Atropisomers of pyridazinone derivatives as herbicides

Abstract

To provide an atropisomer of a specific pyridazinone derivative, a method for preparing the same, and a herbicidal composition containing the specific compound.SOLUTION: There is provided an optically active compound selected from the atropisomers of Formula 1a and Formula 1b, their N-oxides or salts, wherein said atropisomers of Formula 1a or 1b, their N-oxides or salts have a plus (+) rotation value and exist over their corresponding enantiomers, or their N-oxides or salts.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to stereoisomers of certain pyridazinone derivatives, their N-oxides, salts and compositions, and methods of their use to control undesirable vegetation. More specifically, the present disclosure relates to atropisomers of certain pyridazinone derivatives, their N-oxides, salts and compositions, and methods of their use as herbicides. [Background technology]

[0002] Controlling undesirable vegetation is crucial to achieving high yield efficiency. It is particularly desirable to achieve selective control of weed growth in useful crops, such as rice, soybeans, sugar beets, corn, potatoes, wheat, barley, tomatoes, and plantation crops. Allowing weeds to grow in such useful crops can significantly reduce productivity, thereby resulting in increased costs for consumers. Controlling undesirable vegetation in non-cultivated areas is also important. While many products for these purposes are available on the market, there remains a need for new compounds that are more effective, less costly, less toxic, environmentally safer, or have a different mechanism of action.

[0003] US Pat. Nos. 5,899,929 and 5,999,929 disclose herbicidal pyridazinones and synthetic intermediates used to prepare herbicidal pyridazinones. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2015 / 168010 Brochure [Patent Document 2] International Publication No. 2017 / 074988 Brochure Summary of the Invention [Means for solving the problem]

[0005] The present disclosure provides optically active atropisomers of pyridazinone derivatives of compounds of Formula 1a and Formula 1b, their N-oxides or salts; the compound of Formula 1 is a racemic mixture of the atropisomer of Formula 1a and the atropisomer of Formula 1b. [ka] During the ceremony, R 1 is CH3 or halogen; R 2 is CH3, CH2CH3, halogen, trifluoromethyl or difluoromethoxy; R 3 is H, CH or halogen; R 4 is H, CH or halogen; R 5 is H, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl or C1-C4 alkylcarboxymethyl; where: Atropisomers of formula 1a or 1b, their N-oxides or salts exist in addition to their corresponding enantiomers, or their N-oxides or salts.

[0006] In another aspect, the disclosure provides a method for preparing a compound of formula 1a or 1b; [ka] During the ceremony, R 1 is CH3 or halogen; R 2 is CH3, CH2CH3, halogen, trifluoromethyl or difluoromethoxy; R 3 is H, CH or halogen; R 4 is H, CH or halogen; R5 is H, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl or C1-C4 alkylcarboxymethyl; This method is 1) loading a racemic mixture of the compound of Formula 1, including the atropisomers of Formulas 1a and 1b, onto a chiral supported chromatography column and eluting with a mobile phase; 2) Isolating two separate fractions with different retention times; one containing the atropisomer with a positive optical rotation value [α]1(+) and one containing the atropisomer with a negative optical rotation value [α]1(-). Includes.

[0007] Detailed Description of the Invention As used herein, the terms "comprises," "comprising," "includes," "including," "contains," "containing," "has," "having," and "characterized by," or various variations thereof, are intended to cover a non-exclusive inclusion, subject to various limitations expressly indicated. For example, a process or method including any elements is not necessarily limited to only those elements, but may include other elements not expressly indicated or inherent in such composition, process, or method.

[0008] The transitional phrase "consisting of" excludes any unspecified element, step, or ingredient. In patent claims, this is usually the case if the claim is closed to include, apart from impurities, materials different from those recited. When the phrase "consisting of" appears in a clause in the body of a claim rather than immediately following the preamble, it limits only the elements recited in that claim; other elements are not excluded from the claim as a whole.

[0009] The transition phrase "consisting essentially of" means that the additional materials, steps, components, ingredients, or elements are in addition to what is literally disclosed, provided that these additional materials, steps, components, ingredients, or elements do not materially affect the basic and novel characteristics of the disclosure. The term "consisting essentially of" is used to define a process or method that includes, but is not limited to, materials, steps, components, ingredients, or elements. The term "consisting essentially of" occupies a middle ground between "comprising" and "consisting of."

[0010] It should be readily understood that if an applicant defines a disclosure or portion thereof in open-ended terms such as "comprising," then (unless otherwise stated) the statement should be construed as also describing such disclosures using the terms "consisting essentially of" or "consisting of."

[0011] Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not an exclusive "or." For example, the condition "A or B" is satisfied by any of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0012] Furthermore, the indefinite articles "a" and "an" preceding an element or component of the present disclosure are intended to be open-ended regarding the number of instances (i.e., occurrences) of that element or component. Thus, "a" and "an" should be read to include one, or at least one, and such singular forms of the element or component also include the plural, unless it is clear that the number is intended to be singular.

[0013] The term "C1-C4 alkyl" includes straight-chain or branched alkyl having 1 to 4 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl or the different butyl isomers. As used herein, the term "halogen" includes fluorine, chlorine, bromine or iodine. The term "C1-C4 alkylcarbonyl", as used herein, refers to a C1-C4 alkyl bonded via a carbonyl. The term "C1-C4 alkoxycarbonyl" refers to a C1-C4 alkoxy group bonded via a carbonyl. The term "C1-C4 alkylcarboxymethyl" refers to a (C1-C4 alkyl)C=O group bonded via a -CH2- group.

[0014] Compounds of Formula 1a and Formula 1b can typically exist independently in different solid forms. Thus, compounds of Formula 1a and Formula 1b include all crystalline and amorphous forms that the compounds exhibit. Amorphous forms include solid embodiments, such as waxes and rubbers, as well as liquid embodiments, such as solutions and melts. Crystalline forms include embodiments that exhibit a substantially single crystal type and embodiments that exhibit a mixture of polymorphs (i.e., multiple crystalline types). The term "polymorph" refers to a particular crystalline form of a compound that can crystallize in various crystalline forms, which have different molecular arrangements and / or conformations within the crystal lattice. Multiple polymorphs can have the same chemical composition, but they can also differ in composition due to the presence or absence of co-crystallized water or other molecules that can be weakly or strongly bound in the lattice. Polymorphs can differ in chemical, physical, and biological properties such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspendability, dissolution rate, and biological availability.

[0015] As will be appreciated by those skilled in the art, polymorphs of the compounds of Formula 1a and Formula 1b can exhibit advantageous effects (e.g., suitability in preparing useful formulations, improved biological performance) compared to other polymorphs or mixtures of polymorphs of the same compounds of Formula 1a and Formula 1b. The preparation and isolation of specific polymorphs of the compounds of Formula 1a and Formula 1b can be accomplished, for example, by the isolation of selected This can be achieved by methods known to those skilled in the art, such as crystallization using solvents and temperatures. For a comprehensive discussion of polymorphism, see R. Hilfiker, Ed., Polymorphism in the Pharmaceutical Industry, Wiley-VCH, Weinheim, 2006.

[0016] Exemplary procedures for preparing N-oxides include the oxidation of heterocycles and tertiary amines with organic peroxyacids, such as peracetic acid and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides, such as t-butyl hydroperoxide, sodium perborate, and dioxiranes, such as dimethyldioxirane. These methods for preparing N-oxides have been widely described and reviewed in the literature; see, for example, T. L. Gilchrist, Comprehensive Organic Synthesis,vol.7,pp.748-750(SVLey,Ed.,Pergamon Press);M.Tisler and B.Stanovnik,Comprehensive Heterocyclic Chemistry,vol.3,pp.18-20(AJBoulton and A.McKillop,Eds.,Pergamon Press);MRGrimmett and BRTKeene,Advances in Heterocyclic Chemistry, vol. 43, pp. 149-161 (ARKatritzky, Ed., Academic Press); M. Tisler and B. Stanovnik, Advances in Heterocyclic Chemistry, vol. 9, pp. 285-291 (ARKatritzky and AJ Boulton, Eds., Academic Press); and GWHCeeseman and ESGWerstiuk, Advances in Heterocyclic Chemistry, vol. 22, pp. 390-392 (A.R. Katrittzky and A.J. Boulton, Eds., Academic Press). However, those skilled in the art will recognize that not all nitrogen-containing heterocycles can form N-oxides, because nitrogen requires an available lone pair of electrons for oxidation to oxide. Those skilled in the art will recognize those nitrogen-containing heterocycles that can form N-oxides.

