Atropisomers of pyridazinone derivatives as herbicides

Abstract

This disclosure provides atropisomers of pyridazinone derivatives of a compound of formula 1a and formula 1b, N-oxides or salts thereof (see Formulas), wherein R1, R2, R3, R4, and R5 are defined herein. Also disclosed is a composition containing a compound of formula 1a or 1b and methods for controlling unwanted vegetation comprising contacting the unwanted vegetation or its surroundings with an effective amount of a compound of formula 1a or 1b, or a composition thereof. Methods for preparing a compound of formula I are also disclosed.

Description

Atropisomers of pyridazinone derivatives as herbicides FIELD OF INVENTION This disclosure relates to stereoisomers of certain pyridazinone derivatives, their N-oxides, salts, and compositions, and methods for their use in controlling undesirable vegetation. More specifically, this disclosure relates to atropisomers of certain pyridazinone derivatives, their / V-oxides, salts, and compositions, and methods for their use as herbicides. BACKGROUND OF THE INVENTION Controlling unwanted vegetation is extremely important for achieving high crop yields. Selective weed control is highly desirable, especially in valuable crops such as rice, soybeans, sugar beets, corn, potatoes, wheat, barley, tomatoes, and plantation crops, among others. Uncontrolled weed growth in these crops can significantly reduce productivity and, consequently, increase costs for the consumer. Controlling unwanted vegetation in non-crop areas is also important. Many commercially available products exist for these purposes, but new compounds that are more effective, less expensive, less toxic, safer for the environment, or have different sites of action are still needed. Documents WO 2015 / 168010 and WO 2017 / 074988 disclose herbicidal pyridazinones and synthetic intermediates used to prepare herbicidal pyridazinones. SUMMARY OF THE INVENTION This disclosure provides optically active atropisomers of pyridazinone derivatives of a compound of formula 1a and formula 1b, / V-oxides or salts thereof; a compound of formula 1 is a racemic mixture of an atropisomer of formula 1a and an atropisomer of formula 1b. ίΠ / ZZΖηZ / E / YΙΛΙ where R1 is CH3 or halogen; R2 is CH3, CH2CH3, halogen, trifluoromethyl or difluoromethoxy; R3 is H, CH3 or halogen; R4es H, CH3o halogen; R5es H, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl or C1-C4 alkylcarboxymethyl; wherein the atropisomer of formula 1a or 1b, an A / -oxide or salt thereof is present in excess of its corresponding enantiomer or a / V-oxide or salt thereof; In another respect, the present description provides a process for preparing a compound of formula 1a or 1b; ίη / ZZΖΠZ / E / YΙΛΙ the Ib where R1 is CH3 or halogen; R2 is CH3, CH2CH3, halogen, trifluoromethyl or difluoromethoxy; R3es H, CH3o halogen; R4es H, CH3o halogen; R5 is H, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, or C1-C4 alkylcarboxymethyl; comprising the process: 1) loading a racemic mixture of a compound of formula 1 comprising the atropisomers of formulas 1a and 1b onto a chiral support chromatography column and eluting with a mobile phase; 2) isolate two separate fractions with different retention times; one containing an atropisomer with a positive optical rotation value [a]i (+) and an atropisomer with a negative optical rotation value [a]i (-). DETAILED DESCRIPTION OF THE INVENTION The expressions "comprising," "comprising," "includes," "having," "containing," "characterized by," or any other variation thereof, as used herein, are intended to encompass a non-exclusive inclusion, subject to any limitations explicitly stated. For example, a process or method comprising a list of elements is not necessarily limited to those elements alone, but may include other elements not expressly listed or inherent in that composition, process, or method. The transitional expression "consisting of" excludes any unspecified element, step, or ingredient. If it appears in a claim, such expression would preclude the inclusion of materials other than those listed, except for impurities commonly associated with them. When the expression "consisting of" appears in a clause within the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements of the claim as a whole are not excluded. The transitional expression "essentially consists of" is used to define a process or method that includes materials, steps, features, components, or elements, in addition to those explicitly disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel feature(s) of the disclosure. The expression "essentially consists of" occupies a position between "comprising" and "consisting of." When applicants have defined the disclosure or a portion thereof with an open term such as comprising, it is readily understood that (unless otherwise indicated) the description should also be interpreted as describing such a disclosure using the expressions consisting essentially of or consisting of. Furthermore, unless expressly stated otherwise, "or" refers to an inclusive "or" and not an exclusive "or". For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present). Furthermore, the indefinite articles *un*, *uno*, and *una* preceding an element or component of the disclosure are not intended to be restrictive with regard to the number of instances (i.e., occurrences) of the element or component. Therefore, *uno* and *una* should be interpreted to include one or at least one, and the singular form of the element or component should also include the plural, unless it is clear that the number is intended to be singular. The term C1-C4 alkyl includes linear or branched alkyl groups having one to four carbon atoms, for example, methyl, ethyl, ΛZ-propyl, β-propyl, or the various 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 group linked through a carbonyl group. The term C1-C4 alkoxycarbonyl refers to a C1-C4 alkoxy group linked through a carbonyl group. The term C1-C4 alkylcarboxymethyl refers to a (C1-C4)C=O alkyl group linked through a -CH2- group. Typically, compounds of formula 1a and formula 1b can exist independently in different solid forms. Therefore, a compound of formula 1a and formula 1b includes all crystalline and non-crystalline forms of the compounds it represents. Non-crystalline forms include solid embodiments, such as waxes and gums, as well as liquid embodiments, such as solutions and melts. Crystalline forms include embodiments that represent essentially a single crystal type and embodiments that represent a mixture of polymorphs (i.e., different crystal types). The term polymorph refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and / or conformations of the molecules in the crystal lattice.Although polymorphs may have the same chemical composition, they can also differ due to the presence or absence of cocrystallized water or other molecules, which may be weakly or strongly bound to the lattice. Polymorphs can differ in chemical, physical, and biological properties such as crystal form, density, hardness, color, chemical stability, melting point, hygroscopicity, suspension capacity, dissolution rate, and bioavailability. A person skilled in the art will appreciate that a polymorph of a compound of formula 1a and formula 1b may exhibit beneficial effects (e.g., suitability for the preparation of useful formulations, improved biological performance) compared to another polymorph or a mixture of polymorphs of the same compound of formula 1a and formula 1b. The preparation and isolation of a particular polymorph of a compound of formula 1a and formula 1b can be achieved using 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. Example procedures for preparing M-oxides include the oxidation of heterocycles and tertiary amines with peroxyacids such as peracetic acid and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as i-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the preparation of M-oxides have been extensively described and reviewed in the literature; see, for example: T.L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp. 748–750, S.V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp. 18–20, A.J. Boulton and A. McKillop, Eds., Pergamon Press. MR Grimmett and BRT Keene in Advances in Heterocyclic Chemistry, volume 43, pp. 149-161, AR Katritzki, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, volume 9, pp. 285-291, AR Katritzky and AJ Boulton, Eds., Academic Press; and G.W.H.Cheeseman and ESG Werstiuk in Advances in Heterocyclic Chemistry, Volume 22, pp. 390-392, AR Katritzky and AJ Boulton, Eds., Academic Press. That said, a person skilled in the art will appreciate that not all nitrogen-containing heterocycles can form β-oxides, since nitrogen requires a lone pair available for oxidation to the oxide; a person skilled in the art will recognize the nitrogen-containing heterocycles that can form α-oxides. The compounds of the present invention may exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers, and geometric isomers. Stereoisomers are isomers of identical constitution but differing in the spatial arrangement of their atoms and include enantiomers, diastereomers, cis-trans isomers (also known as geometric isomers), and atropisomers. Atropisomers result from restricted rotation around single bonds where the rotational barrier is sufficiently high to allow the isolation of the isomeric species. A person skilled in the art will appreciate that an atropisomer may be more active and / or may exhibit beneficial effects when enriched (i.e., in excess) with respect to the other atropisomer(s) or when separated from the other atropisomer(s).The compounds of the invention may be present as a mixture of atropisomers, an individual atropisomer, or as an optically active form; optionally, one atropisomer is in excess of its corresponding enantiomer. In particular, the compounds of this invention comprise one atropisomer that is more active than the other atropisomer. Some non-limiting realizations of the present disclosure (whereby a compound of formula 1a and formula 1b also includes / V-oxides or salts thereof): Embodiment A1. An optically active compound comprising (or consisting of) an atropisomer of a compound of formula 1a or an A / -oxide or salt thereof, which is present in excess of its corresponding enantiomer of formula 1b or an A / -oxide or salt thereof, ίΠ / ZZΖηZ / E / YΙΛΙ Realization A2. The compound of realization A1 where R1 is CH3. Realization A3. The compound of realization A1 wherein R1 is a halogen. Realization A4. The compound of realization A3 wherein R1 is Cl, F or Br. Realization A5. The compound of realization A4 where R1 is Cl or CH3. Realization A6. The compound of realization A5 where R1 is Cl. Realization A7. The compound of any one of embodiments A1 to A6 wherein R2 is CH3, CH2CH3, halogen or difluoromethoxy. Realization A8. The compound of realization A7 wherein R2 is CH3, CH2CH3, Cl or difluoromethoxy. Realization A9. The compound of realization A8 wherein R2 is CH3 or difluoromethoxy. Realization A10. The compound of realization A9 where R2 is CH3. Realization A11. The compound of any one of realizations A1 to A10 wherein R3 is H 0CH3. Realization A12. The compound of realization A11 wherein R3 is H. Realization A13. The compound of realization A12 where R3 is CH3. Realization A14. The compound of any of realizations A1 to A13 where R4 is H, CH3 or Cl. Realization A15. The compound of realization A14 where R4 is Cl. Realization A16. The compound of realization A14 where R4 is CH3. Realization A17. The compound of realization A14 wherein R4 is H. Realization A18. The compound of any one of embodiments A1 to A17 wherein R5 is H, C3 alkylcarbonyl, C3 alkoxycarbonyl or C3 alkylcarboxymethyl. Realization A19. The compound of realization A18 wherein R5 is H or C3 alkylcarbonyl. Realization A20. The compound of realization A18 wherein R5 is H or (C-OjCHLGHs. Realization A21. The compound of realization A20 wherein R5 is H. AA1 Realization. An optically active compound consisting of an atropisomer of a compound of formula 1a or an Ai-oxide or salt thereof, which is present in excess of its corresponding enantiomer of formula 1a or an Ai-oxide or salt thereof. ίΠ / ZZΖηZ / E / YΙΛΙ R4 Ib Realization AA2. The compound of realization AA1 where R1 is CH3. Realization AA3. The compound of realization AA1 