EP4634178A1 - Dérivés d'imidazo[1,2-a]pyridine - Google Patents

Dérivés d'imidazo[1,2-a]pyridine

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Publication number
EP4634178A1
EP4634178A1 EP23822330.9A EP23822330A EP4634178A1 EP 4634178 A1 EP4634178 A1 EP 4634178A1 EP 23822330 A EP23822330 A EP 23822330A EP 4634178 A1 EP4634178 A1 EP 4634178A1
Authority
EP
European Patent Office
Prior art keywords
6alkyl
6alkoxy
formula
attachment
groups
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23822330.9A
Other languages
German (de)
English (en)
Inventor
Christopher Charles SCARBOROUGH
Martin Pouliot
Peter FINKBEINER
Damien BONVALOT
Nicolas Germain
Stephane André Marie JEANMART
Camille LE CHAPELAIN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syngenta Crop Protection AG Switzerland
Original Assignee
Syngenta Crop Protection AG Switzerland
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Syngenta Crop Protection AG Switzerland filed Critical Syngenta Crop Protection AG Switzerland
Publication of EP4634178A1 publication Critical patent/EP4634178A1/fr
Pending legal-status Critical Current

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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
    • 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
    • A01N47/20—N-Aryl derivatives 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) 2b a 5-8-membered heterocycle, a 6-12-membered aromatic ring or a 5-11-membered heteroaromatic ring, wherein each of the 5-8-membered carbocycle, the 5-8-membered heterocycle, the 6-12-membered aromatic ring or the 5-11-membered heteroaromatic ring is optionally substituted with one to four substituents independently selected from R 1 ;
  • A is CH or N;
  • a 1 is a carbon or nitrogen atom;
  • a 2 is a carbon or nitrogen atom;
  • a 3 are independently CR 4 or N, with the proviso that no more than four A 3 are N, preferably no more than three A 3 are N, preferably no more than two A 3 are N, preferably no more than one A 3 is N, and more
  • R 2a , R 2b and R 2c are independently selected from hydrogen, C1-6alkyl, C3-6cycloalkyl, C1-6alkoxy-C1-6alkyl, C3-6cycloalkyl-C1- 4alkyl, and C1-6alkoxy;
  • R 4 are independently selected from hydrogen, 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
  • 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, 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, 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 disease, such as 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.
  • a group is indicated as being substituted, e.g. alkyl, this includes those groups that are part of other groups, e.g. the alkyl in alkylthio.
  • 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- dimethylbutyl, 2,2-dimethylbut
  • 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-pentenyl, 2-methyl-2-penten
  • Alkenyl groups with 2 to 4 carbon atoms are preferred, for example 2-propenyl, 2-butenyl or 1-methyl-2-propenyl.
  • the term "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, 2-butynyl, 3-butynyl, 1-methyl-2- propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2- methyl-3-butynyl, 1-methyl-2- butynyl, 1,1 -dimethyl-2-propynyl, 1 -ethyl-2-propynyl, 2-hexynyl, 3- hexynyl, 4-hexynyl, 5-hexynyl, 1- methyl-2-pentyn
  • Alkynyls with 2 to 4 carbon atoms are preferred, for example ethynyl, 2- propynyl or 2-butynyl-2-propenyl.
  • 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.
  • alkoxy refers to a radical of the formula -ORa wherein Ra is an alkyl radical as generally defined above. Examples of alkoxy include, but are not limited to methoxy, ethoxy, propoxy, iso-propoxy, and tert-butoxy.
  • alkylsulfanyl refers to a radical of the formula -SRa wherein Ra is an alkyl radical as generally defined above.
  • alkylsulfinyl refers to a radical of the formula -S(O)Ra wherein Ra is an alkyl radical as generally defined above.
  • alkylsulfonyl refers to a radical of the formula -S(O)2Ra wherein Ra is an alkyl radical as generally defined above.
  • alkoxycarbonyl refers to a radical of the formula RaOC(O)-, wherein Ra is an alkyl radical as generally defined above.
  • alkylaminocarbonyl refers to a radical of the formula RaNHC(O)- wherein Ra is an alkyl radical as generally defined above.
  • - Hydroxyl or hydroxy stands for a –OH group.
  • the term "effective amount” refers to the amount of the compound, a salt, or N-oxide thereof, which, upon single or multiple applications provides the desired effect. An effective amount is readily determined by the skilled person in the art, by the use of known techniques and by observing results obtained under analogous circumstances.
  • Compounds of formula (I) which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid,
  • Compounds of formula (I) which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
  • bases for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts
  • salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, die
  • the compounds of formula (I) according to the invention are in free form, in oxidized form as an N-oxide, in covalently hydrated form, or in salt form, e.g., an agronomically usable or agrochemically acceptable salt form.
  • N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
  • the compounds of formula (I) according to the invention also include hydrates, which may be formed during salt formation.
  • the compounds of formula (I) according to the invention also include hydrates which may be formed during the salt formation.
  • a compound of formula (I) according to the present invention wherein four A 3 are CR 4 and one A 3 is N.
  • a compound of formula (I) according to the present invention wherein , and preferably the four A 3 are CR 4 .
  • a compound of formula (I) according to the present invention wherein 3 , and preferably the four A 3 are CR 4 .
  • a compound of formula (I) according to the present invention wherein A 1 is a carbon atom and A 2 is a nitrogen atom. In a further embodiment, there is provided a compound of formula (I) according to the present invention, wherein A 1 is a carbon atom and A 2 is a carbon atom. In a further embodiment, there is provided a compound of formula (I) according to the present invention, wherein A 1 is a nitrogen atom and A 2 is a carbon atom. In a further embodiment, there is provided a compound of formula (I) according to the present invention, wherein A 1 is a nitrogen atom and A 2 is a nitrogen atom.
  • a compound of formula (I) wherein ring W * selected from: , , group , the point of attachment to the ring formed by the A 3 groups, and wherein R 11 is selected from hydrogen, C1-6alkyl, C1-6alkoxy-C1-6alkyl, C3-6cycloalkyl, C3-6cycloalkyl-C1- 4alkyl, C2-6alkenyl and C2-6alkynyl, wherein each of the C1-6alkyl, C1-6alkoxy-C1-6alkyl, C3-6cycloalkyl, C3- 6cycloalkyl-C1-4alkyl, C2-6alkenyl, and C2-6alkynyl groups is optionally substituted with one to three substituents independently selected from halogen, hydroxy and CN.
  • Ring W can be optionally substituted with one to four substituents independently selected from R 1 as defined in the present invention. More preferably, ring W * wherein * represents the point of attachment to the imidazopyridine group in formula (I), and # represents the point of attachment to the ring formed by the A 3 groups, and wherein R 11 is as defined in the present invention. Ring W can be optionally substituted with one to four substituents independently selected from R 1 as defined in the present invention.
  • a compound of formula (I) wherein ring W is a 5-8-membered heterocycle or a 5-11-membered heteroaromatic ring, wherein each of the 5- 8-membered heterocycle or the 5-11-membered heteroaromatic ring is optionally substituted with one to four substituents independently selected from R 1 ,
  • a 1 is a carbon or nitrogen atom;
  • a 2 is a carbon or nitrogen atom; * and more preferably selected from: wherein * represents the point of attachment to the imidazopyridine group in formula (I), and # represents the point of attachment to the ring formed by the A 3 groups, ring W being optionally substituted with one to four substituents independently selected from R 1 as defined in the present invention, and wherein R 11 is as defined in the present invention;
  • A is N;
  • a 3 are independently CR 4 or N, with the proviso that no more than three A 3 are N, preferably no more than two A 3 are N, preferably no more than
  • the compound according to the present invention is selected from: methyl N-[5-[6-[4-(4-fluorophenyl)-5,6-dihydro-1,2,4-oxadiazin-3-yl]-8-methyl-imidazo[1,2-a]pyridin-3- yl]-2-pyridyl]carbamate; methyl N-[5-[8-cyclopropyl-6-[4-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]imidazo[1,2-a]pyridin-3- yl]-2-pyridyl]carbamate; methyl N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-5,6-dihydro-1,2,4-oxadiazin-3-yl]-8-methyl-imidazo[1,2- a]pyridin-3-yl]-2-pyridyl]carbamate;
  • the method according to the present invention has advantageous properties for protecting plants against pathogenic, such as phytopathogenic, especially fungi such as oomycetes, attack or infestation, which result in a disease and damage to the plant; particularly in instance of plants, the present invention can control, limit or prevent pathogenic damage on plant, parts of plant, plant propagation material and/or plant grown.
  • pathogenic such as phytopathogenic, especially fungi such as oomycetes, attack or infestation
  • the present invention can control, limit or prevent pathogenic damage on plant, parts of plant, plant propagation material and/or plant grown.
  • Table 1.1 provides compounds E1.1 to E1.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 is CH3, , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Tables 1.2 to 1.162 discloses individual compounds of the formula (I- 1) in which A, R 2a , R 2c , R 6 and ring W are specifically defined in Tables 1.2 to 1.162, which refer to Table Z wherein A 3a , A 3b , R 2b , R 4 are specifically defined.
  • Table 1.3 provides compounds E3.1 to E3.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 * * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.4 provides compounds E4.1 to E4.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 * * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.5 provides compounds E5.1 to E5.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 * * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.6 provides compounds E6.1 to E6.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 , wherein * represents the point of attachment to the , # represents the point of attachment to the ring formed by the A 3 groups,and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.7 provides compounds E7.1 to E7.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 , wherein * represents the point of attachment to the , represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.8 provides compounds E8.1 to E8.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 * * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.9 provides compounds E9.1 to E9.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 * , wherein * represents the point of attachment to the imidazopyridine group in formula (I-1), and # represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.10 provides compounds E10.1 to E10.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.11 provides compounds E11.1 to E11.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is CH3, , the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.12 provides compounds E12.1 to E12.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.13 provides compounds E13.1 to E13.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.14 provides compounds E14.1 to E14.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.15 provides compounds 1.15.1 to E15.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the imidazopyridine group in formula (I-1), and # represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.16 provides compounds E16.1 to E16.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.17 provides compounds E17.1 to E17.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is CH3, , the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.18 provides compounds E18.1 to E18.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 is CH3, , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.19 provides compounds E19.1 to E19.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.20 provides compounds E20.1 to E20.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.21 provides compounds E21.1 to E21.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the imidazopyridine group in formula (I-1), and # represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.22 provides compounds E22.1 to E22.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.23 provides compounds E23.1 to E23.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the group , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.24 provides compounds E24.1 to E24.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.25 provides compounds E25.1 to E25.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.26 provides compounds E26.1 to E26.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the group , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.27 provides compounds E27.1 to E27.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 is CH3, , wherein * represents the point of attachment to the imidazopyridine group in formula (I-1), and # represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.28 provides compounds E28.1 to * 1), and # represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.29 provides compounds E29.1 to E29.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.30 provides compounds E30.1 to 1.30.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.31 provides compounds E31.1 to E31.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.32 provides compounds E32.1 to E32.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.33 provides compounds E33.1 to E33.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.34 provides compounds E34.1 to E34.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.35 provides compounds E35.1 to E35.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.36 provides compounds E36.1 to E36.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.37 provides compounds E37.1 to E37.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.38 provides compounds E38.1 to E38.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group in formula (I-1), and # represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.39 provides compounds E39.1 to E39.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.40 provides compounds E40.1 to E40.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.41 provides compounds E41.1 to E41.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.42 provides compounds E42.1 to E42.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.43 provides compounds E43.1 to E43.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.44 provides compounds E44.1 to E44.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, imidazopyridine group in formula (I-1), and # represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.45 provides compounds E45.1 to E45.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.46 provides compounds E46.1 to E46.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.47 provides compounds E47.1 to E47.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.48 provides compounds E48.1 to E48.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.49 provides compounds E49.1 to E49.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.50 provides compounds E50.1 to E50.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group in formula (I-1), and # represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.51 provides compounds E51.1 to E51.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.52 provides compounds E52.1 to E52.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.53 provides compounds E53.1 to E53.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the group , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.54 provides compounds E54.1 to E54.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.55 provides compounds E55.1 to E55.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.56 provides compounds E56.1 to E56.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is , , wherein * represents the point of attachment to the imidazopyridine group in formula (I-1), and # represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.57 provides compounds E57.1 to E57.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.58 provides compounds E58.1 to E58.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.59 provides compounds E59.1 to E59.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.60 provides compounds E60.1 to E60.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.61 provides compounds E61.1 to E61.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.62 provides compounds E62.1 to E62.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.63 provides compounds E63.1 to E63.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.64 provides compounds E64.1 to E64.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.65 provides compounds E65.1 to E65.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.66 provides compounds E66.1 to E66.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.67 provides compounds E67.1 to E67.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.68 provides compounds E68.1 to E68.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, , wherein * represents the point of attachment to the , represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.69 provides compounds E69.1 to E69.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.70 provides compounds E70.1 to E70.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.71 provides compounds E71.1 to E71.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.72 provides compounds E72.1 to E72.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.73 provides compounds E73.1 to E73.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.74 provides compounds E74.1 to E74.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * # , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.75 provides compounds E75.1 to E75.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.76 provides compounds E76.1 to E76.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.77 provides compounds E77.1 to E77.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.78 provides compounds E78.1 to E78.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.79 provides compounds E79.1 to E79.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.80 provides compounds E80.1 to E80.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.81 provides compounds E81.1 to E81.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.82 provides compounds E82.1 to E82.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.83 provides compounds E83.1 to E83.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, * R 6 is CH 3 , , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.84 provides compounds E84.1 to E84.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.85 provides compounds E85.1 to E85.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, * R 6 is CH 3 , , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.86 provides compounds E86.1 to E86.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.87 provides compounds E87.1 to E87.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.88 provides compounds E88.1 to E88.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.89 provides compounds E89.1 to E89.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.90 provides compounds E90.1 to E90.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, * R 6 is CH3, , the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.91 provides compounds E91.1 to E91.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the imidazopyridine group in formula (I-1), and # represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.92 provides compounds E92.1 to E92.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.93 provides compounds E93.1 to E93.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.94 provides compounds E94.1 to E94.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.95 provides compounds E95.1 to E95.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.96 provides compounds E96.1 to E96.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.97 provides compounds E97.1 to E97.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the imidazopyridine group in formula (I-1), and # represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.98 provides compounds E98.1 to E98.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, * R 6 is CH3, , wherein * represents the point of attachment to the group , represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.99 provides compounds E99.1 to E99.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, R 6 is CH3, , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.100 provides compounds E100.1 to E100.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is CH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.101 provides compounds E101.1 to E101.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, R 6 is CH3, , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.102 provides compounds E102.1 to E102.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is CH3, , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.103 provides compounds E103.1 to E103.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is CH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.104 provides compounds E104.1 to E104.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is CH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.105 provides compounds E105.1 to E105.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is CH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1106 provides compounds E106.1 to E106.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is CH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.107 provides compounds E107.1 to E107.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c * is H, R 6 is CH3, , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.108 provides compounds E108.1 to E108.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 is CH3, , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.109 provides compounds E109.1 to E109.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is OCH3, , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.110 provides compounds E110.1 to E110.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.111 provides compounds E111.1 to E111.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.112 provides compounds E112.1 to E112.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.113 provides compounds E113.1 to E113.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.114 provides compounds E114.1 to E114.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.115 provides compounds E115.1 to E115.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is OCH3, rin , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.116 provides compounds E116.1 to E116.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1117 provides compounds E117.1 to E117.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.118 provides compounds E118.1 to E118.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.119 provides compounds E119.1 to E119.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.120 provides compounds E120.1 to E120.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.121 provides compounds E121.1 to E121.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.122 provides compounds E122.1 to E122.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.123 provides compounds E123.1 to E123.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.124 provides compounds E124.1 to E124.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * W H, R 6 is OCH3, ring W # is , wherein * represents the point of attachment to the imidazopyridine group in formula (I-1), and # represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.125 provides compounds E125.1 to E125.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.126 provides compounds E126.1 to E126.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group in formula (I-1), and # represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.127 provides compounds E127.1 to E127.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.128 provides compounds E128.1 to E128.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is H, R 6 is OCH 3 , , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1129 provides compounds E129.1 to E129.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is OCH3, , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.130 provides compounds E130.1 to E130.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is OCH3, , wherein * represents the point of attachment to the group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.131 provides compounds E131.1 to E131.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is OCH3, , wherein * represents the point of attachment to the group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.132 provides compounds E132.1 to E132.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is OCH3, , wherein * represents the point of attachment to the imidazopyridine group in formula (I-1), and # represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1133 provides compounds E133.1 to E133.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is OCH3, , wherein * represents the point of attachment to the group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.134 provides compounds E134.1 to E134.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c * is H, R 6 is CH3, , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.135 provides compounds E135.1 to E135.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 is CH3, , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.136 provides compounds E136.1 to E136.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is , , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.137 provides compounds E137.1 to E137.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is , , wherein * represents the point of attachment to the group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.138 provides compounds E138.1 to E138.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is , , wherein * represents the point of attachment to the imidazopyridine group in formula (I-1), and # represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.139 provides compounds E139.1 to E139.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.140 provides compounds E140.1 to E140.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.141 provides compounds E141.1 to E141.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.142 provides compounds E142.1 to E142.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.143 provides compounds E143.1 to E143.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.144 provides compounds E144.1 to E144.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.145 provides compounds E145.1 to E145.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.146 provides compounds E146.1 to E146.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.147 provides compounds E147.1 to E147.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.148 provides compounds E148.1 to E148.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.149 provides compounds E149.1 to E149.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.150 provides compounds E150.1 to E150.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.151 provides compounds E151.1 to E151.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * W H, R 6 is , ring W # is , wherein * represents the point of attachment to the imidazopyridine group in formula (I-1), and # represents the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.152 provides compounds E152.1 to E152.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.153 provides compounds E153.1 to E153.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.154 provides compounds E154.1 to E154.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.155 provides compounds E155.1 to E155.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.156 provides compounds E156.1 to E156.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is , , wherein * represents the point of attachment to the , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.157 provides compounds E157.1 to E157.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is , , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.158 provides compounds E158.1 to E158.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is , , wherein * represents the point of attachment to the group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1159 provides compounds E159.1 to E159.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is , , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.160 provides compounds E160.1 to E160.1078 of formula (I-1) wherein A is N, R 2a is H, R 2c is * H, R 6 is , , wherein * represents the point of attachment to the imidazopyridine group , the point of attachment to the ring formed by the A 3 groups, A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.161 provides compounds E161.1 to E161.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c * is H, R 6 is CH3, , wherein * represents the point of attachment to fthe , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • Table 1.162 provides compounds E162.1 to E162.1078 of formula (I-1) wherein A is CH, R 2a is H, R 2c is H, R 6 is CH3, , wherein * represents the point of attachment to the imidazopyridine , the point of attachment to the ring formed by the A 3 groups, and A 3a , A 3b , R 2b , R 4 are as defined in table Z.