[0017] The compounds of the present invention can exist as one or more stereoisomers. Various stereoisomers include enantiomers, diastereomers, atropisomers, and geometric isomers. Stereoisomers are isomers that have the same constitution but differ in the arrangement of their atoms in space, and include enantiomers, diastereomers, cis-trans isomers (also known as geometric isomers), and atropisomers. Atropisomers result from restricted rotation around a single bond, where the rotational barrier is high enough to allow the isolation of isomeric species. Those skilled in the art will recognize that one atropisomer may be more active and / or exhibit beneficial effects when enriched (i.e., in excess) with respect to other atropisomer(s) or when separated from other atropisomer(s). The compounds of the present invention may exist as a mixture of atropisomers, individual atropisomers, or as optically active forms, optionally with one atropisomer in excess of its corresponding enantiomer.

[0018] In particular, the compounds of the present invention include atropisomers that are more active than other atropisomers.

[0019] Some non-limiting embodiments of the present disclosure (wherein the compounds of Formula 1a and Formula 1b also include N-oxides or salts thereof):

[0020] Embodiment A1. An optically active compound comprising (or consisting of) an atropisomer of a compound of formula 1a, or an N-oxide or salt thereof, which exists in excess of its corresponding enantiomer of formula 1b, or an N-oxide or salt thereof. [ka]

[0021] Embodiment A2. 1 A compound according to embodiment A1, wherein is CH3.

[0022] Embodiment A3. 1 A compound according to embodiment A1, wherein is halogen.

[0023] Embodiment A4. R 1 A compound according to embodiment A3, wherein is Cl, F or Br.

[0024] Embodiment A5. R 1 A compound according to embodiment A4, wherein is Cl or CH3.

[0025] Embodiment A6. 1 A compound according to embodiment A5, wherein is Cl.

[0026] Embodiment A7. R 2 The compound of any one of embodiments A1 through A6, wherein is CH3, CH2CH3, halogen, or difluoromethoxy.

[0027] Embodiment A8. R 2 A compound according to embodiment A7, wherein is CH3, CH2CH3, Cl, or difluoromethoxy.

[0028] Embodiment A9. R 2 A compound according to embodiment A8, wherein is CH3 or difluoromethoxy.

[0029] Embodiment A10. R 2 The compound according to embodiment A9, wherein is CH3.

[0030] Embodiment A11. R 3 The compound according to any one of embodiments A1 to A10, wherein is H or CH3.

[0031] Embodiment A12. R 3 A compound according to embodiment A11, wherein is H.

[0032] Embodiment A13. R 3 A compound according to embodiment A12, wherein is CH3.

[0033] Embodiment A14. R 4The compound according to any one of embodiments A1 to A13, wherein is H, CH3, or Cl.

[0034] Embodiment A15. R 4 A compound according to embodiment A14, wherein is Cl.

[0035] Embodiment A16. R 4 A compound according to embodiment A14, wherein is CH3.

[0036] Embodiment A17. R 4 A compound according to embodiment A14, wherein is H.

[0037] Embodiment A18. R 5 The compound of any one of embodiments A1 to A17, wherein is H, C3 alkylcarbonyl, C3 alkoxycarbonyl, or C3 alkylcarboxymethyl.

[0038] Embodiment A19. R 5 A compound according to embodiment A18, wherein is H or C3 alkylcarbonyl.

[0039] Embodiment A20. R 5 A compound according to embodiment A18, wherein is H or —(C═O)CH 2 CH 3 .

[0040] Embodiment A21. R 5 A compound according to embodiment A20, wherein is H.

[0041] Embodiment AA1. An optically active compound consisting of atropisomers of compounds of formula 1b, or N-oxides or salts thereof, which exist in excess of their corresponding enantiomers of formula 1a, or N-oxides or salts thereof. [ka]

[0042] Embodiment AA2. 1 A compound according to embodiment AA1, wherein is CH3.

[0043] Embodiment AA3. 1 A compound according to embodiment AA1, wherein is halogen.

[0044] Embodiment AA4. 1 A compound according to embodiment AA3, wherein is Cl, F or Br.

[0045] Embodiment AA5. 1 A compound according to embodiment AA4, wherein is Cl or F.

[0046] Embodiment AA6.R 1 A compound according to embodiment A5, wherein is Cl.

[0047] Embodiment AA7. 2 A compound according to any one of embodiments AA1 to AA6, wherein is CH3, CH2CH3, halogen, or difluoromethoxy.

[0048] Embodiment AA8. R 2 A compound according to embodiment AA7, wherein is CH3, CH2CH3, Cl, or difluoromethoxy.

[0049] Embodiment AA9. R 2 A compound according to embodiment AA8, wherein is CH3 or difluoromethoxy.

[0050] Embodiment AA10. R 2 The compound according to embodiment AA9, wherein is CH3.

[0051] Embodiment AA11. R 3 The compound according to any one of embodiments AA1 to AA10, wherein is H or CH3.

[0052] Embodiment AA12. R 3 A compound according to embodiment AA11, wherein is H.

[0053] Embodiment AA13. 3A compound according to embodiment AA12, wherein is CH3.

[0054] Embodiment AA14. R 4 A compound according to any one of embodiments AA1 to AA13, wherein is H, CH3, or Cl.

[0055] Embodiment AA15. R 4 A compound according to embodiment AA14, wherein is Cl.

[0056] Embodiment AA16.R 4 A compound according to embodiment AA14, wherein is CH3.

[0057] Embodiment AA17. R 4 A compound according to embodiment AA14, wherein is H.

[0058] Embodiment AA18. R 5 The compound of any one of embodiments AA1 to AA17, wherein is H, C3 alkylcarbonyl, C3 alkoxycarbonyl, or C3 alkylcarboxymethyl.

[0059] Embodiment AA19. R 5 A compound according to embodiment AA18, wherein is H or C3 alkylcarbonyl.

[0060] Embodiment AA20.R 5 A compound according to embodiment AA18, wherein is H or —(C═O)CH 2 CH 3 .

[0061] Embodiment AA21.R 5 A compound according to embodiment AA20, wherein is H.

[0062] Embodiment B1. A method described in the Summary of the Invention for preparing a compound of Formula 1a or 1b. [ka]

[0063] Embodiment B2. R 1 The method of embodiment B1, wherein is CH3.

[0064] Embodiment B3. 1 The method of embodiment B1, wherein is a halogen.

[0065] Embodiment B4. R 1 The method of embodiment B3, wherein is Cl, F or Br.

[0066] Embodiment B5. R 1 The method of embodiment B4, wherein is Cl or F.

[0067] Embodiment B6. R 1 The method of embodiment B5, wherein is Cl.

[0068] Embodiment B7. R 2 The method of any one of embodiments B1 through B6, wherein is CH3, CH2CH3, halogen, or difluoromethoxy.

[0069] Embodiment B8. R 2 The method of embodiment B7, wherein is CH3, CH2CH3, Cl, or difluoromethoxy.

[0070] Embodiment B9. R 2 The method of embodiment B8, wherein is CH3 or difluoromethoxy.

[0071] Embodiment B10. R 2 The method of embodiment B9, wherein is CH3.

[0072] Embodiment B11. R 3 The method of any one of embodiments B1-B10, wherein is H or CH3.

[0073] Embodiment B12. R 3 The method of embodiment B11, wherein is H.

[0074] Embodiment B13. R3 The method of embodiment B11, wherein is CH3.

[0075] Embodiment B14. R 4 The method of any of embodiments B1-B13, wherein is H, CH3, or Cl.

[0076] Embodiment B15. R 4 The method of embodiment B14, wherein is Cl.

[0077] Embodiment B16. R 4 The method of embodiment B14, wherein is CH3.

[0078] Embodiment B17. R 4 The method of embodiment B14, wherein is H.

[0079] Embodiment B18. R 5 The method of any one of embodiments B1 through B17, wherein is H, C3 alkylcarbonyl, C3 alkoxycarbonyl, or C3 alkylcarboxymethyl.

[0080] Embodiment B19. R 5 The method of embodiment B18, wherein is H or C3 alkylcarbonyl.

[0081] Embodiment B20. 5 The method of embodiment B18, wherein is H or —(C═O)CH 2 CH 3 .

[0082] Embodiment B21. R 5 The method of embodiment B20, wherein is H.

[0083] Embodiment B22 The method of embodiment B1 wherein the chiral support chromatography is supercritical fluid chromatography (SFC).

[0084] Embodiment B23 The method of embodiment B1 wherein the mobile phase is carbon dioxide.

[0085] Embodiment C1. More herbicidally active than its corresponding atropisomer, Embodiments A1-A A compound according to any one of A21.

[0086] Embodiment C2. A compound according to embodiment C1 which is more active against grasses than its corresponding atropisomer.

[0087] The above-mentioned embodiment or any embodiment herein can be combined in any way.The present invention also relates to a method for controlling undesired vegetation, comprising applying a herbicidally effective amount of the compound of formula 1a or formula 1b to the habitat of the vegetation (for example, as the composition described herein).Notable embodiments of the method of use involve the compounds of the above-mentioned embodiments.The compounds of the present invention are particularly useful for selectively controlling weeds in crops such as wheat, barley, corn, soybean, sunflower, cotton, rapeseed and rice, and specialty crops such as sugarcane, citrus, fruit and nut crops.

