Substituted pyridazinones as herbicides.

Abstract

The present invention relates to herbicidal substituted phenyl-pyridazinedione and substituted phenyl-pyridazinone derivatives of formula (I), as well as processes and intermediates used for the preparation of such derivatives. The invention further extends to herbicidal compositions containing such derivatives, and the use of such compounds and compositions in the control of undesired plant growth, particularly in the control of weeds, such as broadleaf dicotyledonous weeds, in crops of useful plants.

Description

Technical Field

[0001] The present invention relates to herbicidal substituted phenyl-pyridazine-diones and substituted phenyl-pyridinone derivatives of formula (I), and to methods and intermediates used in the preparation of such derivatives. The present invention further relates to herbicidal compositions containing such derivatives, and to the use of such compounds and compositions in the control of unwanted plant growth: in particular, their use in the control of weeds such as broad-leaved dicotyledonous weeds in crops of useful plants.

Background Art

[0002] Herbicidal pyridinones are known from WO 2009 / 086041 pamphlet. Further, herbicidal 5 / 6-membered heterocyclyl-substituted pyridinones are known from WO 2011 / 045271 pamphlet. On the other hand, WO 2013 / 160126 pamphlet describes indolyl-pyridinone derivatives showing herbicidal activity.

Summary of the Invention

Means for Solving the Problems

[0003] The present invention is based on the discovery of substituted phenyl-pyridazine-diones and substituted phenyl-pyridinone derivatives of formula (I) which surprisingly exhibit good herbicidal activity.

[0004] Thus, in a first aspect, a compound of formula (I)

Chemical Formula

Chemical formula

[0005] In a second aspect, there is provided a compound of formula (I)

Chemical formula

Chemical formula

[0006] In a third aspect, there is provided a compound of formula (I)

Chemical formula

Chemical formula

[0007] The compounds of formula (I) may contain chiral centers and may exist as a single enantiomer, as a pair of enantiomers in any ratio, or, when two or more chiral centers are present, include all possible ratios of diastereoisomers. Typically, one of the enantiomers has enhanced biological activity compared to the other possible enantiomers.

[0008] Similarly, when there are disubstituted alkenes, these may exist as the E isomer or the Z isomer or as a mixture of both in any ratio.

[0009] Furthermore, the compounds of formula (I) may be in equilibrium with another tautomer. For example, the compound of formula (I-i), i.e., the compound of formula (I) wherein R 2 is hydrogen and G is hydrogen, can be depicted as at least three tautomers:

Chemical formula

[0010] It should be understood that all tautomers (single tautomer or mixture thereof), racemic mixtures and single isomers are included within the scope of the present invention.

[0011] Each alkyl moiety can be linear or branched, either alone or as part of a larger group (such as alkoxy, alkylthio, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, or dialkylaminocarbonyl). Typically, alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, or n-hexyl. The alkyl group is generally a C 1 ~C 6 alkyl group (except when already more narrowly defined), but preferably a C 1 ~C 4 alkyl or a C 1 ~C 3 alkyl group, and more preferably a C 1 ~C 2 alkyl group (such as methyl).

[0012] Alkenyl and alkynyl moieties can be in linear or branched form, and the alkenyl moiety can be in either the (E)- or (Z)-configuration, if necessary. The alkenyl or alkynyl moiety is typically a C 2 ~C 4 alkenyl or a C 2 ~C 4 alkynyl, more particularly vinyl, allyl, ethynyl, propargyl or prop-1-ynyl. The alkenyl and alkynyl moieties can contain one or more double and / or triple bonds in any combination; preferably, they contain only one double bond (in the case of alkenyl) or only one triple bond (in the case of alkynyl).

[0013] Preferably, the term cycloalkyl refers to cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

[0014] In the context of this specification, the term "aryl" preferably means phenyl. The term "heteroaryl", as used herein, means an aromatic ring system containing at least one ring heteroatom and consisting of a single ring. Preferably, the single ring contains one, two or three ring heteroatoms independently selected from nitrogen, oxygen and sulfur. Typically, "heteroaryl" is 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, or 1,3,5-triazinyl.

[0015] Heterocyclyl groups and heterocyclic rings (alone or as part of a larger group, e.g., heterocyclyl-alkyl-) are ring systems containing at least one heteroatom and can be in monocyclic or bicyclic form. Preferably, the heterocyclyl group preferably contains up to two heteroatoms selected from nitrogen, oxygen and sulfur. Examples of heterocyclic groups include oxetanyl, thietanyl, azetidinyl and 7-oxa-bicyclo[2.2.1]hepta-2-yl. Most preferred are heterocyclyl groups containing a single oxygen atom as the heteroatom. The heterocyclyl group is preferably a 3- to 8-membered, more preferably 3- to 6-membered monocyclic ring and can be fully or partially saturated.

[0016] Halogen (or halo) includes fluorine, chlorine, bromine or iodine. Correspondingly, the same applies to halogen in the context of other definitions such as haloalkyl or halophenyl.

[0017] Haloalkyl groups having a chain length of 1 to 6 carbon atoms 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.

[0018] Alkoxy groups preferably have a chain length of 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy or pentyloxy or hexyloxy isomers, preferably methoxy and ethoxy. It should also be understood that two alkoxy substituents may be present on the same carbon atom.

[0019] Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy or 2,2,2-trichloroethoxy, preferably difluoromethoxy, 2-chloroethoxy or trifluoromethoxy.

[0020] C 1 ~C 6 Alkyl-S-(alkylthio) is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.

[0021] C 1 ~C 6Alkyl-S(O)-(alkylsulfinyl) is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl.

[0022] C 1 ~C 6 Alkyl-S(O) 2 -(alkylsulfonyl) is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.

[0023] Group Q

Chemical formula

[0024] The present invention also includes agriculturally acceptable salts that the compounds of formula (I) can form with amines (such as ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the hydroxides, oxides, alkoxides and hydrogen carbonates and carbonates of alkali metals and alkaline earth metals used as salt-forming agents, the hydroxides, alkoxides, oxides and carbonates of lithium, sodium, potassium, magnesium and calcium are emphasized, but the hydroxides, alkoxides, oxides and carbonates of sodium, magnesium and calcium are particularly emphasized. The corresponding trimethylsulfonium salts can also be used. The compounds of formula (I) according to the present invention also include hydrates that can be formed during salt formation.

Embodiments for Carrying Out the Invention

[0025] R 1 、R 2 、R 3 、R 4 、R 5 、R 4a 、R 5a 、R 6 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、W, D, Dp, G, X, Y, and m are as described below, and the compounds of formula (I) according to the present invention may include any combination of said values. Those skilled in the art will understand that any set of values of the embodiments may be combined with any other set of values of the embodiments if the combinations are not mutually contradictory.

[0026] Preferably, R 1 is selected from the group consisting of methyl, ethyl, propyl (especially n- or c-propyl), propargyl or C 1 haloalkyl. More preferably, R 1 is methyl, ethyl, cyclopropyl, propargyl or C 1 fluoroalkyl. Even more preferably, R 1 is methyl, ethyl, cyclopropyl or propargyl. Most preferably, R 1 is methyl.

[0027] Preferably, R 2 is hydrogen, halogen, C 1 ~C 6 alkyl, C 1 ~C 6 haloalkyl, C 1 ~C 6 alkoxy, C 1 ~C 3 alkoxy-C 1 ~C 3 alkyl, C 3 ~C 6 cycloalkyl, C 2~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl and C 2 ~C 6 Selected from the group consisting of haloalkynyl. More preferably, R 2 is chloro, fluoro, methyl, ethyl, cyclopropyl, trifluoromethyl and methoxymethyl, even more preferably selected from the group consisting of chloro, cyclopropyl, trifluoromethyl or methyl, most preferably chloro or methyl. In one set of embodiments of the present invention, R 2 is hydrogen. In a further set of embodiments, R 2 is cyclopropyl, in a third set of embodiments, R 2 is methyl, in a fourth set of embodiments, R 2 is trifluoromethyl, and in a fifth set of embodiments, R 2 is chloro.

[0028] As described herein, G can be hydrogen or -C(O)-R 3 and R 3 is C 1 ~C 6 alkyl, C 2 ~C 6 alkenyl, C 2 ~C 6 alkynyl, C 1 ~C 6 alkyl-S-, C 1 ~C 6 alkoxy, -NR 4 R 5 and phenyl optionally substituted with one or more R 6 selected from the group consisting of.

[0029] As defined herein, R 4 and R 5 are hydrogen, C 1 ~C 6 alkyl, C 1 ~C 6 alkoxy-, and C3 ~C 6 Independently selected from the group consisting of cycloalkyl; or alternatively, together, they can form a morpholinyl ring. In the context of substituent G (and also R 3 ), R 4 and R 5 are preferably each independently selected from the group consisting of methyl, ethyl, propyl, methoxy, ethoxy and propoxy, and each, R 34 and R 35 can be referred to as such. In the context of other substituents (e.g., R 2 , R 8 ), R 4 and R 5 are preferably each independently hydrogen, C 1 ~C 3 alkyl, C 1 ~C 3 alkoxy, or C 3 ~C 6 cycloalkyl, and each R 84 and R 85 can be referred to as such. Those skilled in the art will recognize that when multiple R 4 are in a larger moiety, e.g., the group -NR 4 C(O)NR 4 R 5 , each R 4 is independent, and thus in such a moiety, the two R 4 groups can be the same or they can be different from each other.

[0030] R 6 is selected from the group consisting of halogen, cyano, nitro, C 1 ~C 3 alkyl, C 1 ~C 3 haloalkyl, C 1 ~C 3 alkoxy and C 1 ~C 3 haloalkoxy. Preferably, R 6 is halogen, C 1 ~C 3 alkyl, and C 1 ~C 3It is selected from the group consisting of haloalkyl.

[0031] Preferably, R 3 is C 1 ~C 4 alkyl, C 2 ~C 3 alkenyl, C 2 ~C 3 alkynyl, -C 1 ~C 4 alkoxy, -NR 4 R 5 wherein R 4 and R 5 together form a morpholinyl ring or phenyl. More preferably, R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl, methoxy, ethoxy, or tert-butoxy. More preferably, R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl, or methoxy.

[0032] In one set of embodiments, G is hydrogen or -C(O)-R 3 wherein R 3 is C 1 ~C 4 alkyl, C 2 ~C 3 alkenyl, C 2 ~C 3 alkynyl or -C 1 ~C 4 alkoxy. In a further set of embodiments, G is hydrogen or -C(O)-R 3 wherein R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl or methoxy. However, it is particularly preferred that G is hydrogen or -C(O)-R 3 wherein R 3 is isopropyl.

[0033] When Y is cyclopropyl, X is preferably hydrogen, cyclopropyl, halogen, or C 1Haloalkyl, more preferably hydrogen, fluoro, chloro, bromo, or C 1 fluoroalkyl, more preferably also hydrogen, fluoro, chloro or trifluoromethyl. Most preferably, when Y is cyclopropyl, X is fluoro. In one set of embodiments, X is preferably ortho (6-position) with respect to the pyridazinone / pyridazinedione moiety (group Q). X is fluoro, chloro or C 1 -haloalkyl (especially C 1 fluoroalkyl), and is particularly preferably ortho (6-position) with respect to the pyridazinone / pyridazinedione moiety (group Q). Most preferably, X is fluoro and is ortho (6-position) with respect to the pyridazinone / pyridazinedione moiety (group Q).

[0034] When X is cyclopropyl, in such embodiments, Y is preferably hydrogen, C 1 ~C 3 alkyl, cyclopropyl, C 1 ~C 3 haloalkyl, or halogen, more preferably, Y is hydrogen, chloro, fluoro, or bromo. Most preferably, when X is cyclopropyl, Y is chloro.

[0035] In one set of embodiments, Y is preferably ortho (3-position) with respect to the W-D moiety. In a further set of embodiments, Y is para with respect to the pyridazinone / pyridazine-dione moiety (group Q).

[0036] Y is ortho (3-position) with respect to the W-D moiety and is halogen, especially chloro or fluoro; more preferably chloro, which is particularly preferred.

[0037] As described herein, D is a substituted or unsubstituted phenyl ring (Dp) or a substituted or unsubstituted 5- or 6-membered monocyclic heteroaryl ring containing one, two, or three heteroatoms independently selected from oxygen, nitrogen, and sulfur. When D is a substituted heteroaryl ring or a substituted phenyl ring, it is substituted on at least one ring carbon atom with R 8 and / or, in the case of a heteroaryl ring, on a ring nitrogen atom with R 9 . When D is a substituted or unsubstituted 5- or 6-membered monocyclic heteroaryl ring, it is preferably a substituted (as described herein) or unsubstituted 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, pyridonyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, or 1,3,5-triazinyl ring.

[0038] In such embodiments, D is preferably a substituted (as described herein) or unsubstituted pyridyl, pyrazolyl, thiazolyl, pyrimidinyl, thienyl, triazolyl, or oxadiazolyl ring, more preferably a pyridyl ring.

[0039] In one set of embodiments, D is a substituted (as described herein) or unsubstituted pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridyl, pyridonyl, pyrimidinyl, pyridazinyl, or pyrazinyl ring.

[0040] In a further set of such embodiments, D is a substituted (as described herein) or unsubstituted oxazolyl, thiazolyl, or pyridyl ring. In certain embodiments, D is a substituted or unsubstituted pyridyl ring, or a substituted or unsubstituted thiazolyl ring.

[0041] R 8 The substitution of D by R is determined by the presence or absence of cyclopropyl at positions X and / or Y. However, generally, when D is a substituted 5- or 6-membered heteroaryl ring, it is preferably substituted with one or two R 8 and / or one R 9 , more preferably with one or two R 8 . When D is a 5-membered substituted heteroaryl ring, it is most preferably substituted with one R 8 . When D is a substituted phenyl ring, it is preferably substituted with one or two R 8 , more preferably with one R 8 .

[0042] When at least one of X and Y is cyclopropyl and D is substituted, each R 8 is hydrogen, oxygen, hydroxyl, halogen, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 3 alkoxy-C 1 -C 3 alkyl, C 1 -C 3 haloalkoxy-C 1 -C 3 alkyl-, C 1 -C 3 alkoxy-C 1 -C 3 alkoxy-C1 ~C 3 alkyl-, C 2 ~C 6 alkenyl, C 2 ~C 6 haloalkenyl, C 2 ~C 6 alkynyl, C 2 ~C 6 haloalkynyl, C 1 ~C 6 hydroxyalkyl-, C 1 ~C 6 alkylcarbonyl-, C 1 ~C 6 haloalkylcarbonyl-, C 3 ~C 6 cycloalkylcarbonyl-, -S(O) m -C 1 ~C 6 haloalkyl, -S(O) m -C 3 ~C 6 cycloalkyl, -O-S(O) 2 C 1 ~C 3 alkyl, -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 alkyl, -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 haloalkyl, -C 1 ~C 3 alkyl-S(O) m -C 3 ~C 6 cycloalkyl, cyano-C 1 ~C 6 -alkyl-, NR 4 R 5 、-C(S)NR 4 R 5 、-S(O) 2 NHC(O)C 1 ~C 3 alkyl, -S(O) 2 NR 4 R 5 、-C(O)OH、-C(O)OC1 ~C 6 alkyl, -C(O)NHS-(O) 2 C 1 ~C 6 alkyl, -C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5 , C 1 ~C 6 alkylcarbonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 haloalkylcarbonylamino-, C 1 ~C 6 haloalkylcarbonyl (C 1 ~C 6 alkyl)amino-, -NR 4 C(O)NR 4 R 5 , C 1 ~C 6 alkylsulfonylamino-, C 1 ~C 6 alkylsulfonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 haloalkylsulfonylamino-, C 1 ~C 6 haloalkylsulfonyl (C 1 ~C 6 alkyl)amino-, C 3 ~C 6 cycloalkylsulfonylamino-, C 3 ~C 6 cycloalkylsulfonyl (C 1 ~C 6 alkyl)amino-, hydroxyamino-, hydroxy (C 1 ~C 6 alkyl)amino, C 1 ~C 6 alkoxyamino, C 1 ~C 6 alkoxy (C 1 ~C 6 alkyl)amino, C 1 ~C 6Haloalkoxyamino, C 1 ~C 6 Haloalkoxy(C 1 ~C 6 alkyl)amino; or can be independently selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclic ring, and the said ring system is substituted with 0 to 5 R 16 ; m is an integer of 0, 1, or 2 (preferably 0 or 2); each R 9 is independently hydrogen, C 1 ~C 6 alkyl, C 1 ~C 6 haloalkyl, C 3 ~C 6 -cycloalkyl, C 1 ~C 3 alkoxy-C 1 ~C 3 alkyl, C 1 ~C 3 haloalkoxy-C 1 ~C 3 alkyl-, C 1 ~C 3 alkoxy-C 1 ~C 3 alkoxy-C 1 ~C 3 alkyl-, C 1 ~C 6 hydroxyalkyl-, -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 alkyl, -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 haloalkyl, -C 1 ~C 3 alkyl-S(O) m -C 3 ~C 6 cycloalkyl, cyano-C 1 ~C 6-alkyl-, or a ring system selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclic ring, wherein the ring system is substituted with 0 to 5 R 16 ; Each R 16 is independently halogen, cyano, C 1 ~C 6 alkyl, C 1 ~C 6 haloalkyl, C 1 ~C 6 alkoxy or C 1 ~C 6 haloalkoxy.

[0043] When both X and Y are other than cyclopropyl and D is a phenyl ring, D is C 1 ~C 6 haloalkylcarbonyl-, C 3 ~C 6 cycloalkylcarbonyl-, -S(O) m -C 1 ~C 6 haloalkyl, -S(O) m -C 3 ~C 6 cycloalkyl, -O-S(O) 2 C 1 ~C 3 alkyl, -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 alkyl, -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 haloalkyl, -C 1 ~C 3 alkyl-S(O) m -C 3 ~C 6 cycloalkyl, cyano-C 1 ~C 6 -alkyl-, -NR 4a R 5a 、-C(S)NR 4 R 5 、-S(O) 2NHC(O)C 1 ~C 3 alkyl, -S(O) 2 NR 4 R 5 、-C(O)OH, -C(O)OC 1 ~C 6 alkyl, -C(O)NHS-(O) 2 C 1 ~C 6 alkyl, -C(O)NR 4 R 5 、-NR 4 C(O)NR 4 R 5 、C 1 ~C 6 alkylcarbonyl(C 1 ~C 6 alkyl)amino-, C 1 ~C 6 haloalkylcarbonylamino-, C 1 ~C 6 haloalkylcarbonyl(C 1 ~C 6 alkyl)amino-, C 1 ~C 6 alkylsulfonylamino-, C 1 ~C 6 alkylsulfonyl(C 1 ~C 6 alkyl)amino-, C 1 ~C 6 haloalkylsulfonylamino-, C 1 ~C 6 haloalkylsulfonyl(C 1 ~C 6 alkyl)amino-, C 3 ~C 6 cycloalkylsulfonylamino-, C 3 ~C 6 cycloalkylsulfonyl(C 1 ~C 6 alkyl)amino-, hydroxyamino-, hydroxy(C 1 ~C 6 alkyl)amino, C 1 ~C 6 alkoxyamino, C 1 ~C 6 alkoxy(C 1 ~C6 (alkyl)amino, C 1 ~C 6 haloalkoxyamino, C 1 ~C 6 haloalkoxy(C 1 ~C 6 (alkyl)amino; or at least one R selected from the group consisting of ring systems selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclic ring 8 is substituted, and the ring system is substituted with 0 to 5 R 16 ; m, R 4 , R 5 and R 16 are as defined herein.

