[go: up one dir, main page]

WO2020099404A1 - Herbicidal compounds - Google Patents

Herbicidal compounds Download PDF

Info

Publication number
WO2020099404A1
WO2020099404A1 PCT/EP2019/081022 EP2019081022W WO2020099404A1 WO 2020099404 A1 WO2020099404 A1 WO 2020099404A1 EP 2019081022 W EP2019081022 W EP 2019081022W WO 2020099404 A1 WO2020099404 A1 WO 2020099404A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
hydrogen
phenyl
c6alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2019/081022
Other languages
French (fr)
Inventor
James Nicholas Scutt
Nigel James Willetts
Sean NG
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syngenta Crop Protection AG Switzerland
Original Assignee
Syngenta Crop Protection AG Switzerland
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Syngenta Crop Protection AG Switzerland filed Critical Syngenta Crop Protection AG Switzerland
Publication of WO2020099404A1 publication Critical patent/WO2020099404A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to herbicidally active thiadiazole 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 in controlling undesirable plant growth: in particular the use in controlling weeds, in crops of useful plants.
  • the present invention is based on the finding that thiadiazole derivatives of formula (I) as defined herein, exhibit surprisingly good herbicidal activity.
  • R 1 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl, C2-C6alkenyl, C2- Cealkynyl, Cs-Cecycloalkyl, Ci-Cehaloalkyl, -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 15 ;
  • R 2 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl and Ci-C6haloalkyl; 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;
  • R 1 is selected from the group consisting of -OR 7 , -OR 15a , -N(R 6 )S(0)2R 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 15 , then R 2 is selected from the group consisting of hydrogen and Ci-C6alkyl;
  • R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, -S(0) r R 15 , Ci- Cealkyl, Ci-C6fluoroalkyl, Ci-C6fluoroalkoxy, Ci-C6alkoxy, C3-C6cycloalkyl and -N(R 6 )2;
  • Q is (CR 1a R 2b ) m ;
  • n 0, 1 , 2 or 3;
  • each R 1a and R 2b are independently selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, -OH, -OR 7 , -OR 15a , -NH 2 , -NHR 7 , -NHR 15a , -N(R 6 )CHO, -NR 7b R 7c and - S(0)rR 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 from N and O;
  • each R 6 is independently selected from hydrogen and Ci-Cealkyl
  • each R 7 is independently selected from the group consisting of Ci-Cealkyl, -S(0) 2 R 15 , -C(0)R 15 , -C(0)OR 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)OR 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)OR 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;
  • A is a 5-membered heteroaryl ring comprising 1 , 2, 3 or 4 heteroatoms each independently selected from the group consisting of N, O and S, wherein said 5-membered heteroaryl ring is optionally substituted by 1 , 2, or 3 R 8 substituents; and when A is a 5-membered heteroaryl ring substituted by R 8 on one or more ring carbon atoms, each of said R 8 substitutents is independently selected from the group consisting of halogen, nitro, cyano, -NH2, -NHR 7 , -N(R 7 )2, -OH, -OR 7 , - S(0) r R 15 , -NR 6 S(0) R 15 , -C(0)OR 10 , -C(0)R 15 , -C(0)NR 16 R 17 , -S(0) NR 16 R 17 , Ci-Cealkyl, Ci- Cehaloalkyl, C3-C6cycloalkyl, C3-C6halocyclo
  • R 8 is selected from the group consisting of -OR 7 , Ci-C6alkyl, Ci-C6haloalkyl, C3-C6cycloalkyl, C3- Cehalocycloalkyl, C3-C6cycloalkoxy, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Ci-C3alkoxyCi- C3alkyl-, Ci-C3alkoxyCi-C3alkoxy-, Ci-C6haloalkoxy, Ci-C3haloalkoxyCi-C3alkyl-, C3-C6alkenyloxy and C3-C6alkynyloxy;
  • each R 9 is independently selected from the group consisting of -OH, halogen, cyano, -N(R 6 )2, Ci-C 4 alkyl, Ci-C 4 alkoxy, Ci-C 4 haloalkyl and Ci-C 4 haloalkoxy;
  • X is independently selected from the group consisting of C3-C6cycloalkyl, phenyl, a 5- or 6- membered heteroaryl, which comprises 1 , 2, 3 or 4 heteroatoms independently selected from N, O and S, and a 4- to 6- membered heterocyclyl, which comprises 1 , 2 or 3 heteroatoms independently 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, which may be the same or different, 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 0 or 1 ;
  • Z is selected from the group consisting of -C(0)OR 1 °, -CH2OH, -CHO, -C(0)NHOR 11 , -
  • 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 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-C6haloalkyl
  • 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;
  • 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;
  • an agrochemical composition comprising a herbicidally effective amount of a compound of formula (I).
  • Such an agricultural composition may further comprise at least one additional active ingredient and/or an agrochemically acceptable diluent or carrier.
  • 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-C 4 alkyl and Ci- C2alkyl are to be construed accordingly.
  • Examples of Ci-C6alkyl 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- Cealkyl radical as generally defined above. Ci-C 4 alkoxy is to be construed accordingly. Examples of Ci- 4 alkoxy 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-C 4 haloalkyl 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.
  • C2-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 (Z)-configuration, having from two to six carbon atoms, which is attached to the rest of the molecule by a single bond.
  • C 2 -C 4 alkenyl is to be construed accordingly.
  • Examples of C2-C6alkenyl include, but are not limited to, prop-1-enyl, allyl (prop-2-enyl) and but-1-enyl.
  • C2-C6haloalkenyl refers to a C2-C6alkenyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • Examples of C2-C6haloalkenyl include, but are not limited to chloroethylene, fluoroethylene, 1 , 1-difluoroethylene, 1 , 1-dichloroethylene and 1 ,1 ,2-trichloroethylene.
  • C2-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.
  • C 2 -C 4 alkynyl is to be construed accordingly.
  • Examples of C2-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-C 4 haloalkoxy 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-0-R a - 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 - O- 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.
  • R a is a C3-C6alkynyl radical as generally defined above.
  • the term“hyd roxyCi -Ceal kyl” 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)OR 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 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).
  • 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, dependant 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 thiadiazolium cation) and the integers j, k and q may be selected from 1 , 2 or 3, dependent upon the charge of the respective anion Y and respective cation M.
  • a compound of formula (l-ll) wherein k is 2, j is 1 and Y is selected from the group consisting of halogen, trifluoroacetate and pentafluoropropionate.
  • a nitrogen atom in ring A may be protonated or a nitrogen atom comprised in R 1 , R 2 , Q or X may be protonated.
  • k is 2, j is 1 and Y is chloride, wherein a nitrogen atom in ring A is protonated.
  • Suitable agronomically acceptable salts of the present invention include but are not limited chloride, bromide, iodide, fluoride, 2-naphthalenesulfonate, acetate, adipate, methoxide, ethoxide, propoxide, butoxide, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, butylsulfate, butylsulfonate, butyrate, camphorate, camsylate, caprate, caproate, caprylate, carbonate, citrate, diphosphate, edetate, edisylate, enanthate, ethanedisulfonate, ethanesulfonate, ethylsulfate, formate, fumarate, gluceptate, gluconate, glucoronate, glutamate, glycerophosphate, hepta
  • Suitable cations represented by M include, but are not limited to, metals, conjugate acids of amines and organic cations.
  • suitable metals include aluminium, calcium, cesium, copper, lithium, magnesium, manganese, potassium, sodium, iron and zinc.
  • Suitable amines include allylamine, ammonia, amylamine, arginine, benethamine, benzathine, butenyl-2-amine, butylamine, butylethanolamine, cyclohexylamine, decylamine, diamylamine, dibutylamine, diethanolamine, diethylamine, diethylenetriamine, diheptylamine, dihexylamine, diisoamylamine, diisopropylamine, dimethylamine, dioctylamine, dipropanolamine, dipropargylamine, dipropylamine, dodecylamine, ethanolamine, ethylamine, ethylbutylamine, ethylenediamine, ethylheptylamine, ethyloctylamine, ethylpropanolamine, heptadecylamine, heptylamine, hexadecylamine, he
  • Suitable organic cations include benzyltributylammonium, benzyltrimethylammonium, benzyltriphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, tetraethylammonium, tetraethylphosphonium, tetramethylammonium, tetramethylphosphonium, tetrapropylammonium, tetrapropylphosphonium, tributylsulfonium, tributylsulfoxonium, triethylsulfonium, triethylsulfoxonium, trimethylsulfonium, trimethylsulfoxonium, tripropylsulfonium and tripropylsulfoxonium.
  • Preferred compounds of formula (I), wherein Z comprises an acidic proton can be represented as either (l-l) or (l-ll).
  • Y is chloride, bromide, iodide, hydroxide, bicarbonate, acetate, pentafluoropropionate, triflate, trifluoroacetate, methylsulfate, tosylate and nitrate, wherein j and k are 1.
  • Y is chloride, bromide, iodide, hydroxide, bicarbonate, acetate, trifluoroacetate, methylsulfate, tosylate and nitrate, wherein j and k are 1.
  • emphasis is also given to salts when Y is carbonate and sulfate, wherein j is 2 and k is 1 , and when Y is phosphate, wherein j is 3 and k is 1.
  • R 1 , R 2 , R 3 , A and Z are as defined for compounds of formula (I).
  • R 1 , R 2 , R 1a , R 2b , R 3 , A and Z are as defined for compounds of formula (I).
  • R 1 , R 2 , R 1a , R 2b , R 3 , A and Z are as defined for compounds of formula (I).
  • R 1 , R 2 , R 1a , R 2b , R 3 , A and Z are as defined for compounds of formula (I).
  • R 18 with reference to the compounds of formula (I) according to the invention.
  • R 1 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl, C2-C6alkenyl, C2- Cealkynyl, Cs-Cecycloalkyl, Ci-Cehaloalkyl, -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 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)OR 15 , -NHC(0)NR 16 R 17 , -N(R 7a ) 2 and -S(0 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.
  • R 1 is selected from the group consisting of hydrogen, Ci-C6alkyl, -OR 7 and -N(R 7a )2. 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- Cefluoroalkyl. 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)2R 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 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)OR 15 , -NHC(0)NR 16 R 17 , -N(R 7a ) 2 and -S(0)rR 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.
  • m is 0, 1 , 2 or 3.
  • m is 0, 1 , or 2. More preferably, m is 1 or 2. Most preferably, m is 1.
  • Each R 1a and R 2b are independently selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, -OH, -OR 7 , -OR 15a , -NH 2 , -NHR 7 , -NHR 15a , -N(R 6 )CHO, -NR 7b R 7c and - S(0)rR 15 .
  • each R 1a and R 2b are independently selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-C6fluoroalkyl, -OH, -NH2 and -NHR 7 .
  • each R 1a and R 2b are independently selected from the group consisting of hydrogen, Ci-Cealkyl, -OH and -NH2. Even more preferably, each R 1a and R 2b are independently selected from the group consisting of hydrogen, methyl, -OH and -NH2. 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 is hydrogen, Ci-C6alkyl, -C(0)NH 2 , and -C(0)Ci-C6alkyl; more preferably hydrogen, Ci-C6alkyl, or Ci-C6alkoxy, and more preferably still, hydrogen or methyl. Most preferably R 3 is hydrogen.
  • 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)OR 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)OR 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)OR 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.
  • A is a 5-membered heteroaryl attached to the rest of the molecule via a ring carbon atom, which comprises 1 , 2, or 3 heteroatoms independently selected from the group consisting of N, O and S, and wherein the heteroaryl is optionally substituted (where feasible) by 1 , 2 or 3 R 8 substituents, which may be the same or different.
  • A is a heteroaryl selected from the group consisting of 1 ,2,3,5-oxatriazol-4-yl, 1 ,2,3,5-thiatriazol-4-yl, 1 ,2,4-oxadiazol-3-yl, 1 ,2,4-oxadiazol-5-yl, 1 ,2,4-thiadiazol-3-yl, 1 ,2,4-thiadiazol- 5-yl, 1 ,2,4-triazol-3-yl, 1 ,2,4-triazol-5-yl, 1 ,2,5-oxadiazol-3-yl, 1 ,2,5-thiadiazol-3-yl, 1 ,3,4-oxadiazol-2-yl, 1 ,3,4-thiadiazol-2-yl, 2-furyl, 2-thienyl, 3-furyl, 3-thienyl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, isothiazol-3-yl
  • A is a heteroaryl selected from the group consisting of tetrazol-5-yl, 1 ,2,4- triazol-3-yl, 1 ,2,4-triazol-5-yl, isoxazol-3-yl, oxazol-2-yl, thiazol-2-yl, 1 ,3,4-thiadiazol-2-yl, triazol-4-yl, triazol-5-yl, pyrazol-3-yl, pyrazol-5-yl, 1 ,3,4-oxadiazol-2-yl, 1 ,2,4-thiadiazol-5-yl, oxazol-4-yl, imidazol- 2-yl, isothiazol-5-yl, 2-thienyl, 3-furyl, 2-furyl, isothiazol-4-yl, thiazol-4-yl, 3-thienyl, imidazol-5-yl, isoxazol-5-yl and 1 ,2,
  • A is selected from the group consisting of formula A-l to A-XXVIII below:
  • the jagged line defines the point of attachment to the rest of the molecule
  • R 8a , R 8b , R 8c , R 8d R 6 , R 7 , R 10 , R 15 , R 16 and R 17 are as defined herein.
  • R 8a , R 8b , R 8c , R 8d are examples of R 8 wherein the subscript letter a, b, c and d are used to denote positions within indvidual heterocycles (A- 1 to A-XXVIII).
  • A is selected from the group consisting of formula A-l to A-VIII below
  • R 8a , R 8b , R 8c , R 8d and R 7 is as defined herein. Yet, even more preferably still, A is selected from the group consisting of formula A-la to A-Vllla below
  • A is selected from A-lla, A-Vla and A-Vlla as described above.
  • each R 8 is independently selected from the group consisting of halogen, nitro, cyano, -NH2, -NHR 7 , -N(R 7 )2, -OH, -OR 7 , -S(0) r R 15 , - NR 6 S(0) R 15 , -C(0)OR 10 , -C(0)R 15 , -C(0)NR 16 R 17 , -S(0) NR 16 R 17 , Ci-Cealkyl, Ci-Cehaloalkyl, C 3 - C6cycloalkyl, C3-C6halocycloalkyl, C3-C6cycloalkoxy, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Ci- C3alkoxyCi-C3alkyl-, hydroxyCi-Cealkyl-, Ci-C3alkoxyCi-C3alkoxyCi-C3alkoxyCi-C3alky
  • each R 8 is independently selected from the group consisting of halogen, nitro, cyano, -NH2, -NHR 7 , -N(R 7 )2, -OH, -OR 7 , -S(0) r R 15 , -NR 6 S(0) R 15 , -C(0)OR 10 , -C(0)R 15 , -C(0)NR 16 R 17 , -S(0) NR 16 R 17 , Ci-Cealkyl, Ci-Cehaloalkyl, C 3 - C6cycloalkyl, Ci-C3alkoxyCi-C3alkyl-, hydroxyCi-Cealkyl-, Ci-C3alkoxyCi-C3alkoxy-, Ci-Cehaloalkoxy, phenyl and a 6- membered heteroaryl, which comprises 1 or 2 nitrogen atoms, and wherein said phenyl or heteroaryl are optional
  • each R 8 is independently selected from the group consisting of halogen, nitro, cyano, -NH2, -NHR 7 , -N(R 7 )2, -OH, - OR 7 , -S(0) r R 15 , -NR 6 S(0) R 15 , -C(0)OR 10 , -C(0)R 15 , -C(0)NR 16 R 17 , -S(0) NR 16 R 17 , Ci-Cealkyl, Ci- Cehaloalkyl, C3-C6cycloalkyl, hydroxyCi-Cealkyl-, Ci-Cehaloalkoxy and a 6- membered heteroaryl, which comprises 1 or 2 nitrogen atoms, and wherein said heteroaryl is optionally substituted by 1 R 9 substituent.
  • each R 8 is independently selected from the group consisting of halogen, cyano, -NH2, -NHR 7 , -N(R 7 )2, -OH, -OR 7 , -S(0) r R 15 , -C(0)OR 1 °, -C(0)R 15 , -C(0)NR 16 R 17 , Ci-Cealkyl and Ci-Cehaloalkyl.
  • each R 8 is independently selected from the group consisting of chloro, fluoro, cyano, -NH2, -NHMe, -NMe2, -OH, - OMe, -S(0) 2 Me, -C(0)0Me, -C(0)0H, -C(0)Me, -C(0)NH 2 , -C(0)NHMe, -C(0)NMe 2 , methyl, iso- propyl and trifluoromethyl.
  • each R 8 is independently selected from the group consisting of chloro, -NH 2 , -NHMe, -OMe, methyl, / ' so-propyl and trifluoromethyl.
  • R 8 substituents selected from the group consisting of -OR 7 , Ci-C6alkyl, Ci-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, C3- C6cycloalkoxy, C 2 -C6alkenyl, C 2 -C6haloalkenyl, C 2 -C6alkynyl, Ci-C3alkoxyCi-C3alkyl-, hydroxyC-i- Cealkyl-, Ci-C3alkoxyCi-C3alkoxy-, Ci-C6haloalkoxy, Ci-C3haloalkoxyCi-C3alkyl-, C3-C6alkenyloxy and C3-C6alkynyloxy.
  • said R 8 is selected from the group consisting of -OR 7 , Ci-C6alkyl and Ci- Cehaloalkyl. More preferably, each of said R 8 is -OR 7 or Ci-C6alky. Even more preferably still, each of said R 8 is Ci-C6alky. Most preferably said R 8 is methyl.
  • R 8a (substituted on a ring nitrogen atom) is selected from the group consisting of hydrogen, Ci-C6alkyl and Ci-C6haloalkyl
  • each R 8b , R 8c and R 8d (substituted on a ring carbon atom) are independently selected from the group consisting of hydrogen, 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-Cealkyl and Ci-Cehaloalkyl.
  • R 8a is hydrogen or Ci-C6alkyl and each R 8b , R 8c and R 8d are independently selected from the group consisting of hydrogen, halogen, -NH 2 , -NHR 7 , -N(R 7 ) 2 , -OR 7 , Ci-C6alkyl and Ci-C6haloalkyl. More preferably, R 8a is hydrogen or methyl and each R 8b , R 8c and R 8d are independently selected from the group consisting of hydrogen, chloro, -NH 2 , -NHMe, -OMe, methyl, / ' so-propyl and trifluoromethyl.
  • R 8a (substituted on a ring nitrogen atom) is hydrogen or Ci-C6alkyl
  • each R 8b , R 8c and R 8d (substituted on a ring carbon atom) are independently selected from the group consisting of hydrogen, halogen, -NH 2 , -NHR 7 , -N(R 7 ) 2 , -OR 7 , Ci-C6alkyl and Ci-C6haloalkyl.
  • R 8a is hydrogen or methyl and each R 8b , R 8c and R 8d are independently selected from the group consisting of hydrogen, chloro, -NH 2 , -NHMe, -OMe, methyl, / ' so- propyl and trifluoromethyl.
  • 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.
  • 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. More preferably, each R 9 is independently selected from the group consisting of halogen and Ci-C 4 alkyl.
  • n is 0 or 1.
  • 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 independently selected from N, O and S, and a 4- to 6- membered heterocyclyl, which comprises 1 , 2 or 3 heteroatoms independently 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 and Z, or 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 and thus X is absent.
  • Z is selected from the group consisting of -C(0)OR 1 °, -CH2OH, -CHO, -C(0)NHOR 11 , - C(0)NHCN, -OC(0)NHOR 11 , -OC(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 , - OS(0) 2 NHCN, -0S(0) 2 NHS(0) 2 R 12 , -0S(0) 2
