Cyclic diketones as herbicidal compounds

Abstract

The present invention relates to compounds having formula (I), wherein R 1 , R 2 , R 3 , R 4x , R 4y , m, n and G are as defined herein. The invention further relates to herbicidal compositions comprising compounds of formula (I), their use for controlling weeds, in particular in crops of useful plants.

Description

[0001] The present invention relates to novel herbicidal cyclohexanedione compounds, a preparation method thereof, a herbicidal composition comprising the novel compounds, and use thereof for controlling weeds.

[0002] For example, WO 2008 / 110308, WO 2014 / 191534 and WO 2015 / 197468 disclose phenyl-substituted herbicidal cyclic dione compounds having various substituents. The present invention relates to novel herbicidal cyclohexanedione derivatives having improved properties.

[0003] Therefore, according to the present invention, there is provided a compound having formula (I)

[0004]

[0005] in

[0006] R 1 is selected from the group consisting of 1-propynyl, phenyl and a 5-membered or 6-membered heteroaryl containing one or two nitrogen heteroatoms, the phenyl and heteroaryl being optionally substituted by one or two R 15 Substituent substitution;

[0007] R 2 is methyl, ethyl, methoxy or chloro;

[0008] R 3 selected from the group consisting of methyl, ethyl, methoxy and chloro;

[0009] m is 0 or 1;

[0010] r is 0 or 1;

[0011] R 4x Selected from the group consisting of hydrogen, C1-C6 alkyl, hydroxy, methoxy and halogen;

[0012] R 4y Selected from the group consisting of: R4 a 、R4 b and R4 c :

[0013]

[0014] R 4aa Selected from the group consisting of: hydrogen, C1-C6 alkyl and C1-C6 alkoxy-;

[0015] R 4abSelected from the group consisting of: hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, hydroxy-, hydroxy C1-C6 alkyl-, C1-C6 alkoxy, C3-C6 cycloalkyl, -C1-C4 alkoxy C1-C6 alkyl, -C1-C3 alkoxy C1-C6 haloalkyl, cyano C1-C6 alkyl-, C(O)R 27 、S(O) n R 27 , phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally substituted with one, two or three substituents independently selected from the group consisting of: C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, halogen, cyano and nitro; or

[0016] R 4aa and R 4ab Together they form -(CH2) q -、-CH2CH2X 1 CH2CH2- or -C(O)CH2X 1 CH2CH2-, where X 1 Selected from the group consisting of: O, S(O) n and NR 28 ;and

[0017] R 4ba selected from the group consisting of hydrogen, C1-C4 alkyl and C1-C4 alkoxy-;

[0018] R 4bb Selected from the group consisting of: C1-C4 alkyl, C1-C4 alkoxy-, C1-C4 haloalkyl, -C(O)C1-C4 alkyl, -C(O)C1-C4 haloalkyl, hydroxy C1-C6 alkyl-C(O)-, -S(O) n C1-C6 alkyl, -S(O) n C1-C6 haloalkyl, -S(O) n -(CH2) n -C3-C6 cycloalkyl, -S(O) n C(R 11 )R 12 R 13 、-C(O)H、-C(O)-(CH2) n -C3-C6 cycloalkyl, -C(O)C(R 11 )R 12 R 13 , -C(O)C2-C4alkenyl, -C(O)(CR 9 R 10 )CN、-C(O)(CR9 R 10 )(CR 9 R 10 )CN, -C(O)CH2C(O)-C1-C6 alkyl, -C(O)CH2OC(O)-C1-C6 alkyl, -C(O)OC1-C6 alkyl, -C(O)OC1-C6 haloalkyl, -C(O)(CH2) n S(O) n C1-C6 alkyl, -C(O)C1-C3 alkoxy C1-C6 alkyl, -C(O)C1-C3 alkoxy C2-C6 alkenyl, -C(O)C1-C3 alkoxy C2-C6 alkynyl, -C(O)C1-C3 alkoxy C1-C6 haloalkyl, -C(O)C1-C3 alkoxy C3-C6 cycloalkyl, -C(O)OC1-C3 alkoxy C1-C6 alkyl, -C(O)C1-C3 alkoxy C1-C3 alkoxy C1-C6 alkyl, -C(O)C1-C3 alkoxy C1-C3 alkoxy C1-C6 alkyl, -C(O)(CH2) n NR 5 R 6 、-C(O)-(CH2) n -NR 7 C(O)R 8 、-C(O)-(CH2) n -ON=CR 5 R 5 、-CN、-S(O)2NR 16 R 17 、-S(O)(=NR 18 )R 19 、-C(O)C(O)R 20 、-C(O)C(R 23 )=NOR 24 or -C(O)C(R 23 )=N-NR 25 R 26 、-(CH2) n -phenyl, -C(O)-(CH2) n -phenyl, -S(O) n -(CH2) n -phenyl, -heterocyclic, -C(O)-(CH2) n -Heterocyclic group, -C(O)(CH2) n O-(CH2) n -Heterocyclic group, -S(O) n -(CH2) n- heterocyclyl, wherein each heterocyclyl is a 5-membered or 6-membered heterocyclyl, which may be aromatic, saturated or partially saturated and may contain from 1 to 4 heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulfur, and wherein the heterocyclyl or phenyl group is optionally substituted with one, two or three substituents independently selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, halogen, cyano and nitro;

[0019] R 5 independently selected from the group consisting of hydrogen and C1-C6 alkyl;

[0020] R 6 Selected from the group consisting of: hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, hydroxy-, C1-C6 alkoxy, C3-C6 cycloalkyl, -C1-C4 alkoxy C1-C6 alkyl, -C1-C3 alkoxy C1-C6 haloalkyl, -(CR 9 R 10 )C1-C6 haloalkyl, -(CR 9 R 10 )C(O)NR 5 R 5 , phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally substituted with one, two or three substituents independently selected from the group consisting of: C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, halogen, cyano and nitro; or

[0021] R 5 and R 6 together to form -CH2CH2OCH2CH2-; and

[0022] R 7 Selected from the group consisting of hydrogen and C1-C6 alkyl;

[0023] R 8 Selected from the group consisting of: hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 cycloalkyl, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally substituted with one, two or three substituents independently selected from the group consisting of: C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, halogen, cyano and nitro;

[0024] R 9 is hydrogen or methyl;

[0025] R 10 is hydrogen or methyl; or

[0026] R 9 and R 10 together to form -CH2CH2-; and

[0027] R 11 is hydrogen or methyl;

[0028] R 12 Selected from the group consisting of: hydrogen, C1-C6 alkyl, hydroxyl and C1-C6 alkoxy-;

[0029] R 13 is selected from the group consisting of: hydrogen, C1-C6 alkyl, hydroxyl and C1-C6 alkoxy; or

[0030] R 12 and R 13 Together they form -CH2-X 2 -CH2-, where X 2 Selected from the group consisting of: O, S and NR 14 ;and

[0031] R 14 selected from the group consisting of: hydrogen, C1-C3 alkyl and C1-C3 alkoxy-;

[0032] R 15 independently selected from the group consisting of C1-C4 alkyl, C1-C4 haloalkyl, cyano and halogen;

[0033] R 16 is hydrogen or C1-C6 alkyl; and

[0034] R 17 Selected from the group consisting of: hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy-C1-C3 alkyl-, -C(O)C1-C6 alkyl, -C(O)OC1-C6 alkyl and CH2CN; or

[0035] R 16 and R 17 Together they form -CH2CH2OCH2CH2-, -CH2CH2S(O)2CH2CH2-; and

[0036] R 18 is hydrogen or C1-C6 alkyl;

[0037] R 19Selected from the group consisting of: hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 cycloalkyl, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally substituted with one, two or three substituents independently selected from the group consisting of: C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, halogen, cyano and nitro;

[0038] R 20 Selected from the group consisting of: C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy-, C1-C6 haloalkoxy, -NR 21 R 22 , phenyl and -pyridyl, wherein the phenyl and pyridyl are optionally substituted with one, two or three substituents independently selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, halogen, cyano and nitro;

[0039] R 21 Selected from the group consisting of: hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkoxyC1-C3 alkyl-, C3-C6 cycloalkyl, C1-C6 haloalkyl- and C1-C6 haloalkoxy-, -C(O)C1-C6 alkyl, phenyl, -pyridinyl, wherein the phenyl and pyridinyl are optionally substituted with one, two or three substituents independently selected from the group consisting of: C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, halogen, cyano and nitro;

[0040] R 22 is hydrogen or C1-C6 alkyl; or

[0041] R 21 and R 22 together to form -CH2CH2OCH2CH2-; and

[0042] R 23 Selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy- and C1-C6 haloalkoxy-;

[0043] R 24Selected from the group consisting of: hydrogen, C1-C6 alkyl, C1-C6 alkoxy C1-C3 alkyl-, C3-C6 cycloalkyl, -CH2CN, tetrahydropyranyl-, phenyl and -pyridinyl, wherein the phenyl and pyridinyl are optionally substituted with one, two or three substituents independently selected from the group consisting of: C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, halogen, cyano and nitro;

[0044] R 25 is hydrogen or C1-C6 alkyl;

