OA20324A

OA20324A - Herbicidal compounds.

Info

Publication number: OA20324A
Application number: OA1202100351
Authority: OA
Inventors: James Nicholas Scutt; Nigel James Willetts; John Stephen Delaney
Original assignee: Syngenta Crop Protection Ag
Priority date: 2019-02-06
Filing date: 2020-02-05
Publication date: 2022-05-10

Description

Herbicidal Compounds

The présent invention relates to herbicidally active pyridinium dérivatives, as well as to processes and intermediates used for the préparation of such dérivatives. The invention further 5 extends to herbicidal compositions comprising such dérivatives, as well as to the use of such compounds and compositions for controlling undesirable plant growth: in particular the use for controlling weeds, in crops of useful plants.

The présent invention is based on the finding that pyridinium dérivatives of formula (I) as 10 defined herein, exhibit surprisingly good herbicidal activity. Thus, according to the présent invention there is provided the use of a compound of formula (I) or an agronomically acceptable sait or zwitterionic species thereof, as a herbicide:

wherein

R¹ is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, C2-Cealkenyl, C2C6alkynyl, C3-C6cycloalkyl, Ci-C6haloalkyl, -OR⁷, -OR^15a, -N(R⁶)S(O)2R¹⁵, -N(R⁶)C(O)R¹⁵, 20 N(R⁶)C(O)OR¹⁵, -N(R⁶)C(O)NR¹⁶R¹⁷, -N(R⁶)CHO, -N(R^7a)₂ and -S(O)_rR¹⁵;

R² is selected from the group consisting of hydrogen, halogen, Ci-Côalkyl and Ci-Côhaloalkyl;

and wherein when R¹ is selected from the group consisting of-OR⁷, -OR^15a, -N(R⁶)S(O)2R¹⁵, 25 N(R⁶)C(O)R¹⁵, -N(R⁶)C(O)OR¹⁵, -N(R⁶)C(O)NR¹⁶R¹⁷, -N(R⁶)CHO, -N(R^7a)₂ and -S(O)_rR¹⁵,

R² is selected from the group consisting of hydrogen and Ci-Côalkyl; 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 30 from N and O; and

Q is (CR^laR^2b)_m;

m is 0, 1, 2 or 3;

each R^la and R^2b are independently selected from the group consisting of hydrogen, halogen, Ci-C6alkyl, Ci-C6haloalkyl, -OH, -OR⁷, -OR^15a, -NH2, -NHR⁷, -NHR^15a, -N(R⁶)CHO, NR^7bR^7c and -S(O)_rR¹⁵; or each R^la and R^2b together with the carbon atom to which they are attached form a C310 Côcycloalkyl ring or a 3- to 6- membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O; and

R³, R^3a, R⁴ and R⁵ are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, -S(O)_rR¹⁵, Ci-Côalkyl, Ci-Côfluoroalkyl, Ci-Cefluoroalkoxy, Ci-Côalkoxy, C315 Côcycloalkyl and -N(R⁶)2;

each R⁶ is independently selected from hydrogen and Ci-Côalkyl;

each R⁷ is independently selected from the group consisting of Ci-Cealkyl, -S(O)2R¹⁵, -C(O)R¹⁵, 20 -C(O)OR¹⁵ and -C(O)NR¹⁶R¹⁷;

each R^7a is independently selected from the group consisting of -S(O)2R¹⁵, -C(O)R¹⁵, C(O)OR¹⁵, -C(O)NR¹⁶R¹⁷ and -C(O)NR⁶R^15a;

R^7b and R^7care independently selected from the group consisting of Ci-Cealkyl, -S(O)₂R¹⁵, C(O)R¹⁵, -C(O)OR¹⁵, -C(O)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

R^7b and R^7c together with the nitrogen atom to which they are attached form a 4- to 6-membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N, O and S; and

A is a 5-membered heteroaryl attached to the rest of the molécule via a ring carbon atom, which comprises 1, 2, 3 or 4 heteroatoms independently selected from the group consisting of N, O and S, and wherein the heteroaryl may, where feasible, be optionally substituted by 1, 2 or 3 R⁸ substituents, which may be the same or different, and wherein 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(O)rR¹⁵, -NR⁶S(O)₂R¹⁵, -C(O)OR¹⁰, -C(O)R¹⁵, -C(O)NR¹⁶R¹⁷, S(O)2NR¹⁶R¹⁷, Ci-Cealkyl, Ci-Côhaloalkyl, C3-C6cycloalkyl, Cs-Côhalocycloalkyl, C35 Côcycloalkoxy, C2-C6alkenyl, C2-Câhaloalkenyl, C2-Câalkynyl, Ci-C3alkoxyCi-C3alkyl-, hydroxyCi-Cealkyl-, Ci-C3alkoxyCi-C3alkoxy-, Ci-Côhaloalkoxy, Ci-CshaloalkoxyCiC3alkyl-, C3-Cealkenyloxy, C3-C6alkynyloxy, N-Cs-Cecycloalkylamino, -C(R⁶)=NOR⁶, phenyl, a 3- to 6- membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O, and a 5- or 6- membered heteroaryl, which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein said phenyl, heterocyclyl or heteroaryl are optionally substituted by 1, 2 or 3 R⁹ substituents, which may be the same or different;

and/or when A is substituted on a ring nitrogen atom, R⁸ is selected from the group consisting of -OR⁷, Ci-Cealkyl, Ci-Côhaloalkyl, Cs-Côcycloalkyl, C3-C6halocycloalkyl, Cs-Côcycloalkoxy, C2Côalkenyl, C2-Cehaloalkenyl, C2-Cealkynyl, Ci-CsalkoxyCi-Csalkyl-, hydroxyCi-Cgalkyl-, CiCsalkoxyCi-Csalkoxy-, Ci-Côhaloalkoxy, Ci-CshaloalkoxyCi-Csalkyl-, Cs-Cealkenyloxy and 20 C3-C6alkynyloxy ; and each R⁹ is independently selected from the group consisting of halogen, cyano, -OH, -N(R⁶)₂, Ci-C4alkyl, Ci-C₄alkoxy, Ci-C₄haloalkyl and Ci-C₄haloalkoxy;

X is selected from the group consisting of Cs-Cecycloalkyl, phenyl, a 5- or 6- membered heteroaryl, which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and a 4- to 6- membered heterocyclyl, which comprises 1, 2 or 3 heteroatoms individually selected from N, O and S, and wherein said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties are optionally substituted by 1 or 2 R⁹ substituents, and wherein the aforementioned

CR^!R², Q and Z moieties may be attached at any position of said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties;

n is 0 or 1;

Z is selected from the group consisting of -C(O)OR¹⁰, -CH2OH, -CHO, -C(O)NHORⁿ, C(O)NHCN, -OC(O)NHORⁿ, -OC(O)NHCN, -NR⁶C(O)NHORⁿ, -NR⁶C(O)NHCN, C(O)NHS(O)2R¹², -OC(O)NHS(O)2R¹², -NR⁶C(O)NHS(O)2R¹², -S(O)2OR¹⁰, -OS(O)2OR¹⁰, NR⁶S(O)2OR¹⁰, -NR⁶S(O)OR¹⁰, -NHS(O)2R¹⁴, -S(O)OR¹⁰, -OS(O)OR¹⁰, -S(O)2NHCN, S(O)₂NHC(O)R¹⁸, -S(O)2NHS(O)2R¹², -OS(O)2NHCN, -OS(O)₂NHS(O)₂R¹²,

OS(O)₂NHC(O)R¹⁸, -NR⁶S(O)2NHCN, -NR⁶S(O)2NHC(O)R¹⁸, -N(OH)C(O)R¹⁵, ONHC(O)R¹⁵, -NR⁶S(O)₂NHS(O)₂R¹², -P(O)(R¹³)(OR¹⁰), -P(O)H(OR¹⁰), -OP(O)(R¹³)(OR¹⁰), -NR⁶P(O)(R¹³)(OR¹⁰) and tetrazole;

R¹⁰ is selected from the group consisting of hydrogen, Ci-Cealkyl, 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-Cealkyl 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-Cealkyl, Ci-Côhaloalkyl, Ci-Côalkoxy, -OH, N(R⁶)₂ and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R⁹substituents, which may be the same or different;

R¹³ is selected from the group consisting of -OH_: Ci-Cealkyl, Ci-Cealkoxy and phenyl;

R¹⁴ is Ci-Côhaloalkyl;

R¹⁵ is selected from the group consisting of Ci-Cealkyl and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R⁹ substituents, which may be the same or different;

R^15a 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-Côalkyl; 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; and

R¹⁸ is selected from the group consisting of hydrogen, Ci-Côalkyl, Ci-Cehaloalkyl, CiCealkoxy, -N(R⁶)2 and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R⁹substituents, which may be the same or different;

and r is 0, 1 or 2.

Certain compounds of formula (I) are known (or an agronomically acceptable sait or zwitterionic species thereof):

ethyl 2-[4-(2-thienyl)pyridin-1-ium-1-yl]acetate, ethyl 2-[4-(5-methyl-1 H-pyrazol-3-yl)pyridin-1-ium-1-yl]acetate,

2-[4-[5-(1-ethylpyridin-1-ium-4-yl)-2-furyl]pyridin-1-ium-1-yl]ethylphosphonic acid,

2-[4-[4-(1-ethylpyridin-1-ium-4-yl)-3-thienyl]pyridin-1-ium-1-yl]ethylphosphonic acid and

3-[4-[5-[4-(dihexylamino)phenyl]-2-thienyl]pyridin-1-ium-1-yl]propane-1-sulfonic acid

Thus in a second aspect of the invention there is provided a compound of formula (I) wherein:

i) A is not selected from the group consisting of formula A-Ib to A-IIIb below

A-lb

wherein each R^8b' is independently selected from the group consisting of phenyl, 4methoxyphenyl, 4-butoxyphenyl, 4-fluorophenyl and methoxy, and each R⁸⁰’ is independently hydrogen or methyl;

or ii) the compound of formula (I) is not selected from the group consisting of ethyl 2-[4-(2-thienyl)pyridin-l-ium-l-yl]acetate, ethyl 2-[4-(5-methyl-lH-pyrazoi-3yl)pyridin-1 -ium-1 -yl]acetate, 2-[4-[5-( 1 -ethy Ipyridin-1 -ium-4-yl)-2- furyl]pyridin-l-ium-l-yl]ethylphosphonic acid, 2-[4-[4-(l-ethylpyridin-l-ium15 4-yl)-3-thienyl]pyridin-l-ium-l-yl]ethylphosphonic acid and 3-[4-[5-[4(dihexylamino)phenyl]-2-thienyl]pyridin-1 -ium-1 -yl]propane-l -sulfonic acid shown above

According to a third aspect of the invention there is provided an agrochemical composition 20 comprising a herbicidally effective amount of a compound of formula (I) and an agrochemically-acceptable diluent or carrier. Such an agricultural composition may further comprise at least one additional active ingrédient.

According to a fourth aspect of the invention, there is provided a method of controlling or 25 preventing undesirable plant growth, wherein a herbicidally effective amount of a compound of formula (I), or a composition comprising this compound as active ingrédient, is applied to the plants, to parts thereof or the locus thereof.

According to a fifth aspect of the invention, there is provided the use of a compound of formula (I) as defined herein for pre-harvest desiccation in crops.

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-Cealkyl 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 molécule by a single bond. CiC4alkyl and Ci-C₂alkyl are to be construed accordingly. Examples of Ci-Cealkyl include, but are not limited to, methyl (Me), ethyl (Et), rz-propyl, 1-methylethyl (iso-propyl), w-butyl, and 1-dimethylethyl (Z-butyl).

As used herein, the term Ci-Cealkoxy 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 /-butoxy.

As used herein, the term Ci-Côhaloalkyl refers to a Ci-Côalkyl 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-Côhaloalkyl include, but are not limited to chloromethyl, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl and 2,2,2trifluoroethyL

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 molécule 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 (prop2-enyl) and but-l-enyl.

As used herein, the term “C2-C6haloalkenyl” refers to a Cz-Cealkenyl 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, 1,1difluoroethylene, 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 molécule by a single bond. C2-C4alkynyl is to be construed accordingly. Examples of C2-Côalkynyl 10 include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl) and but-l-ynyl.

As used herein, the term Ci-Côhaloalkoxy refers to a Ci-Côalkoxy 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-Céhaloalkoxy include, but are not limited to, 15 fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy and trifluoroethoxy.

As used herein, the term Ci-CshaloalkoxyCi-Csalkyl refers to a radical of the formula Rb-ORa- where Rb is a Ci-Cshaloalkyl radical as generally defined above, and Ra is a Ci-Csalkylene radical as generally defined above.

As used herein, the term Ci-CaalkoxyCi-Csalkyl refers to a radical of the formula Rb-O-Rawhere Rb is a Ci-Csalkyl radical as generally defined above, and Ra is a Ci-Cjalkylene radical as generally defined above.

As used herein, the term Ci-CaalkoxyCi-Csalkoxy- refers to a radical of the formula Rb-OR_a-O- where Rb is a Ci-Csalkyl radical as generally defined above, and R_a is a Ci-Csalkylene radical as generally defined above.

As used herein, the term Cî-Cealkenyloxy refers to a radical of the formula -ORa where R_a is 30 a Cs-Cealkenyl radical as generally defined above.

As used herein, the term Ca-Cealkynyloxy refers to a radical ofthe formula -ORa where Ra is a Cs-Côalkynyl radical as generally defined above.

As used herein, the term “hydroxyCi-Côalkyl” refers to a Ci-Cealkyl radical as generally defined above substituted by one or more hydroxy groups.

As used herein, the term Ci-Côalkylcarbonyl refers to a radical of the formula -C(O)Ra where 5 Ra is a Ci-Côalkyl radical as generally defined above.

As used herein, the term Ci-Cealkoxycarbonyl refers to a radical of the formula -C(O)ORa where Ra is a Ci-Cealkyl radical as generally defined above.

As used herein, the term “aminocarbonyl” refers to a radical of the formula -C(O)NH2.

As used herein, the term Cs-Cecycloalkyl 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 Cs-Cecycloalkyl include, but are not limited to, 15 cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

As used herein, the term Cs-Côhalocycloalkyl refers to a Cs-Côcycloalkyl radical as generally defined above substituted by one or more of the same or different halogen atoms. C3C4halocycloalkyl is to be construed accordingly.

As used herein, the term Cs-Cecycloalkoxy refers to a radical of the formula -ORa where Ra is a Cs-Côcycloalkyl radical as generally defined above.

As used herein, the term “N-Cs-Côcycloalkylamino” refers to a radical of the formula -NHRa where Ra is a Cs-Cecycloalkyl 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 30 selected from nitrogen, oxygen and sulfur. The heteroaryl radical may be bonded to the rest of the molécule 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 molécule 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 δ-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 resuit of restricted rotation about a single bond, formula (I) is intended to include ail those possible isomeric forms and mixtures thereof. The présent invention includes ail those possible isomeric forms and mixtures thereof for a compound of formula (I). Likewise, formula (I) is intended to include ail possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) where présent. The présent invention includes ail possible tautomeric forms for a compound of formula (I). Similarly, where there are di-substituted alkenes, these may be présent in E or Z form or as mixtures of both in any proportion. The présent invention includes ail 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 sait, a zwitterion or an agronomically acceptable sait of a zwitterion. This invention covers ail such agronomically acceptable salts, zwitterions and mixtures thereof in ail proportions.

For example a compound of formula (I) wherein Z comprises an acidic proton, may exist as a zwitterion, a compound of formula (I-I), or as an agronomically acceptable sait, a compound of formula (I-II) as shown below:

wherein, Y represents an agronomically acceptable anion and j and k represent integers that may be selected from 1, 2 or 3, dépendent upon the charge of the respective anion Y.

A compound of formula (I) may also exist as an agronomically acceptable sait of a zwitterion, a compound of formula (I-III) as shown below:

MqYk

R⁴ ^A\/kx/^R35 JL A V R Mx)h

X^a R¹ R² (l-lll) ^J wherein, Y represents an agronomically acceptable anion, M represents an agronomically acceptable cation (in addition to the pyridinium cation) and the integers j, k and q may be selected from 1, 2 or 3, dépendent 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 (for example a compound of formula (I-II)), the skilled person would appreciate that it could equally be represented in unprotonated or sait form with one or more relevant counter ions.

In one embodiment of the invention there is provided a compound of formula (I-II) 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 the 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 (I-II), k is 2, j is 1 and Y is chloride, wherein a nitrogen atom in the ring comprising A is protonated.

Suitable agronomically acceptable salts of the présent 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, glycérophosphate, 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, césium, copper, lithium, magnésium, manganèse, 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, methylnony lamine, methyloctadecylamine, methylpentadecy lamine, morpholine, N,Ndiethylethanolamine, N-methylpiperazine, nonylamine, octadecy lamine, octylamine, oleylamine, pentadecylamine, pentenyl-2-amine, phenoxyethylamine, picoline, piperazine, piperidine, propanolamine, propylamine, propylenediamine, pyridine, pyrrolidine, secbutylamine, stearylamine, tallowamine, tetradecylamine, tributylamine, tridecylamine, trimethylamine, triheptylamine, trihexylamine, triisobutylamine, triisodecylamine, triisopropy lamine, trimethylamine, tripentylamine, tripropylamine, tris(hydroxymethyl)aminomethane, and undecylamine. Examples of suitable organic cations include benzyltributylammonium, benzyltrimethylammonium, benzyltriphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, tetraethylammonium, 5 tetraethylphosphonium, tétraméthylammonium, 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 (I-I) or (I-II). For compounds of formula (I-II) 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 (I-II) 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 (I-Ia) as shown below:

(l-la) wherein R¹, R², R³, R^3a, R⁴, R⁵, 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 (I-Ib) as shown below:

(l-ib) wherein R¹, R², R^la, R^2b, R³, R^3a, R⁴, R⁵, 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 (I-Ic) as shown below:

(l-lc) wherein R¹, R², R^la, R^2b, R³, R^3a, R⁴, R⁵, 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 (I-Id) as shown below:

wherein R¹, R², R^la, R^2b, R³, R^3a, R⁴, R⁵, A and Z are as defined for compounds of formula (I).

The foilowing list provides définitions, including preferred définitions, for substituents n, m, r, A, Q, X, Z, R¹, R², R^la, R^2b, R², R³, R^3a, R⁴, R⁵, R⁶, R⁷, R^7a, R^7b, R^7c, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R^15a, 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 définitions given below may be combined with any définition of any other substituent given below or elsewhere in this document.

R¹ is selected from the group consisting of hydrogen, halogen, Ci-Cëalkyl, C2-C6alkenyl, C2Côalkynyl, Cs-Cecycloalkyl, Ci-Cehaloalkyl, -OR⁷, -OR^15a, -N(R⁶)S(O)2R¹⁵, -N(R⁶)C(O)R¹⁵, N(R⁶)C(O)OR¹⁵, -N(R⁶)C(O)NR¹⁶R¹⁷, -N(R⁶)CHO, -N(R^7a)2 and -S(O)_rR¹⁵. Preferably, R¹ is selected from the group consisting of hydrogen, halogen, Ci-Cëalkyl, Ci-Cëfluoroalkyl, -OR⁷, -NHS(O)2R¹⁵, -NHC(O)R¹⁵, -NHC(O)OR¹⁵, -NHC(O)NR¹⁶R¹⁷, -N(R^7a)2 and -S(O)_rR¹⁵. More preferably, R¹ is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, CiCôfluoroalkyl, -OR⁷ and -N(R^7a)₂. Even more preferably, R¹ is selected from the group consisting of hydrogen, halogen and Ci-Cealkyl,. Even more preferably still, R¹ is hydrogen or Ci-Côalkyl. 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-Cëalkyl and Ci-Cëhaloalkyl. Preferably, R² is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl and CiCôfluoroalkyl. More preferably, R² is hydrogen or Ci-CëalkyL Even more preferably, R² is hydrogen or methyl. Most preferably R² is hydrogen.

Wherein when R¹ is selected from the group consisting of -OR⁷, -OR^15a, -N(R⁶)S(O)2R¹⁵, N(R⁶)C(O)R¹⁵, -N(R⁶)C(O)OR¹⁵, -N(R⁶)C(O)NR¹⁶R¹⁷, -N(R⁶)CHO, -N(R^7a)2 and -S(O)_rR¹⁵, R² is selected from the group consisting of hydrogen and Ci-Côalkyl. Preferably, when R¹ is selected from the group consisting of -OR⁷, -NHS(O)2R¹⁵, -NHC(O)R¹⁵, -NHC(O)OR¹⁵, NHC(O)NR¹⁶R¹⁷, -N(R^7a)2 and -S(O)_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 C3Cëcycloalkyl 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 Cs-Cëcycloalkyl 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 (CR^laR^2b)_m.

m is 0, 1, 2 or 3. Preferably, m is 0,1 or 2. More preferably, m is 0 or 1. Most preferably, m is 0.

Each R^la and R^2b are independently selected from the group consisting of hydrogen, halogen, Ci-C6alkyl, Ci-C6haloalkyl, -OH, -OR⁷, -OR^15a, -NH2, -NHR⁷, -NHR^15a, -N(R⁶)CHO, NR^7bR^7c and -S(O)rR¹⁵. Preferably, each R^la and R^2b are independently selected from the group consisting of hydrogen, halogen, Ci-Cealkyl, Ci-Côfluoroalkyl, -OH, -NH2 and -NHR⁷. More 10 preferably, each R^la and R^2b are independently selected from the group consisting of hydrogen,

Ci-Côalkyl, -OH and -NH₂. Even more preferably, each R^la and R^2b are independently selected from the group consisting of hydrogen, methyl, -OH and -NH₂. Even more preferably still, each R^la and R^2b are independently selected from the group consisting of hydrogen and methyl. Most preferably R^la and R^2b are hydrogen.

In another embodiment each R^la and R^2b are independently selected from the group consisting of hydrogen and Ci-Côalkyl.

Altematively, each R^la and R^2b together with the carbon atom to which they are attached form 20 a Cs-Côcycloalkyl ring or a 3- to 6- membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O. Preferably, each R^la and R^2b together with the carbon atom to which they are attached form a Cs-Côcycloalkyl ring. More preferably, each R^la and R^2btogether with the carbon atom to which they are attached form a cyclopropyl ring.

R³, R^3a, R⁴ and R⁵ are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, -S(O)rR¹⁵, Ci-Cealkyl, Ci-Côfluoroalkyl, Ci-Côfluoroalkoxy, Ci-Côalkoxy, C3Côcycloalkyl and -N(R⁶)2. Preferably, R³, R^3a, R⁴ and R⁵ are independently selected from the group consisting of hydrogen, halogen, cyano, Ci-Cealkyl, Ci-Côfluoroalkyl, CiCôfluoroalkoxy, Ci-Cealkoxy, Cs-Cecycloalkyl and -N(R⁶)₂. More preferably, R³, R^3a, R⁴ and

R⁵ are independently selected from the group consisting of hydrogen, halogen, cyano, CiCôalkyl and Ci-Côfluoroalkyl. Even more preferably, R³, R^3a, R⁴ and R⁵ are independently selected from the group consisting of hydrogen, chloro, fluoro, bromo, cyano, methyl and trifluoromethyl. Even more preferably still, R³, R^3a, R⁴ and R⁵ are independently selected from the group consisting of hydrogen, chloro, fluoro, bromo and methyl. Yet even more preferably still, R³, R^3a, R⁴ and R⁵ are independently selected from the group consisting of hydrogen, chloro and fluoro. Most preferably, R³, R^3a, R⁴ and R⁵ are hydrogen.

