WO2020169526A1 - Composés hétérocycliques de cyanamide à action pesticide - Google Patents

Composés hétérocycliques de cyanamide à action pesticide Download PDF

Info

Publication number
WO2020169526A1
WO2020169526A1 PCT/EP2020/054091 EP2020054091W WO2020169526A1 WO 2020169526 A1 WO2020169526 A1 WO 2020169526A1 EP 2020054091 W EP2020054091 W EP 2020054091W WO 2020169526 A1 WO2020169526 A1 WO 2020169526A1
Authority
WO
WIPO (PCT)
Prior art keywords
spp
alkyl
independently selected
mono
methyl
Prior art date
Application number
PCT/EP2020/054091
Other languages
English (en)
Inventor
Pierre Joseph Marcel Jung
Aurelien BIGOT
Stefano RENDINE
André Stoller
Nicola COMPAGNONE
Julien Daniel Henri GAGNEPAIN
Original Assignee
Syngenta Crop Protection Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Syngenta Crop Protection Ag filed Critical Syngenta Crop Protection Ag
Publication of WO2020169526A1 publication Critical patent/WO2020169526A1/fr

Links

Classifications

    • 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
    • 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
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/73—Unsubstituted amino or imino radicals
    • 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
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • 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
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • the present invention relates to 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 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):
  • A is a direct link, -O-, or -S(O)p- wherein p is selected from 0, 1 or 2;
  • R 1 is phenyl or naphthyl, each optionally: (i) mono- or polysubstituted by a substituent independently selected from U1a, (ii) mono- or disubstituted by a substituent independently selected from U1b, or (iii) mono- or disubstituted by a substituent independently selected from U1a and monosubstituted by a substituent selected from U1b; or R 1 is a 5- to 12-membered heteroaromatic ring system or a 3- to 12-membered saturated or partially saturated heterocyclic ring system, wherein the ring system is monocyclic or polycyclic and comprises 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, with the proviso that each ring system cannot contain more than 2 oxygen or sulfur atoms, and wherein each ring system is optionally: (i) mono- or
  • U1b is phenyl optionally mono- or disubstituted by a group independently selected from U2; or U1b is a 5- or 6-membered heteroaromatic ring or a 5- or 6-membered saturated or partially saturated heterocyclic ring, wherein each ring comprises 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, with the proviso that each ring cannot contain more than 2 oxygen or sulfur atoms, and wherein each ring is mono- or disubstituted by a group independently selected from U2;
  • U 2 is halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, nitro, cyano, amino, hydroxyl, -SCN, -CO2H, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 3 -C 6 cycloalkyl-
  • n is 0, 1, 2, or 3;
  • U3 is independently selected from halogen, cyano, nitro, hydroxyl, amino, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkoxy-C 1 -C 4 alkyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, C 1 -C 4 alkylsulfanyl, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfanyl, C 1 -C 4 haloalkylsulfinyl, C 1 - C 4 haloalkylsulfonyl, formyl, cyclopropyl, C 1 -C 6 alkylcarbonyl or C 3 -
  • 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 for the treatment of the 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 (Ia) and (Ib) 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 1.276 listed in Table 1 (below) or a compound A1 to A96 listed in Table A (below).
  • Both (E) and (Z) isomeric forms may exist and interconvert as function of temperature or the environment. See for example: Journal of Organic Chemistry (1972), 37(19), 2969-79 or Chemische Berichte 116, 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 -NO 2 group.
  • formyl means a -C(O)H group.
  • C 1 -C 6 alkyl 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.
  • C 1 -C 4 alkyl, C 1 -C3alkyl and C 1 - C 2 alkyl are to be construed accordingly.
  • Examples of C 1 -C 6 alkyl include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, and 1,1-dimethylethyl (t-butyl).
  • A“C 1 - C 4 alkylene” group refers to the corresponding definition of C 1 -C 4 alkyl, except that such radical is attached to the rest of the molecule by two single bonds.
  • C 1 -C 6 haloalkyl refers to a C 1 -C 6 alkyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • Examples of C 1 -C 6 haloalkyl include, but are not limited to fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl, and 3,3,3-trifluoropropyl.
  • C 1 -C 6 alkoxy refers to a radical of the formula RaO- where Ra is a C 1 - C 6 alkyl radical as generally defined above.
  • the term “C 1 -C 4 alkoxy” should be construed accordingly. Examples of C 1 -C 6 alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy, and t- butoxy.
  • C 1 -C 6 haloalkoxy refers to a C 1 -C 6 alkoxy group as defined above substituted by one or more of the same or different halogen atoms.
  • C 1 -C 4 haloalkoxy is to be construed accordingly.
  • Examples of C 1 -C 6 haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy, and trifluoroethoxy.
  • C 2 -C 6 alkenyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond that can be of either the (E)- or (Z)-configuration, having from two to six carbon atoms, which is attached to the rest of the molecule by a single bond.
  • Examples of C 2 -C 6 alkenyl include, but are not limited to, prop-1-enyl, allyl (prop-2-enyl), and but-1-enyl.
  • C 2 -C 6 haloalkenyl refers to a C 2 -C 6 alkenyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C 2 -C 6 alkynyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two to six carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • Examples of C 2 -C 6 alkynyl include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl), and but-1-ynyl.
  • C 2 -C 6 haloalkynyl refers to a C 2 -C 6 alkynyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C 3 -C 6 cycloalkyl refers to a stable, monocyclic ring radical which is saturated or partially unsaturated and contains 3 to 6 carbon atoms.
  • C 3 -C 4 cycloalkyl is to be construed accordingly.
  • Examples of C 3 -C 6 cycloalkyl include, but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclopenten-1-yl, cyclopenten-3-yl, and cyclohexen-3-yl.
  • C 3 -C 6 cycloalkylC 1 -C 4 alkyl refers to a C 3 -C 6 cycloalkyl ring as defined above attached to the rest of the molecule by a C 1 -C 4 alkylene radical as defined above.
  • Examples of C 3 -C 6 cycloalkylC 1 -C 4 alkyl include, but are not limited to cyclopropyl-methyl, cyclobutyl-ethyl, and cyclopentyl-methyl.
  • C 3 -C 6 halocycloalkyl refers to a C 3 -C 6 cycloalkyl ring as defined above substituted by one or more of the same or different halogen atoms.
  • C 3 -C 6 halocycloalkylC 1 -C 4 alkyl refers to a C 3 -C 6 halocycloalkyl radical as defined above attached to the rest of the molecule by a C 1 -C 4 alkylene radical as defined above.
  • C 1 -C 4 alkoxyC 1 -C 4 alkyl refers to a radical of the formula Ry-O-Rx- where Ry is a C 1 -C 4 alkyl radical as generally defined above, and Rx is a C 1 -C 4 alkylene radical as generally defined above.
  • C 1 -C 4 haloalkoxyC 1 -C 4 alkyl refers to a radical of the formula Ry-O-Rx- where Ry is a C 1 -C 4 alkyl radical as generally defined above substituted by one or more of the same or different halogen atoms, and Rx is a C 1 -C 4 alkylene radical as generally defined above.
  • C 1 -C 4 alkoxyC 1 -C 4 alkoxy refers to radical of the formula Ry-O-Rx-O- where Ry is a C 1 -C 4 alkyl radical as generally defined above, and Rx is a C 1 -C 4 alkylene radical as generally defined above.
  • cyanoC 1 -C 4 alkyl refers to a C 1 -C 4 alkyl radical as generally defined above substituted by one or more cyano groups. CyanoC 1 -C 2 alkyl should be construed accordingly.
  • cyanoC 1 -C 4 haloalkyl refers to a C 1 -C 6 haloalkyl radical as generally defined above substituted by one or more cyano groups.
  • C 1 -C 6 alkylsulfanyl refers to a radical of the formula RxS- wherein Rx is a C 1 -C 6 alkyl radical as generally defined above.
  • C 1 -C 6 haloalkylsulfanyl refers to a C 1 -C 6 alkylsulfanyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C 1 -C 6 alkylsulfinyl refers to a radical of the formula RxS(O)- wherein Rx is a C 1 -C 6 alkyl radical as generally defined above.
  • C 1 -C 6 haloalkylsulfinyl refers to a C 1 -C 6 alkylsulfinyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C 1 -C 6 alkylsulfonyl refers to a radical of the formula RxS(O)2- wherein Rx is a C 1 -C 6 alkyl radical as generally defined above.
  • C 1 -C 6 haloalkylsulfonyl refers to a C 1 -C 6 alkylsulfonyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C 1 -C 6 alkylcarbonyl refers to a radical of the formula RxC(O)- where Rx is a C 1 -C 6 alkyl radical as generally defined above.
  • C 1 -C 6 haloalkylcarbonyl refers to a C 1 -C 6 alkylcarbonyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C 1 -C 6 alkoxycarbonyl refers to a radical of the formula RxOC(O)- where Rx is a C 1 -C 6 alkyl radical as generally defined above.
  • C 1 -C 6 haloalkoxycarbonyl refers to a C 1 -C 6 alkoxycarbonyl as generally defined above substituted by one or more of the same or different halogen atoms.
  • C 1 -C 6 alkylcarbonylamino refers to a radical of the formula RxC(O)N(H)- where Rx is a C 1 -C 6 alkyl radical as generally defined above.
  • C 1 -C 6 haloalkylcarbonylamino refers to a C 1 -C 6 alkylcarbonylamino radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C 3 -C 6 cycloalkylcarbonylamino refers to a radical of the formula RxC(O)N(H)- where Rx is a C 3 -C 6 cycloalkyl radical as generally defined above.
