Atropisomers of pyridazinone derivatives as herbicides

Abstract

This disclosure provides transisomers of pyridazinone derivatives having formulas 1a and 1b, their N-oxides or salts, wherein R 1 R 2 R 3 R 4 and R 5 Defined in this disclosure. Compositions containing compounds having formula 1a or 1b are also disclosed, as well as methods for controlling unwanted vegetation, these methods comprising contacting the unwanted vegetation or its environment with an effective amount of a compound having formula 1a or 1b or a composition thereof. A method for preparing a compound having formula I is also disclosed.

Description

Technical Field

[0001] This disclosure relates to stereoisomers of certain pyridazinone derivatives, their N-oxides, salts, and compositions, and methods of using them for controlling unwanted vegetation. More specifically, this disclosure relates to trans-inhibitory isomers of certain pyridazinone derivatives, their N-oxides, salts, and compositions, and methods of using them as herbicides. Background Technology

[0002] Controlling unwanted vegetation is crucial for achieving high crop efficiency. Selective control of weed growth is highly desirable, especially in beneficial crops such as rice, soybeans, sugar beets, corn, potatoes, wheat, barley, tomatoes, and other cultivated crops. Uncontrolled weed growth in these beneficial crops can lead to significant yield reductions and consequently increased costs for consumers. Control of unwanted vegetation in non-crop areas is also important. Many products are commercially available for these purposes, but there remains a continuous need for novel compounds that are more effective, less costly, less toxic, environmentally safer, or have different sites of action.

[0003] WO 2015 / 168010 and WO 2017 / 074988 disclose chlorpyrifos and synthetic intermediates for the preparation of chlorpyrifos. Summary of the Invention

[0004] This disclosure provides optically active transisomers of pyridazinone derivatives having formulas 1a and 1b, their N-oxides or salts; the compounds having formula 1 are racemic mixtures of transisomers having formula 1a and 1b.

[0005]

[0006] in

[0007] R 1 It is CH3 or halogen;

[0008] R 2 It is CH3, CH2CH3, halogen, trifluoromethyl or difluoromethoxy;

[0009] R 3 It is H, CH3, or halogen;

[0010] R 4 It is H, CH3, or halogen;

[0011] R 5 It is H, C1-C4 alkyl carbonyl, C1-C4 alkoxy carbonyl, or C1-C4 alkyl carboxymethyl;

[0012] in

[0013] The N-oxide or salt of the resisted isomer having formula 1a or 1b is present in addition to its corresponding enantiomer or its N-oxide or salt.

[0014] On the other hand, this disclosure provides a method for preparing compounds having formula 1a or 1b;

[0015]

[0016] in

[0017] R 1 It is CH3 or halogen;

[0018] R 2 It is CH3, CH2CH3, halogen, trifluoromethyl or difluoromethoxy;

[0019] R 3 It is H, CH3, or halogen;

[0020] R 4 It is H, CH3, or halogen;

[0021] R 5 It is H, C1-C4 alkyl carbonyl, C1-C4 alkoxy carbonyl, or C1-C4 alkyl carboxymethyl.

[0022] The method includes:

[0023] 1) A racemic mixture of compounds of formula 1 containing the transisomers of formula 1a and 1b is loaded onto a chiral-supported chromatographic column and eluted with the mobile phase;

[0024] 2) Separate two separate fractions with different retention times; one containing a resisted isomer with a positive optical rotation value [α]1(+) and the other containing a resisted isomer with a negative optical rotation value [α]1(-). Attached Figure Description

[0025] Figure 1 This is the analytical chiral HPLC SFC chromatogram of enantiomer 2a (2A).

[0026] Figure 2 This is the analytical chiral HPLC SFC chromatogram of the enantiomer 2b (2B). Detailed Implementation

[0027] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains,” “containing,” “characterized by,” or any other variation thereof, are intended to cover non-exclusive inclusion, subject to any expressly indicated limitations. For example, a process or method that comprises a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or other elements inherent to such compositions, processes, or methods.

[0028] The connecting phrase "composed of..." excludes any unspecified element, step, or component. If in a claim, this phrase makes the claim closed, excluding materials other than those stated, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of a claim rather than immediately following the preamble, the phrase only limits the element set forth in that clause; the claim as a whole does not exclude other elements.

[0029] The connecting phrase "substantially constitutes..." is used to define a process or method that includes materials, steps, features, components, or elements in addition to those explicitly disclosed, provided that such additional materials, steps, features, components, or elements do not materially affect the essential and novel characteristics of this disclosure. The term "substantially constitutes..." falls between "comprising" and "consisting of...".

[0030] Where the applicant has already defined this disclosure or a portion thereof using open-ended terms such as “comprising”, it shall be readily understood (unless otherwise specified) that the description shall also be interpreted as using the terms “substantially constitutes” or “comprises” to describe this disclosure.

[0031] Furthermore, unless explicitly stated to the contrary, "or" refers to an inclusive "or" rather than an exclusive "or". For example, conditions A or B are 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).

[0032] Similarly, the indefinite article “a / an” preceding the elements or components disclosed herein is intended to be non-limiting in terms of the number of examples (i.e., occurrences) of the elements or components. Therefore, “a / an” should be understood to include one / an or at least one / an, and the singular word form of the elements or components also includes the plural, unless the number clearly indicates the singular.

[0033] The term "C1-C4 alkyl" includes straight-chain or branched alkyl groups having one to four carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, or various butyl isomers. As used herein, the term "halogen" includes fluorine, chlorine, bromine, or iodine. As used herein, the term "C1-C4 alkyl carbonyl" refers to a C1-C4 alkyl group bonded by a carbonyl group. The term "C1-C4 alkoxy carbonyl" refers to a C1-C4 alkoxy group bonded by a carbonyl group. The term "C1-C4 alkyl carboxymethyl" refers to a (C1-C4 alkyl) C=O group bonded by a -CH2- group.

[0034] Compounds having formulas 1a and 1b can typically exist independently in different solid forms. Therefore, compounds having formulas 1a and 1b include all crystalline and amorphous forms of the compounds they represent. Amorphous forms include solid embodiments such as waxes and resins, and liquid embodiments such as solutions and melts. Crystalline forms include embodiments representing substantially single-crystal types and embodiments representing mixtures of polymorphs (i.e., different crystal types). The term "polymorph" refers to a specific crystalline form of a compound that can crystallize in different crystal forms, having different molecular arrangements and / or conformations in the crystal lattice. While polymorphs may have the same chemical composition, they can also differ in composition due to the presence or absence of co-crystallization water or other molecules, which may be weakly or strongly bonded within the crystal lattice. Polymorphs can differ in such chemical, physical, and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspendability, dissolution rate, and bioavailability.

[0035] Those skilled in the art will understand that polymorphs of compounds having formulas 1a and 1b can exhibit beneficial effects (e.g., suitability for the preparation of useful formulations, improved biological properties) relative to another polymorph or mixture of polymorphs of the same compounds having formulas 1a and 1b. The preparation and separation of specific polymorphs of compounds having formulas 1a and 1b can be achieved by methods known to those skilled in the art, including, for example, crystallization using selected solvents and temperatures. For a comprehensive discussion of polymorphism, see R. Hilfiker (ed.), *Polymorphism in the Pharmaceutical Industry*, Wiley-VCH, Weinheim, 2006.

[0036] Exemplary procedures for preparing N-oxides include using peroxy acids such as peracetic acid and m-chloroperoxybenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as tert-butyl hydroperoxide, sodium perborate, and diethylene oxides such as dimethyldiethylene oxide to oxidize heterocycles and tertiary amines. These methods for preparing N-oxides have been extensively described and reviewed in the literature, see, for example: T.L. Gilchrist, *Comprehensive Organic Synthesis*, Vol. 7, pp. 748-750, edited by S.V. Ley, Pergamon Press; M. Tisler and B. Stanovnik, *Comprehensive Heterocyclic Chemistry*, Vol. 3, pp. 18-20, edited by A.J. Boulton and A. McKillop, Pergamon Press; M.R. Grimemett and B.T. Keene, *Advances in Heterocyclic Chemistry*, Vol. 43, pp. 149-161, edited by A.R. Katritzky, Academic Press; M. Tisler and B. Stanovnik, *Advances in Heterocyclic Chemistry*. *Advances in Heterocyclic Chemistry*, Vol. 9, pp. 285-291, edited by A.R. Katritzky and A.J. Boulton, Academic Press; and G.W. Heeseman and E.S. G.W. Gerstiuk, *Advances in Heterocyclic Chemistry*, Vol. 22, pp. 390-392, edited by A.R. Katritzky and A.J. Boulton, Academic Press. That is to say, those skilled in the art will understand that not all nitrogen-containing heterocycles can form N-oxides, because nitrogen requires a lone pair of electrons to be oxidized to an oxide; those skilled in the art will recognize those nitrogen-containing heterocycles that can form N-oxides.

