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WO2021058595A1 - Composés herbicides - Google Patents

Composés herbicides Download PDF

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Publication number
WO2021058595A1
WO2021058595A1 PCT/EP2020/076614 EP2020076614W WO2021058595A1 WO 2021058595 A1 WO2021058595 A1 WO 2021058595A1 EP 2020076614 W EP2020076614 W EP 2020076614W WO 2021058595 A1 WO2021058595 A1 WO 2021058595A1
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Prior art keywords
alkyl
group
formula
phenyl
hydrogen
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PCT/EP2020/076614
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English (en)
Inventor
James Nicholas Scutt
Nigel James Willetts
Sunil CHAKAVE
Vanitha ACHARYA
Mangala Phadte
Swarnendu SASMAL
Sandeep Reddy KANDUKURI
Joseph Andrew TATE
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Syngenta Crop Protection AG Switzerland
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Syngenta Crop Protection AG Switzerland
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Publication of WO2021058595A1 publication Critical patent/WO2021058595A1/fr
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems

Definitions

  • the present invention relates to herbicidally active pyridinium derivatives, as well as to processes and intermediates used for the preparation of such derivatives.
  • the invention further extends to herbicidal compositions comprising such derivatives, as well as to the use of such compounds and compositions for controlling undesirable plant growth: in particular the use for controlling weeds, in crops of useful plants.
  • the present invention is based on the finding that pyridinium derivatives of formula (I) as defined herein, exhibit surprisingly good herbicidal activity.
  • R 1 is selected from the group consisting of hydrogen, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, -OR 7 , -OR 15a , -N(R 6 )S(O) 2 R 15 , -N(R 6 )C(O)R 15 , -N(R 6 )C(O)OR 15 , - N(R 6 )C(O)NR 16 R 17 , -N(R 6 )CHO, -N(R 7a ) 2 and -S(O) r R 15 ;
  • R 2 is selected from the group consisting of hydrogen, halogen, C 1 -C 6 alkyl and C 1 -C 6 haloalkyl; and wherein when R 1 is selected from the group consisting of -OR 7 , -OR 15a , -N(R 6 )S(O) 2 R 15 , - N(R 6 )C(O)R 15 , -N(R 6 )C(O)OR 15 , -N(R 6 )C(O)NR 16 R 17 , -N(R 6 )CHO, -N(R 7a ) 2 and -S(O) r R 15 , R 2 is selected from the group consisting of hydrogen and C 1 -C 6 alkyl; or
  • R 1 and R 2 together with the carbon atom to which they are attached form a C 3 -C 6 cycloalkyl ring or a 3- to 6- membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O; and
  • Q is (CR 1a R 2b ) m ; m is 0, 1 , 2 or 3; each R 1a and R 2b are independently selected from the group consisting of hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, -OH, -OR 7 , -OR 15a , -NH 2 , -NHR 7 , -NHR 15a , -N(R 6 )CHO, -NR 7b R 7c and -S(O) r R 15 ; or each R 1a and R 2b together with the carbon atom to which they are attached form a C 3 -C 6 cycloalkyl ring or a 3- to 6- membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O; and
  • R 3 , R 3a , R 4 and R 5 are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, -S(O)rR 15 , C 1 -C 6 alkyl, C 1 -C 6 fluoroalkyl, C 1 -C 6 fluoroalkoxy, C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl and - N(R 6 ) 2 ; each R 6 is independently selected from hydrogen and C 1 -C 6 alkyl; each R 7 is independently selected from the group consisting of C 1 -C 6 alkyl, -S(O) 2 R 15 , -C(O)R 15 , - C(O)OR 15 and -C(O)NR 16 R 17 ; each R 7a is independently selected from the group consisting of -S(O) 2 R 15 , -C(O)R 15 , -C(O)OR 15 - C(O)NR 16 R 17 and
  • R 7b and R 7c are independently selected from the group consisting of C 1 -C 6 alkyl, -S(O) 2 R 15 , -C(O)R 15 , - C(O)OR 15 , -C(O)NR 16 R 17 and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different; or
  • R 7b and R 7c together with the nitrogen atom to which they are attached form a 4- to 6-membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N, O and S; and
  • A is a fused bicyclic structure of general formula; in which:
  • ring A 1 has 5 members and ring A 2 has 6 members;
  • A includes at least one heteroatom selected from N, O and S, with the remainder being carbon atoms;
  • one of the carbon atoms is optionally a carbonyl
  • A is optionally substituted in any available position in either or both of ring A 1 or ring A 2 by p substituents R 8 , which may be the same or different;
  • each R 8 is independently selected from the group consisting of halogen, nitro, cyano, -NH 2 , -NHR 7 , -N(R 7 ) 2 , -OH, -OR 7 , -S(O) r R 15 , - NR 6 S(O) 2 R 15 , -C(O)OR 10 , -C(O)R 15 , -C(O)NR 16 R 17 , -S(O) 2 NR 16 R 17 , C 1 - C a y, C 1 -C 6 haloalkyl, C 3 - C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 3 -C 6 cycloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkenyl,
  • X is selected from the group consisting of C 3 -C 6 cycloalkyl, phenyl, a 5- or 6- membered heteroaryl, which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and a 4- to 6- membered heterocyclyl, which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, and wherein said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties are optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R 9 , and wherein the aforementioned CR 1 R 2 , Q and Z moieties may be attached at any position of said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties; n is 0 or 1 ; Z is selected from the group consisting of -C(O)OR 10 , -CH 2 OH, -CHO, -C(O)NHOR 11 , -C
  • R 10 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, phenyl and benzyl, and wherein said phenyl or benzyl are optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different;
  • R 11 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different;
  • R 12 is selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, -OH, -N(R 6 ) 2 and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different;
  • R 13 is selected from the group consisting of -OH, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and phenyl;
  • R 14 is C 1 -C 6 haloalkyl
  • R 15 is selected from the group consisting of C 1 -C 6 alkyl and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different;
  • R 15a is phenyl, wherein said phenyl is optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different;
  • R 16 and R 17 are independently selected from the group consisting of hydrogen and C 1 -C 6 alkyl; or R 16 and R 17 together with the nitrogen atom to which they are attached form a 4- to 6-membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N, O and S; and
  • R 18 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, -N(R 6 ) 2 and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different; and r is 0, 1 or 2.
  • an agrochemical composition comprising a herbicidally effective amount of a compound of formula (I) and an agrochemically-acceptable diluent or carrier.
  • Such an agricultural composition may further comprise at least one additional active ingredient.
  • a method of controlling or preventing undesirable plant growth wherein a herbicidally effective amount of a compound of formula (I), or a composition comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
  • halogen refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.
  • cyano means a -CN group.
  • hydroxy means an -OH group.
  • nitro means an -NO 2 group.
  • C 1 -C 6 alkyl refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to six carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • C 1 -C 4 alkyl and C 1 - C 2 alkyl are to be construed accordingly.
  • Examples of C 1 -C 6 alkyl include, but are not limited to, methyl (Me), ethyl (Et), n-propyl, 1-methylethyl (iso-propyl), n-butyl, and 1-dimethylethyl (t-butyl).
  • C 1 -C 6 alkoxy refers to a radical of the formula -OR a where R a is a C 1 - C 6 alkyl radical as generally defined above.
  • R a is a C 1 - C 6 alkyl radical as generally defined above.
  • C 1 -C 4 alkoxy is to be construed accordingly. Examples of C 1 - 4 alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy and -butoxy.
  • C 1 -C 6 haloalkyl refers to a C 1 -C 6 alkyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C 1 -C 4 haloalkyl is to be construed accordingly.
  • Examples of C 1 -C 6 haloalkyl include, but are not limited to chloromethyl, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl and 2,2,2-trifluoroethyl.
  • C 2 -C 6 alkenyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond that can be of either the (E)- or (Z)-configuration, having from two to six carbon atoms, which is attached to the rest of the molecule by a single bond.
  • C 2 -C 4 alkenyl is to be construed accordingly.
  • Examples of C 2 -C 6 alkenyl include, but are not limited to, prop-1 -enyl, allyl (prop-2-enyl) and but-1-enyl.
  • C 2 -C 6 haloalkenyl refers to a C 2 -C 6 alkenyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • Examples of C 2 -C 6 haloalkenyl include, but are not limited to chloroethylene, fluoroethylene, 1 ,1-difluoroethylene, 1 ,1-dichloroethylene and 1 ,1 ,2-trichloroethylene.
  • C 2 -C 6 alkynyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two to six carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • C 2 -C 4 alkynyl is to be construed accordingly.
  • Examples of C 2 -C 6 alkynyl include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl) and but-1-ynyl.
  • C 1 -C 6 haloalkoxy refers to a C 1 -C 6 alkoxy group as defined above substituted by one or more of the same or different halogen atoms.
  • C 1 -C 4 haloalkoxy is to be construed accordingly.
  • Examples of C 1 -C 6 haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy and trifluoroethoxy.
  • C 1 -C 3 haloalkoxyC 1 -C 3 alkyl refers to a radical of the formula R b -O-R a - where R b is a C 1 -C 3 haloalkyl radical as generally defined above, and R a is a C 1 -C 3 alkylene radical as generally defined above.
  • C 1 -C 3 alkoxyC 1 -C 3 alkyl refers to a radical of the formula R b -O-R a - where R b is a C 1 -C 3 alkyl radical as generally defined above, and R a is a C 1 -C 3 alkylene radical as generally defined above.
  • C 1 -C 3 alkoxyC 1 -C 3 alkoxy- refers to a radical of the formula R b -O-R a - O- where R b is a C 1 -C 3 alkyl radical as generally defined above, and R a is a C 1 -C 3 alkylene radical as generally defined above.
  • C 3 -C 6 alkenyloxy refers to a radical of the formula -OR a where R a is a C 3 -C 6 alkenyl radical as generally defined above.
  • C 3 -C 6 alkynyloxy refers to a radical of the formula -OR a where R a is a C 3 -C 6 alkynyl radical as generally defined above.
  • hydroxyC 1 -C 6 alkyl refers to a C 1 -C 6 alkyl radical as generally defined above substituted by one or more hydroxy groups.
  • C 1 -C 6 alkylcarbonyl refers to a radical of the formula -C(O)R a where R a is a C 1 -C 6 alkyl radical as generally defined above.
  • C 1 -C 6 alkoxycarbonyl refers to a radical of the formula -C(O)OR a where R a is a C 1 -C 6 alkyl radical as generally defined above.
  • aminocarbonyl refers to a radical of the formula -C(O)NH 2 .
  • C 3 -C 6 cycloalkyl refers to a stable, monocyclic ring radical which is saturated or partially unsaturated and contains 3 to 6 carbon atoms.
  • C 3 -C 4 cycloalkyl is to be construed accordingly. Examples of C 3 -C 6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • C 3 -C 6 halocycloalkyl refers to a C 3 -C 6 cycloalkyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C 3 -C 4 halocycloalkyl is to be construed accordingly.
  • C 3 -C 6 cycloalkoxy refers to a radical of the formula -OR a where R a is a C 3 -C 6 cycloalkyl radical as generally defined above.
  • N-C 3 -C 6 cycloalkylamino refers to a radical of the formula -NHR a where R a is a C 3 -C 6 cycloalkyl radical as generally defined above.
  • heteroaryl refers to a 5- or 6- membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur.
  • the heteroaryl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom.
  • heteroaryl include, furyl, pyrrolyl, imidazolyl, thienyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl or pyridyl.
  • heterocyclyl refers to a stable 4- to 6-membered non-aromatic monocyclic ring radical which comprises 1 , 2, or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur.
  • the heterocyclyl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom.
  • heterocyclyl examples include, but are not limited to, pyrrolinyl, pyrrolidyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidyl, piperazinyl, tetrahydropyranyl, dihydroisoxazolyl, dioxolanyl, morpholinyl or d-lactamyl.