[0088] Also of note as an embodiment are herbicidal compositions of the invention comprising a compound of the above embodiments.

[0089] The present invention further includes herbicidal mixtures comprising: (a) a compound selected from Formula 1a and Formula 1b, their N-oxides, and salts, and (b) at least one additional active ingredient, selected from: (b1) a photosystem II inhibitor, (b2) an acetohydroxyacid synthase (AHAS) inhibitor, (b3) an acetyl-CoA carboxylase (ACCase) inhibitor, (b4) an auxin mimetic, (b5) a 5-enol-pyruvylshikimate-3-phosphate (EPSP) synthase inhibitor, (b6) a photosystem I electron diverter, (b7) a hydroxybenzoate (HPO) inhibitor, (b8) a hydroxybenzoate (HPO) inhibitor, (b9) a hydroxybenzoate (HPO) inhibitor, (b10) a hydroxybenzoate (HPO) inhibitor, (b11) a hydroxybenzoate (HPO) inhibitor, (b12) a hydroxybenzoate (HPO) inhibitor, (b13) a hydroxybenzoate (HPO) inhibitor, (b14) a hydroxybenzoate (HPO) inhibitor, (b15) a hydroxybenzoate (HPO) inhibitor, (b16) a hydroxybenzoate (HPO) inhibitor, (b17) a hydroxybenzoate (HPO) inhibitor, (b18) a hydroxybenzoate (HPO) inhibitor, (b19 ... diverter), (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8) glutamine synthetase (GS) inhibitors, (b9) very long chain fatty acid (VLCFA) elongase inhibitors, (b10) auxin transport inhibitors, (b11) phytoene desaturase (PDS) inhibitors, (b12) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b13) homogentisate solanesyltransferase (HST) inhibitors, (b14) cellulose biosynthesis inhibitors, (b15) other herbicides (including mitotic disruptors, organic arsenic compounds, asulam, bromobutide, cinmethylin, cumyluron, dazomet, difenzoquat, dymron, etobenzanide, flurenol, fosamine, fosamine-ammonium, hydantocidin, metam, methyldymron, oleic acid, oxaziclomefon, pelargonic acid, and biributicarb), (b16) herbicide safeners, and salts of the compounds (b1) to (b16).

[0090] "Photosystem II inhibitor" (b1) is Q B -Binding niche (Q B -binding niche) and thereby bind to the D-1 protein, thereby inhibiting the Q-binding niche in the thylakoid membrane of chloroplasts. A From Q BBlocking electron transport through photosystem II. Electrons blocked from the pathway through photosystem II are transported through a series of reactions to form toxic compounds that disrupt the cell membrane, leading to swelling of the chloroplast, membrane leakage, and ultimately cell destruction. B The binding niche has three different binding sites: binding site A binds triazines such as atrazine, triazinones such as hexazinone, and uracils such as bromacil; binding site B binds phenylureas such as diuron; and binding site C binds benzothiadiazoles such as bentazone, nitriles such as bromoxynil, and phenylpyridazines such as pyridate. Examples of photosystem II inhibitors include ametryn, amicarbazone, atrazine, bentazone, bromacil, bromofenoxime, bromoxynil, chlorbromuron, chloridazon, chlorotoluron, chloroxyuron, cumyluron, cyanazine, dymron, desmedipham, desmetrin, dimefuron, dimethamethrin, diuron, and ethidimuron. , fenuron, fluometuron, hexazinone, ioxynil, isoproturon, isouron, lenacil, linuron, metamitron, methabenzthiazuron, metobromuron, methoxyuron, metribuzin, monolinuron, nebron, pentanochlor, phenmedipham, prometon, prometryn, propanil, propazine, pyridafol, pyridate, siduron, simazine, simetryn, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, and trietazine.

[0091] "AHAS inhibitors" (b2) are compounds that inhibit acetohydroxyacid synthase (AHAS), also known as acetolactate synthase (ALS), and cause plant death by preventing the production of branched-chain aliphatic amino acids, such as valine, leucine, and isoleucine, which are required for protein synthesis and cell growth.Examples of AHAS inhibitors include: amidosulfuron, azimsulfuron, bensulfuron-methyl, bispyribac-sodium, cloransulam-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, diclosulam, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, florasulam, flucarbazone-sodium, flumetsulam, flupyrsulfuron-methyl, flupyrsulfuron-sodium, foramsulfuron, and halosulfuron. -methyl, imazametabunzu-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron-methyl (including sodium salt), iofensulfuron (2-iodo-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide), mezosulfuron-methyl, metazosulfuron (3-chloro-4-(5,6-dihydro-5-methyl-1,4,2-dioxazin-3-yl)-N-[[(4,6-dimethoxazole) 2-chloro-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-1-methyl-1H-pyrazole-5-sulfonamide), metosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, penoxulam, primisulfuron-methyl, propoxycarbazone-sodium, propyrisulfuron (2-chloro-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-6-propylimidazo[1,2-b]pyridazine-3-sulfonamide), prosulfuron, pyrazosulfuron-ethyl, pyribenzoxime, pyrif Thalide, pyriminobac-methyl, pyrithiobac-sodium, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone, thifensulfuron-methyl, triafamone (N-[2-[(4,6-dimethoxy-1,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-1,1-difluoro-N-methylmethanesulfonamide), triasulfuron, tribenuron-methyl, trifloxysulfuron (including sodium salt), triflusulfuron-methyl, and tritosulfuron.

[0092] "ACCase inhibitors" (b3) are compounds that inhibit the enzyme acetyl-CoA carboxylase, which catalyzes an early step in the synthesis of lipids and fatty acids in plants. Lipids are essential components of cell membranes, without which new cells cannot be produced. Inhibition of acetyl-CoA carboxylase and the subsequent lack of lipid production leads to a loss of cell membrane integrity, especially in active growth zones, such as the meristem. Ultimately, shoot and root growth ceases, and the shoot meristem and root bud begin to wither. Examples of ACCase inhibitors include alloxydim, butroxydim, clethodim, clodinafop, cycloxydim, cyhalofop, diclofop, fenoxaprop, fluazifop, haloxyfop, pinoxaden, profoxydim, propaquizafop, quizalofop, sethoxydim, tepraloxydim, and tralkoxydim (including resolved forms such as fenoxaprop-P, fluazifop-P, haloxyfop-P, and quizalofop-P, and ester forms such as clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl, and fenoxaprop-P-ethyl).

[0093] Auxin is a plant hormone that regulates growth in many plant tissues. "Auxin mimetics" (b4) are compounds that mimic the plant growth hormone auxin, resulting in uncontrolled and unregulated growth and, in sensitive species, plant death. Examples of auxin mimetics include: aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid) and its methyl and ethyl esters and its sodium and potassium salts, aminopyralid, benazolin-ethyl, chloramben, clasifos, clomeprop, clopyralid, dicamba, 2,4-D, 2,4-DB, dicloprop, fluroxypyr, halaxifene (4-amino-3-chloro-6-(4-chloro- 2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylic acid), halaxifene-methyl (methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylate), MCPA, MCPB, mecoprop, picloram, quinclorac, quinmerac, 2,3,6-TBA, triclopyr, and methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate.

[0094] "EPSP synthase inhibitors" (b5) are compounds that inhibit 5-enol-pyruvylshikimate-3-phosphate synthase, an enzyme involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan, and phenylalanine. EPSP-inhibiting herbicides are readily absorbed through the plant leaves and translocated to the growing point via the phloem. Glyphosate is a relatively nonselective postemergence herbicide that belongs to this group. Glyphosate includes esters and salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium), and trimesium (also known as sulfosate).

[0095] "Photosystem I electron diverters" (b6) are compounds that accept electrons from photosystem I and, after several cycles, generate hydroxyl radicals. These radicals are highly reactive and readily destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This disrupts the integrity of cell membranes, resulting in "leaks" in cells and organelles, rapid wilting and drying of leaves, and ultimately plant death. Examples of this second type of photosynthesis inhibitor include diquat and paraquat.

[0096] "PPO inhibitors" (b7) are compounds that inhibit the enzyme protoporphyrinogen oxidase, causing the rapid production of highly active compounds in plants that disrupt cell membranes and leak cell fluids. Examples of PPO inhibitors include acifluorfen-sodium, azafenidin, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, clomethoxyfen, cinidon-ethyl, fluazolate, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazin, fluoroglycofen-ethyl, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazole, pyraclonil, and pyraflufen-ethyl. , saflufenacil, sulfentrazone, thidiazimine, trifludimoxadine (dihydro-1,5-dimethyl-6-thioxo-3-[2,2,7-trifluoro-3,4-dihydro-3-oxo-4-(2-propyn-1-yl)-2H-1,4-benzoxazin-6-yl]-1,3,5-triazine-2,4(1H,3H)-dione), and thiafenacil (methyl N-[2-[[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenyl]thio]-1-oxopropyl]-β-alaninate).

