WO2008029084A1

WO2008029084A1 - Herbicidal compounds and compositions

Info

Publication number: WO2008029084A1
Application number: PCT/GB2007/003247
Authority: WO
Inventors: Paul Anthony Worthington; Philip Bentley; William Roderick Mound; John J. Taylor; Kay Fullick
Original assignee: Syngenta Limited
Priority date: 2006-09-06
Filing date: 2007-08-29
Publication date: 2008-03-13
Also published as: CL2007002582A1; AR062640A1; GB0617575D0

Abstract

The present invention provides compounds having the formula (1) wherein X is oxygen or sulphur; Y is oxygen or sulphur; (A) is a 5-membered heterocyclic ring containing one to three heteroatoms, each independently selected from the group consisting of oxygen, nitrogen and sulphur; P is CR12 or N; Q is CR13 or N; S is CR14 or N; T is CR15 or N; Z is a bond or a chain of 1-5 carbon atoms and/or heteroatoms independently selected from the group consisting of oxygen, nitrogen and sulphur forming ring (B), wherein (B) may contain one or more unsaturated bonds and may be optionally substituted wherein B is not an unsubstituted pyrrolidine, an unsubstituted piperidine, an unsubstituted morpholine or an unsubstituted 3-pyrroline or a pyrrolidine, piperidine, morpholine or 3-pyrroline each substituted with 1-2 C1-C2 alkyl. The present invention further relates to methods used to prepare these compounds, to compositions which comprise these compounds and to their use in agriculture or horticulture for controlling undesirable vegetation.

Description

Herbicidal Compounds and Compositions

The present invention relates to novel herbicidal compounds - more specifically to herbicidal azolecarboxamides. It further relates to intermediates used in the preparation of these compounds, to compositions which comprise these compounds and to their use in agriculture or horticulture for controlling undesirable vegetation

Herbicidal pyrazolecarbonylaminobenzene- and pyridinecarboxamides are disclosed in J. Org. Chan., 1997, 62, 5908-5919 and J. Heterocyclic Chem., 1998, 35, 1493-1499. Additionally, azolecarboxamides and their use as herbicides are described in WO04/035545, WO04/106324 and WO05/040152. This application discloses novel azolecarboxamides which exhibit improved properties - in particular improved herbicidal activity and crop selectivity.

Thus, according to the present invention there is provided a compound having the formula (I):-

wherein

X is oxygen or sulphur;

Y is oxygen or sulphur;

R₁, R₂, R-₃, R₄, and R₅ are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, hydroxyl, Ci-Cβalkyl optionally substituted by one or more substituents R^a, C₃-C₆cycloalkyl optionally substituted by one or more substituents R^a, C₂-C₆alkenyl optionally substituted by one or more substituents R^a, C₂-C₆alkynyl optionally substituted by one or more substituents R^a, C₁-C₆alkoxy optionally substituted by one or more substituents R^a and C_1-6 alkythio optionally substituted by one or more substituents R^a; wherein R^a is independently selected from the group consisting of halogen, cyano, nitro, C₁-C₆alkoxy, C₁-C₆ halogenalkoxy, C₃-C₆ cycloalkyl, C₁-C₆ alkylthio, C₁-C₆ halogenalkyltliio or -C(R^b)=N(OR^c); wherein R^b is hydrogen or C₁-C₆alkyl; wherein R^c is C₁-C₆alkyl;

(A) is a 5-membered heterocyclic ring containing one to three heteroatoms, each independently selected from the group consisting of oxygen, nitrogen and sulphur; the heterocyclic ring being substituted by up to three substituents selected from the groups R₆, R₇ and R₈; wherein R₆, R₇, and R₈ are each, independently, selected from the group consisting of hydrogen, halogen, cyano, nitro, C_1-6alkyl, CpC₆ alkoxy, C_1-6halogenalkyl, C_1-6 halogenalkoxy, C_1-6 alkoxy(C_1-6)alkyl, C_1-6 aUcythio(C_1-6)alkyl, C_2-6alkenyl, C_2-6haloalkenyl, C_2-6alkynyl, C_2-6haloalkynyl, C_3-6cycloalkyl, C_4-6alkylcycloalkyl, C_3-6halocycloalkyl, C_1-6halogenalkoxy(C_1-6)alkyl, C_1-6halogenalkylthio(C_1-6)alkyl and SiRg R₁₀ R₁₁ wherein R₉₅R₁₀ and R₁₁ are each independently selected from hydrogen and C_1-6 alkyl;

P is CR₁₂ or N;

Q is CR₁₃ or N;

S is CR₁₄ or N; T is CR₁₅ or N;

wherein R₁₂, R₁₃, R₁₄ and R₁₅ are independently selected from the group consisting of H, halogen, C₁-C₂ alkyl, C₁-C₂ fluoroalkyl, C₁-C₂ alkoxy, C₁-C₂ fluoroalkoxy, C₁-C₂ alkylthio and C₁-C₂ fluoroalkylthio. Preferably one, more preferably two and even more preferably three of P, Q, S or T are N.

Z is a bond or a chain of 1-5 carbon atoms and/or heteroatoms independently selected from the group consisting of oxygen, nitrogen and sulphur forming ring (B), wherein (B) may contain one or more unsaturated bonds and may be optionally substituted with one or more - 3 -

substituents selected from the group consisting halogen, cyano, nitro., hydroxyl, OSO₂Me, carbonyl, oxime, amino optional substituted by Cj_-6 alkyl or C₃-C₆ cycloalkyl, CrC₆alkyl optionally substituted by one or more substituents R^a, C₃-C₆cycloalkyl optionally substituted by one or more substituents R^a, C₂-C₆alkenyl optionally substituted by one or more 5 substituents R^a, C₂-C₆alkynyl optionally substituted by one or more substituents R^a, C₁- C₆alkoxy optionally substituted by one or more substituents R^a, C_1-6 alkythio optionally substituted by one or more substituents R^a, aryloxy optionally substituted by one or more substituents R^a, aryl optionally substituted by one or more substituents R^a, heteroaryl aryl optionally substituted by one or more substituents R^a, wherein each R^a is independently

10 selected from the group consisting of halogen, cyano, nitro, C₁-C₆alkoxy, C₁-

Cβhalogenalkoxy, C₃-C₆cycloalkyl, C_rC₆alkylthio, CrCehalogenalkylthio or -C(R^b)=N(OR^c); wherein R^b is hydrogen or Q-C₆alkyl; and wherein R⁰ is C₁-C₆alkyl; wherein B is not an unsubstituted pyrrolidine, an unsubstituted piperidine, an unsubstituted morpholine or an unsubstituted 3-pyrroline or a pyrrolidine, piperidine, morpholine or 3-

15 pyrroline each substituted with 1 -2 C₁-C₂ alkyl.

Thus, in the context of the present invention Z and the adjacent carbon and/or heteroatoms atoms can form, for example, the following rings:- optionally substituted aziridine, optionally substituted azetidine, substituted pyrrolidine, substituted piperidine, hexamethyleneimine,

20 heptamethyleneimine, substituted morpholine and substituted 3-pyrroline. In the context of the present invention Z may also form a polycyclic ring, for example an indoline, a phthalimide or bicyclic azetidine. These rings can be substituted with halogen, cyano, nitro, hydroxyl, C₁- ^• C₆alkyl, which is unsubstituted or substituted by one or more substituents R^a, C₃- C₆cycloalkyl, which is unsubstituted or substituted by one or more substituents R^a, C₂-

25 Qalkenyl, which is unsubstituted or substituted by one or more substituents R^a or C₂-

C₆alkynyl, which is unsubstituted or substituted by one or more substituents R^a, Q-Cόalkoxy, which is unsubstituted or substituted by one or more substituents R^a, C_1-6 alkythio, which is unsubstituted or substituted by one or more substituents R^a; each R^a independently of each other stand for halogen, cyano, nitro, d-C₆alkoxy, CrQhalogenalkoxy, C3-C₆cycloalkyl, C₁- C₆alkylthio, C_rC₆halogenalkylthio or -C(R^b)=N(OR^c); R^b is hydrogen or C₁-C₆alkyl; R^c is C₁-QaIlCyI; 5

"Alkyl groups" can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, zsσ-propyl, 72-butyl, sec-butyl, wobutyl or fert-butyl. alkoxy, alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned. The alkenyl and alkynyl groups can be mono- or di-unsaturated. 10

"Aryl" can be, for example, phenyl or substituted phenyl.

