 haloalkyl)NH-, (C1-C4 haloalkyl)2N-, (C1-C4 haloalkyl)(Ci-C4alkyl)N-, (Ci-C4alkyl)NH-, (C1-C4 alkyl)2N-, (C3-C6cycloalkyl)NH-, (C3-C6cycloalkyl)(Ci-C4alkyl)N-, (PhCH2)NH-, (PhCH2)(Ci-C4alkyl)N-, Ci-C4alkylcarbonylamino wherein the alkyl group is optionally substituted by cyano, Ci-C4alkoxycarbonylamino, Ci- C4haloalkylcarbonylamino, Ci-C4alkylaminocarbonyl, C3-C6cycloalkylaminocarbonyl, Ci- C4haloalkylaminocarbonyl, C3-C6halocycloalkylaminocarbonyl, -SPh, -0C(0)R6, -O-pyrazine or - C(0)NH2;
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 4- to 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 L4 and optionally a halogen group;
L is halogen, nitro, cyano, amino, hydroxyl, CO2H, Ci-C4alkyl, Ci-C4haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, C3-C6halocycloalkyl-Ci-C4alkyl, C3-C6cycloalkyl-Ci-C4alkyl, Ci-C4alkoxy, Ci- C4alkoxy-Ci-C4alkyl, Ci-C4haloalkoxy, Ci-C4haloalkoxy-Ci-C4alkyl, cyano-Ci-C4alkyl, cyano-Ci- C4haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, Ci-C4alkylsulfanyl, Ci- C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, Ci-C4alkylcarbonyl, Ci-C4alkoxycarbonyl, Ci-C4haloalkylcarbonyl, Ci-C4haloalkoxycarbonyl and - C(0)NH2;
U4 is nitro, cyano, amino, hydroxyl, -SCN, -CO2H, Ci-C4alkyl, C3-C6cycloalkyl, C3- Cehalocycloalkyl, C3-C6cycloalkyl-Ci-C4alkyl, C3-C6halocycloalkyl-Ci-C4alkyl, Ci-C4haloalkyl, Ci- C4alkoxy, Ci-C4alkoxy-Ci-C4alkyl, Ci-C4alkoxy-Ci-C4alkoxy, cyano-Ci-C4alkyl, cyano-Ci-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, Ci-C4haloalkoxy, Ci-C4haloalkoxy-Ci- C4alkyl, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci- C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, Ci-C4alkylcarbonyl, Ci-C4alkoxycarbonyl, Ci- C4haloalkylcarbonyl, Ci-C4haloalkoxycarbonyl, (Ci-C4alkyl)NH-, (Ci-C4alkyl)2N-, (C3-C6cycloalkyl)NH-, (C3-C6cycloalkyl)2N-, Ci-C4alkylcarbonylamino, C3-C6cycloalkylcarbonylamino, Ci-
C4haloalkylcarbonylamino, C3-C6halocycloalkylcarbonylamino, Ci-C4alkylaminocarbonyl, C3- C6cycloalkylaminocarbonyl, Ci-C4haloalkylaminocarbonyl, C3-C6halocycloalkylaminocarbonyl, C3- C6cycloalkylcarbonyl, C3-C6halocycloalkylcarbonyl, -SFs or -C(0)NH2; m is 0, 1 or 2; R2 is independently selected from halogen, cyano, amino, hydroxyl, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4haloalkoxy, Ci-C4alkoxy, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, C1-C4 alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci- C4haloalkylsulfonyl and cyclopropyl;
R3a and R3b are independently selected from hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy and cyano;
R4 is selected from one of Y1 to Y4;
Figure imgf000004_0001
wherein n is 0, 1 or 2;
U is independently selected from halogen, cyano, nitro, hydroxyl, amino, Ci-C4alkyl, Ci- C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, Ci-C4haloalkoxy-Ci-C4alkyl, Ci-C4alkoxy-Ci-C4alkyl, Ci-C4alkylsulfanyl, Ci- C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, formyl, cyclopropyl, Ci-C4alkylcarbonyl or C3-C6cycloalkylcarbonyl; and
R5 is hydrogen, Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, cyanoCi-Cealkyl, nitroCi-C4alkyl, Ci-C4alkoxyCi-C4alkyl, Ci- C4halolkoxyCi-C4alkyl, Ci-C4alkylsulfinylCi-C4alkyl, Ci-C4alkylsulfonylCi-C4alkyl, Ci- C4haloalkylsulfanylCi-C4alkyl, Ci-C4haloalkylsulfinylCi-C4alkyl, Ci-C4haloalkylsulfonylCi-C4alkyl and C3-C6cycloalkylCi-C4alkyl, or
R5 is Ci-C4alkyl or Ci-C4haloalkyl substituted by phenyl or 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, and wherein each phenyl or heteroaryl ring is optionally substituted by 1 or 2 groups independently selected from halogen, cyano, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci- C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl and Ci-C4haloalkylsulfonyl;
R5 is Ci-C6alkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, Ci-C4alkoxy, Ci-C4haloalkoxy, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, Ci- C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci- C4haloalkylsulfonyl, C3-C6cycloalkyl and phenyl or 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, and wherein each phenyl or heteroaryl ring is optionally substituted by 1 or 2 groups independently selected from halogen, cyano, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci- C4haloalkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci- C4haloalkylsulfinyl and Ci-C4haloalkylsulfonyl, or
R5 is Ci-C6haloalkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, Ci-C4alkoxy, Ci-C4haloalkoxy, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, C3-C6cycloalkyl and phenyl or 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, and wherein each phenyl or heteroaryl ring is optionally substituted by 1 or 2 groups independently selected from halogen, cyano, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci- C4haloalkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci- C4haloalkylsulfinyl and Ci-C4haloalkylsulfonyl,
R5 is C3-C6cycloalkoxy;
R6 is hydrogen, Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, Ci-C6haloalkoxy; and
R7 is Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, Ci-C6haloalkoxy, or 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; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.
Surprisingly, it has been found that the novel compounds of Formula (I) have, for practical purposes, a very advantageous level of biological activity for protecting plants against insects.
According to a second aspect of the invention, there is provided a (intermediate) compound of Formula (II): ol)
wherein A, R1 , R2, m, R3a, R3b and R4 are as defined according to the compounds of Formula co
According to a third aspect of the invention, there is provided an agrochemical composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined according to the invention.
According to a fourth aspect of the invention, there is provided 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). According to this particular aspect of the invention, the method may exclude methods for the treatment of the human or animal body by surgery or therapy.
According to a fifth aspect of the invention, there is provided the use of a compound according to Formula (I) as an insecticide, acaracide, nematicide or molluscicide. According to this particular aspect of the invention, the use may exclude methods forthe treatment ofthe human or animal body by surgery or therapy.
The compounds of Formula (I) may exist as geometric isomers (or isomeric mixtures thereof (ie, (E) and/or (Z)) as defined by Formulae (la) and (lb) shown below, wherein A, R1 , R2, m, R3a, R3b and R4 are as defined for Formula (I) according to the invention, including any compound selected from a compound 1 .001 to 1 .051 listed in Table 1 (below) or a compound A1 to A137 listed in Table A (below), a compound C1 or C2 listed in Table C (below) or a compound E1 to E6 listed in Table E (below). Both (E) and (Z) isomeric forms may exist and interconvert as a function of temperature or the environment. See for example: Journal of Organic Chemistry (1972), 37(19), 2969-79 or Chemische Berichte 1 16, 2668-2675. The present invention is not limited to one specific isomer and may relate to the (E)-isomer or (Z)-isomer, or a mixture thereof. Both isomeric forms (E) and (Z) are represented by a crossed bond in the reaction schemes herein and the transition from (E)-form to (Z)- form (or (Z)- form to (E)-form) could be represented, for example, by the following scheme.
Figure imgf000007_0001
(la) (lb)
As used herein, the term "halogen" or“halo” refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.
As used herein, cyano means a -CN group.
As used herein, the term“hydroxyl” or“hydroxy” means an -OH group.
As used herein, amino means an -NH2 group.
As used herein, nitro means an -NO2 group.
As used herein, formyl means a -C(0)H group.
As used herein, the term "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-C4alkyl, 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 (isopropyl), n-butyl, and 1 ,1 -dimethylethyl (f-butyl). A “Ci- C4alkylene” group refers to the corresponding definition of Ci-C4alkyl, except that such radical is attached to the rest of the molecule by two single bonds. Examples of Ci-C4alkylene, are -CH2- and - CH2CH2-.
As used herein, the term "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.
As used herein, the term "Ci-C6alkoxy" refers to a radical of the formula RaO- where Ra is a Ci- C6alkyl radical as generally defined above. The term "Ci-C4alkoxy" should be construed accordingly. Examples of Ci-C6alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy, and t- butoxy.
As used herein, the term "Ci-C6haloalkoxy" refers to a Ci-C6alkoxy group as defined above substituted by one or more of the same or different halogen atoms. Ci-C4haloalkoxy is to be construed accordingly. Examples of Ci-C6haloalkoxy include, but are not limited to, fluoromethoxy, difluoro methoxy, fluoroethoxy, trifluoromethoxy, and trifluoroethoxy.
As used herein, the term "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 (^-configuration, 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.
As used herein, the term "C2-C6haloalkenyl" refers to a C2-C6alkenyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
As used herein, the term "C2-C7alkynyl" 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 seven carbon atoms, and which is attached to the rest of the molecule by a single bond. Examples of C2-C7alkynyl include, but are not limited to, prop-1 -ynyl, propargyl (prop-2-ynyl), and but-1 -ynyl.
As used herein, the term "C2-C6haloalkynyl" refers to a C2-C6alkynyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
As used herein, the term "C3-C6cycloalkyl" refers to a stable, monocyclic ring radical which is saturated or partially unsaturated and contains 3 to 6 carbon atoms. C3-C4cycloalkyl 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.
As used herein, the term "Ci-C4alkoxyCi-C4alkyl" refers to a radical of the formula Ry-O-R*- where Ry is a Ci-C4alkyl radical as generally defined above, and Rx is a Ci-C4alkylene radical as generally defined above.
As used herein, the term“cyanoCi-C4alkyl” refers to a Ci-C4alkyl radical as generally defined above substituted by one or more cyano groups. CyanoCi-C2alkyl should be construed accordingly.
As used herein, the term“Ci-C6alkylsulfanyl” refers to a radical of the formula RxS- wherein Rx is a Ci-C6alkyl radical as generally defined above.
As used herein, the term“Ci-C6alkylsulfonyl” refers to a radical of the formula RxS(0)2- wherein Rx is a Ci-C6alkyl radical as generally defined above.
As used herein, the term " Ci-C6alkylcarbonyl" refers to a radical of the formula RxC(O)- where Rx is a Ci-C6alkyl radical as generally defined above. As used herein, the term "Ci-C6alkoxycarbonyl" refers to a radical of the formula RxOC(O)- where Rx is a Ci-C6alkyl radical as generally defined above.
As used herein, the term“C3-C6cycloalkylcarbonyl” refers to a radical of the formula RxC(O)- where Rx is a C3-C6cycloalkyl radical as generally defined above.
As used herein, the term“C3-C6halocycloalkylcarbonyl” refers to a C3-C6cycloalkylcarbonyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
As used herein, the term "heteroaryl" 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. Examples of heteroaryl include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl, pyridyl, and indolyl.
As used herein, the term "heterocyclyl" or "heterocyclic" refers to a stable 5- or 6-membered non-aromatic monocyclic ring radical, 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. Examples of heterocyclyl include, but are not limited to, pyrrolinyl, pyrrolidyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidyl, piperazinyl, tetrahydropyranyl, dioxolanyl, morpholinyl.
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-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as Ci-C4-alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. 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.
The presence of one or more possible 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). Likewise, 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).
In each case, 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.
The following list provides definitions, including preferred definitions, for substituents A, p, R1 , R2, m, R3a , R3b, R4 (ie, Y1 , Y2, Y3, Y4), U, Ui, U2, U3, LU and n with reference to the compounds of Formula (I) of the present invention. For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document.
A is a direct link (between R1 and the rest of the molecule), -0-, or -S(0)P- wherein p is selected from 0, 1 or 2. Preferably, A is selected from a direct link, O or S (ie, p is 0). In one embodiment of the invention, A is a direct link. In another embodiment of the invention, A is -O-. In yet another embodiment of the invention, A is -S-.
R1 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 C2-C6alkenyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or C2-C6haloalkenyl; or C2-C6alkynyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or C2-C6haloalkynyl; or C3-C6cycloalkyl, wherein the cycloalkyl moiety is optionally substituted by 1 or 2 substituents independently selected from U3 or a single substituent selected from U2; or cyano, halogen, C(0)R5 or C(0)NR6R7.
Preferably, R1 is selected from cyano, Ci-C6alkyl, Ci-C6haloalkyl, cyanoCi-Cealkyl, Ci-C4alkoxyCi- C4alkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, -C(0)0(Ci-C4alkyl), or C3- C6cycloalkyl, -C(0)0(C3-C6cycloalkyl), -CH2(C3-C6cycloalkyl), -OHSRIΊ, -CH2(pyridinyl) or -CH2(furanyl), wherein each cycloalkyl, phenyl, pyridinyl or furanyl group is optionally substituted by 1 , 2 or 3 independently selected halogen groups.
More preferably, R1 is selected from cyano, Ci-C4alkyl, Ci-C4haloalkyl, cyanoCi-C4alkyl, Ci- -C(0)0(Ci-
Figure imgf000010_0001
(pyridinyl) or -ChhCfuranyl), wherein each cycloalkyl, phenyl, pyridinyl or furanyl group is optionally substituted by a single chloro or fluoro group.
Still more preferably, R1 is selected from cyano, Ci-C4alkyl, Ci-C4fluoroalkyl, cyanoCi-C4alkyl, Ci- C2alkoxyCi-C2alkyl, C2-C4alkenyl, C2-C4alkynyl, -C(0)0(Ci-C4alkyl), or C3-C4cycloalkyl, -C(0)0(C3- C4cycloalkyl), -CH2(C3-C4cycloalkyl), -ChhPh, -CH2(pyridinyl), -CH2(furanyl), wherein each cycloalkyl, phenyl, pyridinyl or furanyl group is optionally substituted by a single chloro or fluoro group.
Even more preferably, R1 is selected from cyano, methyl, ethyl, propyl, iso-propyl, butyl (including n- butyl, s-butyl, i-butyl, t-butyl), methoxymethyl, -C(0)CH3 (acetyl), propenyl (including allyl), propynyl (including propargyl), difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, cyclopropyl, cyclobutyl, -C(0)0(cyclopropyl), benzyl, -CH2(2-chloro-pyridin-5-yl), -CH2(furan-2-yl), -CH2(pyridin-2-yl).
In certain embodiments of the invention, R1 is methyl or ethyl each optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or R1 is Ci- C4haloalkyl. In particular, R1 is methyl or ethyl each optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or R1 is Ci-C4fluoroalkyl.
In certain embodiments of the invention, R1 is ethenyl (-CH=CH2) or propenyl (-CH=CHCH3) each optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or R1 is C2-C4fluoroalkenyl. In particular, R1 is ethenyl (-CH=CH2) or propenyl (- CH=CHCH3) each optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or R1 is C2-C4fluoroalkenyl.
In certain embodiments of the invention, R1 is ethynyl (-CHºCH) or propynyl (-CHECChh) each optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or R1 is C2-C4fluoroalkenyl. In particular, R1 is ethynyl (-CHºCH) or propynyl (- CHºCCH3) each optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or R1 is C2-C4fluoroalkynyl. R1 may be ethynyl (-CHºCH) optionally substituted by a single substituent selected from Ui or a single substituent selected from U2,
Ui is nitro, cyano, amino, hydroxyl, CO2H, C3-C6cycloalkyl, C3-C6halocycloalkyl, Ci-C4alkoxy, Ci- C4haloalkoxy, Ci-C2alkoxy-Ci-C2alkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci- C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, Ci-C4alkylcarbonyl, Ci- C4alkoxycarbonyl, Ci-C4haloalkylcarbonyl, Ci-C4haloalkoxycarbonyl, C3-C4cycloalkylcarbonyl, =N- 0(Ci-C4alkyl), =N-0(Ci-C4haloalkyl), -Si(Ci-C4alkyl)3, (Ci-C4haloalkyl)NH-, (Ci-C4 haloalkyl)2N-, (C1-C4 haloalkyl)(Ci-C4alkyl)N-, (Ci-C4alkyl)NH-, (C1-C4 alkyl)2N-, (C3-C6cycloalkyl)NH-, (C3-C6cycloalkyl)(Ci- C4alkyl)N-, Ci-C4alkylcarbonylamino, Ci-C4haloalkylcarbonylamino, Ci-C4alkylaminocarbonyl, C3- C6cycloalkylaminocarbonyl, Ci-C4haloalkylaminocarbonyl, C3-C6halocycloalkylaminocarbonyl or - C(0)NH2.
Preferably, Ui is cyano, amino, hydroxy, methoxy, ethoxy, n-propoxy, methoxymethoxy, methoxyethoxy, methylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, t- butoxycarbonyl, cyclopropyl,
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 L4 and optionally a halogen group.
Preferably (in particular when R1 is methyl, ethenyl or ethynyl), U2 is phenyl, furanyl, pyridinyl, imidazolyl, oxetanyl, thienyl, pyrazolyl, cyclohexyl, N-morpholinyl, pyrrolidinyl, piperidinyl or tetrazolyl, wherein each ring is optionally substituted by 1 , 2 or 3 independently selected halogen, methyl or ethyl groups, or a single trifluoromethyl group. More preferably, U2 is phenyl, furanyl or pyridinyl, each optionally substituted by (i) a single fluoro, chloro or bromo group.
L is halogen, nitro, cyano, amino, hydroxyl, CO2H, Ci-C4alkyl, Ci-C4haloalkyl, C3-C6cycloalkyl, C3- Cehalocycloalkyl, C3-C6halocycloalkyl-Ci-C4alkyl, C3-C6cycloalkyl-Ci-C4alkyl, Ci-C4alkoxy, Ci-C4alkoxy- Ci-C4alkyl, Ci-C4haloalkoxy, Ci-C4haloalkoxy-Ci-C4alkyl, cyano-Ci-C4alkyl, cyano-Ci-C4haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, Ci-
C4alkylcarbonyl, Ci-C4alkoxycarbonyl, Ci-C4haloalkylcarbonyl, Ci-C4haloalkoxycarbonyl and -C(0)NH2.
Preferably, U3 is selected from halogen, Ci-C4alkyl or Ci-C4haloalkyl. More preferably, U3 is selected from fluoro, chloro, bromo, methyl, ethyl, trifluoromethyl.
U4 is nitro, cyano, amino, hydroxyl, -SCN, -CO2H, Ci-C4alkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, C3-C6cycloalkyl-Ci-C4alkyl, C3-C6halocycloalkyl-Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4alkoxy- Ci-C4alkyl, Ci-C4alkoxy-Ci-C4alkoxy, cyano-Ci-C4alkyl, cyano-Ci-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, Ci-C4haloalkoxy, Ci-C4haloalkoxy-Ci-C4alkyl, Ci- C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci- C4haloalkylsulfonyl, Ci-C4alkylcarbonyl, Ci-C4alkoxycarbonyl, Ci-C4haloalkylcarbonyl, Ci-
C4haloalkoxycarbonyl, (Ci-C4alkyl)NH-, (Ci-C4alkyl)2N-, (C3-C6cycloalkyl)NH-, (C3-C6cycloalkyl)2N-, Ci- C4alkylcarbonylamino, C3-C6cycloalkylcarbonylamino, Ci-C4haloalkylcarbonylamino, C3- Cehalocycloalkylcarbonylamino, Ci-C4alkylaminocarbonyl, C3-C6cycloalkylaminocarbonyl, Ci- C4haloalkylaminocarbonyl, C3-C6halocycloalkylaminocarbonyl, C3-C6cycloalkylcarbonyl, C3-C6 halocycloalkylcarbonyl, -SFs or -C(0)NH2. 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.
R2 is independently selected from halogen, cyano, amino, hydroxyl, Ci-C4alkyl, Ci-C4haloalkyl, Ci- C4haloalkoxy, Ci-C4alkoxy, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, C1-C4 alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci- C4haloalkylsulfonyl and cyclopropyl. Preferably, R2 is independently selected from fluoro, chloro, methyl, ethyl, trifluoromethyl, trifluoromethoxy, methoxy or ethoxy. Still more preferably, R2 is fluoro or methyl, in particular, when m is 1 .
In certain embodiments of the invention, in the compounds of Formula (I) R2 is not chloro when m is
1 .
R3a and R3b are independently selected from hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci- C4alkoxy and cyano. Preferably, R3a is hydrogen and R3b is selected from hydrogen, chloro, fluoro, methyl, ethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, methoxy or ethoxy. More preferably, R3a is hydrogen and R3b is hydrogen or methyl. Most preferably, R3a is hydrogen and R3b is hydrogen.
R4 is selected from one of Y1 to Y4;
Figure imgf000013_0001
wherein n is 0, 1 or 2;
U is independently selected from halogen, cyano, nitro, hydroxyl, amino, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, Ci- C4haloalkoxy-Ci-C4alkyl, Ci-C4alkoxy-Ci-C4alkyl, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci- C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, formyl, cyclopropyl, Ci-C4alkylcarbonyl or C3-C6cycloalkylcarbonyl. Preferably, U is halogen, in particular, chloro.
In certain embodiments of the invention, in the compounds of Formula (I), U is not methyl when n is
1 . In some preferred embodiments of the invention, R4 is selected from one of Y2 or Y3. In one embodiment of the invention, R4 is Y2. In another embodiment of the invention, R4 is Y3.
