Herbicidal mixture

Abstract

The present invention relates to (A) a compound of formula (I): TIFF2022519857000083.tif49150 (in the formula, R 1 is methyl or methoxy, and R 2 is hydrogen, methyl, or ethoxy, and A is a substituted heteroaryl group), or an N-oxide or salt form thereof, and (B) one or more additional herbicides; and the use of such compositions in controlling plants or inhibiting the growth of plants.

Description

[Technical field]

[0001] The present invention relates to novel herbicidal compositions and their use in controlling plants or inhibiting the growth of plants. [Background technology]

[0002] Formula in which A is a pyridine ring [ka] Herbicidal dihydro-hydantoins of the formula: are taught in U.S. Patent No. 4,600,430. Additional hydantoins in which A is an isoxazole ring are taught, for example, in U.S. Patent No. 4,302,239 and Canadian Patent No. 1,205,077.

[0003] WO 2015 / 052076 describes compound 1.1 [ka] , 1.2 [ka] , and 1.3 [ka] , and their use as herbicides have been disclosed, while compound 1.4 [ka] is described in WO 2015 / 059262, and compound 1.5 [ka] is described in WO 2015 / 097043, and compound 1.6 [ka] are described in WO 2015 / 193202. WO 2018 / 065311 describes mixtures of these compounds with certain herbicidal pyrrolidonone derivatives. Summary of the Invention [Problem to be solved by the invention]

[0004] It is an object of the present invention to provide herbicidal mixtures which are highly effective against a wide variety of weed species in small doses and / or have improved crop tolerance. [Means for solving the problem]

[0005] The present invention is based on the finding that novel pyrazole-pyrrolidine carboxamides of formula (II) as defined herein are particularly effective as herbicides. They are therefore particularly suitable as mixing partners for herbicidal dihydro-hydantoins. Thus, in one aspect, the present invention provides (A) a compound of formula (I): [ka] (In the formula, R 1 is methyl or methoxy, R 2 is hydrogen, methyl or ethoxy, A is a substituted heteroaryl group, and the compound has [ka] (selected from the group consisting of or an N-oxide or salt form thereof; (B) Formula (II) [ka] (In the formula, R B1 is H, methyl, or methoxy; X is O or S; Q 1 is R at one ring nitrogen. B2 and at least one ring carbon is substituted with R B3 wherein R is a di- or trisubstituted pyrazole substituted byB2 is C1-C3 alkyl or C1-C3 fluoroalkyl, and each R B3 are independently halogen, C1-C3 fluoroalkyl, C1-C3 haloalkoxy, C1-C3 alkoxy, or C1-C3 haloalkyl, C1-C3 fluoroalkyl, C1-C3 haloalkoxy, C1-C3 alkoxy, or C1-C3 alkyl; or Q 1 is R at one ring nitrogen. B2 and at adjacent ring carbons R B3 wherein R is a disubstituted pyrazole substituted by B2 is C1-C3 alkyl, R B3 is C1-C3 fluoroalkyl or C1-C3 alkyl, R B2 and R B3 are the atoms to which they are bonded and Q 1 together with Q to form an 8- or 9-membered fused heterobicyclic ring system; 2 can have 1, 2, or 3 R B5 phenyl, pyridinyl, or thienyl ring systems optionally substituted by substituents; and each R B5 are independently halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, cyano, nitro, C1-C6 alkylthio, C1-C6 alkylsulfinyl, or C1-C6 alkylsulfonyl. or an N-oxide or salt form thereof A composition comprising:

[0006] In a second aspect, the present invention provides the use of a composition of the invention as a herbicide.

[0007] In a third aspect, the present invention provides a method of controlling a plant, comprising the step of applying to the plant or the locus of the plant a herbicidally effective amount of a composition of the present invention.

[0008] In a fourth aspect, the present invention provides a method of inhibiting the growth of a plant, the method comprising the step of applying to the plant or its locus a herbicidally effective amount of a composition of the present invention.

[0009] In a fifth aspect, the present invention provides a method for controlling weeds in a crop of useful plants, comprising the step of applying to the weeds or to the locus of the weeds, or to the useful plants or to the locus of the useful plants, a herbicidally effective amount of a composition of the present invention.

[0010] In a sixth aspect, the present invention provides a method for selectively controlling grasses and / or weeds in a crop of useful plants, comprising the step of applying to the useful plants or their habitat or to the area of ​​cultivation a herbicidally effective amount of a composition of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] When active ingredients are combined, the expected activity (E) for any given combination of active ingredients can be calculated according to the so-called Colby formula (Colby, SR, Calculating synergistic and antagonistic responses of herbicide combination, Weeds, Vol. 15, pages 20-22; 1967): ppm = milligrams of active ingredient (ai) per liter X=% effect of the first active ingredient with p ppm of active ingredient Y = % effect of the second active ingredient with q ppm of active ingredient

[0012] According to Colby, the predicted effect of active ingredients A+B using p+q ppm of active ingredients is given by the following formula:

number

[0013] If the actual observed effect (O) is greater than the predicted effect E, the effect of the combination is superadditive, i.e. there is a synergistic effect. In mathematical terms, synergism corresponds to a positive value of the difference (OE). In the case of purely additive complementary activities (predicted activity), said difference (OE) is zero. A negative value of said difference (OE) indicates a decrease in activity compared to the predicted activity.

[0014] As shown in WO 2015 / 052076, WO 2015 / 059262, WO 2015 / 097043, and WO 2015 / 193202 for the compound of formula (I), and as shown herein for the compound of formula (II), both the compounds of formula (I) and formula (II) are effective herbicidal compounds. Thus, the combination of the present invention takes advantage of its additive activity, and certain embodiments may exhibit synergistic effects. This exists whenever the action of the combination of active ingredients is greater than the sum of the actions of the individual ingredients.

[0015] Moreover, in addition to any actual synergistic effect on herbicidal activity, the composition according to the present invention may also show additional unexpected advantageous properties.Examples of such advantageous properties include improved useful plant characteristics, including emergence, crop yield, more developed root system, increased tillers, increased plant height, larger leaf blades, less dead basal leaves, stronger tillers, greener leaf color, less fertilizer required, less seed required, more productive tillers, earlier flowering, earlier grain maturation, less plant lodging (lodging), increased shoot growth, improved plant vigor, and earlier germination.

[0016] It is further possible that the compositions of the invention may show improved crop resistance compared to the effect of compound A (or B) alone. This occurs when the action of the combination of active ingredients causes less damage to useful crops than the action of one of the active ingredients alone.

[0017] As used herein, the terms "halogen" or "halo" refer to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.

[0018] As used herein, cyano refers to the group -CN.

[0019] As used herein, hydroxy refers to an --OH group.

[0020] As used herein, nitro refers to the group --NO.sub.2.

[0021] Each alkyl moiety, alone or as part of a larger group (e.g., alkoxy, alkylthio, haloalkyl, haloalkoxy, etc.), may be straight-chained or branched, and as used herein, the term also specifically includes cyclopropyl. Typically, alkyl is, for example, methyl, ethyl, n-propyl, cylcopropyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, or n-hexyl. Alkyl groups are generally C1-C6 alkyl groups (except as more narrowly defined above), but are preferably C1-C4 alkyl or C1-C3 alkyl groups, and more preferably C1 or C2 alkyl groups (i.e., methyl or ethyl).

[0022] As used herein, the term "C1-C3 alkoxy" refers to a group of the formula -OR a where R a is a C1-C3 alkyl radical as generally defined above. Examples of C1-C3 alkoxy thus include methoxy, ethoxy, propoxy, and isopropoxy.

[0023] As used herein, the term "C1-C3 haloalkyl" refers to a C1-C3 alkyl radical as generally defined above, substituted by one or more of the same or different halogen atoms. Examples of C1-C3 haloalkyl thus include 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.

[0024] As used herein, the term "C1-C3 haloalkoxy" refers to a C1-C3 alkoxy group as defined above, substituted by one or more of the same or different halogen atoms. Examples of C1-C3 haloalkoxy thus include fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy.

[0025] The term "C1-C6 alkylthio" refers to the group C1-C6 alkyl-S-, for example methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.

[0026] The term "C1-C6 alkylsulfinyl" refers to the group C1-C6 alkyl-S(O)-, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl.

[0027] The term "C1-C6 alkylsulfonyl" refers to the group C1-C6 alkyl-S(O)2-, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.

[0028] The compounds of formula (I) may exist as different geometric isomers or different tautomeric forms. The present invention includes the use of all such isomers and tautomers, and mixtures thereof in all proportions, as well as isotopic forms such as deuterated compounds. They may contain one or more asymmetric centers, and thus may result in optical isomers and diastereomers. Although formula (I) is shown without regard to stereochemistry, the present invention also includes the use of all such optical isomers and diastereomers, as well as racemic and resolved enantiomerically pure R and S stereoisomers, and other mixtures of R and S stereoisomers, and agrochemically acceptable salts thereof. It is recognized that certain optical isomers or diastereomers may have advantageous properties over others. Thus, in disclosing and claiming the present invention, when a racemic mixture is disclosed, it is expressly intended that both optical isomers (including diastereomers) substantially free of the other are also disclosed and claimed.