"Heteroaryl" means a monocyclic or polycyclic aromatic ring comprising carbon atoms, hydrogen atoms, and one or more heteroatoms, preferably, 1 to 3 heteroatoms, independently 15 selected from nitrogen, oxygen, and sulfur. Examples of heteroaryl groups include, pyridinyl, pyrimidyl and pyrrolyl groups. Within the context of the present invention it should be understood that the heteroaryl group can be unsubstituted or substituted.

"Cycloalkyl groups" can be, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. 20

"Halogen" is generally fluorine, chlorine, bromine or iodine, preferably fluorine, bromine or chlorine. This also applies, correspondingly, to halogen in combination with other meanings, such as halogenalkyl or halogenalkoxy.

25 "Halogenalkyl" can be, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fruoroethyl, 2,2- difluoroethyl, 2-chloroethyl, pentafluoroethyl, l,l-difluoro-2,2,2-trichloroethyl, 1,1,2,2- tetrafluoroethyl and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl. Halogenalkyl groups preferably have a chain length of from 1 to 4 carbon atoms.

"Halogenalkenyl" can be, for example, alkenyl groups which are mono- or polysubstituted by halogen, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl,

3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluorobut-2-en- 1-yl.

"Halogenalkynyl" can be, for example, alkynyl groups which are mono- or polysubstituted by halogen, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoro- propynyl and 4,4,4-trifluorobut-2-yn-1-yl.

"Alkoxy" can be, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy and ethoxy.

"Halogenalkoxy" can be, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2- difluoroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.

"Alkylthio" can be, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio and ethylthio.

"Alkoxyalkyl" can be, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.

The term "optionally substituted by one or more substituents" as used herein can mean, for example, optionally substituted by one, two, three, four, five, six, seven, eight, nine, ten, eleven, twelve or thirteen substituents. In the context of the present invention the skilled 6

person will appreciate the maximum number of substituents that are applicable in respect of any particular group.

In the context of the present invention (A) is preferably a pyrazolyl (especially pyrazol-5-yl), dihydropyrazolyl (especially 4,5-dihydropyrazol-5-yl), thiazolyl (especially thiazol-5-yl), pyrrolyl (especially pyrrol-3-yl), 1,2,3 triazolyl, 1,2,4 triazolyl, imidazolyl or oxazolyl (especially oxazol-5-yl). It is preferred that (A) is a 5-membered heterocyclic ring containing one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur; the heterocyclic ring being substituted by the groups R₆, R₇ and R₈.

10

Particularly preferred is wherein (A) is selected from the group consisting of:-

15

10 wherein R₆ is selected from the group consisting of halogen, cyano, nitro, Q-Cβalkyl, C₁-C₆ allcoxy, C₁-C₆ halogenalkyl, CrC_δhalogenalkoxy, CrCealkoxy-CrCealkyl or C₁- C₆halogenalkoxy-C₁-C₆alkyl and SiRgR₁₀R_{1 I};

R₇ is selected from the group consisting of C₁-C₄alkyl, C₁-C₄ alkoxy, C₁-C₄ halogenalkyl, C₁- C₄halogenalkoxy, CrC₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl; and R₈ is

15 selected from the group consisting of hydrogen, halogen or cyano. Preferably, R₈ is fluorine, bromine or chlorine, more preferably fluorine or chlorine. Particularly preferred are compounds wherein A is A₂ and wherein X and Y are oxygen. Even more preferred are wherein R₆ = tert-butyl, R₇ = methyl or ethyl and R₈ = hydrogen. Still even more preferred are compounds wherein Z is such that B forms a ring selected from the group consisting of aziridine, azetidine, substituted pyrrolidine, substituted piperidine wherein the aziridine and azetidine may be optionally substituted. More preferred are compounds wherein Z is such that B is an optionally substituted azetidine. Still more preferred is wherein Z is such that B is a substituted azetidine. More preferably the azetidine is halo, cyano, methoxy or methyl substituted, especially halo substituted, especially fluoro- or chloro- substituted. Still more preferred is wherein the substitution is in the 3-position of the azetidine ring.

The skilled person will appreciate that a number of the compounds referred to in this application can exist in different stereoisomeric forms and thus, for the avoidance of doubt, included in the present invention, where applicable, are individual stereoisomers as well as mixtures thereof. Whilst compounds of formula (I) may be provided in their free form - it is understood that they may also be provided as an agriculturally acceptable salt.

The present invention further relates to a herbicidal composition comprising a compound of the present invention and an agriculturally acceptable carrier or diluent. The composition may be provided in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS)₃ a water dispersible granule (WG), an emulsifϊable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants. The composition may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate inert formulation adjuvants (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners 5 and compounds that provide adjuvancy effects). Also conventional slow release formulations may be employed where long lasting efficacy is intended. Particularly formulations to be applied in spraying forms, such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW₅ EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g. the 10 condensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.

A seed dressing formulation is applied in a manner known per se to the seeds employing the 15 compositions according to the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules. 20

In general, the formulations include from 0.01 to 90% by weight of active ingredient, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active ingredient(s), and optionally other active agents, particularly microbiocides or conservatives or the like. Concentrated forms of compositions generally 25 contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations. - 10 -

The herbicidal composition of the present invention may further comprise at least one additional pesticidal compound (e.g an insecticide, a nematicide, a miticide or bactericide), a fungicide, a herbicide, or a plant growth regulator where appropriate. An additional active 5 ingredient may provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect) of the composition; or help to overcome or prevent the development of resistance to individual components. The particular additional active ingredient will depend upon the intended utility of the composition. Examples of suitable

10 pesticides include the following:

Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or 5-benzyl-3-furylmethyl-(E)-(lR,3S)-2,2-dimethyl-

15 3-(2-oxothiolan-3-ylidenemethyl) cyclopropane carboxylate; Organophosphates, such as, profenofos, sulprofos, acephate, methyl parathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phdxim, pirimiphos-methyl, pirimiphos-ethyl, fenitrothion,

20 fosthiazate or diazinon; Carbamates (including aryl carbamates), such as pirimicarb, triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur, methomyl or oxamyl; Benzoyl ureas, such as difmbenzuron, trifiumuron, hexaflumuroii, flufenoxuron or chlorfluazuron; Organic tin compounds, such as cyhexatin, fenbutatin oxide or azocyclotin; Pyrazoles, such as

25 tebufenpyrad and fenpyroximate; Macrolides, such as avermectins or milbemycins, for example abamectin, emamectin benzoate, ivermectin, milbemycin, spinosad or azadirachtin; Hormones or pheromones; Organochlorine compounds such as endosulfan, benzene hexachloride, DDT, chlordane or dieldrin; Amidines, such as chlordimeform or amitraz; Fumiganf agents, such as chloropicrin, dichloropropane, methyl bromide or metam; Diacylhydrazines, such as tebufenozide, chromafenozide or methoxyfenozide; Diphenyl ethers, such as diofenolan or pyriproxifen; Chlorfenapyr; Pymetrozine; Rynaxypyr or NNI- 001; neonicotinoids such as acetamiprid, clothianidin, dinotefuran, imidacloprid, thiacloprid or thiamethoxam; or indoxacarb. 5

The composition of the present invention may further comprise one or more fungicides, examples of which include: Azoles, such as azaconazole, BAY 14120, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole,

10 metconazole, myclobutanil, pefurazoate, penconazole, prothioconazole, pyrifenox, prochloraz, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, trifiumizole, triticonazole; Pyrimidinyl carbinoles, such as ancymidol, fenarimol, nuarimol; 2- amino-pyrimidines, such as bupirimate, dimethirimol, ethirimol; Morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph; Anilinopyrimidines, such

15 as cyprodinil, mepanipyrim, pyrimethanil; Pyrroles, such as fenpiclonil, fludioxonil; Phenylamides, such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl; Benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole; Dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozoline; Carboxamides, such as boscalid, carboxin, fenfuram, flutolanil, mepronil,

20 oxycarboxin, penthiopyrad, thifluzamide; guanidines, such as guazatine, dodine, iminoctadine; Strobilurines, such as azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, trifioxystrobin, orysastrobin, picoxystrobin, pyraclostrobin; Dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N-halomethylthiotetrahydrophthalimides, such as captafol, captan,

25 dichlofiuanid, fiuoromides, folpet, tolyfluanid; Cu-compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine- copper; Nitrophenol-derivatives, such as dinocap, nitrothal-isopropyl; Organo-p-derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl; and various others, such as acibenzolar-S-methyl, anilazine, benthiavalicarb, blasticidin-S, 12

chinomethionate, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, dichlone, diclocymet, diclomezine, dicloran, diethofencarb, dimethomorph, flumorph, dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, fentin, ferimzone, fluazinam, fluopicolide, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, iprovalicarb, cyazofamid, 5 kasugamycin, mandipropamid, methasulfocarb, metrafenone, nicobifen, pencycuron, phthalide, polyoxins, probenazole, propamocarb, proquinazid, pyroquilon, quinoxyfen, quintozene, sulfur, tiadinil, triazoxide, tricyclazole, triforine, validamycin, or zoxamide.