In some embodiments of the invention, R4 is:
Figure imgf000014_0001
In some embodiments of the invention, R4 is:
Figure imgf000014_0002
R5 is hydrogen, Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, cyanoCi-Cealkyl, nitroCi-C4alkyl, Ci-C4alkoxyCi-C4alkyl, Ci- C4halolkoxyCi-C4alkyl, Ci-C4alkylsulfinylCi-C4alkyl, Ci-C4alkylsulfonylCi-C4alkyl, Ci- C4haloalkylsulfanylCi-C4alkyl, Ci-C4haloalkylsulfinylCi-C4alkyl, Ci-C4haloalkylsulfonylCi-C4alkyl and C3-C6cycloalkylCi-C4alkyl, or
R5 is Ci-C6alkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, Ci-C4alkoxy, Ci-C4haloalkoxy, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, Ci- C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci- C4haloalkylsulfonyl, C3-C6cycloalkyl and phenyl or 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, and wherein each phenyl or heteroaryl ring is optionally substituted by 1 or 2 groups independently selected from halogen, cyano, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci- C4haloalkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci- C4haloalkylsulfinyl and Ci-C4haloalkylsulfonyl, or
R5 is Ci-C6haloalkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, Ci-C4alkoxy, Ci-C4haloalkoxy, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, C3-C6cycloalkyl and phenyl or 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, and wherein each phenyl or heteroaryl ring is optionally substituted by 1 or 2 groups independently selected from halogen, cyano, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci- C4haloalkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci- C4haloalkylsulfinyl and Ci-C4haloalkylsulfonyl, or R5 is C3-C6cycloalkoxy.
Preferably, R5 is Ci-C6alkyl, C3-C6cycloalkyl, or C3-C6cycloalkoxy. More preferably, R5 is Ci-C4alkyl, cyclopropyl or cyclopropoxy. Even more preferably, R5 is methyl, ethyl, cyclopropyl or cyclopropoxy.
R6 is hydrogen, Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, Ci-C6haloalkoxy. Preferably, R6 is hydrogen, methyl or ethyl. More preferably, R6 is hydrogen.
R7 is Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, Ci-C6haloalkoxy, or 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.
In a preferred embodiment of the invention, R1 is:
Ci-C6alkyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or Ci-C6haloalkyl optionally substituted by a single substituent selected from Ui; or
C2-C6alkenyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or C2-C6haloalkenyl;
or
C2-C7alkynyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or C2-C6haloalkynyl;
or
C3-C6cycloalkyl, wherein the cycloalkyl moiety is optionally substituted by a single substituent selected from U3;
or
cyano, nitro, halogen, -C(0)R5, -C(0)NR6R7 or -C(R6)=NOR6;
Ui is nitro, cyano, amino, hydroxyl, CO2H, C3-C6cycloalkyl, C3-C6halocycloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C2alkoxy-Ci-C2alkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, Ci-C4alkylcarbonyl, Ci- C4alkoxycarbonyl, -OSi(Ci-C4alkyl)3, (Ci-C4alkyl)NH-, (Ci-C4alkyl)2N-, (PhCH2)NH-, (PhCH2)(Ci- C4alkyl)N-, Ci-C4alkylcarbonylamino wherein the alkyl group is optionally substituted by cyano, Ci- C4alkoxycarbonylamino, -SPh, -0C(0)R6, -O-pyrazine or -C(0)NH2; U2 is phenyl, furanyl, pyridinyl, thienyl, pyrazolyl, imidazolyl, tetrazolyl, oxetanyl, N-morpholinyl, pyrrolidinyl, piperidinyl wherein each ring is optionally substituted by: (i) 1 or 2 independently selected halogen groups, or (ii) 1 or 2 groups independently selected from L4 and optionally a halogen group;
U3 IS halogen, Ci-C4alkyl, Ci-C4haloalkyl or Ci-C4alkoxy;
U4 is cyano, Ci-C4alkyl, Ci-C4haloalkyl or oxo (=0);
R5 is hydrogen, Ci-C6alkyl, Ci-C4haloalkyl or Ci-C4haloalkoxy, or Ci-C6alkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, C2-C4alkenyl, C2-C4alkynyl, Ci- C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C3-C6cycloalkyl, phenyl, pyridinyl, furanyl or thiazolyl wherein each ring is optionally substituted by 1 or 2 groups independently selected from halogen, methyl, ethyl, methoxy, ethoxy or trifluromethyl;
R6 is hydrogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy; and
R7 is Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy.
In another preferred embodiment of the invention, R1 is:
Ci-C4alkyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or Ci-C4fluorooalkyl optionally substituted by a single substituent selected from Ui ; or
C2-C4alkenyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or C2-C4fluoroalkenyl;
or
C2-C4alkynyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or C2-C4fluoroalkynyl;
or
C3-C6cycloalkyl, wherein the cycloalkyl moiety is optionally substituted by a single substituent selected from U3;
or
cyano, nitro, halogen, -C(0)R5, -C(0)NR6R7 or -C(R6)=NOR6;
Ui is nitro, cyano, amino, hydroxyl, CO2H, C3-C6cycloalkyl, C3-C6fluorocycloalkyl, Ci-C4alkoxy, Ci-C4fluoroalkoxy, Ci-C2alkoxy-Ci-C2alkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4fluoroalkylsulfanyl, Ci-C4fluoroalkylsulfinyl, Ci-C4fluoroalkylsulfonyl, Ci-C4alkylcarbonyl, Ci- C4alkoxycarbonyl, -OSi(Ci-C4alkyl)3, (Ci-C4alkyl)NH-, (Ci-C4alkyl)2N-, (PhCH2)NH-, (PhCH2)(Ci- C4alkyl)N-, Ci-C4alkylcarbonylamino wherein the alkyl group is optionally substituted by cyano, Ci- C4alkoxycarbonylamino, -SPh, -0C(0)R6, -O-pyrazine or -C(0)NH2; U2 is phenyl, furanyl, pyridinyl, thienyl, pyrazolyl, imidazolyl, tetrazolyl, oxetanyl, N-morpholinyl, pyrrolidinyl, piperidinyl wherein each ring is optionally substituted by: (i) 1 or 2 independently selected halogen groups, or (ii) 1 or 2 groups independently selected from L4 and optionally a halogen group;
U3 IS halogen, Ci-C4alkyl, Ci-C4fluoroalkyl or Ci-C4alkoxy;
U4 is cyano, Ci-C4alkyl, Ci-C4fluoroalkyl or oxo (=0);
R5 is hydrogen, Ci-C6alkyl, Ci-C4fluoroalkyl or Ci-C4fluoroalkoxy, or Ci-C6alkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, C2-C4alkenyl, C2-C4alkynyl, Ci- C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C3-C6cycloalkyl, phenyl, pyridinyl, furanyl or thiazolyl wherein each ring is optionally substituted by 1 or 2 groups independently selected from halogen, methyl, ethyl, methoxy, ethoxy or trifluromethyl.
R6 is hydrogen, Ci-C4alkyl, Ci-C4fluoroalkyl, Ci-C4alkoxy, Ci-C4fluoroalkoxy; and
R7 is Ci-C4alkyl, Ci-C4fluoroalkyl, Ci-C4alkoxy.
In still another preferred embodiment of the invention, R1 is: methyl or ethyl each optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or Ci-C2fluorooalkyl optionally substituted by a single substituent selected from Ui;
or
C2-C3alkenyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or C2-C4fluoroalkenyl;
or
C2-C3alkynyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or C2-C4fluoroalkynyl;
or
C3-C4cycloalkyl, wherein the cycloalkyl moiety is optionally substituted by a single substituent selected from U3;
or
cyano, nitro, halogen, -C(0)R5, -C(0)NR6R7 or -C(R6)=NOR6;
Ui is nitro, cyano, amino, hydroxyl, CO2H, C3-C6cycloalkyl, C3-C6fluorocycloalkyl, Ci-C4alkoxy, Ci-C4fluoroalkoxy, Ci-C2alkoxy-Ci-C2alkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4fluoroalkylsulfanyl, Ci-C4fluoroalkylsulfinyl, Ci-C4fluoroalkylsulfonyl, Ci-C4alkylcarbonyl, Ci- C4alkoxycarbonyl, -OSi(Ci-C4alkyl)3, (Ci-C4alkyl)NH-, (Ci-C4alkyl)2N-, (PhCH2)NH-, (PhCH2)(Ci- C4alkyl)N-, Ci-C4alkylcarbonylamino wherein the alkyl group is optionally substituted by cyano, Ci- C4alkoxycarbonylamino, -SPh, -0C(0)R6, -O-pyrazine or -C(0)NH2; U2 is phenyl, furanyl, pyridinyl, thienyl, pyrazolyl, imidazolyl, tetrazolyl, oxetanyl, N-morpholinyl, pyrrolidinyl, piperidinyl wherein each ring is optionally substituted by: (i) 1 or 2 independently selected halogen groups, or (ii) 1 or 2 groups independently selected from L4 and optionally a halogen group;
U3 IS chloro, fluoro, methyl, ethyl, trifluoromethyl, methoxy, ethoxy;
U4 is cyano, methyl, ethyl, trifluoromethyl, or oxo (=0);
R5 is hydrogen, Ci-C6alkyl, Ci-C4fluoroalkyl or Ci-C4fluoroalkoxy, or Ci-C6alkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, C2-C4alkenyl, C2-C4alkynyl, Ci- C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C3-C6cycloalkyl, phenyl, pyridinyl, furanyl or thiazolyl wherein each ring is optionally substituted by 1 or 2 groups independently selected from halogen, methyl, ethyl, methoxy, ethoxy or trifluromethyl.
R6 is hydrogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy; and
R7 is methyl, ethyl, trifluoromethyl, methoxy, ethoxy.
In certain embodiments of the present invention, the compound of Formula (I) is:
Figure imgf000018_0001
wherein R1 is defined in accordance with the present invention, and A is O; or A is S; or A is a direct link.
In certain embodiments of the present invention, the compound of Formula (I) is:
Figure imgf000018_0002
wherein R1 is defined in accordance with the present invention, and A is O, or A is S, or A is a direct link. Preferably, the compound according to Formula (I) is selected from a compound 1 .001 to 1 .051 listed in Table 1 (below) or a compound A1 to A137 listed in Table A (below), a compound C1 or C2 listed in Table C (below) or a compound E1 to E6 listed in Table E (below).
Preferably, the compound according to Formula (II) is selected from a compound B1 to B93 listed in Table B (below), a compound D1 or D2 listed in Table D (below) or a compound F1 to F6 listed in Table F (below).
Compounds of the present invention can be made as shown in the following schemes 1 to 8, in which, unless otherwise stated, the definition of each variable is as defined herein for a compound of formula (I).
As shown in Scheme 1 below, compounds of formula (I) wherein R1, R2, R3a, R3b, R4 and A are as described herein for the compounds of formula (I), can be prepared from compounds of formula (II) via reaction with a compound of formula X-CN, wherein X is a halogen, such as bromine. The reaction occurs in the presence or not of a base (such as triethylamine or sodium hydride), in the presence or not of a catalyst such as 4-dimethylaminopyridine (DMAP) in an appropriate solvent (eg, N,N- dimethylformamide, N,N-dimethylacetamide or acetonitrile (ACN)) or in the absence of a solvent, at temperatures between -78°C and 150°C, and preferably between 0°C and 150°C. Such reactions are well known, for example, see EP 0 427 526; European Journal of Medicinal Chemistry (1993), 28(7- 8), 633-6 or WO 2017/005673.
Scheme 1
Figure imgf000019_0001
As shown in Scheme 2 below, compounds of formula (II), wherein R1 , R2, R3a, R3b, R4 and A are as described herein for the compounds of formula (I), can be prepared from the compounds of formula (III) via alkylation with a compound of formula (IV) with (R3a)(R3b)(R4)C-Xi_G, wherein XLG is a leaving group (such as a halogen, preferably iodide, bromide or chloride) in the presence or not of a base (such as potassium carbonate or sodium hydride) in a appropriate solvent (eg, tetrahydrofuran, N,N- dimethylformamide (DMF), N,N-dimethylacetamide or acetonitrile) or in the absence of a solvent, at temperatures between -78°C and 150°C, and preferably between 0°C and 150°C. A catalyst could be used in this reaction such as sodium iodine or tetrabutylammonium iodide, principally if XLG is different to iodide. Such reactions are well known, for example, see Russian Chemical Bulletin 2018, 67(1), 168- 171 ; EP 2 628 389 or WO 2001/1 1572. Compounds of formula (III) wherein R1 , R2, R3a, R3b, R4 and A are as described herein for the compounds of formula (I), can exist under salt form.
Scheme 2
Figure imgf000020_0001
As shown in Scheme 3 below, compounds of formula (I) wherein R1, R2, R3a, R3b, R4 and A are as described herein for the compounds of formula (I), can be prepared from compounds of formula (V) via alkylation with a compound of formula (IV) with ((R3a)(R3b)(R4)C-Xi_G), wherein XLG is a leaving group (such as a halogen, preferably iodide, bromide or chloride) and using the same conditions described for scheme 2. Such reactions are well known from those skilled in the art, for example, see EP 0 427 526; US 4,803,277 (EP 0 259 738); European Journal of Medicinal Chemistry (1993), 28(7-8), 633-6.
Scheme 3
Figure imgf000020_0002
Compounds of formula (V) are commercially available or can be prepared by those skilled in the art and by analogy to the methodology described in, eg, Annales Pharmaceutiques Francaises (1968), 26(6), 469-72; Journal of Medicinal Chemistry, 61 (6), 2472-2489; 2018; Organic Letters, 16(1 ), 314- SI 7; Synthetic Communications, 48(5), 500-510; 2018; Journal of the American Chemical Society, 140(9), 3331 -3338; 2018 (sup material, method A, B, C and D).
Compounds of formula (III) are commercially available or can be prepared by those skilled in the art, eg, compounds of formula (III) wherein R1 and R2 are as described herein forthe compounds of formula (I) and A is O or S, as shown in Scheme 4 below. Compounds of formula (II) wherein R1 , R2, R3a, R3b, R4 and A is O or S are as described herein for the compounds of formula (I), can be prepared from compounds of formula (VI), wherein R2 is as described herein for the compounds of formula (I) and XLG a leaving group such as chloride or fluoride: via (i) substitution of XLG with compounds of formula R1- AH. R1 is as described herein for the compounds of formula (I) and A is O or S (ii) reduction of the nitro group of compounds of formula (VII). Condition for the reactions of step (i) are well known to those skilled in the art and are described in, eg, in ARKIVOC (Gainesville, FL, United States), (16), 73-82; 2007 or WO 2014028669. In general, compounds of formula (VII) wherein R1 and R2 are as described herein for the compounds of formula (I) and A is O or S, can be prepared from compounds of formula (VI) with reaction of compounds of formula R1-AH in the presence or not of a base (such as potassium carbonate or sodium hydride) in an appropriate solvent (eg, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide or acetonitrile) or in the absence of solvent, at temperatures between -78°C and 150°C, and preferably between 0°C and 100°C. Condition for reactions of step (ii) are well known by those skilled in the art and are described, eg, in Synthetic Organic Methodology : Comprehensive Organic Transformations. A Guide to Functional Group Preparations, Larock, R. C. 1989 p 41 1 . In addition, compounds of formula (VII) could be commercially available or or can be prepared by those skilled in the art (others examples are give in Scheme 6).
Scheme 4
Figure imgf000021_0001
As shown in Scheme 5 below, compounds of formula (III) wherein R1 , R2, R3a, R3b, R4 and A are as described herein for the compounds of formula (I), can be prepared from compounds of formula (Ilia) wherein R1 , R2, R3a, R3b, R4 and A are as described herein for the compounds of formula (I) and XLG could be a leaving group such as fluoride or chloride using substitution of XLG with a compound of formula R1-AH wherein R1 is as described herein for the compounds of formula (I) and A is O or S in the presence or not of a base (such as potassium carbonate or sodium hydride) in an appropriate solvent (eg, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide or acetonitrile) or in the absence of solvent, at temperatures between -78°C and 150°C, and preferably between 0°C and 100°C.
Alternatively, Compounds of formula (II) wherein R1 , R2, R3a, R3b, R4 and A are as described herein for the compounds of formula (I), can be prepared from compounds of formula (lla) wherein R1 , R2, R3a, R3b, R4 and A are as described herein for the compounds of formula (I) and XLG could be a leaving group such iodide or bromide via“metal catalyst”: For example with in HA-Ri wherein A is O or S and using palladium coupling, see Chemistry - A European Journal 2012 18(9), 2498-2502, S2498/1 - S2498/31 ; and cited references; Journal of the American Chemical Society 2010 132(33), 1 1592-1 1598; or Organic Letters 2014 16(4), 1212-1215. The reaction can be catalyzed by a palladium-based catalyst, for example palladium acetate, in the presence of a base, like cesium carbonate or sodium tert-butoxide, in a solvent or a solvent mixture, like, for example toluene, preferably under inert atmosphere and in the presence of chelating phosphine. The reaction temperature can preferentially range from ambient temperature to the boiling point of the reaction mixture. In addition, the metal used for the catalysis could be copper derivative, see for example, Tetrahedron 2013 69(16), 3415-3418; or Journal of Organic Chemistry 2009 74(14), 5075-5078; or Organic & Biomolecular Chemistry 2012 10(13), 2562-2568;. The reaction is commonly performed with one to two equivalents of a base, like potassium phosphate, in presence of a copper catalyst, like for example copper (I) iodide and under an oxygen-containing atmosphere. The reaction can be run in an inert solvent, like dioxane or toluene, usually at temperature between 50 to 150°C and in presence or not of a additional ligand such as for example diamine ligands (e.g. frans-cyclohexyldiamine.) or, for example, 1 ,10-phenanthroline.
When A is a direct linker, compounds of formula (II) wherein R1 , R2, R3a, R3b, R4 and A are as described herein for the compounds of formula (I), can be prepared from compounds of formula (lla) wherein R1 , R2, R3a, R3b, R4 and A are as described herein for the compounds of formula (I) and XLG could be a leaving group such iodide or bromide via“metal catalyst”. These reactions are well known and are could use boronic acid or ester. This reaction is known as Suzuki cross-coupling. Such Suzuki reactions are well known to those skilled in the art and have been reviewed, for example J.Orgmet. Chem. 576, 1999, 147-168 or , Kurti, Laszlo; Czako, Barbara; (Editors) Strategic Applications of Named Reactions in Organic Synthesis (2005) p448. Compounds of formula (II) wherein R1 , R2, m, R3a, R3b, R4 and A are as described herein for the compounds of formula (I), can be prepared from compounds of formula (lla) wherein R1 , R2, m, R3a, R3b, R4 and A are as described herein for the compounds of formula (I) and XLG could be a leaving group such iodine or bromine by reaction with boron-derived functional group, as for example RI B(OH)2 or RI B(OR)2, wherein R can be a Ci-C6alkyl group or the two groups OR can form together with the boron atom a five- or six-membered ring, as for example a pinacol boronic ester. The reaction can be catalyzed by a palladium-based catalyst, for example tetrakis(triphenylphosphine)-palladium(0), bis(triphenyl-phosphine) palladium(ll) dichloride or (1 ,Tbis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane (1 :1 complex), in presence of a base, like sodium carbonate or cesium fluoride, in a solvent (such as 1 ,2-dimethoxyethane, tetrahydrofuran or dioxane) or a solvent mixture, like, for example a mixture of 1 ,2-dimethoxyethane and water, or of dioxane and water, preferably under an inert atmosphere. The reaction temperature can preferentially range from ambient temperature to the boiling point of the reaction mixture, or alternatively heating may be performed under microwave irradiation. Alternatively, tin derivatives, for example RiSnBu3, could be used for these types of reaction. Such Stille reactions are usually carried out in the presence of a palladium catalyst, for example fefra/«s(triphenylphosphine)palladium(0), or (1 ,Tbis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane (1 :1 complex), in an inert solvent such as DMF, acetonitrile, or dioxane, optionally in the presence of an additive, such as cesium fluoride, or lithium chloride, and optionally in the presence of a further catalyst, for example copper (I) iodide. Such Stille couplings are also well known to those skilled in the art, and have been described in for example J. Org. Chem., 2005, 70, 8601 -8604, J. Org. Chem., 2009, 74, 5599-5602, Angew. Chem. Int. Ed., 2004, 43, 1 132-1 136 and Kurti, Laszlo; Czako, Barbara; (Editors) Strategic Applications of Named Reactions in Organic Synthesis (2005) p 438. As function of the desired substitution, others well-known reactions could be used. For example, when A is a direct link and R1 is an alkynyl derivative, reaction such as Sonogashira cross-coupling (e.g. Kurti, Laszlo; Czako, Barbara; (Editors) Strategic Applications of Named Reactions in Organic Synthesis (2005) p425) or Castro-Stephens coupling (e.g. Kurti, Laszlo; Czako, Barbara; (Editors) Strategic Applications of Named Reactions in Organic Synthesis (2005) p 78). Other alternatives could be found, using other metal catalysis approaches.
The preparation of compounds of formula (I) wherein R1 , R2, m, R3a, R3b, R4 and A are as described herein for the compounds of formula (I) starting from compounds of formula (la) wherein R1 , R2, m, R3a, R3b, R4 and A are as described herein for the compounds of formula (I) and wherein XLG is as described for compound of formula (lla) could be done using the same conditions / method that described before.
Scheme 5
Figure imgf000023_0001
Figure imgf000023_0002
As shown in Scheme 6 below, compounds of formula (III) wherein R1 , R2 and A are as described herein for the compounds of formula (I), can be prepared from compounds of formula (Ilia) wherein R2 is as described herein for the compounds of formula (I) and A is O or S, by reaction with a alkylating agent such as R-X, wherein R is alkyl optionally substituted and X is a leaving group such as, for example bromide or iodide. These reactions are well known to those skilled in the art and are usually carried out in the presence of an inert solvent such as DMF, acetonitrile, or dioxane, optionally in the presence of an base, such as sodium hydroxide, cesium carbonate or potassium carbonate, and optionally in the presence of a catalyst such as DMAP or tetrabutyl ammonium bromide. The reaction temperature can preferentially range from ambient temperature to the boiling point of the reaction mixture, or alternatively heating may be performed under microwave irradiation. Examples of this type of reaction are, for example, described in US 6,514,989, WO 2015/165931 , Journal of Medicinal Chemistry 2014, 57(1 1 ), 4720-4744, WO 2014/068095 or Journal of Heterocyclic Chemistry 1984, 21 (4), 1081 -6.