  • Z is selected from the group consisting of -C(0)OR 1 °, -C(0)NHOR 11 , - OC(0)NHOR 11 , -NR 6 C(0)NHOR 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 , -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 NHC(0)R 18 , -S(0) 2 NHS(0) 2 R 12 , -0S(0) 2 NHS(0) 2 R 12 , -0S(0) 2 NHS(0) 2 R 12 , -0S(0) 2 NHS(0) 2 R 12 , -0S(0) 2 NHC(0)R 18 , -NR 6 S(0) 2 NHC(0)R 18 , -N(OH
  • Z is selected from the group consisting of -C(0)OR 1 °, -C(0)NHOR 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 and - P(0)(R 13 )(OR 1 °).
  • Z is selected from the group consisting of -C(0)OR 1 °, -C(0)NHS(0) 2 R 12 , -S(0) 2 0R 10 , and -P(0)(R 13 )(OR 1 °).
  • Z is selected from the group consisting of -C(0)OH, -C(0)OCH3, - 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 OH, -P(0)(OH)( OCH 2 CH 3 ) and -P(0)(0CH 2 CH 3 )(0CH 2 CH 3 ).
  • Z is -C(0)OH or -S(0) 2 OH.
  • 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. Most preferably, R 10 is hydrogen.
  • 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- Cehaloalkyl, Ci-C6alkoxy, -OH, -N(R 6 )2 and phenyl. More preferably, R 12 is selected from the group consisting of Ci-C6alkyl, 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. Preferably, R 16 and R 17 are independently selected from the group consisting of hydrogen and methyl.
  • R 16 and R 17 together with the nitrogen atom to which they are attached form a 4- to 6-membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N, O and S.
  • R 16 and R 17 together with the nitrogen atom to which they are attached form a 5- to 6-membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N and O.
  • R 16 and R 17 together with the nitrogen atom to which they are attached form an pyrrolidyl, oxazolidinyl, imidazolidinyl, piperidyl, piperazinyl or morpholinyl group.
  • R 18 is selected from the group consisting of hydrogen, 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- Cealkyl, 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.
  • R 1 is hydrogen or Ci-C6alkyl
  • R 2 is hydrogen or methyl
  • Q is (CR 1a R 2b )
  • m is 0, 1 or 2
  • R 1a and R 2b are independently selected from the group consisting of hydrogen, Ci-C6alkyl, -OH and -NH2
  • R 3 is hydrogen or methyl
  • each R 6 is independently selected from hydrogen and methyl
  • each R 7 is Ci-C6alkyl
  • A is a 5-membered heteroaryl attached to the rest of the molecule via a ring carbon atom, said 5- membered heteroaryl heteroaryl comprising 1 , 2, 3 or 4 heteroatoms independently selected from the group consisting of N, O and S, and wherein said heteroaryl is optionally substituted, where feasible, by 1 , 2 or 3 R 8 substituents, which may be the same or different; and when A is substituted on one or more ring carbon atoms, each R 8 is
  • R 1 is hydrogen or methyl
  • R 2 is hydrogen or methyl
  • Q is (CR 1a R 2b )
  • m is 1 or 2
  • R 1a and R 2b are independently selected from the group consisting of hydrogen and methyl
  • R 3 is hydrogen
  • A is a heteroaryl selected from the group consisting of tetrazol- 5-yl, 1 ,2,4-triazol-3-yl, 1 ,2,4-triazol-5-yl, isoxazol-3-yl, oxazol-2-yl, thiazol-2-yl, 1 ,3,4-thiadiazol-2-yl, triazol-4-yl, triazol-5-yl, pyrazol-3-yl, pyrazol-5-yl, 1 ,3,4-oxadiazol-2-yl, 1 ,2, 4-th iadiazol-5-yl, oxazol-4-yl, imidazol-2-yl, isothia
  • the compound according to formula (I) is selected from the group consisting of a compound of formula (l-a*), (l-b*), (l-c*), (l-d*), (l-e*), (l-f*), (l-g*), (l-h*), (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-p), (l-q), (l-r) and (l-s), as shown below:
  • R 8a is hydrogen or Ci-C6alkyl
  • each R 8b , R 8c and R 8d are independently selected from the group consisting of hydrogen, halogen, -NH2, -NHR 7 , -N(R 7 )2, -OR 7 , Ci-C6alkyl and Ci-C6haloalkyl
  • Z is - C(0)0H or -S(0) 2 0H.
  • compounds of formula (l-d), (l-f), (l-g), (l-h), (I- n), (l-q) and (l-r) are particularly preferred.
  • 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), (I- mm), (l-nn), (l-pp), (l-qq), (l-rr) or (l-ss),
  • 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:
  • 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):
  • 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.
  • Table 1 1 This table discloses 49 specific compounds of the formula (T-1 1 ):
  • the compounds of the present invention may be prepared according to the following schemes in which the substituents n, m, r, A, Q, X, Z, R 1 , R 2 , R 1a , R 2b , R 2 , R 3 , R 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 39 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 and A are as defined for compounds of formula (I), with a suitable alkylating agent of formula (W), wherein R 1 , R 2 , Q, X, n and Z are as defined for compounds of formula (I) and LG is a suitable leaving group, for example, halide or pseudohalide such as triflate, mesylate or tosylate, in a suitable solvent at a suitable temperature, as described in reaction scheme 1.
  • a suitable alkylating agent of formula (W) wherein R 1 , R 2 , Q, X, n and Z are as defined for compounds of formula (I) and LG is a suitable leaving group, for example, halide or pseudohalide such as triflate, mesylate or tosylate, in a suitable solvent at a suitable temperature, as described in reaction scheme 1.
  • Example conditions include stirring a compound of formula (X) with an alkylating agent of formula (W) in a solvent, or mixture of solvents, such as acetone, dichloromethane, dichloroethane, N,N- dimethylformamide, acetonitrile, 1 ,4-dioxane, water, acetic acid or triflu roacetic acid at a temperature between -78°C and 150°C.
  • 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- N-methoxyacetamide, sodium 2-bromoethanesulphonate, 2,2-dimethylpropyl 2- (trifluoromethylsulfonyloxy)ethanesulfonate, 2-bromo-N-methanesulfonylacetamide, 3-bromo-N- methanesulfonylpropanamide, dimethoxyphosphorylmethyl trifluoromethanesulfonate, dimethyl 3- bromopropylphosphonate, 3-chloro-2, 2-dimethyl-propanoic acid, diethyl 2-bromoethylphosphonate and ethyl 3-(trifluoromethylsulfonyloxy)propanoate.
  • 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 and A 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 1 °) or -C(0)OR 1 ° 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.
  • n 0 and
  • 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 1 °, by treatment with trimethylsilylchloro sulfonate in a suitable solvent at a suitable temperature, as described in reaction scheme 4.
  • Preferred conditions include heating the carboxylate precursor in neat trimethylsilylchlorosulfonate at a temperature between 25°C and 150°C.
  • Preferred conditions include heating the a compound of formula (D) with sodium sulfite in water at a temperature between 30°C and 100°C.
  • An alkylating agent of formula (M) may include, but is not limited to, 2-chloroethyl trifluoromethanesulfonate. Reaction scheme 6
  • compounds of formula (I) may be prepared by reacting compounds of formula (X), wherein R 3 and A are as defined for compounds of formula (I), with a suitable alcohol of formula (WW), wherein R 1 , R 2 , Q, X, n and Z are as defined for compounds of formula (I), under Mitsunobu-type conditions such as those reported by Petit et al, Tet. Lett. 2008, 49 (22), 3663.
  • Suitable phosphines include triphenylphosphine
  • suitable azodicarboxylates include diisopropylazodicarboxylate
  • suitable acids include fluoroboric acid, triflic acid and bis(trifluoromethylsulfonyl)amine, as described in reaction scheme 7.
  • Such alcohols are either known in the literature or may be prepared by known literature methods.
  • R' C r C 6 alkyl
  • Compounds of formula (C), wherein A is as previously defined, may be prepared by the cyclisation of compounds of formula (P) using an appropriate reagent or a combination of reagents, example reagents include Lawesson’s reagent or phosphorus pentasulfide, alternatively ammonium sulfite followed by bromine, in an appropriate solvent, at an appropriate temperature, as outlined in reaction scheme 10. Examples of such a reaction are known in the literature, for example, Gevorgyan et al., Org. Lett., 2016, 18, 1804.
  • R' C 1 -C 6 alkyl
  • Compounds of formula (P), wherein A is as previously defined may be prepared from a compound of formula (A) by reaction with an appropriate diazo transfer reagent, for example, but not limited to, 4-acetamidobenzenesulfonyl azide, in the presence of a suitable base, in an appropriate solvent, at an appropriate temperature, as outlined in reaction scheme 1 1.
  • an appropriate diazo transfer reagent for example, but not limited to, 4-acetamidobenzenesulfonyl azide
  • a suitable base in an appropriate solvent, at an appropriate temperature, as outlined in reaction scheme 1 1.
  • R' C r C 6 alkyl
  • Compounds of formula (Q), wherein A and R 3 are as previously defined, may be prepared from compounds of formula (S) and a hydrazide of formula (U), optionally in the presence of a suitable acid, for example acetic acid, in an appropriate solvent, at an appropriate temperature, as outlined in reaction scheme 13. Examples of such reactions are known in the literature, for example, Semakin et al., Beilstein J. Org. Chem., 2016, 12, 2471. Hydrazide compounds of formula (U) are either known in the literature or may be prepared by known methods.
  • Compounds of formula (S), wherein A and R 3 are as previously defined are either known in the literature or may be prepared by known literature procedures, for example, Wolfe et al., J. Org. Chem., 1981 , 46, 294.
  • compounds of formula (X) may be prepared by the transition metal crosscoupling 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) are either an organostannane, organoboronic acid or ester, organotrifluoroborate, organomagnesium, organocopper or organozinc (M‘), as outlined in reaction scheme 14.
  • Hal is defined as a halogen or pseudo halogen, for example triflate, mesylate or tosylate.
  • Such cross-couplings include Stille (for example Stille, J. K. Angew. Chem. Int. Ed. Engl.
  • An organometallic of formula (J), which is either an organostannane, organoboronic acid or ester, organotrifluoroborate, organomagnesium, organolithium, organocopper or organozinc (M‘), may be prepared from a compound of formula (XX), wherein R 3 is defined for compounds of formula (I), by metallation, as outlined in reaction scheme 16.
  • Example conditions to prepare an organolithium of formula (J) include treatment of a compound of formula (XX) with methyl lithium in an appropriate solvent at an appropriate temperature, see, for example, Thomas, E. W.; Zimmerman, D. C. Synthesis, 1985, 10, 945).
  • an organometallic of formula (J) may be prepared from a compound of formula (K), wherein R 3 is as defined for a compound of formula (I) and Hal is defined as a halogen or pseudo halogen, for example triflate, mesylate or tosylate, as described in scheme 16.
  • Example conditions to prepare an organostannane of formula (J) include treatment of a compound of formula (K) with lithium tributyl tin in an appropriate solvent at an appropriate temperature, see, for example, WO 2010038465.
  • Example conditions to prepare an organoboronic acid or ester of formula (J) 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, see, for example, KR 2015135626).
  • Compounds of formula (K) and formula (XX) are either known in the literature or can be prepared by known methods.
  • compounds of formula (X), wherein A and R 3 are as previously defined may be prepared by C-H activation cross-coupling of compounds of formula (XX) and formula (H), in the presence of an appropriate transition metal catalyst, ligand and base, in a suitable solvent at a suitable temperature, as outlined in reaction scheme 15.
  • Hal is defined as a halogen or pseudo halogen, for example triflate, mesylate or tosylate. Examples of such reactions are known in the literature, for example, Chen et al, US20100152203.
  • Compounds of formula (H) and formula (XX) are known in the literature, or may be prepared by known literature methods.
  • biaryl thiadiazoles of formula (X) may be prepared by classical ring synthesis approaches starting from a compound of formula (ZZ), wherein T is a functional group which can be converted through one or more chemical steps into a 5-membered heteroaryl A, wherein A is as defined for compounds of formula (I).
  • Such functional groups include, but are not limited to, acid, ester, nitrile, amide, thioamide and ketone.
  • Related transformations are known in the literature.
  • Substituted thiadiazoles may be prepared using methodology outlined in the literature, for example, but are not limited to, Minkkiila, A. et al, Eur. J. Med. Chem.
  • 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 %
  • Wettable powders 1 to 40 %, preferably 2 to 30 % Wettable powders:
  • active ingredient 0.5 to 90 %, preferably 1 to 80 %
  • surface-active agent 0.5 to 20 %, preferably 1 to 15 %
  • solid carrier 5 to 95 %, preferably 15 to 90 %
  • active ingredient 0.1 to 30 %, preferably 0.1 to 15 %
  • solid carrier 99.5 to 70 %, preferably 97 to 85 %
  • composition of the present may further comprise at least one additional pesticide.
  • additional pesticide is a herbicide and/or herbicide safener.
  • compounds of formula (I) can be used in combination with one or more other herbicides to provide various herbicidal mixtures.
  • Specific examples of such mixtures include (wherein ⁇ ” represents a compound of formula (I)):- 1 + acetochlor; I + acifluorfen (including acifluorfen-sodium); I + aclonifen; I + alachlor; I + alloxydim; I + ametryn; I + amicarbazone; I + amidosulfuron; I + aminocyclopyrachlor ; I + aminopyralid; I + amitrole; I + asulam; I + atrazine; I + bensulfuron (including bensulfuron-methyl); I + bentazone; I + bicyclopyrone; I + bilanafos; I + bifenox; I + bispyribac-sodium; I + bixlozone; I + bromacil; I + bromoxynil; I + butachlor; I
  • the compound of formula (I) can also be used in mixtures with other agrochemicals such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual.
  • the mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1 : 100 to 1000: 1.
  • mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of compound of formula (I) with the mixing partner).
  • Compounds of formula (I) of the present invention may also be combined with herbicide safeners.
  • Preferred combinations include:- I + benoxacor, I + cloquintocet (including cloquintocet-mexyl); I + cyprosulfamide; I + dichlormid; I + fenchlorazole (including fenchlorazole-ethyl); I + fenclorim; I + fluxofenim; l+ furilazole I + isoxadifen (including isoxadifen-ethyl); I + mefenpyr (including mefenpyr-diethyl); I + metcamifen; I + N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino] benzenesulfonamide and I + oxabetrinil.
  • the safeners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14 th Edition (BCPC), 2006.
  • the reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO 02/34048, and the reference to fenchlorazole-ethyl also applies to fenchlorazole, etc.
  • the mixing ratio of compound of formula (l) to safener is from 100:1 to 1 : 10, especially from 20: 1 to 1 :1.
  • mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of compound of formula (I) with the safener).
  • the compounds of formula (I) of this invention are useful as herbicides.
  • the present invention therefore further comprises a method for controlling unwanted plants comprising applying to the said plants or a locus comprising them, an effective amount of a compound of the invention or a herbicidal composition containing said compound.
  • Controlling means killing, reducing or retarding growth or preventing or reducing germination.
  • the plants to be controlled are unwanted plants (weeds).
  • Locus means the area in which the plants are growing or will grow.
  • the rates of application of compounds of formula (I) may vary within wide limits and depend on the nature of the soil, the method of application (pre-emergence; post-emergence; application to the seed furrow; no tillage application etc.), the crop plant, the weed(s) to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • the compounds of formula (I) according to the invention are generally applied at a rate of from 10 to 2000 g/ha, especially from 50 to 1000 g/ha.
  • the application is generally made by spraying the composition, typically by tractor mounted sprayer for large areas, but other methods such as dusting (for powders), drip or drench can also be used.
  • Useful plants in which the 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.
  • 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.
  • 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. Furthermore, 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.
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • 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 ferf-butyloxycarbonyl
  • HPLC high-performance liquid chromatography (description of the apparatus and the methods used for HPLC are given below)
  • Electrospray positive and negative Cone (V) 20.00, Source Temperature (°C) 120, Cone Gas Flow (L/Hr.) 50
  • the preparative HPLC was conducted using an 11.4 minute run time (not using at column dilution, bypassed with the column selector), according to the following gradient table:
  • Solvent A Water with 0.05% Trifluoroacetic Acid
  • Solvent B Acetonitrile with 0.05% Trifluoroacetic Acid
  • Step 1 Preparation of ethyl 3-oxazol-2-yl-3-oxo-propanoate
  • Step 2 Preparation of ethyl 2-diazo-3-oxazol-2-yl-3-oxo-propanoate
  • reaction mixture was partitioned with dichloromethane and the aqueous phase was carefully acidified to pH1 using concentrated hydrochloric acid.
  • the resulting precipitate was filtered off and washed with diethyl ether to give 5-oxazol-2- ylthiadiazole-4-carboxylic acid as a beige solid.
  • Step 5 Preparation of 3-(5-oxazol-2-ylthiadiazol-3-ium-3-yl)propane-1 -sulfonate (compound A1 )
  • Step 1 Preparation of 3-oxo-A/-prop-2-ynyl-butanamide
  • Step 3 Preparation of A/-[1-methyl-2-(5-methyloxazol-2-yl)ethylidene]amino] benzenesulfonamide
  • Step 5 Preparation of methyl 3-[4-methyl-5-(5-methyloxazol-2-yl)thiadiazol-3-ium-3-yl]propanoate 2,2,2-trifluoroacetate A1 1
  • Step 1 Preparation of pyrrolidin-1-yl-[5-[(E)-2-pyrrolidin-1-ylvinyl]isoxazol-3-yl]methanone
  • Step 3 Preparation of pyrrolidin-1-yl-[5-(thiadiazol-5-yl)isoxazol-3-yl]methanone
  • 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

