Substituted haloalkyl sulfonanilide herbicides

Abstract

To provide novel compounds that control undesired vegetation and that have higher efficacy, lower cost, lower toxicity, are more environmentally safe, or have different sites of action.SOLUTION: Disclosed are compounds of Formula 1, stereoisomers, N-oxides, and salts thereof, wherein G is CONR5R6 or represents a specific substituent. Disclosed are also compositions containing the compounds of Formula 1, and methods for controlling undesired vegetation comprising contacting the undesired vegetation or its environment with an effective amount of a compound or a composition of the invention.SELECTED DRAWING: None

Description

[Technical Field]

[0001] FIELD OF THE INVENTION The present invention relates to certain haloalkylsulfonanilides, their N-oxides, salts and compositions, and methods of their use to control undesirable vegetation. [Background technology]

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

[0003] The present invention relates to compounds of formula 1, all stereoisomers, N-oxides, and salts thereof, agricultural compositions containing them, and their use as herbicides: [ka] During the ceremony, G is CONR 5 R 6 or [ka] is selected from R 1is H, C1-C7 alkyl, halogen, CN, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C2-C3 cyanoalkyl, C1-C7 haloalkyl, C2-C7 haloalkenyl, C3-C7 haloalkynyl, C2-C7 alkoxyalkyl, C1-C7 alkoxy, C1-C5 alkylthio, C2-C3 alkoxycarbonyl or C2-C7 haloalkoxyalkyl; R 2 is H, C1-C7 alkyl, halogen, CN, C1-C7 haloalkyl, C1-C7 alkoxy, C3-C7 cycloalkyl or C1-C5 alkylthio; R 3 is H, C1-C7 alkyl, halogen, CN, C2-C6 alkenyl, C2-C7 alkynyl, C3-C7 cycloalkyl, C2-C3 cyanoalkyl, C1-C7 haloalkyl, C2-C7 haloalkenyl, C3-C7 haloalkynyl, C2-C7 alkoxyalkyl, C1-C7 alkoxy, C1-C5 alkylthio, C2-C3 alkoxycarbonyl or C2-C7 haloalkoxyalkyl; R 4 is H, C(=O)R 19 , -C(=S)R 19 , -CO2R 19 , -C(=O)SR 19 , -S(O)2R 19 , C(=O)NR 19 R 20 , -S(O)NR 19 R 20 , S(OH)NR 19 R 20 , CH2OC(=O)OR 19 , CH2OC(=O)NR 19 R 20 or CH2OC(=O)R 19 and; R 5is H, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C3-C7 alkenylalkyl, C3-C7 alkynylalkyl, C2-C3 cyanoalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy; C2-C7 alkoxyalkyl or C4-C7 alkylcycloalkyl; R 6 is H, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C3-C7 alkenylalkyl, C3-C7 alkynylalkyl, C2-C3 cyanoalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy; C2-C7 alkoxyalkyl or C4-C7 alkylcycloalkyl; or R 5 and R 6 together with the nitrogen atom to which they are attached form a 3- to 7-membered ring containing carbon atoms and optionally 1 to 3 oxygen, sulfur, or nitrogen atoms as ring members, wherein 2 Up to five carbon atom ring members are independently selected from C(=O) and C(=S), and sulfur atom ring members are selected from S, S(O), or S(O)2, and the rings are independently optionally substituted with up to five substituents (R v ) r where r is the number of substituents; R v are independently selected from the group consisting of H, halogen, cyano, nitro, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, and C1-C4 haloalkoxy; or The Two R's v are bonded to the same carbon atom or to two adjacent carbon atoms, the two R vtogether with the carbon atom or atoms to which they are attached form a 3-7 membered ring containing carbon atoms and optionally 1-3 oxygen, sulfur or nitrogen atom ring members, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S) and sulfur atom ring members are selected from S, S(O) or S(O)2, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy; R 7 is H, C1-C7 alkyl, halogen, CN, C1-C7 haloalkyl or C1-C7 alkoxy; R 8 is H, C1-C7 alkyl; or R 7 and R 8 may be taken together to form a 3- to 7-membered ring containing carbon atoms and optionally 1-2 oxygen, sulfur, or nitrogen atoms as ring members, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, and C1-C4 haloalkoxy; R 9 is H, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C7 haloalkyl, C2-C7 haloalkenyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy or C4-C7 alkylcycloalkyl; R 7 and R 9may be taken together to form a fused 3- to 7-membered ring containing carbon atoms and optionally 1-2 oxygen, sulfur, or nitrogen atoms as ring members, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, and C1-C4 haloalkoxy; R 10 is H or C1-C7 alkyl; or R 9 and R 10 can be taken together with the carbon atoms to which they are attached to form a 3- to 7-membered ring containing carbon atoms and optionally 1-2 oxygen, sulfur, or nitrogen atoms as ring members, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and sulfur atom ring members are selected from S, S(O), or S(O)2, and said ring is optionally substituted independently with up to 5 substituents (R v ) r where r is the number of substituents; or The Two R's v are bonded to the same carbon atom or to two adjacent carbon atoms, the two R v together with the carbon atom or atoms to which they are attached form a 3- to 7-membered ring containing carbon atoms and optionally 1-2 oxygen, sulfur, or nitrogen atom ring members, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and sulfur atom ring members are selected from S, S(O), or S(O)2; Q is O, S, CR 11 R 12 or NR 13 and; R 11 and R 12together with the carbon atoms to which they are attached form a 3- to 7-membered ring containing carbon atoms and optionally 1 to 2 oxygen, sulfur, or nitrogen atoms as ring members, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, and C1-C4 haloalkoxy. or R 9 and R 11 are taken together with the carbon atoms to which they are attached to form a six-membered aromatic ring, said ring being independently optionally substituted with up to four substituents; w Selected from; R w is C1-C7 alkyl, halogen, C1-C7 haloalkyl or C1-C7 alkoxy; r is 0, 1, 2, 3, 4 or 5; R 13 is H, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy; C2-C7 alkoxyalkyl or C4-C7 alkylcycloalkyl; R 14 is H, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C7 haloalkyl, C1-C7 thioalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy; C2-C7 alkoxyalkyl or C4-C7 alkylcycloalkyl; R 15 is H, C1-C7 alkyl, halogen, C1-C7 haloalkyl or C1-C7 alkoxy; R 16is H, cyano, C1-C7 alkyl, halogen, C1-C4 alkylthio, C1-C7 haloalkyl or C1-C7 alkoxy; R 17 is H, C1-C7 alkyl, halogen, CN, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C2-C3 cyanoalkyl, C1-C7 haloalkyl, C2-C7 haloalkenyl, C3-C7 haloalkynyl, C2-C7 alkoxyalkyl, C1-C7 alkoxy, C1-C5 alkylthio, C2-C3 alkoxycarbonyl or C2-C7 haloalkoxyalkyl; R 18 is H, C1-C7 alkyl, halogen, C1-C7 haloalkyl or C1-C7 alkoxy; R 19 is C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy; C2-C7 alkoxyalkyl, C4-C7 alkylcycloalkyl; R 20 is H or C1-C7 haloalkyl; R f is a C1-C7 haloalkyl.

[0004] More specifically, the present invention relates to compounds of Formula 1, all stereoisomers, N-oxides, or salts thereof. The present invention also relates to herbicidal compositions comprising a compound of the present disclosure (i.e., a herbicidally effective amount) and at least one component selected from the group consisting of a surfactant, a solid diluent, and a liquid diluent. The present invention further relates to methods for controlling the growth of undesirable vegetation, comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of the present disclosure (e.g., as a composition described herein).

[0005] The present invention also includes herbicidal mixtures comprising (a) a compound selected from Formula 1, all stereoisomers, N-oxides, and salts thereof, and (b) at least one additional active ingredient selected from the following (b1) to (b16), and salts of the compounds (b1) to (b16): DETAILED DESCRIPTION OF THE INVENTION

[0006] As used herein, "comprises," "comprising," "includes," "including," "contains," "co The terms "containing," "has," "having," "characterized by," or various variations thereof are intended to cover non-exclusive inclusions, subject to various limitations expressly indicated. For example, a composition, mixture, process, method, article, or device that includes any elements is not necessarily limited to only those elements, but may include other elements not expressly indicated or inherent in such composition, mixture, process, method, article, or device.

[0007] The transitional phrase "consisting of" excludes any unspecified element, step, or ingredient. In patent claims, this is usually the case if the claim is closed to include, apart from impurities, materials different from those recited. When the phrase "consisting of" appears in a clause in the body of a claim rather than immediately following the preamble, it limits only the elements recited in that claim; other elements are not excluded from the claim as a whole.

[0008] The transitional phrase "consisting essentially of" is used to define compositions, methods, or apparatus that include materials, steps, structures, ingredients, or elements in addition to those literally disclosed, provided that these additional materials, steps, structures, ingredients, or elements do not materially affect the basic and novel characteristics of the claimed invention. It occupies the middle part of "of".

[0009] It should be readily understood that if an applicant defines an invention or portion thereof in open-ended terms such as "comprising," the statement should (unless stated otherwise) be construed as also describing such inventions using the terms "consisting essentially of" or "consisting of."

[0010] Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not an exclusive "or." For example, the condition "A or B" is satisfied by any of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0011] Furthermore, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to be open-ended regarding the number of instances (i.e., occurrences) of that element or component. Thus, "a" and "an" should be read to include one, or at least one, and such singular forms of the element or component also include the plural, unless it is clear that the number is intended to be singular.

[0012] As referred to herein, the term "seedling", used alone or in combination with words, means a young plant that develops from the embryo of a seed.

[0013] As referred to herein, the term "broadleaf," used alone or in terms such as "broadleaf weeds," refers to dicotyledons or dicotyledons, a term used to describe a group of angiosperms characterized by an embryo with two cotyledons.

[0014] In the above citations, the term "alkylthio" or "haloalkyl" may be used singly or in combination, such as "alkylthio" or "haloalkyl". The term "alkyl" as used herein includes straight-chain or branched alkyls such as methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl, or hexyl isomers. "Alkenyl" includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl, and hexenyl isomers. "Alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl, and the different butynyl, pentynyl, and hexynyl isomers. "Alkynyl" also includes moieties consisting of multiple triple bonds, such as 2,5-hexadiynyl. "Alkynylalkyl" refers to an alkynyl substitution on an alkyl. Examples of "alkynylalkyl" include CH≡CCH2, CH3C≡≡CCH2, CH≡CCH2CH2, CH≡CCH(CH3)CH2 and different alkynylalkyl isomers. "Alkylene" means a straight-chain or branched alkanediyl. Examples of "alkylene" include CH2, CH2CH2, CH(CH3), CH2CH2CH2, CH2CH(CH3) and different butylene isomers. "Alkenylene" means a straight-chain or branched alkenediyl containing one olefinic bond. Examples of "alkenylene" include CH═CH, CH2CH═CH, CH═C(CH3) and different butenylene isomers. "Alkynylene" means a straight-chain or branched alkynediyl containing one triple bond. Examples of "alkynylene" include C≡C, CH2C≡C, C≡CCH2, and the different butynylene isomers.

[0015] "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy, and the different butoxy, pentoxy, and hexyloxy isomers. "Alkoxyalkyl" refers to alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CHOCH, CHOCHCH, CHCHOCH, CHCHCHOCH, CHCHCHCHOCH, and CHCHOCHCH. "Alkoxyalkoxy" refers to alkoxy substitution on alkoxy. "Alkenyloxy" includes linear or branched alkenyloxy moieties. Examples of "alkenyloxy" include HC=CHCHO, (CH)C=CHCHO, (CH)CH=CHCHO, (CH)CH=C(CH)CHO, and CH=CHCHCHO. "Alkynyloxy" includes linear or branched alkynyloxy moieties. Examples of "alkynyloxy" include HC≡CCHO, CHC≡CCHO, and CHC≡CCHCHO. "Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio, and hexylthio isomers. "Alkylsulfinyl" includes both enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" include CHS(O)-, CHCHS(O)-, CHCHCHS(O)-, (CH)CHS(O)-, and the different butylsulfinyl, pentylsulfinyl, and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH3S(O)2-, CH3CH2S(O)2-, CH3CH2CH2S(O)2-, (CH3)2CHS(O)2-, and the different butylsulfonyl, pentylsulfonyl, and hexylsulfonyl isomers. "Alkylthioalkyl" denotes alkylthio substitution on alkyl. Examples of "alkylthioalkyl" include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2, and CH3CH2SCH2CH2. "Alkylthioalkoxy" denotes alkylthio substitution on alkoxy."Alkyldithio" refers to a branched or straight-chain alkyldithio moiety. Examples of "alkyldithio" include CH3SS-, CH3CH2SS-, CH3CH2CH2SS-, (CH3)2CHSS-, and the different butyldithio and pentyldithio isomers. "Cyanoalkyl" refers to an alkyl group substituted with a cyano group. Examples of "cyanoalkyl" include NCCH2, NCCH2CH2, and CH3CH(CN)CH2. "Alkylamino", ". "Dialkylamino", "alkenylthio", "alkenylsulfinyl", "alkenylsulfonyl", "alkynylthio", "alkynylsulfinyl", "alkynylsulfonyl", and the like are defined analogously to the above examples.