In one embodiment R³ and R^3a are hydrogen, and R⁴ and R⁵ are independently selected from 5 the group consisting of hydrogen, bromo, chloro, fluoro and -S(O)2Me (preferably, hydrogen, chloro and fluoro).

Each R⁶ is independently selected from hydrogen and Ci-Cealkyl. Preferably, each R⁶ is independently selected from hydrogen and methyl.

Each R⁷ is independently selected from the group consisting of Ci-Côalkyl, -S(O)2R¹⁵, C(O)R¹⁵, -C(O)OR¹⁵ and -C(O)NR¹⁶R¹⁷. Preferably, each R⁷ is independently selected from the group consisting of Ci-Côalkyl, -C(O)R¹⁵ and -C(O)NR¹⁶R¹⁷. More preferably, each R⁷ is Ci-Côalkyl. Most preferably, each R⁷ is methyl.

Each R^7a is independently selected from the group consisting of -S(O)2R¹⁵, -C(O)R¹⁵, C(O)OR¹⁵ -C(O)NR¹⁶R¹⁷ and -C(O)NR⁶R^15a. Preferably, each R^7a is independently -C(O)R¹⁵or-C(O)NR¹⁶R¹⁷.

R⁷¹* and R^7care independently selected from the group consisting of Ci-Côalkyl, -S(O)2R¹⁵, C(O)R¹⁵, -C(O)OR¹⁵, -C(O)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, R^7band R^7c are independently selected from the group consisting of Ci-Cealkyl, -C(O)R¹⁵ and C(O)NR¹⁶R¹⁷. More preferably, R^7b and R^7care Ci-CealkyL Most preferably, R^7band R^7care 25 methyl.

Alternatively, R^7b and R^7c together with the nitrogen atom to which they are attached form a 4to 6-membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N, O and S. Preferably, 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 30 comprises one additional heteroatom individually selected from N and O. More preferably, R^7band 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 molécule via a ring carbon atom, 35 which comprises 1, 2, 3 or 4 heteroatoms independently selected from the group consisting of

N, O and S, and wherein the heteroaryl may, where feasible, be optionally substituted 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 l,2,4-oxadiazol-5-yl, thiadiazol-5-yl, l,2,4-thiadiazol-5-yl, thiadiazol-4-yl, l,2,4-thiadiazol-3-yl, l,2,5-thiadiazol-3yl, l,3,4-thiadiazol-2-yl, l,3,4-oxadiazol-2-yl, l,2,4-oxadiazol-3-yl, l,2,5-oxadiazol-3-yl, l,2,4-triazol-3-yl, l,2,4-triazol-5-yl, triazol-4-yl, triazol-5-yl, 2-methyltetrazol-5-yl, 1methyltetrazol-5-yl, thiazol-2-yl, thiazol-4-yl, isothiazol-5-yl, isothiazol-4-yl, isothiazol-3-yl, oxazol-2-yl, oxazol-4-yl, isoxazol-3-yl, isoxazol-5-yl, imidazol-5-yl, imidazol-2-yl, 3-furyl, 210 furyl, 3-thienyl, pyrazol-5-yl, pyrazol-3-yl and 2-thienyl wherein the heteroaryl may, where feasible, be optionally substituted by 1, 2 or 3 R⁸ substituents, which may be the same or different.

More preferably, A is selected from the group consisting of formula A-I to A-XXXV below

A-XXXI

A-XXXIII

wherein the jagged line defrnes the point of attachment to a compound of formula (I), and _R8a _R8b, _R8c, _R8d, _Rio, _Ri5, _Riô, _Ri7 _ancj _{r are as} d_ef_inecj herein. R^8a, R^8b, R^8c, R^8d are examples 5 of R⁸ wherein the subscript letter a, b, c and d are used to dénoté positions within indvidual heterocycles (A-I to A-XXXV).

Even more preferably, A is selected from the group consisting of formula A-I to A-XXXII below

A-XIV

A-XXV

A-lll

A-VIII

A-XVI

A-XX

A-XXIII A-XXIV

A-XXVII A-XXVIII

wherein the jagged line defines the point of attachaient to a compound of formula (I), and

R^8a, R^8b, R^8c, R^8d, R¹⁰, R¹⁵, R¹⁶, R¹⁷ and r are as defined herein.

Even more preferably still, A is selected from the group consisting of formula A-I to A-X, AXVII, A-XVIII, A-XIX, A-XXIII, A-XXIV and AXXVII below

A-V

A-XXIII

A-XXIV

A-XXVII wherein the jagged line defines the point of attachaient to a compound of formula (I), and

R^8a, R^8b, R^8c, R^8d R¹⁰, R¹⁵, R¹⁶, R¹⁷ and r are as defined herein.

Yet even more preferably still, A is selected from the group consisting of formula A-I to A-III below

R^8b

wherein the jagged line defines the point of attachment to a compound of formula (I), and each R^8b and R¹⁶ and R¹⁷ are as defined herein.

Further more preferably still, A is selected from the group consisting of formula A-Ia to A-Xa below

A-llla

N—O

A-Vlla

A-Xa

wherein the jagged line defines the point of attachment to a compound of formula (I).

In one embodiment, A is selected from the group consisting of formula A-Ia to A-XXXXVIIa below

A-llla

O—N

A-Xlla

N—N

Ο—N

A-Xllla

A-XIVa

A-XIa

A-XVIa

A-XXa

A-XXIVa

A-XXIXa

A-XXXa

A-XXXla

A-XXXIIa

A-XXXilla

S—N

A-XXXIVa

A-XXXVa A-XWla A-XXXVIIa

A-XXXVIIIa

A-XXXJXa A-XXXXa

A-XXXXIIa A-XXXXIIIa A-XXXXIVa

When A is substituted on one or more ring carbon atoms, each R⁸ is independently selected from the group consisting of halogen, nitro, cyano, -ΝΉ2, -NHR⁷, -N(R⁷)2, -OH, -OR⁷, S(O)rR¹⁵, -NR⁶S(O)2R¹⁵, -C(O)OR^l°, -C(O)R¹⁵, -C(O)NR¹⁶R¹⁷, -S(O)2NR¹⁶R¹⁷, Ci-C6alkyl, Ci-Cehaloalkyl, Cs-Côcycloalkyl, Cs-Côhalocycloalkyl, Cs-Cecycloalkoxy, C₂-C6alkenyl, C2Côhaloalkenyl, Ca-Cealkynyl, Ci-CsalkoxyCi-Csalkyl-, hydroxyCi-Côalkyl-, Ci-CsalkoxyCi-

Csalkoxy-, Ci-Côhaloalkoxy, Ci-CahaloalkoxyCi-Csalkyl-, Cs-Cealkenyloxy, C3Cealkynyloxy, N-Cs-Côcycloalkylamino, -C(R⁶)=NOR⁶, phenyl, a 3- to 6- membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O, and a 5- or 6- membered heteroaryl, which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein said phenyl, heterocyclyl 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(O)rR¹⁵, -NR⁶S(O)2R¹⁵, -C(O)OR¹⁰, -C(O)R¹⁵, -C(O)NR¹⁶R¹⁷, -S(O)2NR¹⁶R¹⁷, Ci-C6alkyl, Ci-Côhaloalkyl, Cs-Cecycloalkyl, Cs-Cehalocycloalkyl, Cs-Côcycloalkoxy, C2-C6alkenyl, C2Côhaloalkenyl, C2-Côalkynyl, Ci-CaalkoxyCi-Csalkyl-, hydroxyCi-Cealkyl-, Ci-CsalkoxyCiCsalkoxy-, Ci-Côhaloalkoxy, Ci-CshaloalkoxyCi-Csalkyl-, Cs-Cealkenyloxy, C3Côalkynyloxy, N-C3-C6cycloalkylamino, -C(R⁶)=NOR⁶, phenyl and a 5- or 6- membered heteroaryl, which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, 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(O)rR¹⁵, -NR⁶S(O)₂R¹⁵, -C(O)OR¹⁰, -C(O)R¹⁵, -C(O)NR¹⁶R¹⁷, S(O)2NR¹⁶R¹⁷, Ci-Cealkyl, Ci-Cehaloalkyl, C3-Cecycloalkyl, Ci-CsalkoxyCj-Csalkyl-, hydroxyCi-Cealkyl-, Ci-CsalkoxyCi-Csalkoxy- and Ci-Côhaloalkoxy.

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, nitro, cyano, -NH2, -OH, S(O)_rR¹⁵, -C(O)OR¹⁰, -C(O)R¹⁵, -C(O)NR¹⁶R¹⁷, -S(O)2NR¹⁶R¹⁷, Ci-C6alkyl and CiCôhaloalkyL

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 halogen, cyano, -NH2, -OH, C(O)NR¹⁶R¹⁷, Ci-Côalkyl and Ci-Côhaloalkyl.

Yet 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 halogen, cyano, -NH₂, -C(O)NR¹⁶R¹⁷, Ci-Cealkyl and Ci-Côhaloalkyl.

Further more preferably still, each R⁸ is independently selected from the group consisting of bromo, chloro, fluoro, cyano, -NH2, -C(O)NH₂, -C(O)NHMe, -C(O)N(Me)2, methyl 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 bromo, -NH2, -C(O)NHMe, methyl and trifluoromethyl.

In one embodiment, when A is substituted on one or more ring carbon atoms, each R⁸ is independently selected from the group consisting of bromo, cyano, -NH2, -C(O)NHMe, methyl, trifluoromethyl and phenyl (preferably, each R⁸ is independently selected from the group consisting of -C(O)NHMe, methyl and trifluoromethyl).

When A is substituted on a ring nitrogen atom, R⁸ is selected from the group consisting of OR⁷, Ci-Cealkyl, Ci-Côhaloalkyl, Cs-Cecycloalkyl, Ca-Côhalocycloalkyl, Ca-Cecycloalkoxy, C2-Cealkenyl, C2-C6haloalkenyl, C2-Côalkynyl, Ci-CsalkoxyCi-Cjalkyl-, hydroxyCi-Cealkyl-, Ci-CsalkoxyCi-Csalkoxy-, Ci-Côhaloalkoxy, Ci-CshaloalkoxyCi-Csalkyl-, Cs-Côalkenyloxy and Cs-Côalkynyloxy. Preferably, R⁸ is selected from the group consisting of -OR⁷, Ci-Côalkyl and Ci-Côhaloalkyl. More preferably, each R⁸ is Ci-Cealky or Ci-Côhaloalkyl. Even more preferably still, R⁸ is Ci-Côalky. Most preferably R⁸ is methyl.

When A is selected from the group consisting of formula A-I to A-XXXV, R^8a (substituted on a ring nitrogen atom) is selected from the group consisting of hydrogen, Ci-Cealkyl and Ci20 Cehaloalkyl, and 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, -NH2, -S(O)rR¹⁵, -C(O)OR¹⁰, -C(O)R¹⁵, C(O)NR¹⁶R¹⁷, -S(O)2NR¹⁶R¹⁷, Ci-C₆alkyl and Ci-C₆haloalkyl. Preferably, R^8a is hydrogen or Ci-Côalkyl and each R^8b, R^8c and R^8d are independently selected from the group consisting of hydrogen, halogen, cyano, -NH2, -C(O)NR¹⁶R¹⁷, Ci-Côalkyl and Ci-Côhaloalkyl. 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, bromo, chloro, fluoro, cyano, -NH2, -C(O)NH2, C(O)NHMe, -C(O)N(Me)2, methyl and trifluoromethyl. Even 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, bromo, -ΝΉ2, -C(O)NHMe, methyl and trifluoromethyl. Even more preferably still, R^8a is hydrogen or methyl and each R^8b, R^8c and R^8d are independently selected from the group consisting of hydrogen, -C(O)NHMe, methyl and trifluoromethyl.

When A is selected from the group consisting of formula A-I to A-XXXII, R^8a (substituted on a ring nitrogen atom) is selected from the group consisting of hydrogen, Ci-C₆alkyl and CiCôhaloalkyl, and each R^8b, R^8c and R^8d (substituted on a ring carbon atom) are independently selected from the 5 group consisting of hydrogen, halogen, nitro, cyano, -NH2, -S(O)rR¹⁵, -C(O)OR¹⁰, -C(O)R¹⁵, C(O)NR¹⁶R¹⁷, -S(O)2NR¹⁶R¹⁷, Ci-Côalkyl and Ci-Côhaloalkyl. Preferably, R^8a is hydrogen or

Ci-Cealkyl and each R^8b, R^8c and R^8d are independently selected from the group consisting of hydrogen, halogen, cyano, -NH2, -C(O)NR¹⁶R¹⁷, 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 10 the group consisting of hydrogen, bromo, chloro, fluoro, cyano, -NH2, -C(O)NH2, C(O)NHMe, -C(O)N(Me)2, methyl and trifluoromethyl. Even 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, bromo, -NH2, -C(O)NHMe, methyl and trifluoromethyl. Even more preferably still, R^8a is hydrogen or methyl and each R^8b, R^8c and R^8d are independently selected from the group 15 consisting of hydrogen, -C(O)NHMe, methyl and trifluoromethyl.

When A is selected from the group consisting of formula A-I to A-X, A-XVII, A-XVIII, A-

X IX, A-XXIII, A-XXIV and AXXVII, R^8a (substituted on a ring nitrogen atom) is selected from the group consisting of hydrogen, Ci-Cealkyl and Ci-Côhaloalkyl, and each R^8b, R^8c and 20 R^8d (substituted on a ring carbon atom) are independently selected from the group consisting of hydrogen, halogen, nitro, cyano, -NH2, -S(O)rR¹⁵, -C(O)OR¹⁰, -C(O)R¹⁵, -C(O)NR¹⁶R¹⁷, S(O)2NR¹⁶R¹⁷, Ci-Côalkyl and Ci-Côhaloalkyl. Preferably, R^8a is hydrogen or Ci-Côalkyl and each R^8b, R^8c and R^8d are independently selected from the group consisting of hydrogen, halogen, cyano, -NH₂, -C(O)NR^l6R¹⁷, Ci-Côalkyl and Ci-Côhaloalkyl. 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, bromo, chloro, fluoro, cyano, -NH2, -C(O)NH2, -C(O)NHMe, C(O)N(Me)2, methyl and trifluoromethyl. Even 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, bromo, -NH2, -C(O)NHMe, methyl and trifluoromethyl. Even more preferably still, R^8a is hydrogen or methyl and each R^8b, R^8c and R^8d are independently selected from the group consisting of hydrogen, -C(O)NHMe, methyl and trifluoromethyl.

When A is selected from the group consisting of formula A-I to A-III, each R^8b (substituted on a ring carbon atom) is independently selected from the group consisting of hydrogen, halogen, 35 cyano, -NH₂, -C(O)NR¹⁶R¹⁷, Ci-Cealkyl and Ci-Côhaloalkyl. Preferably, each R^8b is independently selected from the group consisting of hydrogen, bromo, chloro, fluoro, cyano, NH₂, -C(O)NH₂, -C(O)NHMe, -C(O)N(Me)₂, methyl and trifluoromethyl. More preferably, each R^8b is independently selected from the group consisting of hydrogen, bromo, -NH₂, C(O)NHMe, methyl and trifluoromethyl. Even more preferably, each R^8b is independently 5 selected from the group consisting of hydrogen, -C(O)NHMe, methyl and trifluoromethyl.

Each R⁹ is independently selected from the group consisting of halogen, cyano, -OH, -N(R⁶)2, Ci-Cialkyl, Ci-C4alkoxy, Ci-C4haloalkyl and Ci-C4haloalkoxy. Preferably, each R⁹ is independently selected from the group consisting of halogen, cyano, -N(R⁶)2, Ci-C4alkyl, Ci10 C4alkoxy, Ci-C4haloalkyl and Ci-C4haloalkoxy. More preferably, each R⁹ is independently selected from the group consisting of halogen, Ci-C₄alkyl, Ci-C₄alkoxy and Ci-C₄haloalkyl. Even more preferably, each R⁹ is independently selected from the group consisting of halogen and Ci-C4alkyl.

X is selected from the group consisting of Cs-Cecycloalkyl, phenyl, a 5- or 6- membered heteroaryl, which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and a 4- to 6- membered heterocyclyl, which comprises 1, 2 or 3 heteroatoms individually selected from N, O and S, and wherein said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties are optionally substituted by 1 or 2 substituents, which may be the same or different, 20 selected from R⁹, and wherein the aforementioned CR’R², 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 25 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 CR’R², 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 30 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 CR'R², 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 CR'R², 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 CR*R² 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 CR’R², Q and Z moieties may be attached at any position of said phenyl moiety. Preferably, X is phenyl and the aforementioned CR¹ R² and Q moieties are attached in a postion para to the Z moiety.

n is 0 or 1. Preferably, n is 0.

OS(O)₂NHC(O)R¹⁸, -NR⁶S(O)2NHCN, -NR⁶S(O)2NHC(O)R¹⁸, -N(OH)C(O)R¹⁵, ONHC(O)R¹⁵, -NR⁶S(O)2NHS(O)₂R¹², -P(O)(Rⁱ³)(OR¹⁰), -P(O)H(OR¹⁰), -OP(O)(R¹³)(OR'°), -NR⁶P(O)(R¹³)(OR’°) and tetrazole.

Preferably, Z is selected from the group consisting of -C(O)OR¹⁰, -C(O)NHORⁿ, OC(O)NHOR^h, -NR⁶C(O)NHORⁿ, -C(O)NHS(O)2R¹², -OC(O)NHS(O)2R¹²,

NR⁶C(O)NHS(O)2R¹², -S(O)2OR¹⁰, -OS(O)2OR¹⁰, -NR⁶S(O)2OR¹⁰, -NR⁶S(O)OR¹⁰, NHS(O)2R¹⁴, -S(O)OR¹⁰, -OS(O)OR¹⁰, -S(O)2NHC(O)R¹⁸, -S(O)2NHS(O)2R¹², OS(O)2NHS(O)₂R¹², -OS(O)2NHC(O)R¹⁸, -NR⁶S(O)2NHC(O)R¹⁸, -N(OH)C(O)R¹⁵, ONHC(O)R¹⁵, -NR⁶S(O)₂NHS(O)₂R¹², -P(O)(R¹³)(OR¹⁰), -P(O)H(OR¹⁰), -OP(O)(R¹³)(OR¹⁰) and -NR⁶P(O)(R¹³)(OR¹⁰).

More preferably, Z is selected from the group consisting of -C(O)OR¹⁰, -C(O)NHORⁿ, C(O)NHS(O)2R¹², -S(O)2OR¹⁰, -OS(O)2OR¹⁰, -NR⁶S(O)2OR¹⁰, -NHS(O)₂R¹⁴, -S(O)OR¹⁰ and -P(O)(R¹³)(OR¹⁰).

Even more preferably Z is selected from the group consisting of-C(O)OR'°, -C(O)NHS(O)₂R¹², -S(O)2OR¹⁰, -OS(O)2OR¹⁰ and -P(O)(R¹³)(OR¹⁰).

Even more preferably still Z is selected from the group consisting of -C(O)OH, -C(O)OCH₃, 5 C(O)OCH₂CH₃, -C(O)OCH(CH₃)₂, -C(O)OC(CH₃)₃, -C(O)OCH₂C₆H5, -C(O)OC₆H₅, C(O)NHS(O)₂CH₃, -S(O)₂OH, -OS(O)₂OH, -P(O)(OH)(OH), -P(O)(OH)(OCH₂CH₃), P(O)(OH)(OCH₃), -P(O)(OCH₃)(OCH₃), -P(O)(OCH₂CH₃)(OCH₂CH₃), -P(O)(CH₃)(OH) and -P(O)(CH₃)(OCH₂CH₃).

Yet even more preferably still, Z is selected from the group consisting of -C(O)OH, C(O)OCH₃, -C(O)OCH₂CH₃, -C(O)OC(CH₃)₃, -C(O)NHS(O)₂CH₃, -S(O)₂OH, -OS(O)₂OH, P(O)(OH)(OH), -P(O)(OH)(OCH₂CH₃), -P(O)(OH)(OCH₃), -P(O)(OCH₃)(OCH₃), P(O)(OCH₂CH₃)(OCH₂CH₃), -P(O)(CH₃)(OH) and -P(O)(CH₃)(OCH₂CH₃).

Further more preferably still, Z is selected from the group consisting of -C(O)OH, C(O)NHS(O)₂CH₃, -S(O)₂OH, -OS(O)₂OH, -P(O)(OH)(OH), -P(O)(OH)(OCH₂CH₃), P(O)(OH)(OCH₃) and -P(O)(CH₃)(OH).

Most preferably Z is -C(O)OH or -S(O)₂OH.

In one embodiment Z is selected from the group consisting of -C(O)OR^l°, -C(O)NHS(O)2R¹², -S(O)2OR¹⁰, and -P(O)(R¹³)(OR¹⁰) (preferably, -C(O)OH, -C(O)OCH₃, -C(O)OCH₂CH₃, C(O)NHS(O)₂CH₃, -S(O)₂OH, -P(O)(OH)(OH), -P(O)(OH)(OCH₂CH₃), -P(O)(CH₃)(OH) and -P(O)(CH₃)(OCH₂CH₃)).

R¹⁰ is selected from the group consisting of hydrogen, Ci-Côalkyl, 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, 30 Ci-Côalkyl, phenyl and benzyl. More preferably, R¹⁰ is selected from the group consisting of hydrogen and Ci-CealkyL Even more preferably, R¹⁰ is selected from the group consisting of hydrogen, methyl, ethyl and tert-butyl. Most preferably, R¹⁰ is hydrogen.

R¹¹ is selected from the group consisting of hydrogen, Ci-Côalkyl and phenyl, and wherein said 35 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-Cealkyl. Even more preferably, R¹¹ is Ci-Côalkyl. 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 R⁹substituents, which may be the same or different. Preferably, R¹² is selected from the group consisting of Ci-C6alkyl, Ci-C6haloalkyl, 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, R¹^ 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-Cealkyl, Ci-Cealkoxy and phenyl. Preferably R¹³ is selected from the group consisting of -OH, Ci-Côalkyl and Ci-Côalkoxy. More preferably, R¹³ is selected from the group consisting of -OH and Ci-Cealkoxy. Even more preferably, R¹³ is selected from the group consisting of -OH, methoxy and ethoxy. Most preferably, R¹³ is -OH.

R¹⁴ is Ci-Côhaloalkyl. Preferably, R¹⁴ is trifluoromethyl.

R¹⁵ is selected from the group consisting of Ci-Côalkyl 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-Côalkyl and phenyl. More preferably, R¹⁵ is Ci-Côalkyl. Most preferably R¹⁵ is methyl.

R^15a is phenyl, wherein said phenyl is optionally substituted by 1, 2 or 3 R⁹ substituents, which may be the same or different. Preferably, R^15a is phenyl optionally substituted by 1 R⁹substituent. More preferably, R^15a is phenyl.

R¹⁶ and R¹⁷are independently selected from the group consisting of hydrogen and Ci-CôalkyL Preferably, R¹⁶ and R¹⁷ are independently selected from the group consisting of hydrogen and methyl.

Altematively, R¹⁶ and R¹⁷ together with the nitrogen atom to which they are attached form a 4to 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, R¹⁶and R¹⁷ together with the nitrogen atom to which they are attached form an pyrrolidyl, 5 oxazolidinyl, imidazolidinyl, piperidyl, piperazinyl or morpholinyl group.