[0029] In particular, the present invention relates to compounds 1.1 to 1.6 in the following form: [ka] Includes:

[0030] Similarly, the presence of one or more possible asymmetric carbon atoms in the compound of formula (II) means that the compound can exist in chiral isomeric forms, i.e., in enantiomeric or diastereomeric forms. Atropisomers can also occur as a result of restricted rotation around a single bond. Formula (II) is intended to include all these possible isomeric forms and mixtures thereof. The present invention includes the use of all these possible isomeric forms of the compound of formula (II) and mixtures thereof. Similarly, formula (II) is intended to include all possible tautomers, if present, including lactam-lactim tautomerism and keto-enol tautomerism. The present invention therefore includes the use of all possible tautomers of the compound of formula (II).

[0031] Suitable salts include those derived from alkali or alkaline earth metals, as well as those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and salts of the formula N + (R 19 R 20 R 21 R 22 )(wherein, R 19 , R 20 , R 21 and R 22 is independently selected from hydrogen, C1-C6 alkyl, and C1-C6 hydroxyalkyl). Salts of compounds of formula (I) can be prepared by treatment of compounds of formula (I) with metal hydroxides, such as sodium hydroxide, or amines, such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine. Amine salts are often the preferred form of compounds of formula (I) because they are water soluble and aid in the preparation of desirable aqueous herbicidal compositions.

[0032] Acceptable salts, when the compounds of the present invention contain a basic moiety, can be formed from organic and inorganic acids, such as, for example, acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, malonic acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid, naphthalenesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, camphorsulfonic acid, and similar known acceptable acids.

[0033] Throughout this specification, the expression "composition" refers to various mixtures or combinations of components (A) and (B), for example, in a single "ready-mix" form, in combined spray mixtures such as "tank mixes" composed of separate formulations of a single active ingredient, and in a sequential manner, i.e., in combination with a single active ingredient when applied one after the other over a reasonably short period of time, such as a few hours or days. The order in which components (A) and (B) are applied is not critical to the practice of the invention.

[0034] The term "herbicide" as used herein means a compound that controls or modifies the growth of plants. The term "herbicidally effective amount" means an amount of such a compound or a combination of such compounds that can produce a controlling or modifying effect on the growth of a plant. A controlling or modifying effect includes any deviation from natural development, such as killing, retardation, scorching, bleaching, dwarfing, etc.

[0035] The term "locus" as used herein means the field in or on which the plants are growing, or the place where the seeds of cultivated plants are sown, or the place where the seeds are to be sown in soil. It includes the soil, the seeds, and the seedlings, as well as the established vegetation.

[0036] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage and fruits.

[0037] The term "plant propagation material" refers to all reproductive parts of a plant, for example the seeds or vegetative parts of a plant, such as cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes and plant parts.

[0038] As used herein, the term "safener" refers to a chemical that, when used in combination with a herbicide, reduces the undesirable effects of the herbicide on non-target organisms; for example, a safener protects a crop from damage caused by the herbicide but does not prevent the herbicide from killing weeds.

[0039] A preferred embodiment of the present invention is as follows.

[0040] In one embodiment, (A) is compound 1.1.

[0041] In one embodiment, (A) is compound 1.2.

[0042] In one embodiment, (A) is compound 1.3.

[0043] In one embodiment, (A) is compound 1.4.

[0044] In one embodiment, (A) is compound 1.5.

[0045] In one embodiment, (A) is compound 1.6.

[0046] The compounds of formula (I) described herein may be prepared by techniques known to those skilled in the art of organic chemistry. Methods for preparing compounds of formula (I) are described in WO 2015 / 052076, WO 2015 / 059262, WO 2015 / 097043 and WO 2015 / 193202.

[0047] For compounds of formula (II), preferred substituents are as follows, and one of skill in the art will recognize that any definition given below for any one of these substituents and / or integers may be combined with any other substituent and / or integer definition given below or elsewhere herein for compounds of formula (II).

[0048] R B1 is preferably hydrogen or methyl.

[0049] When X is S, the compounds of formula (II) may be procidal, but they may also retain some intrinsic herbicidal activity and therefore find utility in the mixtures of the present invention. However, it is particularly preferred that the compounds of formula (II) may have oxygen as the substituent X.

[0050] As mentioned above, Q 2 can have 1, 2, or 3 R B5 A phenyl, pyridinyl, or thienyl ring system optionally substituted by substituents and thus has the general structure [ka] In the above formula, ring Q 2 is a phenyl, pyridinyl, or thienyl ring, n is an integer of 0, 1, 2, or 3, and the wavy line represents the point of attachment of the ring to the remainder of the molecule, in this case through the amide nitrogen. 2 Q 2 -1, Q 2 -2, Q 2 -3, Q 2 -4, Q 2 -5 and Q 2 -6 [ka] wherein R B5 , n and the wavy line are as previously described.

[0051] Also as defined herein, each R B5 are independently halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, cyano, nitro, C1-C6 alkylthio, C1-C6 alkylsulfinyl, or C1-C6 alkylsulfonyl. Preferably, n is 0, 1, or 2, and each R B5 is supported by a ring carbon atom. More preferably, each R B5 are independently halogen, C1-C4 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy, more preferably chloro, fluoro, bromo, C1-C2 haloalkyl, C1-C2 haloalkoxy, or C1-C2 alkoxy, even more preferably fluoro, ethyl, trifluoromethyl, difluoroethyl, methoxy, difluoromethoxy, or trifluoromethoxy. Even more preferably, the value of n is 1, 2, or 3. Particularly preferred is when n is 2 and at least one R B5 is a compound of formula (II) in which

[0052] One important feature of the compounds of formula (II) is that Q 1 is a pyrazole moiety having at least two substituents, where one of the substituents (R B2 ) is supported by the ring nitrogen and the second substituent (R B3 ) is supported at a ring carbon atom. Obviously, for such a configuration, Q 1 is carbon-bonded to the rest of the molecule.

[0053] Q 1 is disubstituted and R B3 When R is supported on a ring carbon atom adjacent to a substituted ring nitrogen atom, B3 The substituent is R B3SN For the avoidance of doubt, R B3SN is used purely to indicate the positional arrangement within the pyrazole moiety B3 is a partial definition of, and therefore, R B3SNis also selected from the group consisting of halogen, C1-C3 fluoroalkyl, C1-C3 haloalkoxy, C1-C3 alkoxy, and C1-C3 alkyl. 1 When disubstituted, it can be represented by the group Q 1 -2a, Q 1 -2b, Q 1 -2c, Q 1 -2d, or Q1-e [ka] where R B2 , R B3 and R B3SN is as defined above, with the wavy line indicating the point of attachment to the remainder of the molecule, in this case via the 4-position carbon atom of the pyrrolidine ring. 1 -2a and Q 1 -2b is particularly preferred, and Q 1 -2b is most preferred.

[0054] Q 1 When trisubstituted, the group Q 1 -3a or Q 1 -3b [ka] where the third substituent (R B3 ) is also supported at a ring carbon atom. B2 , R B3 and R B3SN and the wavy lines are as defined above.

[0055] Preferably, R B2 is selected from the group consisting of methyl, ethyl, n-propyl, trifluoromethyl and difluoroethyl. More preferably, R B2 is selected from the group consisting of methyl, ethyl, and difluoroethyl.

[0056] Preferably, R B3 and / or R B3SNare each independently selected from chloro, fluoro, bromo, methyl, ethyl, diluoromethyl, trifluoromethyl, C1-C3 haloalkoxy, C1-C3 alkoxy, or C1-C3 alkyl. 1 When is trisubstituted, R B3 and R B3SN It will be appreciated that the may be the same or different.

[0057] In a third set of embodiments, Q 1 is a disubstituted pyrazole ring system, R B2 and R B3 are the atoms to which they are bonded and Q 1 and together form an 8- or 9-membered fused heterobicyclic ring system. In such embodiments, R B2 is C1-C3 alkyl, R B3 is selected from C1-C3 alkyl, C1-C3 fluoroalkyl, and C1-C3 haloalkoxy. Examples of such fused ring systems are the groups Q 1 -F1~Q 1 Shown below as -F12. [ka]

[0058] Particularly preferred compounds of formula (II) for use as component B in the compositions of the present invention are shown in Table 1 below. One of ordinary skill in the art will recognize that Table 1 specifies the stereochemistry of the compounds of formula (II). These are the most preferred stereoisomers of the compounds of formula (II), however, racemic mixtures of the stereoisomers are also herbicidal and therefore may equally be used as component B in the mixtures of the present invention.

[0059] [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

[0060] In one embodiment, B is compound 2.1.

[0061] In one embodiment, B is compound 2.2.