[0016] Examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "alkylcycloalkyl" refers to alkyl substitution on a cycloalkyl moiety, including, for example, ethylcyclopropyl, i-propylcyclobutyl, 3-methylcyclopentyl, and 4-methylcyclohexyl. The term "cycloalkylalkyl" refers to cycloalkyl substitution on an alkyl moiety. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties attached to a straight-chain or branched alkyl group. The term "cycloalkoxy" refers to a cycloalkyl attached through an oxygen atom, such as cyclopentyloxy and cyclohexyloxy. "Cycloalkylalkoxy" refers to a cycloalkylalkyl attached through an oxygen atom attached to an alkyl chain. Examples of "cycloalkylalkoxy" include cyclopropylmethoxy, cyclopentylethoxy, and other cycloalkyl moieties attached to a straight-chain or branched alkoxy group. "Cyanocycloalkyl" refers to a cycloalkyl group substituted with a cyano group. Examples of "cyanocycloalkyl" include 4-cyanocyclohexyl and 3-cyanocyclopentyl. "Cycloalkenyl" includes groups such as cyclopentenyl and cyclohexenyl, as well as groups with multiple double bonds, such as 1,3- and 1,4-cyclohexadienyl.

[0017] The term "halogen," whether used alone or in compound words such as "haloalkyl," or in descriptions such as "alkyl substituted with halogen," includes fluorine, chlorine, bromine, or iodine. Furthermore, when used in compound words such as "haloalkyl," or in descriptions such as "alkyl substituted with halogen," said alkyl may be partially or fully substituted with halogen atoms, which may be the same or different. Examples of "haloalkyl" or "alkyl substituted with halogen" include F3C, ClCH2, CF3CH2, and CFC12. Terms such as "halocycloalkyl," "haloalkoxy," "haloalkylthio," "haloalkenyl," and "haloalkynyl" are defined analogously to "haloalkyl." Examples of "haloalkoxy" include CFO-, CC1CHO-, HCF2CH2CH2O-, and CF3CHO-. Examples of "haloalkylthio" include CC1S-, CF3S-, CC13CH2S-, and ClCH2CH2CH2S-. Examples of "haloalkylsulfinyl" include CF3S(O)-, CC13S(O)-, CF3CH2S(O)-, and CF3CF2S(O)-. Examples of "haloalkylsulfonyl" include CF3S(O)-, CC13S(O)-, CF3CH2S(O)-, and CF3CF2S(O)-. Examples of "haloalkenyl" include (Cl)2C=CHCH2- and CF3CH2CH=CHCH2-. Examples of "haloalkynyl" include HC≡CCHCl-, CF3C≡C-, CC13C≡C-, and FCH2C≡CCH2-. Examples of "haloalkoxyalkoxy" include CF3OCHO-, ClCH2CHOCH2CH2O-, Cl3CCH2OCH2O-, as well as branched alkyl derivatives.

[0018] "Alkylcarbonyl" means a straight-chain or branched alkyl moiety attached to a C(=O) moiety. Examples of "alkylcarbonyl" include CHC(=O)-, CHCHCHC(=O)-, and (CH)CHC(=O)-. Examples of "alkoxycarbonyl" include CHOC(=O)-, CHCHOC(=O)-, CHCHCHOC(=O)-, (CH)CHOC(=O)-, and the different butoxy- or pentoxycarbonyl isomers.

[0019] The total number of carbon atoms in the substituent is indicated by the prefix "C i ~C j " where i and j are numbers from 1 to 7. For example, C1-C4 alkylsulfonyl refers to methylsulfonyl to butylsulfonyl; C2 alkoxyalkyl refers to CHOCH-; C3 alkoxyalkyl refers to, for example, CHCH(OCH3)-, CHOCHCH- or CHCHOCH-; C4 alkoxyalkyl refers to the various isomers of an alkyl group substituted with an alkoxy group containing a total of 4 carbon atoms, examples of which include CHCHCHOCH- and CHCHOCHCH-.

[0020] When a compound is unsubstituted or substituted with a substituent having a subscript indicating the number of said substituents, said substituents are independently selected from the group of defined substituents, e.g., [(R v ) r ], and r is 0, 1, 2, 3, 4, or 5. For example, when r is 0, it indicates that the compound is unsubstituted, and a hydrogen may be present at that position even though it is not mentioned in the definition of the variable. As another example, when r is 2, it indicates that two R independently selected from the group of defined substituents are present. v indicates that the compound is substituted.

[0021] Substituents where the group can be hydrogen, e.g., R 1 or R 2If the substituent is hydrogen, it is recognized that this is equivalent to the group being unsubstituted. When one or more positions of a group are said to be "unsubstituted" or "unsubstituted," a hydrogen atom is attached to occupy any free valence.

[0022] Unless otherwise indicated, a "ring" (e.g., two R groups together with the carbon atoms to which they are attached to form a ring) as a component of Formula 1 is not intended to be limiting. v ) is carbocyclic or heterocyclic. The term "ring member" refers to atoms or other moieties (e.g., C(=O), C(=S), S(O), or S(O)2) that form the backbone of the ring or ring system.

[0023] The terms "carbocyclic," "carbocycle," or "carbocyclic ring system" refer to a ring or ring system in which the atoms forming the ring backbone are selected only from carbon. Unless otherwise specified, a carbocycle can be saturated, partially unsaturated, or fully unsaturated. If a fully unsaturated carbocycle satisfies Hückel's rule, the ring is also called an "aromatic ring." "Saturated carbocyclic" refers to a ring having a backbone made of carbon atoms joined together by single bonds, with the remaining carbon valences being occupied by hydrogen atoms, unless otherwise specified.

[0024] The term "heterocyclic ring," "heterocycle," or "heterocyclic ring system" refers to a ring or ring system in which at least one atom forming the ring backbone is not carbon, e.g., nitrogen, oxygen, or sulfur. Typically, a heterocyclic ring contains up to four nitrogen atoms, up to two oxygen atoms, and up to two sulfur atoms. Unless otherwise specified, a heterocyclic ring can be saturated, partially unsaturated, or fully unsaturated. If a fully unsaturated heterocyclic ring satisfies Hückel's rule, the ring is also referred to as a "heteroaromatic ring" or "heteroaromatic ring." Unless otherwise specified, heterocyclic rings and ring systems can be attached through any available carbon or nitrogen atom by replacement of a hydrogen atom on the carbon or nitrogen.

[0025] "Aromatic" indicates that each of the ring atoms lies essentially in the same plane, has p orbitals perpendicular to the plane of the ring, and (4n+2) pi electrons (n ​​is a positive integer) are associated with the ring according to Hückel's rule. The term "aromatic ring system" means a carbocyclic or heterocyclic ring system in which at least one ring of the ring system is aromatic. The term "aromatic carbocyclic system" means a carbocyclic ring system in which at least one ring of the ring system is aromatic. The term "aromatic heterocyclic system" means a heterocyclic ring system in which at least one ring of the ring system is aromatic. The term "non-aromatic ring system" means a carbocyclic or heterocyclic ring system that may be fully saturated, partially, or fully unsaturated, provided that no ring in the ring system is aromatic. The term "non-aromatic carbocyclic system" means that none of the rings in the ring system are aromatic. The term "non-aromatic heterocyclic system" means that none of the rings in the ring system are aromatic. means a heterocyclic ring system in which none of the rings in the ring system is aromatic.

[0026] The term "optionally substituted" in relation to a heterocycle refers to a group having at least one non-hydrogen substituent that does not abolish the biological activity of the unsubstituted group or the unsubstituted analog. As used herein, the following definitions shall apply unless otherwise indicated. The term "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted" or the term "(un)substituted." Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and each substitution is independent of each other.

[0027] In Equation 1, G is the CONR 5 R 6 If NR 5 R 6 can be (among other things) J. Some non-limiting examples of J are shown in the table in Appendix 1, where each structure is associated with J-#, where # is a number. [ka] [ka] * "a" indicates that the two CH3 moieties are in a cis configuration; "b" indicates that the two CH3 indicates that the moiety is in a trans configuration.

[0028] In Equation 1, G is the CONR 5 R 6 If NR 5 R 6 can also be (among other things) K. Some non-limiting examples of K are shown in the table in Appendix 2, where each structure is associated with K-#, where # is a number. [ka]

[0029] In Formula 1, when G is G-1, some non-limiting examples of G-1 are shown in the table in Appendix 3, where each structure is associated with G-1-#, where # is a number. [ka] [ka] [ka] * "a" indicates that the two H's are in a cis configuration; "b" indicates that the two H's are in a trans configuration, except for the following compounds: for G-1-33a and G-1-33b, "a" indicates that the two Et's are in a cis configuration and "b" indicates that the two Et's are in a trans configuration; for G-1-38a and G-1-38b, "a" indicates that the indicated H and Me are in a cis configuration and "b" indicates that the indicated H and Me are in a trans configuration.

[0030] In Formula 1, when G is G-2, some non-limiting examples of G-2 are shown in the table in Appendix 4, where each structure is associated with G-2-#, where # is a number. [ka] [ka]

[0031] A wide variety of synthetic methods are known in the art that allow for the preparation of aromatic and non-aromatic heterocycles and ring systems; for extensive reviews, see the 8-volume set Comprehensive Heterocyclic Chemistry, A.R. Katrittzky and C.W. Rees editors-in-chief, Pergamon Press, Oxford, 1984, and the 12-volume set Comprehensive Heterocyclic Chemistry II, A.R. Katrittzky, C.W. Rees and E.F.V. Scriven editors-in-chief, Pergamon Press, Oxford, 1996.

[0032] The compounds of the present invention can 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 arrangement of their atoms in space, and include enantiomers, diastereomers, cis-trans isomers (also known as geometric isomers) and atropisomers. Atropisomers are isomers of different structures around a single bond. The rotational barrier results from restricted rotation, where the rotational barrier is high enough to allow isolation of the isomeric species. Those skilled in the art will recognize that one stereoisomer may be more active and / or exhibit beneficial effects when enriched relative to or separated from other stereoisomer(s). Furthermore, those skilled in the art will know how to separate, enrich, and / or selectively prepare said stereoisomers. The compounds of the present invention may exist as a mixture of stereoisomers, individual stereoisomers, or optically active forms.

[0033] For example, when G is G-1 and R7 and R9 together with the carbon atoms to which they are attached form a c-pentyl ring, the compound of Formula 1 can have at least two stereoisomers. The two stereoisomers are represented as Formula 1' and Formula 1", with the chiral center identified by an asterisk (*). For a comprehensive discussion of all aspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994. [ka]

[0034] As another example, G is CONR 5 R 6 If R 5 and R 6 together with the nitrogen atom to which they are attached form a piperidinyl ring having at least one chiral center, and compounds of Formula 1 can have at least two stereoisomers with the chiral center identified with an asterisk (*). [ka]

[0035] Molecular depictions drawn herein follow standard conventions for depicting stereochemistry. To indicate configuration, bonds pointing out of the plane of the drawing toward the viewer are shown as solid wedges, with the wider end of the wedge attached to the atom pointing out of the plane of the drawing toward the viewer. Bonds that are below the plane of the drawing, away from the viewer, are shown as dashed wedges, with the wider end of the wedge attached to the atom away from the viewer. Lines of constant width indicate bonds that are oriented opposite or neutral to the bond indicated by the solid or dashed wedge, and lines of constant width also indicate bonds in molecules or portions of molecules that are not intended to designate a particular configuration.