The composition of the present invention may further comprise one or more herbicides - for

10 example:- 2,3,6-TBA, 2,4-D, 2,4-DB, acetochlor, acifiuorfen-sodium, aclonifen, acrolein, alachlor, alloxydim, ametryn, amicarbazone, amidosulfuron, aminopyralid, aminotriazol, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, aviglycine, azafenidin, azimsulfuron, BAY FOE 5043, beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, benzfendizone, benzobicyclon,

15 benzofenap, bialaphos, bifenox, bispyribac-sodium, borax, bromacil, bromobutide, bromophenoxim, bromoxynil, butachlor, butafenacil, butamifos, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone-ethyl, chloransulam methyl, chlorbromuron, chlorflurenol-methyl, chloridazon, chlorimuron-ethyl, chloroacetic acid, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, cinidon-ethyl, cinmethylin, cinosulfuron,

20 clefoxydim profoxidim, clethodim, clodinafop-propargyl, clomazone, clomeprop, clopyralid, cloransulam, cloransulam-methyl, cumuluron, cumyluron, cyanamide, cyanazine, cyclam^'lide, cycloate, cyclosulfamuron, cycloxydim, cyhalofop, cyhalofop-butyl, cyprosulfamide, daimuron, dalapon, dazomet, desmedipham, ,desmetryn, dicamba, dichlobenil, dichlorprop, dichlorprop-P, diclofop-methyl, diclosulam, difenzoquat metilsulfate, diflufenican,

25 diflufenzopyr, dimefurori, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin, dimethylarsinic acid, dinitramine, dinoterb, diphenamid, dipropetiyn, diquat , ibromide, dithiopyr, diuron, DNOC, DSMA, ,endothal , EPTC₅ esprocarb, ethalfluralin, etliametsulfuron-methyl, ethephon, ethofαmesate,ethoxyfen-ethyl, ethoxysulfuron, etobenzanid, fenclorim, fenoxaprop-P-ethyl, fentrazamide, ferrous sulfate, flamprop, flamprop-M, flazasulfuron, florasulam, ftuazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone sodium, flucetosulfuron, flucliloralin, flufenacet, flufenpyr- thyl, flumetralin, flumetsulam, flumiclorac-pentyl, flumioxazin, flumipropin, fluometuron, fluoroglycofen-ethyl, fluoxaprop, flupoxam, flupropacil, flupropanate, flupyrsulfuron-methyl- 5 sodium, flurenol, fluridone, flurochloridone, fluroxypyr, ,flurtamone, fluthiacet-metliyl, ,flιιxofenim ,fomesafen foramsulfuron, fosamine, glufosinate-ammonium, glyphosate, halosulfuron-methyl, haloxyfop, lialoxyfop-P, HC-252, hexazinone, imazamethabenz-methyl, ,imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, ,indanofan, iodosulforon, iodosulfuron-methyl-sodium, ioxynil, isopropazol, isoproturon, isouron,

10 isoxaben, isoxachlortole, isoxadifen, isoxaflutole, Isoxapyrifop, karbutylate, ,K1H-485 ,lactofen ,lenacil linuron, MCPA, MCPA-tbioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, mefenpyr diethyl, mefluidide, mesosulfuron methyl, mesotrione, metam, metamifop (mefluoxafop), metamitron, metazachlor, methabenzthiazuron, methazole, methyl isothiocyanate, methylarsonic acid, methyldymron, metobenzuron ,metobromuron

15 ,metolachlor metosulam, metoxuron, metribuzin, metsulfuron-methyl, MK-616 ,molinate ,monolinuron , MSMA, naproanilide ,napropamide ,naptalam , NDA-402989, neburon, nefenacet, nicosulfuron, nipyraclofen, n-methyl-glyphosate, nonanoic acid, norflurazon, oleic acid (fatty acids), orbencarb, orthosulfamuron, oryzalin, oxaciclomefone, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, pebulate, pendimethalin, penoxsulam,

20 pentachlorophenol, pentanochlor, pentoxazone, pethoxamid, petrolium oils, phenmedipham, phenoxaprop-P-ethyl (R), picloram, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron-methyl, procarbazone, prodiamine, profluazol, profoxydim, prohexcadion calcium, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyzamide,

25 prosulfocarb, prosulfuron, pyraclonil pyrazogyl, pyraflufen-ethyl, pyrasulfotole, pyrazolynate, pyrazosulfuron-ethyl, pyi-azoxyfen, pyribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac-sodium, quinclorac, quinmerac, quinoclamine, quizalofop, qυizalofop-P, rimsulfuron, sequestren, sethoxydim, siduron, simazine, simetryn, S-metolachlor, sodium chlorate, sulcotrione, sulfentrazone, sulfometuron-methyl, sulfosate, sulfosulfuron, sulfuric acid, tar oils, TCA-sodium, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbumeton, terbuthylazine, terbutryn, thenylchlor, thiazafluron, thiazimin, thiazopyr, thiencarbazone, thifensulfuron-methyl (thiameturon- methyl), thiobencarb, tiocarbazil, Topramezone, tralkoxydim, tri-allate, triasulfuron, 5 triaziflam, tribenuron-methyl, triclopyr, trietazine, triflosulam, trifloxysulfuron, trifloxysulfuron-sodium, trifluralin, triflusulfuron-methyl, trinexapac-ethyl, tritosulfuron.

The composition of the present invention comprising a compound of the present invention or and compound of the present invention + one or more co-herbicides may also further comprise 10 one or more safeners. Safeners are suitable for the protection of useful plants against the phytotoxic action of the compounds or the present invention or other co-herbicides contained in the composition of the present invention. Examples of suitable safeners include those of formulae S-I to S-X below.

15 A compound of formula S-I:

wherein 20 Xs [ is hydrogen or halogen and

Rs₁ is hydrogen, C₃-C₈alkenyl, C₃-C₈alkynyl, QrCgcycloalkyl, Q-Csalkyl, or Q-Csalkoxy- or

CrCsallcenyloxy-substituted C₁-C₈allcyl, or

Rs₁ is a cation selected from the group of the alkali and alkaline earth metals, iron, copper, ahmiinium, ammonium, quaternary ammonium, sulfonium and phosphonium, such cations 25 being described e.g. in WO 02/034048; - 15 -

a compound of formula S-II:

wherein E₁ is nitrogen or methine, the substituents Xs₁ are each independently of the other hydrogen or halogen, and Rs₁ is hydrogen, C₃-C₈alkenyl, Cs-Cgalkynyl, CrCscycloalkyl, C₁-Cgalkyl, or C_t-Cgalkoxy- or Cs-Csalkenyloxy-substituted d-Cgalkyl, OrRs₁ is a cation selected from the group of the alkali and alkaline earth metals, iron, copper, aluminium, ammonium, quaternary ammonium, sulfonium and phosphonium:

a compound of formula S-III:

10

wherein the substituents Xs₁ are each independently of the other hydrogen or halogen, and the substituents Rs₁ are each independently of the other hydrogen, Q-Csalkenyl, Cs-Csalkynyl, C₃-C₈cycloalkyl, C₁-Cgalkyl, or Cj-Csalkoxy- or Cs-Csalkenyloxy-substituted d-Csalkyl, or the substituents Rs₁ are a cation selected from the group of the alkali and alkaline earth 15 metals, iron, copper, aluminium, ammonium, quaternary ammonium, sulfonium and phosphonium;

a compound of formula S-IV:

16

wherein Rsi is hydrogen, C₃-Csalkenyl, C3-C₈alkynyl, C₃-C₈cycloalkyl, Q-Csalkyl, or Q-Qalkoxy- or C₃-C₈alkenyloxy-substituted C₁-Cgalkyl, or Rsi is a cation selected from the group of the alkali and alkaline earth metals, iron, copper, aluminium, ammonium, quaternary ammonium, sulfonium and phosphonium;

a compound of formula S-V

wherein Rs₂ and Rs₃ are each independently of the other Q-Csalkyl, C2-C₈alkenyl or C₃-C₈- cycloalkyl, or Rs₂ and Rs₃ together form a radical of formula