[0044] As defined herein, in the situation where both X and Y are other than cyclopropyl, each R 4a and R 5a is independently selected from the group consisting of C 1 ~C 6 alkoxy, and C 3 ~C 6 cycloalkyl, or R 4 and R 5 can together form a morpholinyl ring.

[0045] Any additional R 8 substituent is oxygen, hydroxyl, halogen, cyano, C 1 ~C 6 alkyl, C 1 ~C 6 haloalkyl, C 3 ~C 6 -cycloalkyl, C 1 ~C 6 alkoxy, C 1 ~C 6 haloalkoxy, C 1 ~C 3 alkoxy-C 1 ~C 3 alkyl, C 1 ~C 3 haloalkoxy-C 1 ~C 3 alkyl-, C1 ~C 3 alkoxy-C 1 ~C 3 alkoxy-C 1 ~C 3 alkyl-, C 2 ~C 6 alkenyl, C 2 ~C 6 haloalkenyl, C 2 ~C 6 alkynyl, C 2 ~C 6 haloalkynyl, C 1 ~C 6 hydroxyalkyl-, C 1 ~C 6 alkylcarbonyl-, C 1 ~C 6 haloalkylcarbonyl-, C 3 ~C 6 cycloalkylcarbonyl-,-S(O) m -C 1 ~C 6 haloalkyl,-S(O) m -C 3 ~C 6 cycloalkyl,-O-S(O) 2 C 1 ~C 3 alkyl,-C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 alkyl,-C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 haloalkyl,-C 1 ~C 3 alkyl-S(O) m -C 3 ~C 6 cycloalkyl, cyano-C 1 ~C 6 -alkyl-,-NR 4 R 5 ,-C(S)NR 4 R 5 ,-S(O) 2 NHC(O)C 1 ~C 3Alkyl, -S(O) 2 NR 4 R 5 , -C(O)OH, -C(O)OC 1 ~C 6 Alkyl, -C(O)NHS-(O) 2 C 1 ~C 6 Alkyl, -C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5 , C 1 ~C 6 Alkylcarbonyl(C 1 ~C 6 Alkyl)amino-, C 1 ~C 6 Haloalkylcarbonylamino-, C 1 ~C 6 Haloalkylcarbonyl(C 1 ~C 6 Alkyl)amino-, -NR 4 C(O)NR 4 R 5 , C 1 ~C 6 Alkylsulfonylamino-, C 1 ~C 6 Alkylsulfonyl(C 1 ~C 6 Alkyl)amino-, C 1 ~C 6 Haloalkylsulfonylamino-, C 1 ~C 6 Haloalkylsulfonyl(C 1 ~C 6 Alkyl)amino-, C 3 ~C 6 Cycloalkylsulfonylamino-, C 3 ~C 6 Cycloalkylsulfonyl(C 1 ~C 6 Alkyl)amino-, hydroxyamino-, hydroxy(C 1 ~C 6 Alkyl)amino, C 1 ~C 6 Alkoxyamino, C 1 ~C 6 Alkoxy(C1 ~C 6 (alkyl)amino, C 1 ~C 6 haloalkoxyamino, C 1 ~C 6 haloalkoxy(C 1 ~C 6 (alkyl)amino; or may be selected from the group consisting of ring systems selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclic ring, and said ring system is substituted with 0 to 5 R 16 as defined herein. m, R 4 , R 5 and R 16 are as defined herein.

[0046] When both X and Y are other than cyclopropyl and D is a monocyclic heteroaryl ring, D is C 1 ~C 6 haloalkylcarbonyl-, C 3 ~C 6 cycloalkylcarbonyl-, -S(O) m -C 1 ~C 6 haloalkyl, -S(O) m -C 3 ~C 6 cycloalkyl, -O-S(O) 2 C 1 ~C 3 alkyl, -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 alkyl, -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 haloalkyl, -C 1 ~C 3 alkyl-S(O) m -C 3 ~C 6 cycloalkyl, cyano-C 1 ~C 6 -alkyl-, NR 4a R 5a , -C(S)NR4 R 5 、 -S(O) 2 NHC(O)C 1 ~C 3 alkyl, -S(O) 2 NR 4 R 5 、 -C(O)OH, -C(O)OC 1 ~C 6 alkyl, -C(O)NHS-(O) 2 C 1 ~C 6 alkyl, -C(O)NR 4 R 5 、 -NR 4 C(O)NR 4 R 5 、 C 1 ~C 6 alkylcarbonyl(C 1 ~C 6 alkyl)amino-, C 1 ~C 6 haloalkylcarbonylamino-, C 1 ~C 6 haloalkylcarbonyl(C 1 ~C 6 alkyl)amino-, C 1 ~C 6 alkylsulfonylamino-, C 1 ~C 6 alkylsulfonyl(C 1 ~C 6 alkyl)amino-, C 1 ~C 6 haloalkylsulfonylamino-, C 1 ~C 6 haloalkylsulfonyl(C 1 ~C 6 alkyl)amino-, C 3 ~C 6 cycloalkylsulfonylamino-, C 3 ~C 6 cycloalkylsulfonyl(C 1 ~C 6 alkyl)amino-, hydroxyamino-, hydroxy(C 1 ~C 6 alkyl)amino, C 1 ~C 6 alkoxyamino, C1 ~C 6 alkoxy(C 1 ~C 6 alkyl)amino, C 1 ~C 6 haloalkoxyamino, C 1 ~C 6 haloalkoxy(C 1 ~C 6 alkyl)amino; and at least one R selected from the group consisting of ring systems selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclyl ring 8 is substituted, and the ring system is substituted with 0 to 5 Rs 16 ; and / or D is C on the ring nitrogen 5 ~C 6 alkyl, C 5 ~C 6 haloalkyl, C 3 ~C 6 -cycloalkyl, C 1 ~C 3 alkoxy-C 3 alkyl-, C 3 alkoxy-C 1 ~C 2 alkyl-, C 1 ~C 3 haloalkoxy-C 1 ~C 3 alkyl-, C 1 ~C 3 alkoxy-C 1 ~C 3 alkoxy-C 1 ~C 3 alkyl-, C 1 ~C 6 hydroxyalkyl-, -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 alkyl, -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 haloalkyl, -C 1 ~C 3 alkyl-S(O) m -C3 ~C 6 Cycloalkyl, cyano-C 1 ~C 6 -alkyl-, and at least one R selected from the group consisting of ring systems selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclyl ring 9 and is substituted, and the ring system is substituted with 0 to 5 R 16 and m, R 4 , R 5 , R 4a , R 5a and R 16 and R are as defined herein.

[0047] In such embodiments, when both X and Y are other than cyclopropyl, any additional ring carbon R 8 substituents are oxygen, hydroxyl, halogen, cyano, C 1 ~C 6 alkyl, C 1 ~C 6 haloalkyl, C 3 ~C 6 -cycloalkyl, C 1 ~C 6 alkoxy, C 1 ~C 6 haloalkoxy, C 1 ~C 3 alkoxy-C 1 ~C 3 alkyl, C 1 ~C 3 haloalkoxy-C 1 ~C 3 alkyl-, C 1 ~C 3 alkoxy-C 1 ~C 3 alkoxy-C 1 ~C 3 alkyl-, C 2 ~C 6 alkenyl, C 2 ~C 6 haloalkenyl, C 2 ~C 6 alkynyl, C 2 ~C 6 haloalkynyl, C1 ~C 6 Hydroxyalkyl-, C 1 ~C 6 Alkylcarbonyl-, C 1 ~C 6 Haloalkylcarbonyl-, C 3 ~C 6 Cycloalkylcarbonyl-, -S(O) m -C 1 ~C 6 Haloalkyl, -S(O) m -C 3 ~C 6 Cycloalkyl, -O-S(O) 2 C 1 ~C 3 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Haloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 3 ~C 6 Cycloalkyl, cyano-C 1 ~C 6 -Alkyl-, -NR 4 R 5 、-C(S)NR 4 R 5 、-S(O) 2 NHC(O)C 1 ~C 3 Alkyl, -S(O) 2 NR 4 R 5 、-C(O)OH、-C(O)OC 1 ~C 6 Alkyl, -C(O)NHS-(O) 2 C 1 ~C 6 Alkyl, -C(O)NR 4 R 5 、-NR 4 C(O)NR 4 R 5 、C1 ~C 6 alkylcarbonyl(C 1 ~C 6 alkyl)amino-, C 1 ~C 6 haloalkylcarbonylamino-, C 1 ~C 6 haloalkylcarbonyl(C 1 ~C 6 alkyl)amino-, C 1 ~C 6 alkylsulfonylamino-, C 1 ~C 6 alkylsulfonyl(C 1 ~C 6 alkyl)amino-, C 1 ~C 6 haloalkylsulfonylamino-, C 1 ~C 6 haloalkylsulfonyl(C 1 ~C 6 alkyl)amino-, C 3 ~C 6 cycloalkylsulfonylamino-, C 3 ~C 6 cycloalkylsulfonyl(C 1 ~C 6 alkyl)amino-, hydroxyamino-, hydroxy(C 1 ~C 6 alkyl)amino, C 1 ~C 6 alkoxyamino, C 1 ~C 6 alkoxy(C 1 ~C 6 alkyl)amino, C 1 ~C 6 haloalkoxyamino, C 1 ~C 6 haloalkoxy(C 1 ~C 6 alkyl)amino; or a ring system selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclic ring, the ring system being substituted with 0 to 5 R 16 ; m, R 4 , R 5 and R 16is as defined herein and / or any additional ring nitrogen R 9 The substituent is C 1 ~C 6 alkyl, C 1 ~C 6 haloalkyl, C 3 ~C 6 -cycloalkyl, C 1 ~C 3 alkoxy-C 1 ~C 3 alkyl, C 1 ~C 3 haloalkoxy-C 1 ~C 3 alkyl-, C 1 ~C 3 alkoxy-C 1 ~C 3 alkoxy-C 1 ~C 3 alkyl-, C 1 ~C 6 hydroxyalkyl-, -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 alkyl, -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 haloalkyl, -C 1 ~C 3 alkyl-S(O) m -C 3 ~C 6 cycloalkyl, cyano-C 1 ~C 6 -alkyl-, and may be selected from the group consisting of ring systems consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclic ring, said ring system being substituted with 0 to 5 R 16 ; m, R 4 , R 5 and R 16 are as defined herein.

[0048] In embodiments where at least one of X and Y is cyclopropyl, each R 8is preferably, independently, oxo, C 1 ~C 4 alkyl, C 1 ~C 4 haloalkyl, halogen, cyano, amino, -NHC(O)CH 3 hydroxyl, C 1 ~C 4 alkoxy, or C 1 ~C 4 alkylthio. More preferably, each R 8 is preferably, independently, oxo, C 1 ~C 4 alkyl, C 1 ~C 4 haloalkyl, halogen, cyano, hydroxyl, C 1 ~C 4 alkoxy, or C 1 ~C 4 alkylthio, and most preferably, each R 8 is preferably, independently, halogen, or C 1 ~C 4 haloalkyl.

[0049] In embodiments where at least one of X and Y is cyclopropyl, each R 9 is preferably, independently, C 1 ~C 4 alkyl, C 1 ~C 4 haloalkyl, hydroxyl, C 1 ~C 4 alkoxy, or C 1 ~C 4 alkylthio.

[0050] In certain embodiments where at least one of X and Y is cyclopropyl and D is a substituted or unsubstituted 5- or 6-membered monocyclic heteroaryl ring as described above, D is selected from the group consisting of 4-chloro-3-pyridyl, 4-trifluoromethylpyridyl, 3-pyridyl, and 2-chloro-thiazol-5-yl, 2-chloro-3-pyridyl, 3-chloro-4-pyridyl, 1-methyl-3-(trifluoromethyl)-pyrazol-4-yl, thiazol-2-yl, thiazol-5-yl, pyrimidin-5-yl, 4-(tert-butoxy)phenyl, 2-chloro-4-pyridyl, 2-methyl-4-pyridyl, 2-trifluoromethyl-4-pyridyl, 4-pyridyl, 2-amino-4-pyridyl, thiophen-3-yl, 1-methyl-pyrazol-4-yl, 2-methyl-triazol-4-yl, 5-methyl-1,3,4-oxadiazol-2-yl, 5-methyl-3-pyridyl, 5-methyl-2-pyridyl, 6-methyl-2-pyridyl, 3-methyl-2-pyridyl, 6-chloro-3-pyridyl, 3-trifluoromethyl-3-pyridyl, 4-methyl-2-pyridyl, 2-acetamidothiazol-5-yl, 2-fluoro-4-pyridyl, and 2-trifluoromethyl-3-pyridyl. In a subset of these embodiments, D is selected from the group consisting of 4-chloro-3-pyridyl, 4-trifluoromethylpyridyl, 3-pyridyl, and 2-chloro-thiazol-5-yl, 2-chloro-3-pyridyl, 3-chloro-4-pyridyl, 1-methyl-3-(trifluoromethyl)-pyrazol-4-yl, thiazol-2-yl, thiazol-5-yl, pyrimidin-5-yl, 4-(tert-butoxy)phenyl, 2-chloro-4-pyridyl, 2-methyl-4-pyridyl, 2-trifluoromethyl-4-pyridyl, 4-pyridyl, thiophen-3-yl, 5-methyl-3-pyridyl, 5-methyl-2-pyridyl, 6-methyl-2-pyridyl, 3-trifluoromethyl-3-pyridyl, 2-fluoro-4-pyridyl, and 2-trifluoromethyl-3-pyridyl.In a further subset of these embodiments, D is selected from the group consisting of 4-chloro-3-pyridyl, 4-trifluoromethylpyridyl, 3-pyridyl, 2-fluoro-4-pyridyl, and 2-chloro-thiazol-5-yl (preferably 2-fluoro-4-pyridyl).

[0051] When D is phenyl ring Dp and is substituted, it may be substituted with 1 to 5 Rs 8 and thus may be represented by the following structure

Chemical formula

[0052] As described above, the substitution of D by R 8 is determined by the presence or absence of cyclopropyl at positions X and / or Y. Thus, in Dp where at least one of X and Y is cyclopropyl, one or more of R 8p1 , R 8p2 , R 8p3 , R 8p4 , and R 8p5 is cyano, amino, C 1 ~C 3 dialkylamino, hydroxy, C 1 ~C3 Alkyl, C 1 ~C 4 Alkoxy, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Independently selected from the group consisting of haloalkoxy and halogen, and b is preferably the point of attachment to the rest of the molecule.

[0053] In one such set of embodiments, R 8p1 , R 8p2 , R 8p3 , R 8p4 and R 8p5 One or more of are cyano, C 1 ~C 3 alkyl, C 1 ~C 4 alkoxy, C 1 ~C 3 haloalkyl, C 1 ~C 3 haloalkoxy, or halogen, respectively independently selected. Preferably, R 8p1 , R 8p2 , R 8p3 , R 8p4 and R 8p5 One or more of are independently selected from cyano, halogen (especially chloro or fluoro), methyl, methoxy, and trifluoromethyl.

[0054] In yet another set of embodiments, R 8p1 , R 8p2 , R 8p4 and R 8p5 each is non-existent, and R 8p3 is cyano, C 1 ~C 3 alkyl, C 1 ~C 4 alkoxy, C 1 ~C 3 haloalkyl, C 1 ~C 3 haloalkoxy, or halogen. Preferably, in this set of embodiments, R 8p3 is halogen, more preferably chloro.

[0055] In a further set of embodiments, further, R 8p1 , R 8p4 and R 8p5 each is absent, and R 8p2 and R 8p3 are each independently cyano, C 1 -C 3 alkyl, C 1 -C 4 alkoxy, C 1 -C 3 haloalkyl, C 1 -C 3 haloalkoxy, or halogen. In this set of embodiments, R 8p2 and R 8p3 are each particularly preferably independently halogen, and R 8p2 and R 8p3 are more preferably both chloro.

[0056] In one particularly preferred set of embodiments where at least one of X and / or Y is cyclopropyl, D is an unsubstituted phenyl ring.

[0057] In a particularly preferred set of further embodiments where at least one of X and / or Y is cyclopropyl, D is selected from the group consisting of 4-chloro-phenyl, 4-trifluoromethyl-phenyl, 4-cyanophenyl, 4-fluoro-phenyl, 3,4-di-fluoro-phenyl, 2-trifluoromethyl-phenyl and 4-tolyl.

[0058] W acts as a linker moiety that connects ring D to the remainder of the molecule (i.e., to the phenyl-pyridazinone / phenyl-pyridazinedione moiety). Compounds of formula (I) where the linker is W1 are herbicidal, while compounds of formula (I) where the linker is W2 are not only herbicidal but can also be useful intermediates in the production of compounds of formula (I) bearing the W1 linker. Thus, in one set of embodiments, W is W1, while in a second set of embodiments, W is W2. In a third set of embodiments, W is -C≡C-.

[0059] Preferably, R 10 , R 11 , R 12 and R 13 are each independently selected from hydrogen or C 1 ~C 3 alkyl. In one set of embodiments, R 10 , R 11 , R 12 , and R 13 are all hydrogen.

[0060] Preferably, R 14 and R 15 are each independently selected from hydrogen or C 1 ~C 3 alkyl. In one set of embodiments, R 14 and R 15 are both hydrogen.