R¹⁸ is selected from the group consisting of hydrogen, Ci-C6alkyl, Ci-C6haloalkyl, CiCealkoxy, -N(R⁶)2 and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R⁹substituents, which may be the same or different. Preferably, R¹⁸ is selected from the group 10 consisting of hydrogen, Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, -N(R⁶)2 and phenyl. More preferably, R¹⁸ is selected from the group consisting of hydrogen, Ci-Cealkyl and CiCôhaloalkyl. Further more preferably, R¹⁸ is selected from the group consisting of Ci-Côalkyl and Ci-CôhaloalkyL 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-Côalkyl;

R² is hydrogen or methyl;

Q is (CR^laR^2b)_m;

m is 0,1 or 2;

R^la and R^2b are independently selected from the group consisting of hydrogen, Ci-Cealkyl, OH and -NH₂;

R³, R^3a, R⁴ and R⁵ are independently selected from the group consisting of hydrogen, chloro, 25 fluoro, bromo and methyl;

each R⁶ is independently selected from hydrogen and methyl;

each R⁷ is Ci-Cealkyl;

A is a 5-membered heteroaryl attached to the rest of the molécule via a ring carbon atom, which comprises 1, 2, 3 or 4 heteroatoms independently selected from the group consisting of N, O 30 and S, and wherein the heteroaryl may, where feasible, be optionally substituted by 1, 2 or 3 R⁸substituents, which may be the same or different;

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, -S(O)rR¹⁵, -C(O)OR¹⁰, -C(O)R¹⁵, C(O)NR¹⁶R¹⁷, -S(O)2NR¹⁶R¹⁷, Ci-C₆alkyl and Ci-C₆haloalkyl;

and/or when A is substituted on a ring nitrogen atom, R⁸ is Ci-Cealky or Ci-Cëhaloalkyl; and n is 0;

Z is selected from the group consisting of -C(O)OR¹⁰, -C(O)NHS(O>2R¹², -S(O)2OR¹⁰, OS(O)₂OR¹⁰ and -P(O)(R¹³)(OR¹⁰);

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, Ci-C₆alkyl and Ci-C₆alkoxy;

R¹⁵ is Ci-C₆alkyl;

R¹⁶ and R¹⁷ are independently selected from the group consisting of hydrogen and methyl; and 10 r is 0 or 2.

More preferably,

R¹ is hydrogen or methyl;

R² is hydrogen or methyl;

Q is (CR^laR^2b)_m;

m is 0 or 1 ;

R^la and R^2b are independently selected from the group consisting of hydrogen and methyl;

R³, R^ja, R⁴ and R⁵ are independently selected from the group consisting of hydrogen, chloro and fluoro;

A is a heteroaryl selected from the group consisting of l,2,4-oxadiazol-5-yl, thiadiazol-5-yl, l,2,4-thiadiazol-5-yl, thiadiazol-4-yl, l,2,4-thiadiazol-3-yl, l,2,5-thiadiazol-3-yl, 1,3,4thiadiazol-2-yl, l,3,4-oxadiazol-2-yl, l,2,4-oxadiazol-3-yl, l,2,5-oxadiazol-3-yl, 1,2,4-triazol3-yl, l,2,4-triazol-5-yl, triazol-4-yl, triazol-5-yl, 2-methyltetrazol-5-yl, l-methyltetrazol-5-yl, thiazol-2-yl, thiazol-4-yl, isothiazol-5-yl, isothiazol-4-yl, isothiazol-3-yl, oxazol-2-yl, oxazol25 4-yl, isoxazol-3-yl, isoxazol-5-yl, imidazol-5-yl, imidazol-2-yl, 3-furyl, 2-furyl, 3-thienyl, pyrazol-5-yl, pyrazol-3-yl and 2-thienyl wherein the heteroaryl may, where feasible, be optionally substituted by 1, 2 or 3 R⁸ substituents, which may be the same or different;

when A is substituted on one or more ring carbon atoms, each R⁸ is independently selected from the group consisting of halogen, cyano, -NH2, -C(O)NR¹⁶R¹⁷, Ci-Cealkyl and Ci-Côhaloalkyl;

and/or when A is substituted on a ring nitrogen atom, R⁸ is Ci-Côalkyl; and n is 0;

Z is selected from the group consisting of -C(O)OH, -C(O)OCH3, -C(O)OCH2CH3, C(O)OCH(CH₃)2, -C(O)OC(CH₃)₃, -C(O)OCH2C₆H₅, -C(O)OC₆H₅, -C(O)NHS(O)₂CH3, 35 S(O)₂OH, -OS(O)₂OH, -P(O)(OH)(OH), -P(O)(OH)(OCH₂CH₃), -P(O)(OH)(OCH₃), 20324

P(O)(OCH₃)(OCH₃), -P(O)(OCH₂CH₃)(OCH₂CH₃), -P(O)(CH₃)(OH) and P(O)(CH₃)(OCH₂CH₃); and

R¹⁶ and R¹⁷ are independently selected from the group consisting of hydrogen and methyl.

In a further set of preferred embodiments, the compound according to formula (I) is selected from a compound of formula (I-a), (I-b), (I-c), (I-d), (I-e) or (I-f),

wherein in a compound of formula (I-a), (I-b), (I-c), (I-d), (I-e) and (I-f), each R^8b is independently selected from the group consisting of hydrogen, bromo, chloro, fluoro, cyano, -NH₂, -C(O)NH₂, -C(O)NHMe, -C(O)N(Me)₂, methyl and trifluoromethyl; and Z is selected from the group consisting of -C(O)OH, -C(O)OCH₃, -C(O)OCH₂CH₃, C(O)OC(CH₃)₃, -C(O)NHS(O)₂CH₃, -S(O)₂OH, -OS(O)₂OH, -P(O)(OH)(OH), 15 P(O)(OH)(OCH₂CH₃), -P(O)(OH)(OCH₃), -P(O)(OCH₃)(OCH₃),

P(O)(OCH₂CH₃)(OCH₂CH₃), -P(O)(CH₃)(OH) and -P(O)(CH₃)(OCH₂CH₃).

In a further more preferred set of embodiments, the compound according to formula (I) is 20 selected from a compound of formula (I-aa), (I-bb), (I-cc), (I-dd), (I-ee) or (I-ff),

wherein in a compound of formula (I-aa), (I-bb), (I-cc), (I-dd), (I-ee) and (I-ff),

Z is -C(O)OH or -S(O)₂OH.

In a another set of preferred embodiments, the compound according to formula (I) is selected from a compound of formula (I-h), (I-k) or (I-m),

(l-m) wherein in a compound of formula (I-h), (I-k) or (I-m),

R¹ is hydrogen or methyl;

R² is hydrogen or methyl;

R³, R^3a, R⁴ and R⁵ are independently selected from the group consisting of hydrogen, chloro, fluoro, bromo, cyano, methyl and trifluoromethyl;

each R⁶ is independently hydrogen or methyl;

each R^8b is independently selected from the group consisting of hydrogen, halogen, cyano, NH2, -C(O)NR¹⁶R¹⁷, Ci-C6alkyl and Ci-C₆haloalkyl;

Z is selected from the group consisting of -C(O)OR¹⁰, -C(O)NHS(O)2R¹², -S(O)2OR¹⁰, and P(O)(R¹³)(OR¹⁰);

R¹⁰ is selected from the group consisting of hydrogen and Ci-Cealkyl;

R¹² is selected from the group consisting of Ci-Côalkyl, Ci-Côhaloalkyl and -N(R⁶)₂;

R¹³ is selected from the group consisting of -OH, Ci-Cealkyl and Ci-Côalkoxy; and

In one set of embodiments, the compound according to formula (I) is selected from a compound Al to A101 listed in Table A.

It should be understood that compounds of formula (I) may exist/be manufactured in ‘procédai form’, wherein they comprise a group ‘G’. Such compounds are referred to herein as compounds of formula (I-IV).

G is a group which may be removed in a plant by any appropriate mechanism including, but not limited to, metabolism and Chemical dégradation to give a compound of formula (I-I), (III) or (I-ΠΙ) wherein Z contains an acidic proton, for example see the scheme below:

Whilst such G groups may be considered as ‘procidal’, and thus yield active herbicidal compounds once removed, compounds comprising such groups may also exhibit herbicidal activity in their own right. In such cases in a compound of formula (I-IV), Z-G may include but is not limited to, any one of (Gl) to (G7) below and E indicates the point of attachment to the remaining part of a compound of formula (I):

(Gl)

O O 03 A O

Rl Y G

O

In embodiments where Z-G is (Gl) to (G7), G, R¹⁹, R²⁰, R²¹, R²² and R²³ are defined as follows:

G is Ci-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, -C(R²¹R²²)OC(O)R¹⁹, phenyl or phenyl-CiC4alkyl-, wherein said phenyl moiety is optionally substituted by 1 to 5 substituents independently selected from halo, cyano, nitro, Ci-Côalkyl, Ci-Côhaloalkyl or Ci-Cealkoxy.

R¹⁹ is Ci-Cealkyl or phenyl,

R²⁰ is hydroxy, Ci-Cealkyl, Ci-Côalkoxy or phenyl,

R²¹ is hydrogen or methyl,

R²² is hydrogen or methyl, 10 R²³ is hydrogen or Ci-Côalkyl.

The compounds in Tables 1 to 27 below illustrate the compounds of the invention. The skilled person would understand that the compounds of formula (I) may exist as an agronomically acceptable sait, a zwitterion or an agronomically acceptable sait of a zwitterion as described 15 hereinbefore.

Table 1:

This table discloses 53 spécifie compounds (1.001 to 1.053) of the formula (T-l):

(T-l)

Wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined in Table 1, R¹ and R² are hydrogen and n is 0.

Compound number	R³	R^3a	R⁴	R⁵	Z	m	Q
1.001	H	H	H	H	-C(O)OH	0	-
1.002	H	H	H	H	-C(O)OMe	0	-
1.003	H	H	H	H	-C(O)NHOMe	0	-

Compound number	R³	R^3a	R⁴	R⁵	Z	m	Q
1.004	H	H	H	H	-OC(O)NHOMe	0	-
1.005	H	H	H	H	-NHC(O)NHOMe	0	-
1.006	H	H	H	H	-NMeC(O)NHOMe	0	-
1.007	H	H	H	H	-C(O)NHS(O)₂Me	0	-
1.008	H	H	H	H	-OC(O)NHS(O)₂Me	0	-
1.009	H	H	H	H	-NHC(O)NHS(O)₂Me	0	-
1.010	H	H	H	H	NMeC(O)NHS(O)₂Me	0	-
1.011	H	H	H	H	-S(O)₂OH	0	-
1.012	H	H	H	H	-OS(O)₂OH	0	-
1.013	H	H	H	H	-NHS(O)₂OH	0	-
1.014	H	H	H	H	-NMeS(O)₂OH	0	-
1.015	H	H	H	H	-S(O)OH	0	-
1.016	H	H	H	H	-OS(O)OH	0	-
1.017	H	H	H	H	-NHS(O)OH	0	-
1.018	H	H	H	H	-NMeS(O)OH	0	-
1.019	H	H	H	H	-NHS(O)₂CF₃	0	-
1.020	H	H	H	H	-S(O)₂NHC(O)Me	0	-
1.021	H	H	H	H	-OS(O)₂NHC(O)Me	0	-
1.022	H	H	H	H	-NHS(O)₂NHC(O)Me	0	-
1.023	H	H	H	H	NMeS(O)₂NHC(O)Me	0	-
1.024	H	H	H	H	-P(O)(OH)(OMe)	0	-
1.025	H	H	H	H	-P(O)(OH)(OH)	0	-
1.026	H	H	H	H	-OP(O)(OH)(OMe)	0	-
1.027	H	H	H	H	-OP(O)(OH)(OH)	0	-
1.028	H	H	H	H	-NHP(O)(OH)(OMe)	0	-
1.029	H	H	H	H	-NHP(O)(OH)(OH)	0	-
1.030	H	H	H	H	-NMeP(O)(OH)(OMe)	0	-
1.031	H	H	H	H	-NMeP(O)(OH)(OH)	0	-
1.032	H	H	H	H	-tetrazole	0	-
1.033	H	H	H	H	-S(O)₂OH	1	CH(NH₂)

Compound number	R³	R^3a	R⁴	R^s	Z	m	Q
1.033	H	H	H	H	-C(O)OH	1	CH(NH₂)
1.035	H	H	H	H	-S(O)₂OH	2	CH(OH)CH₂
1.036	H	H	H	H	-C(O)OH	2	CH(OH)CH₂
1.037	H	H	H	H	-S(O)₂OH	1	CH(OH)
1.038	H	H	H	H	-C(O)OH	1	CH(OH)
1.039	H	H	H	H	-C(O)NHCN	0	-
1.040	H	H	H	H	-OC(O)NHCN	0	-
1.041	H	H	H	H	-NHC(O)NHCN	0	-
1.042	H	H	H	H	-NMeC(O)NHCN	0	-
1.043	H	H	H	H	-S(O)₂NHCN	0	-
1.044	H	H	H	H	-OS(O)₂NHCN	0	-
1.045	H	H	H	H	-NHS(O)₂NHCN	0	-
1.046	H	H	H	H	-NMeS(O)₂NHCN	0	-
1.047	H	H	H	H	-S(O)₂NHS(O)₂Me	0	-
1.048	H	H	H	H	-OS(O)₂NHS(O)₂Me	0	-
1.049	H	H	H	H	-NHS(O)₂NHS(O)₂Me	0	-
1.050	H	H	H	H	NMeS(O)₂NHS(O)₂Me	0	-
1.051	H	H	H	H	-P(O)H(OH)	0	-
1.052	H	H	H	H	-N(OH)C(O)Me	0	-
1.053	H	H	H	H	-ONHC(O)Me	0	-

Table 2:

This table discloses 49 spécifie compounds (2.001 to 2.049) of the formula (T-2):

(T-2)

Wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined in Table 2, R¹ and R² are hydrogen and n is

0.

Compound number	R³	R^3a	R⁴	R⁵	Z	m	Q
2.001	H	H	H	H	-C(O)OH	1	ch₂
2.002	H	H	H	H	-C(O)OMe	1	ch₂
2.003	H	H	H	H	-C(O)NHOMe	1	ch₂
2.004	H	H	H	H	-OC(O)NHOMe	1	ch₂
2.005	H	H	H	H	-NHC(O)NHOMe	1	ch₂
2.006	H	H	H	H	-NMeC(O)NHOMe	1	ch₂
2.007	H	H	H	H	-C(O)NHS(O)₂Me	1	ch₂
2.008	H	H	H	H	-OC(O)NHS(O)₂Me	1	ch₂
2.009	H	H	H	H	-NHC(O)NHS(O)₂Me	1	ch₂
2.010	H	H	H	H	NMeC(O)NHS(O)₂Me	1	ch₂
2.011	H	H	H	H	-S(O)₂OH	1	ch₂
2.012	H	H	H	H	-OS(O)₂OH	1	ch₂
2.013	H	H	H	H	-NHS(O)₂OH	1	ch₂
2.014	H	H	H	H	-NMeS(O)₂OH	1	ch₂
2.015	H	H	H	H	-S(O)OH	1	ch₂
2.016	H	H	H	H	-OS(O)OH	1	ch₂
2.017	H	H	H	H	-NHS(O)OH	1	ch₂
2.018	H	H	H	H	-NMeS(O)OH	1	ch₂
2.019	H	H	H	H	-NHS(O)₂CF₃	1	ch₂
2.020	H	H	H	H	-S(O)₂NHC(O)Me	1	ch₂
2.021	H	H	H	H	-OS(O)₂NHC(O)Me	1	ch₂
2.022	H	H	H	H	-NHS(O)₂NHC(O)Me	1	ch₂
2.023	H	H	H	H	NMeS(O)₂NHC(O)Me	1	ch₂
2.024	H	H	H	H	-P(O)(OH)(OMe)	1	ch₂
2.025	H	H	H	H	-P(O)(OH)(OH)	1	ch₂
2.026	H	H	H	H	-OP(O)(OH)(OMe)	1	ch₂
2.027	H	H	H	H	-OP(O)(OH)(OH)	1	ch₂

Compound number	R³	R^3a	R⁴	R⁵	Z	m	Q
2.028	H	H	H	H	-NHP(O)(OH)(OMe)	1	ch₂
2.029	H	H	H	H	-NHP(O)(OH)(OH)	1	ch₂
2.030	H	H	H	H	-NMeP(O)(OH)(OMe)	1	ch₂
2.031	H	H	H	H	-NMeP(O)(OH)(OH)	1	ch₂
2.032	H	H	H	H	-tetrazole	1	ch₂
2.033	H	H	H	H	-S(O)₂OH	2	CH₂CH(NH₂)
2.034	H	H	H	H	-C(O)OH	2	CH₂CH(NH₂)
2.035	H	H	H	H	-C(O)NHCN	1	ch₂
2.036	H	H	H	H	-OC(O)NHCN	1	ch₂
2.037	H	H	H	H	-NHC(O)NHCN	1	ch₂
2.038	H	H	H	H	-NMeC(O)NHCN	1	ch₂
2.039	H	H	H	H	-S(O)₂NHCN	1	ch₂
2.040	H	H	H	H	-OS(O)₂NHCN	1	ch₂
2.041	H	H	H	H	-NHS(O)₂NHCN	1	ch₂
2.042	H	H	H	H	-NMeS(O)₂NHCN	1	ch₂
2.043	H	H	H	H	-S(O)₂NHS(O)₂Me	1	ch₂
2.044	H	H	H	H	-OS(O)₂NHS(O)₂Me	1	ch₂
2.045	H	H	H	H	-NHS(O)₂NHS(O)₂Me	1	ch₂
2.046	H	H	H	H	NMeS(O)₂NHS(O)₂Me	1	ch₂
2.047	H	H	H	H	-P(O)H(OH)	1	ch₂
2.048	H	H	H	H	-N(OH)C(O)Me	1	ch₂
2.049	H	H	H	H	-ONHC(O)Me	1	ch₂

Table 3:

This table discloses 49 spécifie compounds (3.001 to 3.049) of the formula (T-3):

(T-3) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined in Table 3, R¹ and R² are hydrogen and n is

0.

Compound number	R³	R³	R⁴	R⁵	Z	m	Q
3.001	H	H	H	H	-C(O)OH	2	ch₂ch₂
3.002	H	H	H	H	-C(O)OMe	2	ch₂ch₂
3.003	H	H	H	H	-C(O)NHOMe	2	ch₂ch₂
3.004	H	H	H	H	-OC(O)NHOMe	2	ch₂ch₂
3.005	H	H	H	H	-NHC(O)NHOMe	2	ch₂ch₂
3.006	H	H	H	H	-NMeC(O)NHOMe	2	ch₂ch₂
3.007	H	H	H	H	-C(O)NHS(O)₂Me	2	ch₂ch₂
3.008	H	H	H	H	-OC(O)NHS(O)₂Me	2	ch₂ch₂
3.009	H	H	H	H	-NHC(O)NHS(O)₂Me	2	ch₂ch₂
3.010	H	H	H	H	NMeC(O)NHS(O)₂Me	2	ch₂ch₂
3.011	H	H	H	H	-S(O)₂OH	2	ch₂ch₂
3.012	H	H	H	H	-OS(O)₂OH	2	ch₂ch₂
3.013	H	H	H	H	-NHS(O)₂OH	2	ch₂ch₂
3.014	H	H	H	H	-NMeS(O)₂OH	2	ch₂ch₂
3.015	H	H	H	H	-S(O)OH	2	ch₂ch₂
3.016	H	H	H	H	-OS(O)OH	2	ch₂ch₂
3.017	H	H	H	H	-NHS(O)OH	2	ch₂ch₂
3.018	H	H	H	H	-NMeS(O)OH	2	ch₂ch₂
3.019	H	H	H	H	-NHS(O)₂CF₃	2	ch₂ch₂
3.020	H	H	H	H	-S(O)₂NHC(O)Me	2	ch₂ch₂
3.021	H	H	H	H	-OS(O)₂NHC(O)Me	2	ch₂ch₂
3.022	H	H	H	H	-NHS(O)₂NHC(O)Me	2	ch₂ch₂
3.023	H	H	H	H	NMeS(O)₂NHC(O)Me	2	ch₂ch₂
3.024	H	H	H	H	-P(O)(OH)(OMe)	2	ch₂ch₂
3.025	H	H	H	H	-P(O)(OH)(OH)	2	ch₂ch₂
3.026	^H	H	H	H	-OP(O)(OH)(OMe)	2	ch₂ch₂

Compound number	R³	R^3a	R⁴	R⁵	Z	m	Q
3.027	H	H	H	H	-OP(O)(OH)(OH)	2	ch₂ch₂
3.028	H	H	H	H	-NHP(O)(OH)(OMe)	2	ch₂ch₂
3.029	H	H	H	H	-NHP(O)(OH)(OH)	2	ch₂ch₂
3.030	H	H	H	H	-NMeP(O)(OH)(OMe)	2	ch₂ch₂
3.031	H	H	H	H	-NMeP(O)(OH)(OH)	2	ch₂ch₂
3.032	H	H	H	H	-tetrazole	2	ch₂ch₂
3.033	H	H	H	H	-S(O)₂OH	3	CH₂CH₂CH(NH₂)
3.034	H	H	H	H	-C(O)OH	3	CH₂CH₂CH(NH₂)
3.035	H	H	H	H	-C(O)NHCN	2	ch₂ch₂
3.036	H	H	H	H	-OC(O)NHCN	2	ch₂ch₂
3.037	H	H	H	H	-NHC(O)NHCN	2	ch₂ch₂
3.038	H	H	H	H	-NMeC(O)NHCN	2	ch₂ch₂
3.039	H	H	H	H	-S(O)₂NHCN	2	ch₂ch₂
3.040	H	H	H	H	-OS(O)₂NHCN	2	ch₂ch₂
3.041	H	H	H	H	-NHS(O)₂NHCN	2	ch₂ch₂
3.042	H	H	H	H	-NMeS(O)₂NHCN	2	ch₂ch₂
3.043	H	H	H	H	-S(O)₂NHS(O)₂Me	2	ch₂ch₂
3.044	H	H	H	H	-OS(O)₂NHS(O)₂Me	2	ch₂ch₂
3.045	H	H	H	H	-NHS(O)₂NHS(O)₂Me	2	ch₂ch₂
3.046	H	H	H	H	NMeS(O)₂NHS(O)₂Me	2	ch₂ch₂
3.047	H	H	H	H	-P(O)H(OH)	2	ch₂ch₂
3.048	H	H	H	H	-N(OH)C(O)Me	2	ch₂ch₂
3.049	H	H	H	H	-ONHC(O)Me	2	ch₂ch₂

Table 4:

This table discloses 53 spécifie compounds (4.001 to 4.053) ofthe formula (T-4):

(T-4) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 1, R¹ and R² are hydrogen and n is 0.

Table 5:

This table discloses 49 spécifie compounds (5.001 to 5.049) of the formula (T-5):

(T-5) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 2, R¹ and R² are hydrogen and n is 0.

Table 6:

This table discloses 49 spécifie compounds (6.001 to 6.049) ofthe formula (T-6):

(T-6) wherein m, Q, R , R , R , R⁵ and Z are as defined above in Table 3, R¹ and R² are hydrogen and n is 0.

Table 7:

This table discloses 53 spécifie compounds (7.001 to 7.053) ofthe formula (T-7):

(T-7) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 1, R¹ and R² are hydrogen and n is 0.

Table 8:

This table discloses 49 spécifie compounds (8.001 to 8.049) of the formula (T-8):

(T-8) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 2, R¹ and R² are hydrogen and n is 0.

Table 9:

This table discloses 49 spécifie compounds (9.001 to 9.049) of the formula (T-9):

(T-9) wherein m, Q, R , R , R , R⁵ and Z are as defined above in Table 3, R¹ and R² are hydrogen and n is 0.

Table 10:

This table discloses 53 spécifie compounds (10.001 to 10.053) of the formula (T-10):

(T-10) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 1, R¹ and R² are hydrogen and n is 0.