  • 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) according to the invention can be made as shown in the following schemes 1 to 22, in which, unless otherwise stated, the definition of each variable is as defined in the present invention.
  • Compounds of formula (I) can be prepared via Suzuki cross coupling of compounds of formula (II), wherein X is Cl, Br or I, and a compound of formula (III), wherein either R 8 is independently from each other hydrogen, C1-C6 alkyl or wherein two R 8 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, chloro(2- dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II
  • compounds of formula (Va), wherein X is Cl, Br, I or a triflate group can be prepared by the reaction of a compound of formula (VIIa) with triflic anhydride and, optionally, a base, such as triethylamine or pyridine, or a halogenating agent such as phosphorus oxychloride, phosphorus oxybromide, or by successive reaction with phosphorus oxychloride and sodium iodide.
  • bases such as triethylamine or pyridine
  • a halogenating agent such as phosphorus oxychloride, phosphorus oxybromide
  • These transformations are performed neat or in a suitable solvent such as dichloromethane, toluene or xylene. These transformations are depicted in Scheme 3.
  • Compounds of formula (IV) wherein X is Cl, Br or I, and wherein X is more preferably Cl, and wherein either R 8 is independently from each other hydrogen, C1-C6 alkyl or wherein two R 8 together can form a C3-C8 cycloalkyl can be prepared by the reaction of a compound of formula (VIII) with a halogenating agent such as N-chlorosuccinimide, N-bromosuccinimide or N-iodosuccinimide in a suitable solvent, such as DMF, acetonitrile, dichloromethane or tetrahydrofuran. This transformation is depicted in Scheme 4.
  • a halogenating agent such as N-chlorosuccinimide, N-bromosuccinimide or N-iodosuccinimide
  • Alternatively compounds of formula (VIII) wherein either R 8 is independently from each other hydrogen, C1-C6 alkyl or wherein two R 8 together can form a C3-C8 cycloalkyl can be prepared by the reaction of a compound of formula (IX), wherein X is Cl, Br or I, with a compounds of formula (XI) wherein either R 8 is independently from each other hydrogen, C1-C6 alkyl or wherein two R 8 together can form a C3-C8 cycloalkyl, such as trimethyl borate, triisopropyl borate, isopropoxy 4,4,5,5-tetramethyl-1,3,2- dioxaborolane, or 2-methoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and a metal halogen exchange reagent, such as butyl lithium or ethylmagnesium bromide, in a suitable solvent, such as tetrahydrofuran, diethyl ether or di
  • 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.
  • compounds of formula (II), wherein X is Cl, Br or I, and wherein X is more preferably Cl can be prepared by the reaction of a compound of formula (XV), with a halogenating agent such as N- chlorosuccinimide, N-bromosuccinimide or N-iodosuccinimide in a suitable solvent, such as DMF, acetonitrile, dichloromethane or tetrahydrofuran.
  • a halogenating agent such as N- chlorosuccinimide, N-bromosuccinimide or N-iodosuccinimide in a suitable solvent, such as DMF, acetonitrile, dichloromethane or tetrahydrofuran.
  • compounds of formula (IIa), wherein A 1 is a carbon atom in formula (II) wherein X is Cl, Br or I, and wherein X is more preferably Cl can be prepared by the reaction of a compound of formula (XVIII), wherein either X is independently from each other Cl, Br or I, with a compounds of formula (XIXa) wherein either R 8 is independently from each other hydrogen, C1-C6 alkyl or wherein two R 8 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) chlor
  • Compounds of formula (XXIId), wherein A 1 and A 2 are carbon atoms in formula (XXII), and wherein X is Cl, Br or I, can be prepared via Suzuki cross coupling of compounds of formula (XXIIId), wherein either R 8 is independently from each other hydrogen, C1-C6 alkyl or wherein two R 8 together can form a C3-C8 cycloalkyl, and a compound of formula (XVIII), wherein either X independently is Cl, Br or I, 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
  • Compounds of formula (XVc), wherein A 1 is a nitrogen atom in formula (XV), can be prepared by the reaction of a compound of formula (IX), wherein X is Cl, Br or I, with a compound of formula (XXIVc), wherein A 1 is a nitrogen atom in formula (XXIV) in the presence of a base, such as Cs2CO3, K2CO3, K2HPO4 or NaOtBu, and a suitable palladium catalyst, and a suitable palladium catalyst, such as XPhos Pd G3, t-BuXPhos Pd G3, Me3tBuXPhos Pd G3, JohnPhos Pd G3, RuPhos Pd G3, BrettPhos Pd G3 or tBuBrettPhos Pd G3, in a suitable solvent, such as dimethylformamide, dimethylacetamide, dioxane, tetrahydrofuran or toluene.
  • a base such as Cs2CO3, K2CO3, K
  • compounds of formula (XVc), wherein A 1 is a nitrogen atom in formula (XV) can be prepared by the reaction of a compound of formula (VIII), wherein either R 8 is independently from each other hydrogen, C1-C6 alkyl or wherein two R 8 together can form a C3-C8 cycloalkyl, with a compound of formula (XXIVc) in the presence of a base, such as triethylamine, diisopropylethylamine, pyridine, Cs2CO3, K2CO3, K2HPO4 or NaOtBu, and a suitable catalyst, such as copper(II) acetate, copper(II) carbonate, copper(II) hydroxide, copper oxide, copper(I) iodide or copper(I) bromide, in a suitable solvent, such as dimethylformamide, dimethylacetamide, dioxane, acetonitrile, tetrahydrofuran or
  • the outcome of the reaction can be improved by adding boric acid or molecular sieves to the reaction mixture. It is understood that these transformations are done under air as oxygen is needed as a terminal oxidant. In some cases, the copper species might be used in stochiometric amount. This transformation is depicted in Scheme 18.
  • the person skilled in the art would also recognize that the compounds of formula (I) can alternatively be prepared by the de novo construction of the ring W. Such synthetic routes have been used and are described in the experimental section of the present invention. It is understood by the person skilled in the art that the synthetic routes describing the access to those specific compounds can also be used to synthesize analogous compounds of formula (I) of this specific compound, wherein said compounds have identical ring W.
  • This synthetic route describes the de novo synthesis of a compound of formula (I), wherein ring W is a pyrazole (compounds of formula (I- a)) as well as the synthesis of compounds of formula (II), wherein W is a pyrazole and X is Cl, Br or I (compounds of formula (II-a)).
  • This methodology can be used in general terms to access analogous compounds of formula (I-a) and formula (II-a).
  • (I-a) (II-a)
  • the below compounds of formula (I-b) and (II-b) can be prepared following the synthetic route used in the example 29.
  • the example 29 describes the preparation of methyl N-[5-[6-[4-(4-fluorophenyl)-1,2,4- triazol-3-yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 75).
  • This synthetic route describes the de novo synthesis of a compound of formula (I), wherein ring W is a triazole (compounds of formula (I-b)) as well as the synthesis of compounds of formula (II), wherein W is a triazole and X is Cl, Br or I (compounds of formula (II-b)).
  • This methodology can be used in general terms to access analogous compounds of formula (I-b) and formula (II-b).
  • the below compounds of formula (I-c) and (II-c) can be prepared following the synthetic route used in the examples 25, 27 and 28.
  • the example 28 describes the preparation of methyl N-[5-[6-[2-(4-fluoro- 3-methoxy-phenyl)-1,2,4-triazol-3-yl]imidazo[1,2-a]80yridine-3-yl]-2-pyridyl]carbamate (compound 4)
  • the example 27 describes the preparation of methyl N-[5-[6-[5-cyano-2-(4-fluorophenyl)-1,2,4-triazol-3- yl]imidazo[1,2-a]80yridine-3-yl]-2-pyridyl]carbamate (compound 74)
  • the example 25 describes the preparation of methyl N-[5-[6-[2-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazol-3-yl]imi
  • the example 9 describes the preparation of methyl N-[5-[6-[4-(4-fluoro-3-methoxy- phenyl)-5,6-dihydro-1,2,4-oxadiazin-3-yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 10).
  • This synthetic route describes the de novo synthesis of a compound of formula (I), wherein ring W is an oxadiazine (compounds of formula (I-d)) as well as the synthesis of compounds of formula (II), wherein W is an oxadiazine and X is Cl, Br or I (compounds of formula (II-d)).
  • This synthetic route describes the de novo synthesis of a compound of formula (I), wherein ring W is an oxadiazolone (compounds of formula (I-e)) as well as the synthesis of compounds of formula (II), wherein W is an oxadiazolone and X is Cl, Br or I (compounds of formula (II-e)).
  • This methodology can be used in general terms to access analogous compounds of formula (I-e) and formula (II-e).
  • the below compounds of formula (I-f) and (II-f) can be prepared following the synthetic route used in the example 38.
  • the example 38 describes the preparation of methyl N-[5-[6-[5-(4-fluoro-3-methoxy- phenyl)-1,2,4-triazol-1-yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (Compound 9).
  • This synthetic route describes the de novo synthesis of a compound of formula (I), wherein ring W is a triazole (compounds of formula (I-f)) as well as the synthesis of compounds of formula (II), wherein W is a triazole and X is Cl, Br or I (compounds of formula (II-f)).
  • This methodology can be used in general terms to access analogous compounds of formula (I-f) and formula (II-f).
  • 2b 2b (I-f) (II-f) The below compounds of formula (I-g) and (II-g) can be prepared following the synthetic route used in the example 35.
  • the example 35 describes the preparation of methyl N-[5-[6-[1-(4-fluoro-3-methoxy- phenyl)imidazol-2-yl]-8-methyl-imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (Compound 8).
  • This synthetic route describes the de novo synthesis of a compound of formula (I), wherein ring W is an imidazole (compounds of formula (I-g)) as well as the synthesis of compounds of formula (II), wherein W is an imidazole and X is Cl, Br or I (compounds of formula (II-g)).
  • This methodology can be used in general terms to access analogous compounds of formula (I-h) and formula (II-h).
  • these de novo synthesis might require using compounds of formula (XVI), wherein X is Cl, Br or I, and R 9 is hydrogen or C1-C6 alkyl, or the use of compound of formula (XVII), wherein R9 is hydrogen or C1-C6 alkyl.
  • compounds of formula (XVII), wherein R 9 is hydrogen or C1-C6 alkyl can be prepared by the reaction of a compound of formula (XXV), wherein R 9 is hydrogen or C1-C6 alkyl, and a compound of formula (XIII), wherein X is Cl, Br or I, or its corresponding acetal of formula (XIV), wherein X is Cl, Br or I and either R 10 is independently from each other C1-C6 alkyl or wherein two R 10 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.
  • Compounds of formula (XXV), wherein R 9 is hydrogen or C1-C6 alkyl are prepared by known methods or are commercially available. This transformation is depicted in Scheme 21.
  • compounds of formula (I) can be obtained by acylation of compounds of formula (XXVI) using an acylation reagent of formula (XXVII), wherein X is Cl or Br, in the presence of a base such as triethylamine, pyridine or potassium carbonate.
  • Compounds of formula (XXVI) can be prepared via Suzuki cross coupling of compounds of formula (II), wherein X is Cl, Br or I, and a compound of formula (XXVIII), wherein either R 8 is independently from each other hydrogen, C1-C6 alkyl or wherein two R8 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, chloro(2- dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]pal
  • the term “compound/compounds according to the invention” refers to compounds according to the present invention.