Landscapes

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

Abstract

The present invention relates to herbicidally active thiadiazole 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 in controlling undesirable plant growth: in particular the use in controlling weeds, in crops of useful plants.

Description

Herbicidal Compounds
The present invention relates to herbicidally active thiadiazole 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 in controlling undesirable plant growth: in particular the use in controlling weeds, in crops of useful plants.
The present invention is based on the finding that thiadiazole derivatives of formula (I) as defined herein, exhibit surprisingly good herbicidal activity. Thus, according to the present invention there is provided a compound of formula (I) or an agronomically acceptable salt or zwitterionic species thereof:
Figure imgf000002_0001
wherein: R1 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl, C2-C6alkenyl, C2- Cealkynyl, Cs-Cecycloalkyl, Ci-Cehaloalkyl, -OR7, -OR15a, -N(R6)S(0)2R15, -N(R6)C(0)R15, - N(R6)C(0)0R15, -N(R6)C(0)NR16R17, -N(R6)CHO, -N(R7a)2 and -S(0 R15;
R2 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl and Ci-C6haloalkyl; or R1 and R2 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 wherein when R1 is selected from the group consisting of -OR7, -OR15a, -N(R6)S(0)2R15, - N(R6)C(0)R15, -N(R6)C(0)0R15, -N(R6)C(0)NR16R17, -N(R6)CHO, -N(R7a)2 and -S(0 R15, then R2 is selected from the group consisting of hydrogen and Ci-C6alkyl;
R3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, -S(0)rR15, Ci- Cealkyl, Ci-C6fluoroalkyl, Ci-C6fluoroalkoxy, Ci-C6alkoxy, C3-C6cycloalkyl and -N(R6)2;
Q is (CR1aR2b)m;
m is 0, 1 , 2 or 3;
each R1a and R2b are independently selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, -OH, -OR7, -OR15a, -NH2, -NHR7, -NHR15a, -N(R6)CHO, -NR7bR7c and - S(0)rR15; or
each R1a and R2b 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 R6 is independently selected from hydrogen and Ci-Cealkyl;
each R7 is independently selected from the group consisting of Ci-Cealkyl, -S(0)2R15, -C(0)R15, -C(0)OR15 and -C(0)NR16R17;
each R7a is independently selected from the group consisting of -S(0)2R15, -C(0)R15, -C(0)OR15 -C(0)NR16R17 and -C(0)NR6R15a; R7b and R7c are independently selected from the group consisting of Ci-C6alkyl, -S(0)2R15, - C(0)R15, -C(0)OR15, -C(0)NR16R17 and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different; or R7b and R7c 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;
A is a 5-membered heteroaryl ring comprising 1 , 2, 3 or 4 heteroatoms each independently selected from the group consisting of N, O and S, wherein said 5-membered heteroaryl ring is optionally substituted by 1 , 2, or 3 R8 substituents; and when A is a 5-membered heteroaryl ring substituted by R8 on one or more ring carbon atoms, each of said R8 substitutents is independently selected from the group consisting of halogen, nitro, cyano, -NH2, -NHR7, -N(R7)2, -OH, -OR7, - S(0)rR15, -NR6S(0) R15, -C(0)OR10, -C(0)R15, -C(0)NR16R17, -S(0) NR16R17, Ci-Cealkyl, Ci- Cehaloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, C3-C6cycloalkoxy, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Ci-C3alkoxyCi-C3alkyl-, hydroxyCi-Cealkyl-, Ci-C3alkoxyCi-C3alkoxy-, Ci-C6haloalkoxy, Ci-C3haloalkoxyCi-C3alkyl-, C3-C6alkenyloxy, C3-C6alkynyloxy, -C(R6)=NOR6, phenyl and a 5- or 6- membered heteroaryl, which comprises 1 , 2, 3 or 4 heteroatoms independently selected from N, O and S, and wherein said phenyl or heteroaryl are optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different;
and/or when A is a 5-membered heteroaryl ring substituted by an R8 on a ring nitrogen atom, said R8 is selected from the group consisting of -OR7, Ci-C6alkyl, Ci-C6haloalkyl, C3-C6cycloalkyl, C3- Cehalocycloalkyl, C3-C6cycloalkoxy, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Ci-C3alkoxyCi- C3alkyl-, Ci-C3alkoxyCi-C3alkoxy-, Ci-C6haloalkoxy, Ci-C3haloalkoxyCi-C3alkyl-, C3-C6alkenyloxy and C3-C6alkynyloxy;
each R9 is independently selected from the group consisting of -OH, halogen, cyano, -N(R6)2, Ci-C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl and Ci-C4haloalkoxy;
X is independently selected from the group consisting of C3-C6cycloalkyl, phenyl, a 5- or 6- membered heteroaryl, which comprises 1 , 2, 3 or 4 heteroatoms independently selected from N, O and S, and a 4- to 6- membered heterocyclyl, which comprises 1 , 2 or 3 heteroatoms independently selected from N, O and S, and wherein said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties are optionally substituted by 1 or 2 R9 substituents, which may be the same or different, and wherein the aforementioned CR1R2 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)OR1°, -CH2OH, -CHO, -C(0)NHOR11 , -
Figure imgf000003_0001
0P(0)(R13)(0R1°), -NR6P(0)(R13)(0R1°) and tetrazole; R10 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 R9 substituents, which may be the same or different;
R11 is selected from the group consisting of hydrogen, Ci-C6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different;
R12 is selected from the group consisting of Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, -OH, - N(R6)2 and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different;
R13 is selected from the group consisting of -OH, Ci-C6alkyl, Ci-C6alkoxy and phenyl;
R14 is Ci-C6haloalkyl;
R15 is selected from the group consisting of Ci-C6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different;
R15a is phenyl, wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different;
R16 and R17 are independently selected from the group consisting of hydrogen and Ci-C6alkyl; or R16 and R17 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;
R18 is selected from the group consisting of hydrogen, Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, -N(R6)2 and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different;
and r is 0, 1 or 2.
According to a second aspect of the invention, there is provided an agrochemical composition comprising a herbicidally effective amount of a compound of formula (I). Such an agricultural composition may further comprise at least one additional active ingredient and/or an agrochemically acceptable diluent or carrier.
According to a third aspect of the invention, there is provided 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.
According to a fourth aspect of the invention, there is provided the use of a compound of formula (I) as a herbicide.
As used herein, the term "halogen" or“halo” refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.
As used herein, cyano means a -CN group.
As used herein, hydroxy means an -OH group.
As used herein, nitro means an -NO2 group.
As used herein, the term "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- C2alkyl are to be construed accordingly. Examples of Ci-C6alkyl include, but are not limited to, methyl (Me), ethyl (Et), n-propyl, 1-methylethyl (iso-propyl), n-butyl, and 1-dimethylethyl (f-butyl).
As used herein, the term "Ci-C6alkoxy" refers to a radical of the formula -ORa where Ra is a Ci- Cealkyl 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.
As used herein, the term "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.
As used herein, the term "C2-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 (Z)-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 C2-C6alkenyl include, but are not limited to, prop-1-enyl, allyl (prop-2-enyl) and but-1-enyl.
As used herein, the term“C2-C6haloalkenyl” refers to a C2-C6alkenyl radical as generally defined above substituted by one or more of the same or different halogen atoms. Examples of C2-C6haloalkenyl include, but are not limited to chloroethylene, fluoroethylene, 1 , 1-difluoroethylene, 1 , 1-dichloroethylene and 1 ,1 ,2-trichloroethylene.
As used herein, the term "C2-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 C2-C6alkynyl include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl) and but-1-ynyl.
As used herein, the term "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.
As used herein, the term "Ci-C3haloalkoxyCi-C3alkyl" refers to a radical of the formula Rb-0-Ra- where Rb is a Ci-C3haloalkyl radical as generally defined above, and Ra is a Ci-C3alkylene radical as generally defined above.
As used herein, the term "Ci-C3alkoxyCi-C3alkyl" refers to a radical of the formula Rb-0-Ra- where Rb is a Ci-C3alkyl radical as generally defined above, and Ra is a Ci-C3alkylene radical as generally defined above.
As used herein, the term " Ci-C3alkoxyCi-C3alkoxy-" refers to a radical of the formula Rb-0-Ra- O- where Rb is a Ci-C3alkyl radical as generally defined above, and Ra is a Ci-C3alkylene radical as generally defined above.
As used herein, the term "C3-C6alkenyloxy" refers to a radical of the formula -ORa where Ra is a C3-C6alkenyl radical as generally defined above.
As used herein, the term "C3-C6alkynyloxy" refers to a radical of the formula -ORa where Ra is a C3-C6alkynyl radical as generally defined above. As used herein, the term“hyd roxyCi -Ceal kyl” refers to a Ci-C6alkyl radical as generally defined above substituted by one or more hydroxy groups.
As used herein, the term "Ci-C6alkylcarbonyl" refers to a radical of the formula -C(0)Ra where Ra is a Ci-C6alkyl radical as generally defined above.
As used herein, the term "Ci-C6alkoxycarbonyl" refers to a radical of the formula -C(0)ORa where Ra is a Ci-C6alkyl radical as generally defined above.
As used herein, the term“aminocarbonyl” refers to a radical of the formula -C(0)NH2.
As used herein, the term "C3-C6cycloalkyl" refers to a stable, monocyclic ring radical which is saturated or partially unsaturated and contains 3 to 6 carbon atoms. C3-C4cycloalkyl is to be construed accordingly. Examples of C3-C6cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
As used herein, the term "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-C4halocycloalkyl is to be construed accordingly.
As used herein, the term "C3-C6cycloalkoxy" refers to a radical of the formula -ORa where Ra is a C3-C6cycloalkyl radical as generally defined above.
As used herein, the term“N-C3-C6cycloalkylamino” refers to a radical of the formula -NHRa where Ra is a C3-C6cycloalkyl radical as generally defined above.
As used herein, except where explicitly stated otherwise, the term "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. Examples of heteroaryl include, furyl, pyrrolyl, imidazolyl, thienyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl or pyridyl.
As used herein, except where explicitly stated otherwise, the term "heterocyclyl" or "heterocyclic" 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. Examples of heterocyclyl include, but are not limited to, pyrrolinyl, pyrrolidyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidyl, piperazinyl, tetrahydropyranyl, dihydroisoxazolyl, dioxolanyl, morpholinyl or d-lactamyl.
The presence of one or more possible 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). Likewise, 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). Similarly, 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.
For example 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:
Figure imgf000007_0001
wherein, Y represents an agronomically acceptable anion and j and k represent integers that may be selected from 1 , 2 or 3, dependant 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:
Figure imgf000007_0002
wherein, Y represents an agronomically acceptable anion, M represents an agronomically acceptable cation (in addition to the thiadiazolium 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.
Thus where a compound of formula (I) is drawn in protonated form herein, the skilled person would appreciate that it could equally be represented in unprotonated or salt form with one or more relevant counter ions.
In one embodiment of the invention there is provided a compound of formula (l-ll) wherein k is 2, j is 1 and Y is selected from the group consisting of halogen, trifluoroacetate and pentafluoropropionate. In this embodiment a nitrogen atom in ring A may be protonated or a nitrogen atom comprised in R1 , R2, Q or X may be protonated. Preferably, in a compound of formula (l-ll), k is 2, j is 1 and Y is chloride, wherein a nitrogen atom in ring A is protonated.
Suitable agronomically acceptable salts of the present invention, represented by an anion Y, 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, heptadecanoate, hexadecanoate, hydrogen sulfate, hydroxide, hydroxynaphthoate, isethionate, lactate, lactobionate, laurate, malate, maleate, mandelate, mesylate, methanedisulfonate, methylsulfate, mucate, myristate, napsylate, nitrate, nonadecanoate, octadecanoate, oxalate, pelargonate, pentadecanoate, pentafluoropropionate, perchlorate, phosphate, propionate, propylsulfate, propylsulfonate, succinate, sulfate, tartrate, tosylate, tridecylate, triflate, trifluoroacetate, undecylinate and valerate.
Suitable cations represented by M include, but are not limited to, metals, conjugate acids of amines and organic cations. Examples of suitable metals include aluminium, calcium, cesium, copper, lithium, magnesium, manganese, potassium, sodium, iron and zinc. Examples of 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, hexenyl-2- amine, hexylamine, hexylheptylamine, hexyloctylamine, histidine, indoline, isoamylamine, isobutanolamine, isobutylamine, isopropanolamine, isopropylamine, lysine, meglumine, methoxyethylamine, methylamine, methylbutylamine, methylethylamine, methylhexylamine, methylisopropylamine, methylnonylamine, methyloctadecylamine, methylpentadecylamine, morpholine, N,N-diethylethanolamine, N-methylpiperazine, nonylamine, octadecylamine, octylamine, oleylamine, pentadecylamine, pentenyl-2-amine, phenoxyethylamine, picoline, piperazine, piperidine, propanolamine, propylamine, propylenediamine, pyridine, pyrrolidine, sec-butylamine, stearylamine, tallowamine, tetradecylamine, tributylamine, tridecylamine, trimethylamine, triheptylamine, trihexylamine, triisobutylamine, triisodecylamine, triisopropylamine, trimethylamine, tripentylamine, tripropylamine, tris(hydroxymethyl)aminomethane, and undecylamine. Examples of 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). For compounds of formula (l-ll) emphasis is given to salts when Y is chloride, bromide, iodide, hydroxide, bicarbonate, acetate, pentafluoropropionate, triflate, trifluoroacetate, methylsulfate, tosylate and nitrate, wherein j and k are 1. Preferably, Y is chloride, bromide, iodide, hydroxide, bicarbonate, acetate, trifluoroacetate, methylsulfate, tosylate and nitrate, wherein j and k are 1. For compounds of formula (l-ll) emphasis is also given to salts when Y is carbonate and sulfate, wherein j is 2 and k is 1 , and when Y is phosphate, wherein j is 3 and k is 1.
Where appropriate compounds of formula (I) may also be in the form of (and/or be used as) an N-oxide. Compounds of formula (I) wherein m is 0 and n is 0 may be represented by a compound of formula (l-la) as shown below:
Figure imgf000009_0001
(l-la)
wherein R1 , R2, R3, A and Z are as defined for compounds of formula (I).
Compounds of formula (I) wherein m is 1 and n is 0 may be represented by a compound of formula (l-lb) as shown below:
Figure imgf000009_0002
wherein R1 , R2, R1a, R2b, R3, A and Z are as defined for compounds of formula (I).
Compounds of formula (I) wherein m is 2 and n is 0 may be represented by a compound of formula (l-lc) as shown below:
Figure imgf000009_0003
(l-lc)
wherein R1 , R2, R1a, R2b, R3, A and Z are as defined for compounds of formula (I).
Compounds of formula (I) wherein m is 3 and n is 0 may be represented by a compound of formula (l-ld) as shown below:
Figure imgf000009_0004
(l-ld)
wherein R1 , R2, R1a, R2b, R3, A and Z are as defined for compounds of formula (I).
The following list provides definitions, including preferred definitions, for substituents n, m, r, A,
Q, X, Z, R1 , R2, R1a, R2b, R3, R6, R7, R7a, R7b, R7c, R8, R9, R10, R11 , R12, R13, R14, R15, R15a, R16, R17 and
R18 with reference to the compounds of formula (I) according to the invention. For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document. R1 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl, C2-C6alkenyl, C2- Cealkynyl, Cs-Cecycloalkyl, Ci-Cehaloalkyl, -OR7, -OR15a, -N(R6)S(0)2R15, -N(R6)C(0)R15, - N(R6)C(0)0R15, -N(R6)C(0)NR16R17, -N(R6)CHO, -N(R7a)2 and -S(0 R15. Preferably, R1 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl, Ci-C6fluoroalkyl, -OR7, -NHS(0)2R15, - NHC(0)R15, -NHC(0)OR15, -NHC(0)NR16R17, -N(R7a)2 and -S(0 R15. More preferably, R1 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl, Ci-C6fluoroalkyl, -OR7 and -N(R7a)2. Even more preferably, R1 is selected from the group consisting of hydrogen, Ci-C6alkyl, -OR7 and -N(R7a)2. Even more preferably still, R1 is hydrogen or Ci-C6alkyl. Yet even more preferably still, R1 is hydrogen or methyl. Most preferably R1 is hydrogen.
R2 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl and Ci-C6haloalkyl. Preferably, R2 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl and Ci- Cefluoroalkyl. More preferably, R2 is hydrogen or Ci-C6alkyl. Even more preferably, R2 is hydrogen or methyl. Most preferably R2 is hydrogen.
Wherein when R1 is selected from the group consisting of -OR7, -OR15a, -N(R6)S(0)2R15, - N(R6)C(0)R15, -N(R6)C(0)0R15, -N(R6)C(0)NR16R17, -N(R6)CHO, -N(R7a)2 and -S(0 R15, R2 is selected from the group consisting of hydrogen and Ci-C6alkyl. Preferably, when R1 is selected from the group consisting of -OR7, -NHS(0)2R15, -NHC(0)R15, -NHC(0)OR15, -NHC(0)NR16R17, -N(R7a)2 and -S(0)rR15, R2 is selected from the group consisting of hydrogen and methyl.
Alternatively, R1 and R2 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. Preferably, R1 and R2 together with the carbon atom to which they are attached form a C3-C6cycloalkyl ring. More preferably, R1 and R2 together with the carbon atom to which they are attached form a cyclopropyl ring.