[0061] Specific examples of W include -CH 2 -CH 2 -, and -CH=CH-, cis

Chemical Formula

Chemical Formula

[0062] In one preferred set of embodiments of the compound of formula (I) (wherein both X and Y are other than cyclopropyl); R 1 is methyl, ethyl, cyclopropyl, propargyl or C 1 fluoroalkyl; R 2 is chloro, cyclopropyl, trifluoromethyl or methyl; G is hydrogen or -C(O)-R 3 wherein R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl, methoxy, ethoxy, or tert-butoxy; X is fluoro, chloro or C 1 -haloalkyl and is ortho with respect to the pyridazinone / pyridazinedione moiety; Y is hydrogen, chloro, fluoro, or bromo and is ortho with respect to the -W-D moiety; D is C 1 ~C 6 haloalkylcarbonyl-, C 3 ~C 6 cycloalkylcarbonyl-, -S(O) m -C 1 ~C 6 haloalkyl, -S(O) m -C 3 ~C 6 cycloalkyl, -O-S(O) 2 C 1 ~C 3 alkyl, -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 alkyl, -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 haloalkyl, -C1 ~C 3 alkyl-S(O) m -C 3 ~C 6 cycloalkyl, cyano-C 1 ~C 6 -alkyl-, -NR 4a R 5a 、-C(S)NR 4 R 5 、-S(O) 2 NHC(O)C 1 ~C 3 alkyl, -S(O) 2 NR 4 R 5 、-C(O)OH, -C(O)OC 1 ~C 6 alkyl, -C(O)NHS-(O) 2 C 1 ~C 6 alkyl, -C(O)NR 4 R 5 、-NR 4 C(O)NR 4 R 5 、C 1 ~C 6 alkylcarbonyl(C 1 ~C 6 alkyl)amino-, C 1 ~C 6 haloalkylcarbonylamino-, C 1 ~C 6 haloalkylcarbonyl(C 1 ~C 6 alkyl)amino-, C 1 ~C 6 alkylsulfonylamino-, C 1 ~C 6 alkylsulfonyl(C 1 ~C 6 alkyl)amino-, C 1 ~C 6 haloalkylsulfonylamino-, C 1 ~C 6 haloalkylsulfonyl(C 1 ~C 6 alkyl)amino-, C 3 ~C 6 cycloalkylsulfonylamino-, C 3 ~C6 Cycloalkylsulfonyl(C 1 ~C 6 alkyl)amino-, hydroxyamino-, hydroxy(C 1 ~C 6 alkyl)amino, C 1 ~C 6 alkoxyamino, C 1 ~C 6 alkoxy(C 1 ~C 6 alkyl)amino, C 1 ~C 6 haloalkoxyamino and C 1 ~C 6 haloalkoxy(C 1 ~C 6 alkyl)amino; or a phenyl ring substituted with at least one R 8 selected from the group consisting of ring systems selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclic ring, wherein said ring system is substituted with 0 to 5 R 16 ; Any additional R 8 substituent may be hydroxyl, halogen, cyano, C 1 ~C 6 alkyl, C 1 ~C 6 haloalkyl, C 3 ~C 6 -cycloalkyl, C 1 ~C 6 alkoxy, C 2 ~C 6 alkenyl, and C 2 ~C 6 alkynyl and may be selected from the group consisting of; R 4 and R 5 are each independently hydrogen, C 1 ~C 3 alkyl, C 1 ~C 3 alkoxy, or C 3 ~C 6 cycloalkyl; m is an integer of 0, 1, or 2 (preferably 0 or 2); Each R 4aand R 5a is C 1 ~C 6 alkoxy, and C 3 ~C 6 is independently selected from the group consisting of cycloalkyl, or R 4a and R 5a together can form a morpholinyl ring; Each R 16 is independently halogen, cyano, C 1 ~C 6 alkyl, C 1 ~C 6 haloalkyl, C 1 ~C 6 alkoxy or C 1 ~C 6 haloalkoxy; W is W1; R 10 , R 11 , R 12 , and R 13 are all hydrogen.

[0063] In a more preferred set of embodiments of the compound of formula (I) (wherein both X and Y are other than cyclopropyl); R 1 is methyl; R 2 is methyl; G is hydrogen or -C(O)-R 3 , R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl, methoxy, ethoxy, or tert-butoxy; X is fluoro and is ortho with respect to the pyridazinone / pyridazinedione moiety; Y is chloro and is ortho with respect to the -W-D moiety; D is a phenyl ring substituted with one or two R 8 , at least one R 8 is C 1 ~C 6 haloalkylcarbonyl-, C 3 ~C 6Cycloalkylcarbonyl-, -S(O) m -C 1 ~C 6 Haloalkyl, -S(O) m -C 3 ~C 6 Cycloalkyl, -O-S(O) 2 C 1 ~C 3 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Haloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 3 ~C 6 Cycloalkyl, -S(O) 2 NHC(O)C 1 ~C 3 Alkyl, -S(O) 2 NR 4 R 5 , -C(O)OH, -C(O)OC 1 ~C 6 Alkyl, -C(O)NHS-(O) 2 C 1 ~C 6 Alkyl, -C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5 , C 1 ~C 6 Alkylcarbonyl(C 1 ~C 6 Alkyl)amino-, C 1 ~C 6 Haloalkylcarbonylamino- and C 1 ~C 6 Haloalkylcarbonyl(C 1 ~C 6(alkyl)amino-; or selected from the group consisting of ring systems selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclic ring, said ring system being substituted with 0 to 5 R 16 ; Any further R 8 substituent may be selected from the group consisting of halogen, C 1 ~C 6 alkyl and C 1 ~C 6 haloalkyl; R 4 and R 5 are each independently hydrogen, C 1 ~C 3 alkyl, C 1 ~C 3 alkoxy, or C 3 ~C 6 cycloalkyl; m is 0 or 2 (preferably 0); Each R 16 is independently halogen, cyano, C 1 ~C 4 alkyl, C 1 ~C 3 haloalkyl or C 1 ~C 4 alkoxy; W is W1; R 10 , R 11 , R 12 and R 13 are all hydrogen.

[0064] In a further preferred set of embodiments of the compound of formula (I) (wherein both X and Y are other than cyclopropyl); R 1 is methyl; R 2 is methyl; G is hydrogen or -C(O)-R 3 wherein R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl, or methoxy; X is fluoro and ortho with respect to the pyridazinone / pyridazinedione moiety; Y is chloro and ortho with respect to the -W-D moiety; D is -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 alkyl, -S(O) 2 NHC(O)C 1 ~C 3 alkyl, -S(O) 2 NR 4 R 5 , -C(O)OH, -C(O)OC 1 ~C 6 alkyl and -C(O)NR 4 R 5 ; or a phenyl ring substituted with one R selected from the group consisting of ring systems selected from the group consisting of phenyl, morpholinyl, tetrahydrofuranyl, furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, 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, pyridonyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, or 1,3,5-triazinyl ring, said ring system being substituted with 0 to 2 R 8 ; 16 ; R 4 and R 5 are each independently hydrogen or C 1 ~C 3 alkyl; m is 0 or 2 (preferably 0); each R 16 is independently halogen or C 1 ~C 4 alkyl (preferably methyl); W is W1; R 10 、R 11 、R 12 、and R 13 are all hydrogen

[0065] In a further preferred set of embodiments of the compound of formula (I) wherein both X and Y are other than cyclopropyl; R 1 is methyl; R 2 is methyl; G is hydrogen or -C(O)-R 3 wherein R 3 is isopropyl; X is fluoro and is ortho with respect to the pyridazinone / pyridazinedione moiety; Y is chloro and is ortho with respect to the -W-D moiety; D is methylsulfanylmethyl, isopropylsulfanylmethyl, sulfamoyl, methylsulfamoyl and carbamoyl; or a phenyl ring substituted with one R 8 selected from the group consisting of phenyl, morpholinyl, tetrahydrofuranyl, furyl, thienyl, pyrrolyl, pyrazolyl, 1,2,4-triazolyl, oxazolyl and thiazolyl ring systems, said ring systems being substituted with from 0 to 2 R 16 ; Each R 16 is methyl; W is W1; R 10 、R 11 、R 12 、and R 13 are all hydrogen.

[0066] In an alternative preferred set of embodiments of the compound of formula (I) wherein both X and Y are other than cyclopropyl; R 1 is methyl, ethyl, cyclopropyl, propargyl or C 1 fluoroalkyl; R 2is chloro, cyclopropyl, trifluoromethyl or methyl; G is hydrogen or -C(O)-R 3 wherein R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl, methoxy, ethoxy, or tert-butoxy; X is fluoro, chloro or C 1 -haloalkyl and is ortho to the pyridazinone / pyridazinedione moiety; Y is hydrogen, chloro, fluoro, or bromo and is ortho to the -W-D moiety; D is C 1 ~C 6 haloalkylcarbonyl-, C 3 ~C 6 cycloalkylcarbonyl-, -S(O) m -C 1 ~C 6 haloalkyl, -S(O) m -C 3 ~C 6 cycloalkyl, -O-S(O) 2 C 1 ~C 3 alkyl, -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 alkyl, -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 haloalkyl, -C 1 ~C 3 alkyl-S(O) m -C 3 ~C 6 cycloalkyl, cyano-C 1 ~C 6 -alkyl-, NR 4a R 5a 、-C(S)NR 4 R 5 、-S(O) 2 NHC(O)C 1 ~C 3 alkyl, -S(O) 2NR 4 R 5 ,-C(O)OH, -C(O)OC 1 ~C 6 alkyl, -C(O)NHS-(O) 2 C 1 ~C 6 alkyl, -C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5 C 1 ~C 6 alkylcarbonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 haloalkylcarbonylamino-, C 1 ~C 6 haloalkylcarbonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 alkylsulfonylamino-, C 1 ~C 6 alkylsulfonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 haloalkylsulfonylamino-, C 1 ~C 6 haloalkylsulfonyl (C 1 ~C 6 alkyl)amino-, C 3 ~C 6 cycloalkylsulfonylamino-, C 3 ~C 6 cycloalkylsulfonyl (C 1 ~C 6 alkyl)amino-, hydroxyamino-, hydroxy (C 1 ~C 6 alkyl)amino, C 1 ~C 6 alkoxyamino, C 1 ~C 6 alkoxy (C 1 ~C 6 alkyl)amino, C 1 ~C 6Haloalkoxyamino, C 1 ~C 6 haloalkoxy(C 1 ~C 6 alkyl)amino; and at least one R selected from the group consisting of ring systems selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclyl ring 8 A 5- or 6-membered monocyclic heteroaryl ring containing 1, 2, or 3 heteroatoms independently selected from oxygen, nitrogen, and sulfur, substituted with 16 ; the ring system is substituted with 0 to 5 R Any additional R 8 Substituents may be hydroxyl, halogen, cyano, C 1 ~C 6 alkyl, C 1 ~C 6 haloalkyl, C 3 ~C 6 -cycloalkyl, C 1 ~C 6 alkoxy, C 2 ~C 6 alkenyl, and C 2 ~C 6 alkynyl; and / or D may be C 5 ~C 6 alkyl, C 5 ~C 6 haloalkyl, C 3 ~C 6 -cycloalkyl, C 1 ~C 3 alkoxy-C 3 alkyl-, C 3 alkoxy-C 1 ~C 2 alkyl-, C 1 ~C 3 haloalkoxy-C 1 ~C 3 alkyl-, C 1 ~C 3 alkoxy-C 1 ~C 3 alkoxy-C 1 ~C 3 alkyl-, C 1 ~C6 Hydroxyalkyl-, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Haloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 3 ~C 6 Cycloalkyl, cyano-C 1 ~C 6 -Alkyl-, and at least one R selected from the group consisting of ring systems selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclic ring 9 is substituted, and the ring system is substituted with 0 to 5 Rs 16 ; R 4 and R 5 are each independently hydrogen, C 1 ~C 3 alkyl, C 1 ~C 3 alkoxy, or C 3 ~C 6 cycloalkyl; m is an integer of 0, 1, or 2 (preferably 0 or 2); Each R 4a and R 5a is independently selected from the group consisting of C 1 ~C 6 alkoxy, and C 3 ~C 6 cycloalkyl, or R 4a and R 5a can together form a morpholinyl ring; Each R 16 is independently halogen, cyano, C 1 ~C 6 alkyl, C 1 ~C 6 haloalkyl, C 1 ~C 6Alkoxy or C 1 ~C 6 is haloalkoxy; W is W1; R 10 、R 11 、R 12 、and R 13 are all hydrogen.

[0067] In a more preferred set as an alternative to the embodiment in the compound of formula (I) (wherein both X and Y are other than cyclopropyl); R 1 is methyl; R 2 is methyl; G is hydrogen or -C(O)-R 3 and R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl, methoxy, ethoxy, or tert-butoxy; X is fluoro and is ortho with respect to the pyridazinone / pyridazinedione moiety; Y is chloro and is ortho with respect to the -W-D moiety; D is a 5- or 6-membered monocyclic heteroaryl ring containing one, two, or three heteroatoms independently selected from oxygen, nitrogen, and sulfur, substituted on the ring carbon with one or two R 8 wherein at least one R 8 is C 1 ~C 6 haloalkylcarbonyl-, C 3 ~C 6 cycloalkylcarbonyl-, -S(O) m -C 1 ~C 6 haloalkyl, -S(O) m -C 3 ~C 6 cycloalkyl, -O-S(O) 2 C 1 ~C 3 alkyl, -C 1 ~C 3 alkyl-S(O) m -C 1 ~C6 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Haloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 3 ~C 6 Cycloalkyl, -S(O) 2 NHC(O)C 1 ~C 3 Alkyl, -S(O) 2 NR 4 R 5 , -C(O)OH, -C(O)OC 1 ~C 6 Alkyl, -C(O)NHS-(O) 2 C 1 ~C 6 Alkyl, -C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5 , C 1 ~C 6 Alkylcarbonyl(C 1 ~C 6 Alkyl)amino-, C 1 ~C 6 Haloalkylcarbonylamino- and C 1 ~C 6 Haloalkylcarbonyl(C 1 ~C 6 Alkyl)amino-; or a ring system selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclic ring, said ring system being substituted with 0 to 5 R 16 ; Any additional R 8 substituents may be selected from the group consisting of halogen, C 1 ~C 6 alkyl, and C 1 ~C 6 haloalkyl; and / or D is C 5 ~C 6 alkyl on the ring nitrogen, C 5 ~C 6Haloalkyl, C 3 ~C 6 -Cycloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Haloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 3 ~C 6 Cycloalkyl, and one R selected from the group consisting of ring systems selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclyl ring 9 is substituted, and the ring system is substituted with 0 to 5 R 16 ; R 4 and R 5 are each independently hydrogen, C 1 ~C 3 alkyl, C 1 ~C 3 alkoxy, or C 3 ~C 6 cycloalkyl; m is 0 or 2 (preferably 0); Each R 16 is independently halogen, cyano, C 1 ~C 4 alkyl, C 1 ~C 3 haloalkyl or C 1 ~C 4 alkoxy; W is W1; R 10 , R 11 , R 12 and R 13 are all hydrogen.

[0068] In a further more preferred set as an alternative to the embodiment in the compound of formula (I) (wherein both X and Y are other than cyclopropyl); R 1 is methyl; R 2 is methyl; G is hydrogen or -C(O)-R 3 wherein R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl, or methoxy; X is fluoro and is ortho to the pyridazinone / pyridazinedione moiety; Y is chloro and is ortho to the -W-D moiety; D is -C 1 ~C 3 alkyl-S(O) m -C 1 ~C 6 alkyl, -S(O) 2 NHC(O)C 1 ~C 3 alkyl, -S(O) 2 NR 4 R 5 , -C(O)OH, -C(O)OC 1 ~C 6 alkyl and -C(O)NR 4 R 5 ; or a 5- or 6-membered monocyclic heteroaryl ring containing one, two, or three nitrogen atoms substituted with one R 8 selected from the group consisting of ring systems selected from the group consisting of phenyl, morpholinyl, tetrahydrofuranyl, furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, 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, pyridonyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, or 1,3,5-triazinyl rings, said ring system being substituted with 0 - 2 R 16is replaced by; and / or D is C on the ring nitrogen 5 ~C 6 alkyl, C 3 ~C 6 -cycloalkyl, and one R selected from the group consisting of ring systems selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclyl ring 9 is substituted with, and the ring system is substituted with 0 to 2 R 16 ; R 4 and R 5 are each independently hydrogen or C 1 ~C 3 alkyl; m is 0 or 2 (preferably 0); Each R 16 is independently halogen or C 1 ~C 4 alkyl (preferably methyl); W is W1; R 10 , R 11 , R 12 and R 13 are all hydrogen.

[0069] Furthermore, in a more preferred set as an alternative to the embodiment in the compound of formula (I) (wherein both X and Y are other than cyclopropyl); R 1 is methyl; R 2 is methyl; G is hydrogen or -C(O)-R 3 and R 3 is isopropyl; X is fluoro and is ortho with respect to the pyridazinone / pyridazinedione moiety; Y is chloro and is ortho with respect to the -W-D moiety; D is one R selected from the group consisting of ring systems selected from the group consisting of methylsulfanylmethyl, isopropylsulfanylmethyl, sulfamoyl, methylsulfamoyl and carbamoyl; or phenyl, morpholinyl, tetrahydrofuranyl, furyl, thienyl, pyrrolyl, pyrazolyl, 1,2,4-triazolyl, oxazolyl and thiazolyl rings, on the ring carbon 8 and is pyrazolyl or pyridyl substituted with 8 , wherein the ring system is substituted with 0 to 2 R 16 ; and / or D is substituted with one R selected from cyclopropyl or phenyl on the ring nitrogen 9 ; Each R 16 is methyl; W is W1; R 10 R 11 R 12 and R 13 are all hydrogen.

[0070] The following Tables A-1, A-2, A-3, A-4, B-1, B-2, B-3, B-4, C-1, C-2, C-3, and C-4 illustrate specific examples of the compounds of formula (I) of the present invention.

[0071] The herbicidal compounds of the present invention. The numbering system used to explain the positions of X and Y in the compounds of formula (I) shown below is shown only for the purpose of clarity.

Chemical formula

[0072] Table A-1 provides compounds A-1.001 to A-1.672 of formula (I), where G is -H, W is -CH 2 -CH 2 -, and R 1 R 2 X, Y, D are as defined for compound numbers 1.001 to 1.672 respectively in Table 1 below.

[0073]

Table 1-1

Table 1-2

Table 1-3

Table 1-4

Table 1-5

Table 1-6

Table 1-7

Table 1-8

Table 1-9

Table 1-10

Table 1-11

Table 1-12

Table 1-13

Table 1-14

Table 1-15

Table 1-16

Table 1-17

Table 1-18

Table 1-19

Table 1-20

Table 1-21

Table 1-22

Table 1-23

Table 1-24

Table 1-25

Table 1-26

[0074] Table A-2 provides compounds A-2.001 to A-2.672 of formula (I), where G is H, W is (E)-CH=CH-, and R 1 , R 2 , X, Y, D are as defined for compound numbers 1.001 to 1.672 in Table 1 above, respectively.

[0075] Table A-3 provides compounds A-3.001 to A-3.672 of formula (I), where G is -(C=O)iPr, W is -CH 2 -CH 2 -, and R 1 , R 2 , X, Y, D are as defined for compound numbers 1.001 to 1.672 in Table 1 above, respectively.

[0076] Table A-4 provides compounds A-4.001 to A-4.672 of formula (I), where G is -(C=O)iPr, W is (E)-CH=CH-, and R 1 , R 2 , X, Y, D are as defined for compound numbers 1.001 to 1.672 respectively in Table 1 above.

[0077] Table B-1 provides compounds B-1.001 to B-1.744 of formula (I), where G is -H, W is -CH 2 -CH 2 -, X is 6-cyclopropyl, and R 1 , R 2 , Y, D are as defined for compound numbers 2.001 to 2.744 respectively in Table 2 below.

[0078]

Table 2-1

Table 2-2

Table 2-3

Table 2-4

Table 2-5

Table 2-6

Table 2-7

Table 2-8

Table 2-9

Table 2-10

Table 2-11

Table 2-12

Table 2-13

Table 2-14

Table 2-15

Table 2-16

Table 2-17

Table 2-18

Table 2-19

Table 2-20

Table 2-21

Table 2-22

Table 2-23

Table 2-24

Table 2-25

[0079] Table B-2 provides compounds B-2.001 to B-2.744 of formula (I) with 744, where G is -H, W is (E)-CH=CH-, X is 6-cyclopropyl, and R 1 , R 2 , Y, and D are as defined for compound numbers 2.001 to 2.744 respectively in Table 2 above.

[0080] Table B-3 provides compounds B-3.001 to B-3.744 of formula (I) with 744, where G is -(C=O)iPr, W is -CH 2 -CH 2 -, X is 6-cyclopropyl, and R 1 , R 2 , Y, and D are as defined for compound numbers 2.001 to 2.744 respectively in Table 2 above.