Table 11:

This table discloses 49 spécifie compounds (11.001 to 11.049) of the formula (T-l 1):

(T-ll) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 2, R¹ and R² are hydrogen and n is 0.

Table 12:

This table discloses 49 spécifie compounds (12.001 to 12.049) of the formula (T-12):

(T-12) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 3, R¹ and R² are hydrogen and n is 0.

Table 13:

This table discloses 53 spécifie compounds (13.001 to 13.053) of the formula (T-13):

1/ \ 9 ha R R²K wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 1, R¹ and R² are hydrogen and n is 0.

Table 14:

This table discloses 49 spécifie compounds (14.001 to 14.049) of the formula (T-14):

ha R 'r²r\ (T-14) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 2, R¹ and R² are hydrogen and n is 0.

Table 15:

This table discloses 49 spécifie compounds (15.001 to 15.049) ofthe formula (T-15):

(T-15) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 3, R¹ and R² are hydrogen 5 and n is 0.

Table 16:

This table discloses 53 spécifie compounds (16.001 to 16.053) of the formula (T-16):

(T-16) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 1, R¹ and R² are hydrogen and n is 0.

Table 17:

This table discloses 49 spécifie compounds (17.001 to 17.049) ofthe formula (T-17):

(T-17) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 2, R¹ and R² are hydrogen and n is 0.

Table 18:

This table discloses 49 spécifie compounds (18.001 to 18.049) of the formula (T-18):

F F (T-18) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 3, R¹ and R² are hydrogen and n is 0.

Table 19:

This table discloses 53 spécifie compounds (19.001 to 19.053) ofthe formula (T-19):

(T-19) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 1, R¹ and R² are hydrogen and n is 0.

Table 20:

This table discloses 49 spécifie compounds (20.001 to 20.049) ofthe formula (T-20):

Cl

(T-20) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 2, R¹ and R² are hydrogen and n is 0.

Table 21:

This table discloses 49 spécifie compounds (21.001 to 21.049) ofthe formula (T-21):

(T-21) wherein m, Q, R , R^3a, R⁴, R³ and Z are as defined above in Table 3, R¹ and R² are hydrogen 15 and n is 0.

Table 22:

This table discloses 53 spécifie compounds (22.001 to 22.053) ofthe formula (T-22):

(T-22) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 1, R¹ and R² are hydrogen and n is 0.

Table 23:

This table discloses 49 spécifie compounds (23.001 to 23.049) of the formula (T-23):

Z (T-23) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 2, R¹ and R² are hydrogen and n is 0.

Table 24:

This table discloses 49 spécifie compounds (24.001 to 24.049) of the formula (T-24):

(T-24) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 3, R¹ and R² are hydrogen and n is 0.

Table 25:

This table discloses 53 spécifie compounds (25.001 to 25.053) of the formula (T-25):

(T-25) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 1, R¹ and R² are hydrogen and n is 0.

Table 26:

This table discloses 49 spécifie compounds (26.001 to 26.049) of the formula (T-26):

(T-26) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 2, R¹ and R² are hydrogen and n is 0.

Table Zl·.

This table discloses 49 spécifie compounds (27.001 to 27.049) ofthe formula (T-27):

(T-27) wherein m, Q, R³, R^3a, R⁴, R⁵ and Z are as defined above in Table 3, R¹ and R² are hydrogen and n is 0.

The compounds of the présent invention may be prepared according to the following schemes in which the substituents n, m, r, A, Q, X, Z, R¹, R², R^la, R^2b, R², R³, R^3a, R⁴, R⁵, R⁶, R⁷, R^7a, R^7b R^7c, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R^15a, R¹⁶, r¹⁷ and r¹⁸ are as defined hereinbefore unless explicitly stated otherwise. The compounds of the preceeding Tables 1 to 27 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, R^3a, R⁴, R⁵ 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 température, 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, ΛζΑ-dimethylformamide, acetonitrile, 1,4-dioxane, water, acetic acid or trifluroacetic acid at a température between -78°C and 150°C. An alkylating agent of formula (W) may include, but is not limited to, bromoacetic acid, methyl bromoacetate, 3bromopropionoic acid, methyl 3-bromopropionate, 2-bromo-A-methoxyacetamide, sodium 2bromoethanesulphonate, 2,2-dimethylpropyl 2-(trifluoromethylsulfonyloxy)ethanesulfonate, 2-bromo-A-methanesulfonylacetamide, 3-bromo-A-methanesulfonylpropanamide, dimethoxyphosphorylmethyl trifluoromethanesulfonate, dimethyl 3-bromopropylphosphonate,

3-chloro-2,2-dimethyl-propanoic acid and diethyl 2-bromoethylphosphonate. 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 X-alkyl acids, which include, but are not limited to, esters of carboxylic acids, phosphonic acids, 5 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 température between 0°C and 100°C.

Reaction scheme 1

formula (X)

Additonally, compounds of formula (I) may be prepared by reacting compounds of formula (X), wherein R³, R^3a, R⁴, R⁵ and A are as defined for compounds of formula (I), with a suitably activated electrophilic alkene of formula (B), wherein Z is -S(O)₂OR¹⁰, -P(O)(R^I3)(OR¹⁰) or 15 C(O)OR¹⁰ and R¹, R², R^la, R¹⁰ and R¹³ are as defined for compounds of formula (I), in a suitable solvent at a suitable température. 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 20 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 température, as described in réaction scheme 2.

Reaction scheme 2

, . ... formula (I), wherein formula (I), wherein formula (X) „ _ . . _r.

m=1,n=0and m=1,n=0and

Z=S(O)₂OR¹⁰, P(O)(R¹³)(OR¹⁰), Z=S(O)₂OH, P(O)(R¹³)(OH),

C(O)OR¹⁰ C(O)OH

In a related reaction compounds of formula (I), wherein Q is C(R^laR^2b), m is 1, 2 or 3, n=0 and Z is -S(O)2OH, -OS(O)2OH or -NR⁶S(O)2OH, may be prepared by the reaction of compounds of formula (X), wherein R³, R^3a, R⁴, R⁵ and A are as defined for compounds of formula (I), with 5 a cyclic alkylating agent of formula (E), (F) or (AF), wherein Y^a is C(R^laR^2b), O or NR⁶ and R¹, R², R^la and R^2b are as defined for compounds of formula (I), in a suitable solvent at a suitable température, as described in reaction scheme 3. Suitable solvents and suitable températures 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, 10 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.

Reaction scheme 3

formula (I), wherein m is 1, 2 or 3, n=0 and Z = S(O)₂OH, OS(O)₂OH or NR⁶S(O)₂OH formula (AF)

Where m=1 and n=0

A compound of formula (I), wherein m is 0, n is 0 and Z is -S(O)2OH, may be prepared from a compound of formula (I), wherein m is 0, n is 0 and Z is C(O)OR¹⁰, by treatment with 5 trimethylsilylchlorosulfonate in a suitable solvent at a suitable température, as described in reaction scheme 4. Preferred conditions include heating the carboxylate precursor in neat trimethylsilylchlorosulfonate at a température between 25°C and 150°C.

Reaction scheme 4

formula (I), wherein m=0, n=0

-10 and Z=C(O)OR¹⁰ formula (I), wherein m=0, n=0 and Z=S(O)₂OH

Furthermore, compounds of formula (I) may be prepared by reacting compounds of formula (X), wherein R³, R^3a, R⁴, R⁵ 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 5. Such alcohols are either known in the literature or may be prepared by known literature methods.

Reaction scheme 5

Acid, PhsP

In another approach a compound of formula (I), wherein n, Q, Z, X, R¹, R², R³, R^3a, R⁴, R⁵ and A are as defined for compounds of formula (I), may be prepared from a compound of formula (R) and an oxidant, in a suitable solvent at a suitable température, as outlined in reaction scheme 6. Example oxidants include, but are not limited to, 2,3-dichloro-5,6-dicyano-l,4benzoquinone, tetrachloro-p-benzoquinone, potassium permanganate, manganèse dioxide, 2,2,6,6-tetramethyl-l-piperidinyloxy and bromine. Related reactions are known in the literature.

Reaction scheme 6

formula (R) formula (I)

A compound of formula (R), wherein n, Q, Z, X, R¹, R², R³, R^3a, R⁴, R⁵ and A are as defined for compounds of formula (I), may be prepared from a compound of formula (S) and an organometallic of formula (T), wherein M’ includes, but is not limited to, organomagnesium, organolithium, organocopper and organozinc reagents, in a suitable solvent at a suitable 5 température, optionally in the presence of an additonal transition métal additive, as outlined in reaction scheme 7. Example conditions include treating a compound of formula (S) with a Grignard of formula (T), in the presence of 0.05-100 mol% copper iodide, in a solvent such as tetrahydrofuran at a température between -78°C and 100°C. Organometallics of formula (T) are known in the literature, or may be prepared by known literature methods. Compounds of formula (S) may be prepared by analogous reactions to those for the préparation of compounds of formula (I) from a compound of formula (XX).

Reaction scheme 7

R⁴

formula (R)

Biaryl pyridines of formula (X) are known in the literature or may be prepared using literature methods. Example methods include, but are not limited to, the transition métal cross-coupling of compounds of formula (H) and formula (J), or alternatively compounds of formula (K) and formula (L), in which compounds of formula (J) and formula (L), wherein M’ is either an 20 organostannane, organoboronic acid or ester, organotrifluoroborate, organomagnesium, organocopper or organozinc, as outlined in reaction scheme 8. Hal is defined as a halogen or pseudo halogen, for example triflate, mesylate and tosylate. Such cross-couplings include Stille (for example Sauer, J.; Heldmann, D. K. Tetrahedron, 1998, 4297), Suzuki-Miyaura (for example Luebbers, T.; Flohr, A.; Jolidon, S.; David-Pierson, P.; Jacobsen, H.; Ozmen, L.; 25 Baumann, K. Bioorg. Med. Chem. Lett., 2011, 6554), Negishi (for example Imahori, T.;

Suzawa, K.; Kondo, Y. Heterocycles, 2008, 1057), and Kumada (for example Heravi, Μ. M.;

Hajiabbasi, P. Monatsh. Chem., 2012, 1575). The coupling partners may be selected with reference to the spécifie cross-coupling reaction and target product. Transition métal catalysts, ligands, bases, solvents and températures 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 8

Transition métal catalyst Ligand

Transition métal catalyst Ligand formula QÇ)

A compound of formula (J), wherein M‘ is either an organostannane, organoboronic acid or ester, organotrifluoroborate, organomagnesium, organocopper or organozinc, may be prepared from a compound of formula (XX), wherein R³, R^3a, R⁴ and R⁵ are as defined for compounds 10 of formula (I), by metallation, as outlined in reaction scheme 9. Similar reactions are known in the literature (for example Ramphal et al, WO2015/153683, Unsinn et al., Organic Letters, 15(5), 1128-1131; 2013, Sadleretal., Organic & Biomolecular Chemistry, 12(37), 7318-7327; 2014. Altematively, an organometallic of formula (J) may be prepared from compounds of formula (K), wherein R³, R^3a, R⁴ and R⁵ are as defined for compounds of formula (I), and Hal 15 is defined as a halogen or pseudo halogen, for example triflate, mesylate and tosylate, as described in scheme 9. Example conditions to préparé an compound of formula (J) wherein M’ is an organostannane, include treatment of a compound of formula (K) with lithium tributyl tin in an appropriate solvent at an appropriate température (for example see WO 2010/038465). Example conditions to préparé compound of formula (J) wherein M’ is an organoboronic acid 20 or ester, include treatment of a compound of formula (K) with bis(pinacolato)diboron, in the presence of an appropriate transition métal catalyst, appropriate ligand, appropriate base, in an appropriate solvent at an appropriate température (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 9

formula (XX)

In an addtional approach, outlined in scheme 10, biaryl pyridines of formula (X) may be prepared by classical ring synthesis approaches starting from a compound of formula (ZZ), wherein R³, R^3a, R⁴ and R⁵ are as defined for compounds of formula (I) and T is a functional group which can be converted through one or more Chemical steps into a 5-membered heteroaryl A, wherein A is as defined for compounds of formula (I). Such functional groups 10 include, but are not limited to, acid, ester, nitrile, amide, thioamide and ketone. Related transformations are known in the literature. Substituted pyridines may be prepared using methodology outlined in the literature.

Reaction scheme 10

Functional Group

Transformation

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 20 various physical forms, e.g. in the form of dusting powders, gels, wettable powders, waterdispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrâtes, microemulsifiable concentrâtes, oil-in-water émulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrâtes (with water or a water-miscible organic solvent as carrier), 25 impregnated polymer films or in other forms known e.g. from the Manual on Development and

Use of FAO and WHO Spécifications for Pesticides, United Nations, First Edition, Second Révision (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 ingrédient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or émulsions. The active ingrédients can also be formulated with other adjuvants, such as finely divided solids, minerai oils, oils of vegetable or animal origin, 10 modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.

The active ingrédients can also be contained in very fine microcapsules. Microcapsules contain the active ingrédients in a porous carrier. This enables the active ingrédients to be released into 15 the environment in controlled amounts (e.g. slow-release). Microcapsules usually hâve a diameter of from 0.1 to 500 microns. They contain active ingrédients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingrédients 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 20 rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyuréthane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art. Altematively, very fine microcapsules can be formed in which the active ingrédient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves 25 encapsulated.

The formulation adjuvants that are suitable for the préparation of the compositions according to the invention are knownper se. As liquid carriers there may be used: water, toluene, xylene, Petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, 30 acetonitrile, acetophenone, amyl acetate, 2-butanone, butylène 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/V-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, gammabutyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, 5 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, w-hexane, w-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phénol, polyethylene glycol, propionic acid, propyl lactate, propylene 10 carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, minerai oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, méthanol, éthanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, TV-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 20 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 25 used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surfaceactive 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 30 sodium stéarate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stéarate; block copolymers of ethylene oxide and propylene oxide; and salts 35 of mono- and di-alkylphosphate esters; and also further substances described e.g. in

McCutcheon's Détergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981).

Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, 5 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 minerai oil, alkyl esters of such oils or mixtures of such oils and oil dérivatives. 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 15 can be added to a spray tank in the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise minerai 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 dérivatives, 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 20 dérivatives 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 dérivatives 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 présent invention and from 1 to 30 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 concentrâtes, the end user will normally employ dilute formulations.

The rates of application vary within wide limits and dépend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and 35 other factors govemed 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 1/ha, especially from 10 to 1000 1/ha.

Preferred formulations can hâve the following compositions (weight %):

10	Emulsifiable concentrâtes: active ingrédient: surface-active agent: liquid carrier: Dusts: active ingrédient: solid carrier:	1 to 95 %, preferably 60 to 90 % 1 to 30 %, preferably 5 to 20 % 1 to 80 %, preferably 1 to 35 % 0.1 to 10 %, preferably 0.1 to 5 % 99.9 to 90 %, preferably 99.9 to 99 %
15	Suspension concentrâtes: active ingrédient: water: surface-active agent:	5 to 75 %, preferably 10 to 50 % 94 to 24 %, preferably 88 to 30 % 1 to 40 %, preferably 2 to 30 %
20	Wettable powders: active ingrédient: surface-active agent: solid carrier:	0.5 to 90 %, preferably 1 to 80 % 0.5 to 20 %, preferably 1 to 15 % 5 to 95 %, preferably 15 to 90 %
25	Granules: active ingrédient: solid carrier:	0.1 to 30 %, preferably 0.1 to 15 % 99.5 to 70 %, preferably 97 to 85 %

The composition of the présent may further comprise at least one additionai pesticide. For 30 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 additionai 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. Spécifie examples of such mixtures include (wherein “I” represents a compound of formula (I)):- I + acetochlor, I + acifluorfen (including acifluorfen-sodium), I + aclonifen, I + ametryn, I + amicarbazone, I + aminopyralid, I + aminotriazole, I + atrazine, I + beflubutamid-M, I + bensulfuron (including bensulfuronmethyl), I + bentazone, I + bicyclopyrone, I + bilanafos, I + bispyribac-sodium, I + bixlozone,

1 + bromacil, I + bromoxynil, I + butachlor, I + butafenacil, I + carfentrazone (including carfentrazone-ethyl), I + cloransulam (including cloransulam-methyl), 1+ chlorimuron (including chlorimuron-ethyl), I + chlorotoluron, 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 sait and 2-ethylhexyl ester thereof), I + 2,4DB, I + desmedipham, I + dicamba (including the aluminium, aminopropyl, bisaminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts thereof) I + diclosulam, I + diflufenican, I + diflufenzopyr, I + dimethachlor, I + dimethenamid-P, I + diquat dibromide, diuron, I + ethalfluralin, I + ethofumesate, I + fenoxaprop (including fenoxaprop-P-ethyl), I + fenoxasulfone, I + fenquinotrione, I + fentrazamide, I + flazasulfuron, I + florasulam, I + florpyrauxifen (including florpyrauxifen-benzyl), I + fluazifop (including fluazifop-P-butyl), I + flucarbazone (including flucarbazone-sodium), I + flufenacet, I + flumetsulam, I + flumioxazin, I + fluometuron, I + flupyrsulfuron (including flupyrsulfuron-methyl-sodium), I + fluroxypyr (including fluroxypyr-meptyl), I + fomesafen, I + foramsulfuron, I + glufosinate (including the ammonium sait thereof), I + glyphosate (including the diammonium, isopropylammonium and potassium salts thereof), I + halauxifen (including halauxifenmethyl), I + haloxyfop (including haloxyfop-methyl), I + hexazinone, I + hydantocidin, I + imazamox, I + imazapic, I + imazapyr, I + imazethapyr, I + indaziflam, I + iodosulfuron (including iodosulfuron-methyl-sodium), I + iofensulfuron (including iofensulfuron-sodium), I + ioxynil, I + isoproturon, I + isoxaflutole, I + lancotrione, I + MCPA, I + MCPB, I + mecopropP, I + mesosulfuron (including mesosulfuron-methyl), I + mesotrione, I + metamitron, I + metazachlor, I + methiozolin, I + metolachlor, I + metosulam, I + metribuzin, I + metsulfuron, I + napropamide, I + nicosulfuron, I + norflurazon, I + oxadiazon, I + oxasulfuron, I + oxyfluorfen, I + paraquat dichloride, I + pendimethalin, I + penoxsulam, I + phenmedipham, I + picloram, I + pinoxaden, I + pretilachlor, I + primisulfuron-methyl, I + prometryne, I + propanil, I + propaquizafop, I + propyrisulfuron, I + propyzamide, I + prosulfocarb, I + prosulfuron, I + pyraclonil, I + pyraflufen (including pyraflufen-ethyl), I + pyrasulfotole, I + pyridate, I + pyriftalid, I + pyrimisulfan, 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-metalochlor, I + sulfentrazone, I + sulfosulfuron, I + tebuthiuron, I + tefuryltrione, I + tembotrione, I + terbuthylazine, I + terbutryn, I + tetflupyrolimet, 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 + ethyl 2-[[3[2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-l-yl]phenoxy]-2pyridyl]oxy]acetate, I + 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6dihydropyrimidin-l(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, I + 4-hydroxy-l-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, I + 4-hydroxy-l,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 1 + 5ethoxy-4-hydroxy-l-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, I + 4hydroxy-l-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, I + 4-hydroxy-l,5dimethyl-3-[l-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one, I + (4R)l-(5-tert15 butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one, I + 3-[2-(3,4dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione, I + 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane1,3-dione, I + 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4carbonyl]cyclohexane-1,3-dione, I + 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine20 4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione, I + 6-[2-(3,4-dimethoxyphenyl)-6-methyl-3oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-l,3,5-trione, I + 2-[2-(3,4dimethoxyphenyl)-6-methyI-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-tetramethylcyclohexane-1,3-dione, I + 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-425 carbonyl]-5-methyl-cyclohexane-1,3-dione, I + 3-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione, I + 2-[6-cyclopropyl-2-(3,4dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-l,3-dione, 1 + 6[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethylcyclohexane-1,3,5-trione, I + 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-430 carbonyl]cyclohexane- 1,3-dione, I + 4-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione, I + 4-[6-cyclopropyl-2-(3,4dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5dione, I + 4-amino-3-chloro-5-fluoro-6-(7-fluoro-lH-indol-6-yl)pyridine-2-carboxylic acid (including agrochemically acceptable esters thereof, for example, methyl 4-amino-3-chloro-535 fluoro-6-(7-fluoro-lH-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 ingrédient relates to the respective mixture of compound of formula (I) with the mixing partner).

Compounds of formula (I) of the présent invention may also be combined with herbicide safeners. Preferred combinations (wherein “I” 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; 1+ furilazole I + isoxadifen (including isoxadifen-ethyl); I + mefenpyr (including mefenpyrdiethyl); I + metcamifen 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 metcamifen.

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, magnésium, aluminium, iron, ammonium, quatemary ammonium, sulfonium or phosphonium sait 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 (I) 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 5 active ingrédient 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 présent invention therefore further comprises a method for controlling unwanted plants comprising applying to 10 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 dépend 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 govemed by the method of 20 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 25 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 râpe, sunflower, maize, rice, 30 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 hâve been rendered tolérant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPDinhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolérant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer râpe (canola). Examples of crops that hâve been rendered tolérant 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 hâve been rendered résistant to harmful insects by genetic engineering methods, for example Bt maize (résistant to European corn borer), Bt cotton (résistant to cotton boll weevil) and also Bt potatoes (résistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids ofNK® (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, EPA-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 résistance 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 résistant to herbicides and, at the same time, résistant to insect feeding (stacked transgenic events). For example, seed can hâve the ability to express an insecticidal Cry3 protein while at the same time being tolérant 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 omamental 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. Exampies 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 pererme, 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.

The compounds of formula (I) are also useful for pre-harvest desiccation in crops, for example, but not limited to, potatoes, soybean, sunflowers and cotton. Pre-harvest desiccation is used to desiccate crop foliage without significant damage to the crop itself to aid harvesting.

Compounds/compositions of the invention are particularly useful in non-selective bum-down applications, and as such may also be used to control volunteer or escape crop plants.

Various aspects and embodiments of the présent 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 ingrédients	25 %	50%	75 %
sodium lignosulfonate	5 %	5 %	-
sodium lauryl sulfate	3 %	-	5%
sod ium diisobuty Inaphthalenesulfonate	-	6%	10%
phénol 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.

	74
	Emulsifîable concentrate
	active ingrédients	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 ingrédients	5 %	6%	4%
Talcum	95 %	-	-
Kaolin	-	94%	-
minerai Aller	-	-	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 ingrédients	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 ingrédients 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 ingrédients 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 % émulsion 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 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts oftoluene 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 émulsion 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% ofthe active ingrédients. 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 = fërt-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
5 DMSO	= dimethylsulfoxide
EtOAc	= ethyl acetate
h	= hour(s)
HCl	= 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
15 mL	= millilitre
mp	= melting point
ppm	= parts per million
q quin	= quartet = quintet
20 rt	= room température
s	= singlet
t	= triplet
THF	= tetrahydrofuran
LC/MS	= Liquid Chromatography Mass Spectrometry

Préparative Reverse Phase HPLC Method:

Compounds purified by mass directed préparative 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): 30 210 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 négative: Cône (V) 20.00, Source Température (°C) 120, Cône Gas Flow (L/Hr.) 50

Mass range (Da): positive 100 to 800, négative 115 to 800.