Scheme 6
Figure imgf000024_0001
(Ilia) (III)
As shown in Scheme 7 below, compounds of formula (III) wherein R1 , R2 and A are as described herein for the compounds of formula (I), can be prepared from compounds of formula (Vila) wherein R2 is as described herein for the compounds of formula (I) and A is O or S, by reaction with an alkylating agent such as R-X wherein R is alkyl optionally substituted and X is a leaving group such as, for example bromide or iodide. The conditions used are similar that the one described in scheme 6. In addition, a Mitsunobu-type of reaction using R1-OH, could be used to make this transformation. Mitsunobu types of reaction are very well known by those skilled in the art, see conditions used and described in Kurti, Laszlo; Czako, Barbara; (Editors) Strategic Applications of Named Reactions in Organic Synthesis (2005) p 295. More specifically, examples on substrate type compounds of formula (Vila) using a alcohol of type R1-OH are described in literature: see, for example, Journal of Medicinal Chemistry 2011 , 54(18), 6342-6363 or ACS Medicinal Chemistry Letters 2013, 4(8), 806-810. Conversion of compounds of formula (VII) to compounds of formula (III) are identical to the conditions described in scheme 4.
Scheme 7
Figure imgf000024_0002
(Vila) (VII) (HI) Alternatively to the classical ways described in the previous schemes, compounds of formula (lb), wherein A is a linker, R1 is C(0)R5 and R1 and R2 are as described herein for the compounds of formula (I), can be prepared from compounds of formula (la) wherein R2, R3a, R3b and R4 are as described herein for the compounds of formula (I) and XLG is a leaving group such as, for example bromide or iodide by palladium-catalyzed carbonylation with an aromatic formate such as phenyl formate to give compounds of formula (VIII) wherein R2, R3a, R3b and R4 are as described herein for the compounds of formula (I) and LG is an optionally substituted aryl, such as phenyl.This type of reaction is well known by people skilled in the art and are described, for example, in Organic Letters 2012, 14(12), 3100-3103 or Chinese Journal of Chemistry 2013, 31 (12), 1488-1494. Finaly, compounds of formula (lb), can be prepared from compounds of formula (VIII) by deplacement of -OLG group with an nucleophilic group such as alkoxy in presence of a base, like sodium hydride or lithium diisopropylamide, in a presence of a solvent (such as dimethyl formanide, tetrahydrofuran or dioxane) or not (e.g. in the case of use of alcohol as nucleophile, the alcohol used could be the solvent). The reaction temperature can preferentially range from ambient temperature to the boiling point of the reaction mixture, or alternatively heating may be performed under microwave irradiation. Example of conditions for this reaction are described in ChemistrySelect 2019, 4(1), 175-180 or Journal of Organic Chemistry 2008, 73(18), 7096-7101.
Other palladium-catalyzed carbonylation methodologies of aryl halides with alcohols employing CO gas or without CO gas are known and can be used and could give directly compounds of formula (lb), wherein A is a link, R1 is C(0)R5, R5 is OR and R1 and R2 are as described herein forthe compounds of formula (I), from compounds of formula (la) (see (i)). See for example, Angew. Chem., Int. Ed. 2004, 43, 5580 or Angew. Chem., Int. Ed. 2009, 48, 41 14.
Scheme 8
In accordance with the reactions described in any of Schemes 1 to 8, 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).
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.
Depending on the choice of the reaction conditions and starting materials which are suitable in each case, it is possible, for example, in one reaction step only to replace one substituent by another substituent according to the invention, or a plurality of substituents can be replaced by other substituents according to the invention in the same reaction step.
Salts of compounds of formula (I) can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
Salts of compounds of formula (I) can be converted in the customary manner into the free compounds (I), acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
Depending on the procedure or the reaction conditions, the compounds of formula (I), which have salt-forming properties, can be obtained in free form or in the form of salts.
The compounds of formula (I) and, where appropriate, the 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 diastereomers, from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents.
Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.
It is advantageous to isolate or synthesize in each case the biologically more effective isomer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological activity.
The compounds 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.
Examples of the above-mentioned pests are:
from the order Acarina, for example,
Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp., Tarsonemus spp. and Tetranychus spp.,
from the order Anoplura, for example,
Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp., from the order Coleoptera, for example,
Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Conoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp., Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemLineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladera castanea, Megascelis spp., Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Somaticus spp., Sphenophorus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp. and Trogoderma spp., from the order Diptera, for example,
Aedes spp., Anopheles spp., Antherigona soccata,_Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp., Rivelia quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.,
from the order Hemiptera, for example,
Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Amblypelta nitida, Bathycoelia thalassina, Blissus spp., Cimex spp., Clavigralla tomentosicollis, Creontiades spp., Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp., Euchistus spp., Eurydema pulchrum, Eurygaster spp., Euschistus spp. (stinkbugs), Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp., Margarodes spp., Murgantia histrionic, Neomegalotomus spp., Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus insularis, Piesma spp., Piezodorus spp., Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp., Thyanta spp., Triatoma spp., Vatiga illudens, Acyrthosium pisum, Adalges spp., Agalliana ensigera, Agonoscena targionii, Aleurodicus spp., Aleurocanthus spp., Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp., Brachycaudus spp., Brevicoryne brassicae, Cacopsylla spp., Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp., Cofana spectra, Cryptomyzus spp., Cicadulina spp., Coccus hesperidum, Dalbulus maidis, Dialeurodes spp., Diaphorina citri, Diuraphis noxia, Dysaphis spp., Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp., Hyperomyzus pallidus, Idioscopus clypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp., Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp., Neotoxoptera sp, Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Peregrinus maidis, Perkinsiella spp., Phorodon humuli, Phylloxera spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Sogatella furcifera, Spissistilus festinus, Tarophagus Proserpina, Toxoptera spp., Trialeurodes spp., Tridiscus sporoboli, Trionymus spp., Trioza erytreae7 Unaspis citri, Zygina flammigera, Zyginidia scutellaris,
from the order Hymenoptera, for example,
Acromyrmex, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplo- campa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Pogonomyrmex spp., Slenopsis invicta, Solenopsis spp. and Vespa spp.,
from the order Isoptera, for example,
Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp., Solenopsis geminate
from the order Lepidoptera, for example,
Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp., Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp., Eldana saccharina, Ephestia spp., Epinotia spp., Estigmene acrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia jaculiferia, Gra- pholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp., Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp., Noctua spp., Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Papaipema nebris, Pectinophora gossypiela, Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Pseudoplusia spp., Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate, Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tuta absoluta, and Yponomeuta spp.,
from the order Mallophaga, for example,
Damalinea spp. and Trichodectes spp.,
from the order Orthoptera, for example, Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscus spp., and Schistocerca spp.,
from the order Psocoptera, for example,
Liposcelis spp.,
from the order Siphonaptera, for example,
Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis,
from the order Thysanoptera, for example,
Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp.,
from the order Thysanura, for example, Lepisma saccharina.
The active ingredients according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum, beet, such as sugar or fodder beet, fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries, leguminous crops, such as beans, lentils, peas or soya, oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts, cucurbits, such as pumpkins, cucumbers or melons, fibre plants, such as cotton, flax, hemp or jute, citrus fruit, such as oranges, lemons, grapefruit or tangerines, vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers, Lauraceae, such as avocado, Cinnamonium or camphor, and also tobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines, hops, the plantain family, latex plants and ornamentals.
The active ingredients according to the invention 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).
In a further aspect, 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, Belonolaimus longicaudatus and other Belonolaimus species, Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species, Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species, Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species, Awl nematodes, Dolichodorus species, Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species, Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species, Hirshmanniella species, Lance nematodes, Hoploaimus species, false rootknot nematodes, Nacobbus species, Needle nematodes, Longidorus elongatus and other Longidorus species, Pin nematodes, Pratylenchus species, Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species, Burrowing nematodes, Radopholus similis and other Radopholus species, Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species, Scutellonema species, Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species, Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species, Citrus nematodes, Tylenchulus species, Dagger nematodes, Xiphinema species, and other plant parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp..
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. obvia), Helicidae Helicigona arbustorum), Helicodiscus, Helix (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 .051 listed in Table 1 (below) or a compound A1 to A137 listed in Table A (below), a compound C1 or C2 listed in Table C (below) or a compound E1 to E6 listed in Table E (below)) to a neonicotinoid-resistant insect. Likewise, 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 .051 listed in Table 1 (below) or a compound A1 to A137 listed in Table A (below), a compound C1 or C2 listed in Table C (below) or a compound E1 to E6 listed in Table E (below) as an insecticide against neonicotinoid-resistant insects. Such 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. However, reports of insect resistance to the neonicotinoid class of insecticides are on the increase.
The increase in resistance of such insects to neonicotinoid insecticides thus poses a significant threat to the cultivation of a number of commercially important crops, fruits and vegetables, and there is thus a need to find alternative insecticides capable of controlling neonicotinoid resistant insects (i.e. to find insecticides that do not exhibit any cross- resistance with the neonicotinoid class).
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.
Two of the major mechanisms for neonicotinoid resistance include:-
(i) 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
(ii) Metabolic resistance, such as enhanced oxidative detoxification of neonicotinoids due to overexpression of monooxygenases;
For general review on insect resistance to neonicotinoid insecticides see, for example, Pesticide Biochemistry and Physiology (2015), 121 , 78-87 or Advances in Experimental Medicine and Biology (2010), 683(lnsect Nicotinic Acetylcholine Receptors), 75-83.
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. neonicotinoids) but also seemingly unrelated insecticides. For example, cross- resistance relationships between the neonicotinoids and pymetrozine in Bemisia tabaci have been reported by Gorman et al (Pest Management Science 2010, p.1 186-1 190). Or for example, for evidence on detoxification via P450, see, for example, Harrop, Thomas WR and al. Pest Management Science (2018), 74(7), p1616- 1622 and cited references.
Target site resistance of nicotinoids is well studied and it has been shown that modification of the active site of nicotinic acetylcholine receptor confers the resistance to nicotinoids. For example, see Bass et al BMC Neuroscience (201 1), 12, p 51 , Pest Management Science (2018), 74(6), 1297-1301 . The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae, or insecticidal proteins from Bacillus thuringiensis, such as 5-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. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus, toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins, toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins, agglutinins, proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors, ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin, steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP- glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
In the context of the present invention there are to be understood by 5-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. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G- recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651 .
The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and 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 Cry1 Ab 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 Cry1 Ac toxin), Bollgard II® (cotton variety that expresses a Cryl Ac and a Cry2Ab toxin), VipCot® (cotton variety that expresses a Vip3A and a CrylAb toxin), NewLeaf® (potato variety that expresses a Cry3A toxin), NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt1 1 corn borer (CB) trait) and Protecta®.
Further examples of such transgenic crops are:
1 . Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer ( Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer ( Ostrinia 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.
3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/ES/96/02.
6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1 160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1 F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.
7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 c 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 Cry1 Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
Transgenic crops of insect-resistant plants are also described in BATS (Zentrum fiir Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).
The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191 . The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
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.
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).
Further areas of use of the 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/). In one embodiment, 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. By way of example, an IRS (indoor residual spraying) application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention. In another embodiment, it is contemplated to apply such 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 further object of the invention is therefore a substrate selected from nonwoven and fabric material comprising a composition which contains a compound of formula I.
In one embodiment, 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. Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention. By way of example, 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. In another embodiment, it is contemplated to apply such 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.
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.
Further areas of use of the 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.
In the field of tree injection/trunk treatment, 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:
Examples of exotic woodborers of economic importance.
Figure imgf000037_0001
Table B. Examples of native woodborers of economic importance.
Figure imgf000037_0002
Figure imgf000038_0001
Figure imgf000039_0001
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. In particular, 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. spretulus), Maladera spp. (e.g. Asiatic garden beetle, M. castanea) and 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).
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.
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.
In the hygiene sector, the compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
Examples of such parasites are:
Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp.,
Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp., Of the order Diptera and the suborders Nematocerina and Brachycerina, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp., Of the order Siphonapterida, for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.,
Of the order Heteropterida, for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.,
Of the order Blattarida, for example Blatta orientalis, Periplaneta americana, Blattelagermanica and Supella spp., Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata, for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp., Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp..
The compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
The compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec.,Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur, and termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus, and bristletails such as Lepisma saccharina.
The 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. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo- emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). 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. Alternatively, 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.
The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se. As 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, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1 ,1 ,1 -trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, A/-methyl-2-pyrrolidone and the like.
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 fatty acids, such as polyethylene glycol stearate, block copolymers of ethylene oxide and propylene oxide, and salts of mono- and di- alkylphosphate esters, and also further substances described e.g. in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981).
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.
The 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. For example, 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, 10th Edition, Southern Illinois University, 2010.
The 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. Whereas 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. As 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:
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 %
Dusts:
active ingredient: 0.1 to 10 %, preferably 0.1 to 5 %
solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates:
active ingredient: 5 to 75 %, preferably 10 to 50 %
water: 94 to 24 %, preferably 88 to 30 %
surface-active agent: 1 to 40 %, preferably 2 to 30 %
Wettable powders:
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 %
Granules:
active ingredient: 0.1 to 30 %, preferably 0.1 to 15 %
solid carrier: 99.5 to 70 %, preferably 97 to 85 %
The following Examples further illustrate, but do not limit, the invention.
Figure imgf000044_0001
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 waterto give suspensions of the desired concentration.
Figure imgf000045_0001
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.
Figure imgf000045_0002
Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
Figure imgf000045_0003
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.
Figure imgf000045_0004
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.
Figure imgf000046_0001
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.
Figure imgf000046_0002
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. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
Figure imgf000046_0003
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. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion. Slow Release Capsule Suspension
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. To this emulsion 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.
In a further aspect, the present invention makes available a pesticidal composition comprising a compound of the first aspect, one or more formulation additives and a carrier.
The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/orfungicidally active ingredients. The 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.