[0081] Table B-4 provides compounds B-4.001 to B-4.744 of formula (I) with 744, where G is -(C=O)iPr, W is (E)-CH=CH-, X is 6-cyclopropyl, and R 1 , R 2 , Y, and D are as defined for compound numbers 2.001 to 2.744 respectively in Table 2 above.

[0082] Table C-1 provides compounds C-1.001 to C-1.744 of formula (I) with 744, where G is -H, W is -CH 2 -CH 2 ]-, Y is 3-cyclopropyl, and R 1 , R 2 , X, and D are as defined for compound numbers 3.001 to 3.744 respectively in Table 3 below.

[0083]

Table 3-1

Table 3-2

Table 3-3

Table 3-4

Table 3-5

Table 3-6

Table 3-7

Table 3-8

Table 3-9

Table 3-10

Table 3-11

Table 3-12

Table 3-13

Table 3-14

Table 3-15

Table 3-16

Table 3-17

Table 3-18

Table 3-19

Table 3-20

Table 3-21

Table 3-22

Table 3-23

Table 3-24

Table 3-25

[0084] Table C-2 provides compounds C-2.001 to C-2.744 of formula (I) where G is -H, W is (E)-CH=CH-, Y is 3-cyclopropyl, and R 1 , R 2 , X, Y, and D are as defined for compound numbers 3.001 to 3.744 in Table 3 above, respectively.

[0085] Table C-3 provides compounds C-3.001 to C-3.744 of formula (I) where G is -(C=O)iPr, W is -CH 2 -CH 2 -, Y is 3-cyclopropyl, and R 1 , R 2 , X, and D are as defined for compound numbers 3.001 to 3.744 in Table 3 above, respectively.

[0086] Table C-4 provides compounds C-4.001 to C-4.744 of formula (I) where G is -(C=O)iPr, W is (E)-CH=CH-, Y is 3-cyclopropyl, and R 1 , R 2 , X, and D are as defined for compound numbers 3.001 to 3.744 in Table 3 above, respectively.

[0087] The compounds of the present invention can be prepared according to the following scheme, where the substituent R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , W, D, Dp, G, X, Y, and m have the definitions described above in this specification (unless otherwise explicitly stated).

[0088] A specific compound (I-ii) of the present invention can be prepared from compound (2) as shown in Reaction Scheme 1. Compound (I-ii) is a compound of formula (I), where W is -CH 2 -CH 2 -.

[0089] Reaction Scheme 1

Chemical formula

[0090] Alternatively, compound (I-ii) can also be prepared by catalytic transfer hydrogenation of compound (2) by treatment with a suitable hydrogen source in a suitable solvent in the presence of a suitable catalyst at a temperature of -10 to 100 °C. Examples of suitable systems are Pd / C, Pd(OAc) 2 or Pd(OH) 2Tetrahydroxydiboron in dichloromethane / water or dichloromethane / methanol mixture in the presence of / C (J. Am. Chem. Soc., 2016, 138, 6107 - 6110), or diethyl 1,4 - dihydro - 2,6 - dimethyl - 3,5 - pyridinedicarboxylate in ethanol in the presence of Pd / C (Tetrahedron Letters, 2009, 50, 1026).

[0091] Compound (2) can be prepared from compounds (3) and (4) as shown in Reaction Scheme 2 according to the following Suzuki protocol or Heck protocol. When using the Suzuki protocol, compound (4) is an organoboron compound, such as boric acid, boronic ester or potassium trifluoroborate salt. When using the Heck protocol, compound (4) is styrene.

[0092] Alternatively, compound (I - ii) can also be prepared by reduction with diimide generated in situ from a suitable precursor in a suitable solvent at a temperature of - 10 to 200 °C. Examples of suitable reagents for the generation of diimide include substituted arylsulfonyl hydrazides, such as 2,4,6 - triisopropylbenzenesulfonyl hydrazide, optionally in the presence of a suitable base. Examples of suitable bases include triethylamine, diisopropylethylamine, potassium carbonate and sodium carbonate. Suitable solvents include tetrahydrofuran, 1,4 - dioxane, ethyl acetate, acetonitrile and dimethylformamide.

[0093] Reaction Scheme 2

Chemical Structure

[0094] Those skilled in the art will recognize that the conditions of the Suzuki protocol tend to cleave the ester group, and as a result, reaction scheme 2 can also describe reactions where the starting material (3) contains an ester moiety [such that G is an acyl group] while the product (2) does not contain an ester moiety [such that G is hydrogen].

[0095] Heck protocol Compound (2) can be prepared by treating compound (3) and compound (4) at a temperature of 10 - 150 °C in the presence of a suitable base and a suitable catalyst. An additional solvent may optionally be included. Examples of suitable bases include triethylamine, morpholine, N-methylmorpholine, diisopropylethylamine, and pyridine. Examples of suitable catalysts include tetrakis(triphenylphosphine)palladium(0) [Pd(PPh 3 ) 41. A catalyst system formed in situ from a mixture of palladium(II) acetate and triphenylphosphine, a catalyst system formed in situ from a mixture of tris(dibenzylideneacetone)dipalladium(0) and tri-tert-butylphosphonium tetrafluoroborate, and a catalyst system formed in situ from a paradacycle precatalyst, for example, chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II). Examples of any further solvents include 1,4-dioxane, tetrahydrofuran, acetonitrile, and toluene. Many compounds (4) are commercially available [e.g., 4-cyanostyrene] or can be prepared by known methods. An example of a compound (3) having particular utility in the Heck protocol is isobutyryl ester (3-i), where G is isobutyryl.

[0096] Compound (3-i) can be prepared from compound (5) as shown in Reaction Scheme 3.

[0097] Reaction Scheme 3 [Chemical formula] Compound (3-i) can be prepared by treating compound (5) and isobutyryl chloride in a suitable solvent [e.g., dichloromethane, acetonitrile, or toluene] in the presence of a suitable base [e.g., triethylamine, diisopropylethylamine, or pyridine] at a temperature of -10 to 60 °C. A catalyst [e.g., 4-(dimethylamino)pyridine] may optionally be included.

[0098] Compound (5) can be prepared from compound (6) as shown in Reaction Scheme 4 by heating compound (6) with a base (e.g., 1,8-diazabicyclo[5.4.0]undec-7-ene, sodium hexamethyldisilazide, or lithium hexamethyldisilazide) in a solvent [e.g., acetonitrile, N,N-dimethylformamide, or toluene] at a temperature of 50 to 200 °C. Conventional heating or microwave heating can be used.

[0099] Reaction Scheme 4

Chem.

[0100] Reaction Scheme 5

Chem.

[0101] A specific compound (I-iii) of the present invention can be prepared from compound (11) as shown in Reaction Scheme 6, or from compound (I-iv) as shown in Reaction Scheme 12. Compound (I-iii) is a compound of formula (I), where W is -CH 2 -CH 2 -, and G is hydrogen.

[0102] Reaction Scheme 6

Chem.

[0103] Compound (11) can be prepared from compound (12) as shown in the following Reaction Scheme 7.

[0104] Reaction Scheme 7

Chem.

[0105] Regarding Reaction Scheme 8, phosphorane (15) can be prepared by Reaction Scheme 9.

[0106] Reaction Scheme 8

Chem.

Chem.

[0107] Reaction Scheme 10

Chem.

[0108] Reaction Scheme 11

Chem.

[0109] Reaction Scheme 12

Chem.

[0110] Compound (2) can be prepared from compounds (14) and (15) as shown in Reaction Scheme 13 by the Suzuki protocol or the Heck protocol described below. When using the Suzuki protocol, compound (14) is an organoboron compound, such as boric acid, boronic ester or potassium trifluoroborate salt, and compound (15) is a halide or pseudohalide compound, such as chloride, bromide, iodide or triflate. When using the Heck protocol, compound (14) is styrene and compound (15) is a halide or pseudohalide compound, such as chloride, bromide, iodide or triflate.

[0111] Reaction Scheme 13 [Chemical formula] Suzuki protocol Compound (2) can be prepared by treating compounds (14) and (15) in a suitable solvent at a temperature of 10 - 150 °C in the presence of a suitable base and a suitable catalyst. Examples of suitable bases include potassium carbonate, potassium phosphate, sodium carbonate, sodium hydrogen carbonate and potassium fluoride. Examples of suitable catalysts include [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex [PdCl 2 (dppf)·DCM], tetrakis(triphenylphosphine)palladium(0) [Pd(PPh 3 ) 4 , and catalyst systems formed in situ from a mixture of palladium(II) acetate and triphenylphosphine. Examples of suitable solvents include water, 1,4-dioxane, tetrahydrofuran, acetonitrile and toluene. Many compounds (15) are commercially available or can be prepared by known methods. An example of compound (14) having particular utility in the Suzuki protocol is isobutyryl ester (14-i), where G is isobutyryl.

[0112] The Suzuki protocol conditions tend to cleave ester groups, and as a result, Reaction Scheme 13 can also explain reactions where the starting material (14) contains an ester moiety [such that G is an acyl group] and the product (2) does not contain an ester moiety [such that G is hydrogen], which those skilled in the art will recognize.

[0113] Heck protocol Compound (2) can be prepared by treating compound (14) with compound (15) in the presence of a suitable base and a suitable catalyst at a temperature of 10 - 150 °C. Optionally, an additional solvent may be included. Examples of suitable bases include triethylamine, morpholine, N - methylmorpholine, diisopropylethylamine, and pyridine. Examples of suitable catalysts include tetrakis(triphenylphosphine)palladium(0) [Pd(PPh 3 ) 4 , a catalyst system formed in situ from a mixture of palladium(II) acetate and triphenylphosphine, a catalyst system formed in situ from a mixture of tris(dibenzylideneacetone)dipalladium(0) and tri - tert - butylphosphonium tetrafluoroborate, and a catalyst system formed in situ from a paradacycle precatalyst, for example, chloro[(tri - tert - butylphosphine)-2-(2 - aminobiphenyl)]palladium(II). Examples of optionally additional solvents include 1,4 - dioxane, tetrahydrofuran, acetonitrile, and toluene. Many compounds (15) are commercially available or can be prepared by known methods. An example of a compound (14) having particular utility in the Heck protocol is isobutyryl ester (14 - i), where G is isobutyryl.

[0114] Compound (14 - ii) (where J is an organoboron species, for example, a boronic ester) can be prepared from compound (3) and compound (16) as shown in Reaction Scheme 14.

[0115] Reaction Scheme 14

Chemical formula

[0116] Compound (14-iii) (where J is hydrogen) can be prepared from compound (3) as shown in Reaction Scheme 15.

[0117] Reaction Scheme 15

Chemical Structure

[0118] Compound (18) can be prepared from compound (3) by a Sonogashira reaction as shown in Reaction Scheme 16.

[0119] Reaction Scheme 16

Chemical formula

[0120] Those skilled in the art will recognize that the Sonogashira reaction conditions tend to cleave the ester group, and as a result, reaction scheme 16 can also describe a reaction where starting material (3) contains an ester moiety [such that G is an acyl group] while product (18) does not contain an ester moiety [such that G is hydrogen].

[0121] Compound (19) can be prepared from compound (3) and compound (20) as shown in reaction scheme 17 via a Suzuki reaction, where compound (20) is a suitable organoboron species, for example, boric acid, boronic ester, or potassium trifluoroborate.

[0122] Reaction Scheme 17 [Chemical Formula] Compound (19) can be prepared by treating compound (3) and compound (20) in a suitable solvent at a temperature of 10 to 150 °C in the presence of a suitable base and a suitable catalyst. Examples of suitable bases include potassium carbonate, potassium phosphate, sodium carbonate, sodium hydrogen carbonate, and potassium fluoride. Examples of suitable catalysts include [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex [PdCl 2 (dppf)·DCM], a catalyst system formed in situ from a mixture of tris(dibenzylideneacetone)dipalladium(0) and tri-tert-butylphosphonium tetrafluoroborate, a catalyst system formed in situ from a mixture of tris(dibenzylideneacetone)dipalladium(0) and tricyclohexylphosphine, a paracyclophane catalyst precursor, for example, a catalyst system formed in situ from chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II), and a paracyclophane catalyst precursor, for example, a catalyst system formed in situ from chloro[(tricyclohexylphosphine)-2-(2'-aminobiphenyl)]palladium(II). Examples of suitable solvents include water, 1,4-dioxane, tetrahydrofuran, acetonitrile, and toluene. Some compounds (20) are commercially available [for example, 4,4,5,5-tetramethyl-2-(2-phenyl-cyclopropyl)-[1,3,2]dioxaborolane], or can be prepared by known methods (see, for example, the method described in Org. Process Res. Dev. 2012, 16, 87-95). An example of compound (3) that has particular utility in the Suzuki reaction is benzyl ether (3-ii), where G is benzyl.

[0123] Reaction Scheme 18

Chemical Structure

[0124] A certain specific compound (I-ii) of the present invention can be prepared from compound (21) as shown in Reaction Scheme 19. Compound (I-ii) is a compound of formula (I), wherein W is -CH 2 -CH 2 -.

[0125] Reaction Scheme 19

Chemical formula

[0126] Those skilled in the art will recognize that the conditions of the Suzuki protocol tend to cleave the ester group, such that reaction scheme 19 can also describe a reaction where the starting material (21) contains an ester moiety [such that G is an acyl group], but the product (I-ii) does not contain an ester moiety [such that G is hydrogen].

[0127] Reaction Scheme 20 [Chemical formula] Compound (21) can be prepared by hydroboration of alkene (14-iii) using a suitable hydroborating reagent (22) in a suitable solvent with the optional addition of a suitable catalyst at a temperature of 0 °C to 100 °C. Examples of hydroborating reagents include borane, dichloroborane, dibromoborane, 4,4,5,5-tetramethyl-1,3,2-dioxaborolane [pinacol borane], 1,3,2-benzodioxaborole [catechol borane], or 9-borabicyclo[3.3.1]nonane [9-BBN]. Examples of suitable solvents include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 2-methoxy-2-methyl-propane [MTBE], and diethyl ether. Examples of suitable catalysts include bis(1,5-cyclooctadiene)diiridium(I) dichloride [[Ir(COD)Cl] 2 , and a catalyst system formed in situ from 4-diphenylphosphanylbutyl(diphenyl)phosphane [DPPB] [J. Am. Chem. Soc., 2004, 126, 9200-9201].

[0128] When [B] is an alkyl boronic acid ester, this can be converted to the corresponding boronic acid by treatment with methylboronic acid [MeB(OH) 2 and trifluoroacetic acid in a suitable solvent, such as dichloromethane [DCM], at a temperature of 0 to 40 °C [Org. Lett., 2019, 21, 3048-3052]. When [B] is an alkyl boronic acid or ester, this can be converted to the corresponding alkyl potassium trifluoroborate by treatment with potassium hydrogen fluoride in a suitable solvent, such as methanol or acetone, at a temperature of 0 to 40 °C.

[0129] Reaction Scheme 21

Chemical Structure

[0130] The Suzuki protocol conditions tend to cleave ester groups, and as a result, one skilled in the art will recognize that Reaction Scheme 21 can describe a reaction where the starting material (I-v) contains an ester moiety [such that G is an acyl group], while the product (I-iii) does not contain an ester moiety [such that G is hydrogen].

[0131] The compounds of formula (I) according to the present invention can be used per se as herbicides, but they are generally formulated into herbicidal compositions using formulation adjuvants such as carriers, solvents, and surfactants (SFA). Thus, the present invention further provides a herbicidal composition comprising a herbicidal compound according to any one of the previous claims and an agriculturally acceptable formulation adjuvant. The composition may be in the form of a concentrate to be diluted before use, but compositions that can be used immediately can also be prepared. The final dilution is usually carried out with water, but it can be carried out with, for example, liquid fertilizers, micronutrients, living organisms, oils, or solvents instead of water or in addition to water.

[0132] The herbicidal composition generally comprises 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of the compound of formula I and 1 to 99.9% by weight of a formulation adjuvant preferably containing 0 to 25% by weight of a surface active substance.

[0133] The composition can be selected from several 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) (sustained release or quick 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 selected in any case is determined by the specific intended purpose and by the physical, chemical and biological properties of the compound of formula (I).

[0134] A dustable powder (DP) can be prepared by mixing a compound of formula (I) with one or more solid excipients (for example, natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, porous diatomaceous earth, chalk, diatomaceous earth, calcium phosphate, calcium carbonate and magnesium carbonate, sulfur, lime, wheat flour, talc, and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.

[0135] A soluble powder (SP) can be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (for example, sodium hydrogen carbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (for example, polysaccharides), and optionally one or more wetting agents, one or more dispersing agents or a mixture of said agents, to improve water dispersibility / solubility. The mixture is then ground to a fine powder. Similar compositions can also be granulated to form water-soluble granules (SG).

[0136] The wettable powder (WP) can be prepared by mixing the compound of formula (I) with one or more solid excipients or carriers, one or more wetting agents, and preferably one or more dispersing agents, and optionally one or more suspending agents, and promoting dispersion in a liquid. The mixture is then ground into fine powder. Similar compositions can also be granulated to form water-dispersible granules (WG).

[0137] The granules (GR) can be formed by granulating a mixture of the compound of formula (I) and one or more powdery solid excipients or carriers, or from pre-formed blank granules, by absorbing the compound of formula (I) (or a solution thereof in a suitable agent) into a porous granular material (e.g., pumice, attapulgite clay, fuller's earth, porous diatomaceous earth, diatomaceous earth or ground corn cob), or by adsorbing the compound of formula (I) (or a solution thereof in a suitable agent) onto a hard core material (e.g., sand, silicate, mineral carbonate, mineral sulfate or mineral phosphate), and drying if necessary. Agents commonly used to assist absorption or adsorption include solvents (e.g., aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and fixing agents (e.g., polyvinyl acetate, polyvinyl alcohol, dextrin, sugars and vegetable oils). One or more other additives can also be included in the granules (e.g., emulsifiers, wetting agents or dispersing agents).

[0138] The dispersible concentrate (DC) can be prepared by dissolving the compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions can contain surfactants (e.g., to improve water dilution or prevent crystallization in the spray tank).

[0139] An emulsifiable concentrate (EC) or an oil-in-water emulsion (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., exemplified by alkylbenzenes or alkylnaphthalenes, 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., C 8 ~C 10 fatty acid dimethylamide) and chlorinated hydrocarbons. The EC product spontaneously emulsifies upon addition to water, producing an emulsion with sufficient stability to allow for spray application via a suitable device.

[0140] The preparation of EW involves obtaining the compound of formula (I) as a liquid (which, if not liquid at room temperature, can be melted at a suitable 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 (e.g., chlorobenzene), aromatic solvents (e.g., alkylbenzenes or alkylnaphthalenes) and other suitable organic solvents that are poorly soluble in water.

[0141] Microemulsions (MEs) can be prepared by mixing water with a blend of one or more solvents having one or more SFAs, such that a thermodynamically stable isotropic liquid formulation is spontaneously formed. The compound of formula (I) is initially present in water or the solvent / SFA blend. Suitable solvents for use in MEs include those described above for use in ECs or EWs. MEs can be water-in-oil or oil-in-water systems (which system is present can be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticidal agents in the same formulation. MEs can remain as microemulsions or form normal water-in-oil emulsions and be suitable for dilution in water.