[0036] The present invention includes racemic mixtures, e.g., equal amounts of the enantiomers of formula 1' and 1", or equal amounts of the enantiomers of formula 1'" and 1"". Additionally, the present invention includes compounds enriched in the enantiomers of formula 1 compared to the racemic mixture. Also included are essentially pure enantiomers of compounds of formula 1, e.g., formula 1' or formula 1".

[0037] When an enantiomer is enriched, one enantiomer is present in greater amount than the other, and the degree of enrichment can be defined by the formula enantiomeric excess ("ee"), which is defined as (2x-1)100%, where x is the mole fraction of the major enantiomer in the mixture (e.g., 20% ee corresponds to a 60:40 ratio of enantiomers).

[0038] Preferably, the compositions of the present invention have an enantiomeric excess of at least 50%, more preferably at least 75%, even more preferably at least 90%, and most preferably at least 94% of the more active isomer. Of particular note are enantiomerically pure embodiments of the more active isomer.

[0039] The compounds of Formula 1 may contain additional chiral centers, for example, R vSubstituents and other molecular components such as may themselves contain chiral centers. The present invention includes racemic mixtures as well as enriched, essentially pure stereoconfigurations at these additional chiral centers.

[0040] The compounds of the present invention can exist as one or more conformers due to any restricted bond rotation in Formula 1. The present invention includes mixtures of conformers. Additionally, the present invention includes compounds enriched in one conformer relative to other conformers.

[0041] Compounds of Formula 1 typically exist in multiple forms, and thus Formula 1 encompasses all crystalline and amorphous forms of the compounds they represent. Amorphous forms include solid embodiments, such as waxes and rubbers, as well as liquid embodiments, such as solutions and melts. Crystalline forms include embodiments that exhibit a substantially single crystal type and embodiments that exhibit a mixture of polymorphs (i.e., multiple crystalline types). The term "polymorph" refers to a specific crystalline form of a compound that can crystallize in various crystalline forms, which have different molecular arrangements and / or conformations within the crystal lattice. Polymorphs can have the same chemical composition, but they can also differ in composition due to the presence or absence of co-crystallized water or other molecules that can be weakly or strongly bound in the lattice. Polymorphs can differ in chemical, physical, and biological properties, such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspendability, dissolution rate, and biological availability. As will be appreciated by those skilled in the art, polymorphs of the compound of Formula 1 may exhibit advantageous effects (e.g., suitability in preparing useful formulations, improved biological performance) compared to other polymorphs or mixtures of polymorphs of the same compound of Formula 1. The preparation and isolation of specific polymorphs of the compound of Formula 1 can be achieved by methods known to those skilled in the art, such as, 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.

[0042] Those skilled in the art will recognize that not all nitrogen-containing heterocycles can form N-oxides, since nitrogen requires an available lone pair of electrons for oxidation to an oxide. Those skilled in the art will recognize those nitrogen-containing heterocycles that can form N-oxides. Those skilled in the art will also recognize that tertiary amines can form N-oxides. N-oxides and tertiary amines of heterocycles can be used to form N-oxides. Synthetic methods for the preparation of primary amines include the oxidation of heterocycles and tertiary amines with organic peroxyacids, such as peracetic acid and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides, such as t-butyl hydroperoxide, sodium perborate, and dioxiranes, such as dimethyldioxirane, and are well known to those skilled in the art. These methods for preparing N-oxides have been widely described and reviewed in the literature, see, for example, T. L. Gilchrist, Comprehensive Organic Synthesis, vol. 7, pp. 748-750 (S. V. Ley, Ed., Pergamon Press); M. Tisler and B. Stanovnik, Comprehensive Heterocyclic Chemistry, vol.3, pp.18-20 (AJ Boulton and A. McKillop, Eds., Pergamon Press); MRGrimmett and BRTKeene, Advances in Heterocyclic Chemistry, vol. 43, pp. 149-161 (ARKatritzky, Ed., Academic Press); AJ Boulton, Eds., Academic Press); and GWHCheeseman and ESGWerstiuk, Advances in Heterocyclic Chemistry, vol. 22, pp. 390-392 (ARKatritzky and AJ Boulton, Eds., Academic Press).

[0043] Those skilled in the art will recognize that salts of compounds share the biological utility of their corresponding non-salt forms because salts are in equilibrium with their corresponding non-salt forms under environmental and physiological conditions. Thus, a wide variety of salts of compounds of Formula 1 are useful for controlling undesirable vegetation (i.e., suitable for agriculture). Salts of compounds of Formula 1 include acid addition salts with inorganic or organic acids such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid, or valeric acid. When compounds of Formula 1 contain an acidic moiety such as a carboxylic acid or phenol, salts also include those formed with organic or inorganic bases such as pyridine, triethylamine, or ammonia, or amides, hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium, or barium. Thus, the present invention includes compounds selected from Formula 1, their N-oxides, and agriculturally suitable salts.

[0044] Embodiments of the invention described in the Summary of the Disclosure include those in which the compound of Formula 1 is described in any of the following embodiments:

[0045] Embodiment 1. Compounds of Formula 1, their stereoisomers, N-oxides, and salts, agricultural compositions containing them, and their use as herbicides, as described in the Summary of the Disclosure.

[0046] Embodiment 1a. G is a CONR 5 R 6 2. The compound of embodiment 1, wherein

[0047] Embodiment 1b. The compound of embodiment 1, wherein G is G-1.

[0048] Embodiment 1c. The compound of embodiment 1, wherein G is G-2.

[0049] Embodiment 1d. The compound of embodiment 1, wherein G is G-3.

[0050] Embodiment 1e. The compound of embodiment 1, wherein G is G-4.

[0051] Embodiment 1f. The compound of embodiment 1, wherein G is G-5.

[0052] Embodiment 2. R 1 A compound according to Formula 1 or any one of the previous embodiments, wherein is H, C1-C7 alkyl, halogen, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, or C1-C7 haloalkyl.

[0053] Embodiment 2a. R 1 The compound of embodiment 2, wherein is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl.

[0054] Embodiment 2b. R 1 Compounds according to embodiment 2a, wherein is H, C1-C3 alkyl, halogen, or C3-C4 cycloalkyl.

[0055] Embodiment 2c. R 1Compounds according to embodiment 2b, wherein is H, Me, halogen, or cyclopropyl.

[0056] Embodiment 2d. R 1 Compounds according to embodiment 2c, wherein is H, Me, F, Cl, Br, or cyclopropyl.

[0057] Embodiment 2e. R 1 Compounds according to embodiment 2d, wherein is Me or Cl.

[0058] Embodiment 2f. R 1 The compound of embodiment 2e, wherein is Me.

[0059] Embodiment 2g. R 1 The compound of embodiment 2e, wherein is Cl.

[0060] Embodiment 3. R 2 is H, C1-C7 alkyl, halogen, —CN, C1-C7 haloalkyl, C1-C7 alkoxy, C3-C7 cycloalkyl, or C1-C5 alkylthio.

[0061] Embodiment 3a. R 2 is H, C1-C7 alkyl, C3-C6 cycloalkyl, halogen, or CN.

[0062] Embodiment 3b. R 2 Compounds according to embodiment 3a, wherein is H, Me, F, Cl, or CN.

[0063] Embodiment 3c. R 2 Compounds according to embodiment 3b, wherein is H, Me, or F.

[0064] Embodiment 3d. R 2 is H.

[0065] Embodiment 3e. R 2is F.

[0066] Embodiment 3f. R 2 The compound of embodiment 3c, wherein is Me.

[0067] Embodiment 4. R 3 is H, C1-C7 alkyl, halogen, —CN, C2-C6 alkenyl, C3-C7 alkynyl, C3-C7 cycloalkyl, C2-C3 cyanoalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C3-C7 haloalkynyl, C2-C7 alkoxyalkyl, C1-C7 alkoxy, C1-C5 alkylthio, C2-C3 alkoxycarbonyl, or C2-C7 haloalkoxyalkyl.

[0068] Embodiment 4a. R 3 H, C1-C7 alkyl, halogen, CN, C1-C7 alkoxy The compound of embodiment 4, wherein the aryloxy group is C1-C7 haloalkyl.

[0069] Embodiment 4b. R 3 Compounds according to embodiment 4a, wherein is H, Me, F, Cl, -CN, OMe, or CF3.

[0070] Embodiment 4c. R 3 Compounds according to embodiment 4b, wherein is Me or F.

[0071] Embodiment 4d. R 3 The compound of embodiment 4c, wherein is Me.

[0072] Embodiment 4f. R 3 The compound of embodiment 4c, wherein is Cl.

[0073] Embodiment 4g. R 3 is F.

[0074] Embodiment 5. R 4But H, C(=O)R 19 , C(=S)R 19 , C(=O)OR 19 , C(=O)SR 19 , S(O)2R 19 , C(=O)NR 19 R 20 , S(O)NR 19 R 20 , -S(OH)NR 19 R 20 , CH2OC(=O)OR 19 , CH2OC(=O)NR 19 R 20 or CH2OC(=O)R 19 The compound of formula 1 or any one of the previous embodiments, wherein:

[0075] Embodiment 5a. R 4 But H, C(=O)R 19 , CO2R 19 , C(=O)SR 19 , S(O)2R 19 or CH2OCOR 19 6. The compound of embodiment 5, wherein

[0076] Embodiment 5b. R 4 Compounds according to embodiment 5a, wherein is H, SO2CF3, SO2CH3, CO2Me, COMe, CHOCO-t-Bu, CHOCO-n-Bu, CHOCO-c-hexyl, CHOCO-c-pentyl, CHOCOCH2CH3, COMe, CHOCOPh, CHOCO-i-Bu, CHOCOMe, CHOCO-sec-Bu, or COSMe.

[0077] Embodiment 5c. R 4 But, H, CH2OCOR 19 or S(O)2R 19 The compound of embodiment 5a, wherein

[0078] Embodiment 5d. R 4 The compound of embodiment 5c, wherein is H, CH2OCO-t-Bu, or SO2CF3.

[0079] Embodiment 6. R 5 is H, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C3-C7 alkenylalkyl, C3-C7 alkynylalkyl, C2-C3 cyanoalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy, C2-C7 alkoxyalkyl, or C4-C7 alkylcycloalkyl.

[0080] Embodiment 6a. R 5 is H, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C3-C7 alkenylalkyl, C3-C7 alkynylalkyl, or C2-C3 cyanoalkyl.

[0081] Embodiment 6b. R 5 is H, C1-C3 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C3-C6 cycloalkyl, C4-C7 cycloalkylalkyl, C3-C6 alkenylalkyl, C3-C6 alkynylalkyl or C2-C3 cyanoalkyl A compound according to embodiment 6a.

[0082] Embodiment 6c. R 5 Compounds according to embodiment 6b, wherein is H, methyl, ethyl, propyl, cyanomethyl, CH2CCH, or c-propylmethyl.

[0083] Embodiment 6d. R 5 A compound according to embodiment 6c, wherein is H or methyl.

[0084] Embodiment 6e. R 5 The compound of embodiment 6c, wherein is methyl.

[0085] Embodiment 7. R 6is H, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C3-C7 alkenylalkyl, C3-C7 alkynylalkyl, C2-C3 cyanoalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy, C2-C7 alkoxyalkyl, or C4-C7 alkylcycloalkyl.

[0086] Embodiment 7a. R 6 is H, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C3-C7 alkenylalkyl, C3-C7 alkynylalkyl, or C2-C3 cyanoalkyl.

[0087] Embodiment 7b. R 6 Compounds according to embodiment 7a, wherein is H, C1-C3 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C3-C6 cycloalkyl, C4-C7 cycloalkylalkyl, C3-C6 alkenylalkyl, C3-C6 alkynylalkyl, or C2-C3 cyanoalkyl.

[0088] Embodiment 7c. R 6 Compounds according to embodiment 7b, wherein is H, methyl, ethyl, propyl, cyanomethyl, CH2CCH, or c-propylmethyl.

[0089] Embodiment 7d. R 6 A compound according to embodiment 7c, wherein is H or methyl.