[0045] R 26 is hydrogen or C1-C6 alkyl; and

[0046] R 4ca is selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, hydroxy-, C1-C6 alkoxy, C3-C6 cycloalkyl, -C1-C4 alkoxy C1-C6 alkyl, -C1-C3 alkoxy C1-C6 haloalkyl, cyano C1-C6 alkyl-, C(O)R 27 、S(O) n R 27 , phenyl, -pyridinyl, wherein the phenyl and pyridinyl are optionally substituted with one, two or three substituents independently selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, halogen, cyano and nitro;

[0047] R 4cb is selected from the group consisting of: hydrogen, C1-C6 alkyl and C1-C6 alkoxy-; or

[0048] R 4ca and R 4cb Together they form -(CH2) q -、-CH2CH2X 1 CH2CH2- or -C(O)CH2X 1 CH2CH2-, where X 1 Selected from the group consisting of: O, S(O) n and NR 28 ;

[0049] R 27Selected from the group consisting of: hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C3-C6 cycloalkyl, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally substituted with one, two or three substituents independently selected from the group consisting of: C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, halogen, cyano and nitro;

[0050] R 28 Selected from the group consisting of hydrogen, C1-C3 alkyl, -C(O)C1-C3 alkyl and C1-C3 alkoxy-;

[0051] q is 3, 4, or 5; and

[0052] G is selected from the group consisting of: hydrogen, -(CH2) n -R a 、-C(O)-R a 、-C(O)-(CR c R d ) n -OR b 、-C(O)-(CR c R d ) n -SR b 、-C(O)NR a R a 、-S(O)2-R a and C1-C8 alkoxy-C1-C3 alkyl-;

[0053] R a independently selected from the group consisting of hydrogen, C1-C8 alkyl, C1-C3 haloalkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C6 cycloalkyl, heterocyclyl and phenyl, wherein the heterocyclyl and phenyl groups are optionally substituted with one, two or three substituents independently selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, halogen, cyano and nitro;

[0054] R b Selected from the group consisting of: C1-C8 alkyl, C1-C3 haloalkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C6 cycloalkyl, heterocyclyl and phenyl, wherein the heterocyclyl and phenyl groups are optionally substituted with one, two or three substituents independently selected from the group consisting of: C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, halogen, cyano and nitro;

[0055] R c is hydrogen or C1-C3 alkyl;

[0056] R d is hydrogen or C1-C3 alkyl; and

[0057] n is independently 0, 1 or 2;

[0058] or an agriculturally acceptable salt thereof.

[0059] Alkyl groups (e.g., C1-C6 alkyl) include, for example, methyl (Me, CH3), ethyl (Et, C2H5), n-propyl (n-Pr), isopropyl (i-Pr), n-butyl (n-Bu), isobutyl (i-Bu), sec-butyl (s-Bu) and tert-butyl (t-Bu).

[0060] Alkenyl and alkynyl moieties may be in straight or branched form, and these alkenyl moieties may have (E)- or (Z)-configuration where appropriate. Examples are vinyl, allyl and propargyl. Alkenyl and alkynyl moieties may contain one or more double bonds and / or triple bonds in any combination.

[0061] Halogen (or halo) encompasses fluorine, chlorine, bromine or iodine. The halogen (or halo) is correspondingly applied to halogen in other definition contexts, such as haloalkyl.

[0062] Haloalkyl groups (e.g. C1-C6 haloalkyl) are, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl, heptafluoro-n-propyl and perfluoro-n-hexyl.

[0063] Alkoxy groups (eg C1-C4alkoxy-) are, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, preferably methoxy and ethoxy.

[0064] Alkoxyalkyl groups (eg C1-C8alkoxy-C1-C3alkyl-) include, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.

[0065] Cycloalkyl groups (e.g., C3-C6 cycloalkyl-) include, for example, cyclopropyl (c-propyl or c-Pr), cyclobutyl (c-butyl or c-Bu), cyclopentyl (c-pentyl) and cyclohexyl (c-hexyl or c-hexyl) and may be substituted or unsubstituted as indicated.

[0066] C1-C6Alkyl-S-(alkylthio) is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.

[0067] C1-C6Alkyl-S(O)-(alkylsulfinyl) is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl.

[0068] C1-C6Alkyl-S(O)2-(alkylsulfonyl) is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.

[0069] Heterocyclyl, unless otherwise specified, is a 5- or 6-membered heterocyclyl which may be aromatic, saturated or partially saturated and may contain from 1 to 4 heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulfur.

[0070] The invention further relates to agriculturally acceptable salts of compounds with formula (I). Such salts include those that can be formed with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the alkali metal hydroxides and alkaline earth metal hydroxides as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially the hydroxides of sodium and potassium. Compounds with formula (I) according to the present invention also include hydrates that can be formed during salt formation.

[0071] Examples of amines suitable for forming ammonium salts include ammonia and primary, secondary and tertiary C1-C 18Alkylamines, C1-C4 hydroxyalkylamines and C2-C4 alkoxyalkylamines, such as methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-pentylamine, isopentylamine, 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, diisopropylamine, di-n-butylamine, di-n-pentylamine, diisopentylamine, dihexylamine, diheptylamine amine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-but-2-enamine, n-pent-2-enamine, 2,3-dimethylbut-2-enamine, dibut-2-enamine, n-hex-2-enamine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-pentylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines such as pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and aza ; primary aromatic amines, for example aniline, methoxyaniline, ethoxyaniline, o-, m- and p-toluidine, phenylenediamine, benzidine, naphthylamine and o-, m- and p-chloroaniline; but especially triethylamine, isopropylamine and diisopropylamine.

[0072] In one embodiment of the present invention, R 1 It is 1-propynyl.

[0073] In another embodiment of the present invention, R 1 is optionally replaced by one or two R 15 The phenyl group is substituted with a substituent, for example, selected from the group consisting of cyano, chlorine and fluorine.

[0074] In another embodiment of the present invention, R 1 is a 5- or 6-membered heteroaryl group containing one or two nitrogen heteroatoms, the heteroaryl group is optionally substituted by one or two R 15 The heteroaryl group is substituted with a substituent, for example, the substituent is selected from the group consisting of cyano, chlorine and fluorine. In a preferred embodiment, the heteroaryl group is selected from the group consisting of pyridyl, pyrimidinyl and pyrazolyl.

[0075] In one embodiment of the present invention, R 2 Preferred is methyl.

[0076] In one embodiment of the present invention, R 3 It's methyl.

[0077] In another embodiment of the present invention, R 3 It's a methoxy group.

[0078] In one embodiment of the present invention, m is 1 and r is 0. In another embodiment of the present invention, m is 0 and r is 0. In a preferred embodiment of the present invention, m is 1 and r is 1.

[0079] In one embodiment of the present invention, R 4x It is hydrogen or methyl, most preferably it is hydrogen.

[0080] In one embodiment of the present invention, R 4y YesR 4a In this embodiment, R 4aa is preferably hydrogen or methyl, and R 4ab Preferably selected from the group consisting of: C1-C6 alkyl (eg methyl, tert-butyl), pyridyl, -C(O)CH2X 1 CH2CH2-(where X 1 is O), -CH2CH2X 1 CH2CH2-(where X 1 Yes O, NR 28 , where R 28 is -C(O)C1-C3 alkyl (preferably methyl) or S(O) n , wherein n is 2), hydroxy C1-C6 alkyl- (e.g. HO-CH2CH2-), C1-C6 alkoxy (e.g. MeO), -C1-C4 alkoxy C1-C6 alkyl (e.g. CH3OCH2CH2-) and cyano C1-C6 alkyl- (e.g. -C(CH3)(C2H5)(CN)).

[0081] In another embodiment of the present invention, R 4y YesR 4b In this embodiment, R 4ba is preferably hydrogen or methyl, and R 4bb Selected from the group consisting of: -C(O)C1-C4 alkyl (e.g., -C(O)CH3, -C(O)tert-butyl), -C(O)-(CH2) n -C3-C6 cycloalkyl (e.g. -C(O)-cyclopropyl), -C(O)-heterocyclyl (e.g. pyridyl), -C(O)-(CH2) n -phenyl, -C(O)(CH2) n NR 5 R 6 , -C(O)C1-C3 alkoxy C1-C6 haloalkyl (e.g. CHF2-O-CH2-), -C(O)(CR 9 R 10 )CN (e.g., -C(O)CH2CN), -C(O)(CR 9 R 10)(CR 9 R 10 )CN (e.g., -C(O)CH2CH2CN), -C(O)C1-C4 haloalkyl (e.g., -C(O)CHF2), hydroxyC1-C6 alkyl-C(O)- (e.g., HOCH(CH3)C(O)-), -C(O)CH2OC(O)-C1-C6 alkyl (e.g., CH3OCH2C(O)-) and -C(O)-(CH2) n -NR 7 C(O)R 8 .

[0082] In one embodiment, each of the aforementioned heterocyclic groups is an aromatic heterocyclic group (i.e., heteroaryl), more preferably selected from the group consisting of furanyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyranyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl and triazolyl, more preferably selected from the group consisting of pyridyl, pyridazinyl, pyrimidyl and pyrazinyl, each of which is optionally substituted as previously defined. In another embodiment, each of the aforementioned heterocyclic groups is a partially saturated heterocyclic group, more preferably selected from the group consisting of imidazolinyl, isoxazolinyl and thiazolinyl, each of which is optionally substituted as previously defined. In another embodiment, each of the aforementioned heterocyclic groups is a saturated heterocyclic group, more preferably selected from the group consisting of morpholinyl, tetrahydrofuranyl and tetrahydropyranyl, each of which is optionally substituted as previously defined.

