Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
  • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
  • C07D471/04—Ortho-condensed systems
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
  • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
  • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
• • 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
  • A01P3/00—Fungicides

Definitions

• Imidazo[1,2-a]pyridine derivatives The present invention relates to microbiocidal imidazo[1,2-a]pyridine derivatives, e.g. as active ingredients, which have microbiocidal activity, in particular fungicidal activity, more particularly activity against oomycetes.
• the invention also relates to preparation of these imidazo[1,2-a]pyridine derivatives, to intermediates useful in the preparation of these imidazo[1,2-a]pyridine derivatives, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of the imidazo[1,2- a]pyridine derivatives, to preparation of these compositions and to the use of the imidazo[1,2-a]pyridine derivatives or compositions in agriculture or horticulture for combating, controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi, more particularly oomycetes.
• the present invention provides compounds of formula (I) wherein Z is O or S, and preferably Z is O; R 1 is selected from C1-6alkyl, C1-6alkoxy-C1-6alkyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-4alkyl, C2-6alkenyl, C2- 6alkynyl, C1-6alkoxy, C1-6alkylsulfanyl-C1-6alkyl, C1-6alkylsulfinyl-C1-6alkyl, C1-6alkylsulfonyl-C1-6alkyl, C1- 6alkoxycarbonyl-C1-6alkyl, C1-6alkylaminocarbonyl-C1-6alkyl, diC1-6alkylaminocarbonyl-C1-6alkyl and CN, wherein
• R 3 , R 4 and R 5 are independently selected from H, C1-6alkyl, C1-6alkoxy, C1-6alkoxy-C1-6alkyl, C1-6alkoxy- C1-6alkoxy, halogen, CN, C2-6alkenyl, C2-6alkynyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-6alkyl, C1- 6alkylsulfanyl, C1-6alkylsulfinyl, C1-6alkylsulfonyl, C1-6alkoxycarbonyl, C1-6alkylaminocarbonyl, diC1- 6alkylaminocarbonyl;
• the present invention provides compounds of formula (I) wherein R 3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl, C2- 4alkenyl, C2-4alkynyl, C1-4alkoxy and CN, wherein each of the C1-4alkyl, C1-4alkoxy-C1-4alkyl, C3- 6cycloalkyl, C3-6cycloalkyl-C1-3alkyl, C2-4alkenyl, C2-4alkynyl and C1-4alkoxy groups is optionally substituted with one to three substituents independently selected from halogen and CN; R 2a , R 2b and R 2c are independently selected from H, halogen, CN, C1-4alkyl and C1-4alkoxy; J is CR 4 or N; G is CR 5 or N; wherein when J is N, then G is CR 5 ; and when G is N, then J is CR 4 ; R 3 , R 4 and R 5 are independently
• the present invention provides compounds of formula (I) wherein R 1 is selected from C1-4alkyl, C1-4alkoxy-C1-4alkyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl, C2- 4alkenyl, C2-4alkynyl, C1-4alkoxy and CN, wherein each of the C1-4alkyl, C1-4alkoxy-C1-4alkyl, C3- 6cycloalkyl, C3-6cycloalkyl-C1-3alkyl, C2-4alkenyl, C2-4alkynyl and C1-4alkoxy groups is optionally substituted with one to three substituents independently selected from halogen and CN; R 2a , R 2b and R 2c are independently selected from H, halogen, CN, C1-4alkyl and C1-4alkoxy; J is CR 4 or N; G is CR 5 or N; wherein when J is N, then G is CR 5 ; and when G
• the present invention provides an agrochemical composition comprising a compound of formula (I), and more particularly an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I).
• Said composition can further comprise at least one compound selected among an additional active ingredient, an appropriate formulation inert, a carrier, an adjuvant, and any mixtures thereof.
• Compounds of formula (I) may be used to control phytopathogenic microorganisms.
• a compound of formula (I), or a composition comprising a compound of formula (I) according to the invention may be applied directly to the phytopathogen, or to the locus of a phytopathogen, in particular to a plant susceptible to attack by phytopathogens, or to a propagation material of a plant.
• the present invention provides the use of a compound of formula (I), or a composition comprising a compound of formula (I), as described herein to combat, prevent or control a phytopathogen.
• the present invention provides a method of combating, preventing or controlling phytopathogens, comprising applying a compound of formula (I), or a composition comprising a compound of formula (I), as described herein to said phytopathogen, or to the locus of said phytopathogen, in particular to a plant susceptible to attack by a phytopathogen, or to a propagation material of a plant.
• Compounds of formula (I) are particularly effective in combating, preventing or controlling phytopathogenic fungi, in particular oomycetes.
• the present invention provides the use of a compound of formula (I), or a composition comprising a compound of formula (I), as described herein to control phytopathogenic fungi, in particular oomycetes.
• the present invention provides a method of combating, preventing or controlling phytopathogenic fungi, comprising applying a compound of formula (I), or a composition comprising a compound of formula (I), as described herein to said phytopathogenic fungi, or to the locus of said phytopathogenic fungi, in particular to a plant susceptible to attack by phytopathogenic fungi, in particular oomycetes, or to a propagation material of a plant.
• the present invention provides compounds of formula (XV), formula (XVI), formula (XXI), formula (XXII), formula (II), and formula (XVII), as respectively described in the invention.
• halogen refers to fluorine (fluoro or F), chlorine (chloro or Cl), bromine (bromo or Br) or iodine (iodo or I), preferably fluorine, chlorine or bromine.
• Alkyl as used herein- in isolation or as part of a chemical group - represents straight-chain or branched hydrocarbons, preferably with 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, 1- methylbutyl, 2-methylbutyl, 3-methylbutyl, 1 ,2- dimethylpropyl, 1 ,1 -dimethylpropyl, 2,2- dimethylpropyl, 1 -ethylpropyl, hexyl, 1 -methylpentyl, 2- methylpentyl, 3-methylpentyl, 4- methylpentyl, 1 ,2-dimethylpropyl, 1 ,3-dimethylbutyl, 1 ,4-dimethylbutyl, 2.3-dimethylbutyl, 1 ,1-
• Alkyl groups with 1 to 4 carbon atoms are preferred, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl.
• alkenyl in isolation or as part of a chemical group - represents straight-chain or branched hydrocarbons, preferably with 2 to 6 carbon atoms and at least one double bond, for example vinyl, 2- propenyl, 2-butenyl, 3-butenyl, 1- methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4- pentenyl, 1-methyl-2-butenyl, 2- methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3- butenyl, 3-methyl-3-butenyl, 1 ,1 - dimethyl-2-propenyl, 1 ,2-dimethyl-2-propenyl, 1 -ethyl-2-propenyl, 2- hexenyl, 3-hexenyl, 4- hexenyl, 5-hexenyl, 1 -methyl-2-pentenyl, 2-methyl-2
• Alkynyl in isolation or as part of a chemical group - represents straight-chain or branched hydrocarbons, preferably with 2 to 6 carbon atoms and at least one triple bond, for example 2-propynyl,
• cycloalkyl in isolation or as part of a chemical group - represents saturated or partially unsaturated mono-, bi- or tricyclic hydrocarbons, preferably with 3 to 10 carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1 ]heptyl, bicyclo[2.2.2]octyl or adamantyl. Cycloalkyls with 3, 4, 5, 6 or 7 carbon atoms are preferred, for example cyclopropyl or cyclobutyl.
• - Hydroxyl or hydroxy stands for a -OH group.
• 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.
• A is N
• R 6 is selected from C1-4alkyl and C1-4alkoxy, wherein each of said groups is optionally substituted with one to three substituents independently selected from halogen.
• embodiment 3 there is provided a compound according to embodiment 1 or 2, wherein A is N; and R 6 is selected from methyl, ethyl and methoxy.
• A is CH; and R 6 is selected from C1-4alkyl and C1-4alkoxy, wherein each of said groups is optionally substituted with one to three substituents independently selected from halogen.
• A is CH; and R 6 is selected from methyl, ethyl and methoxy.
• R 6 is methoxy.
• R 1 is selected from C1-4alkyl, C1-4alkoxy-C1-4alkyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl and C2-4alkynyl, wherein each of said groups is optionally substituted with one to three substituents independently selected from halogen and CN.
• R 1 is selected from methyl, ethyl, propyl, -CH2CH2-O-CH3, cyclopropyl, -CH2-cyclopropyl, -CH2-CF3, - CH2-C ⁇ CH, CH2CH2CN, and -CH2-CN.
• R 3 , R 4 and R 5 are independently selected from H, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 alkoxy-C 1-4 alkyl, C 1-4 alkoxy- C1-4alkoxy, halogen, CN, C2-4alkenyl, C2-4alkynyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl and hydroxy, wherein each of the C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, C2-4alkenyl, C2- 4alkynyl, C3-6cycloalkyl and C3-6cycloalkyl-C1-3alkyl groups is optionally substituted with one to three substituents independently selected from halogen.
• R 3 , R 4 and R 5 are independently selected from H, C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy- C 1-4 alkoxy, halogen, CN, C 2-4 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-3 alkyl and hydroxy, wherein each of the C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, C2-4alkynyl C3-6cycloalkyl and C3- 6cycloalkyl-C1-3alkyl groups is optionally substituted with one to three substituents independently selected from halogen.
• a compound according to embodiment 12 wherein J is CR 4 and G is CR 5 ; R 3 and R 5 are H; and R 4 is selected from C1-4alkyl, C1-4alkoxy, halogen, CN, and hydroxy, wherein each of the C1-4alkyl and C1-4alkoxy, groups is optionally substituted with one to three substituents independently selected from halogen.
• J is CR 4 and G is CR 5 ; R 3 and R 5 are H; and R 4 is selected from methyl, methoxy, chloro, fluoro, bromo, CN, and hydroxy.
• R 4 and R 5 are independently selected from C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1- 4alkoxy, halogen, CN, C2-4alkenyl, C2-4alkynyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl and hydroxy, wherein each of the C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, C2-4alkenyl, C2- 4 alkynyl, C 3-6 cycloalkyl and C 3-6 cycloalkyl-C 1-3 alkyl groups is optionally substituted with one to three substituents independently selected from halogen.
• J is CR 4 and G is CR 5 ;
• R 3 is H; and
• R 4 and R 5 are independently selected from C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1- 4alkoxy, halogen, CN, C2-4alkynyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl and hydroxy, wherein each of the C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, C2-4alkynyl, C3-6cycloalkyl and C3- 6cycloalkyl-C1-3alkyl groups is optionally substituted with one to three substituents independently selected from halogen.
• J is CR 4 and G is CR 5 ;
• R 3 is H;
• R 4 is selected from C1-4alkyl, C1-4alkoxy, halogen, CN, and hydroxy, wherein each of the the C1-4alkyl and C1-4alkoxy groups is optionally substituted with one to three substituents independently selected from halogen;
• R 5 is selected from C 1-4 alkyl, C 1-4 alkoxy, C 1-4 alkoxy-C 1-4 alkyl, C 1-4 alkoxy-C 1-4 alkoxy, halogen, CN, C 2- 4alkynyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl and hydroxy, wherein each of the C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, C2-4alkynyl, C3-6cycloalkyl, and C3-6cycloalkyl-C1-3
• J is CR 4 and G is CR 5 ;
• R 3 is H;
• R 4 is selected from methyl, methoxy, chloro, fluoro, bromo, CN, and hydroxy;
• R 5 is selected from methyl, -O-CH2-CH2-O-CH3, -CH2-CH2O-CH3, -O-CH3, -CH2-CF2H, fluoro, chloro, bromo, iodo, cyclopropyl, -C ⁇ CH, CN, -CF3, isopropyl and -O-CF2H.
• R 3 and R 4 are H; and R 5 is selected from C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, halogen, CN, C2- 4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-3 alkyl and hydroxy, wherein each of the C 1-4 alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, C2-4alkenyl, C2-4alkynyl, C3-6cycloalkyl and C3- 6cycloalkyl-C1-3alkyl groups is optionally substituted with one to three substituents independently selected from halogen.
• a compound according to embodiment 19 wherein J is CR 4 and G is CR 5 ; R 3 and R 4 are H; and R 5 is selected from C 1-4 alkyl, C 1-4 alkoxy, C 1-4 alkoxy-C 1-4 alkyl, C 1-4 alkoxy-C 1-4 alkoxy, halogen, CN, C 2- 4alkynyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl and hydroxy, wherein each of the C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, C2-4alkynyl, C3-6cycloalkyl and C3-6cycloalkyl-C1-3alkyl groups is optionally substituted with one to three substituents independently selected from halogen.
• J is CR 4 and G is CR 5 , R 3 and R 4 are H; and
• R 5 is selected from methyl, -O-CH2-CH2-O-CH3, -CH2-CH2O-CH3, -O-CH3, -CH2-CF2H, fluoro, chloro, bromo, iodo, cyclopropyl, -CECH, CN, -CF3, isopropyl and -O-CF2H.
• R 4 is selected from Ci-4alkyl, Ci-4alkoxy, halogen, CN, and hydroxy, wherein the alkyl groups are unsubstituted or substituted with one to three substituents independently selected from halogen; and R 3 and R 5 are independently selected from Ci-4alkyl, Ci-4alkoxy, Ci-4alkoxy-Ci-4alkyl, Ci-4alkoxy-Ci- 4alkoxy, halogen, CN, C2-4alkynyl, Cs ecycloalkyl, Cs ecycloalkyl-Ci-salkyl and hydroxy, wherein each of the Ci-4alkyl, Ci-4alkoxy, Ci-4alkoxy-Ci-4alkyl, Ci-4alkoxy-Ci-4alkoxy, C2-4alkynyl, Cs ecycloalkyl and C3- ecycloalkyl-Ci-salkyl groups is optionally substituted with one to three substituents independently selected from halogen.
• R 4 is selected from methyl, methoxy, chloro, fluoro, bromo, CN and hydroxy;
• R 3 and R 5 are independently selected from methyl, -O-CH2-CH2-O-CH3, -CH2-CH2O-CH3, -O-CH3, -CH2- CF2H, fluoro, chloro, bromo, iodo, cyclopropyl, -CECH, CN, -CF3, isopropyl and -O-CF2H.
• R 3 and R 5 are H;
• R 4 is chloro or fluoro.
• R 3 is H
• R 4 is fluoro
• R 5 is methyl
• R 3 is H
• R 4 is fluoro; and R 5 is -O-CH2-CH2-O-CH3.
• embodiment 28 there is provided a compound according to any one of embodiments 1 to 10, wherein J is CR 4 and G is CR 5 ; R 3 is H; R 4 is chloro, fluoro, bromo or iodo; and R 5 is -O-CH 3 .
• embodiment 29 there is provided a compound according to any one of embodiments 1 to 10, wherein J is CR 4 and G is CR 5 ; R 3 is H; R 4 is H; and R 5 is -CH2-CF2H.
• R 3 and R 4 are independently selected from H, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 alkoxy-C 1-4 alkyl, C 1-4 alkoxy-C 1- 4alkoxy, halogen, CN, C2-4alkenyl, C2-4alkynyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl and hydroxy, wherein each of the C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, C2-4alkenyl, C2- 4alkynyl, C3-6cycloalkyl and C3-6cycloalkyl-C1-3alkyl groups is optionally substituted with one to three substituents independently selected from halogen.
• R 3 is selected from C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, halogen, CN, C2- 4alkenyl, C2-4alkynyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl and hydroxy, wherein each of the C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, C2-4alkenyl, C2-4alkynyl, C3-6cycloalkyl and C3- 6cycloalkyl-C1-3alkyl groups is optionally substituted with one to three substituents independently selected from halogen; R 4 is H.
• J is CR 4 and G is N; and R 3 and R 4 are independently selected from H, methyl, -OCH3, -CF3, -OCF2H, halogen, -C ⁇ CH and CN.
• a compound according to embodiments 34 wherein J is CR 4 and G is N; and R 3 and R 4 are H.