[0090] Embodiment 7e. R 6 The compound according to embodiment 7e, wherein is methyl.

[0091] Embodiment 8. R 5 and R 6are taken together with the nitrogen atom to which they are attached to form a 3- to 7-membered ring containing carbon atoms and optionally 1-3 oxygen, sulfur, or nitrogen atom ring members, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and sulfur atom ring members are selected from S, S(O), or S(O)2, and said ring is optionally substituted independently with up to 5 substituents (R v ) r and r is the number of substituents.

[0092] Embodiment 8a. The compound of embodiment 8, wherein the 3- to 7-membered ring is a 5-membered ring.

[0093] Embodiment 8b. A compound according to embodiment 8a, wherein the five-membered ring is unsubstituted.

[0094] Embodiment 8c. A compound according to embodiment 8a, wherein the five-membered ring is substituted with at least one halogen, OMe, SMe, or methyl.

[0095] Embodiment 8d. A compound according to any one of Embodiments 8a-8c, wherein the five-membered ring is pyrrolidinyl or oxazolidinyl.

[0096] Embodiment 8e. The compound of embodiment 8, wherein the 3- to 7-membered ring is a 6-membered ring.

[0097] Embodiment 8f. The compound of embodiment 8e, wherein the six-membered ring is unsubstituted.

[0098] Embodiment 8g. A compound according to embodiment 8e, wherein the 6-membered ring is substituted with at least one halogen, OMe, SMe, or methyl.

[0099] Embodiment 8h. A compound according to any one of embodiments 8e-8g, wherein the six-membered ring is morpholinyl, thiomorpholinyl, piperidinyl, or piperazinyl.

[0100] Embodiment 8i. The compound of embodiment 8, wherein the 3- to 7-membered ring is a 4-membered ring.

[0101] Embodiment 8j The compound of embodiment 8i, wherein the four-membered ring is unsubstituted.

[0102] Embodiment 8k. A compound according to embodiment 8i, wherein the four-membered ring is substituted with at least one halogen, OMe, SMe, or methyl.

[0103] Embodiment 81. A compound according to any one of embodiments 8i to 8k, wherein the four-membered ring is azetidinyl.

[0104] Embodiment 8m. The compound of embodiment 8, wherein the 3- to 7-membered ring is a 7-membered ring.

[0105] Embodiment 8n The compound of embodiment 8m, wherein the seven-membered ring is unsubstituted.

[0106] Embodiment 8o. A compound according to embodiment 8m, wherein the seven-membered ring is substituted with at least one halogen, OMe, SMe, or methyl.

[0107] Embodiment 8p. The compound of any one of Embodiments 8m through 8o, wherein the seven-membered ring is azepanyl or 1,4-oxazepanyl.

[0108] Embodiment 9. R v are independently selected from the group consisting of H, halogen, cyano, nitro, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, and C1-C4 haloalkoxy.

[0109] Embodiment 9a. R v is independently selected from the group consisting of H, halogen, methyl, ethyl, propyl, c-propylmethyl, propargyl, OMe, or cyano.

[0110] Embodiment 9b. R v The compound according to embodiment 9a, wherein is methyl.

[0111] Embodiment 9b1. R v The compound of embodiment 9a, wherein is OMe.

[0112] Embodiment 9b2. R v The compound of embodiment 9a, wherein is H.

[0113] Embodiment 9c. Two R v are bonded to the same carbon atom or to two adjacent carbon atoms, and the two R v together with the carbon atom or atoms to which they are attached form a 3- to 7-membered ring containing carbon atoms and optionally 1 to 3 oxygen, sulfur, or nitrogen atoms as ring members, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C( ═S), the ring member at the sulfur atom is selected from S, S(O), or S(O), and said ring is unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, and C1-C4 haloalkoxy.

[0114] Embodiment 9d. Two R v are bonded to the same carbon atom, and the two R v taken together with the carbon atoms to which they are attached form a 3- to 7-membered ring.

[0115] Embodiment 9e. The compound of embodiment 9d, wherein the 3- to 7-membered ring is a 5-membered ring.

[0116] Embodiment 9f. A compound according to embodiment 9e, wherein the 5-membered ring is 1,3-dioxolanyl or c-pentyl.

[0117] Embodiment 9g The compound of embodiment 9d, wherein the 3- to 7-membered ring is a 6-membered ring.

[0118] Embodiment 9h The compound of embodiment 9g, wherein the six-membered ring is 1,3-dioxanyl or c-hexyl.

[0119] Embodiment 9i. Two R v are bonded to two adjacent carbon atoms, and the two R v taken together with the carbon atoms to which they are attached form a 3- to 7-membered ring.

[0120] Embodiment 9j The compound of embodiment 9i, wherein the 3- to 7-membered ring is a 5-membered ring.

[0121] Embodiment 9k A compound according to Embodiment 9j, wherein the 5-membered ring is 1,3-dioxolanyl or c-pentyl.

[0122] Embodiment 91. The compound of embodiment 9i, wherein the 3- to 7-membered ring is a 6-membered ring.

[0123] Embodiment 9m The compound of embodiment 9l wherein the six-membered ring is 1,3-dioxanyl or c-hexyl.

[0124] Embodiment 10. R 7 A compound according to Formula 1 or any one of the previous embodiments, wherein is H, C1-C7 alkyl, halogen, —CN, C1-C7 haloalkyl, or C1-C7 alkoxy.

[0125] Embodiment 10a. R 7 The compound of embodiment 10, wherein is H, methyl, F, or Cl.

[0126] Embodiment 10b. R 7 The compound of embodiment 10a, wherein is H.

[0127] Embodiment 11. R 8 A compound according to Formula 1 or any one of the previous embodiments, wherein is H or C1-C7 alkyl.

[0128] Embodiment 11a. R8 is H or Me.

[0129] Embodiment 11b. R 8 The compound of embodiment 11a, wherein is H.

[0130] Embodiment 12. R 7 and R 8 may be taken together to form a 3-7 membered ring containing carbon atoms and optionally 1-2 oxygen, sulfur or nitrogen atoms as ring members.

[0131] Embodiment 12a. The compound of embodiment 12, wherein the 3- to 7-membered ring is a 5-membered ring.

[0132] Embodiment 12b. The compound of embodiment 12, wherein the 3- to 7-membered ring is a 6-membered ring.

[0133] Embodiment 13. R 9 is H, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy; C2-C7 alkoxyalkyl or C4-C7 alkylcycloalkyl.

[0134] Embodiment 13a. R 9 The compound of embodiment 13, wherein is H, C1-C7 alkyl, C1-C7 haloalkyl, or C2-C7 alkoxyalkyl.

[0135] Embodiment 13b. R 9 Compounds according to embodiment 13a, wherein is methyl, ethyl, t-butyl, chloromethyl, or methoxymethyl.

[0136] Embodiment 15. R 7 and R 9taken together form a fused 3-7 membered ring comprising carbon atoms and optionally 1-2 oxygen, sulfur, or nitrogen atom ring members, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, and C1-C4 haloalkoxy.

[0137] Embodiment 15a. The compound of embodiment 15, wherein the 3- to 7-membered ring is a 5- or 6-membered ring.

[0138] Embodiment 15b. A compound according to embodiment 15a, wherein the five-membered ring is c-pentyl.

[0139] Embodiment 15c. The compound of embodiment 15, wherein the 3- to 7-membered ring is a 6-membered ring.

[0140] Embodiment 15d. A compound according to embodiment 15c, wherein the six-membered ring is hexyl or tetrahydropyran.

[0141] Embodiment 15e. The compound of any one of Embodiments 15-15d, wherein the ring is unsubstituted or substituted with at least one substituent independently selected from the group consisting of H, halogen, or C1-C4 alkyl.

[0142] Embodiment 15f The compound of embodiment 15e, wherein the ring is unsubstituted.

[0143] Embodiment 16. R 10 A compound according to Formula 1 or any one of the previous embodiments, wherein is H or C1-C7 alkyl.

[0144] Embodiment 16a. R 10 is methyl or ethyl.

[0145] Embodiment 16b. R 10is H.

[0146] Embodiment 17. R 9 and R 10 are taken together with the carbon atoms to which they are attached to form a 3- to 7-membered ring containing carbon atoms and optionally 1-2 oxygen, sulfur, or nitrogen atoms as ring members, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and sulfur atom ring members are selected from S, S(O), or S(O)2, and said ring is optionally substituted independently with up to 5 substituents (R v ) r where r is the number of substituents; or The Two R's v are bonded to the same carbon atom or to two adjacent carbon atoms, the two R v are taken together with the carbon atom or atoms to which they are attached to form a 3-7 membered ring containing carbon atoms and optionally 1-2 oxygen, sulfur or nitrogen atom ring members, wherein the up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring members are selected from S, S(O) or S(O)2.

[0147] Embodiment 17a. The compound of embodiment 17, wherein the 3- to 7-membered ring is a 5- or 6-membered ring.

[0148] Embodiment 17b. A compound according to embodiment 17a, wherein the five-membered ring is cyclopentane.

[0149] Embodiment 17c. The compound of embodiment 17, wherein the 3- to 7-membered ring is a 6-membered ring.

[0150] Embodiment 17d. A compound according to embodiment 17c, wherein the 6-membered ring is cyclohexane, tetrahydro-2H-pyran, or tetrahydro-2H-thiopyran.

[0151] Embodiment 17e. A compound according to embodiment 17d, wherein the six-membered ring is cyclohexane.

[0152] Embodiment 17f. The compound of embodiment 17, wherein the 3- to 7-membered ring is a 4-membered ring.

[0153] Embodiment 17f. The compound of embodiment 17, wherein the 3- to 7-membered ring is a 7-membered ring.

[0154] Embodiment 18. Q is O, S, CR 11 R 12 or NR 13 The compound of formula 1 or any one of the previous embodiments, wherein:

[0155] Embodiment 18a. The compound of embodiment 18, wherein Q is O or S.

[0156] Embodiment 18b. The compound of embodiment 18, wherein Q is O.

[0157] Embodiment 18c. Q is CR 11 R 12 19. The compound of embodiment 18, wherein

[0158] Embodiment 18d. Q is NR 13 19. The compound of embodiment 18, wherein

[0159] Embodiment 18e. Q is O, S or CR 11 R 12 19. The compound of embodiment 18, wherein

[0160] Embodiment 18f. Q is NR 13 The compound of embodiment 18, wherein

[0161] Embodiment 19. R 11 and R 12taken together with the carbon atoms to which they are attached form a fused 3-7 membered ring containing carbon atoms and optionally 1-2 oxygen, sulfur or nitrogen atoms as ring members, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy.

[0162] Embodiment 19a. The compound of embodiment 19, wherein the 3- to 7-membered ring is a 5-membered ring.

[0163] Embodiment 19b. A compound according to embodiment 19a, wherein the five-membered ring is cyclopentane.

[0164] Embodiment 19c. The compound of embodiment 19, wherein the 3- to 7-membered ring is a 6-membered ring.

[0165] Embodiment 19d. A compound according to embodiment 19c, wherein the six-membered ring is cyclohexane.

[0166] Embodiment 19e. A compound of embodiment 19, wherein the ring is an unsubstituted 5- or 6-membered ring.

[0167] Embodiment 20. A compound according to Formula 1 or any one of the previous embodiments, wherein r is 0, 1, 2, or 3.

[0168] Embodiment 20a. The compound of embodiment 20, wherein r is 0.

[0169] Embodiment 20b. A compound of embodiment 20, wherein r is 1 or 2.

[0170] Embodiment 20c. The compound of embodiment 20, wherein r is 2.

[0171] Embodiment 20d. The compound of embodiment 20, wherein r is 3.

[0172] Embodiment 20e. The compound of embodiment 20, wherein r is 1.

[0173] Embodiment 21. R 13 is H, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy; C2-C7 alkoxyalkyl or C4-C7 alkylcycloalkyl.

[0174] Embodiment 21a. R 13 is H or C1-C7 alkyl.

[0175] Embodiment 21b. R 13 Compounds according to embodiment 21a, wherein is Me or Et.

[0176] Embodiment 21c. R 13 The compound of embodiment 21b, wherein is Me.

[0177] Embodiment 21d. R 13 The compound of embodiment 21d, wherein is Et.