  • asymmetric carbon atoms in a compound of formula (I) means that the compounds may occur in chiral isomeric forms, i.e. , enantiomeric or diastereomeric forms. Also atropisomers may occur as a result of restricted rotation about a single bond.
  • Formula (I) is intended to include all those possible isomeric forms and mixtures thereof.
  • the present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula (I).
  • formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) where present.
  • the present invention includes all possible tautomeric forms for a compound of formula (I).
  • where there are di-substituted alkenes these may be present in E or Z form or as mixtures of both in any proportion.
  • the present invention includes all these possible isomeric forms and mixtures thereof for a compound of formula (I).
  • the compounds of formula (I) will typically be provided in the form of an agronomically acceptable salt, a zwitterion or an agronomically acceptable salt of a zwitterion.
  • This invention covers all such agronomically acceptable salts, zwitterions and mixtures thereof in all proportions.
  • a compound of formula (I) wherein Z comprises an acidic proton may exist as a zwitterion, a compound of formula (l-l), or as an agronomically acceptable salt, a compound of formula (l-ll) as shown below:
  • Y represents an agronomically acceptable anion and j and k represent integers that may be selected from 1 , 2 or 3, dependent upon the charge of the respective anion Y.
  • a compound of formula (I) may also exist as an agronomically acceptable salt of a zwitterion, a compound of formula (l-lll) as shown below: wherein, Y represents an agronomically acceptable anion, M represents an agronomically acceptable cation (in addition to the pyridazinium cation) and the integers j, k and q may be selected from 1 , 2 or 3, dependent upon the charge of the respective anion Y and respective cation M.
  • a compound of formula (l-ll) wherein k is 2, j is 1 and Y is selected from the group consisting of halogen, trifluoroacetate and pentafluoropropionate.
  • a nitrogen atom in ring A may be protonated or a nitrogen atom comprised in R 1 , R 2 , R 8 , Q orX may be protonated.
  • k is 2, j is 1 and Y is chloride, wherein a nitrogen atom in ring A is protonated.
  • Suitable agronomically acceptable salts of the present invention include but are not limited chloride, bromide, iodide, fluoride, 2-naphthalenesulfonate, acetate, adipate, methoxide, ethoxide, propoxide, butoxide, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, butylsulfate, butylsulfonate, butyrate, camphorate, camsylate, caprate, caproate, caprylate, carbonate, citrate, diphosphate, edetate, edisylate, enanthate, ethanedisulfonate, ethanesulfonate, ethylsulfate, formate, fumarate, gluceptate, gluconate, glucoronate, glutamate, glycerophosphate, hepta
  • Suitable cations represented by M include, but are not limited to, metals, conjugate acids of amines and organic cations.
  • suitable metals include aluminium, calcium, cesium, copper, lithium, magnesium, manganese, potassium, sodium, iron and zinc.
  • Suitable amines include allylamine, ammonia, amylamine, arginine, benethamine, benzathine, butenyl-2-amine, butylamine, butylethanolamine, cyclohexylamine, decylamine, diamylamine, dibutylamine, diethanolamine, diethylamine, diethylenetriamine, diheptylamine, dihexylamine, diisoamylamine, diisopropylamine, dimethylamine, dioctylamine, dipropanolamine, dipropargylamine, dipropylamine, dodecylamine, ethanolamine, ethylamine, ethylbutylamine, ethylenediamine, ethylheptylamine, ethyloctylamine, ethylpropanolamine, heptadecylamine, heptylamine, hexadecylamine, he
  • Suitable organic cations include benzyltributylammonium, benzyltrimethylammonium, benzyltriphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, tetraethylammonium, tetraethylphosphonium, tetramethylammonium, tetramethylphosphonium, tetrapropylammonium, tetrapropylphosphonium, tributylsulfonium, tributylsulfoxonium, triethylsulfonium, triethylsulfoxonium, trimethylsulfonium, trimethylsulfoxonium, tripropylsulfonium and tripropylsulfoxonium.
  • Preferred compounds of formula (I), wherein Z comprises an acidic proton can be represented as either (l-l) or (l-ll).
  • Y is chloride, bromide, iodide, hydroxide, bicarbonate, acetate, pentafluoropropionate, triflate, trifluoroacetate, methylsulfate, tosylate and nitrate, wherein j and k are 1.
  • Y is chloride, bromide, iodide, hydroxide, bicarbonate, acetate, trifluoroacetate, methylsulfate, tosylate and nitrate, wherein j and k are 1.
  • R 1 , R 2 , R 1a , R 2b , R 3 , R 3a , R 4 , R 5 , A and Z are as defined for compounds of formula (I).
  • the following list provides definitions, including preferred definitions, for substituents n, m, r, A, Q, X, Z, R 1 , R 2 ,R 1a , R 2b , R 3 , R 3a , R 4 , R 5 , R 6 , R 7 ,R 7a , R 7b ,R 7c ,R 8 ,R 9 , R 10 , R 1 1 , R 12 , R 13 , R 1 4 , R 15 ,R 15a ,R 16 , R 17 and R 18 with reference to the compounds of formula (I) according to the invention.
  • R 1 is selected from the group consisting of hydrogen, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, -OR 7 , -OR 15a , -N(R 6 )S(O) 2 R 15 , -N(R 6 )C(O)R 15 , -N(R 6 )C(O)OR 15 , -N(R 6 )C(O)NR 16 R 17 , -N(R 6 )CHO, -N(R 7a ) 2 and -S(O) r R 15 .
  • R 1 is selected from the groupconsisting of hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 fluoroalkyl, -OR 7 , -NHS(O) 2 R 15 , -NHC(O)R 15 , -NHC(O)OR 15 , -NHC(O)NR 16 R 17 , -N(R 7a ) 2 and -S(O) r R 15 . More preferably, R 1 is selected from the group consisting of hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 fluoroalkyl, -OR 7 and -N(R 7a ) 2 .
  • R 1 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, -OR 7 and -N(R 7a ) 2 . Even more preferably still, R 1 is hydrogen or C 1 -C 6 alkyl. Yet even more preferably still, R 1 is hydrogen or methyl. Most preferably R 1 is hydrogen.
  • R 2 is selected from the group consisting of hydrogen, halogen, C 1 -C 6 alkyl and C 1 -C 6 haloalkyl. Preferably, R 2 is selected from the group consisting of hydrogen, halogen, C 1 -C 6 alkyl and C 1 -C 6 fluoroalkyl. More preferably, R 2 is hydrogen or C 1 -C 6 alkyl.
  • R 2 is hydrogen or methyl. Most preferably R 2 is hydrogen.
  • R 1 is selected from the group consisting of -OR 7 , -OR 15a , -N(R 6 )S(O) 2 R 15 , -N(R 6 )C(O)R 15 ,-N(R 6 )C(O)OR 15 , -N(R 6 )C(O)NR 16 R 17 , -N(R 6 )CHO, -N(R 7a ) 2 and -S(O) r R 15 , R 2 is selected from the group consisting of hydrogen and C 1 -C 6 alkyl.
  • R 1 is selected from the group consisting of -OR 7 , -NHS(O) 2 R 15 , -NHC(O)R 15 , -NHC(O)OR 15 , -NHC(O)NR 16 R 17 , -N(R 7a ) 2 and -S(O) r R 15
  • R 2 is selected from the group consisting of hydrogen and methyl.
  • R 1 and R 2 together with the carbon atom to which they are attached form a C 3 -C 6 cycloalkyl ring or a 3- to 6- membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected fromN and O.
  • R 1 and R 2 together with the carbon atom to which they are attached form a C 3 -C 6 cycloalkyl ring. More preferably, R 1 and R 2 together with the carbon atom to which they are attached form a cyclopropyl ring. In one embodiment R 1 and R 2 are hydrogen.
  • R 1 is methyl and R 2 is hydrogen.
  • R 1 is methyl and R 2 is methyl.
  • Q is (CR 1a R 2b ) m .
  • m is 0, 1 , 2 or 3.
  • m is 0,1 or 2. More preferably, m is 1 or 2. Most preferably, m is 1.
  • Each R 1a and R 2b are independently selected from the group consisting of hydrogen, halogen, C 1 - C 6 alkyl, C 1 -C 6 haloalkyl, -OH, -OR 7 , -OR 15a , -NH 2 , -NHR 7 , -NHR 15a , -N(R 6 )CHO, -NR 7b R 7c and -S(O) r R 15 .
  • each R 1a and R 2b are independently selected from the group consisting of hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 fluoroalkyl, -OH, -NH 2 and -NHR 7 .
  • each R 1a and R 2b are independently selected from the group consisting of hydrogen, C 1 -C 6 alkyl, -OH and -NH 2 . Even more preferably, each R 1a and R 2b are independently selected from the group consisting of hydrogen, methyl, -OH and -NH 2 . Even more preferably still, each R 1a and R 2b are independently selected from the group consisting of hydrogen and methyl. Most preferably R 1a and R 2b are hydrogen.
  • each R 1a and R 2b are independently selected from the group consisting of hydrogen and C 1 -C 6 alkyl.
  • each R 1a and R 2b together with the carbon atom to which they are attached form a C 3 - C 6 cycloalkyl ring or a 3- to 6- membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O.
  • each R 1a and R 2b together with the carbon atom to which they are attached form a C 3 -C 6 cycloalkyl ring.
  • each R 1a and R 2b together with the carbon atom to which they are attached form a cyclopropyl ring.
  • R 3 , R 3a , R 4 and R 5 are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, -S(O)rR 15 , C 1 -C 6 alkyl, C 1 -C 6 fluoroalkyl, C 1 -C 6 fluoroalkoxy, C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl and - N(R 6 ) 2 .
  • R 3 , R 3a , R 4 and R 5 are independently selected from the group consisting of hydrogen, C 1 -C 6 alkyl, C 1 -C 6 fluoroalkyl, C 1 -C 6 fluoroalkoxy, C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl and -N(R 6 ) 2 . More preferably, R 3 , R 3a , R 4 and R 5 are independently selected from the group consisting of hydrogen, C 1 - C 6 alkyl and C 1 -C 6 alkoxy. Even more preferably, R 3 , R 3a , R 4 and R 5 are independently selected from the group consisting of hydrogen and C 1 -C 6 alkyl. Even more preferably still, R 3 , R 3a , R 4 and R 5 are independently selected from the group consisting of hydrogen and methyl. Most preferably, R 3 , R 3a , R 4 and R 5 are hydrogen.
  • Each R 6 is independently selected from hydrogen and C 1 -C 6 alkyl. Preferably, each R 6 is independently selected from hydrogen and methyl.
  • Each R 7 is independently selected from the group consisting of C 1 -C 6 alkyl, -S(O) 2 R 15 , -C(O)R 15 , - C(O)OR 15 and -C(O)NR 16 R 17 .
  • each R 7 is independently selected from the group consisting of C 1 -C 6 alkyl, -C(O)R 15 and -C(O)NR 16 R 17 . More preferably, each R 7 is C 1 -C 6 alkyl. Most preferably, each R 7 is methyl.
  • Each R 7a is independently selected from the group consisting of -S(O) 2 R 15 , -C(O)R 15 , -C(O)OR 15 - C(O)NR 16 R 17 and -C(O)NR 6 R 15a .
  • each R 7a is independently -C(O)R 15 or -C(O)NR 16 R 17 .
  • R 7b and R 7c are independently selected from the group consisting of C 1 -C 6 alkyl, -S(O) 2 R 15 , -C(O)R 15 , - C(O)OR 15 , -C(O)NR 16 R 17 and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different.
  • R 7b and R 7c are independently selected from the group consisting of C 1 -C 6 alkyl, -C(O)R 15 and -C(O)NR 16 R 17 . More preferably, R 7b and R 7c are C 1 -C 6 alkyl. Most preferably, R 7b and R 7c are methyl.
  • R 7b and R 7c together with the nitrogen atom to which they are attached form a 4- to 6- membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N, O and S.
  • R 7b and R 7c together with the nitrogen atom to which they are attached form a 5- to 6-membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N and O.