where R1 is a halogen. Realization AA4. The compound of realization AA3 where R1 is Cl, F or Br. AA5 realization. The composition of the AA4 realization where R1 is Cl or F. Realization AA6. The compound of realization A5 where R1 is Cl. Realization AA7. The compound of any one of realizations AA1 to AA6 wherein R2 is CH3, CH2CH3, halogen or difluoromethoxy. Realization AA8. The compound of realization AA7 wherein R2 is CH3, CH2CH3, Cl or difluoromethoxy. Realization AA9. The compound of realization AA8 wherein R2 is CH3 or difluoromethoxy. Realization AA10. The compound of realization AA9 where R2 is CH3. Realization AA11. The compound of any one of the realizations AA1 AA10 where R3 is H or CH3. AA12 realization. The compound of the AA11 realization where R3 is H. Realization AA13. The compound of realization AA12 where R3 is CH3. Realization AA14. The compound of any of the realizations AA1 to AA13 where R4 is H, CH3 or OI. Realization AA15. The compound of realization AA14 where R4 is Cl. Realization AA16. The compound of realization AA14 where R4 is CH3. AA17 realization. The compound of AA14 realization where R4 is H. Realization AA18. The compound of any one of realizations AA1 to AA17 wherein R5 is H, C3 alkylcarbonyl, C3 alkoxycarbonyl or C3 alkylcarboxymethyl. Realization AA19. The compound of realization AA18 wherein R5 is H or C3 alkylcarbonyl. AA20 realization. The compound of the AA18 realization where R5 is H or -(C-OjCHaCHa. AA21 realization. The compound of the AA20 realization where R5 is H. Embodiment B1. A process as described in the summary of the invention for preparing a compound of formula 1a or 1b. ίΠ / ZZΖηZ / E / YΙΛΙ the Ib Realization B2. The process of realization B1 where R1 is CH3. Realization B3. The process of realization B1 where R1 is halogen. Realization B4. The process of realization B3 where R1 is Cl, F or Br. Realization B5. The process of realization B4 where R1 is Cl or F. Realization B6. The process of realization B5 where R1 is Cl. Realization B7. The process of any one of realizations B1 to B6 wherein R2 is CH3, CH2CH3, halogen or difluoromethoxy. Realization B8. The process of realization B7 wherein R2 is CH3, CH2CH3, Cl or difluoromethoxy. Realization B9. The process of realization B8 wherein R2 is CH3 or difluoromethoxy. Realization B10. The process of realization B9, where R2 is CH3. Realization B11. The process of any one of realizations B1 to B10 where R3 is H or CH3. Realization B12. The process of realization B11 where R3 is H. Realization B13. The process of realization B11, where R3 is CH3. Realization B14. The process of any of realizations B1 to B13 where R4 is H, CH3 or Cl. Realization B15. The process of realization B14 where R4 is Cl. Realization B16. The process of realization B14, where R4 is CH3. Realization B17. The process of realization B14 where R4 is H. Realization B18. The process of any one of embodiments B1 to B17 wherein R5 is H, C3 alkylcarbonyl, C3 alkoxycarbonyl or C3 alkylcarboxymethyl. Realization B19. The process of realization B18 wherein R5 is H or C3 alkylcarbonyl. Realization B20. The process of realization B18 where R5 is H or -(C=O)CH2CH3. Realization B21. The process of realization B20 where R5 is H. Realization B22. The process of realization B1 where chiral support chromatography is supercritical fluid chromatography (SFC). Realization B23. The process of realization B1 where the mobile phase is carbon dioxide. Realization C1. The compound of any one of realizations A1 to AA21 wherein the compound is more herbicidally active than its corresponding atropisomer. Realization C2. The compound of realization C1 wherein the compound is more active on grasses than its corresponding atropisomer. The prior embodiments or any embodiment of this document may be combined in any manner. This invention also relates to a method for controlling unwanted vegetation comprising applying herbicide-effective quantities of a compound of formula 1a or formula 1b (e.g., in the form of a composition described herein) to the vegetation site. Embodiments using the compounds of the previously described embodiments are considered embodiments relating to methods of use. The compounds of the invention are particularly useful for the selective control of weeds in crops such as wheat, barley, corn, soybeans, sunflowers, cotton, rapeseed, and rice, and in specialty crops such as sugarcane, citrus, fruits, and nuts. Also noteworthy as embodiments are the herbicidal compositions of the present invention comprising the compounds of the embodiments described above. This invention also includes a herbicidal mixture comprising (a) a compound selected from formula 1a and formula 1b, A / -oxides and salts thereof, and (b) at least one additional active ingredient selected from (b1) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimetics, (b5) 5-enolpyruvylshikimate-3-phosphate (EPSP) synthase inhibitors, (b6) photosystem I electron diverters, (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 organic arsenical mitotic disruptors, asulam, bromobutide, cinmethylin, cumiluron, dazomet, difenzoquat, dimron, etobenzanid, flurenol, phosamine, phosamine-ammonium, hydantocidin, metam, methyldimron, oleic acid, oxaziclomefone, perlargonic acid and pyributicarb, (b16) herbicide protectants and salts of compounds from (b1) to (b16). Photosystem II (b1) inhibitors are chemical compounds that bind to the D-1 protein in the Qb-binding niche and thus block electron transport from Qa to Qb across the thylakoid membranes of the chloroplast. The electrons whose passage through photosystem II is blocked are transferred through a series of reactions to form toxic compounds that disrupt cell membranes, causing chloroplast swelling, membrane leakage, and ultimately, cell death. The Qb binding niche has three different binding sites: binding site A binds to triazines such as atrazine, triazinones such as hexazinone, and uracils such as bromadlo, binding site B binds to phenylureas such as diuron, and binding site C binds to benzothiadiazoles such as bentazone, nitriles such as bromoxynil, and phenylpyridazines such as pyridate.Examples of photosystem II inhibitors include ametryn, amicarbazone, atrazine, bentazone, bromadlo, bromophenoxim, bromoxynil, chlorbromuron, chloridazone, chlorotoluron, chloroxuron, cumiluron, cyanazine, daimuron, desmedifam, desmetrin, dimefuron, dimethamethrin, diuron, etidimuron, fenuron, fluometuron, hexazinone, ioxinil, isoproturon, isouron, leñadlo, linuron, metamitron, metabenzothiazure, methobromuron, methoxuron, metribuzin, monolinuron, neburon, pentanochlor, fenmedifam, promethon, prometrine, propanyl, propazine, pyridafol, pyridate, siduron, simazine, symmetrine, tebutyuron, and terbacil. terbumeton, terbuthylazine, terbutrine and trietazine. AHAS (b2) inhibitors are chemical compounds that inhibit acetohydroxy acid synthase (AHAS), also known as acetolactate synthase (ALS), and thus kill plants by inhibiting the production of branched-chain aliphatic amino acids, such as valine, leucine, and isoleucine, which are necessary for protein synthesis and cell growth. Examples of AHAS inhibitors include amidosulfuron, azimsulfuron, bensulfuron-methyl, bispiribac-sodium, chloransulam-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, diclosulam, etametsulfuron-methyl, ethoxysulfuron, flazasulfuron, florasulam, flucarbazone-sodium, flumetsulam, flupirsulfuron-methyl, flupirsulfuron-sodium, foramsulfuron, halosulfuron-methyl, imazametabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron-methyl (including the sodium salt), yofensulfuron (2-iodo-A / -[[(4-methoxy-6-methyl-1,3,5-triazin-2-ylaminocarbonylbenzenesulfonamide), mesosulfuron-methyl, metazosulfuron (3-chloro-4-(5,6-dihydro-5-methyl-1,4,2-dioxazin-3-1)-A / -[(4,6-dimethoxy-2-pyrimidinylamino]carbonyl]-1-methyl-1 / 7-pyrazol-5-sulfonamide), metosulam, metsulfuron-methyl, nicosulfuron, oxasulfuron, penoxsulam, primisulfuron-methyl, propoxycarbazone-sodium, propirisulfuron (2-chloro-A / -[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-6-propylimidazo[1,2-b]pyridazine-3-sulfonamide), prosulfuron, pyrazosulfuron-ethyl, pyribenzoxime, pyriftalid, pyriminobac-methyl, pyritiobac-sodium, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone, tifensulfuron-methyl, triafamone (A / -[2-[(4,6-dimethoxy-1,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-1,1-difluoro- / V-methylmethanesulfonamide), triasuFuron, tribenuron-methyl, trifloxysulfuron (including the sodium salt), triflusulfuron-methyl and tritosulfur. ACCase (β3) inhibitors are chemical compounds that inhibit the enzyme acetyl-CoA carboxylase, which is responsible for catalyzing an early step in the synthesis of lipids and fatty acids in plants. Lipids are essential components of cell membranes, and without them, new cells cannot be produced. Inhibition of acetyl-CoA carboxylase and the resulting lack of lipid production leads to a loss of integrity in cell membranes, especially in actively growing regions such as meristems. Over time, the growth of shoots and rhizomes ceases, and the shoot meristems and rhizome buds begin to die.Examples of ACCase inhibitors include aloxidim, butroxidim, clethodim, clodinafop, cycloxidim, cyhalofop, diclofop, fenoxaprop, fluazifop, haloxyfop, pinoxadene, profoxidim, propaquizafop, quizalofop, sethoxidim, tepraloxidim, and tralcoxidim, 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. Auxin is a plant hormone that regulates growth in many plant tissues. Auxin (b4) mimetics are chemical compounds that mimic the plant growth hormone auxin, thereby causing uncontrolled and disorganized growth that leads to plant death in susceptible species.Examples of auxin mimetics include aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropyl-4-pyrimidinocarboxylic acid) and its methyl and ethyl esters and its sodium and potassium salts, aminopyralid, benazoline ethyl, chlorambene, claciphos, clomeprop, clopyralid, dicamba, 2,4-D, 2,4-DB, dichlorprop, fluroxypyr, halauxifen (4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinocarboxylic acid), halauxifen-methyl (methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinocarboxylate), 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. EPSP synthase (b5) inhibitors are chemical compounds that inhibit the enzyme 5-enolpyruvylshikimate-3-phosphate synthase, which is involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan, and phenylalanine. EPSP-inhibiting herbicides are readily absorbed through the plant foliage and translocated via the phloem to the growing points. Glyphosate is a relatively non-selective post-emergence herbicide that belongs to this group. Glyphosate includes esters and salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium), and trimesium (alternatively referred to as sulfosate). Photosystem I (b6) electron diverters are chemical compounds that accept electrons from photosystem I and, after several cycles, generate hydroxyl radicals. These radicals are extremely reactive and readily destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This disrupts the integrity of cell membranes, leading to leakage from cells and organelles, which causes rapid wilting and drying of leaves and, eventually, plant death. Examples of this second type of photosynthesis inhibitors include diquat and paraquat. PPO(b7) inhibitors are chemical compounds that inhibit the protoporphyrinogen oxidase enzyme and rapidly result in the formation of highly reactive compounds in plants that rupture cell membranes and cause leakage of cell fluids.Examples of PPO inhibitors include acifluorphen-sodium, azaphenidine, benzophendizone, bifenox, butafenac, carfentrazone, carfentrazone-ethyl, clomethoxyphene, cinidone-ethyl, fluazolate, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazine, fluoroglycophen-ethyl, flutiacet-methyl, fomesafene, halosaphen, lactophene, oxadiargil, oxadiazone, oxyfluorphen, pentoxazone, profluazole, pyraclonil, pyrafluphen-ethyl, saflufenacil, sulfentrazone, thidiazimine, and trifludimoxazine. (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-triazino-2,4( 1 H,3H)-dione) and thiaphenacil (Methyl A / -[2-[[2-chloro-5-[3,6dihydro-3-methyl-2,6-dioxo-4-(trifliioromethyl)-1(2 / - / )-pyrimidinyl]-4-fluorophenyl]thio]-1-oxopropyl]-p-alaninate). GS (b8) inhibitors are chemical compounds that inhibit the activity of the enzyme glutamine