  • C 3 -C 6 halocycloalkylcarbonylamino refers to a C 3 - C 6 cycloalkylcarbonylamino radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C 1 -C 6 alkylaminocarbonyl refers to a radical of the formula RxNHC(O)- where Rx is a C 1 -C 6 alkyl radical as generally defined above.
  • C 1 -C 6 haloalkylaminocarbonyl refers to a C 1 -C 6 alkylaminocarbonyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C 3 -C 6 cycloalkylaminocarbonyl refers to a radical of the formula RxNHC(O)- where Rx is a C 3 -C 6 cycloalkyl radical as generally defined above.
  • C 3 -C 6 halocycloalkylaminocarbonyl refers to a C 3 - C 6 cycloalkylaminocarbonyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C 3 -C 6 cycloalkylcarbonyl refers to a radical of the formula RxC(O)- where Rx is a C 3 -C 6 cycloalkyl radical as generally defined above.
  • C 3 -C 6 halocycloalkylcarbonyl refers to a C 3 -C 6 cycloalkylcarbonyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • Examples of a 5- to 12-membered heteroaromatic ring system which can be monocyclic or polycyclic and which comprises 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, include pyridyl, pyrimidyl, pyrrolyl, pyrazolyl, furyl, thienyl, imidazolyl, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyrazinyl, pyridazinyl, triazinyl, pyranyl, quinazolinyl, isoquinolinyl, indolizinyl, isobenzofuranylnaphthyridinyl, quinoxalinyl, cinnolinyl, phthalazinyl, benzothiazolyl, benzoxazolyl, benzotriazolyl, ind
  • Examples of a 3- to 12-membered saturated or partially saturated heterocyclic ring system which can be monocyclic or polycyclic and which comprises 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, include dihydropyranyl, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, isoxazolidinyl, isothiazolidinyl, pyrazolidinyl, oxazolidinyl, thiazolidinyl, imidazolidinyl, oxadiazolidinyl, thiadiazolidinyl, dihydrofuranyl, dihydrothienyl, pyrrolinyl, isoxazolinyl, dihydropyrazolyl, dihydrooxazolyl, piperidinyl, dioxanyl, tetrahydropyranyl, hexahydropyridazinyl, hexahydropyrimidinyl, oxirany
  • 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 C 1 -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 C 1 -C 4 -alkane- or arylsulfonic acids which are unsubstituted or
  • 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), -O-, or -S(O)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 phenyl or naphthyl, each optionally: (i) mono- or polysubstituted (including di- or tri-substituted) by a substituent independently selected from U1a, (ii) mono- or disubstituted by a substituent independently selected from U1b, or (iii) mono- or disubstituted by a substituent independently selected from U1a and monosubstituted by a substituent selected from U1b; or R 1 is a 5- to 12-membered heteroaromatic ring system or a 3- to 12-membered saturated or partially saturated heterocyclic ring system, wherein the ring system is monocyclic or polycyclic and comprises 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, with the proviso that each ring system cannot contain more than 2 oxygen or sulfur atoms (or contiguous oxygen or sulfur atoms), and wherein each ring system is optionally: (i) mono- or polysubstituted by a substituent
  • R 1 is phenyl, pyrrolyl, pyrazolyl, furanyl, thienyl, triazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, 1,2,3-benzoxadiazolyl, 2,1,3- benzoxadiazolyl, quinolinyl, quinoxalinyl, 1,3-benzodioxolyl, naphthyridinyl or benzothiazolyl, wherein each ring system is optionally: (i) mono- or polysubstituted (including di- or tri-substituted) by a substituent independently selected from U1a, (ii) mono- or disubstituted by a substituent independently selected from U1b, or (iii) mono- or disubstit
  • R 1 is phenyl, pyrrol-1-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, furan-2-yl, furan-3- yl, thien-2-yl, thien-3-yl, 1,2,3-triazol-2-yl, 1,2,4-triazol-1-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl, pyridazin-3-yl, isoxazol-3-yl, isoxazol-4-yl, isothiazol-3-yl, isothiazol-4-yl, 1,3,4-oxadiazol-2-yl, 2,1,3-benzoxadiazol-5-yl, quinoxalin-5-yl, 1,3-benzodioxol-4
  • R 1 is phenyl, pyridin-3-yl, pyrazol-3-yl, pyrazol-4-yl or thien-3-yl, wherein each ring is optionally substituted by one or two substituents selected from halogen (in particular chloro or fluoro), cyano, C 1 -4alkyl, or a single substituent selected from phenyl.
  • U1a is independently selected from halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy and C 1 - C 6 haloalkoxy.
  • U1a is selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 fluoroalkyl, C 1 -C 4 alkoxy and C 1 - C 4 fluoroalkoxy. More preferably, U1a is selected from halogen, methyl, ethyl, n-propyl, iso-propyl, C 1 - C 2 fluoroalkyl, methoxy, ethoxy and C 1 -C 2 fluoroalkoxy.
  • U1a is selected from is fluoro, chloro, methyl, ethyl, n-propyl, iso-propyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy and trifluoromethoxy.
  • U1b is independently selected from nitro, cyano, amino, hydroxyl, -SCN, -CO2H, C 3 -C 6 cycloalkyl, C 3 - C 6 halocycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 4 alkyl, C 3 -C 6 halocycloalkyl-C 1 -C 4 alkyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, C 1 -C 4 alkoxy-C 1 -C 4 alkoxy, cyano-C 1 -C 4 alkyl, cyano-C 1 -C 4 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 4 haloalkoxy-C 1 -C 4 alkyl, C
  • U1a is independently selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 fluoroalkyl, C 1 -C 4 alkoxy and C 1 -C 4 fluoroalkoxy
  • U1b is independently selected from cyano, amino, hydroxyl, C 1 - C 4 alkoxycarbonyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 alkylaminocarbonyl, C 1 -C 4 alkylcarbonylamino, phenyl, pyrazolyl, oxadiazolyl.
  • U1a is independently selected from chloro, fluoro, bromo, C 1 - C 4 alkyl, difluoromethyl, trifluromethyl, methoxy, ethoxy and trifluoromethoxy
  • U1b is independently selected from cyano, amino, hydroxyl, cyanomethyl, dimethylamino, C 1 -C 4 alkoxycarbonyl, methylsulfonyl, methylaminocarbonyl, methylcarbonylamino, phenyl, pyrazolyl, oxadiazolyl.
  • U 2 is halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, nitro, cyano, amino, hydroxyl, -SCN, -CO2H, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 4 alkyl, C 3 - C 6 halocycloalkyl-C 1 -C 4 alkyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, C 1 -C 4 alkoxy-C 1 -C 4 alkoxy, cyano-C 1 -C 4 alkyl, cyano-C 1 -C 4 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C
  • U1b is selected from nitro, cyano, amino, hydroxyl, cyclopropyl or phenyl optionally substituted by 1 substituent selected from U2. More preferably, U1b is selected from cyano or phenyl optionally substituted by 1 substituent selected from U2.
  • U 2 is selected from chloro, fluoro, methyl, ethyl, methoxy, cyano and trifluoromethyl.
  • m is 0, 1 or 2. In some embodiments of the invention, m is 0. In some embodiments of the invention, m is 1. In some embodiments of the invention, m is 2. Preferably, m is 0 or 1, and more preferably, m is 0.
  • R 2 is independently selected from halogen, cyano, amino, hydroxyl, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 - C 6 haloalkoxy, C 1 -C 6 alkoxy, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 3 - C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkylsulfanyl, C 1 -C 6 alkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 - C 6 haloalkylsulfanyl, C 1 -C 6 haloalkylsulfinyl and C 1 -C 6 haloalkylsulfonyl.
  • R 2 is independently selected from halogen, cyano, amino, hydroxyl, C 1 -C 4 alkyl, C 1 - C 4 fluoroalkyl, C 1 -C 4 fluoroalkoxy, C 1 -C 4 alkoxy, C 2 -C 4 alkenyl, C 2 -C 4 fluoroalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 fluoroalkynyl, C 3 -C 4 cycloalkyl and C 3 -C 4 fluorocycloalkyl.
  • R 2 is independently selected from fluoro, chloro, methyl, ethyl, trifluoromethyl, trifluoromethoxy, methoxy or ethoxy. Most preferably, R 2 is methyl. In certain embodiments of the invention m is 0 or 1, wherein R 2 is methyl.
  • R 3a and R 3b are independently selected from hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 - C 4 alkoxy, C 1 -C 4 haloalkoxy and cyano.
  • R 3a is hydrogen and R 3b is selected from hydrogen, chloro, fluoro, methyl, ethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, methoxy or ethoxy. More preferably, R 3a is hydrogen and R 3b is hydrogen or methyl. Most preferably, R 3a is hydrogen and R 3b is hydrogen. R4 is selected from one of Y1 to Y5;
  • n is 0, 1, 2, or 3.
  • n is 0 or 1.
  • U3 is independently selected from halogen, cyano, nitro, hydroxyl, amino, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkoxy-C 1 -C 4 alkyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, C 1 -C 4 alkylsulfanyl, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfanyl, C 1 -C 4 haloalkylsulfinyl, C 1 - C 4 haloalkylsulfonyl, formyl, cyclopropyl, C 1 -C 6 al
  • U3 is halogen, in particular chloro, when n is 1.
  • 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. In some embodiments of the invention, R 4 is:
  • R 4 is:
  • R 4 is:
  • R 4 is: .
  • R 4 is: .
  • 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 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 1.276 listed in Table 1 (below) or a compound A1 to A96 listed in Table A (below).
  • Compounds of the present invention can be made as shown in the following schemes 1 to 5, in which, unless otherwise stated, the definition of each variable is as defined herein for a compound of formula (I).
  • reaction occurs in the presence or not of a base (such as triethylamine or sodium hydride), in the presence or not of a catalysis, such as 4-dimethylaminopyridine, in an appropriate solvent (eg, 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 150°C.