  • R 7b and R 7c together with the nitrogen atom to which they are attached form an pyrrolidyl, oxazolidinyl, imidazolidinyl, piperidyl, piperazinyl or morpholinyl group.
  • A is a fused bicyclic structure of general formula; in which:
  • ring A 1 has 5 members and ring A 2 has 6 members;
  • A includes at least one heteroatom selected from N, O and S, with the remainder being carbon atoms;
  • At least one of ring A 1 and ring A 2 is aromatic, or A as a whole is aromatic;
  • A is attached to the remainder of the compound of formula (I) at any available position of ring A 2 provided it is a carbon atom;
  • one of the carbon atoms is optionally a carbonyl;
  • A is optionally substituted in any available position in either or both of ring A 1 or ring A 2 by p substituents R 8 , which may be the same or different; and
  • A comprises at least one nitrogen atom in either ring A 1 or A 2 .
  • a as a whole is aromatic.
  • a as a whole is aromatic, and ring A 1 includes at least one heteroatom selected from N, O and S, with the remainder being carbon atoms, and ring A 2 includes at least one heteroatom selected from N with the remainder being carbon atoms.
  • A contains 1 , 2, 3, 4, 5 or 6 heteroatoms, more preferably A contains 2, 3, 4, 5 or 6 heteroatoms.
  • A includes at least one N heteroatom with the remainder being carbon atoms.
  • A contains 1 , 2, 3, 4, 5 or 6 N heteroatoms with the remainder being carbon atoms.
  • A is selected from the group consisting of formula A-l to A-CXIV below (the skilled person would appreciate that if p is 3 1 then R 8 may be substituted on any available position of rings A- I to A-CXIV) ,
  • A is selected from the group consisting of formula A-l to A-LXXI.
  • A is selected from the group consisting of formula A-XLIII to A-LXXI.
  • A is selected from the group consisting of formula A-a, A-b, A-c, A-d, A-e, A-f, A- g, A-h, A-j, A-k, A-m, A-n, A-o, A-p, A-q and A-r below (preferably, A-a, A-b, A-c, A-d, A-e, A-g, A-h, A- j, A-n, A-o, A-p, A-q and A-r, more preferably, A-a, A-c, A-o and A-p) ,
  • X 1 is CH or N
  • W 1 is O, S or N(Me); each A 3 is independently selected from the group consisting of CH, N, O, S and N(Me);
  • R 8a is selected from the group consisting of hydrogen, -NH 2 , -NMe 2 , -OH and methyl; and wherein the jagged line defines the point of attachment to the remaining part of a compound of formula (I).
  • A is selected from the group consisting of formula A-VIII, A-IX, A-X, A-XLIX, A-LIII, A-LVII, A-LVIII, A-LXXII, A-LXXIII, A-LXXV, A-LXXVI, A-LXXX, A-LXXXI, A-LXXII, A-LXXIII, A-XCII and A-XCVI below,
  • A is selected from the group consisting of formula A-IX, A-LVII, A-LVIII, A-LXXV, A-LXXVI,
  • each R 8 is independently selected from the group consisting of halogen, nitro, cyano, -NH 2 , -NHR 7 , -N(R 7 ) 2 , -OH, -OR 7 , -S(O) r R 15 , - NR 6 S(O) 2 R 15 , -C(O)OR 10 , -C(O)R 15 , -C(O)NR 16 R 17 , -S(O) 2 NR 16 R 17 , C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 - C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 3 -C 6 cycloalkoxy, C 2 -C 6 alkenyl, C 2 -C
  • each R 8 is independently selected from the group consisting of halogen, nitro, cyano, -NH 2 , -NHR 7 , -N(R 7 ) 2 , -OH, -OR 7 , -S(O) r R 15 , - NR 6 S(O) 2 R 15 , -C(O)OR 10 , -C(O)R 15 , -C(O)NR 16 R 17 , C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 1 - C 3 alkoxyC 1 -C 3 alkyl-, hydroxyC 1 -C 6 alkyl- and C 1 -C 6 haloalkoxy.
  • each R 8 is independently selected from the group consisting of chloro, fluoro, cyano, -NH 2 , -N(Me) 2 , -OH, -OMe, -S(O) 2 Me, - C(O)OMe, -C(O)OH, -C(O)Me, -C(O)NH 2 , -C(O)NHMe, -C(O)N(Me) 2 , methyl, ethyl and trifluoromethyl.
  • each R 8 is independently selected from the group consisting of -NH 2 , -N(Me) 2 , -OH, and methyl. Even more preferably still, when A is substituted on one or more ring carbon atoms, each R 8 is independently selected from the group consisting of -N(Me) 2 , -OH, and methyl. Most preferably, when A is substituted on one or more ring carbon atoms, each R 8 is methyl.
  • each R 8 is independently selected from the group consisting of -OR 7 , -S(O) r R 12 , C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 - C 6 halocycloalkyl, C 3 -C 6 cycloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 1 -C 3 alkoxyC 1 - C 3 alkyl-, hydroxyC 2 -C 6 alkyl-, C 1 -C 6 haloalkoxy, C 1 -C 3 haloalkoxyC 1 -C 3 alkyl-, C 1 -C 6 alkoxycarbonyl, C 3 - C 6 alkenyloxy, C 3 -C 6 alkyl
  • each R 8 is independently selected from the group consisting of -OR 7 , C 1 -C 6 alkyl and C 1 -C 6 haloalkyl. More preferably, R 8 is C 1 -C 6 alkyl. Even more preferably still, each R 8 is methyl or ethyl. Most preferably R 8 is methyl.
  • each R 9 is independently selected from the group consisting of halogen, cyano, -N(R 6 ) 2 , C 1 - C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl and C 1 -C 4 haloalkoxy. More preferably, each R 9 is independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkyl. Even more preferably, each R 9 is independently selected from the group consisting of halogen and C 1 -C 4 alkyl.
  • X is selected from the group consisting of C 3 -C 6 cycloalkyl, phenyl, a 5- or 6- membered heteroaryl, which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and a 4- to 6- membered heterocyclyl, which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, and wherein said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties are optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R 9 , and wherein the aforementioned CR 1 R 2 , Q and Z moieties may be attached at any position of said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties.
  • X is selected from the group consisting of phenyl and a 4- to 6- membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O, and wherein said phenyl or heterocyclyl moieties are optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R 9 , and wherein the aforementioned CR 1 R 2 , Q and Z moieties may be attached at any position of said phenyl or heterocyclyl moieties.
  • X is a 4- to 6- membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O, and wherein said heterocyclyl moieties is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R 9 , and wherein the aforementioned CR 1 R 2 , Q and Z moieties may be attached at any position of said heterocyclyl moiety.
  • X is a 5-membered heterocyclyl, which comprises 1 heteroatom, wherein said heteroatom is N, and wherein the aforementioned CR 1 R 2 , Q and Z moieties may be attached at any position of said heterocyclyl moiety.
  • X is a 5-membered heterocyclyl, which comprises 1 heteroatom, wherein said heteroatom is N, and wherein the aforementioned CR 1 R 2 and Q moieties are attached adjacent to the N atom and the Z moiety is attached to the N atom.
  • X is phenyl optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R 9 , and wherein the aforementioned CR 1 R 2 , Q and Z moieties may be attached at any position of said phenyl moiety.
  • X is phenyl and the aforementioned CR 1 R 2 and Q moieties are attached in a postion para to the Z moiety.
  • n is 0 or 1 .
  • n is 0.
  • Z is selected from the group consisting of -C(O)OR 10 , -CH 2 OH, -CHO, -C(O)NHOR 11 , -C(O)NHCN, - OC(O)NHOR 11 , -OC(O)NHCN, -NR 6 C(O)NHOR 11 , -NR 6 C(O)NHCN, -C(O)NHS(O) 2 R 12 , - OC(O)NHS(O) 2 R 12 , -NR 6 C(O)NHS(O) 2 R 12 , -S(O) 2 OR 10 , -OS(O) 2 OR 10 , -NR 6 S(O) 2 OR 10 , -NR 6 S(O)OR 10 , -NHS(O) 2 R 14 , -S(O)OR 10 , -OS(O)OR 10 , -S(O) 2 NHCN, -S(O) 2 NHC(O)R 18 , -
  • Z is selected from the group consisting of -C(O)OR 10 , -C(O)NHOR 11 , -C(O)NHCN, - OC(O)NHOR 11 , -NR 6 C(O)NHOR 11 , -C(O)NHS(O) 2 R 12 , -OC(O)NHS(O) 2 R 12 , -NR 6 C(O)NHS(O) 2 R 12 , - S(O) 2 OR 10 , -OS(O) 2 OR 10 , -NR 6 S(O) 2 OR 10 , -NR 6 S(O)OR 10 , -NHS(O) 2 R 14 , -S(O)OR 10 , -OS(O)OR 10 , - S(O) 2 NHC(O)R 18 , -S(O) 2 NHS(O) 2 R 12 , -OS(O) 2 NHS(O) 2 R 12 , -OS(O) 2 NHC(O)R
  • Z is selected from the group consisting of -C(O)OR 10 , -C(O)NHOR 11 , -C(O)NHCN, - C(O)NHS(O) 2 R 12 , -S(O) 2 OR 10 , -OS(O) 2 OR 10 , -NR 6 S(O) 2 OR 10 , -NHS(O) 2 R 14 , -S(O)OR 10 , -
  • Z is selected from the group consisting of -C(O)OR 10 , -C(O)NHCN, - C(O)NHS(O) 2 R 12 , -S(O) 2 OR 10 , and -P(O)(R 13 )(OR 10 ).
  • Z is selected from the group consisting of -C(O)OH, -C(O)OCH3, - C(O)OCH 2 CH 3 , -C(O)OCH(CH 3 ) 2 , -C(O)OC(CH 3 ) 3 , -C(O)OCH 2 C 6 H 5 , -C(O)OC 6 H 5 , -C(O)NHS(O) 2 CH 3 , - S(O) 2 OH, -P(O)(OH)( OCH 2 CH 3 ) and -P(O)(OCH 2 CH 3 )(OCH 2 CH 3 ).
  • Z is selected from the group consisting of -C(O)OH, -C(O)OCH 3 , - C(O)OC(CH 3 ) 3 and -S(O) 2 OH.
  • Z is -C(O)OH or -S(O) 2 OH.
  • R 10 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, phenyl and benzyl, and wherein said phenyl or benzyl are optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different.
  • R 10 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, phenyl and benzyl. More preferably, R 10 is selected from the group consisting of hydrogen and C 1 -C 6 alkyl. Most preferably, R 10 is hydrogen.
  • R 11 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different.
  • R 11 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl and phenyl. More preferably, R 11 is selected from the group consisting of hydrogen and C 1 -C 6 alkyl. Even more preferably, R 11 is C 1 -C 6 alkyl. Most preferably, R 11 is methyl.
  • R 12 is selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, -OH, -N(R 6 ) 2 and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different.
  • R 12 is selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 - C 6 alkoxy, -OH, -N(R 6 ) 2 and phenyl.
  • R 12 is selected from the group consisting of C 1 - C 6 alkyl, C 1 -C 6 haloalkyl and -N(R 6 ) 2 . Even more preferably, R 12 is selected from the group consisting of methyl, -N(Me) 2 and trifluoromethyl. Most preferably, R 12 is methyl.
  • R 13 is selected from the group consisting of -OH, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and phenyl.
  • R 13 is selected from the group consisting of -OH, C 1 -C 6 alkyl and C 1 -C 6 alkoxy. More preferably, R 13 is selected from the group consisting of -OH and C 1 -C 6 alkoxy. Even more preferably, R 13 is selected from the group consisting of -OH, methoxy and ethoxy. Most preferably, R 13 is -OH.
  • R 14 is C 1 -C 6 haloalkyl. Preferably, R 14 is trifluoromethyl.
  • R 15 is selected from the group consisting of C 1 -C 6 alkyl and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different.
