GB2525270A

GB2525270A - Herbicidal compounds

Info

Publication number: GB2525270A
Application number: GB1421274.0A
Authority: GB
Inventors: Jeffrey Steven Wailes; Jonathan Wesley Paul Dallimore; James Nicholas Scutt; Stephen Edward Shanahan
Original assignee: Syngenta Ltd
Current assignee: Syngenta Ltd
Priority date: 2013-12-05
Filing date: 2014-12-01
Publication date: 2015-10-21
Also published as: GB201321498D0; GB201421274D0

Abstract

A compound of formula (I) or a salt or N-oxide thereof: (I) wherein R1, R2, R5, R6 and R7 are each independently H or a substituent; R4 is a substituent; G is H or a substituent; X is O or S; R8 is optionally substituted mono- or bicyclic aryl or an optionally substituted mono- or bicyclic heteroaryl containing a heteroatom selected from N, O and S. Preferably G is H; X is O; R1 is H; R2 is optionally substituted alkyl; R4 is Me or Et; R5 = R6 = R7 = H; R8 is substituted phenyl; substituted pyridyl; substituted quinoxalinyl or substituted benzoxazolyl; In another aspect, the invention relates to herbicidal compositions comprising such compounds, and to their use in controlling weeds such as grassy monocotyledonous weeds, especially in crops of useful plants, or in inhibiting undesired plant growth.

Description

Herbicidal Compounds The present invention relates to herbicidally active thiazolopyridinones, in particular substituted phenyl-ether derivatives thereof, as well as to processes for their preparation, to herbicidal compositions comprising such compounds, and to their use in controlling weeds such as grassy monocotyledonous weeds, especially in crops of useful plants, or in inhibiting undesired plant growth.

The prior art describes various heibicidally active pyridinones forming a condensed ring system with either five-or six-membered heterocyclic rings. For example W0201 1/051212 discloses pyridinones which are condensed with selected five-membered heterocycles and which are substituted in the 3 position of the pyridine ring by aryl and heteroaryl radicals. WO 2012/028582 discloses pyridinones which are condensed with selected five-and six-membered heterocycles and which are substituted in the 3 position of the pyridine ring by aryl radicals. W02013/144096 describes herbicidally and insecticidally active thiazolopyridinones, which are substituted in the 6 position by aryl or heteroaryl radicals.

W02010/081755 describes herbicidally active monocyclic, bicyclic and spirocyclic diones substituted with a phenyl ether moiety.

The present invention is based on the finding that thiazolopyridinones of general formula (I) as shown below, wherein the thiazolopyridinone moiety is substituted at the 6 position with a phenyl-ether or phenyl-thioether moiety are particularly efficacious, and selective herbicides.

Thus, in a first aspect there is provided a compound of formula (I) P5 G.% P..J(P6 RJI8 (I), or a salt or N-oxide thereof, wherein, R1 is hydrogen, halogen, nitro, cyano, or selected from the group consisting of: C1-C6alkyl, 02-Ce alkenyl, C-C alkoxy 01-06 alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, 03-06 cycloalkyl, C1-C6 alkoxy-C1-C6 alkyl-, Cl-Ce alkoxy-C1-C6 alkoxy-, di-C1-C6 alkoxy-C1-C6 alkyl, and C1-C5alkylthio-C1-C6alkyl, each of which is optionally substituted by 1-3 halogen atoms; R2 is hydrogen; or C1-C6alkyl, 02-06 alkenyl, C3-C6alkynyl 03-Ce cycloalkyl, C1-C6 alkoxy-C1-C5 alkyl-, C1-C5alkoxy-C1-C6alkoxy-, di-C1-C6alkoxy-C1- C6alkyl, C1-C6alkylthio-C1-C6alkyl, C1-C5alkylsulfinyl-C1-C6alkyl, C1-C5alkylsulfonyl-C1-C6alkyl, C3-C6cycloalkyl-C1-C5alkyl or cyano-C1-C5alkyl, each of which is optionally substituted by 1-3 halogen atoms; or phenyl optionally substituted by 1-3 substituents independently selected from halogen, C1-C6 alkyl and 01-C5 alkoxy; or benzyl optionally substituted by 1-3 substituents independently selected from halogen, C1-C6 alkyl and C1-C5 alkoxy; G is hydrogen, C1-C10alkyl, CC10alkenyl, C2-C10alkynyl or aryl-C1-C4alkyl-or aryl-C1-C4alkyl-wherein the awl moiety is substituted by one to five substituents independently selected from halo, cyano, nitro, C1-C6alkyl, C1-C6haloalkyl or C1-C6alkoxy, or C(O) R3'; R3 is C1-C10alkyl, C3-C10cycloalkyl, C3-C10cycloalkyl-C1-C10alkyl-, C- C10haloalkyl, CC10alkenyl, C2-C10alkynyl, C1-C4alkoxy-C1-C10alkyl-, C1-C4alkylthio-C1- C4alkyl-, C1-C10alkoxy, C2-C10alkenyloxy, C2-C10alkynyloxy, C1-C10alkylthio-, NR10R11, N-C1-C4alkyl-amino-, N,N-di-(C1-C4alkyl)-amino-, aryl or awl substituted by 1-3 R9, which may be the same or different, heteroaryl or heteroaryl substituted by 1-3 R9, which may be the same or different, aryl-C1-C4alkyl-or aryl-C1-C4alkyl-wherein the awl moiety is substituted by 1-3 to three R9, which may be the same or different, heteroaryl-C1-C4alkyl-or heteroaryl-C1-C4alkyl-wherein the heteroaryl moiety is substituted by 1-3 R9, which may be the same or different, aryloxy-or aryloxy-substituted by 1-3 R9, which may be the same or different, heteroaryloxy-or heteroaryloxy-substituted by 1-3 R9, which may be the same or different, arylthio-or arylthio-substituted by 1-3 R9, which may be the same or different, or heteroarylthio-or heteroarylthio-substituted by one to three R9, which may be the same or different; R4 is methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl, haloethyl, vinyl, propenyl, ethynyl, propynyl, halogen, methoxy, ethoxy, halomethoxy or haloethoxy; R5, R5 and R7 are each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl, haloethyl, vinyl, propenyl, ethynyl, propynyl, halogen, methoxy, ethoxy, halomethoxy or haloethoxy; R8 is an optionally susbtituted mono-or bicyclic awl or an optionally substituted mono-or bicyclic heteroaryl containing a heteroatom selected from nitrogen, oxygen and sulphur; X is 0 or S; each R9 is independently halo, cyano, nitro, C1-C10alkyl, C1-C4haloalkyl, C-C10alkoxy, C1-C4alkoxycarbonyl-, C1-C4haloalkoxy, C1-C10alkylthio-, C1-C4haloalkylthio-, C1-C10alkylsulfinyl-, C1-C4haloalkylsulfinyl-, C1-C10alkylsulfonyl-, C1-C4haloalkylsulfonyl-, aryl or aryl substituted by 1-5 substituents independently selected from halo, cyano, nitro, C1-C5alkyl, C1-C5haloalkyl or C1-C5alkoxy, or heteroaryl or heteroaryl substituted by 1-4 substituents independently selected from halo, cyano, nitro, C1-C3alkyl, C1-C6haloalkyl or C1-C5alkoxy; and, R1° and S11 are independently selected from the group consisting of C1-C6 alkyl and C1-C6 alkoxy, or 10 and 11 together can form a morpholinyl ring.

Compounds of Formula (I) may contain asymmetric centres and may be present as a single enantiomer, pairs of enantiomers in any proportion or, where more than one asymmetric centre are present, contain diastereoisomers in all possible ratios. Typically one of the enantiomers has enhanced biological activity compared to the other possibilities.

Similarly, where there are di-substituted alkenes, these may be present in F or 7 form or as mixtures of both in any proportion.

Furthermore, compounds of formula (I) may be in equilibrium with alternative tautomeric forms. For example, a compound of formula (I-i), i.e. a compound of formula (I) wherein R2 is hydrogen, and G is hydrogen, can be drawn in at least five tautomeric forms: (I-i) 1 RL-_(I I L It should be appreciated that all tautomeric forms (single tautomer or mixtures thereof), racemic mixtures and single isomers are included within the scope of the present invention.

Alkenyl and alkynyl moieties can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (E)-or (Z)-configuration.

Examples are vinyl, allyl and propargyl. Alkenyl and alkynyl moieties can contain one or more double and/or triple bonds in any combination. It is understood, that allenyl and alkylinylalkenyl are included in these terms.

Halogen is fluorine, chlorine, bromine or iodine.

Haloalkyl groups are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, CF3, CF2CI, CF2H, CCI2H, FCH2, CICH2, BrCH2, CH3CHF, (CH3)2CF, CF3CH2 or CHF2CH2.

In the context of the present specification the term "aryl" refers to ring systems which may be mono-or bicyclic. Examples of such rings include phenyl and naphthyl. A preferred aryl group is phenyl.

The term "heteroaryl" preferably refers to an aromatic ring system containing at least one heteroatom and consisting either of a single ring or of two fused rings.

Preferably, single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulphur.

Examples of such groups include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl.

1,2,4-oxadiazolyl, 1 3,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1 2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1 2,4-triazinyl, 1,3,5-triazinyl, benzofuryl, benzisofuryl, benzothienyl, benzisothienyl, indolyl, isoindolyl, indazolyl, benzothiazolyl, benzisothiazolyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, 2,1,3-benzoxadiazole, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, benzotriazinyl, purinyl, pteridinyl and indolizinyl.

The term "heterocyclyl" preferably refers to a non-aromatic preferably monocyclic or bicyclic ring systems containing up to 7 atoms including one or more (preferably one or two) heteroatoms selected from 0, S and N. Examples of such rings include tetrahydropyran, 1,3-dioxolane, oxetane, tetrahydrofuran, morpholine, thiomorpholine and piperazine.

Cycloalkyl includes preferably cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Cycloalkylalkyl is preferentially cyclopropylmethyl. Cycloalkenyl includes preferably cyclopentenyl and cyclohexenyl.

Carbocyclic rings include awl, cycloalkyl or carbocyclic groups, and cycloalkenyl groups.

When present, the optional substituents on alyl, heteroalyl and carbocycles are preferably selected independently, from halogen, nitro, cyano, rhodano, isothiocyanato, C1-C6alkyl, C1-C5haloalkyl, C1-C5alkoxy(C1-C5) alkyl, C2-C5alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C3-C7cycloalkyl (itself optionally substituted with C1-C5alkyl or halogen), C5 7cycloalkenyl (itself optionally substituted with C1-C6alkyl or halogen), hydroxy, C1- C10alkoxy, C1-C10alkoxy(C1-C10)alkoxy, tri(C1-C4alkylsilyl(C1-C6)alkoxy, C-C6alkoxycarbonyl(C1-C10)alkoxy, C1-C10haloalkoxy, aryl(C1-C4)alkoxy (where the aryl group is optionally substituted with halogen or C1-C6alkyl), C3-C7cycloalkyloxy (where the cycloalkyl group is optionally substituted with C1-C5alkyl or halogen), C3- C10alkenyloxy, 03-C10alkynyloxy, mercapto, C1-C10alkylthio, C1-C10haloalkylthio, aryl(C1-C4)alkylthio, C3-C7cycloalkylthio (where the cycloalkyl group is optionally substituted with C1-C6alkyl or halogen), tri(C1-C4-alkylsilyl(C1-C5)alkylthio, arylthio, C1-C5alkylsulfonyl, C1-C6haloalkylsulfonyl, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, arylsulfonyl, tri(C1-C4)alkylsilyl, aryldi(C1-C4)alkylsilyl, C1-C4alkyldiarylsilyl, triarylsilyl, C1-C10alkylcarbonyl, HC2C, C1-C10alkoxycarbonyl, aminocarbonyl, C1-C3alkylaminocarbonyl, di(C1-C6alkyl)-aminocarbonyl, N-(C1-C3 alky-N-(C1-C3alkoxy)aminocarbonyl, C1-C6alkylcarbonyloxy, arylcarbonyloxy, di(C1-C6)alkylaminocarbonyloxy, aryl (itself optionally substituted with C1-C6alkyl or halogen), heteroaryl (itself optionally substituted with C1-C6alkyl or halogen), heterocyclyl (itself optionally substituted with C1-C6alkyl or halogen), aryloxy (where the aryl group is optionally substituted with C1-C6alkyl or halogen), heteroaryloxy (where the heteroaryl group is optionally substituted with C1-C8alkyl or halogen), heterocyclyloxy (where the heterocyclyl group is optionally substituted with C1-C5alkyl or halogen), amino, C1-C6alkylamino, di(C1-C6)alkylamino, C1-C6alkylcarbonylamino, N-(C1-C6)alkylcarbonyl-N-(C1-C6)alkylamino, arylcarbonyl, (where the aryl group is itself optionally substituted with halogen or C1-C5alkyl) or two adjacent positions on an aryl or heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen or C1-C5alkyl. Further substituents for awl or heteroaryl include arylcarbonylamino (where the aryl group is substituted by C1-C6alkyl or halogen), (C1-C6)alkoxycarbonylamino, (C1-C6)alkoxycarbonyl-N-(C1-C6)alkylamino, aryloxycarbonylamino (where the awl group is substituted by C1-C5alkyl or halogen), aryloxycarbonyl-N-(C1-C5)alkylamino, (where the awl group is substituted by C1-C6alkyl 01 halogen), arylsulphonylamino (where the aryl group is substituted by C1-C6alkyl or halogen), arylsulphonyl-N-(C1-C8)alkylamino (where the aryl group is substituted by C1-C6alkyl or halogen), aryl-N-(C1-C5)alkylamino (where the awl group is substituted by C1-C6alkyl or halogen), arylamino (where the awl group is substituted by C1-C6alkyl or halogen), heteroaryl amino (where the heteroaryl group is substituted by C1-C5alkyl or halogen), heterocyclylamino (where the heterocyclyl group is substituted by C1-C6alkyl or halogen), aminocarbonylamino, C-C5alkylaminocarbonylamino, di(C1-C6)alkylaminocarbonylamino, arylaminocarbonylamino where the awl group is substituted by C1-C6alkyl or halogen), awl-N-(C1-C5)alkylaminocarbonylamino where the aryl group is substituted by C1- C6alkyl or halogen), C1-C6alkylaminocarbonyl-N-(C1-C6)alkylamino, di(C1-C5)alkylaminocarbonyl-N-( C1-C5)alkylamino, arylaminocarbonyl-N-(C1-C5)alkylamino where the awl group is substituted by C1-C5alkyl or halogen) and aryl-N-(C1- C5)alkylaminocarbonyl-N-(C1-C5)alkylamino where the aryl group is substituted by C1-C6alkyl or halogen).

The invention relates also to the agriculturally acceptable salts which the compounds of formula I are able to form with transition metal, alkali metal and alkaline earth metal bases, amines, quaternary ammonium bases or tertiary sulfonium bases.

Among the transition metal, alkali metal and alkaline earth metal salt formers, special mention should be made of the hydroxides of copper, iron, lithium, sodium, potassium, magnesium and calcium, and preferably the hydroxides, bicarbonates and carbonates of sodium and potassium.

Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary 01-C15alkylamines, C1-C4hydroxyalkylamines and C2-C4alkoxyalkyl-amines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-n-amylamine, di-isoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N- butylethanolamine, allylamine, n-but-2-enylamine, n-pent-2-enylamine, 2,3-dimethylbut- 2-enylamine, dibut-2-enylamine, n-hex-2-enylamine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, tri-isopropylamine, tri-n-butylamine, tri-isobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m-and p-toluidines, phenylene-diamines, benzidines, naphthylamines and o-, m-and p-chloroanilines; but especially triethylamine, isopropylamine and di-isopropylamine.

Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(Ra Rb R Rd)]OH, wherein Ra, Rb, R and Rd are each independently of the others hydrogen, C1-C4alkyl. Further suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.

Preferred tertiary sulfonium bases suitable for salt formation correspond, for example, to the formula [SReRfRg]OH, wherein Re, R1 and R are each independently of the others C1-C4 alkyl. Trimethylsulfonium hydroxide is especially preferred. Suitable sulfonium bases may be obtained from the reaction of thioethers, in particular dialkylsulfides, with alkyihalides, followed by conversion to a suitable base, for example a hydroxide, by anion exchange reactions.

The compounds of formula I according to the invention also include hydrates which may be formed during the salt formation.

Preferred values of R1, R2G, R3, R4, R5, R6, R7, R°, X, R9, R1° and R11 are as set out below, and a compound of formula (I) according to the invention may comprise any combination of said values. The skilled man will appreciate that values for any specified set of embodiments may combined with values for any other set of embodiments where such combinations are not mutually exclusive.

Preferably R1 is hydrogen, or selected from the group consisting of: C1-C6-alkyl, CrCralkoxy, C1-C5alkoxy-C1-C6alkoxy-, Ci-Cralkylthio, Ci-Cralkylsulfonyl, C3-C5-cycloalkyl, C1-C6-alkoxy-C1-C5-alkyl and C1-C5-alkylthio-C1-C6-alkyl, each of which is optionally substituted by 1-3 halogen atoms. More preferably R1 is selected from hydrogen C1-C6-alkyl, C1-C3-alkoxy, C1-C3alkoxy-C1-C3alkoxy-, C1-C3-alkylthio, C1-C3-alkylsulfonyl, C3-C4-cycloalkyl, C1-C3alkoxy-C1-C3-alkyl and C1-C3-alkylthio-C1-C3-alkyl.

More preferably still, R1 is hydrogen, methyl, cyclopropyl, methoxy, ethoxy, -S-methyl, methylsulfonyl, and methoxyethoxy-. Most preferably R1 is hydrogen.

Preferably R2 is hydrogen or selected from the group consisting of: Ci-Cralkyl, Cr C6-alkenyl, C3-C6-alkynyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6alkoxy-C1-C5alkoxy, C-C-alkylthio-C1-C6-alkyl, C3-C5-cycloalkyl-C1-C6-alkyl, and cyano-Ci-Cralkyl, each of which is optionally substituted by 1-3 halogen atoms; or optionally substituted phenyl or optionally substituted benzyl, wherein said optional substituents are 1-3 substituents independently selected from halogen, C1-C6alkyl, and C1-C5alkoxy. More preferably R2 is selected from C1-C3-alkyl, C1-C3-haloalkyl comprising no more than 3 halogen atoms, C2-C4-alkenyl, C3-C4-alkynyl, cyano-C1-C3-alkyl, C1-C3-alkylthio-C1-C3-alkyl. More preferably still, R2 is methyl, ethyl, isopropyl, allyl, propargyl, difluoroethyl, trifluoroethyl, cyanomethyl, methoxyethyl,or methylthioethyl. Even more preferably R2 is methyl, difluoroethyl, trifluoroethyl, or propargyl, and most preferably R2 is difluoroethyl or propargyl.

Preferably, G is hydrogen or-C(O)-R3, and S3 is selected from the group consisting of C1-C5alkyl, CC6alkenyl, CrC6alkynyl, C1-C6alkyl-S-, C1-C5alkoxy, -NR10R11 and phenyl optionally substituted by one or more As defined herein, 10 and h1 are independently selected from the group consisting of C1-C6 alkyl, C1-C5 alkoxy-; or they can together form a morpholinyl ring.

Preferably 13 and p11 are independently selected from the group consisting of c1-c4 alkyl, C1-C4 alkoxy-; or they can together form a morpholinyl ring. More preferably R and S11 are each independently selected from the group consisting of methyl, ethyl, propyl, methoxy, ethoxy and propoxy.

Preferably each 9 is independently selected from the group consisting of halogen, cyano, nitro, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy and C1-C3haloalkoxy.

Preferably 3 is C1-C4 alkyl, CC3alkenyl, C2-C3alkynyl,-C1-C3alkoxy, or -NR10R11 wherein l0 and I1 together form a morpholinyl ring. More preferably 3 is isopropyl, t-butyl, methyl, ethyl, propargyl or methoxy.

In one set of embodiments G is hydrogen or -C(O)-R wherein R3 is C1-C4 alkyl, C2-C3alkenyl, C2-C3alkynyl or -C1-C3alkoxy. In a further set of embodiments G is hydrogen or -C(O)-53' wherein 3 is isopropyl, t-butyl, methyl, ethyl, propargyl or methoxy. However, it is particularly preferred that G is hydrogen.

Preferably, 4 is methyl, ethyl, n-propyl, cyclopropyl, halogen or C1-C2haloalkoxy.

Preferably, 5, 6 and 7 are independently of each other hydrogen, methyl or halogen. In one set of embodiments 55 is hydrogen. In one set of embodiments, 6 and R7 are each hydrogen.

As stated above, Xis 0 or S. In one set of embodiments X is 0.

R8 is preferably optionally substituted phenyl, optionally substituted naphthyl, an optionally substituted 5-or 6-membered heteroaryl or an optionally substituted bicyclic 8-to lO-membered heteroaryl.

Preferably, in the compounds of formula I, 8 is substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4haloalkylthio, CffC4haloalkylsUlfinyl, C1-C4haloalkylsulfonyl, nitro, cyano, C3-C5cycloalkyl, C1- C3alkylcarbonyl, C1-C4alkoxycarbonyl, aminocarbonyl, C1-C3alkylaminocarbonyl, di-C1-C3alkylaminocarbonyl, C1-C3alkylaminocarbonyloxy, di-C1-C3alkylaminocarbonyloxy, aminothiocarbonyl, C1-C3alkylaminothiocarbonyl, diC1-C3alkylaminothiocarbonyl, C1- C4alkylcarbonylamino, C3-C6cycloalkylcarbonylamino, C1-C4alkoxycarbonylamino,C1- C4alkylthiocarbonylamino, C1-C3alkoxyC1-C3alkyl, C1-C6alkylthioC1-C5alkyl, C- C5alkylsulfinylC1-C6alkyl, C1-C6alkylsulfonylC1-C6alkyl, C1-C3alkylsulfonyloxy, C1-C3haloalkylsulfonyloxy or diC1-C5alkylaniinosulfonyl, or 2 substituents on adjacent carbon atoms of 8 together form a C3-C4alkylene, wherein 1 or 2 methylene groups are optionally substituted by halogen, or wherein 1 or 2 of these methylene groups are replaced by oxygen.