[0062] In one embodiment, B is compound 2.3.

[0063] In one embodiment, B is compound 2.4.

[0064] In one embodiment, B is compound 2.5.

[0065] In one embodiment, B is compound 2.6.

[0066] In one embodiment, B is compound 2.7.

[0067] In one embodiment, B is compound 2.8.

[0068] In one embodiment, B is compound 2.9.

[0069] In one embodiment, B is compound 2.10.

[0070] In one embodiment, B is compound 2.11.

[0071] In one embodiment, B is compound 2.12.

[0072] In one embodiment, B is compound 2.13.

[0073] In one embodiment, B is compound 2.14.

[0074] In one embodiment, B is compound 2.15.

[0075] In one embodiment, B is compound 2.16.

[0076] In one embodiment, B is compound 2.17.

[0077] In one embodiment, B is compound 2.18.

[0078] In one embodiment, B is compound 2.19.

[0079] In one embodiment, B is compound 2.20.

[0080] In one embodiment, B is compound 2.21.

[0081] In one embodiment, B is compound 2.22.

[0082] In one embodiment, B is compound 2.23.

[0083] In one embodiment, B is compound 2.24.

[0084] In one embodiment, B is compound 2.25.

[0085] In one embodiment, B is compound 2.26.

[0086] In one embodiment, B is compound 2.27.

[0087] In one embodiment, B is compound 2.28.

[0088] In one embodiment, B is compound 2.29.

[0089] In one embodiment, B is compound 2.30.

[0090] In one embodiment, B is compound 2.31.

[0091] In one embodiment, B is compound 2.32.

[0092] In one embodiment, B is compound 2.33.

[0093] In one embodiment, B is compound 2.34.

[0094] In one embodiment, B is compound 2.35.

[0095] In one embodiment, B is compound 2.36.

[0096] In one embodiment, B is compound 2.37.

[0097] In one embodiment, B is compound 2.38.

[0098] In one embodiment, B is compound 2.39.

[0099] In one embodiment, B is compound 2.40.

[0100] In one embodiment, B is compound 2.41.

[0101] In one embodiment, B is compound 2.42.

[0102] In one embodiment, B is compound 2.43.

[0103] In one embodiment, B is compound 2.44.

[0104] In one embodiment, B is compound 2.45.

[0105] In one embodiment, B is compound 2.46.

[0106] In one embodiment, B is compound 2.47.

[0107] In one embodiment, B is compound 2.48.

[0108] In one embodiment, B is compound 2.49.

[0109] In one embodiment, B is compound 2.50.

[0110] In one embodiment, B is compound 2.51.

[0111] In one embodiment, B is compound 2.52.

[0112] In one embodiment, B is compound 2.53.

[0113] In one embodiment, B is compound 2.54.

[0114] In one embodiment, B is compound 2.55.

[0115] In one embodiment, B is compound 2.56.

[0116] In one embodiment, B is compound 2.57.

[0117] In one embodiment, B is compound 2.58.

[0118] In one embodiment, B is compound 2.59.

[0119] In one embodiment, B is compound 2.60.

[0120] In one embodiment, B is compound 2.61.

[0121] In one embodiment, B is compound 2.62.

[0122] In one embodiment, B is compound 2.63.

[0123] In one embodiment, B is compound 2.64.

[0124] In one embodiment, B is compound 2.65.

[0125] In one embodiment, B is compound 2.66.

[0126] In one embodiment, B is compound 2.67.

[0127] In one embodiment, B is compound 2.68.

[0128] In one embodiment, B is compound 2.69.

[0129] In one embodiment, B is compound 2.70.

[0130] In one embodiment, B is compound 2.71.

[0131] In one embodiment, B is compound 2.72.

[0132] In one embodiment, B is compound 2.73.

[0133] In one embodiment, B is compound 2.74.

[0134] In one embodiment, B is compound 2.75.

[0135] In one embodiment, B is compound 2.76.

[0136] In one embodiment, B is compound 2.77.

[0137] In one embodiment, B is compound 2.78.

[0138] In one embodiment, B is compound 2.79.

[0139] In one embodiment, B is compound 2.80.

[0140] In one embodiment, B is compound 2.81.

[0141] In one embodiment, B is compound 2.82.

[0142] In one embodiment, B is compound 2.83.

[0143] In one embodiment, B is compound 2.84.

[0144] In one embodiment, B is compound 2.85.

[0145] In one embodiment, B is compound 2.86.

[0146] In one embodiment, B is compound 2.87.

[0147] In one embodiment, B is compound 2.88.

[0148] In one embodiment, B is compound 2.89.

[0149] In one embodiment, B is compound 2.90.

[0150] In one embodiment, B is compound 2.91.

[0151] In one embodiment, B is compound 2.92.

[0152] In one embodiment, B is compound 2.93.

[0153] In one embodiment, B is compound 2.94.

[0154] In one embodiment, B is compound 2.95.

[0155] In one embodiment, B is compound 2.96.

[0156] In one embodiment, B is compound 2.97.

[0157] In one embodiment, B is compound 2.98.

[0158] In one embodiment, B is compound 2.99.

[0159] In one embodiment, B is compound 2.100.

[0160] In one embodiment, B is compound 2.101.

[0161] In one embodiment, B is compound 2.102.

[0162] In one embodiment, B is compound 2.103.

[0163] In one embodiment, B is compound 2.104.

[0164] In one embodiment, B is compound 2.105.

[0165] In one embodiment, B is compound 2.106.

[0166] In one embodiment, B is compound 2.107.

[0167] In one embodiment, B is compound 2.108.

[0168] In one embodiment, B is compound 2.109.

[0169] In one embodiment, B is compound 2.110.

[0170] In one embodiment, B is compound 2.111.

[0171] In one embodiment, B is compound 2.112.

[0172] In one embodiment, B is compound 2.113.

[0173] In one embodiment, B is compound 2.114.

[0174] In one embodiment, B is compound 2.115.

[0175] In one embodiment, B is compound 2.116.

[0176] In one embodiment, B is compound 2.117.

[0177] In one embodiment, B is compound 2.118.

[0178] In one embodiment, B is compound 2.119.

[0179] In one embodiment, B is compound 2.120.

[0180] In one embodiment, B is compound 2.121.

[0181] In one embodiment, B is compound 2.122.

[0182] In one embodiment, B is compound 2.123.

[0183] In one embodiment, B is compound 2.124.

[0184] In one embodiment, B is compound 2.125.

[0185] In one embodiment, B is compound 2.126.

[0186] The compounds of formula (II) described herein may be prepared by racemic and asymmetric synthetic routes as described in WO 2015 / 084796 and in the preparative examples herein.

[0187] The starting materials used in the preparation of the compounds used herein may be purchased from regular commercial suppliers or may be prepared by known methods. The starting materials and intermediates may be purified by state-of-the-art methods such as chromatography, crystallization, distillation and filtration before being used in the next WO2015 / 193202 step.

[0188] Useful plant crops in which the compositions of the present invention can be used include berry plants such as blackberries, blueberries, cranberries, raspberries and strawberries; cereals such as barley, corn (corn), millet, oats, rice, rye, sorghum triticale and wheat; fiber plants such as cotton, flax, hemp, jute and sisal; agricultural crops such as sugar and fodder beet, coffee, hops, mustard, rapeseed (canola), poppy, sugarcane, sunflower, tea and tobacco; fruit trees such as apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses such as bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and zoysia grass; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage ... and thyme; legumes, such as beans, lentils, peas and soybeans; nuts, such as almonds, cashews, groundnuts, hazelnuts, peanuts, pecans, pistachios and walnuts; palms, such as oil palm; ornamental plants, such as flowers, shrubs and trees; other trees, such as cocoa, coconut, olives and rubber; vegetables, such as asparagus, eggplant, broccoli, cabbage, carrots, cucumber, garlic, lettuce, mallow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and perennial and annual crops, such as vines.

[0189] Crops should be understood to be those that occur naturally, are obtained by traditional breeding methods, or are obtained by genetic engineering. These include crops that contain so-called output traits, such as improved storage stability, higher nutritional value, and improved flavor.

[0190] Crops should also be understood to include crops that have been made tolerant to herbicides such as bromoxynil, or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO-inhibitors. An example of a crop that has been made tolerant to imidazolinones, such as imazamox, by conventional breeding methods is Clearfield® summer canola. Examples of crops that have been made tolerant to herbicides by genetic engineering methods include, for example, glyphosate- and glufosinate-resistant corn varieties available under the trade names RoundupReady®, Herculex I® and LibertyLink®.

[0191] It should also be understood that crops are also those that are naturally resistant or made resistant to harmful insects. This includes, for example, plants that have been transformed by the use of recombinant DNA technology to be able to synthesize one or more selectively acting toxins, such as those known to be derived from toxin-producing bacteria. Examples of toxins that can be expressed include δ-endotoxins, plant insecticidal proteins (Vips), insecticidal proteins of bacterial colonizing nematodes, and toxins produced by scorpions, arachnids, wasps and fungi.