[0178] Embodiment 22. R 14 is H, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C7 haloalkyl, C1-C7 thioalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy; C2-C7 alkoxyalkyl or C4-C7 alkylcycloalkyl.

[0179] Embodiment 22a. R 14is H, C1-C4 alkyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C4 haloalkyl, C1-C4 haloalkyl, or C1-C7 alkoxy.

[0180] Embodiment 22b. R 14 The compound according to embodiment 22a, wherein is C1-C4 alkyl.

[0181] Embodiment 22c. R 14 The compound of embodiment 22b, wherein is Me.

[0182] Embodiment 22d. R 14 The compound of embodiment 22b, wherein is Et.

[0183] Embodiment 22e. R 14 The compound of embodiment 22b, wherein is CH2CF3.

[0184] Embodiment 23. R 15 A compound according to Formula 1 or any one of the previous embodiments, wherein is H, C1-C7 alkyl, halogen, C1-C7 haloalkyl, or C1-C7 alkoxy.

[0185] Embodiment 23a. R 15 is H, C1-C3 alkyl, or C1-C3 alkoxy.

[0186] Embodiment 23b. R 15 Compounds according to embodiment 23a, wherein is H or OMe.

[0187] Embodiment 23c. R 15 is H.

[0188] Embodiment 23d. R 15 The compound of embodiment 23b, wherein is OMe.

[0189] Embodiment 24. R16 A compound according to Formula 1 or any one of the previous embodiments, wherein is H, cyano, C1-C7 alkyl, halogen, C1-C4 alkylthio, C1-C7 haloalkyl, or C1-C7 alkoxy.

[0190] Embodiment 24a. R 16 Compounds according to embodiment 24, wherein is H, cyano, C1-C4 alkyl, halogen, C1-C4 alkylthio, C1-C4 haloalkyl, or C1-C4 alkoxy.

[0191] Embodiment 24b. R 16 Compounds according to embodiment 24a, wherein is H or C1-C4 alkyl.

[0192] Embodiment 24c. R 16 Compounds according to embodiment 24a, wherein is H, cyano, methyl, ethyl, propyl, i-propyl, halogen, SMe, CF3, or OMe.

[0193] Embodiment 24d. R 16 Compounds according to embodiment 24c, wherein is H, cyano, methyl, F, SMe, CF3, or OMe.

[0194] Embodiment 25. R 17 is H, C1-C7 alkyl, halogen, —CN, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C2-C3 cyanoalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C3-C7 haloalkynyl, C2-C7 alkoxyalkyl, C1-C7 alkoxy, C1-C5 alkylthio, C2-C3 alkoxycarbonyl, or C2-C7 haloalkoxyalkyl.

[0195] Embodiment 25a. R 17 The compound of embodiment 25, wherein is H, C1-C4 alkyl, halogen, or C1-C4 alkoxy.

[0196] Embodiment 25b. R 17Compounds according to embodiment 25a, wherein is H, methyl, Cl, or OMe.

[0197] Embodiment 26. R 18 A compound according to Formula 1 or any one of the previous embodiments, wherein is H, C1-C7 alkyl, halogen, C1-C7 haloalkyl, or C1-C7 alkoxy.

[0198] Embodiment 26a. R 18 is H or C1-C3 alkoxy.

[0199] Embodiment 26b. R 18 The compound of embodiment 26, wherein is H, methyl, or OMe.

[0200] Embodiment 26c. R 18 The compound of embodiment 26b, wherein is H.

[0201] Embodiment 26d. R 18 The compound of embodiment 26b, wherein is OMe.

[0202] Embodiment 27. R 19 is C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C3 cyanoalkyl, C1-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl, C3-C7 alkylthioalkyl, C1-C7 alkoxy; C2-C7 alkoxyalkyl or C4-C7 alkylcycloalkyl.

[0203] Embodiment 27a. R 19 The compound of embodiment 27, wherein is C1-C7 alkyl or C1-C7 haloalkyl.

[0204] Embodiment 27b. R 19 The compound according to embodiment 27a, wherein is C1-C7 alkyl.

[0205] Embodiment 27c. R 19 Compounds according to embodiment 27b, wherein is methyl, ethyl, i-propyl, t-butyl, n-butyl, s-butyl, i-butyl, c-pentyl, or c-hexyl.

[0206] Embodiment 27d. R 19 The compound according to embodiment 27c, wherein is t-butyl.

[0207] Embodiment 27e. R 19 Compounds according to embodiment 27a, wherein is C1-C3 haloalkyl.

[0208] Embodiment 27f. R 19 The compound of embodiment 27e, wherein is CF3.

[0209] Embodiment 28. R f A compound according to Formula 1 or any one of the previous embodiments, wherein is C1-C7 alkyl or C1-C7 haloalkyl.

[0210] Embodiment 28a. R f is C1-C3 haloalkyl.

[0211] Embodiment 28b. R f The compound of embodiment 28a, wherein is CF3.

[0212] Embodiments of the invention, including embodiments 1-28b above and any other embodiments described herein, can be combined in any manner, and the descriptions of variables in the embodiments relate not only to compounds of Formula 1, but also to starting compounds and intermediate compounds useful for preparing compounds of Formula 1. Additionally, embodiments of the invention, including embodiments 1-28b above and other embodiments described herein, and any combination thereof, relate to compositions and methods of the invention.

[0213] Combinations of embodiments 1-28b are exemplified by the following:

[0214] Embodiment PA. A compound of Formula 1 as described in the Summary of the Disclosure wherein Q is O, S, or CR 11 R 12 A compound.

[0215] Embodiment A. A compound of Formula 1 as described in the Summary of the Disclosure, G, CONR 5 R 6 and; R 1 is H, C1-C7 alkyl, halogen, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, or C1-C7 haloalkyl; R 2 is H, C1-C7 alkyl, C3-C6 cycloalkyl, halogen, or CN; R 3 is H, C1-C7 alkyl, halogen, CN, C1-C7 alkoxy or C1-C7 haloalkyl; R 4 But H, C(=O)R 19 , CO2R 19 , C(=O)SR 19 , S(O)2R 19 or CH2OCOR 19 and; R 5 is H, C1-C3 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C3-C6 cycloalkyl, C4-C7 cycloalkylalkyl, C3-C6 alkenylalkyl, C3-C6 alkynylalkyl or C2-C3 cyanoalkyl; R 6 is H, C1-C3 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C3-C6 cycloalkyl, C4-C7 cycloalkylalkyl, C3-C6 alkenylalkyl, C3-C6 alkynylalkyl or C2-C3 cyanoalkyl; R f is a C1-C3 haloalkyl.

[0216] Embodiment B. R 1is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl; R 2 is H, Me or F; R 3 is H, Me, F, Cl, CN, OMe or CF3; R 4 is H, SO2CF3, SO2CH3, CO2Me, COMe, CHOCO-t-Bu, CHOCO-n-Bu, CHOCO-c-hexyl, CHOCO-c-pentyl, CHOCOCH2CH3, COMe, CHOCOPh, CHOCO-i-Bu, CHOCOMe, CHOCO-sec-Bu or COSMe; R 5 is H, methyl, ethyl, propyl, cyanomethyl, CHCCH or c-propylmethyl; R 6 is H, methyl, ethyl, propyl, cyanomethyl, CHCCH or c-propylmethyl; R f The compound according to embodiment A, wherein is CF3.

[0217] Embodiment C. R 1 is Me or Cl; R 3 But Me; R 4 is H, CH2OCO-t-Bu or SO2CF3; R 5 is methyl; R 6 A compound according to embodiment B, wherein is methyl.

[0218] Embodiment D. A compound of Formula 1 as described in the Summary of the Disclosure, Q is CONR 5 R 6 and; R 1 is H, C1-C7 alkyl, halogen, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, or C1-C7 haloalkyl; R 2is H, C1-C7 alkyl, C3-C6 cycloalkyl, halogen, or CN; R 3 is H, C1-C7 alkyl, halogen, CN, C1-C7 alkoxy or C1-C7 haloalkyl; R 4 But H, C(=O)R 19 , CO2R 19 , C(=O)SR 19 , S(O)2R 19 or CH2OCOR 19 and; R 5 and R 6 are taken together with the nitrogen atom to which they are attached to form a 3- to 7-membered ring containing carbon atoms and optionally 1-3 oxygen, sulfur, or nitrogen atom ring members, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and sulfur atom ring members are selected from S, S(O), or S(O)2, and said ring is optionally substituted independently with up to 5 substituents (R v ) r where r is the number of substituents; R v is independently selected from the group consisting of H, methyl, ethyl, propyl, c-propylmethyl, propargyl, or cyanomethyl; A compound wherein r is 1 or 2.

[0219] Embodiment E. R 1 is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl; R 2 is H, Me or F; R 3 is H, Me, F, Cl, CN, OMe or CF3; R 4is H, SO2CF3, SO2CH3, CO2Me, COMe, CHOCO-t-Bu, CHOCO-n-Bu, CHOCO-c-hexyl, CHOCO-c-pentyl, CHOCOCH2CH3, COMe, CHOCOPh, CHOCO-i-Bu, CHOCOMe, CHOCO-sec-Bu or COSMe; R 5 and R 6 together with the nitrogen atom to which they are attached form a 3- to 7-membered ring, and the ring is a 5-membered ring; R f The compound of embodiment D, wherein is CF3.

[0220] Embodiment F. R 1 is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl; R 2 is H, Me or F; R 3 is H, Me, F, Cl, CN, OMe or CF3; R 4 is H, SO2CF3, SO2CH3, CO2Me, COMe, CHOCO-t-Bu, CHOCO-n-Bu, CHOCO-c-hexyl, CHOCO-c-pentyl, CHOCOCH2CH3, COMe, CHOCOPh, CHOCO-i-Bu, CHOCOMe, CHOCO-sec-Bu or COSMe; R 5 and R 6 together with the nitrogen atom to which they are attached form a 3- to 7-membered ring, and the ring is a 6-membered ring; R f The compound of embodiment D, wherein is CF3.

[0221] Embodiment A1. A compound of Formula 1 as described in the Summary of the Disclosure, G is G-1; R 1 is H, C1-C7 alkyl, halogen, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, or C1-C7 haloalkyl; R 2 is H, C1-C7 alkyl, C3-C6 cycloalkyl, halogen, or CN; R 3 is H, C1-C7 alkyl, halogen, CN, C1-C7 alkoxy or C1-C7 haloalkyl; R 4 But H, C(=O)R 19 , CO2R 19 , C(=O)SR 19 , S(O)2R 19 or CH2OCOR 19 and; R f is a C1-C3 haloalkyl.

[0222] Embodiment B1. R 1 is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl; R 2 is H, Me or F; R 3 is H, Me, F, Cl, CN, OMe or CF3; R 4 is H, SO2CF3, SO2CH3, CO2Me, COMe, CHOCO-t-Bu, CHOCO-n-Bu, CHOCO-c-hexyl, CHOCO-c-pentyl, CHOCOCH2CH3, COMe, CHOCOPh, CHOCO-i-Bu, CHOCOMe, CHOCO-sec-Bu or COSMe; R 7 is H, C1-C7 alkyl, halogen, —CN, C1-C7 haloalkyl, or C1-C7 alkoxy; R 8 is H or C1-C7 alkyl; R 9 is H, C1-C7 alkyl, C1-C7 haloalkyl, or C2-C7 alkoxyalkyl; R 10 is H or C1-C7 alkyl; R f The compound according to embodiment A1, wherein is CF3.

[0223] Embodiment C1. R 1 is Me or Cl; R 3 But Me; R 4 is H, CH2OCO-t-Bu or SO2CF3; R 7 But H; R 8 But H; R 9 is methyl, ethyl, t-butyl, chloromethyl, or methoxymethyl; R 10 A compound according to embodiment B1, wherein is methyl or ethyl.

[0224] Embodiment D1. R 7 and R 9 taken together form a fused 3-7 membered ring containing carbon atoms and optionally 1-2 oxygen, sulfur or nitrogen atom ring members, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy; R 8 But H; R 10 A compound according to embodiment A1, wherein is H.