  • the compounds according to the present invention 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 the present invention can be converted in a manner known per se into another compound according to the present invention by replacing one or more substituents of the starting compound according to the present invention in the customary manner by (an)other substituent(s) according to the invention.
  • Salts of the compounds according to the present invention can be prepared in a manner known per se.
  • acid addition salts of the compounds according to the present invention 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 the present invention 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 the present invention can be converted in a manner known per se into other salts of the compounds according to the present invention, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • an acid for example with silver acetate
  • a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • the compounds according to the present invention, which have salt-forming properties can be obtained in free form or in the form of salts.
  • the compounds according to the present invention 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 the present invention 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 the present invention 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.
  • 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 the present invention 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 the present invention. The below intermediates form a further aspect of the invention.
  • a compound of formula (II) ; group (II), and # represents the point of attachment to the ring formed by the A 3 groups, and wherein R 11 is selected from hydrogen, C1-6alkyl, C1-6alkoxy-C1-6alkyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-4alkyl, C2-6alkenyl and C2- 6alkynyl, wherein each of the C1-6alkyl, C1-6alkoxy-C1-6alkyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-4alkyl, C2- 6alkenyl, and C2-6alkynyl groups is optionally substituted with one to three substituents independently selected from halogen, hydroxy and CN; A 1 is a carbon or nitrogen atom; A 2 is a carbon or nitrogen atom; A 3 are independently CR 4 or N, with the proviso that no more than four A 3 are N, preferably no more than three A 3 are N, preferably no more than two A 3
  • R 2a , R 2b and R 2c are independently selected from hydrogen, C 1-6 alkyl, C 3-6 cycloalkyl, C 1-6 alkoxy-C 1-6 alkyl, C 3-6 cycloalkyl-C 1- 4alkyl, and C1-6alkoxy;
  • R 4 are independently selected from hydrogen, 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, C1-6alk
  • R 2a , R 2b and R 2c are independently selected from hydrogen, C1-6alkyl, C3-6cycloalkyl, C1-6alkoxy-C1-6alkyl, C3-6cycloalkyl-C1- 4alkyl, and C1-6alkoxy; and R 4 are independently selected from hydrogen, 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,
  • a compound of formula (XXVI) wherein * represents the point of attachment to the imidazopyridine group in formula (XXVI), and # represents the point of attachment to the ring formed by the A 3 groups, and wherein R 11 is selected from hydrogen, C1-6alkyl, C1-6alkoxy-C1-6alkyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-4alkyl, C2-6alkenyl and C2- 6alkynyl, wherein each of the C1-6alkyl, C1-6alkoxy-C1-6alkyl, C3-6cycloalkyl, C3-6cycloalkyl-C1-4alkyl, C2- 6alkenyl, and C2-6alkynyl groups is optionally substituted with one to three substituents independently selected from halogen, hydroxy and CN; A is CH or N; A 1 is a carbon or nitrogen atom; A 2 is a carbon or nitrogen atom; A 3 are independently CR 4 or N, with the proviso that no more than four
  • R 2a , R 2b and R 2c are independently selected from hydrogen, C1-6alkyl, C3-6cycloalkyl, C1-6alkoxy-C1-6alkyl, C3-6cycloalkyl-C1- 4alkyl, and C1-6alkoxy; and R 4 are independently selected from hydrogen, C1-6alkyl, C1-6alkoxy, C1-6alkoxy-C1-6alkyl, C1-6alkoxy-C1- 6 alkoxy, halogen, CN, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-6 alkyl, C 1-6 alkylsulfanyl, C1-6alkylsulfinyl, C1-6alkylsulfonyl, C1-6al
  • a 1 is a carbon or nitrogen atom;
  • R 2a , R 2b and R 2c are independently selected from hydrogen, hydroxy, halogen, CN, C1-6alkyl, C3-
  • R 2a , R 2b and R 2c are independently selected from hydrogen, C1-6alkyl, C3-6cycloalkyl, C1-6alkoxy-C1-6alkyl, C3-6cycloalkyl-C1- 4alkyl, and C1-6alkoxy; and X is Cl, Br or I.
  • R 2a , R 2b and R 2c are independently selected from hydrogen, C1-6alkyl, C3-6cycloalkyl, C1-6alkoxy-C1-6alkyl, C3-6cycloalkyl-C1- 4alkyl, and C1-6alkoxy;
  • 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 the C1- 6alkyl, C1-6alkoxy, C3-6cycloalkyl, C3-6cycloalkyl-C1-6alkyl, C1-6alkyl, C1-6alkyl
  • the compounds of formula (I) as defined in the present invention can be used in the agricultural sector and related fields of use e.g. as active ingredients for controlling plant pathogens 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 the present invention can be used to inhibit or destroy the pathogens 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.
  • 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 the present invention 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.
  • plant propagation material e.g., seed, such as fruits, tubers or grains, or plant cuttings (for example rice)
  • the propagation material can be treated with a composition comprising a compound of formula (I) as defined in the present invention before planting: seed, for example, can be dressed before being sown.
  • the compounds of formula (I) as defined in the present invention 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.
  • the compounds of formula (I) as defined in the present invention 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 the present invention and fungicidal compositions containing them may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens.
  • 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.
  • Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. contributing B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora spp. including C.
  • 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.
  • compounds of formula (I) as defined in the present invention 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 the present invention may be used to conrol oomycetes.
  • 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 erythroseptica; Pythium diseases such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare, Pythium sylvaticum and Pythium ultimum; diseases caused by Peronosporales such as Peronospora destructor, Peronospora parasitica, Plasmopara viticola, Plasmopara halstedii, Pseudoperonospora cubens
  • 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 hordei, 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 Cronartium 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 solani, Tha
  • Blastocladiomycetes such as Physoderma maydis. Mucoromycetes, such as Choanephora cucurbitarum.; Mucor spp.; Rhizopus arrhizus. As well as diseases caused by other species and genera closely related to those listed above.
  • the compounds and compositions comprising compounds of formula (I) as defined in the present invention 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.
  • 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 / 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®.
  • the term "useful plants" and/or “target crops” is to be understood as including those which naturally are or have been rendered resistant to harmful insects.
  • toxins which can be expressed include ⁇ -endotoxins, vegetative insecticidal proteins (Vip), 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).
  • VipCot ⁇ Surgera 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-0392225).
  • PRPs pathogenesis-related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0392225, WO 95/33818, and EP-A-0353191.
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • 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 ⁇ - endotoxins, e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins from Bacillus cereus or Bacillus popilliae such as ⁇ - endotoxins, e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • ribosome- inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecd
  • ⁇ -endotoxins for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A
  • Vip vegetative insecticidal proteins
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701).
  • Truncated toxins for example a truncated Cry1Ab, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • 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 WO03/018810).
  • More examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0374753, WO93/07278, WO95/34656, EP-A-0427529, EP-A-451878 and WO03/052073.
  • transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0367 474, EP-A-0401979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and 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 Cry1Ab toxin); YieldGard Rootworm ⁇ (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus ⁇ (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin); Starlink ⁇ (maize variety that expresses a Cry9C toxin); Herculex I ⁇ (maize variety that expresses a Cry1Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B ⁇ (cotton variety that expresses a Cry1Ac toxin); Bollgard I
  • transgenic crops are: 1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 St.
  • This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence.
  • the preparation of such transgenic maize plants is described in WO 03/018810.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9.
  • MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects. 5.
  • NK603 ⁇ MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • locus as used herein 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.
  • seeds in the strict sense
  • 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.
  • 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 the present invention 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.
  • 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.
  • Suitable carriers and/or adjuvants e.g. for agricultural use, 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.
  • 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.
  • 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; and/or stickers such as dextrins, glue or synthetic resins.
  • 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.
  • Other useful formulations 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.
  • 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,
  • 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.
  • 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.18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub.
  • 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
  • block copolymers of ethylene oxide and propylene oxide and salts of mono and dialkyl phosphate esters.
  • compositions of the invention include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti- foaming 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.
  • 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 1.162 and 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, benzpyrim
  • 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 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 WO 2016/156
  • TX Aureobasidium pullulans + TX, Azospirillum (MicroAZ®, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus licheniformis strain HB-2 (e.g, BiostartTM, formerly Rhizoboost®) + TX, Bacillus licheniformis strain 3086 (EcoGuard®, Green Releaf®) + TX, Bacillus circulans + TX, Bacillus firmus (BioSafe®, BioNem-WP®, VOTiVO®) + TX,
  • Bacillus subtilis strain AQ178 + TX Bacillus subtilis strain QST 713 (CEASE®, Serenade®, 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®, Rhizopro®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1Ab + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis israelensis (BMP123®, Aquabac®, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin®, Deliver®, CryMax®, Bonide®, Scutella WP®, Turilav WP®, Astuto®, Dipel WP®, Biobit®, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF / 3P®) + TX,
  • TX Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Bacillus thuringiensis tenebrionis (Novodor®) + TX, BtBooster + TX, Burkholderia cepacia (Deny®, Intercept®, 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®, Biocure®) + TX, Candida sake + TX, Candida spp.
  • TX Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp.
  • TX Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean®, Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop®, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp.
  • Pasteuria spp. Econem® + TX, Pasteuria nishizawae + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart®, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp.
  • TX Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Ps
  • Rhodosporidium diobovatum + TX Rhodosporidium toruloides + TX, Rhodotorula spp.
  • Trichoderma asperellum T34 Biocontrol®
  • Trichoderma gamsii TX
  • Trichoderma atroviride Plantmate®
  • Trichoderma harzianum rifai Mycostar®
  • Trichoderma harzianum T-22 Trianum-P®, PlantShield HC®, RootShield®, 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®, Vertalec®) + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv.
  • Plant extracts including: pine oil (Retenol®) + TX, azadirachtin (Plasma Neem Oil®, AzaGuard®, MeemAzal®, Molt-X®) + TX, Botanical IGR (Neemazad®, Neemix®) + TX, canola oil (Lilly Miller Vegol®) + TX, Chenopodium ambrosioides near ambrosioides (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, extract of neem oil (Trilogy®) + TX, essentials oils of Labiatae (Botania®) + TX, extracts of clove rosemary peppermint and thyme oil (Garden insect killer®) + TX, Glycinebetaine (Greenstim®
  • TX Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug®, 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
  • TX Steinernematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator + TX; other biologicals including: abscisic acid + TX, bioSea® + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Colletotrichum gloeospor
  • NCAIM (P) B001389) (WO 2013/034938) from Certis USA LLC + TX
  • Bacillus pumilus in particular strain BU F-33, having NRRL Accession No.50185 (CARTISSA® from BASF, EPA Reg. No.71840-19) + TX
  • Bacillus subtilis in particular strain QST713/AQ713 (SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, having NRRL Accession No. B21661, U.S.
  • Patent No.6,060,051 + TX
  • Bacillus subtilis strain BU1814 (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 + TX
  • Bacillus sp. in particular strain D747 (available as DOUBLE NICKEL® from Kumiai Chemical Industry Co., Ltd.), having Accession No.
  • 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 (1.2) 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.
  • CNCM No.1-3937, CNCM No.1-3938 or CNCM No.1-3939 (as disclosed in WO 2010/086790 from Lesaffre et Compagnie, FR) + TX;
  • biological fungicides selected from the group of: (2.1) 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. 70127-5)) + TX; 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; 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 + 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.
  • 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.5,061,495 + TX Bacillus subtilis strain GB03 (available as Kodiak® from Bayer AG, DE) + TX; Bacillus subtilis strain BU1814, (available as VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) + TX; Bacillus subtilis CX-9060 from Certis USA LLC + TX; Bacillus subtilis KTSB strain (FOLIACTIVE® from Donaghys) + TX; Bacillus subtilis IAB/BS03 (AVIVTM from STK Bio-Ag Technologies, PORTENTO® from Idai Nature) + TX; 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) + TX; Paenibacillus epiphyticus (WO 2016/020371) from BASF SE + TX; Paen
  • CEDOMON®, CERALL®, and CEDRESS® by Bioagri and Koppert TX
  • Pseudomonas fluorescens strain A506 e.g. BLIGHTBAN® A506 by NuFarm
  • Pseudomonas proradix e.g. PRORADIX® from Sourcon Padena
  • Streptomyces griseoviridis strain K61 also known as Streptomyces galbus strain K61
  • DSM 7206 Streptomyces griseoviridis strain K61 (also known as Streptomyces galbus strain K61) (Accession No. DSM 7206) (MYCOSTOP® from Verdera, PREFENCE® from BioWorks, cf.
  • Streptomyces lydicus strain WYEC108 also known as Streptomyces lydicus strain WYCD108US
  • ACTINO-IRON® and ACTINOVATE® from Novozymes + TX
  • 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 321U from Adjuvants Plus, strain ACM941 as disclosed in Xue A.G (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea, Can. J. Plant Sci.2003, 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’, Australasian Plant Pathol.
  • Trichoderma asperellum in particular, strain kd (e.g. T-Gro from Andermatt Biocontrol) + TX; Trichoderma asperellum, in particular strain SKT-1, having Accession No. FERM P-16510 (e.g. ECO- HOPE® from Kumiai Chemical Industry), strain T34 (e.g. T34 Biocontrol by Biocontrol Technologies S.L., ES) or strain ICC 012 from Isagro + TX; Trichoderma atroviride, in particular strain SC1 (Accession No. CBS 122089, WO 2009/116106 and U.S.
  • Patent No.8,431,120 from Bi-PA
  • strain 77B T77 from Andermatt Biocontrol
  • strain LU132 e.g. Sentinel from Agrimm Technologies Limited
  • Trichoderma atroviride strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR) + TX
  • Trichoderma atroviride strain no. V08/002387 + TX
  • Trichoderma atroviride strain NMI no. V08/002388 + TX
  • Trichoderma atroviride strain NMI no. V08/002389 + TX
  • Trichoderma atroviride strain NMI no.
  • Trichoderma atroviride Trichoderma atroviride, strain LC52 (e.g. Tenet by Agrimm Technologies Limited) + TX; Trichoderma atroviride, strain ATCC 20476 (IMI 206040) + TX; Trichoderma atroviride, strain T11 (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.
  • TrichoPlus from BASF + TX
  • Trichoderma gamsii (formerly T. viride), 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 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
  • strain GL-21 e.g.
  • Trichoderma virens strain G-41 formerly known as Gliocladium virens (Accession No. ATCC 20906) (e.g., ROOTSHIELD® PLUS WP and TURFSHIELD® PLUS WP from BioWorks, US) + TX; Trichoderma viride, strain TV1(e.g. Trianum-P by Koppert) + TX; Trichoderma viride, in particular strain B35 (Pietr et al., 1993, Zesz. Nauk.
  • NM 99/06216 e.g., BOTRY-ZEN® by Botry-Zen Ltd, New Zealand and BOTRYSTOP® from BioWorks, Inc.
  • Verticillium albo-atrum previously 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; (3) 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)
  • Bacillus pumilus in particular strain QST2808 (Accession No. NRRL No. B-30087) + TX; Bacillus pumilus, in particular strain GB34 (e.g.
