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WO2020161162A1 - Composés de pyridinium herbicides - Google Patents

Composés de pyridinium herbicides Download PDF

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Publication number
WO2020161162A1
WO2020161162A1 PCT/EP2020/052813 EP2020052813W WO2020161162A1 WO 2020161162 A1 WO2020161162 A1 WO 2020161162A1 EP 2020052813 W EP2020052813 W EP 2020052813W WO 2020161162 A1 WO2020161162 A1 WO 2020161162A1
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Prior art keywords
group
hydrogen
c6alkyl
phenyl
formula
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PCT/EP2020/052813
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English (en)
Inventor
James Nicholas Scutt
Nigel James Willetts
Mangala Phadte
Swarnendu SASMAL
John Stephen Delaney
Sachin Balu CHAVAN
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Syngenta Crop Protection AG Switzerland
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Syngenta Crop Protection AG Switzerland
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Publication of WO2020161162A1 publication Critical patent/WO2020161162A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
    • 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
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • C07F9/65583—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system each of the hetero rings containing nitrogen as ring hetero atom

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.
  • a 1 , A 2 , A 3 , A 4 and A 5 are each independently selected from the group consisting of C-H, C-R 8 and N; and from 2 to 4 of A 1 , A 2 , A 3 , A 4 and A 5 are N; and the ring comprising A 1 , A 2 , A 3 , A 4 and A 5 is aromatic;
  • R 1 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, Cs-Cecycloalkyl, Ci-C 6 haloalkyl, -OR 7 , -OR 15a , -N(R 6 )S(0) 2 R 15 , -N(R 6 )C(0)R 15 , -N(R 6 )C(0)0R 15 , - N(R 6 )C(0)NR 16 R 17 , -N(R 6 )CHO, -N(R 7a ) 2 and -S(0) r R 15 ;
  • R 2 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl and Ci-C6haloalkyl; and wherein when R 1 is selected from the group consisting of -OR 7 , -OR 15a , -N(R 6 )S(0) 2 R 15 , - N(R 6 )C(0)R 15 , -N(R 6 )C(0)0R 15 , -N(R 6 )C(0)NR 16 R 17 , -N(R 6 )CHO, -N(R 7a ) 2 and -S(0) r R 15 , R 2 is selected from the group consisting of hydrogen and Ci-C6alkyl; or
  • R 1 and R 2 together with the carbon atom to which they are attached form a C3-C6cycloalkyl 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, Ci-C6alkyl, Ci-Cehaloalkyl, -OH, -OR 7 , -OR 15a , -NH 2 , -NHR 7 , -NHR 15a , -N(R 6 )CHO, -NR 7b R 7c and -S(0) r R 15 ; or each R 1a and R 2b together with the carbon atom to which they are attached form a C3-C6cycloalkyl ring or a 3- to 6- membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected
  • R 3 , R 3a , R 4 and R 5 are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, -S(0)rR 15 , Ci-C6alkyl, Ci-C6fluoroalkyl, Ci-C6fluoroalkoxy, Ci-C6alkoxy, C3-C6cycloalkyl and - N(R 6 ) 2 ; each R 6 is independently selected from hydrogen and Ci-C6alkyl; each R 7 is independently selected from the group consisting of Ci-C6alkyl, -S(0) 2 R 15 , -C(0)R 15 , - C(0)0R 15 and -C(0)NR 16 R 17 ; each R 7a is independently selected from the group consisting of -S(0) 2 R 15 , -C(0)R 15 , -C(0)0R 15 - C(0)NR 16 R 17 and -C(0)NR 6 R 15a ;
  • R 7b and R 7c are independently selected from the group consisting of Ci-C6alkyl, -S(0) 2 R 15 , -C(0)R 15 , - C(0)0R 15 , -C(0)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 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(0)rR 15 , -NR 6 S(0) 2 R 15 , -C(0)OR 10 , -C(0)R 15 , -C(0)NR 16 R 17 , -S(0) 2 NR 16 R 17 , CI- Cealkyl, Ci-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, C3-C6cycloalkoxy, C 2 -C6alkenyl, C 2 - C6haloalkenyl, C 2 -C6alkynyl
  • X is selected from the group consisting of C3-C6cycloalkyl, 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 R 9 substituents, 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(0)OR 10 , -CH2OH, -CHO, -C(0)NH0R 11 , -C(0)NHCN, - 0C(0)NH0R 11 , -0C(0)NHCN, -NR 6 C(0)NH0R 11 , -NR 6 C(0)NHCN, -C(0)NHS(0) 2 R 12 , - 0C(0)NHS(0) 2 R 12 , -NR 6 C(0)NHS(0) 2 R 12 , -S(0) 2 0R 10 , -0S(0) 2 0R 10 , -NR 6 S(0) 2 0R 10 , -NR 6 S(0)OR 10 , -NHS(0) 2 R 14 , -S(0)OR 10 , -OS(0)OR 10 , -S(0) 2 NHCN, -S(0) 2 NHC(0)R 18 , -S(0) 2 NHS(0) 2 R 12 , - 0S(0) 2 NHCN, -0S(0) 2 NHS(0) 2 R 12 ,
  • R 10 is selected from the group consisting of hydrogen, Ci-C6alkyl, 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; provided that when A 1 , A 3 and A 5 are all N, A 2 and A 4 are C-H, n is 0, m is 0 and Z is -C(0)OR 10 , then R 10 is selected from the group consisting of C3-C6alkyl, 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, Ci-C6alkyl 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 Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, -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, Ci-C6alkyl, Ci-C6alkoxy and phenyl;
  • R 14 is Ci-Cehaloalkyl
  • R 15 is selected from the group consisting of Ci-C6alkyl 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 Ci-C6alkyl; 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, Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, -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 -NO2 group.
  • Ci-C6alkyl 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. Ci-C4alkyl and Ci- C 2 alkyl are to be construed accordingly.
  • Ci-C6alkyl examples include, but are not limited to, methyl (Me), ethyl (Et), n-propyl, 1 -methylethyl (iso-propyl), n-butyl, and 1 -dimethylethyl (f-butyl).
  • Ci-C6alkoxy refers to a radical of the formula -OR a where R a is a Ci-C6alkyl radical as generally defined above. Ci-C4alkoxy is to be construed accordingly. Examples of Ci-4alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy and f-butoxy.
  • Ci-C6haloalkyl refers to a Ci-C6alkyl radical as generally defined above substituted by one or more of the same or different halogen atoms. Ci-C4haloalkyl is to be construed accordingly. Examples of Ci-C6haloalkyl include, but are not limited to chloromethyl, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl and 2,2,2-trifluoroethyl.
  • C 2 -C6alkenyl 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 ( ⁇ -configuration, having from two to six carbon atoms, which is attached to the rest of the molecule by a single bond.
  • C2-C4alkenyl is to be construed accordingly.
  • Examples of C 2 -C6alkenyl include, but are not limited to, prop-1 -enyl, allyl (prop-2-enyl) and but-1 -enyl.
  • C 2 -C6haloalkenyl refers to a C 2 -C6alkenyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • Examples of C 2 -C6haloalkenyl include, but are not limited to chloroethylene, fluoroethylene, 1 ,1 -difluoroethylene, 1 ,1 -dichloroethylene and 1 ,1 ,2-trichloroethylene.
  • C 2 -C6alkynyl 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.
  • C2-C4alkynyl is to be construed accordingly.