  • R 15 is selected from the group consisting of C 1 -C 6 alkyl and phenyl. More preferably, R 15 is C 1 -C 6 alkyl. Most preferably R 15 is methyl.
  • R 15a is phenyl, wherein said phenyl is optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different.
  • R 15a is phenyl optionally substituted by 1 R 9 substituent. More preferably, R 15a is phenyl.
  • R 16 and R 17 are independently selected from the group consisting of hydrogen and C 1 -C 6 alkyl. Preferably, R 16 and R 17 are independently selected from the group consisting of hydrogen and methyl.
  • R 16 and R 17 together with the nitrogen atom to which they are attached form a 4- to 6- membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N, O and S.
  • R 16 and R 17 together with the nitrogen atom to which they are attached form a 5- to 6-membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N and O.
  • R 16 and R 17 together with the nitrogen atom to which they are attached form an pyrrolidyl, oxazolidinyl, imidazolidinyl, piperidyl, piperazinyl or morpholinyl group.
  • R 18 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, -N(R 6 ) 2 and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R 9 substituents, which may be the same or different.
  • R 18 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, -N(R 6 ) 2 and phenyl.
  • R 18 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl and C 1 -C 6 haloalkyl. Further more preferably, R 18 is selected from the group consisting of C 1 -C 6 alkyl and C 1 -C 6 haloalkyl. Most preferably, R 18 is methyl or trifluoromethyl. r is 0, 1 or 2. Preferably, r is 0 or 2.
  • R 1 is hydrogen or C 1 -C 6 alkyl
  • R 2 is hydrogen or C 1 -C 6 alkyl
  • Q is (CR 1a R 2b ) m ; m is 0, 1 or 2;
  • R 1a and R 2b are independently selected from the group consisting of hydrogen, C 1 -C 6 alkyl, -OH and - NH 2 ;
  • R 3 , R 3a , R 4 and R 5 are independently selected from the group consisting of hydrogen and methyl; each R 6 is independently selected from hydrogen and methyl; each R 7 is C 1 -C 6 alkyl;
  • A is a fused bicyclic structure of general formula; in which:
  • ring A 1 has 5 members and ring A 2 has 6 members;
  • A contains 2,3,4 or 5 heteroatoms selected from N, O and S, with the remainder being carbon atoms;
  • A is attached to the remainder of the compound of formula (I) at any available position of ring A 2 provided it is a carbon atom;
  • one of the carbon atoms is optionally a carbonyl
  • A is optionally substituted in any available position in either or both of ring A 1 or ring A 2 by p substituents R 8 , which may be the same or different;
  • each R 8 is independently selected from the group consisting of halogen, nitro, cyano, -NH 2 , -NHR 7 , -N(R 7 ) 2 , -OR 7 , -S(O) r R 15 , -NR 6 S(O) 2 R 15 , - C(O)OR 10 , -C(O)R 15 , -C(O)NR 16 R 17 , C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 3 alkoxyC 1 -C 3 alkyl- , hydroxyC 1 -C 6 alkyl- and C 1 -C 6 haloalkoxy; when A is substituted on one or more N atoms by one or more R 8 , then each R 8 is C 1 -C 6 alkyl
  • Z is selected from the group consisting of -C(O)OR 10 , -C(O)NHCN, -C(O)NHS(O) 2 R 12 , -S(O) 2 OR 10 , and -P(O)(R 13 )(OR 10 );
  • R 10 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, phenyl and benzyl;
  • R 12 is selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 haloalkyl and -N(R 6 ) 2 ;
  • R 13 is selected from the group consisting of -OH and C 1 -C 6 alkoxy
  • R 15 is C 1 -C 6 alkyl
  • R 16 and R 17 are independently selected from the group consisting of hydrogen and methyl; and r is 0 or 2.
  • R 1 is hydrogen or methyl
  • R 2 is hydrogen or methyl
  • Q is (CR 1a R 2b ) m ; m is 0, 1 or 2;
  • R 1a and R 2b are independently selected from the group consisting of hydrogen and methyl;
  • R 3 , R 3a , R 4 and R 5 are hydrogen
  • A is selected from the group consisting of formula A-l to A-LXXI and p is 0, 1 , or 2, more preferably 0 or 1 , most preferably 0; when A is substituted on one or more ring carbon atoms, each R 8 is independently selected from the group consisting of chloro, fluoro, cyano, -NH 2 , -N(Me) 2 , -OMe, -S(O) 2 Me, -C(O)OMe, -C(O)OH, - C(O)Me, -C(O)NH 2 , -C(O)NHMe, -C(O)N(Me) 2 , methyl, ethyl and trifluoromethyl, even more preferably methyl; when A is substituted on one or more N atoms by one or more R 8 , then each R 8 is C 1 -C 6 alkyl, or most preferably methyl; n is 0; and
  • Z is selected from the group consisting of -C(O)OH, -C(O)OCH 3 , -C(O)OCH 2 CH 3 , -C(O)OCH(CH 3 ) 2 , - C(O)OC(CH 3 ) 3 , -C(O)OCH 2 C 6 H 5 , -C(O)OC 6 H 5 , -C(O)NHS(O) 2 CH 3 , -S(O) 2 OH, -P(O)(OH)( OCH 2 CH 3 ) and -P(O)(OCH 2 CH 3 )(OCH 2 CH 3 ).
  • the compound according to formula (I) is selected from a compound of formula (l-aa) to (l-dj) below
  • each R 8 is independently selected from the group consisting of chloro, fluoro, cyano, -NH 2 , -N(Me) 2 , - OH, -OMe, -S(O) 2 Me, -C(O)OMe, -C(O)OH, -C(O)Me, -C(O)NH 2 , -C(O)NHMe, -C(O)N(Me) 2 , methyl and trifluoromethyl; and
  • Z is selected from the group consisting of -C(O)OH, -C(O)OCH 3 , -C(O)OCH 2 CH 3 , -C(O)OCH(CH 3 ) 2 , - C(O)OC(CH 3 ) 3 , -C(O)OCH 2 C 6 H 5 , -C(O)OC 6 H 5 , -C(O)NHS(O) 2 CH 3 , -S(O) 2 OH, -P(O)(OH)( OCH 2 CH 3 ) and -P(O)(OCH 2 CH 3 )( OCH 2 CH 3 ), preferably Z is -C(O)OH or -S(O) 2 OH.
  • R 1 is hydrogen or methyl;
  • R 2 is hydrogen or methyl
  • Q is (CR 1a R 2b ) m ; m is 0, 1 or 2; R 1a and R 2b are independently selected from the group consisting of hydrogen and methyl;
  • R 3 , R 3a , R 4 and R 5 are hydrogen
  • A is selected from the group consisting of formula A-l to A-CXIV and p is 0, 1 , or 2, more preferably 0 or 1 , most preferably 0; when A is substituted on one or more ring carbon atoms, each R 8 is independently selected from the group consisting of -NH 2 , -N(Me) 2 , -OH, and methyl, even more preferably methyl; when A is substituted on one or more N atoms by one or more R 8 , then each R 8 is C 1 -C 6 alkyl, or most preferably methyl; n is 0; and
  • Z is selected from the group consisting of -C(O)OH, -C(O)OCH 3 , -C(O)OC(CH 3 ) 3 and -S(O) 2 OH.
  • R 1 is hydrogen
  • R 2 is hydrogen
  • Q is (CR 1a R 2b ) m ; m is 0, 1 or 2;
  • R 1a and R 2b are hydrogen
  • R 3 , R 3a , R 4 and R 5 are hydrogen
  • A is selected from the group consisting of formula A-VIII, A-IX, A-X, A-XLIX, A-LIII, A-LVII, A-LVIII, A- LXXII, A-LXXIII, A-LXXV, A-LXXVI, A-LXXX, A-LXXXI, A-LXXII, A-LXXIII, A-XCII and A-XCVI and p is 0 or 1 (preferably p is 0); when p is 1 A is substituted on a ring carbon atom, and each R 8 is independently selected from the group consisting of -NH 2 , -N(Me) 2 , -OH, and methyl, even more preferably methyl; n is 0; and
  • Z is selected from the group consisting of -C(O)OH, -C(O)OCH 3 , -C(O)OC(CH 3 ) 3 and -S(O) 2 OH (preferably, Z is -C(O)OH or -S(O) 2 OH).
  • R 1 is hydrogen
  • R 2 is hydrogen
  • Q is (CR 1a R 2b ) m ; m is 0, 1 or 2;
  • R 1a and R 2b are hydrogen
  • R 3 , R 3a , R 4 and R 5 are hydrogen
  • A is selected from the group consisting of formula A-IX, A-LVII, A-LVIII, A-LXXV, A-LXXVI, A-LXXXI and A-XCVI, and p is 0 or 1 (preferably p is 0); when p is 1 A is substituted on a ring carbon atom, and each R 8 is independently selected from the group consisting of -NH 2 , -N(Me) 2 , -OH, and methyl, even more preferably methyl; n is 0; and Z is selected from the group consisting of -C(O)OH, -C(O)OCH 3 , -C(O)OC(CH 3 ) 3 and -S(O) 2 OH (preferably, Z is -C(O)OH or -S(O) 2 OH).
  • R 1 is hydrogen
  • R 2 is hydrogen
  • Q is (CR 1a R 2b ) m ; m is 0, 1 or 2;
  • R 1a and R 2b are hydrogen
  • R 3 , R 3a , R 4 and R 5 are hydrogen
  • A is selected from the group consisting of formula A-a, A-b, A-c, A-d, A-e, A-f, A-g, A-h, A-j, A-k, A-m, A-n, A-o, A-p, A-q and A-r below (preferably, A-a, A-b, A-c, A-d, A-e, A-g, A-h, A-j, A-n, A-o, A-p, A-q and A-r, more preferably, A-a, A-c, A-o and A-p) , wherein X 1 is CH or N;
  • W 1 is O, S or N(Me); each A 3 is independently selected from the group consisting of CH, N, O, S and N(Me);
  • R 8a is selected from the group consisting of hydrogen, -NH 2 , -N(Me) 2 , -OH and methyl; and wherein the jagged line defines the point of attachment to the remaining part of a compound of formula (I); n is 0; and
  • Z is selected from the group consisting of -C(O)OH, -C(O)OCH 3 , -C(O)OC(CH 3 ) 3 and -S(O) 2 OH (preferably, Z is -C(O)OH or -S(O) 2 OH).
  • the compound according to formula (I) is selected from a compound selected from the group consisting of A1 to A73 listed in Table A. It should be understood that compounds of formula (I) may exist/be manufactured in "procidal form", wherein they comprise a group "G". Such compounds are referred to herein as compounds of formula (l-IV).
  • G is a group which may be removed in a plant by any appropriate mechanism including, but not limited to, metabolism and chemical degradation to give a compound of formula (l-l), (l-ll) or (l-lll) wherein Z contains an acidic proton, for example see the scheme below: Whilst such G groups may be considered as ‘procidal’, and thus yield active herbicidal compounds once removed, compounds comprising such groups may also exhibit herbicidal activity in their own right. In such cases in a compound of formula (l-IV), Z-G may include but is not limited to, any one of (G1) to (G7) below and E indicates the point of attachment to the remaining part of a compound of formula (I):
  • G, R 19 , R 20 , R 21 , R 22 and R 23 are defined as follows:
  • G is C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -C(R 21 R 22 )OC(O)R 19 , phenyl or phenyl-C 1 -C 4 alkyl-, wherein said phenyl moiety is optionally substituted by 1 to 5 substituents independently selected from halo, cyano, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl or C 1 -C 6 alkoxy.
  • R 19 is C 1 -C 6 alkyl or phenyl
  • R 20 is hydroxy, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or phenyl,
  • R 21 is hydrogen or methyl
  • R 22 is hydrogen or methyl
  • R 23 is hydrogen or C 1 -C 6 alkyl.