  • bases such as triethylamine or sodium hydride
  • a catalysis such as 4-dimethylaminopyridine
  • an appropriate solvent eg, N,N- dimethylformamide, N,N-dimethylacetamide or acetonitrile
  • solvent eg, N,N- dimethylformamide, N,N-dimethylacetamide or acetonitrile
  • compounds of formula (II) wherein m, 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 (III) via alkylation with a compound of formula (IV) with (R 3a )(R 3b )(R 4 )C-XLG, wherein XLG is a leaving group (such as a halide, preferably iodide, bromide or chloride) in the presence or not of a base (such as potassium carbonate or sodium hydride) in an appropriate solvent (eg, tetrahydrofuran, N,N- dimethylformamide, acetone or acetonitrile) or in the absence of solvent, at temperatures between - 78°C and 150°C, and preferably between 0°C and 150°C.
  • a leaving group such as a halide, preferably iodide, bromide or chloride
  • a base such as
  • compounds of formula (I) wherein m, 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-XLG, wherein XLG is a leaving group (such as a halide, preferably iodide, bromide or chloride) and using the same conditions described for scheme 2.
  • XLG is a leaving group (such as a halide, preferably iodide, bromide or chloride)
  • the compounds of formula (VII) wherein A is -O- or -S- can be prepared from the compounds of formula (VI) by reaction of the 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 a 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
  • solvent eg, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide or acetonitrile
  • solvent eg,
  • compounds of formula (II) wherein m, 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 (IIIa), wherein XLG is a leaving group, such as iodide or bromide, via“metal catalysis”.
  • XLG is a leaving group, such as iodide or bromide, via“metal catalysis”.
  • HAR1 wherein A is - O- or -S- and using palladium coupling see Chemistry - A European Journal 201218(9), 2498-2502, S2498/1-S2498/31; and cited references; Journal of the American Chemical Society 2010 132(33), 11592-11598; Organic Letters 201416(4), 1212-1215.
  • the reaction can be catalyzed by a palladium-based catalyst, for example palladium acetate, in the presence of a base, such as cesium carbonate or sodium tert-butoxide, in a solvent or a solvent mixture, such as, for example toluene, preferably under an inert atmosphere and in the presence of a chelating phosphine.
  • a base such as cesium carbonate or sodium tert-butoxide
  • solvent or a solvent mixture such as, for example toluene
  • 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 a copper derivative, see for example, Tetrahedron 2013 69(16), 3415-3418; Journal of Organic Chemistry 2009 74(14), 5075-5078; 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 the 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 may be run in an inert solvent, such as dioxane or toluene, usually at a temperature between 50 to 150°C in the presence or not of an additional ligand, such as for example diamine ligands (e.g., trans- cyclohexyldiamine.) or 1,10-phenanthroline.
  • diamine ligands e.g., trans- cyclohexyldiamine.
  • 1,10-phenanthroline 1,10-phenanthroline.
  • the compounds of formula (II) can be prepared from compounds of formula (IIIa) wherein R 2 , R 3a , R 3b and R 4 are as described herein for the compounds of formula (I) and XLG could be a leaving group such iodide or bromide via“metal catalysis”.
  • XLG could be a leaving group such iodide or bromide via“metal catalysis”.
  • Compounds of formula (II) can be prepared from compounds of formula (IIIa) wherein XLG could be a leaving group such iodide or bromide by reaction with a boron-derived functional group, for example R1B(OH)2 or R1B(OR)2, wherein R can be a C 1 -C 6 alkyl 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.
  • XLG could be a leaving group such iodide or bromide by reaction with a boron-derived functional group, for example R1B(OH)2 or R1B(OR)2, wherein R can be a C 1 -C 6 alkyl 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 may be catalyzed by a palladium-based catalyst, for example, tetrakis(triphenylphosphine)-palladium(0), bis(triphenyl- phosphine) palladium(II) dichloride or (1,1'bis(diphenylphosphino)-ferrocene)dichloropalladium- dichloromethane (1:1 complex), in the 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, such as, 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) pal
  • 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 R1SnBu3 may be used for these types of reactions.
  • Such Stille reactions are usually carried out in the presence of a palladium catalyst, for example, tetrakis(triphenylphosphine)palladium(0) or (1,1'bis(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, tetrakis(triphenylphosphine)palladium(0) or (1,1'bis(diphen
  • 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, 1132-1136 an , Kurti, Laszlo; Czako, Barbara; (Editors) Strategic Applications of Named Reactions in Organic Synthesis (2005) p 438.
  • 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 1,8-diazabicyclo[5.4.0]undec-7-ene
  • the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also act as solvents or diluents. Reactions are advantageously carried out in a temperature range from approximately -80 °C to approximately 140 °C, preferably from approximately -30 °C to approximately 100 °C, in many cases in the range between ambient temperature and approximately 80 °C.
  • a compound of formula (I) can be converted in a manner known per se into another compound of formula (I) by replacing one or more substituents of the starting compound of formula (I) in the customary manner by (an)other substituent(s) according to the invention.
  • Salts of compounds of formula (I) can be prepared in a manner known per se.
  • acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in the customary manner into the free compounds (I), acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • an acid for example with silver acetate
  • an inorganic salt which forms, for example silver chloride is insoluble and thus precipitates from the reaction mixture.
  • the compounds of formula (I) which have salt-forming properties, can be obtained in free form or in the form of salts.
  • the compounds of formula (I) and, where appropriate, the tautomer’s thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule, the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and herein below, even when stereochemical details are not mentioned specifically in each case.
  • Diastereomeric mixtures or racemic mixtures of compounds of formula (I), in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
  • Enantiomeric mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the di
  • Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.
  • the compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • the compounds of formula (I) according to the invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and may be well-tolerated by warm-blooded species, fish and plants.
  • the compounds of formula (I) may have a beneficial safety profile towards non-target species, such as bees, and accordingly a good toxicity profile.
  • the active ingredients according to the invention may act against all or individual developmental stages of normally sensitive, but also resistant pests, such as insects or representatives of the order Acarina.
  • the insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate. Examples of the above-mentioned pests are:
  • 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
  • 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 1.276 listed in Table 1 (below) or a compound A1 to A96 listed in Table A (below)) to a neonicotinoid-resistant insect.
  • a compound of Formula (I) eg, a single compound selected from compounds 1.001 to 1.276 listed in Table 1 (below) or a compound A1 to A96 listed in Table A (below)
  • the present invention may relate to the use of a compound of Formula (I) (eg, a single compound selected from compounds 1.001 to 1.276 listed in Table 1 (below) or a compound A1 to A96 listed in Table A (below) as an insecticide against neonicotinoid-resistant insects.
  • a compound of Formula (I) eg, a single compound selected from compounds 1.001 to 1.276 listed in Table 1 (below) or a compound A1 to A96 listed in Table A (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.
  • 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 (60–111) 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.
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae, or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, 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 ⁇ -endotoxins, e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1Fa
  • 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
  • ⁇ -endotoxins for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, 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 Cry1Ab, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • amino acid replacements preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G- recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (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 Cry1Ab toxin), YieldGard Rootworm ® (maize variety that expresses a Cry3Bb1 toxin), YieldGard Plus ® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin), Starlink ® (maize variety that expresses a Cry9C toxin), Herculex I ® (maize variety that expresses a Cry1Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium), NuCOTN 33B ® (cotton variety that expresses a Cry1Ac toxin), Bollgard I