• embodiment 37 there is provided a compound according to any one of embodiments 1 to 9, wherein J is N and G is CR 5 ; and R 3 and R 5 are independently selected from H, C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1- 4alkoxy, halogen, CN, C2-4alkenyl, C2-4alkynyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl and hydroxy, wherein each of the C 1-4 alkyl, C 1-4 alkoxy, C 1-4 alkoxy-C 1-4 alkyl, C 1-4 alkoxy-C 1-4 alkoxy, C 2-4 alkenyl, C 2- 4alkynyl, C3-6cycloalkyl and C3-6cycloalkyl-C1-3alkyl groups is optional
• a compound according to embodiment 37 wherein J is N and G is CR 5 ; R 3 is H; and R 5 is selected from C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, halogen, CN, C2- 4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-3 alkyl and hydroxy, wherein each of the C 1-4 alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, C2-4alkenyl, C2-4alkynyl, C3-6cycloalkyl and C3- 6cycloalkyl-C1-3alkyl groups is optionally substituted with one to three substituents independently selected from halogen.
• R 3 is selected from C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, halogen, CN, C2- 4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-3 alkyl and hydroxy, wherein each of the C 1-4 alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, C2-4alkenyl, C2-4alkynyl, C3-6cycloalkyl and C3- 6cycloalkyl-C1-3alkyl groups is optionally with one to three substituents independently selected from halogen; and R 5 is H.
• a compound according to embodiment 37 wherein J is N and G is CR 5 ; and R 3 and R 5 are independently selected from H, C1-4alkyl, C1-4alkoxy, halogen, CN and C2-4alkynyl, wherein each of the C1-4alkyl, C1-4alkoxy and C2-4alkynyl groups is optionally substituted with one to three substituents independently selected from halogen.
• R 3 and R 5 are independently selected from H, methyl, -OCH3, -CF3, -OCF2H, halogen, -C ⁇ CH and CN.
• a compound according to embodiment 37 wherein J is N and G is CR 5 ; and R 3 and R 5 are H.
• a preferred embodiment 10 there is provided a compound according to any one of embodiments 1 to 9, wherein A is N; R 3 is H; J is CR 4 and G is CR 5 ; R 4 is selected from C1-4alkyl, C1-4alkoxy, halogen, CN, and hydroxy, wherein each of the the C1-4alkyl and C 1-4 alkoxy groups is optionally substituted with one to three substituents independently selected from halogen; R 5 is selected from H, C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, halogen, CN, C2- 4alkynyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl and hydroxy, wherein each of the C1-4alkyl, C1-4alkoxy, C1-4alkoxy, C1-4alkoxy
• Z is S
• a compound according to any one of embodiments 1 to 9 wherein A is N; R 3 and R 5 are H; J is CR 4 and G is CR 5 ; R 4 is halogen or CN; and R 6 is selected from C 1-4 alkyl and C 1-4 alkoxy, wherein each of said groups is optionally substituted with one to three substituents independently selected from halogen.
• Z is O.
• a compound according to any one of embodiments 1 to 42 wherein the compound is selected from: - 3-(4-acetamidophenyl)-N-(4-chlorophenyl)-N-methyl-imidazo[1,2-a]pyridine-6-carboxamide, - methyl N-[4-[6-[(4-chlorophenyl)-methyl-carbamoyl]imidazo[1,2-a]pyridin-3-yl]phenyl]carbamate, - 3-(6-acetamido-3-pyridyl)-N-(4-chlorophenyl)-N-methyl-imidazo[1,2-a]pyridine-6-carboxamide, - methyl N-[5-[6-[(4-chlorophenyl)-methyl-carbamoyl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate, - methyl N-
• Table 1.1 provides compounds of formula (I) wherein Z is O;
• R 2a is H
• R 2b is H
• R 2c is H
• R 6 is methyl
• the values of R 1 , R 3 , J, G and A are as defined in Table Z.1 below.
• Tables 1.2 to 1.36 discloses individual compounds of the formula (I) in which R 2a , R 2b , R 2c and R 6 are specifically defined in Tables 1 .2 to 1 .36, which refer to Table Z.1 wherein R 1 , R 3 , J, G and A are specifically defined.
• Table 1 .2 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is H, R 2c is H and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1 .3 This table discloses specific compounds of formula (I) wherein R 2a is methyl, R 2b is H, R 2c is H and R 6 is methyl and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1 .4 This table discloses specific compounds of formula (I) wherein R 2a is methyl, R 2b is H, R 2c is H and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and Aare as defined in Table Z.1.
• Table 1.5 This table discloses specific compounds of formula (I) wherein R 2a is fluoro, R 2b is H, R 2c is H and R 6 is methyl and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1 .
• Table 1.6 This table discloses specific compounds of formula (I) wherein R 2a is fluoro, R 2b is H, R 2c is H and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1 .7 This table discloses specific compounds of formula (I) wherein R 2a is chloro, R 2b is H, R 2c is H and R 6 is methyl and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1 .
• Table 1 .8 This table discloses specific compounds of formula (I) wherein R 2a is chloro, R 2b is H, R 2c is H and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1 .9 This table discloses specific compounds of formula (I) wherein R 2a is bromo, R 2b is H, R 2c is H and R 6 is methyl and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1 .
• Table 1.10 This table discloses specific compounds of formula (I) wherein R 2a is bromo, R 2b is H, R 2c is H and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1.11 This table discloses specific compounds of formula (I) wherein R 2a is cyano, R 2b is H, R 2c is H and R 6 is methyl and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1 .
• Table 1.12 This table discloses specific compounds of formula (I) wherein R 2a is cyano, R 2b is H, R 2c is H and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1.13 This table discloses specific compounds of formula (I) wherein R 2a is methoxy, R 2b is H, R 2c is H and R 6 is methyl and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1 .
• Table 1.14 This table discloses specific compounds of formula (I) wherein R 2a is methoxy, R 2b is H, R 2c is H and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1.15 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is methyl, R 2c is H and R 6 is methyl and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1 .
• Table 1.16 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is methyl, R 2c is H and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1.17 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is methoxyx, R 2c is H and R 6 is methyl and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1 .
• Table 1.18 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is methoxy, R 2c is H and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1.19 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is fluoro, R 2c is H and R 6 is methyl and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1 .
• Table 1.20 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is fluoro, R 2c is H and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1 .21 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is chloro, R 2c is H and R 6 is methyl and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1 .
• Table 1 .22 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is chloro, R 2c is H and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1 .23 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is bromo, R 2c is H and R 6 is methyl and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1 .
• Table 1 .24 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is bromo, R 2c is H and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1 .25 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is cyano, R 2c is H and R 6 is methyl and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1 .
• Table 1 .26 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is cyano, R 2c is H and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1.27 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is H, R 2c is methyl and R 6 is methyl and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1.28 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is H, R 2c is methyl and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1 .
• Table 1 .29 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is H, R 2c is fluoro and R 6 is methyl and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1 .30 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is H, R 2c is fluoro and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1.31 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is H, R 2c is chloro and R 6 is methyl and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1.32 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is H, R 2c is chloro and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1.33 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is H, R 2c is bromo and R 6 is methyl and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1 .
• Table 1.34 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is H, R 2c is bromo and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1.35 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is H, R 2c is cyano and R 6 is methyl and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Table 1.36 This table discloses specific compounds of formula (I) wherein R 2a is H, R 2b is H, R 2c is cyano and R 6 is methoxy and wherein the values of R 1 , R 3 , J, G and A are as defined in Table Z.1.
• Compounds according to the invention may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi 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).
• Compounds according to the invention have particularly advantageous levels of biological activity for protecting plants against oomycetes such as Phytophthora, Plasmopara and Pythium.
• Compounds of formula (I) can be prepared via Suzuki cross coupling of compounds of formula (II), wherein X is chloro (Cl), bromo (Br) or iodo (I), and a compound of formula (III), wherein either R 7 is independently from each other hydrogen, Ci-Ce alkyl or wherein two R 7 together can form a Cs-Cs cycloalkyl, in the presence of a base, such as CS2CO3, K2CO3 or NaO/Bu, and a suitable palladium catalyst, such as tetrakistriphenylphosphinepalladium, palladium dichloride, [1 ,1- bis(diphenylphosphino)ferrocene]dichloropalladium(ll), palladium acetate or bis(diphenylphosphine)palladium(ll) chloride), in a suitable solvent, such as dimethylformamide, dioxane, tetrahydrofuran, ethanol or water
• Compounds of formula (II), wherein X is Cl, Br or I can be prepared by the reaction of a compound of formula (IV), wherein X is Cl, Br or I, with a compounds of formula (V) and a coupling agent, such as /V,/V-dicyclohexylcarbodiimide, bis(2-oxo-3-oxazolidinyl)phosphinic chloride, 2-(1 /7-benzotriazole-1-yl)- 1 ,1 ,3,3-tetramethyluronium hexafluorophosphate, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, propylphosphonic anhydride or cyanuric chloride, and, optionally, a base such, as triethylamine, ethyldiisopropylamine or /V-methylmorpholine in a suitable solvent such ethyl acetate, dimethylformamide
• compounds of formula (II), wherein X is Cl, Br or I can be prepared directly by the reaction of a compounds of formula (VI), wherein X is Cl, Br or I and R 8 is a Ci-Ce alkyl, and a compounds of formula (V) in the presence of (CHs)3AI or Bis(trimethylaluminum)-1 ,4-diazabicyclo[2.2.2]octane adduct in a suitable solvent, such as tetrahydrofuran or toluene.
• a suitable solvent such as tetrahydrofuran or toluene.
• Compounds of formula (VIII) are commercially available or, alternatively, can be prepared by the reaction of a compound of formula (IX), wherein X is Cl, Br or I, and a compound of formula (X), wherein X is Cl, Br or I, or its corresponding acetal of formula (XI), wherein X is Cl, Br or I and either R 9 is independently from each other C1-C6 alkyl or wherein two R 9 together can form a C3-C8 cycloalkyl, in a solvent, such as water, ethanol, acetone or acetonitrile.
• a solvent such as water, ethanol, acetone or acetonitrile.
• the outcome of the reaction can be improved by using a base, such as sodium bicarbonate or potassium carbonate, or by using an acid, such as p-toluenesulfonic acid or hydrogen bromide.
• a base such as sodium bicarbonate or potassium carbonate
• an acid such as p-toluenesulfonic acid or hydrogen bromide.
• this transformation can be utilized to prepare compounds of formula (VII), wherein R 8 is a C1-C6 alkyl, from a compound of formula (XII), wherein R 8 is a C1-C6 alkyl, and to prepare compounds of formula (XIII) from a compound of formula (XIV).
• compounds of formula (I) can be prepared by the reaction of a compound of formula (XV), with a compounds of formula (V) and a coupling agent, such as N,N'-dicyclohexylcarbodiimide, bis(2- oxo-3-oxazolidinyl)phosphinic chloride, 2-(1H-benzotriazole-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, propylphophonic anhydride or cyanuric chloride, and, optionally, a base such as triethylamine, ethyldiisopropylamine or N-methylmorpholine in a suitable solvent such ethyl acetate, dimethylformamide, tetrahydrofuran or dichloromethane.
• a coupling agent such as N,N'-dic
• Scheme 8 Compound of formula (XV) can be prepared by the saponification of compounds of formula (XVI), wherein R 8 is a C1-C6 alkyl, using a base such as NaOH or LiOH, in a suitable solvent such as methanol, ethanol or water at temperature between RT and reflux. This transformation is depicted in Scheme 9.
• R 8 is a C1-C6 alkyl
• R 8 is a C1-C6 alkyl
• a compound of formula (III) wherein either R 7 is independently from each other hydrogen, C1-C6 alkyl or wherein two R 7 together can form a C3-C8 cycloalkyl, in the presence of a base, such as Cs2CO3, K2CO3 or NaOtBu, and a suitable palladium catalyst, such as tetrakistriphenylphosphinepalladium, palladium dichloride, [1,1- bis(diphenylphosphino)ferrocene]dichloropalladium(II), palladium acetate or bis(diphenylphosphine)palladium(II) chloride), in a suitable solvent, such as dimethylformamide, dioxane,
• compounds of formula (II), wherein X is Cl, Br or I can be prepared by the reaction of a compound of formula (XVII) and a halogenating agent, such as N-chlorosuccinimide, N- bromosuccinimide, N-iodosuccinimide or bromine in a suitable solvent, such as dichloromethane, chloroform, tetrahydrofuran or acetonitrile. This transformation is depicted in schem 11 .
• a halogenating agent such as N-chlorosuccinimide, N- bromosuccinimide, N-iodosuccinimide or bromine
• a suitable solvent such as dichloromethane, chloroform, tetrahydrofuran or acetonitrile.
• Compounds of formula (XVII) can be prepared by the reaction of a compound of formula (XIII), with a compounds of formula (V) and a coupling agent, such as A/./V-dicyclohexylcarbodiimide, bis(2-oxo-3- oxazolidinyl)phosphinic chloride, 2-(1/7-benzotriazole-1-yl)-1 ,1 ,3,3-tetramethyluronium hexafluorophosphate, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, propylphophonic anhydride or cyanuric chloride, and, optionally, a base such as triethylamine, ethyldiisopropylamine or /V-methylmorpholine in a suitable solvent such ethyl acetate, dimethylformamide, tetra hydrofuran or dichloromethane.
• compounds of formula (II) can be prepared by the reaction of a compound of formula
• Compounds of formula (XVIII), wherein X is Cl, Br or I can be prepared by the reaction of a compound of formula (IV), wherein X is Cl, Br or I, with a compounds of formula (XX) and a coupling agent, such as /V,/V-dicyclohexylcarbodiimide, bis(2-oxo-3-oxazolidinyl)phosphinic chloride, 2-(1 /7-benzotriazole-1- yl)-1 ,1 ,3,3-tetramethyluronium hexafluorophosphate, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, propylphosphonic anhydride or cyanuric chloride, and, optionally, a base such, as triethylamine, ethyldiisopropylamine or /V-methylmorpholine in a suitable solvent such ethyl acetate, dimethyl