synthetase, which plants use to convert ammonia into glutamine. Consequently, ammonia accumulates and glutamine levels decrease. Damage to plants likely results from the combined effects of ammonia toxicity and the deficiency 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-(hydroxymethylphosphosphinyl)butanoic acid), and bilafos. VLCFA (b9) elongase inhibitors are herbicides with a wide variety of chemical structures that inhibit elongase. Elongase is one of the enzymes located in or near chloroplasts that participates in VLCFA biosynthesis. In plants, very long-chain fatty acids are the main building blocks of hydrophobic polymers that prevent desiccation on the leaf surface and provide stability to pollen grains.Such herbicides include acetochlor, alachlor, anilophos, butachlor, cafenstrol, dimetachlor, dimethenamid, difenamid, phenoxasulfone (3-[[(2,5-dichloro-4-ethoxyphenyl)methyl]sulfonyl]-4,5-dihydro-5,5-dimethylisoxazole), fentrazamide, flufenacet, indanofane, mefenacet, metazachlor, metolachlor, naproanilide, napropamide, napropamide-M ((2R)- / V, / Vdiethyl-2-(1-naphthalenyloxy)propanamide), petoxamid, piperophos, pretylachlor, propachlor, propisochlor, pyroxasulfone and tenylchlor, including resolved forms such as S-metolachlor and chloroacetamides and oxyacetamides. Auxin transport inhibitors (b10) are chemical substances that inhibit the transport of auxin in plants, such as by binding to an auxin transporter protein. Examples of auxin transport inhibitors include diflufenzopyr and naptala (also known as A / -(1-naphthyl)phthalamic acid and 2-[(1-naphthalenylamino)carbonyl]benzoic acid). PDS(b11) inhibitors are chemical compounds that inhibit the carotenoid biosynthesis pathway at the phytoene desaturase step. Examples of PDS inhibitors include sbeflubutamide, beflubutamide, diflufenican, flundone, flurochloridone, flurtamone, norflurzon, and picolinafene. HPPD (b12) inhibitors are chemical substances that inhibit the biosynthesis of 4-hydroxyphenylpyruvate hydroxyl-1-hydroxygenase. Examples of HPPD inhibitors include benzobicyclon, benzophenap, bicyclopyrone (4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]bicyclo[3.2.1]oct-3-en-2-one), phenquinetrione (2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl]-1,3-cyclohexanedione), isoxachlortol, isoxaflutol, mesotrione, and pyrasulfothrol. Ln / Zznz / E / YIAI pyrazolinate, pyrazoxifeno, sulcotrione, tefuryltrione, tembotrione, tolpyralate (methylcarbonate de 1 -[[1 -ethyl-4[3-(2-methoxyethoxy)-2-met¡l-4-(methylsulfonyl)benzo¡l]-1 H-pyrazol-5-yl]oxy]ethyl), topramezona, 5-chloro-3-[(2hidroxy-6-oxo-1 -ciclohexen-1 -yl)carbo nil] -1 -(4-methoxiphenyl)-2(1 / - / )-quinoxalinone, 4-(2,6-diethyl-4-methylen i I) -5hidroxi-2,6-dimethyl-3(2 / 7)-pir¡daz¡nona, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2methyl-1,2,4-triazino-3,5(2 / 7,4 / - / )-dione, 5-[(2-hydroxy-6-oxo-1 -cyclohexen-1 -yl)carbonyl]-2-(3-methoxyphenyl)-3-(3methoxypropyl)-4(3 / - / )-pyrimidinone, 2-methyl-A / -(4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4(tr¡fluorometil)benzamida and 2-methyl-3-(metilsulfon¡l)-A / -(1 -metil-1 / 7-tetrazol-5-yl)-4-(trifluoromethyl)benzam¡da. HST (b13) inhibitors alter the plant's ability to convert homogentisate into 2-methyl-6-solanyl-1,4-benzoquinone, thereby altering carotenoid biosynthesis. Examples of HST inhibitors include cyclopyrimorate (6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinyl 4-morpholinocarboxylate), haloxidine, pyrichlor, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridin2(1 / - / )-one, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-β]pyrazin-6(5H)-one, and 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2 / - / )-pyridazinone. HST inhibitors also include compounds of formulas A and B. b / 77 ίη / ΖΖΠΖ / Ε / ΥΙΛΙ AB where Rd1 is H, OI or CF3; Rd2is H, Cl or Br; Rd3es H or Cl; Rd4es H, Cl or CF3; Rd5es CH3, CH2CH3 or CH2CHF2 and Rd6es OH or -OC(=O)- / -Pr; and Re1 is H, F, Cl, CH3 or CH2CH3; Re2es H or CF3; Re3is H, CH3 or CH2CH3; Re4es H, F or Br; Re5es Cl, CH3, CF3, OCF3 or CH2CH3; Re6es H, CH3, CH2CHF2o C=CH; Re7es OH, -OC(=O)Et, -OC(=O)- / -Pr u -OC(=O)-í-Bu; and Ae8es N or CH. Cellulose biosynthesis inhibitors (b14) inhibit cellulose biosynthesis in certain plants. They are most effective when applied pre-emergence or early post-emergence to young or rapidly growing plants. Examples of cellulose biosynthesis inhibitors include chlorthiamide, diclobenyl, flupoxam, indaziflam (LA[(1 F?,2S)-2,3-dihydro-2,6-dimethyl-1 H-inden-1 -yl]-6-(1 fluoroethyl)-1,3,5-triazino-2,4-diamine), isoxabene, and triaziflam. Other herbicides (b15) include herbicides that act through various different modes of action, such as mitotic disruptors (e.g., flamprop-M-methyl and flamprop-M-isopropyl), organic arsenicals (e.g., DSMA and MSMA), 7,8-dihydropteroate synthase inhibitors, chloroplast isoprenoid synthesis inhibitors, and cell wall biosynthesis inhibitors. Other herbicides include herbicides with unknown modes of action, those that do not fall into a specific category listed in (b1) to (b14), or those that act through a combination of the modes of action listed above. Examples of other herbicides include aclonifen, asulam, amitrole, bromobutide, cinmethylin, clomazone, cumiluron, daimuron, dimesulfazet (CAS no. 1215111-77-5), difenzoquat, epirifenacil (n.2CAS 353292-31-6), etobenzanid, fluometurón, flurenol, fosamine, fosamine-amonium, dazomet, dimrón, ipfencarbazona (1 -(2,4-d iclorof en i)-A / -(2,4-dif lu orofen i I) -1,5dihydro-A / -(1-methylethyl)-5-oxo-4 / - / -1,2,4-triazol-4-carboxamida), metam, methyldimron, oleic acid, oxaziclomefona, pelargonic acid, piributicarb, tetflupirolimet y 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole. The other herbicides (b15) also include a formula compound (b15A). ίΠ / ΖΖηΖ / Ε / ΥΙΛΙ THE R12(b!5A) where R12es H, alquilo C1-C6, haloalquilo C1-C6 or cycloalquilo C4-C6; R13es H, Ci-Ce alkyl or Ci-Ce alkoxy; Q1 is an optionally substituted ring system selected from the group consisting of phenyl, tingo, pyridinyl, benzodioxolyl, naphthyl, naphthalenyl, benzofuranyl, furanyl, benzothiophenyl and pyrazolyl, wherein when substituted, said ring system is substituted with 1 to 3 R14; Q2 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 substituted with 1 to 3 R15; each R14 is independently halogen, Ci-Ce alkyl, Ci-Ce haloalkyl, Ci-Ce alkoxy, i-Ce haloalkoxy, Cs-Cs cycloalkyl, cyano, Ci-Ce alkylthio, Ci-Ce alkylsulfinyl, Ci-Ce alkylsulfonyl, SFs, NHR17 or phenyl optionally substituted with 1 to 3 R16 or pyrazolyl optionally substituted with 1 to 3 R16; each R15 is independently halogen, alkyl Ci-Ce, haloalkyl Ci-Ce, alkoxy Ci-Ce, haloalkoxy Ci-Ce, cyano, nitro, alkylthio Oí-Ce, alkylsulfinyl Ci-Cs, alkylsulfonyl Ci-Ce; each R16 is independently halogen, Ci-Ce alkyl or Ci-Ce haloalkyl; R17es alkoxycarbonllo C1-C4. In an embodiment where the other herbicides (b15) also include a compound of formula (b15A), R12' is preferably H or C4-C4 alkyl; more preferably R12' is H or methyl. Preferably R13 is H. Preferably Q1 is a phenyl ring or a pyridinyl ring, each ring being substituted with 1 to 3 R14s; more preferably Q1 is a phenyl ring substituted with 1 to 2 R14s. Preferably Q2 is a phenyl ring substituted with 1 to 3 R15s; more preferably Q2 is a phenyl ring substituted with 1 to 2 R15s. Preferably each R14 is independently halogen, C4-C4 alkyl, or haloalkyl. C1-C3, C1-C3 alkoxy, or C1-C3 haloalkoxy; more preferably, each R14 is independently chlorinated, fluoroinfused, bromoinfused, C1-C2 haloalkyl, C1-C2 haloalkoxy, or C1-C2 alkoxy. Preferably, each R15 is independently halogenated, C1-C4 alkyl, or C1-C3 haloalkoxy; more preferably, each R15 is independently chlorinated, fluoroinfused, bromoinfused, C1-C2 haloalkyl, C1-C2 haloalkoxy, or C1-C2 alkoxy. Other specifically preferred herbicides (b15) include any one of the following from (b15A-1) to (b15A-16): The other herbicides (b15) also include a compound with the formula (b15B) (bl5B) where R18 is H, Ci-Ce alkyl, Ci-Ce haloalkyl or C4-C8 cycloalkyl; each R19 is independently a halogen, haloalkyl Ci-Ce or haloalkoxy Oí-Ce; p is an integer of 0, 1, 2 or 3; each R20 is independently a halogen, haloalkyl Ci-Cs or haloalkoxy Oí-Ce and q is an integer of 0, 1, 2 or 3. In an embodiment where the other herbicides (b15) also include a compound of formula (b15B), it is preferred that R18 be H, methyl, ethyl, or propyl; more preferably R18 is H or methyl; most preferably R18 is H. Preferably each R19 is independently chloro, fluoro, C1-C3 haloalkyl, or C1-C3 haloalkoxy; more preferably each R19 is independently chloro, fluoro, C1 fluoroalkyl (i.e., fluoromethyl, difluoromethyl, or trifluoromethyl), or C1 fluoroalkoxy (i.e., trifluoromethoxy, difluoromethoxy, or fluoromethoxy). Preferably each R20 is independently chloro, fluoro, C1 haloalkyl, or C1 haloalkoxy. More preferably, each R20 is independently chlorinated, fluorofluoroalkyl (i.e., fluoromethyl, difluoromethyl, or trifluoromethyl), or C1 fluoroalkoxy (i.e., trifluoromethoxy, difluoromethoxy, or fluoromethoxy). Other (b15) herbicides specifically preferred include any one of the following from (b15B-1) to (b15B-19): (b15B-5) (b15B-6) ίΠ / ΖΖηΖ / Ε / ΥΙΛΙ (b15B-7) (b15B-8) (b15B-9) (b15B-10) (Ó15B-11) (b15B-12) 77. ίη / ZZΖΠZ / E / YΙΛΙ Another embodiment where the other herbicides (b15) also include a compound of formula (b15C), 77. iP / ZZΖ / E / YILI (bl5C) wherein R1 is Cl, Br or CN; and R2 is C(=O)CH2CH2CF3, CH2CH2CH2CH2CF3 or 3-CHF2-isoxazol-5yl. Specific examples include a compound of formula (b15C) selected from (b15C1) 5-chloro2-[3-chloro-2-[3-(difluoromethyl)-5-isoxazolyl]phenoxy]-pyrimidinine and (b15C2) 1 [2-chloro-6-[(5-chloro-2pyrimidinyl)oxy]phenyl]-4,4,4-trifluoro-1-butanone. Herbicide protectants (b16) are substances added to a herbicide formulation to eliminate or reduce the herbicide's phytotoxic effects on certain crops. These compounds protect crops from herbicide damage, but they do not usually prevent the herbicide from controlling unwanted vegetation. Examples of herbicide protectants include, but are not limited to, benoxacor, cloquintocet-mexyl, cumiluron, ciometrinil, cyprosulfamide, daimuron, dichlormid, dicyclonon, dietolate, dimepiperate, fenchlorazol-ethyl, fenchlorim, flurazol, fluxophenim, furylazol, isoxadifeno-ethyl, mefenpyr-diethyl, mefenate, methoxyphenone, naphthalic anhydride, oxabetrinyl, N(aminocarbonyl)-2-methylbenzenesulfonamide and V-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene, 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), 4-(dichloroacetyl)-1-oxa-4azospiro[4.5]decane (MON 4660), 2,2-dichloro-1 -(2,2,5-trimeth¡l-3-oxazolide¡n¡l)ethanone and 2-methox¡-A / -[[4[[(methylam¡no)carbonyl]am¡no]phen¡l]benzenesulda. For improved control of unwanted vegetation (e.g., a lower usage rate such as from superior additive effects, a broader spectrum of weeds controlled, or enhanced crop safety) or to prevent the development of resistant weeds, mixtures of a compound of the present invention with a herbicide selected from the group consisting of atrazine, azimsulfuron, beflubutamide, S-beflubutamid, benzisothiazolinone, carfentrazone-ethyl, chlorimuron-ethyl, chlorsulfuron-methyl, clomazone, clopyralid potassium, chloransulam-methyl, 2-[(2,4-dicly-6-oxo-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5-(2-,4-)dione, flupyralfuron-methyl, and flutiacet-methyl are preferred. fomesafene, imazethapyr, lenacil, mesotrione, metribuzin, metsulfuron-methyl, petoxamid, picloram, pyroxasulfone, quinclorac, rimsulfuron, S-metolachlor, sulfentrazone, tifensulfuron-methyl, triflusulfuron-methyl and tribenuron-methyl. The substituted enantiomers of formula 1a (phi) and formula 1b (s) can be isolated from racemates of formula 1 by chiral support chromatography (see Scheme 1). Racemates of formula 1 can be prepared by the methods taught in WO 2015168010. Absolute stereochemistry can be assigned to a drawn heterobiaryl structure by established nomenclature rules. A person skilled in the art will realize that the two enantiomers comprising the racemate can also be called atropisomers because of the restricted rotation of the naphthalene and pyridazinone rings of this heterobiaryl ring system. The restricted rotation locks the two rings into a fixed stereo orientation that permits asymmetry.With the substitution of naphthalene in the ortho position relative to the bond connected to pyridazinone, both atropisomers are stable to racemization by ring rotation at temperatures generally below 100 °C. 77. ίΠ / ZZΖηZ / E / YΙΛΙ Scheme 1 Racemate (R and S) Chiral chromatography 1a, 1b R enantiomer+S enantiomer EXAMPLE OF SEPARATION 1 A 1.8 g sample of racemate 2 was loaded onto a chiral support for supercritical fluid chromatography (SFC) using carbon dioxide as the mobile phase of the supercritical fluid or with an optional co-solvent such as methanol or actonitrile. The principles used are similar to those of standard achiral high-performance liquid chromatography (HPLC). Two fractions were obtained. The first to elute was the labeled enantiomer 2a (580 mg) and the second was the 2b enantiomer (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%. Scheme 2 Racemate (RyS Enantiomers) Chiral chromatography Enantiomer A + Enantiomer B 2a 2b Figure 1 (chiral analytical SFC HPLC chromatogram of the 2a (2A) enantiomer) shows the chiral chromatography for 2a having a retention time of 2.03 minutes, which further validates the enantiomeric integrity. Figure 2 (chiral analytical SFC HPLC chromatogram of the 2b enantiomer (2B)) shows the chiral chromatography for 2b having a retention time of 3.24 minutes, which further validates the enantiomeric integrity. Figure 1: Chiral HPLC SFC analytical chromatogram of the 2a (2A) enantiomer 2145.12000I O 1500- Enantiomer 2a •H 1000d O 500ω -80.409 0.0031167 Solvent: acetonitrile Temperature: 25 °C Enantiomer 2b 7.0305 Time elapsed (min) 77. ίΠ / ZZΖηZ / E / YΙΛΙ Figure 2: HPLC SFC chiral analytical chromatogram of enantiomer 2b (2B) 1803.6D g 1500Enantiomer 2b i ti 4' rj! C 1000- I Solvent: acetonitrile £ I Temperature: 25°C PI Oi ω। á500'! Enantiomer 2a i — . . ...... . . - v. . — — — · _ .