In one embodiment R1 and R2 are hydrogen.
In another embodiment R1 is methyl and R2 is hydrogen.
In another embodiment R1 is methyl and R2 is methyl.
Q is (CR1aR2b)m.
The value of m is 0, 1 , 2 or 3. Preferably, m is 0, 1 , or 2. More preferably, m is 1 or 2. Most preferably, m is 1.
Each R1a and R2b are independently selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, -OH, -OR7, -OR15a, -NH2, -NHR7, -NHR15a, -N(R6)CHO, -NR7bR7c and - S(0)rR15. Preferably, each R1a and R2b are independently selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-C6fluoroalkyl, -OH, -NH2 and -NHR7. More preferably, each R1a and R2b are independently selected from the group consisting of hydrogen, Ci-Cealkyl, -OH and -NH2. Even more preferably, each R1a and R2b are independently selected from the group consisting of hydrogen, methyl, -OH and -NH2. Even more preferably still, each R1a and R2b are independently selected from the group consisting of hydrogen and methyl. Most preferably R1a and R2b are hydrogen.
In another embodiment each R1a and R2b are independently selected from the group consisting of hydrogen and Ci-C6alkyl.
Alternatively, each R1a and R2b 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. Preferably, each R1a and R2b together with the carbon atom to which they are attached form a C3-C6cycloalkyl ring. More preferably, each R1a and R2b together with the carbon atom to which they are attached form a cyclopropyl ring.
Preferably R3 is hydrogen, Ci-C6alkyl, -C(0)NH2, and -C(0)Ci-C6alkyl; more preferably hydrogen, Ci-C6alkyl, or Ci-C6alkoxy, and more preferably still, hydrogen or methyl. Most preferably R3 is hydrogen.
Each R6 is independently selected from hydrogen and Ci-C6alkyl. Preferably, each R6 is independently selected from hydrogen and methyl.
Each R7 is independently selected from the group consisting of Ci-C6alkyl, -S(0)2R15, -C(0)R15, -C(0)OR15 and -C(0)NR16R17. Preferably, each R7 is independently selected from the group consisting of Ci-C6alkyl, -C(0)R15 and -C(0)NR16R17. More preferably, each R7 is Ci-C6alkyl. Most preferably, each R7 is methyl.
Each R7a is independently selected from the group consisting of -S(0)2R15, -C(0)R15, -C(0)OR15 -C(0)NR16R17 and -C(0)NR6R15a. Preferably, each R7a is independently -C(0)R15 or -C(0)NR16R17.
R7b and R7c are independently selected from the group consisting of Ci-C6alkyl, -S(0)2R15, - C(0)R15, -C(0)OR15, -C(0)NR16R17 and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different. Preferably, R7b and R7c are independently selected from the group consisting of Ci-C6alkyl, -C(0)R15 and -C(0)NR16R17. More preferably, R7b and R7c are Ci-C6alkyl. Most preferably, R7b and R7c are methyl.
Alternatively, R7b and R7c 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. Preferably, R7b and R7c 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. More preferably, R7b and R7c together with the nitrogen atom to which they are attached form an pyrrolidyl, oxazolidinyl, imidazolidinyl, piperidyl, piperazinyl or morpholinyl group.
A is a 5-membered heteroaryl attached to the rest of the molecule via a ring carbon atom, which comprises 1 , 2, or 3 heteroatoms independently selected from the group consisting of N, O and S, and wherein the heteroaryl is optionally substituted (where feasible) by 1 , 2 or 3 R8 substituents, which may be the same or different.
Preferably, A is a heteroaryl selected from the group consisting of 1 ,2,3,5-oxatriazol-4-yl, 1 ,2,3,5-thiatriazol-4-yl, 1 ,2,4-oxadiazol-3-yl, 1 ,2,4-oxadiazol-5-yl, 1 ,2,4-thiadiazol-3-yl, 1 ,2,4-thiadiazol- 5-yl, 1 ,2,4-triazol-3-yl, 1 ,2,4-triazol-5-yl, 1 ,2,5-oxadiazol-3-yl, 1 ,2,5-thiadiazol-3-yl, 1 ,3,4-oxadiazol-2-yl, 1 ,3,4-thiadiazol-2-yl, 2-furyl, 2-thienyl, 3-furyl, 3-thienyl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 1 ,2,3- oxadiazol-4-yl, 1 ,2,3-oxadiazol-5-yl, 1 ,2,3,4-oxatriazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, pyrrol-2-yl, pyrrol-3-yl, tetrazol-5-yl, 1 ,2,3-thiadiazol-4-yl, 1 ,2,3- thiadiazol-5-yl, 1 ,2,3,4-thiatriazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, triazol-4-yl and triazol-5-yl wherein the heteroaryl is optionally substituted (where feasible) by 1 , 2 or 3 R8 substituents, which may be the same or different. More preferably, A is a heteroaryl selected from the group consisting of tetrazol-5-yl, 1 ,2,4- triazol-3-yl, 1 ,2,4-triazol-5-yl, isoxazol-3-yl, oxazol-2-yl, thiazol-2-yl, 1 ,3,4-thiadiazol-2-yl, triazol-4-yl, triazol-5-yl, pyrazol-3-yl, pyrazol-5-yl, 1 ,3,4-oxadiazol-2-yl, 1 ,2,4-thiadiazol-5-yl, oxazol-4-yl, imidazol- 2-yl, isothiazol-5-yl, 2-thienyl, 3-furyl, 2-furyl, isothiazol-4-yl, thiazol-4-yl, 3-thienyl, imidazol-5-yl, isoxazol-5-yl and 1 ,2,4-oxadiazol-5-yl wherein the heteroaryl may, where feasible, be optionally substituted by 1 , 2 or 3 R8 substituents, which may be the same or different.
Even more preferably, A is selected from the group consisting of formula A-l to A-XXVIII below:
Figure imgf000012_0001
Figure imgf000013_0001
wherein the jagged line defines the point of attachment to the rest of the molecule and
R8a, R8b, R8c, R8d R6, R7, R10, R15, R16 and R17 are as defined herein. R8a, R8b, R8c, R8d are examples of R8 wherein the subscript letter a, b, c and d are used to denote positions within indvidual heterocycles (A- 1 to A-XXVIII).
Even more preferably still, A is selected from the group consisting of formula A-l to A-VIII below
Figure imgf000013_0002
wherein the jagged line defines the point of attachment to a compound of formula (I),
R8a, R8b, R8c, R8d and R7 is as defined herein. Yet, even more preferably still, A is selected from the group consisting of formula A-la to A-Vllla below
Figure imgf000014_0001
A-Va
A- Via A- /lla A-Vllla
wherein the jagged line defines the point of attachment to the rest of the molecule. Yet even more prefereably, A is selected from A-lla, A-Vla and A-Vlla as described above.
When A is substituted on one or more ring carbon atoms, each R8 is independently selected from the group consisting of halogen, nitro, cyano, -NH2, -NHR7, -N(R7)2, -OH, -OR7, -S(0)rR15, - NR6S(0) R15, -C(0)OR10, -C(0)R15, -C(0)NR16R17, -S(0) NR16R17, Ci-Cealkyl, Ci-Cehaloalkyl, C3- C6cycloalkyl, C3-C6halocycloalkyl, C3-C6cycloalkoxy, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Ci- C3alkoxyCi-C3alkyl-, hydroxyCi-Cealkyl-, Ci-C3alkoxyCi-C3alkoxy-, Ci-C6haloalkoxy, Ci- C3haloalkoxyCi-C3alkyl-, C3-C6alkenyloxy, C3-C6alkynyloxy, -C(R6)=NOR6, phenyl and a 5- or 6- membered heteroaryl, which comprises 1 , 2, 3 or 4 heteroatoms independently selected from N, O and S, and wherein said phenyl or heteroaryl are optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different.
Preferably, when A is substituted on one or more ring carbon atoms, each R8 is independently selected from the group consisting of halogen, nitro, cyano, -NH2, -NHR7, -N(R7)2, -OH, -OR7, -S(0)rR15, -NR6S(0) R15, -C(0)OR10, -C(0)R15, -C(0)NR16R17, -S(0) NR16R17, Ci-Cealkyl, Ci-Cehaloalkyl, C3- C6cycloalkyl, Ci-C3alkoxyCi-C3alkyl-, hydroxyCi-Cealkyl-, Ci-C3alkoxyCi-C3alkoxy-, Ci-Cehaloalkoxy, phenyl and a 6- membered heteroaryl, which comprises 1 or 2 nitrogen atoms, and wherein said phenyl or heteroaryl are optionally substituted by 1 or 2 R9 substituents, which may be the same or different.
More preferably, when A is substituted on one or more ring carbon atoms, each R8 is independently selected from the group consisting of halogen, nitro, cyano, -NH2, -NHR7, -N(R7)2, -OH, - OR7, -S(0)rR15, -NR6S(0) R15, -C(0)OR10, -C(0)R15, -C(0)NR16R17, -S(0) NR16R17, Ci-Cealkyl, Ci- Cehaloalkyl, C3-C6cycloalkyl, hydroxyCi-Cealkyl-, Ci-Cehaloalkoxy and a 6- membered heteroaryl, which comprises 1 or 2 nitrogen atoms, and wherein said heteroaryl is optionally substituted by 1 R9 substituent.
Even more preferably, when A is substituted on one or more ring carbon atoms, each R8 is independently selected from the group consisting of halogen, cyano, -NH2, -NHR7, -N(R7)2, -OH, -OR7, -S(0)rR15, -C(0)OR1°, -C(0)R15, -C(0)NR16R17, Ci-Cealkyl and Ci-Cehaloalkyl.
Even more preferably still, when A is substituted on one or more ring carbon atoms, each R8 is independently selected from the group consisting of chloro, fluoro, cyano, -NH2, -NHMe, -NMe2, -OH, - OMe, -S(0)2Me, -C(0)0Me, -C(0)0H, -C(0)Me, -C(0)NH2, -C(0)NHMe, -C(0)NMe2, methyl, iso- propyl and trifluoromethyl.
Most preferably, when A is substituted on one or more ring carbon atoms, each R8 is independently selected from the group consisting of chloro, -NH2, -NHMe, -OMe, methyl, /'so-propyl and trifluoromethyl.
When A is substituted on a ring nitrogen atom by R8, said R8 substituent is selected from the group consisting of -OR7, Ci-C6alkyl, Ci-C6haloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, C3- C6cycloalkoxy, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Ci-C3alkoxyCi-C3alkyl-, hydroxyC-i- Cealkyl-, Ci-C3alkoxyCi-C3alkoxy-, Ci-C6haloalkoxy, Ci-C3haloalkoxyCi-C3alkyl-, C3-C6alkenyloxy and C3-C6alkynyloxy. Preferably, said R8 is selected from the group consisting of -OR7, Ci-C6alkyl and Ci- Cehaloalkyl. More preferably, each of said R8 is -OR7 or Ci-C6alky. Even more preferably still, each of said R8 is Ci-C6alky. Most preferably said R8 is methyl.
When A is selected from the group consisting of formula A-l to A-XXVIII, R8a (substituted on a ring nitrogen atom) is selected from the group consisting of hydrogen, Ci-C6alkyl and Ci-C6haloalkyl, and each R8b, R8c and R8d (substituted on a ring carbon atom) are independently selected from the group consisting of hydrogen, halogen, nitro, cyano, -NH2, -NHR7, -N(R7)2, -OH, -OR7, -S(0)rR15, - NR6S(0)2R15, -C(0)OR10, -C(0)R15, -C(0)NR16R17, -S(0)2NR16R17, Ci-Cealkyl and Ci-Cehaloalkyl. Preferably R8a is hydrogen or Ci-C6alkyl and each R8b, R8c and R8d are independently selected from the group consisting of hydrogen, halogen, -NH2, -NHR7, -N(R7)2, -OR7, Ci-C6alkyl and Ci-C6haloalkyl. More preferably, R8a is hydrogen or methyl and each R8b, R8c and R8d are independently selected from the group consisting of hydrogen, chloro, -NH2, -NHMe, -OMe, methyl, /'so-propyl and trifluoromethyl.
When A is selected from the group consisting of formula A-l to A-VIII, R8a (substituted on a ring nitrogen atom) is hydrogen or Ci-C6alkyl, and each R8b, R8c and R8d (substituted on a ring carbon atom) are independently selected from the group consisting of hydrogen, halogen, -NH2, -NHR7, -N(R7)2, -OR7, Ci-C6alkyl and Ci-C6haloalkyl. Preferably, R8a is hydrogen or methyl and each R8b, R8c and R8d are independently selected from the group consisting of hydrogen, chloro, -NH2, -NHMe, -OMe, methyl, /'so- propyl and trifluoromethyl.
Each R9 is independently selected from the group consisting of halogen, cyano, -N(R6)2, Ci- C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl and Ci-C4haloalkoxy. Preferably, each R9 is independently selected from the group consisting of halogen, Ci-C4alkyl, Ci-C4alkoxy and Ci-C4haloalkyl. More preferably, each R9 is independently selected from the group consisting of halogen and Ci-C4alkyl.
As defined herein, n is 0 or 1. When n is 1 , 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 independently selected from N, O and S, and a 4- to 6- membered heterocyclyl, which comprises 1 , 2 or 3 heteroatoms independently 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 R9, and wherein the aforementioned CR1R2 and Z, or Q and Z, moieties may be attached at any position of said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties.
Preferably, 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 R9, and wherein the aforementioned CR1R2, Q and Z moieties may be attached at any position of said phenyl or heterocyclyl moieties.
More preferably, 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 R9, and wherein the aforementioned CR1R2, Q and Z moieties may be attached at any position of said heterocyclyl moiety.
In one embodiment, X is a 5-membered heterocyclyl, which comprises 1 heteroatom, wherein said heteroatom is N, and wherein the aforementioned CR1R2, Q and Z moieties may be attached at any position of said heterocyclyl moiety. Preferably, X is a 5-membered heterocyclyl, which comprises 1 heteroatom, wherein said heteroatom is N, and wherein the aforementioned CR1R2 and Q moieties are attached adjacent to the N atom and the Z moiety is attached to the N atom.
In another embodiment, X is phenyl optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R9, and wherein the aforementioned CR1R2, Q and Z moieties may be attached at any position of said phenyl moiety. Preferably, X is phenyl and the aforementioned CR1R2 and Q moieties are attached in a postion para to the Z moiety.
In further preferred embodiments, n is 0 and thus X is absent.
Z is selected from the group consisting of -C(0)OR1°, -CH2OH, -CHO, -C(0)NHOR11 , - C(0)NHCN, -OC(0)NHOR11 , -OC(0)NHCN, -NR6C(0)NH0R11 , -NR6C(0)NHCN, -C(0)NHS(0)2R12, - 0C(0)NHS(0)2R12, -NR6C(0)NHS(0)2R12, -S(0)20R10, -0S(0)20R10, -NR6S(0)20R10, -NR6S(0)OR10, -NHS(0)2R14, -S(0)OR10, -OS(0)OR10, -S(0)2NHCN, -S(0)2NHC(0)R18, -S(0)2NHS(0)2R12, - OS(0)2NHCN, -0S(0)2NHS(0)2R12, -0S(0)2NHC(0)R18, -NR6S(0)2NHCN, -NR6S(0)2NHC(0)R18, - N(OH)C(0)R15, -ONHC(0)R15, -NR6S(0)2NHS(0)2R12, -P(0)(R13)(OR1°), -P(0)H(OR1°), - 0P(0)(R13)(0R1°), -NR6P(0)(R13)(0R1°) and tetrazole.
Preferably, Z is selected from the group consisting of -C(0)OR1°, -C(0)NHOR11 , - OC(0)NHOR11 , -NR6C(0)NHOR11 , -C(0)NHS(0)2R12, -0C(0)NHS(0)2R12, -NR6C(0)NHS(0)2R12, - S(0)20R10, -0S(0)20R10, -NR6S(0)20R10, -NR6S(0)OR10, -NHS(0)2R14, -S(0)OR10, -OS(0)OR10, - S(0)2NHC(0)R18, -S(0)2NHS(0)2R12, -0S(0)2NHS(0)2R12, -0S(0)2NHC(0)R18, -NR6S(0)2NHC(0)R18, -N(OH)C(0)R15, -ONHC(0)R15, -NR6S(0)2NHS(0)2R12, -P(0)(R13)(OR1°), -P(0)H(OR1°), - 0P(0)(R13)(0R1°) and -NR6P(0)(R13)(0R1°).
More preferably, Z is selected from the group consisting of -C(0)OR1°, -C(0)NHOR11 , - C(0)NHS(0)2R12, -S(0)20R10, -0S(0)20R10, -NR6S(0)20R10, -NHS(0)2R14, -S(0)OR10 and - P(0)(R13)(OR1°).
Even more preferably Z is selected from the group consisting of -C(0)OR1°, -C(0)NHS(0)2R12, -S(0)20R10, and -P(0)(R13)(OR1°).
Even more preferably still Z is selected from the group consisting of -C(0)OH, -C(0)OCH3, - C(0)0CH2CH3, -C(0)0CH(CH3)2, -C(0)0C(CH3)3, -C(0)0CH2C6H5, -C(0)0C6H5, -C(0)NHS(0)2CH3, - S(0)2OH, -P(0)(OH)( OCH2CH3) and -P(0)(0CH2CH3)(0CH2CH3).
Most preferably Z is -C(0)OH or -S(0)2OH.
R10 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 R9 substituents, which may be the same or different. Preferably, R10 is selected from the group consisting of hydrogen, Ci-C6alkyl, phenyl and benzyl. More preferably, R10 is selected from the group consisting of hydrogen and Ci-C6alkyl. Most preferably, R10 is hydrogen.
R11 is selected from the group consisting of hydrogen, Ci-C6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different. Preferably, R11 is selected from the group consisting of hydrogen, Ci-C6alkyl and phenyl. More preferably, R11 is selected from the group consisting of hydrogen and Ci-C6alkyl. Even more preferably, R11 is Ci-C6alkyl. Most preferably, R11 is methyl.
R12 is selected from the group consisting of Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, -OH, - N(R6)2 and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different. Preferably, R12 is selected from the group consisting of Ci-C6alkyl, Ci- Cehaloalkyl, Ci-C6alkoxy, -OH, -N(R6)2 and phenyl. More preferably, R12 is selected from the group consisting of Ci-C6alkyl, Ci-C6haloalkyl and -N(R6)2. Even more preferably, R12 is selected from the group consisting of methyl, -N(Me)2 and trifluoromethyl. Most preferably, R12 is methyl.
R13 is selected from the group consisting of -OH, Ci-C6alkyl, Ci-C6alkoxy and phenyl. Preferably R13 is selected from the group consisting of -OH, Ci-C6alkyl and Ci-C6alkoxy. More preferably, R13 is selected from the group consisting of -OH and Ci-C6alkoxy. Even more preferably, R13 is selected from the group consisting of -OH, methoxy and ethoxy. Most preferably, R13 is -OH.
R14 is Ci-C6haloalkyl. Preferably, R14 is trifluoromethyl.
R15 is selected from the group consisting of Ci-C6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different. Preferably, R15 is selected from the group consisting of Ci-C6alkyl and phenyl. More preferably, R15 is Ci-C6alkyl. Most preferably R15 is methyl.
R15a is phenyl, wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different. Preferably, R15a is phenyl optionally substituted by 1 R9 substituent. More preferably, R15a is phenyl.
R16 and R17 are independently selected from the group consisting of hydrogen and Ci-C6alkyl. Preferably, R16 and R17 are independently selected from the group consisting of hydrogen and methyl.
Alternatively, R16 and R17 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. Preferably, R16 and R17 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. More preferably, R16 and R17 together with the nitrogen atom to which they are attached form an pyrrolidyl, oxazolidinyl, imidazolidinyl, piperidyl, piperazinyl or morpholinyl group.