[0083] In one embodiment of the present invention, R 5 It is hydrogen or methyl, preferably hydrogen.

[0084] In one embodiment of the present invention, R 6 It is C1-C6 alkyl (eg methyl) or pyridyl.

[0085] In one embodiment of the present invention, R 7 It is hydrogen or methyl, preferably hydrogen.

[0086] In one embodiment of the present invention, R 8 It is C1-C6 alkyl (eg tert-butyl) or pyridyl.

[0087] In a preferred embodiment of the present invention, R 9 It's hydrogen.

[0088] In a preferred embodiment of the present invention, R 10 It's hydrogen.

[0089] In one embodiment of the present invention, G is selected from the group consisting of hydrogen, C1-C8 alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl), -C2-C8 alkenyl (e.g., vinyl), C2-C8 alkynyl (e.g., propargyl), -C(O)C1-C8 alkyl (more preferably -C(O)C1-C6 alkyl, such as -C(O)isopropyl and -C(O)tert-butyl) and -C(O)-O-C1-C8 alkyl (more preferably -C(O)-O-C1-C6 alkyl, such as -C(O)-O-methyl). In a preferred embodiment, G is hydrogen.

[0090] Depending on the nature of the substituents, compounds of formula (I) may exist in different isomeric forms. When G is hydrogen, for example, compounds of formula (I) may exist in different tautomeric forms.

[0091] The present invention covers all such isomers and tautomers and mixtures of all ratios thereof. In addition, when the substituent contains a double bond, cis and trans isomers may exist. These isomers are also within the scope of the desired compound with formula (I). The compound with formula (I) may contain an asymmetric center and may exist as a single enantiomer, in any ratio of enantiomer pairs, or in the presence of more than one asymmetric center, contain diastereomers of all possible ratios. Typically, one of these enantiomers has enhanced biological activity compared to other possibilities.

[0092] The compounds with formula (I) according to the present invention can be used as herbicides themselves, but they are usually formulated into herbicidal compositions using formulation adjuvants such as carriers, solvents and surfactants (SFA). Therefore, the present invention further provides a herbicidal composition comprising the herbicidal compound according to any one of the preceding claims and an agriculturally acceptable formulation adjuvant. The composition can be in the form of a concentrate, which is diluted before use, although a ready-to-use composition can also be made. The final dilution is usually carried out with water, but water can be substituted or used in addition to water, such as liquid fertilizers, micronutrients, biological organisms, oils or solvents.

[0093] The herbicidal compositions generally comprise from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of a compound of formula (I) and from 1 to 99.9% by weight of formulation adjuvants, which preferably include from 0 to 25% by weight of surface-active substances.

[0094] The compositions may be selected from a variety of formulation types, many of which are known from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th edition, 1999. These include dustable powders (DP), soluble powders (SP), water-soluble granules (SG), water-dispersible granules (WG), wettable powders (WP), granules (GR) (slow-release or fast-release), soluble concentrates (SL), oil-miscible liquids (OL), ultra-low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil-in-water (EW) and water-in-oil (EO)), microemulsions (ME), suspension concentrates (SC), aerosols, capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any case will depend on the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).

[0095] Dustable powders (DP) can be prepared by mixing a compound of formula (I) with one or more solid diluents (e.g., natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earth, calcium phosphate, calcium and magnesium carbonates, sulfur, lime, flour, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.

[0096] Soluble powders (SP) can be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (such as polysaccharides) and optionally one or more wetting agents, one or more dispersants or a mixture of said agents to improve water dispersibility / water solubility. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-soluble granules (SG).

[0097] Wettable powders (WP) can be prepared by mixing a compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents and preferably, one or more dispersants, and optionally, one or more suspending agents to facilitate dispersion in a liquid. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water dispersible granules (WG).

[0098] Granules (GR) may be formed by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or by absorbing a compound of formula (I) (or a solution thereof in a suitable agent) into a porous granular material such as pumice, attapulgite clay, Fuller's earth, kieselguhr or diatomaceous earth, or corn cob meal, or by adsorbing a compound of formula (I) (or a solution thereof in a suitable agent) onto a hard core material such as sand, silicates, mineral carbonates, sulfates or phosphates and, if necessary, drying from preformed blank particles. Agents commonly used to aid absorption or adsorption include solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters and adhesives such as polyvinyl acetate, polyvinyl alcohol, dextrins, sugars and vegetable oils. One or more other additives may also be included in the granules (e.g., emulsifiers, wetting agents or dispersants).

[0099] Dispersible concentrates (DC) can be prepared by dissolving a compound of formula (I) in water or an organic solvent such as a ketone, alcohol or glycol ether. These solutions may contain surfactants (e.g. to improve water dilution or to prevent crystallization in the spray tank).

[0100] Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) can be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifiers or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (e.g. alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a registered trademark), ketones (e.g. cyclohexanone or methylcyclohexanone) and alcohols (e.g. benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (e.g. N-methylpyrrolidone or N-octylpyrrolidone), dimethylamides of fatty acids (e.g. C8-C 10 EC products can spontaneously emulsify when added to water, producing an emulsion with sufficient stability to allow spray application by appropriate equipment.

[0101] The preparation of EWs involves obtaining a compound of formula (I) as a liquid (if it is not liquid at room temperature, it can be melted at a reasonable temperature, typically below 70° C.) or in solution (by dissolving it in a suitable solvent), and then emulsifying the resulting liquid or solution into water containing one or more SFAs under high shear to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzene), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other suitable organic solvents having low solubility in water.

[0102] Microemulsion (ME) can be prepared in the following manner: water is mixed with a blend of one or more solvents and one or more SFAs to spontaneously produce a thermodynamically stable isotropic liquid formulation. The compound with formula (I) is initially present in water or in a solvent / SFA blend. The suitable solvent used in ME includes those used in EC or EW described above. ME can be an oil-in-water system or an oil-in-water system (which system exists can be measured by conductivity measurement) and can be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. ME is suitable for dilution in water, remains as a microemulsion or forms a conventional oil-in-water emulsion.

[0103] Suspension concentrates (SC) may include aqueous or non-aqueous suspensions of finely dispersed insoluble solid particles of a compound of formula (I). SC may be prepared in the following manner: a solid compound of formula (I) may be optionally ball-milled or bead-milled in a suitable medium with one or more dispersants to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition, and a suspending agent may be included to reduce the rate of particle settling. Alternatively, a compound of formula (I) may be dry-milled and added to water containing the reagents described above to produce a desired end product.

[0104] Aerosol formulations comprise a compound of formula (I) and a suitable propellant (e.g. n-butane). The compound of formula (I) may also be dissolved or dispersed in a suitable medium (e.g. water or a water-miscible liquid such as n-propanol) to provide a composition for use in a non-pressurized manual spray pump.

[0105] Capsule suspensions (CS) can be prepared in a similar manner to the preparation of EW formulations, but with an additional polymerization stage, so that an aqueous dispersion of oil droplets is obtained, wherein each oil droplet is wrapped by a polymer shell and contains a compound with formula (I) and optionally a carrier or diluent for the oil droplet. The polymer shell can be produced by an interfacial polycondensation reaction or by a coagulation procedure. These compositions can provide controlled release of compounds with formula (I) and they can be used for seed treatment. Compounds with formula (I) can also be formulated in a biodegradable polymer matrix to provide slow, controlled release of the compound.

[0106] The composition may include one or more additives to improve the biological performance of the composition, for example by improving wettability, retention or distribution on a surface; rain resistance on a treated surface; or absorption or flow of a compound of formula (I). Such additives include surfactants (SFAs), oil-based spray additives, such as certain mineral oils or natural vegetable oils (such as soybean and rapeseed oils), and blends of these with other bioenhancement adjuvants (ingredients that can assist or modify the action of a compound of formula (I)).

[0107] The wetting agents, dispersants and emulsifiers may be SFAs of the cationic, anionic, amphoteric or nonionic type.

[0108] Suitable SFAs of the cationic type include quaternary ammonium compounds (eg cetyltrimethylammonium bromide), imidazolines and amine salts.

[0109] Suitable anionic SFAs include alkali metal salts of fatty acids, salts of fatty sulfuric acid monoesters (e.g. sodium lauryl sulfate), salts of sulfonated aromatic compounds (e.g. sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butylnaphthalenesulfonate and mixtures of sodium di-isopropyl-naphthalenesulfonate and sodium tri-isopropyl-naphthalenesulfonate), ether sulfates, alcohol ether sulfates (e.g. sodium laureth-3-sulfate), ether carboxylates (e.g. sodium laureth-3-carboxylate), phosphates (products from the reaction of one or more fatty alcohols with phosphoric acid (mainly monoesters) or with phosphorus pentoxide (mainly diesters), for example the reaction of lauryl alcohol with tetraphosphoric acid; alternatively these products may be ethoxylated), sulfosuccinamates, paraffin or olefin sulfonates, taurates and lignosulfonates.