—... . __ ... -69.159- ' , - ,, 0.0031167 2 4 6 7.0351 Elapsed time (min) ίΠ / 77Ω7 / Β / ΥΙΛΙ Without going into further detail, it is believed that a person skilled in the art, using the above description, can derive the full benefit from this disclosure. The following non-limiting examples are illustrative of the disclosure. A compound of formula 1a and formula 1b will generally be used as the active herbicidal ingredient in a composition, i.e., a formulation with at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents. In certain embodiments, the additional component may serve as a carrier. The ingredients of the composition or formulation are selected to match the physical properties of the active ingredient, the mode of application, and environmental factors such as soil type, moisture, and temperature. Useful formulations include liquid and solid compositions comprising the compound of formula 1a and formula 1b. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, fluid concentrates, and / or suspoemulsions), and the like, which may optionally be thickened to form gels. General types of aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion, oil-in-water emulsion, fluid concentrate, and suspoemulsion. General types of non-aqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate, and oil dispersion. The general types of solid compositions are powders, granules, microgranules, beads, tablets, tablets, filled films (including seed coatings), and the like, 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 treatment. The active ingredient may be (micro)encapsulated and further formed in a suspension or solid formulation; alternatively, the entire active ingredient formulation may be encapsulated (or overcoated). Encapsulation may control or delay the release of the active ingredient. An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-concentration compositions are primarily used as intermediates for further formulation. Sprayable formulations are typically spread in a suitable medium before spraying. Such liquid and solid formulations are designed to readily dilute in the spray medium, usually water, but occasionally another suitable medium such as an aromatic or paraffinic hydrocarbon or vegetable oil. Spray volumes can range from approximately one to several thousand liters per hectare, but are more commonly in the range of 1Q approximately ten to several hundred liters per hectare. Sprayable formulations can be tank-mixed with water or another suitable medium for foliar treatment via aerial or ground application, or for application to the plant's growing medium. Liquid and dry formulations can be dosed directly into drip irrigation systems or applied in the furrow during planting. 77. ίη / ZZΖΠZ / E / YΙΛΙ 15 Formulations shall normally contain effective amounts of active ingredient, diluent, and surfactant within the following approximate ranges, totaling up to 100 percent by weight. Active Ingredient Weight Percent Diluent Surfactant 20 Water-dispersible and water-soluble granules, tablets, and powders 0.001-90 0-99.999 0-15 25 Dispersions, suspensions, emulsions, and oily solutions (including emulsifiable concentrates) 1-50 40-99 0-50 Fine powders 1-25 70-99 0-5 Granules and microgranules 0.001-99 5-99.999 0-15 30 High-concentration compositions 90-99 0-10 0-2 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 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. Liquid diluents include, for example, water, A / V-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, LZ-alkylpyrrolidones (e.g., AZ-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 oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerin, glyceryl triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatic hydrocarbons, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactate esters, dibasic esters, alkyl and aryl benzoates and γ-butyrolactone,and alcohols, which can 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, cresol, and benzyl alcohol. Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically, C6-C22), such as vegetable seed and fruit oils (e.g., olive, castor, linseed, sesame, corn, peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut, and palm kernel oils), animal fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid solvents also include alkylated fatty acids (e.g., methylated, ethylated, butylated), where the fatty acids can be obtained by hydrolysis of glycerol esters from vegetable and animal sources and purified by distillation. Typical liquid solvents are described in Marsden, Solvent Guide, 2nd ed., Interscience, New York, 1950. The solid and liquid compositions in this disclosure frequently include one or more surfactants. When added to a liquid, surfactants (also known as surface-active agents) generally modify, and most often reduce, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in a surfactant molecule, surfactants can be useful as wetting agents, dispersants, emulsifiers, or antifoaming agents. Surfactants can be classified as nonionic, anionic, or cationic. Nonionic surfactants useful for the compositions herein include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from alcohols and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof; amine ethoxylates, alkanolamides, and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor, and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonylphenol ethoxylates and dodecylphenol ethoxylates (prepared from phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof);block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers in which the end blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty oils and esters; ethoxylated methyl esters; ethoxylated triestyrylphenol (which includes preparations; 77. ίη / ZZΖΠZ / E / YΙΛΙ from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylated esters such as polyethoxylated fatty acid esters with sorbitan, polyethoxylated fatty acid esters with sorbitol and polyethoxylated fatty acid esters with glycerol; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, PEG (polyethylene glycol) alkyd resins, graft or comb polymers and star polymers; polyethylene glycols (PEG); fatty acid esters with polyethylene glycol; silicone-based surfactants; and sugar derivatives such as sucrose esters, alkyl polyglucosides and alkyl polysaccharides. Useful anionic surfactants include, but are not limited to: alkylarylsulfonic acids and their salts; alkylphenol or carboxylated alcohol ethoxylates; diphenylsulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids, 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 sulfate; 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 Λ / , / V-alkyltaurates; sulfonates of benzene, eumene, toluene, xylene, and dodecyl- and tridecylbenzenes; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkylnaphthalene; sulfonates of fractionated petroleum;sulfosuccinamates; and sulfosuccinates and their derivatives such as dialkyl sulfosuccinate salts.; Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as / V-alkylpropanediamines, tripropylentriamines and dipropylentetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates 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. Also useful for the compositions described herein 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 a variety of published references, including McCutcheon's Emulsifiers and Detergents, U.S. and international annual editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A.S. Davidson and B. Milwidsky, Synthetic Detergents, seventh edition, John Wiley and Sons, New York, 1987. The compositions in this disclosure may also contain formulation aids and additives, known to those skilled in the art as formulation adjuvants (some of which may also be considered to act as solid diluents, liquid diluents, or surfactants). Such formulation adjuvants and additives may control: pH (buffers), foaming during processing (antifoams such as polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), microbial growth in container (antimicrobial agents), product freezing (antifreeze), color (colorants / pigment dispersions), wash separation (film formers or adhesives), evaporation (evaporation retarders), and other formulation attributes.Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohols, polyvinyl alcohol copolymers, and waxes. Examples of formulation auxiliaries and additives include those listed in McCutcheon's Volume 2: Functional Materials, U.S. and international annual editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03 / 024222. The compound of formula 1a and formula 1b and any other active ingredients are normally incorporated into the compositions herein by dissolving the active ingredient in a solvent or by milling it into a liquid or dry diluent. Solutions, including emulsifiable concentrates, can be prepared simply by mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is immiscible in water, an emulsifier is normally added to emulsify the solvent containing the active ingredient when diluted with water. Thick suspensions of active ingredients, with particle diameters up to 2000 pm, can be wet-milled using media mills to obtain particles with average diameters less than 3 pm. Thick aqueous suspensions can be converted into finished suspension concentrates (see, for example, US document3,060,084) or further process by spray drying to form water-dispersible granules. Dry formulations generally require dry milling processes, which produce average particle diameters in the range of 2 to 10 µm. Powders and dusts can be prepared by blending and, usually, milling (such as with a hammer mill or a fluid-powered mill). Granules and microgranules can be prepared by pulverizing the active material onto preformed granular carriers 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, pp. 8–57 et seq., and WO 91 / 13546. Microgranules can be prepared as described in US patent 4,172,714. Water-dispersible and water-soluble granules can be prepared as shown in US documents4 144 050, US 3 920 442 and DE 3 246 493. Tablets may be prepared as taught in documents US 5 180 587, US 5 232 701 and US 5 208 030. Films may be prepared as taught in documents GB 2 095 558 and US 3 299 566. For further information on formulation technique, see TS Woods, The Formulator's Toolbox-Product Forms for Modern Agriculture in Pesticide Chemistry and Bioscience, The FoodEnvironment Challenge, T. Brooks and TR Roberts, Ed., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also document US 3 235 361, from Col. 6, line 16 to Col. 7, line 19 and Examples 