The préparative HPLC was conducted using an 11.4 minute run time (not using at column dilution, bypassed with the column selector), according to the foilowing gradient table:

Time (mins)	Solvent A (%)	Solvent B (%)	Flow (ml / min)
0.00	100	0	35
2.00	100	0	35
2.01	100	0	35
7.0	90	10	35
7.3	0	100	35
9.2	0	100	35
9.8	99	1	35
11.35	99	1	35
11.40	99	1	35

515 pump Oml/min Acetonitrile (ACD)

515 pump Iml/min 90% Methanol/10% Water (make up pump)

Solvent A: Water with 0.05% Trifluoroacetic Acid

Solvent B: Acetonitrile with 0.05% Trifluoroacetic Acid

Préparation Examples

Example 1: Préparation of 2-r4-l3-(trifluoromethvl)-L2,4-thiadiazol-5-vl1pvridin-l-ium-l-

Step 1: Préparation of 4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-l,2,3,6tetrahydropyridin-1 -ium chloride

A mixture of tert-butyl 4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-3,6-dihydro-2Hpyridine-1-carboxylate (2 g) and aqueous hydrochloric acid (4M in 1,4-dioxane, 19 mL) was stirred at room température overnight. The reaction mixture was concentrated and the residue was triturated with ether to give 4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-l,2,3,6tetrahydropyridin-l-ium chloride as a white solid.

1H NMR (400 MHz, D₂O) 6.28-6.21 (m, 1H), 3.69-3.62 (m, 2H), 3.21 (t, 2H), 2.41-2.24 (m, 2H), 1.12 (s, 12H) (NH proton missing)

Step 2: Préparation of tert-butyl 2-[4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-3,6dihydro-2H-pyridin-1 -y 1] acetate

A mixture of 4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-l,2,3,6-tetrahydropyridin-l-ium chloride (1.89 g), acetonitrile (31.6 mL), potassium carbonate (2.62 g) and tert-butyl 215 chloroacetate (1.35 mL) was heated at 90°C for 20 hours. The reaction mixture was cooled and partitioned between water and dichloromethane, then further extracted with dichloromethane (x2). The combined organic phase was dried over magnésium sulfate and concentrated to give tert-butyl 2-[4-(4,4,5,5-tetramethyl-l, 3,2-dioxaborolan-2-yl)-3,6-dihydro-2H-pyridin-lyl]acetate as a yellow gum.

1H NMR (400MHz, CDCh) 6.52-6.43 (m, 1H), 3.24-3.15 (m, 4H), 2.68 (t, 2H), 2.34-2.26 (m, 2H), 1.46 (s, 9H), 1.25 (s, 12H)

Step 3: Préparation of tert-butyl 2-[4-[3-(trifluoromethyl)-l,2,4-thiadiazol-5-yl]-3,6-dihydro2H-pyridin-1 -y l]acetate

A mixture of tert-butyl 2-[4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-3,6-dihydro-2Hpyridin-l-yl]acetate (0.838 g), [l,l'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.155 g), 5-chloro-3-(trifluoromethyl)-l,2,4-thiadiazole (0.4 g), sodium carbonate (0.899 g), 5 1,4-dioxane (7.43 mL) and water (7.43 mL) was degassed with nitrogen then heated at 120°C under microwave irradiation for 1 hour. The reaction mixture was cooled to room température then filtered through diatomaceous earth and partitioned between water and ethyl acetate. The organic phase was concentrated then purified by silica gel chromatography eluting with 0 to 50% ethyl acetate in cyclohexane to give tert-butyl 2-[4-[3-(trifluoromethyl)-l,2,4-thiadiazol10 5-yl]-3,6-dihydro-2H-pyridin-1 -yl]acetate.

1HNMR (400MHz, CDCI3) 6.83-6.99 (m, 1H), 3.44-3.50 (m, 2H), 3.30-3.33 (m, 2H), 2.902.96 (m, 2H), 2.69-2.75 (m, 2H), 1.48-1.51 (m, 9H)

Step 4: Préparation of2-[4-[3-(trifluoromethyl)-l,2,4-thiadiazol-5-yl]pyridin-l-ium-l-yl]acetic 15 acid 2,2,2-trifluoroacetate Al

To a solution of tert-butyl 2-[4-[3-(trifluoromethyl)-l,2,4-thiadiazol-5-yl]-3,6-dihydro-2Hpyridin-l-yl]acetate (0.43 g) in 1,4-dioxane (6.6 mL) was added TV-bromosuccinimide (0.294 g) in one portion followed by stirring at room température for 2 hours. To the reaction mixture 20 was then added aqueous hydrochloric acid (2.4 mL, 4M in 1,4-dioxane) with additional stirring for 5 hours at room température. The reaction mixture was diluted with tert-butyl methyl ether (20 mL) and the resulting solid was filtered, washed with additional tert-butyl methyl ether then purified by préparative reverse phase HPLC (trifluoroacetic acid was présent in the eluent) to afford 2-[4-[3-(trifluoromethyl)-l,2,4-thiadiazol-5-yl]pyridin-l-ium-l-yl]acetic acid 2,2,225 trifluoroacetate.

1H NMR (400 MHz, D₂O) 9.06 (d, 2H), 8.69 (d, 2H), 5.41 (s, 2H) (CO₂H proton missing)

Example 2: Préparation of r4-f3-methvl-L2,4-thiadiazol-5-vl)pyridin-l-ium-lvllmethanesulfonate A2

Ο

Step 1: Préparation of (/VE)-A^r-[l-(dimetliylamino)ethylidene]pyridine-4-carbothioamide

S

A mixture of pyridine-4-carbothioamide (1 g) and 1 J-dimethoxy-7V,7V-dimethyl-ethanamine (1.05 mL) were stirred together at room température for one hour. The reaction was concentrated to give (Æ)-A-[l-(dimethylamino)ethylidene]pyridine-4-carbothioamide as a red gum which crystallised on standing.

1H NMR (400 MHz, CD₃OD) 8.55-8.51 (m, 2H), 8.11-8.08 (m, 2H), 3.37 (s, 3H), 3.26-3.21 (m, 3H), 2.52 (s, 3H)

Step 2: Préparation of 3-methyl-5-(4-pyridyl)-l,2,4-thiadiazole

To a solution of (AÆ)-7V-[l-(dimethylamino)ethylidene]pyridine-4-carbothioamide (1.5 g) and pyridine (1.23 mL) in éthanol (36 mL) at room température was added a second solution of 15 hydroxylamine-O-sulfonic acid (0.9 g) in methanol (14 mL). The reaction mixture was stirred at room température for one hour then quenched with saturated aqueous sodium bicarbonate and extracted with dichloromethane. The organic phase was concentrated, triturated with hexane then dried to give 3-methyl-5-(4-pyridyl)-l,2,4-thiadiazole as a brown solid.

1H NMR (400 MHz, CD3OD) 8.78-8.71 (m, 2H), 8.00-7.96 (m, 2H), 2.72 (s, 3H)

Step 3: Préparation of methyl 2-[4-(3-methyl-l,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]acetate bromide

A mixture of 3-methyl-5-(4-pyridyl)-l,2,4-thiadiazole (1.165 g), acetonitrile (20 mL) and methyl 2-bromoacetate (0.93 mL) was heated at 80°C for 25 hours. The reaction mixture was partitioned between water and dichloromethane and the aqueous phase was concentrated to give methyl 2-[4-(3-methyl-l,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]acetate bromide which was used without further purification.

Step 4: Préparation of 2-[4-(3-methyl-l,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]acetic acid chloride A59

A solution of crude methyl 2-[4-(3-methyl-l,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]acetate bromide (1.7 g) and 2M aqueous hydrochioric acid (45 mL) was heated at 50°C for 4 hours. The reaction mixture was then concentrated to give 2-[4-(3-methyl-l,2,4-thiadiazol-5yl)pyridin-l-ium-l-yl]acetic acid chloride.

1H NMR (400 MHz, D₂O) 8.93-8.89 (m, 2H), 8.51-8.46 (m, 2H), 5.37 (s, 2H), 2.67 (s, 3H) (CO₂H proton missing)

Step 5: Préparation of[4-(3-methy 1-1,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]methanesulfonate A2

A mixture of 2-[4-(3-methyl-l,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]acetic acid chloride (0.83 g) and trimethylsilyl chlorosulfonate (11 mL) was heated at 120°C ovemight. The reaction mixture was cooled to room température and partitioned between water and dichloromethane. The aqueous phase was then concentrated and purified by préparative reverse phase HPLC to afford [4-(3-methyl-l,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]methanesulfonate as a white solid.

1H NMR (400 MHz, D₂O) 9.02-9.20 (m, 2H) 8.55-8.68 (m, 2H) 5.58-5.81 (m, 2H) 2.65-2.82 (m, 3H)

Example 3: Préparation of r4-(thiadiazol-5-vl)pyridin-l-ium-l-yl1methanesulfonate A3

Step 1: Préparation of methyl 2-diazo-3-oxo-3-(4-pyridyl)propanoate

To a mixture of methyl 3-oxo-3-(4-pyridyl)propanoate (4 g) and 4-acetamidobenzenesulfonyl azide (6.082 g) in dichloromethane (130 mL) was added triethylamine (9.43 mL) drop wise at 0°C. The reaction mixture was slowly warmed to room température then stirred overnight. After filtration through silica, followed by and washing with dichloromethane, the filtrate was then concentrated to afford methyl 2-diazo-3-oxo-3-(4-pyridyl)propanoate as a yellow gum. 1H NMR (400MHz, CDCh) 8.78-8.71 (m, 2H), 7.45-7.40 (m, 2H) 3.79 (s, 3H)

Step 2: Préparation of methyl 5-(4-pyridyl)thiadiazole-4-carboxylate

A mixture of methyl 2-diazo-3-oxo-3-(4-pyridyl)propanoate (4.58 g) and Lawesson’s reagent (11.2 g) in toluene (112 mL) was heated at 120°C overnight. The reaction mixture was concentrated then purified by silica gel chromatography eluting with 0 to 50% methanol in dichloromethane to give methyl 5-(4-pyridyl)thiadiazole-4-carboxylate which was used in the next step without further purification.

Step 3: Préparation of 5-(4-pyridyl)thiadiazole-4-carboxylic acid

A mixture of crude methyl 5-(4-pyridyl)thiadiazole-4-carboxylate (4 g) and 2M aqueous hydrochloric acid (150 mL) was heated at reflux for 3 hours. The reaction mixture was concentrated and partitioned between water and ethyl acetate. The aqueous layer was 5 concentrated to give 5-(4-pyridyl)thiadiazole-4-carboxylic acid which was used in the next step without further purification.

Step 4: Préparation of 5-pyridin-l-ium-4-ylthiadiazoIe 2,2,2-trifluoroacetate

A mixture of 5-(4-pyridyl)thiadiazole-4-carboxylic acid (3.35 g), water (5 mL) and 1,4-dioxane (80 mL) was heated at 100°C overnight. The reaction mixture was concentrated and purified by préparative reverse phase HPLC (trifluoroacetic acid was présent in the eluent) to afford 5pyridin-l-ium-4-ylthiadiazole 2,2,2-trifluoroacetate as a white solid.

1H NMR (400 MHz, CD₃OD) 9.45 (s, 1H), 8.90-8.83 (m, 2H), 8.21-8.16 (m, 2H)

Step 5: Préparation of methyl 2-[4-(thiadiazol-5-yl)pyridin-l-ium-l-yl]acetate bromide A8

A mixture of 5-pyridin-l-ium-4-ylthiadiazole 2,2,2-trifluoroacetate (0.5 g), acetonitrile (10 mL) and methyl 2-bromoacetate (0.44 mL) was heated at 80°C for 25 hours. The reaction mixture 20 was concentrated and partitioned between water and dichloromethane. The aqueous layer was concentrated to give methyl 2-[4-(thiadiazol-5-yl)pyridin-l-ium-l-yl]acetate bromide as a brown gum.

1H NMR (400 MHz, D2O) 9.39-9.45 (m, 1H) 8.85-8.93 (m, 2H) 8.35-8.44 (m, 2H) 5.55 (s, 2H)

3.73-3.84 (m, 3H)

Step 6: Préparation of 2-[4-(thiadiazol-5-yl)pyridin-l-ium-l-yl]acetic acid chloride A9

A mixture of methyl 2-[4-(thiadiazol-5-yI)pyridin-l-ium-l-yl]acetate bromide (0.46 g) and 2M aqueous hydrochloric acid (20 mL) was heated at 50°C for 5 hours. The reaction mixture was concentrated to give 2-[4-(thiadiazol-5-yl)pyridin-l-ium-l-yl]acetic acid chloride.

1H NMR (400 MHz, D₂O) 9.38-9.43 (m, 1H) 8.83-8.90 (m, 2H) 8.33-8.40 (m, 2H) 5.40 (s, 2H) (CO₂H proton missing)

Step 7: Préparation of [4-(thiadiazol-5-yl)pyridin-l-ium-l-yl]methanesulfonate A3

A mixture of 2-[4-(thiadiazol-5-yl)pyridin-l-ium-l-yl]acetic acid chloride (0.46 g) and trimethylsilyl chlorosulfonate (5.4 mL) was heated at 120°C ovemight. The reaction mixture was cooled to room température and partitioned between water and dichloromethane. The aqueous phase was concentrated then purified by préparative reverse phase HPLC to afford [4(thiadiazol-5-yl)pyridin-l-ium-l-yl]methanesulfonate as a white solid.

1H NMR (400 MHz, D₂O) 9.41-9.49 (m, 1H) 8.95-9.04 (m, 2H) 8.37-8.49 (m, 2H) 5.68 (br s, 2H)

Example 4: Préparation of 2-r4-(l,2,4-thiadiazol-5-vDpvridin-l-ium-l-vHethanesulfonate A5

A mixture of 5-(4-pyridyl)-l,2,4-thiadiazole (300 mg), sodium 2-bromoethanesulfonic acid (465 mg) and water (6 mL) was heated at 100°C overnight. The reaction mixture was concentrated and purified by préparative reverse phase HPLC to afford 2-[4-(l,2,4-thiadiazol5-yl)pyridin-1 -ium-1 -yl]ethanesulfonate

1H NMR (400 MHz, D₂O) 9.02-9.11 (m, 2H) 8.87-8.99 (m, 1H) 8.47-8.60 (m, 2H) 4.94-5.05 (m, 2H) 3.48-3.61 (m, 2H)

Example 5: Préparation of 3-(4-(L2.4-thiadiazol-5-vl)pyridin-l-ium-1-yllpropanoic acid çhloride A7

O

Step 1: Préparation of methyl 3-[4-(l,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]propanoate 2,2,2trifluoroacetate

A mixture of 5-(4-pyridyl)-l,2,4-thiadiazole (0.3 g), acetonitrile (6 mL) and methyl 3bromopropionate (0.31 mL) was heated at 80°C for 25 hours. The reaction mixture was cooled and partitioned between water and dichloromethane. The aqueous layer was concentrated then purified by préparative reverse phase HPLC to afford methyl 3-(4-(1,2,4-thiadiazol-5yl)pyridin-l-ium-l-yl]propanoate 2,2,2-trifluoroacetate as a white solid

1H NMR (400 MHz, D₂O) 9.07 (d, 2H), 8.94 (s, 1H), 8.54 (d, 2H), 4.90 (t, 2H), 3.60 (s, 3H), 3.18 (t, 2H)

Step 2: Préparation of 3-(4-(1,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]propanoic acid çhloride

A7

A mixture of methyl 3-[4-(l,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]propanoate (50 mg) and 2M aqueous hydrochloric acid (1 mL) was heated at 50°C for 5 hours. The reaction mixture was concentrated to give 3-(4-(1,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]propanoic acid çhloride as a white solid.

1H NMR (400 MHz, D₂O) 9.05 (d, 2H), 8.92 (s, 1H), 8.51 (d, 2H), 4.87 (t, 2H), 3.15 (t, 2H) (CO₂H proton missing)

Example 6: Préparation of [4-(l,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]methanesulfonate A4

Step 1: Préparation oftert-butyl 4-(l,2,4-thiadiazol-5-yl)-3,6-dihydro-2H-pyridine-lcarboxylate

To a mixture of 5-bromo-l,2,4-thiadiazole (5 g), 1,4-dioxane (50 mL) and water (17 mL) was added tert-butyl 4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-3,6-dihydro-2H-pyridine-lcarboxylate (10 g), césium carbonate (15 g) and l,l'-bis(diphenylphosphino)ferrocenepalladium(II)dichloride dichloromethane complex (2.5 g). The mixture was purged with nitrogen then heated at 95°C for 19 hours. The mixture was filtered through celite and the filtrate was concentrated and purified by silica gel chromatography eluting with 0 to 30% ethyl acetate in cyclohexane to give tert-butyl 4-(l,2,4-thiadiazol-5-yl)-3,6-dihydro-2Hpyridine-1-carboxylate as a yellow liquid.

Ή NMR (400MHz, CDC1₃) 8.61 (s, 1H), 6.81 (br s, 1H), 4.18 (br d, 2H), 3.68 (br t, 2H), 2.68 15 (brdd, 2H), 1.49 (s, 9H)

Step 2: Préparation of 5-(l,2,3,6-tetrahydropyridin-4-yl)-l,2,4-thiadiazole hydrochloride

A mixture of tert-butyl 4-(l,2,4-thiadiazol-5-yl)-3,6-dihydro-2H-pyridine-l-carboxylate (5 g) 20 and hydrochloric acid (4M in dioxane, 26 mL) was stirred at room température for 1.5 hours.

The mixture was concentrated, azeotroped with toluene and the resulting residue was washed with ethyl acetate (2x40 mL) and dried to give 5-(l,2,3,6-tetrahydropyridin-4-yl)-l,2,420324

thiadiazole hydrochloride as a pale pink solid.

’H NMR (400 MHz, D₂O) 8.63 (s, 1H), 6.80 (tt, 1H), 3.90 (q, 2H), 3.46 (t, 2H), 2.85 (qt, 2H)

Step 3: Préparation of sodium [4-(l,2,4-thiadiazol-5-yl)-3,6-dihydro-2H-pyridin-l5 yl]methanesulfonate

To a solution of 5-(l,2,3,6-tetrahydropyridin-4-yl)-l,2,4-thiadiazole hydrochloride (2.5 g) in water (12 mL) was added sodium hydroxide (0.54 g). Sodium hydroxymethanesulfonate (formaldéhyde sodium bisulfite adduct, 1.6 g) was added and the mixture was stirred at room température for 1 hour, periodically checking the pH of the solution was maintained between pH 10 and 11 by the addition of further aqueous 2M sodium hydroxide. The mixture was freeze dried to give sodium [4-(l,2,4-thiadiazol-5-yl)-3,6-dihydro-2H-pyridin-lyl]methanesulfonate as an off-white solid, which was used without further purification.

*H NMR (400 MHz, D₂O) 8.61 (s, 1H), 6.86 (td, 1H), 3.90 (s, 2H), 3.66 (q, 2H), 3.15 (t, 2H), 15 2.67 - 2.62 (m, 2H)

Step 4: Préparation of [4-(1,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]methanesulfonate A4

To a mixture of sodium [4-(l,2,4-thiadiazol-5-yl)-3,6-dihydro-2H-pyridin-l20 yl]methanesulfonate (2.452 g) in dry acetonitrile (15.8 mL), under nitrogen atmosphère, was added 2,3-dichloro-5,6-dicyano-l,4-benzoquinone (3.67 g) portion wise over 3 minutes. The mixture was stirred at 25°C for 18 hours. To the mixture was added trimethylsilyl bromide (0.718 mL). After 15 minutes stirring tetrahydrofuran (47.4 mL) was added and the mixture stirred for a further 20 minutes. The solid was filtered off, washed with tetrahydrofuran and dried. The solid was purified by préparative reverse phase HPLC to give [4-(l,2,4-thiadiazol5-yl)pyridin-l-ium-l-yl]methanesulfonate as an off-white solid.

Ή NMR (400 MHz, D₂O) 9.25-9.02 (m, 3H), 8.81-8.66 (m, 2H), 5.85-5.74 (m, 2H)

Example 7: Préparation of 2-r4-(thiadiazol-4-vl)pyridin-l-ium-l-vllethyl sulfate A65

A mixture of 4-(4-pyridyl)thiadiazole (0.1 g), 1,3,2-dioxathiolane 2,2-dioxide (0.087 g) and 1,2-dichloroethane (6 mL) was heated at 85°C for 18 hours. The resulting precipitate was filtered off and air dried to give 2-[4-(thiadiazol-4-yl)pyridin-l-ium-l-yl]ethyl sulfate as a 5 white solid.

Ή NMR (400 MHz, DMSO-t/₆) 10.23 - 10.36 (m, 1H), 9.09 - 9.24 (m, 2H), 8.73 - 8.96 (m,

2H), 4.73 - 4.94 (m, 2H), 4.18 - 4.34 (m, 2H)

Example 8: Préparation of N-methvl-5-(4-pyridyf)isoxazole-3-carboxamide

To a solution of 5-(4-pyridyl)isoxazole-3-carboxylic acid (0.5 g) in dichloromethane (14 mL) was added l-chloro-N,N,2-trimethyl-prop-l-en-1-amine (0.35 mL) drop wise. After stirring for 30 minutes a solution of methanamine (2M in tetrahydrofuran, 2.63 mL) and N,N'diisopropylethylamine (0.504 mL) in dichloromethane was added drop wise. The resulting mixture was stirred overnight at room température. The mixture was partitioned between dichloromethane and water. The organic layer was concentrated to give N-methyl-5-(4pyridyl)isoxazole-3-carboxamide as a yellow solid.

‘H NMR (400 MHz, DMSO-d₆) 8.90 - 8.81 (m, 1H), 8.81 - 8.75 (m, 2H), 7.95 - 7.87 (m, 2H), 7.67 (s, 1 H), 2.81 (d, 3H)

Example 9: Préparation of S-ld-pyridvft-l^A-oxadiazole

Step 1: Préparation of N-(dimethylaminomethylene)pyridine-4-carboxamide

A mixture of pyridine-4-carboxamide (5 g) and l,l-dimethoxy-N,N-dimethyl-methanamine (5.46 mL) were stirred together at room température for 4 hours. The mixture was concentrated and purified by silica gel chromatography eluting with 0 to 50% methanol in acetonitrile to give N-(dimethylaminomethylene)pyridine-4-carboxamide as a white solid. Ή NMR (400MHz, CDC1₃) 8.77 - 8.70 (m, 2H), 8.69 - 8.65 (m, 1H), 8.08 - 8.02 (m, 2H), 3.24 (d, 6H)

Step 2: Préparation of 5-(4-pyridyl)-l,2,4-oxadiazole

To N-(dimethylaminomethylene)pyridine-4-carboxamide (3.99 g) was added a solution of dioxane (27 mL), hydroxylamine (50% aqueous solution, 2.07 mL) and acetic acid (32 mL). The mixture was heated at 90°C for 1 hour. The reaction mixture was concentrated and partitioned between saturated aqueous sodium bicarbonate solution and dichloromethane.

The organic layer was concentrated and purified by préparative reverse phase HPLC to give 5-(4-pyridyl)-l,2,4-oxadiazole as a white solid.

Ή NMR (400 MHz, CD3OD) 8.95 - 8.88 (m, 3H), 8.30 - 8.25 (m, 2H)

Example 10: Préparation of 4-(2-methyltetrazol-5-yl)pyridine

To a mixture of 4-(lH-tetrazol-5-yl)pyridine (0.4 g) and N,N-dimethylformamide (3.5 mL) was added dimethyl carbonate (2.2 mL) and l,4-diazabicyclo[2.2.2]octane (0.032 g) and the mixture was heated at 130°C ovemight. The reaction mixture was cooled to room température and 0.25M aqueous sodium hydroxide (11 mL) was added and the mixture extracted with ethyl acetate (x3). The combined organic layers were washed with water and concentrated to give 4-(2-methyltetrazol-5-yl)pyridine.

