Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
  • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
  • C07D495/04—Ortho-condensed systems
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
  • A01P5/00—Nematocides
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
  • A01P7/00—Arthropodicides
  • A01P7/02—Acaricides
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
  • A01P7/00—Arthropodicides
  • A01P7/04—Insecticides
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
  • A01P9/00—Molluscicides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
  • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
  • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur 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
  • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• • 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
  • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
  • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

• the present invention relates to pesticidally active, in particular insecticidally active heterocyclic derivatives containing sulfur substituents, to processes for their preparation, to compositions comprising those compounds, and to their use for controlling animal pests, including arthropods and in particular insects or representatives of the order Acarina.
• R2 is Ci-C6haloalkyl
• Q is a radical selected from the group consisting of formula Qa and Qb wherein the arrow denotes the point of attachment to the nitrogen atom of the bicyclic ring; and wherein A represents CH or N;
• X is S, SO, or S0 2 ;
• Ri is Ci-C 4 alkyl, or C3-C6cycloalkyl-Ci-C 4 alkyl;
• Qi is a five-membered aromatic ring system linked via a ring nitrogen atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, Ci- C 4 haloalkoxy, Ci-C 4 alkylsulfanyl, Ci-C 4 alkylsulfinyl and Ci-C 4 alkylsulfonyl; and said ring system contains 1 , 2 or 3 ring heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, where said ring system contains at least one ring nitrogen atom and may not contain more than one ring oxygen atom and may not contain more than one ring sulfur atom;
• R3 is hydrogen, halogen or Ci-C 4 alkyl; each R4 independently is hydrogen, Ci-C 4 alkyl or C3-C6cycloalkyl; and R5 is Ci-C6alkyl, Ci-C6haloalkyl or C3-C6cycloalkyl.
• the present invention also provides agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula I.
• Compounds of formula I which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as Ci-C 4 alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as Ci-C 4 alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by
• Compounds of formula I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
• the compounds of formula (I) according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable 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 the salt formation.
• substituents are indicated as being itself further substituted, this means that they carry one or more identical or different substituents, e.g. one to four substituents. Normally not more than three such optional substituents are present at the same time. Preferably not more than two such substituents are present at the same time (i.e. the group is substituted by one or two of the substituents indicated). Where the additional substituent group is a larger group, such as cycloalkyl or phenyl, it is most preferred that only one such optional substituent is present. Where a group is indicated as being substituted, e.g. alkyl, this includes those groups that are part of other groups, e.g. the alkyl in alkylthio.
• Ci-C n alkyl refers to a saturated straight-chain or branched hydrocarbon radical attached via any of the carbon atoms having 1 to n carbon atoms, for example, any one of the radicals methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-pentyl, 1 , 1-dimethylpropyl, 1 , 2-dimethylpropyl, 1- methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 , 1-dimethylbutyl, 1 ,2- dimethylbutyl, 1 , 3- dimethylbutyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbuty
• Ci-C n haloalkyl refers to a straight-chain or branched saturated alkyl radical attached via any of the carbon atoms having 1 to n carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these radicals may be replaced by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2- fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 2-chloro-2- fluoroethyl, 2-chloro-2, 2-difluoroethy
• Ci-C2-fluoroalkyl would refer to a Ci-C2-alkyl radical which carries 1 ,2, 3,4, or 5 fluorine atoms, for example, any one of difluoromethyl, trifluoromethyl, 1- fluoroethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1 ,1 , 2, 2-tetrafluoroethyl or penta- fluoroethyl.
• Ci-C n alkoxy refers to a straight-chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above) which is attached via an oxygen atom, i.e., for example, any one of methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2- methylpropoxy or 1 , 1-dimethylethoxy.
• Ci-C n haloalkoxy refers to a Ci-C n alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2- fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2, 2-difluoroethoxy, 2,2, 2- trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2, 2-difluoroethoxy, 2, 2-dichloro-2-fluoroethoxy, 2,2, 2-trichloroethoxy, pentafluorine, chlorine, bromine and/
• Ci-C n -alkylsulfanyl refers to a straight chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above) which is attached via a sulfur atom, i.e., for example, any one of methylthio, ethylthio, n-propylthio, 1-methylethylthio, butylthio, 1- methylpropylthio, 2- methylpropylthio or 1 , 1-dimethylethylthio.
• Ci-C n alkylsulfinyl refers to a straight chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above) which is attached via the sulfur atom of the sulfinyl group, i.e., for example, any one of methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1- methylethyl-sulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, 1 , 1-dimethyl- ethylsulfinyl, n-pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methyl- butylsulfinyl, 1 , 1-dimethylpropylsulf
• Ci-C n alkylsulfonyl refers to a straight chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above) which is attached via the sulfur atom of the sulfonyl group, i.e., for example, any one of methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl ort-butylsulphonyl.
• Ci-C n cyanoalkyl refers to a straight chain or branched saturated alkyl radicals having 1 to n carbon atoms (as mentioned above) which is substituted by a cyano group, for example cyanomethylene, cyanoethylene, 1 ,1-dimethylcyanomethyl, cyanomethyl, cyanoethyl, and 1-dimethylcyanomethyl.
• C3-C n cycloalkyl refers to a straight chain or branched saturated alkyl radicals which is substituted by C3-Cncycloalkyl.
• An example of C3-C n cycloalkyl-Ci-C n alkyl is for example, cyclopropylmethyl.
• -Ci-C n alkoxy after terms such as “C3-C m cyanocycloalkyl”, wherein n is an integer from 1-4 and m is an integer from 3-6, as used herein refers to a a straight-chain or branched saturated alkoxy radicals which is substituted by C3-C m cyanocycloalkyl.
• An example of C3-C6cyanocycloalkyl-Ci-C 4 alkoxy is for example, (l-cyanocyclopropyl)methoxy.
• Ci-C n alkoxy refers to a straight-chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above) which is attached via an oxygen atom, i.e., for example, any one of methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2- methylpropoxy or 1 , 1-dimethylethoxy.
• C3-C6cycloalkyl refers to 3-6 membered cycloylkyl groups such as cyclopropane, cyclobutane, cyclopropane, cyclopentane and cyclohexane.
• Halogen is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl.
• “mono- or polysubstituted” in the definition of the Qi substituents means typically, depending on the chemical structure of the substituents, monosubstituted to five- times substituted, more preferably mono-, double- or triple-substituted.
• examples of “Qi is a five- to six-membered aromatic ring system, linked via a ring carbon atom to the ring which contains the substituent A, ... ; and said ring system can contain 1 , 2 or 3 ring heteroatoms ... ” are, but not limited to, phenyl, pyrazolyl, triazolyl, pyridinyl and pyrimidinyl; preferably phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrimidin-2-yl, pyrimidin-4-yl, and pyrimidin-5-yl.
• examples of “Qi is a five-membered aromatic ring system linked via a ring nitrogen atom to the ring which contains the substituent A, ... ; and said ring system contains 1 , 2 or 3 ring heteroatoms ... ” are, but not limited to, pyrazolyl, pyrrolyl, imidazolyl and triazolyl; preferably pyrrol-1 -yl, pyrazol-1-yl, triazol-2-yl, 1 ,2,4-triazol-1-yl, triazol-1-yl, and imidazol-1-yl.
• Embodiment 1 provides compounds of formula I, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined above.
• Embodiment 2 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to embodiment 1 wherein Q is Qa and preferred values of R2, A, X, Ri, Qi, R3, R 4 and Rs are, in any combination thereof, as set out below:
• R2 is Ci-C 4 haloalkyl
• R2 is Ci-C2haloalkyl
• R2 is CF2CF3 or CF3;
• A is N or CH
• A is N;
• X is S or SO2
• X is SO2
• Ri is Ci-C 4 alkyl or cyclopropyl-Ci-C 4 alkyl
• Ri is ethyl or cyclopropylmethyl
• Ri is ethyl
• Qi is hydrogen, Ci-C6haloalkyl, C3-C6cycloalkyl, C3-C6cycloalkyl monosubstituted by cyano, Ci-C6cyanoalkyl, Ci-C6cyanoalkoxy, C3-C6cyanocycloalkyl-Ci-C 4 alkoxy, Ci-C6haloalkoxy, - N(R 4 )COR5, (oxazolidin-2-one)-3-yl or 2-pyridyloxy;
• Qi is a five- to six-membered aromatic ring system linked via a ring carbon atom to the ring which contains the substituent A, said ring system is unsubstitued or is monosubstituted by substituents selected from the group consisting of halogen and Ci-C 4 haloalkyl; and said ring system can contain 1 or 2 ring nitrogen atoms;
• Qi is a five-membered aromatic ring system linked via a ring nitrogen atom to the ring which contains the substituent A, said ring system is unsubstitued or is mono-substituted by substituents selected from the group consisting of halogen and Ci-C 4 haloalkyl; and said ring system contains 2 or 3 ring nitrogen atoms.
• Qi is hydrogen, trifluoromethyl, difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, cyanoisopropoxy, cyanocyclopropylmethoxy, trifluoroethoxy, difluoropropoxy, (oxazolidin-2-one)-3-yl, 2-pyridyloxy, N-linked pyrazolyl which can be mono-substituted by chloro or trifluoromethyl, N-linked triazolyl, C-linked pyrimidinyl, or -N(R4)CORs, in which R4 is independently either hydrogen or methyl and R5 is either methyl, ethyl or cyclopropyl;
• Qi is hydrogen, trifluoromethyl, 1 , 1 -difluoroethyl, cyclopropyl, 1-cyanocyclopropyl, 1- cyano-1 -methyl-ethyl, 1 -cyano-1 -methyl-ethoxy, (1 -cyanocyclopropyl)methoxy, 2,2,2-trifluoroethoxy, 2,2-difluoropropoxy, -N(CH3)COCH3, -N(CH3)CO(cyclopropyl), (oxazolidin-2-one)-3-yl, 2-pyridyloxy, 3- chloro-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, 1 ,2,4-triazol-1-yl or pyrimidin-2-yl;
• each R4 independently is hydrogen or Ci-C4alkyl
• each R4 independently is hydrogen or methyl
• each R4 is methyl
• Rs is Ci-C6alkyl or C3-C6cycloalkyl
• Rs is methyl, ethyl or cyclopropyl
• R3 is hydrogen or Ci-C4alkyl
• R3 is hydrogen or methyl; and Most preferably R3 is hydrogen.
• Embodiment 3 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to embodiment 1 wherein Q is Qb and preferred values of R2, Ri, X, Qi, A, R4, Rs and R3 are, in any combination thereof, as set out below:
• R2 is Ci-C4haloalkyl
• R2 is Ci-C2haloalkyl
• R2 is CF2CF3 or CF3;
• A is N or CH
• A is N;
• X is S or SO2
• X is SO2
• Ri is Ci-C 4 alkyl or cyclopropyl-Ci-C 4 alkyl
• Ri is ethyl or cyclopropylmethyl
• Ri is ethyl
• Qi is C3-C6cycloalkyl, -N(R 4 )CORs, or (oxazolidin-2-one)-3-yl;
• Qi is a five- to six-membered aromatic ring system linked via a ring carbon atom to the ring which contains the substituent A, said ring system is unsubstitued or is mono- substituted by substituents selected from the group consisting of halogen and Ci-C 4 haloalkyl; and said ring system can contain 1 or 2 ring nitrogen atoms;
• Qi is a five-membered aromatic ring system linked via a ring nitrogen atom to the ring which contains the substituent A, said ring system is unsubstitued or is mono-substituted by substituents selected from the group consisting of halogen and Ci-C 4 haloalkyl; and said ring system contains 2 or 3 ring nitrogen atoms.
• Qi is cyclopropyl, (oxazolidin-2-one)-3-yl, N-linked pyrazolyl which can be mono- substituted by chloro or trifluoromethyl, N-linked triazolyl, C-linked pyrimidinyl, or -N(R4)CORs, in which R4 is independently either hydrogen or methyl and R5 is either methyl, ethyl or cyclopropyl;
• Qi is cyclopropyl, -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), (oxazolidin-2-one)-3-yl, 3-chloro-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, 1 ,2,4-triazol-1-yl or pyrimidin-2-yl;
• each R4 independently is hydrogen or Ci-C4alkyl
• each R4 independently is hydrogen or methyl
• each R4 is methyl
• Rs is Ci-C6alkyl or C3-C6cycloalkyl
• Rs is methyl, ethyl or cyclopropyl
• R3 is hydrogen or Ci-C4alkyl
• R3 is hydrogen or methyl; and Most preferably R3 is hydrogen.
• a preferred group of compounds of formula I is represented by the compounds of formula 1-1 A
• A is CH or N
• Ri is Ci-C 4 alkyl or cyclopropyl-Ci-C 4 alkyl
• R2 is Ci-C2haloalkyl
• R3 is hydrogen or Ci-C 4 alkyl
• X is S or SO2
• Qi is hydrogen, Ci-C6haloalkyl, C3-C6cycloalkyl, C3-C6cycloalkyl monosubstituted by cyano, Ci-C6cyanoalkyl, Ci-C6cyanoalkoxy, C3-C6cyanocycloalkyl-Ci-C 4 alkoxy, Ci-C6haloalkoxy, - N(R4)COR5, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; in which each R4 independently is hydrogen or Ci- C 4 alkyl; and Rs is Ci-C6alkyl or C3-C6cycloalkyl.