10-41; US document 3,309,192, from 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; US document 2,891,855, from Column 3, line 66 to Column 5, 77. ίΠ / ΖΖηΖ / Ε / ΥΙΛΙ 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, United Kingdom, 2000. In the following examples, all percentages are by weight and all formulations are prepared by conventional means. The compound number, i.e., Comp. No., refers to the compounds in Table 1. Without going into further detail, it is believed that a person skilled in the art, using the above description, can derive the full benefit from this disclosure. Therefore, the following examples are to be interpreted as merely illustrative and not as limiting the disclosure in any way. Percentages are by weight unless otherwise indicated. ίΠ / ZZΖηZ / E / YΙΛΙ Example A High Concentration Concentrate Formula 1a or Formula 1b compound: 98.5% silica aerogel, 0.5% synthetic amorphous fine silica, 1.0% Example B Wettable powder Compound of formula 1a or formula 1b 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0% Example C Granule Compound of formula 1a or formula 1b 10.0% attapulgite granules (low volatile matter, 0.71 / 0.30 mm; 90.0% sieves) USS n.s25-50) Example D extruded microgranule Compound of formula 1a or formula 1b 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium / magnesium bentonite 59.0% Example E Emulsifiable concentrate Compound of formula 1a or formula 1b 10.0% polyoxyethylene sorbitol hexoleate 20.0% Fatty acid methyl ester Ce-Cio 70.0% Example F Microemulsion Compound of formula 1a or formula 1b 5.0% 5 polyvinylpyrrolidone-vinyl acetate copolymer 30.0% alkyl polyglycoside 30.0% glyceryl monooleate 15.0% water 20.0% Example G 10 Concentrated suspension Compound of formula 1a or formula 1b 35% butylpolyoxyethylene / polypropylene block copolymer 4.0% stearic acid / polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0% 15 xanthan gum 0.1% propylene glycol 5.0% silicone-based antifoam 0.1% 1,2-benzoisothiazolin-3-one 0.1% water 53.7% 20 Example H Emulsion in water Compound of formula 1a or formula 1b 10.0% butylpolyoxyethylene / polypropylene block copolymer 4.0% 25 stearic acid / polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone-based antifoam 0.1% 30 1,2-benzoisothiazolin-3-one 0.1% petroleum-based aromatic hydrocarbon 20.0 water 58.7 % Example I Dispersion in oil 35 Compound of formula 1a or formula 1b 25% polyoxyethylene sorbitol hexaoleate 15% organically modified bentonite clay 2.5 % fatty acid methyl ester 57.5 %. 77. ίη / ZZΖΠZ / E / YΙΛΙ Examples A to I above are also disclosed, wherein Compound of formula 1a or formula 1b is replaced by Compound of formula 2 (Enantiomer 2A) or formula 2 (Enantiomer 2B), Compound of formula 3 (Enantiomer 3A) or formula 3 (Enantiomer 3B), Compound of formula 4 (Enantiomer 4A) or formula 4 (Enantiomer 4B) or Compound of formula 5 (Enantiomer 5A) or formula 5 (Enantiomer 5B) Test results indicate that certain Formula 1a or Formula 1b compounds are active pre-emergence and / or post-emergence herbicides and / or plant growth regulators. Formula 1a or Formula 1b compounds generally exhibit the greatest activity in 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 these compounds are useful for broad-spectrum pre- and / or post-emergence weed control in areas where complete control of all vegetation is desired, such as around fuel depots, industrial storage areas, parking lots, drive-in theaters, airfields, riverbanks, irrigation canals and other waterways, and around billboards and road and railway structures.Many of the compounds in this disclosure, by virtue of selective metabolism in crops versus weeds, or selective activity at the site of physiological inhibition in crops and weeds, or selective placement on or within the environment of a crop / weed mixture, are useful for the selective control of grasses and broadleaf weeds within a crop / weed mixture. A person skilled in the art will recognize that the preferred combination of these selectivity factors within a compound or group of compounds can be readily determined by performing routine biological and / or biochemical assays. Formula 1a or Formula 1b compounds may show tolerance to important agronomic crops including, but not limited to, alfalfa, barley, cotton, wheat, rapeseed, sugar beet, corn, sorghum, soybean, rice, oats, peanuts, vegetables, tomato, potato, perennial plantation crops including coffee, cocoa, oil palm, rubber, sugar cane, citrus, grapes, fruit trees, nut trees, banana, cooking banana, pineapple, hops, tea, and forests such as eucalyptus and conifers (e.g. loblolly pine) and turfgrass species (e.g. Kentucky bluegrass, St. Augustine grass, Kentucky fescue, and Bermuda grass). The compounds in this disclosure can be used in genetically transformed or cultivated crops to incorporate herbicide resistance, express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxin) and / or express other useful traits.Those knowledgeable in the technique will appreciate that not all compounds are equally effective against all weeds. Alternatively, the compounds in question are useful for modifying plant growth. Since the compounds in the disclosure have herbicidal activity both pre-emergence and post-emergence, controlling unwanted vegetation by killing or damaging it or reducing its growth, the compounds can be applied effectively using various methods that involve contacting an herbicidal quantity of a compound with the soil. 77. iΠ / ZZΖηZ / E / YΙΛΙ disclosure or a composition comprising said compound and at least one of a surfactant, a solid diluent or a liquid diluent, with the foliage or other part of the unwanted vegetation or with the environment of the unwanted vegetation, such as the soil or water in which the unwanted vegetation grows or surrounding the seed or other propagule of the unwanted vegetation. An effective herbicide rate of a Formula 1a or Formula 1b compound is determined by several factors. These factors include the selected formulation, the application method, the amount and type of vegetation present, growing conditions, and so on. In general, an effective herbicide rate of the compounds in this disclosure is approximately 0.001 to 20 kg / ha, with a preferred range of approximately 0.004 to 1 kg / ha. A person skilled in the art can readily determine the effective herbicide rate required for the desired level of weed control. In a common embodiment, a compound of formula 1a or formula 1b, typically in a formulated composition, is applied to a site comprising desired vegetation (e.g., crops) and undesired vegetation (i.e., weeds), which may both be seeds, seedlings, and / or larger plants, in contact with a growing medium (e.g., soil). At this site, a composition comprising a compound of the disclosure may be applied directly to a plant or a part thereof, particularly the undesired vegetation and / or the growing medium in contact with the plant. Plant varieties and crops of the desired vegetation in the site treated with a compound from the disclosure can be obtained through conventional propagation and plant breeding methods or through genetic engineering methods. Genetically modified plants (transgenic plants) are those in which a heterologous gene (transgene) has been stably integrated into the plant genome. A transgene defined by its particular location in the plant genome is called a transformation or transgenic event. Although disclosure compounds are most commonly used to control unwanted vegetation, contact of desired vegetation in the treated area with disclosure compounds can result in superadditive or synergistic effects with genetic traits in the desired vegetation, including traits incorporated through genetic modification. For example, resistance to phytophagous insect pests or plant diseases, tolerance to biotic / abiotic stresses, or storage stability may be greater than expected based on the genetic traits in the desired vegetation. The compounds in this disclosure may also be mixed with one or more different compounds or biologically active agents, including herbicides, herbicide protectants, fungicides, insecticides, nematicides, bactericides, acaricides, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds, or entomopathogenic bacteria, viruses, or fungi to form a multicomponent pesticide that provides an even broader spectrum of agricultural protection. Mixtures of the 77. The compounds of the disclosure, when combined with other herbicides, may broaden the spectrum of activity against additional weed species and suppress the proliferation of any resistant biotypes. Therefore, this disclosure also relates to a composition comprising a compound of formula 1a and / or formula 1b (in an amount effective as a herbicide) and at least one compound or agent with additional biological activity (in an amount effective from a biological point of view), and may further comprise at least one of a surfactant, a solid diluent, or a liquid diluent. The other compounds or agents with biological activity may be formulated in compositions comprising at least one of a surfactant and a solid or liquid diluent.For the mixtures of this disclosure, one or more different biologically active compounds or agents may be formulated together with a compound of formula 1a or formula 1b to form a premixture, or one or more different biologically active compounds or agents may be formulated separately from the compound of formula 1a or formula 1b and the formulations combined with each other prior to application (e.g., in a spray tank) or, alternatively, applied successively. General references for crop protectants (i.e., herbicides, herbicide protectants, 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, LG Copping, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2001. For embodiments in which one or more of these various mixing partners are used, the mixing partners are normally used in quantities similar to those typically used when the mixing partners are used alone. More specifically, in mixtures, the active ingredients are frequently applied at an application rate of between half and the full application rate specified in the product data sheets for use of the active ingredient alone. These quantities are listed in references such as The Pesticide Manual and The BioPesticide Manual. The weight ratio of these various mixing partners (in total) to the compound of formula 1a or formula 1b is normally between approximately 1:3000 and approximately 3000:1. Of particular note are weight ratios between approximately 1:300 and approximately 300:1 (e.g., ratios between approximately 1:30 and approximately 30:1).An expert in the field can easily determine, through simple experimentation, the biologically effective quantities of active ingredients needed for the desired spectrum of biological activity. It will be evident that the inclusion of these additional components can broaden the spectrum of weeds controlled beyond that controlled by the Formula 1a or Formula 1b compound alone. It is worth noting a composition comprising a compound of the invention (in an amount effective as a herbicide), at least one additional active ingredient selected from the group consisting of other herbicides and herbicide protectants (in an effective amount), and at least one component selected from the group consisting of surfactants, solid diluents, and liquid diluents. Table A1 lists specific combinations of a component (a) with a component (b) illustrative of the mixtures, compositions, and methods of the present invention. The compound number (N.sde) of component A (i.e., N.sde comp. means Compound Number) in the Component (a) column is identified in the index table. The second column of Table A1 lists the compound of the specific component (b) (e.g., 2,4-D in the first line). The third, fourth, and fifth columns of Table A1 list weight ratio ranges for the rates at which the compound of component (a) is normally applied to a field-grown crop with respect to component (b) (i.e., (a):(b)). Therefore, for example, the first line of Table A1 specifically discloses that the combination of component (a) (i.e., compound n.sA in Index Table A) with 2,4-D is normally applied in a weight ratio of between 1:192 - 6:1.The remaining lines of Table A1 should be interpreted similarly. 