[0142] Suspension concentrates (SCs) can comprise an aqueous or non-aqueous suspension of micronized insoluble solid particles of the compound of formula (I). SCs can be prepared by optionally ball milling or bead milling the solid compound of formula (I) in a suitable medium having one or more dispersing agents to produce a fine particle suspension of the compound. One or more wetting agents can be included in the composition, which, including a suspending agent, can reduce the rate at which the particles settle. Alternatively, the compound of formula (I) can be dry milled and added to water containing the above agents to produce the desired final product.

[0143] Aerosol formulations contain the compound of formula (I) and a suitable propellant (e.g., n-butane). The compound of formula (I) can also be dissolved or dispersed in a suitable medium (e.g., water or a water-miscible liquid, e.g., n-propanol) to provide a composition for use in a non-pressurized, manually operated spray pump.

[0144] The capsule suspension (CS) can be prepared in a manner similar to the preparation of the EW formulation, but with an additional polymerization step such that an aqueous dispersion of oil droplets is obtained, where each oil droplet is encapsulated by a polymer shell and contains the compound of formula (I) and thus optionally a carrier or excipient. The polymer shell can be produced by an interfacial polycondensation reaction or a coacervation procedure. The compositions can achieve controlled release of the compounds of formula (I) and these can be used for seed treatment. The compounds of formula (I) can also be formulated in a biodegradable polymer matrix to achieve controlled and sustained release of the compounds.

[0145] The compositions can include one or more additives that improve the biological performance of the compositions, for example, by improving wetting, retention or distribution on the surface; resistance to rain on the treated surface; or uptake or mobility of the compounds of formula (I). Such additives include surfactants (SFA), oils, for example, spray additives based on certain mineral oils or natural vegetable oils (e.g., soybean oil and rapeseed oil), and blends thereof with other adjuvants (components that can assist or modify the action of the compounds of formula (I)) that enhance biological utility.

[0146] Wetting agents, dispersing agents and emulsifying agents can be SFA of the cationic, anionic, amphoteric or non-ionic type.

[0147] Suitable SFA of the cationic type include quaternary ammonium compounds (e.g., cetyltrimethylammonium bromide), imidazolines and amine salts.

[0148] Suitable anionic SFAs include alkali metal salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (e.g., sodium lauryl sulfate), salts of sulfonated aromatic compounds (e.g., sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butylnaphthalene sulfonate, and a mixture of sodium diisopropylnaphthalenesulfonate and sodium triisopropylnaphthalenesulfonate), ether sulfates, alcohol ether sulfates (e.g., sodium laureth-3-sulfate), ether carboxylates (e.g., sodium laureth-3-carboxylate), phosphate esters (the reaction between one or more fatty alcohols and phosphoric acid (mainly monoesters) or phosphorus pentoxide (mainly diesters), e.g., the product from the reaction between lauryl alcohol and tetraphosphoric acid; furthermore, these products can be ethoxylated), sulfosuccinamates, paraffin or olefin sulfonic acids, taurates, and lignosulfonates.

[0149] Suitable SFAs of the amphoteric type include betaines, propionates, and glycineates.

[0150] Suitable SFAs of the nonionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof, with fatty alcohols (e.g., oleyl alcohol or cetyl alcohol) or alkylphenols (e.g., octylphenol, nonylphenol, or octylcresol); partial esters derived from long-chain fatty acids or hexitol anhydrides; condensation products of the partial esters with ethylene oxide; block polymers (including ethylene oxide and propylene oxide); alkanolamides; simple esters (e.g., fatty acid polyethylene glycol esters); amine oxides (e.g., lauryldimethylamine oxide); and lecithin.

[0151] Suitable suspending agents include hydrophilic colloids (e.g., polysaccharides, polyvinylpyrrolidone, or sodium carboxymethylcellulose) and swelling clays (e.g., bentonite or attapulgite).

[0152] The composition of the present invention may further comprise at least one additional pesticidal agent. For example, the compounds according to the invention can also be used in combination with other herbicides or plant growth regulators. In a preferred embodiment, the additional pesticidal agent is a herbicide and / or a herbicide safener. Specific examples of such mixtures are (where "I" represents a compound of formula (I)): - I + acetochlor; I + asiflufen (including asiflufen-sodium); I + acronifen; I + ametryn; I + amicarbazone; I + aminopyralid; I + aminotriazole; I + atrazine; I + beflubutamid-M; I + benquinox; I + bensulfuron (including bensulfuron-methyl); I + bentazone; I + bicyclopyrone; I + bilanafos; I + bispyribac-sodium; I + bispyrazone; I + bromacil; I + bromoxynil; I + butachlor; I + butaphenacyl; I + carfentrazone (including carfentrazone-ethyl); I + chloransulam (including chloransulam-methyl); I + chlorimuron (including chlorimuron-ethyl); I + chlorotoluron; I + chlorosulfuron; I + cinmethylin; I + clathrifos; I + clethodim; I + clodinafop (including clodinafop-propargyl); I + chromazone; I + clopyralid; I + cyclopyranil; I + cyclopyrimorate; I + cyclosulfamuron; I + cyhalofop (including cyhalofop-butyl); I + 2,4-D (including its choline salt and 2-ethylhexyl ester); I + 2,4-DB; I + desmedipham; I + dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts); I + dichlorsulam; I + diflufenican; I + diflufenzoppil; I + dimethachlor; I + dimethenamid-P; I + diquat dibromide; I + diuron; I + epirifluorfen; I + ethalfluralin; I + ethofumesate; I + fenoxaprop (including fenoxaprop-P-ethyl); I + fenoxasulfone; I + fenquinotrione; I + fentrazamide; I + flazasulfuron; I + florasulam;I + flupyradifurone (including flupyradifurone-benzyl); I + fluazinam (including fluazinam-P-butyl); I + flucarbazone (including flucarbazone-sodium); I + flufenacet; I + flumetram; I + flumioxazin; I + flumetsulam; I + flupyrsulfuron (including flupyrsulfuron-methyl-sodium); I + fluroxypyr (including fluroxypyr-meptyl); I + homesisafen; I + halosulfuron; I + glufosinate (including its ammonium salt); I + glyphosate (including its diammonium, isopropylammonium and potassium salts); I + haloxyfop (including haloxyfop-methyl); I + haloxyfop (including haloxyfop-methyl); I + hexazinone; I + hydantocidin; I + imazamox; I + imazapic; I + imazapyr; I + imazethapyr; I + indaziflam; I + iodosulfuron (including iodosulfuron-methyl-sodium); I + iofensulfuron (including iofensulfuron-sodium); I + ioxynil; I + isoproturon; I + isoxaflutole; I + rankotriol; I + MCPA; I + MCPB; I + mecoprop-P; I + mesosulfuron (including mesosulfuron-methyl); I + mesotrione; I + metazachlor; I + methiozolin; I + metolachlor; I + metosulam; I + metribuzin; I + metsulfuron; I + napropamide; I +nicosulfuron; I + norflurazon; I + oxadiazon; I + oxasulfuron; I + oxyfluorfen; I + paraquat dichloride; I + pendimethalin; I + penoxulam; I + fenmedifam; I + picloram; I + pinoxaden; I + pretilachlor; I + primisulfuron-methyl; I + promethrin; I + propanil; I + propaquizafop; I + propyrisulfuron; I + propyzamide; I + prosulfocarb; I + prosulfuron; I + pyraclonil; I + pyraflufen (including pyraflufen-ethyl); I + pyrazosulfuron; I + pyridate; I + pyriftalid; I + pyrimisulfan; I + pyroxasulfone; I + pyroxasulam; I + cinchonachlor; I + cinmethylin;I + Cascade hops (including Cascade hop P ethyl and Cascade-P-tefuryl); I + rimsulfuron; I + thiafenox; I + cythioate; I + simazine; I + S-metolachlor; I + sulfentrazone; I + sulfosulfuron; I + tebuthiuron; I + tefuryltrione; I + tembotrione; I + terbuthylazine; I + terbutryn; I + tetflupyrolimet; I + thienecarbazone; I + thifensulfuron; I + thiafenox; I + toprorate; I + topramezone; I + tralocymox; I + triafamone; I + triazamate; I + triasulfuron; I + tribenuron (including tribenuron-methyl); I + triclopyr; I + trifloxysulfuron (including trifloxysulfuron-sodium); I + triflumizox; I + trifluralin; I + triflusulfuron; I + ethyl 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-carboxylate; I + 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; I + 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; I + 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; I + 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; I + 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one; I + (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one; I + 3-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione; I + 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1,3-dione;I + 2 - [2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]cyclohexane-1,3-dione; I + 2 - [2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione; I + 6 - [2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione; I + 2 - [2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5-ethyl-cyclohexane-1,3-dione; I + 2 - [2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-4,4,6,6-tetramethyl-cyclohexane-1,3-dione; I + 2 - [6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1,3-dione; I + 3 - [6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione; I + 2 - [6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione; I + 6 - [6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione; I + 2 - [6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]cyclohexane-1,3-dione; I + 4 - [2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione; I + 4 - [6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione;I+4-Amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid (including its agrochemically acceptable esters, such as methyl 4-amino-3-chloro-5-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); I+3-Ethylsulfanyl-N-(1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide; I+3-(Isopropylsulfanylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide; I+3-(Isopropylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide; I+3-(Ethylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide; I+Ethyl 2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]acetate; I+6-Chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one;It contains I+1-[2-chloro-6-(5-chloropyrimidin-2-yl)oxy-phenyl]-4,4,4-trifluoro-butan-1-one and I+5-[2-chloro-6-(5-chloropyrimidin-2-yl)oxy-phenyl]-3-(difluoromethyl)isoxazole. The mixing partner of the compound of formula (I) may also be in the form of an ester or a salt, for example, as mentioned in The Pesticide Manual, Fourteenth Edition, British Crop Protection Council, 2006.;

[0153] The compound of formula (I) can also be used in a mixture with other pesticides such as fungicides, nematicides or insecticides, examples of which are shown in The Pesticide Manual.

[0154] The mixing ratio of the compound of formula (I) to the mixing partner is preferably 1:100 to 1000:1.

[0155] The mixture can advantageously be used in the above-mentioned formulations (in which case, the "active ingredient" relates to each mixture of the compound of formula (I) with the mixing partner).

[0156] The compound of formula (I) of the present invention can also be combined with a herbicide safener. Preferred combinations (where "I" represents the compound of formula (I)) include I+benoxacor, I+cloquintocet (including cloquintocet-methyl); I+cyprosulfamide; I+dichlormid; I+fenchlorazole (including fenchlorazole-ethyl); I+fenclorim; I+flurioxyphen; I+furilazole I+isoxadifen (including isoxadifen-ethyl); I+mefenpyr (including mefenpyr-diethyl); I+metcamifene and I+oxabetrinil.

[0157] Particularly preferred are mixtures of the compounds of formula (I) with cyprosulfamide, isoxadifen (including isoxadifen-ethyl), clomazone (including clomazone-methyl) and / or N-(2-methoxybenzoyl)-4-[(methyl-aminocarbonyl)amino]benzenesulfonamide.

[0158] The toxicity alleviating agent of the compound of formula (I) may also be in the form of an ester or a salt, for example, as mentioned in The Pesticide Manual, 14 th Edition (BCPC), 2006. The reference to clomazone-methyl also applies to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as disclosed in WO 02 / 34048 pamphlet, and the reference to fenchlorazole-ethyl also applies to fenchlorazole, etc.

[0159] Preferably, the mixing ratio of the compound of formula (I) to the toxicity alleviating agent is from 100:1 to 1:10, in particular from 20:1 to 1:1.

[0160] The compound of formula (I) can also be used in mixtures with other agrochemicals, such as fungicides, nematicides or insecticides, examples of which are given in the Pesticide Manual.

[0161] The mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1:100 to 1000:1.

[0162] The mixture can advantageously be used in the above formulations (in this case, the "active ingredient" relates to each mixture of the compound of formula I and the mixing partner).

[0163] The present invention further provides a method for selectively controlling weeds in a habitat containing crops and weeds, the method comprising applying to the habitat a composition according to the invention in an amount effective to control weeds. "Controlling" means killing, reducing or delaying growth, or preventing or reducing germination. Generally, the plants to be controlled are unwanted plants (weeds). "Habitat" means an area where plants are growing or will grow.

[0164] 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 furrows; no tillage application, etc.), the crop, the weeds to be controlled, the general climatic conditions, and other factors depending on the method of application, the time of application and the target crop. The compounds of formula I according to the invention are generally applied at a rate of from 10 to 2000 g / ha, in particular from 50 to 1000 g / ha.

[0165] The application is generally made by spraying the composition, typically by means of a sprayer attached to a tractor for large areas, but other methods such as dusting (for powders), drip or drench can also be used.

[0166] Useful plants on which the compositions according to the invention can be used include crops such as cereals, for example barley and wheat, cotton, rape, sunflower, maize, rice, soya beans, sugar beet, sugar cane and turf.

[0167] The crops can also include trees such as fruit trees, palm trees, coconut trees or other fruit-bearing trees. Vining plants such as grapes, fruit bushes, fruit plants and vegetables are also included.

[0168] It should be understood that crops include those that have been given resistance to herbicides or types of herbicides (e.g., ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD inhibitors) by conventional breeding methods or genetic recombination. An example of a crop given resistance to imidazolinones, such as imazamox, by conventional breeding methods is Clearfield® summer rape (canola). Examples of crops given resistance to herbicides by genetic recombination methods include, for example, glyphosate-resistant and glufosinate-resistant maize varieties marketed under the trade names RoundupReady® and LibertyLink®. In a particularly preferred embodiment, the crop is engineered to overexpress homogentisate solanesyltransferase, as taught in, for example, WO 2010 / 029311.

[0169] Crops may also be crops that have been given pest resistance by genetic engineering methods, such as Bt corn (resistant to the European corn borer), Bt cotton (resistant to the pink bollworm), and also Bt potato (resistant to the Colorado potato beetle). Examples of Bt corn are the Bt 176 corn hybrids of NK® (Syngenta Seeds). Bt toxins are proteins that are naturally formed by the soil bacterium Bacillus thuringiensis. Examples of toxins, or transgenic plants that can synthesize such toxins, are described in European Patent Application Publication No. A-451878, European Patent Application Publication No. A-374753, International Publication No. 93 / 07278 Pamphlet, International Publication No. 95 / 34656 Pamphlet, International Publication No. 03 / 052073 Pamphlet, and European Patent Application Publication No. A-427529. Examples of transgenic plants containing one or more genes that encode insecticide resistance and express one or more toxins are KnockOut® (corn), Yield Gard® (corn), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potato), NatureGard® and Protexcta®. Any plant crop or its seed material can be resistant to herbicides and at the same time resistant to insect feeding ("stacked transgenic events"). For example, the seeds can be resistant to glyphosate while having the ability to express the insecticidal Cry3 protein.

[0170] Crops may also include crops obtained by conventional breeding methods or genetic engineering that include so-called output traits (such as improved storage stability, higher nutritional value, and improved flavor).

[0171] Other useful plants include, for example, turfgrasses in golf courses, lawns, parks and along roadsides, or turfgrasses commercially cultivated for lawns, and ornamental plants such as flowers or shrubs.

[0172] The composition can be used to control unwanted plants (collectively, "weeds"). The weeds to be controlled include both monocotyledonous species such as Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria and Sorghum, and dicotyledonous species such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium. The weeds can also include plants that can be considered crops but grow outside the area of the crop ("escape"), or plants that grow from seeds left from a previously planted different crop ("volunteer"). Such volunteers or escapes can be resistant to certain other herbicides.

[0173] Here, various aspects and embodiments of the present invention are illustrated in more detail by way of example. It will be understood that modifications to the details may be made without departing from the scope of the present invention. Another aspect of the present invention may be as follows. 〔1〕A compound of formula (I)

Chemical formula

Chem.

Chem.

Chem.

Chem.

Chem.

[10] above.

[12] The compound according to any one of [1] to

[11] above, wherein D is a substituted or unsubstituted monocyclic heteroaryl ring. 〔13〕The compound according to any one of 〔1〕 to 〔11〕, wherein D is a substituted or unsubstituted phenyl ring. 〔14〕W is W1, and each of R 10 、R11 、R 12 , and R 13 is hydrogen, the compound according to any one of 〔1〕 to 〔13〕. 〔15〕W is W2, and each of R 14 and R 15 is hydrogen, the compound according to any one of 〔1〕 to 〔13〕. 〔16〕The compound according to any one of 〔1〕 to 〔13〕, wherein W is W3. 〔17〕A herbicidal composition comprising the herbicidal compound according to any one of 〔1〕 to 〔16〕 and an agriculturally acceptable formulation adjuvant. 〔18〕The herbicidal composition according to 〔17〕, further comprising at least one additional pest control agent. 〔19〕The herbicidal composition according to 〔18〕, wherein the additional pest control agent is a herbicide or a herbicide mitigator. 〔20〕A method for controlling unwanted plant growth, comprising applying the compound of formula (I) according to any one of 〔1〕 to 〔16〕 or the herbicidal composition according to any one of 〔17〕 to 〔19〕 to the unwanted plant or its location. 〔21〕Use of the compound of formula (I) according to any one of 〔1〕 to 〔16〕 as a herbicide.

[0174] Typical abbreviations used in this specification include the following. br = broadened t Bu = tert-butyl d = doublet dba = dibenzylideneacetone DCM = dichloromethane DMSO = dimethyl sulfoxide DPPA = diphenylphosphoryl azide Et 2 O = diethyl ether EtOAc = ethyl acetate h = hour m = multiplicity Me = methyl MeOH = methanol Ph = phenyl i Pr = isopropyl rt = room temperature s = singlet t = triplet THF = tetrahydrofuran

Examples

[0175] Example 1 Preparation of 4-[3-chloro-6-fluoro-2-[2-(4-biphenylyl)ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.027)

Chemical formula

Chemical formula

[0176] 1.2 2-(2-Bromo-3-chloro-6-fluoro-phenyl)acetic acid A solution of 3-allyl-2-bromo-1-chloro-4-fluoro-benzene (15.0 g, 60.1 mmol) in dichloromethane (200 mL) in a two-necked flask was cooled to -78 °C. One side arm was connected to a trap containing an aqueous solution of KI. Ozone was bubbled through the solution until the starting material was completely consumed (5 h). Air was bubbled through the solution for 10 min to remove excess ozone. Dimethyl sulfide (44 mL, 601 mmol) was added and the mixture was warmed to room temperature. The reaction was continued at room temperature for 16 h.

[0177] The mixture was washed with brine (2 × 100 mL) and the organic layer was retained. The organics were dried over Na 2 SO 4 and filtered, concentrated under reduced pressure to give crude 2-(2-bromo-3-chloro-6-fluoro-phenyl)acetaldehyde (15.3 g), which was used for the next step without further purification.

[0178] Crude 2-(2-bromo-3-chloro-6-fluoro-phenyl)acetaldehyde (15.3 g, 60.8 mmol) was dissolved in a mixture of tert-butanol (92 mL) and water (46 mL), then cooled to 0 °C. 2-Methylbut-2-ene (64.5 mL, 608 mmol), sodium dihydrogen phosphate (34.6 g, 243 mmol) and sodium chlorite (16.5 g, 163 mmol) were added. The mixture was stirred for 2 h, then diluted with brine (150 mL) and 2 M hydrochloric acid (150 mL). The mixture was extracted with ethyl acetate (3 × 100 mL). The combined organic extracts were washed with a saturated aqueous solution of sodium metabisulfite (100 mL), then dried over Na 2 SO 4 filtered, concentrated under reduced pressure to give a pale yellow solid. The crude solid was dissolved in a mixture of water (100 mL) and 2.0 M NaOH (30 mL). The aqueous solution was washed with ethyl acetate (100 mL) and the organics were discarded. The aqueous layer was acidified by adding concentrated hydrochloric acid (20 mL), resulting in the formation of a white suspension. The mixture was extracted with ethyl acetate (3 × 200 mL). The combined organics were washed with brine and dried over Na 2 SO4 It was dried, filtered, evaporated, and 2-(2-bromo-3-chloro-6-fluoro-phenyl)acetic acid (8.0 g, 49%) was obtained as a white solid.