[0110] Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.

[0111] Suitable SFAs of the nonionic type include condensation products of alkylene oxides (e.g. ethylene oxide, propylene oxide, butylene oxide or mixtures thereof) with fatty alcohols (e.g. oleyl alcohol or cetyl alcohol) or with alkylphenols (e.g. octylphenol, nonylphenol or octylcresol); partial esters derived from long-chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; monoesters (e.g. fatty acid polyethylene glycol esters); amine oxides (e.g. lauryl dimethyl amine oxide); and lecithin.

[0112] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

[0113] The herbicidal compounds of the present invention can also be used in mixtures with one or more additional herbicides and / or plant growth regulators. Examples of such additional herbicides or plant growth regulators include acetochlor, acifluorfen (including acifluorfen-sodium), benitobutyl, ametryn, amitriptyline, aminopyralid, cypermethrin, atrazine, flubutyric acid-M, benzylsulfuron-methyl (including benzylsulfuron-methyl), bentazon, bicyclpyrone, bialaphos, bispyribac-sodium, bixlozone, herbicide, bromoxynil, butachlor, fluazifop-butyl, mesotrione (including mesotrione-ethyl), chlorsulfuron (including chlorsulfuron-methyl), chlorsulfuron (including chlorsulfuron-ethyl), chlorotoluron, chlorsulfuron, cyproconazole, clacyfos, clethodim, clodinafop-butyl (including clodinafop-butyl) , clomazone, clopyralid, cyclopyranil, cyclopyrimorate, cyprosulfuron, cyhalofop-butyl (including cyhalofop-butyl-butyl), 2,4-D (including its choline salt and 2-ethylhexyl ester), 2,4-DB, betaine, dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloropropane, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts), bisclostrobin, fluazifop-butyl, fluazifop-butyl, dimethoate, dimethoate-s-propyl, diquat, diuron, epyrifenacil, ethoflufen, ethoflufen, oxazolidinone (including fine oxazolidinone oxadiazine-ethyl), fenoxasulfone, fenquinotrione, tetrazoline, fluazifop-butyl, bispyribac, florpyrauxifen (including florpyrauxifen-benzyl), fluazifop-butyl (including fluazifop-butyl-butyl), fluazifop-butyl (including fluazifop-sodium), flufenacet, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl (including fluazifop-methyl-sodium), fluroxypyr (including fluroxypyr-meptyl), flufenacet-butyl, foramsulfuron, glufosinate (including its ammonium salts), glyphosate (including its hydrazine, isopropyl ammonium and potassium salt), halauxifen (including halauxifen-methyl), haloxalothioate (including haloxalothioate-methyl), hexazinone, hydantocidin, imazamox, imazapic, imazamox, indazine fluazifop, iodosulfuron (including iodosulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium), ioboxynil, isoproturon, isoxathiocarb, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metamitron,Metazachlor, isoxathiachlor, isopropyl metolachlor, sulfamethoxazole, metribuzin, metsulfuron, propamide, nicosulfuron, norfaxan, oxadiazine, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, bendiazole, picloram, pinoxaden, pretilachlor, primisulfuron-methyl, promethazine, propanil, cypermethrin, propyrisulfuron, propyrisulfuron, promethazine, prosulfuron, prosulfuron, pyraflufen (including pyraflufen-ethyl), pyrasulfuron, pyridasulfuron, pyrimidin, pyrimisulfan, pyroxasulfone, sulfamethoxam, quinclorac, clomaclorac, quizalofop-ethyl (including quizalofop-ethyl and quizalofop-P-tefuryl), sulfamethoxam, pyrimidine oxadiazine, sethoxydim, simazine, sulfamethoxam, sulfamethoxam, sulfamethoxam, thiosulfuron, thiosulfuron, tetralone, tetrimide ... bensulfuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifludimoxazin, trifluralin, triflusulfuron, 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridinyl]imidazolin-2-one, 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridinyl]imidazolin-2-one, 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)- imidazolin-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolin-2-one, 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolin-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolin-2-one, 3-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione, 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1,3-dione,2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]cyclohexane-1,3-dione, 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione, 6-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione, 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5-ethyl-cyclohexane-1,3-dione, 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine- 4-carbonyl]-4,4,6,6-tetramethyl-cyclohexane-1,3-dione, 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1,3-dione, 3-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione, 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione, 6-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane -1,3,5-trione, 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]cyclohexane-1,3-dione, 4-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione, 4-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid (including its agrochemically acceptable esters, for example, methyl 4-amino-3-chloro-5-fluoro- fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, prop-2-ynyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate and cyanomethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate), 3-ethylsulfanyl-N-(1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(isopropylsulfanylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide,3-(Isopropylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(ethylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 2-[[3-[[3-chloro-5-fluoro-6-[3 -methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridinyl]oxy]ethyl acetate, 6-chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one, 1-[2-chloro-6-(5-chloropyrimidin-2-yl)oxy-phenyl]-4,4,4-trifluoro-butan-1-one and 5-[2-chloro-6-(5-chloropyrimidin-2-yl)oxy-phenyl]-3-(difluoromethyl)isoxazole.

[0114] Mixture partners of compounds of formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, Sixteenth Edition, British Crop Protection Council, 2012.

[0115] The compounds of formula (I) can also be used in a mixture with other agrochemicals such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual.

[0116] The mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1:100 to 1000:1.

[0117] These mixtures can advantageously be used in the abovementioned formulations ("active ingredient" in this case relates to the corresponding mixture of the compound of formula (I) with the mixing partner).

[0118] Compounds or mixtures of the present invention can also be used in combination with one or more herbicide safeners. Examples of such safeners include fenthiocarb, cloquintocet-mexyl (including cloquintocet-mexyl), cyclopropylsulfonamide, dichloropropene, fenthiocarb (including fenthiocarb-ethyl), fenthiocarb, fluazifop, fenthiocarb, isoxadiazole (including isoxadiazole-ethyl), mefenpyr (including pyrazoles oxalic acid-diethyl), metcamifen and oxalonitrile.

[0119] Particularly preferred are mixtures of compounds of formula (I) with ciprosulfamide, isoxadifen-ethyl, clofometrexate and / or metcamifen.

[0120] The safeners of compounds of formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, 16th edition (BCPC), 2012. References to clofonethiol also apply to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts (as disclosed in WO 02 / 34048).

[0121] Preferably, the mixing ratio of compound of formula (I) to safener is from 100:1 to 1:10, in particular from 20:1 to 1:1.

[0122] These mixtures can advantageously be used in the abovementioned formulations (in this case "active ingredient" relates to the corresponding mixture of the compound of formula (I) with the safener).

[0123] The present invention still further provides a method of controlling weeds at a locus comprising crop plants and weeds, wherein the method comprises applying to the locus a weed controlling amount of a composition according to the invention. 'Control' means killing, reducing or delaying growth or preventing or reducing germination. Typically the plants to be controlled are unwanted plants (weeds). 'Locus' means an area where plants are growing or will grow.

[0124] The application rate of the compound of formula (I) can vary within wide limits and depends on the nature of the soil, the method of application (pre-emergence or post-emergence; seed dressing; application to the seed furrow; no-till application, etc.), the crop plants, one or more weeds 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 compound of formula (I) according to the present invention is usually applied at a rate of from 10 to 2000 g / ha, especially from 50 to 1000 g / ha.

[0125] Application is usually made by spraying the composition, typically by means of a tractor-mounted sprayer for large areas, but other methods such as dusting (for powders), dripping or drenching may also be used.

[0126] Useful plants in which the compositions according to the invention can be used include crops such as cereals, for example barley and wheat, cotton, rapeseed, sunflower, maize, rice, soybean, sugar beet, sugar cane and turf.

[0127] Crop plants may also include trees, such as fruit trees, palm trees, coconut trees or other nuts. Also included are vines (such as grapes), shrub fruit trees, fruit plants and vegetables.

[0128] Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-inhibitors, GS-inhibitors, EPSPS-inhibitors, PPO-inhibitors, ACCase-inhibitors and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering. Examples of crops which have been rendered tolerant to imidazolinones (e.g. imazamox) by conventional methods of breeding are Summer rapeseed (canola). Examples of crops rendered tolerant to herbicides by genetic engineering methods include, for example, glyphosate- and glufosinate-resistant maize varieties that are and It is commercially available under the trademark ANTIQUID®.

[0129] Crops are also to be understood as those crops which have been rendered resistant to harmful insects by genetic engineering methods, such as Bt maize (resistant to European corn borer), Bt cotton (resistant to boll weevil) and also Bt potato (resistant to Colorado beetle). Examples of Bt maize are Bt toxins are proteins naturally produced by the soil bacterium Bacillus thuringiensis. Examples of toxins or transgenic plants capable of synthesizing such toxins are described in EP-A-451878, EP-A-374 753, WO 93 / 07278, WO 95 / 34656, WO 03 / 052073 and EP-A-427 529. Examples of transgenic plants comprising one or more genes encoding insecticide resistance and expressing one or more toxins are (Corn), Yield (corn), (cotton), (cotton), (potato), and Plant crops or their seed material can both be resistant to herbicides and at the same time resistant to insect feeding ("stacked" transgenic events). For example, a seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.