  • Bacillus subtilis strain BU1814 (available as TEQUALIS® from BASF SE), Bacillus subtilis rm303 (RHIZOMAX® from Biofilm Crop Protection) + TX; Bacillus thuringiensis BT013A (NRRL No. B-50924) 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
  • Delftia acidovorans in particular strain RAY209 (e.g. BIOBOOST® from Brett Young Seeds) + TX
  • Mesorhizobium cicer e.g., NODULATOR from BASF SE
  • Lactobacillus sp. e.g.
  • Trichoderma atroviride strain CNCM 1-1237 e.g. Esquive® WP from Agrauxine, FR
  • Trichoderma viride e.g. strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie 161: 125-137) + TX; Trichoderma atroviride strain LC52 (also known as Trichoderma atroviride strain LU132, e.g.
  • Bacillus sphaericus in particular Serotype H5a5b strain 2362 (strain ABTS-1743) (e.g. VECTOLEX® from Valent BioSciences, US) + TX; 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 (e.g.
  • israeltaki strain EG 7841 (CRYMAX® from Certis, US) + TX; Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD-5428, e.g. NOVODOR® FC from BioFa DE) + TX; Brevibacillus laterosporus (LATERAL® from Ecolibrium Biologicals) + TX; Burkholderia spp., in particular Burkholderia rinojensis strain A396 (also known as Burkholderia rinojensis strain MBI 305) (Accession No. NRRL B-50319); WO 2011/106491 and WO 2013/032693; e.g.
  • MBI206 TGAI and ZELTO® from Marrone Bio Innovations + TX
  • Chromobacterium subtsugae in particular strain PRAA4-1T (e.g. MBI-203; e.g. GRANDEVO® from Marrone Bio Innovations) + TX
  • Lecanicillium muscarium Ve6 MYCOTAL from Koppert
  • Paenibacillus popilliae (formerly Bacillus popilliae + TX; e.g. MILKY SPORE POWDERTM or MILKY SPORE GRANULARTM from St.
  • 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 the present invention 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. These 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 the present invention 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 the present invention, 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.
  • 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 the present invention.
  • 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.
  • 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 the present invention, 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 the present invention 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). In crops of water rice such granulates can be applied to the flooded rice field.
  • the compounds of formula (I) as defined in any the present invention 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 the present invention, and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula (I) as defined in the present invention, 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).
  • compositions that is the methods of controlling pathogens 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 pathogens 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.
  • a composition comprising a compound of formula (I) as defined in the present invention 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 (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK
  • 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 of the 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.
  • 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 the present invention 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.
  • Compounds of Formula (I) 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 (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).
  • 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 (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).
  • temperatures are given in degrees Celsius (°C) and “MP” means melting point.
  • LC/MS means Liquid Chromatography Mass Spectrometry and the description of the apparatus and the methods are described below.
  • Wettable powders a) b) c) active ingredient [compound of formula (I)] 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6 % 10 % phenol polyethylene glycol ether - 2 % - (7-8 mol of ethylene oxide) highly dispersed silicic acid 5 % 10 % 10 % Kaolin 62 % 27 % -
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • Powders for dry seed treatment a) b) c) active ingredient [compound of formula (I)] 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % - Kaolin 65 % 40 % - Talcum - 20%
  • active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsifiable concentrate active ingredient [compound of formula (I)] 10 % octylphenol polyethylene glycol ether 3 % (4-5 mol of ethylene oxide) calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 % Cyclohexanone 30 % xylene mixture 50 % Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Coated granules Active ingredient [compound of formula (I)] 8 % polyethylene glycol (mol. wt.200) 3 % Kaolin 89 % The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • Suspension concentrate active ingredient [compound of formula (I)] 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 % Sodium lignosulfonate 10 % carboxymethylcellulose 1 % silicone oil (in the form of a 75 % emulsion in water) 1 % Water 32 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Flowable concentrate for seed treatment active ingredient [compound of formula (I)] 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % tristyrenephenole with 10-20 moles EO 2 % 1,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 % Silicone oil (in the form of a 75 % emulsion in water) 0.2 % Water 45.3 % The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is added.
  • the mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • Method B Spectra were recorded on a Mass Spectrometer from Waters (Acquity QDa Mass Spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8 kV, Cone range: 25 V, Extractor: V (No extractor voltage for QDa detector) Source Temperature: 120°C, Desolvation Temperature: 600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from Waters: Quaternary solvent manager, heated column compartment , diode-array detector.
  • Method C Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350-600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 110 to 950 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment, diode- array detector and ELSD.
  • Method E Spectra were recorded on a Mass Spectrometer from Agilent (Single quad mass spectrometer) equipped with a Multimode- Electron Spray and APCI (Polarity: positive and negative ions), Capillary: 4.00 kV, Corona Current 4.0 ⁇ A, Charging Voltage: 2.00 kV, Nitrogen Gas Flow: 12.0 L/min, Nebulizer Pressure: 40 psig, Mass range: 100 to 1000 m/z), dry gas temperature 250 °C, Vaporizer temperature 200 °C and an UPLC from Waters: quaternary pump, heated column compartment, Variable wave length detector.
  • Agilent Single quad mass spectrometer
  • APCI Multimode- Electron Spray and APCI
  • Method F Spectra were recorded on a on a Mass Spectrometer from Agilent (Single quad mass spectrometer) equipped with Electron Spray (Polarity: positive and negative ions), Capillary: 4.00 kV, Charging Voltage: 2.00 kV, Nitrogen Gas Flow: 12.0 L/min, Nebulizer Pressure: 40 psig, Mass range: 100 to 1000 m/z, dry gas temperature 250 °C, Vaporizer temperature 200 °C and an UPLC from Waters: quaternary pump, heated column compartment, Variable wave length detector.
  • potassium carbonate (4.93 g, 35.7 mmol, 1.00 eq.) was added to a solution of prop-2-en-1-amine (6.11 g, 107 mmol, 3.00 eq.) in dichloromethane (50.0 mL).
  • the mixture of amine was added to the solution of the acid chloride in dichloromethane (50.0 mL).
  • the resulting reaction mixture was stirred at room temperature for 24 hours, then it was diluted with saturated aqueous NaHCO3 solution and extracted with dichloromethane. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Step 3 Preparation of N'-allyl-N-(3-bromoimidazo[1,2-a]pyridin-6-yl)-4-fluoro-benzamidine
  • Example 2 preparation of methyl N-[5-[6-[4-(4-fluorophenyl)-1H-pyrazol-3-yl]imidazo[1,2- a]pyridin-3-yl]-2-pyridyl]carbamate (compound 65) N To a mixture of 6-bromo-3-chloro-imidazo[1,2-a]pyridine (100 mg, 0.432 mmol) and 1H-pyrazol-3- ylboronic acid (48.3 mg, 0.432 mmol, 1.00 eq.) in dioxane/water (8:3, 5.00 mL) was added Pd(dppf)Cl2 (31.6 mg, 0.0432 mmol, 0.100 eq.) and potassium carbonate (179 mg, 1.30 mmol, 3.00 eq.).
  • Pd(dppf)Cl2 (7 mg, 0.01 mmol, 0.10 eq.) and potassium carbonate (40 mg, 0.29 mmol, 3.0 eq.) were added and the mixture was heated at 80 °C for 2 hours under nitrogen atmosphere. The reaction mixture was cooled down, diluted with water, and extracted with dichloromethane.
  • Example 3 preparation of methyl N-[5-[6-[5-(4-fluoro-3-methoxy-phenyl)-1,3-dimethyl-pyrazol-4- yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 19) (Compound 19) Step 1: Preparation of (4-bromo-2,5-dimethyl-pyrazol-3-yl) trifluoromethanesulfonate To a solution of 2,5-dimethyl-4H-pyrazol-3-one (3.00 g, 26.8 mmol) in dichloromethane (50.0 mL) was added 1-bromopyrrolidine-2,5-dione (5.00 g, 28.1 mmol, 1.05 eq.) at 0 °C.
  • reaction mixture was stirred at 0 °C for 30 minutes, after which 2,6-dimethylpyridine (6.23 mL, 53.5 mmol, 2.00 eq.) and trifluoromethanesulfonic anhydride (5.40 mL, 32.1 mmol, 1.20 eq.) were added.
  • the reaction mixture was stirred at 0 °C for 1 hour, and then it was diluted with a NaHCO3 solution, and extracted with dichloromethane. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
  • reaction mixture was stirred at 80 °C for 4 hours, after which it was diluted with water and extracted 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 over silica gel (ethyl acetate/petroleum ether) to afford 3-chloro-6-[5-(4-fluoro-3-methoxy-phenyl)-1,3- dimethyl-pyrazol-4-yl]imidazo[1,2-a]pyridine as a brown oil.
  • Example 4 preparation of methyl N-[5-[6-[5-(4-fluorophenyl)-1,2,4-triazol-1-yl]imidazo[1,2- a]pyridin-3-yl]-2-pyridyl]carbamate (compound 38) (Compound 38) Step 1: Preparation of 2-chloro-5-[5-(4-fluorophenyl)-1,2,4-triazol-1-yl]pyridine A solution of 4-fluorobenzamide (2.80 g, 20.1 mmol) in 1,1-dimethoxy-N,N-dimethyl-methanamine (14.0 mL) was heated at 100 °C for 2 h.
  • reaction mixture was stirred at 80 °C for 4 hours, after which it was diluted with water and extracted with dichloromethane. The combined organic phases were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography over silica gel (dichloromethane/MeOH) to afford N-(2,2-dimethoxyethyl)-5-[5-(4-fluorophenyl)-1,2,4-triazol-1-yl]pyridin-2-amine as a yellow oil.
  • Pd(dppf)Cl2 (9.0 mg, 0.012 mmol, 0.10 eq.) and potassium carbonate (43 mg, 0.31 mmol, 2.50 eq.) were added under nitrogen and the mixture was heated at 65 °C and stirred for 3 hours. The mixture was cooled down, diluted with water, and extracted with dichloromethane. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
  • reaction mixture was stirred for an additional 2 hours at room temperature, and then it was quenched with water resulting in the formation of a white solid in the aqueous layer.
  • the mixture was filtered, the filter cake was washed with water and the residue was dried under reduced pressure to afford 6-(4-bromo-2-methyl-pyrazol-3-yl)-3-chloro-imidazo[1,2-a]pyridine as a brown solid.
  • reaction mixture was heated at 80 °C and stirred for 2 hours under a nitrogen atmosphere.
  • the reaction mixture was then concentrated under reduced pressure and the crude residue was purified by flash chromatography over silica gel (dichloromethane/MeOH) to afford 3-chloro-6-[4-(4-fluorophenyl)-2-methyl-pyrazol-3-yl]imidazo[1,2- a]pyridine as a yellow oil.
  • reaction mixture was heated at 80 °C and stirred for 2 hours under a nitrogen atmosphere.
  • the reaction mixture was then cooled, diluted with water and extracted with dichloromethane.
  • the combined organic layers were concentrated under reduced pressure and the crude residue was purified by flash chromatography over silica gel (ethyl acetate/petroleum ether) to afford the desired target which was further purified by trituration with acetonitrile to afford 5-(4-fluoro-3- methoxy-phenyl)-1-methyl-pyrazole as a colorless oil.
  • reaction mixture was heated at 80 °C and stirred for 2 hours under nitrogen atmosphere.
  • the combined organic layers were concentrated under reduced pressure and the resulting residue was purified by flash chromatography over silica gel (dichloromethane/MeOH) to afford the desired target, which was further purified by trituration with acetonitrile to ultimately afford 3-chloro-6-[5-(4-fluoro-3-methoxy-phenyl)-1-methyl-pyrazol-4- yl]imidazo[1,2-a]pyridine as a white solid.
  • Example 7 preparation of methyl N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-5-oxo-1,2,4-oxadiazol- 3-yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 32)
  • N Compound 32
  • Step 1 Preparation of N-hydroxyimidazo[1,2-a]pyridine-6-carboxamidine
  • reaction mixture was then cooled and concentrated under reduced pressure to remove the pyridine.
  • the cooled reaction mixture was then washed with tert-butyl methyl ether to obtain a crude residue that was further purified by washing with water. Drying the resulting solid in vacuo afforded 3-imidazo[1,2-a]pyridin-6-yl-4H-1,2,4-oxadiazol-5-one as a brown solid.
  • reaction mixture was heated at 45 °C and stirred for 1 hour under an atmosphere of nitrogen.
  • the reaction mixture was then concentrated under reduced pressure, and the crude residue was purified by flash chromatography over silica gel (dichloromethane/MeOH) to give the desired compound, which was further purified by trituration with acetonitrile to afford methyl N-[5-[6-[4- (4-fluoro-3-methoxy- phenyl)-5-oxo-1,2,4-oxadiazol-3-yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate as an off-white powder.
  • Example 8 preparation of methyl N-[5-[6-[2-(4-fluorophenyl)pyrrolidin-1-yl]imidazo[1,2- a]pyridin-3-yl]-2-pyridyl]carbamate (compound 47) (Compound 47) Step 1: Preparation of 6-[2-(4-fluorophenyl)pyrrolidin-1-yl]imidazo[1,2-a]pyridine To a mixture of 2-(4-fluorophenyl)pyrrolidine (201 mg, 1.22 mmol, 1.2 eq.) and 6-bromoimidazo[1,2- a]pyridine (200 mg, 1.02 mmol) in toluene (5.00 mL) was added Pd2(dba)3 (96 mg, 0.10 mmol, 0.10 eq.), XPhos (25 mg, 0.051 mmol, 0.05 eq.) and sodium tert-butoxide (199 mg, 2.03 mmol, 2
  • Step 3 Preparation of methyl N-[5-[6-[2-(4-fluorophenyl)pyrrolidin-1-yl]imidazo[1,2-a]pyridin-3-yl]-2- pyridyl]carbamate (Compound 47)
  • a mixture of 6-[2-(4-fluorophenyl)pyrrolidin-1-yl]-3-iodo-imidazo[1,2-a]pyridine 140 mg, 0.275 mmol, 1.00 eq.
  • methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate 94 mg, 0.33 mmol, 1.2 eq.
  • Potassium carbonate (76 mg, 0.55 mmol, 2.0 eq.) was added and the reaction mixture was degassed with argon for 5 minutes.
  • CataCXium® A Pd G3 (CAS 1651823-59-4, 10 mg, 0.014 mmol, 0.05 mmol) was added and the mixture was heated at 100°C for 1 hour under microwave irraditation. The mixture was cooled down, filtered through a pad of celite and washed with ethyl acetate. The filtrate was washed with water and brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
  • Example 9 preparation of methyl N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-5,6-dihydro-1,2,4- oxadiazin-3-yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 10) (Compound 10) Step 1: Preparation of 2-chloro-N-(-4-fluoro-3-methoxy-phenyl)acetamide To a suspension of 4-fluoro-3-methoxy-aniline (10.0 g, 70.9 mmol) and potassium carbonate (10.8 g, 77.9 mmol, 1.10 eq.) in dimethylformamide (50.0 mL) at 0 °C was added, dropwise, a solution of 2- chloroacetyl chloride (8.80 g, 77.9 mmol, 1.00 eq.) in dimethylformamide (5.00 mL).