  • transgenic crops are:
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 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-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
  • NK603 ⁇ MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 ⁇ 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 Cry1Ab 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-0392225, WO 95/33818 and EP-A-0353191.
  • 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-0392225), 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
  • PRPs pathogenesis-related proteins
  • antipathogenic substances produced by microorganisms for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein
  • 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 https://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 2005113886 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: Examples of exotic woodborers of economic importance.
  • the present invention may be also used to control any insect pests that may be present in turfgrass, including for example beetles, caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites, mole crickets, scales, mealybugs ticks, spittlebugs, southern chinch bugs and white grubs.
  • the present invention may be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.
  • the present invention may be used to control insect pests that feed on the roots of turfgrass including white grubs (such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green June beetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica), Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. (e.g. Black turfgrass ataenius, A.
  • white grubs such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp
  • Maladera spp. e.g. Asiatic garden beetle, M. castanea
  • Tomarus spp. ground pearls
  • Margarodes spp. mole crickets (tawny, southern, and short-winged, Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.).
  • the present invention may also be used to control insect pests of turfgrass that are thatch dwelling, including armyworms (such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta), cutworms, billbugs (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).
  • armyworms such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta
  • cutworms such as S. venatus verstitus and S. parvulus
  • sod webworms such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis.
  • the present invention may also be used to control insect pests of turfgrass that live above the ground and feed on the turfgrass leaves, including chinch bugs (such as southern chinch bugs, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two-lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae family), and greenbugs.
  • 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.
  • 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.
  • Mallophagida Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes 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.
  • 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.
  • formulation adjuvants or addditives such as carriers, solvents and surface-active substances.
  • the formulations can be in various physical forms, e.g.
  • Such formulations can either be used directly or diluted prior to use.
  • the dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
  • the active ingredients can also be contained in very fine microcapsules.
  • Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release).
  • Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art.
  • very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p- diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4- dioxane, dipropylene glycol,
  • 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
  • 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 C 8 -C 22 fatty acids, especially the methyl derivatives of C 12 -C 18 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.
  • 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.
  • a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Preferred formulations can have the following compositions (weight %):
  • Emulsifiable concentrates are:
  • active ingredient 1 to 95 %, preferably 60 to 90 %
  • surface-active agent 1 to 30 %, preferably 5 to 20 %
  • liquid carrier 1 to 80 %, preferably 1 to 35 % Dusts:
  • active ingredient 0.1 to 10 %, preferably 0.1 to 5 %
  • active ingredient 5 to 75 %, preferably 10 to 50 %
  • Wettable powders 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 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 %
  • solid carrier 99.5 to 70 %, preferably 97 to 85 %
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsions of any required dilution which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
  • the combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • the finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol.
  • Non-dusty coated granules are obtained in this manner.
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 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.
  • 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.
  • the activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients.
  • 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.
  • TX means“one compound selected from the group consisting of a compound 1.001 to 1.276 listed in Table 1 (below) or a compound A1 to A96 listed in Table A (below)
  • an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX,
  • an insect control active substance selected from Abamectin + TX, Acequinocyl + TX, Acetamiprid + TX, Acetoprole + TX, Acrinathrin + TX, Acynonapyr + TX, Afidopyropen + TX, Afoxalaner + TX, Alanycarb + TX, Allethrin + TX, Alpha-Cypermethrin + TX, Alphamethrin + TX, Amidoflumet + TX, Aminocarb + TX, Azocyclotin + TX, Bensultap + TX, Benzoximate + TX, Benzpyrimoxan + TX, Betacyfluthrin + TX, Beta-cypermethrin + TX, Bifenazate + TX, Bifenthrin + TX, Binapacryl + TX, Bioallethrin + TX, Bioallethrin S)-cyclopentylisomer +
  • TX Neem tree based products + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria usgae + TX, P-cymene + TX, Plutella xylostella Granulosis virus + TX, Plutella xylostella Nucleopolyhedrovirus + TX, Polyhedrosis virus + TX, pyrethrum + TX, QRD 420 (a terpenoid blend) + TX, QRD 452 (a terpenoid blend) + TX, QRD 460 (a terpenoid blend) + TX, Quillaja saponaria + TX, Rhodococc
  • an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX,
  • an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, Cyclobutrifluram + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,
  • an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX, a bactericide selected from the group of substances consisting of 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicin (1112) + TX, fenaminosulf
  • a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Hopkins (scientific name) (5
  • a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX,
  • a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and
  • an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, (Z)-hexadec-11- enal (IUPAC name) (436) + TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name) (437) + TX, (Z)- hexadec-13-en-11-yn-1
  • an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,
  • a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + T
  • a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1,2-dibromo-3-chloropropane (IUPAC/Chemical Abstracts name) (1045) + TX, 1,2- dichloropropane (IUPAC/ Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3- dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4- dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstracts name) (1065) + TX, 3-(4- chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3- ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alternative
  • a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,
  • a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar- S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX
  • a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alpha- chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91) + TX, bromethalin (92) +
  • a synergist selected from the group of substances consisting of 2-(2- butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex- 2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX,
  • an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX, a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX,
  • a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX,
  • a biologically active substance selected from 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4- dichlorophenyl benzenesulfonate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 4-chlorophenyl phenyl sulfone + TX, acetoprole + TX, aldoxycarb + TX, amidithion + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, aramite + TX, arsenous oxide + TX, azobenzene + TX, azothoate + TX, benomyl + TX, benoxafos + TX, benzyl benzoate + TX, bixafen + TX, brofenvalerate + TX, bromocyclen + TX, bro
  • TX Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp.
  • Acinetobacter lwoffii + TX Acremonium alternatum + TX + TX, Acremonium cephalosporium + TX + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®) + TX, Agrobacterium radiobacter strain K84 (Galltrol-A®) + TX, Alternaria alternate + TX, Alternaria cassia + TX, Alternaria destruens (Smolder®) + TX, Ampelomyces quisqualis (AQ10®) + TX, Aspergillus flavus AF36 (AF36®) + TX, Aspergillus flavus NRRL 21882 (Aflaguard®) + TX, Aspergillus spp.
  • AdoxGV Adoxophyes orana granulovirus
  • Bacillus subtilis strain AQ178 + TX Bacillus subtilis strain QST 713 (CEASE® + TX, Serenade® + TX, Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain AQ153 + TX, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis var.