More preferably, 8 is phenyl, naphthyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzothiazolyl, benzoxazolyl, cinnolinyl, quinolinyl, quinazolinyl, quinoxalinyl or benzotriazinyl in each case optionally substituted by one or more (preferably 1-3) radicals independently selected from halogen, methyl, ethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, nitro and cyano. More preferably still, R8 is phenyl or pyridinyl, optionally substituted by 1-3 radicals independently selected from halogen, methyl, ethyl, trifluoromethyl, methoxy, difluoromethoxy, and trifluoromethoxy.

In one preferred set of embodiments, R1 is hydrogen, R2 is selected from methyl, propargyl, and difluoroethyl, G is hydrogen, R4 is methyl or ethyl, R5, R6 and R7 are each hydrogen, X is oxygen and is selected from phenyl or pyridinyl optionally substituted by 1-3 radicals independently selected from halogen, trifluoromethyl and trifl uorometh oxy.

Particularly preferred compounds of formula (I) are as described in Table 1 below.

Table 1 Compounds of formula (I) Compound Structure Number __________________________________________________________________________ ___ P1 o _-E'_ CI P2 __ I)

__ F P4

CI

OH

CI P5

CI

OH

NLN.'LO Cl

PG

OH CI

CI

__ F P7 F F*F

NNAO P8 F F±F

OH

NNAO __ I) Pg F FtF

OH plo

OH

N N P11

NNAO __ 1 P12

NNAO __ F* P13

CI

OH

CI

N N P14

CI

OH

CI

N N __ I) P15 x'P

CI

N N 0 CI

__ F P16 F

<: F*F

N N P17 F F*F __ I) P18

F FtF A) __ F) Pig F

OH O1N

NNAO P20 F

F

CI

OH-F

NNAO __ I) P21 F

F

CI

OH F P22

F N N 0 P23

F

D OkN) N N 0 P24

F

N

cIxyJ< _ NXt P25 P26 Cl Compounds of formula (I), may in general be made by the general methods described below, in which R1, R2G, R3, R4, R5, R6, R7, R8, X, R9, R1° and R11 are as defined herein, unless explicitly stated otherwise.

F&Js,_. R6 G-Z S x Formula (Ia) Formula (I) Compounds of formula (I) wherein G is other than hydrogen may be prepared by treating a compound of formula (Ia) (which is a compound of formula (I) where G is H) with a reagent G-Z, wherein G-Z is an acylating agent such as a carboxylic acid, HO-Coc)R3, wherein X3 is oxygen, an acid chloride, ClC(Xa)R3, wherein X3 is oxygen, or acid anhydride, [R3C(Xa)]20, wherein Xa is oxygen, or an isocyanate, R3N=C=C, or a carbamoyl chloride, ClC(Xd)N(Rbo)R (wherein Xd is oxygen and with the proviso that neither R1° or is hydrogen, or a chloloformate, ClC(XtiX0s, (wherein Xb and X are oxygen), or a chlorothioformate ClC(Xb)X0Ra (wherein Xb is oxygen and X is sulfur).

The 0-acylation of cyclic 1,3-diones may be effected by procedures similar to those described, for example, by R. Haines, US4175135, and byT. Wheeler, US4422870, US4659372 and US4436666. Typically diones of formula (Ia) may be treated with an acylating agent preferably in the presence of at least one equivalent of a suitable base, and optionally in the presence of a suitable solvent. The base may be inorganic, such as an alkali metal carbonate or hydroxide, or a metal hydride, or an organic base such as a tertiary amine or metal alkoxide. Examples of suitable inorganic bases include sodium carbonate, sodium or potassium hydroxide; a suitable metal hydride is sodium hydride; and suitable organic bases include trialkylamines, such as trimethylamine and triethylamine, pyridines or other amine bases such as 1,4-diazobicyclo[2.2.2]-octane and 1,8-diazabicyclo[5.4.0]undec-7-ene. Preferred bases include triethylamine and pyridine. Suitable solvents for this reaction are selected to be compatible with the reagents and include ethers such as tetrahydrofuran and 1,2-dimethoxyethane and halogenated solvents such as dichloromethane and chloroform.

Certain bases, such as pyridine and triethylamine, may be employed successfully as both base and solvent. For cases where the acylating agent is a carboxylic acid, acylation is preferably effected in the presence of a known coupling agent such as 2- chloro-1 -methylpyridinium iodide, N,NdicyclohexylcarbodHmide, 1 -(3-dimethylaminopropyl)-3-ethylcarbodiimide and N,Mcarbodümidazole, and optionally in the presence of a base such as triethylamine or pyridine in a suitable solvent such as tetrahydrofuran, dichloromethane or acetonitrile. Suitable procedures are described, for example, by W. Zhang and G. Pugh, Tetrahedron Left., (1999), 40 (43), 7595-7598; T. Isobe and T. Ishikawa, J Org. Chem., (1999), 64(19), 6984-6988 and K. Nicolaou, T. Montagnon, G. Vassilikogiannakis, C. Mathison, Ji Am. Chem. Soc., (2005), 127(24), 8872-8888.

The reagent G-Z, may be commercially available or prepared by methods well known in the literature.

R(XLIe RJcc Formula (A) Formula (I) A compound of formula (I) may be prepared via a base-induced cyclisation reaction from a compound of formula (A) in which R12 is (C1-C5)-alkyl, in particular methyl or ethyl. Suitable bases include potassium carbonate or lithium hexamethyl-S disilazide (see for example methods described in W02008/009908 and documents cited therein).

G R 0% R, Formula (B) Formula (N) Formula (I) In an alternative approach, a compound of formula (I) (where R2 is other than hydrogen) may be prepared from a compound of formula (B) via alkylation with a compound of formula (N) optionally in the presence of a suitable base and in a suitable solvent. [Gin this case is a suitable leaving group such as halogen ortrifluoromethyl sulfonate. Suitable bases include potassium carbonate (see for example methods described in W02008/071918 and documents cited therein) and suitable solvents include N,N-dimethylformamide.

Compounds of formula (N) may be commercially available or prepared by methods well known in the literature.

Formula (0) Formula (B) A compound of formula (B) may be prepared via a base-induced cyclisation from a compound of formula (0) in which R12 is (C1-C5)-alkyl, in particular methyl or ethyl.

Suitable bases include potassium carbonate or lithium hexamethyl-disilazide (see for example methods described in W02008/009908 and documents cited therein). x12

Formula (L) Formula (K) Formula (0) A compound of formula (0) may be prepared by means of an amide bond forming reaction between a compound of formula (L) and a compound of formula (K), wherein W is a suitable leaving group (such as Cl or OH), optionally in the presence of a suitable solvent and/or in the presence of a suitable coupling reagent and/or in the presence of a suitable base. Suitable solvents include N,N-dimethylformamide or dichloromethane, suitable coupling reagents include a carbodiimide (e.g. dicyclohexylcarbodhmide) or a phosphonic anhydride (e.g. 2,4,6-tripropyl-1 3,5,2,4,6- trioxatriphosphorinane-2,4,6-trioxide) or a (benzotriazol-1 - yloxy)trialkylaminophosphonium salt (e.g. benzotriazol-1 -yloxy(tripyrrolidin-1 - yl)phosphonium hexafluorophosphate) and suitable bases include N,N-dhsopropylethylamine or triethylamine (see for example methods described in W02008/009908, W02008/071918, W02009/063180 and documents cited therein).

Compounds of formula (L) and of formula (K) may be commercially available or be prepared by methods well known in the literature.

G G

Formula (C) Formula (D) Formula (I) In a further alternative approach, a compound of formula (I) may be prepared from a compound of formula (C) and an aryl or heteroaryl halide of formula (0), wherein Hal represents fluorine, bromine, chlorine or iodine, optionally in the presence of a suitable base and/or in the presence of a suitable catalyst, in a suitable solvent. When the compound of formula (D) is an aryl or heteroaryl bromide or iodide, the reaction may be effected using suitable copper or palladium catalysis, optionally in the presence of a suitable ligand or additive, a suitable base and a suitable solvent, under conditions similar to those described, for example, by S. Hu et a/., J. Org. Chem., (2008), 73, 7814- 7817; P. Chan et at, Tetrahedron Lett., (2008), 49, 2018-2022; ft Hosseinzadeh et al., Synthetic Commun., (2008), 38, 3023-3031; S. Buchwald etat, J. Am. Chem. Soc., (2006), 128, 10694-10695; H. Raoeta/., Chem. Eur. J., (2006), 12, 3636-3646; M. Taillefer at at, Adv. Synth. Catal., (2006), 348, 499-505; M. Belier at at, Tetrahedron Lett., (2005), 46, 3237-3240; M. Taillefer et at, Org. Left., (2004), 6, 913-916; 0. Ma et at, Org. Lett., (2003), 5, 3799-3802; J. Song at at, Org. Lett., (2002), 4, 1623-1626; R. Venkatamaran at at, Org. Left., (2001), 3,4315-4317; S. Buchwald etat, JAm. Chem. Soc., (1999), 121, 4369-4378; S. Buchwald etat, J. Am. Chem. Soc., (1997), 119, 10539-10540; G. Mann etal., Tetrahedron Left., (1997), 38, 8005-8008.

Suitable catalysts include palladium and copper catalysts such as palladium(ll) acetate, bis(dibenzylideneacetone)palladium(l I), copper powder, copper(l I) acetate, copper(l) chloride, copper) bromide, copper(l I) bromide, copper(l) iodide, copper(l) oxide, copper(ll) sulphate, copper(l) trifluoromethane sulfonate and copper(ll) trifluoromethanesulfonate. Optionally the catalysts are used in conjunction with appropriate ligands or additives such as N-methylglycine, N,N-dimethylglycine, 1- butylimidazole, ethyl acetate, ethylene glycol diacetate, 8-hydroxyquinoline, L-proline, 1-napthoic acid, triphenylphosphine, 1,1 -bis(diphenylphosphino)ferrocene, salicylaldoxime, 2-(N,N-dimethylamino)-2'-di-tert-butylphosphinobiphenyl, neocuprine, pyrrolidine-2-phosphonic acid phenyl monoester, 2,2,6,6-tetramethylheptane-3,5-dione, tetrabutylammonium bromide, 2,2-bipyridine or 1,1 0-phenanthroline. Suitable bases include cesium carbonate, cesium fluoride, potassium fluoride, potassium phosphate and sodium hydroxide. Suitable solvents include acetonitrile, N,N-dimethylformamide, 1,4-dioxane or toluene, or mixed solvent systems such as toluene/tetrahydrofuran and 1,4-dioxanelwater.

Alternatively, when R8-Hal is a suitably electron-deficient aryl halide (for example an aryl fluoride or aryl chloride additionally bearing one or more electron withdrawing substituents such as trifluoromethyl, nitro or cyano) or a suitable heteroaryl halide (for example a halopyridine, halopyrimidine or other electron-deficient heteroaryl halide), the reaction may be effected in the presence of a suitable base such as potassium carbonate or cesium carbonate without the need for a catalyst or ligand (see for example methods described in W02010/081755 and documents cited therein).

Compounds of formula (D) may be commercially available or prepared by methods well known in the literature. Fe

Formula (S) Formula (C) A compound of formula (C) may be prepared from a compound of formula (S), wherein PG is a suitable protecting group (for example benzyl). Suitable conditions for removal of the protecting group are well known in the literature but include hydrogenolysis in the presence of a suitable catalyst (for example palladium on carbon) in a suitable solvent (for example ethyl acetate or methanol).

Formula (T) Formula (S) A compound of formula (S) may be prepared via a base-induced cyclisation reaction from a compound of formula (T) in which R12 is (C1-C6)-alkyl, in particular methyl or ethyl. Suitable bases include potassium carbonate or lithium hexamethyl-disilazide (see for example methods described in W02008/009908 and documents cited therein).

Formula (J) Formula (U) Formula (T) A compound of formula (T) may be prepared by means of an amide bond forming reaction between a compound of formula (J) and a compound of formula (U), wherein W is a suitable leaving group (such as Cl or OH), optionally in the presence of a suitable solvent and/or in the presence of a suitable coupling reagent and/or in the presence of a suitable base. Suitable solvents include N,N-dimethylformamide or dichloromethane, suitable coupling reagents include a carbodiimide (e.g. dicyclohexylcarbodiimide) or a phosphonic anhydride (e.g. 2,4,6-tripropyl-1 3,5,2,4,6- trioxatriphosphorinane-2,4,6-trioxide) or a (benzotriazol-1 - yloxy)trialkylaminophosphonium salt (e.g. benzotriazol-1 -yloxy(tripyrrolidin-1 - yl)phosphonium hexafluorophosphate) and suitable bases include N,N-diisopropylethylamine or triethylamine (see for example methods described in W02008/009908, W02008/071918, WO2009/063180 and documents cited therein).

Compounds of formula (U) may be prepared by methods well known in the literature. G% G_

Hal XH 6 Formula (E) Formula (F) Formula (I) In a yet further alternative approach, a compound of formula (I) may be prepared from a compound of formula (F), wherein Hal represents bromine or iodine and a compound of formula (F). The reaction may be effected using suitable copper or palladium catalysis under conditions described previously for the preparation of a compound of formula (I) from a compound of formula (C) and a compound of formula (D).

Compounds of formula (F) may be commercially available or prepared by methods well known in the literature. A6

Formula (O Formula (E) A compound of formula (E) may be prepared via a base-induced cyclisation reaction from a compound of formula (V) in which R12 is (C1-C6)-alkyl, in particular methyl or ethyl. Suitable bases include potassium carbonate or lithium hexamethyl-disilazide (see for example methods described in W02008/009908 and documents cited therein).

Rt<:xT2 _t,xcZ, Formula (L) Formula ( Formula (v) A compound of formula (V) may be prepared by means of an amide bond forming reaction between a compound of formula (L) and a compound of formula (, wherein W is a suitable leaving group (such as Cl or OH), optionally in the presence of a suitable solvent and/or in the presence of a suitable coupling reagent and/or in the presence of a suitable base. Suitable solvents include N,N-dimethylformamide or dichloromethane, suitable coupling reagents include a carbodiimide (e.g. dicyclohexylcarbodhmide) or a phosphonic anhydride (e.g. 2,4,6-tripropyl-1 3,5,2,4,6- trioxatriphosphorinane-2,4,6-trioxide) or a (benzotriazol-1 - yloxy)trialkylaminophosphonium salt (e.g. benzotriazol-1 -yloxy(tripyrrolidin-1 - yl)phosphonium hexafluorophosphate) and suitable bases include N,N-dhsopropylethylamine or triethylamine (see for example methods described in W02008/009908, W02008/071918, W02009/063180 and documents cited therein).

Compounds of formula (L) and compounds of formula (W) may be commercially available or be prepared by methods well known in the literature.

R

Formula (G) Formula (H) Formula (I) In another yet further alternative approach, a compound of formula (I) may be prepared from a compound of formula (G), wherein L is bromine or iodine and a compound of formula (H), wherein Y is a trialkyltin group, a magnesium halide group or preferably a boronic acid or ester thereoL These reactions are usually carried out in the presence of a catalyst such as palladium catalysts and in the presence of a base, such as sodium carbonate or potassium phosphate (see for example J-P Vors at at., Org. Lett., (2007), 9, 271-274).

Compounds of formula (G) are known from WO2013/144096 and compounds of formula (H) may be prepared by methods well known in the literature.

Formula (J) Formula (K) Formula (A) A compound of formula (A) may be prepared by means of an amide bond forming reaction between a compound of formula (J) and a compound of formula (K), wherein W is a suitable leaving group (such as Cl or OH), optionally in the presence of a suitable solvent and/or in the presence of a suitable coupling reagent and/or in the presence of a suitable base. Suitable solvents include N,N-dimethylformamide or dichloromethane, suitable coupling reagents include a carbodiimide (e.g. dicyclohexylcarbodhmide) or a phosphonic anhydride (e.g. 2,4,6-tripropyl-1 3,5,2,4,6- trioxatriphosphorinane-2,4,6-trioxide) or a (benzotriazol-1 - yloxy)trialkylaminophosphonium salt (e.g. benzotriazol-1 -yloxy(tripyrrolidin-1 - yl)phosphonium hexafluorophosphate) and suitable bases include N,N-dhsopropylethylamine or triethylamine (see for example methods described in W02008/009908, W02008!071918, W02009/063180 and documents cited therein).

Compounds of formula (K) may be prepared by methods well known in the literature.

s 002R s C02R92 NH2 R2' H NH Formula (L) Formula (Fv Formula (J) A compound of formula (J) may be prepared from a compound of formula (L) and a compound of formula (M) via methods known in the literature, for example reductive amination i.e. condensing an amino ester of formula L an aldehyde of formula N followed by reduction with a suitable reducing agent e.g. sodium cyanoborohydride. R2' is (C1-C5)-alkyl, (C2-C5)-alkenyl, (C3-C5)-alkynyl, (C3-C5)-cycloalkyl, (C1-C4-alkoxy-(C1- C6)-alkyl, di(C1-C4)-alkoxy-(C1-C6)-alkyl or (C1-C4)-alkylthio-(C1-C5)-alkyl, (C3-C6)-cycloalkyl-(C1-C5)-alkyl substituted in each case by 1-3 halogen atoms.

Compounds of formula (L) and of formula (M) may be commercially available or be prepared by methods well known in the literature.

s C02R12 s C02R12 N H2 N( Formula (L) Formula (N) Formula (J) In an alternative approach, a compound of formula (J) may be prepared from a compound of formula (L) and a compound of formula (N) using methods previously described for the synthesis of compounds of formula (I) from compounds of formula (B) and of formula (N). . LG in this case is a suitable leaving group such as halogen or trifluoromethyl sulfonate.

s CO2R12RA ____________________ GO2R'2R

F R

Formula (0) Formula (D) Formula (A) In a further approach, a compound of formula (A) may be prepared from a compound of formula (0) and a compound of formula (D) using methods previously described for the synthesis of compounds of formula I from compounds of formula (C) and of formula (D). F5

CC2R2R R 002R12R4

L

P F F2

Formula (1) Formula (0) A compound of formula (0) may be prepared from a compound of formula (T) (where PG is for example benzyl) via, for example hydrogenolysis in the presence of a suitable catalyst (for example palladium on carbon) in a suitable solvent (for example ethyl acetate or methanol).

Cc1⁄2R1R

F F -

F F

Formula (P) Formula (F) Formula (A) In a yet further approach, a compound of formula (A) may be prepared from a compound of formula (P) and a compound of formula (F) using methods previously described for the synthesis of compounds of formula I from compounds of formula (E) and of formula (F).

RL.....(jI:_jii!:T: Formula (J) Formula ( Formula (P) A compound of P may be prepared from a compound of formula (J) and a S compound of formula (A using methods previously described for the synthesis of compounds of formula (A) from compounds of formula (J) and of formula (K).

Herbicidal compositions In another aspect, the present invention provides a herbicidal composition, e.g. for use in a method of controlling weeds (e.g. monocotyledonous such as grassy weeds) in crops of useful plants, which composition comprises a compound of formula (I) as defined herein (e.g. a herbicidally effective amount thereofl, and a substantially-inert agrochemically acceptable substance (e.g. an agrochemically acceptable carrier, diluent and/or solvent, an agrochemically acceptable adjuvant, an an agrochemically acceptable emulsifler/surfactant/surface-active substance, and/or another agrochemically acceptable additive).

In a further aspect, the present invention provides a herbicidal composition, e.g. for use in a method of controlling weeds (e.g. monocotyledonous such as grassy weeds) in crops of useful plants, comprising a compound of formula (I) as defined herein (e.g. a herbicidally effective amount thereofl, and an agrochemically acceptable carrier, diluent and/or solvent.

In all aspects of the invention, the compound of the formula (I) is optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.

The compounds of formula (I) according to the invention can be used as crop protection agents in unmodified form, as obtained by synthesis, but, for use as herbicides, they are generally formulated into herbicidal compositions (formulations), e.g. in a variety of ways, containing one or more substantially-inert agrochemically acceptable substances (e.g. an agrochemically acceptable carrier, diluent and/or solvent, an agrochemically acceptable adjuvant, an an agrochemically acceptable emulsifier! surfactant I surface-active substance, and/or another agrochemically acceptable additive).

The formulations (herbicidal compositions) can be in various physical forms, for example in the form of dusting powders, gels, wettable powders, coated or impregnated granules for manual or mechanical distribution on target sites, water-dispersible granules, water-soluble granules, emulsifiable granules, water-dispersible tablets, effervescent compressed tablets, water-soluble tapes, emulsifiable concentrates, micro-'emulsifiable concentrates, oil-in-water (EV\O or water-in-oil (WO) emulsions, other multiphase systems such as oil/water/oil and water/oil/water products, oil flowables, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known, for example, from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. The active ingredient may be incorporated into microfibers or micro-rods formed of polymers or polymerizable monomers and having diameter of about 0.1 to about 50 microns and aspect ratio of between about 10 and about 1000.

Such formulations can either be used directly or are diluted prior to use. They can then be applied through suitable ground or aerial application spray equipment or other ground application equipment such as central pivot irrigation systems or drip/trickle irrigation means.

Diluted formulations can be prepared, for example, with water, liquid fertilisers, micro-nutrients, biological organisms, oil or solvents.

The formulations can be prepared, for example, by mixing the active ingredient with formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be contained in fine microcapsules consisting of a core and a polymeric shell.

Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be present in the form of liquid technical material, in the form of a suitable solution, in the form of fine particles in solid or liquid dispersion or as a monolithic solid. The encapsulating membranes comprise, for example, natural and synthetic gums, cellulose, styrene-butadiene copolymers or other similar suitable membrane forming material, polyacrylonitrile, polyacrylate, polyester, polyamides, polyureas, polyurethane, aminoplast resins or chemically modified starch or other polymers that are known to the person skilled in the art in this connection.

Alternatively it is possible for fine so called microcapsules" to be formed wherein the active ingredient is present in the form of finely divided particles in a solid matrix of a base substance, but in that case the microcapsule is not encapsulated with a diffusion limiting membrane as outlined in the preceding paragraph.