[0097] "GS inhibitors" (b8) are compounds that block the activity of the glutamine synthetase enzyme, which plants use to convert ammonia to glutamine. Thus, ammonia accumulates and glutamine levels decrease. Damage to the plant may result from the combined effects of ammonia toxicity and a lack of amino acids needed for other metabolic processes. GS inhibitors include glufosinate and its esters and salts, such as glufosinate-ammonium and other phosphinothricin derivatives, glufosinate-P ((2S)-2-amino-4-(hydroxymethylphosphinyl)butanoic acid), and viranaphos.

[0098] "VLCFA elongase inhibitors" (b9) are herbicides with a wide variety of chemical structures that inhibit elongase, an enzyme located in or near chloroplasts that is involved in the biosynthesis of VLCFAs. In plants, very long-chain fatty acids are the main components of hydrophobic polymers that prevent desiccation on the leaf surface and provide stability to pollen grains. Such herbicides include acetochlor, alachlor, anilophos, butachlor, cafenstrole, dimethachlor, dimethenamid, diphenamid, fenoxasulfone (3-[[(2,5-dichloro-4-ethoxyphenyl)methyl]sulfonyl]-4,5-dihydro-5,5-dimethylisoxazole), fentrazamide, flufenacet, indanofan, mefenacet, metazachlor, metolachlor, naproanilide, napropamide, napropamide-M ((2R)-N,N-diethyl-2-(1-naphthalenyloxy)propanamide), petoxamide, piperophos, pretilachlor, propachlor, propisochlor, pyroxasulfone, and thenylchlor (including resolved forms, such as S-metolachlor, and chloroacetamides, and oxyacetamides).

[0099] "Auxin transport inhibitors" (b10) are chemical substances that inhibit the transport of auxin in plants, for example, by binding to auxin transport proteins. Examples of auxin transport inhibitors include: diflufenzopyr, naptalam (also known as N-(1-naphthyl)phthalamic acid, and 2-[(1-naphthalenylamino)carbonyl]benzoic acid).

[0100] "PDS inhibitors" (b11) are compounds that inhibit the carotenoid biosynthetic pathway at the phytoene desaturase step. Examples of PDS inhibitors include: beflubutamid, S-beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurzone, and picolinafen.

[0101] "HPPD inhibitors" (b12) are chemical substances that inhibit the biosynthesis of 4-hydroxyphenyl-pyruvate dioxygenase. Examples of HPPD inhibitors include: benzobicyclon, benzofenap, bicyclopyrone (4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]bicyclo[3.2.1]oct-3-en-2-one), fenquinotrione (2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl]-1,3-cyclohexanedione), isoxachlortol, isoxaflutole, and mesotrione. , pyrasulfotole, pyrazolinate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate (1-[[1-ethyl-4-[3-(2-methoxyethoxy)-2-methyl-4-(methylsulfonyl)benzoyl]-1H-pyrazol-5-yl]oxy]ethyl methyl carbonate), topramezone, 5-chloro-3-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalinone, 4-(2,6-diethyl-4-methylphenyl)- 5-Hydroxy-2,6-dimethyl-3(2H)-pyridazinone, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione, 5-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-(3-methoxyphenyl)-3-(3-methoxypropyl)-4(3H)-pyrimidinone, 2-methyl-N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide, and 2-methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide.

[0102] "HST inhibitors" (b13) disrupt the plant's ability to convert homogentisate to 2-methyl-6-solanyl-1,4-benzoquinone, thereby disrupting carotenoid biosynthesis. Examples of HST inhibitors include cyclopyrimorate (6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinyl 4-morpholinecarboxylate), haloxydine, pyriclor, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridin-2(1H)-one, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-b]pyrazin-6(5H)-one, and 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone.

[0103] HST inhibitors also include compounds of Formulas A and B: [ka] In the formula, R d1 is H, Cl, or CF; R d2 is H, Cl, or Br; R d3 is H or Cl; R d4 is H, Cl, or CF; R d5is CH3, CH2CH3, or CH2CHF2; and R d6 is OH, or -OC(=O)-i-Pr; and R e1 is H, F, Cl, CH3, or CH2CH3; R e2 is H or CF; R e3 is H, CH3, or CH2CH3; R e4 is H, F, or Br; R e5 is Cl, CH3, CF3, OCF3, or CH2CH3; R e6 is H, CH, CHCHF, or C≡CH; R e7 is OH, —OC(═O)Et, —OC(═O)-i-Pr, or —OC(═O)-t-Bu; and A e8 is N or CH.

[0104] "Cellulose biosynthesis inhibitors" (b14) inhibit the biosynthesis of cellulose in certain plants. They are most effective when applied to young plants or rapidly growing plants before or shortly after emergence. Examples of cellulose biosynthesis inhibitors include: chlorthiamid, dichlobenil, furopoxam, indaziflam (N 2 -[(1R,2S)-2,3-dihydro-2,6-dimethyl-1H-inden-1-yl]-6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine), Isoxaben, and triaziflam.

[0105] "Other herbicides" (b15) include herbicides that function through a variety of different modes of action, such as: mitotic disruptors (e.g., flamprop-M-methyl and flamprop-M-isopropyl), organoarsenic compounds (e.g., DSMA and MSMA), 7,8-dihydropteroate synthase inhibitors, chloroplast isoprenoid synthesis inhibitors, and cell wall biosynthesis inhibitors. Other herbicides also include herbicides with no known mode of action or that do not fall into the specific categories listed in (b1) to (b14), or that operate through a combination of the modes listed above. Examples of other herbicides include aclonifen, asulam, amitrole, bromobutide, cinmethylin, clomazone, cumylron, dymron, dimesulfazate (CAS number 1215111-77-5), difenzoquat, epirifenacil (CAS number 353292-31-6), etobenzanide, fluometuron, flurenol, fosamine, fosamine-ammonium, dazomet, dymron, ipfencarbazone (1-(2,4-dichlorophenoxy)methyl ... "Other herbicides" (b15) also include compounds of the formula (b15A): [ka] During the ceremony, R 12 is H, C1-C6 alkyl, C1-C6 haloalkyl, or C4-C8 cycloalkyl; R 13 is H, C1-C6 alkyl or C1-C6 alkoxy; Q 1is an optionally substituted ring system selected from the group consisting of phenyl, thienyl, pyridinyl, benzodioxolyl, naphthyl, naphthalenyl, benzofuranyl, furanyl, benzothiophenyl, and pyrazolyl, wherein when substituted, said ring system is selected from the group consisting of 1 to 3 R 14 is replaced by; Q 2 is an optionally substituted ring system selected from the group consisting of phenyl, pyridinyl, benzodioxolyl, pyridinonyl, thiadiazolyl, thiazolyl, and oxazolyl, wherein when substituted, said ring system is selected from the group consisting of 1 to 3 R 15 is replaced by; Each R 14 are independently halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C8 cycloalkyl, cyano, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, SF5, NHR 17 ; or 1 to 3 R 16 phenyl optionally substituted with one to three R 16 is pyrazolyl optionally substituted by Each R 15 are independently selected from halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, cyano, nitro, and C1-C6 alkylthio. , C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl; Each R 16 are independently halogen, C1-C6 alkyl, or C1-C6 haloalkyl; R 17 is a C1-C4 alkoxycarbonyl.

[0106] In one embodiment, where the "other herbicides" (b15) also comprise compounds of formula (b15A), R 12 is preferably H or C1-C6 alkyl; more preferably, R 12 is H or methyl. Preferably, R 13 is H. Preferably, Q1 is a phenyl ring or a pyridinyl ring, and each ring is 14 more preferably, substituted with Q 1 is 1 to 2 R 14 Preferably, Q is a phenyl ring substituted with 2 is 1 to 3 R 15 is a phenyl ring substituted with 2 is 1 to 2 R 15 Preferably, each R 14 are independently halogen, C1-C4 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; more preferably, each R 14 is independently chloro, fluoro, bromo, C1-C2 haloalkyl, C1-C2 haloalkoxy or C1-C2 alkoxy. Preferably, each R 15 are independently halogen, C1-C4 alkyl, C1-C3 haloalkoxy; more preferably, each R 15 is independently chloro, fluoro, bromo, C1-C2 haloalkyl, C1-C2 haloalkoxy, or C1-C2 alkoxy. Particularly preferred "other herbicides" (b15) include any one of the following (b15A-1) to (b15A-16).

[0107] [Table 1]

[0108] [Table 2]

[0109] [Table 3]

[0110] "Other herbicides" (b15) also include compounds of formula (b15B): [ka] During the ceremony, R 18 is H, C1-C6 alkyl, C1-C6 haloalkyl, or C4-C8 cycloalkyl; Each R 19 are independently halogen, C1-C6 haloalkyl, or C1-C6 haloalkoxy; p is an integer of 0, 1, 2 or 3; Each R 20 are independently halogen, C1-C6 haloalkyl, or C1-C6 haloalkoxy; q is an integer of 0, 1, 2 or 3.