10 wherein Rs₄ and Rs₅ are each independently of the other hydrogen or d-Csalkyl, or Rs₂ and

Rs₃ together form a radical of formula , wherein Rs₇ and Rs₈ are each

independently of the other Q-Cβalkyl, or Rs₇ and Rs₈ together form -(CH₂)_S-, and Rs₆ is hydrogen, C₁-C₆alkyl, aryl or heteroaryl;

15 a compound of formula S-VI:

wherein Rs9 is hydrogen or halogen and Rsio is cyano or trifluoromethyl;

20 a compound of formula S-VII:

O wherein Rs₁₁ is hydrogen or methyl;

a compound of formula S-VIII:

wherein sn is 0 or 1,

Rsi2 is hydrogen, C₁-C₈alkyl, C₃-C₈cycloalkyl, C₃-C₈alkenyl, C₃-C₈alkynyl or-N(~Rs₁₃ - Rs₁₄), wherein Rs₁₃ and Rs₁₄ are each independently of the other hydrogen, Cn-Cgalkyl, C₃-C₈cycloalkyl, C₃-Csalkenyl or C₃-Csalkynyl, or Rsj₃ and Rs₁₄ together form a C₄-

10 Cβalkylene group which may be interrupted by oxygen, sulfur, SO, SO₂, NH or by N(C₁- C₄alkyl);

Rs]5 is hydrogen or a cation selected from the group of the alkali and alkaline earth metals, iron, copper, aluminium, ammonium, quaternary ammonium, sulfonium and phosphonium, Rs₁₆ is hydrogen, halogen, Q-Csalkyl or methoxy and

15 Rs₁₇ is hydrogen, halogen, Cj-Csalkyl, trifluoromethyl or Q-Csalkoxy;

a compound of formula S-IX:

.0 a compound of formula S-X: 18

wherein Rs₁₈ is benzyl, hydrogen, QrCsalkenyl, Cs-Csalkynyl, C₃-C₈cycloalkyl, Q-Csalkyl, or C₁-C₈alkoxy- or C₁-Csalkenyloxy-substituted C₁-Cβalkyl, or Rsi₈ is a cation selected from the group of the alkali and alkaline earth metals, iron, copper, aluminium, ammonium, 5 quaternary ammonium, sulfonium and phosphonium.

The safeners of formulae S-I to S-X are known and are described e.g. in US-A-5,041,157, US- A-5,541,148, US-A-5,006,656, EP-A-O 094 349, EP-A-O 551 650, EP-A-O 268 554, EP-A-O 375 061, EP-A-O 174 562, EP-A-492 366, WO 91/7874, WO 94/987, DE-A-196 12 943, WO 10 96/29870, WO 98/13361, WO 98/39297, WO 98/27049, EP-A-O 716073, EP-A-O 613 618, US-A-5,597,776, EP-A-O 430 004, WO 97/45016, WO 99/16744 and WO 03/02205.

Preferred safeners are cloquintocet-mexyl or sulfonium and phosphonium salts thereof, fenchlorazole-ethyl, mefenpyr-diethyl, isoxadifen-ethyl, furilazole, benoxacor, dichlormid, 15 oxabetrinil, cyometrinil, fenclorim, N-cyclopropyl-4-(2-methoxy-benzoylsulfamoyl)- benzamide, N-isoproρyl-4-(2-methoxy-benzoylsulfamoyl)-benzamide, naphthalic anhydride and flurazole.

The present invention further provides a method of manufacture of a compound of formula 20 (I). Compounds of formula (Ia) (Formula (I) wherein X is O) can be prepared by coupling together the appropriately substituted azole acid chloride of Formula (H) with the appropriately substituted amino compound of Formula (JS) as shown in Scheme 1.

Scheme 1

The reaction is carried out in a convenient solvent such as diethyl ether, TBME, THF, dichloromethane, chloroform, DMF or NMP, preferably in the presence of a base such as triethylamine, pyridine, 4-dimethylaminopyridine (DMAP) or N,N-diisopropylethylamine (Hunig base), at a temperature typically between room temperature and 100°C to provide the amide of Formula (Ia).

Alternatively, compounds of Formula (Ia) can be prepared by coupling together the appropriately substituted azole carboxylic acid of Formula (IV) with an appropriately substituted amino compound of Formula (ET) as shown in Scheme 2.

Scheme 2

The reaction is carried out in the presence of a dehydrating coupling reagent such as N₅N'- 5 dicyclohexylcarbodiimide (DCC), N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC), (benzotiϊazol- 1 -yloxy)tris(dimethylamino)-phosphoniumhexafluoiOphosphate (BOP), bis(2- oxo~3-oxazolidinyl)phosphonic chloride (BOP-Cl), propylphosphonic anhydride (PPA), 1,1 '- - 20 -

Garbonyldiimidazole (CDI) in the presence of a base such as triethylamine, pyridine, 4- dimethylaminopyridine (DMAP) or N,N-diisopropyiethylamine (Hunig base) in a convenient solvent such as diethyl ether, TBME, THF, dichloromethane, chloroform, DMF or NMP at a temperature typically between room temperature and 100°C. 5

As a further alternative method, an ester derived from a carboxylic acid of Formula (W) can be condensed with a substituted amine of Formula (Et) to provide the compound of Formula (Ia) by heating in a high boiling solvent such as toluene, xylene or α,α,α-trifluorotoluene.

10 Compounds of Formula (Ib) (Formula I wherein X is S) can be prepared from the corresponding compounds of Formula (Ia) by treatment with a thionating reagent such as P₂S₅ (see for example E. C. Taylor et al., J. Amer. Chem. Soc. 1953, 75 1904) or Lawesson's Reagent (2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulphide; see for example M. P. Cava and M. I. Levinson, Tetrahedron, 1985, 41, 5061) as shown in Scheme 3.

15

Compounds of Formula (Ia) or (Ib) wherein R₅ is alkyl, cycloalkyl, alkenyl or alkynyl can be prepared from the corresponding compounds of Formula (Ia) or (Ib) wherein R₅ is H by treatment with the appropriate alkylating agent in the presence of a convenient base using 20 methods well known in the art. The acid chlorides of Formula (II) can be prepared from the corresponding carboxylic acids of Formula (IV) by using methods well known in the art such as treatment with oxalyl chloride and catalytic DMF in dichloromethane or treatment with thionyl chloride.

In an alternative approach, Compounds of Formula (Ic) (Formula (I) wherein Y is O) can be prepared by coupling together the appropriately substituted acid chloride of Formula (V) with the appropriately substituted amino compound of Formula (VI) as shown in Scheme 4.

0

The reaction is carried out in a convenient solvent such as diethyl ether, TBME, THF₅ dichloromethane, chloroform, DMF or NMP, preferably in the presence of a base such as triethylamine, pyridine, 4-dimethylaminopyridine (DMAP) or N,N-diisopropylethylamine (Hunig base), at a temperature typically between room temperature and 100°C to provide the

5 amide of Formula (Ic).

Alternatively, compounds of Formula (Ic) can be prepared by coupling together the appropriately substituted carboxylic acid of Formula (VII) with an appropriately substituted amino compound of Formula (VI) as shown in Scheme 5. 0

Scheme 5

The reaction is carried out in the presence of a dehydrating coupling reagent such as N,N'- dicyclqhexylcarbodiimide (DCC), N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC), (benzotriazol- 1 -yloxy)tris(dimethylamino)-phosphoniumhexafluorophosphate (BOP), bis(2- oxo-3-oxazolidinyl)phosphonic chloride (BOP-Cl), propylphosphonic anhydride (PPA), 1,1'- carbonyldiimidazole (CDI) in the presence of a base such as triethylamine, pyridine, 4- dimethylaminopyridine (DMAP) or N,N-diisoρropylethylaraine (Hunig base) in a convenient solvent such as diethyl ether, TBME, THF, dichloromethane, chloroform, DMF or NMP at a

10 temperature typically between room temperature and 10O°C.

As a further alternative method, an ester derived from a carboxylic acid of Formula (VH) can be condensed with a substituted amine of Formula (VI) to provide the compound of Formula (Ic) by heating in a high boiling solvent such as toluene, xylene or α,α,α-trifluorotoluene.