The following mixtures of the compounds of formula (I) with active ingredients are preferred (the abbreviation“TX” means“one compound selected from the group consisting of a compound 1 .001 to 1 .051 listed in Table 1 (below) or a compound A1 to A137 listed in Table A (below), a compound C1 or C2 listed in Table C (below) or a compound E1 to E6 listed in Table E (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 (lUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate (lUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro-A/-methyl-A/-1 -naphthylacetamide (lUPAC name) (1295) + TX, 4- chlorophenyl phenyl sulfone (lUPAC name) (981) + TX, abamectin (1) + TX, acequinocyl (3) + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha- cypermethrin (202) + TX, amidithion (870) + TX, amidoflumet [CCN] + TX, amidothioate (872) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, aramite (881) + TX, arsenous oxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (lUPAC name) (888) + TX, azocyclotin (46) + TX, azothoate (889) + TX, benomyl (62) + TX, benoxafos [CCN] + TX, benzoximate (71) + TX, benzyl benzoate (lUPAC name) [CCN] + TX, bifenazate (74) + TX, bifenthrin (76) + TX, binapacryl (907) + TX, brofenvalerate + TX, bromocyclen (918) + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bromopropylate (94) + TX, buprofezin (99) + TX, butocarboxim (103) + TX, butoxycarboxim (104) + TX, butylpyridaben + TX, calcium polysulfide (lUPAC name) (1 1 1 ) + TX, camphechlor (941) + TX, carbanolate (943) + TX, carbaryl (1 15) + TX, carbofuran (1 18) + TX, carbophenothion (947) + TX, CGA 50’439 (development code) (125) + TX, chinomethionat (126) + TX, chlorbenside (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorfenethol (968) + TX, chlorfenson (970) + TX, chlorfensulfide (971) + TX, chlorfenvinphos (131) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, clofentezine (158) + TX, closantel [CCN] + TX, coumaphos (174) + TX, crotamiton [CCN] + TX, crotoxyphos (1010) + TX, cufraneb (1013) + TX, cyanthoate (1020) + TX, cyflumetofen (CAS Reg. No.: 400882- 07-7) + TX, cyhalothrin (196) + TX, cyhexatin (199) + TX, cypermethrin (201) + TX, DCPM (1032) + TX, DDT (219) + TX, demephion (1037) + TX, demephion-O (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-O (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton-S-methylsulfon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diazinon (227) + TX, dichlofluanid (230) + TX, dichlorvos (236) + TX, dicliphos + TX, dicofol (242) + TX, dicrotophos (243) + TX, dienochlor (1071) + TX, dimefox (1081) + TX, dimethoate (262) + TX, dinactin (653) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinobuton (269) + TX, dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinocton (1090) + TX, dinopenton (1092) + TX, dinosulfon (1097) + TX, dinoterbon (1098) + TX, dioxathion (1 102) + TX, diphenyl sulfone (lUPAC name) (1 103) + TX, disulfiram [CCN] + TX, disulfoton (278) + TX, DNOC (282) + TX, dofenapyn (1 1 13) + TX, doramectin [CCN] + TX, endosulfan (294) + TX, endothion (1 121 ) + TX, EPN (297) + TX, eprinomectin [CCN] + TX, ethion (309) + TX, ethoate- methyl (1 134) + TX, etoxazole (320) + TX, etrimfos (1 142) + TX, fenazaflor (1 147) + TX, fenazaquin (328) + TX, fenbutatin oxide (330) + TX, fenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad + TX, fenpyroximate (345) + TX, fenson (1 157) + TX, fentrifanil (1 161) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacrypyrim (360) + TX, fluazuron (1 166) + TX, flubenzimine (1 167) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1 169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1 174) + TX, fluvalinate (1 184) + TX, FMC 1 137 (development code) (1 185) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1 192) + TX, formparanate (1 193) + TX, gamma-HCH (430) + TX, glyodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecyl cyclopropanecarboxylate (lUPAC/Chemical Abstracts name) (1216) + TX, hexythiazox (441 ) + TX, iodomethane (lUPAC name) (542) + TX, isocarbophos (473) + TX, isopropyl 0-(methoxyaminothiophosphoryl)salicylate (lUPAC name) (473) + TX, ivermectin [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, lindane (430) + TX, lufenuron (490) + TX, malathion (492) + TX, malonoben (1254) + TX, mecarbam (502) + TX, mephosfolan (1261) + TX, mesulfen [CCN] + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methidathion (529) + TX, methiocarb (530) + TX, methomyl (531 ) + TX, methyl bromide (537) + TX, metolcarb (550) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime [CCN] + TX, mipafox (1293) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin [CCN] + TX, naled (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, nifluridide (1309) + TX, nikkomycins [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb 1 :1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oils (628) + TX, phenkapton (1330) + TX, phenthoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosphamidon (639) + TX, phoxim (642) + TX, pirimiphos-methyl
(652) + TX, polychloroterpenes (traditional name) (1347) + TX, polynactins (653) + TX, proclonol (1350) + TX, profenofos (662) + TX, promacyl (1354) + TX, propargite (671) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridaphenthion (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinalphos (71 1) + TX, quintiofos (1381) + TX, R-1492 (development code) (1382) + TX, RA-17 (development code) (1383) + TX, rotenone (722) + TX, schradan (1389) + TX, sebufos + TX, selamectin [CCN] + TX, SI-0009 (compound code) + TX, sophamide (1402) + TX, spirodiclofen (738) + TX, spiromesifen (739) + TX, SSI-121 (development code) (1404) + TX, sulfiram [CCN] + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulfur (754) + TX, SZI-121 (development code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbam + TX, tetrachlorvinphos (777) + TX, tetradifon (786) + TX, tetranactin
(653) + TX, tetrasul (1425) + TX, thiafenox + TX, thiocarboxime (1431) + TX, thiofanox (800) + TX, thiometon (801) + TX, thioquinox (1436) + TX, thuringiensin [CCN] + TX, triamiphos (1441) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazuron + TX, trichlorfon (824) + TX, trifenofos (1455) + TX, trinactin (653) + TX, vamidothion (847) + TX, vaniliprole [CCN] and YI-5302 (compound code) + TX,
an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (lUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX,
an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, doramectin [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin [CCN] + TX, ivermectin [CCN] + TX, milbemycin oxime [CCN] + TX, moxidectin [CCN] + TX, piperazine [CCN] + TX, selamectin [CCN] + TX, spinosad (737) and thiophanate (1435) + TX, an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (lUPAC name) (23) and strychnine (745) + TX,
a bactericide selected from the group of substances consisting of 1 -hydroxy-1 H-pyridine-2-thione (lUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (lUPAC name) (170) + TX, copper hydroxide (lUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicin (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargaphen [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (lUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (61 1) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal [CCN] + TX,
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 Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51) + TX, Beauveria bassiana (53) + TX, Beauveria brongniartii (54) + TX, Chrysoperla carnea (151) + TX, Cryptolaemus montrouzieri (178) + TX, Cydia pomonella GV (191) + TX, Dacnusa sibirica (212) + TX, Diglyphus isaea (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (300) + TX, Helicoverpa zea NPV (431) + TX, Heterorhabditis bacteriophora and H. megidis (433) + TX, Hippodamia convergens (442) + TX, Leptomastix dactylopii (488) + TX, Macrolophus caliginosus (491) + TX, Mamestra brassicae NPV (494) + TX, Metaphycus helvolus (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontei NPV (575) + TX, Orius spp. (596) + TX, Paecilomyces fumosoroseus (613) + TX, Phytoseiulus persimilis (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis (742) + TX, Steinernema carpocapsae (742) + TX, Steinernema feltiae (742) + TX, Steinernema glaseri (742) + TX, Steinernema riobrave (742) + TX, Steinernema riobravis (742) + TX, Steinernema scapterisci (742) + TX, Steinernema spp. (742) + TX, Trichogramma spp. (826) + TX, Typhlodromus occidentalis (844) and Verticillium lecanii (848) + TX,
a soil sterilant selected from the group of substances consisting of iodomethane (lUPAC name) (542) and methyl bromide (537) + TX,
a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir [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 (lUPAC name) (222) + TX, (E)-tridec-4-en-1 -yl acetate (lUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (lUPAC name) (541) + TX, (E,Z)-tetradeca-4,10-dien-1 -yl acetate (lUPAC name) (779) + TX, (Z)-dodec-7-en-1 -yl acetate (lUPAC name) (285) + TX, (Z)-hexadec-1 1 - enal (lUPAC name) (436) + TX, (Z)-hexadec-1 1 -en-1 -yl acetate (lUPAC name) (437) + TX, (Z)- hexadec-13-en-1 1 -yn-1 -yl acetate (lUPAC name) (438) + TX, (Z)-icos-13-en-10-one (lUPAC name) (448) + TX, (Z)-tetradec-7-en-1 -al (lUPAC name) (782) + TX, Z)-tetradec-9-en-1 -ol (lUPAC name) (783) + TX, (Z)-tetradec-9-en-1 -yl acetate (lUPAC name) (784) + TX, (7E,9Z)-dodeca-7,9-dien-1 -yl acetate (lUPAC name) (283) + TX, (9Z,1 1 E)-tetradeca-9,1 1 -dien-1 -yl acetate (lUPAC name) (780) + TX, (9Z, 12E)-tetradeca-9,12-dien-1 -yl acetate (lUPAC name) (781) + TX, 14-methyloctadec-1 -ene (lUPAC name) (545) + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one (lUPAC name) (544) + TX, alpha-multistriatin [CCN] + TX, brevicomin [CCN] + TX, codlelure [CCN] + TX, codlemone (167) + TX, cuelure (179) + TX, disparlure (277) + TX, dodec-8-en-1 -yl acetate (lUPAC name) (286) + TX, dodec-9-en-1 -yl acetate (lUPAC name) (287) + TX, dodeca-8 + TX, 10-dien-1 -yl acetate (lUPAC name) (284) + TX, dominicalure [CCN] + TX, ethyl 4-methyloctanoate (lUPAC name) (317) + TX, eugenol [CCN] + TX, frontalin [CCN] + TX, gossyplure (420) + TX, grandlure (421 ) + TX, grandlure I (421) + TX, grandlure II (421) + TX, grandlure III (421) + TX, grandlure IV (421) + TX, hexalure [CCN] + TX, ipsdienol [CCN] + TX, ipsenol [CCN] + TX, japonilure (481) + TX, lineatin [CCN] + TX, litlure [CCN] + TX, looplure [CCN] + TX, medlure [CCN] + TX, megatomoic acid [CCN] + TX, methyl eugenol (540) + TX, muscalure (563) + TX, octadeca-2,13-dien-1 -yl acetate (lUPAC name) (588) + TX, octadeca-3,13-dien-1 -yl acetate (lUPAC name) (589) + TX, orfralure [CCN] + TX, oryctalure (317) + TX, ostramone [CCN] + TX, siglure [CCN] + TX, sordidin (736) + TX, sulcatol [CCN] + TX, tetradec- 1 1 -en-1 -yl acetate (lUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (839) + TX, trimedlure Bi (839) + TX, trimedlure B2 (839) + TX, trimedlure C (839) and trunc-call [CCN] + TX, an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (lUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (lUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (lUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1 137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,
an insecticide selected from the group of substances consisting of 1 -dichloro-1 -nitroethane (lUPAC/Chemical Abstracts name) (1058) + TX, 1 ,1 -dichloro-2,2-bis(4-ethylphenyl)ethane (lUPAC name) (1056), + TX, 1 ,2-dichloropropane (lUPAC/Chemical Abstracts name) (1062) + TX, 1 ,2- dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1 -bromo-2-chloroethane (lUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-1 -(3,4-dichlorophenyl)ethyl acetate (lUPAC name) (1451) + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate (lUPAC name) (1066) + TX, 2-(1 ,3-dithiolan-2-yl)phenyl dimethylcarbamate (lUPAC/ Chemical Abstracts name) (1 109) + TX, 2-(2-butoxyethoxy)ethyl thiocyanate (lUPAC/Chemical Abstracts name) (935) + TX, 2-(4,5- dimethyl-1 ,3-dioxolan-2-yl)phenyl methylcarbamate (lUPAC/ Chemical Abstracts name) (1084) + TX, 2- (4-chloro-3,5-xylyloxy)ethanol (lUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (lUPAC name) (984) + TX, 2-imidazolidone (lUPAC name) (1225) + TX, 2-isovalerylindan-1 ,3-dione (lUPAC name) (1246) + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (lUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (lUPAC name) (1433) + TX, 3-bromo-1 -chloroprop-1 -ene (lUPAC name) (917) + TX, 3-methyl-1 -phenylpyrazol-5-yl dimethylcarbamate (lUPAC name) (1283) + TX, 4- methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (lUPAC name) (1285) + TX, 5,5-dimethyl-3- oxocyclohex-1 -enyl dimethylcarbamate (lUPAC name) (1085) + TX, abamectin (1) + TX, acephate (2) + TX, acetamiprid (4) + TX, acethion [CCN] + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, acrylonitrile (lUPAC name) (861) + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, aldrin (864) + TX, allethrin (17) + TX, allosamidin [CCN] + TX, allyxycarb (866) + TX, alpha- cypermethrin (202) + TX, alpha-ecdysone [CCN] + TX, aluminium phosphide (640) + TX, amidithion (870) + TX, amidothioate (872) + TX, aminocarb (873) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, anabasine (877) + TX, athidathion (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (41) + TX, azamethiphos (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azothoate (889) + TX, Bacillus thuringiensis delta endotoxins (52) + TX, barium hexafluorosilicate [CCN] + TX, barium polysulfide (lUPAC/Chemical Abstracts name) (892) + TX, barthrin [CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bendiocarb (58) + TX, benfuracarb (60) + TX, bensultap (66) + TX, beta-cyfluthrin (194) + TX, beta-cypermethrin (203) + TX, bifenthrin (76) + TX, bioallethrin (78) + TX, bioallethrin S-cyclopentenyl isomer (79) + TX, bioethanomethrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX, bis(2-chloroethyl) ether (lUPAC name) (909) + TX, bistrifluron (83) + TX, borax (86) + TX, brofenvalerate + TX, bromfenvinfos (914) + TX, bromocyclen (918) + TX, bromo-DDT [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921 ) + TX, bufencarb (924) + TX, buprofezin (99) + TX, butacarb (926) + TX, butathiofos (927) + TX, butocarboxim (103) + TX, butonate (932) + TX, butoxycarboxim (104) + TX, butylpyridaben + TX, cadusafos (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (lUPAC name) (1 1 1) + TX, camphechlor (941) + TX, carbanolate (943) + TX, carbaryl (1 15) + TX, carbofuran (1 18) + TX, carbon disulfide (lUPAC/Chemical Abstracts name) (945) + TX, carbon tetrachloride (lUPAC name) (946) + TX, carbophenothion (947) + TX, carbosulfan (1 19) + TX, cartap (123) + TX, cartap hydrochloride (123) + TX, cevadine (725) + TX, chlorbicyclen (960) + TX, chlordane (128) + TX, chlordecone (963) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorethoxyfos (129) + TX, chlorfenapyr (130) + TX, chlorfenvinphos (131) + TX, chlorfluazuron (132) + TX, chlormephos (136) + TX, chloroform [CCN] + TX, chloropicrin (141) + TX, chlorphoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, cis-resmethrin + TX, cismethrin (80) + TX, clocythrin + TX, cloethocarb (999) + TX, closantel [CCNJ + TX, clothianidin (165) + TX, copper acetoarsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, coumithoate (1006) + TX, crotamiton [CCN] + TX, crotoxyphos (1010) + TX, crufomate (101 1) + TX, cryolite (177) + TX, CS 708 (development code) (1012) + TX, cyanofenphos (1019) + TX, cyanophos (184) + TX, cyanthoate (1020) + TX, cyclethrin [CCN] + TX, cycloprothrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201 ) + TX, cyphenothrin (206) + TX, cyromazine (209) + TX, cythioate [CCN] + TX, cf-limonene [CCN] + TX, d-tetramethrin (788) + TX, DAEP (1031) + TX, dazomet (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, deltamethrin (223) + TX, demephion (1037) + TX, demephion-O (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-O (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S- methyl (224) + TX, demeton-S-methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diamidafos (1044) + TX, diazinon (227) + TX, dicapthon (1050) + TX, dichlofenthion (1051) + TX, dichlorvos (236) + TX, dicliphos + TX, dicresyl [CCN] + TX, dicrotophos (243) + TX, dicyclanil (244) + TX, dieldrin (1070) + TX, diethyl 5-methylpyrazol-3-yl phosphate (lUPAC name) (1076) + TX, diflubenzuron (250) + TX, dilor [CCN] + TX, dimefluthrin [CCN] + TX, dimefox (1081) + TX, dimetan (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinphos (265) + TX, dimetilan (1086) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinoprop (1093) + TX, dinosam (1094) + TX, dinoseb (1095) + TX, dinotefuran (271 ) + TX, diofenolan (1099) + TX, dioxabenzofos (1 100) + TX, dioxacarb (1 101 ) + TX, dioxathion (1 102) + TX, disulfoton (278) + TX, dithicrofos (1 108) + TX, DNOC (282) + TX, doramectin [CCN] + TX, DSP (1 115) + TX, ecdysterone [CCN] + TX, El 1642 (development code) (1 1 18) + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, EMPC (1 120) + TX, empenthrin (292) + TX, endosulfan (294) + TX, endothion (1 121 ) + TX, endrin (1 122) + TX, EPBP (1 123) + TX, EPN (297) + TX, epofenonane (1 124) + TX, eprinomectin [CCN] + TX, esfenvalerate (302) + TX, etaphos [CCN] + TX, ethiofencarb (308) + TX, ethion (309) + TX, ethiprole (310) + TX, ethoate-methyl (1 134) + TX, ethoprophos (312) + TX, ethyl formate (lUPAC name) [CCN] + TX, ethyl-DDD (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1 136) + TX, ethylene oxide [CCN] + TX, etofenprox (319) + TX, etrimfos (1 142) + TX, EXD (1 143) + TX, famphur (323) + TX, fenamiphos (326) + TX, fenazaflor (1 147) + TX, fenchlorphos (1 148) + TX, fenethacarb (1 149) + TX, fenfluthrin (1 150) + TX, fenitrothion (335) + TX, fenobucarb (336) + TX, fenoxacrim (1 153) + TX, fenoxycarb (340) + TX, fenpirithrin (1 155) + TX, fenpropathrin (342) + TX, fenpyrad + TX, fensulfothion (1 158) + TX, fenthion (346) + TX, fenthion-ethyl [CCN] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonicamid (358) + TX, flubendiamide (CAS. Reg. No.: 272451 -65-7) + TX, flucofuron (1 168) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1 169) + TX, flufenerim [CCN] + TX, flufenoxuron (370) + TX, flufenprox (1 171) + TX, flumethrin (372) + TX, fluvalinate (1 184) + TX, FMC 1 137 (development code) (1 185) + TX, fonofos (1 191) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1 192) + TX, formparanate (1 193) + TX, fosmethilan (1 194) + TX, fospirate (1 195) + TX, fosthiazate (408) + TX, fosthietan (1 196) + TX, furathiocarb (412) + TX, furethrin (1200) + TX, gamma-cyhalothrin (197) + TX, gamma-HCH (430) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, GY-81 (development code) (423) + TX, halfenprox (424) + TX, halofenozide (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptachlor (121 1) + TX, heptenophos (432) + TX, heterophos [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydramethylnon (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX, hyquincarb (1223) + TX, imidacloprid (458) + TX, imiprothrin (460) + TX, indoxacarb (465) + TX, iodomethane (lUPAC name) (542) + TX, IPSP (1229) + TX, isazofos (1231 ) + TX, isobenzan (1232) + TX, isocarbophos (473) + TX, isodrin (1235) + TX, isofenphos (1236) + TX, isolane (1237) + TX, isoprocarb (472) + TX, isopropyl 0-(methoxyaminothiophosphoryl)salicylate (lUPAC name) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxathion (480) + TX, ivermectin [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, juvenile hormone I [CCN] + TX, juvenile hormone II [CCN] + TX, juvenile hormone III [CCN] + TX, kelevan (1249) + TX, kinoprene (484) + TX, lambda-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin (CCN) + TX, leptophos (1250) + TX, lindane (430) + TX, lirimfos (1251) + TX, lufenuron (490) + TX, lythidathion (1253) + TX, m-cumenyl methylcarbamate (lUPAC name) (1014) + TX, magnesium phosphide (lUPAC name) (640) + TX, malathion (492) + TX, malonoben (1254) + TX, mazidox (1255) + TX, mecarbam (502) + TX, mecarphon (1258) + TX, menazon (1260) + TX, mephosfolan (1261 ) + TX, mercurous chloride (513) + TX, mesulfenfos (1263) + TX, metaflumizone (CCN) + TX, metam (519) + TX, metam- potassium (519) + TX, metam-sodium (519) + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methanesulfonyl fluoride (lUPAC/Chemical Abstracts name) (1268) + TX, methidathion (529) + TX, methiocarb (530) + TX, methocrotophos (1273) + TX, methomyl (531 ) + TX, methoprene (532) + TX, methoquin-butyl (1276) + TX, methothrin (533) + TX, methoxychlor (534) + TX, methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methylchloroform [CCN] + TX, methylene chloride [CCN] + TX, metofluthrin [CCN] + TX, metolcarb (550) + TX, metoxadiazone (1288) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime [CCNj + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin [CCN] + TX, naftalofos [CCN] + TX, naled (567) + TX, naphthalene (lUPAC/Chemical Abstracts name) (1303) + TX, NC-170 (development code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifluridide (1309) + TX, nitenpyram (579) + TX, nithiazine (131 1) + TX, nitrilacarb (1313) + TX, nitrilacarb 1 :1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, novaluron (585) + TX, noviflumuron (586) + TX, 0-5-dichloro-4- iodophenyl O-ethyl ethylphosphonothioate (lUPAC name) (1057) + TX, 0,0-diethyl 0-4-methyl-2-oxo- 2/-/-chromen-7-yl phosphorothioate (lUPAC name) (1074) + TX, 0,0-diethyl 0-6-methyl-2- propylpyrimidin-4-yl phosphorothioate (lUPAC name) (1075) + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate (lUPAC name) (1424) + TX, oleic acid (lUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydemeton-methyl (609) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, para-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-methyl (616) + TX, penfluron [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (lUPAC name) (623) + TX, permethrin (626) + TX, petroleum oils (628) + TX, PH 60-38 (development code) (1328) + TX, phenkapton (1330) + TX, phenothrin (630) + TX, phenthoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosnichlor (1339) + TX, phosphamidon (639) + TX, phosphine (lUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, pirimetaphos (1344) + TX, pirimicarb (651) + TX, pirimiphos-ethyl (1345) + TX, pirimiphos-methyl (652) + TX, polychlorodicyclopentadiene isomers (lUPAC name) (1346) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, prallethrin (655) + TX, precocene I [CCN] + TX, precocene II [CCN] + TX, precocene III [CCN] + TX, primidophos (1349) + TX, profenofos (662) + TX, profluthrin [CCN] + TX, promacyl (1354) + TX, promecarb (1355) + TX, propaphos (1356) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothiofos (686) + TX, prothoate (1362) + TX, protrifenbute [CCN] + TX, pymetrozine (688) + TX, pyraclofos (689) + TX, pyrazophos (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridalyl (700) + TX, pyridaphenthion (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, pyriproxyfen (708) + TX, quassia [CCN] + TX, quinalphos (71 1) + TX, quinalphos-methyl (1376) + TX, quinothion (1380) + TX, quintiofos (1381) + TX, R-1492 (development code) (1382) + TX, rafoxanide [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (development code) (723) + TX, RU 25475 (development code) (1386) + TX, ryania (1387) + TX, ryanodine (traditional name) (1387) + TX, sabadilla (725) + TX, schradan (1389) + TX, sebufos + TX, selamectin [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (lUPAC/Chemical Abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenoxide (623) + TX, sodium selenate (lUPAC name) (1401) + TX, sodium thiocyanate [CCN] + TX, sophamide (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spiropidion (CCN) + TX, spirotetrmat (CCN) + TX, sulcofuron (746) + TX, sulcofuron-sodium (746) + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulfuryl fluoride (756) + TX, sulprofos (1408) + TX, tar oils (758) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, tebupirimfos (764) + TX, teflubenzuron (768) + TX, tefluthrin (769) + TX, temephos (770) + TX, TEPP (1417) + TX, terallethrin (1418) + TX, terbam + TX, terbufos (773) + TX, tetrachloroethane [CCN] + TX, tetrachlorvinphos (777) + TX, tetramethrin (787) + TX, theta-cypermethrin (204) + TX, thiacloprid (791) + TX, thiafenox + TX, thiamethoxam (792) + TX, thicrofos (1428) + TX, thiocarboxime (1431) + TX, thiocyclam (798) + TX, thiocyclam hydrogen oxalate (798) + TX, thiodicarb (799) + TX, thiofanox (800) + TX, thiometon (801) + TX, thionazin (1434) + TX, thiosultap (803) + TX, thiosultap-sodium (803) + TX, thuringiensin [CCN] + TX, tolfenpyrad (809) + TX, tralomethrin (812) + TX, transfluthrin (813) + TX, transpermethrin (1440) + TX, triamiphos (1441) + TX, triazamate (818) + TX, triazophos (820) + TX, triazuron + TX, trichlorfon (824) + TX, trichlormetaphos-3 [CCNJ + TX, trichloronat (1452) + TX, trifenofos (1455) + TX, triflumuron (835) + TX, trimethacarb (840) + TX, triprene (1459) + TX, vamidothion (847) + TX, vaniliprole [CCN] + TX, veratridine (725) + TX, veratrine (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302 (compound code) + TX, zeta-cypermethrin (205) + TX, zetamethrin + TX, zinc phosphide (640) + TX, zolaprofos (1469) and ZXI 8901 (development code) (858) + TX, cyantraniliprole [736994-63-19 + TX, chlorantraniliprole [500008-45-7] + TX, cyenopyrafen [560121-52-0] + TX, cyflumetofen [400882-07-7] + TX, pyrifluquinazon [337458-27-2] + TX, spinetoram [187166-40-1 + 187166-15-0] + TX, spirotetramat [203313-25-1] + TX, sulfoxaflor [946578-00-3] + TX, flufiprole [704886-18-0] + TX, meperfluthrin [915288-13-0] + TX, tetramethylfluthrin [84937-88-2] + TX, triflumezopyrim (disclosed in WO 2012/092115) + TX,
a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (lUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (lUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, trifenmorph (1454) + TX, trimethacarb (840) + TX, triphenyltin acetate (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX, pyriprole [394730-71-3] + TX,