  • amyloliquefaciens strain FZB24 (Taegro® + TX, Rhizopro®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1Ab + 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.
  • 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® + TX, 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 +
  • 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, (E + TX,Z + T
  • 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 Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug® + TX, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica + TX, Dacnusa sibirica (Minusa®) + TX, Diglyphus isaea (Diminex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis
  • TX Steinernematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator; and
  • the ratio (by weight) of active ingredient mixture of the compounds of formula (I) selected from a compound 1.001 to 1.276 listed in Table 1 (below) or a compound A1 to A96 listed in Table A (below) with active ingredients described above is from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 and 1:5, special preference being given to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, 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 1.276 listed in Table 1 (below) or a compound A1 to A96 listed in Table A (below) and one or more active ingredients as described above can be applied, for example, in a single“ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the compounds of formula (I) selected from a compound 1.001 to 1.276 listed in Table 1 (below) or a compound A1 to A96 listed in Table A (below) and the active ingredients as described above is not essential for working the present invention.
  • the present invention provides a combination of active ingredients comprising a compound defined in the first aspect, and one or more further active ingredients (whether chemical or biological).
  • compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
  • auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides
  • compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • compositions that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention.
  • Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient.
  • the rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.
  • a preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question.
  • the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.
  • the compounds of the invention and compositions thereof are also be suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type.
  • the propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing.
  • the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling.
  • These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention.
  • Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.
  • seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
  • the present invention also comprises seeds coated or treated with or containing a compound of formula (I).
  • coated or treated with and/or containing generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application.
  • the seed product When the said seed product is (re)planted, it may absorb the active ingredient.
  • the present invention makes available a plant propagation material adhered thereto with a compound of formula (I). Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula (I).
  • Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
  • the seed treatment application of the compound formula (I) can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.
  • a further aspect is a plant propagation material comprising by way of treatment or coating one or more compounds of formula (I) according to the invention, optionally also comprising a colour pigment.
  • “consisting essentially” and inflections thereof are a preferred embodiment of “comprising” and its inflections
  • “consisting of” and inflections thereof are a preferred embodiment of "consisting essentially of” and its inflections.
  • Table 1 This table discloses the 276 compounds (1.001 to 1.276) of the formula (I) having either the (E)- 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 AI 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 physico- chemical properties, or increased biodegradability).
  • LC/MS means Liquid Chromatography Mass Spectrometry and the description of the apparatus and the method A is outlined below.
  • the characteristic LC/MS values obtained for each compound were the retention time (“Rt”, recorded in minutes (min)) and the measured molecular ion (M+H) + and/or (M- H)-.
  • 1 H NMR measurements were recorded on Brucker 400 MHz or 300 MHz spectrometers, chemical shifts are given in ppm relevant to a TMS standard. Spectra are measured in deuterated solvents (eg, dimethyl sulfoxide (DMSO)) as indicated.
  • deuterated solvents eg, dimethyl sulfoxide (DMSO)
  • LCMS Methods Method A: Standard 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.
  • Step 1 Preparation of 1-[(6-chloro-3-pyridyl)methyl]-3-phenoxy-pyridin-2-imine.
  • Step 1 Preparation of 3-(1-methylpyrazol-4-yl)oxy-2-nitro-pyridine.
  • Step 3 Preparation of 1-[(6-chloro-3-pyridyl)methyl]-3-(1-methylpyrazol-4-yl)oxy-pyridin-2-imine.
  • Step 1 Preparation of 3-(1-methylpyrazol-4-yl)sulfanylpyridin-2-amine.
  • the flask was capped and flushed two times with argon.1-methylpyrazole- 4-thiol (0.685 g, 1.5 equiv.) was added via syringe.
  • the reaction mixture vessel was heated at 85°C for 1.5 hrs and the reaction cooled at room temperature and filtered over a thin pad of Celite.
  • the Celite was rinsed with dioxane (60 mL).
  • the resulting filtrate was dried under vacuum.
  • the resulting solid was diluted in dichloromethane, taken up on Isolute and was directly purified by chromatography to give the title compound (186 mg, 22% yield).
  • Step 2 Preparation of 1-[(6-chloro-3-pyridyl)methyl]-3-(1-methylpyrazol-4-yl)sulfanyl-pyridin-2-imine.
  • Step 1 Preparation of 3-(1-methylpyrazol-4-yl)pyridin-2-amine.
  • Step A Synthesis of 3-bromo-1-[(6-chloro-3-pyridyl)methyl]pyridin-2-imine.
  • Step A Synthesis of 1-ethyl-4-(4,4.5.5-tetramethyl-1.3.2-dioxaborolan-2-vI)pyrazole.
  • Step B Synthesis of 1 -ethylpyrazol-4-ol.
  • Step C Synthesis of 3-(1 -ethylpyrazol-4-yl)oxy-2-nitro-pyridine.
  • Step D Synthesis of 3-(1 -ethylpyrazol-4-vI)oxypyridin-2-amine.
  • Step E Synthesis of 1 -[(6-chloro-3-pyridyl)methyl1-3-(1 -ethylpyrazol-4-yl)oxy-pyridin-2-imine
  • Step F Synthesis of (E)- and/or (Z)-[1 -[(6-chloro-3-pyridyl)methyl1-3-(1 -ethylpyrazol-4-yl)oxy-2- pyridylidenel cvanamide (compound A13).
  • 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 desired product (120 mg, 34%).
  • Example 7 Preparation of (E)- and/or (Z - -[(6-chloro-3-pyridvI)methyl1-3-pyrazol-1 -yl-2-pyridylidene1 cvanamide (compound A14).
  • Step A Synthesis of 2-nitro-3-pyrazol-1 -yl-pyridine.
  • Step B Synthesis of 3-pyrazol-1 -ylpyridin-2-amine.
  • Step C Synthesis of 1 -[(6-chloro-3-pyridvI)methyl1-3-pyrazol-1 -yl-pyridin-2-imine (Compound B12).
  • Step D Synthesis of (E)- and/or (Z)-[1 -[(6--chloro-3-pyridyl)methyll-3-pyrazol-1 -yl-2-pyridylidenel cyanamide (Compound A14).
  • Example 8 Preparation of library of compounds according to Formula (I) A18 to A79.
  • Compounds A18 to A79 were prepared by the following general protocol:
  • Stock Solution B A stock suspension of catalyst (Xphos-Precatalyst (Pd ⁇ )) was prepared by adding 330 mg in 36 mL DME.
  • 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 resulted in at least 80% mortality at an application rate of 200 ppm A2 , A3, A7, A9, A12, A13, A16, A17, A19, A22, A27, A30, A31, A32, A42, A44, A50, A57, A58, A61, A66, A68, A69, A76, A77, A78, A84, A85, A86, A93, A96.
  • Myzus persicae (Green peach aphid): Feeding/contact activity. Sunflower leaf discs were placed onto agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. The samples were assessed for mortality 6 days after infestation.
  • the following compounds resulted in at least 80% mortality at an application rate of 200 ppm: A2, A3, A5, A7, A8, A9, A12, A13, A14, A15, A16, A17, A19, A22, A25, A27, A29, A30, A31, A32, A33, A34, A38, A41, A42, A44, A45, A46, A48, A50, A51, A54, A55, A56, A57, A58, A61, A62, A66, A67, A68, A69, A71, A72, A74, A76, A77, A78, A82, A83, A84, A85, A87, A93, A94, A96.
  • 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 resulted in at least 80% mortality at a test rate of 24 ppm: A2 , A6, A7, A12, A13, A16, A19, A22, A26, A32, A33, A44, A45, A46, A48, A49, A56, A58, A61, A62, A66, A71, A74, A77, A78, A83, A84, A85, A86, A87, A92, A93, A94, A96.
  • 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 resulted in at least 80% mortality at a test rate of 12 ppm: A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, A19, A20, A22, A23, A25, A26, A27, A28, A29, A30, A31, A32, A33, A34, A36, A37, A38, A40, A42, A43, A44, A45, A46, A48, A49, A50, A51, A54, A55, A56, A57, A58, A60, A61, A62, A63, A66, A67, A68, A69, A71, A72, A74, A75, A76, A77, A78, A83, A84, A85, A86, A87, A90, A92, A93, A94, A96.
  • Myzus 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 Table A gave at least 80% control of the neonicotinoid-resistant strain of Myzus persicae at 200 ppm. A2, A7, A12, A13, A48, A61, A84.
  • 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. A48.
  • Bemisia tabaci (neonicotinoid-resistant, cotton whitefly), adult, contact. 5 cm cotton leaf discs were placed upside down in petri dishes poured out with 11 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.
  • RF50 resistance factor 50
  • 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 following compounds in Table A gave at least a RF(50) lower or equal than 20. A2, A7, A13, A84.