15

Compounds of Formula (Id) (Formula I wherein Y is S) can be prepared from the corresponding compounds of Formula (Ic) by treatment with a thionating reagent such as P₂S₅ (see for example E. C. Taylor et al, J. Amer. Chem. Soc. 1953, 75 1904) or Lawesson's Reagent (2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulphide; see for 20 example M. P. Cava and M. I. Levinson, Tetrahedron, 1985, 41, 5061) as shown in Scheme 6.

( )

The acid chlorides of Formula (V) can be prepared from the corresponding carboxylic acids of Formula (VII) by using methods well known in the art such as treatment with oxalyl chloride 5 and catalytic DMF in dichloromethane or treatment with thionyl chloride.

In an alternative approach compounds of Formula (Ia) can be prepared by coupling together the appropriately substituted azole carboxamide of Formula (V1H) with an appropriately substituted halogenated compound of Formula (IX) as shown in Scheme 7, where L is a 10 halogen such as fluorine, chlorine or bromine.

Scheme 7

The reaction is carried out in the presence of a suitable palladium catalyst such as palladium 15 acetate and suitable phosphine ligand such as the Josiphos ligand in a convenient solvent such as DME with a convenient base such as sodium t-butoxide at a temperature typically between room temperature and 100°C (see for example J. F. Hartwig et al. Angew., Chern. Int. Ed. 2005, 44, 1371). Compounάs of Formula (Ic) can also be prepared by the aminocarbonylation reaction of the appropriately substituted azole carboxamide of Formula (X) with the amino compound of Formula (VI) as shown in Scheme 8, where L is a halogen such as fluorine, chlorine, bromine 5 or iodine.

Ro R,

Λ

I ^p R

7 aminocarbonylation X ^* P^ ^S i~ η g ^■

L HN ^{B *};AA^X

-^N

X VI (1°)

Scheme 8

The reaction is carried out in the presence of a suitable palladium catalyst such as palladium 10 acetate and suitable solid carbon monoxide source such as molybdenum hexacarbonyl in a convenient solvent such as THF with a convenient base such as DBU at a temperature typically between room temperature and 100°C (see for example J. Wannberg and M. Larhed, J. Org. Chem., 2003, 68, 5750).

15 The azole carboxylic acids of Formula (IV) can be prepared from the corresponding esters of Formula (XI), where R_i6 is a carbon-based radical such as alkyl (methyl, ethyl) or benzyl as shown in Scheme 9.

O Ester cleavage O

A^O'^Ri6 ^ A^OH

Xl

Scheme 9 rv 20 The ester cleavage conditions are well known in the art.

The heterocyclic carboxylic esters of Formula (XI), where the heterocyclic rings have the values A₁-A₁₂, can be prepared by a variety of methods well known in the art (for example in 5 WO04/106324).

The azole carboxamide of Formula (VIII) can be prepared by reacting the azole acid chloride of Formula (II) or the azole carboxylic ester of Formula (XI) with an amine of Formula (XII) as shown in Scheme 10.

IO Scheme 10

The reaction is carried out in the presence of a base such as triethylamine, pyridine, 4- dimethylaminopyridine (DMAP) or N,N-diisoproρylethylamine (Hunig base) in a convenient solvent such as diethyl ether, TBME, THF, dichloromethane, chloroform, DMF or NMP at a 15 temperature typically between room temperature and 100°C.

The substituted amino compound of Formula Id can be prepared by coupling together the appropriately substituted amino carboxylic acid of Formula (X1H) with the amino compound of general Formula (VI) as shown in Scheme 11. !0 <y -Q^^c

HN^T^V^01-1

+ vi ^ πⁱ

K O

XIII Scheme 11

The reaction is carried out in the presence of a dehydrating coupling reagent such as N,N'- dicyclohexylcarbodϋmide (DCC)₅ N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC), 5 (benzotriazol-1-yloxy)tris(dimethylamino)-phosphoniumhexafluorophosphate (BOP), bis(2- oxo-3-oxazolidinyl)phosphonic chloride (BOP-Cl), propylphosphonic anhydride (PPA), 1,1'- carbonyldiimidazole (CDI) in the presence of a base such as triethylamine, pyridine, 4- dimethylaminopyridine (DMAP) or N,N-diisopropylethylamine (Hunig base) in a convenient solvent such as diethyl ether, TBME, THF, dichloromethane, chloroform, DMF or NMP at a 10 temperature typically between room temperature and 100°C.

Alternatively, compounds of Formula (HT) can be prepared by coupling together the appropriately substituted amino carboxylic acid chloride of Formula (XIV) with the amino compound of Formula (VT) as shown in Scheme 12. 15

vi *- in

27

The acid chlorides of Formula (XIV) can be prepared from the corresponding carboxylic acids of Formula (XVS) by using methods well known in the art such as treatment with oxalyl chloride and catalytic DMF in dichloromethane or treatment with thionyl chloride. The amino carboxylic acid of Formula (XIII) can be prepared by a variety methods well known in the art. For example the amino compound of Formula (XIII) can be prepared by reduction of the corresponding nitro compound of Formula (XV) as shown in Scheme 13. p^^S Reduction

OH *^{* Xffl}

O₂N- T

Q

XV

Scheme 13

The reduction is carried out using iron in hydrochloric acid, tin(II) chloride or hydrogenation 10 over a palladium or platinum catalyst

Alternatively, the amino carboxylic acid of Formula (XTS) can be prepared by oxidation of the corresponding amino methyl compound of Formula (XVI) as shown in Scheme 14.

J f 1 Oxidation L il XIII

^CH₃

XVI

15

Scheme 14

Compounds of Formula (VII) can be prepared by coupling together the amino carboxylic acid of Formula (VIII) with the azole acid chloride of Formula (II) as shown in Scheme 15. - 28 -

π VIII

Scheme 15 ^VH

The reaction is carried out in a convenient solvent such as diethyl ether, TBME, THF, dichloromethane, chloroform, DMF or NMP, preferably in the presence of a base such as 5 triethylamine, pyridine, 4-dimethylaminopyridme (DMAP) or N,N-diisoρroρylethylamine (Hunig base), at a temperature typically between room temperature and 10O°C to provide the amide of Formula (VII).

Alternatively, compounds of Formula (VII) can be prepared by coupling together the amino 10 carboxylic acid of Formula (X1H) with the azole carboxylic acid of Formula (IV) as shown in Scheme 16.

X P-S rv + X_IiI ^ _A A/>v._N^^_T^. -OH

RI O

Scheme 16 ^VI1

15 The reaction is carried out in the presence of a dehydrating coupling reagent such as N,N'- dicyclohexylcarbodiimide (DCC), N-(3-dimethylaminopropyl)-N'-ethylcarbodiinaide (EDC), (benzotriazol- 1 -yloxy)tris(dimethylamino)-phosphoniumhexafluorophosphate (BOP), bis(2- oxo-3-oxazolidinyl)phosphonic chloride (BOP-Cl), propylphosphonic anhydride (PPA), 1,1'- carbonyldiimidazole (CDI) in the presence of abase such as triethylamine, pyridine, A-

20 dimethylaminopyridine (DMAP) or N,N-diisopropyleth.ylamine (Hunig base) in a convenient solvent such as diethyl ether, TBME, THF, dichloromethane, chloroform, DMF or NMP at a temperature typically between room temperature and 100°C.

The acid chlorides of Formula (V) can be prepared from the corresponding carboxylic acids of 5 Formula (VII) by using methods well known in the art such as treatment with oxalyl chloride and catalytic DMF in dichloromethane or treatment with thionyl chloride.

The amino compounds of Formula (VI) can be prepared by a variety of methods well known in the art (see for example 'Heterocyclic Chemistry - Fourth Edition' J. A. Joule and K. Mills, 10 Blackwell Science, 2000). This normally involves the ring closure of an appropriately substituted amino compound of Formula (XVH) as shown in Scheme 17, where L is a leaving group such as chlorine, bromine or iodine.

R₂ R₂ ring closure

H₂N' ^K J HN J

*7 X X xvπ vi

Scheme 17 15

The reaction is carried out in the presence of a suitable base such as potassium t-butoxide or n-butyl lithium in a convenient solvent such as diethyl ether, TBME or THF (see for example K. Hayashi et al., Heterocycles, 2002, 56, 433).