  • reaction mixture was stirred at room temperature for 3 hours, then it was diluted with water and 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 over silica gel (petroleum ether/ethyl acetate) to afford 2-chloro-N-(4-fluoro-3-methoxy- phenyl)acetamide as a colorless oil.
  • reaction mixture was warmed to room temperature and stirred for an additional 3 hours, after which it was poured into ice water and extracted with ethyl acetate. The combined organic layer was washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography over silica gel (petroleum ether/ethyl acetate) to afford N-(2-chloroethyl)-4- fluoro-3-methoxy-aniline as a colorless liquid.
  • reaction mixture was concentrated to dryness under reduced pressure and the crude residue was purified by flash chromatography over silica gel (dichloromethane/MeOH) to afford ethyl 3- bromoimidazo[1,2-a]pyridine-6-carboximidate as white solid.
  • Example 10 preparation of methyl N-[5-[6-[5-(4-fluorophenyl)-1-methyl-imidazol-4- yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 23) (Compound 23) Step 1: Preparation of 5-(4-fluorophenyl)-1-methyl-imidazole To a solution of 1-bromo-4-fluoro-benzene (639 mg, 3.65 mmol, 1.50 eq.) and 1-methylimidazole (200 mg, 2.44 mmol, 1.00 eq.) in dry dimethylformamide (12.0 mL) was added tris(2-furyl)phosphane (57 mg, 0.24 mmol, 0.10 eq.), Pd(OAc)2 (27 mg, 0.12 mmol, 0.05 eq.) and potassium carbonate (673 mg, 4.87 mmol, 2.00 eq.).
  • reaction mixture was heated to 110 °C and stirred under a nitrogen atmosphere until full conversion.
  • the reaction mixture was then cooled, diluted with ethyl acetate/dichloromethane (25.0 mL, 1:1), filtered, and the filtrate was concentrated under reduced pressure.
  • the crude residue was purified by reverse phase chromatography (eluting with acetonitrile/water, from 10% to 90% containing 0.1% formic acid) to afford 5-(4-fluorophenyl)-1-methyl-imidazole as a white solid.
  • Step 2 Preparation of 4-bromo-5-(4-fluorophenyl)-1-methyl-imidazole
  • 5-(4-fluorophenyl)-1-methyl-imidazole 320 mg, 1.82 mmol
  • acetonitrile 4.00 mL
  • 1-bromopyrrolidine-2,5-dione 323 mg, 1.82 mmol, 1.00 eq.
  • the resulting solution was slowly warmed to room temperature and stirred for 16 hours. After the transformation was completed, the resulting mixture was diluted with water and extracted with ethyl acetate.
  • Step 3 Preparation of methyl N-[5-(6-bromoimidazo[1,2-a]pyridin-3-yl)-2-pyridyl]carbamate
  • 6-bromo-3-iodo-imidazo[1,2-a]pyridine (4.00 g, 12.4 mmol) in dioxane/water (5/1; 42.0 mL) was added methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (4.13 g, 14.9 mmol), sodium carbonate (2.63 g, 24.8 mmol) and palladium tetrakistriphenylphosphine (1.43 g, 1.24 mmol) under an atmosphere of nitrogen .
  • Step 4 Preparation of [3-[6-(methoxycarbonylamino)-3-pyridyl]imidazo[1,2-a]pyridin-6-yl]boronic acid
  • methyl N-[5-(6-bromoimidazo[1,2-a]pyridin-3-yl)-2-pyridyl]carbamate (3.00 g, 8.64 mmol) in dioxane (45.0 mL) was added 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- yl)-1,3,2-dioxaborolane (3.29 g, 13.0 mmol), potassium acetate (1.70 g, 17.3 mmol), and Pd(dppf)Cl2 (0.316 g, 0.432 mmol) under an atmosphere of nitrogen .
  • Example 11 preparation of methyl N-[5-[6-[5-(4-fluoro-3-methoxy-phenyl)oxazol-4- yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 21) (Compound 21) Step 1: Preparation of 5-(4-fluoro-3-methoxy-phenyl)oxazole To a solution of 1-(isocyanomethylsulfonyl)-4-methyl-benzene (5.00 g, 25.6 mmol) in MeOH (50.0 mL) was added 4-fluoro-3-methoxy-benzaldehyde (5.92 g, 38.4 mmol, 1.50 eq.) and potassium carbonate (8.85 g, 64.0 mmol, 2.50 eq.).
  • Step 3 Preparation of methyl N-[5-[6-[5-(4-fluoro-3-methoxy-phenyl)oxazol-4-yl]imidazo[1,2-a]pyridin- 3-yl]-2-pyridyl]carbamate (Compound 21)
  • 4-bromo-5-(4-fluoro-3-methoxy-phenyl)oxazole 250 mg, 0.919 mmol
  • [3-[6-(methoxycarbonylamino)-3-pyridyl]imidazo[1,2-a]pyridin-6- yl]boronic acid (287 mg, 0.919 mmol, 1.00 eq.
  • potassium carbonate 317 mg, 2.30 mmol, 2.50 eq.
  • Pd(dppf)Cl2 67.0 mg, 0.092 mmol, 0.100 eq.
  • Example 12 preparation of methyl N-[5-[6-[5-(4-fluorophenyl)oxazol-4-yl]imidazo[1,2-a]pyridin- 3-yl]-2-pyridyl]carbamate (compound 63)
  • 4-fluorobenzaldehyde (10.0 g, 80.6 mmol) in MeOH (100 mL) was added 1- (isocyanomethylsulfonyl)-4-methylbenzene (23.6 g, 121 mmol, 1.50 eq.) and potassium carbonate (27.8 g, 201 mmol, 2.50 eq.).
  • reaction mixture was then heated at 75 °C and stirred for 16 hours, after which it was diluted with water and extracted 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 over silica gel (ethyl acetate/petroleum ether) to afford 5-(4-fluorophenyl)oxazole as a yellow solid.
  • Example 13 preparation of methyl N-[5-[6-[4-(4-fluorophenyl)oxazol-5-yl]imidazo[1,2-a]pyridin- 3-yl]-2-pyridyl]carbamate (compound 62) (Compound 62) Step 1: Preparation of 4-(4-fluorophenyl)oxazole To a solution of 2-bromo-1-(4-fluorophenyl)ethenone (10.0 g, 46.1 mmol) in formic acid (150 mL) at room temperature was added ammonium formate (11.0 g, 175 mmol, 3.80 eq.). The mixture was heated at 110 °C and stirred for 3 hours.
  • Step 2 Preparation of 6-(4-bromo-1-methyl-pyrazol-3-yl)-3-chloro-imidazo[1,2-a]pyridine
  • 3-chloro-6-(1-methylpyrazol-3-yl)imidazo[1,2-a]pyridine 5.90 g, 25.4 mmol
  • 1-bromopyrrolidine-2,5-dione 4.51 g, 25.4 mmol
  • the resulting solution was warmed to room temperature and stirred for an addition 16 hours.
  • the resulting mixture was diluted with water and extracted with ethyl acetate.
  • Step 3 Preparation of 3-chloro-6-[4-(4-fluoro-3-methoxy-phenyl)-1-methyl-pyrazol-3-yl]imidazo[1,2- a]pyridine
  • 6-(4-bromo-1-methyl-pyrazol-3-yl)-3-chloro-imidazo[1,2-a]pyridine 800 mg, 2.57 mmol
  • 4-fluoro-3-methoxy-phenyl)boronic acid (436 mg, 2.57 mmol, 1.00 eq.)
  • potassium carbonate (887 mg, 6.42 mmol, 2.50 eq.
  • Pd(dppf)Cl2 188 mg, 0.257 mmol, 0.100 eq.
  • Example 15 preparation of methyl N-[5-[6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-8- methyl-imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 25) (Compound 25) Step 1: Preparation of methyl 8-methylimidazo[1,2-a]pyridine-6-carboxylate To a stirred solution of methyl 8-bromoimidazo[1,2-a]pyridine-6-carboxylate (500 mg, 1.76 mmol) and methylboronic acid (216 mg, 3.53 mmol) in THF was added potassium carbonate (488 mg, 3.53 mmol) and Pd(dppf)Cl2 (129 mg, 0.176 mmol), and the reaction mixture was degassed with argon for 2 min.
  • the reaction mixture was heated at 80 °C and stirred for 16 hours.
  • the reaction mixture was then cooled to room temperature, filtered through a pad of celite, and the filtrate was washed with water, brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • the crude residue was purified by flash chromatography over silica gel (ethyl acetate/hexane) to afford methyl 8- methylimidazo[1,2-a]pyridine-6-carboxylate as an off white solid.
  • Step 2 Preparation of methyl 3-bromo-8-methyl-imidazo[1,2-a]pyridine-6-carboxylate
  • acetonitrile 13 mL
  • N-bromosuccinimide 0.53 g, 2.9 mmol, 1.1 eq.
  • Step 4 Preparation of 3-bromo-8-methyl-imidazo[1,2-a]pyridine-6-carboxamide
  • THF 14 mL
  • dimethylformamide 0.1 mL
  • oxalyl chloride 584 mg, 4.51 mmol, 1.10 eq.
  • the reaction mixture was then cooled to room temperature, and an ammonium hydroxide solution (25% in water), (2.30 g, 16.4 mmol) was added dropwise.
  • Step 5 Preparation of (N)-3-bromo-N-(dimethylaminomethylene)-8-methyl-imidazo[1,2-a]pyridine-6- carboxamide
  • 3-bromo-8-methyl-imidazo[1,2-a]pyridine-6-carboxamide (2.40 g, 8.97 mmol) in N.N-dimethylformamide dimethyl acetal (18.4 mL) was added acetic acid (1.13 g, 17.9 mmol, 2.00 eq.) and the reaction mixture was heated at 95 °C and stirred for 3 hours.
  • Step 6 Preparation of 3-bromo-6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]-8-methyl- imidazo[1,2-a]pyridine
  • (N)-3-bromo-N-(dimethylaminomethylene)-8-methyl-imidazo[1,2-a]pyridine-6- carboxamide 300 mg, 0.922 mmol
  • dimethylformamide 3.00 mL
  • 4-fluoro-3-methoxy- phenyl)hydrazine hydrochloride 199 mg, 1.01 mmol, 1.10 eq.
  • the reaction mixture was heated at 95 °C and stirred for 3 hours before being slowly poured onto water.
  • Example 16 preparation of ethyl 3-(4-fluorophenyl)-2-[3-[6-(methoxycarbonylamino)-3- pyridyl]imidazo[1,2-a]pyridin-6-yl]imidazole-4-carboxylate (compound 67) (Compound 67) Step 1: Preparation of ethyl 3-(4-fluorophenyl)-2-iodo-imidazole-4-carboxylate To a stirred solution of ethyl 3-(4-fluorophenyl)imidazole-4-carboxylate (CAS 689250, commercially available and synthesis already described in ChemMedChem 2021, 16, 2195; 5.00 g, 21.3 mmol) in acetonitrile (80.0 mL) was added 1-iodopyrrolidine-2,5-dione (48.0 g, 213 mmol, 10.0 eq.) The reaction mixture was heated at 100 °C
  • Step 2 Preparation of ethyl 3-(4-fluorophenyl)-2-imidazo[1,2-a]pyridin-6-yl-imidazole-4-carboxylate
  • ethyl 3-(4-fluorophenyl)-2-iodo-imidazole-4-carboxylate 200 mg, 0.544 mmol
  • imidazo[1,2-a]pyridin-6-ylboronic acid 176 mg, 1.09 mmol, 2.00 eq.
  • cesium carbonate 531 mg, 1.63 mmol, 3.00 eq.
  • reaction mixture was purged with argon for 10 minutes, then PdCl2(PPh3)2 (191 mg, 0.272 mmol, 0.500 eq.) was added and the resulting mixture heated at 100 °C and stirred for 2 hours under microwave irradiation microwave.
  • the reaction mixture was cooled, filtered through a pad of celite, the filtrate was diluted with water and extracted with ethyl acetate.
  • Step 3 Preparation of ethyl 3-(4-fluorophenyl)-2-(3-iodoimidazo[1,2-a]pyridin-6-yl)imidazole-4- carboxylate
  • ethyl 3-(4-fluorophenyl)-2-imidazo[1,2-a]pyridin-6-yl-imidazole-4-carboxylate 430 mg, 1.17 mmol
  • dimethylformamide 30.0 mL
  • 1-iodopyrrolidine-2,5-dione (289 mg, 1.28 mmol, 1.10 eq.
  • reaction mixture then was diluted with ice cold water and extracted 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 over silica gel (ethyl acetate/hexane) to afford ethyl 3-(4- fluorophenyl)-2-(3-iodoimidazo[1,2-a]pyridin-6-yl)imidazole-4-carboxylate.
  • reaction mixture was purged with argon for 10 minutes, then cataCXium® A (7 mg, 0.02 mmol, 0.05 eq.) was added and the resulting reaction mixture was heated at 100 °C and stirred for 1 hour under microwave irradiation.
  • the rection mixture was cooled, filtered through a pad of celite, the filtrate was diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Example 17 preparation of methyl N-[5-[6-[5-cyano-1-(4-fluorophenyl)imidazol-2-yl]imidazo[1,2- a]pyridin-3-yl]-2-pyridyl]carbamate (compound 71) (Compound 71) Step 1: Preparation of 3-(4-fluorophenyl)imidazole-4-carboxamide A solution of ethyl 3-(4-fluorophenyl)imidazole-4-carboxylate (90.0 % purity, 100 mg, 0.384 mmol) in aqueous ammonia (67.3 mg, 1.92 mmol) in seal tube was heated at 120 °C and stirred for 24 hours.
  • Step 2 Preparation of 3-(4-fluorophenyl)imidazole-4-carbonitrile
  • THF 5.00 mL
  • pyridine 1.21 g, 15.4 mmo, 3.00 eq.
  • trifluoro acetic anhydride 1.61 g, 7.68 mmol, 1.50 eq.
  • Step 3 Preparation of 2-bromo-3-(4-fluorophenyl)imidazole-4-carbonitrile
  • 3-(4-fluorophenyl)imidazole-4-carbonitrile 310 mg, 1.62 mmol
  • 1-bromopyrrolidine-2,5-dione 1333 mg, 8.12 mmol
  • the resulting reaction mixture was heated at 120 °C and stirred for 6 hours in a seal tube.
  • the reaction mixture was then cooled and concentrated under reduced pressure, the crude residue was diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Step 4 Preparation of 3-(4-fluorophenyl)-2-imidazo[1,2-a]pyridin-6-yl-imidazole-4-carbonitrile
  • 2-bromo-3-(4-fluorophenyl)imidazole-4-carbonitrile 60.0 mg, 0.223 mmol
  • imidazo[1,2-a]pyridin-6-ylboronic acid 54 mg, 0.34 mmol, 1.5 eq.
  • cesium carbonate 145 mg, 0.447 mmol, 2.00 eq.