a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1 ,2-dibromo-3-chloropropane (lUPAC/Chemical Abstracts name) (1045) + TX, 1 ,2-dichloropropane (lUPAC/ Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1 ,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1 ,1-dioxide (lUPAC/Chemical Abstracts name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (lUPAC name) (980) + TX, 5-methyl-6-thioxo-1 ,3,5-thiadiazinan-3-ylacetic acid (lUPAC name) (1286) + TX, 6- isopentenylaminopurine (210) + TX, abamectin (1) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben + TX, cadusafos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, cloethocarb (999) + TX, cytokinins (210) + TX, dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dichlofenthion (1051) + TX, dicliphos + TX, dimethoate (262) + TX, doramectin [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad + TX, fensulfothion (1158) + TX, fosthiazate (408) + TX, fosthietan (1196) + TX, furfural [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX, iodomethane (lUPAC name) (542) + TX, isamidofos (1230) + TX, isazofos (1231) + TX, ivermectin [CCN] + TX, kinetin (210) + TX, mecarphon (1258) + TX, metam (519) + TX, metam-potassium (519) + TX, metam-sodium (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime [CCN] + TX, moxidectin [CCN] + TX, Myrothecium verrucaria composition (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphocarb [CCN] + TX, sebufos + TX, selamectin [CCN] + TX, spinosad (737) + TX, terbam + TX, terbufos (773) + TX, tetrachlorothiophene (lUPAC/ Chemical Abstracts name) (1422) + TX, thiafenox + TX, thionazin (1434) + TX, triazophos (820) + TX, triazuron + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (210) + TX, fluensulfone [318290-98-1] + TX,
a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,
a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutha sachalinensis extract (720) + TX, a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1 ,3-dione (lUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (850) + TX, coumachlor (1004) + TX, coumafuryl (1005) + TX, coumatetralyl (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, difethialone (249) + TX, diphacinone (273) + TX, ergocalciferol (301) + TX, flocoumafen (357) + TX, fluoroacetamide (379) + TX, flupropadine (1183) + TX, flupropadine hydrochloride (1183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (lUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (lUPAC name) (640) + TX, methyl bromide (537) + TX, norbormide (1318) + TX, phosacetim (1336) + TX, phosphine (lUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371) + TX, scilliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and zinc phosphide (640) + TX,
a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (lUPAC name) (934) + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (lUPAC 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 (lUPAC 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] + TX, hexaconazole [79983-71 -4] + TX, imazalil [35554-44- 0] + TX, imibenconazole [86598-92-7] + TX, ipconazole [125225-28-7] + TX, metconazole [1251 16- 23-6] + TX, myclobutanil [88671 -89-0] + TX, pefurazoate [101903-30-4] + TX, penconazole [66246- 88-6] + TX, prothioconazole [178928-70-6] + TX, pyrifenox [88283-41 -4] + TX, prochloraz [67747-09- 5] + TX, propiconazole [60207-90-1 ] + TX, simeconazole [149508-90-7] + TX, tebuconazole [107534- 96-3] + TX, tetraconazole [1 12281 -77-3] + TX, triadimefon [43121 -43-3] + TX, triadimenol [55219-65- 3] + TX, triflumizole [99387-89-0] + TX, triticonazole [131983-72-7] + TX, ancymidol [12771 -68-5] + TX, fenarimol [60168-88-9] + TX, nuarimol [63284-71 -9] + TX, bupirimate [41483-43-6] + TX, dimethirimol [5221 -53-4] + TX, ethirimol [23947-60-6] + TX, dodemorph [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564-91 -4] + TX, spiroxamine [1 18134-30-8] + TX, tridemorph [81412-43-3] + TX, cyprodinil [121552-61 -2] + TX, mepanipyrim [1 10235-47-7] + TX, pyrimethanil [531 12-28-0] + TX, fenpiclonil [74738-17-3] + TX, fludioxonil [131341 -86-1 ] + TX, benalaxyl [71626- 1 1 -4] + TX, furalaxyl [57646-30-7] + TX, metalaxyl [57837-19-1 ] + TX, R-metalaxyl [70630-17-0] + TX, ofurace [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21 -7] + TX, debacarb [62732-91 -6] + TX, fuberidazole [3878-19-1 ] + TX, thiabendazole [148- 79-8] + TX, chlozolinate [84332-86-5] + TX, dichlozoline [24201 -58-9] + TX, iprodione [36734-19-7] + TX, myclozoline [54864-61 -8] + TX, procymidone [32809-16-8] + TX, vinclozoline [50471 -44-8] + TX, boscalid [188425-85-6] + TX, carboxin [5234-68-4] + TX, fenfuram [24691 -80-3] + TX, flutolanil [66332- 96-5] + TX, mepronil [55814-41 -0] + TX, oxycarboxin [5259-88-1 ] + TX, penthiopyrad [183675-82-3] + TX, thifluzamide [130000-40-7] + TX, guazatine [108173-90-6] + TX, dodine [2439-10-3] [1 12-65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [131860-33-8] + TX, dimoxystrobin [149961 -52-4] + TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1 , 93} + TX, fluoxastrobin [361377-29-9] + TX, kresoxim-methyl [143390-89-0] + TX, metominostrobin [133408-50-1 ] + TX, trifloxystrobin [141517-21 -7] + TX, orysastrobin [248593-16-0] + TX, picoxystrobin [1 17428-22-5] + TX, pyraclostrobin [175013-18-0] + TX, ferbam [14484-64-1 ] + TX, mancozeb [8018-01 -7] + TX, maneb [12427-38-2] + TX, metiram [9006-42-2] + TX, propineb [12071 -83-9] + TX, thiram [137-26-8] + TX, zineb [12122-67-7] + TX, ziram [137-30-4] + TX, captafol [2425-06-1 ] + TX, captan [133-06-2] + TX, dichlofluanid [1085-98-9] + TX, fluoroimide [41205-21 -4] + TX, folpet [133-07-3 ] + TX, tolylfluanid [731 -27-1 ] + TX, bordeaux mixture [801 1 -63-0] + TX, copperhydroxid [20427-59-2] + TX, copperoxychlorid [1332-40-7] + TX, coppersulfat [7758-98-7] + TX, copperoxid [1317-39-1 ] + TX, mancopper [53988-93-5] + TX, oxine-copper [10380-28-6] + TX, dinocap [131 -72-6] + TX, nitrothal- isopropyl [10552-74-6] + TX, edifenphos [17109-49-8] + TX, iprobenphos [26087-47-8] + TX, isoprothiolane [50512-35-1 ] + TX, phosdiphen [36519-00-3] + TX, pyrazophos [13457-18-6] + TX, tolclofos-methyl [57018-04-9] + TX, acibenzolar-S-methyl [135158-54-2] + TX, anilazine [101 -05-3] + TX, benthiavalicarb [413615-35-7] + TX, blasticidin-S [2079-00-7] + TX, chinomethionat [2439-01 -2] + TX, chloroneb [2675-77-6] + TX, chlorothalonil [1897-45-6] + TX, cyflufenamid [180409-60-3] + TX, cymoxanil [57966-95-7] + TX, dichlone [117-80-6] + TX, diclocymet [139920-32-4] + TX, diclomezine [62865-36-5] + TX, dicloran [99-30-9] + TX, diethofencarb [87130-20-9] + TX, dimethomorph [110488- 70-5] + TX, SYP-LI90 (Flumorph) [211867-47-9] + TX, dithianon [3347-22-6] + TX, ethaboxam [162650-77-3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX, fenamidone [161326-34-7] + TX, fenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, ferimzone [89269-64- 7] + TX, fluazinam [79622-59-6] + TX, fluopicolide [2391 10-15-7] + TX, flusulfamide [106917-52-6] + TX, fenhexamid [126833-17-8] + TX, fosetyl-aluminium [39148-24-8] + TX, hymexazol [10004-44-1 ] + TX, iprovalicarb [140923-17-7] + TX, IKF-916 (Cyazofamid) [120116-88-3] + TX, kasugamycin [6980-18-3] + TX, methasulfocarb [66952-49-6] + TX, metrafenone [220899-03-6] + TX, pencycuron [66063-05-6] + TX, phthalide [27355-22-2] + TX, polyoxins [1 1 1 13-80-7] + TX, probenazole [27605-76-1 ] + TX, propamocarb [25606-41 -1 ] + TX, proquinazid [189278-12-4] + TX, pyroquilon [57369-32-1 ] + TX, quinoxyfen [124495-18-7] + TX, quintozene [82-68-8] + TX, sulfur [7704-34-9] + TX, tiadinil [223580- SI -6] + TX, triazoxide [72459-58-6] + TX, tricyclazole [41814-78-2] + TX, triforine [26644-46-2] + TX, validamycin [37248-47-8] + TX, zoxamide (RH7281) [156052-68-5] + TX, mandipropamid [374726-62- 2] + TX, isopyrazam [881685-58-1 ] + TX, sedaxane [874967-67-6] + TX, 3-difluoromethyl-1 -methyl-1 H- pyrazole-4-carboxylic acid (9-dichloromethylene-1 ,2,3,4-tetrahydro-1 ,4-methano-naphthalen-5-yl)- amide (dislosed in WO 2007/048556) + TX, 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide (disclosed in WO 2006/087343) + TX,
[(3S,4R,4aR,6S,6aS, 12R, 12aS, 12bS)-3-[(cyclopropylcarbonyl)oxy]- 1 ,3,4,4a,5,6,6a, 12,12a, 12b- decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-1 1 -oxo-9-(3-pyridinyl)-2/-/,1 1 /-/naphtho[2,1 -b]pyrano[3,4- e]pyran-4-yl]methyl-cyclopropanecarboxylate [915972-17-7] + TX and 1 ,3,5-trimethyl-N-(2-methyl-1 - oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1 -methoxy-1 -(trifluoromethyl)ethyl]phenyl]-1 H- pyrazole-4-carboxamide [926914-55-8] + TX, lancotrione [1486617-21 -3] + TX, florpyrauxifen [943832- SI -3] ] + TX, ipfentrifluconazole[1417782-08-1 ] + TX, mefentrifluconazole [1417782-03-6] + TX, quinofumelin [861647-84-9] + TX, chloroprallethrin [399572-87-3] + TX, cyhalodiamide [1262605-53-7] ] + TX, fluazaindolizine [1254304-22-7] + TX, fluxametamide [928783-29-3] + TX, epsilon-metofluthrin [240494-71 -7] + TX, epsilon-momfluorothrin [1065124-65-3] + TX, pydiflumetofen [1228284-64-7] + TX, kappa-bifenthrin [439680-76-9] + TX, broflanilide [1207727-04-5] + TX, dicloromezotiaz [1263629-39-5] + TX, dipymetitrone [161 14-35-5] + TX, pyraziflumid [942515-63-1 ] + TX, kappa-tefluthrin [391634-71 - 2] + TX, fenpicoxamid [517875-34-2] + TX, fluindapyr [1383809-87-7] + TX, alpha-bromadiolone [28772- 56-7] + TX, flupyrimin [1689566-03-7] + TX, benzpyrimoxan [1449021 -97-9] + TX, acynonapyr [1332838-17-1 ] + TX, inpyrfluxam [1352994-67-2] + TX, isoflucypram [1255734-28-1 ] + TX, rescalure [64309-03-1 ] + TX, aminopyrifen [1531626-08-0] + TX, tyclopyrazoflor [1477919-27-9] + TX, Dichloromezotiaz + TX, Momfluorothrin + TX, Fluopyram + TX, Tioxazafen + TX, Terpenoid blend + TX, Fluhexafon + TX, Cyclaniliprole + TX, and spiropidion [1229023-00-0] + TX; and microbials including: 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. + TX, Aureobasidium pullulans + TX, Azospirillum + TX, (MicroAZ® + TX, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus licheniformis strain HB-2 (Biostart™ Rhizoboost®) + TX, Bacillus licheniformis strain 3086 (EcoGuard® + TX, Green Releaf®) + TX, Bacillus circulans + TX, Bacillus firmus (BioSafe®, BioNem-WP®, VOTiVO®) + TX, Bacillus firmus strain 1-1582 + TX, Bacillus macerans + TX, Bacillus marismortui + TX, Bacillus megaterium + TX, Bacillus mycoides strain AQ726 + TX, Bacillus papillae (Milky Spore Powder®) + TX, Bacillus pumilus spp. + TX, Bacillus pumilus strain GB34 (Yield Shield®) + TX, Bacillus pumilus strain AQ717 + TX, Bacillus pumilus strain QST 2808 (Sonata® + TX, Ballad Plus®) + TX, Bacillus spahericus (VectoLex®) + TX, Bacillus spp. + TX, Bacillus spp. strain AQ175 + TX, Bacillus spp. strain AQ177 + TX, Bacillus spp. 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®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF / 3P®) + TX, Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis strain AQ52 + TX, Bacillus thuringiensis var. 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 reukaufii + TX, Candida saitoana (Bio-Coat® + TX, Biocure®) + TX, Candida sake + TX, Candida spp. + TX, Candida tenius + TX, Cedecea dravisae + TX, Cellulomonas flavigena + TX, Chaetomium cochliodes (Nova-Cide®) + TX, Chaetomium globosum (Nova-Cide®) + TX, Chromobacterium subtsugae strain PRAA4-1 T (Grandevo®) + TX, Cladosporium cladosporioides + TX, Cladosporium oxysporum + TX, Cladosporium chlorocephalum + TX, Cladosporium spp. + TX, Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp. + TX, Cryptococcus albidus (YIELDPLUS®) + TX, Cryptococcus humicola + TX, Cryptococcus infirmo- miniatus + TX, Cryptococcus laurentii + TX, Cryptophlebia leucotreta granulovirus (Cryptex®) + TX, Cupriavidus campinensis + TX, Cydia pomonella granulovirus (CYD-X®) + TX, Cydia pomonella granulovirus (Madex® + TX, Madex Plus® + TX, Madex Max/ Carpovirusine®) + TX, Cylindrobasidium laeve (Stumpout®) + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Drechslera hawaiinensis + TX, Enterobacter cloacae + TX, Enterobacteriaceae + TX, Entomophtora virulenta (Vektor®) + TX, Epicoccum nigrum + TX, Epicoccum purpurascens + TX, Epicoccum 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. (SoilGard®) + TX, Gliocladium virens (Soilgard®) + TX, Granulovirus (Granupom®) + TX, Halobacillus halophilus + TX, Halobacillus litoralis + TX, Halobacillus trueperi + TX, Halomonas 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. + TX, Lagenidium giganteum (Laginex®) + TX, Lecanicillium longisporum (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Lymantria Dispar nucleopolyhedrosis virus (Disparvirus®) + TX, Marinococcus halophilus + TX, Meira geulakonigii + TX, Metarhizium anisopliae (Met52®) + TX, Metarhizium anisopliae (Destruxin WP®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX, Micromonospora coerulea + TX, Microsphaeropsis ochracea + TX, Muscodor albus 620 (Muscudor®) + TX, Muscodor roseus strain A3-5 + TX, Mycorrhizae spp. (AMykor® + TX, Root Maximizer®) + TX, Myrothecium verrucaria strain AARC-0255 (DiTera®) + TX, BROS PLUS® + TX, Ophiostoma piliferum strain D97 (Sylvanex®) + TX, Paecilomyces farinosus + TX, Paecilomyces fumosoroseus (PFR-97® + TX, PreFeRal®) + TX, Paecilomyces linacinus (Biostat WP®) + TX, Paecilomyces lilacinus strain 251 (MeloCon WG®) + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans (BlightBan C9-1 ®) + TX, Pantoea spp. + TX, 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, Pseudomonas fluorescens strain A506 (BlightBan A506®) + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas spp. + TX, Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudomons fluorescens (Zequanox®) + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia canaliculate + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum (Polygandron® + TX, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp. + TX, Rhizobia (Dormal® + TX, Vault®) + TX, Rhizoctonia + TX, Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula spp. + TX, Rhodotorula glutinis + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Saccharomyces cerevisiae + TX, Salinococcus roseus + TX, Sclerotinia minor + TX, Sclerotinia minor (SARRITOR®) + TX, Scytalidium spp. + TX, Scytalidium uredinicola + TX, Spodoptera exigua nuclear polyhedrosis virus (Spod-X® + TX, Spexit®) + TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp. + TX, Sordaria fimicola + TX, Spodoptera littoralis nucleopolyhedrovirus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces ahygroscopicus + TX, Streptomyces albaduncus + TX, Streptomyces exfoliates + TX, Streptomyces galbus + TX, Streptomyces griseoplanus + TX, Streptomyces griseoviridis (Mycostop®) + TX, Streptomyces lydicus (Actinovate®) + TX, Streptomyces lydicus WYEC-108 (ActinoGrow®) + TX, Streptomyces violaceus + TX, Tilletiopsis minor + TX, Tilletiopsis spp. + TX, Trichoderma asperellum (T34 Biocontrol®) + TX, Trichoderma gamsii (Tenet®) + TX, Trichoderma atroviride (Plantmate®) + TX, Trichoderma hamatum TH 382 + TX, Trichoderma harzianum rifai (Mycostar®) + TX, 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, Xenorhabdus nematophilus, and
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, Nepeta cataria (Catnip oil) + TX, Nepeta catarina + TX, nicotine + TX, oregano oil (MossBuster®) + TX, Pedaliaceae oil (Nematon®) + TX, pyrethrum + TX, Quillaja saponaria (NemaQ®) + TX, Reynoutria sachalinensis (Regalia® + TX, Sakalia®) + TX, rotenone (Eco Roten®) + TX, Rutaceae plant extract (Soleo®) + TX, soybean oil (Ortho ecosense®) + TX, tea tree oil (Timorex Gold®) + TX, thymus oil + TX, AGNIQUE® MMF + TX, BugOil® + TX, mixture of rosemary sesame pepermint thyme and cinnamon extracts (EF 300®) + TX, mixture of clove rosemary and peppermint extract (EF 400®) + TX, mixture of clove pepermint garlic oil and mint (Soil Shot®) + TX, kaolin (Screen®) + TX, storage glucam of brown algae (Laminarin®) + TX, and
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 acetate + TX, 13-Hexadecatrienal + TX, (E + TX,Z)-7 + TX,9-Dodecadien-1 -yl acetate + TX, 2-Methyl- 1 -butanol + TX, Calcium acetate + TX, Scenturion® + TX, Biolure® + TX, Check-Mate® + TX, Lavandulyl senecioate, and
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 swirskii® + TX, Swirskii-Mite®) + TX, Amblyseius womersleyi (WomerMite®) + TX, Amitus hesperidum + TX, Anagrus atomus + TX, Anagyrus fusciventris + TX, Anagyrus kamali + TX, Anagyrus loecki + TX, Anagyrus pseudococci (Citripar®) + TX, Anicetus benefices + TX, Anisopteromalus calandrae + TX, Anthocoris nemoralis (Anthocoris- System®) + TX, Aphelinus abdominalis (Apheline® + TX, Aphiline®) + TX, Aphelinus asychis + TX, Aphidius colemani (Aphipar®) + TX, Aphidius ervi (Ervipar®) + TX, Aphidius gifuensis + TX, Aphidius matricariae (Aphipar-M®) + TX, Aphidoletes aphidimyza (Aphidend®) + TX, Aphidoletes aphidimyza (Aphidoline®) + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hagenowii + TX, Atheta coriaria (Staphyline®) + TX, Bombus spp. + 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 rufUabris + 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 fiavipes + 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, Diglyphus isaea + TX, Diglyphus isaea (Miglyphus® + TX, Digline®) + TX, Dacnusa sibirica (DacDigline® + TX, Minex®) + TX, Diversinervus spp. + TX, Encarsia citrina + TX, Encarsia formosa (Encarsia max® + TX, Encarline® + TX, En-Strip®) + TX, Eretmocerus eremicus (Enermix®) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend®) + TX, Eretmoceris siphonini + TX, Eretmocerus californicus + TX, Eretmocerus eremicus (Ercal® + TX, Eretline e®) + TX, Eretmocerus eremicus (Bemimix®) + TX, Eretmocerus hayati + TX, Eretmocerus mundus (Bemipar® + TX, Eretline m®) + TX, Eretmocerus siphonini + TX, Exochomus quadripustulatus + TX, Feltiella acarisuga (Spidend®) + TX, Feltiella acarisuga (Feltiline®) + TX, Fopius arisanus + TX, Fopius ceratitivorus + TX, Formononetin (Wirless Beehome®) + TX, Franklinothrips vespiformis (Vespop®) + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Flabrobracon hebetor + TX, Harmonia axyridis (HarmoBeetle®) + TX, Heterorhabditis spp. (Lawn Patrol®) + TX, Heterorhabditis bacteriophora (NemaShield HB® + TX, Nemaseek® + TX, Terranem-Nam® + TX, Terranem® + TX, Larvanem® + TX, B-Green® + TX, NemAttack ® + TX, Nematop®) + TX, Heterorhabditis megidis (Nemasys H® + TX, BioNem H® + TX, Exhibitline hm® + TX, Larvanem-M®) + TX, Hippodamia convergens + TX, Hypoaspis aculeifer (Aculeifer-System® + TX, Entomite-A®) + TX, Hypoaspis miles (Hypoline m® + TX, Entomite-M®) + TX, Lbalia leucospoides + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + TX, Leptomastix dactylopii (Leptopar®) + TX, Leptomastix epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Lucilia caesar (Natufly®) + TX, Lysiphlebus testaceipes + TX, Macrolophus caliginosus (Mirical-N® + TX, Macroline c® + TX, Mirical®) + TX, Mesoseiulus longipes + TX, Metaphycus fiavus + TX, Metaphycus lounsburyi + TX, Micromus angulatus (Milacewing®) + TX, Microterys fiavus + TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®) + TX, Neodryinus typhlocybae + TX, Neoseiulus californicus + TX, Neoseiulus cucumeris (THRYPEX®) + TX, Neoseiulus fallacis + TX, Nesideocoris tenuis (NesidioBug® + TX, Nesibug®) + TX, Ophyra aenescens (Biofly®) + TX, Orius insidiosus (Thripor-I® + TX, Oriline i®) + TX, Orius laevigatus (Thripor-L® + TX, Oriline I®) + TX, Orius majusculus (Oriline m®) + TX, Orius strigicollis (Thripor-S®) + TX, Pauesia juniperorum + TX, Pediobius foveolatus + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymastichus coffea + TX, Phytoseiulus macropilus + TX, Phytoseiulus persimilis (Spidex® + TX, Phytoline p®) + TX, Podisus maculiventris (Podisus®) + TX, Pseudacteon curvatus + TX, Pseudacteon obtusus + TX, Pseudacteon tricuspis + TX, Pseudaphycus maculipennis + TX, Pseudleptomastix mexicana + TX, Psyllaephagus pilosus + TX, Psyttalia concolor (complex) + TX, Quadrastichus spp. + TX, Rhyzobius lophanthae + TX, Rodolia cardinalis + TX, Rumina decollate + TX, Semielacher petiolatus + TX, Sitobion avenae (Ervibank®) + TX, Steinernema carpocapsae (Nematac C® + TX, Millenium® + TX, BioNem C® + TX, NemAttack® + TX, Nemastar® + TX, Capsanem®) + TX, Steinernema feltiae (NemaShield® + TX, Nemasys F® + TX, BioNem F® + TX, Steinernema-System® + TX, NemAttack® + TX, Nemaplus® + TX, Exhibitline sf® + TX, Scia-rid® + TX, Entonem®) + TX, Steinernema kraussei (Nemasys L® + TX, BioNem L® + TX, Exhibitline srb®) + TX, Steinernema riobrave (BioVector® + TX, BioVektor®) + TX, Steinernema scapterisci (Nematac S®) + TX, Steinernema spp. + 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 gloeosporioides (Collego®) + TX, Copper Octanoate (Cueva®) + TX, Delta traps (Trapline d®) + TX, Erwinia amylovora (Harpin) (ProAct® + TX, Ni-HIBIT Gold CST®) + TX, Ferri-phosphate (Ferramol®) + TX, Funnel traps (Trapline y®) + TX, Gallex® + TX, Grower's Secret® + TX, Homo-brassonolide + TX, Iron Phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait®) + TX, MCP hail trap (Trapline f®) + TX, Microctonus hyperodae + TX, Mycoleptodiscus terrestris (Des- X®) + TX, BioGain® + TX, Aminomite® + TX, Zenox® + TX, Pheromone trap (Thripline ams®) + TX, potassium bicarbonate (MilStop®) + TX, potassium salts of fatty acids (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, potassium iodide + potassiumthiocyanate (Enzicur®) + TX, SuffOil- X® + TX, Spider venom + TX, Nosema locustae (Semaspore Organic Grasshopper Control®) + TX, Sticky traps (Trapline YF® + TX, Rebell Amarillo®) + TX and Traps (Takitrapline y + b®) + TX.
The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium, Thirteenth Edition, Editor: C. D. S. TomLin, The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound, for example, the compound "abamectin" is described under entry number (1). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood, Compendium of Pesticide Common Names. Copyright © 1995-2004], for example, the compound "acetoprole" is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html.
Most of the active ingredients described above are referred to hereinabove by a so-called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular compound, in that case, the lUPAC name, the lUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "development code" is used. “CAS Reg. No” means the Chemical Abstracts Registry Number.
The ratio (by weight) of active ingredient mixture of the compounds of formula (I) selected from a compound 1 .001 to 1 .051 listed in Table 1 (below) or a compound A1 to A137 listed in Table A (below), a compound C1 or C2 listed in Table C (below) or a compound E1 to E6 listed in Table E (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, or 1 :600, or 1 :300, or 1 :150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 : 1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750.
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 .051 listed in Table 1 (below) or a compound A1 to A137 listed in Table A (below), a compound C1 or C2 listed in Table C (below) or a compound E1 to E6 listed in Table E (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 afterthe 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 .051 listed in Table 1 (below) or a compound A1 to A137 listed in Table A (below), a compound C1 or C2 listed in Table C (below) or a compound E1 to E6 listed in Table E (below) and the active ingredients as described above is not essential for working the present invention.
In a further aspect, 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).
The 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.
The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds (I) for the preparation of these compositions are also a subject of the invention.
The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, 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. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.