• A is CH or N
• Ri is ethyl or cyclopropylmethyl
• R2 is CF2CF3 or CF3;
• R3 is hydrogen or methyl
• X is S or SO2
• Qi is hydrogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1 -methyl- ethyl, 1-cyano-1 -methyl-ethoxy, (l-cyanocyclopropyl)methoxy, 2,2,2-trifluoroethoxy, 2,2- difluoropropoxy, -N(CH3)COCH3, -N(CH3)CO(cyclopropyl), (oxazolidin-2-one)-3-yl, or 2-pyridyloxy.
• Qi is a five- to six-membered aromatic ring system linked via a ring carbon atom to the ring which contains the substituent A, said ring system is unsubstitued or is mono-substituted by substituents selected from the group consisting of halogen and Ci-C 4 haloalkyl; and said ring system can contain 1 or 2 ring nitrogen atoms.
• Qi is C-linked pyrimidinyl.
• Also preferred compounds of formula 1-1 A are those wherein Qi is a five-membered aromatic ring system linked via a ring nitrogen atom to the ring which contains the substituent A, said ring system is unsubstitued or is mono-substituted by substituents selected from the group consisting of halogen and Ci-C 4 haloalkyl; and said ring system contains 2 or 3 ring nitrogen atoms.
• Qi is N-linked pyrazolyl which can be mono-substituted by chloro or trifluoromethyl; or Qi is N-linked triazolyl.
• A is CH or N
• Ri is ethyl or cyclopropylmethyl
• R2 is CF2CF3 or CF3;
• R3 is hydrogen or methyl
• X is S or SO2
• Qi is 3-chloro-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, 1 ,2,4-triazol-1-yl or pyrimidin-2-yl.
• A, Ri, R 2 , R3, X, Qi, R 4 and Rs are as defined under formula I above; preferably A is CH or N, most preferably A is N; preferably Ri is ethyl or cyclopropylmethyl; most preferably Ri is ethyl; preferably R2 is Ci-C2haloalkyl; most preferably R2 is CF2CF3 or CF3; preferably X is S or SO2; most preferably X is SO2; preferably R3 is hydrogen; preferably Qi is hydrogen, trifluoromethyl, difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, cyanoisopropoxy, cyanocyclopropylmethoxy, trifluoroethoxy, difluoropropoxy, (oxazolidin-2-one)-3-yl,
• One further preferred group of compounds according to this embodiment are compounds of formula (I- 1A-1) which are compounds of formula (1-1 A) wherein preferably A is N; preferably Ri is Ci-C2alkyl; most preferably Ri is ethyl; preferably R2 is Ci-C2fluoroalkyl; most preferably R2 is CF2CF3 or CF3; preferably X is S or SO 2 ; most preferably X is SO 2 ; preferably R3 is hydrogen; preferably Qi is hydrogen, trifluoromethyl, cyclopropyl, difluoroethyl, cyanocyclopropyl, cyanoisopropyl, cyanoisopropoxy, cyanocyclopropylmethoxy, trifluoroethoxy, difluoropropoxy, (oxazolidin-2-one)-3-yl, 2-pyridyloxy, N-linked pyrazolyl which can be mono-substituted by chloro or trifluoromethyl,
• One further preferred group of compounds according to this embodiment are compounds of formula (I-
• One further preferred group of compounds according to this embodiment are compounds of formula (I- 1A-3) which are compounds of formula (1-1 A-2) wherein preferably A is CH.
• A is CH or N
• Ri is Ci-C 4 alkyl or cyclopropyl-Ci-C 4 alkyl
• R2 is Ci-C2haloalkyl
• R3 is hydrogen or Ci-C 4 alkyl
• X is S or SO2
• Qi is C3-C6cycloalkyl, -N(R 4 )CORs, or (oxazolidin-2-one)-3-yl; in which each R4 independently is hydrogen or Ci-C 4 alkyl; and Rs is Ci-C6alkyl or C3-C6cycloalkyl.
• A is CH or N
• Ri is ethyl or cyclopropylmethyl
• R2 is CF2CF3 or CF3;
• R3 is hydrogen or methyl
• X is S or SO2
• Qi is cyclopropyl, -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), or (oxazolidin-2-one)- 3-yl.
• Qi is a five- to six-membered aromatic ring system linked via a ring carbon atom to the ring which contains the substituent A, said ring system is unsubstitued or is mono-substituted by substituents selected from the group consisting of halogen and Ci-C 4 haloalkyl; and said ring system can contain 1 or 2 ring nitrogen atoms.
• Qi is C-linked pyrimidinyl.
• Also preferred compounds of formula I-2A are those wherein Qi is a five-membered aromatic ring system linked via a ring nitrogen atom to the ring which contains the substituent A, said ring system is unsubstitued or is mono-substituted by substituents selected from the group consisting of halogen and Ci-C 4 haloalkyl; and said ring system contains 2 or 3 ring nitrogen atoms.
• Qi is N-linked pyrazolyl which can be mono-substituted by chloro or trifluoromethyl; or Qi is N-linked triazolyl.
• A is CH or N
• Ri is ethyl or cyclopropylmethyl
• R2 is CF2CF3 or CF3;
• R3 is hydrogen or methyl
• X is S or SO2
• Qi is 3-chloro-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, 1 ,2,4-triazol-1-yl or pyrimidin-2-yl.
• A, Ri, R 2 , R3, X, Qi, R 4 and Rs are as defined under formula I above; preferably A is CH or N, more preferably A is N; preferably Ri is ethyl or cyclopropylmethyl; most preferably Ri is ethyl; preferably R 2 is Ci-C 2 haloalkyl; most preferably R 2 is CF 2 CF3 or CF3; preferably X is S or SO2; most preferably X is SO2; preferably R3 is hydrogen; preferably Qi is cyclopropyl, (oxazolidin-2-one)-3-yl, N-linked pyrazolyl which can be mono-substituted by chloro or trifluoromethyl, N-linked triazolyl, C-linked pyrimidinyl, or -N(R4)CORs, in which R4 is independently either hydrogen or methyl
• One further preferred group of compounds according to this embodiment are compounds of formula (I- 2A-1) which are compounds of formula (I-2A) wherein preferably A is N; preferably Ri is Ci-C2alkyl; most preferably Ri is ethyl; preferably R 2 is Ci-C 2 fluoroalkyl; most preferably R 2 is CF 2 CF3 or CF3; preferably X is S or SO2; most preferably X is SO2; preferably R3 is hydrogen; preferably Qi is cyclopropyl, (oxazolidin-2-one)-3-yl, N-linked pyrazolyl which can be mono-substituted by chloro or trifluoromethyl, N-linked triazolyl, C-linked pyrimidinyl, or -N(R4)CORs, in which R4 is independently either hydrogen or methyl and Rs is either methyl, ethyl or cyclopropyl; more preferably Qi is cyclopropyl, -N(CH
• One further preferred group of compounds according to this embodiment are compounds of formula (I- 2A-3) which are compounds of formula (I-2A-2) wherein preferably A is CH.
• R2 is Ci-C4haloalkyl, preferably CF3 or CF2CF3;
• Q’ is a radical selected from the group consisting of formula Qa1 and Qb1 wherein the arrow denotes the point of attachment to the nitrogen atom of the bicyclic ring; and wherein
• X is S, SO, or SO2, preferably S or SO2, even more preferably SO2;
• Ri is Ci-C 4 alkyl, preferably ethyl
• Qi is hydrogen, Ci-C6haloalkyl, C3-C6cycloalkyl, C3-C6cycloalkyl monosubstituted by cyano, Ci-C6cyanoalkyl, Ci-C6cyanoalkoxy, C3-C6cyanocycloalkyl-Ci-C 4 alkoxy, Ci-C6haloalkoxy, - N(R 4 )COR5, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; preferably Qi is hydrogen, trifluoromethyl, 1 , 1 -difluoroethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano- 1 -methyl-ethyl, 1-cyano-1 -methyl-ethoxy, (l-cyanocyclopropyl)methoxy, 2,2,2-trifluoroethoxy, 2,2- difluoropropoxy, -N(OH 3 )OOOH 3 , -
• Qi is unsubstituted pyrimidinyl, preferably pyrimidin-2-yl; or
• Qi is unsubstituted N-linked triazolyl, preferably 1 ,2,4-triazol-1-yl; or
• Qi is N-linked pyrazolyl which can be mono-substituted by chloro or trifluoromethyl; preferably Qi is 3- chloro-pyrazol-1-yl or 3-trifluoromethyl-pyrazol-1-yl;
• R4 is Ci-C 4 alkyl, preferably methyl; and R5 is Ci-C6alkyl or C3-C6cycloalkyl, preferably methyl, ethyl or cyclopropyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I-3A.
• One further outstanding group of compounds according to this embodiment are compounds of formula (I-3A-1) which are compounds of formula (I-3A) wherein R2 is Ci-C2fluoroalkyl, preferably CF3 or CF2CF3;
• Q’ is a radical selected from the group consisting of formula Qa1 and Qb1 , wherein X is SO2;
• Ri is Ci-C2alkyl, preferably ethyl
• Qi is hydrogen, Ci-C6haloalkyl, C3-C6cycloalkyl, C3-C6cycloalkyl monosubstituted by cyano, Ci-C6cyanoalkyl, Ci-C6cyanoalkoxy, C3-C6cyanocycloalkyl-Ci-C 4 alkoxy, Ci-C6haloalkoxy, - N(R 4 )COR5, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; preferably Qi is hydrogen, trifluoromethyl, 1 , 1 -difluoroethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano- 1 -methyl-ethyl, 1-cyano-1 -methyl-ethoxy, (l-cyanocyclopropyl)methoxy, 2,2,2-trifluoroethoxy, 2,2- difluoropropoxy, -N(CH 3 )COCH 3 , -
• Qi is unsubstituted pyrimidinyl, preferably pyrimidin-2-yl; or
• Qi is unsubstituted N-linked triazolyl, preferably 1 ,2,4-triazol-1-yl; or
• Qi is N-linked pyrazolyl which can be mono-substituted by chloro or trifluoromethyl; preferably Qi is 3- chloro-pyrazol-1-yl or 3-trifluoromethyl-pyrazol-1-yl;
• R4 is Ci-C 4 alkyl, preferably methyl
• R5 is Ci-C6alkyl or C3-C6cycloalkyl, preferably methyl, ethyl or cyclopropyl.
• Q’ is a radical selected from the group consisting of formula Qa1 and Qb1 , wherein X is SO2;
• Ri is ethyl
• Qi is hydrogen, trifluoromethyl, 1 ,1 -difluoroethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1 -methyl- ethyl, 1-cyano-1 -methyl-ethoxy, (l-cyanocyclopropyl)methoxy, 2,2,2-trifluoroethoxy, 2,2- difluoropropoxy, -N(CH 3 )COCH 3 , -N(CH 3 )COCH 2 CH3, -N(CH 3 )CO(cyclopropyl), (oxazolidin-2-one)-3- yl, 2-pyridyloxy, 3-chloro-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, 1 ,2,4-triazol-1-yl or pyrimidin-2-yl.
• R2 is Ci-C4haloalkyl, preferably CF3 or CF2CF3;
• Q is a radical selected from the group consisting of formula Qa2 and Qb2 wherein the arrow denotes the point of attachment to the nitrogen atom of the bicyclic ring; and wherein
• Qi is hydrogen, Ci-C6haloalkyl, C3-C6cycloalkyl, C3-C6cycloalkyl monosubstituted by cyano, Ci-C6cyanoalkyl, Ci-C6cyanoalkoxy, C3-C6cyanocycloalkyl-Ci-C 4 alkoxy, Ci-C6haloalkoxy, - N(R 4 )COR5, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; preferably Qi is hydrogen, trifluoromethyl, 1 , 1 -difluoroethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano- 1 -methyl-ethyl, 1-cyano-1 -methyl-ethoxy, (l-cyanocyclopropyl)methoxy, 2,2,2-trifluoroethoxy, 2,2- difluoropropoxy, -N(CH 3 )COCH 3 , -
• Qi is unsubstituted pyrimidinyl, preferably pyrimidin-2-yl; or
• Qi is unsubstituted N-linked triazolyl, preferably 1 ,2,4-triazol-1-yl; or
• Qi is N-linked pyrazolyl which can be mono-substituted by chloro or trifluoromethyl; preferably Qi is 3- chloro-pyrazol-1-yl or 3-trifluoromethyl-pyrazol-1-yl;
• R4 is Ci-C 4 alkyl, preferably methyl
• R5 is Ci-C6alkyl or C3-C6cycloalkyl, preferably methyl, ethyl or cyclopropyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I-4A.
• One further outstanding group of compounds according to this embodiment are compounds of formula (I-4A-1) which are compounds of formula (I-4A) wherein R2 is Ci-C2fluoroalkyl, preferably CF3 or CF2CF3.
• Q is a radical selected from the group consisting of formula Qa2 and Qb2, wherein Qi is hydrogen, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1 -methyl-ethyl, 1-cyano-1 -methyl-ethoxy, (1- cyanocyclopropyl)methoxy, -N(CH3)COCH3, 2-pyridyloxy, 3-chloro-pyrazol-1-yl, 1 ,2,4-triazol-1-yl or pyrimidin-2-yl.
• One further outstanding group of compounds according to this embodiment are compounds of formula (I-4A-3) which are compounds of formula (I-4A-1) wherein Q” is a radical selected from the group consisting of formula Qa2 and Qb2, wherein Qi is hydrogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1 -methyl- ethyl, 1-cyano-1 -methyl-ethoxy, 2,2,2-trifluoroethoxy, 2,2-difluoropropoxy, -N(CH3)COCH3, 1 ,2,4- triazol-1-yl or pyrimidin-2-yl.