[0111] In one embodiment, the "other herbicides" (b15) also include compounds of formula (b15B), R 18 is preferably H, methyl, ethyl or propyl; more preferably, R 18 is H or methyl; most preferably, R 18 is H. Preferably, each R 19 is independently chloro, fluoro, C1-C3 haloalkyl, or C1-C3 haloalkoxy; more preferably, each R 19 is independently chloro, fluoro, C1 fluoroalkyl (i.e., fluoromethyl, difluoromethyl, or trifluoromethyl), or C1 fluoroalkoxy (i.e., trifluoromethoxy, difluoromethoxy, or fluoromethoxy). Preferably, each R 20 is independently chloro, fluoro, C1 haloalkyl, or C1 haloalkoxy; more preferably, each R 20 are independently chloro, fluoro, C1 fluoroalkyl (i.e., fluoromethyl, difluoromethyl, or trifluoromethyl), or C1 fluoroalkoxy (i.e., trifluoromethoxy, difluoromethoxy, or fluoromethoxy). Particularly preferred examples of (b15B-1) include any one of the following (b15B-1) to (b15B-19):

[0112] [Table 4]

[0113] [Table 5]

[0114] [Table 6]

[0115] In another embodiment, the "other herbicides" (b15) also include compounds of formula (b15C): [ka] In the formula, R 1 is Cl, Br or CN; R 2 is C(=O)CH2CH2CF3, CH2CH2CH2CF3 or 3-CHF2-isoxazol-5-yl. Specific examples include compounds of formula (b15C) selected from (b15C1) 5-chloro-2-[3-chloro-2-[3-(difluoromethyl)-5-isoxazolyl]phenoxy]-pyrimidine and (b15C2) 1-[2-chloro-6-[(5-chloro-2-pyrimidinyl)oxy]phenyl]-4,4,4-trifluoro-1-butanone.

[0116] "Herbicide safeners" (b16) are substances added to herbicide formulations to eliminate or reduce the phytotoxic effects of the herbicide on certain crops. These compounds protect the crop from herbicide damage but typically do not prevent the herbicide from controlling undesirable vegetation. Examples of herbicide safeners include, but are not limited to, benoxacor, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfamide, dymron, dichlormid, dicyclonone, dietholate, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, methoxyphenone, naphthalic anhydride, oxabetrinil, N-(aminocarbonyl)-2-methylbenzenesulfonamide, and N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene, 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), 4-(dichloroacetyl)-1-oxa-4-azospiro[4.5]decane (MON 4660), 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-ethanone, and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide.

[0117] For better control of undesirable vegetation (e.g., lower application rates utilizing greater than additive effects, a broader spectrum of weeds controlled, or improved crop safety) or to prevent the development of resistant weeds, combinations of the compounds of the present invention with atrazine, azimsulfuron, beflubutamid, S-beflubutamid, benzisothiazolinone, carfentrazone-ethyl, chlorimuron-ethyl, chlorsulfuron-methyl, clomazone, clopyralid potassium, chloransulam-methyl, 2-[(2,4-dichloro-6-oxo- and a herbicide selected from the group consisting of [1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5-(2H,4H)-dione, flupyrsulfuron-methyl, fluthiacet-methyl, fomesafen, imazethapyr, lenacil, mesotrione, metribuzin, metsulfuron-methyl, petoxamide, picloram, pyroxasulfone, quinclorac, rimsulfuron, S-metolachlor, sulfentrazone, thifensulfuron-methyl, triflusulfuron-methyl, and tribenuron-methyl.

[0118] The substituted enantiomers of formula 1a (R) and formula 1b (S) can be isolated from the racemic compound of formula 1 by chiral support chromatography (see Scheme 1). The racemic compound of formula 1 is described in WO 2015168010. They can be prepared by the methods taught. Absolute stereochemistry can be assigned to the depicted heterobiaryl structure according to established naming conventions established in the art. Those skilled in the art will recognize that the two enantiomers, including racemates, can also be called atropisomers due to the restricted rotation of the naphthalene and pyridazinone rings of this heterobiaryl ring system. The restricted rotation locks the two rings into a defined stereo orientation, allowing for asymmetry. With the substitution on the naphthalene in the ortho position relative to the bond connecting the pyridazinone, both atropisomers are generally stable to racemization due to ring rotation at temperatures below 100°C. [ka]

[0119] Separation Example 1 A 1.8 g sample of racemic compound 2 was loaded onto a chiral support for supercritical fluid chromatography (SFC) using carbon dioxide as the supercritical fluid mobile phase or with an optional cosolvent, such as methanol or acetonitrile. Principles were used similar to those of standard non-chiral high-performance liquid chromatography (HPLC). Two fractions were obtained. The first eluted was labeled enantiomer 2a (580 mg), and the second was enantiomer 2b (600 mg). The optical rotations for 2a and 2b were +47.34 [20°C, c = 0.4 (methanol)] and −58.29 [20°C, c = 0.4 (methanol)], respectively. The enantiomeric excess (ee) of both samples was determined by chiral HPLC to be greater than 95%. [ka] [Brief explanation of the drawings]

[0120] [Figure 1] Figure 1 (Analytical chiral HPLC SFC chromatogram of enantiomer 2a (2A)) shows the chiral chromatogram for 2a with a retention time of 2.03 min, which further verifies the enantiomeric integrity. [Figure 2] Figure 2 (Analytical chiral HPLC SFC chromatogram of enantiomer 2b (2B)) shows the chiral chromatogram for 2b with a retention time of 3.24 min, further verifying the enantiomeric integrity. DETAILED DESCRIPTION OF THE INVENTION

[0121] Without undue effort, it is believed that one skilled in the art using the preceding description can utilize the present disclosure to its fullest extent. The following non-limiting examples are illustrative of the present disclosure.

[0122] The compounds of formula 1a and formula 1b are generally used as herbicidal active ingredients in compositions, i.e., formulations with at least one additional component selected from the group consisting of surfactants, solid excipients, and liquid excipients.In certain embodiments, the additional component can serve as a carrier.The components of the formulation or composition are selected according to the physical properties of the active ingredient, the application mode, and environmental factors such as soil type, moisture, and temperature.

[0123] Useful formulations include both liquid and solid compositions containing the compounds of Formula 1a and Formula 1b. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, flowable concentrates, and / or suspoemulsions), which may optionally be thickened to form gels. Common types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions, oil-in-water emulsions, flowable concentrates, and suspoemulsions. Common types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates, and oil dispersions.

[0124] Common types of solid compositions include dusts, powders, granules, pellets, prills, pastilles, tablets, and fill films (including seed coatings), which may be water-dispersible ("wettable") or water-soluble. Films and coatings formed from film-forming solutions or fluid suspensions are particularly useful for seed treatments. Active ingredients can be (micro)encapsulated or further processed into suspension or solid formulations; alternatively, the entire active ingredient formulation can be encapsulated (or "overcoated"). Encapsulation can control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsion and dry granular formulations. High-strength compositions are primarily used as intermediates for further formulation.

[0125] Sprayable formulations are typically diluted in a suitable vehicle before being sprayed. Such liquid and solid formulations are formulated for easy dilution into the spray vehicle, usually water, but sometimes other suitable vehicles, such as aromatic or paraffinic hydrocarbons or vegetable oils. Spray volumes can range from about 1 liter to several thousand liters per hectare, but more typically range from about 10 liters to several hundred liters per hectare. Sprayable formulations can be tank-mixed with water or other suitable vehicle for foliar treatment by aerial or ground application, or for application to plant growing media. Liquid and dry formulations can be metered directly into drip irrigation systems. It can be applied by pouring it into the field or by metering it into the furrow at the time of planting.

[0126] The formulations typically contain effective amounts of active ingredient, diluent, and surfactant within the general ranges below, the total of which adds up to 100 weight percent.

[0127] [Table 7]

[0128] Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite, and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and sodium bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.

[0129] Examples of liquid diluents include water, N,N-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), alkyl phosphates (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oil, normal paraffin, isoparaffin), alkylbenzenes, alkylnaphthalenes, glycerin, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatic compounds, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone, and 4-hydroxy-4-methyl-2-methylpropional. -pentanone, acetate esters such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate, and isobornyl acetate, other esters such as alkylated lactates, dibasic esters, alkyl and aryl benzoates, γ-butyrolactone, and alcohols (which may be linear, branched, saturated, or unsaturated, such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol, and benzyl alcohol). Liquid diluents further include saturated and unsaturated fatty acids (typically C6-C8). 22 glycerol esters of vegetable seed and fruit oils (e.g., olive oil, castor oil, linseed oil, sesame oil, corn oil (maize oil), peanut oil, sunflower oil, graham oil, Liquid diluents include vegetable and animal derived fats (e.g., beef tallow, pork fat, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated), which can be obtained by hydrolysis of glycerol esters of vegetable and animal origin and purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.