[0130] Crops are also to be understood as including those crops which have been obtained by conventional breeding methods or genetic engineering and contain so-called output traits, such as improved storage stability, higher nutritional value and improved flavour.

[0131] Other useful plants include turf grasses such as those grown commercially for lawns on golf courses, lawns, parks and roadsides, and ornamental plants such as flowers or shrubs.

[0132] These compositions can be used to control unwanted plants (collectively referred to as 'weeds'). The weeds to be controlled can be either monocotyledonous species, such as bentgrass, alopecurus, avena, brachiaria, brome, tricholoma, sedge, crabgrass, barnyard grass, sedge, ryegrass, rainweed, cyperus, sagittaria, scabrous grass, setaria and sorghum, or dicotyledonous species, such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Ligusticum, Laura, Ipomoea, Nasturtium, Rhizoma Adenophorae, Sinapis, Solanum, Chickweed, Veronica, Viola and Xanthium. The compounds of the invention have been shown to exhibit particularly good activity against certain grass weed species, especially perennial ryegrass (Lolium Perenne). Weeds may also include plants that may be considered crop plants but that grow outside the crop area ('escapes'), or plants that grow from seeds left over from a previously grown different crop ('volunteers'). Such volunteers or escapes may be resistant to certain other herbicides.

[0133] The compounds of the present invention can be prepared according to the following schemes.

[0134]

[0135] Compounds of formula (I) wherein G is not hydrogen can be prepared by treating a compound of formula (I) wherein G is hydrogen with a reagent GZ wherein GZ is an alkylating agent (e.g., an alkyl halide), an acylating agent (e.g., an acyl chloride or anhydride), a sulfonylating agent (e.g., a sulfonyl chloride), a carbamoylating agent (e.g., a carbamoyl chloride), or a carbonating agent (e.g., a chloroformate) using known methods.

[0136]

[0137] A compound having formula (I) (wherein R 4 Belongs to R4 a Type) can be prepared by reacting an iodonium ylide of formula (A) (wherein Ar is an optionally substituted phenyl group) with an arylboronic acid of formula (B) in the presence of a suitable palladium catalyst, a base and in a suitable solvent.

[0138]

[0139] Preferably, the palladium catalyst is palladium acetate, the base is lithium hydroxide and the solvent is aqueous 1,2-dimethoxyethane.

[0140] Alternatively, R can then be added in synthetic order from intermediates of type (D) or (E) through a series of metal-catalyzed cross-coupling reactions using standard literature procedures. 1 .

[0141]

[0142] Compounds of formula (A) can be prepared from 1,3 dione compounds of formula (F) using known procedures by treatment with a hypervalent iodine reagent such as (diacetoxy)iodobenzene or iodosobenzene and a base such as aqueous sodium carbonate, lithium hydroxide or sodium hydroxide in a solvent such as water or an aqueous alcohol such as ethanol.

[0143]

[0144] Boric acid can be prepared by methods such as those in Scheme 5 below. For example, compounds of formula (B) or (C) can be prepared from aryl halides of formula (G) or (I) by known methods. For example, aryl halides of formula (G or I) can be treated with alkyl lithium or alkyl magnesium halides in a suitable solvent (preferably diethyl ether or tetrahydrofuran) at a temperature between -80°C and 30°C, and the obtained aryl magnesium or aryl lithium reagent can then be reacted with a trialkyl borate (preferably trimethyl borate) to give an aryl dialkyl borate, which can be hydrolyzed under acidic conditions to provide a boronic acid of formula (B) or (C).

[0145]

[0146] As shown in the following scheme, compounds of formula (D) can also be prepared by Pb coupling, by reacting a compound of formula (C) to form an organolead reagent of formula (J) and subsequently reacting with a 1,3 diketone (F) under conditions such as described by J. Pinhey, Pure and Appl. Chem., (1996), 68(4), 819 and by M. Moloney et al., Tetrahedron Lett., (2002), 43, 3407. Suitable triarylbismuth compounds can be used as relevant procedures under the conditions described, for example, by A. Yu. Fedorov et al., Russ. Chem. Bull. Int. Ed. [Russian Chemical Bulletin International Edition], (2005), 54 (11), 2602, and by P. Koech and M. Krische, J. Am. Chem. Soc. [Journal of the American Chemical Society], (2004), 126 (17), 5350 and references therein.

[0147]

[0148] Under appropriate conditions, suitable 1,3 diketones can also be coupled directly to halogenated compounds (e.g., having formula (K)) under palladium catalysis. As depicted in Scheme 3, intermediate (L) is prepared by appropriately converting the halide to R 1 Compounds of type (I) are obtained.

[0149]

[0150] Compounds of type (I) can also be obtained by functionalization of the common intermediate acid (O) at a later stage. For example, under alkaline conditions, compound (M) can be converted into intermediate (N) by the method described above and then the ester group can be hydrolyzed. Intermediate acid (O) can then be directly converted into compounds of type (I) by standard amide coupling methods (such as by using HATU).

[0151]

[0152] 1,3 diketones of type (F) and (M) can be prepared using methods as shown below. So commercially available ketones (e.g. of type (P)) can be converted to intermediate (Q), and then to intermediate (R), and finally cyclized to intermediate (S) and decarboxylated to give intermediate (F) (these methods are described in WO 2008 / 110308).

[0153]

[0154] A compound having formula (I) (wherein R 4Belongs to R4 b Type) can be similar to R4 a Type of preparation method for preparation.

[0155] A suitably protected amine (such as the BOC group shown in ketone (T)) can be converted to an intermediate of type (U) by the methods described in Scheme 10. A 1,3 diketone of type (U) can then be converted to a compound of type (V) by the methods described above. Removal of the protecting group (under acidic conditions in this example) affords an amine of type (W).

[0156]

[0157] Alternatively, a suitable monoprotected diketone (such as the acetal group shown in ketone (X)) can be converted to an intermediate of type (Z) by the methods described above. Removal of the ketone protecting group (under acidic conditions in this example) followed by reductive amination with a suitable amine gives an amine of type (AB).

[0158]

[0159] Amides, ureas, acylureas and oxalamides can be prepared from intermediates (W) and (AB) by standard literature methods as known to those skilled in the art, as in Scheme 13.

[0160]

[0161] (a) 2-methoxyacetic acid, HATU, DIPEA, DMF, RT; (b) 2-(methylamino)-2-oxo-acetic acid,

[0162] HATU, NEt3, DCM, RT; (c) 2-isocyanato-2-methyl-propane, NEt3, DCM; (d) 2,2-dimethylpropionyl isocyanate, NEt3, DCM;

[0163] The following non-limiting examples provide specific synthetic methods for representative compounds of the present invention (as mentioned in the table below).

[0164] Example 1: Synthesis of 3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-N-methyl-2,4-dioxo-spiro[5.5]undecane-9-carboxamide (Compound 1.002)

[0165]

[0166] Step 1: Synthesis of N-methyl-4-oxo-cyclohexanecarboxamide

[0167]

[0168] Methylamine solution (9.8M in MeOH, 2.15mL, 21.1mmol), HOAt (1.44g, 10.6mmol), EDC-HCl (1.64g, 10.6mmol) and DIPEA (3.68mL, 21.1mmol) were added to a stirred solution of 4-oxocyclohexanecarboxylic acid (1.00g, 7.03mmol) in DCM (24.0mL). The reaction mixture was stirred at room temperature for 17 hours, diluted with water and extracted with DCM. The combined organic layers were washed with brine, dried over Na2SO4, concentrated and purified by flash column chromatography (0%-50% acetone in hexane) to give N-methyl-4-oxo-cyclohexanecarboxamide (230mg, 1.48mmol, 21% yield) as a white solid. 1H NMR (400MHz, CD3Cl) δppm=5.58(br s,1H),2.83-2.82(d,3H),2.54-2.47(m,3H),2.36-2.28(m,2H),2.17-2.12(m,2H),2.03-1.93(m,2H)

[0169] Step 2: Synthesis of 4-acetonylidene-N-methyl-cyclohexanecarboxamide

[0170]

[0171] 1-dimethoxyphosphoryl propan-2-one (0.624mL, 4.51mmol) was added dropwise to a stirred solution of potassium hydroxide (0.253g, 4.51mmol) in ethanol (7.0mL) and water (1.8mL) at 5°C. N-methyl-4-oxo-cyclohexanecarboxamide (0.500g, 3.22mmol) was added to the mixture in batches at the same temperature. The resulting reaction mixture was stirred at room temperature for 22 hours, then concentrated, diluted with water and extracted with DCM. The combined organic matter was washed with brine, dried over Na2SO4, and concentrated to obtain crude material. The crude material was ground with 20% EtOAc: hexane to obtain 4-acetonyl-N-methyl-cyclohexanecarboxamide (470mg, 2.35mmol, 73% yield) as an off-white solid. 1H NMR (400MHz, CD3Cl) δppm=6.02 (s, 1H), 5.50 (s, 1H), 2.78 (d, 3H), 2.34-1.93 (m, 12H).