  • This table discloses 181 specific compounds of the formula (T-1): (T-1) wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • This table discloses 181 specific compounds of the formula (T-3): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • This table discloses 181 specific compounds of the formula (T-4): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • This table discloses 181 specific compounds of the formula (T-7): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • Table 8 This table discloses 181 specific compounds of the formula (T-8): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • Table 9 discloses 181 specific compounds of the formula (T-7): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • This table discloses 181 specific compounds of the formula (T-11): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • This table discloses 181 specific compounds of the formula (T-14): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • Table 15 This table discloses 181 specific compounds of the formula (T-15): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • Table 16 This table discloses 181 specific compounds of the formula (T-15): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • This table discloses 181 specific compounds of the formula (T-17): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • This table discloses 181 specific compounds of the formula (T-21): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • Table 22 This table discloses 181 specific compounds of the formula (T-22): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • This table discloses 181 specific compounds of the formula (T-24): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • This table discloses 181 specific compounds of the formula (T-25): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • This table discloses 181 specific compounds of the formula (T-27): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • This table discloses 181 specific compounds of the formula (T-28): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • Table 29 This table discloses 181 specific compounds of the formula (T-29): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • Table 30
  • This table discloses 181 specific compounds of the formula (T-31): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • This table discloses 181 specific compounds of the formula (T-34): wherein A is as defined in Table 1 and R 3 , R 3a , R 4 and R 5 are hydrogen.
  • the compounds of the present invention may be prepared according to the following schemes in which the substituents n, m, r, A, Q, X, Z, R 1 , R 2 , R 1a , R 2b , R 2 , R 3 , R 3a , R 4 , R 5 , R 6 , R 7 , R 7a , R 7b R 7c , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 15a , R 16 , R 17 and R 18 are as defined hereinbefore unless explicitly stated otherwise.
  • the compounds of the preceeding Tables 1 to 34 may thus be obtained in an analogous manner.
  • the compounds of formula (I) may be prepared by the alkylation of compounds of formula (X), wherein R 3 , R 3a , R 4 , R 5 and A are as defined for compounds of formula (I), with a suitable alkylating agent of formula (W), wherein R 1 , R 2 , Q, X, n and Z are as defined for compounds of formula (I) and LG is a suitable leaving group, for example, halide or pseudohalide such as triflate, mesylate or tosylate, in a suitable solvent at a suitable temperature, as described in reaction scheme 1.
  • Example conditions include stirring a compound of formula (X) with an alkylating agent of formula (W) in a solvent, or mixture of solvents, such as acetone, dichloromethane, dichloroethane, N,N-dimethylformamide, acetonitrile, 1 ,4-dioxane, water, acetic acid or triflu roacetic acid at a temperature between -78°C and 150°C.
  • solvent such as acetone, dichloromethane, dichloroethane, N,N-dimethylformamide, acetonitrile, 1 ,4-dioxane, water, acetic acid or triflu roacetic acid at a temperature between -78°C and 150°C.
  • An alkylating agent of formula (W) may include, but is not limited to, bromoacetic acid, methyl bromoacetate, 3-bromopropionoic acid, methyl 3-bromopropionate, 2-bromo-N-methoxyacetamide, sodium 2- bromoethanesulphonate, 2,2-dimethylpropyl 2-(trifluoromethylsulfonyloxy)ethanesulfonate, 2-bromo-N- methanesulfonylacetamide, 3-bromo-N-methanesulfonylpropanamide, dimethoxyphosphorylmethyl trifluoromethanesulfonate, dimethyl 3-bromopropylphosphonate, 3-chloro-2, 2-dimethyl-propanoic acid and diethyl 2-bromoethylphosphonate.
  • esters of N- alkyl acids which include, but are not limited to, esters of carboxylic acids, phosphonic acids, phosphinic acids, sulfonic acids and sulfinic acids, may be subsequently partially or fully hydrolysed by treament with a suitable reagent, for example, aqueous hydrochloric acid or trimethylsilyl bromide, in a suitable solvent at a suitable temperature between 0°C and 100°C.
  • a suitable reagent for example, aqueous hydrochloric acid or trimethylsilyl bromide
  • compounds of formula (I) may be prepared by reacting compounds of formula (X), wherein R 3 , R 3a , R 4 , R 5 and A are as defined for compounds of formula (I), with a suitably activated electrophilic alkene of formula (B), wherein Z is -S(O) 2 OR 10 , -P(O)(R 13 )(OR 10 ) or -C(O)OR 10 and R 1 , R 2 , R 1a , R 10 and R 13 are as defined for compounds of formula (I), in a suitable solvent at a suitable temperature.
  • Compounds of formula (B) are known in the literature, or may be prepared by known methods.
  • Example reagents include, but are not limited to, acrylic acid, methacrylic acid, crotonic acid, 3,3-dimethylacrylic acid, methyl acrylate, ethene sulfonic acid, isopropyl ethylenesulfonate, 2,2-dimethylpropyl ethenesulfonate and dimethyl vinylphosphonate.
  • esters of N-alkyl acids which include, but are not limited to, esters of carboxylic acids, phosphonic acids, phosphinic acids, sulfonic acids and sulfinic acids, may be subsequently partially or fully hydrolysed by treament with a suitable reagent in a suitable solvent at a suitable temperature, as described in reaction scheme 2.
  • An alkylating agent of formula (E) or (F) may include, but is not limited to, 1 ,3-propanesultone, 1 ,4-butanesultone, ethylenesulfate, 1 ,3-propylene sulfate and 1 ,2,3-oxathiazolidine 2,2-dioxide.
  • alkylating agents and related compounds are either known in the literature or may be prepared by known literature methods.
  • a compound of formula (I), wherein m is 0, n is 0 and Z is -S(O) 2 OH may be prepared from a compound of formula (I), wherein m is 0, n is 0 and Z is C(O)OR 10 , by treatment with trimethylsilylchlorosulfonate in a suitable solvent at a suitable temperature, as described in reaction scheme 4.
  • Preferred conditions include heating the carboxylate precursor in neat trimethylsilylchlorosulfonate at a temperature between 25°C and 150°C.
  • compounds of formula (I) may be prepared by reacting compounds of formula (X), wherein R 3 , R 3a , R 4 , R 5 and A are as defined for compounds of formula (I), with a suitable alcohol of formula (WW), wherein R 1 , R 2 , Q, X, n and Z are as defined for compounds of formula (I), under Mitsunobu-type conditions such as those reported by Petit et al, Tet. Lett. 2008, 49 (22), 3663.
  • Suitable phosphines include triphenylphosphine
  • suitable azodicarboxylates include diisopropylazodicarboxylate
  • suitable acids include fluoroboric acid, triflic acid and bis(trifluoromethylsulfonyl)amine, as described in reaction scheme 5.
  • Such alcohols are either known in the literature or may be prepared by known literature methods.
  • a compound of formula (I), wherein n, Q, Z, X, R 1 , R 2 , R 3 , R 3a , R 4 , R 5 and A are as defined for compounds of formula (I), may be prepared from a compound of formula (R) and an oxidant, in a suitable solvent at a suitable temperature, as outlined in reaction scheme 6.
  • oxidants include, but are not limited to, tetrachloro-p-benzoquinone, 2,3-dichloro-5,6- dicyanobenzoquinone, bromine, N-bromosuccinimide, manganese dioxide, selenium dioxide, potassium permanganate or biocatalysts.
  • Related reactions are known in the literature.
  • a compound of formula (R), wherein n, Q, Z, X, R 1 , R 2 , R 3 , R 3a , R 4 , R 5 and A are as defined for compounds of formula (I), may be prepared from a compound of formula (S) and an organometallic of formula (T), wherein M' includes, but is not limited to, organomagnesium, organolithium, organocopper and organozinc reagents, in a suitable solvent at a suitable temperature, optionally in the presence of an additonal transition metal additive, as outlined in reaction scheme 7.
  • Example conditions include treating a compound of formula (S) with a Grignard of formula (T), in the presence of 0.05-100 mol% copper iodide, in a solvent such as tetrahydrofuran at a temperature between -78°C and 100°C.
  • Organometallics of formula (T) are known in the literature, or may be prepared by known literature methods.
  • Compounds of formula (S) may be prepared by analogous reactions to those for the preparation of compounds of formula (I) from a compound of formula (X). Reaction scheme 7
  • Compounds of formula (I) may also be prepared by oxidation of a compound of formula (BB), wherein A, R 3 , R 3a , R 4 and R 5 are as defined for compounds of formula (I), as outlined in reaction scheme 8.
  • Example conditions include stirring a compound of formula (BB) in a suitable solvent at a suitable temperature in the presence of a suitable oxidant.
  • oxidants include, but are not limited to, tetrachloro-p-benzoquinone, 2,3-dichloro-5,6-dicyanobenzoquinone, bromine, N- bromosuccinimide, manganese dioxide, selenium dioxide, potassium permanganate or biocatalysts.
  • Compounds of formula (BB) may be prepared from a compound of formula (CC), wherein A, R 3 , R 3a , R 4 and R 5 are as defined for compounds of formula (I), by analogous N-alkylation methods previously described in schemes 1 , 2 and 3, using reagents (W), (B), (E), (F), (AF) and (WW).
  • Reaction scheme 9 Compounds of formula (X) are known in the literature or may be prepared using literature methods. Example methods include, but are not limited to, the transition metal cross-coupling of compounds of formula (H) and formula (J), or alternatively compounds of formula (K) and formula (L), as outlined in scheme 10.
  • M' is either an organostannane, organoboronic acid or ester, organotrifluoroborate, organomagnesium, organocopper or organozinc, and for compounds of formula (H) and (K) Hal is defined as a halogen or pseudo halogen, for example triflate, mesylate and tosylate.
  • Such cross-couplings include Stille (for example Sauer, J.; Heldmann, D. K.
  • Suzuki-Miyaura for example Luebbers, T.; Flohr, A.; Jolidon, S.; David- Pierson, P.; Jacobsen, H.; Ozmen, L.; Baumann, K. Bioorg. Med. Chem. Lett., 2011 , 6554
  • Negishi for example Imahori, T.; Suzawa, K.; Kondo, Y. Heterocycles, 2008, 1057
  • Kumada for example Heravi, M. M.; Hajiabbasi, P. Monatsh. Chem., 2012, 1575.
  • the coupling partners may be selected with reference to the specific cross-coupling reaction and target product.
  • Transition metal catalysts may be selected with reference to the desired cross-coupling and are known in the literature.
  • Compounds of formula (H), formula (K) and formula (L) are known in the literature, or may be prepared by known literature methods.
  • a compound of formula (J), wherein M' is either an organostannane, organoboronic acid or ester, organotrifluoroborate, organomagnesium, organocopper or organozinc, may be prepared from a compound of formula (K), wherein R 3 , R 3a , R 4 and R 5 are as defined for compounds of formula (I), and Hal is defined as a halogen or pseudo halogen, for example triflate, mesylate and tosylate, as described in scheme 11 .
  • Example conditions are well known in the literature, for example halogen-metal exchange (wherein Hal is iodine, bromide and chlorine), or transition metal mediated cross-coupling of either a diboron or distannane reagent (wherein Hal is iodine, bromide, chlorine, triflate, mesylate and tosylate).
  • Example halogen-metal exchange conditions to prepare a compound of formula (J), wherein M' is an organostannane include treatment of a compound of formula (K) with butyl lithium then tri-n-butyltin chloride in an appropriate solvent at an appropriate temperature (for example see Koch, V.; Nieger, M.; Braese, S., Adv. Synth.
  • Example halogen-metal exchange conditions to prepare a compound of formula (J), wherein M’ is an organoboronic acid include treatment of a compound of formula (K) with butyl lithium then triisopropyl borate in an appropriate solvent at an appropriate temperature (for example see Fudickar, W.; Linker, T., J. Org. Chem., 2017, 9258).
  • Example halogen- metal exchange conditions to prepare a compound of formula (J), wherein M’ is an organomagnesium include treatment of a compound of formula (K) with isopropyl magnesium chloride in an appropriate solvent at an appropriate temperature (for example see Salituro et al.