77. ίΠ / ΖΖηΖ / Ε / ΥΙΛΙ 10 TABLE A1 Typical Most typical Most typical Component (a) Ratio in Ratio in Ratio in (Ns of compound) Component (b) weight weight weight weight 2 (Enantiomer A) 2,4-D 1:192-6:1 1:64-2:1 1:24 - 1:3 15 2 (Enantiomer A) Acetochlor 1:768-2:1 1:256- 1:2 1:96-1:11 2 (Enantiomer A) Acyfluorphen 1:96-12:1 1:32-4:1 1:12-1:2 2 (Enantiomer A) Acloniphene 1:857-2:1 1:285 - 1:3 1:107-1:12 2 (Enantiomer A) Alachlor 1:768-2:1 1:256-1:2 1:96-1:11 2 (Enantiomer A) Ametryn 1:384-3:1 1:128-1:1 1:48 - 1:6 20 2 (Enantiomer A) Amicarbazone 1:192-6:1 1:64-2:1 1:24 - 1:3 2 (Enantiomer A) Amidosulfuron 1:6-168:1 1:2-56:1 1:1-11:1 2 (Enantiomer A) Aminocyclopyrachlor 1:48-24:1 1:16-8:1 1:6-2:1 2 (Enantiomer A) Aminopyralid 1:20-56:1 1:6-19:1 1:2-4:1 2 (Enantiomer A) Amitrol 1:768-2:1 1:256- 1:2 1:96-1:11 25 2 (Enantiomer A) Anilophos 1:96-12:1 1:32-4:1 1:12-1:2 2 (Enantiomer A) Asulam 1:960-2:1 1:320 - 1:3 1:120-1:14 2 (Enantiomer A) Atrazine 1:192-6:1 1:64-2:1 1:24 - 1:3 2 (Enantiomer A)Azimsulfuron 1:6-168:1 1:2-56:1 1:1-11:1 2 (Enantiomer A) Beflubutamid 1:342-4:1 1:114-2:1 1:42 - 1:5 30 2 (Enantiomer A) S-Beflubutamide 1:171 -4:0.5 1:57-2:0.5 1:21 - 1:2.5 2 (Enantiomer A) Benfuresate 1:617-2:1 1:205- 1:2 1:77 - 1:9 2 (Enantiomer A) Bensulfuron-methyl 1:25-45:1 1:8-15:1 1:3-3:1 2 (Enantiomer A) Bentazone 1:192-6:1 1:64-2:1 1:24 - 1:3 2 (Enantiomer A) Benzobicyclon 1:85-14:1 1:28-5:1 1:10-1:2 35 2 (Enantiomer A) Benzofenap 1:257-5:1 1:85-2:1 1:32 - 1:4 2 (Enantiomer A) Bicyclopyrone 1:42-27:1 1:14-9:1 1:5-2:1 2 (Enantiomer A) Bifenox 1:257-5:1 1:85-2:1 1:32 - 1:4 2 (Enantiomer A) Bispyribac-sodium 1:10-112:1 1:3-38:1 1:1 -7:1 Typical Most typical Most typical Component (a) Ratio in Ratio in Ratio in (Ns of compound) Component (b) weight weight weight 2 (Enantiomer A) Bixlozone 1:384-3:1 1:128-1:1 1:48 - 1:6 5 2 (Enantiomer A) Bromadyl 1:384-3:1 1:128-1:1 1:48 - 1:6 2 (Enantiomer A) Bromobutide 1:384-3:1 1:128-1:1 1:48 - 1:6 2 (Enantiomer A) Bromoxynyl 1:96-12:1 1:32-4:1 1:12-1:2 2 (Enantiomer A) Butachlor 1:768-2:1 1:256- 1:2 1:96-1:11 2 (Enantiomer A) Butaphenacyl 1:42-27:1 1:14-9:1 1:5-2:1 10 2 (Enantiomer A) Butylate 1:1542-1:2 1:514-1:5 1:192-1:22 2 (Enantiomer A) Carfenstrol 1:192-6:1 1:64-2:1 1:24 - 1:3 2 (Enantiomer A) Carfentrazone-ethyl 1:128-9:1 1:42-3:1 1:16-1:2 2 (Enantiomer A) Chlorimuron-ethyl 1:8-135:1 1:2-45:1 1:1 -9:1 2 (Enantiomer A) Chlorotoluron 1:768-2:1 1:256- 1:2 1:96-1:11 15 2 (Enantiomer A) Chlorsulfuron 1:6-168:1 1:2-56:1 1:1-11:1 2 (Enantiomer A) Cincosulfuron 1:17-68:1 1:5-23:1 1:2-5:1 2 (Enantiomer A) Cynidon-ethyl 1:384-3:1 1:128-1:1 1:48 - 1:6 2 (Enantiomer A)Cinmethylina 1:34-34:1 1:11 - 12:1 1:4-3:1 2 (A-enantiomer) Clacifós 1:34-34:1 1:11 - 12:1 1:4-3:1 20 2 (A-enantiomer) Clethodim 1:48-24:1 1:16-8:1 1:6-2:1 2 (A-enantiomer) Clodinafop-propargyl 1:20-56:1 1:6-19:1 1:2-4:1 2 (A-enantiomer) Clomazone 1:384-3:1 1:128-1:1 1:48 - 1:6 2 (A-enantiomer) Clomeprop 1:171 -7:1 1:57-3:1 1:21 -1:3 2 (A-enantiomer) Clopyralid 1:192-6:1 1:64-2:1 1:24 - 1:3 25 2 (A-enantiomer) Cloransulam-methyl 1:12-96:1 1:4-32:1 1:1 -6:1 2 (A-enantiomer) Cumiluron 1:384-3:1 1:128-1:1 1:48 - 1:6 2 (A-enantiomer) Cyanazine 1:384-3:1 1:128-1:1 1:48 - 1:6 2 (A-enantiomer) Cyclopyrimorate 1:17-68:1 1:5-23:1 1:2-5:1 2 (A-enantiomer) Cyclosulphamuron 1:17-68:1 1:5-23:1 1:2-5:1 30 2 (Enantiomer A) Cycloxidim 1:96-12:1 1:32-4:1 1:12-1:2 2 (Enantiomer A) Cihalofop 1:25-45:1 1:8-15:1 1:3-3:1 2 (Enantiomer A) Daimuron 1:192-6:1 1:64-2:1 1:24 - 1:3 2 (Enantiomer A) Desmedifam 1:322-4:1 1:107-2:1 1:40 - 1:5 2 (Enantiomer A) Dicamba 1:192-6:1 1:64-2:1 1:24 - 1:3 35 2(Enantiomer A) Diclobenil 1:1371 - 1:2 1:457- 1:4 1:171 - 1:20 2 (Enantiomer A) Dichlorprop 1:925-2:1 1:308 - 1:3 1:115-1:13 2 (Enantiomer A) Diclofop-methyl 1:384-3:1 1:128-1:1 1:48 - 1:6 2 (Enantiomer A) Diclosulam 1:10-112:1 1:3-38:1 1:1 -7:1 77. ίη / ΖΖΠΖ / Ε / ΥΙΛΙ Typical Most typical Most typical Component (a) Ratio in Ratio in Ratio in (Ns of compound) Component (b) weight weight weight 2 (Enantiomer A) Difenzoquat 1:288-4:1 1:96-2:1 1:36 - 1:4 5 2 (Enantiomer A) Diflufenican 1:857-2:1 1:285 - 1:3 1:107-1:12 2 (Enantiomer A) Diflufenzopyr 1:12-96:1 1:4-32:1 1:1 -6:1 2 (Enantiomer A) Dimetachlor 1:768-2:1 1:256- 1:2 1:96-1:11 2 (Enantiomer A) Dimethamethrin 1:192-6:1 1:64-2:1 1:24 - 1:3 2 (A-Enantiomer) Dimetenamid-P 1:384-3:1 1:128-1:1 1:48 - 1:6 10 2 (A-Enantiomer) Dithiopyr 1:192-6:1 1:64-2:1 1:24 - 1:3 2 (A-Enantiomer) Diuron 1:384-3:1 1:128-1:1 1:48 - 1:6 2 (Enantiomer A) EPTC 1:768-2:1 1:256- 1:2 1:96-1:11 2 (Enantiomer A) Esprocarb 1:1371 - 1:2 1:457 - 1:4 1:171 - 1:20 2 (Enantiomer A) Ethalfluralin 1:384-3:1 1:128-1:1 1:48 - 1:6 15 2 (Enantiomer A) Etametsulfuron-methyl 1:17-68:1 1:5-23:1 1:2-5:1 2 (Enantiomer A) Ethoxyphene 1:8-135:1 1:2-45:1 1:1 -9:1 2 (Enantiomer A) Ethoxysulfuron 1:20-56:1 1:6-19:1 1:2-4:1 2(A-enantiomer) Etobenzanid 1:257-5:1 1:85-2:1 1:32 - 1:4 2 (A-enantiomer) Phenoxaprop-ethyl 1:120-10:1 1:40-4:1 1:15-1:2 20 2 (A-enantiomer) Phenoxasulfone 1:85-14:1 1:28-5:1 1:10-1:2 2 (A-enantiomer) Fenchynotrione 1:17-68:1 1:5-23:1 1:2-5:1 2 (A-enantiomer) Fentrazamide 1:17-68:1 1:5-23:1 1:2-5:1 2 (A-enantiomer) Flazasulfuron 1:17-68:1 1:5-23:1 1:2-5:1 2 (Enantiomer A) Florasulam 1:2-420:1 1:1 - 140:1 2:1 -27:1 25 2 (Enantiomer A) Fluazifop-butyl 1:192-6:1 1:64-2:1 1:24 - 1:3 2 (Enantiomer A) Flucarbazone 1:8-135:1 1:2-45:1 1:1 -9:1 2 (Enantiomer A) Fluketosulfuron 1:8-135:1 1:2-45:1 1:1 -9:1 2 (Enantiomer A) Flufenacet 1:257-5:1 1:85-2:1 1:32 - 1:4 2 (Enantiomer A) Flumetsulam 1:24-48:1 1:8-16:1 1:3-3:1 30 2 (Enantiomer A) Flumichloroac-pentyl 1:10-112:1 1:3-38:1 1:1-7:1 2 (Enantiomer A) Flumioxazine 1:25-45:1 1:8-15:1 1:3-3:1 2 (Enantiomer A) Fluometuron 1:384-3:1 1:128-1:1 1:48-1:6 2 (Enantiomer A) Flupyrsulfuron-methyl 1:3-336:1 1:1-112:1 2:1-21:1 2(Enantiómero A) Fluridona 1:384-3:1 1:128-1:1 1:48 - 1:6 35 2 (Enantiómero A) Fluroxipir 1:96-12:1 1:32-4:1 1:12-1:2 2 (Enantiómero A) Flurtamona 1:857-2:1 1:285 - 1:3 1:107-1:12 2 (Enantiómero A) Flutiacet-metilo 1:48-42:1 1:16-14:1 1:3-3:1 2 (Enantiómero A) Fomesafeno 1:96-12:1 1:32-4:1 1:12-1:2 77. in / ZZPZ / E / YILI Typical Most typical Most typical Component (a) Ratio in Ratio in Ratio in (Ns of compound) Component (b) weight weight weight 2 (Enantiomer A) Foramsulfuron 1:13-84:1 1:4-28:1 1:1-6:1 5 2 (Enantiomer A) Glufosinate 1:288-4:1 1:96-2:1 1:36-1:4 2 (Enantiomer A) Glyphosate 1:288-4:1 1:96-2:1 1:36-1:4 2 (Enantiomer A) Halosulfuron-methyl 1:17-68:1 1:5-23:1 1:2-5:1 2 (Enantiomer A) Halauxifen 1:20-56:1 1:6-19:1 1:2-4:1 2 (Enantiomer A) Halauxifen-methyl 1:20-56:1 1:6-19:1 1:2-4:1 10 2 (Enantiomer A) Haloxyfop-methyl 1:34-34:1 1:11 - 12:1 1:4-3:1 2 (Enantiomer A) Hexazinone 1:192-6:1 1:64-2:1 1:24 - 1:3 2 (Enantiomer A) Hydantocidin 1:1100-16:1 1:385-8:1 1:144-4:1 2 (Enantiomer A) Imazamox 1:13-84:1 1:4-28:1 1:1 -6:1 2 (Enantiomer A) Imazapic 1:20-56:1 1:6-19:1 1:2-4:1 15 2 (Enantiomer A) Imazapyr 1:85-14:1 1:28-5:1 1:10-1:2 2 (Enantiomer A) Imazaquine 1:34-34:1 1:11 - 12:1 1:4-3:1 2 (Enantiomer A) Imazethabenz-methyl 1:171 -7:1 1:57-3:1 1:21 -1:3 2 (Enantiomer A)Imazetapir 1:24-48:1 1:8-16:1 1:3-3:1 2 (Enantiomer A) Imazosulfuron 1:27-42:1 1:9-14:1 1:3-3:1 20 2 (Enantiomer A) Indanophan 1:342-4:1 1:114-2:1 1:42 - 1:5 2 (Enantiomer A) Indaziflam 1:25-45:1 1:8-15:1 1:3-3:1 2 (Enantiomer A) Iodosulfuron-methyl 1:3-336:1 1:1 - 112:1 2:1 -21:1 2 (Enantiomer A) loxinyl 1:192-6:1 1:64-2:1 1:24 - 1:3 2 (Enantiomer A) Ipfencarbazone 1:85-14:1 1:28-5:1 1:10-1:2 25 2 (Enantiomer A) Isoproturon 1:384-3:1 1:128-1:1 1:48 - 1:6 2 (Enantiomer A) Isoxaben 1:288-4:1 1:96-2:1 1:36 - 1:4 2 (Enantiomer A) Isoxaflutol 1:60-20:1 1:20-7:1 1:7-2:1 2 (Enantiomer A) Lactophene 1:42-27:1 1:14-9:1 1:5-2:1 2 (Enantiomer A) Lenacil 1:384-3:1 1:128-1:1 1:48 - 1:6 30 2 (Enantiomer A) Linuron 1:384-3:1 1:128-1:1 1:6 2 (Enantiomer A) MCPA 1:192-6:1 1:64-2:1 1:24 - 1:3 2 (Enantiomer A) MCPB 1:288-4:1 1:96-2:1 1:36 - 1:4 2 (Enantiomer A) Mecoprop 1:768-2:1 1:256- 1:2 1:96-1:11 2 (Enantiomer A) Mephenacet 1:384-3:1 1:128-1:1 1:48 - 1:6 35 2 (Enantiomer A) .Mefluidide 1:192-6:1 1:64-2:1 1:24 - 1:3 2 (A-enantiomer) Mesosulfuron-methyl 1:5-224:1 1:1 -75:1 1:1 - 14:1 2 (A-enantiomer) Mesotrione 1:42-27:1 1:14-9:1 1:5-2:1 2 (A-enantiomer) Metamifop 1:42-27:1 1:14-9:1 1:5-2:1 77. ίη / ΖΖΠΖ / Ε / ΥΙΛΙ Typical Most typical Most typical Component (a) Ratio in Ratio in Ratio in (Ns of compound) Component (b) weight weight weight 2 (Enantiomer A) Metazachlor 1:384-3:1 1:128-1:1 1:48 - 1:6 5 2 (Enantiomer A) Metazosulfuron 1:25-45:1 1:8-15:1 1:3-3:1 2 (Enantiomer A) Metabenzothiazuron 1:768-2:1 1:256- 1:2 1:96-1:11 2 (Enantiomer A) Metolachlor 1:768-2:1 1:256- 1:2 1:96-1:11 2 (Enantiomer A) Metosulam 1:8-135:1 1:2-45:1 1:1 -9:1 2 (A-enantiomer) Metribucin 1:192-6:1 1:64-2:1 1:24 - 1:3 10 2 (A-enantiomer) Metsulfuron-methyl 1:2-560:1 1:1 - 187:1 3:1 -35:1 2 (A-enantiomer) Molinate 1:1028-2:1 1:342 - 1:3 1:128-1:15 2 (A-Enantiomer) Napropamide 1:384-3:1 1:128-1:1 1:48 - 1:6 2 (A-Enantiomer) Napropamide-M 1:192-6:1 1:64-2:1 1:24 - 1:3 2 (A-enantiomer) Naptalam 1:192-6:1 1:64-2:1 1:24 - 1:3 15 2 (Enantiomer A) Nicosulfuron 1:12-96:1 1:4-32:1 1:1 -6:1 2 (Enantiomer A) Norflurazone 1:1152-1:1 1:384 - 1:3 1:144-1:16 2 (Enantiomer A) Orbencarb 1:1371 - 1:2 1:457- 1:4 1:171 - 1:202 (A-enantiomer) Orthosulfamuron 1:20-56:1 1:6-19:1 1:2-4:1 2 (A-enantiomer) Oryzalin 1:514-3:1 1:171 - 1:2 1:64 - 1:8 20 2 (A-enantiomer) Oxadiaclay 1:384-3:1 1:128-1:1 1:48 - 1:6 2 (A-enantiomer) Oxadiazon 1:548-3:1 1:182-1:2 1:68 - 1:8 2 (A-enantiomer) Oxasulfuron 1:27-42:1 1:9-14:1 1:3-3:1 2 (A-enantiomer) Oxaziclomephone 1:42-27:1 1:14-9:1 1:5-2:1 2 (Enantiomer A) Oxyfluorfen 1:384-3:1 1:128-1:1 1:48 - 1:6 25 2 (Enantiomer A) Paracuate 1:192-6:1 1:64-2:1 1:24 - 1:3 2 (Enantiomer A) Pendimethalin 1:384-3:1 1:128-1:1 1:48 - 1:6 2 (Enantiomer A) Penoxsulam 1:10-112:1 1:3-38:1 1:1 -7:1 2 (Enantiomer A) Pentoxamide 1:384-3:1 1:128-1:1 1:48 - 1:6 2 (Enantiomer A) Pentoxazone 1:102-12:1 1:34-4:1 1:12-1:2 30 2 (A-enantiomer) Phenmedifam 1:102-12:1 1:34-4:1 1:12-1:2 2 (A-enantiomer) Picloram 1:96-12:1 1:32-4:1 1:12-1:2 2 (A-enantiomer) Picolinaphene 1:34-34:1 1:11 - 12:1 1:4-3:1 2 (A-enantiomer) Pinoxadene 1:25-45:1 1:8-15:1 1:3-3:1 2 (A-enantiomer) Pretilachlor 1:192-6:11:64-2:1 1:24 - 1:3 35 2 (Enantiómero A) Primisulfurón-metilo 1:8-135:1 1:2-45:1 1:1 -9:1 2 (Enantiómero A) Prodiamina 1:384-3:1 1:128-1:1 1:48 - 1:6 2 (Enantiómero A) Profoxidim 1:42-27:1 1:14-9:1 1:5-2:1 2 (Enantiómero A) Prometrina 1:384-3:1 1:128-1:1 1:48 - 1:6 77. in / ZZPZ / E / YILI Typical Most typical Most typical Component (a) Ratio in Ratio in Ratio in (Ns of compound) Component (b) weight weight weight 2 (Enantiomer A) Propachlor 1:1152-1:1 1:384 - 1:3 1:144-1:16 5 2 (Enantiomer A) Propanyl 1:384-3:1 1:128-1:1 1:48 - 1:6 2 (Enantiomer A) Propaquizafop 1:48-24:1 1:16-8:1 1:6-2:1 2 (Enantiomer A) Propoxycarbazone 1:17-68:1 1:5-23:1 1:2-5:1 2 (Enantiomer A) Propyrisulfuron 1:17-68:1 1:5-23:1 1:2-5:1 2 (A-Enantiomer) Propyzamide 1:384-3:1 1:128-1:1 1:48 - 1:6 10 2 (A-Enantiomer) Prosulfocarb 1:1200-1:2 1:400- 1:4 1:150-1:17 2 (A-Enantiomer) Prosulfuron 1:6-168:1 1:2-56:1 1:1-11:1 2 (A-enantiomer) Pyraclonyl 1:42-27:1 1:14-9:1 1:5-2:1 2 (A-enantiomer) Pyraflufen-ethyl 1:5-224:1 1:1 -75:1 1:1 - 14:1 2 (A enantiomer) Pirasulfotol 1:13-84:1 1:4-28:1 1:1 -6:1 15 2 (Enantiomer A) Pyrazolinate 1:857-2:1 1:285 - 1:3 1:107-1:12 2 (Enantiomer A) Pyrazosulfuron-ethyl 1:10-112:1 1:3-38:1 1:1 -7:1 2 (Enantiomer A) Pyrazoxyphene 1:5-224:1 1:1 -75:1 1:1 -14:1 2 (Enantiomer A) Pribenzoxim 1:10-112:1 1:3-38:1 1:1-7:1 2 (Enantiomer A) Pyributicarb 1:384-3:1 1:128-1:1 1:48-1:6 20 2 (Enantiomer A) Pyridate 1:288-4:1 1:96-2:1 1:36-1:4 2 (Enantiomer A) Pyrifthalid 1:10-112:1 1:3-38:1 1:1-7:1 2 (Enantiomer A) Piriminobac-methyl 1:20-56:1 1:6-19:1 1:2-4:1 2 (Enantiomer A) Pirimisulfan 1:17-68:1 1:5-23:1 1:2-5:1 2 (Enantiomer A) Pyritiobac 1:24-48:1 1:8-16:1 1:3-3:1 25 2 (Enantiomer A) Pyroxasulfone 1:85-14:1 1:28-5:1 1:10-1:2 2 (Enantiomer A) Pyroxsulam 1:5-224:1 1:1-75:1 1:1-14:1 2 (Enantiomer A) Quinclorac 1:192-6:1 1:64-2:1 1:24-1:3 2 (Enantiomer A) Quizalofop-ethyl 1:42-27:1 1:14-9:1 1:5-2:1 2 (Enantiomer A) Rimsulfuron 1:13-84:1 1:4-28:1 1:1-6:1 30 2 (Enantiomer A) Saflufenacil 1:25-45:1 1:8-15:1 1:3-3:1 2 (Enantiomer A) Sethoxydim 1:96-12:1 1:32-4:1 1:12-1:2 2 (Enantiomer A) Simazine 1:384-3:1 1:128-1:1 1:48-1:6 2 (Enantiomer A) Sulcotrione 1:120-10:1 1:40-4:1 1:15-1:2 2 (Enantiomer A) Sulfentrazone 