[0037] The compounds of the present invention can exist as one or more stereoisomers. Various stereoisomers include enantiomers, diastereomers, transisomers, and geometric isomers. Stereoisomers are isomers that have the same composition but whose atoms are arranged differently in space, and include enantiomers, diastereomers, cis-trans isomers (also called geometric isomers), and transisomers. Transisomers arise from restricted rotation around a single bond, where the rotation barrier is high enough to allow the separation of isomer species. Those skilled in the art will understand that a transisomer may be more active and / or may exhibit beneficial effects when enriched relative to one or more other transisomers, or when separated from one or more other transisomers. The compounds of the present invention can exist as mixtures of transisomers, single transisomers, or as optically active forms, optionally with one transisomer exceeding its corresponding enantiomer.

[0038] In particular, the compounds of the present invention comprise a more active transisomer than another transisomer.

[0039] Some non-limiting examples of this disclosure (wherein compounds having formulas 1a and 1b also include their N-oxides or salts):

[0040] Example A1. An optically active compound comprising (or consisting of) a transisomer of a compound having formula 1a and its N-oxide or salt, wherein the transisomer of the compound having formula 1a and its N-oxide or salt are present in excess of its corresponding enantiomer having formula 1b or its N-oxide or salt.

[0041]

[0042] Example A2. The compound as described in Example A1, wherein R 1 It is CH3.

[0043] Example A3. The compound as described in Example A1, wherein R 1 It is halogen.

[0044] Example A4. The compound as described in Example A3, wherein R 1 It is Cl, F, or Br.

[0045] Example A5. The compound as described in Example A4, wherein R 1 It is Cl or CH3.

[0046] Example A6. The compound as described in Example A5, wherein R 1 It is Cl.

[0047] Example A7. The compound as described in any one of Examples A1 to A6, wherein R2 It is CH3, CH2CH3, halogen, or difluoromethoxy.

[0048] Example A8. The compound as described in Example A7, wherein R 2 It is CH3, CH2CH3, Cl, or difluoromethoxy.

[0049] Example A9. The compound as described in Example A8, wherein R 2 It is CH3 or difluoromethoxy.

[0050] Example A10. The compound as described in Example A9, wherein R 2 It is CH3.

[0051] Example A11. The compound as described in any one of Examples A1 to A10, wherein R 3 It is H or CH3.

[0052] Example A12. The compound as described in Example A11, wherein R 3 It's H.

[0053] Example A13. The compound as described in Example A12, wherein R 3 It is CH3.

[0054] Example A14. The compound as described in any one of Examples A1 to A13, wherein R 4 It is H, CH3, or Cl.

[0055] Example A15. The compound as described in Example A14, wherein R 4 It is Cl.

[0056] Example A16. The compound as described in Example A14, wherein R 4 It is CH3.

[0057] Example A17. The compound as described in Example A14, wherein R 4 It's H.

[0058] Example A18. The compound as described in any one of Examples A1 to A17, wherein R 5 It is H, C3 alkyl carbonyl, C3 alkoxy carbonyl, or C3 alkyl carboxymethyl.

[0059] Example A19. The compound as described in Example A18, wherein R 5 It is an H or C3 alkyl carbonyl group.

[0060] Example A20. The compound as described in Example A18, wherein R 5 It is H or -(C=O)CH2CH3.

[0061] Example A21. The compound as described in Example A20, wherein R 5 It's H.

[0062] Example AA1. An optically active compound comprising a transisomer of a compound having Formula 1b, or an N-oxide or salt thereof, wherein the transisomer of the compound having Formula 1b, or an N-oxide or salt thereof, is present in excess of its corresponding enantiomer of Formula 1a, or an N-oxide or salt thereof.

[0063]

[0064] Example AA2. The compound as described in Example AA1, wherein R 1 It is CH3.

[0065] Example AA3. The compound as described in Example AA1, wherein R 1 It is halogen.

[0066] Example AA4. The compound as described in Example AA3, wherein R 1 It is Cl, F, or Br.

[0067] Example AA5. The compound as described in Example AA4, wherein R 1 It is Cl or F.

[0068] Example AA6. The compound as described in Example A5, wherein R 1 It is Cl.

[0069] Example AA7. The compound as described in any one of Examples AA1 to AA6, wherein R 2 It is CH3, CH2CH3, halogen, or difluoromethoxy.

[0070] Example AA8. The compound as described in Example AA7, wherein R 2 It is CH3, CH2CH3, Cl, or difluoromethoxy.

[0071] Example AA9. The compound as described in Example AA8, wherein R 2 It is CH3 or difluoromethoxy.

[0072] Example AA10. The compound as described in Example AA9, wherein R 2 It is CH3.

[0073] Example AA11. The compound as described in any one of Examples AA1 to AA10, wherein R 3 It is H or CH3.

[0074] Example AA12. The compound as described in Example AA11, wherein R 3 It's H.

[0075] Example AA13. The compound as described in Example AA12, wherein R 3 It is CH3.

[0076] Example AA14. The compound as described in any one of Examples AA1 to AA13, wherein R 4 It is H, CH3, or Cl.

[0077] Example AA15. The compound as described in Example AA14, wherein R 4 It is Cl.

[0078] Example AA16. The compound as described in Example AA14, wherein R 4 It is CH3.

[0079] Example AA17. The compound as described in Example AA14, wherein R 4 It's H.

[0080] Example AA18. The compound as described in any one of Examples AA1 to AA17, wherein R 5 It is H, C3 alkyl carbonyl, C3 alkoxy carbonyl, or C3 alkyl carboxymethyl.

[0081] Example AA19. The compound as described in Example AA18, wherein R 5 It is an H or C3 alkyl carbonyl group.

[0082] Example AA20. The compound as described in Example AA18, wherein R 5 It is H or -(C=O)CH2CH3.

[0083] Example AA21. The compound as described in Example AA20, wherein R 5 It's H.

[0084] Example B1. A method for preparing a compound having formula 1a or 1b as described in the invention.

[0085]

[0086] Example B2. The method as described in Example B1, wherein R 1 It is CH3.

[0087] Example B3. The method as described in Example B1, wherein R 1 It is halogen.

[0088] Example B4. The method as described in Example B3, wherein R 1 It is Cl, F, or Br.

[0089] Example B5. The method as described in Example B4, wherein R 1 It is Cl or F.

[0090] Example B6. The method as described in Example B5, wherein R 1 It is Cl.

[0091] Example B7. The method as described in any one of Examples B1 to B6, wherein R 2 It is CH3, CH2CH3, halogen, or difluoromethoxy.

[0092] Example B8. The method as described in Example B7, wherein R 2 It is CH3, CH2CH3, Cl, or difluoromethoxy.

[0093] Example B9. The method as described in Example B8, wherein R 2 It is CH3 or difluoromethoxy.

[0094] Example B10. The method as described in Example B9, wherein R2 is CH3.

[0095] Example B11. The method as described in any one of Examples B1 to B10, wherein R3 is H or CH3.

[0096] Example B12. The method as described in Example B11, wherein R3 is H.

[0097] Example B13. The method as described in Example B11, wherein R3 is CH3.

[0098] Example B14. The method as described in any one of Examples B1 to B13, wherein R 4 It is H, CH3, or Cl.

[0099] Example B15. The method as described in Example B14, wherein R 4 It is Cl.

[0100] Example B16. The method as described in Example B14, wherein R 4 It is CH3.

[0101] Example B17. The method as described in Example B14, wherein R 4 It's H.

[0102] Example B18. The method as described in any one of Examples B1 to B17, wherein R 5It is H, C3 alkyl carbonyl, C3 alkoxy carbonyl, or C3 alkyl carboxymethyl.

[0103] Example B19. The method as described in Example B18, wherein R 5 It is an H or C3 alkyl carbonyl group.

[0104] Example B20. The method as described in Example B18, wherein R 5 It is H or -(C=O)CH2CH3.

[0105] Example B21. The method as described in Example B20, wherein R 5 It's H.

[0106] Example B22. The method as described in Example B1, wherein the chiral supported chromatography is supercritical fluid chromatography (SFC).