  • Examples of C 2 -C6alkynyl include, but are not limited to, prop-1 -ynyl, propargyl (prop-2-ynyl) and but-1 -ynyl.
  • Ci-C6haloalkoxy refers to a Ci-C6alkoxy group as defined above substituted by one or more of the same or different halogen atoms. Ci-C4haloalkoxy is to be construed accordingly. Examples of Ci-C6haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy and trifluoroethoxy.
  • Ci-C3haloalkoxyCi-C3alkyl refers to a radical of the formula Rb-0-R a - where Rb is a Ci-C3haloalkyl radical as generally defined above, and R a is a Ci-C3alkylene radical as generally defined above.
  • Ci-C3alkoxyCi-C3alkyl refers to a radical of the formula Rb-O-Ra- where Rb is a Ci-C3alkyl radical as generally defined above, and R a is a Ci-C3alkylene radical as generally defined above.
  • Ci-C3alkoxyCi-C3alkoxy- refers to a radical of the formula Rb-0-R a -0- where Rb is a Ci-C3alkyl radical as generally defined above, and R a is a Ci-C3alkylene radical as generally defined above.
  • C3-C6alkenyloxy refers to a radical of the formula -OR a where R a is a C3- C6alkenyl radical as generally defined above.
  • C3-C6alkynyloxy refers to a radical of the formula -OR a where R a is a C3- C6alkynyl radical as generally defined above.
  • hydroxyCi-Cealkyl refers to a Ci-C6alkyl radical as generally defined above substituted by one or more hydroxy groups.
  • Ci-C6alkylcarbonyl refers to a radical of the formula -C(0)R a where R a is a Ci-C6alkyl radical as generally defined above.
  • Ci-C6alkoxycarbonyl refers to a radical of the formula -C(0)0R a where R a is a Ci-C6alkyl radical as generally defined above.
  • aminocarbonyl refers to a radical of the formula -C(0)NH 2 .
  • C3-C6cycloalkyl refers to a stable, monocyclic ring radical which is saturated or partially unsaturated and contains 3 to 6 carbon atoms.
  • C3-C 4 cycloalkyl is to be construed accordingly.
  • Examples of C3-C6cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • C3-C6halocycloalkyl refers to a C3-C6cycloalkyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C3-C 4 halocycloalkyl is to be construed accordingly.
  • C3-C6cycloalkoxy refers to a radical of the formula -OR a where R a is a C3- C6cycloalkyl radical as generally defined above.
  • N-C3-C6cycloalkylamino refers to a radical of the formula -NHR a where R a is a C3-C6cycloalkyl 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 examples 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:
  • Y represents an agronomically acceptable anion
  • M represents an agronomically acceptable cation (in addition to the pyridinium 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 nitrogen atom in the ring comprising A 1 , A 2 , A 3 , A 4 and A 5 may be protonated or a nitrogen atom comprised in R 1 , R 2 , Q or X may be protonated.
  • k is 2
  • j is 1 and Y is chloride, wherein a nitrogen atom in the ring comprising A 1 , A 2 , A 3 , A 4 and A 5 is protonated.
  • Suitable agronomically acceptable salts ofthe 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 3 , R 3a , R 4 , R 5 , A 1 , A 2 , A 3 , A 4 , A 5 and Z are as defined for compounds of formula (I).
  • R 1 , R 2 , R 1a , R 2b , R 3 , R 3a , R 4 , R 5 , A 1 , A 2 , A 3 , A 4 , A 5 and Z are as defined for compounds offormula
  • R 1 , R 2 , R 1a , R 2b , R 3 , R 3a , R 4 , R 5 , A 1 , A 2 , A 3 , A 4 , A 5 and Z are as defined for compounds offormula
  • R 1 , R 2 , R 1a , R 2b , R 3 , R 3a , R 4 , R 5 , A 1 , A 2 , A 3 , A 4 , A 5 and Z are as defined for compounds offormula
  • a 1 , A 2 , A 3 , A 4 and A 5 are each independently selected from the group consisting of C-H, C-R 8 and N, preferably A 1 , A 2 , A 3 , A 4 and A 5 are each independently C-H or N.
  • a 3 is C-H or C-R 8 .
  • the ring comprising A 1 , A 2 , A 3 , A 4 and A 5 is aromatic.
  • R 1 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, Cs-Cecycloalkyl, Ci-C 6 haloalkyl, -OR 7 , -OR 15a , -N(R 6 )S(0) 2 R 15 , -N(R 6 )C(0)R 15 , -N(R 6 )C(0)0R 15 , - N(R 6 )C(0)NR 16 R 17 , -N(R 6 )CHO, -N(R 7a ) 2 and -S(0) r R 15 .
  • R 1 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl, Ci-C6fluoroalkyl, -OR 7 , -NHS(0) 2 R 15 , -NHC(0)R 15 , - NHC(0)0R 15 , -NHC(0)NR 16 R 17 , -N(R 7a ) 2 and -S(0) r R 15 . More preferably, R 1 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl, Ci-C6fluoroalkyl, -OR 7 and -N(R 7a )2. Even more preferably, R 1 is selected from the group consisting of hydrogen, halogen and Ci-C6alkyl,. Even more preferably still, R 1 is hydrogen or Ci-C6alkyl. 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, Ci-C6alkyl and Ci-C6haloalkyl.
  • R 2 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl and Ci- C6fluoroalkyl. More preferably, R 2 is hydrogen or Ci-C6alkyl. Even more preferably, 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(0) 2 R 15 , -N(R 6 )C(0)R 15 , -N(R 6 )C(0)0R 15 , -N(R 6 )C(0)NR 16 R 17 , -N(R 6 )CHO, -N(R 7a ) 2 and -S(0) r R 15
  • R 2 is selected from the group consisting of hydrogen and Ci-C6alkyl.
  • R 1 is selected from the group consisting of -OR 7 , -NHS(0) 2 R 15 , -NHC(0)R 15 , -NHC(0)0R 15 , -NHC(0)NR 16 R 17 , -N(R 7a ) 2 and -S(0) 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 C3-C6cycloalkyl ring or a 3- to 6- membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O.
  • R 1 and R 2 together with the carbon atom to which they are attached form a C3- C6cycloalkyl ring.
  • R 1 and R 2 together with the carbon atom to which they are attached form a cyclopropyl ring.
  • 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 0 or 1. Most preferably, m is 0.
  • Each R 1a and R 2b are independently selected from the group consisting of hydrogen, halogen, Ci- Cealkyl, Ci-C 6 haloalkyl, -OH, -OR 7 , -OR 15a , -NH 2 , -NHR 7 , -NHR 15a , -N(R 6 )CHO, -NR 7b R 7c and -S(0) r R 15 .
  • each R 1a and R 2b are independently selected from the group consisting of hydrogen, halogen, Ci-C6alkyl, Ci-C6fluoroalkyl, -OH, -NH 2 and -NHR 7 .
  • each R 1a and R 2b are independently selected from the group consisting of hydrogen, Ci-C6alkyl, -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 Ci-C6alkyl.
  • each R 1a and R 2b together with the carbon atom to which they are attached form a C3- C6cycloalkyl 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 C3-C6cycloalkyl 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(0)rR 15 , Ci-C6alkyl, Ci-C6fluoroalkyl, Ci-C6fluoroalkoxy, Ci-C6alkoxy, C3-C6cycloalkyl and - N(R 6 ) 2 .