  • reaction mixture was purged with argon for 10 minutes, and then [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex (18 mg, 0.23 mmol, 0.10 eq.) was added and the reaction was heated at 100 °C and stirred for 2 hours under microwave irradiation.
  • the reaction mixture was then cooled, filtered through at pad of celite, the filtrate was diluted with water and the aqueous layer extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Step 5 Preparation of 3-(4-fluorophenyl)-2-(3-iodoimidazo[1,2-a]pyridin-6-yl)imidazole-4-carbonitrile
  • 3-(4-fluorophenyl)-2-imidazo[1,2-a]pyridin-6-yl-imidazole-4-carbonitrile 180 mg, 0.588 mmol
  • 1-iodopyrrolidine-2,5-dione 145 mg, 0.646 mmol, 1.10 eq.
  • Step 6 Preparation of methyl N-[5-[6-[5-cyano-1-(4-fluorophenyl)imidazol-2-yl]imidazo[1,2-a]pyridin-3- yl]-2-pyridyl]carbamate (Compound 71)
  • 3-(4-fluorophenyl)-2-(3-iodoimidazo[1,2-a]pyridin-6-yl)imidazole-4-carbonitrile 150 mg, 0.343 mmol
  • reaction mixture was purged with argon for 10 minutes and then cataCXium® A (6 mg, 0.017mmol, 0.050 eq.) was added and the resulting reaction mixture heated at 100 °C and stirred for 1 hour under microwave irradiation.
  • the reaction mixture was cooled to room temperature, filtered through a pad of celite, the filtrate was diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
  • Example 18 preparation of methyl N-[5-[6-[3-(4-fluorophenyl)-5-methyl-imidazol-4- yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 41) (Compound 41) Step 1: Preparation of 1-(4-fluorophenyl)-5-iodo-4-methyl-imidazole A solution of 1-(4-fluorophenyl)-4-methyl-imidazole (CAS 924709-34-2; synthesized as described in J. Org.
  • Step 2 Preparation of 6-[3-(4-fluorophenyl)-5-methyl-imidazol-4-yl]imidazo[1,2-a]pyridine
  • 1-(4-fluorophenyl)-5-iodo-4-methyl-imidazole 250 mg, 0.786 mmol
  • imidazo[1,2- a]pyridin-6-ylboronic acid 153 mg, 0.943 mmol, 1.20 eq.
  • cesium carbonate 512 mg, 1.57 mmol, 2.00 eq.
  • Step 3 Preparation of 6-[3-(4-fluorophenyl)-5-methyl-imidazol-4-yl]-3-iodo-imidazo[1,2-a]pyridine
  • a solution of 6-[3-(4-fluorophenyl)-5-methyl-imidazol-4-yl]imidazo[1,2-a]pyridine (100 mg, 0.325 mmol) in dimethylformamide (5.00 mL) was charged with N-iodosuccinimide (80.4 mg, 0.357 mmol, 1.10 eq.) and the reaction mixture was stirred at room temperature for 16 hours. Afterwards it was diluted with water (20.0 mL) and extracted with ethyl acetate.
  • Step 4 Preparation of methyl N-[5-[6-[3-(4-fluorophenyl)-5-methyl-imidazol-4-yl]imidazo[1,2-a]pyridin-3- yl]-2-pyridyl]carbamate (Compound 41)
  • 6-[3-(4-fluorophenyl)-5-methyl-imidazol-4-yl]-3-iodo-imidazo[1,2-a]pyridine 8.0.0 mg, 0.182 mmol
  • reaction mixture was concentrated under reduced pressure and purified by silica gel column chromatography (ethyl acetate/hexane) to afford the title compound, which was further purified by C-18 column chromatography (water/acetonitrile) to afford methyl N-[5-[6-[3-(4-fluorophenyl)-5-methyl-imidazol-4- yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate as an off-white solid.
  • Example 19 preparation of methyl N-[5-[6-[5-chloro-1-(4-fluorophenyl)imidazol-2-yl]imidazo[1,2- a]pyridin-3-yl]-2-pyridyl]carbamate (compound 72) (Compound 72) Step 1: Preparation of 2-bromo-5-chloro-1-(4-fluorophenyl)imidazole To a solution of 5-chloro-1-(4-fluorophenyl)imidazole (synthesized as described in Science of Synthesis 2002, 12, 325-528; 250 mg, 1.08 mmol) in chloroform (5.00 mL) was added N-bromosuccinimide (226 mg, 1.24 mmol, 1.15 eq.), followed by 2-[(E)-(1-cyano-1-methyl-ethyl)azo]-2-methyl-propanenitrile (17.7 mg, 0.108 mmol, 0.100 eq.)
  • Step 2 Preparation of 6-[5-chloro-1-(4-fluorophenyl)imidazol-2-yl]imidazo[1,2-a]pyridine
  • 2-bromo-5-chloro-1-(4-fluorophenyl)imidazole 50.0 mg, 0.163 mmol
  • imidazo[1,2-a]pyridin-6-ylboronic acid 30 mg, 0.19 mmol, 1.15 eq.
  • reaction mixture was degassed with argon for 2 minutes, then Pd(dppf)Cl2 (12 mg, 0.016 mmol, 0.10 eq.) was added. The mixture was then heated to 100 °C under microwave irradiation for 45 min. After cooling to room temperature, the reaction mixture was filtered and washed with ethyl acetate. The filtrate was concentrated under reduced pressure and crude residue was purified by flash chromatography over silica gel (ethyl acetate/hexane) to afford 6-[5-chloro-1-(4-fluorophenyl)imidazol-2-yl]imidazo[1,2- a]pyridine as a brown solid.
  • Step 3 Preparation of 6-[5-chloro-1-(4-fluorophenyl)imidazol-2-yl]-3-iodo-imidazo[1,2-a]pyridine
  • 6-[5-chloro-1-(4-fluorophenyl)imidazol-2-yl]imidazo[1,2-a]pyridine 160 mg, 0.435 mmol
  • dimethylformamide 5.00 mL
  • N-iodosuccinimide 108 mg, 0.478 mmol, 1.10 eq.
  • Example 20 preparation of methyl N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazol- 3-yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 26) (Compound 26) Step 1: Preparation of 3-bromoimidazo[1,2-a]pyridine-6-carbohydrazide To a solution of methyl 3-bromoimidazo[1,2-a]pyridine-6-carboxylate (1.00 g, 3.80 mmol) in methanol (5.43 mL) was added hydrazine hydrate (0.226 mL, 4.56 mmol, 1.20 eq.).
  • Step 2 Preparation of 2-(3-bromoimidazo[1,2-a]pyridin-6-yl)-5-methyl-1,3,4-oxadiazole
  • 3-bromoimidazo[1,2-a]pyridine-6-carbohydrazide 500 mg, 1.96 mmol
  • triethyl orthoacetate 3.67 mL, 19.6 mmol, 10.0 eq.
  • the reaction mixture was heated at 130 °C and stirred for 90 min.
  • the reaction mixture was cooled and 1,8-diazabicyclo[5.4.0]undec-7-ene (0.359 mL, 2.35 mmol, 1.20 eq.) was added.
  • the reaction mixture was heated again at 130 °C and stirred for an additional 20 min.
  • Step 3 Preparation of 3-bromo-6-[4-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazol-3- yl]imidazo[1,2-a]pyridine
  • 2-(3-bromoimidazo[1,2-a]pyridin-6-yl)-5-methyl-1,3,4-oxadiazole 200 mg, 0.717 mmol
  • 4-fluoro-3-methoxyaniline 532 mg, 3.58 mmol, 5.00 eq.
  • reaction mixture was then cooled down to room temperature and slowly quenched with a saturated NaHCO3 solution.
  • aqueous phase was extracted with ethyl acetate, and 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 over silica gel (ethylacetate/EtOH/cyclohexane) to afford 3-bromo-6-[4-(4-fluoro- 3-methoxy-phenyl)-5-methyl-1,2,4-triazol-3-yl]imidazo[1,2-a]pyridine as a beige solid.
  • Step 4 Preparation of methyl N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazol-3- yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (Compound 26)
  • 3-bromo-6-[4-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazol-3- yl]imidazo[1,2-a]pyridine 260 mg, 0.646 mmol
  • 2-methoxycarbonylaminopyridine-5-boronic acid pinacol ester (265 mg, 0.905 mmol, 1.40 eq.
  • cesium carbonate (319 mg, 0.970 mmol, 1.50 eq.
  • 2- methyltetrahydrofuran (8.40 mL)
  • water 2.80 mL
  • the reaction mixture was purged with argon and heated at 100 °C for 30 min under microwave irradiation.
  • the suspension was cooled to room temperature, petroleum ether was added, the suspension was filtered and successively washed with water and petroleum ether.
  • the precipitate was dissolved in chloroform at 50 °C and filtered.
  • the filtrate was concentrated to give methyl N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazol-3-yl]imidazo[1,2-a]pyridin-3-yl]-2- pyridyl]carbamate as a white solid.
  • the reaction mixture was degassed with argon for 5 minutes, then Pd(PPh3)4 (330 mg, 0.286 mmol, 0.100 eq.) was added and it was stirred under nitrogen at 100 °C for 16 hours.
  • the reaction mixture was then cooled down to room temperature, NaOH (2N, 5.00 mL) was added and stirring continued for 10 minutes.
  • the reaction mixture was extracted with ethyl acetate, the aqueous layer was acidified with aqueous HCl 1N and extracted again with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Step 2 Preparation of 4-chloro-5-(4-fluorophenyl)pyrimidine
  • a mixture of 5-(4-fluorophenyl)pyrimidin-4-ol (500 mg, 2.23 mmol) and phosphoryl trichloride (2.05 mL, 22.3 mmol, 10.0 eq.) was heated at 110 °C and stirred for 3 hours. The mixture was then cooled and concentrated under reduced pressure. The residue was diluted with ethyl acetate, washed with saturated NaHCO3 and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Step 3 Preparation of 6-[5-(4-fluorophenyl)pyrimidin-4-yl]imidazo[1,2-a]pyridine
  • 4-chloro-5-(4-fluorophenyl)pyrimidine 350 mg, 1.51 mmol
  • imidazo[1,2- a]pyridin-6-ylboronic acid 293 mg, 1.81 mmol, 1.20 eq.
  • cesium carbonate 984 mg, 3.02 mmol, 2.00 eq.
  • reaction mixture was degassed with argon for 2 minutes, then Pd(dppf)Cl2 (110 mg, 0.151 mmol, 0.100 eq.) was added and the reaction mixture was heated at 100 °C and stirred 1 hour under microwave irradiation. After cooling down to room temperature, the reaction mixture was filtered through a pad of celite which was further washed with ethyl acetate. The filtrate was washed with water and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Step 4 Preparation of 6-[5-(4-fluorophenyl)pyrimidin-4-yl]-3-iodo-imidazo[1,2-a]pyridine
  • 6-[5-(4-fluorophenyl)pyrimidin-4-yl]imidazo[1,2-a]pyridine 100 mg, 0.310 mmol
  • dimethylformamide 2.00 mL
  • N-iodosuccinimide 76.7 mg, 0.341 mmol, 1.10 eq.
  • Step 5 Preparation of methyl N-[5-[6-[5-(4-fluorophenyl)pyrimidin-4-yl]imidazo[1,2-a]pyridin-3-yl]-2- pyridyl]carbamate (Compound 69)
  • 6-[5-(4-fluorophenyl)pyrimidin-4-yl]-3-iodo-imidazo[1,2-a]pyridine 200 mg, 0.432 mmol
  • methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate 153 mg, 0.541 mmol, 1.25 eq.
  • cesium carbonate 282 mg, 0.865 mmol, 2.00 eq.
  • reaction mixture was degassed with argon for 2 minutes, then [2-(2- aminophenyl)phenyl]-chloro-palladium;dicyclohexyl-[3-(2,4,6-triisopropylphenyl)phenyl]phosphane (XPhosPdG2; 17.0 mg, 0.0216 mmol, 0.05 eq.) was added and the resulting reaction mixture was heated at 100 oC under microwave irradiation for 1 hour. The reaction mixture was then cooled to room temperature, filtered through a pad of celite which was further washed using ethyl acetate. The filtrate was extracted with water and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • the reaction mixture was degassed with argon for 2 minutes, then Pd(PPh3)4 (132 mg, 0.114 mmol, 0.100 eq.) was added and it was heated at 100 °C and stirred for 16 hours. The reaction mixture was then cooled to room temperature, NaOH (2N, 2.00 mL) was added and stirring continued for 10 minutes. The reaction mixture was diluted with ethyl acetate, the organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The aqueous layer was acidified with 1N HCl and again extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Step 2 Preparation of 3-chloro-4-(4-fluorophenyl)pyridazine
  • a suspension of 4-(4-fluorophenyl)pyridazin-3-ol (230 mg, 1.09 mmol) in phosphoryl trichloride (0.996 mL, 10.9 mmol, 10.0 eq.) was heated at 110 °C for 6 hours.
  • the reaction mixture was then cooled to room temperature, concentrated under reduced pressure and the residue obtained was diluted with ethyl acetate.
  • the solution was washed with saturated aqueous NaHCO3 and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Step 3 Preparation of 6-[4-(4-fluorophenyl)pyridazin-3-yl]imidazo[1,2-a]pyridine
  • 3-chloro-4-(4-fluorophenyl)pyridazine (2.25 g, 9.71 mmol)
  • reaction mixture was degassed with argon for 5 minutes, then Pd(dppf)Cl2 (710 mg, 0.971 mmol, 0.100 eq.) was added and the mixture was heated at 100 °C and stirred for 1 hour under microwave irradiation.
  • the reaction mixture was filtered through a pad of celite which was further washed with ethyl acetate. The filtrate was washed with water, brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Step 4 Preparation of 6-[4-(4-fluorophenyl)pyridazin-3-yl]-3-iodo-imidazo[1,2-a]pyridine
  • 6-[4-(4-fluorophenyl)pyridazin-3-yl]imidazo[1,2-a]pyridine 500 mg, 1.60 mmol
  • dimethylformamide 5.00 mL
  • 1-iodopyrrolidine-2,5-dione 432 mg, 1.92 mmol, 1.20 eq.
  • the resulting mixture was stirred for 16 hours at room temperature and then poured into water.
  • Step 5 Preparation of methyl N-[5-[6-[4-(4-fluorophenyl)pyridazin-3-yl]imidazo[1,2-a]pyridin-3-yl]-2- pyridyl]carbamate (Compound 70)
  • 6-[4-(4-fluorophenyl)pyridazin-3-yl]-3-iodo-imidazo[1,2-a]pyridine 150 mg, 0.324 mmol
  • methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate 115 mg, 0.405 mmol, 1.25 eq.
  • cesium carbonate 211 mg, 0.649 mmol, 2.00 eq.