.0 The present invention further provides a method of undesirable vegetation comprising applying a locus comprising the undesirable vegetation ail effective amount of a composition comprising a compound having the formula (I). It is understood that the locus may also comprise "desired vegetation" that is not substantially affected by the application of the composition to the locus. The present invention thus further provides a method of selectively controlling weeds at a locus comprising desired vegetation and undesirable vegetation, the method comprising applying to the locus a' weed controlling amount of a compound or composition of the present invention. "Undesirable vegetation" includes weed species, or, for 5 example, carry-over or "rogue" or "volunteer" crop plants in a field of crop plants. The compounds of the present invention show good efficacy toward dicot weed species, especially Amaranthus species and methods to control one of more dicot weed species is particularly preferred. The compounds of the present invention may be applied pre-or post emergence of the crop plants or of the unwanted plant species. Examples of "desired vegetation" are crop

10 plants examples of which include grape vines; cereals, such as wheat, barley, rye or oats; beet, such as sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts; cucumber

15 plants, such as marrows, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceae, such as avocados, cinnamon or camphor; maize; tobacco; nuts; coffee; sugar cane; tea; vines; hops; durian; bananas; natural rubber plants; turf or ornamentals, such as flowers,

.0 shrubs, broad-leaved trees or evergreens, for example conifers. This list does not, however, represent any limitation. For the avoidance of doubt the term "desired vegetation" also includes transgenic plants - including those which have been engineered to be tolerant and/or resistant to the compound(s) contained in the composition.

!5 The present invention further relates to the use of a compound having the formula (I) as a herbicide.

The following non-limiting Examples illustrate the above-described invention in greater detail. Example Pl: Preparation of 2-[[[3-(l,l-dimethylethyl)-1-ethyl-1H-pyrazoI-S- yl] carb ony 1] amino]-4-pyridylcarb onyl-(4-flu oropiperidin e)

Step A: Preparation of 2-[[[3-(l,l-dimethylethyl)-1-ethyl-1H-pyrazol-5-yl]carbonyl]amino]-4-

5 pyridinecarboxylic acid

To a solution of S-^l-dimethylemyty-1-ethyl-1H-pyrazol-S-cafboxylic acid (35 g, 178 mmol) in DCM (300 ml) were added oxalyl chloride (45 g, 356 mmol) and DMF (10 drops). The solution was stirred for 1.5 h and the solvent and excess oxalyl chloride removed under reduced pressure.

0 The resulting residue was taken up in DCM (100 ml) and added to a well stirred mixture of methyl 2-amino-4-pyridinecarboxylate (13.6 g, 89 mmol), triethylamine (35 g, 350 mmol) and DMAP (0.6 g) in DCM (300 ml) and then stirred overnight at 2O°C. The reaction mixture was poured into water (300 ml), extracted with DCM (2 x 200 ml) and the extracts dried over anhydrous magnesium sulphate. Removal of the solvent gave the residue as a gum.

5 The gum was taken up in a mixture of sodium hydroxide (19.5 g) and methanol (300 ml) and the mixture stirred for 3 h at 2O°C. The solvent was removed and the residue partitioned between water (300 ml) and ethyl acetate. The aqueous phase was neutralised with c. HCl, the precipitate extracted into ethyl acetate, dried over anhydrous magnesium sulphate. Removal of the solvent gave a crude residue which was washed with DCM (100 ml) for 10 min at 2O°C

10 and filtered to give the title acid as a white solid (21.0 g).

¹H NMR (DMSO-J₆) δ 1.22 (s, 9H), 1.28 (t, 3H), 4.41 (q, 2H), 7.20 (s, 1H), 7.53 (dd, 1H),

8.49 (dd, 1H), 8.58 (d, 1H), 10.85 (bs, 1H) ppm.

Step B: Preparation of 2-[[[3-(l,l-dimethylethyl)-1-ethyl-1H-pyrazol-5-yl]carbonyl]amino]-4- ρyridylcarbonyl-(4-fluoroρiperidine)

5 A mixture of 2-[[[3-(l,l-dimethylethyl)-1-ethyl-1H-pyrazol-5-yl]carbonyl]amino]-4- pyridinecarboxylic acid (200 mg, 0.63 mmol), 4-fluoropiperidine hydrochloride (88 mg, 0.63 mmol), propylphosphonic anhydride (620 mg, 0.94 mmol, 50% solution in EtOAc), triethylamine (63 mg, 0.63 mmol), DMAP (77 mg, 0.63 mmol) in DCM (8 ml) were stirred at 2O°C for 3 h. The reaction was poured into water, extracted with DCM, dried over anhydrous magnesium sulphate. Removal of the solvent gave a crude product that was purified by column chromatography (silica eluted with EtOAc : DCM = 1 :2) to give the title compound as a solid (180 mg), mp l72°C.

¹H NMR (CDCl₃) δ 1.33 (s, 9H), 1.46 (t, 3H), 1.78-2.07 (m, 4H), 3.38-3.66 (m, 3H), 4.11 (m, 1H), 4.58 (q, 2H), 4.86-5.02 (m, 1H), 6.58 (s, 1H), 7.08 (dd, 1H), 8.33 (d, 1H), 8.37 (dd, 1H), 8.54 (bs, 1H) ppm.

Example P2: Preparation of 2-[[[3-(l,l-dimethylethyl)-1-ethyI-1H-pyrazol-5- yl]carbonyl]amino]-4-pyridylcarbonyl-(3-methoxyazetidine) A mixture of 2-[[[3-(l,l-dimethylethyl)-1-ethyl-1H-pyrazol-5-yl]carbonyl]amino]-4- pyridinecarboxylic acid (140 mg, 0.44 mrnol) (see Step A of Example Pl), 3- methoxyazetidine hydrochloride (54 mg, 0.44 mmol), propylphosphonic anhydride (430 mg, 0.66 mmol, 50% solution in EtOAc), triethylamine (44 mg, 0.44 mmol), DMAP (54 mg, 0.44 mmol) in DCM (8 ml) were stirred at 2O°C for 3 h. The reaction was poured into water, extracted with DCM, dried over anhydrous magnesium sulphate. Removal of the solvent gave a crude product that was purified by column chromatography (silica eluted with EtOAc : DCM = 1:1) to give the title compound as a solid (110 mg), mp 132°C. 1H NMR (CDCl₃) δ 1.33 (s, 9H), 1.47 (t, 3H), 3.33 (s, 3H), 4.11 (m, 1H), 4.23 (m, 1H), 4.29 (m, 1H), 4.38 (m, 1H), 4.49 (m, 1H), 4.58 (q, 2H), 6.57 (s, 1H), 7.33 (dd, 1H), 8.38 (dd, 1H), 8.44 (d, 1H), 8.52 (bs, 1H) ppm.

Example P3: Preparation of 2-[[[3-(l,l-dimethylethyl)-1-ethyl-1H-pyrazol-5- yljcarbonyl] amino] -4-pyridylcarbonyl-(3,3-difluoroazetidine)

A mixture of 2-[[[3-(l,l-dimethylethyl)-1-ethyl-1H-pyrazol-5-yl]carbonyl]amino]-4- pyridinecarboxylic acid (140 mg, 0.44 mmol) (see Step A of Example Pl), 3,3- difluoroazetidine hydrochloride (57 mg, 0.44 mmol), propylphosphonic anhydride (430 mg, 0.67 mmol, 50% solution in EtOAc), triethylamine (44 mg, 0.44 mmol), DMAP (53 mg, 0.44 mmol) in DCM (10 ml) were stirred at 20°C for 3 h. The reaction was poured into water, 33

extracted with ethyl acetate, dried over anhydrous magnesium sulphate. Removal of the solvent gave the title compound as a white crystalline solid (160 mg), mp 140-141°C. 1H NMR (CDCl₃) δ 1.32 (s, 9H), 1.48 (t, 3H), 4.50-4.72 (m, 6H), 6.60 (s, 1H), 7.38 (dd, 1H), 8.43 (m, 1H), 8.46 (m, 1H), 8.55 (bs, 1H) ppm.

5

Example P4: Preparation of 2-[[[3-(l,l-dimethylethyI)-4-fluoro-1-ethyl-1H-pyrazol-5- yI]carbonyl]amino]-4-pyridylcarbonyl-(3,3-difluoroazetidme)

A mixture of 2-[[[3-(l,l-dimethylethyl)-1-©thyl-1H-pyrazol-5-yl]carbonyl]amino]-4- pyridylcarbonyl-(3,3-difluoroazetidine) (600 mg, 1.53 mmol) (see Example P3), Selectfluor™

10 (1.2g, 3.38 mmol) in acetonitrile (15 ml) were heated under reflux for 5 h. The reaction was cooled to room temperature, poured into water, extracted with DCM and dried over anhydrous magnesium sulphate. Removal of the solvent gave a crude product that was purified by column chromatography (silica eluted with EtOAc : hexane = 1:2) to give the title compound as a white solid (172 mg), mp 96-97°C.