Ή NMR (400MHz, CDCI3) 8.80 - 8.75 (m, 2H), 8.04 - 7.99 (m, 2H), 4.45 (s, 3H)

The material is isolated as a mixture with 4-(l-methyItetrazol-5-yl)pyridine.

*H NMR (400MHz, CDC1₃) 8.91 - 8.85 (m, 2H), 7.72 - 7.68 (m, 2H), 4.26 (s, 3H) Séparation of the isomers occurred after alkylation of the pyridine.

Example 11: Préparation of methoxy-rr4-(L2.4-thiadiazol-5-yl)pyridin-l-ium-lyl1methyl1phosphinate A30

Step 1 : Préparation of dimethoxyphosphorylmethanol

O I Il .O HO AJ /

To a solution of methoxyphosphonoyloxymethane (8 g) in methanol (40 mL) was added paraformaldéhyde (2.18 g) and potassium carbonate (0.502 g) at room température. The reaction mixture was stirred at room température for 1 hour. The reaction mixture was filtered through celite and washed with dichloromethane (50 mL). The filtrate was concentrated then purified by silica gel chromatography eluting with a mixture of ethyl acetate in n-hexanes to give dimethoxyphosphorylmethanol as colourless liquid.

*H NMR (400 MHz, CDCI3) 3.96 - 3.94 (d, 2H), 3.83 - 3.80 (d, 6H) (OH proton missing)

Step 2: Préparation of dimethoxyphosphorylmethyl trifluoromethanesulfonate

To a solution of dimethoxyphosphorylmethanol (5 g) in dichloromethane (50 mL) at -78°C, under nitrogen atmosphère, was added 2,6-lutidine (6.94 mL) and triflic anhydride (6.0 mL). The resulting reaction mixture was allowed to warm to room température and stirred at room température for 1 hour. The reaction mixture was poured into water and extracted with dichloromethane (2x50 mL). The combined organic layers were washed with IM aqueous hydrochloric acid (50 mL), dried over sodium sulfate and concentrated to afford dimethoxyphosphorylmethyl trifluoromethanesulfonate as pale yellow liquid.

Ή NMR (400 MHz, CDC1₃) 4.67 - 4.64 (d, 2H), 3.90 - 3.87 (d, 6H)

Step 3: Préparation of 5-[l-(dimethoxyphosphorylmethyl)pyridin-l-ium-4-yl]-l,2,4thiadiazole trifluoromethanesulfonate A77

To a solution of 5-(4-pyridyl)-l,2,4-thiadiazole (1.5 g) in tetrahydrofuran (20 mL) was added dimethoxyphosphorylmethyl trifluoromethanesulfonate (3.56 g) at room température. The resulting mixture was heated at 60°C for 16 hours. The réaction mixture was concentrated and the residue was dissolved in water (25 mL) and washed with dichloromethane (2x25 mL). The water layer was concentrated and purified by reverse phase HPLC (100% water) to afford 5-[ 1 -(dimethoxyphosphorylmethyl)pyridin-1 -ium-4-yl]-1,2,4-thiadiazole trifluoromethanesulfonate as a light brown solid.

’H NMR (400 MHz, DMSO-d₆) 9.33 (s, 1H), 9.22 - 9.17 (m, 2H), 8.88 - 8.83 (m, 2H), 5.54 (d, 2H), 3.83 - 3.76 (m, 6H)

Step 4: Préparation of methoxy-[[4-(l,2,4-thiadiazol-5-yl)pyridin-l-ium-lyl]methyl]phosphinate A30

To a mixture of 5-[l-(dimethoxyphosphorylmethyl)pyridin-l-ium-4-yl]-l,2,4-thiadiazole trifluoromethanesulfonate (0.3 g) in dichloromethane (10 mL) was added bromotrimethylsilane (0.1 mL) at room température. The reaction mixture was stirred at room température for 2 hours. The reaction mixture was concentrated and the residue was dissolved in water (25 mL) and washed with dichloromethane (2><25 mL). The water layer was concentrated and purified by reverse phase HPLC (100% water) to give methoxy-[[4(l,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]methyl]phosphinate as an off-white solid.

Ή NMR (400 MHz, D₂O) 8.96 - 8.88 (m, 3H), 8.54 (d, 2H), 4.90 - 4.83 (m, 2H), 3.54 (d, 3H)

Example 12: Préparation of hydroxv-rr4-(L2,4-thiadiazol-5-vl)pyridin-l-ium-lyl1methyl]phosphinate Λ32

To a solution of 5-[l-(dimethoxyphosphorylmethyl)pyridin-l-ium-4-yl]-l,2,4-thiadiazole trifluoromethanesulfonate (0.3 g) in dichloromethane (10 mL) was added bromotrimethylsilane (0.5 mL) at room température. The reaction mixture was stirred at room température for 4 hours. The reaction mixture was concentrated and the residue was dissolved in water (25 mL) and washed with dichloromethane (2x25 mL). The water layer was concentrated and purified by reverse phase HPLC (100% water) to give hydroxy-[[4(l,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]methyl]phosphinate as a colourless gum.

’H NMR (400 MHz, D₂O) 9.01 - 8.86 (m, 3H), 8.54 (d, 2H), 4.84 - 4.78 (m, 2H) (POH proton missing)

Example 13: Préparation of methvl-114-f l,2,4-thiadiazol-5-yl)pyridin-l-ium-lvllmethyflphosphinate A10

Step 1 : Préparation of [ethoxy(methyl)phosphoryl]methanol

ho_x/p^/

To a solution of l-[ethoxy(methyl)phosphoryl]oxyethane (3 g) in acetonitrile (30 mL) was added triethylamine (0.668 g), paraformaldéhyde (0.727 g) and water (0.436 mL) at room température. The reaction mixture was stirred at room température for 16 hours. The reaction mixture was concentrated and purified by silica gel chromatography eluting with a mixture of méthanol in dichloromethane to give [ethoxy(methyl)phosphoryl]methanol as a colourless liquid.

Ή NMR (400 MHz, CDCh) 5.31 - 5.17 (m, 1H), 4.12 - 4.08 (m, 2H), 3.87 - 3.82 (m, 2H),

1.55-1.51 (d, 3H), 1.35-1.31 (t, 3H)

Step 2: Préparation of [ethoxy(methyl)phosphoryl]methyl trifluoromethanesulfonate

To a solution of [ethoxy(methyl)phosphoryl]methanol (2 g) in dichloromethane (30 mL) at 78°C, under nitrogen atmosphère, was added 2,6-lutidine (2.68 g) and triflic anhydride (2.8 mL). The resulting reaction mixture was allowed to warm to room température and stirred at room température for 3 hours. The reaction mixture was poured into water (50 mL) and extracted with dichloromethane (3x50 mL). The combined organic layers were washed with IM aqueous hydrochioric acid (50 mL), dried over sodium sulfate and concentrated to afford [ethoxy(methyl)phosphoryl]methyl trifluoromethanesulfonate as light orange oil.

Ή NMR (400 MHz, CDCh) 4.71 -4.55 (m, 2H), 4.24-4.10 (m, 2H), 1.68 - 1.64 (d, 3H), 1.40- 1.37 (t, 3H)

Step 3: Préparation of 5-[l-[[ethoxy(methyI)phosphoryl]methyl]pyridin-l-ium-4-yl]-l,2,4thiadiazole trifluoromethanesulfonate A47

To a solution of 5-(4-pyridyl)-l,2,4-thiadiazole (1 g) in tetrahydrofuran (20 mL) was added [ethoxy(methyl)phosphoryl]methyl trifluoromethanesulfonate (1.67 g) at room température.

The resulting mixture was heated at 65°C for 16 hours. The reaction mixture was concentrated and the residue was dissolved in water (25 mL) and washed with dichloromethane (2*50 mL). The water layer was concentrated and purified by reverse phase HPLC (100% water) to afford 5-[l-[[ethoxy(methyl)phosphoryl]methyl]pyridin-l-ium-4-yl]5 1,2,4-thiadiazole trifluoromethanesulfonate as a brown solid.

‘H NMR (400 MHz, DMSO-dô) 9.33 (s, 1H), 9.16 (d, 2H), 8.85 (d, 2H), 5.37 (d, 2H), 4.14 - .03 (m, 2H), 1.69 (d, 3H), 1.27 - 1.19 (m, 3H)

Step 4: Préparation of methyl-[[4-(l,2,4-thiadiazol-5-yl)pyridin-l-ium-l10 yl]methyl]phosphinate A10

To a stirred solution of 5-[l-[[ethoxy(methyl)phosphoryl]methyl]pyridin-l-ium-4-yl]-l,2,4thiadiazole trifluoromethanesulfonate (0.3 g) in dichloromethane (15 mL) was added bromotrimethylsilane (0.361 g) at room température. The reaction mixture was stirred at 15 room température for 16 hours. The reaction mixture was concentrated and purified by reverse phase HPLC (100% water) to give methyl-[[4-(l,2,4-thiadiazol-5-yl)pyridin-l-ium-lyl]methyl]phosphinate as a light green gum.

^lH NMR (400 MHz, CD₃OD) 9.08 (s, 3H), 8.77 (br d, 2H), 5.12 (br s, 2H), 1.71 - 1.46 (m, 3H)

Example 14: Préparation of 3-r4-r5-(trifluoromethvl)-l,2,4-oxadiazol-3-vl1pyridin-l-ium-lvl1propane-l-sulfonate Al5

A mixture of 1,3-propanesultone (0.082 g) and 3-(4-pyridyl)-5-(trifluoromethyl)-1,2,425 oxadiazole (0.095 g) in 1,4-dioxane (2.2 mL) was heated at 100°C for 20 hours. The resulting precipitate was filtered off and washed with acetone to give 3-[4-[5-(trifluoromethyl)-l,2,4oxadiazol-3-yl]pyridin-l-ium-l-yl]propane-l-sulfonate as a colourless solid.

‘H NMR (400 MHz, D₂O) 9.09 (d, 2H), 8.65 (br d, 2H), 4.78 - 4.84 (m, 2H), 2.95 (t, 2H),

2.44 (br t, 2H)

Example 15: Préparation of 3-r4-r3-(trifluoromethvr)-L2,4-thiadiazol-5-yf|pvridin-l-ium-lyllpropanoic acid acetate A48

Step 1: Préparation of ethyl 3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,6-dihydro2H-pyridin-1 -y l]propanoate

To a solution of 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine hydrochloride (3 g) in acetonitrile (60 mL) was added potassium carbonate (5.065 g) followed 10 by ethyl 3-bromopropanoate (1.644 mL). After heating at reflux for 16 hours the mixture was concentrated. The resulting residue was stirred in tert-butyl methyl ether, then filtered. The filtrate was concentrated to give ethyl 3-[4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-3,6dihydro-2H-pyridin-l-yl]propanoate, which was used without further purification.

Step 2: Préparation of ethyl 3-[4-[3-(trifluoromethyl)-l,2,4-thiadiazol-5-yl]-3,6-dihydro-2Hpyridin-1 -yl]propanoate

A mixture of ethyl 3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,6-dihydro-2Hpyridin-l-yl]propanoate (0.81 g), [1,1'20324 bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.175 g), 5-chloro-3(tnfluoromethyl)-l,2,4-thiadiazole (0.45 g), sodium carbonate (1.012 g), 1,4-dioxane (8.35 mL) and water (8.35 mL) was degassed with nitrogen then heated at 120°C under microwave irradiation for 1 hour. The reaction mixture was cooled to room température then filtered through diatomaceous earth. The filtrate was concentrated then purified by silica gel chromatography eluting with a mixture of ethyl acetate in cyclohexane to give ethyl 3-[4-[3(trifluoromethyl)-l,2,4-thiadiazol-5-yl]-3,6-dihydro-2H-pyridin-l-yl]propanoate.

Step 3: Préparation of 3-[4-[3-(trifluoromethyl)-l,2,4-thiadiazol-5-yl]pyridin-l-ium-lyl]propanoic acid acetate A48

To a solution of ethyl 3-[4-[3-(trifluoromethyl)-l,2,4-thiadiazol-5-yl]-3,6-dihydro-2Hpyridin-l-yl]propanoate (0.2 g) in 1,4-dioxane (4.78 mL) was added l-bromopyrroIidine-2,5dione (0.19 g). The reaction mixture was stirred at room température for 1 hour. To this was added cyclohexane (20 mL) and the mixture was stirred for 10 minutes. The solvent was decanted from a residue, which was washed with ethyl acetate. The residue was purified by préparative reverse phase HPLC to give the ester. The ester was dissolved in 1:1 acetic acid and water and heated at 80°C for 18 hours. The reaction mixture was concentrated and the residue triturated with acetone to give 3-[4-[3-(trifluoromethyl)-l,2,4-thiadiazol-5-yl]pyridinl-ium-l-yl]propanoic acid acetate.

Ή NMR (400 MHz, D₂O) 9.20 (d, 2H), 8.67 (d, 2H), 4.98 (t, 2H), 3.19 (t, 2H), 2.02 (s, 3H) (CO₂H proton missing)

Also isolated from this reaction and hydrolysed in a similar way was 3-[3-bromo-4-[3(trifluoromethyI)-l,2,4-thiadiazol-5-yl]pyridin-l-ium-l-yl]propanoic acid acetate A79

'H NMR (400 MHz, D₂O) 9.68 (s, 1H), 9.21 (dd, 1H), 8.96 (d, 1H), 4.99 (t, 2H), 3.25 (t, 2H),

2.04 (s, 3H) (CO₂H proton missing)

Example 16: Préparation of 3-14-(3-hydroxy-L2,4-thiadiazol-5-yl)pyridin-l-ium-Iyllpropanoie acid bromide A97

Step 1: Préparation of 5-(4-pyridyl)-l,2,4-thiadiazol-3-ol

To a solution of 3-bromo-5-(4-pyridyl)-l,2,4-thiadiazole (0.25 g) in ΛζΑ-dimethylformamide (1.9 mL) was added césium carbonate (0.673 g) followed by (E)-benzaldehyde oxime (0.126 g). The reaction mixture was heated at 40°C overnight. It was then heated at 80°C for 30 hours. The reaction was concentrated and the residue was washed with tert-butyl methyl ether (x3) and dried to give crude 5-(4-pyridyl)-l,2,4-thiadiazol-3-ol, which was used without further purification.

Ή NMR (400 MHz, DMSO-J6) 8.63 - 8.67 (m, 2H), 7.64 - 7.67 (m, 2H) (OH proton missing)

Step 2: Préparation of [5-(4-pyridyl)-l,2,4-thiadiazol-3-yl] 2,2-dimethylpropanoate

A solution of 5-(4-pyridyl)-l,2,4-thiadiazoI-3-ol (0.05 g) in dichloromethane (2.5 mL) was cooled to ~0°C then triethylamine (0.024 mL) and 2,2-dimethylpropanoyl chloride (0.021 mL) were added. The reaction was stirred at ~0°C for 2 hours. The reaction mixture was partitioned between water and dichloromethane. The aqueous layer was extracted with further dichloromethane (x2). The combined organic phases were dried over sodium sulfate and concentrated to give [5-(4-pyridyl)-l,2,4-thiadiazol-3-yl] 2,2-dimethylpropanoate, which was used without further purification.

Step 3: Préparation of 3-[4-(3-hydroxy-l,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]propanoic acid bromide A97

A mixture of [5-(4-pyridyl)-l,2,4-thiadiazol-3-yl] 2,2-dimethylpropanoate (0.5 g), acetonitrile (10 mL) and 3-bromopropanoic acid (0.36 g) was heated at 60°C for 12 hours. The reaction was concentrated and the residue washed with tert-butyl methyl ether and dried to give 3-[410 (3-hydroxy-l,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]propanoic acid bromide.

Ή NMR (400 MHz, D₂O) 9.07 (d, 2H), 8.45 (d, 2H), 4.90 (t, 2H), 3.18 (t, 2H) (CO₂H and OH protons missing)

Example 17: Préparation of 3-r3-methylsulfonvl-4-(l,2,4-thiadiazol-5-vl)pvridin-l-ium-l15 yllpropanoic acid bromide A93

To a solution of 3-chloropyridine-4-carbonitrile (0.1 g) in ΛζΑ-dimethylformamide (1 mL) 20 was added sodium methanesulfinate (0.174 g) and the mixture was heated at 140°C for 4 hours. The reaction mixture was cooled to room température and partitioned between ethyl acetate (20 mL) and water (10 mL). The aqueous layer was extracted with further ethyl acetate (2x20 mL). The combined organic layers were dried over sodium sulfate, concentrated and purified by silica gel chromatography eluting with 0 to 50% ethyl acetate in 25 cyclohexane to give 3-methylsulfonylpyridine-4-carbonitrile as a yellow solid.

Ή NMR (400 MHz, CDC1₃) 9.30 (br s, 1H), 9.02 (br s, 1H), 7.75 (br s, 1H), 3.25 ppm (br s,

3H)

Step 2: Préparation of 3-methylsulfonylpyndine-4-carbothioamide

To a solution of 3-methylsulfonylpyridine-4-carbonitrile (1.7 g) in pyridine (1.7 mL) was added triethylamine (1.2 mL) and ammonium polysulfide (48%, 3.4 mL) and the mixture was heated at 60°C for 2 hours. The reaction mixture was cooled to room température and partitioned between ethyl acetate (120 mL) and water (30 mL). The aqueous layer was extracted with further ethyl acetate (2x100 mL). The combined organic layers were dried over sodium sulfate and concentrated. The residue was triturated with /er/-butyl methyl ether (30 mL) to give 3-methylsulfonylpyridine-4-carbothioamide as a light yellow solid.

Ή NMR (400 MHz, DMSO-r/6) 10.47 (br s, 1H), 10.09 (br s, 1H), 8.99 (s, 1H), 8.85 (d, 1H), 7.39 (d, 1H), 3.47 ppm (s, 3H)

Step 3: Préparation ofN-(dimethylaminomethylene)-3-methylsulfonyl-pyridine-4carbothioamide

A mixture of 3-methylsulfonylpyridine-4-carbothioamide (1.45 g) and l,l-dimethoxy-N,Ndimethyl-methanamine (7.25 mL) was stirred at room température for 3 hours. The reaction mixture was concentrated and the residue was triturated with /erkbutyl methyl ether (40 mL) and dried to give N-(dimethylaminomethylene)-3-methylsulfonyl-pyridine-4-carbothioamide, which was used without further purification.

Step 4: Préparation of 5-(3-methylsulfonyl-4-pyridyl)-l,2,4-thiadiazole

100

To a mixture of N-(dimethylaminomethylene)-3-methylsulfonyl-pyridine-4-carbothioamide (1.52 g), pyridine (0.906 mL) and methanol (15.2 mL), at room température, was added a solution of amino hydrogen sulfate (0.697 g) in methanol (7.6 mL). The reaction mixture was stirred at room température for 1 hour. The reaction mixture was quenched with sat. aqueous sodium bicarbonate solution and extracted with ethyl acetate (20 mL). The organic layer was dried over sodium sulfate, concentrated and purified by silica gel chromatography eluting with a mixture of ethyl acetate in cyclohexane to give 5-(3-methylsulfonyl-4-pyridyl)-1,2,4thiadiazole.

Ή NMR (400 MHz, CDC1₃) 9.45 (s, 1H), 9.04 (d, 1H), 8.84 (s, 1H), 7.62 (d, 1H), 3.46 (s, 3H)

Step 5: Préparation of 3-[3-methylsulfonyl-4-(l,2,4-thiadiazol-5-yl)pyridin-l-ium-lyl]propanoic acid bromide A93

A mixture of 5-(3-methylsulfonyl-4-pyridyl)-l,2,4-thiadiazole (0.2 g) and 3-bromopropanoic acid (0.14 g) in acetonitrile (2 mL) was heated at 80°C for 40 hours. The reaction mixture was concentrated and the residue was triturated with tert-butyl methyl ether (40 mL) and dried to give 3-[3-methylsulfonyl-4-(l,2,4-thiadiazol-5-yl)pyridin-l-ium-l-yl]propanoic acid bromide. ¹H NMR (400 MHz, D₂O) 9.85 (s, 1H), 9.50 (d, 1H), 9.07 (s, 1H), 8.60 (d, 1H), 5.13 (t, 2H), 3.67 (s, 3H), 3.30 (t, 2H) (CO2H proton missing)

Example 18: Préparation of 2-f4-(5-phenyl-L3.4-oxadiazol-2-yl)pyridin-l-ium-l-yl1ethanol

2.2,2-trifluoroacetate A69

101

A mixture of 2-phenyl-5-(4-pyridyl)-l,3,4-oxadiazole (0.1 g), 1,2-dichloroethane (6 mL) and

1,3,2-dioxathiolane 2,2-dioxide (0.064 g) was heated at 85°C ovemight. The resulting precipitate is filtered off and the filtrate was concentrated and purified by préparative reverse phase HPLC (trifluoroacetic acid was présent in the eluent) to afford 2-[4-(5-phenyl-l,3,4oxadiazol-2-yl)pyridin-l-ium-l-yl]ethanol 2,2,2-trifluoroacetate.

’H NMR (400 MHz, DMSO-d6) 9.16 - 9.33 (m, 2H), 8.75 - 8.88 (m, 2H), 8.17 - 8.32 (m, 2H), 7.55 - 7.80 (m, 3H), 4.68 - 4.83 (m, 2H), 3.82 - 4.00 (m, 2H) (OH proton missing)

Additional compounds in Table A (below) were prepared by analogues procedures, from appropriate starting materials. The skilled person would understand that the compounds of formula (I) may exist as an agronomically acceptable sait, a zwitterion or an agronomically acceptable sait of a zwitterion as described hereinbefore. Where mentioned the spécifie counterion is not considered to be limiting, and the compound of formula (I) may be formed with any suitable counter ion.

NMR spectra contained herein were recorded on either a 400MHz Bruker AVANCE III HD equipped with a Bruker SMART probe unless otherwise stated. Chemical shifts are expressed as ppm downfield from TMS, with an internai reference of either TMS or the residual solvent signais. The following multiplicities are used to describe the peaks: s = singlet, d = doublet, t = triplet, dd = double doublet, dt = double triplet, q = quartet, quin = quintet, m = multiplet. Additionally br. is used to describe a broad signal and app. is used to describe and apparent multiplicity.