The 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. Alternatively, 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.
The term 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). The term "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. When the said seed product is (re)planted, it may absorb the active ingredient. In an embodiment, 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.
In each aspect and embodiment of the invention, "consisting essentially" and inflections thereof are a preferred embodiment of "comprising" and its inflections, and "consisting of" and inflections thereof are a preferred embodiment of "consisting essentially of and its inflections. The disclosure in the present application makes available each and every combination of embodiments disclosed herein.
Table 1 : This table discloses the 51 compounds of the formula (I) having either the (£)- or (Z)- isomeric form, or a mixture of the (E)- or (Z)- isomeric forms:
Figure imgf000068_0001
wherein m is 0, R3a and R3b are hydrogen, and A, R1 and R4 are as defined in the below Table.
Figure imgf000068_0002
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
EXAMPLES
The Examples which follow serve to illustrate the invention.
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, 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 m2.
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).
Throughout this description, temperatures are given in degrees Celsius (°C) and“mp.” means melting point.
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 are given in ppm relevant to a TMS standard. Spectra are measured in deuterated solvents (eg, dimethyl sulfoxide (DMSO)) as indicated.
LCMS Methods:
Method A:
Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions,
Capillary: 3.00 kV, Cone range: 30 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 350°C, Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650 l/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment, diode-array detector and ELSD detector. Column: Waters UPLC HSS T3, 1 .8 mhi, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH, gradient: 10-100% B in 1 .2 min; Flow (ml/min) 0.85.
Method B:
Spectra were recorded on a ACQUITY Mass Spectrometer from Waters Corporations (SQD or SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150°C, Desolvation Temperature: 400°C, Cone Gas Flow: 60 L/hr, Desolvation Gas Flow: 700 L/hr, Mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters Corporations with solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1 .8 pm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 400, Solvent Gradient: A = Water/Methanol 9:1 + 0.1 % formic acid, B= Acetonitrile + 0.1 % formic acid, gradient: 0-100% B in 2.5 min; Flow (ml/min) 0.75.
Method C:
MS: ZQ Mass Spectrometer from Waters (Single quadrupole mass spectrometer)
Instrument Parameter: Ionisation method: Electrospray Polarity: positive (negative) ions Capillary (kV) 3.00, Cone (V) 30.00, Extractor (V) 2.00, Gas Temperature (°C) 350, Drying Gas Flow (mL/min) 9.8, Neb press 45 psig, Mass range: 90 to 1000 Da. HPLC: HP 1 100 HPLC from Agilent: solvent degasser, quaternary pump (ZCQ) / binary pump (ZDQ), heated column compartment and diode-array detector. Column: porpshell 120 C18, 2.7mhi particle size, 120 Angstrom, 4.6 x 50 mm, Temp: 30 °C. DAD Wavelength range (nm): 190 to 400 Solvent Gradient:. A = water + 0.1 % HCOOH. B= Acetonitrile+ 0.08% HCOOH . Mobile phase:
Figure imgf000075_0002
Method D:
Mass Spectrometer as method C.
HPLC: Shimadzu LC-20A. Column: Dikma, DiamonsilC18(2) (5 pm,150*4.6mm). Mobile phase A:H20(add 0.1 %TFA) and mobile phase B: CAN (add 0.1 %TFA). Flow: 1 .0mL/min. Detection:UV@254nm. Oven Temperature: 40°C. The mobile phase gradient:
Figure imgf000075_0003
Example 1 : Preparation of (E) and/or (Z)-[1 -[(6-chloro-3-pyridyl)methyl]-3-(difluoromethoxy)-2- pyridylidene] cyanamide (compound A5).
Figure imgf000075_0001
Step 1 : Preparation of 1 -[(6-chloro-3-pyridyl)methyl]-3-(difluoromethoxy)pyridin-2-imine. To a flask equipped with a Teflon-coated magnetic stir bar was added 2-chloro-5- (chloromethyl)pyridine (2 g, 1 1.97 mmol), 3-(difluoromethoxy)pyridin-2-amine (1 equiv., 11 .9740mmol) and sodium iodide (1 equiv., 11.974 mmol) in acetone (1.8 ml/mmol). The resulting mixture was stirred overnight at reflux. The reaction mixture was diluted with acetone (~ 50 mL) and the solids filtered out. The filtrate was concentrated under reduced pressure to afford the crude solid which was dissolved in 8 mL dimethylsulfoxide (DMSO), filtered and purified on preparative reverse phase column to afford 2.027 g (7.1 mmol) of the desired compound. Yield 59.26%. The product was used without extra purification in the next step. LC-MS (method A): Rt = 0.33min, M+H+ = 286.
Step 2: Preparation of (E) and/or (Z)-[1-[(6-chloro-3-pyridyl)methyl]-3-(difluoromethoxy)-2-pyridylidene] cyanamide_(compound A5).
Figure imgf000076_0001
To a 3 mL vial equipped with a Teflon-coated magnetic stir bar were added 1-[(6-chloro-3- pyridyl)methyl]-3-(difluoromethoxy)pyridin-2-imine (See step 1 , 66 mg, 0.2310 mmol), triethylamine (3 equiv., 0.6931 mmol.) and 4-dimethylaminopyridine (0.5 equiv., 0.1155 mmol) in N,N- dimethylformamide (5 mL/mmol). Then was added cyanogen bromide (1.2 equiv., 0.2772 mmol), the vial was sealed and the resulting mixture stirred overnight at room temperature. The reaction mixture was poured into a saturated solution of sodium hydrogen carbonate and extracted (3x) with dichloromethane (DCM). The combined organic phases were dried over sodium sulfate, filtered and concentrated. The crude was dissolved in 1 mL of dimethylsulfoxide, loaded on Isolute and purified by chromatography to afford the title compound A5 (15 mg, 0.04828 mmol, 21 % Yield).
Example 2: Preparation of (E) and/or (Z)-[1-[(6-chloro-3-pyridyl)methyl]-3-(methoxymethyl)-2- pyridylidene]cyanamide (compound A7). Step 1 : Preparation of 1 -[(6-chloro-3-pyridyl)methyl]-3-(methoxymethyl)pyridin-2-imine (compound B7).
Figure imgf000077_0001
In a vial equipped with a magnetic stirring bar, under a nitrogen atmosphere, was dissolved 3- (methoxymethyl)pyridin-2-amine (CAS# 124851 1 -27-4, synthesis described in WO 2005/016381) (0.25 g, 1 .8 mmol) in acetone (3.6 ml_). Sodium iodide (0.27 g, 1 .8 mmol) was added, followed by 2-chloro-5- chloromethylpyridine (commercially available) (0.31 g, 1 .9 mmol). The mixture was heated at reflux temperature for 22 hours. The conversion was checked by LC-MS of aliquots of the reaction mixture. The reaction mixture was then cooled to 20°C and filtered through a short path of Hyflo, which was rinsed with acetone. The filtrate was evaporated under reduced pressure and the residue dissolved in DMSO (0.5 ml) and purified by reverse phase chromatography, eluting with a gradient of 20% to 60% of acetonitrile in water. The evaporation of the selected fractions yielded the title compound as a bright yellow oil. Ή-NMR (CDCIs): d (ppm) 8.46 - 8.41 (m, 2 H), 8.1 1 (d, 1 H), 8.04 (d, 1 H), 7.75 (d, 1 H), 7.37 (d, 1 H), 6.91 (t, 1 H), 6.10 (s, 2 H), 4.55 (s, 2 H), 3.43 (s, 3 H). LC-MS (method A): Rt = 0.32 min, M+H+ = 265.
Step 2: Preparation of (E) and/or (Z)-[1 -[(6-chloro-3-pyridyl)methyl]-3-(methoxymethyl)-2- pyridylidene]cyanamide (compound A7).
Figure imgf000077_0002
In a vial equipped with a magnetic stirring bar, under nitrogen atmosphere, was dissolved 1 -[(6- chloro-3-pyridyl)methyl]-3-(methoxymethyl)pyridin-2-imine (preparation described herein above) (0.24 g, 0.91 mmol) in N,N-dimethylformamide (5.5 mL) followed by triethylamine (0.38 mL, 2.7 mmol), 4- dimethylaminopyridine (0.056 g, 0.46 mmol) and cyanogen bromide (0.13 g, 1 .2 mmol). The vial was sealed and the red brown solution was stirred at 20 °C for 7.5 hours, after which time, the reaction mixture was treated with aqueous saturated ammonium chloride. The mixture was extracted twice with ethyl acetate. After drying over anhydrous magnesium sulfate, the solvent was removed under reduced pressure and the residue was dissolved in DMSO (0.5 ml) and submitted to reverse phase column chromatography, eluting with a gradient of 20% to 60% of acetonitrile in water. The evaporation of the selected fractions yielded the title compound as a solid. 1H-NMR (CDCI3): 5 (ppm) 8.34 (d, 1 H), 7.72 (dd, 1 H), 7.62 (d, 1 H), 7.59 (d, 1 H), 7.30 (d, 1 H), 6.56 (t, 1 H), 5.29 (s, 2 H), 4.82 (s, 2 H), 3.49 (s, 3 H). LC-MS (method A): Rt = 0.65 min, M+H+ = 290.
Example 3: Preparation of ethyl ( 2E ) and/or (2Z)-1 -[(6-chloro-3-pyridvDmethyl1-2-cvanoimino-pyridine-
3-carboxylate (compound A26).
Figure imgf000078_0001
Step 1 : Preparation of 1 -[(6-chloro-3-pyridyl)methyl]-3-(methoxymethyl)pyridin-2-imine (compound B25)
Step A: Synthesis of 3-bromo-1 -[(6-chloro-3-pyridyl)methyl]pyridin-2-imine.
Figure imgf000078_0002
A suspension of 2-chloro-5-(chloromethyl)pyridine (10.00 g, 59.87 mmol, 1 .0 equiv.), 3- bromopyridin-2-amine (10.57 g, 59.87 mmol, 1 .0 equiv.) and sodium iodide (8.974 g, 59.87 mmol, 1 .0 equiv.) in acetonitrile (1 19.7 ml, 2 ml/mmol) was refluxed overnight. The reaction mixture was diluted with acetone and the solids filtered out. The filtrate was concentrated under reduced pressure. The crude was purified by chromatography over silica gel to afford 3-bromo-1 -[(6-chloro-3- pyridyl)methyl]pyridin-2-imine (3.5 g, 20 %) as a beige solid. LC-MS (Method A): Rt = 0.27 min, M+H+ = 298.
Step B : Synthesis of (E and/or Z)-[3-bromo-1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]cyanamide
(A25). To a solution under argon of 3-bromo-1 -[(6-chloro-3-pyridyl)methyl]pyridin-2-imine (16.0 g, 32.15 mmol, 1 .0 equiv.) in N,N-dimethylformamide (160.8 ml_, 5 mL/mmol), were added triethylamine (15.8 mL, 1 12.5 mmol, 3.5 equiv.) and DMAP (1 .984 g, 16.08 mmol, 0.5 equiv.). Then cyanogen bromide (4.74 g, 43.41 mmol, 1 .35 equiv.) was added in one portion and the resulting mixture was stirred at room temperature overnight. The reaction mixture was poured dropwise in an ice/NaHCC>3 aq. solution and stirred for 30 min. The resulting brown suspension was filtered and dry over night at 40°C over P205 to afford (E)-[3-bromo-1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]cyanamide (9.8 g, 94.2 %) as a light brown solid.
Ή NMR (400 MHz, DMSO-d6) d ppm 5.39 (s, 2 H) 6.68 (dd, 1 H) 7.54 (d, 1 H) 7.77 (dd, 1 H) 8.09 (dd, 1 H) 8.32 (dd, 1 H) 8.41 (d, 1 H).
Step 2: Preparation of intermediate phenyl (2E)-1 -[(6-chloro-3-pyridyl)methyl]-2-cyanoimino-pyridine-3- carboxylate.
Figure imgf000079_0001
Palladium(ll) acetate (0.02124 g, 0.0927 mmol, 0.03 equiv.) and tri-tert-butylphosphonium tetrafluoroborate (0.1 1 1 g, 0.371 mmol, 0.12 equiv.) were added to a vial and then a degassed solution of phenyl formate (0.688 ml, 6.181 mmol, 2.0 equiv), (E)-[3-bromo-1 -[(6-chloro-3-pyridyl)methyl]-2- pyridylidene]cyanamide A25 (1 .00 g, 3.0904 mmol, 1 .0 equiv.) and triethylamine (0.866 ml, 6.181 mmol, 2.0 equiv.) in acetonitrile (5.872 ml, 1 .9 mL/mmol) was added at room temperature under a flow of argon. The reaction mixture was heated to 80 °C for 2 hours and then allowed to cool to room temperature. The mixture was diluted with ethyl acetate, washed with water, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude was stirred in methanol for 15 minutes and then filtered to afford phenyl (2E and/or 2Z)-1 -[(6-chloro-3-pyridyl)methyl]-2-cyanoimino-pyridine-3-carboxylate (0.598 g, 53 %) as a light beige solid. LC-MS (Method A): Rt = 0.87 min, M+H+ = 365. Step 3: ethyl (2E) and/or (2Z)-1-[(6-chloro-3-pyridyl)methyl]-2-cyanoimino-pyridine-3-carboxylate (compound A26).
General method A:
Figure imgf000080_0001
To a suspension of phenyl (2E) and/or (2Z)-1-[(6-chloro-3-pyridyl)methyl]-2-cyanoimino- pyridine-3-carboxylate (0.50 g, 1.4 mmol) in ethanol was added at room temperature sodium ethoxide (21 % in ethanol, 0.51 ml_, 1.4 mmol, 1 .0 equiv.). The reaction mixture was stirred at room temperature for 2 hours. The resulting suspension was filtered and washed with hexane and ethyl acetate to afford the desired product as a beige solid (0.25 mg, 0.80 mmol).
General method B:
Figure imgf000080_0002
To a solution of phenyl (2E) and/or (2Z)-1-[(6-chloro-3-pyridyl)methyl]-2-cyanoimino-pyridine-3- carboxylate (0.10 g, 0.27 mmol) in N,N-dimethylformamide (1 ml_) was added at room temperature sodium ethoxide (21 % in ethanol, 0.10 ml_, 0.27 mmol, 1.0 equiv.). The reaction mixture was stirred at room temperature for 2 hours. Water and ethyl acetate were added to the reaction mixture and it was extracted with more ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure to afford crude desired product (60 mg, 0.19 mmol). LC-MS (method A): Rt = 0.74 min, M+H+ = 317.
General method A, general method B or a classical method such as described in example 1 or 2 could be used to synthesize these type of derivatives.
Example 4: Preparation of 2-furylmethyl (2E) and/or (2Z)-1-[(6-chloro-3-pyridyl)methyl1-2-cvanoimino- pyridine-3-carboxylate (compound A27) To a solution of furfuryl alcohol (CAS 98-00-0, 1 ml_) was added at room temperature sodium hydride (49 mg, 1.2 mmol, 1.5 equiv.). The reaction was stirred at room temperature for 30 minutes, then phenyl (2E) and/or (2Z)-1-[(6-chloro-3-pyridyl)methyl]-2-cyanoimino-pyridine-3-carboxylate (0.30 g, 0.82 mmol) was added and it was stirred for 1 hour at room temperature. Water and ethyl acetate were added to the reaction mixture and it was extracted with more ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. Purification of the crude material by flash chromatography over silica gel (ethyl acetate in cyclohexane, then methanol in dichloromethane) afforded the desired product (0.17 g, 0.46 mmol). LC-MS (method A): Rt = 0.81 min, M+H+ = 369.
Figure imgf000081_0001
Example 5: Preparation of (E) and/or (ZH1-[1-(6-chloro-3-pyridyl)ethyl1-3-(trifluoromethyl)-2- pyridylidenelcvanamide (compound C1).
Figure imgf000081_0002
Step 1 : Preparation of 1-[1-(6-chloro-3-pyridyl)ethyl]-3-(trifluoromethyl)pyridin-2-imine (intermediate compound D1). A suspension of 2-chloro-5-(1-chloroethyl)pyridine (1.50 g, 8.52 mmol), 3- (trifluoromethyl)pyridine-2-amine (CAS 183610-70-0, 1.38 g, 8.52 mmol, 1.00 equiv.) and sodium iodide (1.27 g, 8.52 mmol, 1.00 equiv.) in acetonitrile (17 ml_) was stirred at 82 °C for 3 days. After cooling at room temperature, the reaction mixture was diluted with acetone and filtered over Celite. The filtrate was concentrated under reduced pressure. Purification of the crude material by flash chromatography over silica gel (methanol in dichloromethane) afforded the desired product as a golden solid (75%, 0.627 g, 1.56 mmol). LC-MS (method A): Rt = 0.33 min, M+H+ = 302. Step 2: Preparation of (E) and/or (Z)-[1-[1-(6-chloro-3-pyridyl) ethyl]-3-(trifluoromethyl)-2-pyridylidene] cyanamide (compound C1).
Figure imgf000082_0001
To a degassed solution of 1-[1-(6-chloro-3-pyridyl)ethyl]-3-(trifluoromethyl)pyridin-2-imine D1 (prepared as described above, 75%, 0.35 g, 0.87 mmol) in N,N-dimethylformamide (4.4 ml_) were added first triethylamine (0.35 ml_, 2.6 mmol, 3.0 equiv.), then 4-dimethylaminopyridine (54 mg, 0.44 mmol, 0.50 equiv.) and cyanogen bromide (0.11 g, 1 .0 mmol, 1.2 equiv.). The reaction mixture was stirred at room temperature for 30 minutes. The reaction mixture was poured on ice, diluted with water and extracted twice with dichloromethane. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. Purification of the crude material by flash chromatography over silica gel (methanol in dichloromethane) afforded the desired product as an off- white solid (95 mg, 0.29 mmol). LC-MS (method A): Rt = 0.77 min, M+H+ = 327.
Example 6: Preparation of (E) and/or (Z)-f1-f(6-chloro-3-pyridyl)methyll-3-f(E)-2-ethoxyvinyll-2- pyridylidenel cvanamide (compound A28). To a degassed solution of (E) and/or (Z)-[3-bromo-1-[(6-chloro-3-pyridyl)methyl]-2- pyridylidene]cyanamide (0.500 g, 1.54 mmol) and 2-[(E)-2-ethoxyvinyl]-4,4,5,5-tetramethyl-1 ,3,2- dioxaborolane (0.406 g, 2.01 mmol, 1.30 equiv.) in dry tetrahydrofuran (5.42 mL) were added sodium carbonate (2 M in water, 1.78 mL, 3.55 mmol, 2.30 equiv.) and tetrakis(triphenylphosphine) palladium(O) (90 mg, 0.077 mmol, 0.050 equiv.). The reaction mixture was stirred at 85 °C for 18 hours. After cooling at room temperature, the reaction mixture was poured on water and extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. Purification of the crude material by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded the desired product as a yellow solid (0.250 g, 0.794 mmol). LC-MS (method A): Rt = 0.82 min, M+H+ = 315.
Figure imgf000083_0001
Example 7: Preparation of (E) and/or (Z)-[1-[(6-chloro-3-pyridyl)methyl1-3-(tetrazol-1-ylmethyl)-2- pyridylidenelcvanamide (compound A29).
Figure imgf000083_0002
Step 1 : Preparation of 3-(tetrazol-1-ylmethyl)pyridin-2-amine.
Figure imgf000083_0003
To a solution of 1 H-tetrazole (0.45 M in acetonitrile, 12.0 mL, 5.42 mmol, 2.00 equiv.) in N,N- dimethylformamide (8.13 mL) was added potassium carbonate (1.51 g, 10.8 mmol, 4.00 equiv.). The resulting white suspension was stirred at room temperature for 15 minutes. Then 3-chloromethyl-pyridin- 2-yl-amine:hydrochloride (0.500 g, 2.71 mmol) was added slowly to the reaction mixture which was stirred for 1 hour at room temperature. The reaction mixture was concentrated under reduced pressure. Purification of the crude material by flash chromatography over silica gel (1 % aq. Nhh/methanol in dichloromethane) afforded the desired product as a yellow solid (0.1 12 g, 0.636 mmol). 1H NMR (400 MHz, chloroform-d) d ppm: 8.60 (1 H, s), 8.17 (1 H, dd), 7.47 (1 H, dd,), 6.75 (1 H, dd), 5.48 (2 H, s), 4.90 (2 H, br. s). LC-MS (method A): Rt = 0.17 min, M+H+ = 177.
Step 2: Preparation of 1 -[(6-chloro-3-pyridyl)methyl]-3-(tetrazol-1 -ylmethyl)pyridin-2-imine;hydroiodide
(B26).
Figure imgf000084_0001
To a solution of 3-(tetrazol-1 -ylmethyl)pyridin-2-amine prepared as described above, 0.1 12 g, 0.636 mmol) in acetonitrile (1 .27 mL) were added 2-chloro-5-(chloromethyl)pyridine (0.107 g, 0.636 mmol, 1 .00 equiv.) and sodium iodide (96 mg, 0.636 mmol, 1 .00 equiv.). The reaction mixture was stirred at 85 °C for 16 hours. After cooling down at room temperature, the reaction mixture was concentrated under reduced pressure to afford the desired product as a brown gum which was used without further purification. LC-MS (method A): Rt = 0.22-0.24 min, M+H+ = 302.
Step 3: Preparation of (E) and/or (Z)-[1 -[(6-chloro-3-pyridyl)methyl]-3-(tetrazol-1 -ylmethyl)-2- pyridylidenejcyanamide (compound A29).