  • R 3 , R 3a , R 4 and R 5 are independently selected from the group consisting of hydrogen, halogen, cyano, Ci-C6alkyl, Ci-C6fluoroalkyl, Ci-C6fluoroalkoxy, Ci-C6alkoxy, C3-C6cycloalkyl 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, halogen, cyano, Ci-C6alkyl and Ci-C6fluoroalkyl.
  • R 3 , R 3a , R 4 and R 5 are independently selected from the group consisting of hydrogen, chloro, fluoro, bromo, cyano, methyl and trifluoromethyl. 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.
  • R 3 and R 3a are hydrogen or trifluoromethyl
  • R 4 and R 5 are independently selected from the group consisting of hydrogen, chloro, fluoro, bromo, cyano and trifluoromethyl.
  • Each R 6 is independently selected from hydrogen and Ci-C6alkyl. Preferably, each R 6 is independently selected from hydrogen and methyl.
  • Each R 7 is independently selected from the group consisting of Ci-C6alkyl, -S(0) 2 R 15 , -C(0)R 15 , - C(0)0R 15 and -C(0)NR 16 R 17 .
  • each R 7 is independently selected from the group consisting of Ci-C6alkyl, -C(0)R 15 and -C(0)NR 16 R 17 . More preferably, each R 7 is Ci-C6alkyl. Most preferably, each R 7 is methyl.
  • Each R 7a is independently selected from the group consisting of -S(0) 2 R 15 , -C(0)R 15 , -C(0)0R 15 - C(0)NR 16 R 17 and -C(0)NR 6 R 15a .
  • each R 7a is independently -C(0)R 15 or -C(0)NR 16 R 17 .
  • R 7b and R 7c are independently selected from the group consisting of Ci-C6alkyl, -S(0) 2 R 15 , -C(0)R 15 , - C(0)0R 15 , -C(0)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 Ci-C6alkyl, -C(0)R 15 and -C(0)NR 16 R 17 . More preferably, R 7b and R 7c are Ci-C6alkyl. 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.
  • each R 8 is independently selected from the group consisting of halogen, nitro, cyano,
  • Cealkyl, Ci-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, C3-C6cycloalkoxy, C2- C6haloalkenyl, C2-C6alkynyl, Ci-C3alkoxyCi-C3alkyl-, hydroxyCi-Cealkyl-, Ci-C3alkoxyCi Cehaloalkoxy, Ci-C3haloalkoxyCi-C3alkyl-, C3-C6alkenyloxy, C3-C6alkynyloxy, N-C3-C6cycloalkylamino, -C(R 6 ) NOR 6 , phenyl, a 3- to 6- membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O, and a 5- or 6- membered heteroaryl, which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and where
  • 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(0)rR 15 , -NR 6 S(0) 2 R 15 , -C(0)OR 10 , -C(0)R 15 , -C(0)NR 16 R 17 , - S(0) 2 NR 16 R 17 , Ci-C6alkyl, Ci-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, C3-C6cycloalkoxy, C 2 - C6alkenyl, C 2 -C6haloalkenyl, C 2 -C6alkynyl, Ci-C3alkoxyCi-C3alkyl-, hydroxyCi-Cealkyl-, Ci-C3alkoxyCi- C3alkoxy-, Ci-C3
  • 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(0) r R 15 , -NR 6 S(0) 2 R 15 , -C(0)OR 10 , -C(0)R 15 , -C(0)NR 16 R 17 , - S(0) 2 NR 16 R 17 , Ci-C6alkyl, Ci-C6haloalkyl, C3-C6cycloalkyl, Ci-C3alkoxyCi-C3alkyl-, hydroxyCi-Cealkyl-, Ci-C3alkoxyCi-C3alkoxy- and Ci-C6haloalkoxy.
  • 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(0) r R 15 , -NR 6 S(0) 2 R 15 , -C(0)OR 10 , -C(0)R 15 , -C(0)NR 16 R 17 , - S(0) 2 NR 16 R 17 , Ci-C6alkyl, Ci-C6haloalkyl, C3-C6cycloalkyl, Ci-C3alkoxyCi-C3alkyl-, hydroxyCi-Cealkyl-, Ci-C3alkoxyCi-C3alkoxy- and Ci-Cehaloalkoxy.
  • each R 8 is independently selected from the group consisting of halogen, nitro, cyano, -NH 2 , -S(0) r R 15 , -C(0)OR 10 , -C(0)R 15 , -C(0)NR 16 R 17 , -S(0) 2 NR 16 R 17 , Ci-C 6 alkyl and Ci- Cehaloalkyl.
  • each R 8 is independently selected from the group consisting of chloro, fluoro, cyano, -NH 2 , -SMe, -S(0) 2 Me, -C(0)0Me, -C(0)0CH 2 CH 3 , -C(0)0H, -C(0)Me, -C(0)NH 2 , - C(0)NHMe, -C(0)N(Me) 2 , methyl and trifluoromethyl.
  • each R 8 is independently selected from the group consisting of cyano, -NH 2 , -SMe, -C(0)0CH 2 CH 3 , -C(0)NH 2 , methyl and trifluoromethyl.
  • each R 8 is independently selected from the group consisting of -NH 2 , -SMe and methyl
  • each R 8 is independently selected from the group consisting of chloro, fluoro, cyano, -NH 2 , -S(0) 2 Me, -C(0)0Me, -C(0)0CH 2 CH 3 , -C(0)0H, -C(0)Me, -C(0)NH 2 , -C(0)NHMe, - C(0)N(Me) 2 , methyl and trifluoromethyl.
  • each R 8 is independently selected from the group consisting of cyano, -C(0)0CH2CH3, -C(0)NH2, methyl and trifluoromethyl.
  • Each R 9 is independently selected from the group consisting of halogen, cyano, -OH, -N(R 6 )2, Ci-C 4 alkyl, Ci-C 4 alkoxy, Ci-C 4 haloalkyl and Ci-C 4 haloalkoxy.
  • each R 9 is independently selected from the group consisting of halogen, cyano, -N(R 6 )2, Ci-C 4 alkyl, Ci-C 4 alkoxy, Ci-C 4 haloalkyl and Ci- C 4 haloalkoxy. More preferably, each R 9 is independently selected from the group consisting of halogen, Ci-C 4 alkyl, Ci-C 4 alkoxy and Ci-C 4 haloalkyl. Even more preferably, each R 9 is independently selected from the group consisting of halogen and Ci-C 4 alkyl.