[0172] Step 3: Synthesis of N-methyl-2,4-dioxo-spiro[5.5]undecane-9-carboxamide

[0173]

[0174] To a stirred solution of 4-acetonyl-N-methyl-cyclohexanecarboxamide (4.10 g, 21.0 mmol) in ethanol (26.0 mL), diethyl malonate (3.20 mL, 21.0 mmol) was added, followed by dropwise addition of sodium ethoxide (21.0%, 61 mL, 3.61 mmol). The reaction mixture was stirred at room temperature for 3 hours, then heated to reflux for 4 hours, then allowed to stand overnight at room temperature. The reaction mixture was concentrated, diluted with water and washed with ethyl acetate. The aqueous layer was then acidified with aqueous citric acid and extracted with DCM. The combined organics were washed with brine, dried over Na2SO4, and concentrated to give 9-(methylcarbamoyl)-2,4-dioxo-spiro[5.5]undecane-5-carboxylic acid ethyl ester (3.80 g) as a brown viscous liquid. Crude 9-(methylcarbamoyl)-2,4-dioxo-spiro [5.5] undecane-5-carboxylic acid ethyl ester (3.80 g, 12.3 mmol) was absorbed into ethanol (10.0 mL). Sodium hydroxide (12.0 M, 21.7 mL, 260 mmol) was added at room temperature, and the reaction mixture was stirred at room temperature for 23 hours. The reaction mixture was concentrated, acidified with citric acid solution and extracted with ethyl acetate. The combined organics were dried over Na2SO4, concentrated and purified by flash column chromatography (MeOH-DCM) to obtain N-methyl-2,4-dioxo-spiro [5.5] undecane-9-carboxamide (2.3 g, 9.69 mmol, 79% yield) as off-white foam. 1H NMR (400MHz, CD3OD) δppm=2.92-2.88(m,2H),2.80-2.76(m,2H),2.69(s,3H) ,2.16-2.30(m,1H),1.82-1.78(m,2H),1.66-1.62(m,4H),1.28-1.23(m,2H)

[0175] Step 4: Synthesis of [diacetoxy-(4-bromo-2,6-dimethyl-phenyl)lead alkyl] acetate

[0176]

[0177] Lead (IV) acetate (2.32g, 5.24mmol) and mercuric acetate (0.139g, 0.437mmol) are dissolved in chloroform (20mL) and the solution is warmed to 40°C for 10 minutes. (4-bromo-2,6-dimethyl-phenyl) boronic acid (1.00g, 4.37mmol) is added and the mixture is heated at 40°C for 3 hours. The reaction mixture is cooled to 0°C and potassium carbonate (4.52g, 32.7mmol) is added. Then the reaction mixture is vigorously stirred at room temperature for 1 hour. The reaction mixture is filtered through a celite pad and washed with chloroform. The filtrate is concentrated, and the resulting solid is ground with hexane to obtain [diacetoxy-(4-bromo-2,6-dimethyl-phenyl) lead alkyl] acetate (1.94g, 3.41mmol, 78% yield) as a white solid. 1H NMR (400MHz, CD3Cl) δppm=7.33 (s, 2H), 2.62-2.54 (m, 6H), 2.08 (s, 9H).

[0178] Step 5: Synthesis of 3-(4-bromo-2,6-dimethyl-phenyl)-N-methyl-2,4-dioxo-spiro[5.5]undecane-9-carboxamide

[0179]

[0180] To a stirred solution of compound N-methyl-2,4-dioxo-spiro[5.5]undecane-9-carboxamide (0.810 g, 3.41 mmol) in chloroform (28 mL) was added 4,4-dimethylaminopyridine (2.08 g, 17.1 mmol). The reaction mixture was stirred under nitrogen for 15 min at room temperature, then toluene (6 mL) was added, followed by [diacetoxy-(4-bromo-2,6-dimethyl-phenyl)lead alkyl] acetate (1.94 g, 3.41 mmol). The reaction mixture was stirred at 80 ° C for 3 hours and then allowed to stand at room temperature overnight. The reaction mixture was cooled on ice, acidified with citric acid solution, and filtered through celite. The aqueous layer was extracted with chloroform, and the combined organics were washed with brine, dried over Na2SO4, evaporated and purified by flash column chromatography (acetone-hexanes) to give 3-(4-bromo-2,6-dimethyl-phenyl)-N-methyl-2,4-dioxo-spiro[5.5]undecane-9-carboxamide (125 mg, 0.275 mmol, 8% yield) as an off-white solid. 1H NMR (400 MHz, CD3OD) δ ppm = 7.18 (s, 2H), 2.71-2.67 (m, 5H), 2.40 (s, 2H), 2.19-2.14 (m, 1H), 2.02 (s, 6H), 1.96-1.93 (m, 2H), 1.72-1.63 (m, 4H), 1.41-1.24 (m, 2H).

[0181] Step 6: Synthesis of 3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-N-methyl-2,4-dioxo-spiro[5.5]undecane-9-carboxamide (Compound 1.002)

[0182]

[0183] 3-(4-Bromo-2,6-dimethyl-phenyl)-N-methyl-2,4-dioxo-spiro[5.5]undecane-9-carboxamide (0.125 g, 0.297 mmol), 4-diphenylphosphanibutyl(diphenyl)phosphane (0.0253 g, 0.0594 mmol), bis(triphenylphosphine)palladium(II) chloride (0.0209 g, 0.0297 mmol) and 2-butynoic acid (0.0750 g, 0.892 mmol) were placed in a round bottom flask. Dimethyl sulfoxide (2.00 mL) and DBU (0.272 g, 1.78 mmol) were added, and the reaction mixture was stirred at 110° C. for 20 hours. The reaction mixture was acidified with 10% citric acid solution and extracted with EtOAc. The combined organics were dried over Na2SO4, concentrated and purified by preparative HPLC to give 3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-N-methyl-2,4-dioxo-spiro[5.5]undecane-9-carboxamide (24 mg, 0.063 mmol, 21% yield) as a white solid. 1H NMR (400 MHz, CD3OD) δ ppm = 7.81 (br s, 1H), 7.02 (s, 2H), 2.71-2.67 (m, 5H), 2.39 (br s, 2H), 2.20-2.14 (m, 1H), 2.03-1.98 (m, 10H), 1.94 (m, 1H), 1.69-1.67 (m, 4H), 1.40-1.33 (m, 2H).

[0184] Example 2: Synthesis of N-[3-[4-(5-chloro-2-pyridinyl)-2,6-dimethyl-phenyl]-2,4-dioxo-spiro[5.5]undec-9-yl]acetamide (Compound 2.026)

[0185]

[0186] Step 1: Synthesis of tert-butyl N-(4-acetonylidenecyclohexyl)carbamate

[0187]

[0188] To a stirred solution of potassium hydroxide (1.5 eq., 70.333 mmol) in ethanol (20 eq., 937.78 mmol) and water (5 eq., 234.44 mmol) at 0°C was added dimethyl (2-oxopropyl)phosphonate (1.4 eq., 65.644 mmol) dropwise and the reaction mixture was stirred for 5 minutes. Then, tert-butyl N-(4-oxocyclohexyl)carbamate (10 g, 46.889 mmol) was added and the reaction mixture was allowed to stir at room temperature for 2 hours before being extracted with EtOAc, washed with brine, and dried over MgSO. The volatiles were removed in vacuo and the residue was purified by flash column chromatography (0%-100% ethyl acetate in isohexane) to give tert-butyl N-(4-acetonylidenecyclohexyl)carbamate (10.3 g, 40.7 mmol, 87% yield) as a white solid. 1H NMR (400MHz, CD3Cl) δppm=6.07-5.97(m,1H), 3.63-3.52(m,1H), 2.46-2.38(m,2H), 2.28-2.21(m,2H), 2.18(s,3H), 1.48-1.42(m,13H).

[0189] Step 2: Synthesis of tert-butyl N-(2,4-dioxospiro[5.5]undec-9-yl)carbamate

[0190]

[0191] To a stirred solution of sodium methoxide in methanol (1 eq., 19.65 mmol, 25% by mass) was added dimethyl malonate (1.05 eq., 20.63 mmol) dropwise at 0°C and the mixture was stirred for 1 hour. Then, a solution of tert-butyl N-(4-acetonylcyclohexyl)carbamate (4.977 g, 19.65 mmol) in methanol (20 mL, 490 mmol) was added dropwise at 0°C and the mixture was stirred for 10 minutes at room temperature and heated to 60°C overnight. After cooling, a solution of potassium hydroxide (5 eq., 98.25 mmol) in water (0.3 mL / mmol, 327.2 mmol) was added and the reaction mixture was stirred at 60°C for 24 hours. The mixture was cooled, acidified to pH=5 with aqueous citric acid and extracted with ethyl acetate. The combined organics were dried over Na2SO4, filtered and concentrated to give tert-butyl N-(2,4-dioxaspiro[5.5]undec-9-yl)carbamate (4.164 g, 14.10 mmol, 72% yield) as a brown solid. 1H NMR (400 MHz, CD3OD) δ ppm = 3.37-3.32 (m, 1H), 2.41 (s, 2H), 2.26-2.20 (m, 2H), 1.79-1.69 (m, 4H), 1.43 (s, 9H), 1.40-1.32 (m, 4H).