Chemical formula

[0179] 1.3 2-(2-Bromo-3-chloro-6-fluoro-phenyl)-N-methyl-acetohydrazide To a stirred solution of 2-(2-bromo-3-chloro-6-fluoro-phenyl)acetic acid (2.0 g, 7.5 mmol) in dichloromethane (20 ml) at 0 °C, N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride [EDC·HCl] (1.4 g, 9.0 mmol) was added, followed by dropwise addition of methylhydrazine (0.4 ml, 7.5 mmol). The temperature of the reaction mixture was maintained at 0 °C for 3 hours. Then, the reaction was quenched with water and extracted into dichloromethane. The organic layer was separated, washed with brine, and dried over Na 2 SO 4 It was dried over. By concentration under reduced pressure, crude 2-(2-bromo-3-chloro-6-fluoro-phenyl)-N-methyl-acetohydrazide (1.8 g, 81%) was obtained and used in the next step without further purification.

Chemical formula

[0180] 1.4 Ethyl 2-{[2-(2-bromo-3-chloro-6-fluoro-phenyl)-acetyl]-methyl-hydrazono}-propionate To a stirred solution of 2-(2-bromo-3-chloro-6-fluoro-phenyl)-N-methyl-acetohydrazide (1.8 g, 6.09 mmol) in ethanol (5 ml) was added ethyl pyruvate (0.7 ml, 6.7 mmol) dropwise. The reaction was heated at 80 °C for 4 h. Then the reaction mixture was cooled to room temperature and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel (eluent, gradient of ethyl acetate / hexane) to afford the desired compound ethyl 2-{[2-(2-bromo-3-chloro-6-fluoro-phenyl)-acetyl]-methyl-hydrazono}-propionate (1.8 g, 75%) as an off-white solid. [Chemical formula] 1 H NMR (400 MHz, CDCl 3 ) δ H : 7.40 - 7.35 (m, 1H), 7.04 - 6.98 (m, 1H), 4.32 (q, J = 7.1, 2H), 4.24 (s, 2H), 3.41 (s, 3H), 2.32 (s, 3H), 1.36 (t, J = 7.1, 3H).

[0181] 1.5 4-(2-Bromo-3-chloro-6-fluoro-phenyl)-5-hydroxy-2,6-dimethyl-pyridazin-3-one Ethyl 2-{[2-(2-bromo-3-chloro-6-fluoro-phenyl)-acetyl]-methyl-hydrazono}-propionate (500 mg, 1.27 mmol) was dissolved in acetonitrile (2.5 ml) and treated with 1,8-diazabicyclo[5.4.0]undec-7-ene [DBU] (0.47 ml, 3.2 mmol). The mixture was heated to 125 °C using microwave irradiation for 1 h. Then the reaction mixture was evaporated under reduced pressure. The residue was dissolved in water and acidified to pH 1 with 2N hydrochloric acid. The mixture was extracted with DCM, the organic layer was separated and washed with brine solution. The organic solution was dried over Na 2 SO4 It was dried above, concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel (eluent, gradient of ethyl acetate / hexane), and 4-(2-bromo-3-chloro-6-fluoro-phenyl)-5-hydroxy-2,6-dimethyl-pyridazin-3-one (340 mg, 77.1%) was obtained as an off-white solid.

Chemical formula

[0182] 1.6 [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate To a stirred solution of 4-(2-bromo-3-chloro-6-fluoro-phenyl)-5-hydroxy-2,6-dimethyl-pyridazin-3-one (1.4 g, 4.02 mmol) in dichloromethane (32 ml) were added triethylamine (1.1 ml, 8.06 mmol), 4-(dimethylamino)pyridine [DMAP] (49 mg, 0.40 mmol) and isobutyryl chloride (0.6 ml, 4.83 mmol) at room temperature.

[0183] When judged to be complete, the reaction mixture was diluted with dichloromethane and water. The organic layer was separated, dried over Na 2 SO 4 and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel (eluent, gradient of ethyl acetate / hexane) to obtain [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (1.47 g, 87%).

Chemical formula

[0184] 1.7 4-[3-Chloro-6-fluoro-2-[(E)-2-(4-biphenylyl)vinyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-2.027) [5-(2-Bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (0.54 g, 1.3 mmol), K 2 CO 3 (0.55 g, 3.9 mmol), trans-2-(4-biphenylyl)vinylboronic acid (0.44 g, 2.00 mmol), PdCl 2 (dppf).DCM (53 mg, 0.065 mmol), 1,4-dioxane (13 ml) and H 2 O (3.3 mL) were combined in a 20 mL microwave vial and then heated at 140 °C for 30 minutes under microwave irradiation.

[0185] The reaction mixture was concentrated in vacuo to remove 1,4-dioxane and then partitioned between 2N HCl (aqueous solution) and DCM. The organic layer was separated and the aqueous layer was extracted with further portions of DCM (×2). The combined organics were concentrated in vacuo to give a crude residue which was purified by column chromatography on silica gel (eluent, gradient of ethyl acetate / hexane) to afford 4-[3-chloro-6-fluoro-2-[(E)-2-(4-biphenylyl)vinyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (343 mg, 53%, A-2.027)) as a yellow foam.

Chemical Structure

[0186] 1.8 4-(3-Chloro-6-fluoro-2-phenethyl-phenyl)-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.027) To a 10 mL round bottom flask was added 5% Pd / C (73 mg, 0.034 mmol), followed by a 10:1 (v / v) DCM / MeOH (4 mL) solution of 4-[3-chloro-6-fluoro-2-[(E)-2-(4-phenylphenyl)vinyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (308 mg, 0.69 mmol). Then, B 2 (OH) 4 (325 mg, 3.45 mmol) was added and the reaction mixture was stirred overnight at room temperature.

[0187] The reaction mixture was then filtered through Celite® eluting with 10:1 (v / v) DCM / MeOH. The filtrate was dried onto silica and purified by column chromatography on silica gel (eluent, gradient of ethyl acetate / hexane) to afford 4-[3-chloro-6-fluoro-2-[2-(4-phenylphenyl)ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (299 mg, 97% yield, A-1.027) as a yellow oil which solidified on standing.

Chemical Structure

[0188] Example 2 Preparation of 4-[2-[6-chloro-3-fluoro-2-(5-hydroxy-2,6-dimethyl-3-oxo-pyridazin-4-yl)phenyl]ethyl]benzonitrile (A-1.036) [Chemical formula] 2.1 [5-[3-chloro-2-[(E)-2-(4-cyanophenyl)vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (4.036) [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (1.10 g, 2.63 mmol) [prepared as described in Example 1] and chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II) (68 mg, 0.13 mmol) were combined in degassed toluene (12 mL). Then, 4-vinylbenzonitrile (408 mg, 3.16 mmol) and Hunig's base (0.92 mL, 5.27 mmol) were added, and the reaction mixture was heated to 95 °C for 2.5 hours.

[0189] The reaction mixture was cooled to room temperature, then diluted with dichloromethane, filtered through celite, and washed with additional dichloromethane. The filtrate was concentrated in vacuo and then purified by column chromatography on silica gel (eluent, gradient of ethyl acetate / hexane) to give [5-[3-chloro-2-[(E)-2-(4-cyanophenyl)vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (781 mg, 64% yield, A-4.036) as a white solid. [Chemical formula] 11H NMR (400 MHz, chloroform) δ = 7.62 - 7.55 (m, 2H), 7.45 (dd, J = 5.0, 8.5 Hz, 1H), 7.45 - 7.40 (m, 1H), 7.13 (d, J = 16.5 Hz, 1H), 7.05 (t, J = 8.5 Hz, 1H), 6.68 (d, J = 16.5 Hz, 1H), 3.69 (s, 3H), 2.65 (spt, J = 7.0 Hz, 1H), 2.23 (s, 3H), 1.11 (d, J = 7.0 Hz, 3H), 1.07 (d, J = 7.0 Hz, 3H).

[0190] 2.2 [5-[3-Chloro-2-[2-(4-cyanophenyl)ethyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (A-3.036) [5-[3-Chloro-2-[(E)-2-(4-cyanophenyl)vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (900 mg, 1.93 mmol) was subjected to catalytic hydrogenation in EtOAc (20 mL) over 5% Pd / C (50% wet) catalyst (0.82 g) at 4 bar H 2 and.

[0191] After 1.5 hours, LC / MS indicated a complete reaction. The reaction mixture was filtered through a pad of Celite® and washed with ethyl acetate. The filtrate was concentrated in vacuo to give a crude residue.

[0192] The residue was adsorbed onto silica and purified by column chromatography on silica gel (eluent, gradient of ethyl acetate / hexane) to give [5-[3-chloro-2-[2-(4-cyanophenyl)ethyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (800 mg, 81% yield, A-3.036) as a white solid.

Chemical Structure

[0193] 2.3 4-[2-[6-Chloro-3-fluoro-2-(5-hydroxy-2,6-dimethyl-3-oxo-pyridazin-4-yl)phenyl]ethyl]benzonitrile (A-1.036) [5-[3-Chloro-2-[2-(4-cyanophenyl)ethyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (400 mg, 0.855 mmol) was dissolved in ethanol (6 mL). The mixture was treated with an aqueous solution of lithium hydroxide (108 mg, 2.56 mmol) in water (2 mL). The reaction was stirred at room temperature for 2 hours.

[0194] The reaction mixture was concentrated in vacuo to remove ethanol. The remaining aqueous solution was diluted with water (15 mL), then acidified to about pH 3 with 2 M HCl and extracted with DCM (3 × 10 mL). The combined organics were dried over MgSO 4 and filtered, and concentrated in vacuo to give the crude product.

[0195] The crude product was purified by column chromatography on silica gel (eluent, gradient of ethyl acetate / hexane) to give 4-[2-[6-chloro-3-fluoro-2-(5-hydroxy-2,6-dimethyl-3-oxo-pyridazin-4-yl)phenyl]ethyl]benzonitrile (83 mg, 91% yield, A-1.036)) as a white solid.

Chemical Structure

[0196] Example 4 Preparation of 4-[2-[6-chloro-3-fluoro-2-(5-hydroxy-2,6-dimethyl-3-oxo-pyridazin-4-yl)phenyl]ethyl]-N-ethyl-2-fluoro-N-methyl-benzamide (A-1.028) [Chemical formula] 4.1 [5-[3-chloro-6-fluoro-2-[(E)-2-(6-methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-yl)vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (5.00 g, 11.97 mmol, 1.0 eq), 6-methyl-2-vinyl-1,3,6,2-dioxazaborocane-4,8-dione (2.63 g, 14.36 mmol, 1.2 eq) and chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II) (307 mg, 0.60 mmol, 0.05 eq) were charged into a 250 ml round bottom flask equipped with a condenser, stir bar and nitrogen bubbler. To the nitrogen stream, THF (100 mL) was added followed by N,N-diisopropylethylamine (4.2 mL, 23.94 mmol, 2.0 eq) and the mixture was heated to reflux for 3 h.

[0197] The reaction mixture was cooled to room temperature then diluted in DCM, filtered through Celite® and washed with further portions of DCM. The eluent was then concentrated to dryness.

[0198] The crude product was purified by flash column chromatography to obtain [5-[3-chloro-6-fluoro-2-[(E)-2-(6-methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-yl)vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (5.91 g, 11.4 mmol, 95% yield) as an off-white solid.

Chem.

[0199] 4.2 [5-[3-chloro-2-[2-[4-[ethyl(methyl)carbamoyl]-3-fluoro-phenyl]ethyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (A-3.028) [5-[3-chloro-6-fluoro-2-[(E)-2-(6-methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-yl)vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (500 mg, 0.96 mmol), K 3 PO 4(886 mg, 3.85 mmol) and 1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex [PdCl2(dppf).DCM] (39 mg, 0.05 mmol) were added to a 20 mL microwave vial. THF (10 mL), 4-bromo-N-ethyl-2-fluoro-N-methyl-benzamide (500 mg, 1.92 mmol) and water (0.35 mL) were added, and then the reaction mixture was heated to 100 °C for 2 hours under microwave irradiation.

[0200] The reaction mixture was concentrated in vacuo to remove THF, then diluted with water (20 mL) and DCM (20 mL). The organic layer was separated and the aqueous layer was extracted with DCM (3 × 5 mL). The combined organics were dried and concentrated in vacuo to give a crude residue, which was purified by column chromatography on silica gel eluting with a gradient of cyclohexane / ethyl acetate to give [5-[3-chloro-2-[(E)-2-[4-[ethyl(methyl)carbamoyl]-3-fluoro-phenyl]vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (397 mg, 76% yield, A-4.028) as an off-white solid.

[0201] [5-[3-chloro-2-[(E)-2-[4-[ethyl(methyl)carbamoyl]-3-fluoro-phenyl]vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (300 mg, 0.55 mmol) was subjected to catalytic hydrogenation in EtOAc (6 mL) over 5% Pd / C (50% wet) catalyst (0.12 g) at 3 bar H 2 for 5.5 hours. LC / MS indicated complete reaction after 5.5 hours. The reaction mixture was filtered through a pad of Celite® and washed with ethyl acetate / methanol. The filtrate was concentrated in vacuo to give a crude residue.

[0202] After 5.5 hours, LC / MS indicated complete reaction. The reaction mixture was filtered through a pad of Celite® and washed with ethyl acetate / methanol. The filtrate was concentrated in vacuo to give a crude residue.

[0203] The residue was adsorbed onto silica and purified by column chromatography on silica gel (eluent, gradient of ethyl acetate / hexane) to obtain [5-[3-chloro-2-[2-[4-[ethyl(methyl)carbamoyl]-3-fluoro-phenyl]ethyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (285 mg, 95% yield, A-3.028) as a colorless gum.

Chem.

[0204] 4.3 4-[2-[6-chloro-3-fluoro-2-(5-hydroxy-2,6-dimethyl-3-oxo-pyridazin-4-yl)phenyl]ethyl]-N-ethyl-2-fluoro-N-methyl-benzamide (A-1.028) [5-[3-Chloro-2-[2-[4-[Ethyl(methyl)carbamoyl]-3-fluoro-phenyl]ethyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (300 mg, 0.55 mmol) was dissolved in ethanol (3 mL). The mixture was treated with an aqueous solution of lithium hydroxide (69 mg, 1.65 mmol) in water (3 mL). The reaction was stirred at room temperature for 2 hours.

[0205] The reaction mixture was concentrated in vacuo to remove ethanol. The remaining aqueous solution was diluted with water (15 mL), then acidified to about pH 3 with 2 M HCl and extracted with DCM (3 × 10 mL). The combined organics were dried and concentrated in vacuo to give the crude product.

[0206] The crude product was purified by column chromatography on silica gel (eluent, gradient of DCM / methanol) to give 4-[2-[6-Chloro-3-fluoro-2-(5-hydroxy-2,6-dimethyl-3-oxo-pyridazin-4-yl)phenyl]ethyl]-N-ethyl-2-fluoro-N-methyl-benzamide (224 mg, 86% yield, A-1.028) as a white solid. [Chemical formula] [NMR of the mixture of rotational isomers] 1 H NMR (400 MHz, DMSO-d6) δ = 10.86 (br s, 1H), 7.55 - 7.49 (m, 1H), 7.25 - 7.19 (m, 2H), 6.95 - 6.89 (m, 2H), 3.61 (s, 3H), 3.46 (q, J = 7.1 Hz, 1H), 3.12 (q, J = 7.1 Hz, 1H), 2.95 (s, 1.5H), 2.78 (s, 1.5H), 2.78 - 2.63 (m, 4H), 2.26 (s, 3H), 1.11 (t, J = 7.1 Hz, 1.5H), 1.00 (t, J = 7.1 Hz, 1.5H).

[0207] Example 5 Preparation of [[5-[3-chloro-2-[(E)-2-(4-cyclopropylphenyl)vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (A-4.038)]] [Chemical formula] 5.1 [[5-(3-chloro-6-fluoro-2-vinyl-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate]] [[5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (4.177 g, 10.00 mmol, 1.0 equivalent) and tributyl(vinyl)stannane (4.384 mL, 15.00 mmol, 1.50 equivalents) were dissolved in toluene (60.00 mL), and then [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex [PdCl2(dppf).DCM] (408 mg, 0.50 mmol, 0.05 equivalent) was added. The reaction mixture was heated to reflux overnight.]]

[0208] The reaction mixture was cooled to room temperature and then concentrated in vacuo. The crude product was then purified by flash column chromatography to give [[5-(3-chloro-6-fluoro-2-vinyl-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate]] as an off-white solid (3.02 g, 83% yield).]] [Chemical formula] 1 H NMR (400 MHz, CDCl 3 ) δ = 7.40 (dd, J = 5.1, 8.7 Hz, 1H), 6.99 (t, J = 8.7 Hz, 1H), 6.65 (dd, J = 11.6, 17.6 Hz, 1H), 5.37 - 5.30 (m, 2H), 3.79 (s, 3H), 2.59 (spt, J = 7.0 Hz, 1H), 2.23 (s, 3H), 1.04 (d, J = 7.0 Hz, 4H), 1.03 (d, J = 7.0 Hz, 1H)]]

[0209] 5.2 [5-[3-Chloro-2-[(E)-2-(4-cyclopropylphenyl)vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (A-4.038) A stirred mixture of [5-(3-chloro-6-fluoro-2-vinyl-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (300 mg, 1.0 eq), chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II) (21 mg, 0.05 eq), 1-bromo-4-cyclopropylbenzene (243 mg, 1.5 eq) and N,N-diisopropylethylamine (0.29 mL, 2.0 eq) in toluene (5 mL) was heated to reflux under nitrogen for 3 h.

[0210] The reaction mixture was cooled to room temperature, then diluted with DCM and filtered through a pad of Celite eluting with further portions of DCM. The filtrate was concentrated in vacuo to afford the crude product.

[0211] The crude product was purified by flash column chromatography to afford [5-[3-chloro-2-[(E)-2-(4-cyclopropylphenyl)vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (285 mg, 72% yield) as a pale yellow gum.

Chemical Structure

[0212] Example 6 Preparation of 4-[3-chloro-6-fluoro-2-[2-(4-methylsulfanylphenyl)ethyl]-phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.039) [Chemical formula] 6.1 [5-[3-chloro-6-fluoro-2-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate Next, an oven-dried round-bottom flask was charged with Ir(COD)Cl 2 (299 mg, 0.45 mmol) and 4-diphenylphosphanylbutyl(diphenyl)phosphane (0380 mg, 0.89 mmol). The flask was evacuated and refilled with nitrogen (×3), then THF (75 mL) was added and the reaction was stirred at room temperature for 30 minutes. A THF solution of [5-(3-chloro-6-fluoro-2-vinyl-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate [prepared as described in Example 4] (6.7 g, 17.8 mmol) was added dropwise, the mixture was stirred for 10 minutes, followed by the dropwise addition of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.02 mL, 20.8 mmol). The reaction was stirred at 60 °C overnight.