  • X is selected from the group consisting of C3-C6cycloalkyl, 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 0f -C(O)OR 1 °, -CH 2 OH, -CHO, -C(0)NH0R 11 , -C(0)NHCN, - 0C(0)NH0R 11 , -0C(0)NHCN, -NR 6 C(0)NH0R 11 , -NR 6 C(0)NHCN, -C(0)NHS(0) 2 R 12 , - 0C(0)NHS(0) 2 R 12 , -NR 6 C(0)NHS(0) 2 R 12 , -S(0) 2 0R 10 , -0S(0) 2 0R 10 , -NR 6 S(0) 2 0R 10 , -NR 6 S(0)OR 10 , -NHS(0) 2 R 14 , -S(0)OR 10 , -OS(0)OR 10 , -S(0) 2 NHCN, -S(0) 2 NHC(0)R 18 , -S(0) 2 NHS(0) 2 R 12 , - 0S(0) 2 NHCN, -0S(0) 2 NHS
  • Z is selected from the group consisting of -C(0)OR 10 , -C(0)NH0R 11 , -0C(0)NH0R 11 , - NR 6 C(0)NH0R 11 , -C(0)NHS(0) 2 R 12 , -0C(0)NHS(0) 2 R 12 , -NR 6 C(0)NHS(0) 2 R 12 , -S(0) 2 0R 10 , - OS(0) 2 OR 10 , -NR 6 S(0) 2 0R 10 , -NR 6 S(0)OR 10 , -NHS(0) 2 R 14 , -S(0)OR 10 , -OS(0)OR 10 , -
  • Z is selected from the group consisting of -C(0)OR 10 , -C(0)NH0R 11 , - C(0)NHS(0) 2 R 12 , -S(0) 2 0R 10 , -0S(0) 2 0R 10 , -NR 6 S(0) 2 0R 10 , -NHS(0) 2 R 14 , -S(0)OR 10 , -
  • Z is selected from the group consisting of -C(0)OR 10 , -C(0)NHS(0) 2 R 12 , - S(0) 2 0R 10 , -P(0)(R 13 )(OR 10 ) and -0P(0)(R 13 )(0R 1 °).
  • Z is selected from the group consisting of -C(0)OR 10 , -S(0) 2 OR 10 and - 0P(0)(R 13 )(0R 1 °).
  • Z is selected from the group consisting of -C(0)0H, -C(0)0CH3, -S(0) 2 0H, - 0P(0)(0H)(0H), -0P(0)(0H)(0CH 2 CH 3 ) and -0P(0)(0CH 2 CH3)(0CH 2 CH 3 ).
  • Z is selected from the group consisting of -C(0)0H, -C(0)0CH 3 and - S(0) 2 0H.
  • Z is -C(0)0H or -S(0) 2 0H.
  • Z is selected from the group consisting of -C(0)OR 10 , -C(0)NHS(0) 2 R 12 , - S(0) 2 0R 10 , and -P(0)(R 13 )(OR 10 ).
  • Z is selected from the group consisting of -C(0)0H, - C(0)0CH 3 , -C(0)0CH 2 CH 3 , -C(0)0CH(CH 3 ) 2 , -C(0)0C(CH 3 ) 3 , -C(0)0CH 2 C 6 H 5 , -C(0)0C 6 H 5 , - C(0)NHS(0) 2 CH 3 , -S(0) 2 0H, -P(0)(0H)( OCH 2 CH 3 ) and -P(0)(0CH 2 CH 3 )(0CH 2 CH 3 ).
  • R 10 is selected from the group consisting of hydrogen, Ci-C6alkyl, 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, Ci-C6alkyl, phenyl and benzyl. More preferably, R 10 is selected from the group consisting of hydrogen and Ci-C6alkyl. Even more preferably, R 10 is hydrogen or methyl. Most preferably, R 10 is hydrogen.
  • R 10 is selected from the group consisting of C3-C6alkyl, 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 C3-C6alkyl, phenyl and benzyl. More preferably, when A 1 , A 3 and A 5 are all N, A 2 and A 4 are C-H, n is 0, m is 0 and Z is -C(0)OR 10 , then R 10 is C3-C6alkyl.
  • R 11 is selected from the group consisting of hydrogen, Ci-C6alkyl 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, Ci-C6alkyl and phenyl. More preferably, R 11 is selected from the group consisting of hydrogen and Ci-C6alkyl. Even more preferably, R 11 is Ci-C6alkyl. Most preferably, R 11 is methyl.
  • R 12 is selected from the group consisting of Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, -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 Ci-C6alkyl, Ci-C6haloalkyl, Ci- C6alkoxy, -OH, -N(R 6 )2 and phenyl. More preferably, R 12 is selected from the group consisting of Ci- Cealkyl, Ci-C6haloalkyl 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, Ci-C6alkyl, Ci-C6alkoxy and phenyl.
  • R 13 is selected from the group consisting of -OH, Ci-C6alkyl and Ci-C6alkoxy. More preferably, R 13 is selected from the group consisting of -OH and Ci-C6alkoxy. 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 Ci-C6haloalkyl. Preferably, R 14 is trifluoromethyl.
  • R 15 is selected from the group consisting of Ci-C6alkyl 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 Ci-C6alkyl and phenyl. More preferably, R 15 is Ci-C6alkyl. 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 Ci-C6alkyl.
  • 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, Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, -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, Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, -N(R 6 )2 and phenyl. More preferably, R 18 is selected from the group consisting of hydrogen, Ci-C6alkyl and Ci-C6haloalkyl.
  • R 18 is selected from the group consisting of Ci-C6alkyl and Ci-C6haloalkyl. Most preferably, R 18 is methyl or trifluoromethyl. r is 0, 1 or 2. Preferably, r is 0 or 2.
  • a 1 , A 2 , A 3 , A 4 and A 5 are each independently selected from the group consisting of C-H, C-R 8 and N; and from 2 to 3 of A 1 , A 2 , A 3 , A 4 and A 5 are N;
  • R 1 is hydrogen or Ci-C6alkyl
  • R 2 is hydrogen or methyl
  • Q is (CR 1a R 2b ) m ;
  • n 0,1 or 2;
  • R 1a and R 2b are independently selected from the group consisting of hydrogen, Ci-C6alkyl, -OH and - NH 2 ;
  • R 3 , R 3a , R 4 and R 5 are independently selected from the group consisting of hydrogen, halogen, cyano, Ci-C6alkyl and Ci-C6fluoroalkyl;
  • each R 6 is independently selected from hydrogen and methyl
  • each R 7 is Ci-C6alkyl
  • each R 8 is independently selected from the group consisting of halogen, nitro, cyano, -NH2, -S(0) r R 15 , - C(0)OR 10 , -C(0)R 15 , -C(0)NR 16 R 17 , -S(0) 2 NR 16 R 17 , Ci-C 6 alkyl and Ci-C 6 haloalkyl;
  • n 0;
  • Z is selected from the group consisting of -C(0)OR 10 , -C(0)NHS(0) 2 R 12 , -S(0) 2 0R 10 , and - P(0)(R 13 )(OR 10 );
  • R 10 is selected from the group consisting of hydrogen, Ci-C6alkyl, phenyl and benzyl; Provided that when A 1 , A 3 and A 5 are all N, A 2 and A 4 are C-H, n is 0, m is 0 and Z is -C(0)OR 10 , then R 10 is selected from the group consisting of C3-C6alkyl, phenyl and benzyl;
  • R 12 is selected from the group consisting of Ci-C6alkyl, Ci-C6haloalkyl and -N(R 6 )2;
  • R 13 is selected from the group consisting of -OH and Ci-C6alkoxy
  • R 15 is Ci-Cealkyl
  • R 16 and R 17 are independently selected from the group consisting of hydrogen and methyl; and r is 0 or 2.