Landscapes

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

Abstract

Un composé de formule (I), dans laquelle les substituants sont tels que définis dans la revendication 1, et les sels, stéréoisomères, énantiomères, tautomères et N-oxydes agrochimiquement acceptables de ces composés peuvent être utilisés en tant qu'insecticides.
PCT/EP2020/054091 2019-02-18 2020-02-17 Composés hétérocycliques de cyanamide à action pesticide WO2020169526A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19157756.8 2019-02-18
EP19157756 2019-02-18

Publications (1)

Publication Number Publication Date
WO2020169526A1 true WO2020169526A1 (fr) 2020-08-27

Family

ID=65493920

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2020/054091 WO2020169526A1 (fr) 2019-02-18 2020-02-17 Composés hétérocycliques de cyanamide à action pesticide

Country Status (1)

Country Link
WO (1) WO2020169526A1 (fr)

Citations (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0259738A2 (fr) 1986-09-10 1988-03-16 Nihon Tokushu Noyaku Seizo K.K. Composés hétérocycliques
EP0353191A2 (fr) 1988-07-29 1990-01-31 Ciba-Geigy Ag Séquences d'ADN codant des polypeptides avec activité béta-1,3-glucanase
EP0367474A1 (fr) 1988-11-01 1990-05-09 Mycogen Corporation Souche de bacillus thuringiensis appelée b.t. ps81gg, active contre les lépidoptères nuisibles et gène codant une toxine active contre les lépidoptères.
EP0374753A2 (fr) 1988-12-19 1990-06-27 American Cyanamid Company Toxines insecticides, gènes les codant, anticorps les liant, ainsi que cellules végétales et plantes transgéniques exprimant ces toxines
EP0392225A2 (fr) 1989-03-24 1990-10-17 Ciba-Geigy Ag Plantes transgéniques résistantes aux maladies
WO1990013651A1 (fr) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Genes bacteriens
EP0401979A2 (fr) 1989-05-18 1990-12-12 Mycogen Corporation Souches de bacillus thuringiensis actives contre les lépidoptères nuisibles, et gènes codant pour des toxines actives contre les lépidoptères
EP0427526A1 (fr) 1989-11-07 1991-05-15 Richter Gedeon Vegyeszeti Gyar R.T. Dérivés de la pyridine, procédé pour leur préparation et compositions pharmaceutiques les contenant
EP0427529A1 (fr) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Lectines larvicides, et résistance induite des plantes aux insectes
EP0451878A1 (fr) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modification de plantes par techniques de génie génétique pour combattre ou contrôler les insectes
WO1993007278A1 (fr) 1991-10-04 1993-04-15 Ciba-Geigy Ag Sequence d'adn synthetique ayant une action insecticide accrue dans le mais
WO1995033818A2 (fr) 1994-06-08 1995-12-14 Ciba-Geigy Ag Genes pour la synthese des substances antipathogenes
WO1995034656A1 (fr) 1994-06-10 1995-12-21 Ciba-Geigy Ag Nouveaux genes du bacillus thuringiensis codant pour des toxines actives contre les lepidopteres
US5631072A (en) 1995-03-10 1997-05-20 Avondale Incorporated Method and means for increasing efficacy and wash durability of insecticide treated fabric
WO2002015701A2 (fr) 2000-08-25 2002-02-28 Syngenta Participations Ag Nouvelles toxines insecticides derivees de proteines cristallines insecticides de $i(bacillus thuringiensis)
WO2003000906A2 (fr) 2001-06-22 2003-01-03 Syngenta Participations Ag Genes de resistance aux maladies chez les plantes
WO2003018810A2 (fr) 2001-08-31 2003-03-06 Syngenta Participations Ag Toxines cry3a modifiees et sequences d'acides nucleiques les codant
WO2003034823A1 (fr) 2001-10-25 2003-05-01 Siamdutch Mosquito Netting Company Limited Traitement d'une matiere textile au moyen d'un insecticide
WO2003052073A2 (fr) 2001-12-17 2003-06-26 Syngenta Participations Ag Nouvel evenement du mais
WO2005064072A2 (fr) 2003-12-22 2005-07-14 Basf Aktiengesellschaft Composition destinee a l'impregnation de fibres, de tissus et de nappes de filet possedant une activite protectrice contre les parasites
WO2005113886A1 (fr) 2004-05-12 2005-12-01 Basf Aktiengesellschaft Procede de traitement de substrats flexibles
EP1724392A2 (fr) 2005-05-04 2006-11-22 Fritz Blanke Gmbh & Co. Kg Procédé d'apprêtage anti-microbien de surfaces textiles
WO2006128870A2 (fr) 2005-06-03 2006-12-07 Basf Aktiengesellschaft Composition pour impregnation de fibres, tissus et filets a action protectrice contre les ravageurs
WO2007090739A1 (fr) 2006-02-03 2007-08-16 Basf Se Procede de traitement de substrats
WO2008151984A1 (fr) 2007-06-12 2008-12-18 Basf Se Formulation aqueuse et processus d'imprégnation de matières non vivantes exerçant une action protectrice contre les parasites
WO2010111572A1 (fr) 2009-03-27 2010-09-30 Abbott Laboratories Composés utilisés en tant que ligands des récepteurs des cannabinoïdes
WO2011138281A2 (fr) 2010-05-06 2011-11-10 Bayer Cropscience Ag Procédé de production de dithiine-tétracarboxy-diimides
EP2628389A1 (fr) 2010-08-31 2013-08-21 Meiji Seika Pharma Co., Ltd. Agent de lutte contre des organismes nuisibles
EP2634174A2 (fr) 2012-02-29 2013-09-04 Meiji Seika Pharma Co., Ltd. Dérivé hétérocyclique contenant de l'azote ayant un groupe 2-imino et agent antiparasitaire comprenant celui-ci
WO2014006945A1 (fr) 2012-07-04 2014-01-09 アグロカネショウ株式会社 Dérivé d'ester d'acide 2-aminonicotinique et bactéricide le contenant comme principe actif
WO2014028669A1 (fr) 2012-08-15 2014-02-20 Biogen Idec Ma Inc. Nouveaux composés pour la modulation de l'activité ror-gamma
WO2014095675A1 (fr) 2012-12-19 2014-06-26 Bayer Cropscience Ag Utilisation de carboxamides difluorométhyl-nicotinique-indanyle comme fongicides
WO2016156290A1 (fr) 2015-04-02 2016-10-06 Bayer Cropscience Aktiengesellschaft Nouveaux dérivés d'imidazole à substitution en position 5
WO2016202742A1 (fr) 2015-06-15 2016-12-22 Bayer Cropscience Aktiengesellschaft Phénoxyphénylamidines à substitution halogène et utilisation de celles-ci en tant que fongicides
WO2017005673A1 (fr) 2015-07-06 2017-01-12 Bayer Cropscience Aktiengesellschaft Hétérocycles contenant de l'azote utiles en tant que pesticides
WO2017029179A1 (fr) 2015-08-14 2017-02-23 Bayer Cropscience Aktiengesellschaft Dérivés de triazole, leurs intermédiaires et leur utilisation comme fongicides
WO2017055469A1 (fr) 2015-10-02 2017-04-06 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017055473A1 (fr) 2015-10-02 2017-04-06 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017093348A1 (fr) 2015-12-02 2017-06-08 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017118689A1 (fr) 2016-01-08 2017-07-13 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2018153707A1 (fr) 2017-02-22 2018-08-30 Basf Se Formes cristallines d'un composé de type strobilurine pour lutter contre des champignons phytopathogènes