[0192] An example of a crop modified to express a Bacillus thuringiensis toxin is Bt corn KnockOut® (Syngenta Seeds). An example of a crop containing more than one gene encoding insecticide resistance and thus expressing more than one toxin is VipCot® (Syngenta Seeds). A crop or its seed material can also be resistant to more than one type of pest (when formed by genetic modification, so-called overlapping transgenic events). For example, a plant can have the ability to express an insecticidal protein and be herbicide resistant at the same time, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

[0193] The compositions of the present invention can generally be used to control a wide variety of monocotyledonous and dicotyledonous weed species. Examples of monocotyledonous species that can usually be controlled are Alopecurus myosuroides, Avena fatua, Brachiaria plantaginea, Bromus tectorum, Cyperus esculentus, Digitaria sanguinalis, Echinochloa crus-galli, Lolium perenne, Lolium multiflorum, Panicum miliaceum, Poa annua, Setaria viridis, Setaria faberi, and others. faberi and Sorghum bicolor. Examples of dicotyledonous species that can be controlled include Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Euphorbia heterophylla, Galium aparine, Ipomoea hederacea, Kochia scoparia, Polygonum convolvulus, Sida spinosa, Sinapis arvensis, Solanum nigrum, Stellaria media, Veronica persica, persica and Xanthium strumarium.

[0194] In all aspects of the invention, in any particular embodiment, for example, the weeds to be controlled and / or inhibited may be monocotyledonous or dicotyledonous weeds that are tolerant or resistant to one or more other herbicides, for example, HPPD-inhibiting herbicides such as mesotrione, PSII-inhibiting herbicides such as atrazine, or EPSPS-inhibiting herbicides such as glyphosate. Such weeds include, but are not limited to, resistant Amaranthus biotypes.

[0195] The compositions of the present invention may be mixed with one or more further pesticides including herbicides (usually different from the herbicides of formula (I) and formula (II)], fungicides, insecticides, nematicides, bactericides, acaricides, growth regulators, sterilizers, semiochemicals, repellents, attractants, pheromones, feeding stimulants, or other biologically active compounds to form multi-component pesticides which provide even broader agricultural protection.

[0196] Similar compositions of the present invention (including those that contain one or more additional pesticides described in the paragraph above) may further include one or more safeners. In particular, the following safeners are particularly preferred: AD67 (MON4660), benoxacor, cloquintocet-mexyl, cyometrinil, cyprosulfamide, dichlormid, dicyclonone, diethrate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, furilazome, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, oxabetrinil, naphthalic anhydride (CAS RN 81-84-5), TI-35, N-isopropyl-4-(2-methoxy-benzoylsulfamoyl)-benzamide (CAS RN 221668-34-4) and N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide. Such safeners may also be used in the form of esters or salts, as described, for example, in The Pesticide Manual, 15th Ed. (BCPC), 2009. Thus, a reference to cloquintocet-mexyl also applies to cloquintocet as well as its lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as disclosed in WO 02 / 34048, a reference to fenchlorazole-ethyl also applies to fenchlorazole, etc.

[0197] Generally, the mixing ratio (by weight) of the compound of formula (I) to the compound of formula (II) is from 0.01:1 to 100:1, more preferably from 0.05:1 to 20:1, even more preferably from 0.1:1 to 20:1, most preferably from 0.2:1 to 20:1, for example, 0.3125:1, 0.625:1, 1:1, 1.25:1, 2.5:1, 5:1, 10:1 and 20:1.

[0198] The amount of the composition of the present invention applied may depend on various factors such as the compound used; the target of the treatment, e.g., plant (crops and / or weeds), soil or seed; the part of the plant to which the treatment is applied (e.g., foliar application, irrigation, in-furrow application), the type of treatment, e.g., spraying, dusting or seed dressing; and the time of application (pre-emergence or post-emergence).

[0199] When applied as such to useful plants or their habitat, component (A) may be applied in an amount of 50 to 2000 g ai / ha, in particular 100 to 1000 g ai / ha, more particularly 300 to 500 g ai / ha, for example 300, 350, 400, 450 or 500 g ai / ha. However, in certain embodiments, component (A) is preferably applied in smaller amounts of 5 to 25 g ai / ha, in particular 5, 10, 15, 20 or 25 g ai / ha.

[0200] Component (B), i.e. the compound of formula (II), when used on its own, is usually applied in an amount of 5 to 2000 g ai / ha, in particular in an amount of 10, 25, 30, 60, 75, 100, 125, 200, 250, 300, 350, 400, 450, 500 or 1000 g ai / ha.

[0201] In agricultural practice, the application rates of the compositions according to the invention depend on the type of effect desired and usually range from 10 to 4000 g of total composition per hectare. Thus, in a particular composition according to the invention, component (A) may be applied in amounts of 5, 10, 15, 20, 25, 50, 300, 350, 400, 450, 500 or 1000 g ai / ha, in conjunction with component B in amounts of usually 10, 25, 30, 60, 75, 100, 125, 200, 250, 300, 350, 400, 450, 500 or 1000 g ai / ha.

[0202] The compounds of the invention can be applied before or after the planting of the crop, before weed emergence (pre-emergence applications), or after weed emergence (post-emergence applications), and are particularly effective when applied to weeds pre-emergence.

[0203] When safeners are combined with the mixtures according to the invention, the mixing ratio of compound of formula (I) to safener is preferably from 100:1 to 1:10, in particular from 20:1 to 1:1.

[0204] The safener and the composition of the present invention can be applied simultaneously. For example, the safener and the composition of the present invention can be applied to the locus pre-emergence or to the crop post-emergence. The safener and the composition of the present invention can also be applied sequentially. For example, the safener can be applied as a seed treatment before sowing the seed. And the composition of the present invention can be applied to the locus pre-emergence or to the crop post-emergence.

[0205] The compositions of the invention can be advantageously used in the following formulations (in which "active ingredient" refers to the respective mixture of the compound of formula (I) with the compound of formula (II) or, if a safener is also used, to the respective mixture of the compound of formula (I) with the compound of formula (II) and the safener):

[0206] The individual components of the compositions of the present invention may be utilized as the technical active ingredients as manufactured, however, more generally, the compositions of the present invention may be formulated in a variety of ways using formulation aids such as carriers, solvents and surfactants. The formulations can be in various physical forms, such as dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil flowables, aqueous dispersions, oil dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as a carrier), impregnated polymer films, or other forms known, for example, from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can be used directly or are diluted before use. Dilutions can be made, for example, with water, liquid fertilizers, micronutrients, biological organisms, oils, or solvents.

[0207] The formulations can be prepared, for example, by mixing the active ingredient with formulation auxiliaries to obtain a composition in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredient can also be formulated with other auxiliaries, such as finely divided solids, mineral oils, vegetable or animal oils, vegetable or animal modified oils, organic solvents, water, surface-active substances or combinations thereof.

[0208] The active ingredient can also be contained in very fine microcapsules. Microcapsules contain the active ingredient in a porous carrier. This allows the active ingredient to be released in controlled amounts (e.g., slow release) into the environment. Microcapsules usually have a diameter of 0.1 to 500 microns. They contain the active ingredient in an amount of about 25 to 95% by weight based on the capsule weight. The active ingredient can be in the form of a bulk solid, fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulating membrane can include, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane or chemically modified polymers and starch xanthate, or other polymers known to those skilled in the art. Alternatively, very fine microcapsules can be formed containing the active ingredient in the form of fine particles in a base solid matrix, but the microcapsules themselves are not encapsulated.

[0209] Formulation auxiliaries suitable for the preparation of the compositions according to the invention are known per se. Liquid carriers include: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietic acid, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-heptanone, α-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate , oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc. may be used. Water is the carrier of choice when diluting concentrates.

[0210] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, Kiesslager, limestone, calcium carbonate, bentonite, calcium montmorillonite, cotton hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin, and similar materials.

[0211] A large number of surface-active substances can be advantageously used in both solid and liquid formulations, especially in formulations which can be diluted with a carrier before use. Surface-active substances can be anionic, cationic, nonionic or polymeric and can be used as emulsifying agents, wetting agents or suspending agents, or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylaryl sulfonates, such as calcium dodecylbenzene sulfonate; alkylphenol / alkylene oxide adducts, such as nonylphenol ethoxylate; alcohol / alkylene oxide adducts, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalene sulfonates, such as sodium dibutylnaphthalene sulfonate; dialkyl esters of sulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethyl ammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkyl phosphate esters; and further substances, for example, as described in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey, 1981.

[0212] Further adjuvants that may be used in the pest control formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbing agents, mixing aids, defoamers, complexing agents, neutralizing or pH adjusting and buffering agents, corrosion inhibitors, fragrances, wetting agents, uptake enhancers, trace elements, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, fungicides, and liquid and solid fertilizers.