  • CataCXium® A Pd G3 (24 mg, 0.032 mmol, 0.10 eq.) was added to the reaction mixture and it was heated at 100 oC and stirred for 1 hour under microwave irradiation. The reaction mixture was cooled and then filtered through a pad of celite which was further washed with ethyl acetate. The filtrate was extracted with water and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Example 23 preparation of methyl N-[5-[6-[3-(4-fluorophenyl)pyrazin-2-yl]imidazo[1,2-a]pyridin- 3-yl]-2-pyridyl]carbamate (compound 28)
  • Step 2 Preparation of 6-[3-(4-fluorophenyl)pyrazin-2-yl]imidazo[1,2-a]pyridine
  • reaction mixture was poured into water and extracted 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 over silica gel (ethyl acetate/hexane) to afford 6-[3-(4-fluorophenyl)pyrazin-2-yl]imidazo[1,2-a]pyridine.
  • Step 3 Preparation of 6-[3-(4-fluorophenyl)pyrazin-2-yl]-3-iodo-imidazo[1,2-a]pyridine
  • Step 4 Preparation of methyl N-[5-[6-[3-(4-fluorophenyl)pyrazin-2-yl]imidazo[1,2-a]pyridin-3-yl]-2- pyridyl]carbamate (Compound 28)
  • a solution of 6-[3-(4-fluorophenyl)pyrazin-2-yl]-3-iodo-imidazo[1,2-a]pyridine (200 mg, 0.471 mmol) in 1,4-dioxane/water (v/v 5:1, 30.0 mL) was purge with argon for 5 minutes and then methyl N-[5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-pyridyl]carbamate (157 mg, 0.565 mmol, 1.20 eq.), cesium carbonate (307 mg, 0.942 mmol, 2.00 eq.) and cataCXium® A
  • reaction mixture was heated at 100 °C and stirred for 1 hour under microwave irradiation.
  • the reaction mixture was then cooled to room temperature, diluted with water and extracted 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 over silica gel (ethyl acetate/n-hexane) to afford methyl N-[5-[6-[3-(4- fluorophenyl)pyrazin-2-yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate as an off-white solid.
  • Example 24 preparation of methyl N-[5-[6-[2-(4-fluorophenyl)-5-oxo-pyrrolidin-1-yl]imidazo[1,2- a]pyridin-3-yl]-2-pyridyl]carbamate (compound 49) (Compound 49) Step 1: Preparation of 5-(4-fluorophenyl)-1-imidazo[1,2-a]pyridin-6-yl-pyrrolidin-2-one To a stirred solution of 5-(4-fluorophenyl)pyrrolidin-2-one (commercially available CAS 90432-58-9; 259 mg, 1.44 mmol, 1.20 eq.) and 6-bromoimidazo[1,2-a]pyridine (237 mg, 1.20 mmol) in dioxane (4.00 mL) was added copper(I) iodide (23 mg, 0.12 mmol, 0.10 eq.), potassium carbonate (333 mg, 2.41 mmol, 2.00
  • reaction mixture was stirred overnight at 100 °C, then it was cooled down to room temperature, diluted with water and extracted with ethyl acetate. The combined organic layers were washed with water twice and once with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude residue was purified by flash chromatography over silica gel (ethyl acetate/hexane) to afford 5-(4-fluorophenyl)- 1-imidazo[1,2-a]pyridin-6-yl-pyrrolidin-2-one.
  • Step 2 Preparation of 1-(3-bromoimidazo[1,2-a]pyridin-6-yl)-5-(4-fluorophenyl)pyrrolidin-2-one
  • 5-(4-fluorophenyl)-1-imidazo[1,2-a]pyridin-6-yl-pyrrolidin-2-one 210 mg, 0.711 mmol
  • N-bromosuccinimide 153 mg, 0.853 mmol, 1.20 eq.
  • Step 3 Preparation of methyl N-[5-[6-[2-(4-fluorophenyl)-5-oxo-pyrrolidin-1-yl]imidazo[1,2-a]pyridin-3- yl]-2-pyridyl]carbamate (Compound 49)
  • a 25 mL vial containing methyl N-[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2- pyridyl]carbamate (162 mg, 0.582 mmol, 1.10 eq.)
  • 1-(3-bromoimidazo[1,2-a]pyridin-6-yl)-5- (4-fluorophenyl)pyrrolidin-2-one 198 mg, 0.5291 mmol
  • potassium carbonate 1 M in water (2.00 mL, 2.00 mmol, 3.78 eq.
  • 2-methyltetrahydrofuran (4.00 mL)
  • reaction mixture was degassed with argon and left to stir in a sealed tube heated at 80 °C for 2 hours.
  • the reaction mixture was then cooled and diethyl ether was added to the reaction mixture.
  • the resulting solid that formed was filtered, and further washed with diethyl ether to afford methyl N-[5-[6-[2-(4-fluorophenyl)-5-oxo-pyrrolidin-1-yl]imidazo[1,2-a]pyridin-3-yl]-2- pyridyl]carbamate.
  • Example 25 preparation of methyl N-[5-[6-[2-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazol- 3-yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 33) (Compound 33) Step 1: Preparation of 3-bromoimidazo[1,2-a]pyridine-6-carboxamide To a solution of 3-bromoimidazo[1,2-a]pyridine-6-carboxylic acid (430 mg, 1.69 mmol) in THF (5.65 mL) was added a drop of dimethylformamide followed by a slow addition of oxalyl chloride (0.159 mL, 1.78 mmol, 1.05 eq.).
  • reaction mixture was stirred for 40 minutes at 50 °C, and then ammonium hydroxide solution (28% in water, 0.848 mL, 6.78 mmol, 4.00 eq.) was added slowly and stirring continued for 30 minutes at 50 °C.
  • ammonium hydroxide solution (28% in water, 0.848 mL, 6.78 mmol, 4.00 eq.) was added slowly and stirring continued for 30 minutes at 50 °C.
  • the reaction mixture was cooled to room temperature, ice was added, the precipitate that formed was filtered, and washed with water to afford 3-bromoimidazo[1,2-a]pyridine-6-carboxamide as a white solid.
  • Step 2 Preparation of (NE)-3-bromo-N-[1-(dimethylamino)ethylidene]imidazo[1,2-a]pyridine-6- carboxamide
  • acetic acid 0.014 mL, 0.25 mmol, 0.20 eq.
  • Step 3 Preparation of 3-bromo-6-[2-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazol-3- yl]imidazo[1,2-a]pyridine
  • (NE)-3-bromo-N-[1-(dimethylamino)ethylidene]imidazo[1,2-a]pyridine-6-carboxamide 150 mg, 0.485 mmol
  • dimethylformamide 0.70 mL
  • 1-(4-fluoro-3- methoxyphenyl)hydrazine hydrochloride 118 mg, 0.582 mmol, 1.20 eq.
  • the reaction mixture was heated at 90 °C and stirred for 30 minutes, and then heated to 95 °C and stirred for an additional 3 hours.
  • the reaction mixture was cooled and then water was added and the mixture was extracted with ethyl acetate.
  • the combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure to afford 3-bromo-6-[2-(4-fluoro-3-methoxy-phenyl)-5-methyl- 1,2,4-triazol-3-yl]imidazo[1,2-a]pyridine as a brown solid.
  • the product was used without further purification.
  • Step 4 Preparation of methyl N-[5-[6-[2-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazol-3- yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (Compound 33)
  • 3-bromo-6-[2-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4-triazol-3- yl]imidazo[1,2-a]pyridine 140 mg, 0.348 mmol
  • 2-methoxycarbonylaminopyridine-5-boronic acid pinacol ester 143 mg, 0.487 mmol, 1.43 eq.
  • cesium carbonate 172 mg, 0.522 mmol, 1.50 eq.
  • 2-methyltetrahydrofuran 4.5 mL
  • water 1.5 mL
  • the reaction mixture was purged with argon and heated at 100 °C for 30 min under microwave irradiation.
  • the solution was cooled to room temperature, water was added, and the solution was extracted with dichloromethane.
  • the combined organic layers were washed with brine, dried over sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography (dichloromethane/methanol) to afford methyl N-[5-[6-[2-(4-fluoro-3-methoxy-phenyl)-5-methyl-1,2,4- triazol-3-yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate as a brown solid.
  • Example 26 preparation of methyl N-[5-[6-[1-(4-fluorophenyl)imidazol-2-yl]imidazo[1,2-a]pyridin- 3-yl]-2-pyridyl]carbamate (compound 43)
  • copper(I) chloride 113 mg, 1.12 mmol, 0.100 eq.
  • potassium carbonate (1.64 g, 11.8 mmol, 1.05 eq.)
  • acetylacetone (0.290 mL, 2.80 mmol, 0.250 eq.) and NMP (2.24 mL) was added under argon imidazole (924 mg, 13.4 mmol, 1.20 eq.) and 1-bromo-4- fluorobenzene (1.26 mL, 11.2 mmol).
  • the reaction mixture was heated at 120 °C and stirred. The reaction mixture was then cooled down to room temperature, mixed with saturated aqueous NaHCO3 solution and dichloromethane and stirred for 15 minutes at room temperature. The suspension was filtered through a pad of celite, and the filtrate was extracted with dichloromethane. 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 over silica gel (ethyl acetate/ethanol) to afford 1-(4-fluorophenyl)imidazole as a yellow liquid.
  • Step 2 Preparation of 3-bromo-6-[1-(4-fluorophenyl)imidazol-2-yl]imidazo[1,2-a]pyridine
  • 1-(4-fluorophenyl)imidazole 300 mg, 1.85 mmol
  • THF 2.50 mL
  • n-buthyllithium in hexane 2.50 mol/L, 0.890 mL, 2.22 mmol, 1.20 eq.
  • reaction mixture was stirred for 30 minutes at 0 °C, then zinc chloride in methyl tetrahydrofuran (1.90 mol/L, 1.60 mL, 2.96 mmol, 1.60 eq.) was added and stirring continued for 30 minutes at room temperature.
  • the reaction mixture was then concentrated to remove half of the solvent, and to that mixture was added dry toluene (1.85 mL), 3-bromo-6-iodoimidazo[1,2-a]pyridine (677 mg, 2.04 mmol, 1.10 eq.) and Pd(PPh3)4 (108 mg, 0.093 mmol, 0.05 eq.).
  • the reaction mixture was heated at 100 °C and stirred overnight, then it was cooled to room temperature and stirred in a mixture of saturated aqueous NaHCO3 solution and ethyl acetate for 20 minutes. The mixture was then extracted with ethyl acetate, and 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 over silica gel (cyclohexane/ethyl acetate/ethanol) to afford 3-bromo-6-[1-(4-fluorophenyl)imidazol-2- yl]imidazo[1,2-a]pyridine as a yellow solid.
  • Step 3 Preparation of methyl N-[5-[6-[1-(4-fluorophenyl)imidazol-2-yl]imidazo[1,2-a]pyridin-3-yl]-2- pyridyl]carbamate (Compound 43)
  • 3-bromo-6-[1-(4-fluorophenyl) imidazol-2-yl]imidazo[1,2-a]pyridine 80.0 mg, 0.220 mmol
  • 2-methyltetrahydrofuran (2.90 mL) water (0.970 mL) and tetrakis(triphenylphosphine) palladium(0) (13.0 mg, 0.011 mmol, 0.0500 eq
  • the reaction mixture was purged with argon and heated at 100 °C for 30 minutes under microwave irradiation.
  • the solution was cooled to room temperature, water was added, and the solution was extracted 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 over silica gel (dichloromethane/methanol) to afford methyl N-[5-[6-[1-(4- fluorophenyl)imidazol-2-yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate as a white solid.
  • Example 27 preparation of methyl N-[5-[6-[5-cyano-2-(4-fluorophenyl)-1,2,4-triazol-3- yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 74) (Compound 74) Step 1: Preparation of dimethyl 2-[(3-bromoimidazo[1,2-a]pyridine-6-carbonyl)amino]propanedioate To a solution of 3-bromoimidazo[1,2-a]pyridine-6-carboxylic acid (500 mg, 2.03 mmol) in ethyl acetate (8.13 mL) was added dimethyl aminomalonate hydrochloride (500 mg, 2.64 mmol, 1.30 eq.) followed by N,N-diisopropylethylamine (1.79 mL, 10.2 mmol, 5.00 eq.) and propylphosphonic anhydride in e
  • Step 2 Preparation of methyl 5-(3-bromoimidazo[1,2-a]pyridin-6-yl)-1-(4-fluorophenyl)-1,2,4-triazole-3- carboxylate
  • sodium nitrite (112 mg, 1.62 mmol, 1.20 eq.) in water (0.794 mL) was added dropwise to a mixture of 4-fluoroaniline (182 mg, 1.62 mmol, 1.20 eq.) and conc. HCl (0.397 mL) in acetic acid (1.17 mL) at 0 °C.
  • Step 3 Preparation of 5-(3-bromoimidazo[1,2-a]pyridin-6-yl)-1-(4-fluorophenyl)-1,2,4-triazole-3-
  • methyl 5-(3-bromoimidazo[1,2-a]pyridin-6-yl)-1-(4-fluorophenyl)-1,2,4- triazole-3-carboxylate 100 mg, 0.240 mmol
  • ammonia in methanol (6.90 mL).
  • the reaction mixture was stirred for 5 minutes at 80 °C and then 1 additional hour at room temperature. The volatiles were removed under reduced pressure and the residue was solubilized in dichloromethane (1.60 mL).
  • Triethylamine (0.101 mL, 0.721 mmol, 3.00 eq.) was added to the solution, followed by a slow addition of trifluoro acetic anhydride (0.0675 mL, 0.481 mmol, 2.00 eq.).
  • the reaction mixture was stirred for 30 minutes at room temperature, then it was quenched with a saturated aqueous NaHCO 3 solution and extracted with dichloromethane. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Step 4 Preparation of methyl N-[5-[6-[5-cyano-2-(4-fluorophenyl)-1,2,4-triazol-3-yl]imidazo[1,2- a]pyridin-3-yl]-2-pyridyl]carbamate (Compound 74)
  • 5-(3-bromoimidazo[1,2-a]pyridin-6-yl)-1-(4-fluorophenyl)-1,2,4- triazole-3-carbonitrile (65.0 mg, 0.170 mmol) followed by 2-methoxycarbonylaminopyridine-5-boronic acid, pinacol ester (70.0 mg, 0.240 mmol, 1.40 eq.), cesium carbonate (84.0 mg, 0.250 mmol, 1.50 eq.), 2-methyltetrahydrofuran (2.20 mL), water (0.730 mL) and tetrakis(triphenylphosphine) palladium(0) (10 mg
  • the reaction mixture was purged with argon and heated at 100 °C for 30 minutes under microwave irradiation.
  • the solution was cooled to room temperature, water was added, and the solution was extracted with ethyl acetate.
  • the combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
  • Example 28 preparation of methyl N-[5-[6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3- yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 4) (Compound 4) Step 1: Preparation of (NE)-3-bromo-N-(dimethylaminomethylene)imidazo[1,2-a]pyridine-6- carboxamide To a suspension of 3-bromoimidazo[1,2-a]pyridine-6-carboxamide (see synthetic example 25, step 1; 0.82 g, 3.41 mmol) in N,N-dimethylformamide dimethyl acetal (0.623 g, 0.695 mL, 5.12 mmol) was added acetic acid (0.041 g, 0.039 mL, 0.683 mmol).