[0213] After 24 hours, the reaction mixture was cooled to room temperature and then concentrated in vacuo. The crude product was purified by column chromatography on silica gel eluting with a cyclohexane / ethyl acetate gradient to afford [5-[3-chloro-6-fluoro-2-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (4.50 g, 51% yield) as a yellow solid.

Chemical formula

[0214] 6.2 4-[3-Chloro-6-fluoro-2-[2-(4-methylsulfanylphenyl)ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.039) [5-[3-Chloro-6-fluoro-2-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (100 mg, 0.20 mmol), 1-bromo-4-methylsulfanyl-benzene (62 mg, 0.30 mmol), chloro(2-dicyclohexylphosphino-2’,6’-diisopropoxy-1,1’-biphenyl)[2-(2’-amino-1,1’-biphenyl)]palladium(II) (24 mg, 0.03 mmol), K 2 CO 3(84 mg, 0.61 mmol), 1,4-dioxane (2 mL), and water (0.2 mL) were combined in a 5 mL microwave vial. The reaction mixture was then heated at 140 °C for 90 minutes under microwave irradiation.

[0215] The reaction mixture was cooled to room temperature, then diluted with water (10 mL), acidified to approximately pH 3 with 2 M HCl, and extracted with DCM (4×). The combined organics were concentrated in vacuo, and the crude product was purified by reverse-phase HPLC based on mass to give 4-[3-chloro-6-fluoro-2-[2-(4-methylsulfanylphenyl)ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one as a white solid (22 mg, 22% yield, A-1.039).

Chemical formula

[0216] Example 7 Preparation of 4-[3-chloro-6-fluoro-2-[2-[4-(methylsulfanylmethyl)phenyl]ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.388)

Chemical formula

[0217] The reaction mixture was concentrated to dryness. The residue was treated with water (20 ml), and the aqueous phase was acidified to pH 3 by the addition of 2 M HCl, resulting in the formation of a precipitate. DCM (20 ml) was added to dissolve the precipitate. Brine (20 ml) was added and the phases were separated. The aqueous phase was extracted with two further portions of DCM, and then the combined organic extracts were dried and concentrated directly onto silica. The crude material was purified by automated flash chromatography on silica gel eluting with a gradient of cyclohexane / ethyl acetate to give 4-[3-chloro-6-fluoro-2-[(E)-2-[4-(methylsulfanylmethyl)phenyl]vinyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (341 mg, 82% yield) as an off-white solid.

Chemical Structure

[0218] 7.2 4-[3-Chloro-6-fluoro-2-[2-[4-(methylsulfanylmethyl)phenyl]ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.388) To a solution of 4-[3-chloro-6-fluoro-2-[(E)-2-[4-(methylsulfanylmethyl)phenyl]vinyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (335 mg, 0.78 mmol) in tetrahydrofuran (12 ml) under a nitrogen atmosphere, N,N-diisopropylethylamine (1.08 ml, 6.20 mmol) was added. The stirred reaction mixture was heated to 70 °C, and 2,4,6-triisopropylbenzenesulfonyl hydrazide (2.06 g, 6.21 mmol) was added portionwise over 6 hours, and then the mixture was heated to reflux for 16 hours. A further amount of N,N-diisopropylethylamine (0.68 ml, 3.89 mmol) was added to the reaction mixture, followed by 2,4,6-triisopropylbenzenesulfonyl hydrazide (1.29 g, 3.89 mmol), and the mixture was heated to reflux for a further 6 hours.

[0219] The reaction mixture was cooled to room temperature and then concentrated directly onto silica. The crude material was partially purified by automated flash chromatography on silica gel eluting with a gradient of cyclohexane / ethyl acetate. The material obtained was further purified by reverse-phase HPLC based on mass to give 4-[3-chloro-6-fluoro-2-[2-[4-(methylsulfanylmethyl)phenyl]ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one as a white solid (208 mg, 62% yield, A-1.388). [Chemical formula] 11H NMR (400 MHz, d6-DMSO), δ = 10.83 (s, 1H), 7.56 - 7.53 (m, 1H), 7.23 - 7.16 (m, 3H), 6.96 - 6.94 (d, 2H), 3.62 (s, 2H), 3.60 (s, 3H), 2.68 - 2.54 (m, 4H), 2.26 (s, 3H), 1.92 (s, 3H)

[0220] Example 8 4-[3-Chloro-6-fluoro-2-[2-[4-(1,2,4-triazol-1-yl)phenyl]ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.385) [Chemical Structure] 8.1 [4-(1,2,4-Triazol-1-yl)phenyl]trifluoromethanesulfonate 4-(1,2,4-Triazol-1-yl)phenol (1.22 g, 7.57 mmol) was dissolved in dichloromethane (10 ml) under nitrogen and cooled to approximately 0 °C. A solution of pyridine (1.22 ml, 15.1 mmol) in dichloromethane (5 ml) was added dropwise over approximately 2 minutes. The mixture was stirred for 5 minutes, and then a solution of trifluoromethanesulfonic anhydride (1.53 ml, 9.08 mmol) in dichloromethane (5 ml) was added dropwise over approximately 2 minutes. The cooling was removed, the reaction mixture was warmed to room temperature, and then stirred at room temperature for 16 hours.

[0221] The reaction was quenched by adding 2 M aqueous HCl (20 ml), and then the organic phase was separated. The aqueous phase was further extracted with dichloromethane (2 × 20 ml). The combined organics were washed with water (20 ml), dried, and then concentrated under reduced pressure to give a cream-colored solid. The crude material was purified by automated flash chromatography on silica eluting with a gradient of cyclohexane / ethyl acetate to give [4-(1,2,4-triazol-1-yl)phenyl]trifluoromethanesulfonate as a white solid (2.02 g, 91% yield). [Chemical Structure] 1 1H NMR (400 MHz, chloroform) δ = 8.59 (s, 1H), 8.14 (s, 1H), 7.86 - 7.78 (m, 2H), 7.50 - 7.41 (m, 2H).

[0222] 8.2 [5-[3-Chloro-6-fluoro-2-[(E)-2-[4-(1,2,4-triazol-1-yl)phenyl]vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate [5-[3-Chloro-6-fluoro-2-[(E)-2-(6-methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-yl)vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (500 mg, 0.96 mmol), [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex [PdCl2(dppf).DCM] (39 mg, 0.048 mmol), [4-(1,2,4-triazol-1-yl)phenyl]trifluoromethanesulfonate (367 mg, 1.25 mmol) and potassium phosphate (834 mg, 3.85 mmol) were added to a 10 - 20 ml microwave vial.

[0223] Tetrahydrofuran (10 ml) and water (0.5 ml) were added, then the reaction mixture was degassed by stirring under vacuum and then refilled with nitrogen (×3). The reaction mixture was heated at 120 °C in the microwave for 60 minutes under microwave irradiation.

[0224] The reaction mixture was filtered through a plug of celite (registered trademark) and washed with EtOAc and EtOH. The filtrate was concentrated under reduced pressure to afford a brown gum (840 mg). The crude material was purified by automated flash chromatography on silica gel eluting with a cyclohexane / ethyl acetate gradient to afford a pale yellow gum (389 mg). The purified material was dissolved in acetonitrile (10 mL) and treated with SiliCycle SiliaMetS (registered trademark) thiol (SH) metal scavenger resin (365 mg) at room temperature. The suspension was stirred at room temperature for 3 h, then filtered to remove the resin and washed with additional acetonitrile. The filtrate was concentrated in vacuo to afford [5-[3-chloro-6-fluoro-2-[(E)-2-[4-(1,2,4-triazol-1-yl)phenyl]vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate as a colorless gum (361 mg, 73% yield).

Chemical Structure

[0225] 8.3 [5-[3-Chloro-6-fluoro-2-[2-[4-(1,2,4-triazol-1-yl)phenyl]ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (A-3.385) [5-[3-Chloro-6-fluoro-2-[(E)-2-[4-(1,2,4-triazol-1-yl)phenyl]vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (365 mg, 0.72 mmol) was placed in 3 bar of H 2It was subjected to catalytic hydrogenation in EtOAc (10 mL) over 5% Pd / C (50% wet) catalyst (0.15 g) for 24 hours.

[0226] The reaction mixture was filtered through a pad of Celite® and washed with ethyl acetate. The filtrate was concentrated in vacuo to give a crude residue (350 mg), which was adsorbed onto silica and purified by automated flash chromatography on silica gel eluting with a gradient of cyclohexane / ethyl acetate. [5-[3-Chloro-6-fluoro-2-[2-[4-(1,2,4-triazol-1-yl)phenyl]ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (A-3.385) was obtained as a colorless gum (321 mg, 88% yield).

Chemical formula

[0227] 8.4 4-[3-Chloro-6-fluoro-2-[2-[4-(1,2,4-triazol-1-yl)phenyl]ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.385) [5-[3-Chloro-6-fluoro-2-[2-[4-(1,2,4-triazol-1-yl)phenyl]ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (320 mg, 0.63 mmol) was stirred in ethanol (5 ml) at room temperature.

[0228] A solution of lithium hydroxide monohydrate (81 mg, 1.88 mmol) in water (2 ml) was added dropwise, and the reaction mixture was stirred at room temperature for 1 hour.

[0229] The ethanol solvent was removed under reduced pressure, and then the residue was diluted with water (20 ml). The aqueous phase was acidified to about pH 3 - 4 by adding 2 M HCl (aqueous solution), and then extracted with EtOAc (3 × 10 ml). The combined organic extracts were concentrated under reduced pressure to give a white solid (292 mg). The crude residue was purified by automated flash chromatography on silica eluting with a gradient of cyclohexane / ethyl acetate and ethyl acetate / ethanol to give 4-[3-chloro-6-fluoro-2-[2-[4-(1,2,4-triazol-1-yl)phenyl]ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.365) as a white solid (260 mg, 94% yield).

Chemical Structure

[0230] Example 9 4-[3-Cyclopropyl-6-fluoro-2-[2-(2-fluoropyridin-4-yl)ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (C-1.013) [5-[3-chloro-6-fluoro-2-[2-(2-fluoro-4-pyridyl)ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (250 mg, 0.54 mmol), tripotassium phosphate monohydrate (374 mg, 1.62 mmol) and RuPhos Pd G2 (42 mg, 0.05 mmol) were charged into a 2-5 ml microwave vial equipped with a stir bar. The reaction vessel was evacuated and refilled with nitrogen (×3). 1,4-dioxane (4 ml) was added, followed by cyclopropylboronic acid (139 mg, 1.62 mmol) and water (1 ml) (both solvents were degassed). The mixture was then heated to 120 °C for 1 hour under microwave irradiation.

[0231] The reaction was cooled to room temperature, then additional cyclopropylboronic acid (139 mg, 1.62 mmol) and RuPhos Pd G2 (42 mg, 0.05 mmol) were added and the reaction was heated to 120 °C for an additional 2.5 hours. The reaction mixture was concentrated in vacuo to remove dioxane. The residue was diluted with water (20 ml) and DCM (20 mL) and the layers were separated. The aqueous phase was extracted with additional portions of DCM (3 × 5 ml), then the combined organic extracts were dried, concentrated to afford a dark-colored solid (331 mg).

[0232] The crude residue was purified by reverse-phase HPLC based on mass to afford 4-[3-cyclopropyl-6-fluoro-2-[2-(2-fluoro-4-pyridyl)ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (C-1.013) as a white solid. [Chemical Structure] 11H NMR (400 MHz, methanol) δ = 8.01 (d, J = 5.1 Hz, 1H), 7.13 (dd, J = 5.6, 8.3 Hz, 1H), 7.02 - 6.93 (m, 2H), 6.72 (br s, 1H), 3.72 (s, 3H), 3.02 - 2.75 (m, 4H), 2.32 (s, 3H), 1.97 - 1.87 (m, 1H), 1.02 - 0.89 (m, 2H), 0.74 - 0.61 (m, 2H)

[0233] Compounds A-1.023, A-1.024, A-1.025, A-1.026, A-1.027, A-1.028, A-1.029, A-1.030, A-1.031, A-1.032, A-1.033, A-1.034, A-1.035, A-1.036, A-1.037, A-1.038, A-1.039, A-1.040, A-1.041, A-1.042, A-1.043, A-1.044, A-2.027, A-2.030, A-2.037, A-3.028, A-3.029, A-3.030, A-3.035, A-3.036, A-3.038, A-4.029, A-4.030, A-4.035, A-4.036, A-1.373, A-1.374, A-1.375, A-1.376, A-1.377, A-1.378, A-1.379, A-1.380, A-1.381, A-1.382, A-1.383, A-1.384, A-1.386, A-1.387, A-1.389, A-1.390, A-1.391 and A-1.392 were prepared using the general method as described above. Table 4 below shows the structures and NMR characterization data of these compounds.

[0234]

Table 4-1

Table 4-2

Table 4-3

Table 4-4

Table 4-5

Table 4-6

Table 4-7

Table 4-8

Table 4-9

Table 4-10

Table 4-11

Table 4-12

Table 4-13

Table 4-14

Table 4-15

Table 4-16

Table 4-17

[0235] Effectiveness after B1 budding - Test 1 Seeds of various test species are sown in standard soil in pots: Solanum nigrum (SOLNI), Amaranthus retoflexus (AMARE), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE), Lolium perenne (LOLPE). Eight days after cultivation (after germination) under controlled conditions in a greenhouse (24 / 16 °C, day / night; 14 hours of lighting; 65% humidity), a spray aqueous 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) is sprayed onto the plants. The compound is applied at 1000 g / ha. The test plants are then grown in the greenhouse under controlled conditions (24 / 16 °C, day / night; 14 hours of lighting; 65% humidity) in the greenhouse and watered twice a day. After 13 days, the test is evaluated for the percentage of damage inflicted on the plants. The biological activity is assessed on a 5-point scale (5 = 80 - 100%; 4 = 60 - 79%; 3 = 40 - 59%; 2 = 20 - 39%; 1 = 0 - 19%). The blank value in the table indicates that the compound was not tested on that species.

[0236]

Table 5

[0237] B2 Efficacy after germination - Test 2 Seeds of various test species are sown in standard soil in pots: Black nightshade (Solanum nigrum) (SOLNI), Redroot pigweed (Amaranthus retroflexus) (AMARE), Giant foxtail (Setaria faberi) (SETFA), Barnyard grass (Echinochloa crus-galli) (ECHCG), Ivy-leaved morning glory (Ipomoea hederacea) (IPOHE), Perennial ryegrass (Lolium perenne) (LOLPE). After 8 days of cultivation (after germination) in a greenhouse under controlled conditions (24 / 16 °C, day / night; 14 hours of lighting; 65% humidity), a spray aqueous solution derived from a formulation of industrial active ingredients in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5) is sprayed onto the plants. The compound is applied at 250 g / ha. The test plants are then grown in the greenhouse under controlled conditions (24 / 16 °C, day / night; 14 hours of lighting; 65% humidity) in the greenhouse and watered twice a day. After 13 days, the test is evaluated for the percentage of damage caused to the plants. Biological activity is evaluated on a 5-point scale (5 = 80 - 100%; 4 = 60 - 79%; 3 = 40 - 59%; 2 = 20 - 39%; 1 = 0 - 19%). Empty test values in the table indicate that the compound was not tested for the corresponding species.

[0238]

Table 6

[0239] B3 Efficacy after germination - Test 3 Seeds of various test species are sown in standard soil in pots: - Amaranthus retoflexus (AMARE), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE), Zea mays (ZEAMX), Abutilon theophrasti (ABUTH). After 8 days of cultivation (after germination) in a greenhouse under controlled conditions (24 / 16 °C, day / night; 14 hours of lighting; 65% humidity), a spray aqueous solution derived from a formulation of the industrial active ingredient in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5) is sprayed onto the plants. The compound is applied at 250 g / ha. Then, the test plants are grown in the greenhouse under controlled conditions (24 / 16 °C, day / night; 14 hours of lighting; 65% humidity) in the greenhouse, and watered twice a day. After 13 days, the test is evaluated for the percentage of damage inflicted on the plants. The biological activity is assessed on a 5-point scale (5 = 80 - 100%; 4 = 60 - 79%; 3 = 40 - 59%; 2 = 20 - 39%; 1 = 0 - 19%). The blank values in the table indicate that the compound was not tested on that species.

[0240]

Table 7

[0241] B4 Pre-emergence efficacy - Test 1 Seeds of various test species were sown in standard soil in pots: black nightshade (Solanum nigrum) (SOLNI), redroot pigweed (Amaranthus retroflexus) (AMARE), giant foxtail (Setaria faberi) (SETFA), barnyard grass (Echinochloa crus-galli) (ECHCG), ivy-leaved morning glory (Ipomoea hederacea) (IPOHE), perennial ryegrass (Lolium perenne) (LOLPE). After one day of cultivation (before germination) in a greenhouse under controlled conditions (24 / 16 °C, day / night; 14 hours of lighting; 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 1000 g / ha. The test plants were then grown in the greenhouse under controlled conditions (24 / 16 °C, day / night; 14 hours of lighting; 65% humidity) and watered twice a day. After 13 days, the test was evaluated for the percentage of damage inflicted on the plants. The biological activity was assessed on a 5-point scale (5 = 80 - 100%; 4 = 60 - 79%; 3 = 40 - 59%; 2 = 20 - 39%; 1 = 0 - 19%). The blank values in the table indicate that the compound was not tested on that species.

[0242]

Table 8

[0243] B5 Efficacy before germination - Test 2 Seeds of various test species were sown in standard soil in pots: Black Nightshade (Solanum nigrum) (SOLNI), Redroot Pigweed (Amaranthus retroflexus) (AMARE), Giant Foxtail (Setaria faberi) (SETFA), Barnyard Grass (Echinochloa crus-galli) (ECHCG), Ivy-leaved Morning Glory (Ipomoea hederacea) (IPOHE), Perennial Ryegrass (Lolium perenne) (LOLPE). After 1 day of cultivation (before germination) in a greenhouse under controlled conditions (24 / 16 °C, day / night; 14 hours of lighting; 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 / ha. The test plants were then grown in the greenhouse under controlled conditions (24 / 16 °C, day / night; 14 hours of lighting; 65% humidity) and watered twice a day. After 13 days, the test was evaluated for the percentage of damage inflicted on the plants. The biological activity was assessed on a 5-point scale (5 = 80 - 100%; 4 = 60 - 79%; 3 = 40 - 59%; 2 = 20 - 39%; 1 = 0 - 19%). The blank values in the table indicate that the compound was not tested for that species.

[0244]

Table 9

[0245] B6 Efficacy before germination - Test 3 Seeds of various test species were sown in standard soil in pots: Amaranthus retoflexus (AMARE), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE), Zea mays (ZEAMX), Abutilon theophrasti (ABUTH). After one day of cultivation (before germination) in a greenhouse under controlled conditions (24 / 16 °C, day / night; 14 hours of lighting; 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 / ha. The test plants were then grown in the greenhouse under controlled conditions (24 / 16 °C, day / night; 14 hours of lighting; 65% humidity) and watered twice a day. After 13 days, the test was evaluated for the percentage of damage inflicted on the plants. The biological activity was assessed on a 5-point scale (5 = 80 - 100%; 4 = 60 - 79%; 3 = 40 - 59%; 2 = 20 - 39%; 1 = 0 - 19%). The blank values in the table indicate that the compound was not tested on that species.