1:147-8:11:49-3:1 1:18-1:3 35 2 (A-enantiomer) Sulfometuron-methyl 1:34-34:1 1:11 - 12:1 1:4-3:1 2 (A-enantiomer) Sulfosulfuron 1:8-135:1 1:2-45:1 1:1 -9:1 2 (A-enantiomer) Tebutyurón 1:384-3:1 1:128-1:1 1:48 - 1:6 2 (A-enantiomer) Tefuryltrione 1:42-27:1 1:14-9:1 1:5-2:1 77. ίη / ΖΖΠΖ / Ε / ΥΙΛΙ Typical Most typical Most typical Component (a) Ratio in Ratio in Ratio in (Ns of compound) Component (b) weight weight weight 2 (Enantiomer A) Tembotrione 1:31 -37:1 1:10-13:1 1:3-3:1 2 (Enantiomer A) Tepraloxydim 1:25-45:1 1:8-15:1 1:3-3:1 2 (Enantiomer A) Terbacil 1:288-4:1 1:96-2:1 1:36 - 1:4 2 (Enantiomer A) Terbuthylazine 1:857-2:1 1:285 - 1:3 1:107-1:12 2 (Enantiomer A) Terbutrine 1:192-6:1 1:64-2:1 1:24 - 1:3 2 (Enantiomer A) Tenylchlor 1:85-14:1 1:28-5:1 1:10-1:2 2 (Enantiomer A) Thiazopyr 1:384-3:1 1:128-1:1 1:48 - 1:6 2 (Enantiomer A) Thiencarbazone 1:3-336:1 1:1 - 112:1 2:1 -21:1 2 (Enantiomer A) Thifensulfuron-methyl 1:5-224:1 1:1 -75:1 1:1 - 14:1 2 (Enantiomer A) Thiaphenacil 1:17-68:1 1:5-23:1 1:2-5:1 2 (Enantiomer A) Thiobencarb 1:768-2:1 1:256- 1:2 1:96-1:11 2 (A-enantiomer) Tolpyralate 1:31 -37:1 1:10-13:1 1:3-3:1 2 (A-enantiomer) Topramzone 1:6-168:1 1:2-56:1 1:1-11:1 2 (A-enantiomer) Tralkoxydim 1:68-17:1 1:22-6:1 1:8-2:1 2 (Enantiomer A) Triaphamone1:2-420:1 1:1 - 140:1 2:1 -27:1 2 (Enantiomer A) Trialate 1:768-2:1 1:256- 1:2 1:96-1:11 2 (Enantiomer A) Triasulfuron 1:5-224:1 1:1 -75:1 1:1 - 14:1 2 (Enantiomer A) Triaziflam 1:171 -7:1 1:57-3:1 1:21 -1:3 2 (Enantiomer A) Tribenuron-methyl 1:3-336:1 1:1 - 112:1 2:1 -21:1 2 (Enantiomer A) Triclopyr 1:192-6:1 1:64-2:1 1:24 - 1:3 2 (Enantiomer A) Trifloxysulfuron 1:2-420:1 1:1 - 140:1 2:1 -27:1 2 (Enantiomer A) Trifludimoxazine 1:25-45:1 1:8-15:1 1:3-3:1 2 (Enantiomer A) Trifluralin 1:288-4:1 1:96-2:1 1:36 - 1:4 2 (Enantiomer A) Trifloxysulfuron-methyl 1:17-68:1 1:5-23:1 1:2-5:1 2 (Enantiomer A) Tritosulfuron 1:13-84:1 1:4-28:1 1:1 -6:1 Table A2 is constructed the same as Table A1 above, except that the entries under the Component (a) column heading (Compound No. 2) are replaced by the respective Component (a) column entry shown below. The compound number in the Component (a) column is identified in Index Table 1. Thus, for example, in Table A2, the entries under the Component (a) column heading refer to 2 (Enantiomer B) (Compound No. 2 identified in Index Table 1), and the first line under the column headings in Table A2 specifically discloses a mixture of Compound No. 2 (Enantiomer B) with 2,4-D. Table Number Component Column Entries (a) A2 A3 (2B enantiomer) (3A enantiomer) 77. ίΠ / ZZΖηZ / E / YΙΛΙ Table Number Component Column Entries (a) A4 3 (enantiomer 3B) A5 4 (enantiomer 4A) A6 4 (enantiomer 4B) A7 5 (enantiomer 5B) A8 5 (enantiomer 5A) 77. in / ZZPZ / E / YILI In certain cases, combinations of a compound from this disclosure with other compounds or biologically active agents (particularly herbicides) (i.e., active ingredients) may result in an effect greater than the additive (i.e., synergistic) on weeds and / or an effect less than the additive (i.e., protective) on crops or other desirable plants. It is always desirable to reduce the amount of active ingredients released into the environment while ensuring effective pest control. It is also desirable to be able to use larger quantities of active ingredients to provide more effective weed control without excessively damaging crops.When the synergy of herbicide active ingredients occurs on weeds at application rates that provide agronomically satisfactory levels of weed control, such combinations can be advantageous for reducing crop production costs and decreasing the environmental burden. When the herbicide active ingredients protect crops, such combinations can be advantageous for increasing crop protection by reducing weed competition. It is worth noting the combination of a compound in the disclosure with at least one other herbicidal active ingredient. Particular note should be given to such a combination where the other herbicidal active ingredient has a different site of action than the compound in the 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 will be particularly advantageous for resistance management. Therefore, a composition in the present disclosure may further comprise (in an amount effective as a herbicide) at least one additional herbicidal active ingredient having a similar control spectrum but a different site of action. Compounds in this disclosure may also be used in combination with herbicide protectants such as alidochlor, benoxacor, cloquintocet-mexyl, cumiluron, cytometrinil, cyprosulfonamide, daimuron, dichlormid, dicyclonon, dietolate, dimepiperate, fenchlorazol-ethyl, fenchlorim, flurazol, fluxophenim, furylazol, isoxadifeno-ethyl, mefenpyr-diethyl, mefenate, methoxyphenone, naphthalic anhydride (1,8-naphthalic anhydride), oxabetrinyl, A / -(aminocarbonyl)-2-methylbenzenesulfonamide, A / -(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene (BCS), 4-(dichloroacetyl)-1 -oxa-4azoespiro[4.5]decane (MON 4660), 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), ethyl 1,6-dihydro-1-(2methoxyphenyl)-6-oxo-2-phenyl-5-pyridinecarboxylate, and 2-methoxy- / V-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]benzamide to increase safety for certain crops. Effective amounts may be applied as an antidote to herbicide protectants at the same time as the compounds in this disclosure or may be applied as seed treatments. Therefore, one aspect of this disclosure relates to a herbicide mixture comprising a compound in this disclosure and an amount effective as an antidote to a herbicide protectant.Seed treatment is particularly useful for selective weed control, as it physically restricts the herbicide to the crop plants. Therefore, a particularly useful embodiment of the present disclosure is a method for selectively controlling unwanted vegetation growth in a crop, comprising contacting the crop site with an herbicide-effective amount of a compound of this disclosure, wherein the seed from which the crop grows is treated with an effective herbicide amount of the protectant. The effective herbicide amounts of the protectants can be readily determined by simple experimentation. The disclosure compounds may also be mixed with: (1) polynucleotides including, but not limited to, chemically modified DNA, RNA and / or nucleotides that influence the amount of a particular target through negative regulation, interference, suppression or silencing of the genetically derived transcript that produces a herbicidal effect; or (2) polynucleotides including, but not limited to, chemically modified DNA, RNA and / or nucleotides that influence the amount of a particular target through negative regulation, interference, suppression or silencing of the genetically derived transcript that produces a protective effect. The following trial A demonstrates the control efficacy of the representative compounds in this disclosure against representative weeds, but the weed control provided by these compounds is not limited to these species. See Index Table 1 for descriptions of the compounds. TABLE 1 INDEX 77. ίΠ / ZZΖηZ / E / YΙΛΙ (enantiomer 2A) 2 (enantiomer 2B) stereoisomer (-) stereoisomer (+) 77. ίΠ / ΖΖηΖ / Ε / ΥΙΛΙ (3A enantiomer) (3B enantiomer) (enantiomer 4A) stereoisomer (-) (enantiomer 4B) stereoisomer (+) (enantiomer 5A) stereoisomer (-) (enantiomer 5B) stereoisomer (+) ESSAY A Seeds of selected plant species of striped grass (BYG, Echinochloa crus-galli), coquia (KOC, Kochia scoparia), ragweed (common ragweed, Ambrosia elatior), Italian ryegrass (RGI, Lolium multiflorurri), giant foxtail (FTI, Setaria faberii), green foxtail (Setaria viridis), and pigweed (PWR, Amaranto retroflexus) were planted in a mixture of loam soil and sand and treated prior to emergence with a directed soil spray using test chemicals formulated in a non-phytotoxic solvent mixture that included a surfactant. At the same time, selected plants of these weed species, as well as wheat (WWT, Triticum aestivum), maize (IPC, Zea mays), blackgrass (BKG, Alopecuros myosuroides), and kelp (GAL, Galium aparine), were planted in pots containing the same loam and sand mixture and treated with post-emergence applications of the same formulated test chemicals. Plant height ranged from 2 to 10 cm, and plants were at the one- to two-leaf stage for post-emergence treatment. Treated and untreated controls were maintained in a greenhouse for approximately 10 days, after which all treated plants were compared to untreated controls and visually assessed for lesions. Plant response ratings, summarized in Tables 1–4, are based on a scale of 0 to 100, where 0 is no effect and 100 is complete control.A guión (-) as a response means absence of result of the test. The classifications are followed by a letter that represents the symptomatology, where S is albinism, C is chlorosis, G is growth inhibition and E is emergency. Table 1: Activity of emergence (POS-) and pre-emergence (PRE-) of enantiomers that include racemate 2 at 125 and 31 qbramos / ha. 77. ίΠ / ΖΖηΖ / Ε / ΥΙΛΙ ΆΡ. Rccpoccxcn g pa / ha CPI wwr g __(faias hierbas —Jfalas hierbas— cüoot. GAL KD2 EWR PNC BKG mcnooot. RGT BYG ETI LX Λ. YH. POS- 125 30 G 0 100 C 80 S 100 C 90 S 31$ 40 s 60 S Ck X Oh Y Ύ 31 10G 0 100 C eos iooc 90s ja)JW ,N. .¿.L !·,<:' N c PRE- 125 80S 100C 200 50 G 40 S Enantiamer A 3! tOGTooc 2DG0 W „ m.....„ POS- 125 30 G 30 S 90 C 70 S 100 C 100 C 40 S 100C 90 C 90 S 0.1. OH 31 0 0 100 c 60S 100C 100C ¡30G\ 100C 80C 80 S yX Η.ΓΥΝχΝ^Ό 2 Enantlómero B PRE- 125 31 90C 100 CL>J 100 c 100 S 100 c 80 S 90 S 100 C 100 c Table 2: Post-emergence (POS-) and pre-emergence (PRE-) activity of enantiomers comprising the racemate 3 to 125 and 31 qramos / ha. 77. ίΠ / ZZΖηZ / E / YΙΛΙ O11—Weeds— —Weeds— ΆΡ. Prcporcicn g pa / ha CPI WWT GAL dioot. mcnooot. BKG RGI BYG ΕΠ KDC E«R EMC TrT POS- 12? 10 G 0 100C 90 S 100 C 100 c [ 40 s eo s «o s 31 0 0 90 C 80 S 90 C 00 c 0. 1 C H PRE- I2r 90 G 100 E 100 E 80 S 50 5 80 S T 31 90 C 53 S ___ liWHEiaOHHB N T4,CZ Al POS- 125 20 G 10 s 100C 90 S 100 C 100 c 1^. 80 S 50 5 50 S 3 Enantiómero A 31 10 G 0 100C 60 s 100 C 90 C PRE- 125 IMS 100 E 100 E 50 S 50 S 70 $ 31 70 S loo c 80 S TtTi POS- • 20 S 33 S 100C 90 S 100 C 90 S Ϊ2β^ 100 S 90 S 90 S -y' \H; 31 10C 0 100C 60 S 100 c 100 C jIOOS 70 S 70 s O 1 OH PRE- 125- 90 S 100 E 100 E 10OC 90 S IDO C 31 90 c 80 S 100 C 80 S 90 S aA XCI POS- 1C0P 5C S 100C 100 c 100 c 90 S SOS 100 S 90 S IDOS 3 12? 10 G 30 S 100C 90 S 100 c 100 C 1Q$)1OOS 90 C 90 s Enantiómero B 31 10 G 0 100c 80 S 100 c 100 C IJtL. 90 S 60 S 90 s PRE- 1COO 100 C 100 c 100 E 100 S 100 C 100 c 125- 80 S 100 E ICO E 90 S 100C 100C 31 (-fóff'j 90 C 100 E 4C S 80 S 80 S Table 3: Postemergence (POS-) and preemergence (PRE-) activity of enantiomers comprising racemate 4 at 125 and 31 qrams / ha. --Cultivos-- --don't worry -- --If you don't __ IQ . Rxporcicn AP · g pa / ha CPI WWT GAL dioot. mcnoc house. KDC EWR EMC BKG RGI BYG ETI HJZC i- . or 1 c pos- 125 0 0 100 c 60 S 100 C 90 S WIW) Til ι·Α NC 4 Enantiomer A Ot 31 PRE- 125 31 0 0 80 S 50 S 90 S 80 S 50 C <90 C. Chapter 0 9 ! ''CH; pos- 125 10 S 20 S 100 C 50 S 100 C 100 C 70 S 90 C 90 S 90 S ΎΎΤ N / XO HA Ν' >2 4 Enantiomer B 31 PRE- 120 31 $91 S 100 S 0 1 C 0 1 80C 70 S 100 C 90 S .WjllOOC 80 S 7CS 80 S 100 C 100 c 100 C 100 c Table-4: Post-emergence (POS-) and pre-emergence (PRE-) activity of enantiomers comprising racemate 5 at 125 and 31 qrams / ha. 77. ίη / ΖΠΖ / Ε / ΥΙΛΙ --The bad hiorfog-- --The bad hiArtia-- AP. Pzxnordcn g pa / ha CPI WWT (30, dicot. KDC EWR FWC mcnooot. BKG RGI BYG FTI POS- 125· 10 S 0 100 s 80 S 90 S 90 S Jífc | 70 c 3ÍÑB-> jfó; 12-· 0 0 100 s 70 S 90 S 90 S «W eos CC1 62 0 0 100 s 80 S 90 S 90 S 50 s -t'lfe- 31 0 0 90 S 70 S 90 S 90 S ιιφ wf; ir· 0 0 90 S 73 $ 80 S 80 S ,¡'¿r .·*& jft w o C Φ 0 5 31 3W; ec c :#í -JA Enantiomer A 31 Bq;, roo c 29¿ ¡Oi -® 16 i«C © Λ 7« :< -O·''' . POS- Enantiomer B PRE- » “>r 20 S IDOS 80 S 100 S 100 s 50 S 90 C 80 S 90 S • c. 30 C 50 S 10OS 90 S 100 S 90 S eos 100 C 90 S 90 S »··? 0 10 s 100 S 70 3 90 S 90 S 40 S 80 C 4C S 60 S 31 0 0 90 S 70 S SOS SOS 3βΟ 1 7S C 30« 60 S 31 4Ü C 20 G 100 s 0 13 90 S 90 S 5Π S 80 C 80 S 5'2 S 16 31 31 16 0 0 90 S 50 S 90 S 90 S 70S 100 E 100 C 50 S 100 E 90 C t’Ü S Ά *3 70 S 750 s JOFf 70 S fftC 100 E 50 S SR3 ; 40 c 310^3®^ tW®? 00 s 100 C ~9Ó S ' 60 C 90 S Í30W syiil eo s 1.·:«. ·Κ o ।