[0107] Example B23. The method as described in Example B1, wherein the mobile phase is carbon dioxide.

[0108] Example C1. The compound as described in any one of Examples A1 to AA21, wherein the compound has greater herbicidal activity than its corresponding transtransisomer.

[0109] Example C2. The compound as described in Example C1, wherein the compound is more active against grasses than its corresponding transisomer.

[0110] The above embodiments or any of the embodiments herein can be combined in any manner. The invention also relates to a method for controlling unwanted vegetation, the method comprising applying a herbicidally effective amount of a compound having formula 1a or 1b (e.g., as the composition described herein) to the site of the vegetation. It should be noted that the embodiments relating to the method of use are those involving the compounds described above. The compounds of the invention are particularly useful for selectively controlling weeds in crops such as wheat, barley, corn, soybean, sunflower, cotton, oilseed rape, and rice, as well as specialty crops such as sugarcane, citrus, fruit, and nut crops.

[0111] It is also worth noting that the herbicidal composition of the present invention, which includes the compounds described in the above embodiments, is an example.

[0112] The present invention also includes a weed control mixture comprising (a) a compound selected from formulas 1a and 1b, its N-oxide and salt, and (b) at least one additional active ingredient selected from: (b1) a photosystem II inhibitor, (b2) an acetylhydroxy acid synthase (AHAS) inhibitor, (b3) an acetyl-CoA carboxylase (ACCase) inhibitor, (b4) an auxin mimic, (b5) a 5-enol-pyruvate-shikimate-3-phosphate (EPSP) synthase inhibitor, (b6) a photosystem I electron diverter, (b7) a protoporphyrinogen oxidase (PPO) inhibitor, (b8) a glutamine synthase (GS) inhibitor, and (b9) a very long-chain fatty acid (VLCFA) elongation enzyme inhibitor. (b10) Auxin transport inhibitors, (b11) phytopenic lycopene dehydrogenase (PDS) inhibitors, (b12) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b13) urosine solanyltransferase (HST) inhibitors, (b14) cellulose biosynthesis inhibitors, (b15) other herbicides, including mitosis disruptors, organoarsenic compounds, sulfadiazine, bromobutyroxyfen, cyclohexane, bensulfuron, dazomet, fenbendazim, ethoxybenzamide, chlorpyrifos, phosphonoammonium phosphate, phosphonoammonium phosphate, chlorpyrifos, methyl chlorpyrifos, oleic acid, oxadiazon, nonanoic acid and barnyardgrass, (b16) herbicide safeners; and salts of compounds (b1) to (b16).

[0113] "Optical System II inhibitor" (b1) is in Q B - It binds to the D-1 protein at the binding site and thus blocks electrons from passing through the Q-cell membrane in the chloroplast. A Transmit to Q B Chemical compounds. Electrons blocked from passing through photosystem II are transferred through a series of reactions to form toxic compounds. These toxic compounds damage cell membranes, causing chloroplast swelling, membrane leakage, and ultimately cell rupture. Q B- The binding site has three different binding sites: binding site A binds triazine such as atrazine, triazinone such as cycloazinone, and uracil such as chlorpyrifos; binding site B binds phenylurea such as diuron; and binding site C binds benzothiadiazole such as metribuzin, nitrile such as bromobenzonitrile, and phenylpyridazine such as pyrazosulfuron. Examples of photosystem II inhibitors include atrazine, azoxystrobin, atrazine, bentazon, chlorpyrifos, bromofenac, chlorobromofenac, chlorpyrifos ...

[0114] "AHAS inhibitors" (b2) are chemical compounds that inhibit acetylhydroxy acid synthase (AHAS) (also known as acetyllactic acid synthase (ALS)), and thus kill plants by inhibiting the production of branched-chain aliphatic amino acids such as valine, leucine, and isoleucine, which are essential for protein synthesis and cell growth. Examples of AHAS inhibitors include pyrimisulfuron, tetrazolium-sulfuron, bensulfuron-methyl, bispyribac-sodium salt, chlorpyrifos, chlorpyrifos, chlorsulfuron, chlorpyrifos, chlorpyrifos, cyclopyrimisulfuron, dichlorvos, acesulfuron, ethoxysulfuron, pyrimisulfuron, flusulfuron-methyl, flusulfuron-methyl, pyrimisulfuron-methyl, flusulfuron-methyl sodium salt, formamide sulfuron, chlorpyrifos, imazalil, methoxysulfuron, methoxysulfuron, methoxysulfuron, metsulfuron-methyl, and fensulfuron-methyl. Metazolidinone, imazalil, azoxystrobin, mesosulfuron (including sodium salt), iofensulfuron (2-iodo-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide), sulfanilamide, iofensulfuron (3-chloro-4-(5,6-dihydro-5-methyl-1,4,2-dioxazin-3-yl)-N-[[(4-... (6-Dimethoxy-2-pyrimidinyl)amino]carbonyl]-1-methyl-1H-pyrazole-5-sulfonamide), sulfadiazine, mesosulfuron, nicosulfuron, cyclosulfuron, penoxsulam, flusulfuron, sodium propensulfuron, promethazine (2-chloro-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-6-propylimidazo[1,2-b]pyridazine-3-sulfonamide), flusulfuron, pyrimidinyl Sulfuron, pyrimisulfuron, cyclopyrimisulfuron, pyrimisulfuron sodium, sulfadiazine, mesosulfuron, sulfonylsulfuron, thiamethoxam, thifensulfuron, flufensulfuron (N-[2-[(4,6-dimethoxy-1,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-1,1-difluoro-N-methylmethanesulfonamide), etherbenzylsulfuron, benzylsulfuron, trifluridinesulfuron (including sodium salt), flumethanil, and trifluridinesulfuron.

[0115] "ACCase inhibitors" (b3) are chemical compounds that inhibit acetyl-CoA carboxylase, an enzyme responsible for catalyzing early steps in lipid and fatty acid synthesis in plants. Lipids are major components of cell membranes, and without lipids, new cells cannot be produced. Inhibition of acetyl-CoA carboxylase and the resulting lack of lipid production lead to a loss of cell membrane integrity, especially in actively growing areas such as meristems. Ultimately, seedling and rhizome growth ceases, and seedling meristems and rhizome buds begin to die. Examples of ACCase inhibitors include quizalofop-P-ethyl, clethodim, clodinafop-propargyl, thiamethoxam, cyhalofop-propargyl, quizalofop-P-ethyl, haloxyfop-propargyl, clodinafop-propargyl, cyclobenzanone, quizalofop-P-ethyl, quizalofop-P-ethyl, quizalofop-P-ethyl, and quizalofop-P-ethyl, including analytical forms such as quizalofop-P-ethyl, quizalofop-P-ethyl, quizalofop-P-ethyl, and quizalofop-P-ethyl, as well as ester forms such as clodinafop-propargyl, cyhalofop-propargyl, quizalofop-P-ethyl, and quizalofop-P-ethyl.

[0116] Auxins are plant hormones that regulate the growth of many plant tissues. "Auxin mimics" (b4) are compounds that mimic the plant growth hormone auxin, thus leading to uncontrolled and disordered growth, resulting in the death of susceptible species. Examples of auxin mimics include cyclopropylpyrimidine acid (6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid) and its methyl and ethyl esters and their sodium and potassium salts, chlorpyrifos, glyphosate-ethyl ester, glyphosate, chlorpyrifos, barnyardgrass, dichloropyridine acid, dicamba, 2,4-D, 2,4-DB, propionic acid, clopyralid, halauxifen (4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2- Pyridine carboxylic acid), halauxifen-methyl (4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylic acid methyl ester), MCPA, MCPB, 2-methyl-4-chloropropionic acid, doxycycline, dichloroquinoline acid, chloroquinoline acid, 2,3,6-TBA, chlorpyrifos, and 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylic acid methyl ester.

[0117] "EPSP synthase inhibitor" (b5) is a chemical compound that inhibits the enzyme 5-enol-pyruvate-shikimate-3-phosphate synthase, which is involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan, and phenylalanine. EPSP inhibitor herbicides are readily absorbed through plant leaves and translocated from the phloem to the growing point. Glyphosate is a relatively non-selective post-emergence herbicide belonging to this group. Glyphosate includes esters and salts such as ammonium salts, isopropylammonium salts, potassium salts, sodium salts (including sesquisodium salts), and trimethylsulfonium salts (alternatively known as glyphosate).