[0213] The formulations according to the invention can contain additives including vegetable or animal oils, mineral oils, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the compositions according to the invention is generally 0.01-10% based on the mixture to be applied. For example, the oil additive can be added in the desired concentration in the spray tank after the spray mixture has been prepared. Preferred oil additives include mineral oils or vegetable oils, e.g. rapeseed oil, olive oil or sunflower oil, emulsified vegetable oils, alkyl esters of vegetable oils, e.g. methyl derivatives, or animal oils, e.g. fish oil or beef tallow. Preferred oil additives are C8-C 22 Alkyl esters of fatty acids, especially C 12 ~C 18 Methyl derivatives of fatty acids, such as the methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are described in the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.

[0214] The formulations will generally contain from 0.1 to 99% by weight, especially from 0.1 to 95% by weight, of compound (A) and from 1 to 99.9% by weight of (B) a formulation aid, preferably comprising from 0 to 25% by weight of a surface-active substance. Although commercial products will preferably be formulated as concentrates, end users will normally utilise dilute formulations.

[0215] The application rates may vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pests to be controlled, the prevailing weather conditions and other factors governed by the method of application, the time of application and the target crop. As a general guideline, the compounds may be applied in amounts of 1 to 2000 l / ha, in particular 10 to 1000 l / ha.

[0216] Preferred formulations may have the following compositions (by weight %), where the term "active ingredients" refers to the total weight % of the combination of all active ingredients in the composition.

[0217] Emulsifiable concentrate: Active ingredient: 1-95%, preferably 60-90% Surface-active agents: 1-30%, preferably 5-20% Liquid carrier: 1-80%, preferably 1-35%

[0218] Powder: Active ingredient: 0.1-10%, preferably 0.1-5% Solid carrier: 99.9-90%, preferably 99.9-99%

[0219] Suspension concentrates: Active ingredient: 5-75%, preferably 10-50% Water: 94-24%, preferably 88-30% Surface-active agent: 1-40%, preferably 2-30%

[0220] Wettable powder: Active ingredient: 0.5-90%, preferably 1-80% Surface-active agents: 0.5-20%, preferably 1-15% Solid carrier: 5-95%, preferably 15-90%

[0221] Granules: Active ingredient: 0.1-30%, preferably 0.1-15% Solid carrier: 99.5-70%, preferably 97-85%

[0222] The following examples further illustrate the present invention without, however, limiting it.

[0223] [Table 2]

[0224] This combination is thoroughly mixed with an adjuvant and the mixture thoroughly ground in a suitable mill to give a wettable powder, which can be diluted with water to give a suspension of the desired concentration.

[0225] [Table 3]

[0226] This combination is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a powder, which can be used directly as a seed treatment.

[0227] [Table 4]

[0228] Emulsifiable concentrates of any desired dilution usable for plant protection can be obtained from these concentrates by dilution with water.

[0229] [Table 5]

[0230] Ready-to-use dusts are obtained by mixing this combination with a carrier and grinding the mixture in a suitable mill. Such dusts can also be used for dry dressing of seeds.

[0231] [Table 6]

[0232] The combination is mixed with the auxiliary and ground, the mixture is moistened with water, extruded and then dried in a stream of air.

[0233] [Table 7]

[0234] The finely ground combination is homogeneously applied in a mixer to kaolin moistened with polyethylene glycol. Non-dust-coated granules are thus obtained.

[0235] [Table 8]

[0236] The finely ground combination is intimately mixed with adjuvants to obtain a suspension concentrate, which can be diluted with water to obtain a suspension of any desired dilution ratio, and can be used to treat and protect living plants as well as plant propagation material from microbial infestation by spraying, pouring or immersion.

[0237] [Table 9]

[0238] The finely ground combination is intimately mixed with adjuvants to obtain a suspension concentrate, which can be diluted with water to obtain a suspension of any desired dilution ratio, and can be used to treat and protect living plants as well as plant propagation material from microbial infestation by spraying, pouring or immersion.

[0239] Sustained Release Capsule Suspension 28 parts of the combination are mixed with 2 parts of aromatic solvent and 7 parts of toluene diisocyanate / polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of antifoaming agent and 51.6 parts of water until the desired particle size is obtained. To this emulsion is added a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts of thickener and 3 parts of dispersant. The capsule suspension formulation contains 28% active ingredient. The capsule median diameter is 8-15 μm. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for the purpose in question.

[0240] In one set of embodiments, the composition of the invention may comprise A and B as set forth in Table 2 below. Particularly preferred compositions of the invention are those from Table 2 that comprise compounds of formula (II) as described herein in the Examples.

[0241] [Table 10-1] [Table 10-2] [Table 10-3] [Table 10-4] [Table 10-5] [Table 10-6] [Table 10-7] [Table 10-8] [Table 10-9] [Table 10-10] [Table 10-11] [Table 10-12] [Table 10-13] [Table 10-14] [Table 10-15] [Table 10-16] [Table 10-17]

[0242] One of ordinary skill in the art will recognize that the most preferred range of A:B ratios for any one of composition numbers 1-756 listed in Table 2 above is 0.2:1 to 20:1, and that each one of composition numbers 1-756 listed in Table 2 may be used with an A:B ratio of 0.3125:1, or an A:B ratio of 0.625:1, or an A:B ratio of 1.25:1, or an A:B ratio of 2.5:1, or an A:B ratio of 5:1, or an A:B ratio of 10:1, or an A:B ratio of 20:1.

[0243] Although 756 binary mixtures of the compound of formula (I) with another herbicide are explicitly disclosed above, one skilled in the art will recognize that the present invention extends to ternary and even multi-combinations, including the above binary mixtures. In particular, the present invention provides compositions comprising ternary mixtures, wherein each of the binary mixtures set forth in Table 2 above is selected from the group consisting of: (a) mesotrione (mixtures 3a1 to 3a756, respectively); (b) bicyclopyrone (mixtures 3b1 to 3b756, respectively); (c) atrazine (mixtures 3c1 to 3c756, respectively); (d) S-metolachlor (mixtures 3d1 to 3d756, respectively); (e) terbuthylazine (mixtures 3e1 to 3e756, respectively). (f) dimethaclor (mixtures 3F1 to 3F756, respectively); (g) flufenacet (mixtures 3G1 to 3G756, respectively); (h) glyphosate (mixtures 3H1 to 3H756, respectively); (i) isoxaflutole (mixtures 3I1 to 3I756, respectively); (j) nicosulfuron (mixtures 3J1 to 3J756, respectively); (k) ametryne (mixtures 3K1 to 3K756, respectively); (l) hexazinone (mixtures 3L1 to 3L256, respectively); ~3l756);(m) paraquat (mixtures 3m1 to 3m756, respectively);(n) diquat (mixtures 3n1 to 3n756, respectively);(o) pyridate (mixtures 3o1 to 3o756, respectively);(p) acetochlor (mixtures 3p1 to 3p756, respectively);(q) dimethenamide-P (mixtures 3q1 to 3q756, respectively);(r) alachlor (mixtures 3r1 to 3r756, respectively);(s) petoxamide (mixtures 3s1 to 3s756, respectively);(t) (u) trifloxysulfuron sodium (mixtures 3u1 to 3u756, respectively); (v) flazasulfuron (mixtures 3v1 to 3v756, respectively); (w) prosulfocarb (mixtures 3w1 to 3w756, respectively); (x) metolachlor (mixtures 3x1 to 3x756, respectively); or (y) pretilachlor (mixtures 3y1 to 3y756, respectively).

[0244] Various aspects and embodiments of the invention will now be illustrated in more detail by way of example, it being recognized that modifications of detail may be made without departing from the scope of the invention.

[0245] Where book references, patent applications or patents are mentioned in the text of this application, the text to which said reference relates is incorporated herein by reference and should not be construed as limiting the scope of the invention. EXAMPLES

[0246] Preparation examples of compounds of formula (II) General Experiment Chiral HPLC was recorded on the following columns using the solvents and gradients indicated:

[0247] column: Regis Whelk O1(s,s)4.6x100mm,3.5μm Chiralpak IC 4.6x100mm,3.0μm

[0248] solvent: A: Isohexane + 0.1% glacial acetic acid (v / v) B: Ethanol + 0.1% glacial acetic acid (v / v)

[0249] [Table 11]

[0250] Synthesis method (I): Racemic synthesis route Exemplary compound: N-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxamide Synthesis Scheme (I) [ka] Salt (I) can be prepared as described in Tetrahedron Lett. 1995, 36, 9409.