• Compounds according to the invention 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, improved physico-chemical properties, or increased biodegradability or environmental profile).
• 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, improved physico-chemical properties, or increased biodegradability or environmental profile.
• certain compounds of formula (I) may show an advantageous safety profile with respect to non-target arthropods, in particular pollinators such as honey bees, solitary bees, and bumble bees.
• Apis mellifera is particularly, bumble bees.
• the present invention provides a composition
• a composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in any of the embodiments under compounds of formula (1-1 A), (1-1 A-1), (1-1 A-2), (1-1 A-3), (I-2A), (I-2A- 1), (I-2A-2), (I-2A-3), (I-3A), (I-3A-1), (I-3A-2), (I-4A), (I-4A-1), (I-4A-2), and (I-4A-3) and, optionally, an auxiliary or diluent.
• the present invention provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in any of the embodiments under compounds of formula (I- 1 A), (1-1 A-1), (1-1 A-2), (1-1 A-3), (I-2A), (I-2A-1), (I-2A-2), (I-2A-3), (I-3A), (I-3A-1), (I-3A-2), (I-4A), (I-4A- 1), (I-4A-2), and (I-4A-3) (above) or a composition as defined above.
• the present invention provides a method for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the propagation material or the site, where the propagation material is planted, with a composition as defined above.
• reaction can be performed with reagents such as a peracid, for example peracetic acid or m-chloroperbenzoic acid, or a hydroperoxide, as for example, hydrogen peroxide ortert-butylhydroperoxide, or an inorganic oxidant, such as a monoperoxo-disulfate salt or potassium permanganate.
• reagents such as a peracid, for example peracetic acid or m-chloroperbenzoic acid, or a hydroperoxide, as for example, hydrogen peroxide ortert-butylhydroperoxide, or an inorganic oxidant, such as a monoperoxo-disulfate salt or potassium permanganate.
• a peracid for example peracetic acid or m-chloroperbenzoic acid
• hydroperoxide as for example, hydrogen peroxide ortert-butylhydroperoxide
• an inorganic oxidant such as a mono
• compounds of formula l-a3, wherein X is SO2 and A, Ri, R2, R3, and Qi are defined as under formula I above can be prepared by oxidation of compounds of formula l-a1 , wherein X is S and A, Ri, R2, R3, and Qi are defined as under formula I above, under analogous conditions described above. These reactions can be performed in various organic or aqueous solvents compatible to these conditions, by temperatures from below 0°C up to the boiling point of the solvent system.
• the transformation of compounds of the formula l-a1 into compounds of the formula l-a2 and l-a3 is represented in Scheme 1.
• Scheme 1 Compounds of formula l-aa2 and l-aa3 (scheme 2), wherein X is SO and SO2 respectively, and A, Ri, R2, R3, and Qi are defined as under formula I above, may be prepared by analogous procedure as described in scheme 1 for the synthesis of compounds of formula l-a2 and l-a3.
• Scheme 2 Compounds of formula I wherein R2 and Q are defined as under formula I above, Scheme 3: may be prepared (scheme 3) by reacting compounds of formula VI, wherein F3 ⁇ 4 is as defined in formula I above, with compounds of formula VII, wherein Q is as defined in formula I above and in which LG3 is a halogen (or a pseudo-halogen leaving group, such as a triflate), in the presence of a base, such as sodium carbonate, potassium carbonate or cesium carbonate, or sodium hydride, in an appropriate solvent such as for example tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N- dimethylacetamide or acetonitrile, at temperatures between 0 and 150°C, optionally under microwave irradiation.
• a base such as sodium carbonate, potassium carbonate or cesium carbonate, or sodium hydride
• an appropriate solvent such as for example tetrahydrofuran, dioxane, N,N-d
• compounds of formula I wherein R2 and Q are defined as under formula I above may be prepared by reacting compounds of formula VI, wherein R2 is as defined in formula I above, with compounds of formula VII, wherein Q is as defined in formula I above and in which LG3 is a halogen, preferably bromo or iodo (or a pseudo-halogen leaving group, such as a triflate), in the presence of a base, such as sodium carbonate, potassium carbonate or cesium carbonate, or potassium fe/f-butoxide, in the presence of a metal catalyst, either a copper catalyst, for example copper(l) iodide, optionally in the presence of a ligand, for example diamine ligands (e.g.
• compounds of formula I wherein F3 ⁇ 4 and Q are defined as under formula I above may be prepared by reacting compounds of formula III, wherein F3 ⁇ 4 is as defined in formula I above and LG2 is a leaving group, for example Br, Cl or I, preferably bromo, and R is Ci-C6alkyl, benzyl or a phenyl group, with compounds of formula IV, wherein Q is as defined in formula I above, in the presence of a base such as sodium carbonate, potassium carbonate or cesium carbonate, sodium hydride, N,N- diisopropylethylamine or KOtBu, and in the presence of a solvent such as ethanol, methanol, dioxane, toluene, acetonitrile, DMF, DMA, DMSO, or THF, at temperatures between 0 and 150°C, optionally under microwave irradiation.
• a base such as sodium carbonate, potassium carbonate or cesium carbonate
• sodium hydride sodium hydride
• compounds of formula I wherein R2 and Q are defined as under formula I above can be prepared by cyclizing compounds of formula V, wherein R2 and Q are as defined in formula I, for example in the presence of phosphorus oxychloride (other amide coupling reagent may also be used, such as thionyl chloride SOCI2, HATU or EDCI), optionally in the presence of a base, such as triethylamine, pyridine or Hiinig’s base, optionally in the presence of a solvent or diluent, such as toluene or xylene, at temperatures between 0 and 180°C, preferably between 20 and 120°C.
• phosphorus oxychloride other amide coupling reagent may also be used, such as thionyl chloride SOCI2, HATU or EDCI
• Compounds of formula Va wherein R2 and Q are defined as under formula I above, and in which Xo is halogen, preferably chlorine, orXo is either X01 or Xo2, can be prepared by activation of compound of formula V, wherein R2 and Q are defined as under formula I above, by methods known to those skilled in the art and described in, for example, Tetrahedron, 2005, 61 (46), 10827-10852. Preferred is the formation of an activated species Va, wherein F3 ⁇ 4 and Q are defined as under formula I above, and in which Xo is halogen, preferably chlorine.
• compounds Va where Xo is halogen, preferably chlorine, are formed by treatment of V with, for example, oxalyl chloride (COCI)2 orthionyl chloride SOCI2 in the presence of catalytic quantities of N,N-dimethylformamide DMF in inert solvents such as methylene chloride CH2CI2 or tetrahydrofuran THF at temperatures between 20 to 100°C, preferably 25°C.
• COCI oxalyl chloride
• SOCI2 thionyl chloride
• Compounds of formula VI, wherein R2 is as defined in formula I above, can be prepared (scheme 3) by reacting compounds of formula III, wherein R2 is as defined in formula I above and LG2 is a leaving group, for example Br, Cl or I, preferably bromo, and R is Ci-C6alkyl, benzyl or a phenyl group, with ammonia or surrogates of ammonia, for example NH4OH, in the presence of a solvent such as ethanol, methanol, dioxane, toluene, DMF, DMA, DMSO, or THF, at temperatures between 0 and 150°C, optionally under microwave irradiation.
• a solvent such as ethanol, methanol, dioxane, toluene, DMF, DMA, DMSO, or THF
• R2 and Q are defined as under formula I above, and in which R is Ci-C6alkyl, benzyl or a phenyl group.
• the in situ generated unhydrolyzed ester compound of formula Ilia may be isolated and can also be converted via a saponification reaction into the carboxylic acid of formula V, under conditions known to a person skilled in the art, for example in the presence of suitable base, such as sodium hydroxide NaOH, lithium hydroxide LiOH, or barium hydroxide Ba(OH)2 (optionally in form of a hydrate), in the presence of a solvent such as ethanol, methanol, dioxane, tetrahydrofuran or water (or mixtures thereof).
• suitable base such as sodium hydroxide NaOH, lithium hydroxide LiOH, or barium hydroxide Ba(OH)2 (optionally in form of a hydrate
• a solvent such as ethanol, methanol, dioxane, tetrahydrofuran or water (or mixtures thereof).
• Krapcho-type conditions e.g.
• heating the substrate Ilia in the presence of sodium or lithium chloride in N-methyl pyrrolidone or aqueous dimethylsulfoxide DMSO, optionally under microwave irradiation) can also be used to convert compounds of formula Ilia into compounds of formula V.
• the direct conversion of compound of formula III to compound of formula Ilia can be carried out in the presence of base, such as sodium hydride, KOtBu, butyllithium, or lithium diisopropylamide amongst others, and in the presence of a solvent, such as dioxane, DMF, DMA, DMSO, orTHF, at temperatures between -30 and 150°C.
• reaction for the preparation of compounds of formula V can also be carried out by reacting compounds of formula III, with compounds of formula IVa, wherein Q is as defined in formula I above, and PG is an amino protecting group, for example tert-butyloxycarbonyl (BOC), under similar conditions as described above (as for the preparation of compounds of formula V by reacting compounds of formula III and compounds of formula IV), followed by deprotection of the amino protecting group PG.
• Q is as defined in formula I above
• PG is an amino protecting group, for example tert-butyloxycarbonyl (BOC)
• BOC protecting groups can be removed in the presence of acids, such as hydrochloric acid, or trifluoroacetic acid, optionally in the presence of an inert solvent, such as dichloromethane, tetrahydrofuran, dioxane or benzotrifluoride, at temperatures between 0 and 70°C.
• acids such as hydrochloric acid, or trifluoroacetic acid
• an inert solvent such as dichloromethane, tetrahydrofuran, dioxane or benzotrifluoride
• Compounds of formula III and compounds of formula XXI react to compounds of formula lllc, in the presence of a base, such as sodium carbonate, potassium carbonate or cesium carbonate, or sodium hydride, or N,N-diisopropylethylamine or potassium fe/f-butoxide KOtBu, in the presence of a solvent such as ethanol, methanol, dioxane, toluene, acetonitrile, DMF, N,N-dimethylacetamide DMA, DMSO, or THF, at temperatures between 0 and 150°C, optionally under microwave irradiation.
• a base such as sodium carbonate, potassium carbonate or cesium carbonate, or sodium hydride, or N,N-diisopropylethylamine or potassium fe/f-butoxide KOtBu
• a solvent such as ethanol, methanol, dioxane, toluene, acetonitrile,
• tert-Butyloxycarbonyl (BOC) group removal in compounds of formula lllc mediated by acids, such as hydrochloric acid, or trifluoroacetic acid, optionally in the presence of an inert solvent, such as dichloromethane, tetrahydrofuran, dioxane or benzotrifluoride, at temperatures between 0 and 70°C, generates compounds of formula Ilia.
• acids such as hydrochloric acid, or trifluoroacetic acid
• an inert solvent such as dichloromethane, tetrahydrofuran, dioxane or benzotrifluoride
• Saponification of compounds of formula Ilia in the presence of a suitable base for example sodium hydroxide NaOH, lithium hydroxide LiOH or barium hydroxide Ba(OH)2, in the presence of a solvent such as ethanol, methanol, dioxane, tetrahydrofuran or water (or mixtures thereof), forms the carboxylic acids of formula V (alternatively, Krapcho-type conditions as described above may be used).
• a suitable base for example sodium hydroxide NaOH, lithium hydroxide LiOH or barium hydroxide Ba(OH)2
• a solvent such as ethanol, methanol, dioxane, tetrahydrofuran or water (or mixtures thereof
• Cyclization of compounds of formula V to compounds of formula I is achieved, for example, in the presence of phosphorus oxychloride (other amide coupling reagent may also be used, such as thionyl chloride SOCI2, HATU or EDCI), optionally in the presence of a base, such as triethylamine, pyridine or Hiinig’s base, optionally in the presence of a solvent or diluent, such as toluene or xylene, at temperatures between 0 and 180°C, preferably between 20 and 120°C.
• a direct cyclization of compounds of formula Ilia into compounds of formula I may be achieved under conditions mentioned below in scheme 9.
• reaction are well known to those skilled in the art and may be carried out in the presence of electrophilic halogenating reagents such as bromine Br2, N-bromosuccinimide NBS, chlorine CI2, N-chlorosuccinimide NCS or N- iodosuccinimide NIS amongst others, and in the presence of radical initiator, for example AIBN (azobisisobutyronitrile) or benzoyl peroxide, or under photochemical conditions, in the presence of solvents such as toluene, xylene, acetonitrile, hexane, dichloroethane, or carbon tetrachloride, and at temperatures ranging from 20°C to the boiling point of the reaction mixture.
• electrophilic halogenating reagents such as bromine Br2, N-bromosuccinimide NBS, chlorine CI2, N-chlorosuccinimide NCS or N- iodosuccinimide NIS amongst others
• R2 is as defined under formula I above, and in which LG2 is a leaving group, for example bromo Br, chloro Cl or iodo I, and R is Ci-C6alkyl, benzyl or a phenyl group, are novel, especially developed for the preparation of the compounds of formula I according to the invention and therefore represent a further object of the invention.
• the preferences and preferred embodiments of the substituents of the compounds of formula I are also valid for the compounds of formula III.
• LG2 is bromo or chloro; even more preferably LG2 is bromo.
• R is Ci-C6alkyl; even more preferably R is methyl or ethyl.