The active ingredients may be adsorbed on a porous carrier. This may enable the active ingredients to be released into their surroundings in controlled amounts (e.g. slow release). Other forms of controlled release formulations are granules or powders in which the active ingredient is dispersed or dissolved in a solid matrix consisting of a polymer, a wax or a suitable solid substance of lower molecular weight. Suitable polymers are polyvinyl acetates, polystylenes, polyolefins, polyvinyl alcohols, polyvinyl pyrrolidones, alkylated polyvinyl pyrrolidones, copolymers of polyvinyl pyrrolidones and maleic anhydride and esters and half-esters thereof, chemically modified cellulose esters like carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, examples of suitable waxes are polyethylene wax, oxidized polyethylene wax, ester waxes like montan waxes, waxes of natural origin like carnauba wax, candelilla wax, bees wax etc. Other suitable matrix materials for slow release formulations are starch, stearin, lignin.

The formulation ingredients (e.g. inert ingredients) suitable for the preparation of the compositions according to the invention are generally known per Se.

As a liquid carrier and/or solvent (e.g. organic solvent), e.g. for use in the herbicidal composition(s) according to the invention, there may be used: water, an aromatic solvent such as toluene, m-xylene, o-xylene, p-xylene or a mixture thereof, cumene, an aromatic hydrocarbon blend with a boiling range between 140 and 320 00 (e.g. known under various trademarks such as Solvesso®, ShelIsol A®, Caromax®, Hydrosol®), a paraffinic or isoparaffinic carrier such as paraffin oil, mineral oil, a de-aromatized hydrocarbon solvent with a boiling range between 50 and 320 °C (e.g. known for instance under the trademark Exxsol®), a non-dearomatized hydrocarbon solvent with a boiling range between 100 and 320 DC (e.g. known under the tradename Varsol®), an isoparaffinic solvent with a boiling range between 100 and 320°C (e.g. known known under tradenames like Isopal® or ShelIsol T®), a hydrocarbon such as cyclo-'hexane, tetrahydronaphthalene (tetralin), decahydronaphthalene, alpha-pinene, d-limonene, hexadecane, isooctane; an ester solvent such as ethyl acetate, n-or iso-butyl acetate, amyl acetate, i-bornyl acetate, 2-ethylhexyl acetate, a 06-C alkyl ester of acetic acid (e.g. known under the tradename Exxate®), lactic acid ethylester, lactic acid propylester, lactic acid butylester, benzyl benzoate, benzyl lactate, dipropyleneglycol dibenzoate, or a dialkyl ester of succinic, maleic or fumaric acid; a polar solvent such as N-methyl pyrrolidone, N-ethyl pyrrolidone, C3-C18-alkyl pyrrolidones, gamma- butyrolactone, dimethylsulfoxide, N, N-dimethylformamide, N,N-dimethylacetamide, N, N-dimethyllactamide, a C4-C18 fatty acid dimethylamide, benzoic acid dimethylamide, acetonitrile, acetone, methyl ethyl ketone, methyl-isobutyl ketone, isoamyl ketone, 2-heptanone, cyclohexanone, isophorone, methyl isobutenyl ketone (mesityl oxide), acetophenone, ethylene carbonate, propylene carbonate, or butylene carbonate; an alcoholic solvent or diluent such as methanol, ethanol, propanol, n-or iso-butanol, n-or iso-pentanol, 2-ethyl hexanol, n-octanol, tetrahydrofurfuryl alcohol, 2-methyl-2,4-pentanediol, 4-hydroxy-4-methyl-2-pentanone, cyclohexanol, benzyl alcohol, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, diethylene glycol, diethylene glycol butyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, or another similar glycol monoether solvent based on a ethylene glycol, propylene glycol or butylene glycol feedstock, triethylene glycol, polyethylene glycol (e.g. PEG 400), a polypropylenglycol with a molecular mass of 400 -4000, or glycerol; glycerol acetate, glycerol diacetate, glycerol triacetate, 1,4-dioxane, diethylene glycol abietate, chlorobenzene, chlorotoluene; a fatty acid ester such as methyl octanoate, isopropyl myristate, methyl laurate, methyl oleate, a mixture of 08-dO fatty acid methyl esters, rapeseed oil methyl ester, rapeseed oil ethyl ester, soybean oil methyl ester, soybean oil ethyl ester; a vegetable oil (e.g. rapeseed oil or soybean oil); a fatty acid such as oleic acid, linoleic acid, or linolenic acid; or an ester of phosphoric or phosphonic acid such as triethyl phosphate, a C3-C18-tris-alkyl phosphate, an alkylaryl phosphate, or bis-octyl-octyl phosphonate.

Water is generally the liquid carrier of choice for the dilution of the concentrates.

Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica (fumed or precipated silica and optionally functionalised or treated, for instance silanised), attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montomorillonite, cottonseed husks, wheatmeal, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar materials, as described, for example, in the EPA CER 180.1001. (c) & (d). Powdered or granulated fertilisers can also be used as solid carriers.

A large number of surface-active substances can advantageously be used both in solid and in liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, amphoteric, non-ionic or polymeric and they may be used as emulsifiying, wetting, dispersing or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; Sodium lauryl sulfate, salts of alkylarylsulfonates, such as calcium or sodium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonyiphenol ethoxylates; alcohol-alkylene oxide addition products, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono-and di-alkyl phosphate esters; and also further substances described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, 1981.

Further adjuvants which can usually be used in pesticidal formulations include crystallisation inhibitors, viscosity-modifying substances, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing aids, anti-foams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion-inhibitors, fragrances, wetting agents, absorption improvers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, anti-freezes, microbiocides, compatibility agents and solubilisers and also liquid and solid fertilisers.

The formulations may also comprise additional active substances, for example further herbicides, herbicide safeners, plant growth regulators, fungicides or insecticides.

The compositions according to the invention can additionally include an additive (commonly referred to as an adjuvant), comprising a mineral oil, an oil of vegetable or animal origin, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive used in the composition according to the invention is generally from 0.01 to 10 %, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsifiable vegetable oil, such as AMIGO® (Loveland Products Inc.), C1-C5alkyl esters of oils of vegetable origin, for example the methyl esters, or an oil of animal origin, such as fish oil or beef tallow. A preferred oil additive contains methylated rapeseed oil. Another preferred oil additive contains, for example, as active components essentially 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers. Especially preferred oil additives comprise Ci--alkyl ester(s) of C8-C22 fatty acid(s), especially the methyl ester(s) of C8-C22 (especially C12-C18) fatty acid(s); preferably the methyl ester of lauric acid, of palmitic acid, or of oleic acid. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9) respectively. A preferred fatty acid methyl ester derivative is AGNIQUE ME 18 RD-F® (e.g. available from Cognis). Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000.

The application and action of the oil additives can be further improved by combining them with surface-active substances, such as non-ionic, anionic, cationic or amphoteric surfactants. Examples of suitable anionic, non-ionic, cationic or amphoteric surfactants are listed on pages 7 and S of W097/34455. Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type.

Special preference is given to ethoxylated C12-C22 fatty alcohols preferably having a degree of ethoxylation of from 5 to 40. Examples of commercially available suifactants are the Genapol types (Clariant). Also preferred are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltrisiloxanes, which are commercially available e.g. as SILWET L-77®, and also perfiuorinated surfactants. The concentration of surface-active substances in relation to the total additive is generally from 1 to 50 % by weight.

Examples of oil additives that consist of mixtures of oils or mineral oils or derivatives thereof with surfactants are TURBOCHARGE®, ADIGOR® (both (Syngenta Crop Protection AG), ACTIPRON® (BR Oil UK Limited), AGRI-DEX® (Helena Chemical Company).

The above-mentioned surface-active substances may also be used in the formulations alone, that is to say without oil additives.

Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture can contribute to a further enhancement of action. Suitable solvents are, for example, SOLVESSO® and AROMATIC® solvents (Exxon Corporation).The concentration of such solvents can be from 10 to 80 % by weight of the total weight.

Such oil additives, which may be in admixture with solvents, are described, for example, in US 4 834 908. A commercially available oil additive disclosed therein is known by the name MERGE® (BASE). Further oil additives that are preferred according to the invention are SCORE® and ADIGOR® (both Syngenta Crop Protection AG).

In addition to the oil additives listed above, in order to enhance the activity of the compositions according to the invention it is also possible for formulations of alkylpyrrolidones, (e.g. AGRIMAX® from ISP) to be added to the spray mixture.

Formulations of synthetic latices, such as, for example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g. BOND®, COURIER® or EMERALD®) can also be used.

Such adjuvant oils as described in the preceding paragraphs may be employed as the carrier liquid in which an active compound is dissolved, emulsified or dispersed as appropriate to the physical form of the active compound.

The pesticidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95% by weight, of a compound of formula 0) and from ito 99.9% by weight ofa formulation adjuvant, which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

The rate of application of the compounds of formula (I) may vary within wide limits and depends upon the nature of the soil, the method of application (pre-or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed or grass to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. The compounds of formula I according to the invention are generally applied at a rate of 1-2000 g/ha, preferably 1-1000 g / ha and most preferably at 1-500 g / ha.

Preferred formulations / compositions have especially the following representative compositions: = percent by weight of the composition): Emulsifiable concentrates: active ingredient: 0.3 to 95 %, preferably 0.5 to 60 % such as ito 40 % surface-active agents: ito 30 %, preferably 3 to 20% such ass to i5% solvents as liquid carrier: ito 80 %, preferably ito 60% such as ito 40 % Dusts: active ingredient: 0.i to iO %, preferably 0.1 to 5 % solid carriers: 99.9 to 90 %, preferably 99.9 to 99 % Suspension concentrates: active ingredient: ito 75 %, preferably 3 to 50 % or iO to 50 % water: 98 to 24 %, preferably 95 to 30 % or 88 to 30 % surface-active agents: ito 40 %, preferably 2 to 30 %

Wettable powders:

active ingredient: 0.5 to 90 %, preferably i to 80 % surface-active agents: 0.5 to 20 %, preferably ito 15 % solid carriers: 5 to 95 %, preferably i5 to 90 % Granules: active ingredient: 0.1 to 30 %, preferably 0.1 to 15% solid carriers: 99.5 to 70 %, preferably 97 to 85 % Waterdispersible granules: active ingredient: ito 90 %, preferably 10 to 80 % surface-active agents: 0.5 to 80 %, preferably 5 to 30 % solid carriers: 90 to 10%, preferably 70 to 30 % The following Examples further illustrate, but do not limit, the invention.

Fl. Emulsifiable concentrates a) b) c) d) active ingredient 5 % 10 % 25% 50 % calcium dodecylbenzene-sulfonate 6% 8% 6% 8% castor oil polyglycol ether 4 % -4% 4 % (36 mol of ethylene oxide) octylphenol polyglycol ether -4 % -2 % (7-8 mol of ethylene oxide) NMP (N-methyl-2-pyrrolidone) -10 % -20 % aromatic hydrocarbon 85 % 68 % 65 % 16 % mixture C9-C12 Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

F2. Solutions a) b) c) d) active ingredient 5 % 10 % 50% 90 % 1 -methoxy-3-(3-methoxy- propoxy)-propane 40 % 50 % -- polyethylene glycol MW 400 20% 10% --NMP (N-methyl-2-pyrrolidone) --50 % 10 % aromatic hydrocarbon 35 % 30 % --mixture 09-012 The solutions are suitable for application undiluted or after dilution with water.

F3. Wettable powders a) b) c) d) active ingredient 5 % 25 % 50 % 80 % sodium lignosulfonate 4 % -3 % -sodium lauryl sulfate 2 % 3 % -4 % sodium diisobutylnaphthalene-sulfonate -6% 5% 6% octylphenol polyglycol ether -1 % 2 % - (7-8 mol of ethylene oxide) highly disperse silicic acid 1 % 3 % 5 % 10 % kaolin 88% 62% 35% -The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, yielding wettable powders which can be diluted with water to give suspensions of any desired concentration.

F4. Coated granules a) b) c) active ingredient 0.1 % 5 % 15% highly dispersed silica 0.9 % 2 % 2 % inorganic carrier 99.0 % 93 % 83 % (diameter 0.1 -1 mm) e.g. CaCO3 or Si02 The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier and the solvent is subsequently evaporated off in vacuo.

ES. Coated granules a) b) c) active ingredient 0.1 % 5 % 15 % polyethylene glycol MW 200 1.0 % 2 % 3 % highly dispersed silica 0.9 % 1 % 2 % inorganic carrier 98.0 % 92 % 80 % (diameter 0.1 -1 mm) e.g. CaCO3 or Si02 The finely ground active ingredient is applied uniformly, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

F6. Extruded granules a) b) c) d) active ingredient 0.1 % 3 % 5 % 15 % sodium lignosulfonate 1.5% 2 % 3% 4% carboxymethylcellulose 1.4 % 2 % 2 % 2 % kaolin 97.0% 93% 90% 79% The active ingredient is mixed and ground with the adjuvants and the mixture is moistened with water. The resulting mixture is extruded and then dried in a stream of air.

S F7. Water-dispersible granules a) b) c) d) active ingredient 5 % 10 % 40% 90 % sodium lignosulfonate 20% 20 % 15% 7 % dibutyl naphthalene sulfonate 5 % 5 % 4 % 2 % Gumarabic 2% 1% 1% 1% Diatomaceous earth 20 % 30 % 5 % - Sodium sulfate -4 % 5 % - kaolin 48% 30% 30% -The active ingredient is mixed and ground with the adjuvants and the mixture is moistened with water. The resulting mixture is extruded and then dried in a stream of air.

F7. Dusts a) b) c) active ingredient 0.1 % 1 % 5 % talcum 39.9% 49 % 35 % kaolin 60.0% 50 % 60 % Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.

F8. Suspension concentrates a) b) c) d) active ingredient 3 % 10 % 25% 50 % propylene glycol 5 % 5 % 5 % 5 % nonylphenol polyglycol ether -1 % 2 % - (15 mol of ethylene oxide) sodium lignosulfonate 3 % 3 % 7 % 6 % heteropolysacharide (Xanthan) 0.2 % 0.2 % 0.2 % 0.2 % 1,2-benzisothiazolin-3-one 0.1 % 0.1 % 0.1 % 0.1 % silicone oil emulsion 0.7 % 0.7 % 0.7 % 0.7 % water 88% 80% 60% 38% The finely ground active ingredient is intimately mixed with the adjuvants, yielding a suspen-sion concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

Herbicidal uses -crops of useful plants, weeds, application rates, et a!.

In a further aspect, the present invention provides a method of controlling weeds (e.g. monocotyledonous such as grassy weeds) in crops of useful plants, which comprises applying a compound of the formula (I), or a herbicidal composition comprising such a compound, to the weeds and/or to the plants and/or to the locus thereof.

In a further aspect, the present invention provides a herbicidal composition, in particular for use in a method of controlling weeds (e.g. monocotyledonous such as grassy weeds) in crops of useful plants, comprising a compound of formula (I) as defined herein (e.g. a herbicidally effective amount thereofl, and an agrochemically acceptable carrier, diluent and/or solvent.

In all aspects of the invention, the compound of the formula (I) is optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof In one embodiment, the herbicidal composition also comprises one or more further herbicides, e.g. as mixture partner(s) for the compound of formula (I), and/or a safener.

See the combinations and mixtures section herein for more details of examples of these.

In all aspects of the invention (e.g. the methods of use of the invention), crops of useful plants, e.g. on or in which or at the locus of which the compounds or compositions according to the invention can be used, comprise (e.g. are), in particular, cereals (e.g. non-oat cereals, in particular wheat, barley, rye and/or triticale), rice, corn (maize), sugarcane, leguminous crops (preferably soybean, peanut, and/or pulse crops; more preferably soybean; wherein typically the pulse crops comprise dry beans (e.g. kidney or haricot or pinto bean which is Phaseolus vulgaris, or mung bean which is Vigna radiata), chickpea, blackeye bean (i.e. black-eyed pea, Vigna unguiculata), lentil, dry broad beans, and/or dry peas such as garden peas), cotton, rape (in particular oilseed rape or canola), sunflower, linseed, sugarbeet, fodder beet, potato, vegetables (preferably dicotyledonous vegetables), flax, tobacco, plantation crops (such as conifer trees, olives and/or olive trees, oil palms, coffee, or vines), and/or fruit crops (in particular dicotyledonous and/or broadleaved fruit, and/or in particular pome fruit, stone fruit, bush fruit, citrus fruit, pineapple, banana, and/or strawberry).

Preferably, in all aspects of the invention, the crops of useful plants, e.g. on or in which or at the locus of which the compounds or compositions according to the invention can be used, comprise (e.g. are) cereals (in particular non-oat cereals, more particularly wheat, barley, rye and/or triticale), rice, corn (maize), sugarcane, leguminous crops (preferably soybean, peanut, and/or pulse crops (more preferably soybean)), cotton, rape (in particular oilseed rape or canola), sunflower, linseed, sugarbeet, fodder beet, potato, and/or vegetables (preferably dicotyledonous vegetables); or, more preferably, leguminous crops (preferably soybean, peanut, and/or pulse crops; more preferably soybean; wherein typically the pulse crops comprise dry beans (e.g. kidney or haricot or pinto bean which is Phaseolus vulgaris, or mung bean which is Vigna radiata), chickpea, blackeye bean (i.e. black-eyed pea, Vigna unguiculata), lentil, dry broad beans, and/or dry peas such as garden peas), cotton, rape (in particular oilseed rape or canola), sunflowel, sugarbeet, potato, and/or vegetables (preferably dicotyledonous vegetables).

The term "crops" is to be understood as also including crops that have been rendered tolerant to herbicides or classes of herbicides (for example ALS, GS, EPSPS, PPO and HPPD inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant e.g. to imidazolinones, such as imazamox, by conventional methods of breeding is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate-and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.

Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example St maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt-176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins and transgenic plants able to synthesise such toxins are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants that contain one or more genes which code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLea (potatoes), NatureGard® and Protexcta®. Plant crops and their seed material can be resistant to herbicides and at the same time also to insect feeding ("stacked" transgenic events). Seed can, for example, have the ability to express an insecticidally active CryS protein and at the same time be glyphosate-tolerant. The term "crops" is to be understood as also including crops obtained as a result of conventional methods of breeding or genetic engineering which contain so-called output traits (e.g. improved flavour, storage stability, nutritional content).

In all aspects of the invention, the weeds, e.g. to be controlled and/or growth-inhibited, may be either monocotyledonous (e.g. grassy) and/or dicotyledonous weeds.

Preferably the weeds, e.g. to be controlled and/or growth-inhibited, comprise or are monocotyledonous weeds, more preferably grassy monocotyledonous weeds.

In all aspects of the invention, typically, the monocotyledonous (preferably grassy) weeds, e.g. to be controlled and/or growth-inhibited, comprise (e.g. are) weeds from the genus Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cyperus (a genus of sedges), Digitaria, Echinochloa, Eriochloa, Fimbristylis (a genus of sedges), Juncus (a genus of rushes), Leptochloa, Lolium, Monochoria, Panicum, Phalaris, Poa, Rottboellia, Sagittaria, Scirpus (a genus of sedges), Setaria and/or Sorghum; in particular: Alopecurus myosuroides (ALOMY, English name "blackgrass"), Apera spica-venti, Avena fatua (AVEFA, English name "wild oats"), Avena ludoviciana, Avena sterilis, Avena sativa (English name "oats" (volunteer)), Brachiaria plantaginia, Bromus tectorum, Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (English name "common barnyard grass", ECHCG), Echinochloa oryzoides, Echinochloa colona or colonum, Eriochloa villosa (English name "woolly cupgrass"), Leptochloa chinensis, Leptochloa panicoides, Lolium perenne (LOLPE, English name "perennial ryegrass"), Lolium multiflorum (LOLMU, English name "Italian ryegrass"), Lolium persicum (English name "Persian darnel"), Lolium rigidum, Panicum miliaceum (English name "wild proso millet"), Phalaris minor, Phalaris paradoxa, Poa annua (POAAN, English name "annual bluegrass"), Scirpus maritimus, Scirpus juncoides, Setaria viridis (SETVI, English name "green foxtail"), Setaria faberi (SETFA, English name "giant foxtail"), Setaria lutescens (English name "yellow foxtail") and/or Sorghum halapense (English name "Johnson grass").

In one preferred embodiment of all aspects of the invention, the monocotyledonous weeds, e.g. to be controlled and/or growth-inhibited, are grassy weeds; in which case they typically comprise (e.g. are) weeds from the genus Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Digitaria, Echinochloa, Eriochloa, Leptochloa, Lolium, Panicum, Phalaris, Poa, Rottboellia, Setaria and/or Sorghum.

In one particular embodiment of all aspects of the invention, the grassy monocotyledonous weeds, e.g. to be controlled and/or growth-inhibited, are "warm-season" grassy weeds; in which case they typically comprise (e.g. are) weeds from the genus Brachiaria, Digitaria, Echinochloa, Eriochloa, Leptochloa, Panicum, Setaria and/or Sorghum.

In another particular embodiment of all aspects of the invention, the grassy monocotyledonous weeds, e.g. to be controlled and/or growth-inhibited, are "cool-season" grassy weeds; in which case they typically comprise (e.g. are) weeds from the genus Agrostis, Alopecurus, Apera, Avena, Bromus, Lolium and/or Poa.

In non-oat cereal crops such as wheat and/or barley, control and/or growth inhibition of weeds from the genus Alopecurus, Apera, Avena, especially Avena fatua, Bromus, Lolium, Phalaris, and/or Setaria is preferred; in particular Alopecurus, Avena (especially Avena fatua), Lolium and/or Setaria (especially Setaria viridis, Setaria lutescens and/or Setaria faberi).

In all aspects of the invention, in a particular embodiment, the weeds, e.g. to be controlled and/or growth-inhibited e.g. by applying a compound of formula (I), may be grassy monocotyledonous weeds (e.g. Alopecurus, Apera, Avena, Brachiaria, Bromus, Digitaria, Echinochloa, Eriochloa, Lolium, Panicum, Phalaris, Poa, Setaria and/or Sorghum weeds), -which are resistant to one or more ACCase inhibitor herbicides (ACCase = acetyl-coenzyme A carboxylase) selected from the group consisting of pinoxaden, clodinafop-propargyl, fenoxaprop-P-ethyl, diclofop-methyl, fluazifop-P-butyl, haloxyfop-P-methyl, quizalofop-P-ethyl, propaquizafop, cyhalofop-butyl, clethodim, sethoxydim, cycloxydim, tralkoxydim and butroxydim; -and/or which are resistant to glyphosate; -and/or which are resistant to one or more ALS inhibitor herbicides (ALS = acetolactate synthase), such as one or more sulfonyl urea herbicides (e.g. iodosulfuron-methyl, mesosulfuron-methyl, tribenuron-methyl, triasulfuron, prosulfuron, sulfosulfuron, pyrazosulfuron-ethyl, bensulfuron-methyl, nicosulfuron, or any other sulfonyl urea herbicide disclosed in The Pesticide Manual, 15th edition, 2009, ed. C.D.S. Tomlin, British Crop Protection Council) and/or one or more triazolopyrimidine herbicides (e.g. florasulam, pyroxsulam or penoxsulam) and/or one or more pyrimidinyl-(thio or oxy)-benzoate herbicides (e.g. bispyribac-sodium or pyriftalid) and/or one or more sulfonylamino-carbonyl-triazolinone herbicides (e.g. thiencarbazone-methyl, propoxycarbazone-sodium or flucarbazone-sodium).