[0118] "Photosystem I electron diverters" (b6) are compounds that receive electrons from photosystem I and generate hydroxyl radicals after several cycles. These radicals are highly reactive and readily destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This disrupts cell membrane integrity, causing cells and organelles to "leak," leading to rapid leaf wilting and drying, and ultimately plant death. Examples of this second type of photosynthesis inhibitor include diquat and paraquat.

[0119] "PPO inhibitors" (b7) are compounds that inhibit the enzyme protoporphyrinogen oxidase, rapidly leading to the formation of highly reactive compounds in plants that disrupt cell membranes, resulting in cell sap leakage. Examples of PPO inhibitors include trifluralin-sodium, pyrazosulfuron, pyrazosulfuron, methoxyfenozide, flufenoxuron, trifluralin, methoxyfenozide, indole-methyl, isopyrazosulfuron, flupyridaben, flumetsulam, propyzoxystrobin, ethoxysulfuron, fluthiamethoxam, flusulfanilamide, halosafen, quizalofop-P-ethyl, propyzoxystrobin, oxadiazon, ethoxysulfuron, cyclopentoxane, flupyrazosulfuron, pyrazosulfuron, pyrazosulfuron, mesotrione, thiamethoxam, trifluralin. udimoxazin (dihydro-1,5-dimethyl-6-thio-3-[2,2,7-trifluoro-3,4-dihydro-3-oxo-4-(2-propyl-1-yl)-2H-1,4-benzoxazin-6-yl]-1,3,5-triazin-2,4(1H,3H)-dione) and flupyrimisulfuron (N-[2-[[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxy-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenyl]thio]-1-oxopropyl]-β-alanine methyl ester).

[0120] "GS inhibitors" (b8) are compounds that inhibit the activity of glutamine synthase, an enzyme used by plants to convert ammonia into glutamine. As a result, ammonia accumulates and glutamine levels decrease. Plant damage can occur due to the combined effects of ammonia toxicity and the lack of amino acids required for other metabolic processes. GS inhibitors include glufosinate and its esters and salts, such as glufosinate and other glufosinate derivatives, glufosinate P ((2S)-2-amino-4-(hydroxymethylphosphono)butyric acid), and bilanaphos.

[0121] "VLCFA elongase inhibitor" (b9) is a herbicide with various chemical structures that inhibits elongation enzymes. Elongation enzymes are enzymes located in or near chloroplasts that are involved in the biosynthesis of VLCFAs. In plants, very long-chain fatty acids are major components of hydrophobic polymers that prevent drying at the leaf surface and provide stability to pollen grains. Such herbicides include acetochlor, metolachlor, sphagnum molybdate, butachlor, benzoyl sulfone, metolachlor, thifensulfonamide, fenoxasulfone (3-[[(2,5-dichloro-4-ethoxyphenyl)methyl]sulfonyl]-4,5-dihydro-5,5-dimethylisoxazole), tetrazolium-methyl, fluthiamethoxam, indicarb, bensulfuron-methyl, pyrazosulfuron, metolachlor, naphthylpropane, diltiazem, diltiazem-M ((2R)-N,N-diethyl-2-(1-naphthoxy)propamide), pethoxamid, piperazine, pretilachlor, doxycycline, pyroxasulfone, and methoxythiamethoxam, including analytical forms such as metolachlor and chloroacetamide and oxyacetamide.

[0122] Auxin transport inhibitors (b10) are chemicals that inhibit auxin transport in plants, such as by binding to auxin-carrier proteins. Examples of auxin transport inhibitors include flupyradifurone, naphthalenesulfonamide (also known as N-(1-naphthyl)-o-carbamoylbenzoic acid and 2-[(1-naphthylamino)carbonyl]benzoic acid).

[0123] "PDS inhibitors (b11)" are compounds that inhibit the carotenoid biosynthesis pathway during the phytoene desaturase step. Examples of PDS inhibitors include flubutyramide, S-flubutyramide, pyrifluramide, flupyridine, flurfluridine, furazolidone, norflurzon, and flupyridine.

[0124] HPPD inhibitors (b12) are biosynthetic chemicals that inhibit the synthesis of 4-hydroxyphenylpyruvate dioxygenase. Examples of HPPD inhibitors include bicyclosulfonamide, pyrazinamide, flupyrazinamide (4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridyl]carbonyl]bicyclo[3.2.1]oct-3-en-2-one), fenquinolone (2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl]-1,3-cyclohexanedione), isoxachlor Sulphazoline, isoxazolidinone, mesotrione, sulfonylpyridinium, pyrazolium, benzylpyridinium, sulfonylpyridinium, terfurantoin, cyclosulfonyl, tolpyralate (1-[[1-ethyl-4-[3-(2-methoxyethoxy)-2-methyl-4-(methylsulfonyl)benzoyl]-1H-pyrazol-5-yl]oxy]ethyl methyl carbonate), benzylpyridinium, 5-chloro-3-[(2-hydroxy-6-oxo-1 [-cyclohexen-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalone, 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-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione [-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.

[0125] HST inhibitors (b13) disrupt the ability of plants to convert homogentisic acid 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-morpholinocarboxylate), flupyridine, chlorpyrifos, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthidium-2(1H)-one, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrrolo[2,3-b]pyrazin-6(5H)-one, and 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone.

[0126] HST inhibitors also include compounds of formulas A and B.

[0127]

[0128] Where R d1 It is H, Cl, or CF3; R d2 It is H, Cl, or Br; R d3 It is H or Cl; R d4 It is H, Cl, or CF3; R d5 It is CH3, CH2CH3, or CH2CHF2; and R d6 It is OH, or -OC(=O)-i-Pr; and R e1 It is H, F, Cl, CH3 or CH2CH3; R e2 It is H or CF3; R e3 It is H, CH3, or CH2CH3; R e4 It is H, F, or Br; R e5 It is Cl, CH3, CF3, OCF3, or CH2CH3; R e6 It is H, CH3, CH2CHF2 or C≡CH; R e7 It is OH, -OC(=O)Et, -OC(=O)-i-Pr or -OC(=O)-t-Bu; and A e8 It is N or CH.

[0129] Cellulose biosynthesis inhibitors (b14) inhibit the biosynthesis of cellulose in certain plants. They are most effective when applied to young or rapidly growing plants before or early after emergence. Examples of cellulose biosynthesis inhibitors include glyphosate, fenpropathrin, flumetsulam, and triazinon (N... 2 -[(1R,2S)-2,3-dihydro-2,6-dimethyl-1H-indene-1-yl]-6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine), isoxaflutole and triazineflutole.

[0130] "Other herbicides" (b15) includes herbicides that act through a variety of different modes of action, such as mitosis disruptors (e.g., methyl methacrylate and isopropyl methacrylate), organoarsenic compounds (e.g., DSMA and MSMA), 7,8-dihydrofolate synthase inhibitors, chloroplast isoprene synthesis inhibitors, and cell wall biosynthesis inhibitors. Other herbicides include those with unknown modes of action, those not falling into the specific categories listed in (b1) to (b14), or those acting through a combination of the modes of action listed above. Other examples of herbicides include bensulfuron, sulfadiazine, chlorpyrifos, bromobutyrazosulfuron, cyclohexane, isoxaflutole, bensulfuron, chlorpyrifos, dimesulfazet (CAS No. 1215111-77-5), chlorpyrifos, epyrifenacil (CAS No. 353292-31-6), ethoxybenzamide, fenpropathrin, chlorpyrifos-ammonium, dazomet, chlorpyrifos, triazolyl acetamiprid (1-( 2,4-Dichlorophenyl)-N-(2,4-difluorophenyl)-1,5-dihydro-N-(1-methylethyl)-5-oxo-4H-1,2,4-triazol-4-carboxamide), methylparaben, methyl sulfadiazine, oleic acid, oxadiazon, nonanoic acid, barnyardgrass, tetflupyrolimet, and 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole. "Other herbicides" (b15) also includes compounds having the formula (b15A).