[0130] The solid and liquid compositions of the present disclosure often contain one or more surfactants. When added to a liquid, a surfactant (also known as a "surface-active agent") generally modifies, and in most cases reduces, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, surfactants can be useful as wetting agents, dispersants, emulsifiers, or antifoaming agents.

[0131] Surfactants can be classified as nonionic, anionic, or cationic. Nonionic surfactants useful in the compositions of the present invention include, but are not limited to, alcohol alkoxylates, such as those based on natural and synthetic alcohols (which may be branched or linear) and prepared from alcohols with ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof; amine ethoxylates, alkanolamides, and ethoxylated alkanolamides; alkoxylated triglycerides, such as ethoxylated soybean oil, linseed oil, and rapeseed oil; alkylphenol alkoxylates, such as octylphenol ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate, and dodecylphenol ethoxylate (prepared from phenol and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide, and the end blocks of which are propylene oxide. reverse block polymers prepared from ethylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenols (including those prepared from ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters, and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd PEG (polyethylene glycol) resins, graft or comb polymers, and star polymers; polyethylene glycol (PEG); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar derivatives such as sucrose esters, alkyl polyglycosides, and alkyl polysaccharides.

[0132] Useful anionic surfactants include, but are not limited to, alkylarylsulfonic acids and their salts; carboxylate alcohols or alkylphenol ethoxylates; diphenylsulfonate derivatives; lignin and lignin derivatives, such as lignosulfonates; maleic or succinic acid or their anhydrides; olefin sulfonates; phosphate esters, such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates, and phosphate esters of styrylphenol ethoxylates; protein-based surfactants; sarcosine derivatives; styrylphenol ether sulfates; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; Sulfates of coal; sulfates of ethoxylated alcohols; sulfonates of amines and amides, such as N,N-alkyl taurates; sulfonates of benzene, cumene, toluene, xylene, and dodecylbenzene and tridecylbenzene; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkylnaphthalenes; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their derivatives, such as salts of dialkyl sulfosuccinates.

[0133] Useful cationic surfactants include, but are not limited to, amides and ethoxylated amides; amines such as N-alkylpropanediamines, tripropylenetriamine, and dipropylenetetramine, and ethoxylated amines, ethoxylated diamines, and propoxylated amines (prepared from amines with ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); amine salts such as acetate salts of amines and salts of diamines; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts, and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

[0134] Also useful in the compositions of the present invention are mixtures of nonionic and anionic surfactants, or mixtures of nonionic and cationic surfactants. Nonionic, anionic, and cationic surfactants, and their recommended uses, are disclosed in various published references, such as McCutcheon's Emulsifiers and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publishein Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and AS Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.

[0135] The compositions of the present disclosure may further include formulation aids and additives known to those skilled in the art as formulation aids, some of which may also be considered to function as solid diluents, liquid diluents, or surfactants. Such formulation aids and additives can adjust: pH (buffers), foaming during processing (defoamers, e.g., polyorganosiloxanes), active ingredient settling (suspending agents), viscosity (thixotropic thickeners), microbial growth in the container (antimicrobial agents), product freezing (antifreeze), color (dye / pigment dispersions), wash-off (film formers, or stickers), evaporation (evaporation inhibitors), and other formulation attributes. Film formers include, for example, polyvinyl acetate, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol, polyvinyl alcohol copolymers, and waxes. Examples of formulation aids and additives include those listed in McCutcheon's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and WO 03 / 024222.

[0136] The compounds of Formula 1a and Formula 1b and various other active ingredients are typically incorporated into the compositions of the present invention by dissolving the active ingredient in a solvent or by triturating it in a liquid or dry diluent. Solutions, including emulsions, can be prepared by simply mixing the ingredients. When the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added and diluted with water to emulsify the active ingredient-containing solvent. Slurries of the active ingredient having particle diameters up to 2,000 μm can be wet-milled using a media mill to obtain particles with an average diameter of less than 3 μm. The aqueous slurry can be made into a final suspension concentrate (see, e.g., U.S. Pat. No. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry blends typically require a dry milling process, resulting in average particle diameters in the range of 2 to 10 μm. Fine powders and powders can be prepared by blending and typically milling (e.g., using a hammer mill or fluid energy mill). Granules and pellets can be prepared by spraying the active onto a preformed granular carrier or by agglomeration techniques. See Browning, "Agglomeration," Chemical Engineering, December 4, 1967, pp. 147-48; Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57; and WO 91 / 13546. Pellets can be prepared as described in U.S. Pat. No. 4,172,714. Water-dispersible and water-soluble granules can be prepared according to the teachings of U.S. Pat. Nos. 4,144,050, 3,920,442, and German Patent No. 3,246,493. Tablets can be prepared according to the teachings of U.S. Pat. Nos. 5,180,587, 5,232,701, and 5,208,030. Films can be prepared according to the teachings of British Patent No. 2,095,558 and US Pat. No. 3,299,566.

[0137] For more information on formulation techniques, see T. S. Woods, "The Formulator's Toolbox - Product Forms for Modern Agriculture," in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also the following: U.S. Pat. No. 3,235,361, column 6, line 16 to column 7, line 19, and Examples 10-41; U.S. Pat. No. 3,309,192, column 5, line 43 to column 7, line 62, and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, and 169-182; U.S. Pat. No. 2,891,855, column 3, line 66 to column 5, line 17, and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

[0138] In the following examples, all percentages are by weight and all formulations are prepared in a conventional manner. Compound numbers, i.e., "Cpd. No.", refer to compounds in Table 1. It is believed that one skilled in the art using the preceding description will be able, without undue effort, to utilize the present disclosure to its fullest extent. Accordingly, the following examples are to be construed as merely illustrative and not limiting of the disclosure in any way. Percentages, where otherwise indicated, may be used interchangeably. Other than the above, all amounts are by weight. [Example]

[0139] Example A high strength concentrate Compound of formula 1a or formula 1b 98.5% Silica aerogel 0.5% Synthetic amorphous fine silica 1.0%

[0140] Example B Wettable powder Compound of formula 1a or formula 1b 65.0% Dodecylphenol polyethylene glycol ether 2.0% Sodium lignosulfonate 4.0% Sodium silicoaluminate 6.0% Montmorillonite (calcined) 23.0%

[0141] Example C granules Compound of formula 1a or formula 1b 10.0% Attapulgite Granules (Low Volatility, 0.71 / 0.30 mm; USS No. 25-50 Sieve) 90.0%

[0142] Example D Extrusion processed pellets Compound of formula 1a or formula 1b 25.0% Anhydrous sodium sulfate 10.0% Crude calcium lignosulfonate 5.0% Sodium alkylnaphthalene sulfonate 1.0% Calcium / Magnesium Bentonite 59.0%

[0143] Example E emulsifiable concentrate Compound of formula 1a or formula 1b 10.0% Polyoxyethylene sorbitol hexaoleate 20.0% C6~C 10 Fatty acid methyl ester 70.0%

[0144] Example F Microemulsion Compound of formula 1a or formula 1b 5.0% Polyvinylpyrrolidone-vinyl acetate copolymer 30.0% Alkyl polyglycoside 30.0% Glyceryl monooleate 15.0% Water 20.0%

[0145] Example G Suspension concentrate Compound of formula 1a or formula 1b 35% Butyl polyoxyethylene / polypropylene block copolymer 4.0% Stearic acid / polyethylene glycol copolymer 1.0% Styrene acrylic polymer 1.0% Xanthan gum 0.1% Propylene glycol 5.0% Silicone-based antifoam agent 0.1% 1,2-benzisothiazolin-3-one 0.1% Water 53.7%

[0146] Example H Emulsion in water Compound of formula 1a or formula 1b 10.0% Butyl polyoxyethylene / polypropylene block copolymer 4.0% Stearic acid / polyethylene glycol copolymer 1.0% Styrene acrylic polymer 1.0% Xanthan gum 0.1% Propylene glycol 5.0% Silicone-based antifoam agent 0.1% 1,2-benzisothiazolin-3-one 0.1% Aromatic Petroleum-Based Hydrocarbons 20.0 Water 58.7%

[0147] Example I Oil dispersion 25% of a compound of formula 1a or formula 1b Polyoxyethylene sorbitol hexaoleate 15% Organically modified bentonite clay 2.5% Fatty acid methyl esters 57.5%

[0148] Also disclosed are Examples A-I above, where "a compound of Formula 1a or Formula 1b" is replaced with "a compound of Formula 2 (enantiomer 2A) or Formula 2 (enantiomer 2B)," a compound of Formula 3 (enantiomer 3A) or Formula 3 (enantiomer 3B), "a compound of Formula 4 (enantiomer 4A) or Formula 4 (enantiomer 4B)," or "a compound of Formula 5 (enantiomer 5A) or Formula 5 (enantiomer 5B)."