[0225] Embodiment E1. R 1 is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl; R 2 is H, Me or F; R 3 is H, Me, F, Cl, CN, OMe or CF3; R 4is H, SO2CF3, SO2CH3, CO2Me, COMe, CHOCO-t-Bu, CHOCO-n-Bu, CHOCO-c-hexyl, CHOCO-c-pentyl, CHOCOCH2CH3, COMe, CHOCOPh, CHOCO-i-Bu, CHOCOMe, CHOCO-sec-Bu or COSMe; R 7 and R 9 taken together form a fused 3- to 7-membered ring, which is a 5- or 6-membered ring.

[0226] Embodiment F1.R 7 and R 9 are taken together to form a 5- or 6-membered ring of c-pentyl, c-hexyl, or tetrahydropyran, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of H, halogen, or C1-C4 alkyl.

[0227] Embodiment G1. R 9 and R 10 are taken together with the carbon atoms to which they are attached to form a 3- to 7-membered ring containing carbon atoms and optionally 1-2 oxygen, sulfur, or nitrogen atoms as ring members, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and sulfur atom ring members are selected from S, S(O), or S(O)2, and said ring is optionally substituted independently with up to 5 substituents (R v ) r where r is the number of substituents; or The Two R's v are bonded to the same carbon atom or to two adjacent carbon atoms, the two R v together with the carbon atom or atoms to which they are attached form a 3- to 7-membered ring containing carbon atoms and optionally 1-2 oxygen, sulfur, or nitrogen atom ring members, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and sulfur atom ring members are selected from S, S(O), or S(O)2; R 7 But H; R 8 A compound according to embodiment A1, wherein is H.

[0228] Embodiment H1. R 1 is H, C1-C3 alkyl, halogen or C3-C4 cycloalkyl R 2 is H, Me or F; R 3 is H, Me, F, Cl, CN, OMe or CF3; R 4 is H, SO2CF3, SO2CH3, CO2Me, COMe, CHOCO-t-Bu, CHOCO-n-Bu, CHOCO-c-hexyl, CHOCO-c-pentyl, CHOCOCH2CH3, COMe, CHOCOPh, CHOCO-i-Bu, CHOCOMe, CHOCO-sec-Bu or COSMe; R 9 and R 10 together with the carbon atoms to which they are attached form a 3- to 7-membered ring, and the ring is a 5- or 6-membered ring; R v is independently selected from the group consisting of H, methyl, ethyl, propyl, c-propylmethyl, propargyl, or cyanomethyl; A compound according to embodiment G1, wherein r is 1 or 2.

[0229] Embodiment I1. R 9 and R 10 are taken together with the carbon atoms to which they are attached to form a 3- to 7-membered ring, which is a 5- or 6-membered ring of cyclopentane, cyclohexane, tetrahydro-2H-pyran, or tetrahydro-2H-thiopyran.

[0230] Embodiment A2. A compound of Formula 1 as described in the Summary of the Disclosure, G is G-2; R 1is H, C1-C7 alkyl, halogen, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, or C1-C7 haloalkyl; R 2 is H, Me or F; R 3 is H, Me, F, Cl, CN, OMe or CF3; R 4 is H, SO2CF3, SO2CH3, CO2Me, COMe, CHOCO-t-Bu, CHOCO-n-Bu, CHOCO-c-hexyl, CHOCO-c-pentyl, CHOCOCH2CH3, COMe, CHOCOPh, CHOCO-i-Bu, CHOCOMe, CHOCO-sec-Bu or COSMe; R f is a C1-C3 haloalkyl.

[0231] Embodiment B2. Q is O or S; R 7 But H; R 8 But H; R f is CF3, R 9 and R 10 together with the carbon atoms to which they are attached form a 3- to 7-membered ring, and the ring is a 5- or 6-membered ring; R v is independently selected from the group consisting of H, methyl, ethyl, propyl, c-propylmethyl, propargyl, or cyanomethyl; A compound according to embodiment A2, wherein r is 1 or 2.

[0232] Embodiment C2. R 9 and R 10 together with the carbon atom to which they are attached to form cyclopentane, cyclohexane, tetrahydro-2H-pyran or tetrahydro-2H-thiopyran; R v A compound according to embodiment B2, wherein is H.

[0233] Embodiment D2. Q is CR 11 R 12 and; R 7 But H; R 8 But H; R 9 But H; R 10 But H; R 11 and R 12 together with the carbon atoms to which they are attached form a fused 3- to 7-membered ring containing carbon atoms and optionally 1-2 oxygen, sulfur or nitrogen atoms as ring members, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy; R f The compound according to embodiment A2, wherein is CF3.

[0234] Embodiment E2.R 11 and R 12 are taken together with the carbon atoms to which they are attached to form a fused 3- to 7-membered ring, which is an unsubstituted 5- or 6-membered ring.

[0235] Embodiment A3. A compound of Formula 1 as described in the Summary of the Disclosure, G is G-3; R 1 is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl; R 2 is H, Me or F; R 3 is H, Me, F, Cl, CN, OMe or CF3; R 4is H, SO2CF3, SO2CH3, CO2Me, COMe, CHOCO-t-Bu, CHOCO-n-Bu, CHOCO-c-hexyl, CHOCO-c-pentyl, CHOCOCH2CH3, COMe, CHOCOPh, CHOCO-i-Bu, CHOCOMe, CHOCO-sec-Bu or COSMe; R 13 is C1-C7 alkyl; R 14 is C1-C4 alkyl; R 15 But H; R f is a C1-C3 haloalkyl.

[0236] Embodiment A4. A compound of Formula 1 as described in the Summary of the Disclosure, G is G-4; R 1 is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl; R 2 is H, Me or F; R 3 is H, Me, F, Cl, CN, OMe or CF3; R 4 is H, SO2CF3, SO2CH3, CO2Me, COMe, CHOCO-t-Bu, CHOCO-n-Bu, CHOCO-c-hexyl, CHOCO-c-pentyl, CHOCOCH2CH3, COMe, CHOCOPh, CHOCO-i-Bu, CHOCOMe, CHOCO-sec-Bu or COSMe; R 13 is C1-C7 alkyl; R f is C1-C3 haloalkyl; R 15 is H, C1-C3 alkyl or C1-C3 alkoxy; R 16 is H, cyano, C1-C4 alkyl, halogen, C1-C4 alkylthio, C1-C4 haloalkyl, or C1-C4 alkoxy.

[0237] Embodiment A5. A compound of Formula 1 as described in the Summary of the Disclosure, G is G-5; R 1 is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl; R 2 is H, Me or F; R 3 is H, Me, F, Cl, CN, OMe or CF3; R 4 is H, SO2CF3, SO2CH3, CO2Me, COMe, CHOCO-t-Bu, CHOCO-n-Bu, CHOCO-c-hexyl, CHOCO-c-pentyl, CHOCOCH2CH3, COMe, CHOCOPh, CHOCO-i-Bu, CHOCOMe, CHOCO-sec-Bu or COSMe; R f is C1-C3 haloalkyl; R 16 is H or C1-C4 alkyl; R 17 is H, C1-C4 alkyl, halogen or C1-C4 alkoxy; R 18 is H or C1-C3 alkoxy.

[0238] Certain embodiments include compounds of Formula 1 selected from the group consisting of: N-[2,4-dimethyl-5-(1-piperidinylcarbonyl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 260); N-[2-chloro-4-methyl-5-(4-morpholinylcarbonyl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 16); N-[2,4-dimethyl-5-(4-morpholinylcarbonyl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 6); N-[2-chloro-4-methyl-5-(1-piperidinylcarbonyl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 18); 3-Fluoro-N,N,2,4-tetramethyl-5-[[(trifluoromethyl)sulfonyl]amino]benzamide (compound 128); 1,1,1-trifluoro-N-[3-fluoro-2,4-dimethyl-5-(4-morpholinylcarbonyl)phenyl]methanesulfonamide (compound 190); N-[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.4]non-2-en-3-yl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 207); N-[2,4-dimethyl-5-[(3aR,6aR)-3a,5,6,6a-tetrahydro-4H-cyclopenta[d]isoxazol-3-yl]phenyl]-1,1,1-trifluoromethanesulfonamide (compound 103); N-[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.5]dec-2-ene] -3-yl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 197); N-[2,4-dimethyl-5-(3a,4,7,7a-tetrahydro-5H-pyrano[4,3-d]isoxazol-3-yl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 121); N-[2,4-dimethyl-5-(3a,6,7,7a-tetrahydro-4H-pyrano[3,4-d]isoxazol-3-yl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 120); N-[2,4-dimethyl-5-(1-oxo-2-azaspiro[4.5]dec-2-yl)phenyl]-1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide (compound 267); [[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.4]non-2-en-3-yl)phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropanoate (compound 140); [[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.5]dec-2-en-3-yl)phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropanoate (compound 159); [[2,4-dimethyl-5-[(3aR,6aR)-3a,5,6,6a-tetrahydro-4H-cyclopenta[d]isoxazol-3-yl]phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropanoate (compound 100); [[2,4-dimethyl-5-(1-oxo-2-azaspiro[4.5]dec-2-yl)phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropanoate (compound 268); Other embodiments include compounds of Formula 1 selected from the group consisting of: Certain embodiments include compounds of Formula 1 selected from the group consisting of: [[(Trifluoromethyl)sulfonyl][2,3,4-trimethyl-5-(4-morpholinylcarbonyl)phenyl]amino]methyl 2,2-dimethylpropanoate (compound 324); Ethyl N-[(trifluoromethyl)sulfonyl]-N-[2,3,4-trimethyl-5-(1-piperidinylcarbonyl)phenyl]carbamate (compound 330); [[(Trifluoromethyl)sulfonyl][2,3,4-trimethyl-5-(1-piperidinylcarbonyl)phenyl]amino]methyl 2,2-dimethylpropanoate (compound 329); 1,1,1-trifluoro-N-[2,3,4-trimethyl-5-(4-morpholinylcarbonyl)phenyl]methanesulfonamide (Compound 289); and [[(Trifluoromethyl)sulfonyl][2,3,4-trimethyl-5-[(3aR,6aR)-3a,5,6,6a-tetrahydro-4H-cyclopento[d]isoxazol-3-yl]phenyl]amino]methyl 2,2-dimethylpropanoate (compound 336); Other particular embodiments include compounds of formula 1, wherein: G is CONR 5 R 6 and NR 5 R 6 is J-3a and R 1 is Me and R 2 is Me and R 3 is Me and R 4 is CHOCO-t-Bu, and R f is CF3 (compound 331); G is CONR 5 R 6 and NR 5 R 6 is J-4 and R 1 is Me and R 2 is Me and R 3 is Me and R 4 is CO2Et and R f is CF3 (compound 325)

[0239] The present invention also provides a method for controlling undesirable vegetation comprising applying to the locus of the vegetation (e.g., as a composition described herein) a herbicidally effective amount of a compound of the present invention. Notable embodiments of the method of use involve the compounds of the above embodiments. The compounds of the present invention are particularly useful for the selective control of weeds in crops such as wheat, barley, corn, soybean, sunflower, cotton, oilseed rape, and rice, and specialty crops such as sugarcane, citrus, fruit, and nut crops.

[0240] Also of note as an embodiment are herbicidal compositions of the invention comprising compounds of the above embodiments.

[0241] The present invention further includes herbicidal mixtures comprising: (a) a compound selected from Formula 1, their N-oxides, and salts, and (b) at least one additional active ingredient, selected from: (b1) a photosystem II inhibitor, (b2) an acetohydroxyacid synthase (AHAS) inhibitor, (b3) an acetyl-CoA carboxylase (ACCase) inhibitor, (b4) an auxin mimetic, (b5) a 5-enol-pyruvylshikimate-3-phosphate (EPSP) synthase inhibitor, (b6) a photosystem I electron diverter, diverter), (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8) glutamine synthetase (GS) inhibitors, (b9) very long chain fatty acid (VLCFA) elongase inhibitors, (b10) auxin transport inhibitors, (b11) phytoene desaturase (PDS) inhibitors, (b12) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b13) homogentisate solanesyltransferase (HST) inhibitors, (b14) cellulose biosynthesis inhibitors, (b15) other herbicides (including mitotic disruptors, organic arsenic compounds, asulam, bromobutide, cinmethylin, cumyluron, dazomet, difenzoquat, dymron, etobenzanide, flurenol, fosamine, fosamine-ammonium, hydantocidin, metam, methyldymron, oleic acid, oxaziclomefon, pelargonic acid, and biributicarb), (b16) herbicide safeners, and salts of the compounds (b1) to (b16).