• R2 and Q are as defined under formula I above, and in which Ra is hydrogen, Ci-C6alkyl, benzyl or a phenyl group, are novel, especially developed for the preparation of the compounds of formula I according to the invention and therefore represent a further object of the invention.
• the preferences and preferred embodiments of the substituents of the compounds of formula I are also valid for the compounds of formula lllb.
• Ra is hydrogen or Ci-C6alkyl; even more preferably, Ra is hydrogen, methyl or ethyl; most preferably Ra is hydrogen.
• Ligand for eg using Ru(bpy) 3 CI 2 in the MeBF 3 K or presence of blue LED and MeB(OFI afluoropropionic anhydride ) 2 o Pent (MeBO) 3 as CF 3 CF 2 - source may be prepared (scheme 5) by a Suzuki reaction, which involves for example, reacting compounds of formula XIV, wherein R2 is as defined in formula I above, LGi is a halogen Br, Cl, or I, preferably Cl, and in which R is Ci-C6alkyl, benzyl or a phenyl group, with trimethylboroxine (MeBO)3 or potassium methyltrifluoroborate MeBFsK, amongst other methyl boronic acid equivalents.
• the reaction may be catalyzed by a palladium based catalyst, for example tetrakis(triphenyl-phosphine)palladium(0),
• reaction temperature can preferentially range from room temperature to the boiling point of the reaction mixture, or the reaction may be performed under microwave irradiation.
• Suzuki reactions are well known to those skilled in the art and have been reviewed, for example, in J. Organomet. Chem. 576, 1999, 147-168.
• photocatalyst examples include tris(2,2'-bipyridyl)dichlororuthenium(ll) hexahydrate, tris(2,2'-bipyrimide)ruthe- nium(ll) dichloride, dichlorotris(1 ,10-phenanthroline)ruthenium(ll) chloride, [lr ⁇ dFCF3ppy ⁇ 2 (bpy)]PF6, or lr(dFppy)3, amongst other ruthenium or iridium based catalysts.
• R2 haloalkyl radical source examples include trifluoromethanesulfonyl chloride, trifluoromethanesulfonic anhydride, trifluoroacetic anhydride, pentafluoropropionic anhydride amongst others.
• a reaction in the presence of trifluoroacetic anhydride or pentafluoropropionic anhydride, and similar others can be carried out optionally in the presence of a pyridine N-oxide derivative, for example 4-phenylpyridine-N-oxide or pyridine N-oxide, which facilitates the formation of haloalkyl radical.
• the photoredox reaction can be carried out in the presence of a suitable solvent, such as acetonitrile, tetrahydrofuran, toluene, or trilfuorotoluene amongst others, at temperature in the range of 0°C to the boiling point of the reaction mixture, preferably between 25 to 40°C.
• a suitable solvent such as acetonitrile, tetrahydrofuran, toluene, or trilfuorotoluene amongst others.
• Compounds of formula XIII, wherein LGi is a halogen Br, Cl, or I, preferably Cl, and in which R is Ci- Cealkyl, benzyl or a phenyl group can be prepared by reacting compounds of formula XII, wherein LGi is a halogen Br, Cl, or I, preferably Cl, and in which R is Ci-C6alkyl, benzyl or a phenyl group, with a compound of formula ROH, wherein R is Ci-C6alkyl, benzyl or a phenyl group, in the presence of an acid catalyst, for example, sulfuric acid or a Lewis acid such as Sc(OTf)3 or FeCh.
• an acid catalyst for example, sulfuric acid or a Lewis acid such as Sc(OTf)3 or FeCh.
• esterification reactions are well known to those skilled in the state of art, and known, for example, by the name of Fischer Esterification reaction, and are reported in literature, for example, in J. Org. Chem., 2006, 71, 3332-3334, Chem. Commun., 1997, 351-352 and Synthesis, 2008, 3407-3410.
• Such esterification reaction can also be carried out by reacting compounds of formula XII with trimethylsilyldiazomethane TMSCHN2 to form compounds of formula XIII, wherein LGi is a halogen Br, Cl, or I, preferably Cl, and in which R is methyl, and are reported in Angew. Chem. Int. Ed. 2007, 46, 7075.
• compounds of formula II wherein F3 ⁇ 4 is as defined in formula I above, and R is Ci- Cealkyl, benzyl or a phenyl group
• R is Ci- Cealkyl, benzyl or a phenyl group
• LG h ai is a halogen, for example chloro, bromo or iodo
• haloalkyl reagents such as methyl difluoro(fluoro- sulfonyl)acetate (XV), sodium trifluoroacetate(XVa), trifluoromethyltrimethylsilane (XVaa) or methyl chlorodifluoroacetate (XVaaa), amongst other nucleophilic (metal)-haloalkyl reagents.
• the reaction is carried out in the presence of a metal catalyst, for example copper catalysts, such as copper chloride CuCI, copper iodide Cul, or [Cu(MeCN) 4 ]BF 4 , amongst others, optionally in the presence of a ligand, such as tetramethylethylenediamine, 1 ,10-phenanthroline, amongst other amino ligands.
• a metal catalyst for example copper catalysts, such as copper chloride CuCI, copper iodide Cul, or [Cu(MeCN) 4 ]BF 4 , amongst others, optionally in the presence of a ligand, such as tetramethylethylenediamine, 1 ,10-phenanthroline, amongst other amino ligands.
• the reaction is generally carried out in the presence of a solvent such as dimethylacetamide, N,N-dimethyl- formamide, toluene, N-methyl-2-pyrrolidone, N,N'-dimethylprop
• esterification reaction can also be carried out by reacting compounds of formula IX with trimethylsilyldiazomethane TMSCHN2 to form compounds of formula X, wherein R is methyl, and are reported in Angew. Chem. Int. Ed. 2007, 46, 7075.
• Compounds of formula X wherein R is Ci-C6alkyl, benzyl or a phenyl group, can also be prepared by reacting compounds of formula IX with compounds of formula R-LG1, wherein R is Ci-C6alkyl, benzyl or a phenyl group, and LGi is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl- or alkylsulfonate such as trifluoromethanesulfonate, in the presence of base such as potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, amongst other bases.
• base such as potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, amongst other bases.
• the reductive amination reaction to convert compounds of formula XVII to compounds of formula V can be carried out in the presence of a reducing agent, for example sodium cyanoborohydride or sodium triacetoxyborohydride, amongst others, and optionally in the presence of an acid such as trifluoroacetic acid, formic acid, or acetic acid (and the like), at temperatures ranging from 0°C to the boiling point of the reaction mixture.
• the reaction can be carried out in the presence of inert solvents, such as ethanol, methanol, dioxane ortetrahydrofuran.
• Compounds of formula XVII, wherein F3 ⁇ 4 is as defined in formula I above may be prepared (scheme 6) from compound of formula XVI, wherein F3 ⁇ 4 is as defined in formula I above, and in which LG2 is chloro, bromo or iodo, preferably bromo, and R is Ci-C6alkyl, benzyl or a phenyl group, by a hydrolysis and intramolecular cyclization reaction.
• the reaction can be carried out either under basic conditions using metal hydroxides, such as aqueous sodium or potassium hydroxide, in the presence of a solvent such as dioxane, tetrahydrofuran or water, and at temperatures ranging from 20 to 150°C, as reported in, for example, Synlett 1992, (6), 531-533, or under aqueous acidic conditions, for example using acetic acid, hydrochloric acid or sulfuric acid, in the presence of a solvent such as water, dioxane, or a halogenated solvent such as dichloroethane, as reported in, for example, Tetrahedron 62 (2006) 9589-9602.
• metal hydroxides such as aqueous sodium or potassium hydroxide
• a solvent such as dioxane, tetrahydrofuran or water
• a solvent such as dioxane, tetrahydrofuran or water
• a solvent such as dioxane, tetrahydrofuran or
• Scheme 8 may be prepared (scheme 8) from compounds of formula XX, wherein R2 and Q are defined as under formula I above, via a selective reduction of one of the carbonyl functional group.
• the reaction can be carried out in the presence of a reducing agent, for example sodium borohydride NaBhU, lithium aluminum hydride LiAlhU, or hydrogen in the presence of palladium on carbon, or a combination of two reducing agents, for example NaBhU followed by triethylsilane.
• a reducing agent for example sodium borohydride NaBhU, lithium aluminum hydride LiAlhU
• hydrogen for example palladium on carbon
• a combination of two reducing agents for example NaBhU followed by triethylsilane.
• the reaction can be carried out in the presence of oxidative reagents, such as potassium permanganate KMNO4, tetrabutylammonium permanganate NnBu 4 MnC> 4 , potassium persulfate K2S2O8 (also known as potassium peroxydisulfate) in the presence of oxygen, or under photochemical conditions in the presence of oxygen, and at temperatures ranging from 20°C to the boiling point of the reaction mixture.
• oxidative reagents such as potassium permanganate KMNO4, tetrabutylammonium permanganate NnBu 4 MnC> 4
• potassium persulfate K2S2O8 also known as potassium peroxydisulfate
• the reaction is carried out in the presence of inert solvent, such as acetonitrile, ethyl acetate, DMSO, or dichloroethane.
• inert solvent such as acetonitrile, ethyl acetate, DM
• Scheme 9 may be prepared (scheme 9) by a direct cyclization reaction of compounds of formula Ilia, wherein R2 and Q are as defined in formula I above, and R is Ci-C6alkyl, benzyl or a phenyl group.
• a direct cyclization reaction can be carried out in the presence of a base, for example potassium fe/f-butoxide, lithium diisopropylamide, or sodium hydride, amongst others, at temperature ranging from -20°C to the boiling point of the reaction mixture, and in the presence of an inert solvent, such as tetrahydrofuran, dioxane, or DMF.
• a base for example potassium fe/f-butoxide, lithium diisopropylamide, or sodium hydride, amongst others, at temperature ranging from -20°C to the boiling point of the reaction mixture, and in the presence of an inert solvent, such as tetrahydrofuran, dioxane, or D
• Compounds of formula Ilia wherein R2 and Q are as defined in formula I above, and R is Ci-C6alkyl, benzyl or a phenyl group, may be prepared by reacting compounds of formula XVIIIa, wherein R2 is as defined in formula I above, and R is Ci-C6alkyl, benzyl or a phenyl group, with compounds of formula IV, wherein Q is as defined in formula I above, under Mitsunobu conditions.
• Such reactions known to those skilled in art can be carried out in the presence of phosphine reagent, such as triphenyl- phosphine, tributylphosphine, or polymer supported triphenyl phosphine, amongst others, in the presence of an azodicarboxylate reagent, such as diethyl azodicarboxylate or diisopropyl azodicarboxylate, at temperature ranging from 0°C to 100°C, and in the presence of an inert solvent, such as acetonitrile, dichloromethane, tetrahydrofuran, or toluene.
• phosphine reagent such as triphenyl- phosphine, tributylphosphine, or polymer supported triphenyl phosphine, amongst others
• an azodicarboxylate reagent such as diethyl azodicarboxylate or diisopropyl azodica
• reaction can be carried out in the presence of an acid, such as trifluoroacetic acid, hydrochloric acid or sulfuric acid, amongst others, and under conditions known to those skilled in the art and already described above.
• an acid such as trifluoroacetic acid, hydrochloric acid or sulfuric acid, amongst others, and under conditions known to those skilled in the art and already described above.
• Compounds of formula XXI, wherein Q is as defined in formula I above may be prepared by the reaction of compounds of formula XXIIa, wherein Q is as defined in formula I above, with an organo- azide, in the presence of a suitable base, and tert-butanol f-BuOH, optionally in the presence of a coupling agent, optionally in the presence of Lewis acid, and in the presence of an inert solvent, at temperatures between 50°C and boiling point of the reaction mixture.
• the reaction can be carried out in the presence of coupling agent such as T3P or via activation of the carboxylic acid with thionyl chloride SOCI2 or oxalyl chloride, or other coupling agents as described in scheme 4 for the conversion of compounds of formula V into compounds of formula Va.
• coupling agent such as T3P
• organo-azide compounds include trimethylsilyl azide TMSN3, sodium azide, ortosyl azide
• suitable solvents may be toluene, xylene, THF or acetonitrile.
• suitable Lewis acids may include zinc triflate Zn(OTf)2, Sc(OTf)2, or Cu(OTf)2, amongst others.
• Compounds of formula XXI can also be prepared by reacting compounds of formula XXIIa with diphenylphosphorylazide in the presence of an organic base such as triethylamine ordiisopropylethylamine, amongst others, in the presence of fe/f-butanol t- BuOH and an inert solvent, for example halogenated solvents such as dichloromethane or dichloroethane, or cyclic ethers such as tetrahydrofuran, amongst others, and at temperatures ranging from 50°C to the boiling point of the reaction mixture.
• an organic base such as triethylamine ordiisopropylethylamine, amongst others
• fe/f-butanol t- BuOH an inert solvent
• halogenated solvents such as dichloromethane or dichloroethane
• cyclic ethers such as tetrahydrofuran, amongst
• tert-butyl N-[3-ethylsulfonyl-6-(1 ,2,4-triazol-1-yl)-2-pyridyl]carbamate (CAS 2641574-60-7, described in WO2021085370); tert-Butyl N-[5-(1-cyano-1-methylethyl)-3-ethylsulfanyl-2-pyridyl]carbamate (CAS 2484397-79-5, described in W02020174094); tert-Butyl N-[3-(ethylsulfonyl)-2-pyridyl]carbamate (CAS 2484398-04-9, described in W02020174094).