[0246]

Table 10

Claims

1. A compound of formula (I) 【Chemistry 1】 or an agriculturally acceptable salt or N-oxide thereof [In the formula, R 1 is C 1 ~C 4 Alkyl, C 3 ~C 6 Cycloalkyl, C 3 ~C 6 Alkoxy, C 1 ~C 2 Alkoxy-C 1 ~C 2 Alkyl, C 2 ~C 4 Alkenyl, C 1 ~C 4 Haloalkyl, Cyano-C 1 ~C 4 Alkyl, C 2 ~C 4 Haloalkenyl, C 2 ~C 4 Alkynyl and C 2 ~C 4 haloalkynyl; R 2 is hydrogen, halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 3 Haloalkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 6 Alkoxy, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 3 ~C 6 Cycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 6 Hydroxyalkyl-, C 1 ~C 6 Alkylcarbonyl-, -S(O) m C 1 ~C 6 Alkyl, Amino, C 1 ~C 6 Alkylamino, C 1 ~C 6 Dialkylamino, -C(C 1 ~C 3 alkyl)=N-O-C 1 ~C 3 Alkyl and C 2 ~C 6 haloalkynyl; G is hydrogen or C(O)R 3 and R 3 is C 1 ~C 6 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 6 Alkyl-S-, C 1 ~C 6 Alkoxy, -NR 4 R 5 and one or more R 6 phenyl optionally substituted with; Each R 4 and R 5 is hydrogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, and C 3 ~C 6 cycloalkyl; or R 4 and R 5 can be taken together to form a morpholinyl ring; Each R 4a and R 5a is C 1 ~C 6 Alkoxy, and C 3 ~C 6 cycloalkyl; or R 4a and R 5a can be taken together to form a morpholinyl ring; R 6 is halogen, cyano, nitro, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy and C 1 ~C 3 haloalkoxy; X and Y are each independently hydrogen, C 1 ~C 3 Alkyl, cyclopropyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 Haloalkyl, C 1 ~C 3 haloalkoxy, or halogen; D is R on at least one ring carbon atom. 8 and / or substituted on at least one ring nitrogen atom with R 9 is a substituted monocyclic heteroaryl ring containing 1, 2, or 3 heteroatoms independently selected from oxygen, nitrogen, and sulfur, substituted with At least one R 8 is C 1 ~C 6 Haloalkylcarbonyl-, C 3 ~C 6 Cycloalkylcarbonyl-, -S(O) m -C 1 ~C 6 Haloalkyl, -S(O) m -C 3 ~C 6 Cycloalkyl, -O-S(O) 2 C 1 ~C 3 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Haloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 3 ~C 6 Cycloalkyl, cyano-C 1 ~C 6 -Alkyl-, -NR 4a R 5a , -C(S)NR 4 R 5 , -S(O) 2 NHC(O)C 1 ~C 3 Alkyl, -S(O) 2 N.R. 4 R 5 , -C(O)OH, -C(O)OC 1 ~C 6 Alkyl, -C(O)NHS-(O) 2 C 1 ~C 6 Alkyl, —C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5 , C 1 ~C 6 Alkylcarbonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Haloalkylcarbonylamino-, C 1 ~C 6 Haloalkylcarbonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Alkylsulfonylamino-, C 1 ~C 6 Alkyl sulfonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Haloalkylsulfonylamino-, C 1 ~C 6 Haloalkylsulfonyl (C 1 ~C 6 alkyl)amino-, C 3 ~C 6 Cycloalkylsulfonylamino-, C 3 ~C 6 Cycloalkylsulfonyl (C 1 ~C 6 alkyl)amino-, hydroxyamino-, hydroxy(C 1 ~C 6 alkyl)amino, C 1 ~C 6 Alkoxyamino, C 1 ~C 6 Alkoxy (C 1 ~C 6 alkyl)amino, C 1 ~C 6 Haloalkoxyamino, C 1 ~C 6 Haloalkoxy (C 1 ~C 6 and a ring system selected from the group consisting of a phenyl ring, a 5-6 membered heteroaryl ring, and a 3-6 membered heterocyclyl ring, said ring system being selected from the group consisting of 0-5 R 16 is substituted with; At least one R 9 is C 5 ~C 6 Alkyl, C 5 ~C 6 Haloalkyl, C 3 ~C 6 -Cycloalkyl, C 1 ~C 3 Alkoxy-C 3 Alkyl-, C 3 Alkoxy-C 1 ~C 2 Alkyl-, C 1 ~C 3 Haloalkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 6 Hydroxyalkyl-, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Haloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 3 ~C 6 Cycloalkyl, cyano-C 1 ~C 6 -alkyl- and a ring system selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclyl ring, said ring system being selected from the group consisting of 0-5 R 16 is substituted with; m is an integer of 0, 1, or 2; Each R 16 are independently halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Alkoxy or C 1 ~C 6 is haloalkoxy; Alternatively, D is at least one R 8 is a phenyl ring substituted with; W is a group of the formula 【Chemistry 2】 wherein: "a" represents the point of attachment to the phenyl-pyridazinedione / phenyl-pyridazinone moiety; "b" represents the point of attachment to ring D; R 10 , R 12 , R 14 and R 15 are each independently hydrogen, C 1 ~C 3 Alkyl, or C 1 ~C 3 haloalkyl; Or R 10 and R 12 together with the carbon atom to which they are attached, C 3 ~C 6 forming a carbocyclic ring; R 11 and R 13 are each independently hydrogen, halogen, or C 1 ~C 3 Alkyl, or C 1 ~C 3 haloalkyl; However, R 11 Or R 13 One of them is halogen, C 1 ~C 3 Alkyl or C 1 ~C 3 when one is haloalkyl, the other is hydrogen.

2. A compound of formula (I) 【Chemistry 3】 or an agriculturally acceptable salt or N-oxide thereof [In the formula, R 1 is C 1 ~C 4 Alkyl, C 3 ~C 6 Cycloalkyl, C 3 ~C 6 Alkoxy, C 1 ~C 2 Alkoxy-C 1 ~C 2 Alkyl, C 2 ~C 4 Alkenyl, C 1 ~C 4 Haloalkyl, Cyano-C 1 ~C 4 Alkyl, C 2 ~C 4 Haloalkenyl, C 2 ~C 4 Alkynyl and C 2 ~C 4 haloalkynyl; R 2 is hydrogen, halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 3 Haloalkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 6 Alkoxy, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 3 ~C 6 Cycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 6 Hydroxyalkyl-, C 1 ~C 6 Alkylcarbonyl-, -S(O) m C 1 ~C 6 Alkyl, -NR 4 R 5 , -C(C 1 ~C 3 alkyl)=N-O-C 1 ~C 3 Alkyl and C 2 ~C 6 haloalkynyl; G is hydrogen or C(O)R 3 and R 3 is C 1 ~C 6 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 6 Alkyl-S-, C 1 ~C 6 Alkoxy, -NR 4 R 5 and one or more R 6 phenyl optionally substituted with; Each R 4 and R 5 is hydrogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, and C 3 ~C 6 cycloalkyl; or R 4 and R 5 can be taken together to form a morpholinyl ring; R 6 is halogen, cyano, nitro, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy and C 1 ~C 3 haloalkoxy; X is cyclopropyl; Y is hydrogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 Haloalkyl, C 1 ~C 3 haloalkoxy, or halogen; D is a substituted or unsubstituted monocyclic heteroaryl ring containing 1, 2, or 3 heteroatoms independently selected from oxygen, nitrogen, and sulfur, and when D is substituted, it is selected from the group consisting of R 8 and / or substituted on the ring nitrogen atom with R 9 is substituted with; Each R 8 are independently hydroxyl, halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 3 ~C 6 -Cycloalkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Haloalkoxy, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 6 Hydroxyalkyl-, C 1 ~C 6 Alkylcarbonyl-, C 1 ~C 6 Haloalkylcarbonyl-, C 3 ~C 6 Cycloalkylcarbonyl-, -S(O) m -C 1 ~C 6 Haloalkyl, -S(O) m -C 3 ~C 6 Cycloalkyl, -O-S(O) 2 C 1 ~C 3 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Haloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 3 ~C 6 Cycloalkyl, cyano-C 1 ~C 6 -Alkyl-, -NR 4 R 5 , -C(S)NR 4 R 5 , -S(O) 2 NHC(O)C 1 ~C 3 Alkyl, -S(O) 2 N.R. 4 R 5 , -C(O)OH, -C(O)OC 1 ~C 6 Alkyl, -C(O)NHS-(O) 2 C 1 ~C 6 Alkyl, —C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5 , C 1 ~C 6 Alkylcarbonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Haloalkylcarbonylamino-, C 1 ~C 6 Haloalkylcarbonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Alkylsulfonylamino-, C 1 ~C 6 Alkyl sulfonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Haloalkylsulfonylamino-, C 1 ~C 6 Haloalkylsulfonyl (C 1 ~C 6 alkyl)amino-, C 3 ~C 6 Cycloalkylsulfonylamino-, C 3 ~C 6 Cycloalkylsulfonyl (C 1 ~C 6 alkyl)amino-, hydroxyamino-, hydroxy(C 1 ~C 6 alkyl)amino, C 1 ~C 6 Alkoxyamino, C 1 ~C 6 Alkoxy (C 1 ~C 6 alkyl)amino, C 1 ~C 6 Haloalkoxyamino, C 1 ~C 6 Haloalkoxy (C 1 ~C 6 or a ring system selected from the group consisting of a phenyl ring, a 5-6 membered heteroaryl ring, and a 3-6 membered heterocyclyl ring, said ring system being selected from the group consisting of 0-5 R 16 is substituted with; m is an integer of 0, 1, or 2; Each R 9 are independently 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 3 ~C 6 -Cycloalkyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 6 Hydroxyalkyl-, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Haloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 3 ~C 6 Cycloalkyl, cyano-C 1 ~C 6 -alkyl-, or a ring system selected from the group consisting of a phenyl ring, a 5-6 membered heteroaryl ring, and a 3-6 membered heterocyclyl ring, said ring system being selected from the group consisting of 0-5 R 16 is substituted with; Each R 16 are independently halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Alkoxy or C 1 ~C 6 is haloalkoxy; or D is a substituted or unsubstituted phenyl ring, and when said phenyl ring is substituted it is selected from 1 to 5 R 8 is substituted with; W is a group of the formula 【Chemistry 4】 wherein: "a" represents the point of attachment to the phenyl-pyridazinedione / phenyl-pyridazinone moiety; "b" represents the point of attachment to ring D; R 10 , R 12 , R 14 and R 15 are each independently hydrogen, C 1 ~C 3 Alkyl, or C 1 ~C 3 haloalkyl; Or R 10 and R 12 together with the carbon atom to which they are attached, C 3 ~C 6 forming a carbocyclic ring; R 11 and R 13 are each independently hydrogen, halogen, or C 1 ~C 3 Alkyl, or C 1 ~C 3 haloalkyl, where R 11 Or R 13 One of them is halogen, C 1 ~C 3 Alkyl or C 1 ~C 3 when one is haloalkyl, the other is hydrogen.

3. A compound of formula (I) 【Chemistry 5】 or an agriculturally acceptable salt or N-oxide thereof [In the formula, R 1 is C 1 ~C 4 Alkyl, C 3 ~C 6 Cycloalkyl, C 3 ~C 6 Alkoxy, C 1 ~C 2 Alkoxy-C 1 ~C 2 Alkyl, C 2 ~C 4 Alkenyl, C 1 ~C 4 Haloalkyl, Cyano-C 1 ~C 4 Alkyl, C 2 ~C 4 Haloalkenyl, C 2 ~C 4 Alkynyl and C 2 ~C 4 haloalkynyl; R 2 is hydrogen, halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 3 Haloalkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 6 Alkoxy, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 3 ~C 6 Cycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 6 Hydroxyalkyl-, C 1 ~C 6 Alkylcarbonyl-, -S(O) m C 1 ~C 6 Alkyl, -NR 4 R 5 , -C(C 1 ~C 3 alkyl)=N-O-C 1 ~C 3 Alkyl and C 2 ~C 6 haloalkynyl; G is hydrogen or C(O)R 3 and R 3 is C 1 ~C 6 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 6 Alkyl-S-, C 1 ~C 6 Alkoxy, -NR 4 R 5 and one or more R 6 phenyl optionally substituted with; Each R 4 and R 5 is hydrogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, and C 3 ~C 6 cycloalkyl; or R 4 and R 5 can be taken together to form a morpholinyl ring; R 6 is halogen, cyano, nitro, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy and C 1 ~C 3 haloalkoxy; X is hydrogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 Haloalkyl, C 1 ~C 3 haloalkoxy, or halogen; Y is cyclopropyl; D is a substituted or unsubstituted monocyclic heteroaryl ring containing 1, 2, or 3 heteroatoms independently selected from oxygen, nitrogen, and sulfur, and when D is substituted, it is selected from the group consisting of R 8 and / or substituted on the ring nitrogen atom with R 9 is substituted with; Each R 8 are independently hydroxyl, halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 3 ~C 6 -Cycloalkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Haloalkoxy, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 6 Hydroxyalkyl-, C 1 ~C 6 Alkylcarbonyl-, C 1 ~C 6 Haloalkylcarbonyl-, C 3 ~C 6 Cycloalkylcarbonyl-, -S(O) m -C 1 ~C 6 Haloalkyl, -S(O) m -C 3 ~C 6 Cycloalkyl, -O-S(O) 2 C 1 ~C 3 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Haloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 3 ~C 6 Cycloalkyl, cyano-C 1 ~C 6 -Alkyl, -NR 4 R 5 , -C(S)NR 4 R 5 , -S(O) 2 NHC(O)C 1 ~C 3 Alkyl, -S(O) 2 N.R. 4 R 5 , -C(O)OH, -C(O)OC 1 ~C 6 Alkyl, -C(O)NHS-(O) 2 C 1 ~C 6 Alkyl, —C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5 , C 1 ~C 6 Alkylcarbonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Haloalkylcarbonylamino-, C 1 ~C 6 Haloalkylcarbonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Alkylsulfonylamino-, C 1 ~C 6 Alkyl sulfonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Haloalkylsulfonylamino-, C 1 ~C 6 Haloalkylsulfonyl (C 1 ~C 6 alkyl)amino-, C 3 ~C 6 Cycloalkylsulfonylamino-, C 3 ~C 6 Cycloalkylsulfonyl (C 1 ~C 6 alkyl)amino-, hydroxyamino-, hydroxy(C 1 ~C 6 alkyl)amino, C 1 ~C 6 Alkoxyamino, C 1 ~C 6 Alkoxy (C 1 ~C 6 alkyl)amino, C 1 ~C 6 Haloalkoxyamino, C 1 ~C 6 Haloalkoxy (C 1 ~C 6 or a ring system selected from the group consisting of a phenyl ring, a 5-6 membered heteroaryl ring, and a 3-6 membered heterocyclyl ring, said ring system being selected from the group consisting of 0-5 R 16 is substituted with; m is an integer of 0, 1, or 2; Each R 9 are independently 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 3 ~C 6 -Cycloalkyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 6 Hydroxyalkyl-, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Haloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 3 ~C 6 Cycloalkyl, cyano-C 1 ~C 6 -alkyl-, or a ring system selected from the group consisting of a phenyl ring, a 5-6 membered heteroaryl ring, and a 3-6 membered heterocyclyl ring, said ring system being selected from the group consisting of 0-5 R 16 is substituted with; Each R 16 are independently halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Alkoxy or C 1 ~C 6 is haloalkoxy; or D is a substituted or unsubstituted phenyl ring, and when said phenyl ring is substituted it is selected from 1 to 5 R 8 is substituted with; W is a group of the formula 【Chemistry 6】 wherein: "a" represents the point of attachment to the phenyl-pyridazinedione / phenyl-pyridazinone moiety; "b" represents the point of attachment to ring D; R 10 , R 12 , R 14 and R 15 are each independently hydrogen, C 1 ~C 3 Alkyl, or C 1 ~C 3 Is it haloalkyl; Or R 10 and R 12 together with the carbon atom to which they are attached, C 3 ~C 6 forming a carbocyclic ring; R 11 and R 13 are each independently hydrogen, halogen, or C 1 ~C 3 Alkyl, or C 1 ~C 3 haloalkyl, where R 11 Or R 13 One of them is halogen, C 1 ~C 3 Alkyl or C 1 ~C 3 when one is haloalkyl, the other is hydrogen.

4. G is hydrogen or -C(O)R 3 and R 3 But, C 1 ~C 4 Alkyl, C 2 ~C 3 Alkenyl, C 2 ~C 3 Alkynyl, C 1 ~C 4 Alkoxy, -NR 4 R 5 and R 4 and R 5 The compound according to any one of claims 1 to 3, wherein together form a morpholinyl ring, or phenyl.

5. G is hydrogen or C(O)R 3 and R 3 The compound according to any one of claims 1 to 4, wherein is isopropyl, t-butyl, methyl, ethyl, propargyl, methoxy, ethoxy, or tert-butoxy.

6. X is hydrogen, C 1 ~C 3 Alkyl, halogen, or C 1 6. The compound of claim 1, 3, 4, or 5, which is a haloalkyl.

7. Y is hydrogen, C 1 ~C 3 Alkyl, C 1 ~C 3 7. The compound of claim 1, 3, 4, 5, or 6, which is haloalkyl or halogen.

8. A compound according to any one of claims 1 to 7, wherein X is ortho with respect to the pyridazinone / pyridazinedione moiety.

9. The compound of any one of claims 1 to 8, wherein Y is ortho relative to the -WD moiety.

10. R 1 is methyl, ethyl, n-propyl, cyclopropyl, propargyl, or C 1 The compound of any one of claims 1 to 9, which is haloalkyl.

11. R 2 But hydrogen, halogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Alkoxy, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 3 ~C 6 Cycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl and C 2 ~C 6 The compound of any one of claims 1 to 10, selected from the group consisting of haloalkynyl.

12. The compound of any one of claims 1 to 11, wherein D is a substituted or unsubstituted monocyclic heteroaryl ring.

13. The compound of any one of claims 1 to 11, wherein D is a substituted or unsubstituted phenyl ring.

14. W is W1, R 10 , R 11 , R 12 , and R 13 The compound of any one of claims 1 to 13, wherein each of is hydrogen.

15. W is W2, R 14 and R 15 The compound of any one of claims 1 to 13, wherein each of is hydrogen.

16. The compound according to any one of claims 1 to 13, wherein W is W3.

17. 17. A herbicidal composition comprising the herbicidal compound according to any one of claims 1 to 16 and an agriculturally acceptable formulation auxiliary.

18. 20. The herbicidal composition of claim 17 further comprising at least one additional pesticide.

19. 20. The herbicidal composition of claim 18, wherein the additional pest control agent is a herbicide or a herbicide safener.

20. A method for controlling undesirable plant growth, comprising the step of applying a compound of formula (I) as defined in any one of claims 1 to 16, or a herbicidal composition as defined in any one of claims 17 to 19, to said undesirable plants or to the locus thereof.

21. Use of a compound of formula (I) according to any one of claims 1 to 16 as a herbicide.

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