15 ¹H NMR (CDCl₃) δ 1.36 (s, 9H), 1.43 (t, 3H), 4.55 (q, 2H), 4.55-4.66 (m, 4H), 7.35 (dd, 1H), 8.45 (m, 2H), 8.68 (d, 1H), 8.54 ppm.

Example P5: Preparation of 2-[[[3-(l,l-dimethylethyl)-1-ethyl-1H-pyrazol-5- yl]carbonyl]amino]-6-pyridylcarbonyl-(3-chIoroazetidine)

20 Step A: Preparation of 2-[[[3-(l,l-dimethylethyl)-1-ethyl-1H-pyrazol-5-yl]carbonyl]amino]-6- pyridinecarboxylic acid

To a solution of 3-(l,l-dimethylethyl)-1-ethyl-1H-pyrazol-5-carboxylic acid (10 g, 51 mmol) in DCM (100 ml) were added oxalyl chloride (13 g, 102 mmol) and DMF (10 drops). The solution was stirred for 1.5 h and the solvent and excess oxalyl chloride removed under

25 reduced pressure.

The resulting residue was taken up in DCM (25 ml) and added to a well stirred mixture of methyl 2-amino-6-pyridinecarboxylate (3.88 g₅ 26 mmol), triethylamine (14.2ml, 102 mmol) and DMAP (0.15g) in DCM (125 ml) and then stirred overnight at 2O°C. The reaction mixture was poured into water (100 ml), extracted with DCM (2 x 70 ml) and the extracts dried over anhydrous magnesium sulphate. Removal of the solvent gave the residue as a gum. The gum was taken up in a mixture of sodium hydroxide (5.5 g) and methanol (75 ml) and the mixture stirred for 3 h at 2O°C. The solvent was removed and the residue partitioned between 5 water (300 ml) and ethyl acetate. The aqueous phase was neutralised with c. HCl, the precipitate extracted into DCM, dried over anhydrous magnesium sulphate. Removal of the solvent gave a crude residue which was washed with DCM (30 ml) for 10 min at 2O°C and filtered to give the title acid as a white solid (1.9 g). 1H NMR (NaOD + D₂O) δ 1.00 (s, 9H), 1.10 (t, 3H), 4.12 (m, 2H), 6.17 (s, 1H), 6.87 (d, 1H),

10 7.27 (d, 1H), 7.50 (t, 1H), ppm.

Step B: Preparation of 2-[[[3-(l,l-dimethylethyl)-1-ethyl-1H-pyrazol-5-yl]carbonyl]amino]-6- pyridylcarbonyl-(3-chloroazetidine)

A mixture of 2-[[[3-(l,l-dimethylethyl)-1-ethyl-1H-ρyi-azol-5-yl]carbonyl]amino]-6- pyridinecarboxylic acid (280 mg, 0.88 mmol), 3-chloroazetidine hydrochloride (112 mg, 0.88

15 mmol), propylphosphonic anhydride (860 mg, 1.34 mmol, 50% solution in EtOAc), triethylamine (0.12ml, 0.88 mmol), DMAP (106 mg, 0.88 mmol) in DCM (20 ml) were stirred at 2O°C for 3 h. The reaction was poured into water, extracted with DCM, dried over anhydrous magnesium sulphate. Removal of the solvent gave the title compound as a white crystalline solid (280 mg), mp 205-206°C.

20 ¹H NMR (CDCl₃) δ 1.35 (s, 9H), 1.47 (t, 3H), 4.60 (q, 2H), 4.30-5.20 (m, 5H), 6.52 (s, 1H), 7.82-7.90 (m, 2H), 8.15 (bs, 1H), 8.40 (m, 1H) ppm.

Example P6: Preparation of 2-[[[3-(l,l-dimethyIethyI)-1-ethyl-1H-pyrazol-5- yl]carbonyl]ammo]-4-pyrimidylcarbonyl-(3,3-difluoroazetidine)

25 Step A: Preparation of 2-[[[3-(l,l-dimethylethyl)-1-ethyl-1H-pyrazol-5-yl]carbonyl]ammo]-4- pyrimidinecarboxylic acid

To a solution of 3-(l,l-dimethylethyl)-1-ethyl-1H-pyrazol-5-carboxylic acid (12.8 g, 65mmol) in DCM (100 ml) were added oxalyl chloride (16 g, 131 mmol) and DMF (3 drops). 35

The solution was stirred for 1.5 h and the solvent and excess oxalyl chloride removed under reduced pressure.

The resulting residue was taken up in DCM (25 ml) and added to a well stirred mixture of methyl 2-amino-4-pyrimidinecarboxylate (5.0 g, 33 mmol), triethylamine (18.2 ml, 131 5 mmol) and DMAP (0.2g) in DCM (125 ml) and then stirred overnight at 2O°C and heated under reflux for 2 h. The reaction mixture was cooled to room temperature, poured into water (100 ml), extracted with DCM (2 x 70 ml) and the extracts dried over anhydrous magnesium sulphate. Removal of the solvent gave the residue as a gum. The gum was taken up in a mixture of sodium hydroxide (7.0 g) and methanol (75 ml) and the

10 mixture stirred for 3 h at 2O°C. The solvent was removed and the residue partitioned between water (300 ml) and ethyl acetate. The aqueous phase was neutralised with c. HCl, the precipitate extracted into DCM, dried over anhydrous magnesium sulphate. Removal of the solvent gave a crude residue which was washed with DCM (30 ml) for 10 min at 20°C and filtered to give the title acid as a white solid (0.7g). This was used in the next step without

15 further purification .

Step B: Preparation of 2-[[[3-(l,l-dimethylethyl)-1-ethyl-1H-pyrazol-5-yl]carbonyl]amino]-4- pyrimidylcarbonyl-(3,3-difluoroazetidine).

A mixture of 2-[[[3-(l,l-dimethylethyl)-1-ethyl-1H-ρyrazol-5-yl]carbonyl]amino]-4- pyrimidinecarboxylic acid (220 mg, 0.69 mmol), 3,3-difluoroazetidine hydrochloride (89 mg,

20 0.69 mmol), propylphosphonic anhydride (670 mg, 1.05 mmol, 50% solution in EtOAc), triethylamine (0.1ml, 0.69 mmol), DMAP (84 mg, 0.69 mmol) in DCM (20 ml) were stirred at 2O°C for 3 h. The reaction was poured into water, extracted with DCM, dried over anhydrous magnesium sulphate. Removal of the solvent gave the title compound as a white crystalline solid (140 mg), mρ 215-218°C. ^'

25 ¹H NMR (CDCl₃) δ 1.32 (s, 9H), 1.37 (t, 3H), 4.50-4.65 (m, 4H), 5.27 (m, 2H) 6.57 (s, 1H)₅ 7.80 (d, 1H), 8.50 (bs, 1H), 8.80 (d, 1H) ppm.

EXAMPLES OF PREFERRED COMPOUNDS The following tables provide examples of preferred compounds of the present invention.

TABLE Cl

24^' CF₂H C₂H₅ N CH CH CH CHOH

1

R₆ R₇ Q

TABLE C2

H H

)

N r I i / ft O

311 t-Bu C₂H₅ N CH CH CH CHOH 312 i-Pr C₂H₅ N CH CH CH CHOH

R₆ R₇ S Z

502 i-Pr C₂H₅ N CH CH CH CH₂CF₂ 503 t-Bu C₂H₅ N CH CH CH CH₂CHOH 504 i-Pr C₂H₅ N CH CH CH CH₂CHOH

Rfi R₇

R₆ R₇

TABLE C3

R₆ R₇

1007 CF₂H C₂H₅ N CH CH CH CH₂CF₂ 1008 CF₃ C₂H₅ N CH CH CH CH₂CHOH 1009 CF₂H C₂H₅ N CH CH CH CH₂CHOH

1104 t-Bu C₂H₅ N CH N CH CH₂CHOH 1105 t-Bu C₂H₅ N CH N CH CH₂CHOH

1296 t-Bu C₂H₅ N CH N CH CH₂CHOH CH₂ 1297 t-Bu C₂H₅ N CH N CH CH₂CHOH CH₂

TABLE C4

R₁

1464 t-Bu C₂H₅ N CH CH CH CHOH 1465 i-Pr C₂H₅ N CH CH CH CHOH

R₆ R₇

Table C5

Table C6

Q H H

Table C7

H H

2017 C₂H₅ CH CH N CH CF₂

Table Ml - Melting point Information.