• Compounds of formula XXII, wherein Q is as defined in formula I above may be prepared by the reaction of compounds of formula XXI la, wherein Q is as defined in formula I above, with ammonia Nhh, or ammonia surrogates, such as, for example, NhUOH, in the presence of carboxylic acid activating agents as described in scheme 4.
• Compounds of formula IV-1 can be prepared by an amination reaction, which involves for example, reacting compounds of formula IV-1 a, wherein Ri, R3 and Qi are as defined in formula I, and LG4 is a halogen, preferably F, Br or Cl, with ammonia, or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or any other equivalent salt).
• the source of nitrogen may be ammonia NH3 itself or an ammonia equivalent such as for example ammonium hydroxide NhUOH, ammonium chloride NFUCI, ammonium acetate NFUOAc, ammonium carbonate (NH 4 ) 2 CC>3, and other NH3 surrogates.
• This transformation is preferably performed in suitable solvents (or diluents) such as alcohols, amides, esters, ethers, nitriles and water, particularly preferred are methanol, ethanol, 2,2,2- trifluoroethanol, propanol, iso-propanol, N,N-dimethylformamide, N,N-dimethylacetamide, dioxane, tetrahydrofuran, dimethoxyethane, acetonitrile, ethyl acetate, water or mixtures thereof, optionally in presence of a base, at temperatures between 0-150°C, preferably at temperatures ranging from room temperature to the boiling point of the reaction mixture, optionally under microwave irradiation.
• suitable solvents such as alcohols, amides, esters, ethers, nitriles and water
• suitable solvents such as alcohols, amides, esters, ethers, nitriles and water
• suitable solvents such as alcohols,
• Compounds of formula IV-1 b, wherein Ri, R3 and Qi are as defined in formula I, and LG 4 is halogen, preferably F, Br or Cl, can be prepared by reacting compounds of formula IV-1 c, wherein R3 and Qi are as defined in formula I, and LG 4 is halogen, preferably F, Br or Cl, with a disulfide R 1 S-SR 1 or alternatively a thiol RiSH, wherein Ri is as defined in formula I above, in the presence of a nitrite, such as tert-butyl nitrite t-BuONO, isoamyl nitrite, or sodium nitrite, and in presence of a hydrohalic acid (preferably HBr or HCI), under Sandmeyer-type reaction conditions.
• a nitrite such as tert-butyl nitrite t-BuONO
• isoamyl nitrite or sodium nitrite
• a hydrohalic acid preferably HB
• This transformation is preferably performed in an inert solvent, such as acetonitrile or a halogenated solvent, like 1 ,2-dichloroethane, at temperatures between 0-150°C, preferably at temperatures ranging from room temperature to the boiling point of the reaction mixture, optionally in the presence of copper salts.
• an inert solvent such as acetonitrile or a halogenated solvent, like 1 ,2-dichloroethane
• Ri and X are as defined under formula I above, and Qi a is 1-cyanocyclopropyl, 1-cyano-1 -methyl-ethyl or 2-pyridyloxy, are novel, especially developed forthe preparation of the compounds of formula I according to the invention and therefore represent a further object of the invention.
• the preferences and preferred embodiments of the substituents of the compounds of formula I are also valid forthe compounds of formula IV-A.
• compounds of formula l-Qb wherein X is SO or SO 2
• compounds of formula l-Qb may be prepared from compounds of formula XXIIIb, wherein A, R3, Ri and R 2 are as defined in formula I above, and in which X is SO or SO 2 , and wherein Xb is a leaving group like, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl- or alkylsulfonate such as trifluoromethanesulfonate, by reaction (C-N bond formation) with an optionally substituted triazole Qi-H (which contains an appropriate NH functionality) (XXIVaa), wherein Qi is N-linked triazolyl, in solvents such as alcohols (eg.
• methanol, ethanol, isopropanol, or higher boiling linear or branched alcohols pyridine or acetic acid, optionally in the presence of an additional base, such as potassium carbonate K 2 CO3 or cesium carbonate CS 2 CO3, optionally in the presence of a copper catalyst, for example copper(l) iodide, at temperatures between 30-180°C, optionally under microwave irradiation.
• an additional base such as potassium carbonate K 2 CO3 or cesium carbonate CS 2 CO3
• a copper catalyst for example copper(l) iodide
• compounds of formula l-Qb wherein X is SO or S02, may be prepared from compounds of formula XXI I lb, wherein A, Ri, R2 and Rsare as defined in formula I, and in which X is SO or SO2, and wherein Xb is a leaving group like, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl- or alkylsulfonate such as trifluoromethanesulfonate, by reaction (C-N bond formation) with a reagent Qi-H (XXIVaa) equivalent to HN(R4)COR5, wherein R4 and R5 are as defined in formula I.
• XXI I lb wherein A, Ri, R2 and Rsare as defined in formula I, and in which X is SO or SO2, and wherein Xb is a leaving group like, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl- or alkyls
• Such a reaction is performed in the presence of a base, such as potassium carbonate, cesium carbonate, sodium hydroxide, in an inert solvent, such as toluene, dimethylformamide DMF, N-methyl pyrrolidine NMP, dimethyl sulfoxide DMSO, dioxane, tetrahydrofuran THF, and the like, optionally in the presence of a catalyst, for example palladium(ll)acetate, bis(dibenzylideneacetone)palladium(0) (Pd(dba)2) or tris(dibenzylideneacetone)dipalladium(0) (Pd 2 (dba)3, optionally in form of a chloroform adduct), or a palladium pre-catalyst such as for example fe/f-BuBrettPhos Pd G3 [(2-Di-fe/f-butylphosphino-3,6- dimethoxy-2',4',6'-tri
• compounds of formula l-Qb, wherein X is SO or S02 may be prepared from compounds of formula XXIIIb, wherein A, Ri, R2 and R3are as defined in formula I, and in which X is SO or S02, and wherein Xb is a leaving group like, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl- or alkylsulfonate such as trifluoromethanesulfonate, by reaction (C-N bond formation) with a reagent Qi-H (XXIVaa) equivalent to HN(R4)2, or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein R4 is as defined in formula I.
• a reagent Qi-H (XXIVaa) equivalent to HN(R4)2, or a salt thereof such as a hydrohal
• Such a reaction is commonly performed in an inert solvent such as alcohols, amides, esters, ethers, nitriles and water, particularly preferred are methanol, ethanol, 2,2,2-trifluoroethanol, propanol, isopropanol, N,N-dimethylformamide, N,N- dimethylacetamide, dioxane, tetrahydrofuran, dimethoxyethane, acetonitrile, ethyl acetate, toluene, water or mixtures thereof, at temperatures between 0-150 °C, optionally under microwave irradiation or pressurized conditions using an autoclave, optionally in the presence of a copper catalyst, such as copper powder, copper(l) iodide or copper sulfate (optionally in form of a hydrate), or mixtures thereof, optionaly in presence a ligand, for example diamine ligands (e.g.
• Reagents HN(R4)2, or HN(R4)COR5, wherein R4 and Rs are as defined in formula I are either known, commercially available or may be prepared by methods known to a person skilled in the art.
• compounds of formula l-Qb, wherein X is SO or SO2 may be prepared by a Suzuki reaction, which involves for example, reacting compounds of formula XXIIIb, wherein A, Ri, R2 and R3 are as defined in formula I, and in which X is SO or SO2, and wherein Xb is a leaving group like, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl- or alkylsulfonate such as trifluoromethanesulfonate, with compounds of formula (XXIV), wherein Qi is as defined in formula I, and wherein Ybi can be a boron-derived functional group, such as for example B(OH)2 or B(ORbi)2 wherein Rbi can be a
• reaction temperature can preferentially range from room temperature to the boiling point of the reaction mixture, or the reaction may be performed under microwave irradiation.
• Suzuki reactions are well known to those skilled in the art and have been reviewed, for example, in J.Organomet. Chem. 576, 1999, 147-168.
• compounds of formula l-Qb wherein X is SO or SO2 may be prepared by a Stille reaction between compounds of formula (XXIVa), wherein Qi is as defined above, and wherein Yb2 is a trialkyltin derivative, preferably tri-n-butyl tin or tri-methyl-tin, and compounds of formula XXIIIb, wherein A, Ri, R2 and R3are as defined in formula I, and in which X is SO or S0 2 , and wherein Xb is a leaving group like, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl- or alkylsulfonate such as trifluoromethanesulfonate.
• XXIVa compounds of formula (XXIVa)
• Qi is as defined above
• Yb2 is a trialkyltin derivative, preferably tri-n-butyl tin or tri-methyl-tin
• XXIIIb wherein A
• Such Stille reactions are usually carried out in the presence of a palladium catalyst, for example tetrakis(triphenylphosphine)palladium(0), or bis(triphenylphosphine)palladium(ll) dichloride, in an inert solvent such as N,N-dimethylformamide, acetonitrile, toluene 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(l)iodide.
• a palladium catalyst for example tetrakis(triphenylphosphine)palladium(0), or bis(triphenylphosphine)palladium(ll) dichloride
• an inert solvent such as N,N-dimethylformamide, acetonitrile, toluene or dioxane
• an additive such as cesium fluoride, or lithium chloride
• compounds of formula l-Qb wherein X is SO or SO 2
• compounds of formula l-Qb may be prepared from compounds of formula XXIIIb, wherein A, Ri, R2 and R3are as defined in formula I, and in which X is SO or SO 2 , and wherein Xb is a leaving group like, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl- or alkylsulfonate such as trifluoromethanesulfonate, by reaction with a heterocycle Qi-H (which contains an appropriate NH functionality) (XXIVaa), wherein Qi is as defined above, in the presence of a base, such as potassium carbonate K 2 CO3 or cesium carbonate CS 2 CO3, optionally in the presence of a copper catalyst, for example copper(l) iodide, with or without an additive such as L
• compounds of formula l-Qb wherein X is SO or SO2
• compounds of formula XXIIIb wherein X is S (sulfide) by involving the same chemistry as described above, but by changing the order of the steps (i.e. by running the sequence XXIIIb (X is S) to l-Qb (X is S) via Suzuki, Stille or C-N bond formation, followed by an oxidation step to form l-Qb (X is SO or SO2).
• the subgroup of compounds of formula I, wherein R2 is as defined above, and wherein Q is defined as Qa, in which A, Qi, R3, X and Ri are as defined in formula I, may be defined as compounds of formula l-Qa (scheme 12).
• the chemistry described previously in scheme 11 to access compounds of formula l-Qb from compounds of formula XXIIIb, can be applied analogously (scheme 12) for the preparation of compounds of formula l-Qa from compounds of formula XXIIIa, wherein all substituent definitions mentioned previously remain valid.
• the reactants can be reacted in the presence of a base.
• suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
• Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert- butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4- (N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
• the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also act as solvents or diluents.
• the 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, and by post modification of compounds of with reactions such as oxidation, alkylation, reduction, acylation and other methods known by those skilled in the art.
• 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
• a suitable solvent in which 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 saltforming properties can be obtained in free form or in the form of salts.
• the compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.
• Diastereomer mixtures or racemate mixtures of compounds of formula I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
• Enantiomer mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl celulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is 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
• 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.
• N-oxides can be prepared by reacting a compound of the formula I with a suitable oxidizing agent, for example the H2C>2/urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride.
• a suitable oxidizing agent for example the H2C>2/urea adduct
• an acid anhydride e.g. trifluoroacetic anhydride.
• 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.
• Table A-1 provides 18 compounds A-1 .001 to A-1.018 of formula 1-1 wherein F3 ⁇ 4 is CF3, A is N, X is S, Ri is ethyl and Qi are as defined in table B.
• Table A-2 provides 18 compounds A-2.001 to A-2.018 of formula 1-1 wherein R2 is CF3, A is N, X is SO, Ri is ethyl and Qi are as defined in table B.
• Table A-3 provides 18 compounds A-3.001 to A-3.018 of formula 1-1 wherein R2 is CF3, A is N, X is SO2, Ri is ethyl and Qi are as defined in table B.
• Table A-4 provides 18 compounds A-4.001 to A-4.018 of formula 1-1 wherein R2 is CF3, A is CH, X is S, Ri is ethyl and Qi are as defined in table B.
• Table A-5 provides 18 compounds A-5.001 to A-5.018 of formula 1-1 wherein R2 is CF3, A is CH, X is SO, Ri is ethyl and Qi are as defined in table B.
• Table A-6 provides 18 compounds A-6.001 to A-6.018 of formula 1-1 wherein R2 is CF3, A is CH, X is SO2, Ri is ethyl and Qi are as defined in table B.
• Table A-7 provides 18 compounds A-7.001 to A-7.018 of formula 1-1 wherein R 2 is CF 2 CF3, A is N, X is S, Ri is ethyl and Qi are as defined in table B.
• Table A-8 provides 18 compounds A-8.001 to A-8.018 of formula 1-1 wherein R 2 is CF 2 CF3, A is N, X is SO, Ri is ethyl and Qi are as defined in table B.
• Table A-9 provides 18 compounds A-9.001 to A-9.018 of formula 1-1 wherein R 2 is CF 2 CF3, A is N, X is SO2, Ri is ethyl and Qi are as defined in table B.
• Table A-10 provides 18 compounds A-10.001 to A-10.018 of formula 1-1 wherein R 2 is CF 2 CF3, A is CH, X is S, Ri is ethyl and Qi are as defined in table B.