[0251] Step 1: Ethyl (E)-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]prop-2-enoate In a large microwave vial, 3-iodo-1-methyl-5-(trifluoromethyl)pyrazole (3.62 mmol, 1.00 g) was dissolved in acetonitrile (15.2 mL), ethyl acrylate (1.19 mL, 10.9 mmol), triethylamine (0.507 mL, 3.64 mmol), tri-ortho-tolylphosphine (0.362 mmol, 0.110 g) and palladium(II) acetate (0.362 mmol, 0.0813 g) were added, the air space above the stirred orange solution was swept with nitrogen, the vial was sealed and heated under microwave irradiation at 110° C. for 60 min. The reaction mixture was filtered (rinsing with a small amount of EtOAc) and the combined filtrate and washings were concentrated to remove most of the solvent. The remaining orange-brown liquid was diluted with water (12 mL) and extracted with EtOAc (3×15 mL). The organic extracts were combined, washed with water (10 mL), passed through a phase separation cartridge and concentrated. Column chromatography (gradient elution with EtOAc / isohexane) afforded ethyl (E)-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]prop-2-enoate as a yellow oil, 0.51 g (57%). 1 H NMR:(400MHz,CDCl3):δ=7.58(d,J=16.1Hz,1H),6.81(s,1H),6.43(d,J=16. 1Hz,1H),4.26(q,J=7.1Hz,2H),4.01(d,J=0.6Hz,3H),1.33(t,J=7.1Hz,3H).

[0252] Step 2 Ethyl-6-methyl-8-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-1,4-dithia-6-azaspiro[4.4]nonane-9-carboxylate To a suspension of finely divided cesium fluoride (12.7 mmol, 1.93 g) in tetrahydrofuran (9.51 mL) stirred at −50° C. under nitrogen, a solution of ethyl (E)-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]prop-2-enoate (3.17 mmol, 0.787 g) and 1,3-dithiolan-2-ylidene-methyl-(trimethylsilylmethyl)ammonium; trifluoromethanesulfonic acid (5.55 mmol, 2.06 g) in tetrahydrofuran (39.51 mL) was added dropwise over approximately 15 minutes, keeping the reaction temperature below −45° C. The resulting very pale yellow cloudy suspension was allowed to warm slowly to room temperature and stirring was continued overnight. The reaction mixture was then diluted with DCM, filtered, and rinsed with a further portion of DCM. The combined filtrate and washings were concentrated and the crude material was purified by column chromatography (gradient elution of EtOAc / cyclohexane) to give ethyl-6-methyl-8-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-1,4-dithia-6-azaspiro[4.4]nonane-9-carboxylate as a pale yellow oil, 566 mg (45%). 1 H NMR:(400MHz,CDCl3):δ=6.45(s,1H),4.31-4.17(m,2H),3.90(d,J=0.6Hz,3H),3.89- 3.79(m,2H),3.35-3.06(m,5H),2.97-2.91(m,1H),2.47(s,3H),1.31(t,J=7.2Hz,3H).

[0253] Step 3: 1-Methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-thioxo-pyrrolidine-3-carboxylic acid To a solution of ethyl 6-methyl-8-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-1,4-dithia-6-azaspiro[4.4]nonane-9-carboxylate (1.43 mmol, 0.566 g) in dioxane (34.3 mL) and water (11.4 mL) was added LiOH (14.3 mmol, 0.343 g) and the stirred mixture was heated to 60° C. for 1 h under a nitrogen atmosphere. The reaction mixture was then allowed to cool to about 35° C. and concentrated to remove most of the dioxane. The remaining mixture was diluted with water (10 mL) and partitioned between dilute HCl (5 mL, pH 3) and DCM (20 mL). The biphasic mixture was filtered to remove fine solids and the organic phase was separated. The aqueous phase was further extracted with DCM (2x15mL) and all organic extracts were combined, dried over MgSO4, filtered and the filtrate was concentrated to give 1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-thioxo-pyrrolidine-3-carboxylic acid as a pale yellow solid, 399mg (90%). 1 H NMR:(400MHz,CDCl3):δ=6.66(s,1H),4.19-4.03(m,4H),3.93(d,J=0.5Hz,3H),3.34(s,3H).

[0254] Step 4 N-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-thioxo-pyrrolidine-3-carboxamide To a solution of 1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-thioxo-pyrrolidine-3-carboxylic acid (0.340 g, 1.11 mmol) in DCM (8.0 mL) was added 2,3-difluoroaniline (0.112 mL, 1.11 mmol) to give a pale yellow solution. Propylphosphonic anhydride (50% by weight) in ethyl acetate (1.88 mmol, 1.12 mL) was added followed by N,N-diisopropylamine (3.32 mmol, 0.578 mL) and the reaction mixture was stirred at room temperature for 1 h. The reaction mixture was then quenched by the addition of water (2 mL) with stirring, transferred to a phase separation cartridge and the organics were collected and concentrated. Column chromatography (gradient elution with EtOAc / isohexane) afforded N-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-thioxo-pyrrolidine-3-carboxamide as a colourless crystalline solid, 264 mg (57%). 1 H NMR:(400MHz,CDCl3):δ=10.25(br s,1H),8.01(tdd,J=1.6,6.6,8.3Hz,1H),7.04(ddt,J=2.1,5.9,8.3Hz,1H),6.94-6.86(m,1H),6.58(s,1H) ,4.40(td,J=6.3,8.6Hz,1H),4.20(d,J=6.4Hz,1H),4.13(dd,1H),4.00(dd,1H),3.93(d,3H),3.33(s,3H).

[0255] Step 5 N-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxamide To a solution of N-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-thioxo-pyrrolidine-3-carboxamide (0.621 mmol, 0.260 g) in acetonitrile (6.21 mL) stirred and cooled to ca. 0-5° C. in an ice-salt bath was added 50% hydrogen peroxide (0.746 mL) dropwise to give a white suspension. After 5 min, 45% aqueous hydrobromic acid (0.0750 mL, 0.621 mmol) was added dropwise and after stirring for 10 min, the mixture was allowed to warm to room temperature. After 3 h, the reaction mixture was recooled to 5° C. and quenched with sodium thiosulfate solution (ca. 10 mL). The mixture was diluted with EtOAc (15 mL) and water (10 mL) and the organic phase was separated. The aqueous phase was further extracted with EtOAc (2x10mL) then the organic extracts were combined, passed through a phase separation cartridge and concentrated to give a colourless gum. Column chromatography (gradient elution with EtOAc / isohexane) afforded N-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxamide as a white crystalline solid, 210mg (84%). 1 H NMR:(400MHz,CDCl3):δ=10.15(br s,1H),8.04(dd,J=6.6,8.3Hz,1H),7.06-6.99(m,1H),6.89(br dd,J=1.1,8.6Hz,1H),6.69(s,1H),4.09(q,1H),3.94(s,3H),3.78(d,J=9.5Hz,1H),3.76-3.65(m,2H),2.98(d,3H).

[0256] Chiralpak using isostatic conditions: 85% solvent A: 15% solvent B with sc-CO2 (solvent A) and isopropanol (solvent B) at 15 mL / min Using an IA, 10x250mm, 5μm column, racemic N-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxamide could be separated to give the enantiomers (3S,4R)-N-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxamide and (3R,4S)-N-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxamide.

[0257] Synthesis method (II): Asymmetric synthesis route Exemplary compound: (3S,4R)-N-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxamide Synthesis Scheme (II) [ka] The nickel catalyst used in step 3, which catalyzes the asymmetric malonate addition to nitroolefins, can be prepared as found in J. Am. Chem. Soc. 2005, 127, 9958-9959.

[0258] Step 1: 3-iodo-1-methyl-5-(trifluoromethyl)pyrazole The compound 1-methyl-5-(trifluoromethyl)pyrazol-3-amine (5.00 g, 30.3 mmol) was stirred in 9 M sulfuric acid (818 mmol, 91 mL) in a 500 mL beaker at 0° C. (ice bath) with an overhead stirrer until a homogenous mixture was obtained. Sodium nitrite (60.6 mmol, 4.18 g) in 10 mL of water was then added dropwise over 5 minutes to give a colorless solution and the reaction was stirred at 0° C. for an additional 20 minutes. Potassium iodide (75.7 mmol, 12.6 g) in 20 mL of water was then added dropwise to the reaction and the mixture was stirred for an additional 4 hours. The reaction was quenched with saturated sodium thiosulfate until the mixture was clear. The mixture was then diluted with dichloromethane and the phases were separated. The aqueous phase was further extracted with dichloromethane and the combined organic extracts were washed with water, dried (MgSO4), filtered and concentrated under vacuum to give a pale yellow oil. The crude product was purified by column chromatography (gradient elution of EtOAc / hexanes) to give 3-iodo-1-methyl-5-(trifluoromethyl)pyrazole as a colorless oil, 3.9 g (47%). 1 H NMR(400MHz, CDCl3)δ=6.76(s,1H)4.01(d,J=0.61Hz,3H).