[0242] "Photosystem II inhibitor" (b1) is Q B -Binding niche (Q B -binding niche) and thereby bind to the D-1 protein, thereby inhibiting the Q-binding niche in the thylakoid membrane of chloroplasts. A From Q B Blocking electron transport through photosystem II. Electrons blocked from the pathway through photosystem II are transported through a series of reactions to form toxic compounds that disrupt the cell membrane, leading to swelling of the chloroplast, membrane leakage, and ultimately cell destruction.B The binding niche has three different binding sites: binding site A binds triazines such as atrazine, triazinones such as hexazinone, and uracils such as bromacil; binding site B binds phenylureas such as diuron; and binding site C binds benzothiadiazoles such as bentazone, nitriles such as bromoxynil, and phenylpyridazines such as pyridate. Examples of photosystem II inhibitors include ametryn, amicarbazone, atrazine, bentazone, bromacil, bromofenoxime, bromoxynil, chlorbromuron, chloridazon, chlorotoluron, chloroxyuron, cumyluron, cyanazine, dymron, desmedipham, desmetrin, dimefuron, dimethametryn, diuron, ethidimuron, fenuron, fluometuron, hexazinone, ioxynil. ru, isoproturon, isouron, lenacil, linuron, metamitron, methabenzthiazuron, metobromuron, methoxyuron, metribuzin, monolinuron, nebron, pentanochlor, phenmedipham, prometon, prometryn, propanil, propazine, pyridafol, pyridate, siduron, simazine, simetryn, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, and trietazine.

[0243] "AHAS inhibitor" (b2) inhibits acetohydroxyacid synthase (AHAS). The compound, also known as acetolactate synthase (ALS), kills plants by inhibiting the production of branched-chain aliphatic amino acids, such as valine, leucine, and isoleucine, which are required for protein synthesis and cell growth.Examples of AHAS inhibitors include: amidosulfuron, azimsulfuron, bensulfuron-methyl, bispyribac-sodium, cloransulam-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, diclosulam, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, florasulam, flucarbazone-sodium, flumetsulam, flupyrsulfuron-methyl, flupyrsulfuron-sodium, foramsulfuron, and halosulfuron. -methyl, imazametabunzu-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron-methyl (including sodium salt), iofensulfuron (2-iodo-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide), mezosulfuron-methyl, metazosulfuron (3-chloro-4-(5,6-dihydro-5-methyl-1,4,2-dioxazin-3-yl)-N-[[(4,6-dimethoxazole) 2-chloro-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-1-methyl-1H-pyrazole-5-sulfonamide), metosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, penoxulam, primisulfuron-methyl, propoxycarbazone-sodium, propyrisulfuron (2-chloro-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-6-propylimidazo[1,2-b]pyridazine-3-sulfonamide), prosulfuron, pyrazosulfuron-ethyl, pyribenzoxime, pyrif Thalide, pyriminobac-methyl, pyrithiobac-sodium, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone, thifensulfuron-methyl, triafamone (N-[2-[(4,6-dimethoxy-1,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-1,1-difluoro-N-methylmethanesulfonamide), triasulfuron, tribenuron-methyl, trifloxysulfuron (including sodium salt), triflusulfuron-methyl, and tritosulfuron.

[0244] "ACCase inhibitors" (b3) are compounds that inhibit the enzyme acetyl-CoA carboxylase, which catalyzes an early step in the synthesis of lipids and fatty acids in plants. Lipids are essential components of cell membranes, without which new cells cannot be produced. Inhibition of acetyl-CoA carboxylase and the subsequent lack of lipid production leads to a loss of cell membrane integrity, especially in active growth zones, such as the meristem. Ultimately, shoot and root growth ceases, and the shoot meristem and root bud begin to wither. Examples of ACCase inhibitors include alloxydim, butroxydim, clethodim, clodinafop, cycloxydim, cyhalofop, diclofop, fenoxaprop, fluazifop, haloxyfop, pinoxaden, profoxydim, propaquizafop, quizalofop, sethoxydim, tepraloxydim, and tralkoxydim (including resolved forms such as fenoxaprop-P, fluazifop-P, haloxyfop-P, and quizalofop-P, and ester forms such as clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl, and fenoxaprop-P-ethyl).

[0245] Auxin is a plant hormone that regulates growth in many plant tissues. "Auxin mimetics" (b4) are compounds that mimic the plant growth hormone auxin, resulting in uncontrolled and unregulated growth and, in sensitive species, plant death. Examples of auxin mimetics include: aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid) and its methyl and ethyl esters and its sodium and potassium salts, aminopyralid, benazolin-ethyl, chloramben, clasifos, clomeprop, clopyralid, and dicamba. , 2,4-D, 2,4-DB, dicloprop, fluroxypyr, halaxifene (4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylic acid), halaxifene-methyl (methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylate), MCPA, MCPB, mecoprop, picloram, quinclorac, quinmerac, 2,3,6-TBA, triclopyr, and methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate.

[0246] "EPSP synthase inhibitors" (b5) are compounds that inhibit 5-enol-pyruvylshikimate-3-phosphate synthase, an enzyme involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan, and phenylalanine. EPSP-inhibiting herbicides are readily absorbed through the plant leaves and translocated to the growing point via the phloem. Glyphosate is a relatively nonselective postemergence herbicide that belongs to this group. Glyphosate includes esters and salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium), and trimesium (also known as sulfosate).

[0247] "Photosystem I electron diverters" (b6) are compounds that accept electrons from photosystem I and, after several cycles, generate hydroxyl radicals. These radicals are highly reactive and readily destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This disrupts the integrity of cell membranes, resulting in "leaks" in cells and organelles, rapid wilting and drying of leaves, and ultimately plant death. Examples of this second type of photosynthesis inhibitor include diquat and paraquat.

[0248] "PPO inhibitors" (b7) are compounds that inhibit the enzyme protoporphyrinogen oxidase, causing the rapid production of highly active compounds in plants that disrupt cell membranes and leak cell fluids. Examples of PPO inhibitors include acifluorfen-sodium, azafenidin, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, clomethoxyfen, cinidon-ethyl, fluazolate, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazin, fluoroglycofen-ethyl, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazole, pyraclonil, and pyraflufen-ethyl. , saflufenacil, sulfentrazone, thidiazimine, trifludimoxadine (dihydro-1,5-dimethyl-6-thioxo-3-[2,2,7-trifluoro-3,4-dihydro-3-oxo-4-(2-propyn-1-yl)-2H-1,4-benzoxazin-6-yl]-1,3,5-triazine-2,4(1H,3H)-dione), and thiafenacil (methyl N-[2-[[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenyl]thio]-1-oxopropyl]-β-alaninate).

[0249] "GS inhibitors" (b8) are compounds that inhibit the activity of the glutamine synthetase enzyme, which plants use to convert ammonia to glutamine. Thus, ammonia accumulates and glutamine levels decrease. Damage to the plant may result from the combined effects of ammonia toxicity and a 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-(hydroxymethylphosphinothricin)). finyl)butanoic acid), and viranaphos.

[0250] "VLCFA elongase inhibitors" (b9) are herbicides with a wide variety of chemical structures that inhibit elongase, an enzyme located in or near chloroplasts that is involved in the biosynthesis of VLCFAs. In plants, very long-chain fatty acids are the main components of hydrophobic polymers that prevent desiccation on the leaf surface and provide stability to pollen grains. Such herbicides include acetochlor, alachlor, anilophos, butachlor, cafenstrole, dimethachlor, dimethenamid, diphenamid, fenoxasulfone (3-[[(2,5-dichloro-4-ethoxyphenyl)methyl]sulfonyl]-4,5-dihydro-5,5-dimethylisoxazole), fentrazamide, flufenacet, indanofan, mefenacet, metazachlor, metolachlor, naproanilide, napropamide, napropamide-M ((2R)-N,N-diethyl-2-(1-naphthalenyloxy)propanamide), petoxamide, piperophos, pretilachlor, propachlor, propisochlor, pyroxasulfone, and thenylchlor (including resolved forms, such as S-metolachlor, and chloroacetamides, and oxyacetamides).

[0251] "Auxin transport inhibitors" (b10) are chemical substances that inhibit the transport of auxin in plants, for example, by binding to auxin transport proteins. Examples of auxin transport inhibitors include: diflufenzopyr, naptalam (also known as N-(1-naphthyl)phthalamic acid, and 2-[(1-naphthalenylamino)carbonyl]benzoic acid).

[0252] "PDS inhibitors" (b11) are compounds that inhibit the carotenoid biosynthetic pathway at the phytoene desaturase step. Examples of PDS inhibitors include: beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurzone, and picolinafen.

[0253] "HPPD inhibitors" (b12) are chemical substances that inhibit the biosynthesis of 4-hydroxyphenyl-pyruvate dioxygenase. Examples of HPPD inhibitors include: benzobicyclone, benzofenap, bicyclopyrone (4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]bicyclo[3.2.1]oct-3-en-2-one), fenquinotrione (2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl] -1,3-cyclohexanedione), isoxachlorthol, isoxaflutole, mesotrione, pyrasulfotole, pyrazolinate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate (1-[[1-ethyl-4-[3-(2-methoxyethoxy)-2-methyl-4-(methylsulfonyl)benzoyl]-1H-pyrazol-5-yl]oxy]ethyl methyl carbonate), topramezone, 5-chloro-3-[ (2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalinone, 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-di ion, 5-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-(3-methoxyphenyl)-3-(3-methoxypropyl)-4(3H)-pyrimidinone, 2-methyl-N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide, and 2-methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide. Fluoromethyl)benzamide.

[0254] "HST inhibitors" (b13) disrupt the plant's ability to convert homogentisate to 2-methyl-6-solanyl-1,4-benzoquinone, thereby disrupting carotenoid biosynthesis. Examples of HST inhibitors include haloxydine, pyriclor, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridin-2(1H)-one, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-b]pyrazin-6(5H)-one, and 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone.

[0255] HST inhibitors also include compounds of Formulas A and B: [ka] In the formula, R d1 is H, Cl, or CF; R d2 is H, Cl, or Br; R d3 is H or Cl; R d4 is H, Cl, or CF; R d5 is CH3, CH2CH3, or CH2CHF2; and R d6 is OH, or -OC(=O)-i-Pr; and R e1 is H, F, Cl, CH3, or CH2CH3; R e2 is H or CF; R e3 is H, CH3, or CH2CH3; R e4 is H, F, or Br; R e5 is Cl, CH3, CF3, OCF3, or CH2CH3; R e6 is H, CH, CHCHF, or C≡CH; R e7 is OH, —OC(═O)Et, —OC(═O)-i-Pr, or —OC(═O)-t-Bu; and A e8 is N or CH.

[0256] "Cellulose biosynthesis inhibitors" (b14) inhibit the biosynthesis of cellulose in certain plants. They are most effective when applied to young plants or rapidly growing plants before or shortly after emergence. Examples of cellulose biosynthesis inhibitors include: chlorthiamid, dichlobenil, furopoxam, indaziflam (N 2 -[(1R,2S)-2,3-dihydro-2,6-dimethyl-1H-inden-1-yl]-6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine), isoxaben, and triaziflam.

[0257] "Other herbicides" (b15) include herbicides that function through a variety of different modes of action, such as mitotic disruptors (e.g., flamprop-M-methyl and flamprop-M-isopropyl), organoarsenic compounds (e.g., DSMA and MSMA), 7,8-dihydropteroate synthase inhibitors, chloroplast isoprenoid synthesis inhibitors, and cell wall biosynthesis inhibitors. Other herbicides also include herbicides with no known mode of action or that do not fall into the specific categories listed in (b1) to (b14), or that operate through a combination of the modes listed above. Examples of other herbicides include aclonifen, asulam, amitrole, bromobutide, cinmethylin, clomazone, cumyluron, cyclopyrimorate (6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinyl 4-morpholinecarboxylate), dymron, difenzoquat, etobenzanid, fluometuron, flurenol, fosamine, fosamine-ammonium, dazomet, dymron, ipfencarbazone (1-( 2,4-dichlorophenyl)-N-(2,4-difluorophenyl)-1,5-dihydro-N-(1-methylethyl)-5-oxo-4H-1,2,4-triazole-4-carboxamide), metam, methyldymron, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, and 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole.