R18 is selected from the group consisting of hydrogen, Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, -N(R6)2 and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different. Preferably, R18 is selected from the group consisting of hydrogen, Ci- Cealkyl, Ci-C6haloalkyl, Ci-C6alkoxy, -N(R6)2 and phenyl. More preferably, R18 is selected from the group consisting of hydrogen, Ci-C6alkyl and Ci-C6haloalkyl. Further more preferably, R18 is selected from the group consisting of Ci-C6alkyl and Ci-C6haloalkyl. Most preferably, R18 is methyl or trifluoromethyl. r Is 0, 1 or 2. Preferably, r is 0 or 2. In a set of preferred embodiments, in a compound according to formula (I) of the invention: R1 is hydrogen or Ci-C6alkyl; R2 is hydrogen or methyl; Q is (CR1aR2b) ; m is 0, 1 or 2; R1a and R2b are independently selected from the group consisting of hydrogen, Ci-C6alkyl, -OH and -NH2; R3 is hydrogen or methyl; each R6 is independently selected from hydrogen and methyl; each R7 is Ci-C6alkyl; A is a 5-membered heteroaryl attached to the rest of the molecule via a ring carbon atom, said 5- membered heteroaryl heteroaryl comprising 1 , 2, 3 or 4 heteroatoms independently selected from the group consisting of N, O and S, and wherein said heteroaryl is optionally substituted, where feasible, by 1 , 2 or 3 R8 substituents, which may be the same or different; and when A is substituted on one or more ring carbon atoms, each R8 is independently selected from the group consisting of halogen, nitro, cyano, -NH2, -NHR7, -N(R7)2, -OH , -OR7, -S(0)rR15, -NR6S(0)2R15, -C(0)OR10, -C(0)R15, -C(0)NR16R17, - S(0)2NR16R17, Ci-C6alkyl and Ci-C6haloalkyl; and/or when A is substituted on a ring nitrogen atom, each R8 is selected from the group consisting of -OR7, Ci-C6alkyl and Ci-C6haloalkyl; and n is 0; Z is selected from the group consisting of -C(0)OR1°, -C(0)NHS(0)2R12, -S(0)2OR10, -OS(0)2OR10 and - P(0)(R13)(OR1°); R10 is selected from the group consisting of hydrogen, Ci-C6alkyl, phenyl and benzyl; R12 is selected from the group consisting of Ci-C6alkyl, Ci-C6haloalkyl and -N(R6)2; R13 is selected from the group consisting of -OH and Ci-C6alkoxy; R15 is Ci-C6alkyl; R16 and R17 are independently selected from the group consisting of hydrogen and methyl; and r is 0 or 2.
More preferably in said preferred set of embodiments, R1 is hydrogen or methyl; R2 is hydrogen or methyl; Q is (CR1aR2b) ; m is 1 or 2; R1a and R2b are independently selected from the group consisting of hydrogen and methyl; R3 is hydrogen; A is a heteroaryl selected from the group consisting of tetrazol- 5-yl, 1 ,2,4-triazol-3-yl, 1 ,2,4-triazol-5-yl, isoxazol-3-yl, oxazol-2-yl, thiazol-2-yl, 1 ,3,4-thiadiazol-2-yl, triazol-4-yl, triazol-5-yl, pyrazol-3-yl, pyrazol-5-yl, 1 ,3,4-oxadiazol-2-yl, 1 ,2, 4-th iadiazol-5-yl, oxazol-4-yl, imidazol-2-yl, isothiazol-5-yl, 2-thienyl, 3-furyl, 2-furyl, isothiazol-4-yl, thiazol-4-yl, 3-thienyl, imidazol-5- yl, isoxazol-5-yl and 1 ,2,4-oxadiazol-5-yl wherein said heteroaryl is optionally substituted by 1 , 2 or 3 R8 substituents, which may be the same or different; and when A is substituted on one or more ring carbon atoms, each R8 is independently selected from the group consisting of chloro, -NH2, -NHMe, - OMe, methyl, iso-propyl and trifluoromethyl; and/or when A is substituted on a ring nitrogen atom, R8 is Ci-C6alkyl; n is 0; Z is selected from the group consisting of -C(0)OR1°, -S(0)2OR10, and -OS(0)2OR10; and R10 is hydrogen or Ci-C6alkyl.
In a further set of preferred embodiments, the compound according to formula (I) is selected from the group consisting of a compound of formula (l-a*), (l-b*), (l-c*), (l-d*), (l-e*), (l-f*), (l-g*), (l-h*), (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-p), (l-q), (l-r) and (l-s), as shown below:
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
wherein in a compound of formula (l-a*), (l-b*), (l-c*), (l-d*), (l-e*), (l-f*), (l-g*), (l-h*), (l-a), (l-b), (l-c), (I- d), (l-e), (l-f), (l-g), (l-h), (l-j), (l-k), (l-m), (l-n), (l-p), (l-q), (l-r) and (l-s):
R8a is hydrogen or Ci-C6alkyl; each R8b, R8c and R8d are independently selected from the group consisting of hydrogen, halogen, -NH2, -NHR7, -N(R7)2, -OR7, Ci-C6alkyl and Ci-C6haloalkyl; and Z is - C(0)0H or -S(0)20H. Within this set of embodiments, compounds of formula (l-d), (l-f), (l-g), (l-h), (I- n), (l-q) and (l-r) are particularly preferred.
In a further more preferred set of embodiments, 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), (I- mm), (l-nn), (l-pp), (l-qq), (l-rr) or (l-ss),
Figure imgf000022_0001
(l-gg) (l-hh)
Figure imgf000023_0001
( -rr)
wherein in 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-pp), (l-qq), (l-rr) or (l-ss), Z is -C(0)0H or -S(0)20H. Within this set of embodiments, compounds of formula (l-dd), (l-ff), (l-gg), (l-hh), (l-nn), (l-qq), (l-rr) and (l-ss) are particularly preferred.
It should be understood that compounds of formula (I) may exist/be manufactured in‘procidal form’, wherein they comprise a group‘G’. Such compounds are referred to herein as compounds of Formula (l-IV).
G is a group which may be removed in a plant by any appropriate mechanism including, but not limited to, metabolism and chemical degradation to give a compound of Formula (l-l), (l-ll) or (l-lll) wherein Z contains an acidic proton, for example see the scheme below:
Figure imgf000023_0002
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):
Figure imgf000024_0001
G is C
Figure imgf000024_0003
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;
R19 is Ci-C6alkyl or phenyl;
R20 is hydroxy, Ci-C6alkyl, Ci-C6alkoxy or phenyl;
R21 is hydrogen or methyl;
R22 is hydrogen or methyl;
R23 is hydrogen or Ci-C6alkyl.
The compounds in Tables 1 to 39 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.
Table 1 :
This table discloses 53 specific compounds of the formula (T-1 ):
Figure imgf000024_0002
wherein m, Q, R3, and Z are as defined in Table 1 , R1 and R2 are hydrogen and n is 0.
Table 1
Figure imgf000025_0001
Table 2:
This table discloses 49 specific compounds of the formula (T-2):
Figure imgf000026_0001
wherein m, Q, R3, and Z are as defined in Table 2, R1 and R2 are hydrogen and n is 0.
Table 2
Figure imgf000026_0002
Figure imgf000027_0002
Table 3:
This table discloses 49 specific compounds of the formula (T-3):
Figure imgf000027_0001
wherein m, Q, R3, and Z are as defined in Table 3, R1 and R2 are hydrogen and n is 0.
Table 3
Figure imgf000027_0003
Figure imgf000028_0004
Table 4:
This table discloses 53 specific compounds of the formula (T-4):
Figure imgf000028_0001
(T-4),
wherein m, Q, R3, and Z are as defined above in Table 1 , R1 and R2 are hydrogen and n is 0.
Table 5:
This table discloses 49 specific compounds of the formula (T-5):
Figure imgf000028_0002
wherein m, Q, R3, and Z are as defined above in Table 2, R1 and R2 are hydrogen and n is 0.
Table 6:
This table discloses 49 specific compounds of the formula (T-6):
Figure imgf000028_0003
wherein m, Q, R3, and Z are as defined above in Table 3, R1 and R2 are hydrogen and n is 0. Table 7:
This table discloses 53 specific compounds of the formula (T-7):
Figure imgf000029_0001
wherein m, Q, R3, and Z are as defined above in Table 1 , R1 and R2 are hydrogen and n is 0. Table 8:
This table discloses 49 specific compounds of the formula (T-8):
Figure imgf000029_0002
wherein m, Q, R3, and Z are as defined above in Table 2, R1 and R2 are hydrogen and n is 0.
Table 9:
This table discloses 49 specific compounds of the formula (T-9):
Figure imgf000029_0003
wherein m, Q, R3, and Z are as defined above in Table 3, R1 and R2 are hydrogen and n is 0.
Table 10:
This table discloses 53 specific compounds of the formula (T-10):
Figure imgf000029_0004
wherein m, Q, R3, and Z are as defined above in Table 1 , R1 and R2 are hydrogen and n is 0.
Table 1 1 : This table discloses 49 specific compounds of the formula (T-1 1 ):
Figure imgf000030_0001
wherein m, Q, R3, and Z are as defined above in Table 2, R1 and R2 are hydrogen and n is 0. Table 12:
This table discloses 49 specific compounds of the formula (T-12):
Figure imgf000030_0002
wherein m, Q, R3, and Z are as defined above in Table 3, R1 and R2 are hydrogen and n is 0. Table 13:
This table discloses 53 specific compounds of the formula (T-13):
Figure imgf000030_0003
wherein m, Q, R3, and Z are as defined above in Table 1 , R1 and R2 are hydrogen and n is 0. Table 14:
This table discloses 49 specific compounds of the formula (T-14):
Figure imgf000030_0004
wherein m, Q, R3, and Z are as defined above in Table 2, R1 and R2 are hydrogen and n is 0. Table 15:
This table discloses 49 specific compounds of the formula (T-15):
Figure imgf000031_0001
wherein m, Q, R3, and Z are as defined above in Table 3, R1 and R2 are hydrogen and n is 0.
Table 16:
This table discloses 53 specific compounds of the formula (T-16):
Figure imgf000031_0002
wherein m, Q, R3, and Z are as defined above in Table 1 , R1 and R2 are hydrogen and n is 0.
Table 17:
This table discloses 49 specific compounds of the formula (T-17):
Figure imgf000031_0003
wherein m, Q, R3, and Z are as defined above in Table 2, R1 and R2 are hydrogen and n is 0.
Table 18:
This table discloses 49 specific compounds of the formula (T-18):
Figure imgf000031_0004
wherein m, Q, R3, and Z are as defined above in Table 3, R1 and R2 are hydrogen and n is 0. Table 19:
This table discloses 53 specific compounds of the formula (T-19):
Figure imgf000032_0001
wherein m, Q, R3, and Z are as defined above in Table 1 , R1 and R2 are hydrogen and n is 0.
Table 20:
This table discloses 49 specific compounds of the formula (T-20):
Figure imgf000032_0002
wherein m, Q, R3, and Z are as defined above in Table 2, R1 and R2 are hydrogen and n is 0.
Table 21 :
This table discloses 49 specific compounds of the formula (T-21 ):
Figure imgf000032_0003
wherein m, Q, R3, and Z are as defined above in Table 3, R1 and R2 are hydrogen and n is 0.
Table 22:
This table discloses 53 specific compounds of the formula (T-22):
Figure imgf000032_0004
wherein m, Q, R3, and Z are as defined above in Table 1 , R1 and R2 are hydrogen and n is 0. Table 23:
This table discloses 49 specific compounds of the formula (T-23):
Figure imgf000033_0001
wherein m, Q, R3, and Z are as defined above in Table 2, R1 and R2 are hydrogen and n is 0.
Table 24:
This table discloses 49 specific compounds of the formula (T-24):
Figure imgf000033_0002
wherein m, Q, R3, and Z are as defined above in Table 3, R1 and R2 are hydrogen and n is 0.
Table 25:
This table discloses 53 specific compounds of the formula (T-25):
Figure imgf000033_0003
wherein m, Q, R3, and Z are as defined above in Table 1 , R1 and R2 are hydrogen and n is 0.
Table 26:
This table discloses 49 specific compounds of the formula (T-26):
Figure imgf000033_0004
wherein m, Q, R3, and Z are as defined above in Table 2, R1 and R2 are hydrogen and n is 0. Table 27:
This table discloses 49 specific compounds of the formula (T-27):
Figure imgf000034_0001
wherein m, Q, R3, and Z are as defined above in Table 3, R1 and R2 are hydrogen and n is 0.
Table 28:
This table discloses 53 specific compounds of the formula (T-28):
Figure imgf000034_0002
wherein m, Q, R3, and Z are as defined above in Table 1 , R1 and R2 are hydrogen and n is 0.
Table 29:
This table discloses 49 specific compounds of the formula (T-29):
Figure imgf000034_0003
wherein m, Q, R3, and Z are as defined above in Table 2, R1 and R2 are hydrogen and n is 0. Table 30:
This table discloses 49 specific compounds of the formula (T-30):
Figure imgf000034_0004
wherein m, Q, R3, and Z are as defined above in Table 3, R1 and R2 are hydrogen and n is 0. Table 31 :
This table discloses 53 specific compounds of the formula (T-31 ):
Figure imgf000035_0001
wherein m, Q, R3, and Z are as defined above in Table 1 , R1 and R2 are hydrogen and n is 0.
Table 32:
This table discloses 49 specific compounds of the formula (T-32):
Figure imgf000035_0002
wherein m, Q, R3, and Z are as defined above in Table 2, R1 and R2 are hydrogen and n is 0.
Table 33:
This table discloses 49 specific compounds of the formula (T-33):
Figure imgf000035_0003
wherein m, Q, R3, and Z are as defined above in Table 3, R1 and R2 are hydrogen and n is 0.
Table 34:
This table discloses 53 specific compounds of the formula (T-34):
Figure imgf000035_0004
wherein m, Q, R3, and Z are as defined above in Table 1 , R1 and R2 are hydrogen and n is 0. Table 35:
This table discloses 49 specific compounds of the formula (T-35):
Figure imgf000036_0001
(T-35),
wherein m, Q, R3, and Z are as defined above in Table 2, R1 and R2 are hydrogen and n is 0.
Table 36:
This table discloses 49 specific compounds of the formula (T-36):
Figure imgf000036_0002
(T-36),
wherein m, Q, R3, and Z are as defined above in Table 3, R1 and R2 are hydrogen and n is 0.
Table 37:
This table discloses 53 specific compounds of the formula (T-37):
Figure imgf000036_0003
wherein m, Q, R3, and Z are as defined above in Table 1 , R1 and R2 are hydrogen and n is 0.
Table 38:
This table discloses 49 specific compounds of the formula (T-38):
Figure imgf000036_0004
wherein m, Q, R3, and Z are as defined above in Table 2, R1 and R2 are hydrogen and n is 0.
Table 39:
This table discloses 49 specific compounds of the formula (T-39):
Figure imgf000036_0005
(T-39), wherein m, Q, R3, and Z are as defined above in Table 3, R1 and R2 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, Q, X, Z, R1, R2, R1a, R2b, R2, R3, R6, R7, R7a, R7b R7c, R8, R9, R10, R11 , R12, R13, R14, R15, R15a, R16, R17 and R18 are as defined hereinbefore unless explicitly stated otherwise. The compounds of the preceeding Tables 1 to 39 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 R3 and A are as defined for compounds of formula (I), with a suitable alkylating agent of formula (W), wherein R1 , R2, Q, X, n and Z are as defined for compounds of formula (I) and LG is a suitable leaving group, for example, halide or pseudohalide such as triflate, mesylate or tosylate, in a suitable solvent at a suitable temperature, as described in reaction scheme 1.
Reaction scheme 1
Figure imgf000037_0001
formula (X) fo
Figure imgf000037_0002
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. An alkylating agent of formula (W) may include, but is not limited to, bromoacetic acid, methyl bromoacetate, 3-bromopropionoic acid, methyl 3-bromopropionate, 2-bromo- N-methoxyacetamide, sodium 2-bromoethanesulphonate, 2,2-dimethylpropyl 2- (trifluoromethylsulfonyloxy)ethanesulfonate, 2-bromo-N-methanesulfonylacetamide, 3-bromo-N- methanesulfonylpropanamide, dimethoxyphosphorylmethyl trifluoromethanesulfonate, dimethyl 3- bromopropylphosphonate, 3-chloro-2, 2-dimethyl-propanoic acid, diethyl 2-bromoethylphosphonate and ethyl 3-(trifluoromethylsulfonyloxy)propanoate. Such alkylating agents and related compounds are either known in the literature or may be prepared by known literature methods. Compounds of formula (I) which may be described as 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.
Additonally, compounds of formula (I) may be prepared by reacting compounds of formula (X), wherein R3 and A are as defined for compounds of formula (I), with a suitably activated electrophilic alkene of formula (B), wherein Z is -S(0)20R10, -P(0)(R13)(OR1°) or -C(0)OR1° and R1 , R2, R1a, R10 and R13 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. The direct products of these reactions, which may be described as 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.
Reaction scheme 2
1a
R
Figure imgf000038_0001
formula (X) form ula (I), wherein formula (I), wherein
m=1 , n=0 and m=1 , n=0 and
Z=S(0)2OR10, P(0)(R13)(OR10), Z=S03H, P(0)(R13)(OH), C(0)OR10 C(0)OH
In a related reaction compounds of formula (I), wherein Q is C(R1aR2b), m is 1 , 2 or 3, n=0 and Z is -S(0)20H, -0S(0)20H or -NR6S(0)20H, may be prepared by the reaction of compounds of formula (X), wherein R3 and A are as defined for compounds of formula (I), with a cyclic alkylating agent of formula (E), (F) or (AF), wherein Ya is C(R1aR2b), O or NR6 and R1 , R2, R1a and R2b are as defined for compounds of formula (I), in a suitable solvent at a suitable temperature, as described in reaction scheme 3.
Reaction scheme 3
Figure imgf000039_0001
formula (E), Where
m=1 and n=0
Figure imgf000039_0002
Figure imgf000039_0003
formula (X) formula (I), wherein
m is 1 , 2 or 3, n=0 and
Z = SO3H, OSO3H or
Figure imgf000039_0004
NR6S03H
formula (F), Where m=2 and
n=0
orO
Figure imgf000039_0005
formula (AF)
Where m=1 and
n=0
Suitable solvents and suitable temperatures are as previously described. 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. Such 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)20H, may be prepared from a compound of formula (I), wherein m is 0, n is 0 and Z is C(0)OR1°, by treatment with trimethylsilylchloro sulfonate in a suitable solvent at a suitable temperature, as described in reaction scheme 4. Preferred conditions include heating the carboxylate precursor in neat trimethylsilylchlorosulfonate at a temperature between 25°C and 150°C. Reaction scheme 4
Figure imgf000040_0001
formula (I), wherein formula (I), wherein m=0, n=0 m=0, n=0
and Z=C(0)OR10 and Z=SO H A compound of formula (I), wherein Z is -S(0)20H, may be further prepared from a compound of formula (D), wherein n=0 and R1, R2, R3, A, and Q are as defined for a compound of formula (I), and LG is a suitable leaving group, for example, but not limited to, halide or pseudohalide such as triflate, mesylate or tosylate, by treatment with sodium sulfite in a suitable solvent at a suitable temperature, as described in reaction scheme 5. Preferred conditions include heating the a compound of formula (D) with sodium sulfite in water at a temperature between 30°C and 100°C.
Reaction scheme 5
Figure imgf000040_0002
formula (D), wherein formula (I), wherein n=0 n=0
A compound of formula (D) may be prepared by the alkylation of compounds of formula (X), wherein R3 and A are as defined for compounds of formula (I), with a suitable alkylating agent of formula (M), wherein n=0 and R1, R2 and Q are as defined for compounds of formula (I) and LG is a suitable leaving group, for example, but not limited to, halide or pseudohalide such as triflate, mesylate or tosylate, in a suitable solvent at a suitable temperature, as described in reaction scheme 6. An alkylating agent of formula (M) may include, but is not limited to, 2-chloroethyl trifluoromethanesulfonate. Reaction scheme 6
Figure imgf000041_0001
formula (X) formula (D), wherein