• Table A-11 provides 18 compounds A-11 .001 to A-11 .018 of formula 1-1 wherein R 2 is CF 2 CF3, A is CH, X is SO, Ri is ethyl and Qi are as defined in table B.
• Table A-12 provides 18 compounds A-12.001 to A-12.018 of formula 1-1 wherein R 2 is CF 2 CF3, A is CH, X is SO2, Ri is ethyl and Qi are as defined in table B.
• Table C-1 provides 9 compounds C-1.001 to C-1.009 of formula I-2 wherein R2 is CF3, A is N, X is S, Ri is ethyl and Qi are as defined in Table D.
• Table D Substituent definitions of Qi Table C-2 provides 9 compounds C-2.001 to C-2.009 of formula I-2 wherein R2 is CF3, A is N, X is SO, Ri is ethyl and Qi are as defined in Table D.
• Table C-3 provides 9 compounds C-3.001 to C-3.009 of formula I-2 wherein R2 is CF3, A is N, X is SO2, Ri is ethyl and Qi are as defined in Table D.
• Table C-4 provides 9 compounds C-4.001 to C-4.009 of formula I-2 wherein R2 is CF3, A is CH, X is S, Ri is ethyl and Qi are as defined in Table D.
• Table C-5 provides 9 compounds C-5.001 to C-5.009 of formula I-2 wherein R2 is CF3, A is CH, X is SO, Ri is ethyl and Qi are as defined in Table D.
• Table C-6 provides 9 compounds C-6.001 to C-6.009 of formula I-2 wherein R2 is CF3, A is CH, X is SO2, Ri is ethyl and Qi are as defined in Table D.
• Table C-7 provides 9 compounds C-7.001 to C-7.009 of formula I-2 wherein R2 is CF2CF3, A is N, X is S, Ri is ethyl and Qi are as defined in Table D.
• Table C-8 provides 9 compounds C-8.001 to C-8.009 of formula I-2 wherein R2 is CF2CF3, A is N, X is SO, Ri is ethyl and Qi are as defined in Table D.
• Table C-9 provides 9 compounds C-9.001 to C-9.009 of formula I-2 wherein R2 is CF2CF3, A is N, X is SO2, Ri is ethyl and Qi are as defined in Table D.
• Table C-10 provides 9 compounds C-10.001 to C-10.009 of formula I-2 wherein R2 is CF2CF3, A is CH, X is S, Ri is ethyl and Qi are as defined in Table D.
• Table C-11 provides 9 compounds C-11 .001 to C-11 .009 of formula I-2 wherein R2 is CF2CF3, A is CH, X is SO, Ri is ethyl and Qi are as defined in Table D.
• Table C-12 provides 9 compounds C-12.001 to C-12.009 of formula I-2 wherein R2 is CF2CF3, A is CH, X is SO2, Ri is ethyl and Qi are as defined in Table D.
• the compounds of formula I according to the invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants.
• the active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina.
• the insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e.
• Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order Coleoptera, for example,
• Agriotes spp. Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis, Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemLineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp, Maladera castanea, Megas
• Thyanta spp Triatoma spp., Vatiga illudens; Acyrthosium pisum, Adalges spp, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp, Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aoni
• Coptotermes spp Corniternes cumulans, Incisitermes spp, Macrotermes spp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsis geminate from the order Lepidoptera, for example,
• Blatta spp. Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp. , Scapteriscus spp, and Schistocerca spp.; from the order Psocoptera, for example,
• Liposcelis spp. from the order Siphonaptera, for example,
• Calliothrips phaseoli Frankliniella spp., Heliothrips spp, Hercinothrips spp., Parthenothrips spp, Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp; from the order Thysanura, for example, Lepisma saccharina.
• the active ingredients according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
• Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts,
• compositions and/or methods of the present invention may be also used on any ornamental and/or vegetable crops, including flowers, shrubs, broad-leaved trees and evergreens.
• the invention may be used on any of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperfiorens, B. tubereux), Bougainvillea spp., Brachycome spp., Brassica spp.
• Calceolaria spp. (ornamental), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemum spp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp.,
• Gomphrena globosa Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, I mpatiens spp. (/. Walleriana), Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp., Dianthus spp.
• Canna spp. (carnation), Canna spp., Oxalis spp., Beilis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp. (pansy), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp., Parthenocissus spp. (P. quinquefolia, P. tricuspidata), Primula spp., Ranunculus spp., Rhododendron spp., Rosa spp.
• the invention may be used on any of the following vegetable species: Allium spp. (A. sativum, A. cepa, A. oschaninii, A. Porrum, A. ascalonicum, A. fistulosum), Anthriscus cerefolium, Apium graveolus, Asparagus officinalis, Beta vulgarus, Brassica spp. (B. Oleracea, B. Pekinensis, B. rapa), Capsicum annuum, Cicer arietinum, Cichorium endivia, Cichorum spp. (C. intybus, C. endivia), Citrillus lanatus, Cucumis spp. (C. sativus, C.
• Preferred ornamental species include African violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper, tomato and cucumber.
• the active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops.
• the active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca(preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
• the active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops.
• the active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca(preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
• 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
• Needle nematodes Longidorus elongatus and other Longidorus species; Pin nematodes,
• Pratylenchus species Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species, such
• 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.
• crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
• Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as d-endotoxins, e.g. CrylAb, CrylAc, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 orVip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
• insecticidal proteins for example insecticidal proteins from Bacillus cereus or Bacillus popilliae
• Bacillus thuringiensis such as d-endotoxins, e.g. CrylAb, CrylAc, Cry1F, Cry1Fa2,
• Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
• toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
• toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
• agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
• steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecd
• d-endotoxins for example CrylAb, CrylAc, Cry1F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins.
• Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701).
• Truncated toxins for example a truncated CrylAb, are known.
• modified toxins one or more amino acids of the naturally occurring toxin are replaced.
• 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 374753, WO 93/07278, WO 95/34656, EP-A-0427 529, EP-A-451 878 and WO 03/052073.
• Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0401 979 and WO 90/13651.
• the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
• insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).
• Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available.
• YieldGard® (maize variety that expresses a Cry1 Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1 Ab 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 Cry1 Ac toxin); Bollgard I® (cotton variety that expresses a Cry1 Ac toxin); Bollgard II® (cotton variety that expresses a Cry1 Ac and a Cry2Ab
• transgenic crops are:
• MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
• MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
• NK603 c MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1 Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
• crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392225).
• PRPs pathogenesis-related proteins
• Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392225, WO 95/33818 and EP-A-0 353 191.
• the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
• Crops may also be modified for enhanced resistance to fungal (for example Fusarium, Anthracnose, or Phytophthora), bacterial (for example Pseudomonas) or viral (for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens.
• fungal for example Fusarium, Anthracnose, or Phytophthora
• bacterial for example Pseudomonas
• viral for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus
• Crops also include those that have enhanced resistance to nematodes, such as the soybean cyst nematode.
• Crops that are tolerance to abiotic stress include those that have enhanced tolerance to drought, high salt, high temperature, chill, frost, or light radiation, for example through expression of NF-YB or other proteins known in the art.
• Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A-0 392225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g.
• compositions according to the invention are the protection of stored goods and store rooms 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) application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention.
• 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 2003/034823, US 5631072, WO 2005/64072, W02006/128870, 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 tables A and B:
• 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
• 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..
• Nematocerina and Brachycerina for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Glossina spp., Calliphora spp., Glossina spp., Call
• Siphonaptrida for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp..
• Heteropterida for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp..
• Actinedida Prostigmata
• Acaridida Acaridida
• Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp..
• compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
• compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec.,Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus
• the compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances.
• formulation adjuvants 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.
• the formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known perse.
• liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p- diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, A/,A/-dimethylformamide, dimethyl sulfoxide, 1 ,4- dioxan
• Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
• a large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
• Surface- active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
• Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of
• Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.
• compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives.
• the amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied.
• the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared.
• Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
• Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively).
• Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
• inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
• a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
• commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.
• the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
• a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
• Preferred formulations can have the following compositions (weight %):
• Emulsifiable concentrates active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agent: 1 to 30 %, preferably 5 to 20 % liquid carrier: 1 to 80 %, preferably 1 to 35 %
• Dusts active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
• Suspension concentrates active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %
• Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
• Granules active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
• active ingredient 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
• the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
• the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
• Emulsions of any required dilution which can be used in plant protection, can be obtained from this concentrate by dilution with water.
• Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
• the combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
• the mixture is extruded and then dried in a stream of air.
• the finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol.
• Non-dusty coated granules are obtained in this manner.
• the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
• a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
• living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
• the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
• a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
• living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
• 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1).
• This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved.
• a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added.
• the mixture is agitated until the polymerization reaction is completed.
• the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
• the capsule suspension formulation contains 28% of the active ingredients.
• the medium capsule diameter is 8-15 microns.
• the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
• Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
• EC emulsion concentrate
• SC suspension concentrate
• SE suspo- emulsion
• CS capsule suspension
• WG water dispersible granule
• Mp means melting point in °C. Free radicals represent methyl groups. 1 H NMR measurements were recorded on a Brucker 400MHz spectrometer, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated. Either one of the LCMS or GCMS methods below was used to characterize the compounds. The characteristic LCMS and GCMS values obtained for each compound were the retention time (“Rt”, recorded in minutes) and the measured molecular ion (M+H) + , (M-H)- or (M) + .
• Spectra were recorded on a Gas Chromatography Mass Sectrometer (GC-MS) from Shimadzu Corporation equipped with AOC-20i autosampler, GC-2010 gas chromatography spectrometer with electron ionization (El) source. Ion Source Temperature 200°C; Interface Temperature 220°C; Solvent Cut Time 2.00 min. Detector Gain Mode-Relative; Detector Gain: +0.00 kV. Threshold: 1000;
• Example I-4 Preparation oftert-butyl N-[5-(1-cvanocvclopropyD-3-ethylsulfonyl-2-pyridyl1carbamate (intermediate 1-4)
• Step 1 Preparation of tert-butyl N-[5-(1-cvanocvclopropyl)-3-ethylsulfanyl-2-pyridyl1carbamate (intermediate 1-1) and 1-(6-amino-5-ethylsulfanyl-3-pyridyl)cvclopropanecarbonitrile (intermediate I-2) (i-2)
• To a solution of 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (CAS 2225113-77-7, prepared as described in WO 2018/108726) 50.0 g, 191.3 mmol
• toluene 500 ml_
• triethylamine 47.1 ml_, 334.8 mmol
• tert-butanol 260 ml_, 2755 mmol
• the reaction mass was heated at 90°C and diphenylphosphoryl azide (71.94 ml_, 327.1 mmol) was added in two hours.
• the reaction mixture was stirred at 90°C for one hour, then allowed to cool to room temperature. After dilution with water (400 ml_) and with a saturated aqueous solution of sodium bicarbonate (300 ml_), the aqueous layer was extracted with ethyl acetate (400 ml_).
• Step 2 Preparation of 1-(6-amino-5-ethylsulfanyl-3-pyridyl)cvclopropanecarbonitrile (intermediate I-2)
• Step 3 Preparation of 1-(6-amino-5-ethylsulfonyl-3-pyridyl)cvclopropanecarbonitrile (intermediate I-3)
• Step 4 Preparation of tert-butyl N-[5-(1-cvanocvclopropyl)-3-ethylsulfonyl-2-pyridyl1carbamate (intermediate 1-4)
• Step 1 Preparation of ethyl 2-methylthiophene-3-carboxylate (intermediate I-5)
• Step 2 Preparation of ethyl 5-iodo-2-methyl-thiophene-3-carboxylate (Intermediate I-6)
• Step 3 Preparation of ethyl 2-methyl-5-(trifluoromethvDthiophene-3-carboxylate (intermediate I-?)
• Step 4 Preparation of ethyl 2-(bromomethyl)-5-(trifluoromethyl)thiophene-3-carboxylate (intermediate I-8)
• Step 5 Preparation of ethyl 2-[[tert-butoxycarbonyl-[5-(1-cyanocyclopropyl)-3-ethylsulfonyl-2- pyridyl1amino1methyl1-5-(trifluoromethyl)thiophene-3-carboxylate (intermediate 1-9)
• tert-butyl N-[5-(1-cyanocyclopropyl)-3-ethylsulfonyl-2-pyridyl]carbamate (intermediate I-4 prepared as described above) (300 mg, 0.85 mmol) in N,N-dimethylformamide (6 ml_) at 0°C was added sodium hydride (60 mass%, 44 mg, 1.11 mmol) and the mixture stirred at 0°C for 15 minutes.
• Step 6 Preparation of ethyl 2-[[[5-(1-cyanocyclopropyl)-3-ethylsulfonyl-2-pyridyllaminolmethyll-5-
• Step 7 Preparation of 2-[[[5-(1-cvanocvclopropyD-3-ethylsulfonyl-2-pyridyl1amino1methyl1-5- (trifluoromethyr)thiophene-3-carboxylic acid (intermediate 1-11)
• Step 8 Preparation of 1-[5-ethylsulfonyl-6-[4-oxo-2-(trifluoromethyl)-6H-thieno[2,3-clpyrrol-5-yl1-3- pyridyllcyclopropanecarbonitrile (compound P1)
• Example P2 Preparation of 1-[5-ethylsulfonyl-6-[4-oxo-2-(1 ,1 .2.2.2-pentafluoroethvD-6H-thieno[2,3- clPyrrol-5-yl1-3-pyridyl1cvclopropanecarbonitrile (compound P2)
• Step 1 Preparation of methyl 2-bromothiophene-3-carboxylate (intermediate 1-121
• 2-bromothiophene-3-carboxylic acid (4.00 g, 19.3 mmol) in N,N-dimethylformamide (30 mL) was added cesium carbonate (7.55 g, 23.2 mmol).