[0192] Step 3: Synthesis of tert-butyl N-[2,4-dioxo-3-(phenyl-$1^{3}-iodoalkylene)spiro[5.5]undec-9-yl]carbamate

[0193]

[0194] Sodium carbonate (2 equivalents, 24.04mmol) is dissolved in a mixture of water (15mL / g) and ethanol (3mL / g). Disposable addition of N-(2,4-dioxo spiro [5.5] undecane-9-yl) tert-butyl carbamate (3.551g, 12.02mmol) and the mixture is stirred at room temperature (5 minutes) until the diketone dissolves. The solution is cooled to 5 ° C and (diacetoxy iodine) benzene (1 equivalent, 12.02mmol) is added in batches. The reaction mixture is stirred at 5 ° C for 15 minutes and then at room temperature for 3 hours. The mixture is diluted with water and extracted with DCM. The combined organics were washed with brine, dried over MgSO 4 , concentrated and triturated in diethyl ether to give tert-butyl N-[2,4-dioxo-3-(phenyl-$1^{3}-iodoalkylidene)spiro[5.5]undec-9-yl]carbamate (2.040 g, 4.10 mmol, 34% yield) as a brown solid. 1H NMR (400MHz, CDCl3) δppm=7.88-7.78(m,2H),7.58-7.50(m,1H),7.42-7.31(m,2H),4.50-4.35(m,1H),3.47-3.36(m, H),2.67-2.57(m,2H),2.54-2.44(m,2H),1.86-1.77(m,2H),1.72-1.69(m,2H),1.47-1.41(m,9H),1.38-1.27(m,4H).

[0195] Step 4: Synthesis of tert-butyl N-[3-(4-bromo-2,6-dimethyl-phenyl)-2,4-dioxo-spiro[5.5]undec-9-yl]carbamate

[0196]

[0197] Tert-butyl N-[2,4-dioxo-3-(phenyl-$1^{3}-iodoalkylene)spiro[5.5]undecane-9-yl]carbamate (2.04 g, 4.10 mmol, 100% by mass) was dissolved in 1,2-dimethoxyethane (8 mL / mmol, 312 mmol), and the mixture was treated with (4-bromo-2,6-dimethyl-phenyl)boric acid (1.2 eq., 4.92 mmol) and palladium(II) acetate (0.05 eq., 0.205 mmol). The reaction mixture was stirred at room temperature for 5 min and finally a solution of lithium hydroxide (3 eq., 12.3 mmol) in water (2 mL / mmol, 442 mmol) was added. The mixture was stirred at 50 ° C for 20 hours, cooled, diluted with aqueous citric acid and extracted with ethyl acetate. The organics were dried over MgSO4, concentrated, and purified by flash column chromatography (0%-100% EtOAc in iso-hexanes) to give tert-butyl N-[3-(4-bromo-2,6-dimethyl-phenyl)-2,4-dioxo-spiro[5.5]undec-9-yl]carbamate (594 mg, 1.24 mmol, 30% yield) as a light yellow solid. 1H NMR (400 MHz, CD3OD) δ ppm = 7.19-7.16 (m, 2H), 2.60-2.56 (m, 2H), 2.44-2.40 (m, 2H), 2.04-2.01 (m, 6H), 1.93-1.85 (m, 2H), 1.81-1.72 (m, 2H) 1.47-1.41 (m, 13H).

[0198] Step 5: Synthesis of tert-butyl N-[3-[2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-2,4-dioxo-spiro[5.5]undec-9-yl]carbamate

[0199]

[0200] N-[3-(4-bromo-2,6-dimethyl-phenyl)-2,4-dioxo-spiro[5.5]undec-9-yl]carbamic acid tert-butyl ester (261 mg, 0.5456 mmol) and bis(pinacolato)diboron (3 eq., 1.637 mmol) were dissolved in degassed 1,4-dioxane (5 mL). 2-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.2 eq., 0.1091 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.1 eq., 0.05456 mmol) and potassium acetate (3 eq., 1.637 mmol) were added to the mixture. The mixture was stirred at 85 °C for 24 h, concentrated and purified by flash column chromatography (0%-100% ethyl acetate in cyclohexane) to give tert-butyl N-[3-[2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-2,4-dioxo-spiro[5.5]undec-9-yl]carbamate (264 mg, 0.467 mmol, 86% yield). 1H NMR (400MHz, CD3OD) δppm=7.44(s,2H),3.43-3.37(m,1H),2.63(s,2H),2.48(s,2H),2.09-2.06( m,6H),1.98-1.89(m,2H),1.84-1.77(m,2H),1.51-1.47(m,4H),1.47-1.45(m,9H),1.35(s,12H).

[0201] Step 6: Synthesis of tert-butyl N-[3-[4-(5-chloro-2-pyridinyl)-2,6-dimethyl-phenyl]-2,4-dioxo-spiro[5.5]undec-9-yl]carbamate

[0202]

[0203] To a mixture of tert-butyl N-[3-[2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-2,4-dioxo-spiro[5.5]undec-9-yl]carbamate (0.264 g, 0.5024 mmol), 2-bromo-5-chloro-pyridine (0.1257 g, 0.6531 mmol) and 1,1'-bis(diphenylphosphino)ferrocene-dichloropalladium(II) dichloromethane complex (0.08459 g, 0.1005 mmol) was added 1,2-dimethoxyethane (10 mL) followed by a solution of tripotassium phosphate (0.4266 g, 2.010 mmol) in water (5 mL) at room temperature. The reaction mixture was stirred at 100°C for 18 hours. After cooling, the mixture was diluted with 10% aqueous citric acid and extracted with ethyl acetate. The combined organics were dried over Na2SO4, passed through a phase separation column, concentrated, and purified by flash column chromatography (0%-100% ethyl acetate in DCM) to give tert-butyl N-[3-[4-(5-chloro-2-pyridinyl)-2,6-dimethyl-phenyl]-2,4-dioxo-spiro[5.5]undec-9-yl]carbamate (100 mg, 0.180 mmol, 36% yield) as a brown solid. 1H NMR (400MHz, CD3OD) δppm=8.54(d,1H),7.87-7.76(m,2H),7.62(s,2H),3.43-3.33(m,1H),2.6 2(s,2H),2.47(s,2H),2.13(s,6H),1.96-1.86(m,2H),1.84-1.73(m,2H),1.52-1.37(m,13H).

[0204] Step 7: Synthesis of N-[3-[4-(5-chloro-2-pyridinyl)-2,6-dimethyl-phenyl]-2,4-dioxo-spiro[5.5]undec-9-yl]acetamide (Compound 2.026)

[0205]

[0206] Tert-butyl N-[3-[4-(5-chloro-2-pyridinyl)-2,6-dimethyl-phenyl]-2,4-dioxo-spiro[5.5]undec-9-yl]carbamate (122 mg, 0.2387 mmol) was dissolved in dichloromethane (0.2 M, 18.5 mmol) at room temperature and 4.0 M hydrogen chloride in dioxane (5 eq, 1.194 mmol, 4.0 mol / L) was added dropwise. The mixture was stirred at room temperature for 2.5 hours and then concentrated. The resulting solid was redissolved in isopropenyl acetate (0.1 M, 20.3 mmol) and triethylamine (3 eq, 0.6705 mmol) was added. The mixture was stirred at room temperature overnight, concentrated, and purified by flash column chromatography (0%-30% methanol in DCM) to give N-[3-[4-(5-chloro-2-pyridinyl)-2,6-dimethyl-phenyl]-2,4-dioxo-spiro[5.5]undec-9-yl]acetamide (60 mg, 0.1325 mmol, 59% yield). 1H NMR (400MHz, CD3OD) δppm=8.59-8.53(m,1H),7.90-7.80(m,2H),7.67-7.60(m,2H),3.73-3.64(m,1H), 2.65(s,2H),2.49(s,2H),2.14(s,6H),1.98(s,2H),1.93(s,3H),1.85-1.75(m,2H),1.55-1.42(m,4H)

[0207] Example 3: Synthesis of N-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-2,4-dioxo-spiro[5.5]undec-9-yl]acetamide (Compound 2.001)

[0208]

[0209] Step 1: Synthesis of tert-butyl N-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-2,4-dioxo-spiro[5.5]undec-9-yl]carbamate

[0210]

[0211] Dimethyl sulfoxide (6 mL / mmol) was added to a mixture of tert-butyl N-[3-(4-bromo-2,6-dimethyl-phenyl)-2,4-dioxo-spiro[5.5]undec-9-yl]carbamate (237 mg, 0.4954 mmol), 1,4-bis(diphenylphosphino)butane (0.1 eq., 0.04954 mmol) and but-2-ynoic acid (1.2 eq., 0.5945 mmol). The reaction mixture was degassed and bis(triphenylphosphine)palladium(II) dichloride (0.05 eq., 0.02477 mmol) was added followed by DBU (3 eq., 1.486 mmol). The reaction mixture was stirred at 100° C. for 2.5 hours. After cooling, the reaction mixture was adjusted to pH=6 with aqueous citric acid and extracted with ethyl acetate. The organics were dried over Na2SO4, concentrated, and purified by flash column chromatography (20%-100% EtOAc in iso-hexane) to give tert-butyl N-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-2,4-dioxo-spiro[5.5]undec-9-yl]carbamate (125 mg, 0.286 mmol, 58% yield) as a light yellow oil. 1H NMR (400MHz, CD3OD) δppm=7.04-7.01(m,2H),3.42-3.32(m,1H),2.64-2.56(m,2H),2.48-2.42(m,2H),2. 00(s,6H),1.99-1.98(m,3H),1.94-1.85(m,2H),1.82-1.74(m,2H),1.45-1.45(m,4H),1.44-1.43(m,9H).