[0149] Test results indicate that certain compounds of Formula 1a or Formula 1b are active pre-emergence and / or post-emergence herbicides and / or plant growth regulators. Compounds of Formula 1a or Formula 1b generally exhibit the highest activity for post-emergence weed control (i.e., applied after weed seedlings emerge from the soil) and pre-emergence weed control (i.e., applied before weed seedlings emerge from the soil). Many of them are useful for broad-spectrum pre-emergence and / or post-emergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, airports, riverbanks, irrigation and other waterways, around large billboards, and railroad facilities. Many of the compounds of the present disclosure are useful for the selective control of grasses and broadleaf weeds in crop / weed mixtures because they have selective crop versus weed metabolism, or selective activity in areas of physiological inhibition in crops and weeds, or selective placement on or in the mixed crop and weed environment. As will be recognized by those skilled in the art, suitable combinations of selectivity factors within a single compound or group of compounds can be readily determined by routine biological and / or biochemical assays.

[0150] Compounds of formula 1a or 1b can exhibit resistance to important agricultural crops such as: The crops that can be treated include, but are not limited to: alfalfa, barley, cotton, wheat, rapeseed, sugar beet, corn (maize), sorghum, soybeans, rice, oats, peas, vegetables, tomatoes, potatoes, perennial plantation crops (including coffee, cocoa, oil palm, rubber), sugarcane, citrus, grapeseed, fruit trees, nut trees, bananas, plantain, pineapple, hops, tea bushes, and woodlands such as eucalyptus and conifers (e.g., loblolly pine), and turf species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue, and cypress). The compounds of the present disclosure may be useful in genetically transformed crops, or crops bred to incorporate herbicide resistance, express proteins toxic to invertebrate pests (e.g., Bacillus thuringiensis toxins), and / or express other useful traits. As one of ordinary skill in the art will recognize, not all compounds are equally effective against all weeds. However, the compounds that are the subject of the present invention are useful for regulating plant growth.

[0151] Because the compounds of the present disclosure have herbicidal activity (both pre- and post-emergence) and control undesirable vegetation by killing or damaging the vegetation or inhibiting its growth, they can be usefully applied by a variety of methods, including contacting a herbicidally effective amount of a compound of the present disclosure, or a composition comprising said compound and at least one surfactant, solid diluent, or liquid diluent, with the foliage or other parts of the undesirable vegetation, or with the environment of the undesirable vegetation, e.g., soil or water, in which the undesirable vegetation is growing or surrounding the seeds or other propagules of the undesirable vegetation.

[0152] The herbicidally effective amount of a compound of Formula 1a or Formula 1b depends on several factors, including the formulation selected, the method of application, the amount and type of vegetation present, and growing conditions. Generally, a herbicidally effective amount of a compound of the present disclosure ranges from about 0.001 to 20 kg / ha, preferably about 0.004 to 1 kg / ha. One skilled in the art can readily determine the herbicidally effective amount required to achieve the desired level of weed control.

[0153] In one general embodiment, a compound of Formula 1a or Formula 1b, typically in the form of a formulated composition, is applied to an area containing desirable vegetation (e.g., crops) and undesirable vegetation (i.e., weeds), both of which may be seeds, seedlings, and / or more mature plants, in contact with a growing medium (e.g., soil). In this area, a composition containing a compound of the present disclosure can be applied directly to the plants or parts thereof of the undesirable vegetation, and / or to the growing medium in contact with the plants.

[0154] Plant varieties and cultivars of the desired vegetation in the habitat treated with the compounds of the present disclosure can be obtained by conventional propagation and breeding methods or by genetic engineering methods. A genetically modified plant (transgenic plant) is one in which a heterologous gene (transgene) is stably integrated into the plant's genome. A transgene, defined by its specific location in the plant genome, is called a transformation or transgenic event.

[0155] Although compounds of the present disclosure are most typically used to control undesirable vegetation, contacting desirable vegetation in a treated area with a compound of the present disclosure may result in superadditive or synergistic effects with genetic traits in the desirable vegetation, including traits incorporated through genetic modification. For example, resistance to herbivorous pests or plant diseases, resistance to biotic / abiotic stresses, or storage stability may be achieved. may be greater than would be expected from the genetic characteristics of desirable vegetation.

[0156] The compounds of the present disclosure can also be mixed with one or more other biologically active compounds or agents, including herbicides, herbicide safeners, fungicides, insecticides, nematicides, bactericides, acaricides, growth regulators such as insect molting inhibitors and root stimulators, chemosterilants, signal chemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds, or insect pathogenic bacteria, viruses, or fungi, to form multi-component biocides that provide even broader agricultural protection. Mixtures of the compounds of the present disclosure with other herbicides can expand the spectrum of activity against additional weed species and suppress the growth of various resistant biotypes. Thus, the present disclosure also relates to compositions comprising a herbicidally effective amount of a compound of Formula 1a and / or Formula 1b and a biologically effective amount of at least one additional biologically active compound or agent, and can further comprise at least one surfactant, solid diluent, or liquid diluent. The other biologically active compounds or agents can be formulated into a composition that includes at least one surfactant, solid diluent, or liquid diluent. In the mixtures of the present disclosure, one or more other biologically active compounds or agents can be formulated with the compound of Formula 1a or Formula 1b to form a premix, or one or more other biologically active compounds or agents can be formulated separately from the compound of Formula 1a or Formula 1b, and the formulations can be combined (e.g., in a spray tank) before application, or alternatively, applied sequentially.

[0157] General references for agricultural protectants (i.e., herbicides, herbicide safeners, insecticides, fungicides, nematicides, acaricides, and biological agents) include: The Pesticide Manual, 13th Edition, CDS Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2003, and The BioPesticide Manual, 2nd Edition, L.G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2001.

[0158] In embodiments in which one or more of these various mixing partners are used, the mixing partners are typically used in amounts similar to those customarily used when the mixing partners are used alone. More specifically, in mixtures, the active ingredient is often applied at a rate between half and all of the rate prescribed on the product label for the active ingredient used alone. These amounts are described, for example, in the following references: The Pesticide Manual and The BioPesticide Manual. The weight ratio of these various mixing partners (combined) to the compound of Formula 1a or Formula 1b is typically between about 1:3000 and about 3000:1. Of note are weight ratios between about 1:300 and about 300:1 (e.g., ratios between about 1:30 and about 30:1). Those skilled in the art can easily determine by simple experimentation the biologically effective amount of active ingredient required to achieve the desired spectrum of biological activity. It will be apparent that the inclusion of these additional ingredients makes it possible to extend the spectrum of weeds controlled beyond that controlled by the compounds of Formula 1a or Formula 1b alone.

[0159] Of note are compositions comprising a compound of the present invention (in a herbicidally effective amount), at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners (in an effective amount), and at least one component selected from the group consisting of surfactants, solid excipients, and liquid excipients.

[0160] Table A1 lists specific combinations of component (a) and component (b) that are illustrative of the mixtures, compositions, and methods of the present invention. Compound No. A in the component (a) column (i.e., "Cpd. No." is an abbreviation for "Compound No.") is identified in the Index Table. The second column of Table A1 lists specific component (b) compounds (e.g., "2,4-D" in the first row). The third, fourth, and fifth columns of Table A1 list a series of weight ratios for the rate at which component (a) compounds relative to component (b) are typically applied to field-grown crops (i.e., (a):(b)). Thus, for example, the first row of Table A1 specifically discloses that combinations of component (a) (i.e., Compound No. A in the Index Table) and 2,4-D are typically applied in weight ratios of 1:192 to 6:1. The remaining rows of Table A1 are interpreted similarly.

[0161] [Table 8]

[0162] [Table 9]

[0163] [Table 10]

[0164] [Table 11]

[0165] [Table 12]

[0166] [Table 13]

[0167] [Table 14]

[0168] Table A2 is organized the same as Table A1 above, except that the content under the "Component (a) (Compound Number)" column heading has been replaced with the content of the respective Component (a) column shown below. The Compound Numbers in the Component (a) column are identified in Index Table 1. Thus, for example, in Table A2, the content under the "Component (a)" column heading all lists "2 (Enantiomer B)" (Compound Number 2 identified in Index Table 1), and the first row under the column heading in Table A2 specifically discloses a mixture of Compound Number 2 (Enantiomer B) with 2,4-D.

[0169] [Table 15]

[0170] In certain cases, the compounds of the present disclosure may be combined with other biologically active (especially herbicidal) compounds or agents (i.e., active ingredients) to achieve greater than additive (i.e., synergistic) effects against weeds and / or less than additive (i.e., safening) results for crops or other desirable plants. Reducing the amount of active ingredient released into the environment while still effectively controlling pests is always desirable. The ability to use greater amounts of active ingredient for more effective weed control without excessive crop damage is also desirable. If synergistic effects of herbicidal active ingredients occur with weeds at application rates that provide agronomically satisfactory levels of weed control, such combinations may be advantageous for reducing crop production costs and reducing environmental impact. If safening of herbicidal active ingredients occurs with crops, such combinations may be advantageous for reducing weed competition and enhancing crop protection.