[0131]

[0132] in

[0133] R 12 It is H, C1-C6 alkyl, C1-C6 haloalkyl or C4-C8 cycloalkyl;

[0134] R 13 It is H, C1-C6 alkyl, or C1-C6 alkoxy;

[0135] Q 1 It is a ring system with optional substitutions selected from the group consisting of: phenyl, thiophene, pyridyl, benzodioxanepentenyl, naphthyl, naphthalenyl, benzofuranyl, furanyl, benzothiophene, and pyrazolyl, wherein when substituted, the ring system is composed of 1 to 3 R groups. 14 replace;

[0136] Q 2It is a ring system with optional substitutions selected from the group consisting of: phenyl, pyridinyl, benzodioxanepentenyl, pyridinonyl, thiadiazolyl, thiazolyl, and oxazolyl, wherein when substituted, the ring system is composed of 1 to 3 R groups. 15 replace;

[0137] Each R 14 Independently, it is 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 optionally by 1 to 3 R 16 Substituted phenyl groups; or optionally with 1 to 3 R groups. 16 Substituted pyrazol group;

[0138] Each R 15 Independently, it is halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, cyano, nitro, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl;

[0139] Each R 16 It is independently a halogen, a C1-C6 alkyl group, or a C1-C6 haloalkyl group;

[0140] R 17 It is a C1-C4 alkoxycarbonyl group.

[0141] In one embodiment, the "other herbicides" (b15) further include a compound having the formula (b15A), preferably, R 12 It is H or C1-C6 alkyl; more preferably, R 12 It is H or methyl. Preferably, R 13 It is H. Preferably, Q 1 It is a benzene ring or a pyridine ring, each ring being separated by 1 to 3 R... 14 Replace; more preferably, Q 1 It is by 1 to 2 Rs 14 Substituted benzene ring. Preferably, Q 2 It is by 1 to 3 Rs 15 Substituted benzene ring; more preferably, Q 2 It is by 1 to 2 Rs 15 Substituted benzene ring. Preferably, each R 14 Independently, it is a halogen, a C1-C4 alkyl, a C1-C3 haloalkyl, a C1-C3 alkoxy, or a C1-C3 haloalkoxy; more preferably, each R 14Independently, it is chlorine, fluorine, bromine, C1-C2 haloalkyl, C1-C2 haloalkoxy, or C1-C2 alkoxy. Preferably, each R 15 Independently, it is a halogen, a C1-C4 alkyl, or a C1-C3 haloalkoxy; more preferably, each R 15 Independently, it is chlorine, fluorine, bromine, C1-C2 haloalkyl, C1-C2 haloalkoxy, or C1-C2 alkoxy. Specifically, preferred "other herbicides" (b15) include any one of the following (b15A-1) to (b15A-16):

[0142]

[0143]

[0144]

[0145] "Other herbicides" (bl5) also include compounds having the formula (b15B).

[0146]

[0147] in

[0148] R 18 It is H, C1-C6 alkyl, C1-C6 haloalkyl or C4-C8 cycloalkyl;

[0149] Each R 19 It is independently a halogen, a C1-C6 haloalkyl, or a C1-C6 haloalkoxy;

[0150] p is an integer of 0, 1, 2 or 3;

[0151] Each R 20 It is independently a halogen, a C1-C6 haloalkyl, or a C1-C6 haloalkoxy; and

[0152] q is an integer of 0, 1, 2 or 3.

[0153] In one embodiment, the "other herbicides" (bl5) further include compounds having the formula (b15B), preferably, R 18 It is H, methyl, ethyl or propyl; more preferably, R 18 It is H or methyl; most preferably, R 18 It is H. Preferably, each R 19 Independently, it is chlorine, fluorine, C1-C3 haloalkyl, or C1-C3 haloalkoxy; more preferably, each R 19 Independently, it is chlorine, fluorine, C1 fluoroalkyl (i.e., fluoromethyl, difluoromethyl, or trifluoromethyl) or C1 fluoroalkoxy (i.e., trifluoromethoxy, difluoromethoxy, or fluoromethoxy). Preferably, each R20 Independently, it is chlorine, fluorine, C1 haloalkyl, or C1 haloalkoxy; more preferably, each R 20 Independently, it is chlorine, fluorine, C1 fluoroalkyl (i.e., fluoromethyl, difluoromethyl, or trifluoromethyl) or C1 fluoroalkoxy (i.e., trifluoromethoxy, difluoromethoxy, or fluoromethoxy). Specifically, preferred “other herbicides” (b15) include any one of the following (b15B-1) to (b15B-19):

[0154]

[0155]

[0156]

[0157] In another embodiment, the "other herbicides" (b15) further includes a compound having the formula (b15C).

[0158]

[0159] Where R 1 It is Cl, Br, or CN; and R 2 It is C(=O)CH2CH2CF3, CH2CH2CH2CH2CF3, 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.

[0160] "Herbicide safeners" (B16) are substances added to herbicide formulations to eliminate or reduce the phytotoxic effects of herbicides on certain crops. These compounds protect crops from herbicide damage but generally do not prevent herbicide control of unwanted vegetation. Examples of herbicide safeners include, but are not limited to, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, dicyclonon, dietholate, piperazine, chlorpyrifos, chlorpyrifos, chlorpyrifos, fluroxypyr, chlorpyrifos, chlorpyrifos, pyrazosulfuron, mephenate, chlorpyrifos, naphthalenecarboxylic anhydride, chlorpyrifos, 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-azaspiro[4.5]decane (MON 4660), 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-acetone and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]benzamide.

[0161] Preferred for better control of unwanted vegetation (e.g., lower application rates, such as from additive effects, broader-spectrum weed control, or enhanced crop safety) or for preventing the development of resistant weeds, are mixtures of the compounds of the present invention with herbicides selected from the group consisting of: atrazine, tetrazolium-sulfuron, flubutyramide, S-flubutyramide, benzisothiazolinone, pyrazosulfuron, chlorimuron-methyl, isoxaflutole, dichloropyridinic acid. Potassium, chlorpyrifos, 2-[(2,4-dichloro-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5-(2H,4H)-dione, flupyrimisulfuron, fluthiamethoxam, flusulfanilamide, imazalil, cyclosporine, mesotrione, methamidophos, clethodim, sulfadiazine, sulfonyl sulfone, quinclorac, pyrimisulfuron, succinylmethrin, metolachlor, mesotrione, thifensulfuron, flusulfanilamide, and bensulfuron.

[0162] The substituted enantiomers having formula 1a(R) and formula 1b(S) can be separated from the racemate having formula 1 by chiral support chromatography (see Scheme-1). The racemate having formula 1 can be prepared by the methods taught in WO 2015168010. The absolute stereochemistry can be designated as the drawn heterodiaryl structure according to the established nomenclature rules established in the art. Those skilled in the art will appreciate that, due to the restriction of rotation of the naphthalene and pyridazinone rings in this heterodiaryl ring system, the two enantiomers comprising the racemate can also be called transisomers. The restriction of rotation locks the two rings in a fixed stereo orientation that allows for asymmetry. When naphthalene is substituted at the position adjacent to the bond connected to the pyridazinone, both transisomers are stable to the racemate by ring rotation at temperatures generally below 100°C.

[0163] Option 1

[0164]

[0165] Separation Example 1

[0166] A sample of 1.8 g of racemic 2 was loaded onto a chiral support for supercritical fluid chromatography (SFC), using carbon dioxide as the supercritical mobile phase or an optional co-solvent such as methanol or acetonitrile. The principles used are similar to those in standard achiral high-performance liquid chromatography (HPLC). Two fractions were obtained. The first eluted fraction was labeled as enantiomer 2a (580 mg) and the second eluted fraction as enantiomer 2b (600 mg). The optical rotations of 2a and 2b were +47.34 [20 °C, c = 0.4 (methanol)] and -58.29 [20 °C, c = 0.4 (methanol)], respectively. The enantiomer excess (ee) of both samples was determined by chiral HPLC to be greater than 95%.

[0167] Option 2

[0168]

[0169] Figure 1 (Analytical chiral HPLC SFC chromatogram of enantiomer 2a (2A)) shows the chiral chromatogram of 2a with a retention time of 2.03 min, further confirming the integrity of the enantiomer.

[0170] Figure 2 (Analytical chiral HPLC SFC chromatogram of enantiomer 2b (2B)) shows the chiral chromatogram of 2b with a retention time of 3.24 minutes, further confirming the integrity of the enantiomer.

[0171] Without further elaboration, it is believed that those skilled in the art can utilize this disclosure to its fullest extent using the foregoing description. The following non-limiting examples are illustrative of this disclosure.

[0172] Compounds having formulas 1a and 1b are generally used as the herbicidal active ingredient in a composition (i.e., formulation) having at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents. In some embodiments, the additional component may act as a carrier. The formulation or composition components are selected to be consistent with the physical properties of the active ingredient, the application method, and environmental factors such as soil type, moisture, and temperature.