102

Table A - Physical Data for Compounds of the Invention

Compound Number	Structure	Ή NMR
Al	F ° -Y Y- Îî IL JL ^OH	(400 MHz, D₂O) 9.06 (d, 2H), 8.69 (d, 2H), 5.41 (s, 2H) (CO₂H proton missing)
A2	z ω Y=z O Co o^x \ ^O!	(400 MHz, D₂O) 9.02-9.20 (m, 2H) 8.55-8.68 (m, 2H) 5.58-5.81 (m, 2H) 2.65-2.82 (m, 3H)
A3	z_xω^ζ J^z J o^x \ o I	(400 MHz, D₂O) 9.41-9.49 (m, 1H) 8.95-9.04 (m, 2H) 8.37-8.49 (m, 2H) 5.68 (br s, 2H)
A4	\ JL o I ₊ w .o M M o	(400 MHz, D₂O) 9.25-9.02 (m, 3H), 8.81-8.66 (m, 2H), 5.85-5.74 (m, 2H)
A5	i O X // y--Z z=\ L J ^Z^Z______	(400 MHz, D₂O) 9.02-9.11 (m, 2H) 8.87-8.99 (m, 1H) 8.47-8.60 (m, 2H) 4.94-5.05 (m, 2H) 3.48-3.61 (m, 2H)

103

Compound Number	Structure	'HNMR
A6	0 F JL ⁰zi ^{F s} \|X1. y A NÏ JL ++ OH	(400 MHz, D₂O) 8.96-8.88 (m, 3H), 8.58-8.54 (m, 2H), 5.40 (s, 2H)
A7	n 1 Cl Ο tx T L o	(400 MHz, D₂O) 9.05 (d, 2H), 8.92 (s, 1H), 8.51 (d, 2H), 4.87 (t, 2H), 3.15 (t, 2H) (CO₂H proton missing)
A8	z_xc/ ^x.^zp O\	(400 MHz, D₂O) 9.39-9.45 (m, 1H) 8.85-8.93 (m, 2H) 8.35-8.44 (m, 2H) 5.55 (s, 2H) 3.73-3.84 (m, 3H)
A9	/ A ^cr ^s [Χΐ. y A At ++ OH	(400 MHz, D₂O) 9.38-9.43 (m, 1H) 8.83-8.90 (m, 2H) 8.33-8.40 (m, 2H) 5.40 (s, 2H) (CO₂H proton missing)
A10	Z^— o A 1 O	(400 MHz, CD₃OD) 9.08 (s, 3H), 8.77 (br d, 2H), 5.12 (br s, 2H), 1.71 - 1.46 (m, 3H)
AH	p z- /O ω^χ o W 1 o	(400 MHz, D₂O) 9.13 (d, 2H), 8.98 (s, 1H), 8.62 (d, 2H), 5.86 (d, 1H), 2.02 (d, 3H)

104

Compound Number	Structure	‘HNMR
A12	Z // \ 1 z=/ /O o+ \ o 1	(400 MHz, D₂O) 9.41 (s, 1H), 9.01 (d, 2H), 8.66 (d, 2H), 4.72 - 4.79 (m, 2H), 2.99-3.02 (m, 2H), 2.472.53 (m, 2H)
A13	o Tl Y °' ° T'L u A N* JL ++ ^OH	(400 MHz, D₂O) 9.06 - 9.00 (m, 2H), 8.91 (s, 1H), 8.68 (d, 2H), 5.48 (s, 2H) (CO₂H Proton missing)
A14	0 Ri ^F^°⁰ \|Ύ. ^F^^^ΝΤ/-+'Χ^/'^ΟΗo	(400 MHz, D₂O) 9.08 - 9.19 (m, 2H), 8.86 - 8.96 (m, 1H), 8.64 (d, 2H), 4.85 - 4.96 (m, 2H), 3.15 (t, 2H) (CO₂H proton missing)
A15	z- /O o W । O	(400 MHz, D₂O) 9.09 (d, 2H), 8.65 (br d, 2H), 4.78 - 4.84 (m, 2H), 2.95 (t, 2H), 2.44 (brt, 2H)
A16	Cl L JL / +/ \/ +q+	(400 MHz, D₂O) 9.17 (s, 1 H), 9.03 (d, 2H), 8.66 (d, 2H), 5.62 (s, 2H), 3.79 (s, 3H)
A17	O \=z \\ / z--' /O ο Ά 1 o	(400 MHz, D₂O) 9.15 (d, 1H), 9.09 (d, 2H), 8.61 (brd, 2H), 4.80 (t, 2H), 2.90 - 2.98 (m, 2H), 2.39 2.49 (m, 2H)

105

Compound Number	Structure	‘HNMR
A18	o \J ¹ / — i / \ Y / z--' /O o 1 O	(400 MHz, D₂O) 8.89 (br d, 2H), 8.30 (br d, 2H), 2.91 (t, 2H), 2.45 2.34 (m, 2H) (one CH₂ under water peak, oxadiazole proton exchanged)
A19	z^ Z--' ^xcn // ^XO O 1	(400 MHz, D₂O) 9.35 - 9.41 (m, 1H), 8.89 - 8.97 (m, 2H), 8.32 (d, 2H), 4.89 - 5.01 (m, 2H), 3.52 (s, 1H), 3.55 (d, 1H)
A20	°\\ X en r--Z \ ^ΧωLL^ \ LL	(400 MHz, D₂O) 9.08 (d, 2H), 8.66 (d, 2H), 8.63 (s, 1H), 5.75 (s, 2H)
A21	ΊΊ \ ΊΊ ω V=z z— cT^O1	(400 MHz, D₂O) 9.06 (d, 2H), 8.54 - 8.62 (m, 3H), 5.07 (t, 2H), 3.65 (t, 2H)
A22	F \,F fY c K ^Br~ ^s iO· s LL A ^OH	(400 MHz, D₂O) 8.95 (d, 2H), 8.62 (t, 3H), 5.40 (s, 2H) (CO₂H proton missing)
A23	Z W —^O G ,cn θ' \ O 1	(400 MHz, D₂O) 8.98 (d, 2H), 8.54 (d, 2H), 8.18 (d, 1H), 7.54 (d, 1H), 5.65 (s, 2H)

106

Compound Number	Structure	’HNMR
A24	ZA-s S I ^Cl n^aW^ 0 L· .Ύ JL W AA ^oh	(400 MHz, D₂O) 8.83 (d, 2H), 8.51 (d, 2H), 8.17 (d, 1H), 8.04 (d, 1H), 5.33 (s, 2H) (CO₂H proton missing)
A25	O Y o ^z=\	(400 MHz, D₂O) 8.95 (d, 2H), 8.46 (d, 2H), 8.14 (d, 1H), 8.01 (d, 1H), 4.86 (t, 2H), 3.18 (t, 2H) (CO₂H proton missing)
A26	u J—' / ''O O I	(400 MHz, D₂O) 9.04-9.21 (m, 2H), 8.43 - 8.55 (m, 2H), 5.00 5.13 (m, 2H), 4.23 - 4.35 (m, 3H), 3.49- 3.68 (m, 2H)
A27	Hr \=^z Z--J A / O I	(400 MHz, D₂O) 8.97-9.10 (m, 2H), 8.54 - 8.66 (m, 2H), 4.95 5.06 (m, 2H), 4.41 - 4.53 (m, 3H), 3.50 - 3.63 (m, 2H)
A28	,^N—-s # I Cl A JL AA AA \_OH	(400 MHz, D₂O) 9.03 - 8.90 (m, 3H), 8.52 (d, 2H), 5.39 - 5.32 (m, 1H), 1.84 (d, 3H) (CO₂H proton missing)
A29	Y z i A ω^χ U W O	(400 MHz, D₂O) 8.96 (s, 1H), 8.92 (d, 2H), 8.59 (d, 2H), 5.52 (s, 2H), 3.17 (s, 3H)

107

Compound Number	Structure	’HNMR
A30	v—ω O G. m o i o	(400 MHz, D₂O) 8.96 - 8.88 (m, 3H), 8.54 (d, 2H), 4.90 - 4.83 (m, 2H), 3.54 (d, 3H)
A31	Ci JL oG\ I o	(400 MHz, D₂O) 8.95 - 8.87 (m, 3H), 8.56-8.51 (m, 2H), 4.864.79 (m, 2H), 3.90 - 3.82 (m, 2H), 1.12 (t, 3H)
A3 2	Ο I v o O JJ	(400 MHz, D₂O) 9.01 - 8.86 (m, 3H), 8.54 (d, 2H), 4.84 - 4.78 (m, 2H) (POH proton missing)
A33	o n Y· γΥγ! o G XL A Y H	(400 MHz, D₂O) 9.03 (d, 2H), 8.50 (d, 2H), 5.44 (s, 2H), 4.28 (s, 3H) (CO₂H proton missing)
A34	O ^ΡγΥ^_ο- —n' \ ^F' । ^F ° G Y JL OH	(400 MHz, D₂O) 8.91 - 8.85 (m, 2H), 8.63 - 8.59 (m, 2H), 5.35 (s, 2H), 4.44 (s, 3H) (CO₂H proton missing)
A3 5	)=^ z—' A .a o' \ o I	(400 MHz, D₂O) 9.13 - 9.05 (m, 2H), 8.78 - 8.67 (m, 2H), 5.77 5.70 (m, 2H), 4.56 - 4.48 (m, 3H)

108

Compound Number	Structure	Ή NMR
A36	Z--J _xo o i o	(400 MHz, D₂O) 9.05 (d, 2H), 8.52 (d, 2H), 4.78 (t, 2H), 2.94 (t, 2H), 2.63 (s, 3H), 2.43 (t, 2H)
A3 7	0 N—0 F 1 / 1 >r ⁰ ^F A/^N\Ay^OH0	(400 MHz, D₂O) 9.02 (d, 2H), 8.67 (s, 1H), 8.43 (d, 2H), 7.39 (d, 1H), 4.90 (t, 2H), 3.20 (t, 2H) (CO₂H proton missing)
A3 8	i O Οχ // ^ωχ (po r--Z z=\ LL / \ \ Y^x ^W LL \ LL	(400 MHz, D₂O) 9.14 (d, 2H), 8.63 (d, 2H), 5.06 (t, 2H), 3.60 (t, 2H)
A3 9	\=z z=7 / ^XO O 1	(400 MHz, D₂O) 8.97 (d, 2H), 8.47 (d, 2H), 8.14 (d, 1H), 7.50 (d, 1H), 3.55 (t, 2H) 4.97 (t, 2H)
A40	c? \\ // “Π “Π A o	(400 MHz, D₂O) 8.89 (d, 2H), 8.67 (d, 1H), 8.46 (d, 2H), 7.42 (d, 1H), 5.37 (s, 2H) (CO₂H proton missing)
A41	1 O o_Y / / ^x° + / r--Z A Ζχ γ	(400 MHz, D₂O) 9.03 (d, 2H), 8.67 (d, 1H), 8.45 (d, 2H), 7.41 (d, 1H), 5.01 - 5.07 (m, 2H), 3.60 - 3.64 (m, 2H)

109

Compound Number	Structure	'HNMR
A42	S \| ^nXiîV ° 1. w .o L Y \ 0	(400 MHz, DMSO-dô) 9.39 (d, 1H), 9.08 (d, 2H), 8.72 (d, 2H), 8.37 (d, 1H), 5.45 (s, 2H)
A43	n Y n Ο \=Z Z=J X ut/! x \ o 1	(400 MHz, D₂O) 9.13 (d, 2H), 8.75 (d, 1H), 8.66 (d, 2H), 5.75 (s, 2H)
A44	F F F —Δ/ ^cr ° 19Y î L /X JL NY OH	(400 MHz, D₂O) 8.97 (d, 2H), 8.70 - 8.76 (m, 1H), 8.60 (d, 2H), 5.38 (s, 2H) (CO₂H proton missing)
A45	F F F—y y—n \ JL ^Br~ ογχ/γ O	(400 MHz, D₂O) 9.11 (d, 2H), 8.65 - 8.79 (m, 1H), 8.56 (d, 2H), 4.93 (t, 2H), 3.20 (t, 2H) (CO₂H proton missing)
A46	1 O / ^w\ r—^zZ=A LL	(400 MHz, D₂O) 9.09 (d, 2H), 8.71 (d, 1H), 8.57 (d, 2H), 5.11 -5.02 (m, 2H), 3.56-3.66 (m, 2H)

110

Compound Number	Structure	Ή NMR
A47	z \ /-n T¹ 2=⁷ \ / i C Y z° v° 7 7 ο o ' o \	(400 MHz, DMSO-d₆) 9.33 (s, 1H), 9.16 (d, 2H), 8.85 (d, 2H), 5.37 (d, 2H), 4.14 - 4.03 (m, 2H), 1.69 (d, 3H), 1.27- 1.19 (m, 3H)
A48	F \Y o ^F \ Il nY Ύ o	(400 MHz, D₂O) 9.20 (d, 2H), 8.67 (d, 2H), 4.98 (t, 2H), 3.19 (t, 2H), 2.02 (s, 3H) (CO₂H proton missing)
A49	YY Br~ I N 1 1 Tày	(400 MHz, DMSO-d₆) 9.71 (s, 1H), 9.25 (d, 2H), 8.81 (d, 2H), 5.75 (s, 2H), 4.27 (q, 2H), 1.27 (t, 3H)
A50	\ ° a—N Y \ 1 _F>r ⁰ ⁰ \|Yb ^f 0	(400 MHz, D₂O) 9.14 (d, 2H), 8.58 (d, 2H), 4.91 (t, 2H), 3.16 (t, 2H), 2.45 (s, 3H) (CO₂H proton missing)
A51	IZ^ o A ir° z— z° ω^χ O i O	(400 MHz, D₂O) 9.06 (d, 2H), 8.64 (d, 2H), 4.80 (t, 2H), 2.97 - 2.90 (m, 5H), 2.49 - 2.39 (m, 2H) (NH proton missing)

111

Compound Number	Structure	Ή NMR
A52	IZ^Xz Jv _o ^z Υ-Ύθ z—^z /O O । o	(400 MHz, D₂O) 8.88 - 9.03 (m, 2H), 8.36 - 8.48 (m, 2H), 7.53 7.66 (m, 1H), 4.64 - 4.82 (m, 2H), 2.93 (t, 2H), 2.87 (s, 3H), 2.42 (quin, 2H) (NH proton missing)
A53	0 s— ^FJJ Nr Y^x x>. o 11 /N* JL Y Yx \)H	(400 MHz, D₂O) 9.80 (s, 1H), 8.84 (d, 2H), 8.62 (d, 2H), 5.39 (s, 2H) (CO₂H proton missing)
A54	S^, liA. v· IL Yt y γχ \\ o	(400 MHz, DMSO-d₆) 10.32 (s, 1H), 9.09 - 9.20 (m, 2H), 8.88 (d, 2H), 5.43 - 5.52 (m, 2H)
A55	<1 ε-'ΆΥΥ JL Jn* xx /^0H o	(400 MHz, D₂O) 9.34 - 9.45 (m, 1H), 8.94-9.10 (m, 2H), 8.748.83 (m, 1H), 4.88 - 5.03 (m, 2H), 3.11 - 3.25 (m, 2H) (CO₂H proton missing)
A56	\ L s^YYY ci JL Jn7 OH cr y^ o	(400 MHz, D₂O) 9.40 - 9.52 (m, 1H), 8.98-9.11 (m, 2H), 8.82- 8.92 (m, 1H), 4.87 - 4.96 (m, 2H), 3.08 - 3.26 (m, 2H) (CO₂H proton missing)
A57	O L ω o W i o	(400 MHz, DMSO-d₆) 9.34 - 9.15 (m, 2H), 8.78 - 8.60 (m, 2H), 5.59 (br s, 2H), 4.37 (br s, 3H)

112

Compound Number	Structure	Ή NMR
A58	0 ^F>r'⁰· N 1 F^l F । o	(400 MHz, D₂O) 9.07 (d, 2H), 8.94 (s, 1H), 8.54 (d, 2H), 4.90 (t, 2H), 3.60 (s, 3H), 3.18 (ΐ, 2H)
A59	^ΝΓΧ ^crfi M JL ^OH	(400 MHz, D₂O) 8.93-8.89 (m, 2H), 8.51-8.46 (m, 2H), 5.37 (s, 2H), 2.67 (s, 3H) (CO₂H proton missing)
A60	V=z z=/ ° o° JW o \\ 1 o	(400 MHz, DMSO-dô) 9.18-9.10 (m, 2H), 8.69 (d, 2H), 8.21 (s, 1H), 8.01 (d, 2H), 7.61 - 7.47 (m, 3H), 4.91 - 4.82 (m, 2H), 4.34 - 4.21 (m, 2H)
A61	O 1 W° o^x \ o r—z Z=\ O^^Z	(400 MHz, DMSO-dô) 10.02 (s, IH), 9.28 - 9.19 (m, 2H), 8.72 (br d, 2H), 4.99 - 4.88 (m, 2H), 4.28 (br s, 2H)
A62	p Z₊— o \ H O 1 O	(400 MHz, DMSO-dô) 14.94 (br s, 1H), 9.07 (d, 2H), 8.93 (s, 1H), 8.60 (d, 2H), 4.90 - 4.77 (m, 2H), 4.30-4.19 (m, 2H)
A63	z—7 o \ ω O \\ 1 o	(400 MHz, DMSO-dô) 8.94 - 9.08 (m, 2H), 8.79 - 8.90 (m, 1H), 8.47 8.61 (m, 2H), 4.69 - 4.85 (m, 2H), 4.14 - 4.31 (m, 2H), 2.69 - 2.84 (m, 3H)

113

Compound Number	Structure	'HNMR
A64	z z J \—o z—' o \ o W । o	(400 MHz, DMSO-dô) 9.60 - 9.79 (m, 1H), 9.17 - 9.31 (m, 2H), 8.64 8.81 (m, 2H), 4.83 - 5.02 (m, 2H), 4.19-4.36 (m, 2H)
A65	z—y I ( I \ V» O W 1 O	(400 MHz, DMSO-dô) 10.23 10.36 (m, 1H), 9.09 - 9.24 (m, 2H), 8.73 - 8.96 (m, 2H), 4.73 - 4.94 (m, 2H), 4.18-4.34 (m, 2H)
A66	z- O \ A O W 1 o	(400 MHz, DMSO-dô) 9.16 (d, 2H), 8.56 (d, 2H), 7.61 - 7.57 (m, 1H), 4.89 - 4.78 (m, 2H), 4.32 - 4.19 (m, 2H), 2.39 (s, 3H)
A67	O 1 WA .w \ o ,—z O. J	(400 MHz, DMSO-dô) 8.95 (d, 2H), 8.76 - 8.91 (m, 1H), 8.36 (d, 2H), 7.98 (s, 1H), 7.22 - 7.41 (m, 1H), 4.61 - 4.84 (m, 2H), 4.12 - 4.34 (m, 2H)
A68	O 1 WA ω cZ \ O >—z ζζ	(400 MHz, DMSO-dô) 8.83 - 9.01 (m, 2H), 8.24 - 8.36 (m, 2H), 8.13 - 8.23 (m, 1H), 7.75 - 7.90 (m, 1H), 6.89 (dd, 1H), 4.62 - 4.87 (m, 2H), 4.08 - 4.30 (m, 2H)
A69	T ' ° AS / \ .—z LL LL H A / z	(400 MHz, DMSO-dô) 9.16 - 9.33 (m, 2H), 8.75 - 8.88 (m, 2H), 8.17 8.32 (m, 2H), 7.55 - 7.80 (m, 3H), 4.68 - 4.83 (m, 2H), 3.82 - 4.00 (m, 2H) (OH proton missing)
A70	M ό _n L \ A A +AA+ w o	(400 MHz, D₂O) 9.45 (s, 1H), 9.08 (d, 2H) 8.65 (d, 2H), 4.80 - 4.83 (m, 2H), 2.98 (t, 2H), 2.48 - 2.53 (m, 2H)

114

Compound Number	Structure	'HNMR
A71	o Il । >—ω—o / ¹¹y /—²	(400 MHz, D₂O) 9.09 (d, 2H) 8.60 (d, 2H), 4.83 - 4.87 (m, 2H), 3.01 (t, 2H), 2.74 (s, 3H), 2.49 - 2.53 (m, 2H)
A72	A° \=Z o \ ! Il / Ο—ω—o II o	(400 MHz, D₂O) 9.07 (d, 2H) 8.61 (d, 2H), 4.98 - 5.02 (m, 2H), 4.534.56 (m, 2H), 2.74 (s, 3H)
A73	M z— / ⁺ τι m M ¹ o 1	(400 MHz, DMSO-d₆) 9.02 - 9.13 (m, 2H), 8.32 - 8.45 (m, 2H), 7.60 7.73 (m, 1H), 6.89 - 7.14 (m, 1H), 4.63 - 4.75 (m, 2H), 4.04 - 4.17 (m, 2H), 3.82 - 3.97 (m, 3H) (OH proton missing)
A74	/Y r9 2—99 ω O । o	(400 MHz, DMSO-dô) 8.99 - 9.16 (m, 2H), 8.30 - 8.45 (m, 2H), 7.61 7.70 (m, 1H), 7.02 - 7.13 (m, 1H), 4.78 - 4.91 (m, 2H), 4.22 - 4.33 (m, 2H), 4.05 - 4.16 (m,3H)
A75	o=/ 1 \_____ m + / /=z	(400 MHz, D₂O) 9.12 (d, 2H), 9.02 (s, 1H), 8.65 (d, 2H), 5.83 (q, 1H), 3.80 (s, 3H), 1.99 (d, 3H)

115

Compound Number	Structure	*HNMR
A76	z tn P X^Z \ __/ -π τι G o' W ° ' °	(400 MHz, DMSO-d₆) 9.33 (s, 1H), 9.18 (br d, 2H), 8.87 (d, 2H), 5.54 5.46 (m, 2H), 4.21-4.10 (m, 4H), 1.28- 1.19 (m, 6H)
A77	°\ ^0 F /Ί ^F>\| ^X°^- Ν_χ U F s^yG ο l Il ₊ w G P 0	(400 MHz, DMSO-dô) 9.33 (s, 1H), 9.22 - 9.17 (m, 2H), 8.88 - 8.83 (m, 2H), 5.54 (d, 2H), 3.83 - 3.76 (m, 6H)
A78	'o O G U. U- Z--Z z=\ i J zz γζ	(400 MHz, D₂O) 8.64 (d, 2H), 8.19 (d, 2H), 7.79 (d, 1H), 6.98 (d, 1H), 5.34 (s, 2H) (CO₂H and NH protons missing)
A79	F \_F ^F O λ—Ν Br II <XA G- o	(400 MHz, D₂O) 9.68 (s, 1H), 9.21 (dd, 1H), 8.96 (d, 1H), 4.99 (t, 2H), 3.25 (t, 2H), 2.04 (s, 3H) (CO₂H proton missing)
A80	ω ^Hp G o G	(400 MHz, D₂O) 9.15 (d, 1H), 8.87 (d, 2H), 8.60 (d, 2H), 8.12 (d, 1H), 5.46 (s, 2H), 1.48 (s, 9H)

116

Compound Number	Structure	’hnmr
A81	sfr ^cr i ++ ^XOH	(400 MHz, D₂O) 9.10 (d, 1H), 8.82 (d, 2H), 8.53 (d, 2H), 8.07 (d, 1H), 5.37 (s, 2H) (CO₂H proton missing)
A82	/+z \\ 1 /—° z— <Jo /W o^z \ o 1	(400 MHz, D₂O) 9.02 (d, 2H), 8.66 (d, 1H), 8.50 (d, 2H), 7.43 (d, 1H), 5.69 (s, 2H)
A83	0 ς ^F+ /Y - / ^N O Y+ Y O L a JL +/ ^XOH	(400 MHz, D₂O) 10.33 (s, 1H), 8.93 (d, 2H), 8.81 (d, 2H), 5.36 (s, 2H) (CO₂H proton missing)
A84	O Il । y—ω—O Z~Λ o ^z=\	(400 MHz, D₂O) 9.02 (d, 2H), 8.62 (d, 2H), 8.25 (d, 1H), 8.13 (d, 1H), 5.73 (s, 2H)
A85	F F+\ \ Jl ^s/y\ o 1 ₊ w /0 + /N? S' O	(400 MHz, D₂O) 9.25 (d, 2H), 8.81 (d, 2H), 5.84 (s, 2H)
A86	\ JL ^ci~ HO L /N* J/ ++ \+ \q	(400 MHz, D₂O) 8.87 (d, 2H), 8.68 (d, 1H), 8.36 (d, 2H), 8.05 (d, 1H), 5.44 (s, 2H) (CO₂H proton missing)