Such resistant (in particular ACCase-inhibitor-resistant, glyphosate-resistant, and/or ALS-inhibitor-resistant) grassy weeds can more particularly comprise Alopecurus myosuroides, Apera spica-venti, Avena fatua, Avena sterilis, Digitaria sanguinalis, Echinochloa colona, Echinochloa crus-galli, Lolium multiflorum, Lolium rigidum, Lolium perenne, Phalaris minor, Phalaris paradoxa, Setaria viridis, Setaria faberi and/or Sorghum halapense.

In an even more particular embodiment of the invention, the compound of formula (I) can be applied to grassy monocotyledonous weeds (e.g. selected from one of the above-mentioned list(s) of grassy weeds): (al) which are resistant to one or more ACCase inhibitor herbicides (e.g. selected from the above-mentioned list of ACCase inhibitor herbicides) at least partly by means of mutation (e.g. substitution) of one or more amino acids on the ACCase target site in the weed (e.g. see S.B. Powles and Qin Yu, "Evolution in Action: Plants Resistant to Herbicides", Annu. Rev. Plant Biol., 2010, 61, pp. 317-347, e.g. see pages 325-327 therein in particular Table 3, incorporated herein by reference, for examples of such resistant weeds and/or amino acid (a2) which are resistant to glyphosate at least partly by means of mutation (e.g. substitution) of one or more amino acids on the EPSPS target site in the weed targeted by glyphosate (e.g. see above-mentioned S.B. Powles and Qin Yu article, pp. 327-329); and/or (a3) which are resistant to one or more ALS inhibitor herbicides (e.g. selected from the above-mentioned list of ALS inhibitor herbicides) at least partly by mutation (e.g. substitution) of one or more amino acids on the ALS target site in the weed (e.g. see SB.

Powles and Qin Yu, "Evolution in Action: Plants Resistant to Herbicides", Annu. Rev.

Plant Biol., 2010, 61, pp. 317-347, e.g. see pages 322-324 therein in particular Table 2, incorporated herein by reference, for examples of such resistant weeds and/or amino (b) which are resistant to: one or more ACCase inhibitor herbicides (e.g. selected from the above-mentioned list), and/or glyphosate, and/or one or more ALS inhibitor herbicides (e.g. selected from the above-mentioned list); at least partly by metabolic-type herbicidal resistance e.g. at least partly by cytochrome P450-mediated herbicide metabolism (e.g. see SB. Powles and Qin Yu, "Evolution in Action: Plants Resistant to Herbicides", Annu. Rev. PlantBiol., 2010, 61, pp. 317-347, e.g. seeTable4on page 328 therein, incorporated herein by reference, for examples of such resistant weeds).

Typically, dicotyledonous weeds, e.g. to be controlled, comprise (e.g. are) Abutilon, Amaranthus, Chenopodium, Chrysanthemum, Galium, lpomoea, Kochia, Nasturtium, Polygonum, Sida, Sinapsis, Solanum, Stellaria, Viola, Veronica and/or Xa nth i u m.

Areas under cultivation, and/or the locus (e.g. of weeds and/or of crops of useful plants), are to be understood as including land where the crop plants are already growing as well as land intended for the cultivation of those crop plants.

In all aspects of the invention, the rate of application of the compound of formula (I) (which optionally may be an agrochemically acceptable salt thereof) is generally from 1 to 2000 g of the compound of formula (I) per hectare (ha) (measured as the salt-free compound), in particular from 5 to 1000 or from 10 to 500 g/ha, preferably from 20 to 300 g/ha, of the compound of formula (I) (measured as the salt-free compound).

In all aspects of the invention, the compound of formula (I) can be applied pre-and/or post-emergence, but preferably is applied post-emergence.

Combinations and mixtures In a further aspect, the present invention provides a herbicidal composition, e.g. for use in a method of controlling weeds (e.g. monocotyledonous such as grassy weeds) in crops of useful plants, comprising a compound of formula (I) as defined herein (e.g. a herbicidally effective amount thereof), and an agrochemically acceptable carrier, diluent and/or solvent, and also comprising one or more further herbicides, and/or a safener.

Examples of these mixtures / compositions, comprising one or more further herbicides and/or a safener, follow.

The compounds of formula (I) according to the invention can be used in combination with one or more further herbicides, e.g. as mixture partner(s) for the compound of formula (I).

In particular, the following mixtures of the compound of formula (I) with one or more further herbicides are particularly disclosed: compound of formula (I) + acetochlor, compound of formula (I) + acifluorfen, compound of formula (l)+ acifluorfen-sodium, compound of formula (I) + aclonifen, compound of formula (I) + acrolein, compound of formula (I) + alachlor, compound of formula (I) + alloxydim, compound of formula (I) ÷ allyl alcohol, compound of formula (I) + ametryn, compound of formula (I) + amicarbazone, compound of formula (I) + amidosulfuron, compound of formula (I) + aminopyralid, compound of formula (I) + amitrole, compound of formula (I) + ammonium sulfamate, compound of formula (I) + anilofos, compound of formula (I) + asulam, compound of formula (I) + atraton, compound of formula (I) + atrazine, compound of formula (I) + azimsulfuron, compound of formula (I) + BCPC, compound of formula (I) + beflubutamid, compound of formula (I) + benazolin, compound of formula (I) + benfluralin, compound of formula (I) + benfuresate, compound of formula (I) + bensulfuron, compound of formula (I) + bensulfuron-methyl, compound of formula (I) + bensulide, compound of formula (I) + bentazone, compound of formula (I) + benzfendizone, compound of formula (I) + benzobicyclon, compound of formula (I) + benzofenap, compound of formula (I) + bifenox, compound of formula (I) + bilanafos, compound of formula (I) + bispyribac, compound of formula (I) + bispyribac-sodium, compound of formula (I) + borax, compound of formula (I) + bromacil, compound of formula (I) + bromobutide, compound of formula (I) + bromoxynil, compound of formula (I) + bromoxynil heptanoate, compound of formula (I) + bromoxynil octanoate, compound of formula (I) + bromoxynil heptanoate + bromoxynil octanoate, compound of formula (I) + butachlor, compound of formula (I) + butafenacil, compound of formula (I) + butamifos, compound of formula (I) + butralin, compound of formula (I) + butroxydim, compound of formula (I) + butylate, compound of formula (I) + cacodylic acid, compound of formula (I) + calcium chlorate, compound of formula (I) + cafenstrole, compound of formula (I) + carbetamide, compound of formula (I) + carfentrazone, compound of formula (I) + carfentrazone-ethyl, compound of formula (I) + CDEA, compound of formula (I) + CEPC, compound of formula (I) + chloransulam, compound of formula (I) + chloransulam-methyl, compound of formula (I) + chlorflurenol, compound of formula (I) ÷ chlorflurenol-methyl, compound of formula (I) + chloridazon, compound of formula (I) + chlorimuron, compound of formula (I) + chlorimuron-ethyl, compound of formula (I) + chloroacetic acid, compound of formula (I) + chlorotoluron, compound of formula (I) + chlorpropham, compound of formula (I) + chlorsulfuron, compound of formula (I) ÷ chlorthal, compound of formula (I) + chlorthal-dimethyl, compound of formula (I) + cinidon-ethyl, compound of formula (I) + cinmethylin, compound of formula (I) + cinosulfuron, compound of formula (I) + cisanilide, compound of formula (I) + clethodim, compound of formula (I) + clodinafop, compound of formula (I) + clodinafop-propargyl, compound of formula (I) + clomazone, compound of formula (I) + clomeprop, compound of formula (I) + clopyralid, compound of formula (I) + cloransulam, compound of formula (I) + cloransulam-methyl, compound of formula (I) + CMA, compound of formula (I) ÷ 4-CPB, compound of formula (I) + CPMF, compound of formula (I) + 4-CPP, compound of formula (I) + CPPC, compound of formula (I) + cresol, compound of formula (I) + cumyluron, compound of formula (I) + cyanamide, compound of formula (I) + cyanazine, compound of formula (I) + cycloate, compound of formula (I) + cyclosulfamuron, compound of formula (I) + cycloxydim, compound of formula (I) + cyhalofop, compound of formula (I) + cyhalofop-butyl, compound of formula (I) + 2,4-0, compound of formula (I) + 2,4 0 dimethylammonium, compound of formula (I) + 2,4 D 2 ethylhexyl, compound of formula (I) + 2,4-D + glyphosate, compound of formula (I) + 2,4 D dimethylammonium + glyphosate, compound of formula (I) + 2,4 D 2 ethylhexyl + glyphosate, compound of formula (I) + 3,4-DA, compound of formula (I) + daimuron, compound of formula (I) + dalapon, compound of formula (I) + dazomet, compound of formula (I) + 2,4-03, compound of formula (I) + 3,4-DB, compound of formula (I) + 2,4-DEB, compound of formula (I) + desmedipham, compound of formula (I) + dicamba, compound of formula (I) + dicamba-dimethylammonium, compound of formula (I) + dicamba-potassium, compound of formula (I) + dicamba-sodium, compound of formula (I) + dicamba + glyphosate, compound of formula (I) + dicamba-dimethylammonium + glyphosate, compound of formula (I) + dicamba-potassium + glyphosate, compound of formula (I) + dicamba-sodium + glyphosate, compound of formula (I) + dichlobenil, compound of formula (I) + ortho-dichlorobenzene, compound of formula (I) + para-dichlorobenzene, compound of formula (I) + dichiorprop, compound of formula (I) + dichlorprop-P, compound of formula (I) + diclofop, compound of formula (I) + diclofop-methyl, compound of formula (I) + diclosulam, compound of formula (I) + difenzoquat, compound of formula (I) + difenzoquat metilsulfate, compound of formula (I) + diflufenican, compound of formula (I) + diflufenzopyr, compound of formula (I) + dimefuron, compound of formula (I) + dimepiperate, compound of formula (I) + dimethachlor, compound of formula (I) + dimethametryn, compound of formula (I) + dimethenamid, compound of formula (I) + dimethenamid-P, compound of formula (I) + dimethipin, compound of formula (I) + dimethylarsinic acid, compound of formula (I) + dinitramine, compound of formula (I) + dinoterb, compound of formula (I) + diphenamid, compound of formula (I) + diquat, compound of formula (I) ÷ diquat dibromide, compound of formula (I) + dithiopyr, compound of formula (I) + diuron, compound of formula (I) + DNOC, compound of formula (I) + 3,4-DP, compound of formula (I) + DSMA, compound of formula (I) + EBEP, compound of formula (I) + endothal, compound of formula (I) + EPTC, compound of formula (I) + esprocarb, compound of formula (I) + ethalfluralin, compound of formula (I) + ethametsulfuron, compound of formula (I) + ethametsulfuron-methyl, compound of formula (I) + ethofumesate, compound of formula (I) + ethoxyfen, compound of formula (I) + ethoxysulfuron, compound of formula (I) + etobenzanid, compound of formula (I) + fenoxaprop, compound of formula (I) + fenoxaprop-ethyl, compound of formula (I) + fenoxaprop-P, compound of formula (I) + fenoxaprop-P-ethyl, compound of formula (I) + fenoxasulfone (CAS Reg. No. 639826-16-7), compound of formula (I) + fentrazamide, compound of formula (I) + ferrous sulfate, compound of formula (I) + flamprop-M, compound of formula (I) + flazasulfuron, compound of formula (I) + florasulam, compound of formula (I) + fluazifop, compound of formula (I) + fluazifop-butyl, compound of formula (I) + fluazifop-P, compound of formula (I) + fluazifop-P-butyl, compound of formula (I) + flucarbazone, compound of formula (I) + flucarbazone-sodium, compound of formula (I) + flucetosulfuron, compound of formula (I) + fluchloralin, compound of formula (I) + flufenacet, compound of formula (I) + flufenpyr, compound of formula (I) + flufenpyr-ethyl, compound of formula (I) + flumetsulam, compound of formula (I) + flumiclorac, compound of formula (I) + flumiclorac-pentyl, compound of formula (I) + flumioxazin, compound of formula (I) + fluometuron, compound of formula (I) + fluoroglycofen, compound of formula (I) + fluoroglycofen-ethyl, compound of formula (I) + flupropanate, compound of formula (I) + flupyrsulfuron, compound of formula (I) + flupyrsulfuron-methyl-sodium, compound of formula (I) + flurenol, compound of formula (I) + fluridone, compound of formula (I) + flurochioridone, compound of formula (I) + fluroxypyr, compound of formula (I) + fluroxypyr-meptyl, compound of formula (I) + fluroxypyr-butometyl, compound of formula (I) + flurtamone, compound of formula (I) + fluthiacet, compound of formula (I) + fluthiacet-methyl, compound of formula (I) + fomesafen, compound of formula (I) + foramsulfuron, compound of formula (I) + fosamine, compound of formula (I) + glufosinate, compound of formula (I) + glufosinate-ammonium, compound of formula (I) + glufosinate-P, compound of formula (I) + glyphosate, compound of formula (I) + glyphosate-diammonium, compound of formula (I) + glyphosate-isopropylammonium, compound of formula (I) + glyphosate-potassium, compound of formula (I) + halosulfuron, compound of formula (I) + halosulfuron-methyl, compound of formula (I) + haloxyfop, compound of formula (I) + haloxyfop-P, compound of formula (I) + haloxyfop-methyl, compound of formula (I) + haloxyfop-P-methyl, compound of formula (I) + HC-252, compound of formula (I) + hexazinone, compound of formula (I) + imazamethabenz, compound of formula (I) + imazamethabenz-methyl, compound of formula (I) + imazamox, compound of formula (I) + imazapic, compound of formula (I) + imazapyr, compound of formula (I) + imazaquin, compound of formula (I) + imazethapyr, compound of formula (I) + imazosulfuron, compound of formula (I) + indanofan, compound of formula (I) + lodomethane, compound of formula (I) + iodosulfuion, compound of formula (I) + iodosulfuron-methyl-sodium, compound of formula (I) + ioxynil, compound of formula (I) + ipfencarbazone (CAS Reg. No. 212201- 70-2), compound of formula (I) + isoproturon, compound of formula (I) + isouron, compound of formula (I) + isoxaben, compound of formula (I) + isoxachlortole, compound of formula (I) + isoxaflutole, compound of formula (I) + karbutilate, compound of formula (I) + lactofen, compound of formula (I) + lenacil, compound of formula (I) + linuron, compound of formula (I) + MAA, compound of formula (I) + MAMA, compound of formula (I) + MCPA, compound of formula (I) + MCPA-thioethyl, compound of formula (I) + MCPB, compound of formula (I) + mecoprop, compound of formula (I) + mecoprop-P, compound of formula (I) + mefenacet, compound of formula (I) + mefluidide, compound of formula (I) + mesosulfuron, compound of formula (I) + mesosulfuron-methyl, compound of formula (I) + mesotrione, compound of formula (I) + metam, compound of formula (I) + metamifop, compound of formula (I) + metamitron, compound of formula (I) + metazachlor, compound of formula (I) + metazosulfuron (NC-620, CAS Reg. No. 868680-84-6), compound of formula (I) + methabenzthiazuron, compound of formula (I) + methylarsonic acid, compound of formula (I) + methyldymron, compound of formula (I) + methyl isothiocyanate, compound of formula (I) + metobenzuron, compound of formula (I) + metolachlor, compound of formula (I) + S-metolachlor, compound of formula (I) + metosulam, compound of formula (I) + metoxuron, compound of formula (I) + metribuzin, compound of formula (I) + metsulfuron, compound of formula (I) + metsulfuron-methyl, compound of formula (I) + MK-616, compound of formula (I) + molinate, compound of formula (I) + monolinuron, compound of formula (I) + MSMA, compound of formula (I) + S naproanilide, compound of formula (I) + napropamide, compound of formula (I) + naptalam, compound of formula (I) + neburon, compound of formula (I) + nicosulfuron, compound of formula (I) + nonanoic acid, compound of formula (I) + norflurazon, compound of formula (I) + oleic acid (fatty acids), compound of formula (I) + orbencarb, compound of formula (I) + orthosulfamuron, compound of formula (I) + oryzalin, compound of formula (I) + oxadiargyl, compound of formula (I) + oxadiazon, compound of formula (I) + oxasulfuron, compound of formula (I) + oxaziclomefone, compound of formula (I) ÷ oxyfluorfen, compound of formula (I) + paraquat, compound of formula (I) + paraquat dichloride, compound of formula (I) + pebulate, compound of formula (I) + pendimethalin, compound of formula (I) + penoxsulam, compound of formula (I) + pentachlorophenol, compound of formula (I) + pentanochlor, compound of formula (I) + pentoxazone, compound of formula (I) + pethoxamid, compound of formula (I) + petrolium oils, compound of formula (I) + phenmedipham, compound of formula (I) + phenmedipham-ethyl, compound of forniula (I) + picloram, compound of formula 0) + picolinafen, compound of formula (I) + pinoxaden, compound of formula (I) ÷ piperophos, compound of formula (I) + potassium arsenite, compound of formula (I) + potassium azide, compound of formula (I) + pretilachlor, compound of formula (I) + primisulfuron, compound of formula (I) + primisulfuron-methyl, compound of formula (I) + prodiamine, compound of formula (I) + profluazol, compound of formula (I) + profoxydim, compound of formula (I) + prometon, compound of formula (I) + prometryn, compound of formula (I) + propachlor, compound of formula (I) + propanil, compound of formula (I) + propaquizafop, compound of formula (I) + propazine, compound of formula (I) + propham, compound of formula (I) + propisochlor, compound of formula (I) + propoxycarbazone, compound of formula (I) + propoxycarbazone-sodium, compound of formula (I) + propyrisulfuron (TH-547, CAS Reg. No. 570415-88-2), compound of formula (I) + propyzamide, compound of formula (I) + prosulfocarb, compound of formula (I) + prosulfuron, compound of formula (I) + pyraclonil, compound of formula (I) + pyraflufen, compound of formula (I) + pyraflufen-ethyl, compound of formula (I) + pyrazolynate, compound of formula (I) + pyrazosulfuron, compound of formula (I) + pyrazosulfuron-ethyl, compound of formula (I) + pyrazoxyfen, compound of formula (I) + pyribenzoxim, compound of formula (I) + pyributicarb, compound of formula (I) + pyridafol, compound of formula (I) + pyridate, compound of formula (I) + pyriftalid, compound of formula (I) + pyriminobac, compound of formula (I) + pyriminobac-methyl, compound of formula (I) + pyrimisulfan, compound of formula (I) + pyrithiobac, compound of formula (I) + pyrithiobac-sodium, compound of formula (I) + quinclorac, compound of formula (I) + quinmerac, compound of formula (I) + quinoclamine, compound of formula (I) + quizalofop, compound of formula (I) + quizalofop-ethyl, compound of formula (I) + quizalofop-P, compound of formula (I) + quizalofop-P-ethyl, compound of formula (I) + quizalofop-P-tefuryl, compound of formula (I) + rimsulfuron, compound of formula (I) + sethoxydim, compound of formula (I) + siduron, compound of formula (I) + simazine, compound of formula (I) + simetryn, compound of formula (I) + SMA, compound of formula (I) + sodium arsenite, compound of formula (I) + sodium azide, compound of formula (I) + sodium chlorate, compound of formula (I) + sulcotrione, compound of formula (I) + sulfentrazone, compound of formula (I) + sulfometuron, compound of formula (I) + sulfometuron-methyl, compound of formula (I) + sulfosate, compound of formula (I) + sulfosulfuron, compound of formula (I) + sulfuric acid, compound of formula (I) + tar oils, compound of formula (I) + 2,3,6-TBA, compound of formula (I) + TCA, compound of formula (I) + TCA-sodium, compound of formula (I) + tebuthiuron, compound of formula (I) + tepraloxydim, compound of formula (I) + terbacil, compound of formula (I) + terbumeton, compound of formula (I) + terbuthylazine, compound of formula (I) + terbutryn, compound of formula (I) + thenylchlor, compound of formula (I) + thiazopyr, compound of formula (I) + thifensulfuron, compound of formula (I) + thifensulfuron-methyl, compound of formula (I) + thiobencarb, compound of formula (I) + tiocarbazil, compound of formula (I) + topramezone, compound of formula (I) + tralkoxydim, compound of formula (I) + tri-allate, compound of formula (I) + triasulfuron, compound of formula (I) + triaziflam, compound of formula (I) + tribenuron, compound of formula (I) + tribenuron-methyl, compound of formula (I) + tricamba, compound of formula (I) + triclopyr, compound of formula (I) + trietazine, compound of formula (I) + trifloxysulfuron, compound of formula (I) + trifloxysulfuron-sodium, compound of formula (I) + trifluralin, compound of formula (I) + triflusulfuron, compound of formula (I) + triflusulfuron-methyl, compound of formula (I) + trihydroxytriazine, compound of formula (I) + tritosulfuron, compound of formula (I) + [3-[2-chloro-4-fluoro-5-(i-niethyl-6-trifluoromethyl-2,4-dioxo-1,2,3, 4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester (CAS Reg. No. 353292-31-6), compound of formula (I) + 4-[(4,5-dihydro- 3-methoxy-4-methyl-5-oxo)-1 H-i,2,4-triazol-1 -ylcarbonylsulfamoyl]-5-methylthiophene- 3-carboxylic acid (BAY636), compound of formula 0) + BAY747(CAS Reg. No. 335104- 84-2), compound of formula (I) + topramezone (CAS Reg. No. 210631 -68-8), compound of formula (I) + 4-hydroxy-3-[2-[(2-methoxyethoxy)'methyl]-6-(trifluoro'methy-3-pyridinyl] carbonyl]-bicyclo[3.2. 1]oct-3-en-2-one (which is bicyclopyrone, CAS Reg. No. 352010-68-5), compound of formula (I) + 4-hydroxy-3-[2-(3-methoxypropyl)-6- (difluoro-'methyl)-3-pyridinyl]carbonyl]-bicyclo[3.2. 1]oct-3-en-2-one, compound of formula (I) + 4-(4'-chloro-4-cyclopropyl-2'-fluorobiphenyl-3-y-2,2,6,6-tetramethyl-2H- pyran-3,5(4H,6H)-dione (which is the compound of Example P8 disclosed on pages 31- 32 and 35-36 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-13 disclosed in pages 4,5,7 and 11 of WO 2011/073616A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'-dichloro-4-cyclopropylbiphenyl-3-yl)-2,2,6, 6-tetramethyl-2H-pyran- 3,5(4H,6H)-dione (which is the compound of Example P9 disclosed on pages 36-37 and 40-41 of WO 20101136431 A9 (Syngenta Limited), and which is also compound A-12 disclosed in page 10 of WO 2011/073616 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(4'-chloro-4-ethyl-2'-fluorobiphenyl-3-y-2,2,6,6-tetramethyl-2H-pyran-3, 5(4H,6H)-dione (which is compound A-66 disclosed on page 95 of WO 2008/071405 Al (Syngenta Participations AG and Syngenta Limited), and which is also compound A-4 disclosed on page 7 of WO 2011/073615 A2 (Syngenta Limited), these pads of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'-dichloro-4-ethylbiphenyl-3-y-2,2,6,6-tetramethyl-2H-pyran-3,5(4H, 6H)-dione (which is compound A-45 disclosed on page 93 of WO 2008/071405 Al (Syngenta Participations AG and Syngenta Limited), and which is also the compound of Example PlO disclosed on pages 41 and 45 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-7 disclosed on page 7 of WO 2011/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'- dichloro-4-ethylbiphenyl-3-y-5-(methoxycarbonyloxy)-2,2,6, 6-tetramethyl-2H-pyran- 3(6H)-one (which is compound D-26 disclosed on page 231 of WO 2008/071405 Al (Syngenta Participations AG and Syngenta Limited), and which is also compound A-9 disclosed on page 8 of WO 2011/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 2010/059676 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus cloquintocet-mexyl as safener) these parts of which are incorporated herein by reference, compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 2010/059680 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus cloquintocet-mexyl or another safener) these parts of which are incorporated herein by reference, and compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 2010/059671 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus a safener) these parts of which are incorporated herein by reference, compound of formula (I) + halauxifen (which is 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenypyridine-2-carboxylic acid, CAS Reg. No. 943832-60-8), compound of formula (I) + halauxifen-methyl (which is methyl 4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxyphenypyridine-2-carboxylate, CAS Reg. No. 943831-98-9), compound of formula (I) + aminocyclopyrachlor (which is 6-amino-5-chloro-2-cyclopropylpyrimidine-4-carboxylic acid, CAS Reg. No. 858956-08-8), compound of formula (I) + aminocyclopyrachlor-methyl (which is methyl 6-amino-5-chloro-2-cyclopropylpyrimidine- 4-carboxylate, CAS Reg. No. 858954-83-3), compound of formula (I) + aminocyclopyrachlor-potassium (which is potassium 6-amino-5-chloro-2-cyclopropylpyrimidine-4-carboxylate, CAS Reg. No. 858956-35-1), compound of formula (I) + saflufenacil (which is N -{2-chloro-4-fluoro-5-[1,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4- (trifluoromethyl)pyrimidin-1 -yl]benzoyl}-N-isopropyl-N-methylsulfamide, CAS Reg. No. 372137-35-4), compound of formula (I) + iofensulfuron (which is 1-(2-iodophenylsulfonyl)-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea, CAS Reg. No. 1144097-22-2), compound of formulaW+ iofensulfuron-sodium (which is sodium N-(2-iodophenylsulfonyl)-N' -(4-methoxy-6-rrethyl-1,3,5-triazin-2-yl)carbamimidate, CAS Reg. No. 1144097-30-2), compound of formula (I) + clacyfos (which is dimethyl [(iRS)- 1 -(2,4-dichlorophenoxyacetoxy)ethyl]phosphonate, also named lvxiancaolin or luxiancaolin, CAS Reg. No. 215655-76-8), compound of formula (I) + cyclopyrimorate (which is 6-chloro-3-(2-cyclopropyl-6-methylphenoxy)pyridazin-4-yl moipholine-4-carboxylate, CAS Reg. No. 499231-24-2), or compound of formula (I) + triafamone (which is N-[2-[(4,6-dimethoxy-1,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl] -N-methyl-1, 1-difluoromethanesulfonamide, CAS Reg. No. 874195-61-6).