  • Example halogen-metal exchange conditions to prepare a compound of formula (J), wherein M’ is an organozinc include treatment of a compound of formula (K) with isopropyl magnesium chloride then dichloro(N,N,N',N'-tetramethylethylenediamine)zinc in an appropriate solvent at an appropriate temperature (for example see Baba et al. JP 2013227251).
  • Example transition metal mediated conditions to prepare a compound of formula (J), wherein M’ is an organostannane include treatment of a compound of formula (K) with hexamethyldistannane and bis(triphenylphosphine)palladium(ll) dichloride in an appropriate solvent at an appropriate temperature (for example see Barbachyn, M. R. et al., J. Med. Chem., 2003, 284).
  • Example transition metal mediated conditions to prepare a compound of formula (J), wherein M’ is an organboronic acid include treatment of a compound of formula (K) with bis(pinacolato)diboron, bis(triphenylphosphine)palladium(ll) dichloride and potassium acetate in an appropriate solvent at an appropriate temperature (for example see Meng et al. CN 104276997).
  • Compounds of formula (K) are either known in the literature or can be prepared by known methods.
  • compounds of formula (X) may be prepared by classical ring synthesis approaches starting from a compound of formula (ZZ), wherein R 3 , R 3a , R 4 and R 5 are as defined for compounds of formula (I) and T is a functional group which can be converted through one or more chemical steps into a bicylic fused heteroaromatic A, wherein A is as defined for compounds of formula (I).
  • Example functional groups include, but are not limited to, -CO2H, -C(O)NH 2 , -C(O)Me, -C(O)H, -CN and -Hal, and such transformations are are known in the literature.
  • a compound of formula (X) may also be prepared from a compound of formula (DD) or a compound of formula (CC) using similar oxidation conditions as described previously, as outlined in reaction scheme 13.
  • Compounds of formula (CC) may be prepared by deprotection of a compound of formula (DD), wherein A, R 3 , R 3a , R 4 and R 5 are as defined for compounds of formula (I) and G 1 is a suitable protecting group, as outlined in reaction scheme 14. Examples of suitable protecting groups and conditions are well known in the literature.
  • Compounds of formula (DD) are known in the literature or may be prepared using literature methods, (for example see Dyckman et al. WO 2019126082).
  • Example methods include, but are not limited to, the transition metal cross-coupling of compounds of formula (H) and formula (EE), wherein M' is either an organostannane, organoboronic acid or ester, organotrifluoroborate, organomagnesium, organocopper or organozinc, as outlined in reaction scheme 14.
  • Such cross-couplings include Stille, see for example Lee, Ju-Hyeon et al, European Journal of Medicinal Chemistry, 74, 246-257; 2014, Suzuki-Miyaura, see for example Kim, Eunkyung et al, Bioorganic & Medicinal Chemistry Letters, 18(18), 4993-4996; 2008 and Negishi, see for example Baskaran, Subramanian et al, PCT Int. Appl. , 2010091409.
  • the coupling partners may be selected with reference to the specific cross-coupling reaction and target product. Transition metal catalysts, ligands, bases, solvents and temperatures may be selected with reference to the desired cross-coupling and are known in the literature.
  • Compounds of formula (H) and formula (EE) are known in the literature, or may be prepared by known literature methods.
  • the compounds according to the invention can be used as herbicidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances.
  • formulation adjuvants such as carriers, solvents and surface-active substances.
  • the formulations can be in various physical forms, e.g.
  • soluble liquids soluble liquids, water-soluble concentrates or water soluble granules are preferred.
  • Such formulations can either be used directly or diluted prior to use.
  • the dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
  • the active ingredients can also be contained in very fine microcapsules.
  • Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release).
  • Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art.
  • very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p- diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1 ,4- dioxane, dipropy
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
  • a large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface- active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosu coin ate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters
  • Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.
  • compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives.
  • the amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied.
  • the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • Preferred oil additives comprise alkyl esters of C 8 -C 22 fatty acids, especially the methyl derivatives of C 12 -C 18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively).
  • Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
  • the herbicidal compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, compounds of formula (I) and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • the inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.
  • the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Preferred formulations can have the following compositions (weight %):
  • Emulsifiable concentrates active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agent: 1 to 30 %, preferably 5 to 20 % liquid carrier: 1 to 80 %, preferably 1 to 35 %
  • Dusts active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
  • Granules active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • composition of the present may further comprise at least one additional pesticide.
  • additional pesticide is a herbicide and/or herbicide safener.
  • compounds of formula (I) can be used in combination with one or more other herbicides to provide various herbicidal mixtures.
  • specific examples of such mixtures include (wherein “I” represents a compound of formula (I)): I + acetochlor, I + acifluorfen (including acifluorfen-sodium), I + aclonifen, I + ametryn, I + amicarbazone, I + aminopyralid, I + aminotriazole, I + atrazine, I + beflubutamid-M, I + benquitrione, I + bensulfuron (including bensulfuron-methyl), I + bentazone, I + bicyclopyrone, I + bilanafos, I + bispyribac-sodium, I + bixlozone, I + bromacil, I + bromoxynil, I + butachlor, I + butafenacil, I + carfentrazone (including carfentrazone-ethyl),
  • the mixing partners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, Fourteenth Edition, British Crop Protection Council, 2006.
  • the compound of formula (I) can also be used in mixtures with other agrochemicals such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual.
  • the mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1 : 100 to 1000:1 .
  • mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of compound of formula (I) with the mixing partner).
  • Compounds of formula (I) of the present invention may also be combined with herbicide safeners.
  • Preferred combinations include:- I + benoxacor, I + cloquintocet (including cloquintocet-mexyl); I + cyprosulfamide; I + dichlormid; I + fenchlorazole (including fenchlorazole-ethyl); I + fenclorim; I + fluxofenim; l+ furilazole I + isoxadifen (including isoxadifen-ethyl); I + mefenpyr (including mefenpyr-diethyl); I + metcamifen; I + N-(2-methoxybenzoyl)- 4-[(methylaminocarbonyl)amino] benzenesulfonamide and I + oxabetrinil.
  • the safeners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14 th Edition (BCPC), 2006.
  • the reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO 02/34048, and the reference to fenchlorazole-ethyl also applies to fenchlorazole, etc.
  • the mixing ratio of compound of formula (I) to safener is from 100:1 to 1 :10, especially from 20:1 to 1 :1.
  • mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of compound of formula (I) with the safener).
  • the compounds of formula (I) of this invention are useful as herbicides.
  • the present invention therefore further comprises a method for controlling unwanted plants comprising applying to the said plants or a locus comprising them, an effective amount of a compound of the invention or a herbicidal composition containing said compound.
  • Controlling means killing, reducing or retarding growth or preventing or reducing germination.
  • the plants to be controlled are unwanted plants (weeds).
  • Locus means the area in which the plants are growing or will grow.
  • the rates of application of compounds of formula (I) may vary within wide limits and depend on the nature of the soil, the method of application (pre-emergence; post-emergence; application to the seed furrow; no tillage application etc.), the crop plant, the weed(s) to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • the compounds of formula (I) according to the invention are generally applied at a rate of from 10 to 2000 g/ha, especially from 50 to 1000 g/ha.
  • the application is generally made by spraying the composition, typically by tractor mounted sprayer for large areas, but other methods such as dusting (for powders), drip or drench can also be used.
  • composition according to the invention can be used include crops such as cereals, for example barley and wheat, cotton, oilseed rape, sunflower, maize, rice, soybeans, sugar beet, sugar cane and turf.
  • crops such as cereals, for example barley and wheat, cotton, oilseed rape, sunflower, maize, rice, soybeans, sugar beet, sugar cane and turf.
  • Crop plants can also include trees, such as fruit trees, palm trees, coconut trees or other nuts. Also included are vines such as grapes, fruit bushes, fruit plants and vegetables. Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering.
  • herbicides or classes of herbicides e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors
  • An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola).
  • crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties
  • Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle).
  • Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds).
  • the Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria.
  • Examples of toxins, or transgenic plants able to synthesise such toxins are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529.
  • transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®.
  • Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events).
  • seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.
  • Crops are also to be understood to include those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
  • output traits e.g. improved storage stability, higher nutritional value and improved flavour.
  • turf grass for example in golf-courses, lawns, parks and roadsides, or grown commercially for sod
  • ornamental plants such as flowers or bushes.
  • Compounds of formula (I) and compositions of the invention can typically be used to control a wide variety of monocotyledonous and dicotyledonous weed species.
  • monocotyledonous species that can typically be controlled include Alopecurus myosuroides, Avena fatua, Brachiaria plantaginea, Bromus tectorum, Cyperus esculentus, Digitaria sanguinalis, Echinochloa crus-galli, Lolium perenne, Lolium multiflorum, Panicum miliaceum, Poa annua, Setaria viridis, Setaria faberi and Sorghum bicolor.
  • dicotyledonous species that can be controlled include Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Euphorbia heterophylla, Galium aparine, Ipomoea hederacea, Kochia scoparia, Polygonum convolvulus, Sida spinosa, Sinapis arvensis, Solanum nigrum, Stellaria media, Veronica persica and Xanthium strumarium.
  • the compounds of formula (I) are also useful for pre-harvest desiccation in crops, for example, but not limited to, potatoes, soybean, sunflowers and cotton. Pre-harvest desiccation is used to desiccate crop foliage without significant damage to the crop itself to aid harvesting. Compounds/compositions of the invention are particularly useful in non-selective burn-down applications, and as such may also be used to control volunteer or escape crop plants.
  • Wettable powders a) b) c) active ingredients 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate 6 % 10 % phenol polyethylene glycol ether 2 %
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • Emulsifiable concentrate active ingredients 10 % octylphenol polyethylene glycol ether 3 %
  • Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water. Dusts a) b) c)
  • Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill.
  • the combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • Active ingredients 8 % polyethylene glycol (mol. wt. 200) 3 %
  • the finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol.
  • Non-dusty coated granules are obtained in this manner.
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1).
  • This mixture is emulsified in a mixture of 1 .2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved.
  • To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • Electrospray positive and negative Capillary (kV) 3.0, Cone (V) 35.0, Source Temperature (°C) 150, Cone Gas Flow (L/Hr.) 10, Desolvation Gas Flow (L/Hr.) 500.
  • Solvent A H 2 O with 0.05% TFA
  • Solvent B CH 3 CN with 0.05% TFA
  • Electrospray positive and negative Cone (V) 20.00, Source Temperature (°C) 120, Cone Gas Flow (L/Hr.) 50
  • the preparative HPLC was conducted using an 11.4 minute run time (not using at column dilution, bypassed with the column selector), according to the following gradient table:
  • Step 1 Preparation of 3-(dimethylamino)-1-(4-pyridyl)prop-2-en-1-one
  • Step 3 Preparation of 3-[4-([1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-yl)pyridin-1-ium-1-yl]propanoic acid 2,2,2- trifluoroacetate A1
  • Step 1 Preparation of 3-chloro-6-(4-pyridyl)pyridazine
  • Step 3 Preparation of 3-[4-(tetrazolo[1 ,5-b]pyridazin-6-yl)pyridin-1-ium-1-yl]propanoic acid 2,2,2- trifluoroacetate A3
  • Step 1 Preparation of 8-(4-pyridyl)-[1 ,2,4]triazolo[4,3-b]pyridazine
  • Step 2 Preparation of 3-[4-([1 ,2,4]triazolo[4,3-b]pyridazin-8-yl)pyridin-1-ium-1-yl]propanoic acid bromide A2
  • a microwave vial was charged with tributyl(4-pyridyl)stannane (0.257 g), 7-chlorothiazolo[5,4- d]pyrimidine (0.1 g), tetrakis(triphenylphosphine)palladium(0) (0.067 g) and 1 ,4-dioxane (2.62 mL).
  • the mixture was heated at 140°C under microwave irradiation for 1 hour.
  • the reaction mixture was concentrated and purified by silica gel chromatography eluting with a mixture of acetonitrile and dichloromethane to give 7-(4-pyridyl)thiazolo[5,4-d]pyrimidine as a brown solid.