• compounds of formula (I) can be prepared by the reaction of a compound of formula (XXI) with a compound of formula (XXII), wherein Y is OH, and a coupling agent, such as N,/V- dicyclohexylcarbodiimide, bis(2-oxo-3-oxazolidinyl)phosphinic chloride, 2-(1 /-/-benzotriazole-1 -yl)- 1 ,1 ,3,3-tetramethyluronium hexafluorophosphate, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, propylphosphonic anhydride or cyanuric chloride, and, optionally, a base such as triethylamine, ethyldiisopropylamine or /V-methylmorpholine in a suitable solvent such ethyl acetate, dimethylformamide, tetra hydrofuran or
• the transformation can also be accomplished by the reaction of a compound of formula (XXI) with a compound of formula (XXII), wherein Y is Cl, and, optionally, a base such as, triethylamine, ethyldiisopropylamine or pyridine in a suitable solvent such as ethyl acetae, pyridine or tetrahydrofuran.
• a base such as, triethylamine, ethyldiisopropylamine or pyridine
• a suitable solvent such as ethyl acetae, pyridine or tetrahydrofuran.
• Compounds of formula (XXI) can be prepared via Suzuki cross coupling of compounds of formula (II), wherein X is Cl, Br or I, and a compound of formula (XXIII), wherein either R 7 is independently from each other hydrogen, Ci-Ce alkyl or wherein two R 7 together can form a C3-C8 cycloalkyl, in the presence of a base, such as CS2CO3, K2CO3 or NaO/Bu, and a suitable palladium catalyst, such as tetrakistriphenylphosphinepalladium, palladium dichloride, [1 ,1- bis(diphenylphosphino)ferrocene]dichloropalladium(ll), palladium acetate or bis(diphenylphosphine)palladium(ll) chloride), in a suitable solvent, such as dimethylformamide, dioxane, tetrahydrofuran, ethanol or water. This transformation is depicted in Scheme 16.
• compounds of formula (lb), wherein Z is S can be prepared by the reaction of a compound of formula (XXIV) with a compound of formula (XXII), wherein Y is OH, and a coupling agent, such as /V,/V-dicyclohexylcarbodiimide, bis(2-oxo-3-oxazolidinyl)phosphinic chloride, 2-(1 /7-benzotriazole-1-yl)- 1 ,1 ,3,3-tetramethyluronium hexafluorophosphate, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, propylphosphonic anhydride or cyanuric chloride, and, optionally, a base such as triethylamine, ethyldiisopropylamine or /V-methylmorpholine in a suitable solvent such ethyl acetate, dimethylformamide, t
• the transformation can also be accomplished by the reaction of a compound of formula (XXI) with a compound of formula (XXII), wherein Y is Cl, and, optionally, a base such as, triethylamine, ethyldiisopropylamine or pyridine in a suitable solvent such as ethyl acetae, pyridine or tetrahydrofuran.
• a base such as, triethylamine, ethyldiisopropylamine or pyridine
• a suitable solvent such as ethyl acetae, pyridine or tetrahydrofuran.
• the compounds according to any one of embodiments 1 to 43 can be obtained by using standard synthesis techniques known to the person skilled in the art.
• Non-exhaustive examples include oxidation reactions, reduction reactions, hydrolysis reactions, coupling reactions, aromatic nucleophilic or electrophilic substitution reactions, nucleophilic substitution reactions, nucleophilic addition reactions, olefination reactions, oxime formation, alkylation and halogenation reactions.
• a compound according to any one of embodiments 1 to 43 can be converted in a manner known per se into another compound according to any one of embodiments 1 to 43 by replacing one or more substituents of the starting compound according to any one of embodiments 1 to 43 in the customary manner by (an)other substituent(s) according to the invention.
• Salts of the compounds according to any one of embodiments 1 to 43 can be prepared in a manner known per se.
• acid addition salts of the compounds according to any one of embodiments 1 to 43 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 the compounds according to any one of embodiments 1 to 43 can be converted in the customary manner into the free compounds, 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 the compounds according to any one of embodiments 1 to 43 can be converted in a manner known per se into other salts of the compounds according to any one of embodiments 1 to 43, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
• a salt of inorganic acid such as hydrochloride
• a suitable metal salt such as a sodium, barium or silver salt
• the compounds according to any one of embodiments 1 to 43, which have salt-forming properties can be obtained in free form or in the form of salts.
• the compounds according to any one of embodiments 1 to 43 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 stereoisomers which are possible or as a mixture of these, for example in the form of pure stereoisomers, such as antipodes and/or diastereomers, or as stereoisomer 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 stereoisomers and also to all stereoisomer 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 the compounds according to any one of embodiments 1 to 43, 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
• N-oxides can be prepared by reacting a compound according to any one of embodiments 1 to 5 with a suitable oxidizing agent, for example the H2O2/urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride.
• a suitable oxidizing agent for example the H2O2/urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride.
• an acid anhydride e.g. trifluoroacetic anhydride.
• stereoisomer for example enantiomer or diastereomer, or stereoisomer mixture, for example enantiomer mixture or diastereomer mixture
• the individual components have a different biological activity.
• the compounds according to any one of embodiments 1 to 5 and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
• the following Examples illustrate, but do not limit, the invention.
• the present invention also provides intermediates useful for the preparation of compounds according to any one of embodiments 1 to 43.
• R 2a , R 2b and R 2c are independently selected from H, halogen, CN, C1-4alkyl and C1-4alkoxy.
• the preferences for A, R 2a , R 2b , R 2c , and R 6 are the same as the preferences set out for the corresponding substituents of the compound of formula (I).
• R 6 is selected from C1-6alkyl, C1-6alkoxy, C3-6cycloalkyl, C3-6cycloalkyl-C1-6alkyl, C1-6alkoxyC1-6alkyl, C1- 6alkylamino, diC1-6alkylamino, C1-6alkoxyamino, and C1-6alkylC1-6alkoxyamino, wherein each of said groups is optionally substituted with one to three substituents independently selected from halogen and CN; and preferably R 6 is selected from C1-4alkyl, C1-4alkoxy, C3-6cycloalkyl and C3-6cycloalkyl-C1-3alkyl, wherein each of said groups is optionally substituted with one to three substituents independently selected from halogen;
• R 8 is C1-C6 alkyl, and preferably R 8 is selected from methyl and ethyl; and
• R 2a , R 2b and R 2c are independently selected
• R 2a , R 2b and R 2c are independently selected from H, halogen, CN, C1-4alkyl and C1-4alkoxy.
• the preferences for A, R 2a , R 2b , R 2c , and R 6 are the same as the preferences set out for the corresponding substituents of the compound of formula (I).
• R 2a , R 2b and R 2c are independently selected from H, hydroxy, halogen, CN, C1-6alkyl, C3-6cycloalkyl, C1- 6alkoxy-C1-6alkyl, C3-6cycloalkyl-C1-4alkyl, C1-6alkylsulfanyl.
• C1-6alkylsulfinyl, C1-6alkylsulfonyl, C1-6alkoxy, amino, and NHC(O)C1-6alkyl, and preferably R 2a , R 2b and R 2c are independently selected from H, halogen, CN, C1-4alkyl and C1-4alkoxy.
• R 2a , R 2b and R 2c are the same as the preferences set out for the corresponding substituents of the compound of formula (I).
• a compound of formula (XXII) w R 8 is C1-C6 alkyl, and preferably R 8 is selected from methyl and ethyl; and R 2a , R 2b and R 2c are independently selected from H, hydroxy, halogen, CN, C1-6alkyl, C3-6cycloalkyl, C1- 6alkoxy-C1-6alkyl, C3-6cycloalkyl-C1-4alkyl, C1-6alkylsulfanyl.
• R 2a , R 2b and R 2c are independently selected from H, halogen, CN, C1-4alkyl and C1-4alkoxy.
• the preferences for R 2a , R 2b and R 2c are the same as the preferences set out for the corresponding substituents of the compound of formula (I).
• R 1 is selected from C1-4alkyl, C1-4alkoxy-C1-4alkyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl, C2- 4alkenyl, C2-4alkynyl, C1-4alkoxy and CN, wherein each of the C1-4alkyl, C1-4alkoxy-C1-4alkyl, C3- 6cycloalkyl, C3-6cycloalkyl-C1-3alkyl, C2-4alkenyl, C2-4alkynyl and C1-4alkoxy groups is optionally substituted with one to three substituents independently selected from halogen and CN;
• R 2a , R 2b and R 2c are independently selected from H, hydroxy, halogen, CN, C1-6alkyl, C3-6cycloalkyl, C1- 6alkoxy-C1-6alkyl, C3-6cycloalkyl-C1-4alkyl, C1-6alkylsulfanyl.
• R 2a , R 2b and R 2c are independently selected from H, halogen, CN, C1-4alkyl and C1-4alkoxy; J is CR 4 or N; G is CR 5 or N; wherein when J is N, then G is CR 5 ; and when G is N, then J is CR 4 ; R 3 , R 4 and R 5 are independently selected from H, C1-6alkyl, C1-6alkoxy, C1-6alkoxy-C1-6alkyl, C1-6alkoxy- C1-6alkoxy, halogen, CN, C2-6alkenyl, C2-6alkynyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-6alkyl, C1- 6alkylsulfanyl, C1-6alkylsulfinyl, C1-6alky
• R 3 and R 5 are independently selected from H, C1-6alkyl, C1-6alkoxy, C1- 6alkoxy-C1-6alkyl, C1-6alkoxy-C1-6alkoxy, halogen, CN, C2-6alkenyl, C2-6alkynyl, C3-6cycloalkyl, C3- 6cycloalkyl-C1-6alkyl, C1-6alkylsulfanyl, C1-6alkylsulfinyl, C1-6alkylsulfonyl, C1-6alkoxycarbonyl, C1- 6alkylaminocarbonyl, diC1-6alkylaminocarbonyl, C1-6alkylcarbonyl, and hydroxy, wherein each of the C1- 6alkyl, C1-6alkoxy, C1-6alkoxy-C1-6alkyl, C1-6alkoxy-C1-6alkoxy, C2-6alkenyl, C2-6alkynyl, C3-6cycloalkyl, C3
• R 4 is independently selected from H, C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, halogen, C2-4alkenyl, C2- 4alkynyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl and hydroxy, wherein each of the C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, C2-4alkenyl, C2-4alkynyl, C3-6cycloalkyl and C3-6cycloalkyl-C1- 3 alkyl groups is optionally substituted with one to
• R 1 is selected from C1-4alkyl, C1-4alkoxy-C1-4alkyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl, C2- 4alkenyl, C2-4alkynyl, C1-4alkoxy and CN, wherein each of the C1-4alkyl, C1-4alkoxy-C1-4alkyl, C3- 6cycloalkyl, C3-6cycloalkyl-C1-3alkyl, C2-4alkenyl, C2-4alkynyl and C1-4alkoxy groups is optionally substituted with one to three substituents independently selected from halogen and CN;
• R 2a , R 2b and R 2c are independently selected from H, hydroxy, halogen, CN, C1-6alkyl, C3-6cycloalkyl, C1- 6alkoxy-C1-6alkyl, C3-6cycloalkyl-C1-4alkyl, C1-6alkylsulfanyl.
• R 2a , R 2b and R 2c are independently selected from H, halogen, CN, C1-4alkyl and C1-4alkoxy; J is CR 4 or N; G is CR 5 or N; wherein when J is N, then G is CR 5 ; and when G is N, then J is CR 4 ; and R 3 , R 4 and R 5 are independently selected from H, C1-6alkyl, C1-6alkoxy, C1-6alkoxy-C1-6alkyl, C1-6alkoxy- C1-6alkoxy, halogen, CN, C2-6alkenyl, C2-6alkynyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-6alkyl, C1- 6alkylsulfanyl, C1-6alkylsulfinyl, C1-6al
• R 3 , R 4 and R 5 are the same as the preferences set out for the corresponding substituents of the compound of formula (I).
• at least one of R 3 , R 4 and R 5 is not H, and more particularly: - R 3 and R 4 are independently selected from C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1- 4alkoxy, halogen, CN, C2-4alkenyl, C2-4alkynyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl and hydroxy, wherein each of the C 1-4 alkyl, C 1-4 alkoxy, C 1-4 alkoxy-C 1-4 alkyl, C 1-4 alkoxy-C 1-4 alkoxy, C 2-4 alkenyl, C 2- 4al
• - R 3 is selected from H, C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, F, Br, I, CN, C2- 4alkenyl, C2-4alkynyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl and hydroxy, wherein each of the C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, C2-4alkenyl, C2-4alkynyl, C3-6cycloalkyl and C3- 6cycloalkyl-C1-3alkyl groups is optionally substituted with one to three substituents independently selected from halogen; and - R 4 and R 5 are independently selected from H, C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-
• R 3 and R 5 are more particularly not Cl.
• - R 3 is selected from C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, F, Br, I, CN, C2- 4alkenyl, C2-4alkynyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-3alkyl and hydroxy, wherein each of the C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy, C2-4alkenyl, C2-4alkynyl, C3-6cycloalkyl and C3- 6 cycloalkyl-C 1-3 alkyl groups is optionally substituted with one to three substituents independently selected from halogen; and - R 4 and R 5 are independently selected from H, C1-4alkyl, C1-4alkoxy,
• R 3 and R 5 are more particularly not Cl.
• the compounds of formula (I) as defined in any one of embodiments 1 to 43 can be used in the agricultural sector and related fields of use e.g. as active ingredients for controlling plant pests or on non-living materials for control of spoilage microorganisms or organisms potentially harmful to man.
• the novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and may be used for protecting numerous cultivated plants.
• the compounds of formula (I) as defined in any one of embodiments 1 to 43 can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.
• fungicide as used herein means a compound that controls, modifies, or prevents the growth of fungi.
• fungicidally effective amount means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.
• compounds of formula (I) as defined in any one of embodiments 1 to 43 as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings (for example rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
• the propagation material can be treated with a composition comprising a compound of formula (I) as defined in any one of embodiments 1 to 43 before planting: seed, for example, can be dressed before being sown.
• the compounds of formula (I) as defined in any one of embodiments 1 to 43 can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation.
• the composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing.
• the invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.
• any one of embodiments 1 to 43 can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management.
• the invention could be used to protect non-living materials from fungal attack, e.g. lumber, wall boards and paint.
• Compounds of formula (I) as defined in any one of embodiments 1 to 43 and fungicidal compositions containing them may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens. They are effective in controlling a broad spectrum of plant diseases, such as foliar pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops.
• fungi and fungal vectors of disease are for example: Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. comprising B.
• Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora spp. including C. arachidicola, Cercosporidium personatum, Cladosporium spp, Claviceps purpurea,
• Coccidioides immitis Cochliobolus spp, Colletotrichum spp. including C. musae, Cryptococcus neoformans, Diaporthe spp, Didymella spp, Drechslera spp, Elsinoe spp, Epidermophyton spp, Erwinia amylovora, Erysiphe spp. including E. cichoracearum, Eutypa lata, Fusarium spp. including F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F.
• capsulatum Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp, Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp. Including P. maydis, P.
• leucotricha Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia Spp. including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. including P. oryzae, Pythium spp. including P.
• Sclerotinia spp Sclerotium spp, Septoria spp, including S. nodorum, S. tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp, Stagonospora nodorum, Stemphylium spp,. Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp, Trichoderma spp. including T. harzianum, T. pseudokoningii, T. viride,