• cesium carbonate (7.55 g, 23.2 mmol).
• the reaction mixture was stirred at room temperature for 5 minutes, then iodomethane (1.80 mL, 29.0 mmol) was added and stirring continued at room temperature for 5 hours.
• the reaction mixture was diluted with ice water (50 mL) and extracted with ethyl acetate (2x 50 mL).
• reaction mixture was degassed with nitrogen for 20 minutes, then 2,2,3,3,3-pentafluoropropanoyl 2, 2, 3,3,3- pentafluoropropanoate (13.0 mL, 63.0 mmol) was added and stirring continued under irradiation of blue LED light (465 nm; 50 W) for 22 hours. Completion of reaction was monitored by TLC and GCMS. After the irradiation time, the mixture was added to water (100 mL) and extracted with cyclohexane (2x 50 mL). The combined organic layers were washed with brine (50 mL), dried over sodium sulfate, filtered and concentrated in vacuo.
• Step 3 Preparation of methyl 2-methyl-5-(1 ,1 ,2.2.2-pentafluoroethyl)thiophene-3-carboxylate
• Methyl 2-bromo-5-(1 ,1 ,2,2,2-pentafluoroethyl)thiophene-3-carboxylate (0.700 g, 2.06 mmol), methylboronic acid (0.637 g, 10.3 mmol), tricyclohexyl- phosphane (0.347 g, 1.24 mmol) and tripotassium phosphate (2.19 g, 10.3 mmol) were stirred in toluene (8 mL) and water (1 .60 mL) while purged with nitrogen for 15 minutes.
• Step 4 Preparation of methyl 2-(bromomethyl)-5-(1 ,1 ,2.2.2-pentafluoroethyl)thiophene-3-carboxylate
• N-bromosuccinimide 0.039 g, 2.19 mmol
• 2,2’-azobis(iso- butyronitrile) 0.036 g, 0.21 mmol
• the reaction mixture was diluted with water (20 ml_) and extracted with ethyl acetate (3x 30 ml_). The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo.
• Step 5 Preparation of methyl 2-[[tert-butoxycarbonyl-[5-(1-cvanocvclopropyD-3-ethylsulfonyl-2- pyridyl1amino1methyl1-5-(1 ,1 ,2.2.2-pentafluoroethyl)thiophene-3-carboxylate (intermediate 1-16)
• reaction mixture was stirred at 50°C for 5 hours, completion of reaction was monitored by TLC and LCMS.
• the reaction mass was quenched with ice cold water (20 mL) and extracted with ethyl acetate (2x 50 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo.
• Step 6 Preparation of methyl 2-[[[5-(1-cvanocvclopropyl)-3-methylsulfonyl-2-pyridyl1amino1methyl1-5- (1 ,1 ,2.2.2-pentafluoroethyl)thiophene-3-carboxylate (intermediate 1-17) (1-17)
• reaction mixture was stirred at room temperature for 5 hours, then additional 2,2,2-trifluoroacetic acid (0.417 ml_, 5.45 mmol) was added and stirring continued at room temperature overnight. Completion of reaction was monitored by TLC and LCMS. The reaction mixture was slowly added to a saturated aqueous solution of potassium carbonate (10 ml_) and extracted with ethyl acetate (2x 10 ml_).
• Step 7 Preparation of 2-[[[5-(1-cvanocvclopropyD-3-ethylsulfonyl-2-pyridyl1amino1methyl1-5-(1 ,1 ,2,2,2- pentafluoroethyl)thiophene-3-carboxylic acid (intermediate 1-18)
• Step 8 Preparation of 1-[5-ethylsulfonyl-6-[4-oxo-2-(1 ,1 .2.2.2-pentafluoroethyl)-6H-thieno[2,3-clpyrrol-
• reaction mixture was added to water (10 mL) and extracted with ethyl acetate (2x 10 mL). The combined organic layers were washed with brine (10 mL), dried over sodium sulfate, filtered and concentrated in vacuo.
• Example P3 Preparation of 2-[[5-ethylsulfonyl-6-[4-oxo-2-(1 ,1 .2.2,2-pentafluoroethyl)-6H-thieno[2.3- clpyrrol-5-yl1-3-pyridyl1oxy1-2-methyl-propanenitrile (compound P3)
• Step-1 Preparation of ethyl 2-bromo-5-(1 ,1 ,2,2,2-pentafluoroethyl)thiophene-3-carboxylate
• Step-2 Preparation of ethyl 2-methyl-5-(1 ,1 ,2.2.2-pentafluoroethyl)thiophene-3-carboxylate (intermediate-20)
• Step-4 Preparation of ethyl 2-(bromomethvD-5-(1 ,1 .2.2.2-pentafluoroethvDthiophene-3-carboxylate (intermediate-21)
• Step-5 Preparation of tert-butyl N-[5-(1 -cvano-1 -methyl-ethoxy)-3-ethylsulfanyl-2-pyridyl1carbamate (intermediate 1-23)
• Step-6 Preparation of tert-butyl N-[5-(1 -cvano-1 -methyl-ethoxy)-3-ethylsulfonyl-2-pyridyl1carbamate (intermediate-24)
• Step-7 Preparation of ethyl 2-[[tert-butoxycarbonyl-[5-(1-cvano-1-methyl-ethoxy)-3-ethylsulfonyl-2- pyridyl1amino1methyl1-5-(1 ,1 .2,2.2-pentafluoroethyr)thiophene-3-carboxylate (intermediate-25 ' )
• Step-8 Preparation of ethyl 2-[[[5-(1 -cvano-1 -methyl-ethoxy)-3-ethylsulfonyl-2-pyridyl1amino1methyl1-5- (1 ,1 ,2.2.2-pentafluoroethyl)thiophene-3-carboxylate (intermediate-26)
• Step-9 Preparation of 2-[[[5-(1 -cvano-1 -methyl-ethoxy)-3-ethylsulfonyl-2-pyridyl1amino1methyl1-5- (1 ,1 ,2.2.2-pentafluoroethyl)thiophene-3-carboxylic acid (intermediate-27)
• Step-10 Preparation of 2-[[5-ethylsulfonyl-6-[4-oxo-2-(1 ,1 .2.2,2-pentafluoroethyl)-6H-thieno[2.3- clpyrrol-5-yl1-3-pyridyl1oxy1-2-methyl-propanenitrile (compound P3)
• reaction mixture stirred at room temperature for 2 hours, then more phosphorus oxychloride (0.028 mL, 0.303 mmol) was added and stirring continued at room temperature for an additional 2 hours.
• the reaction mass was acidified with an aqueous 2N hydrochloric acid (15 mL) solution and the product extracted with ethyl acetate (2x 30 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo.
• Example P4 Preparation of 5-[3-ethylsulfonyl-5-(2.2.2-trifluoroethoxy)-2-pyridyl1-2-(1 ,1 ,2,2,2- pentafluoroethyl)-6H-thieno[2,3-clpyrrol-4-one (compound P4)
• Step-1 Preparation of ethyl 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate (intermediate I-28)
• Step-2 Preparation of ethyl 3-ethylsulfanyl-5-hvdroxy-pyridine-2-carboxylate (intermediate i-29)
• Step-3 Preparation of ethyl 3-ethylsulfanyl-5-(2.2.2-trifluoroethoxy)pyridine-2-carboxylate (intermediate I-30)
• Step-4 Preparation of ethyl 3-ethylsulfonyl-5-(2.2.2-trifluoroethoxy)pyridine-2-carboxylate (intermediate 1-31)
• Step-5 Preparation of 3-ethylsulfonyl-5-(2.2.2-trifluoroethoxy)pyridine-2-carboxylic acid
• Step-6 Preparation of tert-butyl N-[3-ethylsulfonyl-5-(2.2.2-trifluoroethoxy)-2-pyridyl1carbamate
• Step-7 Preparation of ethyl 2-[[tert-butoxycarbonyl-[3-ethylsulfonyl-5-(2.2.2-trifluoroethoxy)-2- pyridyl1amino1methyl1-5-(1 ,1 ,2.2.2-pentafluoroethyl)thiophene-3-carboxylate (intermediate I-34)
• Step-8 Preparation of ethyl 2-[[[3-ethylsulfonyl-5-(2.2.2-trifluoroethoxy)-2-pyridyl1amino1methyl1-5- (1 ,1 ,2.2.2-pentafluoroethyl)thiophene-3-carboxylate (intermediate I-35)
• reaction mass was concentrated in vacuo and neutralised with an aqueous sodium carbonate solution.
• aqueous layer was extracted with ethyl acetate (2x 50 ml_), the combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo.
• Step-9 Preparation of 2-[[[3-ethylsulfonyl-5-(2.2.2-trifluoroethoxy)-2-pyridyl1amino1methyl1-5-(1 ,1 ,2,2,2- pentafluoroethyl)thiophene-3-carboxylic acid (intermediate i-36) To solution of ethyl 2-[[[3-ethylsulfonyl-5-(2,2,2-trifluoroethoxy)-2-pyridyl]amino]methyl]-5-(1 ,1 ,2,2,2- pentafluoroethyl)thiophene-3-carboxylate (intermediate I-35 prepared as described above) (0.535 g, 0.9378 mmol) in tetrahydrofuran (10 ml_) was added a solution of lithium hydroxide monohydrate (0.1657 g, 3.751 mmol) in water (3.5 ml_) at
• Step-10 Preparation of 5-[3-ethylsulfonyl-5-(2,2.2-trifluoroethoxy)-2-pyridyl1-2-(1 ,1 ,2,2,2- pentafluoroethyl)-6H-thieno[2,3-clpyrrol-4-one (compound P4)
• reaction mass was quenched with water (30 ml_), and the product extracted with ethyl acetate (3x 30 ml_).
• the combined organic layers were washed with water (3x 40 ml_), brine (30 ml_), dried over sodium sulfate, filtered and concentrated in vacuo.
• Example P6 Preparation of 5-[5-(2,2-difluoropropoxy)-3-ethylsulfonyl-2-pyridyll-2-(1 ,1 ,2,2,2- pentafluoroethyl)-6H-thienof2,3-clpyrrol-4-one (compound P6)
• Step-1 Preparation of methyl 5-acetonyloxy-3-ethylsulfanyl-pyridine-2-carboxylate (intermediate i-37)
• Step-2 Preparation of methyl 5-(2.2-difluoropropoxy)-3-ethylsulfanyl-pyridine-2-carboxylate
• Step-4 Preparation of tert-butyl N-[5-(2.2-difluoropropoxy)-3-ethylsulfanyl-2-pyridyl1carbamate (intermediate 1-40)
• Step-5 Preparation of tert-butyl N-[5-(2,2-difluoropropoxy)-3-ethylsulfonyl-2-pyridyllcarbamate
• Step-6 Preparation of ethyl 2-[[tert-butoxycarbonyl-[5-(2.2-difluoropropoxy)-3-ethylsulfonyl-2- pyridvnamino1methvn-5-(1 ,1 .2.2.2-pentafluoroethvDthiophene-3-carboxylate (intermediate i-42)
• Step-8 Preparation of 2-[[[5-(2.2-difluoropropoxy)-3-ethylsulfonyl-2-pyridyl1amino1methyl1-5-(1 ,1 ,2,2,2- pentafluoroethyl)thiophene-3-carboxylic acid (intermediate I-44)
• Step-9 Preparation of 5-[5-(2.2-difluoropropoxy)-3-ethylsulfonyl-2-pyridyl1-2-(1 ,1 ,2,2,2- pentafluoroethvD-6H-thieno[2,3-clpyrml-4-one (compound P6)
• reaction mass was acidified with an aqueous 2N hydrochloric acid (15 mL) solution, and the product extracted with ethyl acetate (2x 30 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo.
• the crude compound was purified by combiflash (silica gel, 50% ethyl acetate in cyclohexane) to afford 5-[5-(2,2-difluoropropoxy)-3- ethylsulfonyl-2-pyridyl]-2-(1 ,1 ,2,2,2-pentafluoroethyl)-6H-thieno[2,3-c]pyrrol-4-one (compound P6) as a white solid.
• Example P8 Preparation of 5-[5-(1 .1-difluoroethyl)-3-ethylsulfonyl-2-pyridyl1-2-(1 ,1 ,2,2,2- pentafluoroethyl)-6H-thieno[2,3-clpyrrol-4-one (compound P8)
• Step-1 Preparation of ethyl 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate (intermediate I-45)
• Step-2 Preparation of ethyl 5-bromo-3-ethylsulfonyl-pyridine-2-carboxylate (intermediate I-46)
• Step-3 Preparation of ethyl 5-acetyl-3-ethylsulfonyl-pyridine-2-carboxylate (intermediate I-47)
• reaction mixture was cooled and an aqueous 2N HCI solution (20 mL) was added. After stirring at room temperature for 30 minutes, the reaction mass was quenched with an aqueous KF solution, diluted with water (100 ml) and ethyl acetate (100 mL). The solution was filtered through celite and the residue washed with ethyl acetate (20 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo.