Patent Citations (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0451878A1 (fr) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modification de plantes par techniques de génie génétique pour combattre ou contrôler les insectes
US4803277A (en) 1986-09-10 1989-02-07 Nihon Tokushu Noyaku Seizo K.K. Novel heterocyclic compounds
EP0259738A2 (fr) 1986-09-10 1988-03-16 Nihon Tokushu Noyaku Seizo K.K. Composés hétérocycliques
EP0353191A2 (fr) 1988-07-29 1990-01-31 Ciba-Geigy Ag Séquences d'ADN codant des polypeptides avec activité béta-1,3-glucanase
EP0367474A1 (fr) 1988-11-01 1990-05-09 Mycogen Corporation Souche de bacillus thuringiensis appelée b.t. ps81gg, active contre les lépidoptères nuisibles et gène codant une toxine active contre les lépidoptères.
EP0374753A2 (fr) 1988-12-19 1990-06-27 American Cyanamid Company Toxines insecticides, gènes les codant, anticorps les liant, ainsi que cellules végétales et plantes transgéniques exprimant ces toxines
EP0392225A2 (fr) 1989-03-24 1990-10-17 Ciba-Geigy Ag Plantes transgéniques résistantes aux maladies
WO1990013651A1 (fr) 1989-05-09 1990-11-15 Imperial Chemical Industries Plc Genes bacteriens
EP0401979A2 (fr) 1989-05-18 1990-12-12 Mycogen Corporation Souches de bacillus thuringiensis actives contre les lépidoptères nuisibles, et gènes codant pour des toxines actives contre les lépidoptères
EP0427526A1 (fr) 1989-11-07 1991-05-15 Richter Gedeon Vegyeszeti Gyar R.T. Dérivés de la pyridine, procédé pour leur préparation et compositions pharmaceutiques les contenant
EP0427529A1 (fr) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Lectines larvicides, et résistance induite des plantes aux insectes
WO1993007278A1 (fr) 1991-10-04 1993-04-15 Ciba-Geigy Ag Sequence d'adn synthetique ayant une action insecticide accrue dans le mais
WO1995033818A2 (fr) 1994-06-08 1995-12-14 Ciba-Geigy Ag Genes pour la synthese des substances antipathogenes
WO1995034656A1 (fr) 1994-06-10 1995-12-21 Ciba-Geigy Ag Nouveaux genes du bacillus thuringiensis codant pour des toxines actives contre les lepidopteres
US5631072A (en) 1995-03-10 1997-05-20 Avondale Incorporated Method and means for increasing efficacy and wash durability of insecticide treated fabric
WO2002015701A2 (fr) 2000-08-25 2002-02-28 Syngenta Participations Ag Nouvelles toxines insecticides derivees de proteines cristallines insecticides de $i(bacillus thuringiensis)
WO2003000906A2 (fr) 2001-06-22 2003-01-03 Syngenta Participations Ag Genes de resistance aux maladies chez les plantes
WO2003018810A2 (fr) 2001-08-31 2003-03-06 Syngenta Participations Ag Toxines cry3a modifiees et sequences d'acides nucleiques les codant
WO2003034823A1 (fr) 2001-10-25 2003-05-01 Siamdutch Mosquito Netting Company Limited Traitement d'une matiere textile au moyen d'un insecticide
WO2003052073A2 (fr) 2001-12-17 2003-06-26 Syngenta Participations Ag Nouvel evenement du mais
WO2005064072A2 (fr) 2003-12-22 2005-07-14 Basf Aktiengesellschaft Composition destinee a l'impregnation de fibres, de tissus et de nappes de filet possedant une activite protectrice contre les parasites
WO2005113886A1 (fr) 2004-05-12 2005-12-01 Basf Aktiengesellschaft Procede de traitement de substrats flexibles
EP1724392A2 (fr) 2005-05-04 2006-11-22 Fritz Blanke Gmbh & Co. Kg Procédé d'apprêtage anti-microbien de surfaces textiles
WO2006128870A2 (fr) 2005-06-03 2006-12-07 Basf Aktiengesellschaft Composition pour impregnation de fibres, tissus et filets a action protectrice contre les ravageurs
WO2007090739A1 (fr) 2006-02-03 2007-08-16 Basf Se Procede de traitement de substrats
WO2008151984A1 (fr) 2007-06-12 2008-12-18 Basf Se Formulation aqueuse et processus d'imprégnation de matières non vivantes exerçant une action protectrice contre les parasites
WO2010111572A1 (fr) 2009-03-27 2010-09-30 Abbott Laboratories Composés utilisés en tant que ligands des récepteurs des cannabinoïdes
WO2011138281A2 (fr) 2010-05-06 2011-11-10 Bayer Cropscience Ag Procédé de production de dithiine-tétracarboxy-diimides
EP2628389A1 (fr) 2010-08-31 2013-08-21 Meiji Seika Pharma Co., Ltd. Agent de lutte contre des organismes nuisibles
EP2634174B1 (fr) * 2012-02-29 2017-05-17 Meiji Seika Pharma Co., Ltd. Dérivé hétérocyclique contenant de l'azote ayant un groupe 2-imino et agent antiparasitaire comprenant celui-ci
EP2634174A2 (fr) 2012-02-29 2013-09-04 Meiji Seika Pharma Co., Ltd. Dérivé hétérocyclique contenant de l'azote ayant un groupe 2-imino et agent antiparasitaire comprenant celui-ci
WO2014006945A1 (fr) 2012-07-04 2014-01-09 アグロカネショウ株式会社 Dérivé d'ester d'acide 2-aminonicotinique et bactéricide le contenant comme principe actif
WO2014028669A1 (fr) 2012-08-15 2014-02-20 Biogen Idec Ma Inc. Nouveaux composés pour la modulation de l'activité ror-gamma
WO2014095675A1 (fr) 2012-12-19 2014-06-26 Bayer Cropscience Ag Utilisation de carboxamides difluorométhyl-nicotinique-indanyle comme fongicides
WO2016156290A1 (fr) 2015-04-02 2016-10-06 Bayer Cropscience Aktiengesellschaft Nouveaux dérivés d'imidazole à substitution en position 5
WO2016202742A1 (fr) 2015-06-15 2016-12-22 Bayer Cropscience Aktiengesellschaft Phénoxyphénylamidines à substitution halogène et utilisation de celles-ci en tant que fongicides
WO2017005673A1 (fr) 2015-07-06 2017-01-12 Bayer Cropscience Aktiengesellschaft Hétérocycles contenant de l'azote utiles en tant que pesticides
WO2017029179A1 (fr) 2015-08-14 2017-02-23 Bayer Cropscience Aktiengesellschaft Dérivés de triazole, leurs intermédiaires et leur utilisation comme fongicides
WO2017055469A1 (fr) 2015-10-02 2017-04-06 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017055473A1 (fr) 2015-10-02 2017-04-06 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017093348A1 (fr) 2015-12-02 2017-06-08 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2017118689A1 (fr) 2016-01-08 2017-07-13 Syngenta Participations Ag Dérivés d'oxadiazole microbiocides
WO2018153707A1 (fr) 2017-02-22 2018-08-30 Basf Se Formes cristallines d'un composé de type strobilurine pour lutter contre des champignons phytopathogènes