Figure imgf000084_0002
To a solution of 1 -[(6-chloro-3-pyridyl)methyl]-3-(tetrazol-1 -ylmethyl)pyridin-2-imine:hydroiodide prepared as described above, 0.273 g, 0.635 mmol) in N,N-dimethylformamide (3.2 ml_) were added first triethylamine (0.31 ml_, 2.2 mmol, 3.5 equiv.), then 4-dimethylaminopyridine (24 mg, 0.19 mmol, 0.30 equiv.) and cyanogen bromide (90 mg, 0.83 mmol, 1 .3 equiv.). The reaction mixture was stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure. The crude material was purified twice by flash chromatography over silica gel (first ethyl acetate in cyclohexane, then methanol in dichloromethane). The resulting residue was diluted with water and extracted twice with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure to afford the desired product as a yellow solid (56 mg, 0.18 mmol). Ή NMR (400 MHz, chloroform-d) d ppm: 9.28 (1 H, s), 8.36 (1 H, d), 7.75 (1 H, dd), 7.70 (1 H, dd), 7.68 (1 H, dd), 7.37 (1 H, d), 6.69 (1 H, t), 6.07 (2 H, s), 5.31 (2 H, s). LC-MS (method A): Rt = 0.60 min, M+H+ = 327. Example 8: Preparation of (E) and/or Z-[1-[(6-chloro-3-pyridvDmethyl1-3-[2-(oxetan-3-vDethvnyl1-2- pyridylidenel cvanamide .
Figure imgf000085_0001
Figure imgf000085_0002
A solution of (E) and/or (Z)-[3-bromo-1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]cyanamide A26 (0.300 g, 0.927 mmol, 1.0 equiv.), 3-ethynyloxetane (0.0951 g, 1.16 mmol, 1.25 equiv.), copper iodide (0.00180 g, 0.00927 mmol, 0.01 equiv.) and triethylamine (0.389 ml, 2.78 mmol, 3 equiv.) in acetonitrile (9.27 mL, 10 mL/mmol) was degassed with argon and then Pd(PPH3)2Cl2 (0.0657 g, 0.0927 mmol, 0.1 equiv.) was added in one portion. The reaction mixture was stirred for 2 hours at 80°C and then at room temperature overnight. The mixture was filtered over Celite and the residue was concentrated under reduced pressure. The crude was purified by reverse phase chromatography to afford (E)-[1-[(6-chloro-3-pyridyl)methyl]-3-[2-(oxetan-3-yl)ethynyl]-2-pyridylidene]cyanamide (0.130 g, 43.2%) as a beige solid. LC-MS (Method A): Rt = 0.72 min, M+H+ = 325.
Example 9: Preparation of (2Z and/or 2E)-1-[(6-chloro-3-pyridyl)methyl1-2-cvanoimino-N-methyl-N-
(2.2.2-trifluoroethyl)pyridine-3-carboxamide A31.
Figure imgf000085_0003
Step 1 : Preparation of 2-amino-N-methyl-N-(2,2,2-trifluoroethyl)pyridine-3-carboxamide 3.
To a stirred solution of compound 2-aminopyridine-3-carboxylic acid (0.91 g, 6.6 mmol) and 2,2,2-trifluoro-N-methyl-ethanaminehydrochloride 2(0.99 g, 6.6 mmol)in DMF(30 ml) was added pyBOP (3.77 g, 7.26 mmol) and DIPEA (2.6 mg, 20 mmol) at 25 °C under N2. The reaction mixture was stirred at 40 °C for 18 h. The reaction mixture was quenched into water (100 mL) and extracted with ethyl acetate (2 x 100 mL). The combined organic layers dried over anhydrous sodium sulfate and concentrated in vacuum. The resulting residue was purified by column chromatography (silica gel, 300- 400 mesh, EA) affording product (1.1 g, 71 %) Ή NMR (400 MHz, DMSO) d 8.06 - 7.97 (m, 1 H), 7.36 (d, J = 7.3 Hz, 1 H), 6.58 (dd, J = 7.2, 5.1 Hz, 1 H), 5.98 (s, 2H), 4.21 (s, 2H), 2.99 (s, 3H).
Step 2: Preparation of 1 -[(6-chloro-3-pyridyl)methyl]-2-imino-N-methyl-N-(2,2,2-trifluoroethyl)pyridine- 3-carboxamide B27.
To a stirred solution of 2-amino-N-methyl-N-(2,2,2-trifluoroethyl)pyridine-3-carboxamide 3 (0.466 g, 2 mmol) and 2-chloro-5-(chloromethyl)pyridine 4 (0.32 g, 2 mmol) in acetonitrile (10ml_) was added Nal (0.3 g, 2 mmol) at 25 °C under N2. The reaction mixture was stirred at 80 °C for 18 h. The organic layers were concentrated in vacuum. The resulting residue was purified by column chromatography (silica gel, 300-400 mesh, 10 % MeOH in dichloromethane) affording product (0.56 g, 72%). Ή NMR (400 MHz, DMSO) d 8.39 (d, 3H), 8.29 (d, 1 H), 7.93 (d, 1 H), 7.73 (dd, 1 H), 7.59 (d, 1 H), 7.05 (t, , 1 H), 5.52 (d, 2H), 4.36 - 4.14 (m, 2H), 3.04 (d, 3H).
Step 3: Preparation of (2Z and/or 2E)-1 -[(6-chloro-3-pyridyl)methyl]-2-cyanoimino-N-methyl-N-(2,2,2- trifluoroethyl)pyridine-3-carboxamide A31.
To stirred
Figure imgf000086_0001
solution
Figure imgf000086_0002
1 -[(6-chloro-3-pyridyl)methyl]-2-imino-N-methyl-N-(2,2,2- trifluoroethyl)pyridine-3-carboxamide B27 (0.394 g, 1 mmol) and Et3N (0.303 g, 3 mmol) in DMF (10 ml) was added DMAP (61 mg, 0.5 mmol) and BrCN (127 mg, 1.2 mmol) at 25 °C under N2. The reaction mixture was stirred at 25 °C for 18 h. The reaction mixture was quenched into water (100 mL) and extracted with ethyl acetate (2 x 100 mL). The combined organic layers dried over anhydrous sodium sulfate and concentrated in vacuum. The resulting residue was purified by column chromatography (silica gel, 300-400 mesh, 5 % MeOH in dichloromethane) to afford the product (126 mg, 33%). 1H NMR (400 MHz, DMSO) d 8.44 - 8.38 (m, 1 H), 8.38 - 8.27 (m, 1 H), 7.79 (m, 1 H), 7.68 - 7.57 (m, 1 H), 7.52 (d, 1 H), 6.81 (m, 1 H), 5.35 (m, 2H), 4.71 - 4.05 (m, 2H), 2.95 (d, 3H).
Example 10: Preparation of (Z) or (El -H -l(6-chloro-3-pyridyl')methyl1-3-(2-pyridylmethyl')-2-pyridylidene1 cvanamide A32
Step 1 : Preparation of (2-amino-3-pyridyl)-(2-pyridyl)methanol 3.
To a stirred solution of 2-bromopyridine 2 (3.16 g, 20 mmol) in THF (40 mL) was added n-BuLi (8 ml, 20mmol) at -78 °C under N2. The reaction mixture was stirred at -78 °C for 30 min. 2- aminopyridine-3-carbaldehyde 1 (1.95g, 16mmol) in THF (6ml) was added dropwise and the resulting mixture was stirred at -78 °C for 2 h. The reaction mixture was slowly quenched into saturated aqueous ammonium chloride solution (200 mL) and extracted with ethyl acetate (2 x 100 mL). The combined organic layers were dried over anhydrous sodium sulfate and concentrated in vacuum. The resulting residue was purified by column chromatography (silica gel, 300-400 mesh, ethyl acetate) affording (2- amino-3-pyridyl)-(2-pyridyl)methanol 3 (0.96 g, 30%). Ή NMR (400 MHz, DMSO) d 8.48 - 8.36 (m, 1 H),
7.86 - 7.73 (m, 2H), 7.57 (d, 1 H), 7.48 (d, 1 H), 7.24 (dd, 1 H), 6.54 (dd, 1 H), 6.18 (d, 1 H), 5.88 (s, 2H),
5.60 (d, 1 H).
Step 2: Preparation of (2-amino-3-pyridyl)-(2-pyridyl) methanone 4.
To a stirred solution of (2-amino-3-pyridyl)-(2-pyridyl)methanol 3 (2 g,10 mmol) in dichloromethane (50 ml) was added DCC (4.3 g, 20mmol) at 25 °C. The reaction mixture was stirred at 25 °C for 18h. The reaction mixture was quenched into saturated aqueous NaHCC>3 (100 mL) and extracted with dichloromethane (2x 100 mL). The combined organic layers dried over anhydrous sodium sulfate and concentrated in vacuum. The resulting residue was purified by column chromatography (silica gel, 300-400 mesh, EA) affording (2-amino-3-pyridyl)-(2-pyridyl)methanone 4 (1.69 g, 85%). 1H NMR (400 MHz, DSMO) d 8.66 (d, 1 H), 8.22 (dd, 1 H), 8.00 (dd, 2H), 7.82 - 7.75 (m, 1 H), 7.70 (s, 2H),
7.59 (dd, 1 H), 6.58 (dd, 1 H).
Step 3: Preparation of 3-(2-pyridylmethyl)pyridin-2-amine 5. To a stirred solution of (2-amino-3-pyridyl)-(2-pyridyl)methanone 4 (1.59 g, 8 mmol) in ethylene glycol (50 ml) was added N2H4.H2O (2.4g, 40mmol) and KOH (2.24 g, 40 mmol)at 25 °C. The reaction mixture was stirred at 190 °C for 4 h. The reaction mixture was quenched into saturated aqueous NaHCC>3 (100 mL) and extracted with ethyl acetate (2 x 100 ml_). The combined organic layers dried over anhydrous sodium sulfate and concentrated in vacuum. The resulting residue was purified by column chromatography (silica gel, 300-400 mesh, ethyl acetate) affording 3-(2-pyridylmethyl)pyridin-2- amine 5 (0.67g, 45%). Ή NMR (400 MHz, DMSO) d 8.46 (d, 1 H), 7.79 (d, 1 H), 7.70 (t, 1 H), 7.31 (d, 1 H), 7.28 - 7.18 (m, 2H), 6.48 (dd, 1 H), 5.88 (s, 2H), 3.87 (s, 2H).
Step 4: Preparation of 1 -[(6-chloro-3-pyridyl)methyl]-3-(2-pyridylmethyl)pyridin-2-imine hydrochloride
B28.
To a stirred solution of 3-(2-pyridylmethyl)pyridin-2-amine 5 (0.37g, 2mmol) and 2-chloro-5- (chloromethyl) pyridine 6 (0.32g, 2mmol) in acetonitrile (10 ml) was added Nal (0.3 g, 2 mmol) at 25 °C under N2. The reaction mixture was stirred at 80 °C for 18 h. The organic layers were concentrated in vacuum. The resulting residue was purified by column chromatography (silica gel, 300-400 mesh, 10 % MeOH in dichloromethane) affording product B28 (0.43 g, 62%) Ή NMR (400 MHz, DMSO) d 8.46 (d, 1 H), 8.32 (d, 3H), 8.13 (d, 1 H), 7.78 (dd, 2H), 7.64 (d, 1 H), 7.57 (d, 1 H), 7.40 (d,1 H), 7.31 - 7.24 (m, 1 H), 6.98 (t, 1 H), 5.56 (s, 2H), 4.16 (s, 2H).
Step 5: Preparation of (Z) or (E) -[1 -[(6-chloro-3-pyridyl) methyl]-3-(2-pyridylmethyl)-2-pyridylidene] cyanamide A32.
To a stirred solution of 1 -[(6-chloro-3-pyridyl)methyl]-3-(2-pyridylmethyl)pyridin-2-imine hydrochloride B28 (0.346 g, 1 mmol) and Et3N(0.303 g, 3 mmol) in DMF(10 ml)was added DMAP(61 mg, 0.5 mmol) and BrCN(127 mg, 1.2 mmol) at 25°C under N2. The reaction mixture was stirred at 25 °C for 18 h. The reaction mixture was quenched into water (100 ml_) and extracted with ethyl acetate (2 x 100 ml_). The combined organic layers were dried over anhydrous sodium sulfate and concentrated in vacuum. The resulting residue was purified by column chromatography (silica gel, 300-400 mesh, 5 % MeOH in DCM) affording product A32 (176mg, 53%). Ή NMR (400 MHz, DMSO) d 8.41 (d, 1 H), 8.35 (d, 1 H), 8.13 (d, 1 H), 7.71 (dd, 2H), 7.51 (d, 1 H), 7.45 (d, 1 H), 7.30 (d, 1 H), 7.22 - 7.16 (m, 1 H), 6.71 (t, 1 H), 5.37 (s, 2H), 4.48 (s, 2H).
Example 1 1 : Preparation of library of compounds according to Fornula (P A33 to A59 and A124 to A130.
Compounds A33 to A59 and A124 to A130 were prepared by the following general protocol:
Stock Solution Preparation: - The scaffold, ((E) and/or (Z)-[3-bromo-1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene] cyanamide A25, 673 mg, 2.08 mmol) was introduced in a 20 ml_ flask and dissolved in 10.4 ml_ of degassed DMF to afford the scaffold stock solution.
- Catalyst stock solution : PdCl2(PPh3)2 (146 mg, 0.208 mmol) was introduced in a 20 ml_ flask and dissolved in 10.4 ml_ of degassed DMF to afford the catalyst stock solution.
- Cul (79 mg, 0.416 mmol) was introduced in 20 mL flask and dissolved in 10.4 ml_ of degassed DMF to afford the Cul stock solution.
Dispersion and reaction:
Reactions were carried out in microwave (MW) vials. In each well was successively dispensed:
- The corresponding building block (0.12 mmol/reaction).
- 200mI_ of the Scaffold stock solution (0.04 mmol/reaction).
- 22mI_ of triethylamine (0.16 mmol/reaction).
- 200mI_ of the Cul stock solution (0.008 mmol/reaction). The vials were then slightly flushed with argon.
- 200mI_ of the catalyst stock solution (0.004 mmol/reaction). Microwave vials were submitted again to a slight flush of argon before being sealed and submitted to a 10 min run under microwave irradiation at 1 10°C.
Work-up: Reaction mixtures were filtered through Silicycle Si-Thiol cartridges to trap metals, then cartridges were washed with 1 ml_ of DMF. Filtrates were then partially concentrated by evaporation and purified.
Purification: The desired compounds were isolated by HPLC and identified by LC-MS (Method B) then concentrated and dried under vacuum.
Figure imgf000089_0001
Figure imgf000090_0003
Example 12: Preparation of (Z) or (EH3-[2-[tert-butyl(dimethvDsilyl1oxy-3.3.3-trifluoro-propoxy1-1-[(6- chloro-3-pyridvDmethyl1-2-pyridylidene1cvanamide (compound A137) and (Z) or (E) [1-[(6-chloro-3- pyridvDmethvn-3-(3.3.3-trifluoro-2-hvdroxy-propoxy)-2-pyridylidenelcvanamide (compound A136).
Figure imgf000090_0001
Step 1 : Preparation of 1 ,1 ,1-trifluoro-3-[(2-chloro-3-pyridyl)oxy]propan-2-ol.
Figure imgf000090_0002
A 50 mL flask was charged with 2-chloropyridin-3-ol (1 g, 7.72 mmol), N,N-dimethylformamide
(7.7 mL), potassium carbonate (1.12 g, 8.11 mmol) and 4-(trifluoromethyl)-1 ,3-dioxolan-2-one (1.2 g, 7.72 mmol). The resulting brown suspension is stirred at 85 °C overnight, cooled at room temperature and the reaction solvent then evaporated. Purification by chromatography on silica gel eluting with (dichloromethane/ethyl acetate gradient, 1 :0 1 :1) affords 1 ,1 ,1-trifluoro-3-[(2-chloro-3- pyridyl)oxy]propan-2-ol (766 mg, 41 %) as a solid. LCMS (method A): Rt 0.77, m/z = 242.0 (M+1).
Step 2: Preparation of fe/f-butyl-[1 -[(2-chloro-3-pyridyl)oxymethyl]-2,2,2-trifluoro-ethoxy]-dimethyl- silane. A 10 mL flask was charged with 1 ,1 ,1 -trifluoro-3-[(2-chloro-3-pyridyl)oxy]propan-2-ol (208 mg, 0.86 mmol), dichloromethane (3.4 mL), 2,6-dimethylpyridine (0.4 mL, 3.44 mmol), is cooled at 0 °C and [tert-butyl(dimethyl)silyl] trifluoromethanesulfonate (0.59 mL, 2.58 mmol) is slowly added. The reaction mixture waes stirred at 0 °C for two hours and is finally evaporated. Purification by chromatography on silica gel eluting with (dichloromethane) afforded fe/?-butyl-[1 -[(2-chloro-3-pyridyl)oxymethyl]-2,2,2- trifluoro-ethoxy]-dimethyl-silane (306 mg, 100%) as a yellow oil. LCMS (method A): Rt 1 .32, /z = 356.3 (M+1). Step 3: Preparation of 3-[2-[tert-butyl(dimethyl)silyl]oxy-3,3,3-trifluoro-propoxy]pyridin-2-amine.
Figure imgf000091_0001
A 25 mL vial was charged with fe/f-butyl-[1 -[(2-chloro-3-pyridyl)oxymethyl]-2,2,2-trifluoro- ethoxy]-dimethyl-silane (356 mg, 1 mmol), sodium fe/f-butoxide (107 mg, 1 .10 mmol), f-BuBrettPhos- Pd-G3 (42.7 mg, 0.05 mmol) and a 0.5 M solution of ammonia in 1 ,4-dioxane (20 mL). The reaction was then stirred at 100 °C overnight reduced to dryness. Purification by chromatography on silica gel eluting with (dichloromethane/methanol gradient, 1 :0®10:1) afforded 3-[2-[tert-butyl(dimethyl)silyl]oxy-3,3,3- trifluoro-propoxy]pyridin-2-amine (134 mg, 40%) as a brown gum. LCMS (method A): Rt 0.90, m/z = 337.5 (M+1). Step 4: Preparation of 3-[2-[tert-butyl(dimethyl)silyl]oxy-3,3,3-trifluoro-propoxy]-1 -[(6-chloro-3- pyridyl)methyl]pyridin-2-imine. A 5 mL vial was charged with 3-[2-[tert-butyl(dimethyl)silyl]oxy-3,3,3-trifluoro-propoxy]pyridin-2- amine (82 mg, 0.24 mmol), acetonitrile (0.5 mL), sodium iodide (37 mg, 0.24 mmol) and 2-chloro-5- (chloromethyl)pyridine (39 mg, 0.24 mmol). The reaction mixture was stirred at 80°C overnight and reduced to dryness. Purification by chromatography on silica gel eluting with (dichloromethane/methanol gradient, 1 :0 ® 10:1) afforded 3-[2-[tert-butyl(dimethyl)silyl]oxy-3,3,3-trifluoro-propoxy]-1 -[(6-chloro-3- pyridyl)methyl]pyridin-2-imine (77 mg, 68%) as a yellow solid. LCMS (method A): Rt 0.92, m/z = 462.4 (M+1).
Step 5: Preparation of [3-[2-[tert-butyl(dimethyl)silyl]oxy-3,3,3-trifluoro-propoxy]-1 -[(6-chloro-3- pyridyl)methyl]-2-pyridylidene]cyanamide (compound A137).
Figure imgf000092_0001
A 5 mL vial was charged with 3-[2-[tert-butyl(dimethyl)silyl]oxy-3,3,3-trifluoro-propoxy]-1 -[(6- chloro-3-pyridyl)methyl]pyridin-2-imine (77 mg, 0.17 mmol), N,N-dimethylformamide (0.8 mL), triethylamine (0.08 mL, 0.58 mmol), 4-(dimethylamino)pyridine (10 mg, 0.08 mmol) and cyanogen bromide (24 mg, 0.23 mmol). The resulting suspension was stirred at 80°C for three hours, cooled at room temperature and slowly added to an ice-cold aqueous solution of sodium hydrogen carbonate (2 mL). The aqueous phase is extracted with ethyl acetate (2 x 2 mL), the combined organic phases washed with water (2 x 3 mL) and brine (3 mL), and then dried with sodium sulfate, filtered and evaporated to give [3-[2-[tert-butyl(dimethyl)silyl]oxy-3,3,3-trifluoro-propoxy]-1 -[(6-chloro-3- pyridyl)methyl]-2-pyridylidene]cyanamide (80 mg, 99%) as a yellow oil which is used without any further purification in the next step. LCMS (method A): Rt 1 .16, m/z = 487.4 (M+1).
(a) Preparation of [1 -[(6-chloro-3-pyridyl)methyl]-3-(3,3,3-trifluoro-2-hydroxy-propoxy)-2- pyridylidene]cyanamide (compound A136). A 5 mL vial was charged with [3-[2-[tert-butyl(dimethyl)silyl]oxy-3,3,3-trifluoro-propoxy]-1-[(6- chloro-3-pyridyl)methyl]-2-pyridylidene]cyanamide (80 mg, 0.16 mmol), N,N-dimethylformamide (0.6 mL), water (0.06 mL) and cesium carbonate (27 mg, 0.082 mmol). The resulting mixture was stirred at 80 °C for two hours and quenched with water (1 mL). The aqueous phase was extracted with ethyl acetate (2 x 2 mL), the combined organic phases were then washed with water (3 x 3 mL), brine (3 mL), dried with sodium sulfate, filtered and then evaporated. Purification by chromatography on silica gel eluting with (dichloromethane/methanol gradient, 1 :0 10:1) afford the desired [1-[(6-chloro-3- pyridyl)methyl]-3-(3,3,3-trifluoro-2-hydroxy-propoxy)-2-pyridylidene]cyanamide (54 mg, 88%) as a yellow oil. LCMS (method A): Rt 0.80, m/z = 373.2 (M+1).
Table A: This table discloses 137 compounds of the formula (I) having either the (£)- or (Z)- isomeric form, or a mixture of the (E)- or (Z)- isomeric forms.
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
Figure imgf000102_0001
Figure imgf000103_0001
Figure imgf000104_0001
Figure imgf000105_0001
Figure imgf000106_0001
Figure imgf000107_0001
Figure imgf000108_0001
Figure imgf000109_0001
Figure imgf000110_0001
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Figure imgf000118_0001
Figure imgf000119_0001
Figure imgf000120_0001
Figure imgf000121_0001
Figure imgf000122_0002
Table B: This table discloses 93 intermediate compounds of the formula (II):
Figure imgf000122_0001
wherein m is 0, R3a and R3b are hydrogen, and A, R1 and R4 are as defined in the following
Table.