• Trichophyton spp Trichophyton spp, Typhula spp, Uncinula necator, Urocystis spp, Ustilago spp, Venturia spp. including V. inaequalis, Verticillium spp, and Xanthomonas spp.
• compounds of formula (I) as defined in any one of embodiments 1 to 43 and fungicidal compositions containing them may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and/or Deuteromycete, Blasocladiomycete, Chrytidiomycete, Glomeromycete and/or Mucoromycete classes. More particularly, the compounds of formula (I) as defined in any one of embodiments 1 to 43 may be used to conrol oomycetes. These pathogens may include:
• Oomycetes including Phytophthora diseases such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora and Phytophthora erythrose ptica; Pythium diseases such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare, Pythium sylvaticum and Pythium ultimurr diseases caused by Peronosporales such as Peronospora destructor, Peronospora parasitica, Plasmopara viticola, Plasmopara halstedii, Pseudoperonospora cubensis, Albugo Candida
• Ascomycetes including blotch, spot, blast or blight diseases and/or rots for example those caused by Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva, Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii, Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bi
• Gerlachia nivale Gibberella fujikuroi
• Gibberella zeae Gibberella zeae
• Gliocladium spp. Myrothecium verrucaria
• Nectria ramulariae Trichoderma viride
• Trichothecium roseum Trichothecium roseum
• Verticillium theobromae Myrothecium verrucaria
• Basidiomycetes including smuts for example those caused by Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, rusts for example those caused by Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia horde!, Puccinia striiformis f.sp.
• Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae
• rusts for example those caused by Pucciniales such as Cerotelium fici, Chr
• Puccinia striiformis f.sp. Secalis Pucciniastrum coryli, or Uredinales such as Cron art! urn ribicola, Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fabae; and other rots and diseases such as those caused by Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia so
• Blastocladiomycetes such as Physoderma maydis.
• Mucoromycetes such as Choanephora cucurbitarum.; Mucor spp.; Rhizopus arrhizus.
• the compounds and compositions comprising compounds of formula (I) as defined in any one of embodiments 1 to 43 may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species as well as certain protozoa.
• bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species as well as certain protozoa.
• target crops and/or useful plants to be protected typically comprise perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St.
• perennial and annual crops such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries
• cereals for example barley, maize (corn), millet, oats
• Augustine grass and Zoysia grass herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.
• herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme
• legumes for example beans, lentils, peas and soya beans
• the useful plants and I or target crops in accordance with the invention include conventional as well as genetically enhanced or engineered varieties such as, for example, insect resistant (e.g. Bt. and VIP varieties) as well as disease resistant, herbicide tolerant (e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®) and nematode tolerant varieties.
• suitable genetically enhanced or engineered crop varieties include the Stoneville 5599BR cotton and Stoneville 4892BR cotton varieties.
• useful plants and/or “target crops” is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5- enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering.
• herbicides like bromoxynil or classes of herbicides
• EPSPS 5- enol-pyrovyl-shikimate-3-phosphate-synthase
• GS glutamine synthetase
• PPO protoporphyrinogen-oxidase
• An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola).
• crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® , Herculex I® and LibertyLink®.
• useful plants and/or “target crops” is to be understood as including those which naturally are or have been rendered resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria. Examples of toxins which can be expressed include 8-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi.
• Vip vegetative insecticidal proteins
• insecticidal proteins of bacteria colonising nematodes and toxins produced by scorpions, arachnids, wasps and fungi.
• An example of a crop that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut® (Syngenta Seeds).
• An example of a crop comprising more than one gene that codes for insecticidal resistance and thus expresses more than one toxin is VipCot® (Syngenta Seeds).
• Crops or seed material thereof can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification).
• a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).
• useful plants and/or “target crops” is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225).
• PRPs pathogenesis-related proteins
• Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191 .
• the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
• Toxins that can be expressed by transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as 8- endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
• insecticidal proteins from Bacillus cereus or Bacillus popilliae such as 8- endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (
• 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
• ribosomeinactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
• steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdy
• 8-endotoxins for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins.
• Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701).
• Truncated toxins for example a truncated CrylAb, are known.
• modified toxins one or more amino acids of the naturally occurring toxin are replaced.
• amino acid replacements preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G- recognition sequence is inserted into a Cry3A toxin (see W003/018810).
• toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO93/07278, WO95/34656, EP-A-0 427 529, EP-A-451 878 and WG03/052073.
• the processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
• Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
• the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
• insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
• Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1 Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses
• transgenic crops are:
• MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810. 4.
• 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 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
• NK603 x 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.
• locus means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
• plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
• plant propagation material is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably “plant propagation material” is understood to denote seeds.
• Pesticidal agents referred to herein using their common name are known, for example, from "The Pesticide Manual", 19th Ed., British Crop Protection Council 2021.
• the compounds of formula (I) as defined in any one of embodiments 1 to 43 may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they may be conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
• adjuvants conventionally employed in the art of formulation
• Suitable carriers and/or adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.
• Such carriers are for example described in WO 97/33890.
• Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
• Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers.
• the particles contain the active ingredient retained in a solid matrix.
• Typical solid matrices include fuller’s earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.
• Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
• Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required.
• Typical carriers for granular formulations include sand, fuller’s earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound.
• Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils
• Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
• Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter.
• the enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound.
• Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores.
• Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and granular carbon.
• Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
• compositions for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents.
• Pressurised sprayers wherein the active ingredient is dispersed in finely-divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used.
• Suitable agricultural adjuvants and/or carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to those skilled in the art.
• Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol
• Water is generally the carrier of choice for the dilution of concentrates.
• suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller’s earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.
• a broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application.
• These agents when used, normally comprise from 0.1 % to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes.
• Typical surface active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub.
• alcohol-alkylene oxide addition products such as tridecyl alcohol-C.sub. 16 ethoxylate
• soaps such as sodium stearate
• alkylnaphthalenesulfonate salts 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 lauryl trimethylammonium chloride
• polyethylene glycol esters of fatty acids such as polyethylene glycol stearate
• salts of mono and dialkyl phosphate esters such as mono and dialkyl phosphate esters.
• adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.
• biocidally active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank. These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides, plant growth regulators, and/or biologicals.
• TX means “one compound selected from the compounds defined in the Tables 1 .1 to 1 .36” or “one compound selected from the compounds defined in the Table A”
• an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX; 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, benzoximate + TX
• TX Neem tree based products + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria usgae + TX, P-cymene + TX, Plutella xylostella Granulosis virus + TX, Plutella xylostella Nucleopolyhedrovirus + TX, Polyhedrosis virus + TX, pyrethrum + TX, QRD 420 (a terpenoid blend) + TX, QRD 452 (a terpenoid blend) + TX, QRD 460 (a terpenoid blend) + TX, Quillaja saponaria + TX, Rhodococc
• TX Streptomyces sp. (NRRL Accession No. B-30145) + TX, Terpenoid blend + TX, and Verticillium spp. + TX; an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name
• TX Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575) + TX, Orius spp.
• TX Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp.
• TX TX
• a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1 ,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alphachlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (including alpha-bromadiolone) + TX, bromethalin (92) + TX, calcium cyanide (44
• TX TX, octhilinone (590) and thiophanate-methyl (802) + TX; a biologically active substance selected from 1 ,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4- dichlorophenyl benzenesulfonate + TX, 2-fluoro-N-methyl-N-1 -naphthylacetamide + TX, 4-chlorophenyl phenyl sulfone + TX, acetoprole + TX, aldoxycarb + TX, amidithion + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, aramite + TX, arsenous oxide + TX, azobenzene + TX, azothoate + TX, benomyl + TX, benoxafos + TX, benzyl benzoate
• TX 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, DiPei®) + TX, bacteria 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® I Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop® + TX, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp.
• Pasteuria spp. Econem® + TX, Pasteuria nishizawae + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart® + TX, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp.
• TX Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Ps
• Rhodosporidium diobovatum + TX Rhodosporidium toruloides + TX, Rhodotorula spp.
• Trichoderma asperellum T34 Biocontrol®
• Trichoderma gamsii TX
• Trichoderma atroviride Plant®
• Trichoderma harzianum rifai Mycostar®
• Trichoderma harzianum T-22 Trianum-P® + TX, Plantshield HC® + TX, Rootshield® + TX, Trianum-G®) + TX, Trichoderma harzianum T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma spp.
• LC 52 (Sentinel®) + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma taxi + TX, Trichoderma virens + TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®) + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium spp.
• TX Trichothecium roseum + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplementary micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Verticillium lecanii (Mycotal® + TX, Vertalec®) + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhab
• Plant extracts including: pine oil (Retenol®) + TX, azadirachtin (Plasma Neem Oil ® + TX, AzaGuard® + TX, MeemAzal® + TX, Molt-X® + TX, Botanical IGR (Neemazad® + TX, Neemix®) + TX, canola oil (Lilly Miller Vegol®) + TX, Chenopodium ambrosioides near ambrosioides (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, extract of neem oil (Trilogy®) + TX, essentials oils of Labiatae (Botania®) + TX, extracts of clove rosemary peppermint and thyme oil (Garden insect killer®) + TX, Glycinebetaine (Greenstim®) + TX, garlic + TX, lemongrass oil (GreenMatch®) + TX, neem oil
• TX Coccidoxenoides perminutus (Pianopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug® + TX, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica + TX, Dacnusa sibirica (Minusa®) + TX, Diglyphus isaea (Diminex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis
• TX Steinemematid 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 gloeosporio
• antibacterial agents selected from the group of:
• Bacillus mojavensis strain R3B accesion No. NCAIM (P) B001389) (WO 2013/034938) from Certis USA LLC, a subsidiary of Mitsui & Co. + TX
• Bacillus pumilus in particular strain BU F-33, having NRRL Accession No. 50185 (available as part of the CARTISSA® product from BASF, EPA Reg. No. 71840-19) + TX
• Bacillus subtilis in particular strain QST713/AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRL Accession No. B21661 , U.S. Patent No.
• Bacillus subtilis strain BU1814 (available as VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) + TX; Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No. 70127-5)) + TX; Bacillus subtilis CX-9060 from Certis USA LLC, a subsidiary of Mitsui & Co.
• Bacillus sp. in particular strain D747 (available as DOUBLE NICKEL® from Kumiai Chemical Industry Co., Ltd.), having Accession No. FERM BP-8234, U.S. Patent No. 7,094,592 + TX; Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129, WO 2016/154297 + TX;
• Paenibacillus polymyxa in particular strain AC-1 (e.g. TOPSEED® from Green Biotech Company Ltd.) + TX; Pantoea agglomerans, in particular strain E325 (Accession No. NRRL B-21856) (available as BLOOMTIME BIOLOGICALTM FD BIOPESTICIDE from Northwest Agri Products) + TX; Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX; and