[0259] Step 2: 1-Methyl-3-[(E)-2-nitrovinyl]-5-(trifluoromethyl)pyrazole Isopropylmagnesium chloride-lithium chloride in THF (23.55 mmol, 1.3 mol / L) was added dropwise to 3-iodo-1-methyl-5-(trifluoromethyl)pyrazole (5.0 g, 18.12 mmol) in THF (90 mL) at -20°C and the mixture was stirred for 2 h. 1-Dimethylamino-2-nitroethylene (27.17 mmol, 3.321 g) was added and the reaction was allowed to warm slowly to RT over 1 h. The reaction mixture was then carefully quenched with 2 M HCl and extracted with ethyl acetate. The organic extract was washed with brine, dried (MgSO4), filtered, concentrated and purified by chromatography (gradient elution of EtOAc / cyclohexane) to give 1-methyl-3-[(E)-2-nitrovinyl]-5-(trifluoromethyl)pyrazole (74.6%) as a yellow oil, 2.99 g (74.6%). 1 H NMR(400MHz, CDCl3)δ=7.89(d,J=13.7Hz,1H),7.63(d,J=13.7Hz,1H),6.88(s,1H),4.05(d,J=0.6Hz,3H).

[0260] Step 3: Diethyl 2-[(1S)-1-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-nitro-ethyl]propanedioate To a solution of 1-methyl-3-[(E)-2-nitrovinyl]-5-(trifluoromethyl)pyrazole (0.650 g, 2.94 mmol) in toluene (19.5 mL) was added diethyl malonate (0.676 mL, 4.41 mmol) followed by nickel(II) bis[(1R,2R)-N1,N2-bis(phenylmethyl)-1,2-cyclohexanediamine-N1,N2]dibromide (0.0588 mmol, 0.0472 g) and the mixture was stirred at ambient temperature for 20 h.

[0261] The reaction mixture was washed with water (2x10 mL) and the organic phase was separated, concentrated and purified by chromatography (gradient elution of EtOAc / cyclohexane) to give diethyl 2-[(1S)-1-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-nitro-ethyl]propanedioate as a pale yellow oil, 1.07 g (95%). 1 H NMR(400MHz,CDCl3)δ=6.53(s,1H),5.01(dd,1H),4.88(dd,J=4.3,13.9Hz,1H),4.35(ddd,J=4.4,7.7,9.0 Hz,1H),4.22(q,2H),4.16(q,J=7.1Hz,2H),3.90(s,3H),3.89(d,1H),1.26(t,3H),1.20(t,J=7.2Hz,3H).

[0262] Step 4: Ethyl (3R,4R)-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxylate To a solution of diethyl 2-[(1R)-1-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-nitro-ethyl]propanedioate (1.07 g, 2.81 mmol) in ethanol (42.1 mL) cooled to 0-5 °C (ice bath) under nitrogen, dichloronickel hexahydrate (2.95 mmol, 0.700 g) was added. Sodium borohydride (8.42 mmol, 0.325 g) was then added in portions to the pale green-blue solution. After 30 min, the cooling was removed and the reaction mixture was allowed to warm to ambient temperature. After stirring at ambient temperature for 5 h, the reaction mixture was cooled to 5-10 °C in an ice-water bath and slowly quenched with ammonium chloride solution, and the mixture was stirred for an additional 20 min. The mixture was then diluted with EtOAc (20 mL), filtered through a bed of Celite, and rinsed several times with water and EtOAc. The combined biphasic mixture was concentrated to remove most of the solvent, the residue was transferred to a separatory funnel, diluted with EtOAc (20 mL) and the organic phase was separated. The aqueous phase was further extracted with EtOAc (2x25 mL) and all organic extracts were combined, passed through a phase separator, concentrated and purified by chromatography (gradient elution of EtOAc / hexanes) to give 0.61 g (77%) of a pale yellow oil that crystallized on standing. 1H NMR (400MHz, CDCl3)δ=6.91(br s,1H),6.47(s,1H),4.28(q,J=7.2Hz,2H),4.14(q,1H),3.94(d,3H),3.80(dt,J=1.0, 9.0Hz,1H),3.63(d,J=9.3Hz,1H),3.52(dd,J=8.2,9.5Hz,1H),1.32(t,J=7.2Hz,3H).

[0263] Step 5: (3R,4R)-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxylic acid To a solution of ethyl (3R,4R)-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxylate (0.61 g, 2.0 mmol) in ethanol (6.0 mL) and water (2.0 mL) at 0° C. (ice bath) was added 2 M sodium hydroxide (3 mL, 6.0 mmol). The reaction mixture was stirred at 0° C. for 30 min, then diluted with water (15 mL) and extracted with EtOAc (25 mL). The organic extract was washed with water (10 mL) and the aqueous extracts were combined and acidified to pH 2 with dilute HCl. The acidified aqueous extract was then re-extracted with EtOAc (3×20 mL) and these organic extracts were passed through a phase separation cartridge and concentrated to give 0.54 g (quantitative) of a pale yellow oil that crystallized on standing. 1 H NMR(400MHz,CDCl3)□=6.59(s,1H),4.09(q,1H),3.94(s,3H),3.85-3.77(m,1H),3.72(d,J=10.0Hz,1H),3.66-3.58(m,1H).

[0264] Step 6: (3R,4R)-1-Methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxylic acid To a stirred solution of (3R,4R)-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxylic acid (0.57 g, 2.1 mmol, 0.57 g) in tetrahydrofuran (16 mL) at room temperature under nitrogen atmosphere was added potassium tert-butoxide (1.0 M in THF) (4.5 mL, 4.5 mmol) to give a pale yellow fine suspension. To this suspension was added iodomethane (0.19 mL, 3.1 mmol) and stirring was continued at room temperature for 20 h. The stirred reaction mixture was acidified to pH 2 with dilute HCl, the mixture was diluted with water (10 mL) and extracted with EtOAc (3x30 mL). The combined organic extracts were washed with brine (15 mL), dried over magnesium sulfate, filtered and the filtrate was concentrated to give a clear amber gum, 0.63 g (quantitative). 1H NMR:(400MHz,CDCl3)δ=6.68(s,1H),3.97(q,1H),3.94(s,3H),3.76-3.68(m,3H),2.99(s,3H).

[0265] Step 7 (3S,4R)-N-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxamide To a solution of (3R,4R)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxylic acid (0.61 g, 2.1 mmol) in dichloromethane (15 mL) was added 2,3-difluoroaniline (0.21 mL, 2.1 mmol). Propylphosphonic anhydride (50% by weight) in ethyl acetate (2.3 g, 3.6 mmol, 2.1 mL) was then added before immersing the reaction mixture in a room temperature water bath. N,N-diisopropylethylamine (1.1 mL, 6.3 mmol) was added dropwise and the reaction was stirred at room temperature for 2.5 hours. The reaction mixture was quenched by the addition of water (15 mL) and transferred to a phase separation cartridge. The aqueous phase was further extracted with DCM (2x10mL) and the combined organic extracts were concentrated and purified by chromatography (gradient elution with EtOAc / hexanes) to give a pink oil. Trituration with isohexane gave 398mg (47%) of a pale pink solid. 1H NMR:(400MHz,CDCl3)δ=10.16(br s,1H),8.08-8.01(m,1H),7.02(ddt,J=2.1,5.9,8.3Hz,1H),6.93-6.84(m,1H),6.69(s ,1H),4.09(q,1H),3.94(s,3H),3.78(d,J=9.5Hz,1H),3.76-3.65(m,2H),2.98(s,3H).

[0266] Chiral HPLC analysis by the method described above confirmed an enantiomeric ratio of 97:3.

[0267] Using the above two synthetic routes, additional compounds of formula (II) were synthesized in an analogous manner and are shown in Tables 3 and 4 below.

[0268] [Table 12-1] [Table 12-2] [Table 12-3]

[0269] [Table 13]

[0270] Biological Examples Herbicidal activity of the compounds of formula (II) Seeds of various test species [Ipomoea hederacea (IPOHE); Zea mays (ZEAMX); Echinochloa crus-galli (ECHCG); Setaria faberi (SETFA); Abutilon theophrasti (ABUTH); Amaranthus retroflexus (AMARE)] were sown in standard sterile soil in pots. After 1 day of cultivation (pre-emergence) or 8 days of cultivation (post-emergence) under controlled conditions in a greenhouse (24 / 16°C, day / night; 14 hours of light; 65% humidity), the plants were sprayed with an aqueous spray solution obtained from a formulation of the technical active ingredient in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN9005-64-5), subsequently diluted in water and sprayed to give the specified application rate.

[0271] The test plants were then grown in a greenhouse under controlled conditions (24 / 16° C., day / night; 14 hours light; 65% humidity) and watered twice a day.

[0272] The tests were visually assessed for percent phytotoxicity to the plants pre-emergence and 13 days post-emergence (100 = complete damage to the plants; 0 = no damage to the plants). The results are shown in Tables B1 and B2.