• Step-4 Preparation of ethyl 5-(1 .1-difluoroethyl)-3-ethylsulfonyl-pyridine-2-carboxylate
• Step-5 Preparation of 5-(1.1-difluoroethyl)-3-ethylsulfonyl-pyridine-2-carboxylic acid
• Step-6 Preparation of tert-butyl N-[5-(1 .1-difluoroethyl)-3-ethylsulfonyl-2-pyridyl1carbamate
• Step-7 Preparation of methyl 2-[[tert-butoxycarbonyl-[5-(1 ,1-difluoroethyl)-3-ethylsulfonyl-2- pyridyl1amino1methyl1-5-(1 ,1 ,2.2.2-pentafluoroethyl)thiophene-3-carboxylate (intermediate 1-51)
• reaction mixture was heated at 60 °C for 12 hours.
• the reaction mass was diluted with water and the product extracted with ethyl acetate.
• the organic layer was washed with water (2x) followed by brine, dried over sodium sulfate, filtered and concentrated in vacuo.
• Step-8 Preparation of methyl 2-[[[5-(1 .1-difluoroethyl)-3-ethylsulfonyl-2-pyridyl1amino1methyl1-5-
• Step-9 Preparation of 2-[[(5-acetyl-3-ethylsulfonyl-2-pyridyl)amino1methyl1-5-(1 ,1 ,2,2,2- pentafluoroethyl)thiophene-3-carboxylic acid (intermediate I-53)
• Step-10 Preparation of 5-(5-acetyl-3-ethylsulfonyl-2-pyridyl)-2-(1 ,1 ,2,2,2-pentafluoroethyl)-6H- thieno[2,3-clpyrrol-4-one (compound P9)
• reaction mass was acidified with an aqueous 2N hydrochloric acid (15 ml_) solution, and the product extracted with ethyl acetate (2x 30 ml_). The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo.
• the crude compound was purified by combiflash (silica gel, 10-50% ethyl acetate in cyclohexane) to afford 5-(5-acetyl-3-ethylsulfonyl-2-pyridyl)-2- (1 ,1 ,2,2,2-pentafluoroethyl)-6H-thieno[2,3-c]pyrrol-4-one (compound P9) as a light yellow solid.
• Step-11 Preparation of 5-[5-(1 .1-difluoroethyl)-3-ethylsulfonyl-2-pyridyl1-2-(1 ,1 ,2.2.2-pentafluoroethyl)- 6H-thieno[2,3-clpyrrol-4-one (compound P8)
• reaction mixture was quenched with a saturated solution of sodium bicarbonate, followed by ice-cold water (500ml_).
• aqueous phase was extracted with ethyl acetate (3x 75 ml_).
• the combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo.
• Step-1 Preparation of ethyl 6-chloro-3-ethylsulfonyl-pyridine-2-carboxylate (intermediate I-54)
• Step-2 Preparation of ethyl 6-cvclopropyl-3-ethylsulfonyl-pyridine-2-carboxylate (intermediate I-55)
• Step-3 Preparation of 6-cvclopropyl-3-ethylsulfonyl-pyridine-2-carboxylic acid (intermediate I-56)
• Step-4 Preparation of tert-butyl N-(6-cvclopropyl-3-ethylsulfonyl-2-pyridyl)carbamate (intermediate I-57)
• Step-5 Preparation of methyl 2-[[tert-butoxycarbonyl-(6-cvclopropyl-3-ethylsulfonyl-2- pyridvDamino1methvn-5-(1 ,1 .2.2.2-pentafluoroethvDthiophene-3-carboxylate (intermediate I-58)
• Step-6 Preparation of methyl 2-[[(6-cvclopropyl-3-ethylsulfonyl-2-pyridyl)amino1methyl1-5-(1 ,1 ,2,2,2- pentafluoroethyl)thiophene-3-carboxylate (intermediate I-59)
• Step-7 Preparation of 2-[[(6-cvclopropyl-3-ethylsulfonyl-2-pyridvDamino1methyl1-5-(1 ,1 ,2,2,2- pentafluoroethyr)thiophene-3-carboxylic acid (intermediate I-60)
• Step-8 Preparation of 5-(6-cvclopropyl-3-ethylsulfonyl-2-pyridyl)-2-(1 ,1 ,2.2.2-pentafluoroethyl)-6H- thieno[2,3-clpyrrol-4-one (compound P10)
• reaction mass was acidified with an aqueous 2N hydrochloric acid (15 mL) solution and the product extracted with ethyl acetate (2x 30 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo.
• the crude compound was purified by combiflash (silica gel, 10-50% ethyl acetate in cyclohexane) to afford 5-(6-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-2- (1 ,1 ,2,2,2-pentafluoroethyl)-6H-thieno[2,3-c]pyrrol-4-one (compound P10) as a light yellow solid.
• compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients.
• mixtures of the compounds of formula I with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use.
• Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
• TX means “one compound selected from the group consisting of the compounds described in Tables A-1 to A-12, Tables C-1 to C-12 and Table P of the present invention”: 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, afoxolaner + TX, alanycarb + TX, allethrin + TX, alpha-cypermethrin + TX, alphamethrin + TX, amidoflumet + TX, aminocarb + TX, azocyclotin + TX, bensultap + TX
• TX flumethrin + TX, fluopyram + TX, flupentiofenox + TX, flu pyradifu rone + TX, flupyrimin + TX, fluralaner + TX, fluvalinate + TX, fluxametamide + TX, fosthiazate + TX, gamma-cyhalothrin + TX, GossyplureTM + TX, guadipyr + TX, halofenozide + TX, halfenprox + TX, heptafluthrin + TX, hexythiazox + TX, hydramethylnon + TX, imicyafos + TX, imidacloprid + TX, imiprothrin + TX, indoxacarb + TX, iodomethane + TX, iprodione + TX, isocycloseram + TX, isothioate + TX, i
• Bacillus sp. AQ175 (ATCC Accession No. 55608) + TX, Bacillus sp. AQ177 (ATCC Accession No. 55609) + TX, Bacillus subtilis unspecified + TX, Bacillus subtilis AQ153 (ATCC Accession No. 55614) + TX, Bacillus subtilis AQ30002 (NRRL Accession No. B-50421) + TX, Bacillus subtilis AQ30004 (NRRL Accession No. B- 50455) + TX, Bacillus subtilis AQ713 (NRRL Accession No. B-21661) + TX, Bacillus subtilis AQ743 (NRRL Accession No.
• 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, Rhodoc
• TX Streptomyces sp. (NRRL Accession No. B- 30145) + TX, Terpenoid blend + TX, and Verticillium spp.; 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) (3
• 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 chlor
• TX hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal (alternative name) [CCN] + TX; a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX,
• Bacillus thuringiensis subsp. tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla carnea (alternative name) (151) + TX, Cryptolaemus montrouzieri (alternative name) (178) + TX, Cydia pomonella GV (alternative name) (191) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (alternative name) (300) + TX, Helicoverpa zea NPV (alternative name) (431) + TX, Heterorhabditis bacteriophora and H
• TX 6-isopentenylaminopurine (alternative name) (210) + TX, abamectin (1) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, cloethocarb (999) + TX, cyclobutrifluram + TX, cytokinins (alternative name) (210) + TX, dazomet
• 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.
• the compounds in this paragraph may be prepared from the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3- pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1- yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound may be prepared from the methods described in
• Bacillus subtilis strain AQ178 + TX Bacillus subtilis strain QST 713 (CEASE® + TX, Serenade® + TX, Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain AQ153 + TX, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis var.
• amyloliquefaciens strain FZB24 (Taegro® + TX, Rhizopro®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1 Ab + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis israelensis (BMP123® + TX, Aquabac® + TX, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin® + TX, Deliver® + TX, CryMax® + TX, Bonide® + TX, Scutella WP® + TX, Turilav WP ® + TX, Astuto® + TX, Dipel WP® + TX, Biobit® + TX, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone
• aizawai (XenTari® + TX, DiPel®) + TX, bacteria spp. (GROWMEND® + TX, GROWSWEET® + TX, Shootup®) + TX, bacteriophage of Clavipacter michiganensis (AgriPhage®) + TX, Bakflor® + TX, Beauveria bassiana (Beaugenic® + TX, Brocaril WP®) + TX, Beauveria bassiana GHA (Mycotrol ES® + TX, Mycotrol O® + TX, BotaniGuard®) + TX, Beauveria brongniartii (Engerlingspilz® + TX, Schweizer Beauveria® + TX, Melocont®) + TX, Beauveria spp.
• TX Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Bacillus thuringiensis tenebrionis (Novodor®) + TX, BtBooster + TX, Burkholderia cepacia (Deny® + TX, Intercept® + TX, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp.
• TX Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reuêtii + TX, Candida saitoana (Bio-Coat® + TX, Biocure®) + TX, Candida sake + TX, Candida spp.
• TX Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp.
• TX Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean® / Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop® + TX, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp.
• Pasteuria spp. Econem® + TX, Pasteuria nishizawae + TX, PeniciIHum aurantiogriseum + TX, PeniciIHum billai (Jumpstart® + TX, TagTeam®) + TX, PeniciIHum brevicompactum + TX, PeniciIHum frequentans + TX, PeniciIHum griseofulvum + TX, PeniciIHum purpurogenum + TX, PeniciIHum spp.
• 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 Chilocorus nigritus + TX, Chrysoperla carnea (Chrysoline®) + TX, Chrysoperla carnea (Chrysopa®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus spp.
• TX Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia fiavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug® + TX, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica + TX, Dacnusa sibirica (Minusa®) + TX, Diglyphus isaea (Diminex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis
• TX Eretmocerus siphonini + TX, Exochomus quadripustulatus + TX, Feltiella acarisuga (Spidend®) + TX, Feltiella acarisuga (Feltiline®) + TX, Fopius arisanus + TX, Fopius ceratitivorus + TX, Formononetin (Wirless Beehome®) + TX, Franklinothrips vespiformis (Vespop®) + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Flabrobracon hebetor + TX, Harmonia axyridis (HarmoBeetle®) + TX, Heterorhabditis spp.
• TX Psyttalia concolor (complex) + TX, Quadrastichus spp. + TX, Rhyzobius lophanthae + TX, Rodolia cardinalis + TX, Rumina decollate + TX, Semielacher petiolatus + TX, Sitobion avenae (Ervibank®) + TX, Steinernema carpocapsae (Nematac C® + TX, Millenium® + TX, BioNem C® + TX, NemAttack®
• TX 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, other biologicals including: abscisic acid + TX, bioSea® + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Colletotrichum gloeosporioides
• the designation is not a "common name”, the nature of the designation used instead is given in round brackets for the particular compound; in that case, the lUPAC name, the lUPAC/Chemical Abstracts name, a "chemical name”, a “traditional name”, a “compound name” or a “develoment code” is used or, if neither one of those designations nor a "common name” is used, an "alternative name” is employed. “CAS Reg. No” means the Chemical Abstracts Registry Number.
• the active ingredient mixture of the compounds of formula I selected from Tables A-1 to A-12, Tables C-1 to C-12 and Table P with active ingredients described above comprises a compound selected from Tables A-1 to A-12, Tables C-1 to C-12 and Table P and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1 :6000, especially from 50:1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10:1 to 1 :10, very especially from 5:1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1 :1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1
• 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 Tables A-1 to A-12, Tables C-1 to C- 12 and Table P and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
• the order of applying the compounds of formula I selected from Tables A-1 to A-12, Tables C-1 to C-12 and Table P and the active ingredients as described above is not essential for working the present invention.
• 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.
• Example B1 Activity against Bemisia tabaci (Cotton white fly): Feedinq/contact activity Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10 ⁇ 00 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: P1 , P2, P10, P11 , P14.
• Example B2 Activity against Diabrotica balteata (Corn root worm)
• Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10 ⁇ 00 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation.
• the following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1 , P2, P10, P11 , P12, P13, P14, P15.
• Example B3 Activity against Euschistus herns (Neotropical Brown Stink Bug)
• Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10 ⁇ 00 ppm DMSO stock solutions. After drying the leaves were infested with N2 nymphs. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation.
• the following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1 , P2, P11 , P13, P15.
• Example B4 Activity against Frankliniella occidentalis (Western flower thrips): Feedinq/contact activity Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10 ⁇ 00 DMSO stock solutions. After drying the leaf discs were infested with a Frankliniella population of mixed ages. The samples were assessed for mortality 7 days after infestation.
• Example B5 Activity against Plutella xylostella (Diamond back moth)
• 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10 ⁇ 00 ppm DMSO stock solutions by pipetting. After drying, Plutella eggs were pipetted through a plastic stencil onto a gel blotting paper and the plate was closed with it. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 8 days after infestation.
• the following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1 , P2, P10, P11 , P12, P13, P14, P15.
• Example B6 Activity against Mvzus persicae (Green peach aphid): Feedinq/Contact activity Sunflower leaf discs were placed onto agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10 ⁇ 00 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: P1 , P2, P10, P11 , P12, P13, P14, P15.
• Example B7 Activity against Spodoptera littoralis (Egyptian cotton leaf worm)
• Cotton leaf discs were placed onto agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10 ⁇ 00 ppm DMSO stock solutions. After drying the leaf discs were infested with five L1 larvae. The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.
• Example B8 Activity against Mvzus 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 ⁇ 00 DMSO stock solutions. The samples were assessed for mortality 6 days after placing seedlings into test solutions.
• Example B9 Activity against Chilo suppressalis (Striped rice stemborer)
• 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10 ⁇ 00 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (6-8 per well). The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 6 days after infestation. Control of Chilo suppressalis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.

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• 2021
  • 2021-07-16 WO PCT/EP2021/069946 patent/WO2022017975A1/fr active Application Filing

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