The mixture partners for the compound of formula (I) are optionally in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible). The above-mentioned mixture partners for the compound of formula (I), are generally mentioned e.g. in The Pesticide Manual, 15th Edition, 2009, ed. C.D.S. Tomlin, British Crop Production Council.

In the present patent specification, "CAS Reg. No." or CAS RN" means the Chemical Abstracts Service Registry Number of the stated compound.

For applications in cereals, the following mixtures are preferred: compound of formula (I) ÷ aclonifen, compound of formula (I) + amidosulfuron, compound of formula (I) + aminopyralid, compound of formula (I) + beflubutamid, compound of formula (I) + benfluralin, compound of formula (I) + bifenox, compound of formula (I) + bromoxynil, compound of formula (I) + bromoxynil heptanoate, compound of formula (I) + bromoxynil octanoate, compound of formula (I) + bromoxynil heptanoate + bromoxynil octanoate, compound of formula (I) + butafenacil, compound of formula (I) + carbetamide, compound of formula (I) + carfentrazone, compound of formula (I) + carfentrazone-ethyl, compound of formula (I) + chlorotoluron, compound of formula (I) + chlorpropham, compound of formula (I) + chlorsulfuron, compound of formula (I) + cinidon-ethyl, compound of formula (I) + clodinafop, compound of formula (I) + clodinafop-propargyl, compound of formula (I) + clopyralid, compound of formula (I) + 2,4-0, compound of formula (I) + dicamba, compound of formula (I) + dicamba-dimethylammonium, compound of formula (I) + dicamba-potassium, compound of formula (I) + dicamba-sodium, compound of formula (I) + dichlobenil, compound of formula (I) + dichlorprop, compound of formula (I) + diclofop, compound of formula (I) + diclofop-methyl, compound of formula (I) + difenzoquat, compound of formula (I) + difenzoquat metilsulfate, compound of formula (I) + diflufenican, compound of formula (I) + diquat, compound of formula (I) + diquat dibromide, compound of formula (I) + fenoxaprop, compound of formula (I) + fenoxaprop-ethyl, compound of formula (I) + fenoxaprop-P, compound of formula (I) + fenoxaprop-P-ethyl, compound of formula (I) + flamprop-M, compound of formula (I) + florasulam, compound of formula (I) + fluazifop-P-butyl, compound of formula (I) + flucarbazone, compound of formula (I) + flucarbazone-sodium, compound of formula (I) + flufenacet, compound of formula (I) + flupyrsulfuron, compound of formula (I) + flupyrsulfuron-methyl-sodium, compound of formula (I) + flurochloridone, compound of formula (I) + fluroxypyr, compound of formula (I) + fluroxypyr-meptyl, compound of formula (I) + fluroxypyr-butometyl, compound of formula (I) + flurtamone, compound of formula (I) + imazamethabenz-methyl, compound of formula (I) + imazamox, compound of formula (I) + iodosulfuron, compound of formula (I) + iodosulfuron-methyl-sodium, compound of formula (I) + ioxynil, compound of formula (I) + isoproturon, compound of formula (I) + linuron, compound of formula (I) + MCPA, compound of formula (I) + mecoprop, compound of formula (I) + mecoprop-P, compound of formula (I) + mesosulfuron, compound of formula (I) + mesosulfuron-methyl, compound of formula (I) + mesotrione, compound of formula (I) + metribuzin, compound of formula (I) + metsulfuron, compound of formula (I) + metsulfuron-methyl, compound of formula (I) + pendimethalin, compound of formula (I) + picolinafen, compound of formula (I) + pinoxaden, compound of formula (I) + prodiamine, compound of formula (I) + propanil, compound of formula (I) + propoxycarbazone, compound of formula (I) + propoxycarbazone-sodium, compound of formula (I) + prosulfocarb, compound of formula (I) + pyrasulfotole, compound of formula (I) + pyridate, compound of formula 0) + pyroxasulfone (KIH-485), compound of formula (I) + pyroxsulam compound of formula (I) + sulfosulfuron, compound of formula 1 + tembotrione, compound of formula (I) + terbutryn, compound of formula (I) + thifensulfuron, S compound of formula (I) + thiencarbazone, compound of formula (I) + thifensulfuron-methyl, compound of formula (I) + topramezone, compound of formula (I) + tralkoxydim, compound of formula (I) + tri-allate, compound of formula (I) + triasulfuron, compound of formula (I) ÷ tribenuron, compound of formula (I) + tribenuron-methyl, compound of formula (I) + trifluralin, compound of formula (I) + trinexapac-ethyl and compound of formula (I) + tritosulfuron, compound of formula (I) + 4-hydroxy-3-[2-[(2- methoxyethoxy)-'methyl]-6-(trifluoro-'methyl)-3-pyridinyl]carbonyl] -bicyclo[3.2. 1]oct-3-en- 2-one (which is bicyclopyrone, CAS Reg. No. 352010-68-5), compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 201 0/059676 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus cloquintocet-mexyl as safener) these parts of which are incorporated herein by reference, compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 201 0/059680 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus cloquintocet-mexyl or another safener) these parts of which are incorporated herein by reference, compound of formula (I) ÷ halauxifen (which is 4-amino-3-chloro-6-(4-chloro- 2-fluoro-3-methoxyphenypyridine-2-carboxylic acid, CAS Reg. No. 943832-60-8), compound of formula (I) + halauxifen-methyl (which is methyl 4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxyphenypyridine-2-carboxylate, CAS Reg. No. 943831-98-9), compound of formula (I) + iofensulfuron (which is 1-(2-iodophenylsulfony-3-(4-methoxy- 6-methyl-i,3,5-triazin-2-yurea, CAS Reg. No. 1144097-22-2), or compound of formula (I) + iofensulfuron-sodium (which is sodium N-(2-iodophenylsulfonyl)-N' -(4-methoxy-6-methyl-i,3,5-triazin-2-yl)carbamimidate, CAS Reg. No. 1144097-30-2); wherein the mixture partners for the compound of formula (I) may optionally be in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible).

For applications in cereals, more preferred is a mixture comprising: a compound of formula (I) + amidosulfuron, compound of formula (I) + aminopyralid, compound of formula (I) + beflubutamid, compound of formula (I) + bromoxynil, compound of formula (I) + bromoxynil heptanoate, compound of formula (I) ÷ bromoxynil octanoate, compound of formula (I) + bromoxynil heptanoate + bromoxynil octanoate, compound of formula (I) + carfentrazone, compound of formula (I) + carfentrazone-ethyl, compound of formula (I) + chlorotoluron, compound of formula (I) + chlorsulfuron, compound of formula (I) + clodinafop, compound of formula (I) + clodinafop-propargyl, compound of formula (I) + clopyralid, compound of formula (I) + 2,4-D, compound of formula (I) + dicamba, compound of formula (I) + dicamba, compound of formula (I) + dicamba-dimethylammonium, compound of formula (I) + dicamba-potassium, compound of formula (I) + dicamba-sodium, compound of formula (I) + difenzoquat, compound of formula (I) + difenzoquat metilsulfate, compound of formula (I) + diflufenican, compound of formula (I) + fenoxaprop-P, compound of formula (I) + fenoxaprop-P-ethyl, compound of formula (I) + florasulam, compound of formula (I) + flucarbazone, compound of formula (I) + flucarbazone-sodium, compound of formula (I) + flufenacet, compound of formula (I) + flupyrsulfuron, compound of formula (I) + flupyrsulfuron-methyl-sodium, compound of formula (I) + fluroxypyr, compound of formula (I) + fluroxypyr-meptyl, compound of formula (I) + fluroxypyr-butometyl, compound of formula (I) + flurtamone, compound of formula (I) + iodosulfuron, compound of formula (I) + iodosulfuron-methyl-sodium, compound of formula (I) + MCFA, compound of formula (I) + mesosulfuron, compound of formula (I) + mesosulfuron-methyl, compound of formula (I) + metsulfuron, compound of formula (I) + metsulfuron-methyl, compound of formula (I) + pendimethalin, compound of formula (I) + picolinafen, compound of formula (I) + pinoxaden, compound of formula (I) + prosulfocarb, compound of formula (I) + pyrasulfotole, compound of formula (I) + pyroxasulfone (KIH-485), compound of formula (I) + pyroxsulam, compound of formula (I) + sulfosulfuron, compound of formula (I) + thifensulfuron, compound of formula (I) + thifensulfuron-methyl, compound of formula (I) + topramezone, compound of formula (I) + tralkoxydim, compound of formula (I) + triasulfuron, compound of formula (I) + tribenuron, compound of formula (I) + tribenuron-methyl, compound of formula (I) + trifluralin, compound of formula (I) + trinexapac-ethyl, compound of formula (I) + tritosulfuron, compound of formula (I) + 4-hydroxy-3-[2-[(2- methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3. 2. 1]oct-3-en-2-one (which is bicyclopyrone, CAS Reg. No. 352010-68-5), compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 2010/059676 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus cloquintocet-mexyl as safener) these parts of which are incorporated herein by reference, compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 201 0/059680 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus cloquintocet-mexyl or another safener) these parts of which are incorporated herein by reference, compound of formula (I) + halauxifen (which is 4-amino-3-chloro-6-(4-chloro- 2-fluoro-3-methoxyphenypyridine-2-carboxylic acid, CAS Reg. No. 943832-60-8), compound of formula (I) + halauxifen-methyl (which is methyl 4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxyphenypyridine-2-carboxylate, CAS Reg. No. 943831-98-9), compound of formula (I) + iofensulfuron (which is 1-(2-iodophenylsulfony-3-(4-methoxy- 6-methyl-i,3,5-triazin-2-yurea, CAS Reg. No. 1144097-22-2), or compound of formula (I) + iofensulfuron-sodium (which is sodium N-(2-iodophenylsulfonyl)-N I -(4-methoxy-6-S methyl-i,3,5-triazin-2-yl)carbamimidate, CAS Reg. No. 1144097-30-2); wherein the mixture partners for the compound of formula (I) may optionally be in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible).

For applications in rice, the following mixtures are preferred: compound of formula (I) + azimsulfuron, compound of formula (I) ÷ bensulfuron, compound of formula (I) + bensulfuron-methyl, compound of formula (I) + benzobicyclon, compound of formula (I) + benzofenap, compound of formula (I) + bispyribac, compound of formula (I) + bispyribac-sodium, compound of formula (I) + butachlor, compound of formula (I) + cafenstrole, compound of formula (I) + cinosulfuron, compound of formula (I) + clomazone, compound of formula (I) + clomeprop, compound of formula (I) + cyclosulfamuron, compound of formula (I) + cyhalofop, compound of formula (I) + cyhalofop-butyl, compound of formula (I) + 2,4-0, compound of formula (I) + daimuron, compound of formula (I) + dicamba, compound of formula (I) + dicamba-dimethylammonium, compound of formula (I) + dicamba-potassium, compound of formula (I) + dicamba-sodium, compound of formula (I) + diquat, compound of formula (I) + diquat dibromide, compound of formula (I) + esprocarb, compound of formula (I) + ethoxysulfuron, compound of formula (I) + fenoxaprop, compound of formula (I) + fenoxaprop-ethyl, compound of formula (I) + fenoxaprop-P, compound of formula (I) + fenoxaprop-P-ethyl, compound of formula (I) + fenoxasulfone (CAS Reg. No. 639826- 16-7), compound of formula (I) + fentrazamide, compound of formula (I) + florasulam, compound of formula (I) + glufosinate-ammonium, compound of formula (I) + glyphosate, compound of formula (I) + glyphosate-diammonium, compound of formula (I) + glyphosate-isopropylammonium, compound of formula (I) + glyphosate-potassium, compound of formula (I) + halosulfuron, compound of formula (I) + halosulfuron-methyl, compound of formula (I) + imazosulfuron, compound of formula (I) + ipfencarbazone (CAS Reg. No. 212201-70-2), compound of formula (I) + MCPA, compound of formula 0) + mefenacet, compound of formula (I) + mesotrione, compound of formula (I) + metamifop, compound of formula (I) + metazosulfuron (NC-620, CAS Reg. No. 868680- 84-6), compound of formula (I) + metsulfuron, compound of formula (I) + metsulfuron-methyl, compound of formula (I) + n-methyl glyphosate, compound of formula (I) + orthosulfamuron, compound of formula (I) + oryzalin, compound of formula (I) + oxadiargyl, compound of formula (I) + oxadiazon, compound of formula (I) + paraquat dichioride, compound of formula (I) + pendimethalin, compound of formula (I) + penoxsulam, compound of formula (I) + pretilachlor, compound of formula (I) + profoxydim, compound of formula (I) + propanil, compound of formula (I) + S propyrisulfuron (TH-547, GAS Reg. No. 570415-88-2), compound of formula (I) + pyrazolynate, compound of formula (I) + pyrazosulfuron, compound of formula (I) + pyrazosulfuron-ethyl, compound of formula (I) + pyrazoxyfen, compound of formula (I) + pyribenzoxim, compound of formula (I) + pyriftalid, compound of formula (I) ÷ pyriminobac, compound of formula (I) + pyriminobac-methyl, compound of formula (I) + pyrimisulfan, compound of formula (I) + quinclorac, compound of formula (I) + tefuryltrione, compound of formula (I) + triasulfuron and compound of formula (I) + trinexapac-ethyl, compound of formula (I) + 4-(4'-chloro-4-cyclopropyl-2'-fluorobiphenyl- 3-y-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione (which is the compound of Example P8 disclosed on pages 31-32 and 35-36 of WO 201 0/1 36431 A9 (Syngenta Limited), and which is also compound A-13 disclosed in pages 4, 5, 7 and 11 of WO 2011/073616 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'-dichloro-4-cyclopropylbiphenyl-3-yl)- 2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione (which is the compound of Example P9 disclosed on pages 36-37 and 40-41 of WO 2010/1 36431 A9 (Syngenta Limited), and which is also compound A-12 disclosed in page 10 of WO 2011/073616 A2 (Syngenta Limited), these pads of these publications being incorporated herein by reference), compound of formula (I) + 4-(4'-chloro-4-ethyl-2'-fluorobiphenyl-3-yl)-2,2,6,6-tetramethyl- 2H-pyran-3,5(4H,6H)-dione (which is compound A-66 disclosed on page 95 of WO 2008/071405 Al (Syngenta Participations AG and Syngenta Limited), and which is also compound A-4 disclosed on page 7 of WO 2011/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'-dichloro-4-ethylbiphenyl-3-y-2,2,6,6-tetramethyl-2H-pyran- 3,5(4H,6H)-dione (which is compound A-45 disclosed on page 93 of WO 2008/071405 Al (Syngenta Participations AG and Syngenta Limited), and which is also the compound of Example PlO disclosed on pages 41 and 45 of WO 201 0/1 36431 AG (Syngenta Limited), and which is also compound A-7 disclosed on page 7 of WO 2011/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'-dichloro-4-ethylbiphenyl-3-yl)-5- (methoxycarbonyloxy)-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (which is compound D- 26 disclosed on page 231 of WO 2008/071405 Al (Syngenta Participations AG and Syngenta Limited), and which is also compound A-9 disclosed on page 8 of WO 2011/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 2010/059671 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus a safener) these parts of which are incorporated herein by reference, compound of formula (I) + halauxifen (which is 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenypyridine-2-carboxylic acid, CAS Reg. No. 943832-60-6), compound of formula (I) + halauxifen-methyl (which is methyl 4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxyphenypyridine-2-carboxylate, CAS Reg.

No. 943831-98-9), compound of formula (I) + iofensulfuron (which is 1-(2-iodophenylsulfonyl)-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea, CAS Reg. No. 1144097-22-2), compound of formulaW+ iofensulfuron-sodium (which is sodium N-(2-iodophenylsulfonyl)-N' -(4-methoxy-6-rrethyl-1,3,5-triazin-2-yl)carbamimidate, CAS Reg. No. 1144097-30-2), or compound of formula (I) + triafamone (which is N-[2-[(4,6- dimethoxy-1,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-N-methyl-1, 1-difluoromethanesulfonamide, CAS Reg. No. 874195-61-6); wherein the mixture partners for the compound of formula (I) may optionally be in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible).