[0171] Of note, the combination of the compounds of the present disclosure with at least one other herbicidal active ingredient Of particular note are combinations in which the other herbicidal active ingredient has a different site of action than the compounds of the present disclosure. In certain cases, a combination with at least one other herbicidal active ingredient having a similar control spectrum but a different site of action may be particularly advantageous for resistance management. Thus, the compositions of the present disclosure may further include at least one additional herbicidal active ingredient (in a herbicidally effective amount) having a similar control spectrum but a different site of action.

[0172] The compounds of the present disclosure may also be used in combination with herbicide safeners to increase safety in certain crops, such as, for example, allidochlor, benoxacor, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfonamide, dymron, dichlormid, dicyclonone, dietholate, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, methoxyphenone, naphthalic anhydride (1,8-naphthalic anhydride), oxabetrinil, N-(aminocarbonyl)-2-methylbenzenesulfonamide, N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene (BCS), 4-(dichloroacetyl)-1-oxa-4-azospiro[4.5]decane (MON 4660), 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), ethyl 1,6-dihydro-1-(2-methoxyphenyl)-6-oxo-2-phenyl-5-pyrimidinecarboxylate, 2-hydroxy-N,N-dimethyl-6-(trifluoromethyl)pyridine-3-carboxamide, 1-(3,4-dimethylphenyl)-1,6-dihydro-6-oxo-2-phenyl-5-pyrimidinecarboxylate, 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-ethanone, and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide. An additional effective amount of a herbicide safener can be applied simultaneously with the compound of the present disclosure or as a seed treatment. Accordingly, an embodiment of the present disclosure relates to a herbicide mixture comprising a compound of the present disclosure and an antidotal effective amount of a herbicide safener. Seed treatments are particularly useful for selective weed control because they limit the antidote effect to the crop. Thus, a particularly useful embodiment of the present disclosure is a method for selectively controlling the growth of undesirable vegetation in a crop, comprising contacting a region of the crop with a herbicidally effective amount of a compound of the present disclosure, wherein the seeds from which the crop grows are treated with an antidote-effective amount of a safener. The antidote-effective amount of the safener can be readily determined by one skilled in the art through simple experimentation.

[0173] The compounds of the present disclosure can also be mixed with: (1) polynucleotides, including but not limited to, DNA, RNA, and / or chemically modified nucleotides that affect the abundance of specific targets through, for example, downregulation, interference, suppression, or silencing of engineered transcripts to confer a herbicidal effect; or (2) polynucleotides, including but not limited to, DNA, RNA, and / or chemically modified nucleotides that affect the abundance of specific targets through, for example, downregulation, interference, suppression, or silencing of engineered transcripts to confer a safening effect.

[0174] Test A below demonstrates the effectiveness of control of representative compounds of the present disclosure against representative weeds, although the weed control provided by these compounds is not limited to these species. See Index Table 1 for compound descriptions.

[0175] [Table 16]

[0176] Test A Seeds of plant species selected from barnyardgrass (BYG, Echinochloa crus-galli), kochia (KOC, Kochia scoparia), common ragweed (Ambrosia elatior), wild rye (RGI, Lolium multiflorum), foxtail (FTI, Setaria faberii), green foxtail (Setaria viridis), and pigweed (PWR, Amaranthus retroflexus) were planted in a blend of loam soil and sand and pre-emergence treated with a directional soil application of test chemicals formulated in a non-phytotoxic solvent mixture containing a surfactant.

[0177] Concurrently, plants selected from these weed species, as well as wheat (WWT, wheat (Triticum aestivum)), corn (CPI, corn (Zea mays)), blackgrass (BKG, blackgrass (Alopecurus myosuroides)), and cleaver (GAL, cleaver, cleaver (Galium aparine)), were planted in pots containing the same blend of loam soil and sand and treated with postemergence applications of the formulated test chemicals in the same manner. Plants ranged in height from 2 to 10 cm and were at the one- to two-leaf stage for postemergence treatment. Treated plants and untreated controls were maintained in the greenhouse for approximately 10 days, after which time all treated plants were compared to untreated controls and visually assessed for injury. Plant response ratings, summarized in Tables 1-4, were based on a 0-100 scale, where 0 was no effect and 100 was complete control. A response of dash (-) means no test result. The rating is followed by a letter representing the symptom, where S is chlorosis, C is chlorosis, G is stunted growth, and E is emergence.

[0178] [Table 17]

[0179] [Table 18]

[0180] [Table 19]

[0181] [Table 20]

Claims

1. Optically active compounds selected from atropisomers of formula 1a and formula 1b, all stereoisomers, N-oxides and salts thereof, compositions containing them, and their use as herbicides, comprising 【Chemistry 1】 During the ceremony, R １ is Me or halogen; R ２ is CH ３ , C.H. ２ CH ３ , halogen, trifluoromethyl or difluoromethoxy; R ３ is hydrogen, CH ３ or a halogen; R ４ is hydrogen, CH ３ or a halogen; R ５ is hydrogen, C １ ~C ４ Alkylcarbonyl, C １ ~C ４ Alkoxycarbonyl or C １ ~C ４ alkylcarboxymethyl; where: Optically active compounds, compositions containing them, and their use as herbicides, in which the atropisomers of formula 1a or 1b, their N-oxides or salts exist in excess of their corresponding enantiomers, or their N-oxides or salts.

2. 2. The compound of claim 1, comprising an atropisomer of a compound of formula 1a, or an N-oxide or salt thereof, which exists in excess of its corresponding enantiomer of formula 1b, or an N-oxide or salt thereof.

3. R １ is Cl or CH ３ and R ２ But CH ３ or difluoromethoxy; R ３ But CH ３ or H; R ４ is H; R ５ is H or -(C=O)CH ２ CH ３ 2. The compound of claim 1, wherein:

4. R １ is Cl; R ２ But CH ３ and R ３ But CH ３ or H; R ４ is H; R ５ is H or -(C=O)CH ２ CH ３ 2. The compound of claim 1, wherein:

5. R １ is Cl; R ２ But CH ３ and R ３ But CH ３ and R ４ is H; R ５ The compound of claim 4 , wherein is H.

6. 2. The compound of claim 1, comprising an atropisomer of a compound of formula 1b, or an N-oxide or salt thereof, which exists beyond its corresponding enantiomer of formula 1, or an N-oxide or salt thereof.

7. The compound according to any one of claims 1 to 6, having a positive (+) rotation value.

8. The compound according to any one of claims 1 to 6, having a negative (-) rotation value.

9. 7. The compound of any one of claims 1 to 6, wherein one atropisomer is more herbicidally active than the corresponding enantiomer.

10. A process for preparing a compound of formula 1a or 1b, comprising: 【Chemistry 2】 During the ceremony, R １ is CH ３ or a halogen; R ２ is CH ３ , C.H. ２ CH ３ , halogen, trifluoromethyl or difluoromethoxy; R ３ is H, CH ３ or a halogen; R ４ is H, CH ３ or a halogen; R ５ is H, C １ ~C ４ Alkylcarbonyl, C １ ~C ４ Alkoxycarbonyl or C １ ~C ４ alkylcarboxymethyl; 1) loading a racemic mixture of the compound of Formula 1, including the atropisomers of Formula 1a and 1b, onto a chiral supported chromatography column and eluting with a mobile phase; 2) Isolating two separate fractions with different retention times; one with a positive optical rotation value [α] １ (+) atropisomers, one with a negative optical rotation value [α] １ containing an atropisomer having (-) A method comprising:

11. R １ is Cl or CH ３ and R ２ But CH ３ or difluoromethoxy; R ３ But CH ３ or H; R ４ is H; R ５ is H or -(C=O)CH ２ CH ３ The method of claim 10, wherein

12. R １ is Cl; R ２ But CH ３ and R ３ But CH ３ or H; R ４ is H; R ５ is H or -(C=O)CH ２ CH ３ The method of claim 11, wherein

13. R １ is Cl; R ２ But CH ３ and R ３ But CH ３ and R ４ is H; R ５ The method of claim 12 , wherein is H.

14. A herbicidal composition comprising the compound of any one of claims 1 to 9 and at least one component selected from the group consisting of a surfactant, a solid excipient, and a liquid excipient.

15. 10. A herbicidal composition comprising a compound according to any one of claims 1 to 9, at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners, and at least one component selected from the group consisting of surfactants, solid excipients, and liquid excipients.

16. 10. A herbicidal mixture comprising (a) a compound according to any one of claims 1 to 9, and (b) at least one further active ingredient.

17. 10. A method for controlling the growth of undesired vegetation which comprises contacting the undesired vegetation or its environment with a herbicidally effective amount of a compound of any one of claims 1 to 9.

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