n=0 Furthermore, compounds of formula (I) may be prepared by reacting compounds of formula (X), wherein R3 and A are as defined for compounds of formula (I), with a suitable alcohol of formula (WW), wherein R1, R2, 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 and suitable acids include fluoroboric acid, triflic acid and bis(trifluoromethylsulfonyl)amine, as described in reaction scheme 7. Such alcohols are either known in the literature or may be prepared by known literature methods.
Reaction scheme 7
Figure imgf000041_0002
formula (X)
Figure imgf000041_0004
Acid, Ph3P
Compounds of formula (X), wherein A is as previously defined and R3 is H, may be prepared through the decarboxylation of compounds of formula (O), in an appropriate solvent, at an appropriate temperature, as outlined in reaction scheme 8.
Reaction scheme 8
Figure imgf000041_0003
formula (O) formula (X)
wherein R3=H Examples of such a reaction are known in the literature, for example, Demaree et al., J. Heterocyclic Chem., 1978, 15, 1295.
Compounds of formula (O), wherein A is as previously defined, may be prepared through the hydrolysis of compounds of formula (C), in the presence of a suitable base or acid, in an appropriate solvent, at an appropriate temperature, as outlined in reaction scheme 9. Related reactions are known in the literature.
Reaction scheme 9
Figure imgf000042_0001
formula (C)
formula (O)
R' = CrC6alkyl
Compounds of formula (C), wherein A is as previously defined, may be prepared by the cyclisation of compounds of formula (P) using an appropriate reagent or a combination of reagents, example reagents include Lawesson’s reagent or phosphorus pentasulfide, alternatively ammonium sulfite followed by bromine, in an appropriate solvent, at an appropriate temperature, as outlined in reaction scheme 10. Examples of such a reaction are known in the literature, for example, Gevorgyan et al., Org. Lett., 2016, 18, 1804.
Reaction scheme 10
Figure imgf000042_0002
formula (P) formula (C)
R' = C1-C6alkyl
Compounds of formula (P), wherein A is as previously defined, may be prepared from a compound of formula (A) by reaction with an appropriate diazo transfer reagent, for example, but not limited to, 4-acetamidobenzenesulfonyl azide, in the presence of a suitable base, in an appropriate solvent, at an appropriate temperature, as outlined in reaction scheme 1 1. Examples of such a reaction are known in the literature, for example, Moody et al., Tetrahedron, 2004, 60, 3967. Compounds of formula (A), wherein A is as previously defined are either known in the literature or can be prepared by known methods. Reaction scheme 11
Figure imgf000043_0001
formula (A) formula (P)
R' = CrC6alkyl
Compounds of formula (X), wherein A and R3 are as previously defined, may also be prepared by a cyclisation of compounds of formula (Q) using an appropriate reagent, for example, but not limited to, thionyl chloride, in an appropriate solvent, at an appropriate temperature, as outlined in reaction scheme 12. Examples of such a reaction are known in the literature, for example, Gevorgyan et al., Org. Lett., 2016, 18, 1804 and Thomas et al., J. Med. Chem. 1985, 28, 442. Reaction scheme 12
Figure imgf000043_0002
Compounds of formula (Q), wherein A and R3 are as previously defined, may be prepared from compounds of formula (S) and a hydrazide of formula (U), optionally in the presence of a suitable acid, for example acetic acid, in an appropriate solvent, at an appropriate temperature, as outlined in reaction scheme 13. Examples of such reactions are known in the literature, for example, Semakin et al., Beilstein J. Org. Chem., 2016, 12, 2471. Hydrazide compounds of formula (U) are either known in the literature or may be prepared by known methods. Compounds of formula (S), wherein A and R3 are as previously defined, are either known in the literature or may be prepared by known literature procedures, for example, Wolfe et al., J. Org. Chem., 1981 , 46, 294.
Reaction scheme 13
Figure imgf000043_0003
formula (U) formula (S) formula (Q)
Figure imgf000043_0004
In a further approach, compounds of formula (X) may be prepared by the transition metal crosscoupling 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) are either an organostannane, organoboronic acid or ester, organotrifluoroborate, organomagnesium, organocopper or organozinc (M‘), as outlined in reaction scheme 14. Hal is defined as a halogen or pseudo halogen, for example triflate, mesylate or tosylate. Such cross-couplings include Stille (for example Stille, J. K. Angew. Chem. Int. Ed. Engl. 1986, 25, 508), Suzuki-Miyaura (for example Lindsley et al, WO2013063549A1 ), Negishi (for example King, A. O.; Okukado, N.; Negishi, E. Chem. Comm. 1977, 19, 683), and Kumada (for example Tamao, K.; Sumitani, K.; Kumada, M. J. Am. Chem. Soc. 1972, 94, 4374). The coupling partners may be selected with reference to the specific cross-coupling reaction and target product. Transition metal catalysts, ligands, bases, solvents and temperatures may be selected with reference to the desired cross-coupling and are known in the literature. Compounds of formula (H), formula (K) and formula (L) are known in the literature, or may be prepared by known literature methods.
Reaction scheme 14
Transition metal
catalyst
Ligand
A— Hal +
Figure imgf000044_0002
Figure imgf000044_0001
formula (H) formula (J) formula (X)
Transition metal
catalyst
Ligand
A-M' +
Figure imgf000044_0004
Figure imgf000044_0003
formula (L) formula (K) formula (X)
An organometallic of formula (J), which is either an organostannane, organoboronic acid or ester, organotrifluoroborate, organomagnesium, organolithium, organocopper or organozinc (M‘), may be prepared from a compound of formula (XX), wherein R3 is defined for compounds of formula (I), by metallation, as outlined in reaction scheme 16. Example conditions to prepare an organolithium of formula (J) include treatment of a compound of formula (XX) with methyl lithium in an appropriate solvent at an appropriate temperature, see, for example, Thomas, E. W.; Zimmerman, D. C. Synthesis, 1985, 10, 945). Alternatively, an organometallic of formula (J) may be prepared from a compound of formula (K), wherein R3 is as defined for a compound of formula (I) and Hal is defined as a halogen or pseudo halogen, for example triflate, mesylate or tosylate, as described in scheme 16. Example conditions to prepare an organostannane of formula (J) include treatment of a compound of formula (K) with lithium tributyl tin in an appropriate solvent at an appropriate temperature, see, for example, WO 2010038465. Example conditions to prepare an organoboronic acid or ester of formula (J) 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, see, for example, KR 2015135626). Compounds of formula (K) and formula (XX) are either known in the literature or can be prepared by known methods.
Reaction scheme 15
Figure imgf000045_0001
formula (K) formula (J) formula (XX)
In a further approach, compounds of formula (X), wherein A and R3 are as previously defined, may be prepared by C-H activation cross-coupling of compounds of formula (XX) and formula (H), in the presence of an appropriate transition metal catalyst, ligand and base, in a suitable solvent at a suitable temperature, as outlined in reaction scheme 15. Hal is defined as a halogen or pseudo halogen, for example triflate, mesylate or tosylate. Examples of such reactions are known in the literature, for example, Chen et al, US20100152203. Compounds of formula (H) and formula (XX) are known in the literature, or may be prepared by known literature methods.
Reaction scheme 16
Transition metal
catalyst
Ligand
Base
A— Hal
Figure imgf000045_0002
Figure imgf000045_0003
formula (H) formula (XX) formula (X)
Finally, in an addtional approach outlined in scheme 17, biaryl thiadiazoles of formula (X) may be prepared by classical ring synthesis approaches starting from a compound of formula (ZZ), wherein T is a functional group which can be converted through one or more chemical steps into a 5-membered heteroaryl A, wherein A is as defined for compounds of formula (I). Such functional groups include, but are not limited to, acid, ester, nitrile, amide, thioamide and ketone. Related transformations are known in the literature. Substituted thiadiazoles may be prepared using methodology outlined in the literature, for example, but are not limited to, Minkkiila, A. et al, Eur. J. Med. Chem. 2009, 44, 2994,Aoyama, Iwamoto and Shioiri Heterocycles, 1986, 24, 589 and Sakai, Hida and Kondo Bull. Chem. Soc. Jpn. 1986, 59, 179. Reaction scheme 17
Functional Group
Transformation
Figure imgf000046_0003
Figure imgf000046_0001
Figure imgf000046_0002
formula (ZZ) formula (X)
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. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water- dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil- in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water- miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). 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. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se. As 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, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1 , 1 , 1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, A/-methyl-2-pyrrolidone and the like.
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 fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di- alkylphosphate esters; and also further substances described e.g. in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981 ).
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.
The 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. For example, 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, 10th 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. As a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
Preferred formulations can have the following compositions (weight %):
Emulsifiable concentrates:
active ingredient: 1 to 95 %, preferably 60 to 90 %
surface-active agent: 1 to 30 %, preferably 5 to 20 %
liquid carrier: 1 to 80 %, preferably 1 to 35 %
Dusts:
active ingredient: 0.1 to 10 %, preferably 0.1 to 5 %
solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates:
active ingredient: 5 to 75 %, preferably 10 to 50 %
water: 94 to 24 %, preferably 88 to 30 %
surface-active agent: 1 to 40 %, preferably 2 to 30 % Wettable powders:
active ingredient: 0.5 to 90 %, preferably 1 to 80 %
surface-active agent: 0.5 to 20 %, preferably 1 to 15 %
solid carrier: 5 to 95 %, preferably 15 to 90 %
Granules:
active ingredient: 0.1 to 30 %, preferably 0.1 to 15 %
solid carrier: 99.5 to 70 %, preferably 97 to 85 %
The composition of the present may further comprise at least one additional pesticide. For example, the compounds according to the invention can also be used in combination with other herbicides or plant growth regulators. In a preferred embodiment the additional pesticide is a herbicide and/or herbicide safener.
Thus, compounds of formula (I) can be used in combination with one or more other herbicides to provide various herbicidal mixtures. Specific examples of such mixtures include (wherein Ί” represents a compound of formula (I)):- 1 + acetochlor; I + acifluorfen (including acifluorfen-sodium); I + aclonifen; I + alachlor; I + alloxydim; I + ametryn; I + amicarbazone; I + amidosulfuron; I + aminocyclopyrachlor ; I + aminopyralid; I + amitrole; I + asulam; I + atrazine; I + bensulfuron (including bensulfuron-methyl); I + bentazone; I + bicyclopyrone; I + bilanafos; I + bifenox; I + bispyribac-sodium; I + bixlozone; I + bromacil; I + bromoxynil; I + butachlor; I + butafenacil; I + cafenstrole; I + carfentrazone (including carfentrazone-ethyl); cloransulam (including cloransulam-methyl); I + chlorimuron (including chlorimuron-ethyl); I + chlorotoluron; I + cinosulfuron; I + chlorsulfuron; I + cinmethylin; I + clacyfos; I + clethodim; I + clodinafop (including clodinafop-propargyl); I + clomazone; I + clopyralid; I + cyclopyranil; I + cyclopyrimorate; I + cyclosulfamuron; I + cyhalofop (including cyhalofop-butyl); I + 2,4-D (including the choline salt and 2-ethylhexyl ester thereof); I + 2,4-DB; I + daimuron; I + desmedipham; I + dicamba (including the aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts thereof); I + diclofop-methyl; I + diclosulam; I + diflufenican; I + difenzoquat; I + diflufenican; I + diflufenzopyr; I + dimethachlor; I + dimethenamid-P; I + diquat dibromide; I + diuron; I + esprocarb; I + ethalfluralin; I + ethofumesate; I + fenoxaprop (including fenoxaprop-P-ethyl); I + fenoxasulfone; I + fenquinotrione; I + fentrazamide; I + flazasulfuron; I + florasulam; I + florpyrauxifen; I + fluazifop (including fluazifop-P-butyl); I + flucarbazone (including flucarbazone-sodium);; I + flufenacet; I + flumetralin; I + flumetsulam; I + flumioxazin; I + flupyrsulfuron (including flupyrsulfuron-methyl-sodium);; I + fluroxypyr (including fluroxypyr-meptyl);; I + fluthiacet-methyl; I + fomesafen; I + foramsulfuron; I + glufosinate (including the ammonium salt thereof); I + glyphosate (including the diammonium, isopropylammonium and potassium salts thereof); I + halauxifen (including halauxifen-methyl); I + halosulfuron-methyl; I + haloxyfop (including haloxyfop- methyl); I + hexazinone; I + hydantocidin; I + imazamox; I + imazapic; I + imazapyr; I + imazaquin; I + imazethapyr; I + indaziflam; I + iodosulfuron (including iodosulfuron-methyl-sodium); I + iofensulfuron; I + iofensulfuron-sodium; I + ioxynil; I + ipfencarbazone; I + isoproturon; I + isoxaben; I + isoxaflutole; I + lactofen; I + lancotrione; I + linuron; I + MCPA; I + MCPB; I + mecoprop-P; I + mefenacet; I + mesosulfuron; I + mesosulfuron-methyl; I + mesotrione; I + metamitron; I + metazachlor; I + methiozolin; I + metobromuron; I + metolachlor; I + metosulam; I + metoxuron; I + metribuzin; I + metsulfuron; I + molinate; I + napropamide; I + nicosulfuron; I + norflurazon; I + orthosulfamuron; I + oxadiargyl; I + oxadiazon; I + oxasulfuron; I + oxyfluorfen; I + paraquat dichloride; I + pendimethalin; I + penoxsulam; I + phenmedipham; I + picloram; I + picolinafen; I + pinoxaden; I + pretilachlor; I + primisulfuron-methyl; I + prodiamine; I + prometryn; I + propachlor; I + propanil; I + propaquizafop; I + propham; I + propyrisulfuron, I + propyzamide; I + prosulfocarb; I + prosulfuron; I + pyraclonil; I + pyraflufen (including pyraflufen-ethyl): I + pyrasulfotole; I + pyrazolynate, I + pyrazosulfuron-ethyl; I + pyribenzoxim; I + pyridate; I + pyriftalid; I + pyrimisulfan, I + pyrithiobac-sodium; I + pyroxasulfone; I + pyroxsulam ; I + quinclorac; I + quinmerac; I + quizalofop (including quizalofop-P-ethyl and quizalofop-P-tefuryl),; I + rimsulfuron; I + saflufenacil; I + sethoxydim; I + simazine; I + S-metolachlor; I + sulcotrione; I + sulfentrazone; I + sulfosulfuron; I + tebuthiuron; I + tefuryltrione; I + tembotrione; I + terbuthylazine; I + terbutryn; I + thiencarbazone; I + thifensulfuron; I + tiafenacil; I + tolpyralate; I + topramezone; I + tralkoxydim; I + triafamone; I + triallate; I + triasulfuron; I + tribenuron (including tribenuron-methyl); I + triclopyr; I + trifloxysulfuron (including trifloxysulfuron-sodium); I + trifludimoxazin; I + trifluralin; I + triflusulfuron; I + tritosulfuron; I + 4-hydroxy-1-methoxy-5-nnethyl-3-[4-(trifluoronnethyl)-2- pyridyl]imidazolidin-2-one; I + 4-hydroxy-1 ,5-dimethyl-3-[4-(trifluoronnethyl)-2-pyridyl]innidazolidin-2-one; I + 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoronnethyl)-2-pyridyl]innidazolidin-2-one; I + 4-hydroxy-1- methyl-3-[4-(trifluoronnethyl)-2-pyridyl]innidazolidin-2-one; I + 4-hydroxy-1 ,5-dimethyl-3-[1-nnethyl-5- (trifluoromethyl)pyrazol-3-yl]innidazolidin-2-one; I + (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-
3-methyl-innidazolidin-2-one; I + 3-[2-(3,4-dimethoxyphenyl)-6-nnethyl-3-oxo-pyridazine-4- carbonyl]bicyclo[3.2.1]octane-2,4-dione; I + 2-[2-(3,4-dimethoxyphenyl)-6-nnethyl-3-oxo-pyridazine-4- carbonyl]-5-methyl-cyclohexane-1 ,3-dione; I + 2-[2-(3,4-dimethoxyphenyl)-6-nnethyl-3-oxo-pyridazine-
4-carbonyl]cyclohexane-1 ,3-dione; I + 2-[2-(3,4-dimethoxyphenyl)-6-nnethyl-3-oxo-pyridazine-4- carbonyl]-5,5-dimethyl-cyclohexane-1 ,3-dione; I + 6-[2-(3,4-dimethoxyphenyl)-6-nnethyl-3-oxo- pyridazine-4-carbonyl]-2,2,4,4-tetrannethyl-cyclohexane-1 ,3,5-trione; I + 2-[2-(3,4-dimethoxyphenyl)-6- methyl-3-oxo-pyridazine-4-carbonyl]-5-ethyl-cyclohexane-1 ,3-dione; I + 2-[2-(3,4-dimethoxyphenyl)-6- methyl-3-oxo-pyridazine-4-carbonyl]-4,4,6,6-tetrannethyl-cyclohexane-1 ,3-dione; I + 2-[6-cyclopropyl-2- (3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5-nnethyl-cyclohexane-1 ,3-dione; I + 3-[6- cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione; I + 2- [6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5,5-dinnethyl-cyclohexane-1 ,3- dione; I + 6-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetrannethyl- cyclohexane-1 , 3, 5-trione; I + 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4- carbonyl]cyclohexane-1 ,3-dione; I + 4-[2-(3,4-dimethoxyphenyl)-6-nnethyl-3-oxo-pyridazine-4-carbonyl]- 2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione and I + 4-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo- pyridazine-4-carbonyl]-2,2,6,6-tetrannethyl-tetrahydropyran-3,5-dione, I + 4-amino-3-chloro-5-fluoro-6- (7-fluoro-1 H-indol-6-yl)pyridine-2-carboxylic acid as well as I + agrochemically acceptable esters thereof, for example, l+ methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1 H-indol-6-yl)pyridine-2- carboxylate). 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.
The 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 (wherein Ί” represents a compound of formula (I)) include:- I + benoxacor, I + cloquintocet (including cloquintocet-mexyl); I + cyprosulfamide; I + dichlormid; I + fenchlorazole (including fenchlorazole-ethyl); I + fenclorim; I + fluxofenim; l+ furilazole I + isoxadifen (including isoxadifen-ethyl); I + mefenpyr (including mefenpyr-diethyl); I + metcamifen; I + N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino] benzenesulfonamide and I + oxabetrinil.