  • a 1 , A 2 , A 3 , A 4 and A 5 are each independently selected from the group consisting of C-H, C-R 8 and N; and from 2 to 3 of A 1 , A 2 , A 3 , A 4 and A 5 are N;
  • a 3 is C-H or C-R 8 ;
  • R 1 is hydrogen or methyl
  • R 2 is hydrogen or methyl
  • Q is (CR 1a R 2b ) m ;
  • n 0 or 1 ;
  • 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 independently selected from the group consisting of hydrogen, chloro, fluoro, bromo, cyano, methyl and trifluoromethyl;
  • each R 8 is independently selected from the group consisting of chloro, fluoro, cyano, -NH2, -SMe, - S(0) 2 Me, -C(0)0Me, -C(0)0CH 2 CH 3 , -C(0)0H, -C(0)Me, -C(0)NH 2 , -C(0)NHMe, -C(0)N(Me) 2 , methyl and trifluoromethyl;
  • n 0;
  • Z is selected from the group consisting of -C(0)0H, -C(0)0CH 3 , -S(0) 2 0H, -0P(0)(0H)(0H), - 0P(0)(0H)(0CH 2 CH 3 ) and -0P(0)(0CH 2 CH 3 )(0CH 2 CH 3 ).
  • a 1 , A 2 , A 3 , A 4 and A 5 are each independently selected from the group consisting of C-H, C-R 8 and N; and from 2 to 3 of A 1 , A 2 , A 3 , A 4 and A 5 are N;
  • a 3 is C-H or C-R 8 ;
  • R 1 is hydrogen or methyl
  • R 2 is hydrogen or methyl
  • Q is (CR 1a R 2b ) m ;
  • n 0 or 1 ;
  • 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 independently selected from the group consisting of hydrogen, chloro, fluoro, bromo, cyano, methyl and trifluoromethyl; each R 8 is independently selected from the group consisting of chloro, fluoro, cyano, -NH 2 , -N(Me)2, - OH, -OMe, -S(0) 2 Me, -C(0)0Me, -C(0)0H, -C(0)Me, -C(0)NH 2 , -C(0)NHMe, -C(0)N(Me) 2 , methyl and trifluoromethyl;
  • n 0;
  • Z is selected from the group consisting 0f -C(O)OH, -C(0)0CH 3 , -C(0)0CH 2 CH 3 , -C(0)0CH(CH 3 ) 2 , - C(0)0C(CH 3 ) 3 , -C(0)0CH 2 C 6 H5, -C(0)0C 6 H 5 , -C(0)NHS(0) 2 CH 3 , -S(0) 2 0H, -P(0)(0H)( OCH 2 CH 3 ) and -P(0)(0CH 2 CH 3 )(0CH 2 CH 3 ).
  • the compound according to formula (I) is selected from a compound of formula (l-a), (l-b), (l-c), (l-d), (l-e), (l-f), (l-g), (l-h), (l-j), (l-k), (l-m), (l-n), (l-o) or (l-p),
  • p 0, 1 or 2;
  • each R 8 is independently selected from the group consisting of chloro, fluoro, cyano, -NH 2 , -SMe, - S(0) 2 Me, -C(0)0Me, -C(0)0CH 2 CH 3 , -C(0)0H, -C(0)Me, -C(0)NH 2 , -C(0)NHMe, -C(0)N(Me) 2 , methyl and trifluoromethyl; and
  • Z is selected from the group consisting of -C(0)0H, -C(0)0CH3 and -S(0) 2 0H.
  • the compound according to formula (I) is selected from a compound of formula (l-ab), (l-bb), (l-cc), (l-da), (l-ee), (l-ff), (l-gg), (l-hh), (l-ja), (l-kk), (l-mm), (l-na), (l-oo) or (l-pp),
  • each R 8 is independently selected from the group consisting of hydrogen, cyano, -Nhh, -SMe, - C(0)0CH2CH3, -C(0)NH2, methyl and trifluoromethyl;
  • Z is -C(0)0H or -S(0) 2 0H.
  • the compound according to formula (I) is selected from a compound of formula (l-aa), (l-bb), (l-cc), (l-dd), (l-ee), (l-ff), (l-gg), (l-hh), (l-jj), (l-kk), (l-mm), (l-nn), (l-oo) or (l-pp),
  • Z is -C(0)0H or -S(0) 2 0H.
  • the compound according to formula (I) is selected from a compound A1 to A102 listed in Table A.
  • the compound according to formula (I) is selected from a compound of formula (l-qa) or (l-ra) below,
  • each R 8 is independently selected from the group consisting of hydrogen, cyano, -Nhh, -SMe, - C(0)0CH 2 CH3, -C(0)NH 2 , methyl and trifluoromethyl (preferably, each R 8 is independently selected from the group consisting of hydrogen, -Nhh, -SMe); and
  • Z is -C(0)0H or -S(0) 2 0H.
  • 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 Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, -C(R 21 R 22 )0C(0)R 19 , phenyl or phenyl-Ci-C 4 alkyl-, wherein said phenyl moiety is optionally substituted by 1 to 5 substituents independently selected from halo, cyano, nitro, Ci-C6alkyl, Ci-C6haloalkyl or Ci-C6alkoxy.
  • R 19 is Ci-C6alkyl or phenyl
  • R 20 is hydroxy, Ci-C6alkyl, Ci-C6alkoxy or phenyl, R 21 is hydrogen or methyl,
  • R 22 is hydrogen or methyl
  • R 23 is hydrogen or Ci-C6alkyl.
  • Tables 1 to 45 below illustrate the compounds of the invention.
  • the skilled person would understand that the compounds of formula (I) may exist as an agronomically acceptable salt, a zwitterion or an agronomically acceptable salt of a zwitterion as described hereinbefore.
  • T-5 wherein m, Q, R 3 , R 3a , R 4 , R 5 and Z are as defined above in Table 2, R 1 and R 2 are hydrogen and n is 0.
  • Table 6 This table discloses 49 specific compounds (6.001 to 6.049) of the formula (T-6):
  • T-6 wherein m, Q, R 3 , R 3a , R 4 , R 5 and Z are as defined above in Table 3, R 1 and R 2 are hydrogen and n is 0.
  • T-7 wherein m, Q, R 3 , R 3a , R 4 , R 5 and Z are as defined above in Table 1 , R 1 and R 2 are hydrogen and n is 0.
  • T-8 wherein m, Q, R 3 , R 3a , R 4 , R 5 and Z are as defined above in Table 2, R 1 and R 2 are hydrogen and n is 0.
  • This table discloses 49 specific compounds (9.001 to 9.049) of the formula (T-9): (T-9) wherein m, Q, R 3 , R 3a , R 4 , R 5 and Z are as defined above in Table 3, R 1 and R 2 are hydrogen and n is 0.
  • T-10 wherein m, Q, R 3 , R 3a , R 4 , R 5 and Z are as defined above in Table 1 , R 1 and R 2 are hydrogen and n is 0.
  • T-1 1 wherein m, Q, R 3 , R 3a , R 4 , R 5 and Z are as defined above in Table 2, R 1 and R 2 are hydrogen and n is 0.
  • This table discloses 49 specific compounds (12.001 to 12.049) of the formula (T-12): (T-12) wherein m, Q, R 3 , R 3a , R 4 , R 5 and Z are as defined above in Table 3, R 1 and R 2 are hydrogen and n is 0.
  • This table discloses 49 specific compounds (18.001 to 18.049) of the formula (T-18): (T-18) wherein m, Q, R 3 , R 3a , R 4 , R 5 and Z are as defined above in Table 3, R 1 and R 2 are hydrogen and n is 0.
  • This table discloses 49 specific compounds (21 .001 to 21 .049) of the formula (T-21): (T-21) wherein m, Q, R 3 , R 3a , R 4 , R 5 and Z are as defined above in Table 3, R 1 and R 2 are hydrogen and n is 0.