  • a microwave vial was charged, under nitrogen atmosphere, with 4-iodopyridine (0.1 g), 5-(4,4,5,5- tetramethyl-1 ,3, 2-dioxaborolan-2-yl)-2,1 ,3-benzoxadiazole (0.132 g), cesium carbonate (0.238 g), 1 ,1'- bis(diphenylphosphino)ferrocene-palladium(ll)dichloride dichloromethane complex (0.04 g), 1 ,4- dioxane (0.805 mL) and water (0.268 mL). The mixture was heated at 120°C under microwave irradiation for 30 minutes.
  • the reaction mixture was diluted with dichloromethane, filtered through a pad of celite, which was washed with further dichloromethane.
  • the filtrate was concentrated and purified by silica gel chromatography eluting with a mixture of ethyl acetate and hexanes to give 5-(4- pyridyl)-2,1 ,3-benzoxadiazole as a yellow solid.
  • a microwave vial was charged, under nitrogen atmosphere, with 4-iodopyridine (0.1 g), 5-(4, 4,5,5- tetramethyl-1 ,3, 2-dioxaborolan-2-yl)-2,1 ,3-benzothiadiazole (0.141 g), 1 ,1'- bis(diphenylphosphino)ferrocene-palladium(ll)dichloride dichloromethane complex (0.04 g), cesium carbonate (0.239 g), 1 ,4-dioxane (0.805 mL) and water (0.268 mL). The mixture was heated at 120°C under microwave irradiation for 30 minutes.
  • reaction mixture was diluted with dichloromethane, filtered through a pad of celite, which was washed with further dichloromethane.
  • the filtrate was concentrated and purified by silica gel chromatography eluting with a mixture of ethyl acetate and hexanes to give 5-(4-pyridyl)-2,1 ,3-benzothiadiazole as an off-white solid.
  • a microwave vial was charged with tributyl(4-pyridyl)stannane (0.286 g), 4-chloro-2,1 ,3- benzoxadiazole (0.1 g), tetrakis(triphenylphosphine)palladium(0) (0.0748 g) and 1 ,4-dioxane (2.91 mL).
  • the mixture was heated at 140°C under microwave irradiation for 1 hour.
  • the reaction mixture was concentrated and purified by silica gel chromatography eluting with a mixture of ethyl acetate and hexanes to give 4-(4-pyridyl)-2,1 ,3-benzoxadiazole as an off-white solid.
  • Example 8 Preparation of 6-(4-pyridyl)-[1 ,2,41triazolo[1 ,5-a]pyrimidine A microwave vial was charged with 4H-1 ,2,4-triazol-3-amine (0.1 g), 2-(4-pyridyl)propanedial (0.177 g) and acetic acid (2.02 mL). The mixture was heated at 150°C under microwave irradiation for 1 hour. The reaction mixture was concentrated and purified by silica gel chromatography eluting with a mixture of methanol in dichloromethane to give 6-(4-pyridyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine as a white solid.
  • Step 2 Preparation of N'-[5-bromo-3-(methylamino)pyrazin-2-yl]-N,N-dimethyl-formamidine
  • N,N-dimethylformamide dimethyl acetal 8.36 g
  • the reaction mixture was heated at 50°C for 8 hours.
  • the reaction mixture was cooled and concentrated to give crude N'-[5- bromo-3-(methylamino)pyrazin-2-yl]-N,N-dimethyl-formamidine as a brown solid, which was used without further purification.
  • Step 5 Preparation of tert-butyl 3-[4-(3-methylimidazo[4,5-b]pyrazin-5-yl)pyridin-1-ium-1-yl]propanoate bromide A9 To a mixture of 3-methyl-5-(4-pyridyl)imidazo[4,5-b]pyrazine (0.5 g), tetrahydrofuran (5 mL) and acetonitrile (5 mL) was added tert-butyl 3-bromopropanoate (0.705 g) at room temperature. The reaction mixture was heated at 80°C for 16 hours, then cooled and concentrated.
  • Step 6 Preparation of 3-[4-(3-methylimidazo[4,5-b]pyrazin-5-yl)pyridin-1-ium-1-yl]propanoic acid chloride A8
  • Step 1 Preparation of 5-chlorothiazolo[5,4-b]pyridin-2-amine To a mixture of 2,6-dichloropyridin-3-amine (10 g) in acetic acid (100 mL) was added potassium thiocyanate (14.4 g) and this mixture was heated at 90°C for 16 hours. The resulting mixture was poured onto ice and this mixture was adjusted to pH 6 with aqueous ammonia and extracted with ethyl acetate (2x150 mL).
  • Step 1 Preparation of 3-amino-6-chloro-pyridine-2-thiol
  • a mixture of 5-chlorothiazolo[5,4-b]pyridin-2-amine (2.7 g) in 20% aqueous sodium hydroxide (100 mL) was added sodium sulfite (3.59 g) and this mixture was heated at 100°C for 16 hours.
  • the reaction mixture was cooled and neutralized with formic acid ( ⁇ 3 mL).
  • the resulting precipitate was filtered off to give 3-amino-6-chloro-pyridine-2-thiol as a yellow solid, which was used without further purification.
  • Step 1 Preparation of N'-(6-chloropyridazin-3-yl)-N,N-dimethyl-formamidine
  • Step 3 Preparation of 6-chloro-[1 ,2,4]triazolo[1 ,5-b]pyridazine
  • Step 4 Preparation of 6-(4-pyridyl)-[1 ,2,4]triazolo[1 ,5-b]pyridazine
  • reaction mixture was filtered through celite, washing with 5% methanol in dichloromethane (2x30 mL). The filtrate was concentrated and the residue purified by silica gel chromatography eluting with a mixture of methanol and dichloromethane to afford 6-(4- pyridyl)-[1 ,2,4]triazolo[1 ,5-b]pyridazine as an off-white solid.
  • Step 5 Preparation of tert-butyl 3-[4-([1 ,2,4]triazolo[1 ,5-b]pyridazin-6-yl)pyridin-1-ium-1-yl]propanoate bromide A18
  • Step 6 Preparation of 3-[4-([1 ,2,4]triazolo[1 ,5-b]pyridazin-6-yl)pyridin-1-ium-1-yl]propanoic acid chloride A13
  • Example 13 Preparation of 3-[4-([1 ,2,4]triazolo[1 ,5-a]pyrazin-5-yl)pyridin-1 -ium-1 -yl]propanoic acid chloride A14 Step 1 : Preparation of 6-(4-pyridyl)pyrazin-2-amine
  • Step 3 Preparation of N'-hydroxy-N-[6-(4-pyridyl)pyrazin-2-yl]formamidine
  • methanol 50 mL
  • hydroxylamine hydrochloride 1.16 g
  • sodium acetate 1 .36 g
  • Step 4 Preparation of 5-(4-pyridyl)-[1 ,2,4]triazolo[1 ,5-a]pyrazine
  • Step 5 Preparation of tert-butyl 3-[4-([1 ,2,4]triazolo[1 ,5-a]pyrazin-5-yl)pyridin-1-ium-1-yl]propanoate bromide A19
  • Step 6 Preparation of 3-[4-([1 ,2,4]triazolo[1 ,5-a]pyrazin-5-yl)pyridin-1-ium-1-yl]propanoic acid chloride A14
  • Step 1 Preparation of 5-chloro-1-oxido-[1 ,2,5]oxadiazolo[3,4-b]pyridin-1-ium
  • Step 3 Preparation of 5-(4-pyridyl)-[1 ,2,5]oxadiazolo[3,4-b]pyridine
  • Step 4 Preparation of methyl 3-[4-([1 ,2,5]oxadiazolo[3,4-b]pyridin-5-yl)pyridin-1-ium-1-yl]propanoate bromide A17
  • Step 5 Preparation of 3-[4-([1 ,2,5]oxadiazolo[3,4-b]pyridin-5-yl)pyridin-1-ium-1-yl]propanoic acid chloride A10
  • Step 3 Preparation of 5-(4-pyridyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine
  • Step 1 Preparation of 3-methylsulfanyl-5-(4-pyridyl)-1 ,2,4-triazine
  • Step 3 Preparation of 7-(4-pyridyl)-[1 ,2,4]triazolo[4,3-b][1 ,2,4]triazine
  • Step 1 Preparartion of 1-(4-pyridyl)-N-(1 ,2,4-triazol-4-yl)ethanimine
  • Step 3 Preparation of 6-(4-pyridyl)-[1 ,2,4]triazolo[4,3-b]pyridazine
  • Step 1 Preparation of 3-(dimethylamino)-1-(4-pyridyl)prop-2-en-1-one
  • Step 2 Preparation of 7-(4-pyridyl)pyrazolo[1 ,5-a]pyrimidine
  • a microwave vial was charged with 1 H-pyrazol-5-amine (0.2 g), 3-(dimethylamino)-1-(4-pyridyl)prop-2- en-1-one (0.424 g) and acetic acid (3 mL) and heated at 150°C under microwave irradiation for 30 minutes.
  • the reaction mixture was concentrated and triturated with methyl t-butyl ether and the residue was purified by silica gel chromatography eluting with a mixture of ethyl acetate and methanol to give 7-(4-pyridyl)pyrazolo[1 ,5-a]pyrimidine as a light yellow solid.
  • a microwave vial was charged with 4-pyridylboronic acid (0.44 g), 5-chloropyrazolo[1 ,5-a]pyrimidine (0.5 g), 1 ,4-dioxane (5 mL) and water (2.5 mL) then tripotassium phosphate (1 .38 g) was added. After degassing for 10 minutes with nitrogen, tetrakis(triphenylphosphine)palladium(0) (0.188 g) was added and the reaction mass was degassed for a further 10 minutes. The mixture was heated at 120°C under microwave irradiation for 45 minutes then diluted with water and extracted with ethyl acetate.
  • a microwave vial was charged with 4-amino-4H-1 ,2,4-triazole (1 g), 3-(dimethylamino)-1-(4- pyridyl)prop-2-en-1-one (2.05 g) and acetic acid (20 mL) and heated at 150°C under microwave irradiation for 60 minutes.
  • the reaction mixture was concentrated and the residue was purified by silica gel chromatography eluting with a mixture of ethyl acetate and methanol to give 8-(4-pyridyl)- [1 ,2,4]triazolo[4,3-b]pyridazine as a yellow solid.
  • Step 1 Preparation of 1-(4-pyridyl)-N-pyrrol-1-yl-ethanimine
  • Step 2 Preparation of N,N-dimethyl-3-(4-pyridyl)-3-pyrrol-1-ylimino-prop-1-en-1 -amine
  • Example 22 Preparation of 4-(4-pyridyl)pyrrolo[1 ,2-b]pyridazine A microwave vial was charged with 1-aminopyrrole (0.7 g), 3-(dimethylamino)-1-(4-pyridyl)prop-2-en- 1 -one (1.5 g) and acetic acid (12.5 mL) and heated at 150°C under microwave irradiation for 60 minutes.
  • reaction mixture was concentrated and triturated with methyl t-butyl ether and the residue was purified by silica gel chromatography eluting with a mixture of ethyl acetate and cyclohexane to give 4-(4-pyridyl)pyrrolo[1 ,2-b]pyridazine as a light yellow solid.
  • Step 1 Preparation of 7-(4-pyridyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine
  • reaction mixture was concentrated and purified by silica gel chromatography eluting with a mixture of ethyl acetate and methanol to give 7-(4-pyridyl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine as a light yellow solid.
  • Step 2 Preparation of tert-butyl 2-[4-([1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-yl)pyridin-1-ium-1-yl]acetate bromide A41
  • Step 3 Preparation of 2-[4-([1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-yl) pyridin-1 -ium-1 -yl]acetic acid 2,2,2- trifluoroacetate A34
  • reaction mixture was concentrated and the residue was purified by using reverse phase chromatography eluting with a mixture of acetonitrile and water (trifluoroacetic acid was present in the eluent) to give 2-[4-([1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-yl)pyridin-1- ium-1-yl]acetic acid 2,2,2-trifluoroacetate.