Particularly preferred are mixtures of a compound of formula (I) with cyprosulfamide, isoxadifen (including isoxadifen-ethyl), cloquintocet (including cloquintocet-mexyl) and/or N-(2-methoxybenzoyl)-4- [(methyl-aminocarbonyl)amino]benzenesulfonamide.
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, 14th 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.
Preferably the mixing ratio of compound of formula (l) to safener is from 100:1 to 1 : 10, especially from 20: 1 to 1 :1.
The 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. Generally the plants to be controlled are unwanted plants (weeds). ‘Locus’ means the area in which the plants are growing or will grow.
The rates of application of compounds of formula (I) may vary within wide limits and depend on the nature of the soil, the method of application (pre-emergence; post-emergence; application to the seed furrow; no tillage application etc.), the crop plant, the weed(s) to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. The compounds of formula (I) according to the invention are generally applied at a rate of from 10 to 2000 g/ha, especially from 50 to 1000 g/ha.
The application is generally made by spraying the composition, typically by tractor mounted sprayer for large areas, but other methods such as dusting (for powders), drip or drench can also be used. Useful plants in which the 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.
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. 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). Examples of 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). Examples of 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. Examples of 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). For example, 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).
Other useful plants include turf grass for example in golf-courses, lawns, parks and roadsides, or grown commercially for sod, and 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. Examples of 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. Examples of 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.
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. Furthermore, 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.
Various aspects and embodiments of the present invention will now be illustrated in more detail by way of example. It will be appreciated that modification of detail may be made without departing from the scope of the invention.
EXAMPLES
The Examples which follow serve to illustrate, but do not limit, the invention.
Formulation Examples
Wettable powders a) b) c)
active ingredients 25 % 50 % 75 %
sodium lignosulfonate 5 % 5 %
sodium lauryl sulfate 3 % - 5 %
sodium diisobutylnaphthalenesulfonate 6 % 10 %
phenol polyethylene glycol ether 2 %
(7-8 mol of ethylene oxide)
highly dispersed silicic acid 5 % 10 % 10 %
Kaolin 62 % 27 %
The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
Emulsifiable concentrate
active ingredients 10 %
octylphenol polyethylene glycol ether 3 %
(4-5 mol of ethylene oxide)
calcium dodecylbenzenesulfonate 3 %
castor oil polyglycol ether (35 mol of ethylene oxide) 4 %
Cyclohexanone 30 %
xylene mixture 50 %
Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water. Dusts a) b) c)
Active ingredients 5 % 6 % 4 %
Talcum 95 %
Kaolin - 94 %
mineral filler - - 96 %
Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill.
Extruder granules
Active ingredients 15 %
sodium lignosulfonate 2 %
carboxymethylcellulose 1 %
Kaolin 82 %
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.
Coated granules
Active ingredients 8 %
polyethylene glycol (mol. wt. 200) 3 %
Kaolin 89 %
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.
Suspension concentrate
active ingredients 40 %
propylene glycol 10 %
nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
Sodium lignosulfonate 10 %
carboxymethylcellulose 1 %
silicone oil (in the form of a 75 % emulsion in water) 1 %
Water 32 %
The finely ground 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.
Slow Release Capsule Suspension
28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1 ). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns.
The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
List of Abbreviations:
Boc = ferf-butyloxycarbonyl
br = broad
CDCI3 = chloroform-d
CD3OD = methanol-d
°C = degrees Celsius
D2O = water-d
DCM = dichloromethane
d = doublet
dd = double doublet
dt = double triplet
DMSO = dimethylsulfoxide
EtOAc = ethyl acetate
h = hour(s)
HCI = hydrochloric acid
HPLC = high-performance liquid chromatography (description of the apparatus and the methods used for HPLC are given below)
m = multiplet
M = molar
min = minutes
MHz = mega hertz
mL = millilitre
mp = melting point
ppm = parts per million
q = quartet
quin = quintet
rt = room temperature
s = singlet
t = triplet
THF = tetrahydrofuran
LC/MS = Liquid Chromatography Mass Spectrometry Preparative Reverse Phase HPLC Method:
Compounds purified by mass directed preparative HPLC using ES+/ES- on a Waters FractionLynx Autopurification system comprising a 2767 injector/collector with a 2545 gradient pump, two 515 isocratic pumps, SFO, 2998 photodiode array (Wavelength range (nm): 210 to 400), 2424 ELSD and QDa mass spectrometer. A Waters Atlantis T3 5micron 19x10mm guard column was used with a Waters Atlantis T3 OBD, 5micron 30x100mm prep column.
Ionisation method: Electrospray positive and negative: Cone (V) 20.00, Source Temperature (°C) 120, Cone Gas Flow (L/Hr.) 50
Mass range (Da): positive 100 to 800, negative 115 to 800.
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:
Figure imgf000056_0002
515 pump Oml/min Acetonitrile (ACD)
515 pump I ml/min 90% Methanol/10% Water (make up pump)
Solvent A: Water with 0.05% Trifluoroacetic Acid
Solvent B: Acetonitrile with 0.05% Trifluoroacetic Acid
PREPARATION EXAMPLES
Example 1 : Preparation of 3-(5-oxazol-2-ylthiadiazol-3-ium-3-yl)propane-1 -sulfonate:
compound A1
Figure imgf000056_0001
Step 1 : Preparation of ethyl 3-oxazol-2-yl-3-oxo-propanoate
Figure imgf000057_0001
To a suspension of sodium hydride (1.88 g) in tetrahydrofuran (168 ml_), under nitrogen atmosphere, was added ethyl oxazole-2-carboxylate (5 g) portionwise. The reaction mixture was heated at 75°C and ethyl acetate (4.47 g) was added dropwise and heating continued for 20 hours. The reaction mixture was quenched with saturated ammonium chloride and extracted with ethyl acetate. The organic layer was washed with brine, dried with magnesium sulfate, filtered and concentrated to give ethyl 3- oxazol-2-yl-3-oxo-propanoate as an orange oil. The product was used in the subsequent step without further purification.
Step 2: Preparation of ethyl 2-diazo-3-oxazol-2-yl-3-oxo-propanoate
Figure imgf000057_0002
To a solution of ethyl 3-oxazol-2-yl-3-oxo-propanoate (5.1 g) and 4-acetamidobenzenesulfonyl azide (7.59 g) in dichloromethane (167 ml_) at 0°C was added triethylamine (8.54 g) dropwise. The reaction was slowly warmed to room temperature over 1 hour and stirred for an additional 1 hour. The reaction mixture was filtered through a plug of silica, washing through with further dichloromethane. The filtrate was concentrated to give ethyl 2-diazo-3-oxazol-2-yl-3-oxo-propanoate as a pale red solid. The product was used in the subsequent step without further purification.
Step 3: Preparation of 5-oxazol-2-ylthiadiazole-4-carboxylic acid
Figure imgf000057_0003
A solution of ethyl 2-diazo-3-oxazol-2-yl-3-oxo-propanoate (5.8 g) and Lawesson’s reagent (13.88 g) in toluene (139 mL) was heated at 120°C for 2 hours. The cooled reaction mixture was filtered through a plug of silica, washing through with dichloromethane. The filtrate was concentrated to afford a crude brown gum. The crude gum was stirred in tetrahydrofuran (1 1 1 mL) and 2M aqueous sodium hydroxide (1 1 1 mL) at room temperature for 4 hours. The reaction mixture was partitioned with dichloromethane and the aqueous phase was carefully acidified to pH1 using concentrated hydrochloric acid. The resulting precipitate was filtered off and washed with diethyl ether to give 5-oxazol-2- ylthiadiazole-4-carboxylic acid as a beige solid.
1 H NMR (400MHz, DMSO-c/e) 8.50 (d, 1 H), 7.62 (d, 1 H) (one C02H proton missing). Step 4: Preparation of 2-(thiadiazol-5-yl)oxazole
Figure imgf000058_0001
A mixture of 5-oxazol-2-ylthiad iazole-4-carboxyl ic acid (1.06 g) and 1 ,4-dioxane (54 ml_) was heated at 100°C for 24 hours. The reaction mixture was concentrated to give 2-(thiadiazol-5-yl)oxazole as a beige solid.
1 H NMR (400MHz, CDCIs) 9.18 (s, 1 H), 7.83 (d, 1 H), 7.37 (s, 1 H).
Step 5: Preparation of 3-(5-oxazol-2-ylthiadiazol-3-ium-3-yl)propane-1 -sulfonate (compound A1 )
A solution of 2-(thiadiazol-5-yl)oxazole (0.08 g) and 1 ,3-propanesultone (0.097 g) was heated in 1 ,4-dioxane (3 ml_) at 100°C for 5 days. The resulting precipitate was filtered off and washed with ethanol to give 3-(5-oxazol-2-ylthiadiazol-3-ium-3-yl)propane-1-sulfonate as a beige solid.
1 H NMR (400 MHz, D20) 10.12 (s, 1 H), 8.15 (s, 1 H), 7.51 (s, 1 H), 5.17 (t, 2 H), 3.05 - 2.96 (m, 2 H), 2.64 - 2.51 (m, 2 H).
Example 2 Preparation of 2-(5-oxazol-2-ylthiadiazol-3-ium-3-yl)ethanesulfonate: compound
A2
Figure imgf000058_0002
To a solution of 2-chloroethanol (0.08 g) and pyridine (0.094 g) in dichloromethane (7 ml_) at - 10°C was added trifluoromethanesulfonic anhydride (0.34 g) dropwise. The reaction was stirred at - 10°C for 1 hour and a solution of 2-(thiadiazol-5-yl)oxazole (0.1 g) in dichloromethane (2 mL) was added. The reaction was allowed to warm to room temperature and stirred for 20 hours. The reaction mixture was concentrated and the residue was dissolved in water (3 mL). Sodium sulfite (0.125 g) was added in one portion and the mixture heated at 100°C for 2 hours. The cooled reaction mixture was extracted with dichloromethane and the aqueous phase was concentrated and purified by preparative reverse phase HPLC to give 2-(5-oxazol-2-ylthiadiazol-3-ium-3-yl)ethanesulfonate as a colourless solid.
1 H NMR (400MHz, D2O) 10.16 (s, 1 H), 8.13 (d, 1 H), 7.49 (d, 1 H), 5.41 - 5.33 (m, 2 H), 3.69 (dd, 2 H).
Example 3 Preparation of methyl 3-[4-methyl-5-(5-methyloxazol-2-yl)thiadiazol-3-ium-3- yl]propanoate 2,2,2-trifluoroacetate: compound A11
Figure imgf000059_0004
Step 1 : Preparation of 3-oxo-A/-prop-2-ynyl-butanamide
Figure imgf000059_0001
To a solution of tert-butyl 3-oxobutanoate (20 g) in toluene (160 nriL) was added prop-2-yn-1- amine (6.27 g) drop wise at room temperature. The reaction mixture was heated at 1 10°C for 16 hours. The reaction mixture was concentrated and partitioned between water and ethyl acetate (300 nriL). The organic layer was dried over anhydrous sodium sulfate and concentrated to afford 3-oxo -N- prop-2-ynyl-butanamide as a light brown solid, which was used crude in the next step. Step 2: Preparation of 1-(5-methyloxazol-2-yl)propan-2-one
Figure imgf000059_0002
To a solution of 3-oxo-A/-prop-2-ynyl-butanamide (4 g) in acetonitrile (50 nriL) was added trichlorogold (0.785 g) and the reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was filtered through celite and partitioned between water and ethyl acetate (200 nriL). The organic layer was dried over anhydrous sodium sulfate, concentrated and purified on silica eluting with 50% ethyl acetate in n-hexanes to afford 1-(5-methyloxazol-2-yl)propan-2-one as a violet liquid.
Ή NMR (400MHz, CDCIs) 6.61 (s, 1 H), 3.76 (s, 2H), 2.23 (s, 3H), 2.16 (s, 3H)
Step 3: Preparation of A/-[1-methyl-2-(5-methyloxazol-2-yl)ethylidene]amino] benzenesulfonamide
Figure imgf000059_0003
A solution of 1-(5-methyloxazol-2-yl)propan-2-one (1.1 g) in chloroform (20 nriL) was added to a mixture of benzenesulfonohydrazide (1.09 g) and acetic acid (1.12 nriL) at room temperature. The resulting mixture was heated at 70°C for 6 hours. The reaction mixture was concentrated under reduced pressure to afford A/-[1-methyl-2-(5-methyloxazol-2-yl)ethylidene]amino] benzenesulfonamide as a red solid, which was used crude in the next step.
Step 4: Preparation of 5-methyl-2-(4-methylthiadiazol-5-yl)oxazole
Figure imgf000060_0001
A mixture of N-[1-methyl-2-(5-methyloxazol-2-yl)ethylidene]amino] benzenesulfonamide (2.1 g) and thionyl chloride (20 ml_) was was stirred at room temperature for 16 hours. The reaction mixture was concentrated and purified by chromatography on silica eluting with 0-50% ethyl acetate in hexanes to afford 5-methyl-2-(4-methylthiadiazol-5-yl)oxazole as a light brown solid.
Ή NMR (400MHz, CDCI3) 6.90 (s, 1 H), 2.97 (s, 3H), 2.36 (s, 3H)
Step 5: Preparation of methyl 3-[4-methyl-5-(5-methyloxazol-2-yl)thiadiazol-3-ium-3-yl]propanoate 2,2,2-trifluoroacetate A1 1
A mixture of 5-methyl-2-(4-methylthiadiazol-5-yl)oxazole (0.2 g) and methyl 3- bromopropanoate (8.16 g) was heated at 85°C for 5 days. The reaction mixture was dissolved in water (25 ml_) and washed with dichloromethane (2 * 25 ml_). The aqueous layer was concentrated and purified by preparative reverse phase HPLC to give (trifluoroacetic acid was present in the eluent) to afford methyl 3-[4-methyl-5-(5-methyloxazol-2-yl)thiadiazol-3-ium-3-yl]propanoate 2,2,2- trifluoroacetate as light yellow liquid.
Ή NMR (400 MHz, D2O) 7.12 (s, 1 H), 5.05 (t, 2H), 3.62 (s, 3H), 3.29 (t, 2H), 3.03 (s, 3H), 2.37 (s, 3H)
Example 4 Preparation of 3-(5-oxazol-2-ylthiadiazol-3-ium-3-yl)propanoic acid bromide:
compound A6
Figure imgf000060_0002
A mixture of 2-(thiadiazol-5-yl)oxazole (0.15 g) and methyl 3-bromopropanoate (0.5 g) was heated at 70°C for for 16 hours. The reaction mixture was dissolved in water (10.0 ml_) and washed with dichloromethane (2 * 20 ml_). The aqueous layer was concentrated and purified by preparative reverse phase HPLC (100% water) to afford 3-(5-oxazol-2-ylthiadiazol-3-ium-3-yl)propanoic acid bromide as an off-white solid.
Ή NMR (400 MHz, DMSO-de) 10.55 (s, 1 H), 8.66 (d, 1 H), 7.77 (d, 1 H), 5.19 (t, 2H), 3.21 (t, 2H) (CO2H proton missing) Example 5: Preparation of pyrrolidin-1-yl-[5-(thiadiazol-5-yl)isoxazol-3-yl]methanone
Figure imgf000061_0001
Step 1 : Preparation of pyrrolidin-1-yl-[5-[(E)-2-pyrrolidin-1-ylvinyl]isoxazol-3-yl]methanone
Figure imgf000061_0002
To a mixture of methyl 5-methylisoxazole-3-carboxylate (0.5 g) and pyrrolidine (0.591 ml_), under nitrogen atmosphere, was added A/,A/-dimethylformamide dimethyl acetal (0.970 ml_) and the resulting pale yellow solution was heated at 90°C for 2 hours, then left to cool overnight. No product was observed so the reaction mixture was heated at 90°C for a further 96 hours. The reaction was cooled and concentrated. Diethyl ether was added to the resulting residue and the mixture was stirred for 30 minutes. The resulting brown precipitate was collected by filtration, washed with diethyl ether and air dried to give pyrrolidin-1-yl-[5-[(E)-2-pyrrolidin-1-ylvinyl]isoxazol-3-yl]methanone.
Ή NMR (400MHz, CDCIs) 7.30 (d, 1 H), 6.03 (s, 1 H), 4.95 (d, 1 H), 3.85 (t, 2H), 3.63 (t, 2H), 3.33 - 3.22 (m, 4H), 2.00 - 1.87 (m, 8H)
Step 2: Preparation of [5-[(tert-butylhydrazono)methyl]isoxazol-3-yl]-pyrrolidin-1-yl-methanone
Figure imgf000061_0003
To a solution of pyrrolidin-1-yl-[5-[(E)-2-pyrrolidin-1-ylvinyl]isoxazol-3-yl]methanone (0.4 g) in 1 ,4-dioxane (2 ml_) was added (tert-butylamino)ammonium chloride (0.191 g) and the reaction was heated at 80°C for 60 minutes. The reaction was allowed to cool and used in the next step without further purification.
Step 3: Preparation of pyrrolidin-1-yl-[5-(thiadiazol-5-yl)isoxazol-3-yl]methanone
A solution of [5-[(tert-butylhydrazono)methyl]isoxazol-3-yl]-pyrrolidin-1-yl-methanone (0.2 g) in dichloromethane (3 ml_) was cooled to -78°C and thionyl chloride (0.262 ml_) was added drop wise. The reaction was allowed to warm slowly to room temperature. The mixture was partitioned between dichloromethane and water and the water layer was extracted with further dichloromethane. The combined organic layers were concentrated and purified by chromatography on silica eluting with a dichloromethane and methanol mixture to give pyrrolidin-1-yl-[5-(thiadiazol-5-yl)isoxazol-3- yl]methanone.
Ή NMR (400MHz, CDCIs) 9.41 (s, 1 H), 8.24 (s, 1 H), 3.96 - 3.80 (m, 3H), 3.37 - 3.27 (m, 2H), 2.09 - 1.95 (m, 4H)
Additional compounds in Table A were prepared by analogous procedures, from appropriate starting materials.
Table A Physical data for compounds of the invention
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
BIOLOGICAL EXAMPLES
Post-emergence efficacy
Seeds of a variety of test species were sown in standard soil in pots. After cultivation for 14 days (post-emergence) under controlled conditions in a glasshouse (at 24/16 °C, day/night; 14 hours light; 65 % humidity), the plants were sprayed with an aqueous spray solution derived from the dissolution of the technical active ingredient formula (I) in a small amount of acetone and a special solvent and emulsifier mixture referred to as IF50 (1 1.12% Emulsogen EL360 TM + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether), to create a 50g/l solution which was then diluted to required concentration using 0.25% or 1 % Empicol ESC70 (Sodium lauryl ether sulphate) + 1 % ammonium sulphate as diluent. The test plants were then grown in a glasshouse under controlled conditions (at 24/16 °C, day/night; 14 hours light; 65 % humidity) and watered twice daily. After 13 days the test was evaluated (100 = total damage to plant; 0 = no damage to plant).
The results are shown in Table B (below). A value of n/a indicates that this combination of weed and test compound was not tested/assessed.
Test plants:
Ipomoea hederacea (IPOHE), Euphorbia heterophylla (EPHHL), Chenopodium album (CHEAL), Amaranthus palmeri (AMAPA), Lolium perenne (LOLPE), Digitaria sanguinalis (DIGSA), Eleusine indica (ELEIN), Echinochloa crus-galli (ECHCG), Setaria faberi (SETFA)
Table B Control of weed species by compounds of formula (I) after post-emergence application
Figure imgf000064_0002