[0212] Step 2: Synthesis of 9-amino-3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)spiro[5.5]undecane-2,4-dione hydrochloride

[0213]

[0214] Tert-butyl N-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-2,4-dioxo-spiro[5.5]undec-9-yl]carbamate (125 mg, 0.2856 mmol) was suspended in dichloromethane (1 mL / mmol, 4.42 mmol) and then 4.0 M hydrogen chloride in 1,4-dioxane (5 eq., 1.428 mmol) was added dropwise. The reaction mixture was stirred at room temperature for 20 hours and then at 40° C. for 4 hours. The reaction mixture was concentrated, redissolved in acetone (5 mL) and treated with additional 4.0 M hydrogen chloride in 1,4-dioxane (5 eq., 1.428 mmol). The mixture was stirred at 60 °C for 5 hours and concentrated to give 9-amino-3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)spiro[5.5]undecane-2,4-dione hydrochloride (95 mg, 0.254 mmol, 89% yield) as a sticky yellow solid. 1H NMR (400 MHz, CD3OD) δ ppm = 7.07-7.01 (m, 2H), 3.19-3.08 (m, 1H), 2.67-2.61 (m, 2H), 2.51-2.48 (m, 2H), 2.01 (s, 6H), 2.00-1.99 (m, 3H), 1.98-1.85 (m, 4H), 1.67-1.56 (m, 2H), 1.54-1.43 (m, 2H).

[0215] Step 3: Synthesis of N-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-2,4-dioxo-spiro[5.5]undec-9-yl]acetamide (Compound 2.001)

[0216]

[0217] [3-(2,6-Dimethyl-4-prop-1-ynyl-phenyl)-2,4-dioxo-spiro[5.5]undecane-9-yl]ammonium hydrochloride (100 mg, 0.208 mmol) was dissolved in DCM (1.040 mL, 0.2 M), cooled to 0 ° C, and treated with triethylamine (0.117 mL, 4 eq.) and acetyl chloride (0.0379 mL, 2.5 eq.). The mixture was allowed to stir at room temperature for 3 hours, acidified with dilute hydrochloric acid, and extracted with DCM. The organics were concentrated, redissolved in methanol (2.081 mL, 0.1 M), and treated with potassium carbonate (0.05751 g, 2.0 eq.). The mixture was stirred at room temperature for 20 hours, diluted with 2M HCl and extracted with ethyl acetate. The organics were dried over Na2SO4, concentrated, and purified by flash column chromatography (0%-30% methanol in DCM) to give N-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-2,4-dioxo-spiro[5.5]undec-9-yl]acetamide (47 mg, 0.124 mmol, 60% yield) as a white solid. 1H NMR (400MHz, CD3OD) δppm=8.04-7.98(m,1H),7.03(s,2H),3.72-3.64(m,1H),2.62(s,2H),2.46(s, 2H),2.00(s,6H),1.99(s,3H),1.92(s,3H),1.92-1.88(m,2H),1.82-1.73(m,2H)1.53-1.41(m,4H).

[0218] Examples of the herbicidal compounds of the present invention.

[0219] Table 1

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227] Table 2

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238] Table 3

[0239]

[0240] Biological Examples

[0241] Seeds of various test species were sown in standard soil in pots (Lolpe, Setaria faberi, Alopecurus myosuroides, Echinochloa crus-galli, Avena fatua (AVEFA)). After one day (pre-emergence) or 8 days (post-emergence) of cultivation under controlled conditions in a greenhouse (24°C / 16°C, day / night; 14 h light; 65% humidity), the plants were sprayed with an aqueous spray solution derived from a formulation of the technical active ingredient in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5). The compound was applied at 250 g / h. The test plants were then grown in a greenhouse under controlled conditions (at 24°C / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice daily. The percentage of damage to the plants caused by the test was evaluated before emergence and 13 days after emergence. The biological activity is shown in the following table on a five-point scale (5 = 80%-100%; 4 = 60%-79%; 3 = 40%-59%; 2 = 20%-39%; 1 = 0%-19%).

[0242] Table B1

[0243]

[0244]

[0245]

Claims

1. A compound having formula (I) in R 1 is selected from the group consisting of: 1-propynyl, phenyl and a 5-membered or 6-membered heteroaryl containing one or two nitrogen heteroatoms, wherein the heteroaryl is pyridyl or pyrimidinyl, and the phenyl and heteroaryl are optionally substituted by one or two R 15 Substituent substitution; R 2 is methyl or methoxy; R 3 selected from the group consisting of: methyl and methoxy; m is 0 or 1; r is 0 or 1; R 4x It is hydrogen; R 4y Selected from the group consisting of: R4 a 、R4 b and R4 c : R 4aa Selected from the group consisting of: hydrogen and C1-C6 alkyl; R 4ab Selected from the group consisting of: hydrogen, C1-C6 alkyl, hydroxy C1-C6 alkyl-, C1-C6 alkoxy, -C1-C4 alkoxy C1-C6 alkyl, cyano C1-C6 alkyl-, C(O)R 27 , -pyridyl; or R 4aa and R 4ab Together they form -CH2CH2X 1 CH2CH2- or -C(O)CH2X 1 CH2CH2-, where X 1 Selected from the group consisting of: O, S(O) n and NR 28 ;and R 4ba selected from the group consisting of: hydrogen and C1-C4 alkyl; R 4bb Selected from the group consisting of: -C(O)C1-C4 alkyl, -C(O)C1-C4 haloalkyl, hydroxy C1-C6 alkyl-C(O)-, -S(O) n C1-C6 alkyl, -C(O)-(CH2) n -C3-C6 cycloalkyl, -C(O)C(R 11 )R 12 R 13 , -C(O)C1-C3 alkoxy C1-C6 alkyl, -C(O)C1-C3 alkoxy C1-C6 haloalkyl, -C(O)(CH2) n NR 5 R 6 、-C(O)-(CH2) n -NR 7 C(O)R 8 、-C(O)C(O)R 20 、-C(O)-(CH2) n -phenyl, -C(O)-(CH2) n - heterocyclyl, wherein each heterocyclyl is a 5-membered or 6-membered heterocyclyl, said heterocyclyl being aromatic, saturated or partially saturated and containing from 1 to 4 heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulfur, and wherein said heterocyclyl or phenyl group is optionally substituted with one, two or three substituents independently selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, halogen, cyano and nitro; R 5 independently selected from the group consisting of hydrogen and C1-C6 alkyl; R 6 is selected from the group consisting of: hydrogen, C1-C6 alkyl, and -pyridyl; and R 7 Selected from the group consisting of hydrogen and C1-C6 alkyl; R 8 is selected from the group consisting of: C1-C6 alkyl and -pyridyl; and R 11 is hydrogen or methyl; R 12 Selected from the group consisting of: hydrogen, C1-C6 alkyl, hydroxyl and C1-C6 alkoxy-; R 13 is selected from the group consisting of: hydrogen, C1-C6 alkyl, hydroxyl and C1-C6 alkoxy; or R 12 and R 13 Together they form -CH2-X 2 -CH2-, where X 2 Selected from the group consisting of: O, S and NR 14 ;and R 14 selected from the group consisting of: hydrogen, C1-C3 alkyl and C1-C3 alkoxy-; R 15 independently selected from the group consisting of C1-C4 alkyl, C1-C4 haloalkyl, cyano and halogen; R 20 Yes - NR 21 R 22 ; R 21 is a C1-C6 alkyl group; R 22 is hydrogen or C1-C6 alkyl; and R 4ca is selected from hydrogen and C1-C6 alkyl; R 4cb Selected from the group consisting of: hydrogen and C1-C6 alkyl; R 27 is -pyridinyl; R 28 is -C(O)C1-C3 alkyl; and G is hydrogen or -C(O)-(CR c R d ) n -OR b ; R b is methyl; and n is independently 0; or an agriculturally acceptable salt thereof.

2. The compound according to claim 1, wherein R 1 It is 1-propynyl.

3. The compound according to claim 1, wherein R 1 It is pyridyl or pyrimidinyl.

4. The compound according to claim 1, wherein R 2 It's methyl.

5. The compound according to claim 1, wherein R 3 It's methyl.

6. The compound according to claim 1, wherein R 4 YesR 4a .

7. The compound according to claim 1, wherein R 4 YesR 4b .

8. The compound of claim 1, wherein G is hydrogen.

9. The compound of claim 1, wherein G is -C(O)-O-methyl.

10. A herbicidal composition comprising the compound of formula (I) according to claim 1 and an agriculturally acceptable formulation adjuvant.

11. The herbicidal composition according to claim 10, further comprising at least one additional pesticide.

12. The herbicidal composition according to claim 11, wherein the additional pesticide is a herbicide or a herbicide safener.

13. A method of controlling weeds at a locus, the method comprising applying to the locus a weed controlling amount of a composition according to any one of claims 10 to 12.

14. Use of the compound of formula (I) according to claim 1 as a herbicide.

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