• fungi examples of which are Aureobasidium pullulans, in particular blastospores of strain DSM14940, blastospores of strain DSM 14941 or mixtures of blastospores of strains DSM14940 and DSM14941 (e.g., BOTECTOR® and BLOSSOM PROTECT® from bio-ferm, CH) + TX; Pseudozyma aphidis (as disclosed in WO2011/151819 by Yissum Research Development Company of the Hebrew University of Jerusalem) + TX; Saccharomyces cerevisiae, in particular strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938 or CNCM No. 1-3939 (WO 2010/086790) from Lesaffre et Compagnie, FR;
• Aureobasidium pullulans in particular blastospores of strain DSM14940, blastospores of strain DSM 14941 or mixtures of blastospores
• bacteria examples of which are Agrobacterium radiobacter strain K84 (e.g. GALLTROL-A® from AgBioChem, CA) + TX; Agrobacterium radiobacter strain K1026 (e.g. NOGALLTM from BASF SE) + TX; Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No.
• Agrobacterium radiobacter strain K84 e.g. GALLTROL-A® from AgBioChem, CA
• Agrobacterium radiobacter strain K1026 e.g. NOGALLTM from BASF SE
• Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No.
• Bacillus amyloliquefaciens in particular strain D747 (available as Double NickelTM from Kumiai Chemical Industry Co., Ltd., having accession number FERM BP-8234, US Patent No. 7,094,592) + TX; Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL Accession No. B-50768, WO 2014/028521) (STARGUS® from Marrone Bio Innovations) + TX; Bacillus amyloliquefaciens strain FZB42, Accession No.
• DSM 23117 (available as RHIZOVITAL® from ABiTEP, DE) + TX; Bacillus amyloliquefaciens isolate B246 (e.g. AVOGREENTM from University of Pretoria) + TX; Bacillus licheniformis, in particular strain SB3086, having Accession No. ATCC 55406, WO 2003/000051 (available as ECOGUARD® Biofungicide and GREEN RELEAFTM from Novozymes) + TX + TX;
• Bacillus amyloliquefaciens isolate B246 e.g. AVOGREENTM from University of Pretoria
• Bacillus licheniformis in particular strain SB3086, having Accession No. ATCC 55406, WO 2003/000051 (available as ECOGUARD® Biofungicide and GREEN RELEAFTM from Novozymes) + TX + TX;
• Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (QUARTZO® (WG) and PRESENCE® (WP) from FMC Corporation) + TX; Bacillus methylotrophicus strain BAC-9912 (from Chinese Academy of Sciences’ Institute of Applied Ecology) + TX; Bacillus mojavensis strain R3B (Accession No. NCAIM (P) B001389) (WO 2013/034938) from Certis USA LLC, a subsidiary of Mitsui & Co. + TX; Bacillus mycoides, isolate, having Accession No.
• Bacillus pumilus, in particular strain QST2808 (available as SONATA® from Bayer CropScience LP, US, having Accession No. NRRL B-30087 and described in U.S. Patent No. 6,245,551) + TX; Bacillus pumilus, in particular strain GB34 (available as Yield Shield® from Bayer AG, DE) + TX; Bacillus pumilus, in particular strain BU F-33, having NRRL Accession No. 50185 (available as part of the CARTISSA product from BASF, EPA Reg. No.
• Bacillus subtilis in particular strain QST713/AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRL Accession No. B21661 and described in U.S. Patent No. 6,060,051) + TX; Bacillus subtilis Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos. 4764, 5454, 5096 and 5277) + TX; Bacillus subtilis strain MBI 600 (available as SUBTILEX from BASF SE), having Accession Number NRRL B-50595, U.S. Patent No.
• Bacillus subtilis strain GB03 (available as Kodiak® from Bayer AG, DE) + TX
• Bacillus subtilis CX-9060 from Certis USA LLC, a subsidiary of Mitsui & Co. + TX;
• Bacillus subtilis KTSB strain FOLIACTIVE® from Donaghys
• Bacillus subtilis IAB/BS03 AVIVTM from STK Bio-Ag Technologies, PORTENTO® from Idai Nature
• Bacillus subtilis strain Y1336 available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos. 4764, 5454, 5096 and 5277
• Paenibacillus epiphyticus (WO 2016/020371) from BASF SE + TX
• Paenibacillus polymyxa ssp. plantarum WO 2016/020371 from BASF SE + TX
• strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129, WO 2016/154297 + TX; Pseudomonas chlororaphis strain AFS009, having Accession No. NRRL B-50897, WO 2017/019448 (e.g., HOWLERTM and ZIO® from AgBiome Innovations, US) + TX; Pseudomonas chlororaphis, in particular strain MA342 (e.g. CEDOMON®, CERALL®, and CEDRESS® by Bioagri and Koppert) + TX; Pseudomonas fluorescens strain A506 (e.g.
• (2.2) fungi examples of which are Ampelomyces quisqualis, in particular strain AQ 10 (e.g. AQ 10® by IntrachemBio Italia) + TX; Ampelomyces quisqualis strain AQ10, having Accession No.
• CNCM 1-807 e.g., AQ 10® by IntrachemBio Italia
• TX Aspergillus flavus strain NRRL 21882 (products known as AFLA-GUARD® from Syngenta/ChemChina) + TX
• Aureobasidium pullulans in particular blastospores of strain DSM14940 + TX
• Aureobasidium pullulans in particular blastospores of strain DSM 14941 + TX
• Aureobasidium pullulans in particular mixtures of blastospores of strains DSM14940 and DSM 14941 (e.g. Botector® by bio-ferm, CH) + TX
• Chaetomium cupreum accesion No.
• CABI 353812 e.g. BIOKUPRUMTM by AgriLife
• TX Chaetomium globosum (available as RIVADIOM® by Rivale) + TX
• Coniothyrium minitans, in particular strain CON/M/91-8 accesion No. DSM9660, e.g.
• Prestop ® by Lallemand + TX; Gliocladium roseum (also known as Clonostachys rosea f rosea), in particular strain 321 U from Adjuvants Plus, strain ACM941 as disclosed in Xue (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea, Can Jour Plant Sci 83(3): 519-524), or strain IK726 (Jensen DF, et al. Development of a biocontrol agent for plant disease control with special emphasis on the near commercial fungal antagonist Clonostachys rosea strain ’IK726’, Australas Plant Pathol.
• Penicillium steckii (DSM 27859, WO 2015/067800) from BASF SE + TX; Penicillium vermiculatum + TX; Phlebiopsis gigantea strain VRA 1992 (ROTSTOP® C from Danstar Ferment) + TX; Pichia anomala, strain WRL-076 (NRRL Y-30842), U.S. Patent No.
• Trichoderma atroviride in particular strain SC1 (having Accession No. CBS 122089, WO 2009/116106 and U.S. Patent No. 8,431 ,120 (from Bi-PA)), strain 77
• Trichoderma atroviride strain NMI no. V08/002389 + TX
• Trichoderma atroviride strain NMI no. V08/002390 + TX
• Trichoderma atroviride strain LC52 (e.g. Tenet by Agrimm Technologies Limited) + TX
• Trichoderma atroviride strain ATCC 20476 (IMI 206040) + TX;
• Trichoderma atroviride strain T1 1 (IMI352941 / CECT20498) + TX; Trichoderma atroviride, strain SKT- 1 (FERM P-16510), JP Patent Publication (Kokai) 11-253151 A + TX; Trichoderma atroviride, strain SKT-2 (FERM P-16511), JP Patent Publication (Kokai) 11-253151 A + TX; Trichoderma atroviride, strain SKT-3 (FERM P-17021), JP Patent Publication (Kokai) 11-253151 A + TX; Trichoderma fertile (e.g. product TrichoPlus from BASF) + TX; Trichoderma gamsii (formerly T.
• Trichoderma fertile e.g. product TrichoPlus from BASF
• strain ICC080 (IMI CC 392151 CABI, e.g. BioDerma by AGROBIOSOL DE MEXICO, S.A. DE C.V.) + TX; Trichoderma gamsii (formerly T. viride), strain ICC 080 (IMI CC 392151 CABI) (available as BIODERMA® by AGROBIOSOL DE MEXICO, S.A. DE C.V.) + TX; Trichoderma harmatum + TX; Trichoderma harmatum, having Accession No. ATCC 28012 + TX; Trichoderma harzianum strain T-22 (e.g.
• Trianum-P from Andermatt Biocontrol or Koppert or strain Cepa SimbT5 (from Simbiose Agro) + TX; Trichoderma harzianum + TX; Trichoderma harzianum rifai T39 (e.g. Trichodex® from Makhteshim, US) + TX; Trichoderma harzianum, strain ITEM 908 (e.g. Trianum-P from Koppert) + TX; Trichoderma harzianum, strain TH35 (e.g.
• Trichoderma harzianum, strain DB 103 available as T-GRO® 7456 by Dagutat Biolab) + TX; Trichoderma polysporum, strain IMI 206039 (e.g. Binab TF WP by BINAB Bio-Innovation AB, Sweden) + TX; Trichoderma stromaticum, having Accession No. Ts3550 (e.g. Tricovab by CEPLAC, Brazil) + TX; Trichoderma virens (also known as Gliocladium virens), in particular strain GL-21 (e.g. SoilGard by Certis, US) + TX; Trichoderma virens strain G-41 , formerly known as Gliocladium virens (Accession No. ATCC 20906) (e.g.,
• Trichoderma viride strain TV1 (e.g. Trianum-P by Koppert) + TX; Trichoderma viride, in particular strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie 161 : 125-137) + TX; mixtures of Trichoderma asperellum strain ICC 012 (also known as Trichoderma harzianum ICC012), having Accession No. CABI CC IMI 392716 and Trichoderma gamsii (formerly T. viride) strain ICC 080, having Accession No.
• IMI 392151 e.g., BIO-TAMTM from Isagro USA, Inc. and BIODERMA® by Agrobiosol de Mexico, S.A. de C.V.
• Ulocladium oudemansii strain U3, having Accession No. NM 99/06216 e.g., BOTRY-ZEN® by Botry-Zen Ltd, New Zealand and BOTRYSTOP® from BioWorks, Inc.
• Verticillium albo-atrum (formerly V. dahliae), strain WCS850 having Accession No. WCS850, deposited at the Central Bureau for Fungi Cultures (e.g., DUTCH TRIG® by Tree Care Innovations) + TX
• Verticillium chlamydosporium + TX e.g., BIO-TAMTM from Isagro USA, Inc. and BIODERMA® by Agrobiosol de Mexico, S.A. de C.V.
• biological control agents having an effect for improving plant growth and/or plant health selected from the group of:
• (3.1) bacteria examples of which are Azospirillum brasilense (e.g., VIGOR® from KALO, Inc.) + TX; Azospirillum lipoferum (e.g., VERTEX-IFTM from TerraMax, Inc.) + TX; Azorhizobium caulinodans, in particular strain ZB-SK-5 + TX; Azotobacter chroococcum, in particular strain H23 + TX; Azotobacter vinelandii, in particular strain ATCC 12837 + TX; a mixture of Azotobacter vinelandii and Clostridium pasteurianum (available as INVIGORATE® from Agrinos) + TX; Bacillus amyloliquefaciens pm414 (LOLI-PEPTA® from Biofilm Crop Protection) + TX; Bacillus amyloliquefaciens SB3281 (ATCC # PTA- 7542, WO 2017/205258) + TX; Bacillus
• Bacillus pumilus in particular strain QST2808 (having Accession No. NRRL No. B-30087) + TX; Bacillus pumilus, in particular strain GB34 (e.g.
• Bacillus subtilis in particular strain AQ30002 (having Accession Nos. NRRL B-50421 and described in U.S. Patent Application No. 13/330,576) + TX; Bacillus subtilis, in particular strain AQ30004 (and NRRL B-50455 and described in U.S. Patent Application No. 13/330,576) + TX; Bacillus subtilis strain BU1814, (available as TEQUALIS® from BASF SE), Bacillus subtilis rm303 (RHIZOMAX® from Biofilm Crop Protection) + TX; Bacillus thuringiensis BT013A (NRRL No.
• Bacillus thuringiensis 4Q7 + TX also known as Bacillus thuringiensis 4Q7 + TX; a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (available as QUARTZO® (WG), PRESENCE® (WP) from FMC Corporation) + TX; Bacillus subtilis, in particular strain MBI 600 (e.g. SUBTILEX® from BASF SE) + TX; Bacillus tequilensis, in particular strain NII-0943 + TX; Bradyrhizobium japonicum (e.g. OPTIMIZE® from Novozymes) + TX; Delftia acidovorans, in particular strain RAY209 (e.g. BIOBOOST® from Brett Young Seeds) + TX; Mesorhizobium cicer (e.g., NODULATOR from BASF SE) + TX; Lactobacillus sp. (e.g., Bac
• Trianum-P from Andermatt Biocontrol or Koppert TX
• Myrothecium verrucaria strain AARC-0255 e.g. DiTeraTM from Valent Biosciences
• Pythium oligandrum strain M1 ATCC 38472, e.g. Polyversum from Bioprepraty, CZ
• Trichoderma virens strain GL-21 e.g. SoilGard® from Certis, USA
• Verticillium albo-atrum (formerly V. dahliae) strain WCS850 (CBS 276.92, e.g.
• Trichoderma atroviride in particular strain no. V08/002387, strain no. NMI No. V08/002388, strain no. NMI No. V08/002389, strain no. NMI No. V08/002390 + TX; Trichoderma harzianum strain ITEM 908, Trichoderma harzianum, strain TSTh20 + TX; Trichoderma harzianum strain 1295-22 + TX; Pythium oligandrum strain DV74 + TX; Rhizopogon amylopogon (e.g. comprised in Myco-Sol from Helena Chemical Company) + TX; Rhizopogon fulvigleba (e.g. comprised in Myco- Sol from Helena Chemical Company) + TX;Trichoderma virens strain GI-3 + TX;
• Rhizopogon amylopogon e.g. comprised in Myco-Sol from Helena Chemical Company
• Rhizopogon fulvigleba e.
• bacteria examples of which are Agrobacterium radiobacter strain K84 (Galltrol from AgBiochem Inc.) + TX; Bacillus amyloliquefaciens, in particular strain PTS-4838 (e.g. AVEO from Valent Biosciences, US) + TX; Bacillus firmus, in particular strain CNMC 1-1582 (e.g. VOTIVO® from BASF SE) + TX; Bacillus mycoides, isolate J. (e.g. BmJ from Certis USA LLC, a subsidiary of Mitsui & Co.) + TX; Bacillus sphaericus, in particular Serotype H5a5b strain 2362 (strain ABTS-1743) (e.g.
• Bacillus thuringiensis subsp. aizawai in particular strain ABTS-1857 (SD-1372, e.g. XENTARI® from Valent BioSciences) + TX; Bacillus thuringiensis subsp. aizawai, in particular serotype H-7
• israelensis (serotype H-14) strain AM65-52 (Accession No. ATCC 1276) (e.g. VECTOBAC® by Valent BioSciences, US) + TX; Bacillus thuringiensis subsp. aizawai strain GC-91 + TX; Bacillus thuringiensis var. Colmeri (e.g. TIANBAOBTC by Changzhou Jianghai Chemical Factory) + TX; Bacillus thuringiensis var. japonensis strain Buibui + TX; Bacillus thuringiensis subsp. kurstaki strain BMP 123 from Becker Microbial Products, IL + TX; Bacillus thuringiensis subsp.
• israeltaki strain SA 11 (JAVELIN from Certis, US) + TX; Bacillus thuringiensis subsp. kurstaki strain SA 12 (THURICIDE from Certis, US) + TX; Bacillus thuringiensis subsp. kurstaki strain EG 2348 (LEPINOX from Certis, US) + TX; Bacillus thuringiensis subsp. kurstaki strain EG 7841 (CRYMAX from Certis, US) + TX; Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD-5428, e.g.
• Chromobacterium subtsugae in particular strain PRAA4-1T (MBI-203 + TX; e.g. GRANDEVO® from Marrone Bio Innovations) + TX; Lecanicillium muscarium Ve6 (MYCOTAL from Koppert) + TX; Paenibacillus popilliae (formerly Bacillus popilliae + TX; e.g. MILKY SPORE POWDERTM and MILKY SPORE GRANULARTM from St. Gabriel Laboratories) + TX; Pasteuria nishizawae strain Pn1 (CLARIVA from Syngenta/ChemChina) + TX;Serratia entomophila (e.g.
• (4.2) fungi examples of which are Beauveria bassiana strain ATCC 74040 (e.g. NATURALIS® from Intrachem Bio Italia) + TX; Beauveria bassiana strain GHA (Accession No. ATCC74250, e.g. BOTANIGUARD® ES and MYCONTROL-O® from Laverlam International Corporation) + TX; Beauveria bassiana strain ATP02 (Accession No. DSM 24665) + TX;/sa/7a fumosorosea (previously known as Paecilomyces fumosoroseus) strain Apopka 97) PREFERAL from SePRO + TX;
• Beauveria bassiana strain ATCC 74040 e.g. NATURALIS® from Intrachem Bio Italia
• GHA Accession No. ATCC74250, e.g. BOTANIGUARD® ES and MYCONTROL-O® from Laverlam International Corporation
• Metarhizium anisopliae 3213-1 (deposited under NRRL accession number 67074) (WO 2017/066094 + TX; Pioneer Hi-Bred International) + TX; Metarhizium robertsii 15013-1 (deposited under NRRL accession number 67073) + TX; Metarhizium robertsii 23013-3 (deposited under NRRL accession number 67075) + TX; Paecilomyces lilacinus strain 251 (MELOCON from Certis, US) + TX; Zoophtora radicans + TX;
• Viruses selected from the group consisting of Adoxophyes orana (summer fruit tortrix) granulosis virus (GV) + TX; Cydia pomonella (codling moth) granulosis virus (GV) + TX; Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis virus (NPV) + TX; Spodoptera exigua (beet armyworm) mNPV + TX; Spodoptera frugiperda (fall armyworm) mNPV + TX; Spodoptera littoralis (African cotton leafworm) NPV + TX;
• Bacteria and fungi which can be added as ’inoculant’ to plants or plant parts or plant organs and which, by virtue of their particular properties, promote plant growth and plant health selected from Agrobacterium spp. + TX; Azorhizobium caulinodans + TX; Azospirillum spp. + TX; Azotobacter spp. + TX; Bradyrhizobium spp. + TX; Burkholderia spp., in particular Burkholderia cepacia (formerly known as Pseudomonas cepacia) + TX; Gigaspora spp., or Gigaspora monosporum + TX; Glomus spp.
• compositions of the invention may also be applied with one or more systemically acquired resistance inducers (“SAR” inducer).
• SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
• the compounds of formula (I) as defined in any one of embodiments 1 to 43 are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds.
• further compounds can be e.g. fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or non-selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
• the compounds of formula (I) as defined in any one of embodiments 1 to 43 may be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula (I) as defined in any one of embodiments 1 to 43 or of at least one preferred individual compound as above-defined, in free form or in agrochemically usable salt form, and at least one of the above-mentioned adjuvants.
• the invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I) as defined in any one of embodiments 1 to 43, an agriculturally acceptable carrier and optionally an adjuvant.
• An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use.
• Agricultural carriers are well known in the art.
• said composition may comprise at least one or more pesticidally active compounds, for example an additional fungicidal active ingredient in addition to the compound of formula (I) as defined in any one of embodiments 1 to 43.
• a further aspect of invention is related to a method of controlling or preventing an infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or of non-living materials by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula (I) as defined in any one of embodiments 1 to 43 or of a preferred individual compound as above-defined as active ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.
• plants e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or of non-living materials by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms
• a compound of formula (I) as defined in any one of embodiments 1 to 43 or of
• Controlling or preventing means reducing infestation by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, to such a level that an improvement is demonstrated.
• a preferred method of controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, which comprises the application of a compound of formula (I) as defined in any one of embodiments 1 to 43, or an agrochemical composition which contains at least one of said compounds, is foliar application.
• the frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen or insect.
• the compounds of formula (I) as defined in any one of embodiments 1 to 43 can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application).
• Such granulates can be applied to the flooded rice field.
• the compounds of formula (I) as defined in any one of embodiments 1 to 43 may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
• a formulation e.g. a composition containing the compound of formula (I) as defined in any one of embodiments 1 to 43, and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula (I) as defined in any one of embodiments 1 to 43, may be prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active compounds (surfactants).
• extenders for example solvents, solid carriers and, optionally, surface active compounds (surfactants).
• 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 preferably 1g to 2000 g of active ingredient per hectare, more preferably 10 to 1000 g/ha, most preferably 10 to 600 g/ha.
• convenient dosages are from 10mg to 1g of active substance per kg of seeds.
• rates of 0.001 to 50 g of a compound of formula (I) per kg of seed preferably from 0.01 to 10g per kg of seed are generally sufficient.
• composition comprising a compound of formula (I) as defined in any one of embodiments 1 to 43 according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development.
• compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), 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 (EG), 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
• compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects).
• appropriate formulation inerts diiluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects.
• conventional slow release formulations may be employed where long lasting efficacy is intended.
• Particularly formulations to be applied in spraying forms such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g.
• a seed dressing formulation is applied in a manner known per se to the seeds employing the combination ofthe invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds.
• suitable seed dressing formulation form e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds.
• seed dressing formulations are known in the art.
• Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules.
• the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of formula (I) as defined in any one of embodiments 1 to 43 together with component (B) and (C), and optionally other active agents, particularly microbiocides or conservatives or the like.
• Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent.
• Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.
• LC/MS Liquid Chromatography Mass Spectrometry and the description of the apparatus and the method is as follows:
• Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 3.00 kV, Cone range: 30 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 350°C, Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650 l/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment, diode-array detector and ELSD detector.
• Compound 129 was specifically characterized by NMR on a Brucker AVANCE III 400 MHz:
• Example 1 This example illustrates the preparation of methyl N-[4-[6-[(4-fluorophenyl)-methyl- carbamoyl]imidazo[1 ,2-a]pyridin-3-yl]phenyl]carbamate (compound 11)
• Methyl 3-bromoimidazo[1 ,2-a]pyridine-6-carboxylate 1000 mg, 3.80 mmol, 1.00 eq.
• (4- aminophenyl)boronic acid hydrochloride salt 893 mg, 4.94 mmol, 1 .30 eq.
• dioxane 57 mL
• water 5.7 mL
• Cesium carbonate (3130 mg, 9.51 mmol, 2.50 eq.) was added and the mixture was purged with a stream of argon for 5 minutes.
• CATACXIUM(R) Pd G3 (146 mg, 0.190 mmol, 0.05 eq.) was then added and the reaction mixture was heated over night at 80°C. The mixture was cooled down, diluted with ethyl acetate, and treated with a saturated solution of NaHCCh. The desired material was extracted with ethyl acetate, the combined organic layers were washed with water, brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified over silica gel cartridge (ethyl acetate/MeOH) to afford methyl 3-(4- aminophenyl)imidazo[1 ,2-a]pyridine-6-carboxylate as a beige solid .
• Step 3 Preparation of 3-[4-(methoxycarbonylamino)phenyl1imidazo[1 ,2-alpyridine-6-carboxylic acid
• Methyl 3-[4-(methoxycarbonylamino)phenyl]imidazo[1 ,2-a]pyridine-6-carboxylate (818 mg, 2.34 mmol, 1 .00 eq.) was dissolved in THF/water 3:1 (40 mL). Lithium hydroxide (150 mg, 3.51 mmol, 1 .50 eq.) was then added and the mixture was stirred at room temperature for 4 hours. The mixture was then diluted with water (10 mL) and the THF was evaporated under reduced pressure. The residue was acidified with HCI 2N to obtain a pH of 4.
• Step 4 Preparation of methyl N-[4-[6-[(4-fluorophenyl)-methyl-carbamoyl1imidazo[1 ,2-alpyridin-3- yllphenyllcarbamate
• Example 2 This example illustrates the preparation of methyl N-[4-[6-[(4-chlorophenyl)-methyl- carbamoyl]-8-methyl-imidazo[1 ,2-a]pyridin-3-yl]phenyl]carbamate (compound 19)
• the reaction mixture was degassed with argon for 2 minutes, then chloro(2- dicyclohexylphosphino-2',4',6'-triisopropyl-1 ,1 '-biphenyl)[2-(2'-amino-1 ,1 '-biphenyl)]palladium(ll) (104 mg, 0.132 mmol, 0.05 eq) was added.
• the reaction mixture was stirred at 80 °C for 6 hours. After cooling down to room temperature, the reaction mixture was filtered through a Celite pad and washed with ethyl acetate. The filtrate was washed with water, then brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
• the crude residue was purified by flash chromatography to give methyl 8-methylimidazo[1 ,2-a]pyridine-6-carboxylate as an off-white solid.
• Step 3 Preparation of methyl 3-[4-(methoxycarbonylamino)phenyl1-8-methyl-imidazo[1 ,2-alpyridine-6- carboxylate
• the reaction mixture was degassed with argon for 2 minutes, then chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1 ,1 '-biphenyl)[2-(2'-amino-1 ,1 '- biphenyl)]palladium(l I) (4.98 mg, 0.00633 mmol, 0.05 eq) was added.
• the reaction mixture was stirred under microwave irradiation at 80 °C for 6 hours. After cooling down to room temperature, the reaction mixture was filtered through a Celite pad which was further flushed with ethyl acetate.
• Step 4 Preparation of 3-[4-(methoxycarbonylamino)phenyl1-8-methyl-imidazo[1 ,2-alpyridine-6- carboxylic acid
• Step 5 Preparation of methyl N-[4-[6-[(4-chlorophenyl)-methyl-carbamoyl1-8-methyl-imidazo[1 ,2- alpyridin-3-yllphenyllcarbamate
• Example 3 This example illustrates the preparation of methyl N-[4-[6-[(4-chlorophenyl)-methyl- carbamoyl]-5-methyl-imidazo[1,2-a]pyridin-3-yl]phenyl]carbamate (compound 20)
• Step 1 Preparation of methyl 5-methylimidazo[1,2-a]pyridine-6-carboxylate A sealed tube was charged with methyl 6-amino-2-methyl-pyridine-3-carboxylate (50.0 mg, 0.295 mmol, 1 eq), ethanol (3 mL) and 2-chloroacetaldehyde (231 mg, 1.47 mmol, 5 eq). The reaction mixture was stirred at 80 °C for 16 hours.
• Step 3 Preparation of methyl 3-[4-(methoxycarbonylamino)phenyl1-5-methyl-imidazo[1 ,2-alpyridine-6- carboxylate
• a microwave vial was charged with methyl 3-iodo-5-methyl-imidazo[1 ,2-a]pyridine-6-carboxylate (450 mg, 1.42 mmol, 1 eq), methyl N-[4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)phenyl]carbamate (commercially available, CAS 844500-75-0, 592 mg, 2.14 mmol, 1.5 eq), cesium carbonate (928 mg, 2.85 mmol, 2 eq), 1 ,4-dioxane (10 mL) and water (2 mL).
• reaction mixture was degassed with argon for 5 minutes, then Pd(dppf)Cl2 (104 mg, 0.142 mmol, 0.1 eq) was added and it was degassed for an additional 2 minutes.
• the reaction mixture was heated to 90 °C under microwave irradiation and stirred for 16 hours. After cooling down to room temperature, the reaction mixture was diluted with water and extracted twice with ethyl acetate. The combined organic layers were washed with water, then brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
• Step 4 Preparation of 3-[4-(methoxycarbonylamino)phenyl1-5-methyl-imidazo[1 ,2-alpyridine-6- carboxylic acid
• the aqueous layer was acidified with saturated NaHSCM aq., after which a precipitate appeared.
• the precipitate was dissolved in ethyl acetate, washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give 3-[4- (methoxycarbonylamino)phenyl]-5-methyl-imidazo[1 ,2-a]pyridine-6-carboxylic acid that was used in the next step without further purification.
• Step 5 Preparation of methyl N-[4-[6-[(4-chlorophenyl)-methyl-carbamoyl1-5-methyl-imidazo[1 ,2- alpyridin-3-yllphenyllcarbamate
• Example 4 This example illustrates the preparation of methyl N-[4-[7-chloro-6-[(4-chlorophenyl)- methyl-carbamoyl]imidazo[1 ,2-a]pyridin-3-yl]phenyl]carbamate (compound 23)
• Step 7 Preparation of methyl 2-amino-4-chloro-1 ,2-dihydropyridine-5-carboxylate
• Step 3 Preparation of methyl 7-chloro-3-iodo-imidazo[1 ,2-alpyridine-6-carboxylate
• Step 4 Preparation of methyl 7-chloro-3-[4-(methoxycarbonylamino)phenyl1imidazo[1 ,2-alpyridine-6- carboxylate
• a microwave vial was charged with methyl 7-chloro-3-iodo-imidazo[1 ,2-a]pyridine-6-carboxylate (800 mg, 2.26 mmol, 1 eq), methyl N-[4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)phenyl]carbamate (commercially available, CAS 844500-75-0, 939 mg, 3.39 mmol, 1 .5 eq), cesium carbonate (1 .47 g, 4.52 mmol, 2 eq), 1 ,4-dioxane (15 mL) and water (2 mL).
• reaction mixture was degassed with argon for 5 minutes, then Pd(dppf)Cl2 (165 mg, 0.226 mmol, 0.1 eq) was added and it was again degassed for 2 additional minutes.
• the reaction mixture was heated under microwave irradiation at 90 °C and stirred for 16 hours. After cooling down to room temperature, the reaction mixture was diluted with water and extracted twice with ethyl acetate. The combined organic layers were washed with water, then brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
• Step 6 Preparation of methyl N-[4-[7-chloro-6-[(4-chlorophenyl)-methyl-carbamoyl1imidazo[1 ,2- alpyridin-3-yllphenyllcarbamate
• 7-chloro-3-[4-(methoxycarbonylamino)phenyl]imidazo[1 ,2-a]pyridine-6- carboxylic acid 200 mg, 0.550 mmol, 1 eq
• 4-chloro-N-methyl-aniline 93.4 mg, 0.659 mmol, 1.2 eq).
• Example 5 This example illustrates the preparation of N-[5-[6-[(4-fluorophenyl)-methyl- carbamoyl]imidazo[1 ,2-a]pyridin-3-yl]-2-pyridyl]carbamate (example 25).
• Step 7 Preparation of methyl N-[5-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-2-pyridyl1carbamate
• 2-Aminopyridine-5-boronic acid pinacol ester 2000 mg, 8.63 mmol, 1 .00 eq.
• pyridine (2.79 g, 2.85 mL, 34.5 mmol, 4.00 eq.) were dissolved in ethyl acetate (50 mL) and cooled down to 10°C.
• Methyl chloroformate (3.30 g, 2.70 mL, 34.5 mmol, 4.00 eq.) was then added dropwise at 10°-15°C. After the addition was completed, the mixture was stirred at room temperature for an additional 2 hours.
• Methyl 3-bromoimidazo[1 ,2-a]pyridine-6-carboxylate (3000 mg, 11.76 mmol, 1.00 eq.) and methyl N-[5- (4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (5010 mg, 17.1 mmol, 1.50 eq.) were dissolved in dioxane (75 mL) and water (7.5 mL). Cesium carbonate (7510 mg, 22.8 mmol, 2.0 eq.) was added and the mixture was purged with a stream of argon for 5 minutes.
• Step 3 Preparation of methyl N-[5-[6-[(4-fluorophenyl)-methyl-carbamoyl1imidazo[1 ,2-alpyridin-3-yl1-2- pyridyllcarbamate
• Example 6 This example illustrates the preparation of methyl N-[4-[6-[(4-chlorophenyl)- (cyanomethyl)carbamoyl]imidazo[1 ,2-a]pyridin-3-yl]phenyl]carbamate (compound 31 )
• Step 7 Preparation of 3-bromo-N-(4-chlorophenyl)imidazo[1 ,2-alpyridine-6-carboxamide
• Step 3 Preparation of methyl N-[4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)phenyl1carbamate
• Step 4 Preparation of methyl N-[5-[6-[(4-chlorophenyl)-methyl-carbamoyl1imidazo[1 ,2-alpyridin-3-yl1-2- pyridyllcarbamate
• Example 7 This example illustrates the preparation of methyl N-[4-[6-[(4-chlorophenyl)-prop-2- ynyl-carbamoyl]imidazo[1 ,2-a]pyridin-3-yl]phenyl]carbamate (compound 33)
• Step 7 Preparation of 3-bromo-N-(4-chlorophenyl)-N-prop-2-ynyl-imidazo[1 ,2-alpyridine-6- carboxamide
• 3-bromoimidazo[1 ,2-a]pyridine-6-carboxylic acid (112 mg, 0.44 mmol, 1.0 eq.) in methyltetrahydrofuran (4.5 mL) at room temperature was added dimethylformamide (3.3 mg, 0.003 mL, 0.044 mmol, 0.1 eq.) and oxalyl chloride (68.6 mg, 0.047 mL, 0.53 mmol, 1.20 eq,).
• reaction mixture was then cooled down to room temperature, diluted with ethyl acetate, treated with a saturated solution of NaHCCb, extracted with ethyl acetate.
• the combined organic layers were washed with water and brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
• the crude residue was purified by flash chromatography (cyclohexane/ethyl acetate) to afford 3-bromo-N-(4-chlorophenyl)-N-prop-2-ynyl- imidazo[1 ,2-a]pyridine-6-carboxamide as a yellow resin.
• Example 8 This example illustrates the preparation of methyl N-[4-[7-bromo-6-[(4-chlorophenyl)- methyl-carbamoyl]imidazo[1 ,2-a]pyridin-3-yl]phenyl]carbamate (compound 34)
• Step 3 Preparation of methyl 7-bromoimidazo[1 ,2-alpyridine-6-carboxylate
• reaction mixture was stirred at 80 °C for 16 hours under CO atmosphere (200 PSI). After cooling down to room temperature, the reaction mixture was concentrated under reduced pressure. The crude residue was purified by flash chromatography to give methyl 7-bromoimidazo[1 ,2-a]pyridine-6-carboxylate as a brown solid.
• Step 4 Preparation of 7-bromoimidazo[1 ,2-alpyridine-6-carboxylic acid