Claims

1. An optically active compound selected from atropisomers of formula 1a and formula 1b, all stereoisomers, / V-oxides and salts thereof, compositions containing them and their use as herbicides:

77. iP / ZZΖηZ / E / YILI wherein R1 is Me or halogen; R2 is CH3, CH2CH3, halogen, trifluoromethyl or difluoromethoxy; R3 is hydrogen, CH3 or halogen; R4 is hydrogen, CH3 or halogen and R5 is hydrogen, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl or C1-C4 alkylcarboxymethyl; wherein the atropisomer of formula 1a or 1b, a / V-oxide or salt thereof, is present in excess of its corresponding enantiomer or a / V-oxide or salt thereof:

2. The compound of claim 1 comprising an atropisomer of a compound of formula 1a or a / V-oxide or salt thereof being present in excess of its corresponding enantiomer of formula 1b or a / V-oxide or salt thereof. 3.The compound of claim 1 wherein R1 is Cl or CH3; R2 is CH3 or difluoromethoxy; R3 is CH3OH; R4 is H; and R5 is H or -(C=O)CH2CH3.

4. The compound of claim 1 wherein R1 is Cl; R2 is CH3; R3 is CH3OH; R4 is H; and R5 is H or -(C=O)CH2CH3.

5. The compound of claim 4 wherein R1 is Cl; R2 is CH3; R3 is CH3; R4 is H; and R5 is H.

6. The compound of claim 1 comprising an atropisomer of a compound of formula 1b or an Λ-oxide or salt thereof being present in excess of its corresponding enantiomer of formula 1a or an ΛZ-oxide or salt thereof.

7. The compound of any of claims 1 to 6 has a positive (+) rotation value.

8. The compound of any of claims 1 to 6 has a negative (-) rotation value.

9. The compound of any of claims 1 to 6 wherein an atropisomer is more herbicidally active than the corresponding enantiomer. 10.A process for preparing a compound of formula 1a or 1b 77 Ln / Zznz / E / YIAI the Ib wherein R1 is CH3 or halogen; R2 is CH3, CH2CH3, halogen, trifluoromethyl or difluoromethoxy; R3 is H, CH3 or halogen; R4 is H, CH3 or halogen; R5 is H, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl or C1-C4 alkylcarboxymethyl; the process comprising: 1) loading a racemic mixture of a compound of formula 1 comprising the atropisomers of formulas 1a and 1b onto a chiral support chromatography column and eluting with a mobile phase; 2) isolating two separate fractions with different retention times; one containing an atropisomer with a positive optical rotation value [a]1(+) and an atropisomer with a negative optical rotation value [a]i(-), 11. The process of claim 10 wherein R1 is Cl or CH3; R2 is CH3 or difluoromethoxy; R3 is CH3 or H; R4 is H and R5 is H or -(CO)CH2CH3.

12. The process of claim 11 wherein R1 is Cl; R2 is CH3; R3 is CH3 or H; R4 is H and R5 is H or -(C=O)CH2CH3.

13. The process of claim 12 wherein R1 is Cl; R2 is CH3; R3 is CH3; R4 is H and R5 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 surfactants, solid diluents, and liquid diluents. 15.A herbicidal composition comprising a compound of any one of claims 1 to 9, at least one additional active ingredient selected from the group consisting of other herbicides and herbicide protectants, and at least one component selected from the group consisting of surfactants, solid diluents, and liquid diluents.

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

17. A method for controlling the growth of unwanted vegetation comprising contacting the vegetation or its surroundings with a herbicidal amount of a compound of any one of claims 1 to 9.