[0173] The formulations that can be used include both liquid and solid compositions comprising compounds having formulas 1a and 1b. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, flowable concentrates, and / or suspension emulsions), which can optionally be thickened into a gel. Typical types of aqueous liquid compositions include soluble concentrates, suspensions, capsule suspensions, concentrated emulsions, microemulsions, oil-in-water emulsions, flowable concentrates, and suspension emulsions. Typical types of non-aqueous liquid compositions include emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates, and oil dispersions.

[0174] Solid compositions are generally of the following types: powders, granules, pellets, beads, granules, lozenges, tablets, filler films (including seed coatings), etc., and can be water-dispersible (“wettable”) or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. Active ingredients can be (micro)encapsulated and further formed into suspensions or solid formulations; alternatively, the entire formulation of the active ingredient can be encapsulated (or “coated”). Encapsulation can control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of emulsifiable concentrate formulations and dry granule formulations. High-strength compositions are primarily used as intermediates for further formulation.

[0175] Sprayable formulations are typically dispersed in a suitable medium before spraying. These liquid and solid formulations are formulated in a spraying medium, usually water, but occasionally another suitable medium that is easily diluted, such as aromatic hydrocarbons, paraffinic hydrocarbons, or vegetable oils. Spray volumes can range from about one liter to several thousand liters per hectare, but are more typically in the range of about ten to several hundred liters per hectare. Sprayable formulations can be mixed with water or another suitable medium for foliar application via air or ground application, or for application to the plant's growing medium. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into furrows during planting.

[0176] Formulations typically contain a total of up to 100% by weight of an effective amount of the active ingredient, diluent, and surfactant within the following approximate ranges.

[0177]

[0178] 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, 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.

[0179] Liquid diluents include, for example, water, N,N-dimethylalkanamide (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidone (e.g., N-methylpyrrolidone), alkyl phosphate esters (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butyl carbonate, paraffin (e.g., white mineral oil, n-alkanes, isoalkanes), alkylbenzenes, alkylnaphthalenes, glycerol, glycerol triacetate esters, sorbitol, aromatics, dearomatized aliphatic compounds, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, and isoflavones. Alkyl ketone and 4-hydroxy-4-methyl-2-pentanone, acetate esters such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate, and isobornyl acetate, other esters such as alkyl lactates, diesters, alkyl and aryl benzoates, and γ-butyrolactone, and alcohols that can be straight-chain, branched, saturated, or unsaturated, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecanol, isoctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oily alcohols, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol, and benzyl alcohol. Liquid diluents also include saturated and unsaturated fatty acids (typically C6-C). 22Glycerides of plant seeds and fruits (e.g., olive oil, castor oil, flaxseed oil, sesame oil, corn oil, peanut oil, sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil, and palm kernel oil), animal fats (e.g., beef tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated (e.g., methylated, ethylated, butylated) fatty acids, wherein the fatty acids can be obtained by hydrolysis of glycerides from plant and animal sources and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Edition, Interscience, New York, 1950.

[0180] The solid and liquid compositions disclosed herein often include one or more surfactants. When added to a liquid, a surfactant (also known as a “surfactant”) typically alters, and most frequently reduces, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, a surfactant can be used as a wetting agent, dispersant, emulsifier, or defoamer.

[0181] Surfactants can be classified as nonionic, anionic, or cationic. Nonionic surfactants that can be used in the compositions of this 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 and ethylene oxide, propylene oxide, butyl oxide, or mixtures thereof; amine ethoxylates, alkanolamides, and ethoxylated alkanolamides; alkoxylated triglycerides, such as ethoxylated soybean oil, castor oil, and rapeseed oil; alkylphenol alkoxylates, such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonylphenol ethoxylates, and dodecylphenol ethoxylates (prepared from phenol and ethylene oxide, propylene oxide, butyl oxide, or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide, and trans-block polymers wherein the terminal blocks are prepared from propylene oxide. Ethoxylated fatty acids; ethoxylated fatty acid esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenols (including those prepared from ethylene oxide, propylene oxide, butane oxide, or mixtures thereof); fatty acid esters, glycerides, lanolin-based derivatives, polyethoxylated esters (such as polyethoxylated sorbitol fatty acid esters, polyethoxylated sorbitol fatty acid esters, and polyethoxylated glycerol fatty acid esters); other sorbitol derivatives such as sorbitol esters; polymer surfactants such as random copolymers, block copolymers, alkyd PEG (polyethylene glycol) resins, grafted 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.

[0182] Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohols or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives, such as lignin sulfonates; maleic acid 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 alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides, such as N,N-alkyl taurine; sulfonates of benzene, cumene, toluene, xylene, and dodecylbenzene and tridecylbenzene; sulfonates of condensed naphthalene; sulfonates of naphthalene and alkylnaphthalene; petroleum-grade sulfonates; sulfosuccinates; and sulfosuccinates and their derivatives, such as dialkylsulfosuccinates.

[0183] Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkylpropylenediamine, tripropylenetriamine and dipropylenetetraamine, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butyl oxide or mixtures thereof); amine salts such as ammonium acetate and diamine salts; 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.

[0184] Also usable in the compositions of the present invention are mixtures of nonionic and anionic surfactants, or mixtures of nonionic and cationic surfactants. Nonionic surfactants, anionic surfactants, and cationic surfactants, and their recommended uses, are disclosed in several published references, including McCutcheon's Emulsifiers and Detergents, annual American and International Editions, published by The Manufacturing Confectioner Publishing Co., McCutcheon Division; Sisley and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A.S. Davidson and B. Milwidsky, Synthetic Detergents, 7th edition, John Wiley and Sons, New York, 1987.

[0185] The compositions disclosed herein may also contain formulation adjuvants and additives known to those skilled in the art as auxiliary formulations (some of which may also be considered as solid diluents, liquid diluents, or surfactants). Such formulation adjuvants and additives can control: pH (buffers), foaming during processing (defoamers, such as polysiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), microbial growth within the container (antimicrobial agents), product freezing (antifreeze agents), color (dye / pigment dispersions), elution (film-forming agents or adhesives), evaporation (evaporation inhibitors), and other formulation properties. Film-forming agents include, for example, polyvinyl acetate, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol, polyvinyl alcohol copolymers, and waxes. Examples of formulation adjuvants and additives include those listed below: McCutcheon's Volume 2: Functional Materials, published by the McCutcheon division of Manufacturing Confectioner, annual International and North American editions; and PCT Publication WO03 / 024222.

[0186] Compounds having formulas 1a and 1b, along with any other active ingredients, are typically incorporated into the compositions of the present invention by dissolving the active ingredient in a solvent or by milling in a liquid or dry diluent. Solutions comprising emulsifiable concentrates can be prepared by simply mixing these ingredients. If the solvent of the liquid composition intended to be used as an emulsifiable concentrate is immiscible with water, an emulsifier is typically added to emulsify the solvent containing the active ingredient upon dilution with water. Active ingredient slurries with particle sizes up to 2,000 μm can be wet-milled using a media mill to obtain particles with an average particle size of less than 3 μm. Aqueous slurries can be formulated as finished suspensions (see, for example, US 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations typically require a dry milling process, producing an average particle size in the range of 2 to 10 μm. Powders and powders can be prepared by blending and typically by milling (e.g., using a hammer mill or kinetic mill). Granules and pellets can be prepared by spraying the active material onto a pre-formed granule carrier or by agglomeration techniques. See Browning, “Agglomeration,” Chemical Engineering, December 4, 1967, pp. 147-48; Perry’s Chemical Engineer’s Handbook, 4th edition, McGraw-Hill, New York, 1963, pp. 8-57 and following pages; and WO 91 / 13546. Pellets can be prepared as described in US4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in US4,144,050, US3,920,442, and DE3,246,493. Tablets can be prepared as taught in US5,180,587, US5,232,701 and US5,208,030. Films can be prepared as taught in GB 2,095,558 and US3,299,566.

[0187] For further information on formulation, see “The Formulator’s Toolbox – Product Forms for Modern Agriculture” in T. Woods, Pesticide Chemistry and Bioscience, The Food-Environment Challenge, edited by T. Brooks and TR Roberts, Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120–133. See also US 3,235,361, column 6, lines 16-7, line 19 and examples 10-41; US ​​3,309,192, column 5, lines 43-7, line 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; US 2,891,855, column 3, lines 66-5, 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 edition, Blackwell Scientific. Publications [Blackwell Science Publishing], Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

[0188] In the following examples, all percentages are by weight, and all formulations were prepared in a conventional manner. Compound numbers, i.e., “Cpd. numbers,” refer to the compounds in Table 1. No further exhaustive explanation is required, and it is believed that those skilled in the art will utilize this disclosure to its fullest extent using the foregoing description. Therefore, the following examples should be interpreted as illustrative only and do not limit this disclosure in any way. Percentages are by weight unless otherwise stated.