  • T-23 wherein m, Q, R 3 , R 3a , R 4 , R 5 and Z are as defined above in Table 2, R 1 and R 2 are hydrogen and n is 0.
  • This table discloses 49 specific compounds (27.001 to 27.049) of the formula (T-27): wherein m, Q, R 3 , R 3a , R 4 , R 5 and Z are as defined above in Table 3, R 1 and R 2 are hydrogen and n is 0.
  • T-36 wherein m, Q, R 3 , R 3a , R 4 , R 5 and Z are as defined in Table 3, R 1 and R 2 are hydrogen and n is 0.
  • T-42 wherein m, Q, R 3 , R 3a , R 4 , R 5 and Z are as defined in Table 3, R 1 and R 2 are hydrogen and n is 0.
  • the compounds of the present invention may be prepared according to the following schemes in which the substituents n, m, r, A 1 , A 2 , A 3 , A 4 , A 5 , 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 45 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 , A 1 , A 2 , A 3 , A 4 and A 5 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 inflate, 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.
  • a 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- /V-methoxyacetamide, sodium 2-bromoethanesulphonate, 2,2-dimethylpropyl 2- (trifluoromethylsulfonyloxy)ethanesulfonate, 2-bromo-A/-methanesulfonylacetamide, 3-bromo-A/- methanesulfonylpropanamide, dimethoxyphosphorylmethyl trifluoromethanesulfonate, dimethyl 3- bromopropylphosphonate, 3-chloro-2, 2-dimethyl-propanoic acid and diethyl 2-bromoethylphosphonat e.
  • 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 , A 1 , A 2 , A 3 , A 4 and A 5 are as defined for compounds of formula (I), with a suitably activated electrophilic alkene of formula (B), wherein Z is -S(0) 2 0R 10 , -P(0)(R 13 )(OR 10 ) or - C(0)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(0) 2 0H, may be prepared from a compound of formula (I), wherein m is 0, n is 0 and Z is C(0)OR 10 , by treatment with
  • reaction scheme 4 trimethylsilylchlorosulfonate in a suitable solvent at a suitable temperature, as described in reaction scheme 4.
  • Preferred conditions include heating the carboxylate precursor in neat
  • compounds of formula (I) may be prepared by reacting compounds of formula (X), wherein R 3 , R 3a , R 4 , R 5 , A 1 , A 2 , A 3 , A 4 and A 5 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
  • a compound of formula (I) wherein n, Q, Z, X, R 1 , R 2 , R 3 , R 3a , R 4 , R 5 , A 1 , A 2 , A 3 , A 4 and A 5 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.
  • Example oxidants include, but are not limited to, 2,3-dichloro-5,6-dicyano-1 ,4-benzoquinone, tetrachloro-p-benzoquinone, potassium permanganate, manganese dioxide, 2,2,6,6-tetramethyl-1 - piperidinyloxy and bromine. Related reactions are known in the literature. Reaction scheme 6
  • a compound of formula (R), wherein n, Q, Z, X, R 1 , R 2 , R 3 , R 3a , R 4 , R 5 , A 1 , A 2 , A 3 , A 4 and A 5 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 (XX).
  • Biaryl pyridines 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), in which compounds of formula (J) and formula (L), wherein M’ is either an organostannane, organoboronic acid or ester, organotrifluoroborate, organomagnesium, organocopper or organozinc, as outlined in reaction scheme 8.
  • 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., 201 1 , 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 crosscoupling 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 (XX), wherein R 3 , R 3a , R 4 and R 5 are as defined for compounds of formula (I), by metallation, as outlined in reaction scheme 9. Similar reactions are known in the literature (for example Ramphal et al, WO2015/153683, Unsinn et al., Organic Letters, 15(5), 1 128-1 131 ; 2013, Sadler et al., Organic & Biomolecular Chemistry, 12(37), 7318-7327; 2014.
  • an organometallic of formula (J) may be prepared from compounds 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 9.
  • Example conditions to prepare an compound of formula (J) wherein M’ is an organostannane include treatment of a compound of formula (K) with lithium tributyl tin in an appropriate solvent at an appropriate temperature (for example see WO 2010/038465).
  • Example conditions to prepare compound of formula (J) wherein M’ is an organostannane include treatment of a compound of formula (K) with lithium tributyl tin in an appropriate solvent at an appropriate temperature (for example see WO 2010/038465).
  • Example conditions to prepare compound of formula (J) wherein M’ is an organostannane include treatment of a compound of formula (K) with lithium tributyl
  • organoboronic acid or ester include treatment of a compound of formula (K) with bis(pinacolato) diboron, in the presence of an appropriate transition metal catalyst, appropriate ligand, appropriate base, in an appropriate solvent at an appropriate temperature (for example KR 2015135626).
  • biaryl pyridines 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 6-membered heteroaryl comprising A 1 , A 2 , A 3 , A 4 and A 5 , wherein A 1 , A 2 , A 3 , A 4 and A 5 are as defined for compounds of formula (I).
  • Such functional groups include, but are not limited to, acid, ester, nitrile, amide, thioamide and ketone.
  • 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.
  • 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, A/,A/-dimethylformamide, dimethyl sulfoxide, 1 ,4- dioxane, di
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
  • a large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface- active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of
  • Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.
  • compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives.
  • the amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied.
  • the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively).
  • Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
  • 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 are:
  • active ingredient 1 to 95 %, preferably 60 to 90 %
  • surface-active agent 1 to 30 %, preferably 5 to 20 %
  • liquid carrier 1 to 80 %, preferably 1 to 35 %
  • active ingredient 0.1 to 10 %, preferably 0.1 to 5 %
  • solid carrier 99.9 to 90 %, preferably 99.9 to 99 %
  • active ingredient 5 to 75 %, preferably 10 to 50 %
  • surface-active agent 1 to 40 %, preferably 2 to 30 %
  • 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 %
  • 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.
  • mixtures include (wherein “I” represents a compound of formula (I)):- 1 + acetochlor, I + acifluorfen (including acifluorfen-sodium), I + aclonifen, I + ametryn, I + amicarbazone, I + aminopyralid, I + aminotriazole, I + atrazine, I + beflubutamid-M, 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), I + cloransulam (including cloransulam-methyl), l+ chlorimuron (including chlorimuron-ethyl), I
  • 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 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.
  • weeds unwanted plants
  • 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 commercially available under the trade names RoundupReady® and LibertyLink®.
  • 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.
  • 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 waterto give suspensions of the desired concentration.
  • 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.
  • 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.
  • nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
  • silicone oil (in the form of a 75 % emulsion in water) 1 %
  • 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.
  • 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.
  • Boc fe/ -butyloxycarbonyl
  • HPLC high-performance liquid chromatography (description of the apparatus and the methods used for HPLC are given below)
  • 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:
  • Solvent A Water with 0.05% Trifluoroacetic Acid
  • Solvent B Acetonitrile with 0.05% Trifluoroacetic Acid
  • Step 1 Preparation of 4-(4-pyridyl)pyrimidine
  • 4-chloropyrimidine 0.5 g
  • tripotassium phosphate 3.71 g
  • 4-(4,4,5,5-tetramethyl-1 ,3,2- dioxaborolan-2-yl)pyridine 1 .35 g
  • dimethoxyethane (16.35 ml_)
  • [1 ,1 - bis(diphenylphosphino)ferrocene]palladium(ll) dichloride dichloromethane adduct 0.356 g
  • water 3.5 mL
  • reaction mixture was partitioned between water and dichloromethane.