117

Compound Number	Structure	Ή NMR
A87	V’ A ,N N/ \/ \\ O	(400 MHz, D₂O) 8.99 (d, 2H), 8.71 (d, 1H), 8.42 (d, 2H), 8.10 (d, 1H), 5.71 (s, 2H)
A88	N. Y i «A Y· ^S^AX₊ ^F \Α^Ν\Αγ^0Η 0	(400 MHz, D₂O) 9.08 (d, 2H), 8.86 (s, 1H), 8.59 (d, 2H), 4.93 (t, 2H), 3.22 (t, 2H) (CO₂H proton missing)
A89	N, A-n ύ JL < A Ai ° ^F 0	(400 MHz, D₂O) 9.17 (d, 2H), 8.63 (d, 2H), 4.95 (t, 2H), 3.21 (t, 2H) (CO₂H proton missing)
A90	h₂n ^lï \ A ^S'?AX r. IL sY o	(400 MHz, D₂O) 9.05 (d, 2H), 8.52 (d, 2H), 5.70 (s, 2H) (NH protons missing)
A91	^.z z A V> y=z z=/ 1 ) O / <«x // ^XO O	(400 MHz, D₂O) 9.20 (d, 2H), 8.69 (d, 2H), 5.12 (t, 2H), 3.66 (t, 2H)

118

Compound Number	Structure	’hnmr
A92	H₂n o /r—N F. JL <1 .. Y° ^{s f} o	(400 MHz, D₂O) 9.04 (d, 2H), 8.44 (d, 2H), 4.89 (t, 2H), 3.16 (t, 2H) (CO₂H and NH protons missing)
A93	—N O=S=O N H 1 sG/Y ^Br O	(400 MHz, D₂O) 9.85 (s, 1H), 9.50 (d, 1H), 9.07 (s, 1H), 8.60 (d, 1H), 5.13 (t, 2H), 3.67 (s, 3H), 3.30 (t, 2H) (CO₂H proton missing)
A94	h₂n \ ^Cl \ΥγΥ^ OH L J^ Y3	(400 MHz, D₂O) 8.88 (d, 2H), 8.36 (d, 2H), 5.49 (s, 2H) (CO₂H and NH protons missing)
A95	\ JL ^Cl JY\/Y HO il yy yy	(400 MHz, D₂O) 8.92 (d, 2H), 8.53 (d, 2H), 5.38 (s, 2H), 2.87 (s, 3H) (CO₂H proton missing)
A96	_zz ? ω^Ζ\=z G M o । o	(400 MHz, D₂O) 9.16 (d, 2H), 8.66 (d, 2H), 5.77 (s, 2H)

119

Compound Number	Structure	Ή NMR
A97	HO \ JL Br- ^S Ί o	(400 MHz, D₂O) 9.07 (d, 2H), 8.45 (d, 2H), 4.90 (t, 2H), 3.18 (t, 2H) (CO₂H and OH protons missing)
A98	0 HO II \ Ύ Z—N PC o \ 1 F ^S^YY. y Y Y JL ^xOH	(400 MHz, D₂O) 8.90 (d, 2H), 8.46 (d, 2H), 5.33 (s, 2H) (CO₂H and OH protons missing)
A99	I o ô z— o^x \ O 1	(400 MHz, D₂O) 9.08 (d, 2H) 8.56 (d, 2H) 5.72 (s, 2H) (OH proton missing)
A100	ΝΥγΥ o=s=o 1 0	(400 MHz, D₂O) 9.02 (d, 2H), 8.62 (d, 2H), 8.25 (d, 1H), 8.13 (d, 1H), 5.73 (s, 2H)
A101	s__ J 1 * ^B<bryY \|\| ° Y JL / \z	(400 MHz, D₂O) 9.84 (s, 1H), 8.87 (d, 2H), 8.67 (d, 2H), 5.55 (s, 2H), 3.79 (s, 3H)

BIOLOGICAL EXAMPLES

Post-emergence effîcacy

120

Method A

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 5 hours light; 65 % humidity), the plants were sprayed with an aqueous spray solution derived from the dissolution ofthe technical active ingrédient formula (I) in a small amount of acetone and a spécial solvent and emulsifier mixture referred to as IF50 (11.12% 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).

Method B

Seeds of a variety of test species were sown in standard loam based soil in pots. Plants were cultivated from between 21 and 28 days (post-emergence) under controlled conditions in a glasshouse (at 24/16 °C, day/night; 14 hours light; 65 % humidity) for warm climate species 20 and (at 20/16°C day/night; 15 hours light; 65% humidity) for cool climate species.

The plants were sprayed with an aqueous spray solution derived from dissolving the technical active ingrédient formula in a small amount of acetone and a spécial solvent and emulsifier mixture referred to as IF50 (11.12% Emulsogen EL360 TM + 44.44% N-methylpyrrolidone + 25 44.44% Dowanol DPM glycol ether), to create a 50g/l solution which was then diluted to required concentration using 0.5% or 1% Empicol ESC70 (Sodium lauryl ether sulphate) + 1% ammonium sulphate as diluent.

The delivery ofthe aqueous spray solution was via a laboratory track sprayer which delivered 30 the aqueous spray composition at a rate of 200 litres per hectare, using a fiat fan nozzle (Teejet 11002VS) and an application volume of 2001itre/ha (at 2 bar).

The test plants were then grown in a glasshouse under controlled conditions (at 24/16 °C, day/night; 14 hours light; 65 % humidity) for warm climate species and (at 20/16°C day/night;

121 hours light; 65% humidity) for cool climate species and watered twice daily. After 7 and 14 days the test was evaluated (100 = total damage to plant; 0 = no damage to plant).

The results from method A are shown in Table B (below). A value of n/a indicates that this 5 combination of weed and test compound was not tested/assessed.

Test plants for method A:

Ipomoea hederacea (IPOHE), Euphorbia heterophylla (EPHEIL), Chenopodium album 10 (CHEAL), Amaranthus palmeri (ΑΜΑΡΑ), Lolium perenne (LOLPE), Digitaria sanguinalis (DIGSA), Eleusine indica (ELEIN), Echinochloa crus-galli (ECHCG), Setariafaberi (SETFA)

Test plants for method B:

Brassica napus (BRSNN), Solanum turberosum (SOLTU), Glycine Max (GLXMA), and Helianthus annus (HELAN)

Table B - Control of weed species by compounds of formula (I) after post-emergence application

Compound Number	Application Rate g/Ha	ΑΜΑΡΑ	CHEAL	EPHHL	IPOHE	ELEIN	LOLPE	DIGSA	SETFA	ECHCG
Al	500	100	90	n/a	40	90	70	70	90	60
A2	500	100	90	n/a	70	80	60	90	70	60
A3	500	100	90	80	80	50	20	70	80	40
A4	500	100	100	100	100	80	80	70	80	70
A5	500	100	90	100	70	80	70	70	60	40
A6	500	100	100	100	80	90	30	70	80	90
A7	500	100	90	80	30	70	30	90	70	50
A8	500	n/a	70	60	10	30	0	50	30	20
A9	500	30	0	10	20	n/a	0	n/a	0	n/a
A10	500	90	90	n/a	50	90	40	90	100	90
Ail	500	100	90	n/a	80	90	60	80	60	100
A12	1000	0	0	20	0	20	10	20	0	0
A13	500	100	50	70	30	50	10	60	70	50

122

A14	500	100	70	30	20	40	10	50	60	50
A15	500	0	0	n/a	20	10	0	30	30	30
A16	500	0	0	20	20	10	0	40	30	20
A17	500	70	70	50	20	10	0	40	40	30
A18	500	100	50	50	20	30	10	30	40	50
A19	500	100	50	50	50	30	30	30	40	40
A21	500	70	0	n/a	10	80	20	70	70	90
A22	500	10	10	40	0	n/a	0	n/a	0	n/a
A23	500	0	20	n/a	10	0	0	20	0	0
A24	500	0	40	40	20	0	0	10	0	0
A25	500	0	10	0	10	10	0	10	0	0
A26	500	0	10	20	10	10	10	20	10	10
A27	500	10	10	20	10	0	0	0	0	0
A28	500	100	80	20	70	n/a	30	n/a	80	n/a
A29	500	90	30	n/a	90	50	40	90	50	90
A30	500	90	70	n/a	50	90	30	90	90	90
A31	500	70	70	n/a	30	80	20	80	40	70
A32	500	60	20	n/a	0	40	10	50	20	70
A33	500	90	40	40	0	20	0	20	0	0
A34	500	70	0	0	0	0	0	0	0	0
A35	500	70	60	50	40	20	n/a	20	30	40
A36	500	70	60	60	30	10	0	30	10	10
A38	500	90	60	n/a	60	80	70	50	40	60
A39	500	40	30	n/a	20	0	0	0	0	0
A40	500	10	0	n/a	20	0	0	0	0	0
A41	500	10	0	n/a	0	0	0	10	10	10
A42	500	90	20	n/a	10	0	0	10	10	10
A43	500	40	40	n/a	30	60	10	30	20	60
A44	500	30	10	n/a	0	10	10	20	0	10
A45	500	0	0	n/a	0	50	0	20	0	10
A46	500	30	0	0	0	0	0	0	0	0
A47	500	60	60	10	10	10	0	10	10	10
A48	125	90	10	30	0	0	10	0	20	0
A49	500	10	50	n/a	10	20	20	50	20	10

123

A50	500	40	70	n/a	30	40	50	90	80	20
A51	500	10	60	n/a	10	10	20	50	30	30
A52	500	20	30	n/a	10	10	10	20	10	10
A53	500	10	10	20	20	0	0	0	10	10
A54	500	20	20	n/a	20	20	0	10	0	0
A55	500	50	40	10	30	n/a	30	n/a	20	n/a
A56	500	60	30	100	30	n/a	10	n/a	30	n/a
A57	500	100	80	20	0	20	0	30	0	60
A64	500	50	30	30	20	20	10	30	20	50
A65	500	30	20	20	20	20	10	30	10	20
A69	500	20	30	20	20	30	10	10	10	20
A71	500	20	50	40	30	20	0	30	10	20
A74	500	10	40	20	10	20	10	30	20	20
A79	500	90	40	60	40	90	30	80	70	80
A81	500	70	40	20	0	40	0	10	10	10
A83	500	20	30	50	10	10	10	20	10	0
A84	500	70	60	50	10	50	10	10	10	30
A85	500	100	90	100	100	100	90	100	100	100
A86	500	40	10	40	10	20	0	10	10	20
A87	500	0	10	20	0	0	0	0	20	20
A88	500	10	20	90	0	0	0	0	0	0
A89	500	30	30	20	10	80	10	90	80	60
A90	500	100	80	90	50	90	60	90	60	50
A92	500	100	60	80	20	20	10	80	60	60
A93	500	60	30	30	30	30	10	n/a	30	40
A94	500	30	40	30	10	40	10	30	10	20
A95	500	40	30	10	10	60	0	10	10	20
A96	500	100	100	100	30	90	100	100	80	100
A97	500	0	50	10	10	10	10	0	10	0
A98	500	50	40	30	10	10	0	70	20	40
A100	500	70	60	50	10	50	10	10	10	30

The results from method B are shown in Table C (below). A value of n/a indicates that this combination of weed and test compound was not tested/assessed.

124

Table C - Control of weed species by compounds of formula (I) after post-emergence application

Compound Number	Application Rate g/Ha	BRSNN	SOLTU	GLXMA	HELAN
A4	50	23	15	45
A4	150	32	30	83
A4	600	43	82	93
A4	50	43	50	52	97
A4	150	57	60	62	100
A4	600	80	67	85	100

Claims

CLAIMS:

1. Use of a compound of formula (I) or an agronomically acceptable sait or zwitterionic species thereof, as a herbicide:

wherein

R¹ is selected from the group consisting of hydrogen, halogen, Ci-Côalkyl, C2Côalkenyl, C2-C6alkynyl, C3-C6cycloalkyl, Ci-Côhaloalkyl, -OR⁷, -OR^15a, N(R⁶)S(O)2R¹⁵, -N(R⁶)C(O)R¹⁵, -N(R⁶)C(O)OR¹⁵, -N(R⁶)C(O)NR¹⁶R¹⁷, -N(R⁶)CHO, N(R^7a)₂ and -S(O)_rR¹⁵;

R² is selected from the group consisting of hydrogen, halogen, Ci-Cealkyl and CiCôhaloalkyl;

and wherein when R¹ is selected from the group consisting of -OR⁷, -OR^15a, 20 N(R⁶)S(O)2R¹⁵, -N(R⁶)C(O)R¹⁵, -N(R⁶)C(O)OR¹⁵, -N(R⁶)C(O)NR¹⁶R¹⁷, -N(R⁶)CHO, N(R^7a)2 and -S(O)_rR¹⁵, R² is selected from the group consisting of hydrogen and CiCôalkyl; or

R¹ and R² together with the carbon atom to which they are attached form a C325 Côcycloalkyl ring or a 3- to 6- membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O; and

Q is (CR^laR^2b)_m;

m is 0, 1, 2 or 3;

126 each R^la and R^2b are independently selected from the group consisting of hydrogen, halogen, Ci-C₆alkyl, Ci-C₆haloalkyl, -OH, -OR⁷, -OR^15a, -NH2, -NHR⁷, -NHR^l5a, N(R⁶)CHO, -NR^7bR^7c and -S(O)rR¹⁵; or each R^la and R^2b together with the carbon atom to which they are attached form a C3Côcycloalkyl ring or a 3- to 6- membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O; and

R³, R^3a, R⁴ and R⁵ are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, -S(O)rR¹⁵, Ci-Cealkyl, Ci-Côfluoroalkyl, Ci-Côfluoroalkoxy, CiCôalkoxy, C3-C6cycloalkyl and -N(R⁶)₂;

each R⁶ is independently selected from hydrogen and Ci-Cealkyl;

each R⁷ is independently selected from the group consisting of Ci-Cealkyl, -S(O)₂R¹⁵, C(O)R¹⁵, -C(O)OR¹⁵ and -C(O)NR¹⁶R¹⁷;

each R^7a is independently selected from the group consisting of-S(O)₂R¹³, -C(O)R¹⁵, C(O)OR¹⁵, -C(O)NR¹⁶R¹⁷ and -C(O)NR⁶R^15a; .

R^7b and R^7c are independently selected from the group consisting of Ci-Cealkyl, S(O)₂R¹⁵, -C(O)R¹⁵, -C(O)OR¹⁵, -C(O)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

R^7b and R^7c together with the nitrogen atom to which they are attached form a 4- to 6membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N, O and S; and

A is a 5-membered heteroaryl attached to the rest of the molécule via a ring carbon atom, which comprises 1, 2, 3 or 4 heteroatoms independently selected from the group consisting of N, O and S, and wherein the heteroaryl may, where feasible, be optionally substituted by 1, 2 or 3 R⁸ substituents, which may be the same or different, and wherein 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(O)rR¹⁵, -NR⁶S(O)2R¹⁵, -C(O)OR¹⁰, -C(O)R¹⁵, 20324

127

C(O)NR¹⁶R¹⁷, -S(O)2NR¹⁶R¹⁷, Ci-C6alkyl, Ci-C₆haloalkyl, C₃-C₆cycloalkyl, C₃Côhalocycloalkyl, C₃-C6cycloalkoxy, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, Ci-C₃alkoxyCi-C₃alkyl-, hydroxyCi-Côalkyl-, Ci-C₃alkoxyCi-C₃alkoxy-, CiCôhaloalkoxy, Ci-C₃haloalkoxyCi-C₃alkyl-, C₃-C6alkenyloxy, C₃-C6alkynyloxy, N-C₃. Côcycloalkylamino, -C(R⁶)=NOR⁶, phenyl, a 3- to 6- membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O, and a 5- or 6membered heteroaryl, which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein said phenyl, heterocyclyl or heteroaryl are optionally substituted by 1, 2 or 3 R⁹ substituents, which may be the same or different;

and/or when A is substituted on a ring nitrogen atom, R⁸ is selected from the group consisting of -OR⁷, Ci-Côalkyl, Ci-Côhaloalkyl, C₃-C6cycloalkyl, C₃-C6halocycloalkyl, C₃Côcycloalkoxy, C₂-C6alkenyl, C₂-C6haloalkenyl, C₂-Côalkynyl, Ci-C₃alkoxyCiC₃alkyl-, hydroxyCi-Côalkyl-, Ci-C₃alkoxyCi-C₃alkoxy-, Ci-Côhaloalkoxy, CiC₃haloalkoxyCi-C₃alkyl-, C₃-C₆alkenyloxy and C₃-C₆alkynyloxy ; and each R⁹ is independently selected from the group consisting of halogen, cyano, -OH, N(R⁶)₂, Ci-C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl and Ci-C4haloalkoxy;

X is selected from the group consisting of C₃-C6cycloalkyl, phenyl, a 5- or 6- membered heteroaryl, which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and a 4- to 6- membered heterocyclyl, which comprises 1, 2 or 3 heteroatoms individually selected from N, O and S, and wherein said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties are optionally substituted by 1 or 2 R⁹ substituents, and wherein the aforementioned CR*R², Q and Z moieties may be attached at any position of said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties;

n is 0 or 1;

Z is selected from the group consisting of-C(O)OR¹⁰, -CH2OH, -CHO, -C(O)NHOR, -C(O)NHCN, -OC(O)NHORⁿ, -OC(O)NHCN, -NR⁶C(O)NHORⁿ, -NR⁶C(O)NHCN, -C(O)NHS(O)2R¹², -OC(O)NHS(O)2R¹², -NR⁶C(O)NHS(O)2R¹², -S(O)2OR^w, OS(O)2OR¹⁰, -NR⁶S(O)2OR’°, -NR⁶S(O)OR¹⁰, -NHS(O)2R¹⁴, -S(O)OR¹⁰, -OS(O)OR'°,

128

-S(O)₂NHCN, -S(O)₂NHC(O)R¹⁸, -S(O)2NHS(O)2R¹², -OS(O)2NHCN,

OS(O)₂NHS(O)₂R¹², -OS(O)2NHC(O)R¹⁸, -NR⁶S(O)2NHCN, -NR⁶S(O)2NHC(O)R¹⁸, -N(OH)C(O)R¹⁵, -ONHC(O)R¹⁵, -NR⁶S(O)2NHS(O)₂R¹², -P(O)(R¹³)(OR¹⁰), P(O)H(OR¹⁰), -OP(O)(R¹³)(OR¹⁰), -NR⁶P(O)(R¹³)(OR^w) and tetrazole;

R¹⁰ is selected from the group consisting of hydrogen, Ci-Côalkyl, 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-Côalkyl 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-Côalkyl, Ci-Côhaloalkyl, Ci-Cealkoxy, 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-Côalkyl, Ci-Cealkoxy and phenyl;

R¹⁴ is Ci-Côhaloalkyl;

R¹⁵ is selected from the group consisting of Ci-Côalkyl and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R⁹ substituents, which may be the same or different;

R^15a 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 CiCôalkyl; or

R¹⁶ and R¹⁷ together with the nitrogen atom to which they are attached form a 4- to 6membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N, O and S; and

129

R¹⁸ is selected from the group consisting of hydrogen, Ci-Côalkyl, Ci-Côhaloalkyl, CiC6alkoxy, -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;

5 and r is 0, 1 or 2.
2. A compound of formula (I) or an agronomically acceptable sait or zwitterionic species

10 thereof, as defined in claim 1, with the proviso that:

i) in the compound of formula (I), A is not selected from the group consisting of formula A-Ib to A-IIIb below

wherein each R^8b‘ is independently selected from the group consisting of phenyl, 4methoxyphenyl, 4-butoxyphenyl, 4-fluorophenyl and methoxy, and each R^8c is independently hydrogen or methyl;

or ii) the compound of formula (I) is not selected from the group consisting of:

130

ethyl 2-[4-(2-thienyl)pyridin-1-ium-1-yl]acetate, ethyl 2-[4-(5-methyl-1 H-pyrazol-3-yl)pyridin-1-ium-1-yl]acetate,

2-[4-[5-(1-ethylpyridin-1-ium-4-yl)-2-furyl]pyridin-1-ium-1-yl]ethylphosphonic acid,

2-[4-[4-(1-ethylpyridin-1-ium-4-yl)-3-thienyl]pyridin-1-ium-1-yl]ethylphQsphonic acid and

3-[4-[5-[4-(dihexylamino)phenyl]-2-thienyl]pyridin-1-ium-1-yl]propane-1-sulfonic acid.

131
3. The compound of formula (I) according to claim 2, wherein R¹ and R² are independently selected from the group consisting of hydrogen and Ci-Cëalkyl.
4. The compound of formula (I) according to claim 2 or claim 3, wherein R¹ and R² are hydrogen.
5. The compound of formula (I) according to any one of claims 2 to 4, wherein each R^laand R^2b are independently selected from the group consisting of hydrogen, Ci-Côalkyl, -OH and -NH2.
6. The compound of formula (I) according to any one of claims 2 to 5, wherein each R^laand R^2b are hydrogen.
7. The compound of formula (I) according to any one of claims 2 to 6, wherein m is 0, 1 or 2.
8. The compound of formula (I) according to any one of claims 2 to 7, wherein R³, R^3a, R⁴and R⁵ are independently selected from the group consisting of hydrogen, halogen, cyano, Ci-Côalkyl and Ci-CôfluoroalkyL
9. The compound of formula (I) according to any one of claims 2 to 8, wherein R³, R^3a, R⁴ and R⁵ are hydrogen.
10. The compound of formula (I) according to any one of claims 2 to 9, wherein A is selected from the group consisting of formula A-I to A-XXXII below

132

A-XVII

A-XXI

A-XXV

A-XXII

A-XIX A-XX

A-XXVII

A-XXVIII

wherein the jagged line defines the point of attachment to a compound of formula (I);

R^8a is selected from the group consisting of hydrogen, Ci-Cealkyl and Ci-Côhaloalkyl;

5 each R^8b, R^8c and R^8d are independently selected from the group consisting of hydrogen, halogen, nitro, cyano, -NH2, -S(O)rR¹⁵, -C(O)OR¹⁰, -C(O)R¹⁵, -C(O)NR¹⁶R¹⁷, S(O)2NR¹⁶R¹⁷, Ci-C₆alkyl and Ci-C₆haloalkyl;

and R¹⁰, R¹⁵, R¹⁶, R¹⁷ and r are as defined in claim 1.

10
11. The compound of formula (I) according to any one of daims 2 to 10, wherein A is selected from the group consisting of formula A-I to A-III below

N—O

A-l A-ll A-III

15 wherein the jagged line defines the point of attachment to a compound of formula (I); each R^8b is independently selected from the group consisting of hydrogen, halogen, cyano, -NH2, -C(O)NR¹⁶R¹⁷, Ci-C6alkyl and Ci-C₆haloalkyl;

and R¹⁶ and R¹⁷ are as defined in claim 1.

20
12. The compound of formula (I) according to any one of daims 2 to 11, wherein A is selected from the group consisting of formula A-Ia to A-Xa below

134

Br

A-Xa

A-llla

N—O

A-Vlla
13. The compound of formula (I) according to any one of daims 2 to 12, wherein Z is 5 selected from the group consisting of -C(O)OR¹⁰, -C(O)NHS(O)2R¹², -OS(O)2OR¹⁰, S(O)₂OR¹⁰, and -P(O)(R¹³)(OR¹⁰).
14. A compound according to any one of daims 1 to 13, wherein Z is -C(O)OH or S(O)₂OH.
15. A compound according to any one of daims 1 to 14, wherein n is 0.
16. The use of a compound of formula (I) as defined in any one of daims 2 to 15, or an agronomically acceptable sait or zwitterionic species thereof, as a herbicide.
17. The use of a compound of formula (I) as defined in any one of daims 1 to 15 for preharvest desiccation in crops.
18. An agrochemical composition comprising a herbicidally effective amount of a

20 compound of formula (I) as defined in any one of daims 1 to 15 and an agrochemicallyacceptable diluent or carrier.

135
19. A method of controlling unwanted plant growth, comprising applying a compound of formula (I) as defined in any one of claims 1 to 15, or a composition according to claim 18, to the unwanted plants or to the locus thereof.