For applications in rice, more preferred is a mixture comprising: a compound of formula (I) + azimsulfuron, compound of formula (I) + bensulfuron, compound of formula (I) + bensulfuron-methyl, compound of formula (I) + benzobicyclon, compound of formula (I) + benzofenap, compound of formula (I) + bispyribac, compound of formula (I) + bispyribac-sodium, compound of formula (I) + clomazone, compound of formula (I) + clomeprop, compound of formula (I) + cyhalofop, compound of formula (I) + cyhalofop-butyl, compound of formula (I) + 2,4-D, compound of formula (I) + daimuron, compound of formula (I) + dicamba, compound of formula (I) + dicamba-dimethylammonium, compound of formula (I) + dicamba-potassium, compound of formula (I) + dicamba-sodium, compound of formula (I) + esprocarb, compound of formula (I) + ethoxysulfuron, compound of formula (I) + fenoxaprop-P, compound of formula (I) + fenoxaprop-P-ethyl, compound of formula (I) + fenoxasulfone (CAS Reg. No. 639826-16-7), compound of formula (I) + fentrazamide, compound of formula (I) + florasulam, compound of formula (I) + halosulfuron, compound of formula (I) + halosulfuron-methyl, compound of formula (I) + imazosulfuron, compound of formula (I) + ipfencarbazone (CAS Reg. No. 212201- 70-2), compound of formula (I) + MCPA, compound of formula (I) + mefenacet, compound of formula (I) + mesotrione, compound of formula (I) + metazosulfuron (NC- 620, CAS Reg. No. 868680-84-6), compound of formula (I) + metsulfuron, compound of formula (I) + metsulfuron-methyl, compound of formula (I) + orthosulfamuron, compound of formula (I) + oxadiargyl, compound of formula (I) + oxadiazon, compound of formula (I) + pendimethalin, compound of formula (I) + penoxsulam, compound of formula (I) + pretilachlor, compound of formula (I) + propyrisulfuron (TH-547, CAS Reg. No. 570415- 88-2), compound of formula (I) + pyrazolynate, compound of formula (I) + pyrazosulfuron, compound of formula (I) + pyrazosulfuron-ethyl, compound of formula (I) + pyrazoxyfen, compound of formula (I) + pyribenzoxim, compound of formula (I) + pyriftalid, compound of formula (I) + pyriminobac, compound of formula (I) ÷ pyriminobac-methyl, compound of formula (I) + pyrimisulfan, compound of formula (I) + quinclorac, compound of formula (I) + tefuryltrione, compound of formula (I) + triasulfuron and compound of formula (I) + trinexapac-ethyl, compound of formula (I) + 4-(4'-chloro-4-cyclopropyl-2'-fluorobiphenyl-3-yl)-2,2,6, 6-tetramethyl-2H-pyran- 3,5(4H,6H)-dione (which is the compound of Example P8 disclosed on pages 31-32 and 35-36 of WO 201 0/136431 A9 (Syngenta Limited), and which is also compound A-13 disclosed in pages 4, 5, 7 and 11 of WO 2011/073616 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'-dichloro-4-cyclopropylbiphenyl-3-yl)-2,2,6, 6-tetramethyl-2H-pyran- 3,5(4H,6H)-dione (which is the compound of Example P9 disclosed on pages 36-37 and 40-41 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-12 disclosed in page 10 of WO 2011/073616 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(4'-chloro-4-ethyl-2'-fluorobiphenyl-3-y-2,2,6,6-tetramethyl-2H-pyran-3, 5(4H,6H)-dione (which is compound A-66 disclosed on page 95 of WO 2008/071405 Al (Syngenta Participations AG and Syngenta Limited), and which is also compound A-4 disclosed on page 7 of WO 201 l/073615A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'-dichloro-4-ethylbiphenyl-3-y-2,2,6,6-tetramethyl-2H-pyran-3,5(4H, 6H)-dione (which is compound A-45 disclosed on page 93 of WO 2008/071405 Al (Syngenta Participations AG and Syngenta Limited), and which is also the compound of Example PlO disclosed on pages 41 and 45 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-7 disclosed on page 7 of WO 2011/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'- dichloro-4-ethylbiphenyl-3-y-5-(methoxycarbonyloxy)-2,2,6, 6-tetramethyl-2H-pyran- 3(6H)-one (which is compound D-26 disclosed on page 231 of WO 2008/071405 Al (Syngenta Participations AG and Syngenta Limited), and which is also compound A-9 disclosed on page 8 of WO 2011/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 2010/059671 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus a safener) these pails of which are incorporated herein by reference, compound of formula (I) + halauxifen (which is 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenypyridine-2-carboxylic acid, CAS Reg. No. 943832-60-8), compound of formula (I) + halauxifen-methyl (which is methyl 4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxyphenypyridine-2-carboxylate, CAS Reg.

No. 943831-98-9), compound of formula (I) + iofensulfuron (which is 1-(2-iodophenylsulfonyQ-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yDurea, CAS Reg. No. 1144097-22-2), compound of formula(l)+ iofensulfuron-sodium (which is sodium N-(2-iodophenylsulfonyl)-N' -(4-methoxy-6-methyl-1,3,5-triazin-2-yl)carbamimidate, CAS Reg. No. 1144097-30-2), or compound of formula (I) + triafamone (which is N-[2-[(4,6- dimethoxy-1,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-N-methyl-1, 1-difluoromethanesulfonamide, CAS Reg. No. 874195-61-6); wherein the mixture partners for the compound of formula (I) may optionally be in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible).

For applications in soybean, the following mixtures are preferred: compound of formula (I) + acifluorfen, compound of formula (I) + acifluorfen-sodium, compound of formula (I) + ametryn, compound of formula (I) + atrazine, compound of formula (I) + bentazone, compound of formula (I) + bicyclopyrone, compound of formula (I) + bromoxynil, compound of formula (I) + bromoxynil heptanoate, compound of formula (I) + bromoxynil octanoate, compound of formula (I) + bromoxynil heptanoate + bromoxynil octanoate, compound of formula (I) + carfentrazone, compound of formula (I) + carfentrazone-ethyl, compound of formula (I) + chloransulam, compound of formula (I) + chloransulam-methyl, compound of formula (I) + chlorimuron, compound of formula (I) + chlorimuron-ethyl, compound of formula (I) + clethodim, compound of formula (I) + clomazone, compound of formula (I) + cyanazine, compound of formula (I) + 2,4-D (especially for applications to 2,4-D-tolerant soybean, e.g. genetically-modified), compound of formula (I) + 2,4-D-dimethylammonium (especially for applications to 2,4-D-tolerant soybean, e.g. genetically-modified), compound of formula (I) + 2,4 D 2 ethylhexyl (especially for applications to 2,4-D-tolerant soybean, e.g. genetically-modified), compound of formula (I) + 2,4-D + glyphosate (especially for applications to 2,4-D-tolerant soybean, e.g. genetically-modified), compound of formula (I) + 2,4-D-dimethylammonium + glyphosate (especially for applications to 2,4-D-tolerant soybean, e.g. genetically-modified), compound of formula (I) + 2,4 D 2 ethylhexyl + glyphosate (especially for applications to 2,4-0-tolerant soybean, e.g. genetically-modified), compound of formula (I) + dicamba (especially for applications to dicamba-tolerant soybean, e.g. genetically-modified), compound of formula (I) + dicamba-dimethylammonium (especially for applications to dicamba-tolerant soybean, e.g. S genetically-modified), compound of formula (I) + dicamba-potassium (especially for applications to dicamba-tolerant soybean, e.g. genetically-modified), compound of formula (I) + dicamba-sodium (especially for applications to dicamba-tolerant soybean, e.g. genetically-modified), compound of formula (I) ÷ dicamba ÷ glyphosate (especially for applications to dicamba-tolerant soybean, e.g. genetically-modified), compound of formula (I) + dicamba-dimethylammonium + glyphosate (especially for applications to dicamba-tolerant soybean, e.g. genetically-modified), compound of formula (I) + dicamba-potassium + glyphosate (especially for applications to dicamba-tolerant soybean, e.g. genetically-modified), compound of formula (I) + dicamba-sodium + glyphosate (especially for applications to dicamba-tolerant soybean, e.g. genetically-modified), compound of formula (I) + diclosulam, compound of formula (I) + dimethenamid, compound of formula (I) + dimethenamid-P, compound of formula (I) + diquat, compound of formula (I) + diquat dibromide, compound of formula (I) + diuron, compound of formula (I) + fenoxaprop, compound of formula (I) + fenoxaprop-ethyl, compound of formula (I) + fenoxaprop-P, compound of formula (I) + fenoxaprop-P-ethyl, compound of formula (I) + fluazifop, compound of formula (I) + fluazifop-butyl, compound of formula (I) + fluazifop-P, compound of formula (I) + fluazifop-P-butyl, compound of formula (I) + flufenacet, compound of formula (I) + flumetsulam, compound of formula (I) + flumioxazin, compound of formula (I) + fluthiacet, compound of formula (I) + fluthiacet-methyl, compound of formula (I) + fomesafen, compound of formula (I) + glufosinate, compound of formula (I) + glufosinate-ammonium, compound of formula (I) + glyphosate, compound of formula (I) + glyphosate-diammonium, compound of formula (I) + glyphosate-isopropylammonium, compound of formula (I) + glyphosate-potassium, compound of formula (I) + imazethapyr, compound of formula (I) + lactofen, compound of formula (I) + mesotrione, compound of formula (I) + metolachlor, compound of formula (I) + S-metolachlor, compound of formula (I) + metribuzin, compound of formula (I) + oxyfluorfen, compound of formula (I) + paraquat, compound of formula (I) + paraquatdichloride, compound of formula (I) + pendimethalin, compound of formula (I) + pyroxasulfone, compound of formula (I) + quizalofop, compound of formula (I) + quizalofop-ethyl, compound of formula (I) + quizalofop-P, compound of formula (I) + quizalofop-P-ethyl, compound of formula (I) + quizalofop-P-tefuryl, compound of formula (I) + saflufenacil, compound of formula (I) + sethoxydim, compound of formula (I) + sulfentrazone, compound of formula (I) + thifensulfuron, compound of formula (I) + thifensulfuron-methyl, compound of formula (I) + tribenuron, compound of formula (I) + tribenuron-methyl, compound of formula (I) + trifluralin, compound of formula (I) + 4-(4'- chloro-4-cyclopropyl-2'-fluorobiphenyl-3-yl)-2,2,6, 6-tetramethyl-2H-pyran-3,5(4H,6H)-S dione (which is the compound of Example P8 disclosed on pages 31-32 and 35-36 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-13 disclosed in pages 4, 5, 7 and 11 of WO 2011/073616 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'-dichloro-4-cyclopropylbiphenyl-3-yl)-2,2,6, 6-tetramethyl-2H-pyran-3,5(4H,6H)-dione (which is the compound of Example P9 disclosed on pages 36-37 and 40-41 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-12 disclosed in page 10 of wo 2011/073616 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(4'-chloro-4-ethyl- 2'-fluorobiphenyl-3-yQ-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione (which is compound A-66 disclosed on page 95 of wo 2008/071405 Al (Syngenta Participations AG and Syngenta Limited), and which is also compound A-4 disclosed on page 7 of WO 2011/073615 A2 (Syngenta Limited), these pads of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'-dichloro-4-ethylbiphenyl-3-y-2,2,6,6-tetramethyl-2H-pyran-3,5(4H, 6H)-dione (which is compound A-45 disclosed on page 93 of WO 2008/071405 Al (Syngenta Participations AG and Syngenta Limited), and which is also the compound of Example PlO disclosed on pages 41 and 45 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-7 disclosed on page 7 of wo 2011/073615 A2 (Syngenta Limited), these pads of these publications being incorporated herein by reference), or compound of formula (I) + 4- (2',4'-dichloro-4-ethylbiphenyl-3-y-5-(methoxycarbonyloxy)-2,2,6, 6-tetramethyl-2H-pyran-3(6H)-one (which is compound D-26 disclosed on page 231 of WO 2008/071405 Al (Syngenta Participations AG and Syngenta Limited), and which is also compound A- 9 disclosed on page 8 of WO 2011/073615 A2 (Syngenta Limited), these pads of these publications being incorporated herein by reference); wherein the mixture partners for the compound of formula (I) may optionally be in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible).

In the above-mentioned compositions or mixtures comprising a compound of formula (I) (e.g. a compound from Table 1) and one or more further herbicides, the weight ratio of the compound of formula (I) to each further herbicide can vary over a large range and is, typically, from 500:1 to 1:200, especially from 200:1 to 1:100, more especially from 100:1 to 1:50, even more especially from 30:1 to 1:30. Typically, these weight ratios are measured as the free compound(s), i.e. excluding the weight of any associated salt counterion(s).

The compounds of formula (I) according to the invention can also be used in S combination with a safener. Preferably, in these mixtures, the compound of the formula (I) is one of those compounds listed in Table 1.The following mixtures with safeners, especially, come into consideration: compound of formula (I) ÷ cloquintocet-mexyl, compound of formula (I) + cloquintocet acid or an agrochemically acceptable salt thereof, compound of formula (I) + fenchlorazole-ethyl, compound of formula (I) + fenchlorazole acid or an agrochemically acceptable salt thereof, compound of formula (I) + mefenpyr-diethyl, compound of formula (I) ÷ mefenpyr diacid, compound of formula (I) + isoxadifen-ethyl, compound of formula (I) + isoxadifen acid, compound of formula (I) + furilazole, compound of formula (I) + furilazole R isomer, compound of formula (I) + N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide, compound of formula (I) + benoxacor, compound of formula (I) + dichlormid, compound of formula (I) + AD-67, compound of formula (I) + oxabetrinil, compound of formula (I) + cyometrinil, compound of formula (I) + cyometrinil Z-isomer, compound of formula (I) + fenclorim, compound of formula (I) ÷ cyprosulfamide, compound of formula (I) + naphthalic anhydride, compound of formula (I) + flurazole, compound of formula (I) + CL 304,415, compound of formula (I) + dicyclonon, compound of formula (I) + fluxofenim, compound of formula (I) + DKA-24, compound of formula (I) + R-29148 and compound of formula (I) + PPG-1292.

Benoxacor, cloquintocet acid, cloquintocet-mexyl, cyprosulfamide, mefenpyr-diethyl and N-(2-methoxybenzoy-4-[(methylaminocarbonyl)amino]benzenesulfonamide are preferred, with cloquintocet acid, cloquintocet-mexyl and mefenpyr-diethyl being more preferred. The use of cloquintocet-mexyl is particularly valuable.

The ratio of safener relative to the herbicide is largely dependent upon the mode of application. However, typically the weight ratio of the compound of formula (I) to the safener can vary over a large range and is, typically, from 200:1 to 1:200, especially from 50:1 to 1:50, more especially from 20:1 to 1:20, even more especially from 20:1 to 1:10. As stated above, in one set of embodiments the safener comprises (e.g. is) cloquintocet-mexyl, cloquintocet acid or an agrochemically acceptable salt thereof, and/or mefenpyr-diethyl, and the weight ratio of the compound of formula (I) to the safener is preferably from 20:1 to 1:10, more preferably from 15:1 to 1:2. Typically, these weight ratios are measured as the free compound(s), i.e. excluding the weight of any associated salt counterion(s).

Application rates of herbicide and/or safener: The rate of application of safener relative to the herbicide (e.g. composund of formula (I) is largely dependent upon the mode of application. In the case of field treatment, generally from 0.001 to 5.0 kg (e.g. from ito 1000 g) of safener per ha, preferably from 0.001 to 0.5 kg (in particular from 2 to 200 g or from 5 to 200 g) of safener per ha; and/or generally from 0.001 to 2 kg of herbicide (e.g. compound of formula (I)) per ha, but preferably from 0.005 to 1 kg (more preferably from 10 to 300 g or from 20 to 200 g) of herbicide (e.g. compound of formula (0) per ha, are applied, ha = hectare. Typically, these application rates are measured as the free compound, i.e. excluding the weight of any associated salt counterion(s). In field treatment, the application of the herbicide (e.g. compound of formula (0) is preferably post-emergence.

The above-mentioned safeners and herbicides are described, for example, in the Pesticide Manual, Twelfth Edition, British Crop Protection Council, 2000. R-29148 is described, for example by P.B. Goldsbrough et al., Plant Physiology, (2002), Vol. 130 pp. 1497-1505 and references therein, PPG-1292 is known from W009211761 and N-(2-methoxybenzoy-4-[(methylaminocarbonyl)amino]benzenesulfonamide is known from EP365484.

The compounds and/or herbicidal compositions according to the invention are suitable for all methods of application customary in agriculture, such as, for example, pre-emergence application, post-emergence application and seed dressing. Post-emergence application is preferred. Depending upon the intended use, the safeners can be used for pretreating the seed material of the crop plant (dressing the seed or seedlings) or introduced into the soil before or after sowing, followed by the application of the (unsafened) compound of the formula (I), optionally in combination with a co-herbicide. It can, however, also be applied alone or together with the herbicide before or after emergence of the plants. The treatment of the plants or the seed material with the safener can therefore take place in principle independently of the time of application of the herbicide. The treatment of the plant by simultaneous application of herbicide and safener (e.g. in the form of a tank mixture) is generally preferred. The rate of application of safener relative to herbicide is largely dependent upon the mode of application. In the case of field treatment, generally from 0.001 to 5.0 kg of safenerlha, preferably from 0.001 to 0.5 kg of safener/ha, are applied. In the case of seed dressing, generally from 0.001 to 10 g of safener/kg of seed, preferably from 0.05 to 2 g of safener/kg of seed, are applied. When the safener is applied in liquid form, with seed soaking, shortly before sowing, it is advantageous to use safener solutions which contain the active ingredient in a concentration of from ito 10000 ppm, preferably from 100 to 1000 ppm.

In the invention, in the case of field treatment (e.g. post-emergence application), generally from ito 2000 g of herbicide (in particular compound of formula (0) / ha, but preferably from 5to 1000 g of herbicide (in particular compound of formula (I))! ha, more preferably from 10 to 400 g of herbicide (in particular compound of formula (0) / ha, is applied. If a safener is used, in the case of field treatment (e.g. post-emergence application), generally from 0.5 to 1000 g of safener/ha, preferably from 2 to 500 g of safener/ha, more preferably from 5 to 200 g of safener/ha, is applied.

In one particular embodiment, the one or more further herbicides (e.g. as mentioned hereinabove) can be applied together with one of the safeners mentioned hereinabove.

Various aspects and embodiments of the present invention will now be illustrated in more detail by way of example. It will be appreciated that modification of detail may be made without departing from the scope of the invention.

PREPARATION EXAMPLES

Throughout this section the following abbreviations will be used: br broad d doublet DCM dichloromethane DMSO dimethyl sulfoxide Et20 diethyl ether EtOAc ethyl acetate H PLC high performance/pressure liquid chromatography m multiplet MeOH methanol q quartet s singlet triplet THE tetrahydrofuran Example 1 Synthesis of 6-[5-(6-chloroquinoxalin-2-yl)oxy-2-ethyl-phenyl]-4-(2,2-difluoroethyl) -7-hydroxy-thiazolo[4,5-b]pyridin-5-one (compound P26) <1oox:xydl 1.1 Step 1: Synthesis of ethyl 2-(5-benzyloxy-2-ethyl-phenyl)acetate 1I ________,-. 0JL50!L. °_ A flask was charged with (5-benzyloxy-2-ethyl-phenyl)boronic acid* (5.08g. 19.8 mmol), potassium phosphate (7.98g, 59.5 mmol), tetrakis(triphenylphosphine)palladium (0.627g. 0.54 mmol) and copper) oxide (0.077g. 0.5411 mmol) then purged with two vacuum/nitrogen cycles. Degassed toluene (75 mL) was added followed by two further nitrogen purges. Ethyl 2-bromoacetate (2.0 mL, 18.04 mmol) was added and the reaction heated at 80°C for 5 hours.

Upon cooling, the reaction mixture was filtered through a pad of celite and then washed through with EtOAc. The filtrate was evaporated to dryness under reduced pressure to give a yellow oil. The crude material was purified by flash chromatography on silica using a gradient of 10% EtOAc/isohexane to 35% EtOAc/isohexane as eluent to give the desired product (1.60g, 30%) as a colourless oil.

1H NMR (500 MHz, CDCI3) ö ppm 1.18 (t, 3H) 1.22-1.28(m, 3H) 2.55-2.65(m, 2H) 4.08-4.18 (m, 2H) 5.00-5.06 (m, 2H) 6.81 -6.90 (m, 2H) 7.11 (d, 1H) 7.28-7.33 (m, 1H) 7.35-7.40 (m, 2H) 7.40-7.45 (m, 2H).

1.2 Step 2: Synthesis of 2-(5-benzyloxy-2-ethyl-phenyl)acetic acid To a solution of ethyl 2-(5-benzyloxy-2-ethyl-phenyl)acetate (1.57g, 5.26 mmol) in THF (26 mL) was added a solution of potassium hydroxide (0.39g, 6.83 mmol) in water (9 mL). The reaction was stirred at room temperature for 80 hours.

The reaction was washed with EtOAc and the aqueous was adjusted to pH2 by the addition of conc HCI and then extracted with EtOAc. The combined organic extracts were dried over MgSO4 and evaporated to dryness under reduced pressure to give the desired product (1.26g, 68%) as an orange gum.

1H NMR (400 MHz, COd3) ö ppm 1.19 (t, 3H) 2.60 (q, 2H) 3.66 (s, 2H) 5.03 (s, 2H) 6.83 -6.91 (m, 2H) 7.10-7.16 (m, 1H) 7.28-7.45 (m, 5H) 1.3 Step 3: Synthesis of methyl 4-[2-(5-benzyloxy-2-ethyl-phenyl)acetyl]-amino]thiazole-5-carboxylate

HOAOQ

To suspension of 2-(5-benzyloxy-2-ethyl-phenyl)acetic acid (1.26g, 4.65 mmol) in DCM (15 mL) was added 2 drops of DMF followed by portionwise addition of oxalyl chloride (0.53 mL, 6.04 mmol), effervescence was observed. The reaction was stirred at room temperature for two hours then evaporated to dryness under reduced pressure to give the intermediate acid chloride as a yellow gum.

The crude acid chloride was taken up into CH3CN (5 mL) and added dropwise to a suspension of methyl 4-aminothiazole-5-carboxylate (0.74g, 4.65 mmol) and pyridine (0.71 mL, 8.67 mmol) in CH3CN (5 mL). The reaction was stirred at room temperature overnight then diluted with 2M HCI and extracted with EtOAc (2x). The combined organic extracts were dried over MgSO4 and evaporated to dryness to give an orange gum. The crude product was purified by flash chromatography on silica using a gradient from 10% EtOAc in isohexane to 100% EtOAc as eluent to give a pale yellow solid which was triturated with acetone to give the desired product (0.74g, 39%) as a white solid.

1H NMR (400 MHz, COd3) O ppm 1.15-1.25 (m, 3H) 2.65 (q, 2H) 3.68-3.78 (m, 3H) 3.87 (s, 2H) 5.10 (s, 2H) 6.88-6.99 (m, 2H) 7.20 (d, 1H) 7.30-7.39 (m, 2H) 7.40-7.49 (m, 2H) 8.83 (s, 1H) 9.62 (br, 1H).