  • the organic phase was dried over magnesium sulfate, concentrated then purified by silica gel chromatography eluting with 0-70% acetonitrile in dichloromethane to give 4-(4-pyridyl)pyrimidine as a yellow solid.
  • Step 2 Preparation of methyl 2-(4-pyrimidin-4-ylpyridin-1 -ium-1 -yl)acetate 2,2,2-trifluoroacetate A7
  • Step 4 Preparation of (4-pyrimidin-4-ylpyridin-1 -ium-1 -yl)methanesulfonate A2
  • Step 1 Preparation of 3-methyl-5-(4-pyridyl)-1 ,2,4-triazine
  • Step 2 Preparation of methyl 2-[4-(3-methyl-1 ,2,4-triazin-5-yl)pyridin-1 -ium-1 -yl]acetate 2,2,2- trifluoroacetate
  • methyl 2-bromoacetate (0.66 ml_) and the mixture was heated at 80°C for 24 hours. After cooling to room temperature solvents were removed in vacuo and the residue was partitioned between water (10 ml_) and dichloromethane (20 ml_).
  • the aqueous layer was purified by preparative reverse phase HPLC (trifluoroacetic acid was present in the eluent) to afford 2-[4-(3-methyl-1 ,2,4-triazin-5-yl) pyridin-1 -ium-1 - yljacetate 2,2,2-trifluoroacetate as a brown gum.
  • Step 3 Preparation of 2-[4-(3-methyl-1 ,2,4-triazin-5-yl)pyridin-1 -ium-1 -yl]acetic acid chloride
  • A6 A mixture of methyl 2-[4-(3-methyl-1 ,2,4-triazin-5-yl)pyridin-1 -ium-1 -yl]acetate 2,2,2-trifluoroacetate (0.29 g) and 2M aqueous hydrochloric acid (5.67 ml_) was heated at 50°C for 20 hours. The reaction mixture was concentrated and triturated with acetone to give 2-[4-(3-methyl-1 ,2,4-triazin-5-yl)pyridin-1 - ium-1 -yl]acetic acid chloride as a beige solid.
  • Step 1 Preparation of pyridine-4-carboxamidine hydrochloride
  • Step 2 Preparation of [(E)-2-cyano-3-(dimethylamino)prop-2-enylidene]-dimethyl-ammonium 2- hyd roxy-2-oxo-acetate
  • Step 3 Preparation of 2-(4-pyridyl)pyrimidine-5-carbonitrile
  • reaction mixture was concentrated and chromatographed then purified by silica gel chromatography eluting with 0-100% ethyl acetate in cyclohexane to give 2-(4-pyridyl)pyrimidine-5-carbonitrile.
  • Step 4 Preparation of 3-[4-(5-cyanopyrimidin-2-yl)pyridin-1 -ium-1 -yl]propanoic acid bromide
  • A4 A mixture of 2-(4-pyridyl)pyrimidine-5-carbonitrile (0.2 g), 3-bromopropionic acid (0.208 g) and acetonitrile (4 mL) was heated at 85°C for 24 hours.
  • Step 1 Preparation of 4-bromo-6-(trifluoromethyl)pyridazin-3-amine
  • Step 4 Preparation of ethyl 2-[4-[6-(trifluoromethyl)pyridazin-4-yl]pyridin-1 -ium-1 -yl]acetate bromide
  • Step 5 Preparation of 2-[4-[6-(trifluoromethyl)pyridazin-4-yl]pyridin-1 -ium-1 -yljacetic acid 2,2,2- trifluoroacetate A6
  • aqueous phase was filtered and purified by preparative reverse phase HPLC (trifluoroacetic acid was present in the eluent) to give methyl 3-[4-(3-methyl-1 ,2,4-triazin-5-yl)pyridin-1 -ium-1 -yl]propanoate 2,2,2-trifluoroacetate as a yellow gum.
  • Step 2 Preparation of 3-[4-(3-methyl-1 ,2,4-triazin-5-yl)pyridin-1 -ium-1 -yl]propanoic acid chloride A61 A solution of methyl 3-[4-(3-methyl-1 ,2,4-triazin-5-yl)pyridin-1 -ium-1 -yl]propanoate 2,2,2- trifluoroacetate (0.39 g) and 2M aqueous hydrochloric acid (7.33 mL) was heated at 80°C for 4 hours. The reaction mixture was cooled to room temperature and allowed to stand overnight.
  • Step 1 Preparation of 4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-1 ,2,3,6-tetrahydropyridine hydrochloride
  • Step 2 Preparation of tert-butyl 2-[4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-3,6-dihydro-2H- pyridin-1 -yl]acetate
  • Step 3 Preparation of tert-butyl 2-(4-pyridazin-4-yl-3,6-dihydro-2H-pyridin-1 -yl)acetate
  • a microwave vial was charged with 4-bromopyridazine;hydrobromide (0.831 g), tert-butyl 2-[4- (4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-3,6-dihydro-2H-pyridin-1 -yl]acetate (1 .12 g), cyclopentyl(diphenyl)phosphane dichloropalladium iron (0.254 g), 1 ,4-dioxane (6.93 ml_), water (6.93 ml_) and sodium carbonate (1 .47 g), purged with nitrogen, then heated at 120°C under microwave irradiation for 30 minutes.
  • reaction mixture was partitioned between water and dichloromethane.
  • the aqueous was then extracted with further dichloromethane (x2).
  • the combined organic extracts were dried with magnesium sulfate, concentrated and purified by silica gel chromatography eluting with a mixture of methanol and dichloromethane to give tert-butyl 2-(4-pyridazin-4-yl-3,6-dihydro-2H- pyridin-1 -yl)acetate as an orange gum.
  • Step 4 Preparation of 2-(4-pyridazin-1 -ium-4-yl-1 ,2,3,6-tetrahydropyridin-1 -ium-1 -yl)acetic acid 2,2,2- trifluoroacetate
  • Step 5 Preparation of 2-(4-pyridazin-4-ylpyridin-1 -ium-1 -yl)acetic acid 2,2,2-trifluoroacetate
  • Step 3 Preparation of 3-[4-pyrimidin-2-yl-2-(trifluoromethyl)pyridin-1 -ium-1 -yl]propane-1 -sulfonate A16 A mixture of 2-[2-(trifluoromethyl)-4-pyridyl]pyrimidine (0.35 g) and oxathiolane 2,2-dioxide (3.797 g) was heated at 100°C for 40 hours.
  • Example 1 Preparation of ethyl 5-(4-pyridyl ' )pyridazine-3-carboxylate
  • Step 1 Preparation of 5-chloro-3-vinyl-pyridazine A microwave vial was charged with 3,5-dichloropyridazine (1 g), 4,4,5,5-tetramethyl-2-vinyl-1 ,3,2- dioxaborolane (1 .03 g), potassium carbonate (2.81 g), cyclopentyl(diphenyl)phosphane
  • dichloropalladium iron (0.049 g), 1 ,4-dioxane (10.1 ml_) and water (4.03 ml_), purged with nitrogen, then heated at 120°C under microwave irradiation for 30 minutes.
  • the reaction mixture was partitioned between water and dichloromethane.
  • the organic phase was concentrated then purified by silica gel chromatography eluting with a mixture of ethyl acetate in iso-hexane to give 5-chloro-3-vinyl- pyridazine as a yellow solid.