Non-Patent Citations (31)

* Cited by examiner, † Cited by third party
Title
"Chemical Abstracts", Database accession no. 3878-19-1
"lnsect Nicotinic Acetylcholine Receptors", vol. 683, 2010, article "Advances in Experimental Medicine and Biology", pages: 75 - 83
"Manual on Development and Use of FAO and WHO Specifications for Pesticides", 2010, SOUTHERN ILLINOIS UNIVERSITY
"McCutcheon's Detergents and Emulsifiers Annual", 1981, MC PUBLISHING CORP.
"Organic Synthesis", 2005, article "Strategic Applications of Named Reactions", pages: 448
"Pesticide Biochemistry and Physiology", vol. 121, 2015, pages: 78 - 87
A. ALBINIS. PIETRA: "Heterocyclic N-oxides", 1991, CRC PRESS
A. WOOD, COMPENDIUM OF PESTICIDE COMMON NAMES, 1995
ANGEW. CHEM. INT. ED., vol. 43, 2004, pages 1132 - 1136
ARKIVOC, vol. 16, 2007, pages 73 - 82
BASS ET AL., BMC NEUROSCIENCE, vol. 12, 2011, pages 51
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 2249718-27-0
CHEMISCHE BERICHTE, vol. 116, pages 2668 - 2675
CHEMISTRY - A EUROPEAN JOURNAL, vol. 201218, no. 52, 2018, pages 13788 - 13791
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY, vol. 28, no. 7-8, 1993, pages 633 - 6
GORMAN ET AL., PEST MANAGEMENT SCIENCE, 2010, pages 1186 - 1190
HARROP, THOMAS WR ET AL., PEST MANAGEMENT SCIENCE, vol. 74, no. 6, 2018, pages 1297 - 1301
J. ORG. CHEM., vol. 70, 2005, pages 8601 - 8604
J. ORG. CHEM., vol. 74, 2009, pages 5599 - 5602
J.ORGMET. CHEM., vol. 576, 1999, pages 147 - 168
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY, vol. 65, no. 36, 2017, pages 7865 - 7873
JOURNAL OF ORGANIC CHEMISTRY, vol. 37, no. 19, 1972, pages 2969 - 79
JOURNAL OF ORGANIC CHEMISTRY, vol. 74, no. 14, 2009, pages 5075 - 5078
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 132, no. 33, 2010, pages 11592 - 11598
LAROCK, R. C., SYNTHETIC ORGANIC METHODOLOGY: COMPREHENSIVE ORGANIC TRANSFORMATIONS. A GUIDE TO FUNCTIONAL GROUP PREPARATIONS, 1989, pages 411
NAUENDENHOLM, ARCHIVES OF INSECT BIOCHEMISTRY AND PHYSIOLOGY, vol. 58, 2005, pages 200 - 215
ORGANIC & BIOMOLECULAR CHEMISTRY, vol. 10, no. 13, 2012, pages 2562 - 2568
ORGANIC LETTERS, vol. 16, no. 4, 2014, pages 1212 - 1215
RUSSIAN CHEMICAL BULLETIN, vol. 67, no. 1, 2018, pages 168 - 171
TETRAHEDRON, vol. 69, no. 16, 2013, pages 3415 - 3418
Y. ONOZAKI ET. AL.: "Flupyrimin: A Novel Insecticide Acting at the Nicotinoc Acetylcholine Receptors.", JOURNAL OF AGRICULTIRAL AND FOOD CHEMISTRY, vol. 65, 18 August 2017 (2017-08-18), pages 7865 - 7873, XP002790142, DOI: 10.1021/acs/jafc.7b02924 *

Similar Documents

Publication Publication Date Title
EP3867237B1 (fr) Composés azole-amide actifs sur le plan pesticide
EP3849312A2 (fr) Composés azole-amide à action pesticide
WO2021037614A1 (fr) Composés de pyrazine-amide à action pesticide
EP3849967A1 (fr) Composés azole-amide à action pesticide
EP3877380A1 (fr) Composés azole-amide à action pesticide
EP3947359A1 (fr) Composés de diazine-amide à action pesticide
WO2020169445A1 (fr) Composés azole-amide à action pesticide
AU2020272472A1 (en) Pesticidally active diazine-amide compounds
WO2020201079A1 (fr) Composés de diazine-amide à action pesticide
WO2020188027A1 (fr) Composés azole-amides à action pesticide
WO2021122645A1 (fr) Composés azole-amide à action pesticide
EP4069688A1 (fr) Composés aminés hétéroaromatiques bicycliques fusionnés à action pesticide
WO2021053161A1 (fr) Composés amines cycliques à action pesticide
WO2022053567A1 (fr) Dérivés hétérocycliques à action pesticide comprenant des substituants contenant du soufre
WO2022017975A1 (fr) Dérivés hétérocycliques à action pesticide comprenant des substituants contenant du soufre
EP4143177A1 (fr) Dérivés hétérocycliques à action pesticide comprenant des substituants contenant du soufre
WO2023148368A1 (fr) Dérivés hétérocycliques à activité pesticide comprenant des substituants contenant du soufre
WO2022013417A1 (fr) Dérivés hétérocycliques à action pesticide comprenant des substituants contenant du soufre
WO2021213929A1 (fr) Dérivés de 1,3-dihydro-2h-imidazo[4,5-c]pyridin-2-one substitués à action pesticide comprenant des substituants contenant du soufre
EP4103549A1 (fr) Composés d'amine cyclique à action pesticide
WO2020254530A1 (fr) Dérivés de 7-sulfonyl-n-(1,3,4-thiadiazol-2-yl)-quinoxaline-6-carboxamide et dérivés respectifs de -benzimidazole-5-, -imidazo[4,5-b]pyridine-5-, -3h-furo[3,2b]pyridine-5-, -quinoléine-2- et -naphtalène-2-carboxamide utilisés en tant que pesticides
WO2021144354A1 (fr) Composés hétéroaromatiques bicycliques à action pesticide
WO2020169526A1 (fr) Composés hétérocycliques de cyanamide à action pesticide
WO2022101265A1 (fr) Composés hétéroaromatiques bicycliques fusionnés à action pesticide
WO2021175822A1 (fr) Composés amides d'acide benzoïque substitués par amidine pesticides

Legal Events

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

Ref document number: 20708440

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20708440

Country of ref document: EP

Kind code of ref document: A1