• reaction mixture was diluted with ethyl acetate, washed with water, then brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
• the crude residue was purified by flash chromatography to give 7-bromo-N-(4-chlorophenyl)-N-methyl-imidazo[1 ,2-a]pyridine-6- carboxamide as an off-white solid.
• Step 6 Preparation of 7-bromo-N-(4-chlorophenyl)-3-iodo-N-methyl-imidazo[1 ,2-alpyridine-6- carboxamide
• Step 7 Preparation of methyl N-[4-[7-bromo-6-[(4-chlorophenyl)-methyl-carbamoyl1imidazo[1 ,2- alpyridin-3-yllphenyllcarbamate
• a microwave vial was charged with 7-bromo-N-(4-chlorophenyl)-3-iodo-N-methyl-imidazo[1 ,2- a]pyridine-6-carboxamide (50.0 mg, 0.0917 mmol, 1 eq), methyl N-[4-(4,4,5,5-tetramethyl-1 ,3,2- dioxaborolan-2-yl)phenyl]carbamate (commercially available, CAS 844500-75-0, 42.4 mg, 0.138 mmol, 1 .5 eq), cesium carbonate (59.8 mg, 0.183 mmol, 2 eq), 1 ,4-dioxane (1 .5 mL) and water (0.5 mL).
• reaction mixture was degassed with argon for 2 minutes, then cataCXium® A Pd G3 (3.34 mg, 0.00459 mmol, 0.05 eq) was added.
• the reaction mixture was then stirred under microwave irradiation at 90 °C for 1 hour. After cooling down to room temperature, the reaction mixture was filtered through a Celite pad and washed with ethyl acetate. The filtrate was washed with water, then brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
• Example 9 This example illustrates the preparation of methyl N-[4-[8-bromo-6-[(4-chlorophenyl)- methyl-carbamoyl]imidazo[1 ,2-a]pyridin-3-yl]phenyl]carbamate (compound 35)
• Step 7 Preparation of 8-bromoimidazo[1 ,2-alpyridine-6-carboxylic acid
• Step 3 Preparation of 8-bromo-N-(4-chlorophenyl)-3-iodo-N-methyl-imidazo[1 ,2-alpyridine-6- carboxamide
• Step 4 Preparation of methyl N-[4-[8-bromo-6-[(4-chlorophenyl)-methyl-carbamoyl1imidazo[1 ,2- alpyridin-3-yllphenyllcarbamate
• a microwave vial was charged with 8-bromo-N-(4-chlorophenyl)-3-iodo-N-methyl-imidazo[1 ,2- a]pyridine-6-carboxamide (200 mg, 0.408 mmol, 1 eq), methyl N-[4-(4,4,5,5-tetramethyl-1 ,3,2- dioxaborolan-2-yl)phenyl]carbamate (commercially available, CAS 844500-75-0, 113 mg, 0.408 mmol, 1 eq), cesium carbonate (265 mg, 0.816 mmol, 2 eq), 1 ,4-dioxane (10 mL) and water (2 mL).
• reaction mixture was degassed with argon for 5 minutes, then cataCXium (7.30 mg, 0.0204 mmol, 0.05 eq) and Pd(OAc)2 (2.7 mg, 0.012 mmol, 0.03 eq.) were added.
• the reaction mixture was stirred at 80 °C for 30 minutes under microwave irradiation. After cooling down to room temperature, the reaction mixture was diluted with water and extracted twice with ethyl acetate. The combined organic layers were washed with water, then brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
• Example 10 This example illustrates the preparation of methyl N-[4-[6-[(4-chlorophenyl)-methyl- carbamoyl]-7-methoxy-imidazo[1 ,2-a]pyridin-3-yl]phenyl]carbamate (Coumpound 39)
• Step 3 Preparation of methyl 7-methoxyimidazo[1 ,2-alpyridine-6-carboxylate
• methyl 6-amino-4-methoxy-pyridine-3-carboxylate 100 mg, 0.521 mmol, 1 eq
• water 5 mL
• bromoacetaldehyde dimethyl acetal (0.186 g, 1.04 mmol, 2 eq).
• the reaction mixture was stirred at room temperature for 16 hours.
• the reaction mixture was poured into a pre-stirred cold solution of saturated NaHCO3 aq. and was left stirring for 10 minutes. Then the reaction mixture was diluted with dichloromethane.
• Step 4 Preparation of methyl 3-iodo-7-methoxy-imidazo[1,2-a]pyridine-6-carboxylate
• methyl 7-methoxyimidazo[1,2-a]pyridine-6-carboxylate 100 mg, 0.364 mmol, 1 eq
• dimethylformamide 0.5 mL
• N-iodosuccinimide 123 mg, 0.546 mmol, 1.2 eq
• a microwave vial was charged with methyl 3-iodo-7-methoxy-imidazo[1,2-a]pyridine-6-carboxylate (400 mg, 1.14 mmol, 1 eq), methyl N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbamate (commercially available, CAS 844500-75-0, 349 mg, 1.26 mmol, 1.1 eq), cesium carbonate (746 mg, 2.29 mmol, 2 eq), 1,4-dioxane (3 mL) and water (0.5 mL).
• reaction mixture was degassed with argon for 5 minutes, then cataCXium® A Pd G3 (43.9 mg, 0.0572 mmol, 0.05 eq) was added and it was again degassed for 2 additional minutes.
• the reaction mixture was stirred under microwave irradiation at 95 °C for 1 hour. After cooling down to room temperature, the reaction mixture was diluted with water and extracted twice with ethyl acetate. The combined organic layers were washed with water, then brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
• Step 6 Preparation of 7-methoxy-3-[4-(methoxycarbonylamino)phenyl]imidazo[1,2-a]pyridine-6- carboxylic acid
• a stirred solution of methyl 7-methoxy-3-[4-(methoxycarbonylamino)phenyl]imidazo[1,2-a]pyridine-6- carboxylate (150 mg, 0.401 mmol, 1 eq) in THF (10 mL) and methanol (5 mL) was added at room temperature a solution of lithium hydroxide monohydrate (33.7 mg, 0.802 mmol, 2 eq) in water (5 mL). The reaction mixture was stirred for 1 hour at room temperature. The reaction mixture was concentrated under reduced pressure.
• Step 7 Preparation of methyl N-[4-[6-[(4-chlorophenyl)-methyl-carbamoyl1-7-methoxy-imidazo[1 ,2- alpyridin-3-yllphenyllcarbamate
• Example 11 This example illustrates the preparation of methyl N-[4-[6-[(4-chlorophenyl)-methyl- carbamoyl]-8-cyano-imidazo[1 ,2-a]pyridin-3-yl]phenyl]carbamate (compound 40)
• a sealed tube was charged with 8-bromo-N-(4-chlorophenyl)-N-methyl-imidazo[1 ,2-a]pyridine-6- carboxamide (previously described in example 9, step 2, 300 mg, 0.740 mmol, 1 eq), Zn(CN)2 (87.0 mg, 0.740 mmol, 1 eq) and dimethylformamide (2 mL).
• the reaction mixture was degassed with nitrogen for 15 minutes, then Xantphos (41.1 mg, 0.0740 mmol, 0.1 eq) and tris(dibenzylideneacetone)dipalladium(0) (67.8 mg, 0.0740 mmol, 0.1 eq) were added.
• reaction mixture was heated to at 140 °C and stirred for 16 hours. After cooling down to room temperature, the reaction mixture was poured into iced water and extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by column chromatography to give N-(4- chlorophenyl)-8-cyano-N-methyl-imidazo[1 ,2-a]pyridine-6-carboxamide.
• N-(4-chlorophenyl)-8-cyano-N-methyl-imidazo[1 ,2-a]pyridine-6-carboxamide 250 mg, 0.603 mmol, 1 eq
• dimethylformamide 0.5 mL
• N- iodosuccinimide 136 mg, 0.603 mmol, 1 eq
• the reaction mixture was stirred for 16 hours at room temperature.
• the reaction mixture was diluted with water and extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
• Step 3 Preparation of methyl N-[4-[6-[(4-chlorophenyl)-methyl-carbamoyl1-8-cyano-imidazo[1 ,2- alpyridin-3-yllphenyllcarbamate
• reaction mixture was degassed with argon for 5 minutes, then cataCXium® A Pd G3 (8.34 mg, 0.0109 mmol, 0.05 eq) was added.
• the reaction mixture was stirred at 95 °C for 1 hour under microwave irradiation. After cooling down to room temperature, the reaction mixture was diluted with water and extracted twice with ethyl acetate. The combined organic layers were washed with water, then brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
• Example 12 This example illustrates the preparation of methyl N-[4-[6-[(4-chlorophenyl)-methyl- carbamoyl]-7-cyano-imidazo[1 ,2-a]pyridin-3-yl]phenyl]carbamate (compound 41 )
• reaction mixture was degassed with nitrogen for 5 minutes, then Xantphos (0.137 g, 0.247 mmol, 0.1 eq) and tris(dibenzylideneacetone)dipalladium(0) (0.226 g, 0.247 mmol, 0.1 eq) were added.
• the reaction mixture was stirred at 140 °C for 16 hours. After cooling down to room temperature, the reaction mixture was poured into iced water and extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by column chromatography to give N-(4-chlorophenyl)-7-cyano-N-methyl-imidazo[1 ,2-a]pyridine-6-carboxamide as an off-white solid.
• N-(4-chlorophenyl)-7-cyano-N-methyl-imidazo[1 ,2-a]pyridine-6-carboxamide 450 mg, 1.32 mmol, 1 eq
• N-iodosuccinimide 593 mg, 2.64 mmol, 2 eq
• the reaction mixture was stirred for 16 hours at room temperature.
• the reaction mixture was diluted with water and extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
• the crude residue was purified by flash chromatography to give N-(4-chlorophenyl)-7-cyano- 3-iodo-N-methyl-imidazo[1 ,2-a]pyridine-6-carboxamide as a brown solid.
• Step 3 Preparation of methyl N-[4-[6-[(4-chlorophenyl)-methyl-carbamoyl1-7-cyano-imidazo[1 ,2- alpyridin-3-yllphenyllcarbamate
• reaction mixture was degassed with argon for 2 minutes, then cataCXium® A Pd G3 (24.3 mg, 0.0333 mmol, 0.05 eq) was added.
• the reaction mixture was stirred at 90 °C for 1 hour under microwave irradiation. After cooling down to room temperature, the reaction mixture was filtered through a Celite pad and washed with ethyl acetate. The filtrate was washed with water, then brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
• Example 13 This example illustrates the preparation of methyl N-[5-[6-[(4-fluoro-3-methoxy- phenyl)-methyl-carbamoyl]imidazo[1 ,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 45)
• Step 7 Preparation of 3-bromo-N-(4-fluoro-3-methoxy-phenyl)-N-methyl-imidazo[1 ,2-alpyridine-6- carboxamide
• Step 2 Preparation of N-[5-[6-[(4-fluoro-3-methoxy-phenyl)-methyl-carbamoyl]imidazo[1,2-a]pyridin-3- yl]-2-pyridyl]carbamate A mixture of 3-bromo-N-(4-fluoro-3-methoxy-phenyl)-N-methyl-imidazo[1,2-a]pyridine-6-carboxamide (0.809 g, 2.14 mmol, 1eq.), methyl N-[5-[6-[(4-fluoro-3-methoxy-phenyl)-methyl-carbamoyl]imidazo[1,2- a]pyridin-3-yl]-2-pyridyl]carbamate (0.877 g, 3.00 mmol, 1.4 eq.) and cesium carbonate (1.045 g, 3.21 mmol, 1.5 eq.) in water (4.3) and 1,4-dioxane
• Tetrakis(triphenylphosphine)palladium(0) (0.127 g, 0.107 mmol, 0.05 eq.) was then added and the reaction mixture was heated under microwave irradiation at 100°C and stirred for 1h. The reaction mixture was cooled down to room temperature and then water was added. The aqueous layer was extracted ethyl acetate and the combined organic layers were washed with brine, dried over Na2SO4, filtered, and concentrated under reduced pressure.
• Step 2 Preparation of methyl N-[5-[6-[(4-cyano-3-methoxy-phenyl)-methyl-carbamoyl1imidazo[1 ,2- alpyridin-3-yl1-2-pyridyl1carbamate
• 3-bromo-N-(4-cyano-3-methoxy-phenyl)-N-methyl-imidazo[1 ,2- a]pyridine-6-carboxamide 130 mg, 0.338 mmol
• 2-methoxycarbonylaminopyridine-5-boronic acid pinacolester 136 mg, 0.473 mmol
• cesium carbonate 167 mg, 0.506 mmol
• water 3.4 mL
• reaction mixture was purged with argon and heated at 100°C under MW irradiation for 30min.
• the reaction mixture was cooled down to room temperature, water was added to it, and the resulting mixture was extracted with ethyl acetate.
• the combined organic layers were washed with brine, dried over Na2SC>4, filtered, concentrated under reduced pressure, and purified over a silica gel cartridge (CH2Cl2/MeOH) to afford methyl N-[5-[6-[(4-cyano-3-methoxy-phenyl)-methyl-carbamoyl]imidazo[1 ,2-a]pyridin-3-yl]-2- pyridyl]carbamate as a beige solid.
• Example 15 This example illustrates the preparation of methyl N-[5-[6-[(4-fluorophenyl)-(2- methoxyethyl)carbamoyl]imidazo[1 ,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 76)
• Step 7 Preparation of 3-bromo-N-(4-fluorophenyl)imidazo[1 ,2-alpyridine-6-carboxamide
• Step 2 Preparation of 3-bromo-N-(4-fluorophenyl)-N-(2-methoxyethyl)imidazo[1,2-a]pyridine-6- carboxamide
• 2-bromoethyl methyl ether 0.064 g, 0.043 mL, 0.45 mmol
• cesium carbonate 0.294 g, 0.898 mmol
• Step 3 Preparation of methyl N-[5-[6-[(4-fluorophenyl)-(2-methoxyethyl)carbamoyl]imidazo[1,2- a]pyridin-3-yl]-2-pyridyl]carbamate
• 3-bromo-N-(4-fluorophenyl)-N-(2-methoxyethyl)imidazo[1,2- a]pyridine-6-carboxamide 0.085 g, 0.22 mmol
• 2-methoxycarbonylaminopyridine-5-boronic acid pinacolester 0.087 g, 0.30 mmol
• cesium carbonate (0.107 g, 0.325 mmol
• 1,4-dioxane 6.5 mL
• water 2.2 mL
• tetrakis(triphenylphosphine)palladium(0) 0.013 mg, 0.011 mmol.
• the reaction mixture was purged with argon and heated at 100°C under MW irradiation for 30min.
• the reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate.
• the combined organic layers were washed with brine, dried over Na2SO4, filtered, concentrated under reduced pressure.
• the crude residue was purified over a silica gel cartridge (dichloromethane/MeOH) to afford methyl N-[5-[6-[(4-fluorophenyl)-(2- methoxyethyl)carbamoyl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate as a beige solid.
• Example 16 This example illustrates the preparation of methyl N-[5-[6-[[4-fluoro-3-(2- methoxyethoxy)phenyl]-methyl-carbamoyl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 77)
• Step 1 Preparation of 3-bromo-N-(4-fluoro-3-hydroxy-phenyl)-N-methyl-imidazo[1,2-a]pyridine-6- carboxamide
• step 1 Preparation of 3-bromo-N-(4-fluoro-3-hydroxy-phenyl)-N-methyl-imidazo[1,2-a]pyridine-6- carboxamide
• step 1 To a suspension of 3-bromo-N-(4-fluoro-3-methoxy-phenyl)-N-methyl-imidazo[1,2-a]pyridine-6- carboxamide (previously described in example 13, step 1, 0.910 g, 2.41 m
• the reaction mixture was stirred at room temperature for 72h. The reaction mixture was then very slowly poured into water, basified with saturated NaHCO3 aq. and extracted with dichloromethane. The combined organic layers were washed with brine, dried over MgSO4, filtered, and concentrated under reduced pressure. The crude residue was purified over a silica gel cartridge (cyclohexane/[ethyl acetate/EtOH 3/1]) as eluent to give 3-bromo-N-(4-fluoro-3-hydroxy-phenyl)-N- methyl-imidazo[1,2-a]pyridine-6-carboxamide as a brown gum.
• Step 3 Preparation of methyl N-[5-[6-[[4-fluoro-3-(2-methoxyethoxy)phenyl1-methyl-
• 2- methoxycarbonylaminopyridine-5-boronic acid pinacolester 0.084 g, 0.29 mmol
• cesium carbonate 0.103 g, 0.313 mmol
• 1 ,4-dioxane 6.3 mL
• water 2.1 mL
• tetrakis(triphenylphosphine)palladium(0) 0.012 g, 0.010 mmol.
• reaction mixture was purged with argon and heated at 100°C under MW irradiation for 30min.
• the reaction was quenched with water and the resulting mixture was extracted with ethyl acetate.
• the combined organic layers were washed with brine, dried over Na2SC>4, filtered, and concentrated under reduced pressure.
• Example 17 This example illustrates the preparation of N-(4-fluoro-3-methoxy-phenyl)-N-methyl- 3-[6-(propanoylamino)-3-pyridyl]imidazo[1 ,2-a]pyridine-6-carboxamide (compound 151)
• Example 18 This example illustrates the preparation of N-(4-fluoro-3-methoxy-phenyl)-3-[6- [[methoxy(methyl)carbamoyl]amino]-3-pyridyl]-N-methyl-imidazo[1 ,2-a]pyridine-6-carboxamide (compound 79)
• Step 7 Preparation of 3-(6-amino-3-pyridyl)-N-(4-fluoro-3-methoxy-phenyl)-N-methyl-imidazo[1 ,2- alpyridine-6-carboxamide
• Tetrakis(triphenylphosphine)palldium(0) (0.046 g, 0.040 mmol) was then added and the reaction mixture was heated under microwave irradiation at 100°C for 1 h. The reaction mixture was cooled down to room temperature and then water was added.
• Example 19 This example illustrates the preparation of methyl N-[5-[6-[(4-fluorophenyl)-methyl- carbamothioyl]imidazo[1 ,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 164)
• Step 7 Preparation of methyl N-[5-[6-[(4-fluorophenyl)-methyl-carbamothioyl1imidazo[1 ,2-alpyridin-3- yll-2-pyridyllcarbamate
• Tomato leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
• the leaf disks are inoculated with a spore suspension of the fungus 1 day after application.
• the inoculated leaf disks are incubated at 16 °C and 75% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application).
• Grape vine leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
• the leaf disks are inoculated with a spore suspension of the fungus 1 day after application.
• the inoculated leaf disks are incubated at 19 °C and 80% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (6 - 8 days after application).
• Mycelia fragments and oospores of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal mycelia/spore mixture is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 2-3 days after application.
• DMSO DMSO