Claims

CLAIMS:
1. A compound of formula (I) or an agronomically acceptable salt or zwitterionic species thereof:
Figure imgf000065_0001
wherein
R1 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl, C2-C6alkenyl, C2- Cealkynyl, Cs-Cecycloalkyl, Ci-Cehaloalkyl, -OR7, -OR15a, -N(R6)S(0)2R15, -N(R6)C(0)R15, - N(R6)C(0)0R15, -N(R6)C(0)NR16R17, -N(R6)CHO, -N(R7a)2 and -S(0 R15;
R2 is selected from the group consisting of hydrogen, halogen, Ci-C6alkyl and Ci-C6haloalkyl; or R1 and R2 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 wherein when R1 is selected from the group consisting of -OR7, -OR15a, -N(R6)S(0)2R15, - N(R6)C(0)R15, -N(R6)C(0)0R15, -N(R6)C(0)NR16R17, -N(R6)CHO, -N(R7a)2 and -S(0 R15, then R2 is selected from the group consisting of hydrogen and Ci-Cealkyl;
R3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, -S(0)rR15, Ci- Cealkyl, Ci-C6fluoroalkyl, Ci-C6fluoroalkoxy, Ci-C6alkoxy, C3-C6cycloalkyl and -N(R6)2;
Q is (CR1aR2b)m; m is 0, 1 , 2 or 3; each R1a and R2b are independently selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Cehaloalkyl, -OH, -OR7, -OR15a, -NH2, -NHR7, -NHR15a, -N(R6)CHO, -NR7bR7c and -S(0)rR15; or each R1a and R2b 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 R6 is independently selected from hydrogen and Ci-C6alkyl; each R7 is independently selected from the group consisting of Ci-C6alkyl, -S(0)2R15, - C(0)R15, -C(0)OR15 and -C(0)NR16R17; each R7a is independently selected from the group consisting of -S(0)2R15, -C(0)R15, - C(0)OR15 -C(0)NR16R17 and -C(0)NR6R15a;
R7b and R7c are independently selected from the group consisting of Ci-C6alkyl, -S(0)2R15, - C(0)R15, -C(0)OR15, -C(0)NR16R17 and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different; or R7b and R7c 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;
A is a 5-membered heteroaryl ring comprising 1 , 2, 3 or 4 heteroatoms each independently selected from the group consisting of N, O and S, wherein said 5-membered heteroaryl ring is optionally substituted by 1 , 2, or 3 R8 substituents;
and when A is a 5-membered heteroaryl ring substituted by R8 on one or more ring carbon atoms, each of said R8substitutents is independently selected from the group consisting of halogen, nitro, cyano, -NH2, -NHR7, -N(R7)2, -OH, -OR7, -S(0)rR15, - NR6S(0) R15, -C(0)OR10, -C(0)R15, -C(0)NR16R17, -S(0) NR16R17, Ci-Cealkyl, Ci- Cehaloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, C3-C6cycloalkoxy, C2-C6alkenyl, C2- Cehaloalkenyl, C2-C6alkynyl, Ci-C3alkoxyCi-C3alkyl-, hydroxyCi-Cealkyl-, Ci- C3alkoxyCi-C3alkoxy-, Ci-C6haloalkoxy, Ci-C3haloalkoxyCi-C3alkyl-, C3-C6alkenyloxy, C3-C6alkynyloxy, -C(R6)=NOR6, phenyl and a 5- or 6- membered heteroaryl, which comprises 1 , 2, 3 or 4 heteroatoms independently selected from N, O and S, and wherein said phenyl or heteroaryl are optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different;
and/or when A is a 5-membered heteroaryl ring substituted by an R8 on a ring nitrogen atom, said R8 is selected from the group consisting of -OR7, Ci-C6alkyl, Ci- Cehaloalkyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, C3-C6cycloalkoxy, C2-C6alkenyl, C2- Cehaloalkenyl, C2-C6alkynyl, Ci-C3alkoxyCi-C3alkyl-, Ci-C3alkoxyCi-C3alkoxy-, Ci- Cehaloalkoxy, Ci-C3haloalkoxyCi-C3alkyl-, C3-C6alkenyloxy and C3-C6alkynyloxy; each R9 is independently selected from the group consisting of -OH, halogen, cyano, -N(R6)2, Ci-C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl and Ci-C4haloalkoxy;
X is independently selected from the group consisting of C3-C6cycloalkyl, phenyl, a 5- or 6- membered heteroaryl, which comprises 1 , 2, 3 or 4 heteroatoms independently selected from N, O and S, and a 4- to 6- membered heterocyclyl, which comprises 1 , 2 or 3 heteroatoms independently selected from N, O and S, and wherein said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties are optionally substituted by 1 or 2 R9, substituents and wherein the aforementioned CR1R2 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)OR1°, -CH2OH, -CHO, -C(0)NHOR11 , - C(0)NHCN, -OC(0)NHOR11 , -OC(0)NHCN, -NR6C(0)NH0R11 , -NR6C(0)NHCN, - C(0)NHS(0) R12, -0C(0)NHS(0)2R12, -NR6C(0)NHS(0)2R12, -S(0)20R10, -0S(0)20R10, - NR6S(0)20R10, -NR6S(0)OR10, -NHS(0)2R14, -S(0)OR10, -OS(0)OR10, -S(0)2NHCN, - S(0)2NHC(0)R18, -S(0)2NHS(0)2R12, -OS(0)2NHCN, -0S(0)2NHS(0)2R12, - 0S(0)2NHC(0)R18, -NR6S(0)2NHCN, -NR6S(0)2NHC(0)R18, -N(OH)C(0)R15, -ONHC(0)R15, -NR6S(0)2NHS(0)2R12, -P(0)(R13)(OR10), -P(0)H(OR10), -OP(0)(R13)(OR10), - NR6P(0)(R13)(0R1°) and tetrazole;
R10 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 R9 substituents, which may be the same or different;
R11 is selected from the group consisting of hydrogen, Ci-C6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different;
R12 is selected from the group consisting of Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, -OH, - N(R6)2 and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different;
R13 is selected from the group consisting of -OH, Ci-C6alkyl, Ci-C6alkoxy and phenyl;
R14 is Ci-C6haloalkyl;
R15 is selected from the group consisting of Ci-C6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different;
R15a is phenyl, wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different;
R16 and R17 are independently selected from the group consisting of hydrogen and Ci-C6alkyl; or R16 and R17 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; R18 is selected from the group consisting of hydrogen, Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, -N(R6)2 and phenyl, and wherein said phenyl is optionally substituted by 1 , 2 or 3 R9 substituents, which may be the same or different; and r is 0, 1 or 2.
2. A compound according to claim 1 , wherein R1 and R2 are each independently hydrogen or Ci- Cealkyl.
3. A compound according to claim 1 or claim 2, wherein m is 1 or 2.
4. A compound according to any one of claims 1 to 3, wherein R3, is selected from the group consisting of hydrogen, Ci-C6alkyl and Ci-C6alkoxy.
5. A compound according to any one of claims 1 to 4, wherein R3 is hydrogen.
6. A compound according to any one of claims 1 to 5, wherein A is selected from the group consisting of tetrazol-5-yl, 1 ,2,4-triazol-3-yl, 1 ,2,4-triazol-5-yl, isoxazol-3-yl, oxazol-2-yl, thiazol- 2-yl, 1 ,3,4-thiadiazol-2-yl, triazol-4-yl, triazol-5-yl, pyrazol-3-yl, pyrazol-5-yl, 1 ,3,4-oxadiazol-2- yl, 1 ,2,4-thiadiazol-5-yl, oxazol-4-yl, imidazol-2-yl, isothiazol-5-yl, 2-thienyl, 3-furyl, 2-furyl, isothiazol-4-yl, thiazol-4-yl, 3-thienyl, imidazol-5-yl, isoxazol-5-yl and 1 ,2,4-oxadiazol-5-yl wherein the heteroaryl may, where feasible, be optionally substituted by 1 , 2 or 3 R8 substituents, which may be the same or different and R8 is as defined in claim 1.
7. A compound according to any one of claims 1 to 6, wherein A is selected from the group consisting of formula A-l to A-XXVIII below
A-XXV wherein the jagged line defines the point of attachment to the thiadiazole moiety of the compound;
R8a is selected from the group consisting of hydrogen, Ci-C6alkyl and Ci-C6haloalkyl;
each R8b, R8c and R8d are independently selected from the group consisting of hydrogen, halogen, nitro, cyano, -NH2, -NHR7, -N(R7)2, -OH, -OR7, -S(0 R15, -NR6S(0)2R15, -C(0)OR1°, - C(0)R15, -C(0)NR16R17, -S(0)2NR16R17, Ci-Cealkyl and Ci-Cehaloalkyl;
and R6, R7, R10, R15, R16, R17 and r are as defined in claim 1.
8. A compound according to any one of claims 1 to 7, wherein A is selected from the group consisting of formula A-l to A-V 111 below
Figure imgf000070_0001
wherein the jagged line defines the point of attachment to the thiadiazole moiety of the compound ;
R8a is hydrogen or Ci-C6alkyl;
each R8b, R8c and R8d are independently selected from the group consisting of hydrogen, halogen, -NH2, -NHR7, -N(R7)2, -OR7, Ci-Cealkyl and Ci-Cehaloalkyl;
and R7 is as defined in claim 1.
9. A compound according to claims 7 or 8, wherein R8a is hydrogen or methyl and each R8b, R8c and R8d are independently selected from the group consisting of hydrogen, chloro, -NH2, -NHMe, -OMe, methyl, /so-propyl and trifluoromethyl.
10. A compound according to any one of claims 1 to 9, wherein A is selected from the group consisting of formula A-la to A-V Ilia below A-Va
A- Via A-Vlla A-Vllla wherein the jagged line denotes the point of attachment to the thiadiazole moiety of the compound.
11. A compound according to any one of claims 1 to 10, wherein Z is selected from the group consisting of -C(0)OR1°, -C(0)NHS(0)2R12, -S(0)2OR10, -OS(0)2OR10 and -P(0)(R13)(0R1°).
12. A compound according to any one of claims 1 to 11 , wherein Z is -C(0)OH or -S(0)2OH.
13. An agrochemical composition comprising a herbicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 12 and an agrochemically-acceptable diluent or carrier.
14. A method of controlling unwanted plant growth, comprising applying a compound of formula (I) as defined in any one of claims 1 to 12, or a herbicidal composition according to claim 13 or claim 13, to the unwanted plants or to the locus thereof.
15. Use of a compound of formula (I) as defined in any one of claims 1 to 12, as a herbicide.
PCT/EP2019/081022 2018-11-12 2019-11-12 Herbicidal compounds Ceased WO2020099404A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1818348.3 2018-11-12
GBGB1818348.3A GB201818348D0 (en) 2018-11-12 2018-11-12 Herbicidal compounds

Publications (1)

Publication Number Publication Date
WO2020099404A1 true WO2020099404A1 (en) 2020-05-22

Family

ID=64739506

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2019/081022 Ceased WO2020099404A1 (en) 2018-11-12 2019-11-12 Herbicidal compounds

Country Status (2)

Country Link
GB (1) GB201818348D0 (en)
WO (1) WO2020099404A1 (en)

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3557133A (en) * 1967-03-25 1971-01-19 Bayer Ag Thiadiazolinium chlorides and process for their preparation
EP0374753A2 (en) 1988-12-19 1990-06-27 American Cyanamid Company Insecticidal toxines, genes coding therefor, antibodies binding them, transgenic plant cells and plants expressing these toxines
EP0427529A1 (en) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Larvicidal lectins and plant insect resistance based thereon
EP0451878A1 (en) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modifying plants by genetic engineering to combat or control insects
WO1993007278A1 (en) 1991-10-04 1993-04-15 Ciba-Geigy Ag Synthetic dna sequence having enhanced insecticidal activity in maize
WO1995034656A1 (en) 1994-06-10 1995-12-21 Ciba-Geigy Ag Novel bacillus thuringiensis genes coding toxins active against lepidopteran pests
US5482916A (en) * 1989-08-22 1996-01-09 Tosoh Corporation Thiadiazole derivatives and herbicide compositions containing same
WO2002034048A1 (en) 2000-10-23 2002-05-02 Syngenta Participations Ag Agrochemical compositions with quinoline safeners
WO2003052073A2 (en) 2001-12-17 2003-06-26 Syngenta Participations Ag Novel corn event
WO2010038465A1 (en) 2008-10-02 2010-04-08 旭化成ファーマ株式会社 8-substituted isoquinoline derivative and use thereof
US20100152203A1 (en) 2008-12-16 2010-06-17 Li Chen Thiadiazole-substituted arylamides as p2x3 and p2x2/3 antagonists
WO2013063549A1 (en) 2011-10-28 2013-05-02 Vanderbilt University Substituted 2-(4-heterocyclylbenzyl)isoindolin-1-one analogs as positive allosteric modulators of the muscarinic acetylcholine receptor m1
CN103896934A (en) * 2014-02-28 2014-07-02 盐城工学院 Thiadiazole-containing oxadiazole compound as well as preparation method and application thereof
KR20150135626A (en) 2014-05-22 2015-12-03 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3557133A (en) * 1967-03-25 1971-01-19 Bayer Ag Thiadiazolinium chlorides and process for their preparation
EP0451878A1 (en) 1985-01-18 1991-10-16 Plant Genetic Systems, N.V. Modifying plants by genetic engineering to combat or control insects
EP0374753A2 (en) 1988-12-19 1990-06-27 American Cyanamid Company Insecticidal toxines, genes coding therefor, antibodies binding them, transgenic plant cells and plants expressing these toxines
US5482916A (en) * 1989-08-22 1996-01-09 Tosoh Corporation Thiadiazole derivatives and herbicide compositions containing same
EP0427529A1 (en) 1989-11-07 1991-05-15 Pioneer Hi-Bred International, Inc. Larvicidal lectins and plant insect resistance based thereon
WO1993007278A1 (en) 1991-10-04 1993-04-15 Ciba-Geigy Ag Synthetic dna sequence having enhanced insecticidal activity in maize
WO1995034656A1 (en) 1994-06-10 1995-12-21 Ciba-Geigy Ag Novel bacillus thuringiensis genes coding toxins active against lepidopteran pests
WO2002034048A1 (en) 2000-10-23 2002-05-02 Syngenta Participations Ag Agrochemical compositions with quinoline safeners
WO2003052073A2 (en) 2001-12-17 2003-06-26 Syngenta Participations Ag Novel corn event
WO2010038465A1 (en) 2008-10-02 2010-04-08 旭化成ファーマ株式会社 8-substituted isoquinoline derivative and use thereof
US20100152203A1 (en) 2008-12-16 2010-06-17 Li Chen Thiadiazole-substituted arylamides as p2x3 and p2x2/3 antagonists
WO2013063549A1 (en) 2011-10-28 2013-05-02 Vanderbilt University Substituted 2-(4-heterocyclylbenzyl)isoindolin-1-one analogs as positive allosteric modulators of the muscarinic acetylcholine receptor m1
CN103896934A (en) * 2014-02-28 2014-07-02 盐城工学院 Thiadiazole-containing oxadiazole compound as well as preparation method and application thereof
KR20150135626A (en) 2014-05-22 2015-12-03 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof

Non-Patent Citations (17)

* Cited by examiner, † Cited by third party
Title
"McCutcheon's Detergents and Emulsifiers Annual", 1981, MC PUBLISHING CORP.
"the Manual on Development and Use of FAO and WHO Specifications for Pesticides", 2010, SOUTHERN ILLINOIS UNIVERSITY
"The Pesticide Manual", 2006, BRITISH CROP PROTECTION COUNCIL
AOYAMAIWAMOTOSHIOIRI, HETEROCYCLES, vol. 24, 1986, pages 589
DEMAREE ET AL., J. HETEROCYCLIC CHEM., vol. 15, 1978, pages 1295
GEVORGYAN ET AL., ORG. LETT., vol. 18, 2016, pages 1804
KING, A. O.OKUKADO, N.NEGISHI, E., CHEM. COMM., vol. 19, 1977, pages 683
MINKKIILA, A. ET AL., EUR. J. MED. CHEM., vol. 44, 2009, pages 2994
MOODY ET AL., TETRAHEDRON, vol. 60, 2004, pages 3967
PETIT ET AL., TET. LETT., vol. 49, no. 22, 2008, pages 3663
SAKAIHIDAKONDO, BULL. CHEM. SOC. JPN., vol. 59, 1986, pages 179
SEMAKIN ET AL., BEILSTEIN J. ORG. CHEM., vol. 12, 2016, pages 2471
STILLE, J. K., ANGEW. CHEM. INT. ED. ENGL., vol. 25, 1986, pages 508
TAMAO, K.SUMITANI, K.KUMADA, M., J. AM. CHEM. SOC., vol. 94, 1972, pages 4374
THOMAS ET AL., J. MED. CHEM., vol. 28, 1985, pages 442
THOMAS, E. W.ZIMMERMAN, D. C., SYNTHESIS, vol. 10, 1985, pages 945
WOLFE ET AL., J. ORG. CHEM., vol. 46, 1981, pages 294

Also Published As

Publication number Publication date
GB201818348D0 (en) 2018-12-26

Similar Documents

Publication Publication Date Title
AU2019240902A1 (en) Herbicidal compounds
WO2020161162A1 (en) Herbicidal pyridinium compounds
WO2020165310A1 (en) Pyridinium compounds and their use as herbicides
EP3924347A1 (en) Pyridazinium compounds for use in a method of controlling unwanted plant growth
EP3935054A1 (en) Herbicidal compounds
EP3879983A1 (en) Herbicidal compounds
WO2020161208A1 (en) Herbicidal fused pyridazine compounds
WO2020099404A1 (en) Herbicidal compounds
WO2020099406A1 (en) Herbicidal compounds
WO2020099407A1 (en) Herbicidal compounds
EP3923728A1 (en) Herbicidal compounds
EP3920701A1 (en) Herbicidal compounds
WO2021064073A1 (en) Herbicidal compounds
EP3927697A1 (en) Pyridazines herbicidal compounds
WO2020161138A1 (en) Pyridazinium compounds for use in controlling unwanted plant growth
WO2021058592A1 (en) Herbicidal compounds
GB2584175A (en) Herbicidal compounds
WO2020161248A1 (en) Herbicidal compounds
WO2020161270A1 (en) Herbicidal pyridazinum based compounds
EP3898594A1 (en) Herbicidal cinnolinium compounds
OA20324A (en) Herbicidal compounds.

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19801653

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19801653

Country of ref document: EP

Kind code of ref document: A1