1.4 Step 4: Synthesis of methyl 4-[2-(5-benzyloxy-2-ethyl-phenyl)acetyl]-(2,2-difluoroethyl)amino] thiazole-5-carboxylate / To a solution of methyl 4-[2-(5-benzyloxy-2-ethyl-phenyl)acetyl]amino]thiazole-5-carboxylate (0.72g, 1.75 mmol) in THE (20 mL) was added sodium hydride (60% dispersion in mineral oil) (0.105g, 2.63 mmol). The reaction was stirred at room temperature for five minutes before dropwise addition of a solution of difluoroethyl triflate (0.75g, 3.51 mmol) in THF (10 mL). The reaction was stirred at room temperature for4 hours, cautiously quenched with 2M HCI and then extracted with EtOAc (x2). The combined organic extracts were dried over MgSO4 and evaporated to dryness under reduced pressure to give an orange oil. The crude product was purified by flash chromatography on silica using a gradient of 10% EtOAc in isohexane to 100% EtOAc as eluent to give the desired product (0.854g. quant.).

1H NMR (400 MHz, COd3) ö ppm 1.02-1.12 (m, 3H)2.39(q, 2 H) 3.56 (s, 2H) 3.81 - 3.87 (m, 3H) 4.01 -4.15 (m, 2H) 4.99 (s, 2H) 5.92-6.27 (m, 1H) 6.59 (br, 1H) 6.77 (dd, 1 H) 7.01 (d, 1H) 7.30-7.43 (m, 5H) 8.76-8.82 (m, 1 H).

1.5 Step 5: Synthesis of 6-(5-benzyloxy-2-ethyl-phenyl)-4-(2,2-difluoroethyl)-7-hydroxy-thiazolo(4, 5-b]pyridin-5-one FQ Li To a solution of methyl 4-[2-(5-benzyloxy-2-ethyl-phenyl)acetyl]-(2,2-difluoro-ethyamino] thiazole-5-carboxylate (0.833g. 1.76 mmol) in THE (25 mL) under an N2 atmosphere was added sodium hydride (60% dispersion in mineral oil) (0.14g, 3.51 mmol) in a single portion. The reaction was stirred at room temperature for 4 hours and then cautiously diluted with 2M HCI and extracted with EtOAc (x2). The combined organic extracts were dried over MgSO4 and evaporated to dryness under reduced pressure to give an orange gum. The crude material was purified by flash chromatography on silica using a gradient of 10% EtOAc in isohexane to 100% EtOAc as eluent to give the desired product (0.643g, 83%) as a yellow gum.

1H NMR (400 MHz, CDCI3) O ppm 1.01 -1.14 (m, 3H) 2.35-2.54 (m, 2H) 4.79-4.95 (m, 2H) 4.99-5.10 (m, 2H) 5.95 (br, 1H) 6.11 -6.47 (m, 1H) 6.82-6.89 (m, 1H) 6.98-7.08 (m, 1H) 7.29-7.46 (m, OH) 8.87-8.94 (m, 1 H).

1.6 Step 6: Synthesis of 4-(2,2-difluoroethyl)-6-(2-ethyl-5-hydroxy-phenyl)-7-hydroxy-thiazolo[4, 5-b]pyridin-5-one 1H OH

L

Concentrated sulfuric acid (7 mL) was cooled to 0C and with srring a solution of 6-(5-benzyloxy-2-ethyl-phenyl)-4-(2,2-difluoroethyl)-7-hydroxy-thiazolo[4, 5-b]pyridin-5-one (0.59g, 1.33 mmol) in DCM (12 mL) was added portionwise over 5 mins, maintaining the temperature below 0°C.

The reaction was stirred at 0°C for 1.5 hours then carefully poured over ice, diluted with brine and extracted with DCM. The organic extracts were dried over MgSO4 and evaporated to dryness under reduced pressure to give a yellow foam (297mg). The aqueous phase was further extracted with EtOAc and the organic extracts were dried over MgSO4 and evaporated to dryness under reduced pressure to give an orange gum (232mg). The two concentrated extracts were combined to give the desired product (0.529g, quant) as an orange gum.

1H NMR (400 MHz, CDCI3) ö ppm 1.00-1.06 (m, 3H) 2.22-2.37 (m, 2H) 4.53-4.86 (m, 2H) 5.91 -6.26 (m, 1H) 6.63 (d, 1H) 6.73 (d, 1H) 7.13-7.21 (m, 1H) 8.87-8.93 (m, 1H).

1.7 Step 7: Synthesis of 6-[5-(6-chloroquinoxalin-2-yl)oxy-2-ethyl-phenyl]-4- (2,2-difluoroethyl)-7-hydroxy-thiazolo[4,5-b]pyridin-5-one >1-

L

To a solution of 4-(2,2-difluoroethyl)-6-(2-ethyl-5-hydroxy-phenyl)-7-hydroxy- thiazolo[4,5-b]pyridin-5-one (0.10 g, 0.284 mmol) in CH3CN (3 mL) was added 2,6-dichloroquinoxaline (0.057g, 0.284 mmol) and potassium carbonate (0.05g, 0.355 mmol). The reaction was heated at reflux for 2 hours and then allowed to cool to RT.

The reaction mixture was diluted with 2M HCI and extracted with EtOAc (x2). The combined organic extracts were dried over MgSO4 and evaporated to dryness under reduced pressure to give a yellow residue. The crude product was purified by flash chromatography on silica using a gradient of 5% EtOAc in isohexane to 100% EtOAc as eluent to give the desired product (0.lOg, 68%) as a yellow solid (-85% pure).

1H NMR (400 MHz, CDCI3) 6 ppm 1.16 (t, 3H) 2.47-2.67 (m, 2H) 4.75-4.93 (m, 2H) 6.10-6.45 (m, 1H) 7.17 (d, 1H) 7.24 (d, 1H) 7.44 (d, 1H) 7.56-7.64(rn, 2H) 8.01 (d, 1H) 8.66-8.68 (m, 1 H) 8.88-8.95 (m, 1 H).

Example 2 Synthesis 6-[5-[(6-chloro-1,3-benzoxazol-2-yl)oxy]-2-ethyl-phenyl]-4- (2,2-difluoroethyl)-7-hydroxy-thiazolo[4,5-b]pyridin-5-one (compound P25) 2.1 Step 1: Synthesis of 6-[5-[(6-chloro-1,3-benzoxazol-2-yl)oxy]-2-ethyl-phenylj-4-(2, 2-difluoroethyl)-7-hydroxy-thiazolo[4,5-b]pyridin-5-one <sOH 67 To a solution of 4-(2,2-difluoroethyl)-6-(2-ethyl-5-hydroxy-phenyl)-7-hydroxy- thiazolo[4,5-b]pyridin-5-one (0.lOg, 0.284 mmol) in acetonitrile (5 mL) was added 2,6-dichloro-1,3-benzoxazole (0.053g, 0.28 mmol) and potassium carbonate (0.049g, 0.355 mmol). The reaction was heated at reflux for 4 hours and then allowed to cool to RT.

The reaction mixture was diluted with 2M HCI and extracted with EtOAc (x2). The combined organic extracts were dried over MgSO4 and evaporated dryness under reduced pressure to give a yellow residue. The crude product was purified by flash chromatography on silica using a gradient of 100% isohexane to 60% EtOAc/isohexane as eluent and further purified by mass-directed HPLC to give the desired product (46mg, 32%) as an off-white foam.

1H NMR (400 MHzCDCI3) 6 ppm 1.05-1.22 (m, 3H) 2.56 (qq, 2H) 4.73-4.92 (m, 2H) 6.12-6.45 (m, 1H) 7.21 -7.37 (m, 4H) 7.44-7.53 (m, 2H) 8.91 (s, 1H).

Example 3 Synthesis of 6-[5-(2,4-dichlorophenoxy)-2-methyl-phenyl]-7-hydroxy- 4-methyl-thiazolo[4,5-b]pyridin-5-one (compound P4) 3.1 Step 1: Synthesis of diethyl 2-(5-bromo-2-methyl-phenyl)propanedioate A three necked flask was charged with 4-bromo-2-iodo-1-methyl-benzene (15.0 g, 50.5 mmol), diethyl malonate (101 mmol, 15.3 mL, 16.2 g), 1,4-dioxane (389 mL), pyridine-2-carboxylic acid (1.24 g, 10.1 mmol), copper (I) iodide (0.962 g, 5.05 mmol) and cesium carbonate (49.7 g, 152 mmol). The resulting suspension was stirred at 110°C (bath temperature) under an N2 atmosphere for 16 hours.

A further portion of copper (I) iodide (5.05 mmol, 0.962 g) and pyridine-2-carboxylic acid (1.24 g, 10.1 mmol) was added and the reaction mixture was stirred at 110°C (bath temperature) for a further 8 hours and then allowed to cool to room temperature overnight. The reaction was partitioned between EtOAc and sat. aq. NH4CI.

The aq. phase was extracted with further EtOAc (x2). The combined organic extracts were dried over MgSO and evaporated to dryness under reduced pressure to give a brown liquid. The crude product was purified by flash chromatography on silica using a gradient of 100% isohexane to 100% EtOAc as eluent to give the desired product (15.16g, 91%) as a colourless oil.

1H NMR (400 MHz, Chloroform) 5 ppm 7.55 (d, 1H), 7.33(s, 1H), 7.06(d, 1H), 4.80(s, 1H), 4.16-4.29 (m, 4H), 2.28 (s, 3H), 1.28 (td, 6H).

3.2 Step 2: Synthesis of ethyl 2-(5-bromo-2-methyl-phenyl)acetate To a solution of diethyl 2-(5-brorno-2-methyl-phenyl)propanedioate (5.0 g, 15.2 mmol) in DMSO (19.1 mL) were added lithium chloride (0.71 g, 16.71 mmol) and water (0.38 mL). The reaction stirred at 120°C for a total of 12.5 hours and then allowed to cool to room temperature overnight.

The reaction mixture was then partitioned between water and Et20 and the combined organic extracts dried over MgSO and evaporated to dryness under reduced pressure to give a colourless liquid. The crude product was purified by flash chromatography on 3i02 using a gradient of 100% iso-hexane to 100% ethyl acetate as eluent to give the desired product (3.16g, 81%) as a pale yellow oil.

1H NMR (500MHz, CDCI3) S = 7.34 (d, 1H), 7.29 (dd, 1H), 7.04 (d, 1H), 4.16 (q, 2H), 3.58 (s, 2H), 2.25 (s, 3H), 1.25 (t, 3H).

3.3 Step 3: Synthesis of 2-(5-bromo-2-methyl-phenyl)acetic acid To a solution of ethyl 2-(5-bromo-2-methyl-phenyacetate (2.8 g, 11 mmol) in THF (26 mL) was added a solution of potassium hydroxide (0.81g, 14 mmol) in water (9 mL). The reaction was stirred at room temperature for 72 hours and then washed with EtOAc. The aqueous was adjusted to pH2 by the addition of cone HCI then extracted with EtOAc.

The combined organic extracts were dried over MgSO4 and evaporated to dryness under reduced pressure to give a colourless gum which crystallised on standing. The crude product was triturated with isohexane to give the desired product (1.87g, 75%) as a white solid.

1H NMR (500 MHz, CDCI3) 6 ppm 2.27 (s, 3H) 3.63 (s, 2H) 7.06 (d, 1H) 7.32 (dd, 1H) 7.35-7.36(m, 1H).

3.4 Step 4: Synthesis of methyl 4-((2-(5-bromo-2-methyl-phenyl)acetyl]amino] thiazole-5-carboxylate 4j-y OH Br To a suspension of 2-(5-bromo-2-methyl-phenyl)acetic acid (1.88 g, 8.2 mmol) in DCM (20 mL) was added 3 drops of DMF followed by poitionwise addition of oxalyl chloride (0.93 mL, 10.7 mmol) (effervecence). The reaction was stirred at room temperature for 2 hours then evaporated to dryness under reduced pressure.

The crude acid chloride was dissolved in CH3CN (20m1) and added dropwise to a suspension of methyl 4-aminothiazole-5-carboxylate (1.30g, 8.2 mmol) and pyridine (1.25 mL, 15.30 mmol) in acetonitrile (20m1). The reaction was stirred at room temperature for 51 hours then diluted with 2M HCI and extracted with EtCAc (x2). The combined organic extracts were dried over MgSC4 and evaporated to dryness under reduced pressure to give a yellow solid. The crude product was triturated with Et20 to give the desired product (1.75g, 58%) as a white powder.

1H NMR (400 MHz, CDCI3) 6 ppm 2.28-2.36 (m, 3H) 3.83 (s, 3H) 3.87 (s, 2H) 7.05- 7.16 (m, 1H) 7.33-7.40 (m, 1H) 7.45 (d, 1H) 8.83 (s, 1H) 9.67 (br, 1H).

3.5 Step 5: Synthesis of methyl 4-[2-(5-bromo-2-methyl-phenyl)acetyl]-methyl-amino]thiazole-5-carboxylate / / s)/Br To a suspension of methyl 4-[2-(5-bromo-2-methyl-phenyl)acetyl]amino]thiazole- 5-carboxylate ( 0.90 g, 2.44 mmol) in CH3CN (35 mL) was added cesium carbonate (1.99g, 6.09 mmol) followed by iodomethane (0.304 mL, 4.88 mmol) and the reaction was stirred at 50°C for 3 hours.

The reaction was allowed to cool then quenched by the addition of 2M HCI and extracted with EtOAc (x2). The combined organic extracts were dried over MgSO4 and evaporated to dryness under reduced pressure to give a yellow gum. The crude product was purified by flash chromatography on silica using a gradient of 10% EtOAc in isohexane to 100% EtOAc as eluent to give the desired product (0.846g. 90%) as a yellow solid.

1H NMR (400 MHz, CDCI3) 6 ppm 2.11 -2.18 (m, 3H) 3.28 (br, 3H) 3.52 (br, 2H) 3.83- 3.89 (m, 3H) 6.94 (d, 2H) 7.19 (d, 1H) 8.79-8.86 (m, 1H).

3.6 Step 6: Synthesis of 6-(5-bromo-2-methyl-phenyl)-7-hydroxy-4-methyl-thiazolo[4,5-b] pyridin-5-one To a solution of methyl 4-[2-(5-bromo-2-methyl-phenyl)acetyl]-methyl-amino]thiazole-5-carboxylate (0.83 g, 2.17 mmol) in THF(25 mL) under an N2 atmosphere was added sodium hydride (60% dispersion in mineral oil) (0.173g, 4.33 mmol) in a single portion and the reaction stirred at RT for 4 hours. The reaction was cautiously diluted with 2M HCI upon which a pale solid crashed out of solution and was collected by filtration and dried on the sinter. The filtrate was extracted with EtOAc (x2) and the combined organic extracts were dried over MgSO4 and evaporated to dryness under reduced pressure to give a pale yellow solid. This solid was triturated with Et20 and a pale yellow solid was collected by filtration, combining with the previously collected solid. This solid was washed with hexane and dried on the sinter to give the desired product (0.62g, 81%) as pale yellow powder.

1H NMR (400 MHz, CDCI3/ DMSO-d6) 6 ppm 2.13 (s, 3H) 3.82 (s, 3H) 7.19 (d, 1H) 7.31 (s, 1H) 7.37 (d, 1H) 9.06 (s, 1H).

3.7 Step 7: Synthesis of [6-(5-bromo-2-methyl-phenyl)-4-methyl-5-oxo-thiazolo[4,5-b]pyridin-7-yl] 2-methylpropanoate SJ(Lj1OX To a suspension of 6-(5-bromo-2-methyl-pheny-7-hydroxy-4-methyl-thiazolo[4,5-b]pyridin-5-one (0.15g, 0.427 mmol) in DCM (2 mL) was added pyridine (0.052 mL, 0.641 mmol) followed by isobutyryl chloride (0.063 mL, 0.598 mmol) and the reaction was stirred at room temperature for 2 hours. The reaction was diluted with 2M HCI and extracted with DCM (x2). The combined organic extracts were dried over Mg304 and evaporated to dryness under reduced pressure to give a yellow gum. The crude product was purified by flash chromatography on silica using a gradient of 5% EtOAc/isohexane to 50% EtOAc/isohexane as eluentto give the desired product (0.169g. 94%) as a white solid.

1H NMR (400 MHz, COd3) 6 ppm 0.94-1.04 (m, 6H) 2.11 -2.17 (m, 3H) 2.57 (spt, 1 H) 3.86-3.98 (m, 3 H) 7.14 (d, 1H) 7.21 -7.28 (m, 1H) 7.35-7.43 (m, 1 H) 8.89-8.97 (m, 1 H).

3.8 Step 8: Synthesis of 6-[5-(2,4-dichlorophenoxy)-2-methyl-phenyl]-7-hydroxy-4-methyl-thiazolo[4, 5-b]pyridin-5-one (Sj(I3Br A microwave vial was charged with [6-(5-bromo-2-methyl-pheny-4-methyl-5- oxo-thiazolo[4,5-b]pyridin-7-yl] 2-methylpropanoate (0.169 g, 0.401 mmol) 2,4-dichiorophenol (0.327g, 2.01 mmol), cesium carbonate (0.263g, 0.802 mmol), copper (II) triflate (0.007g, 0.0201 mmol), activated powdered molecular sieves (0.0002g) and toluene (2.4 mL), capped and heated to 160°C under microwave irradiation for 45 minutes. The reaction mixture was diluted with EtOAc and filtered through a pad of Celite. The filtrate was evaporated to dryness under reduced pressure to give a brown residue. The crude product was purified by flash chromatography on silica using a gradient of 5% EtOAc in isohexane to 100% EtOAc as eluent, followed by mass-directed HPLC purification to give the desired product (0.021g, 12%) as an orange foam.

1H NMR (400 MHz, CDCI3)O ppm 2.14-2.22 (m, 3H) 3.84-3.91 (m, 3H)6.84(d, 1H) 6.92-7.01 (m, 2H) 7.16 (dd, 1H) 7.33 (d, 1H) 7.43(d, 1H) 8.89-8.94 (m, 1H).

Example 4 Synthesis of 6-[5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]oxy]-2- ethyl-phenyl]-4-(2,2-difluoroethyl)-7-hydroxy-thiazolo[4,5-b]pyridin- 5-one (compound P24)

L

4.1 Step 1: Synthesis of 6-[5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]oxy]-2-ethyl-phenyl]-4-(2, 2-difluoroethyl)-7-hydroxy-thiazolo[4,5-b]pyridin-5-one

L

To a solution of 4-(2,2-difluoroethyl)-6-(2-ethyl-5-hydroxy-phenyl)thiazolo[45- b]pyridine-5,7-dione (0.232g, 0.658 mmol) in CH3CN (5 mL) was added 3-chloro-2-fluoro-5-(trifluoromethyl)pyridine (0.131 g, 0.658 mmcl) and potassium carbonate (0.1 14g, 0.823 mmol). The reaction was heated at reflux for 4 hours and then allowed to cool to room temperature. The reaction was diluted with 2M HCI and extracted with EtOAc (x2), the combined organic extracts were dried over MgSO4 and evaporated to dryness under reduced pressure to give a yellow residue.

The crude product was purified via mass-directed HPLC to give the desired product (0.039g, 11%) cN9O% purity.

1H NMR (400 MHz, CDCI3) 6 ppm 1.10-1.20 (m, 3H) 2.44-2.64 (m, 2H) 4.76-4.91 (m, 2H) 6.10-6.45 (m, 1H) 7.05(d, 1H)7.19 (dd, 1H) 7.47 (d, 1H) 7.97(d, 1H) 8.11 -8.21 (m, 1H)8.88-8.96(m, 1H).

Example 5 Synthesis of 7-hydroxy-4-methyl-6-[2-methyl-5-[4-(trifluoromethoxy)-phenoxy]phenyl] thiazolo[4,5-b]pyridin-5-one (compound P7) oZ o%< 5.1 Step 1: Synthesis of 7-hydroxy-4-methyl-6-[2-methyl-5-[4-(trifluoromethoxy) phenoxy]phenyl]thiazolo[4,5-b]pyridin-5-one A microwave vial was charged with 6-(5-bromo-2-methyl-pheny-7-hydroxy-4-methyl-thiazolo[4,5-b]pyridin-5-one (0.1 5g, 0.427 mmol) 4-(trifluoromethoxy)phenol (0.38g, 2.14 mmol), cesium carbonate (0.28g, 0.854 mmol), copper (II) triflate (0.008g, 0.0214 mmol), activated powdered molecular sieves (0.0003g) and anhydrous toluene (2.5 mL) capped and heated to 160°C under microwave irradiation for 60 minutes. The reaction mixture was diluted with DCM and washed with 2M HCI. The organic phase was dried over MgSO4 and evaporated to dryness under reduced pressure to give an orange residue. The crude product was purified by mass-directed HPLC to give the desired product (0.038g, 20%).

1H NMR (400 MHz, CDCI3) 6 ppm 2.08-2.20 (m, 3H) 3.79-3.87 (m, 3H) 6.85-6.93 (m, 2H) 6.95-7.01 (m, 2H) 7.10(d, 2H) 7.22-7.32 (m, 1H) 8.86-8.93 (m, 1H).

Example 6 Synthesis of 6-[5-(4-chlorophenoxy)-2-ethyl-phenylj-7-hydroxy-4-methyl-thiazolo[4,5-b] pyridin-5-one (compound PlO) 6.1 Step 1: Synthesis of 5-bromo-2-ethyl-aniline NO2 N H2 To a stirred suspension of 5-bromo-2-ethyl-nitrobenzene (23.0g. 0.1 mol) in MeOH (250 mL) and H20 (50 mL) was added portionwise Zn powder (46.6g, 0.7lmol).

Once the addition was complete and the exotherm abated, the reaction was heated at reflux for 1 hour then allowed to cool to room temperature. The reaction was filtered through celite and washed through with MeOH. The filtrate was evaporated to dryness under reduced pressure and partitioned between EtOAc and H20. The aqueous phase was further extracted with EtOAc (x2) and the combined organic extracts washed with brine, dried over Mg304 and evaporated to dryness under reduced pressure to give the desired product (19.32g, 97%) as a light brown liquid which was used without further purification.

1H NMR (400MHz, CDCI3) 6 ppm 1.22 (t, 3H), 2.43 (q, 2H), 3.64 (br, 2H), 6.81 (d, 1H), 6.85 (m, 1H), 6.90 (d, 1H).