  • Step 2 Preparation of 3-bromo-6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]imidazo[1,2- a]pyridine (Intermediate I-1) (Intermediate I-1) To a solution of (NE)-3-bromo-N-(dimethylaminomethylene)imidazo[1,2-a]pyridine-6-carboxamide (750 mg, 2.54 mmol) in dimethylformamide (25.4 mL) was added 1-(4-fluoro-3-methoxyphenyl)hydrazine hydrochloride (618 mg, 3.05 mmol, 1.20 eq.). The reaction mixture was heated at 90 °C and stirred overnight.
  • Step 3 Preparation of methyl N-[5-[6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]imidazo[1,2- a]pyridin-3-yl]-2-pyridyl]carbamate (Compound 4)
  • 3-bromo-6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]imidazo[1,2- a]pyridine (Intermediate I-1, 785 mg, 1.92 mmol) and methyl N-[5-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-2-pyridyl]carbamate (748 mg, 2.69 mmol, 1.40 eq.) were dissolved in 2- methyltetrahydrofuran (11.5 mL) and water (3.84 mL).
  • Example 29 preparation of methyl N-[5-[6-[4-(4-fluorophenyl)-1,2,4-triazol-3-yl]imidazo[1,2- a]pyridin-3-yl]-2-pyridyl]carbamate (compound 75) (Compound 75) Step 1: Preparation of 2-(3-bromoimidazo[1,2-a]pyridin-6-yl)-1,3,4-oxadiazole N To 3-bromoimidazo[1,2-a]pyridine-6-carbohydrazide (see synthetic example 20, step 1; 360 mg, 1.41 mmol) was added triethyl orthoformate (2.40 mL, 14.1 mmol, 10.0 eq.) and the reaction mixture was stirred overnight at 140 °C.
  • Step 2 Preparation of 3-bromo-6-[4-(4-fluorophenyl)-1,2,4-triazol-3-yl]imidazo[1,2-a]pyridine
  • 2-(3-bromoimidazo[1,2-a]pyridin-6-yl)-1,3,4-oxadiazole 160 mg, 0.604 mmol
  • 4-fluoroaniline 0.289 mL, 3.02 mmol, 5.00 eq.
  • the reaction mixture was heated at 120 °C and stirred for 4 hours, then it was cooled down to room temperature, saturated aqueous aq.
  • Step 3 Preparation of methyl N-[5-[6-[4-(4-fluorophenyl)-1,2,4-triazol-3-yl]imidazo[1,2-a]pyridin-3-yl]-2- pyridyl]carbamate (Compound 75)
  • 3-bromo-6-[4-(4-fluorophenyl)-1,2,4-triazol-3-yl]imidazo[1,2-a]pyridine 90.0 mg, 0.251 mmol
  • 2-methoxycarbonylaminopyridine-5-boronic acid pinacol ester 101 mg, 0.352 mmol, 1.40 eq.
  • Example 30 preparation of methyl N-[5-[6-[2-(4-fluorophenyl)pyrazol-3-yl]imidazo[1,2-a]pyridin- 3-yl]-2-pyridyl]carbamate (compound 76)
  • methyl 3-bromoimidazo[1,2-a]pyridine-6-carboxylate (1.00 g, 3.84 mmol) and N,O- dimethylhydroxylamine hydrochloride (574 mg, 5.76 mmol, 1.50 eq.) in THF (12.8 mL) at 0 °C under argon was added methyl magnesium bromide in methyltetrahydrofuran (5.40 mL, 17.3 mmol).
  • Step 2 Preparation of 1-(3-bromoimidazo[1,2-a]pyridin-6-yl)-3-(dimethylamino)prop-2-en-1-one
  • acetic acid 0.0053 mL, 0.092 mmol, 0.2 eq.
  • Step 3 Preparation of 3-bromo-6-[2-(4-fluorophenyl)pyrazol-3-yl]imidazo[1,2-a]pyridine
  • 1-(3-bromoimidazo[1,2-a]pyridin-6-yl)-3-(dimethylamino)prop-2-en-1-one 130 mg, 0.442 mmol
  • 4-fluorophenylhydrazine hydrochloride 89 mg, 0.53 mmol, 1.2 eq.
  • Step 4 Preparation of methyl N-[5-[6-[2-(4-fluorophenyl)pyrazol-3-yl]imidazo[1,2-a]pyridin-3-yl]-2- pyridyl]carbamate (Compound 76)
  • 3-bromo-6-[2-(4-fluorophenyl)pyrazol-3-yl]imidazo[1,2-a]pyridine 110 mg, 0.308 mmol
  • 2-methoxycarbonylaminopyridine-5-boronic acid pinacol ester 124 mg, 0.431 mmol, 1.40 eq.
  • cesium carbonate 152 mg, 0.462 mmol, 1.5 eq.
  • 1,4-dioxane (9.2 mL), water (3.1 mL) and tetrakis(triphenylphosphine) palladium(0) (18.0 mg, 0.0154 mmol, 0.0500 eq.).
  • the reaction mixture was purged with argon and heated at 100 °C under microwave irradiation for 30 minutes. The reaction mixture was then cooled, water was added and the solution was extracted 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 over silica gel (dichloromethane/methanol) to afford methyl N-[5-[6-[2-(4-fluorophenyl)pyrazol-3- yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate as a beige solid.
  • Example 31 preparation of methyl N-[5-[6-[4-(4-fluoro-3-methyl-phenyl)-5-methyl-1,2,4-triazol-3- yl]-8-methyl-imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 5)
  • a solution of 2-amino-5-bromo-3-methylpyridine (2.0 g, 10.7 mmol) in ethanol (42.8 mL) was stirred under nitrogen atmosphere. Then chloroacetaldehyde solution (2.33 g, 13.37 mmol, 1.89 mL, 1.25 eq.) was added.
  • the bomb was then flushed with carbon monoxide, sealed, and pressurized to 2.5 MPa with carbon monoxide.
  • the reaction was stirred at 100 °C for 8 hours.
  • the vessel was then cooled to room temperature and the pressure released.
  • the reaction mixture was concentrated to dryness and purified by silica gel column chromatography (eluting with dichloromethane/MeOH) to obtain the methyl 8-methylimidazo[1,2- a]pyridine-6-carboxylate as a brown solid.
  • Step 3 Preparation of methyl 3-bromo-8-methyl-imidazo[1,2-a]pyridine-6-carboxylate
  • acetonitrile 13 mL
  • N-bromosuccinimide 0.53 g, 2.9 mmol, 1.1 eq.
  • Step 5 Preparation of 2-(3-bromo-8-methyl-imidazo[1,2-a]pyridin-6-yl)-5-methyl-1,3,4-oxadiazole (Intermediate I-3) (Intermediate I-3) A mixture of 3-bromo-8-methyl-imidazo[1,2-a]pyridine-6-carbohydrazide (Intermediate I-2, 9.4 g, 35 mmol) and triethyl orthoacetate (58 g, 65 mL, 350 mmol, 10 eq.) was stirred for 3 hours at 130 °C.1,8- diazabicyclo[5.4.0]undec-7-ene (6.5 g, 6.4 mL, 42 mmol, 1.2 eq.) was then added.
  • Step 6 Preparation of 5-[8-methyl-6-(5-methyl-1,3,4-oxadiazol-2-yl)imidazo[1,2-a]pyridin-3-yl]pyridin- 2-amine
  • 2-(3-bromo-8-methyl-imidazo[1,2-a]pyridin-6-yl)-5-methyl-1,3,4-oxadiazole (Intermediate I-3, 0.34 g, 1.16 mmol)
  • 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2- amine 0.383 g, 1.74 mmol, 1.50 eq.
  • reaction mixture was stirred at room temperature overnight.
  • the reaction mixture was concentrated under reduced pressure and purified by flash chromatography on neutral alumina (eluting 15-20% methanol in ethyl acetate) to afford methyl N-[5-[8-methyl-6-(5-methyl-1,3,4-oxadiazol-2-yl)imidazo[1,2- a]pyridin-3-yl]-2-pyridyl]carbamate.
  • the aqueous layer was extracted ethyl acetate and the combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
  • the crude residue was purified over a silica gel cartridge (cyclohexane/ethyl acetate, 3:2) to afford methyl 8-cyclopropylimidazo[1,2-a]pyridine-6-carboxylate as brown solid.
  • the reaction mixture was stirred for overnight at 120 °C.
  • the reaction mixture was cooled down to room temperature and then water was added.
  • the aqueous layer was extracted with ethyl acetate and the combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
  • the crude residue was purified over a silica gel cartridge (eluting cyclohexane/ethyl acetate, 3:7) to afford 2-(8-cyclopropylimidazo[1,2-a]pyridin-6-yl)- 1,3,4-oxadiazole as white solid.
  • the aqueous layer was extracted with ethyl acetate, the combined organic layers were washed with sodium thiosulphate pentahydrate, dried over sodium sulfate, filtered, and concentrated under reduced pressure.
  • the crude was purified by flash chromatography over silical gel (eluting cyclohexane/ethyl acetate, 8:2) to afford ethyl acetate 2-(3-bromo-8-cyclopropyl-imidazo[1,2-a]pyridin-6-yl)-1,3,4-oxadiazole as a yellow solid.
  • reaction mixture was stirred at 80 °C for 16 hours. The reaction mixture was then concentrated under reduced pressure. Saturated aqueous NaHCO3 and dichloromethane were added. The aqueous layer was extracted with dichloromethane, the combined organic phases were dried with sodium sulfate, filtered and concentrated under reduced pressure. The residual was purified by silica gel column chromatography (eluting with ethyl acetate/petroleum ether, 0% to 75%) to afford 6-iodo-8-methyl-imidazo[1,2-a]pyridine as a yellow solid.
  • Example 36 Preparation of methyl N-[5-[6-[4-(4-fluoro-3-methoxy-phenyl)-5,6-dihydro-1,2,4- oxadiazin-3-yl]-8-methyl-imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (compound 3) (Compound 3) Step 1: Preparation of 8-methylimidazo[1,2-a]pyridine-6-carbonitrile To a solution of 6-iodo-8-methyl-imidazo[1,2-a]pyridine (Intermediate I-4, 17.0 g, 59.3 mmol), zinc cyanide (13.9 g, 119 mmol, 2 eq.) and 1,1'-bis(diphenylphosphino)ferrocene (3.29 g, 5.93 mmol, 0.10 eq.) in dimethylformamide (300 mL) was added Pd2(dba)3 (2.71
  • reaction mixture was stirred at 120 °C for 3 hours under nitrogen. After being cooled to room temperature, the reaction mixture was diluted with water and the mixture was filtered through celite. The filtrate was extracted with ethyl acetate, the combined organic layers were washed with water and brine, dried with sodium sulfate, and concentrated under vacuum. The residue was purified by silica gel column chromatography (eluting with dichloromethane/MeOH, 2% to 5%) to provide 8-methylimidazo[1,2-a]pyridine-6-carbonitrile as a brown solid.
  • reaction mixture was stirred at room temperature for 3 hours, then it was diluted with water and 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 over silical gel (petroleum ether/ethyl acetate) to afford 2-chloro-N-(4-fluoro-3-methoxy- phenyl)acetamide as a colorless oil.
  • reaction mixture was warmed to room temperature and stirred for an additional 3 hours, after which it was poured into ice water and extracted with ethyl acetate. The combined organic layer was washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography over silica gel (petroleum ether/ethyl acetate) to afford N-(2-chloroethyl)-4- fluoro-3-methoxy-aniline as a colorless liquid.
  • Example 37 Preparation of methyl N-[5-[6-[4-(4-fluorophenyl)-5,6-dihydro-1,2,4-oxadiazin-3-yl]- 8-methyl-imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (Compound 1) (Compound 1) Step 1: Preparation of N-(2-chloroethyl)-4-fluoro-aniline To a solution of 4-fluoroaniline (2.00 g, 18.0 mmol) in a mixture of methanol (30 mL) and acetic acid (1.03 mL, 18.0 mmol, 1.00 eq.) at room temperature was added portionwise sodium cyanoborohydride (1.79 g, 27.0 mmol, 1.50 eq.) followed by 2-chloroacetaldehyde (2.59 mL, 21.6 mmol, 1.20 eq.).
  • Example 38 Preparation of methyl N-[5-[6-[5-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-1- yl]imidazo[1,2-a]pyridin-3-yl]-2-pyridyl]carbamate (Compound 9) (Compound 9) Step 1: Preparation of 2-chloro-5-[5-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-1-yl]pyridine A solution of 4-fluoro-3-methoxy-benzamide (1.60 g, 9.46 mmol) in 1,1-dimethoxy-N,N-dimethyl- methanamine (8.00 mL) was heated at 100 °C for 2 hours.
  • the mixture was concentrated under reduced pressure. The residue was taken up in acetic acid (16.0 mL), and (6-chloro-3-pyridyl)hydrazine (1.36 g, 9.46 mmol, 1.00 eq.) was added. Then the mixture was heated at 95 °C for 3 hours. The reaction mixture was then concentrated under vacuum. The mixture was adjusted to pH 7 with saturated aqueous NaHCO3 solution. The aqueous layer was extracted with dichloromethane. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under vacuum.
  • Example 39 Preparation of 5-[6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]imidazo[1,2- a]pyridin-3-yl]pyridin-2-amine
  • a solution of sodium carbonate (12.9 mg, 0.122 mmol, 3.05 eq.) in water (0.200 mL) was added to 2- aminopyridine-5-boronic acid pinacol ester (14.1 mg, 0.0638 mmol, 1.60 eq.), followed by addition of a solution of 3-bromo-6-[2-(4-fluoro-3-methoxy-phenyl)-1,2,4-triazol-3-yl]imidazo[1,2-a]pyridine (Intermediate I-1, 15.5 mg, 0.0400 mmol) in acetonitrile (0.200 mL).
  • 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).
  • the following compounds gave at least 80% control of Phytophthora infestans at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 77, 80, 81, 85, 86, 87, 90, 92, 95, 101, 104, 107, 108, 111, 112.
  • 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).
  • test compound 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
  • the following compounds gave at least 80% control of Pythium ultimum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 48, 49, 50, 51, 53, 54, 55, 56, 57, 61, 65, 68, 69, 70, 71, 75, 76, 77, 79, 80, 85, 86, 87, 90, 92, 95, 104, 107, 109, 112, 113.

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Abstract

La présente invention concerne des composés de formule (I), dans laquelle les substituants sont tels que définis dans la revendication 1, des processus et des procédés de préparation de composés de formule (I), des compositions agrochimiques comprenant des composés de formule (I) tels que définis dans la revendication 1, la préparation de ces compositions et l'utilisation des composés ou compositions en agriculture ou horticulture pour combattre, prévenir ou lutter contre l'infestation de plantes, de cultures vivrières récoltées, de graines ou de matériaux non vivants par des micro-organismes phytopathogènes, en particulier des champignons.
EP23822330.9A 2022-12-14 2023-12-11 Dérivés d'imidazo[1,2-a]pyridine Pending EP4634178A1 (fr)

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AR131324A1 (es) 2025-03-05
PY23101700A (es) 2024-06-20
WO2024126404A1 (fr) 2024-06-20
TW202440570A (zh) 2024-10-16
MX2025006737A (es) 2025-07-01

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