  • a microwave vial was charged with 5-chloro-3-vinyl-pyridazine (0.24 g), 4-(4,4,5,5-tetramethyl-1 ,3,2- dioxaborolan-2-yl)pyridine (0.525 g), tripotassium phosphate (1 .45 g), [1 ,1 - bis(diphenylphosphino)ferrocene]palladium(ll) dichloride dichloromethane adduct (0.139 g), 1 ,2- dimethoxyethane (6.40 ml_) and water (1 .37 ml_), purged with nitrogen, then heated at 120°C under microwave irradiation for 30 minutes.
  • reaction mixture was partitioned between water and dichloromethane.
  • the organic phase was concentrated then purified by silica gel chromatography eluting with a mixture of acetonitrile in dichloromethane to give 5-(4-pyridyl)-3-vinyl-pyridazine as a white solid (190mg).
  • Step 3 Preparation of ethyl 5-(4-pyridyl)pyridazine-3-carboxylate
  • Potassium permanganate (0.634 g) was added portion wise to a stirred solution of 5-(4-pyridyl)-3- vinyl-pyridazine (0.147 g) in acetone (6.42 ml_) and water (6.42 ml_), then stirred at room temperature for 3 hours.
  • the reaction mixture was filtered and solid sodium metabisulfite was added to the filtrate until the purple colour disappeared.
  • the solution was concentrated and the residue was suspended in ethanol (49.7 ml_) and cone sulfuric acid (0.802 ml_) was added. The mixture was heated at reflux for 2 hours then cooled to room temperature and allowed to stand overnight. Further cone sulfuric acid (0.802 ml_) was added and the mixture was heated at reflux overnight.
  • a microwave vial was charged with tributyl(4-pyridyl)stannane (2.209 g), 2-chloropyrimidine (0.722 g), palladium (0) tetrakis(triphenylphosphine) (0.354 g) and 1 ,4-dioxane (18 ml_), sparged with nitrogen for 3 minutes, then heated at 140°C under microwave irradiation for 2x1 hours. The mixture was concentrated then purified by silica gel chromatography eluting with a mixture of ethyl acetate and cyclohexane to give 2-(4-pyridyl)pyrimidine as a pale brown solid.
  • Step 2 Preparation of (4-pyrimidin-2-ylpyridin-1 -ium-1 -yl)methyl sulfate A96
  • Step 1 Preparation of dibutyl chloromethyl phosphate
  • Step 2 Preparation of dibutyl (4-pyrimidin-2-ylpyridin-1 -ium-1 -yl)methyl phosphate chloride A98
  • a microwave vial was charged with dibutyl chloromethyl phosphate (0.232 g), 2-(4-pyridyl)pyrimidine (0.1 g) and acetonitrile then heated at 60°C under microwave irradiation for 80 minutes. The mixture was then heated at 50°C under microwave irradiation for 3 hours. The mixture was purified by preparative reverse phase HPLC (trifluoroacetic acid was present in the eluent) to give dibutyl (4- pyrimidin-2-ylpyridin-1 -ium-1 -yl)methyl phosphate chloride.
  • Butyl (4-pyrimidin-2-ylpyridin-1 -ium-1 -yl)methyl hydrogen phosphate 2,2,2-trifluoroacetate A97 was also isolated from this reaction as a brown gum.
  • Step 1 Preparation of 3-methylsulfanyl-5-(4-pyridyl)-1 ,2,4-triazine
  • reaction mass was diluted with ethyl acetate (100 mL) and washed with brine (2 x 100 mL).
  • the organic layer was dried over anhydrous sodium sulfate, concentrated and purified by silica gel chromatography eluting with 30% ethyl acetate in cyclohexane to afford 3-methylsulfanyl-5- (4-pyridyl)-1 ,2,4-triazine as a yellow solid.
  • Step 2 Preparation of 3-[4-(3-methylsulfanyl-1 ,2,4-triazin-5-yl)pyridin-1 -ium-1 -yl]propanoic acid 2,2,2- trifluoroacetate A22
  • Example 15 Preparation of 3-[4-(6-methylsulfanyl-1 ,2,4,5-tetrazin-3-yl)pyridin-1 -ium-1 -yllpropanoic acid chloride A21 Step 1 : Preparation of 1 ,3-diamino-2-methyl-isothiourea hydroiodide
  • Step 2 Preparation of 3-methylsulfanyl-6-(4-pyridyl)-1 ,2-dihydro-1 ,2,4,5-tetrazine
  • Step 3 Preparation of 3-methylsulfanyl-6-(4-pyridyl)-1 ,2,4,5-tetrazine
  • Step 4 Preparation of methyl 3-[4-(6-methylsulfanyl-1 ,2,4,5-tetrazin-3-yl)pyridin-1 -ium-1 -yl]propanoate bromide A58
  • Step 5 Preparation of 3-[4-(6-methylsulfanyl-1 ,2,4,5-tetrazin-3-yl)pyridin-1 -ium-1 -yl]propanoic acid chloride A21
  • Ipomoea hederacea IPHE
  • Euphorbia heterophylla EPHHL
  • Chenopodium album CHEAL
  • Amaranthus palmeri AMAPA
  • Lolium perenne LLOLPE
  • Digitaria sanguinalis DIGSA
  • Eleusine indica ELEIN
  • Echinochloa crus-galli EHCG
  • Setaria faberi SETFA

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

Abstract

L'invention concerne des composés de formule (I) dans laquelle les substituants sont tels que définis dans la revendication 1, utiles en tant que pesticides, en particulier en tant qu'herbicides.
PCT/EP2020/052813 2019-02-06 2020-02-05 Composés de pyridinium herbicides Ceased WO2020161162A1 (fr)

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JP2022152762A (ja) * 2021-03-29 2022-10-12 三菱瓦斯化学株式会社 化合物、ゴム組成物、及び変性ジエン系ゴム
JP2022152764A (ja) * 2021-03-29 2022-10-12 三菱瓦斯化学株式会社 ゴム組成物、及び変性ジエン系ゴム
US11993580B1 (en) 2022-12-02 2024-05-28 Neumora Therapeutics, Inc. Methods of treating neurological disorders
WO2025185608A1 (fr) * 2024-03-04 2025-09-12 西藏海思科制药有限公司 Procédé de préparation d'un inhibiteur de pde4b

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022152762A (ja) * 2021-03-29 2022-10-12 三菱瓦斯化学株式会社 化合物、ゴム組成物、及び変性ジエン系ゴム
JP2022152764A (ja) * 2021-03-29 2022-10-12 三菱瓦斯化学株式会社 ゴム組成物、及び変性ジエン系ゴム
JP7627428B2 (ja) 2021-03-29 2025-02-06 三菱瓦斯化学株式会社 ゴム組成物、及び変性ジエン系ゴム
JP7727259B2 (ja) 2021-03-29 2025-08-21 三菱瓦斯化学株式会社 化合物、ゴム組成物、及び変性ジエン系ゴム
US11993580B1 (en) 2022-12-02 2024-05-28 Neumora Therapeutics, Inc. Methods of treating neurological disorders
US12371414B2 (en) 2022-12-02 2025-07-29 Neumora Therapeutics, Inc. Methods of treating neurological disorders
WO2025185608A1 (fr) * 2024-03-04 2025-09-12 西藏海思科制药有限公司 Procédé de préparation d'un inhibiteur de pde4b

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