Figure imgf000123_0001
Figure imgf000124_0001
Figure imgf000125_0001
Figure imgf000126_0001
Figure imgf000127_0001
Figure imgf000128_0001
Figure imgf000129_0001
Figure imgf000130_0001
Figure imgf000131_0001
Table C: This table discloses 2 compounds of the formula (I) having either the (E)- or (Z)- isomeric form, or a mixture of the (E)- or (Z)- isomeric forms.
Figure imgf000131_0002
Table D: This table discloses 2 intermediate compounds of the formula (II):
Figure imgf000132_0001
wherein m is 0, R3a is hydrogen, R3b is methyl, and A, R1 and R4 are as defined in the following Table.
Figure imgf000132_0002
Table E: This table discloses 6 compounds of the formula (I) having either the (E)- or (Z)- isomeric form, or a mixture of the (E)- or (Z)- isomeric forms.
Figure imgf000132_0003
Figure imgf000133_0002
Table F: This table discloses 6 intermediate compounds of the formula (lie):
Figure imgf000133_0001
wherein m is 0, R3a and R3b are hydrogen, R4 is 2-chloropyrid-5-yl, and A, R1 and R2a, R2b and R2c are as defined in the following Table.
Figure imgf000134_0001
BIOLOGICAL EXAMPLES:
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.
The following compounds from Table A resulted in at least 80% mortality at an application rate of 200 ppm:
A1 , A2, A3, A4, A5, A7, A8, A9, A10, A1 1 , A13, A14, A15, A16, A21 , A24, A25, A26, A28, A30, A33, A34, A35, A36, A37, A43, A50, A51 , A53, A55, A57, A59, A63, A64, A66, A67, A70, A71 , A72, A73, A74, A75, A76, A77, A80, A82, A83, A84, A85, A88, A89, A92, A94, A95, A96, A97, A98, A100, A101 , A103, A1 13, A1 14, A1 15, A1 16, A124, A125, A127, A129, A130, A132, A135, A136.
Euschistus herns (Neotropical Brown Stink Bug)
Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying, the leaves were infested with N2 nymphs. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation. The following compounds from Table A gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:
A24, A28, A51 , A74, A129, A135.
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 from Tables A, C and E resulted in at least 80% mortality at an application rate of 200 ppm:
A1 , A2, A3, A4, A5, A6, A7, A8, A9, A10, A1 1 , A13, A14, A15, A16, A17, A20, A21 , A23, A24, A25,
A26, A30, A33, A34, A35, A37, A41 , A43, A44, A47, A49, A50, A51 , A52, A53, A54, A55, A57, A59,
A60, A62, A63, A64, A68, A69, A70, A71 , A72, A74, A75, A76, A78, A79, A80, A81 , A82, A83, A85,
A86, A87, A88, A89, A90, A91 , A92, A93, A94, A95, A96, A97, A98, A99, A100, A103, A104, A109,
A1 10, A1 1 1 , A1 12. A1 13, A114, A1 15, A1 16, A1 17, A123, A124, A125, A126, A127, A129, A132, A133, A135, A136, A137, C1 , E1 , E3, E6.
Myzus persicae (Green peach aphid). Systemic activity.
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.
The following compounds from Table A resulted in at least 80% mortality at a test rate of 24 ppm:
A1 , A2, A3, A4, A5, A6, A7, A8, A1 1 , A13, A16, A20, A21 , A23, A24, A26, A30, A41 , A51 , A52, A54, A59, A63, A70, A74, A76, A80, A81 , A83, A85, A87, A88, A91 , A92, A93, A95, A97, A98, A108, A1 14, A1 15, A1 16, A1 17, A127, A129, A132, A135, A136.
Myzus persicae (Green peach aphid). Intrinsic activity.
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.
The following compounds from Tables A, C and E resulted in at least 80% mortality at a test rate of 12 ppm: A1 , A2, A3, A4, A5, A7, A8, A9, A10, A1 1 , A13, A14, A15, A16, A17, A20, A21 , A22, A23, A24, A25,
A26, A28, A29, A30, A31 , A33, A34, A35, A36, A37, A39, A40, A41 , A43, A46, A47, A48, A50, A51 ,
A52, A53, A54, A55, A57, A59, A60, A62, A63, A64, A68, A69, A70, A71 , A72, A73, A74, A75, A76,
A78, A79, A81 , A82, A83, A84, A85, A86, A88, A89, A90, A91 , A92, A93, A94, A96, A97, A98, A99,
A100, A101 , A103. A104, A108, A109, A1 12, A1 13, A1 14, A1 15, A1 16, A1 17, A1 18, A1 19, A120, A123, A125, A126, A127, A129, A130, A132, A133, A135, A136, A137, C1 , E3, E6.
Mvzus persicae (neonicotinoid-resistant, Green peach aphid), mixed population, contact/feeding. Pepper plants were infested with mixed aged neonicotinoid-resistant aphid population and were treated 1 day after infestation in a spray chamber with diluted aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. 5 days after treatment, samples were assessed for mortality.
The following compounds described in Tables A, C and E gave at least 80% control of the neonicotinoid- resistant strain of Myzus persicae at 200 ppm.
A2, A4, A5, A7, A13, A14, A23, A24, A26, A30, A75, A89, A91 , A93, A132.
Nilaparvata lugens (Brown plant hopper - metabolic neonicotinoid-resistant).
Rice plants were treated with the diluted aqueous test solutions prepared from a 10,000 ppm DMSO stock solution 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.
The following compounds from Table A gave at least 80% control of the neonicotinoid-resistant strain of Nilaparvata lugens at 50 ppm.
A21 , A23, A26.
Bemisia tabaci (neonicotinoid-resistant, Cotton whitefly), adult, contact.
5 cm cotton leaf discs were placed upside down in petri dishes poured out with 1 1 ml_ 0.8% water agar and applied in a turntable spraying chamber for spraying with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying of the spray deposits, leaf discs were infested with 10 adult neonicotinoid-resistant Bemisia tabaci. Dishes were covered with a fabric filter and sealed with a perforated plastic lid. Evaluation was made 4 days after infestation on % adult mortality.
The following compounds in Table A gave at least 80% control of the neonicotinoid resistant Bemisia tabaci at 200 ppm.
A2, A4, A5, A7, A13, A23, A30, A89.
Mvzus persicae (Test method for resistance factor 50 (RF50)). Cabbage leaf discs were infested with approximately 20-25 insects and sprayed in a Potter Tower with respective aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. Insect mortality was assessed five days after treatment. The RF(50) is calculated by the following formula: 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.
The following compounds in Table A gave at least a RF(50) lower or equal than 20.
A2, A4, A5, A7, A13, A26, A30, A59, A89.

Claims

CLAIMS:
1 . A compound of Formula (I):
Figure imgf000138_0001
wherein:
A is a direct link, O, or S(0)P wherein p is selected from 0, 1 or 2;
R1 is Ci-C6alkyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or Ci-C6haloalkyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2;
or
C2-C6alkenyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or C2-C6haloalkenyl;
or
C2-C7alkynyl optionally substituted by 1 or 2 substituents independently selected from Ui or a single substituent selected from U2, or C2-C6haloalkynyl;
or
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
cyano, nitro, halogen, -C(0)R5, -C(0)NR6R7 or -C(R6)=NOR6;
Ui is nitro, cyano, amino, hydroxyl, CO2H, C3-C6cycloalkyl, C3-C6halocycloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C2alkoxy-Ci-C2alkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, Ci-C4alkylcarbonyl, Ci- C4alkoxycarbonyl, Ci-C4haloalkylcarbonyl, Ci-C4haloalkoxycarbonyl, C3-C4cycloalkylcarbonyl, =N- 0(Ci-C4alkyl), =N-0(Ci-C4haloalkyl), -Si(Ci-C4alkyl)3, -OSi(Ci-C4alkyl)3, (Ci-C4haloalkyl)NH-, (C1-C4 haloalkyl)2N-, (C1-C4 haloalkyl)(Ci-C4alkyl)N-, (Ci-C4alkyl)NH-, (Ci-C4alkyl)2N-, (C3-C6cycloalkyl)NH-, (C3-C6cycloalkyl)(Ci-C4alkyl)N-, (PhCH2)NH-, (PhCH2)(Ci-C4alkyl)N-, Ci-C4alkylcarbonylamino wherein the alkyl group is optionally substituted by cyano, Ci-C4alkoxycarbonylamino, Ci- C4haloalkylcarbonylamino, Ci-C4alkylaminocarbonyl, C3-C6cycloalkylaminocarbonyl, Ci- C4haloalkylaminocarbonyl, C3-C6halocycloalkylaminocarbonyl, -SPh, -0C(0)R6, -O-pyrazine or - C(0)NH2;
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 4- to 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 L4 and optionally a halogen group;
L is halogen, nitro, cyano, amino, hydroxyl, CO2H, Ci-C4alkyl, Ci-C4haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, C3-C6halocycloalkyl-Ci-C4alkyl, C3-C6cycloalkyl-Ci-C4alkyl, Ci-C4alkoxy, Ci- C4alkoxy-Ci-C4alkyl, Ci-C4haloalkoxy, Ci-C4haloalkoxy-Ci-C4alkyl, cyano-Ci-C4alkyl, cyano-Ci- C4haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, Ci-C4alkylsulfanyl, Ci- C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, Ci-C4alkylcarbonyl, Ci-C4alkoxycarbonyl, Ci-C4haloalkylcarbonyl, Ci-C4haloalkoxycarbonyl and - C(0)NH2;
U4 is nitro, cyano, amino, hydroxyl, -SCN, -CO2H, Ci-C4alkyl, C3-C6cycloalkyl, C3- Cehalocycloalkyl, C3-C6cycloalkyl-Ci-C4alkyl, C3-C6halocycloalkyl-Ci-C4alkyl, Ci-C4haloalkyl, Ci- C4alkoxy, Ci-C4alkoxy-Ci-C4alkyl, Ci-C4alkoxy-Ci-C4alkoxy, cyano-Ci-C4alkyl, cyano-Ci-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, Ci-C4haloalkoxy, Ci-C4haloalkoxy-Ci- C4alkyl, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci- C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, Ci-C4alkylcarbonyl, Ci-C4alkoxycarbonyl, Ci- C4haloalkylcarbonyl, Ci-C4haloalkoxycarbonyl, (Ci-C4alkyl)NH-, (Ci-C4alkyl)2N-, (C3-C6cycloalkyl)NH-, (C3-C6cycloalkyl)2N-, Ci-C4alkylcarbonylamino, C3-C6cycloalkylcarbonylamino, Ci-
C4haloalkylcarbonylamino, C3-C6halocycloalkylcarbonylamino, Ci-C4alkylaminocarbonyl, C3- C6cycloalkylaminocarbonyl, Ci-C4haloalkylaminocarbonyl, C3-C6halocycloalkylaminocarbonyl, C3- C6cycloalkylcarbonyl, C3-C6halocycloalkylcarbonyl, -SFs or -C(0)NH2; m is 0, 1 or 2;
R2 is independently selected from halogen, cyano, amino, hydroxyl, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4haloalkoxy, Ci-C4alkoxy, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, C1-C4 alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci- C4haloalkylsulfonyl and cyclopropyl;
R3a and R3b are independently selected from hydrogen, halogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy and cyano; R4 is selected from one of Y1 to Y4;
Figure imgf000140_0001
wherein n is 0, 1 or 2;
U is independently selected from halogen, cyano, nitro, hydroxyl, amino, Ci-C4alkyl, Ci- C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, Ci-C4haloalkoxy-Ci-C4alkyl, Ci-C4alkoxy-Ci-C4alkyl, Ci-C4alkylsulfanyl, Ci- C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, formyl, cyclopropyl, Ci-C4alkylcarbonyl or C3-C6cycloalkylcarbonyl; and
R5 is hydrogen, Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, Ci-C6haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, cyanoCi-Cealkyl, nitroCi-C4alkyl, Ci-C4alkoxyCi-C4alkyl, Ci- C4halolkoxyCi-C4alkyl, Ci-C4alkylsulfinylCi-C4alkyl, Ci-C4alkylsulfonylCi-C4alkyl, Ci- C4haloalkylsulfanylCi-C4alkyl, Ci-C4haloalkylsulfinylCi-C4alkyl, Ci-C4haloalkylsulfonylCi-C4alkyl and C3-C6cycloalkylCi-C4alkyl, or
R5 is Ci-C4alkyl or Ci-C4haloalkyl substituted by phenyl or 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, and wherein each phenyl or heteroaryl ring is optionally substituted by 1 or 2 groups independently selected from halogen, cyano, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci- C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl and Ci-C4haloalkylsulfonyl;
R5 is Ci-C6alkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, Ci-C4alkoxy, Ci-C4haloalkoxy, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, Ci- C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci- C4haloalkylsulfonyl, C3-C6cycloalkyl and phenyl or 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, and wherein each phenyl or heteroaryl ring is optionally substituted by 1 or 2 groups independently selected from halogen, cyano, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci- C4haloalkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci- C4haloalkylsulfinyl and Ci-C4haloalkylsulfonyl, or R5 is Ci-C6haloalkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, Ci-C4alkoxy, Ci-C4haloalkoxy, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, C3-C6cycloalkyl and phenyl or 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, and wherein each phenyl or heteroaryl ring is optionally substituted by 1 or 2 groups independently selected from halogen, cyano, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci- C4haloalkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci- C4haloalkylsulfinyl and Ci-C4haloalkylsulfonyl, or
R5 is C3-C6cycloalkoxy;
R6 is hydrogen, Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, Ci-C6haloalkoxy; and
R7 is Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, Ci-C6haloalkoxy, or 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; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.
2. A compound according to claim 1 , wherein A is selected from a direct link, O, or S.
3. A compound according to claim 1 or claim 2, wherein R1 is:
Ci-C6alkyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or Ci-C6haloalkyl optionally substituted by a single substituent selected from Ui ; or
C2-C6alkenyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or C2-C6haloalkenyl;
or
C2-C7alkynyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or C2-C6haloalkynyl;
or
C3-C6cycloalkyl, wherein the cycloalkyl moiety is optionally substituted by a single substituent selected from U3; or
cyano, nitro, halogen, -C(0)R5, -C(0)NR6R7 or -C(R6)=NOR6;
Ui is nitro, cyano, amino, hydroxyl, CO2H, C3-C6cycloalkyl, C3-C6halocycloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C2alkoxy-Ci-C2alkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, Ci-C4alkylcarbonyl, Ci- C4alkoxycarbonyl, -OSi(Ci-C4alkyl)3, (Ci-C4alkyl)NH-, (Ci-C4alkyl)2N-, (PhCH2)NH-, (PhCH2)(Ci- C4alkyl)N-, Ci-C4alkylcarbonylamino wherein the alkyl group is optionally substituted by cyano, Ci- C4alkoxycarbonylamino, -SPh, -0C(0)R6, -O-pyrazine or -C(0)NH2;
U2 is phenyl, furanyl, pyridinyl, thienyl, pyrazolyl, imidazolyl, tetrazolyl, oxetanyl, N-morpholinyl, pyrrolidinyl, piperidinyl wherein each ring is optionally substituted by: (i) 1 or 2 independently selected halogen groups, or (ii) 1 or 2 groups independently selected from L4 and optionally a halogen group;
L is halogen, Ci-C4alkyl, Ci-C4haloalkyl or Ci-C4alkoxy;
U4 is cyano, Ci-C4alkyl, Ci-C4haloalkyl or oxo (=0);
R5 is hydrogen, Ci-C6alkyl, Ci-C4haloalkyl or Ci-C4haloalkoxy, or Ci-C6alkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, C2-C4alkenyl, C2-C4alkynyl, Ci- C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C3-C6cycloalkyl, phenyl, pyridinyl, furanyl or thiazolyl wherein each ring is optionally substituted by 1 or 2 groups independently selected from halogen, methyl, ethyl, methoxy, ethoxy or trifluromethyl;
R6 is hydrogen, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy; and
R7 is Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy.
4. A compound according to any one of claims 1 to 3, wherein R1 is selected from:
Ci-C4alkyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or Ci-C4fluorooalkyl optionally substituted by a single substituent selected from Ui ; or
C2-C4alkenyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or C2-C4fluoroalkenyl;
or
C2-C4alkynyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or C2-C4fluoroalkynyl;
or
C3-C6cycloalkyl, wherein the cycloalkyl moiety is optionally substituted by a single substituent selected from U3;
or cyano, nitro, halogen, -C(0)R5, -C(0)NR6R7 or -C(R6)=NOR6;
Ui is nitro, cyano, amino, hydroxyl, CO2H, C3-C6cycloalkyl, C3-C6fluorocycloalkyl, Ci-C4alkoxy, Ci-C4fluoroalkoxy, Ci-C2alkoxy-Ci-C2alkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4fluoroalkylsulfanyl, Ci-C4fluoroalkylsulfinyl, Ci-C4fluoroalkylsulfonyl, Ci-C4alkylcarbonyl, Ci- C4alkoxycarbonyl, -OSi(Ci-C4alkyl)3, (Ci-C4alkyl)NH-, (Ci-C4alkyl)2N-, (PhCH2)NH-, (PhCH2)(Ci- C4alkyl)N-, Ci-C4alkylcarbonylamino wherein the alkyl group is optionally substituted by cyano, Ci- C4alkoxycarbonylamino, -SPh, -0C(0)R6, -O-pyrazine or -C(0)NH2;
U2 is phenyl, furanyl, pyridinyl, thienyl, pyrazolyl, imidazolyl, tetrazolyl, oxetanyl, N-morpholinyl, pyrrolidinyl, piperidinyl wherein each ring is optionally substituted by: (i) 1 or 2 independently selected halogen groups, or (ii) 1 or 2 groups independently selected from L4 and optionally a halogen group;
L is halogen, Ci-C4alkyl, Ci-C4fluoroalkyl or Ci-C4alkoxy;
U4 is cyano, Ci-C4alkyl, Ci-C4fluoroalkyl or oxo (=0);
R5 is hydrogen, Ci-C6alkyl, Ci-C4fluoroalkyl or Ci-C4fluoroalkoxy, or Ci-C6alkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, C2-C4alkenyl, C2-C4alkynyl, Ci- C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C3-C6cycloalkyl, phenyl, pyridinyl, furanyl or thiazolyl wherein each ring is optionally substituted by 1 or 2 groups independently selected from halogen, methyl, ethyl, methoxy, ethoxy or trifluromethyl.
R6 is hydrogen, Ci-C4alkyl, Ci-C4fluoroalkyl, Ci-C4alkoxy, Ci-C4fluoroalkoxy; and
R7 is Ci-C4alkyl, Ci-C4fluoroalkyl, Ci-C4alkoxy.
5. A compound according to any one of claims 1 to 4, wherein R1 is selected from: methyl or ethyl each optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or Ci-C2fluorooalkyl optionally substituted by a single substituent selected from Ui ;
or
C2-C3alkenyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or C2-C4fluoroalkenyl;
or
C2-C3alkynyl optionally substituted by a single substituent selected from Ui or a single substituent selected from U2, or C2-C4fluoroalkynyl;
or
C3-C4cycloalkyl, wherein the cycloalkyl moiety is optionally substituted by a single substituent selected from U3;
or cyano, nitro, halogen, -C(0)R5, -C(0)NR6R7 or -C(R6)=NOR6;
Ui is nitro, cyano, amino, hydroxyl, CO2H, C3-C6cycloalkyl, C3-C6fluorocycloalkyl, Ci-C4alkoxy, Ci-C4fluoroalkoxy, Ci-C2alkoxy-Ci-C2alkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4fluoroalkylsulfanyl, Ci-C4fluoroalkylsulfinyl, Ci-C4fluoroalkylsulfonyl, Ci-C4alkylcarbonyl, Ci- C4alkoxycarbonyl, -OSi(Ci-C4alkyl)3, (Ci-C4alkyl)NH-, (Ci-C4alkyl)2N-, (PhCH2)NH-, (PhCH2)(Ci- C4alkyl)N-, Ci-C4alkylcarbonylamino wherein the alkyl group is optionally substituted by cyano, Ci- C4alkoxycarbonylamino, -SPh, -0C(0)R6, -O-pyrazine or -C(0)NH2;
U2 is phenyl, furanyl, pyridinyl, thienyl, pyrazolyl, imidazolyl, tetrazolyl, oxetanyl, N-morpholinyl, pyrrolidinyl, piperidinyl wherein each ring is optionally substituted by: (i) 1 or 2 independently selected halogen groups, or (ii) 1 or 2 groups independently selected from L4 and optionally a halogen group;
L is chloro, fluoro, methyl, ethyl, trifluoromethyl, methoxy, ethoxy;
U4 is cyano, methyl, ethyl, trifluoromethyl, or oxo (=0);
R5 is hydrogen, Ci-C6alkyl, Ci-C4fluoroalkyl or Ci-C4fluoroalkoxy, or Ci-C6alkoxy optionally substituted by 1 or 2 substituents independently selected from cyano, C2-C4alkenyl, C2-C4alkynyl, Ci- C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, C3-C6cycloalkyl, phenyl, pyridinyl, furanyl or thiazolyl wherein each ring is optionally substituted by 1 or 2 groups independently selected from halogen, methyl, ethyl, methoxy, ethoxy or trifluromethyl.
R6 is hydrogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy; and
R7 is methyl, ethyl, trifluoromethyl, methoxy, ethoxy.
6. A compound according to any one of claims 1 to 5, wherein m is 0 or 1 , and preferably 0.
7. A compound according to any one of claims 1 to 6, wherein R3a is hydrogen and R3b is hydrogen.
8. A compound according to any one of claims 1 to 7, wherein R4 is selected from Y2 or Y3.
9. A compound according to any one of claims 1 to 8, wherein n is 1.
10. A compound according to any one of claims 1 to 9, wherein R4 is:
Figure imgf000144_0001
1 1 . A compound of Formula (II):
Figure imgf000145_0001
wherein A, R1 , R2, m, R3a, R3b and R4 are as defined for Formula (I) according to any one of claims 1 to 10.
12. An agrochemical composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound according to any one of claims 1 to 10.
13. The composition according to claim 12, further comprising at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier.
14. 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 in any one of claims 1 to 10, 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).
15. Use of a compound according to any one of claims 1 to 10 as an insecticide, acaracide, nematicide or molluscicide.
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