Landscapes

• Life Sciences & Earth Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Environmental Sciences (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Organic Chemistry (AREA)
• Agronomy & Crop Science (AREA)
• Health & Medical Sciences (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Microbiology (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Mycology (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Cultivation Of Plants (AREA)
• Pretreatment Of Seeds And Plants (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Priority Applications (12)

Applications Claiming Priority (4)

Publications (1)

Family

ID=84331387

Family Applications (1)

Country Status (15)

Cited By (10)

Families Citing this family (1)

Citations (64)

• 2022
  • 2022-10-06 KR KR1020247015201A patent/KR20240089416A/ko active Pending
  • 2022-10-06 IL IL312020A patent/IL312020A/en unknown
  • 2022-10-06 WO PCT/EP2022/077777 patent/WO2023061838A1/en not_active Ceased
  • 2022-10-06 EP EP22801734.9A patent/EP4416144A1/en active Pending
  • 2022-10-06 AU AU2022364034A patent/AU2022364034B2/en active Active
  • 2022-10-06 PE PE2024000802A patent/PE20240951A1/es unknown
  • 2022-10-06 MX MX2024004237A patent/MX2024004237A/es unknown
  • 2022-10-06 US US18/700,358 patent/US20240425500A1/en active Pending
  • 2022-10-06 CA CA3233795A patent/CA3233795A1/en active Pending
  • 2022-10-06 JP JP2024522247A patent/JP2024539634A/ja active Pending
  • 2022-10-11 AR ARP220102744A patent/AR127315A1/es unknown
  • 2022-10-12 TW TW111138624A patent/TW202334133A/zh unknown
  • 2022-10-14 PY PY202202289695A patent/PY2289695A/es unknown
• 2024
  • 2024-04-08 CL CL2024001036A patent/CL2024001036A1/es unknown
  • 2024-04-09 CO CONC2024/0004470A patent/CO2024004470A2/es unknown

Patent Citations (65)

Non-Patent Citations (12)

Also Published As

Similar Documents

Legal Events