[0189] Example A

[0190] High-strength concentrate

[0191] 98.5% of compounds having formula 1a or formula 1b

[0192] 0.5% silica aerogel

[0193] Synthetic amorphous fine silica 1.0%

[0194] Example B

[0195] wettable powder

[0196]

[0197]

[0198] Example C

[0199] Granules

[0200] 10.0% of compounds having formula 1a or formula 1b

[0201] Attapulgite granules (low volatile matter, 0.71 / 0.30 mm; 90.0%)

[0202] USS size 25-50 sieve)

[0203] Example D

[0204] Extruded pellets

[0205]

[0206] Example E

[0207] Emulsifiable concentrate

[0208] 10.0% of compounds having formula 1a or formula 1b

[0209] Polyoxyethylene sorbitan hexaoleate 20.0%

[0210] C6-C 10 Fatty acid methyl esters 70.0%

[0211] Example F

[0212] microemulsion

[0213]

[0214] Instance G

[0215] Suspension

[0216]

[0217] Instance H

[0218] Emulsion in water

[0219]

[0220] Example I

[0221] oil dispersion

[0222]

[0223]

[0224] Examples A to I above are also disclosed, wherein "compounds having formula 1a or formula 1b" are replaced with "compounds having formula 2 (enantiomer 2A) or formula 2 (enantiomer 2B)," "compounds having formula 3 (enantiomer 3A) or formula 3 (enantiomer 3B)," "compounds having formula 4 (enantiomer 4A) or formula 4 (enantiomer 4B)," or "compounds having formula 5 (enantiomer 5A) or formula 5 (enantiomer 5B)."

[0225] Test results indicate that certain compounds having formula 1a or formula 1b are active pre-emergence and / or post-emergence herbicides and / or plant growth regulators. Compounds having formula 1a or formula 1b typically exhibit the highest activity for both post-emergence weed control (i.e., application after weeds have emerged from the soil) and pre-emergence weed control (i.e., application before weeds have emerged from the soil). Many of these compounds are effective 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 cinemas, airports, riverbanks, irrigation and other waterways, billboards, and highway and railway structures. Many of the compounds disclosed herein can be used for selective control of grasses and broadleaf weeds in crop / weed mixed environments by means of selective metabolism in the crop-comparison weeds, selective activity at physiological inhibition sites in the crop and weeds, or selective application above or within the crop-weed mixed environment. Those skilled in the art will recognize that, within a compound or group of compounds, the preferred combination of these selectivity factors can be readily determined by routine biological and / or biochemical assays.

[0226] Compounds having formula 1a or 1b may exhibit tolerance to important crops, including but not limited to alfalfa, barley, cotton, wheat, oilseed rape, sugar beets, corn, sorghum, soybean, rice, oats, peanuts, vegetables, tomatoes, potatoes, perennial crops including coffee, cocoa, oilseed palm, rubber, sugarcane, citrus, grapes, fruit trees, nut trees, bananas, plantain, pineapple, hops, tea, and trees such as eucalyptus and conifers (e.g., slash pine), as well as turfgrasses (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky yew, and Bermuda grass). The compounds disclosed herein may be used in or on genetically modified or bred crops to incorporate herbicide resistance, express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxins), and / or express other useful traits. Those skilled in the art will understand that not all compounds are equally effective against all weeds. Alternatively, the subject compound can be used to alter plant growth.

[0227] Because the compounds disclosed herein have (pre-emergence and post-emergence) herbicidal activity to control unwanted vegetation by killing or damaging it or slowing its growth, the compounds are typically applied effectively by a variety of methods. These methods involve contacting the leaves or other parts of the unwanted vegetation, or a composition comprising at least one of the compounds disclosed herein and a surfactant, a solid diluent, or a liquid diluent, with the leaves or other parts of the unwanted vegetation, or with the environment in which the unwanted vegetation grows, such as soil or water, or with the environment surrounding the seeds or other propagules of the unwanted vegetation.

[0228] The herbicidal effective amount of compounds having formula 1a or formula 1b is determined by a number of factors. These factors include: the selected formulation, the method of application, the amount and type of vegetation present, growing conditions, etc. Typically, the herbicidal effective amount of the compounds disclosed herein is from about 0.001 to 20 kg / ha, preferably from about 0.004 to 1 kg / ha. Those skilled in the art can readily determine the herbicidal effective amount required for the desired level of weed control.

[0229] In a common embodiment, compounds having formula 1a or 1b are typically applied as formulated compositions to a location comprising desired vegetation (e.g., crops) and undesirable vegetation (i.e., weeds), both of which may be seeds, seedlings, and / or larger plants in contact with a growth medium (e.g., soil). At this location, compositions comprising the disclosed compounds may be applied directly to the plant or a portion thereof, particularly the undesirable vegetation, and / or to the growth medium in contact with the plant.

[0230] Plant varieties and cultivars of desired vegetation in locations treated with the compounds disclosed herein can be obtained through conventional propagation and breeding methods or through genetic engineering methods. Genetically modified plants (transgenic plants) are those in which a heterologous gene (transgenic gene) has been stably integrated into the plant genome. A transgene defined by a specific location of the transgene in the plant genome is called a transformation or transgenic event.

[0231] While the compounds disclosed herein are most typically used to control undesirable vegetation, exposing desired vegetation to the compounds disclosed herein in a treated location can result in a super-additive or synergistic effect with the genetic traits of the desired vegetation, including traits introduced through genetic modification. For example, resistance to herbivorous pests or plant diseases, tolerance to biotic / abiotic stresses, or storage stability may be greater than expected in the genetic traits of the desired vegetation.

[0232] The compounds disclosed herein can also be mixed with one or more other biologically active compounds or reagents to form multi-component insecticides, thereby conferring even broader-spectrum agricultural protection. These biologically active compounds or reagents include herbicides, herbicide safeners, fungicides, insecticides, nematicides, fungicides, acaricides, growth regulators such as insect molting inhibitors and rooting stimulants, chemical sterilizers, chemical pheromones, insect repellents, attractants, pheromones, feeding stimulants, phytonutrients, other biologically active compounds, or insect pathogenic bacteria, viruses, or fungi. Mixtures of the compounds disclosed herein with other herbicides can broaden the spectrum of activity against additional weed species and inhibit the proliferation of any resistant organism type. Therefore, this disclosure also relates to compositions comprising compounds having formula 1a and / or formula 1b (at a herbicidal effective amount) and at least one additional biologically active compound or reagent (at a biologically effective amount), and the composition may further comprise at least one of a surfactant, a solid diluent, or a liquid diluent. Other biologically active compounds or agents can be formulated into compositions comprising at least one of a surfactant, a solid or liquid diluent. For the mixtures disclosed herein, one or more other biologically active compounds or reagents may be formulated together with a compound having formula 1a or formula 1b to form a premix, or one or more other biologically active compounds or reagents may be formulated separately from a compound having formula 1a or formula 1b and the formulations may be combined together (e.g., in a spray can) prior to application, or alternatively, applied sequentially.

[0233] General references for agricultural protectants (i.e., herbicides, herbicide safeners, insecticides, fungicides, nematicides, acaricides, and biological agents) include The Pesticide Manual, 13th edition, edited by CDSTomlin, British Crop Protection Council, Farnham, Surrey, UK, 2003, and The BioPesticide Manual, 2nd edition, edited by LGCopping, British Crop Protection Council, Farnham, Surrey, UK, 2001.

[0234] In embodiments where one or more of these different blending components are used, these blending components are typically used in amounts similar to those conventionally used when the blending components are used alone. More specifically, in the blend, the active ingredient is typically applied at an amount between half and the total amount of the active ingredient specified on the product label. These amounts are listed in references such as The Pesticide Manual and The BioPesticide Manual. The weight ratio of these different blending components (total) to the compound having formula 1a or formula 1b is typically between about 1:3000 and about 3000:1. It is noteworthy that weight ratios between about 1:300 and about 300:1 (e.g., ratios between about 1:30 and about 30:1) are also possible. Those skilled in the art can readily determine, through simple experiments, the bioeffective amount of the active ingredient necessary for the desired biological activity spectrum. It will be apparent that including these additional components allows the controlled weed spectrum to be extended beyond the controllable spectrum by the individual compounds having formula 1a or formula 1b.