- 105 -

Biological Examples

Example Bl: Herbicidal action

Monocotyledonous and dicotyledonous test plants were sown in sterilised standard soil in seed trays each having 96 cells. After one day (pre-emergence) or after 8 to 9 days cultivation (post-emergence) under controlled conditions in a climatic chamber (cultivation at 23/17°C, day/night ; 13 hours light; 50-60% humidity); the plants were treated with an aqueous spray solution of 1000 mg/1 of the active ingredient used (incl. 10% DMSO as solvent). The plants were grown on in the climatic chamber (at 24/19°C, day/night; 13 hours lights; 50-60% humidity) until the test was evaluated (10 = total damage to plant, 0 = no damage to plant) after 9 or 13 days.

Table BIa: Application pre-emergence

Table BIb: Application post-emergence

Example B2: Herbicidal action

Seeds of a variety of test species were sown in standard soil in pots. After cultivation for one day (pre-emergence) or after 10 days cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in 0.6 ml acetone and 45 ml formulation solution containing 10.6% Emulsogen EL (Registry number 61791-12-6), 42.2% N-methyl pyrrolidone, 42.2% dipropylene glycol monomethyl ether (CAS RN 34590-94-8) and 0.2 % X-77 (CAS RN 11097-66-8). 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 14 days for post- emergence and 21 days for pre-emergence, the test was evaluated (10 = total damage to plant; 0 = no damage to plant).

Table B2a: Application pre-emergence (weed species^').

Compound A = Compound 245 disclosed in WO2004/106324

These results show that the compounds of the present invention exhibit improved weed control and improved crop safety.

Claims

- 108 -Claims

1. A compound having the formula

R₂ ) ^■i

A -%" ^{K )}

*i ^\ I l

Y (I)

wherein

X is oxygen or sulphur;

Y is oxygen or sulphur;

R₁, R₂, R₃, R₄, and R₅ are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, hydroxyl, C₁-C₆alkyl optionally substituted by one or more substituents R^a, C₃-C₆cycloalkyl optionally substituted by one or more substituents R^a, C₂-C₆alkenyl optionally substituted by one or more substituents R^a, C₂-C₆alkynyl optionally substituted by one or more substituents R^a, C₁-C₆alkoxy optionally substituted by one or more substituents R^a and C_1-6 alkythio optionally substituted by one or more substituents R^a; wherein each R^a is independently selected from the group consisting of halogen, cyano, nitro, C₁-C₆alkoxy, C₁-C₆ halogenalkoxy, C₃-C₆ cycloalkyl, C₁-C₆ alkylthio, C₁-C₆ halogenalkylthio or -C(R^b)=N(OR^c); wherein R^b is hydrogen or C₁-C₆alkyl; wherein R^c is C₁-C₆alkyl;

(A) is a 5-membered heterocyclic ring containing one to three heteroatoms, each independently selected from the group consisting of oxygen, nitrogen and sulphur; the heterocyclic ring being substituted by up to 3 substituents selected from the groups R₆, R₇ and R₈; wherein - 109 -

R₆, R₇, and R₈ are each, independently, selected from the group consisting of hydrogen, halogen, cyano, nitro, C_1-6alkyl, C_1-6 alkoxy, d-ehalogenalkyl, C_1-6halogenalkoxy, C_1-6 alkoxy(C_1-6)alkyl, C_1-6 alkythio(C_1-6)alkyl, C_2-6alkenyl, C_2-6haloalkenyl, C_2-6alkynyl, C_2-6haloalkynyl, C_3-6cycloalkyl, C_4-6alkylcycloalkyl, C_3-6halocycloalkyl, C_1-6halogenalkoxy(C_1-6)alkyl, C_1-6halogenalkylthio(C_1-6)alkyl and SiR₉R₁₀R₁₁ wherein R₉,R₁o and Rn are each independently selected from hydrogen and C_1-6 alkyl;

P is CR₁₂ or N; Q is CR₁₃ or N; S is CR₁₄ or N; T is CR₁₅ or N;

wherein R₁₂, R₁₃, R₁₄ and R₁₅ are independently selected from the group consisting of H, halogen, C₁-C₂ alkyl, C₁-C₂ fluoroalkyl, C₁-C₂ alkoxy, C₁-C₂ fluoroalkoxy, C₁-C₂ alkylthio and C₁-C₂ fluoroalkylthio;

Z is a bond or a chain of 1-5 carbon atoms and/or heteroatoms independently selected from the group consisting of oxygen, nitrogen and sulphur forming a ring (B), wherein (B) may contain one or more unsaturated bonds and may be optionally substituted by a group selected from the group consisting halogen, cyano, nitro, hydroxyl, OSO₂Me, carbonyl, oxime, amino optional substituted by C₁-C₆ alkyl or C₃-C₆ cycloalkyl, C₁- C₆alkyl optionally substituted by one or more substituents R^a, C₃-C6cycloalkyl optionally substituted by one or more substituents R^a, C₂-C₆alkenyl optionally substituted by one or more substituents R^a, C₂-C₆alkynyl optionally substituted by one or more substituents R^a, C]-C₆alkoxy optionally substituted by one or more substituents R^a and C_1-6 alkythio optionally substituted by one or more substituents R^a, aryloxy optionally substituted by one or more substituents R^a, aryl optionally substituted by one or more substituents R^a ₅ heteroaryl aryl optionally substituted by one or more substituents R^a> wherein each R^a is independently selected from the^* group consisting of 110

halogen, cyano, nitro, C₁-Cealkoxy, Q-Qhalogenalkoxy, Cs-Cβcycloalkyl, C_1-

C₆alkylthio, C₁-C₆halogenalkylthio or -C(R^b)=N(OR^c); wherein R^b is hydrogen or C₁-Cβalkyl; and wherein R^c is CrC₆alkyl; wherein B is not an unsubstituted pyrrolidine, an unsubstituted piperidine, an unsubstituted morpholine or an unsubstituted 3-pyrroline or a pyrrolidine, piperidine, morpholine or 3-pyrroline each substituted with 1-2 C₁-C₂ alkyl.

2. A compound according to claim 1, wherein (A) is selected from the group consisting of:-

FL

N (A₁),

R₀

R₇

(A₂),

(A₃),

N Pi₀

R,

N (A₄),

N . ./

N Ro

R,

- 112 -

and

wherein R₆ is selected from the group consisting of halogen, cyano, nitro, Q-Cealkyl,

C₁-C₆ alkoxy, C₁ -C₆halogenalkyl, C₁-C₆halogenalkoxy, C₁-Cβalkoxy-C₁-Cδalkyl or C₁-

Cehalogenalkoxy-d-Cealkyl and SiRgR₁₀Rn;

R₇ is selected from the group consisting of Q^alkyl, C₁-C₄ alkoxy, C₁-

C₄halogenalkyl, d-C^alogenalkoxy, C₁~C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenallcoxy-

C₁-C₄alkyl; and

R₈ is selected from the group consisting of hydrogen, halogen or cyano.

3. A compound according to claim 1 or claim 2, wherein X and Y are oxygen.

4. A compound according to any one of the previous claims, wherein A is A₂.

A compound according to claim 4, wherein R₆ = tert-bntyl, R₇ = methyl or ethyl and R₈ = hydrogen.

A compound according to any one of the previous claims wherein Z is such that B is an aziridine, azetidine, substituted pyrrolidine or substituted piperidine wherein the aziridine and azetidine may be optionally substituted.

A compound according to any one of the previous claims, wherein Z is such that B is an optionally substituted azetidine.

A compound according to claim 7, wherein Z is such that B is an azetidine substituted with a substituent selected form the group consisting of halo- , cyano-, methoxy- and methyl.

A compound according to claim 8, wherein B is an azetidine substituted with fluorine and/or chlorine.

A herbicidal composition comprising a compound according to any one of claims 1 to 9 and an agriculturally acceptable carrier or diluent.

A herbicidal composition according to claim 10, further comprising at least one additional pesticidal compound.

A method of manufacture of a compound according to any one of the previous claims the method comprising coupling together the appropriately substituted azole acid chloride of Formula (II) or the appropriately substituted azole carboxylic acid of Formula (IV) with the appropriately substituted amino compound of Formula (1H).

13. A method of controlling undesirable vegetation comprising applying a locus comprising the undesirable vegetation an effective amount of a composition according to claim 10 or claim 11.

14. Use of a compound according to any one of claims 1 to 9 as a herbicide.