6.2 Step 2: Synthesis of 4-bromo-1 -ethyl-2-(2,2,2-trichloroethyl)benzene yH2 A solution of 5-bromo-2-ethyl-aniline (19.32g, 0.097mo1) in CH3CN (30m1) was added dropwise to a stirred mixture of anhydrous Cu(ll)C12(15.66g, 0.116 mol), t-butyl nitrite (19 mL, 0.16 mol) and vinylidene chloride (116m1, 1.4Smol) in CH3CN (80m1) maintaining the internal temperature <30°C and monitoring evolution of N2. Once gas evolution had ceased, the reaction was heated at 40°C for 1 hour. The reaction was poured into 20% aq. HCI (300 mL) and extracted with Et20 (x2). The combined organic extracts were washed with 20% aq HCI, brine, dried over MgSO4 and evaporated to dryness under reduced pressure to give the crude product (28g) as a brown liquid which was used without further purification.

6.3 Step 3: Synthesis of methyl 2-(5-bromo-2-ethyl-phenyl)acetate ym< . To a solution of sodium methoxide (34.32g, 0.635mo1) in MeCH (300 mL) at 0°C was added dropwise a solution of 4-bromo-1 -ethyl-2-(2,2,2-trichloroethyl)benzene (14.3g. 0.045mo1) in MeOH (lOOmI). Once the addition was complete, the reaction was allowed to warm to room temperature and then heated at reflux for 24h. The reaction was allowed to cool to room temperature, further cooled to 0°C and then c.H2304 (21 mL) was added dropwise with vigorous stirring. Once the addition was complete, the reaction was allowed to warm to room temperature then heated at reflux for 2h. The reaction was allowed to cool to ST and then the excess solvent was removed under reduced pressure to give an orange semi-solid residue. To this residue at 0°C was added carefully saturated aqueous NaHCO3 solution until the solution pH was >7. The reaction mixture was extracted with CH2CI2 (x4), the combined organic extracts were dried over MgSO4 and evaporated to dryness under reduced pressure to give a red/brown liquid (10.6g). The crude product was purified by flash chromatography on silica using a gradient of 100% isohexane to 100% EtOActo give the desired product.

1H NMR (400MHz, CDCI3) 6 ppm 1.19 (t, 3H), 2.60 (q, 2H), 3.61 (s, 2H), 3.79 (5, 3H), 7.08 (d, 1H), 7.34 (m, 2H).

6.4 Step 4: Synthesis of 2-(5-bromo-2-ethyl-phenyl)acetic acid

OH

To a solution of methyl 2-(5-bromo-2-ethyl-phenyacetate (6.31 g, 24.53 mmol) in THF (60 mL) was added a solution of potassium hydroxide (1.83g, 31.88 mmol) in water (30 mL) The reaction mixture was stirred at room temperature for 48 hours and then washed with EtOAc. The aqueous phase was adjusted to pH2 by the addition of conc. HCI then extracted with EtOAc. The combined organic extracts were dried over MgSO4 and evaporated to dryness under reduced pressure to give the desired product (5.62g, 94%) as an orange gum which was used without further purification.

IS

1H NMR (400 MHz, CDCI3) 6 ppm 1.19 (t, 3H) 2.60 (q, 2H) 3.65 (s, 2 H) 7.09 (d, 1H) 7.32-7.40 (m, 2H).

6.5 Step 5: Synthesis of methyl 4-[2-(5-bromo-2-ethyl-phenyl)acetyl] amino]thiazole-5-carboxylate jIT0H To a suspension of 2-(5-bromo-2-ethyl-phenyQacetic acid (1.800 g, 7.404 mmol) in DCM (20 mL) was added 3 drops of DMF followed by portionwise addition of oxalyl chloride (0.842 mL, 9.63 mmol) (effervecence). The reaction was stirred at RT for 2 hours then evaporated to dryness under reduced pressure to give a yellow gum.

The crude acid chloride was dissolved in CH3CN (20m1) and added dropwise to a suspension of methyl 4-aminothiazole-5-carboxylate (1.171g, 7.404 mmol) and pyridine (1.13 mL, 13.82 mmol) in CH3CN (20m1). The reaction was stirred at room temperature for 72 hours and then quenched with 2M HCI. The reaction was extracted with EtOAc (x2) and the combined organic extracts dried over MgSO4 and evaporated to dryness under reduced pressure to give a yellow solid. The crude product was triturated with Et20 to give the desired product (1.45g, 58%) as a white solid of 80% purity.

1H NMR (400 MHz, COd3) ö ppm 1.15-1.24 (m, 3H) 2.61 -2.71 (m, 2H) 3.80-3.86 (m, 3H) 3.89 (s, 2H) 7.07-7.20 (m, 1 H) 7.37-7.47 (m, 2H) 8.83 (s, 1 H) 9.67 (br, 1 H).

6.6 Step 6: Synthesis of methyl 4-[2-(5-bromo-2-ethyl-phenyl)acetyl]-methyl-amino]thiazole-5-carboxylate ccC To a suspension of methyl 4-[2-(5-bromo-2-ethyl-phenyl)acetyl]amino]thiazole-5-carboxylate (1.45g, 3.78 mmol) in CHZCN (56 mL) was added cesium carbonate (3.OBg, 9.45 mmol) followed by iodomethane (0.471 mL, 7.561 mmol). The reaction was stirred at 50°C for 3 hours and then allowed to cool to room temperature.The reaction was quenched by the addition of 2M HCI and extracted with EtOAc (x2). The combined organic extracts were dried over MgSO4 and evaporated to dryness under reduced pressure to give a yellow gum. The crude product was purified by flash chromatography on silica using a gradient of 10% EtOAc in isohexane to 100% EtOAc as eluent to give the desired product (1.39g, 93%) as a yellow gum of -80% purity.

1H NMR (400 MHz, Cod3) O ppm 1.07-1.14 (m, 3H) 2.38-2.51 (m, 2H) 3.28 (br, 3H) 3.53 (br, 2H) 3.84-3.88 (m, 3H) 6.93-7.03 (m, 2H) 7.21 -7.26 (m, 1 H) 8.79-8.85 (m, 1 H).

6.7 Step 7: Synthesis of 6-(5-bromo-2-ethyl-phenyl)-7-hydroxy-4-methyl-thiazolo[4,5-b]pyridin-5-one To a solution of methyl 4-[2-(5-bromo-2-ethyl-phenyl)acetyl]-methyl-amino]thiazole-5-carboxylate (1.39g, 3.50 mmol) in THF (42 mL) under an N2 atmosphere was added sodium hydride (60% dispersion in mineral oil) (0.280g, 7.00 mmol) portion wise over 3 mins. The reaction mixture was stirred at room temperature for 2.5 hours. The reaction was cautiously diluted with 2M HCI and extracted with EtOAc (x2). The combined organic extracts were dried over MgSO4 and evaporated to dryness under reduced pressure to give a pale orange solid. The crude product was triturated with Et20 to give the desired product (0.89g, 70%) as a pale yellow solid of -85% purity.

1H NMR (400 MHz, CDCI3) O ppm 1.07-1.15 (m, 3H) 2.38-2.60 (m, 2H) 3.84-3.95 (m, 3H) 5.66-5.80 (m, 1H) 7.30 (d, 1H) 7.36 (d, 1H) 7.52 (dd, 1H) 8.90-8.95 (m, 1H).

6.8 Step 8: Synthesis of 6-[5-(4-chlorophenoxy)-2-ethyl-phenyl]-7-hydroxy-4-methyl-thiazolo4,5-b] pyridin-5-one A microwave vial was charged with 6-(5-bromo-2-ethyl-pheny-7-hydroxy-4-methyl-thiazolo[4,5-b]pyridin-5-one (0.150 g, 0.411 mmol), 4-chlorophenol (0.264g, 2.05 mmol), cesium carbonate (0.269g, 0.82 mmol), copper (II) triflate (0.050g, 0.0205 mmol) and anhydrous toluene (2.4 mL) capped and heated to 160°C under microwave irradiation for 45 minutes. The reaction mixture was diluted with EtOAc and filtered through celite, washing through with further EtOAc. The filtrate was evaporated to dryness under reduced pressure to give a yellow semi-solid. The crude product was purified by mass directed HPLC to give the desired product (0.022g, 13%) as an orange gum.

1H NMR (400 MHz CDCI3) 6 ppm 1.01 -1.17 (m, 3H) 2.39-2.59 (m, 2H) 3.85-3.92 (m, 3H) 6.85 (d, 1H) 6.90-6.99 (m, 2H) 7.02 (d, 1H) 7.22-7.28 (m, 2H) 7.36 (d, 1H) 8.86- 8.96(m,1H).

* (5-benzyloxy-2-ethyl-phenyl)boronic acid may be prepared from the known compound 4-ethyl-3-bromo-phenol (see for example P.J. Wagner eta/Org. Lett (2006) 645) via the route below by methods well known in the literature.

Table 2 NMR characterising data for compound of the invention Compound Structure 1H NMR (400 MHz, CDCI3) ____________ ________________________________________________________ 5 ppm P10 1.01-1.17 (iii, 3H) 2.39- 2.59 (ni, 2H) 3.85-3.92 (m, 3H) 6.85 (d, I H) 6.90 -6.99 (m, 2H) 7.02 (d, 1H) 7.22- 7.28 (ni, 2H) 7.36 (d, 1 H) 8.86 -8.96 (m, 1 H).

N

P7 F 2.08 -2.20 (ni, 3H) 3.79 -F±F 3.87 (m, 3H) 6.85-6.93 (m, 2H) 6.95-7.01 (m, 2H) 7.10 (d,2H)7.22-7.32(m, 1H) 8.86-8.93 (ni, 1 H). N N 0

P24 F 1.10-1.20(ni,3H)2.44- 4od1 F 2.64 (m, 2H) 4.76-4.91 (m, F 2H) 6.10-6.45 (m, IH) 7.05 I (d, 1H)7.19(dd, 1H)7.47(d, 1H) 7.97 (d, 1H) 8.11-8.21 N 0 (in, 1H) 8.88-8.96 (in, 1H).

N

F

P4 2.14-2.22 (m, 3H) 3.84- 3.91 (iii, 3H) 6.84 (d, 1 H) 6.92-7.01 (in, 2H) 7.16 (dd, 1 H) 7.33 (d, 1 H) 7.43 (d, 1 H) Cl 8.89 -8.94 (m, 1 H).

P25 1.05-1.22 (in, 3H) 2.56 (qq, Cl -6.45 (rn, 1H) 7.21 -7.37 2H) 4.73-4.92 (in, 2H) 6.12 (m, 4H) 7.44 -7.53 (m, 2H) 0 8.91 (s, 1H).

__ LF ____

P26 1.16 (t, 3H) 2.47-2.67 (ni, 2H) 4.75-4.93 (m, 2H) 6.10 I oX:Ei <\ I 1H) &66 -8.68 (ni, 1H) 8.88 N N 0 -8.95 (m, 1H).

BIOLOGICAL EXAMPLES

Bi Pre-emergence herbicidal activity Seeds of a variety of test species were sown in standard soil in pots: Lot/urn perenne (LOLPE), Alopecurus myosuroides (ALOMY), Echinochloa crus-galli (ECHCG), Avena fatua (AVEFA). After cultivation for one day (pre-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 acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5). 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 is evaluated (10 = total damage to plant; 0 = no damage to plant). Results are shown in Table 3.

Table 3 Control of weed species by compound of formula (I) after pre-emergence application at a rate of l000q/Ha Compound LOLPE ALOMY ECHCG AVEFA P10 9 6 8 6 P7 10 7 9 7 P24 7 5 8 5 P4 6 4 3 4 P25 7 5 8 5 P26 9 7 9 8 B2 Post-emergence herbicidal activity Seeds of a variety of test species are sown in standard soil in pots: Lot/urn perenne (LOLPE), Alopecurus rnyosuroides (ALOMY), Ech/noch/oa crus-ga/li (ECHCG), Avena fatua (AVEFA). After 8 days cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65% humidity), the plants are sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5). The test plants are then grown under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65% humidity) and watered twice daily. After 13 days, the test is evaluated (10 = total damage to plant; 0 = no damage to plant). The results are shown below in Table 4.

Table 4 Control of weed species by compound of formula (I) after post-emergence application at a rate of l000g/Ha Compound LOLPE ALOMY ECHCG AVEFA PlO 6 4 9 7 P7 7 7 9 6 P24 7 6 10 8 P4 5 2 7 P25 3 3 10 6 P26 10 9 10 9

Claims

CLAIMSA compound of formula (I) R5G(I), or a salt or N-oxide thereof, wherein, S1 is hydrogen, halogen, nitro, cyano, or selected from the group consisting of: C1-C5alkyl, 02-Ce alkenyl, Cl-Ce alkoxy Cl-Cs alkylthio, Ci-C5alkylsulfinyl, C- C5alkylsulfonyl, C3-C5cycoalkyl, Cl-Ce alkoxy-C1-C5alkyl-, Ci-C5alkoxy-C1-C6alkoxy-, di-C1-C5alkoxy-C1-C5alkyl, and C1-C6alkylthio-C1-C5alkyl, each of which is optionally substituted by 1-3 halogen atoms; 2 is hydrogen; or C1-C5alkyl, C2-C5 alkenyl, C3-C5alkynyl C3-C5cycoalkyl, C1-C5 alkoxy-C1-C5alkyl-, C1-C5alkoxy-C1-C5alkoxy-, di-C1-C5alkoxy-C1-C5alkyl, C1- C6alkylthio-C1-C6alkyl, C1-C6alkylsulfinyl-C1-C6alkyl, C1-C6alkylsulfonyl-C1-C5alkyl, C3-C6cycoalkyl-C1-C6alkyl,or cyano-C1-C6alkyl, each of which is optionally substituted by 1-3 halogen atoms; or phenyl optionally substituted by 1-3 substituents independently selected from halogen, Cl-Ce alkyl and C1-C5 alkoxy; or benzyl optionally substituted by 1-3 substituents independently selected from halogen, C1-C6 alkyl and C1-C6 alkoxy; G is hydrogen, C1-C10alkyl, C2-C10alkenyl, C2-C10alkynyl or aryl-C1-C4alkyl-or aryl-C1-C4alkyl-wherein the aryl moiety is substituted by one to five substituents independently selected from halo, cyano, nitro, C1-C5alkyl, C1-C5haloalkyl or C1-C6alkoxy, or C(O)R3; 3 is C1-C10alkyl, C3-C10cycloalkyl, C3-C10cycloalkyl-C1-C10alkyl-, C1-C10haloalkyl, C2-C10alkenyl, C2-C10alkynyl, C1-C4alkoxy-C1-C10alkyl-, C1-C4alkylthio-C1-C4alkyl-, C1-C10alkoxy, C2-C10alkenyloxy, C2-C10alkynyloxy, C1-C10alkylthio-, NR10511, N-C1-C4alkyl-amino-, N,N-di-(C1-C4alkyl)-amino-, aryl or aryl substituted by 1-3 9, which may be the same or different, heteroaryl or heteroaryl substituted by 1-3 R9, which may be the same or different, aryl-C1-C4alkyl-or aryl-C1-C4alkyl-wherein the aryl moiety is substituted by 1-3 to three R9, which may be the same or different, heteroaryl-C1-C4alkyl-or heteroaiyl-C1-C4alkyl-wherein the heteroaryl moiety is substituted by 1-3 R9, which may be the same or different, aryloxy-or aryloxy-substituted by 1-3 R9, which may be the same or different, heteroaryloxy-or heteroaryloxy-substituted by 1-3 R9, which may be the same or different, arylthio-or arylthio-substituted by 1-3 R9, which may be the same or different, or heteroaiylthio-or heteroarylthio-substituted by one to three R9, which may be the same or different; S4 is methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl, haloethyl, vinyl, propenyl, ethynyl, propynyl, halogen, methoxy, ethoxy, halomethoxy or haloethoxy; 5, 6 and 7 are each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl, haloethyl, vinyl, propenyl, ethynyl, propynyl, halogen, methoxy, ethoxy, halomethoxy or haloethoxy; 8 is an optionally susbtituted mono-or bicyclic aryl or an optionally substituted mono-or bicyclic heteroaryl containing a heteroatom selected from nitrogen, oxygen and sulphur; Xis 0 or 3; each 9 is independently halo, cyano, nitro, C1-C10alkyl, C1-C4haloalkyl, C1- C10alkoxy, C1-C4alkoxycarbonyl-, C1-C4haloalkoxy, C1-C10alkylthio-, C1-C4haloalkylthio-, C1-C10alkylsulfinyl-, C1-C4haloalkylsulfinyl-, C1-C10alkylsulfonyl-, C1-C4haloalkylsulfonyl-, awl or awl substituted by 1-5 substituents independently selected from halo, cyano, nitro, C1-C5alkyl, C1-C6haloalkyl or C1-C6alkoxy, or heteroaryl or heteroaryl substituted by 1-4 substituents independently selected from halo, cyano, nitro, C1-C5alkyl, C1-C5haloalkyl or C1-C5alkoxy; and, and 511 are independently selected from the group consisting of C1-C5 alkyl and C1-C5 alkoxy, or 10 and h1 together can form a morpolinyl ring.
2. The compound according to claim 1, wherein R1 is hydrogen, or selected from the group consisting of: C1-C6-alkyl, C1-C6-alkoxy, C1-C6alkoxy-C1-C6alkoxy-, C1-C6-alkylthio, C1-C5-alkylsulfonyl, C3-C5-cycloalkyl, C1-C6-alkoxy-C1-C6-alkyl and Ci-C6-alkylthio-Ci-Cralkyl, each of which is optionally substituted by 1-3 halogen atoms.
3. The compound according to claim 1 or claim 2, wherein R1 is selected from hydrogen C1-C6-alkyl, C1-C3-alkoxy, C1-C3alkoxy-C1-C3alkoxy-, C1-C3-alkylthio, C1-C3-alkylsulfonyl, C3-04-cycloalkyl, C1-C3alkoxy-C1-C3-alkyl and C1-C3-alkylthio-C1-C3-alkyl.
4. The compound according to any one of the preceding claims, wherein R2 is hydrogen or selected from the group consisting of: C1-C6-alkyl, CC6-alkenyl, C3- Calkynyl, C1-Calkoxy-C1-C6-alkyl, C1-C5alkoxy-C1-C6alkoxy, C1-C5-alkylthio-C1-C6-alkyl, C3-C6-cycloalkyl-C1-C6-alkyl, and cyano-C1-C6-alkyl, each of which is optionally substituted by 1-3 halogen atoms; or optionally substituted phenyl or optionally substituted benzyl, wherein said optional substituents are 1-3 substituents independently selected from halogen, C1-C5alkyl, and C1-C5alkoxy.
5. The compound according to any one of the preceding claims, wherein R2 is selected from C1-C3-alkyl, C1-C3-haloalkyl comprising no more than 3 halogen atoms, C2-C4-alkenyl, C3-C4-alkynyl, cyano-C1-C3-alkyl, C1-C3-alkylthio-C1-C3-al kyl.
6. The compound according to any one of the preceding claims, wherein S4 is methyl, ethyl, n-propyl, cyclopropyl, halogen or C1-C2haloalkoxy.
7. The compound according to any one of the preceding claims, wherein 5, 6 and are independently of each other hydrogen, methyl or halogen.
8. The compound according to any one of the preceding claims wherein X is 0.
9. The compound according to any one of the preceding claims wherein 8 is optionally substituted phenyl, optionally substituted naphthyl, an optionally substituted 5-or 6-membered heteroaryl or an optionally substituted bicyclic 8-to 1 0-membered heteroaryl.
10. The compound according to any one of the preceding claims wherein 8 is substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, 02-C4alkenyl, 02- C4haloalkenyl, C2-C4alkynyl, C1-C4alkoxy, 01-C4haloalkoxy, C1-C4alkylthio, C- C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4haloalkylthio, C1-C4haloalkylsulfinyl, C1- C4haloalkylsulfonyl, nitro, cyano, C3-C6cycloalkyl, C1-C3alkylcarbonyl, C- C4alkoxycarbonyl, aminocarbonyl, C1-C3alkylaminocarbonyl, di-C1- C3alkylaminocarbonyl, C1-C3alkylaminocarbonyloxy, di-C1- C3alkylaminocarbonyloxy, aminothiocarbonyl, C1-C3alkylaminothiocarbonyl, diC1- C3alkylaminothiocarbonyl, C1-C4alkylcarbonylamino, C3- C6cycloalkylcarbonylamino, C1-C4alkoxycarbonylamino,C1- C4alkylthiocarbonylamino, C1-C3alkoxyC1-C3alkyl, C1-C5alkylthioc1-C6alkyl, C- C6alkylsulfinylC1-C6alkyl, C1-C6alkylsulfonylC1-C6alkyl, C1-C3alkylsulfonyloxy, C1-C3haloalkylsulfonyloxy or diC1-C6alkylaminosulfonyl, 012 substituents on adjacent carbon atoms of R8 together form a C3-C4alkylene, wherein 1 or 2 methylene groups are optionally substituted by halogen, or wherein 1 or 2 of these methylene groups are replaced by oxygen.
11. The compound according to any one of the preceding claims wherein G is C(O)R3, and R3 is selected from the group consisting of C1-C5alkyl, C1-C5alkenyl, C1-C5alkynyl, C1-C6alkyl-S-, -NR10R11 and phenyl optionally substituted by one or more R9.
12. The compound according to anyone of the preceding claims wherein 3 is C(O)NR10R11, and R1° and R11 are independently selected from the group consisting of C1-C5 alkyl and C1-C5 alkoxy, or R1° and R11 together can form a morpolinyl ring.
13. The compound according to any one of claims 1-11, wherein each R9 is independently selected from the group consisting of halogen, cyano, nitro, C1-C3alkyl, C1-C3haloalky, C1-C3alkoxy and C1-C3haloalkoxy.
14. The compound according to any one of claims 1-10, wherein G is hydrogen.
15. A herbicidal composition comprising a herbicidal compound according to any one of claims 1-l4and an agriculturally acceptable formulation adjuvant.
16. A herbicidal composition according to claim 15, further comprising at least one additional pesticide.
17. A herbicidal composition according to claim 16, wherein the additional pesticide is a herbicide or herbicide safener.
18. A method of controlling unwanted plant growth, comprising applying a compound of formula (I) as defined in any one of claims ito 14, or a herbicidal composition according to any one of claims 15 to 17, to the unwanted plants or to the locus thereof.
19. Use of a compound of Formula (I) as defined in any one of claims 1 to 14 as a herbicide.