[0235] It is noteworthy that a composition comprises the compound of the present invention (in a herbicidal amount), at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners (in a herbicidal amount), and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.

[0236] Table A1 lists specific combinations of components (a) and (b), illustrating the mixtures, compositions, and methods of the present invention. The compound number A (i.e., “Cpd.No.” representing “Compound Number”) in the component (a) column 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 the range of weight ratios (i.e., (a):(b)) at which component (a) compound is typically applied to field-grown crops. Thus, for example, the first row of Table A1 specifically discloses that the combination of component (a) (i.e., compound number A in index table A) and 2,4-D is typically applied at a weight ratio between 1:192 and 6:1. The remaining rows of Table A1 will be constructed similarly.

[0237] Table A1

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248] Table A2 has the same structure as Table A1 above, except that the entries under the “Component (a) (Cpd. No.)” column heading are replaced with the corresponding Component (a) column entries shown below. The compound numbers in Component (a) column are identified in Index Table 1. Thus, for example, in Table 2A, the entries under the “Component (a)” column heading are all listed as “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) and 2,4-D.

[0249]

[0250] In certain circumstances, combinations of the disclosed compounds with other biologically active (particularly herbicidal) compounds or agents (i.e., active ingredients) can result in a greater-than-additive (i.e., synergistic) effect on weeds and / or a less-than-additive (i.e., safetyation) effect on crops or other desired plants. Reducing the amount of active ingredient released into the environment while ensuring effective pest control has always been desirable. The ability to use larger amounts of active ingredient to provide more effective weed control without excessive crop damage is also desirable. Such combinations can be advantageously used to reduce crop production costs and environmental impact when the application rate of the herbicidal active ingredient synergizes with weeds to achieve agronomically satisfactory weed control levels. When the safetyation of the herbicidal active ingredient occurs on the crop, such combinations can be advantageously used to increase crop protection by reducing weed competition.

[0251] It is noteworthy that the disclosed compounds are combined with at least one other herbicidal active ingredient. Particularly noteworthy are combinations of other herbicidal active ingredients with compounds having different sites of action. In some cases, combination with at least one other herbicidal active ingredient having a similar control spectrum but a different site of action will be particularly advantageous for resistance management. Therefore, the compositions disclosed may further comprise (at a herbicidally effective amount) at least one additional herbicidal active ingredient having a similar control spectrum but a different site of action.

[0252] The compounds disclosed herein may also be used in combination with the following herbicide safeners to increase safety for certain crops: dipropionylamine, cyproconazole, cyproconazole ester, bensulfuron-methyl, cyproconazole nitrile, propanesulfonamide, cyproconazole, dichloropropionylamine, cyproconazole, cyproconazole nitrile, cyproconazole nitrile, cyproconazole nitrile, fluroxypyr, cyproconazole nitrile, pyrazole nitrile, mefenoxam, cyproconazole nitrile, 1,8-naphthalenecarboxylic anhydride, cyproconazole nitrile, N-(aminocarbonyl)-2-methylbenzenesulfonamide, N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene (BCS), 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON 4660), 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), ethyl 1,6-dihydro-1-(2-methoxyphenyl)-6-oxy-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)-acetone, and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]benzamide. An effective amount of the herbicide safener can be applied simultaneously with the compounds disclosed herein or as a seed treatment. Therefore, one aspect of this disclosure relates to a herbicidal mixture comprising the compounds disclosed herein and an effective amount of the herbicide safener. Seed treatment is particularly useful for selective weed control because it physically confines the detoxification effect to the crop plant. Therefore, a particularly useful embodiment of this disclosure is a method for selectively controlling unwanted vegetation growth in a crop, the method comprising contacting the site of the crop with a herbicidally effective amount of the compound of this disclosure, wherein the crop, from its seed stage, is treated with a detoxifyingly effective amount of a safener. The detoxifyingly effective amount of the safener can be readily determined by those skilled in the art through simple experiments.

[0253] The compounds disclosed herein may also be mixed with: (1) polynucleotides, including but not limited to DNA, RNA and / or chemically modified nucleotides, which affect the amount of a specific target by modulating, interfering with, inhibiting or silencing gene-derived transcripts that exhibit herbicidal effects; or (2) polynucleotides, including but not limited to DNA, RNA and / or chemically modified nucleotides, which affect the amount of a specific target by modulating, interfering with, inhibiting or silencing gene-derived transcripts that exhibit safety-enhancing effects.

[0254] Test A below demonstrates the control efficacy of the representative compounds disclosed herein against representative weeds; however, the weed control provided by these compounds is not limited to these species. See Index Table 1 for compound descriptions.

[0255] Index Table 1

[0256]

[0257] Test A

[0258] Seeds of the following plant species were planted in a mixture of fertile soil and sand and pre-emergence treated by targeted soil spraying with a test chemical formulated in a mixture of non-phytotoxic solvents containing surfactants: barnyard grass (BYG, Echinochloa crus-galli), kochia scoparia (KOC, Kochia scoparia), ragweed (common ragweed, Ambrosia elatior), Italian ryegrass (RGI, Lolium multiflorum), large foxtail grass (FTI, Setaria faberii), green foxtail grass (Setaria viridis), and wild amaranth (PWR, Amaranthus retroflexus).

[0259] Simultaneously, plants selected from these weed species, along with wheat (WWT, Triticum aestivum), maize (CPI, Zea mays), black grass (BKG, Alopecurus myosuroides), and cleavers (GAL, Galiumaparine), were planted in pots containing the same mixture of fertile soil and sand, and post-emergence treated with test chemicals formulated in the same manner. For post-emergence treatment, the plants ranged in height from 2 to 10 cm and were at the one- to two-leaf stage. The treated plants were kept in a greenhouse with untreated controls for approximately 10 days, after which all treated plants were compared with the untreated controls and damage was visually assessed. The plant response ratings summarized in Tables 1-4 are based on a scale of 0 to 100, where 0 represents no effect and 100 represents complete control. A dash (-) response indicates no test result. The rank is followed by a letter indicating symptomology, where S is albinism, C is chlorosis, G is growth inhibition, and E is emergence.

[0260] Table 1: Post-emergence (POST) and pre-emergence (PEE) of enantiomers containing racemate 2 at 125 and 31 g / ha. (PRE) activity.

[0261]

[0262] Table 2: Post-emergence (POST) and emergence times of enantiomers containing racemic 3 at 125 and 31 g / ha. Pre-reactivity (PRE)

[0263]

[0264] Table 3: Post-emergence (POST) and emergence times of enantiomers containing racemic 4 at 125 and 31 g / ha. Pre-reactivity (PRE)

[0265]

[0266] Table 4: Post-emergence (POST) and emergence times of enantiomers containing racemic 5 at 125 and 31 g / ha. Pre-reactivity (PRE)

[0267]

Claims

1. An optically active compound selected from the transisomers having formula 1a and formula 1b or their salts: in R 1 is CI; R 2 is CH3; R 3 is CH3; R 4 is H; and R 5 is H; in The steganous isomer of formula 1a or 1b or its salt has a positive optical rotation value (+) and exists in a manner exceeding that of its corresponding enantiomer or its salt.

2. The optically active compound of claim 1, comprising a resisted isomer of formula 1a or 1b having a positive optical rotation value (+) or a salt thereof.

3. A method for preparing a compound having formula 1a or 1b according to claim 1, in, R 1 is Cl; R 2 is CH3; R 3 is CH3; R 4 is H; and R 5 is H; The method includes: 1) A racemic mixture of compounds containing the transisomers of formulas 1a and 1b is loaded onto a chiral supercritical fluid chromatography column and eluted with a mobile phase containing carbon dioxide. 2) Two separate fractions with different retention times are separated: one containing a resisted isomer with a positive optical rotation value [α]1(+); and the other containing a resisted isomer with a negative optical rotation value [α]1(-).

4. A weed control composition comprising the optically active compound as described in claim 1 or 2 and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.

5. A weed control composition comprising the optically active compound as claimed in claim 1 or 2, 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 diluents and liquid diluents.

6. A weed control mixture comprising (a) the optically active compound as claimed in claim 1 or 2 and (b) at least one additional active ingredient.

7. A method for controlling the growth of unwanted vegetation, the method comprising contacting the vegetation or its environment with a herbicidal amount of the optically active compound as claimed in claim 1 or 2.

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