[0273] [Table 14]

[0274] [Table 15] Yet another aspect of the present invention may be as follows. [1] (A) Formula (I): [ka] (In the formula, R 1 is methyl or methoxy, R 2 is hydrogen, methyl or ethoxy, A is a substituted heteroaryl group, and the compound has [ka] (selected from the group consisting of or an N-oxide or salt form thereof; (B) Formula (II) [ka] (In the formula, R B1 is H, methyl, or methoxy; X is O or S; Q 1 is R at one ring nitrogen. B2 and at least one ring carbon is substituted with R B3 and di- or trisubstituted pyrazoles substituted by R B2 is C1 ~C 3 Alkyl or C 1 ~C 3 fluoroalkyl, and each R B3 are independently halogen, C 1 ~C 3 Fluoroalkyl, C 1 ~C 3 Haloalkoxy, C 1 ~C 3 Alkoxy or C 1 ~C 3 Haloalkyl, C 1 ~C 3 Fluoroalkyl, C 1 ~C 3 Haloalkoxy, C 1 ~C 3 Alkoxy or C 1 ~C 3 Is it alkyl; Or, Q. 1 is R at one ring nitrogen. B2 and at adjacent ring carbons R B3 and disubstituted pyrazoles substituted by R B2 is C 1 ~C 3 is alkyl, R B3 is C 1 ~C 3 Fluoroalkyl or C 1 ~C 3 is alkyl, R B2 and R B3 are the atoms to which they are bonded and Q 1 together with forming an 8- or 9-membered fused heterobicyclic ring system; Q 2 can have 1, 2, or 3 R B5 a phenyl, pyridinyl, or thienyl ring system optionally substituted by substituents; and Each R B5 are independently halogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Haloalkoxy, Cyano, Nitro, C 1 ~C 6 Alkylthio, C 1 ~C 6 Alkylsulfinyl, or C 1 ~C 6 alkylsulfonyl) or an N-oxide or salt form thereof A composition comprising: 〔2〕R B1 The composition according to claim 1, wherein is H or methyl. [3] The composition according to [1] or [2] above, wherein X is O. 〔4〕Q 2 i, Q 2 -1、Q 2 -2、Q 2 -3、Q 2 -4、Q 2 -5 and Q 2 -6

change

change

[10] The 8- or 9-membered fused heterobicyclic ring system is represented by the formula Q shown below. 1 -F1~Q 1 -F12:

change

change

[11] above, wherein is selected from the group consisting of methyl, ethyl, n-propyl, trifluoromethyl and difluoroethyl.

[13] The composition according to any one of [1] to

[12] above, further comprising a third component (C) selected from the group consisting of mesotrione, bicyclopyrone, atrazine, S-metolachlor, terbuthylazine, dimethachlor, flufenacet, glyphosate, isoxaflutole, nicosulfuron, ametryn, hexazinone, paraquat, diquat, pyridate, acetochlor, dimethenamide-P, alachlor, petoxamide, pyroxosulfone, trifloxysulfuron sodium, flazasulfuron, prosulfocarb, metolachlor, and pretilachlor.

[14] The composition according to any one of [1] to

[13] above, further comprising one or more safeners selected from the group consisting of AD67, benoxacor, cloquintocet-mexyl, cyometrinil, cyprosulfamide, dichlormid, dicyclonone, diethrate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, furilazone, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, oxabetrinil, naphthalic anhydride, TI-35, N-isopropyl-4-(2-methoxy-benzoylsulfamoyl)-benzamide, and N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.

[15] A method for controlling a plant, comprising the step of applying to the plant or a habitat of the plant a herbicidally effective amount of the composition described in any one of [1] to

[14] .

[16] A method for inhibiting plant growth, comprising the step of applying to the plant or its growing area an herbicidally effective amount of the composition described in any one of [1] to

[14] .

[17] A method for controlling weeds in a crop of a useful plant, comprising the step of applying a herbicidally effective amount of the composition according to any one of [1] to

[14] to the weeds or the habitat of the weeds, or to the useful plant or the habitat of the useful plant.

[18] A method for selectively controlling grasses and / or weeds in a crop of a useful plant, comprising the step of applying a herbicidally effective amount of the composition described in any one of [1] to

[14] to the useful plant or its habitat, or to a cultivated area.

[19] The method according to any one of

[15] to

[18] above, wherein the weight ratio of component (A) to component (B) is 0.01:1 to 100:1.

[20] The method according to any one of

[15] to

[18] , wherein the component (A) is applied in an amount of 50 to 2000 g ai / ha.

[21] The method according to any one of

[15] to

[18] , wherein the component (A) is applied in an amount of 5 to 25 g ai / ha.

Claims

1. Formula (II) (In the formula, R B1 is methyl; X is O or S; Q 1 is R at one ring nitrogen B2 and at least one ring carbon is substituted by R B3 and disubstituted pyrazoles substituted by R B2 is selected from the group consisting of methyl, ethyl, n-propyl, trifluoromethyl, and difluoroethyl; B3 are independently chloro, fluoro, bromo, difluoromethyl, trifluoromethyl, C 1 ~C 3 Haloalkoxy, C 1 ~C 3 Alkoxy or C 1 ~C 3 is alkyl; Q 1 Is, Q 1 -2a, Q 1 -2b, Q 1 -2c, Q 1 -2d and Q 1 -2e (In the formula, R B3SN is halogen, C 1 ~C 3 Fluoroalkyl, C 1 ~C 3 Haloalkoxy, C 1 ~C 3 Alkoxy, and C 1 ~C 3 alkyl, and the wavy line indicates the point of attachment to the remainder of the molecule. ; Q 2 is one, two, or three R B5 is a phenyl ring optionally substituted by substituents; and Each R B5 are independently fluoro, ethyl, trifluoromethyl, difluoroethyl, methoxy, difluoromethoxy, or trifluoromethoxy. or an N-oxide or salt thereof.

2. The compound of claim 1 , wherein X is O.

3. Q 2 But, Q 2 -1 (wherein n is an integer of 0, 1, 2, or 3; R B5 is as defined in claim 1, where the wavy line represents the point of attachment to the remainder of the molecule.

3. The compound according to claim 1 or 2,

4. (A) Formula (I): (In the formula, R 1 is methyl or methoxy, R 2 is hydrogen, methyl or ethoxy, A is a substituted heteroaryl group, and the compound has (selected from the group consisting of or an N-oxide or salt thereof; (B) Formula (II) (In the formula, R B1 is methyl; X is O; Q 1 is R at one ring nitrogen B2 and at least one ring carbon is substituted by R B3 and disubstituted pyrazoles substituted by R B2 is selected from the group consisting of methyl, ethyl, n-propyl, trifluoromethyl, and difluoroethyl; B3 are independently chloro, fluoro, bromo, difluoromethyl, trifluoromethyl, C 1 ~C 3 Haloalkoxy, C 1 ~C 3 Alkoxy or C 1 ~C 3 is alkyl; Q 1 Is, Q 1 -2a, Q 1 -2b, Q 1 -2c, Q 1 -2d and Q 1 -2e (In the formula, R B3SN is halogen, C 1 ~C 3 Fluoroalkyl, C 1 ~C 3 Haloalkoxy, C 1 ~C 3 Alkoxy, and C 1 ~C 3 alkyl, where the wavy line indicates the point of attachment to the remainder of the molecule; Q 2 is one, two, or three R B5 a phenyl ring substituted by a substituent; and Each R B5 are independently halogen, C 1 ~C 4 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy or C 1 ~C 3 haloalkoxy) or a salt thereof A composition comprising:

5. Q 2 But, Q 2 -1 (wherein n is an integer of 0, 1, 2, or 3; R B5 is as defined in claim 4, where the wavy line represents the point of attachment to the remainder of the molecule. The composition of claim 4 ,

6. 6. A method of controlling plants comprising the step of applying to said plants or to the locus of said plants a herbicidally effective amount of a composition according to claim 4 or 5.

7. 6. A method of inhibiting the growth of a plant, comprising the step of applying to said plant or its locus a herbicidally effective amount of a composition according to claim 4 or 5.

8. 6. A method for controlling weeds in a crop of useful plants, comprising the step of applying to the weeds or to the locus of the weeds or to the useful plants or to the locus of the useful plants a herbicidally effective amount of a composition according to claim 4 or 5.

9. 6. A method for selectively controlling grasses and / or weeds in a crop of useful plants, comprising the step of applying to said useful plants or their habitat or to the area of ​​cultivation a herbicidally effective amount of a composition according to claim 4 or 5.

10. 4. A method for controlling plants, comprising the step of applying to said plants or to the locus of said plants a herbicidally effective amount of a compound of formula (II) as defined in any one of claims 1 to 3.

11. 4. A method for inhibiting the growth of plants, comprising the step of applying to said plants or their locus a herbicidally effective amount of a compound of formula (II) as defined in any one of claims 1 to 3.

12. A method for controlling weeds in crops of useful plants, comprising the step of applying to said weeds or to the locus of said weeds or to said useful plants or to the locus of said useful plants a herbicidally effective amount of a compound of formula (II) according to any one of claims 1 to 3.

13. A method for selectively controlling grasses and / or weeds in crops of useful plants, comprising the step of applying to said useful plants or their habitat or to the area of ​​cultivation a herbicidally effective amount of a compound of formula (II) as defined in any one of claims 1 to 3.

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