  • a microwave vial was charged with 4-pyridylboronic acid (0.5 g), 6-chloroimidazo[1 ,2-b]pyridazine (0.5 g), 1 ,4-dioxane (5 mL) and water (2.5 mL) then tripotassium phosphate (1 .38 g) was added. After degassing for 10 minutes with nitrogen, tetrakis(triphenylphosphine)palladium(0) (0.188 g) was added and the reaction mass was degassed for a further 10 minutes. The mixture was heated at 120°C under microwave irradiation for 30 minutes then diluted with water and extracted with ethyl acetate.
  • Step 1 Preparation of N-imidazol-1-yl-1-(4-pyridyl)ethanimine
  • Step 2 Preparation of 3-imidazol-1-ylimino-N,N-dimethyl-3-(4-pyridyl)prop-1-en-1 -amine
  • Step 3 Preparation of 2-(4-pyridyl)imidazo[1 ,5-b]pyridazine
  • the aqueous layer was concentrated and purified by reverse phase HPLC eluting with a mixture of water and acetonitrile to give 2-[4-([1 ,2,4]triazolo[1 ,5-b]pyridazin-6- yl)pyridin-1-ium-1-yl]ethanesulfonate as an off-white solid.
  • Step 2 Preparation of 8-chloro-[1 ,2,4]triazolo[4,3-a]pyrazine
  • Step 3 Preparation of 8-(4-pyridyl)-[1 ,2,4]triazolo[4,3-a]pyrazine
  • a microwave vial was charged with 8-chloro-[1 ,2,4]triazolo[4,3-a]pyrazine (0.5 g), 2- methyltetrahydrofuran (10 mL) and water (10 mL). After degassing for 10 minutes with nitrogen, tetrakis(triphenylphosphine)palladium(0) (0.578 g) and 4-pyridylboronic acid (0.47 g) was added and the reaction mass was degassed for a further 10 minutes. The mixture was heated at 120°C under microwave irradiation for 1 hour then diluted with water and extracted with ethyl acetate (3x30 mL).
  • Step 4 Preparation of 3-[4-([1 ,2,4]triazolo[4,3-a]pyrazin-8-yl)pyridin-1-ium-1-yl]propanoic acid bromide A42
  • Step 1 Preparation of tert-butyl 2-[4-([1 ,2,4]triazolo[4,3-b]pyridazin-6-yl)pyridin-1-ium-1-yl]acetate bromide A48
  • Step 2 Preparation of [4-([1 ,2,4]triazolo[4,3-b]pyridazin-6-yl)pyridin-1-ium-1-yl]methanesulfonate A45 [Chlorosulfonyloxy(dimethyl)silyl]methane (10 mL) was heated at 120°C, in order to have an internal temperature of 105°C, then tert-butyl 2-[4-([1 ,2,4]triazolo[4,3-b]pyridazin-6-yl)pyridin-1-ium-1-yl]acetate bromide (0.76 g) was added portion wise. After heating for 24 hours, the reaction mixture was cooled to room temperature.
  • Step 1 Preparation of 5-(4-pyridyl)-1 ,2,4-triazin-3-amine
  • Step 2 Preparation of 3-(4-pyridyl)imidazo[1 ,2-b][1 ,2,4]triazine
  • Step 3 Preparation of 5-chloro-[1 ,2,4]triazolo[4,3-a]pyrazine
  • Step 4 Preparation of 5-(4-pyridyl)-[1 ,2,4]triazolo[4,3-a]pyrazine
  • Step 1 Preparation of N-(1H-1 ,2,4-triazol-5-yl)pyridine-4-carboxamidine
  • Step 2 Preparation of 7-methyl-5-(4-pyridyl)-[1 ,2,4]triazolo[1 ,5-a][1 ,3,5]triazine
  • Step 1 Preparation of N'-(1 ,2,4-triazol-4-yl)pyridine-4-carboxamidine
  • Step 2 Preparation of N-(dimethylaminomethylene)-N'-(1 ,2,4-triazol-4-yl)pyridine-4-carboxamidine
  • N'-(1 ,2,4-triazol-4-yl)pyridine-4-carboxamidine (1 g) in N,N-dimethylformamide (11 mL), under nitrogen atmosphere, was added tert-butoxy bis(dimethylamino)methane (3.4 mL) and the mixture was heated at 100°C for 2 hours.
  • the reaction mass was cooled to room temperature, concentrated and the residue was triturated with methyl t-butyl ether to give N- (dimethylaminomethylene)-N'-(1 ,2,4-triazol-4-yl)pyridine-4-carboxamidine as a light brown solid.
  • Step 3 Preparation of N,N-dimethyl-6-(4-pyridyl)-[1 ,2,4]triazolo[3,4-f][1 ,2,4]triazin-8-amine
  • Step 1 Preparation of 3-chloro-N-[(2,4-dimethoxyphenyl)methyl]pyrazin-2-amine
  • 2,3-dichloropyrazine (5 g) and (2,4-dimethoxyphenyl)methanamine (16.8 g) was stirred at room temperature for 16 hours.
  • the reaction was partitioned between water and ethyl acetate.
  • the organic layer was dried over sodium sulfate, concentrated and the residue was purified by silica gel chromatography eluting with a mixture of ethyl acetate and cyclohexane to give 3-chloro-N-[(2,4- dimethoxyphenyl)methyl]pyrazin-2-amine.
  • Step 2 Preparation of N-[(2,4-dimethoxyphenyl)methyl]-3-(4-pyridyl)pyrazin-2-amine
  • tetrakis(triphenylphosphine)palladium(0) 5.11 g
  • Step 5 Preparation of N-hydroxy-N'-[3-(4-pyridyl)pyrazin-2-yl]formamidine
  • hydroxylamine hydrochloride 0.672 g
  • reaction mixture was concentrated and the residue was purified by silica gel chromatography eluting with a mixture of ethyl acetate and cyclohexane to give N-hydroxy-N'-[3-(4- pyridyl)pyrazin-2-yl]formamidine.
  • Step 6 Preparation of 8-(4-pyridyl)-[1 ,2,4]triazolo[1 ,5-a]pyrazine
  • Step 2 Preparation of 5-chloro-2-methyl-triazolo[4,5-d]pyrimidine
  • iodomethane 2.5 mL
  • the reaction mass was cooled to ⁇ 0°C and sodium bis(trimethylsilyl)amide (1 M in tetrahydrofuran, 30 mL) was added over 15 minutes.
  • the reaction was stirred at room temperature for 12 hours.
  • the mixture was quenched with saturated aqueous ammonium chloride, diluted with water and extracted with ethyl acetate.
  • a microwave vial was charged with tributyl(4-pyridyl)stannane (1 .075 g), 5-chloro-2-methyl- triazolo[4,5-d]pyrimidine (0.45 g), tetrakis(triphenylphosphine)palladium(0) (0.307 g) and 1 ,4-dioxane (9 mL) and the reaction mass was degassed with nitrogen for 15 minutes. The mixture was heated at 120°C under microwave irradiation for 1 hour. The reaction mixture was diluted with water (50 mL) and extracted with ethyl acetate (2x50 mL).
  • a microwave vial was charged with tributyl(4-pyridyl)stannane (1 .146 g), 5-chloro-3-methyl- triazolo[4,5-d]pyrimidine (0.48 g), tetrakis(triphenylphosphine)palladium(0) (0.328 g) and 1 ,4-dioxane (10 mL) and the reaction mass was degassed with nitrogen for 15 minutes. The mixture was heated at 120°C under microwave irradiation for 1 hour. The reaction mixture was diluted with water (50 mL) and extracted with ethyl acetate (2x50 mL).
  • Example 36 Preparation of 7-(4-pyridyl)-[1 ,2,4]triazolo[1 ,5-b][1 ,2,4]triazine
  • Step 1 Preparation of N,N-dimethyl-N'-[5-(4-pyridyl)-1 ,2,4-triazin-3-yl]formamidine
  • a microwave vial was charged with 5-(4-pyridyl)-1 ,2,4-triazin-3-amine (1 .7 g) and 1 ,1-dimethoxy-N,N- dimethyl-methanamine (17 mL). The mixture was heated at 100°C under microwave irradiation for 1 hour. The reaction mixture was concentrated to give crude N,N-dimethyl-N'-[5-(4-pyridyl)-1 ,2,4-triazin- 3-yl]formamidine, which was used without further purification.
  • Step 2 Preparation of N-hydroxy-N'-[5-(4-pyridyl)-1 ,2,4-triazin-3-yl]formamidine
  • Step 3 Preparation of 7-(4-pyridyl)-[1 ,2,4]triazolo[1 ,5-b][1 ,2,4]triazine
  • Step 1 Preparation of ethyl-2-(4-pyridyl)-2-(1 H-1 ,2,4-triazol-5-ylhydrazono)acetate
  • Step 2 Preparation of 3-(4-pyridyl)-[1 ,2,4]triazolo[5,1-c][1 ,2,4]triazin-4-ol
  • Step 2 Preparation of N-[1-(dimethylamino)ethylidene]-N'-(1 ,2,4-triazol-4-yl)pyridine-4-carboxamidine
  • a microwave vial was charged with N'-(1 ,2,4-triazol-4-yl)pyridine-4-carboxamidine (0.5 g), toluene (7.5 mL) and 1 ,1-dimethoxy-N,N-dimethyl-ethanamine (0.43 mL). The mixture was heated at 140°C under microwave irradiation for 1 hour. The reaction mixture was concentrated and the resulting residue was triturated with tert-butyl methyl etherto give N-[1-(dimethylamino)ethylidene]-N'-(1 ,2,4-triazol-4- yl)pyridine-4-carboxamidine as a light brown gummy mass.
  • Step-3 Preparation of 8-methyl-6-(4-pyridyl)-[1 ,2,4]triazolo[3,4-f][1 ,2,4]triazine
  • reaction mixture was concentrated and purified by silica gel chromatography eluting with a mixture of ethyl acetate and cyclohexane to give 8- methyl-6-(4-pyridyl)-[1 ,2,4]triazolo[3,4-f][1 ,2,4]triazine as an off-white solid.
  • Example 39 Preparation of 5-(4-pyridyl)-[1 ,2,4]triazolo[1 ,5-c]pyrimidine To a microwave vial, purged with nitrogen, was added the 5-chloro-[1 ,2,4]triazolo[1 ,5-c]pyrimidine (0.2 g), 1 ,T-bis(diphenylphosphino)ferrocene-palladium(ll)dichloride dichloromethane complex (0.109 g), 4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)pyridine (0.328 g) and potassium phosphate tribasic (0.841 g).
  • IF50 11.12% Emulsogen EL360 TM + 44.44% N-methylpyrrolidon
  • Test plants Ipomoea hederacea (IPOHE), Euphorbia heterophylla (EPHHL), Chenopodium album (CHEAL), Amaranthus palmeri (AMAPA), Lolium perenne (LOLPE), Digitaria sanguinalis (DIGSA), Eleusine indica (ELEIN), Echinochloa crus-galli (ECHCG), Setaria faberi (SETFA)

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

Abstract

Les composés de formule (I) dans laquelle les substituants sont tels que définis dans la revendication 1, sont utiles en tant que pesticides, en particulier en tant qu'herbicides.
PCT/EP2020/076614 2019-09-24 2020-09-23 Composés herbicides Ceased WO2021058595A1 (fr)

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GB201913752A GB201913752D0 (en) 2019-09-24 2019-09-24 Herbicidal compounds

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023025682A1 (fr) 2021-08-25 2023-03-02 Bayer Aktiengesellschaft Nouveaux composés de pyrazinyle-triazole utilisés comme pesticides

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Publication number Priority date Publication date Assignee Title
WO2023025682A1 (fr) 2021-08-25 2023-03-02 Bayer Aktiengesellschaft Nouveaux composés de pyrazinyle-triazole utilisés comme pesticides

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