[0258] "Other herbicides" (b15) also include compounds of formula (b15A), [ka] During the ceremony, R 12’ is H, C1-C6 alkyl, C1-C6 haloalkyl, or C4-C8 cycloalkyl; R 13’ is H, C1-C6 alkyl or C1-C6 alkoxy; Q 1 is an optionally substituted ring system selected from the group consisting of phenyl, thienyl, pyridinyl, benzodioxolyl, naphthalenyl, benzofuranyl, furanyl, benzothiophenyl, and pyrazolyl, wherein when substituted, said ring system is selected from the group consisting of 1 to 3 R 14’ is replaced by; Q 2 is an optionally substituted ring system selected from the group consisting of phenyl, pyridinyl, benzodioxolyl, pyridinonyl, thiadiazolyl, thiazolyl, and oxazolyl, wherein when substituted, said ring system is selected from the group consisting of 1 to 3 R15’ is replaced by; Each R 14’ are independently halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C8 cycloalkyl, cyano, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, SF5, NHR 17 ; or 1 to 3 R 16 phenyl optionally substituted with one to three R 16 is pyrazolyl optionally substituted by Each R 15’ are independently halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, cyano, nitro, C1-C6 alkylthio, C1-C6 alkylsulfinyl, or C1-C6 alkylsulfonyl; Each R 16’ are independently halogen, C1-C6 alkyl, or C1-C6 haloalkyl; R 17’ is a C1-C4 alkoxycarbonyl.

[0259] In one embodiment, where the "other herbicides" (b15) also comprise compounds of formula (b15A), R 1 2’ is preferably H or C1-C6 alkyl; more preferably, R 12’ is H or methyl. Preferably, R 13’ is H. Preferably, Q 1 is a phenyl ring or a pyridinyl ring, and each ring is 14’ more preferably, substituted with Q 1 is 1 to 2 R 14’ Preferably, Q is a phenyl ring substituted with 2 is 1 to 3 R 15’ is a phenyl ring substituted with 2 is 1 to 2 R 15’ Preferably, each R 14’are independently halogen, C1-C4 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; more preferably, each R 14’ is independently chloro, fluoro, bromo, C1-C2 haloalkyl, C1-C2 haloalkoxy or C1-C2 alkoxy. Preferably, each R 15’ are independently halogen, C1-C4 alkyl, C1-C3 haloalkoxy; more preferably, each R 15’ is independently chloro, fluoro, bromo, C1-C2 haloalkyl, C1-C2 haloalkoxy, or C1-C2 alkoxy. Particularly preferred "other herbicides" (b15) include any one of the following (b15A-1) to (b15A-19). [ka] [ka] [ka]

[0260] "Other herbicides" (b15) also include compounds of formula (b15B): [ka] During the ceremony, R 18’ is H, C1-C6 alkyl, C1-C6 haloalkyl, or C4-C8 cycloalkyl; Each R 19’ are independently halogen, C1-C6 haloalkyl, or C1-C6 haloalkoxy; p is an integer of 0, 1, 2 or 3; Each R 20’ are independently halogen, C1-C6 haloalkyl, or C1-C6 haloalkoxy; q is an integer of 0, 1, 2 or 3.

[0261] In one embodiment, the "other herbicides" (b15) also include compounds of formula (b15B), R 18 is preferably H, methyl, ethyl or propyl; more preferably, R 18 is H or methyl; most preferably, R 18 is H. Preferably, each R 19 is independently chloro, fluoro, C1-C3 haloalkyl, or C1-C3 haloalkoxy; more preferably, each R 19 is independently chloro, fluoro, C1 fluoroalkyl (i.e., fluoromethyl, difluoromethyl, or trifluoromethyl), or C1 fluoroalkoxy (i.e., trifluoromethoxy, difluoromethoxy, or fluoromethoxy). Preferably, each R 20 is independently chloro, fluoro, C1 haloalkyl, or C1 haloalkoxy; more preferably, each R 20 is independently chloro, fluoro, C1 fluoroalkyl (i.e., fluoromethyl, difluoromethyl, or trifluoromethyl), or C1 fluoroalkoxy (i.e., trifluoromethoxy, difluoromethoxy, or fluoromethoxy). Particularly preferred "other herbicides" (b15) include any one of the following (b15B-1) to (b15B-19). [ka] [ka] [ka]

[0262] In another embodiment, the "other herbicides" (b15) also include compounds of formula (b15C): [ka] In the formula, R 1’is Cl, Br or CN; R 2’ is C(=O)CH2CH2CF3, CH2CH2CH2CH2CF3 or 3-CHF2-isoxazol-5-yl.

[0263] "Herbicide safeners" (b16) are substances added to herbicide formulations to eliminate or reduce the phytotoxic effects of the herbicide on certain crops. These compounds protect the crop from herbicide damage but typically do not prevent the herbicide from controlling undesirable vegetation. Examples of herbicide safeners include, but are not limited to, benoxacor, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfamide, dymron, dichlormid, dicyclonone, dietholate, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, methoxyphenone, naphthalic anhydride, oxabetrinil, N-(aminocarbonyl)-2-methylbenzenesulfonamide, and N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene, 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), 4-(dichloroacetyl)-1-oxa-4-azospiro[4.5]decane (MON 4660), 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-ethanone, and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide.

[0264] The compounds of formula 1 can be prepared by general methods known in the art of organic synthetic chemistry. Compounds of formula 1 can be prepared using one or more of the following methods and variations described in Schemes 1-14. G, R in the compounds of formulas 1-15 below 1 ~R 19 , R v and R fare as defined above in the Summary of the Disclosure unless otherwise indicated. The compounds of Formulae 1a, 1b, 3a, 3b, 3b', 3c, 3d, 3e, and 3f are various subsets of the compounds of Formulae 1 and 3, and all substituents of Formulae 1a, 1b, 3a, 3b, 3b', 3c, 3d, 3e, and 3f are as defined above for Formula 1 unless otherwise indicated in the disclosure, including the schemes.

[0265] As shown in Scheme 1, a compound of formula 1a (i.e., R 4 is H) can be prepared by reacting an appropriately substituted aniline of formula 2 with one equivalent (or a slight excess of one equivalent) of R f SO2Cl compound or the corresponding R f Alternatively, compounds of formula 1b (i.e., R 4 SO2R 19 and R 19 R f The compound of formula 1, wherein the compound of formula 1 is a compound of formula 2, is prepared by reacting an aniline of formula 2 with 2 equivalents (or an excess of more than 2.0 equivalents) of a compound of formula R f SO2Cl or a compound of formula R f The bis-sulfonamides of formula 1b can be readily obtained by reacting them with the corresponding anhydrides of (SO)O under similar reaction conditions as above. Treatment of the bis-sulfonamides of formula 1b with an excess of aqueous base, followed by neutralization or acidification with acid, readily affords the corresponding mono-sulfonamides of formula 1a. Preferred conditions for this hydrolysis are typically aqueous sodium or potassium hydroxide, optionally with a cosolvent such as methanol, ethanol, dioxane, or tetrahydrofuran, followed by neutralization or acidification with concentrated hydrochloric acid or aqueous hydrochloric acid. [ka]

[0266] As shown in Scheme 2, substituted anilines of formula 2 are readily obtained by hydrogenation of nitrobenzenes of formula 3 under conditions including, but not limited to, catalytic hydrogenation using 5-10% palladium metal over carbon or platinum oxide in solvents such as methanol, ethanol, or ethyl acetate under a hydrogen atmosphere. This reaction is typically carried out in a Parr Hydrogenator. Alternatively, reduction of the nitro group can be achieved with activated zinc metal in acetic acid, stannous chloride in aqueous hydrochloric acid, metallic iron in acetic acid, aqueous alcohol, or aqueous ethyl acetate mixtures with ammonium chloride (e.g., 3 equivalents of ammonium chloride and Fe in aqueous ethanol), or sodium borohydride in methanol in the presence of NiCl2.6HO (see Journal of the American Chemical Society, volume 127, p. 119 (2005)). [ka]

[0267] As shown in Scheme 3, an amide-substituted nitrobenzene of formula 3a (i.e., where G is C ONR 5 R 6 The compound of formula 3, which is a substituted nitrobenzene carboxylic acid of formula 4, can be prepared by first forming an acid chloride, which can then be reacted with the compound of formula HNR 5 R 6 Alternatively, compounds of formula 3a can be prepared by reacting a carboxylic acid of formula 4 with an amine of formula HNR 5 R 6 The acid chlorides can be prepared by reacting 4 with amines of formula HNR in the presence of a dehydrating amide coupling reagent, optionally with a base in a suitable solvent. Formation of the acid chloride from 4 can be achieved with either oxalyl chloride or thionyl chloride, along with a catalytic amount of N,N-dimethylformamide in a suitable solvent such as dichloromethane, toluene, or dichloroethane. The resulting acid chloride can be reacted with a compound of formula HNR 5 R 6The reaction of carboxylic acid 4 with an amine HNR can be carried out in a solvent such as tetrahydrofuran, dioxane, or dichloromethane in the presence of triethylamine, diisopropylethylamine (Hunig's base), or pyridine. 5 R 6 Dehydration amide coupling reagents suitable for direct coupling with include N,N'-dicyclohexylcarbodiimide (DCC), (benzotriazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate (BOP reagent), or propanephosphonic anhydride (T3P reagent), or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC). A base such as triethylamine, diisopropylethylamine, pyridine, or N,N-dimethylaminopyridine (DMAP) is typically added to the dehydration coupling reaction in a solvent such as N,N-dimethylformamide, acetonitrile, or dichloromethane. The temperature for these reactions typically ranges from 0°C to ambient temperature. [ka]

[0268] As shown in Scheme 4, the isoxazoline-substituted nitrobenzene intermediate of formula 3b (i.e., a compound of formula 3 where G is an isoxazolinyl ring) can be converted to a nitrobenzene chlorooxime of formula 5 by reaction with a nitrobenzene chlorooxime of formula R in a suitable solvent such as chloroform, dichloromethane, acetonitrile, tetrahydrofuran, toluene, dioxane, dichloroethane, and the like, in the presence of a suitable base such as triethylamine, diisopropylethylamine, or pyridine at a temperature generally ranging from 0° C. to ambient temperature. 7 R 8 C=CR 9 R 10 This cycloaddition reaction produces the asymmetric olefin R 7 R 8 C=CR 9 R 10Use of 3b' gives a regioisomeric mixture of isoxazoline nitrobenzenes of formula 3b and 3b', which may require separation of the two regioisomers by silica gel chromatography. [ka]

[0269] Chloroximes of formula 5 can be prepared by chlorination of oximes of formula 6 with chlorinating agents that typically include, but are not limited to, N-chlorosuccinimide, sodium hypochlorite, or chlorine gas in solvents such as N,N-dimethylformamide, acetonitrile, dichloromethane, dichloroethane, toluene, and the like, at temperatures generally ranging from 0° C. to ambient temperature, as shown in Scheme 5. [ka]

[0270] Oximes of formula 6 can be obtained from nitrobenzaldehydes of formula 7 by reaction with hydroxylamine as the free base or as the hydrochloride or acetate salt with a base such as sodium acetate, pyridine, or potassium carbonate in a compatible solvent including, but not limited to, methanol, ethanol, acetonitrile, dichloromethane at temperatures generally ranging from 0° C. to ambient temperature, as shown in Scheme 6. [ka]

[0271] Compounds of formula 7 can be prepared by oxidizing nitrobenzyl alcohols of formula 8 with a suitable oxidizing agent, such as pyridinium chlorochromate (PCC, optionally containing Celite® diatomaceous earth filter aid), chromic acid, or manganese(IV) oxide, in a suitable solvent, including, but not limited to, dichloromethane or dichloroethane, as shown in Scheme 7. Alternatively, oxidation can be carried out under Swern conditions using oxalyl chloride, dimethyl sulfoxide, and triethylamine. The oxidation of benzyl alcohols to benzaldehydes is well documented in the field of synthetic organic chemistry. [ka]

[0272] Nitrobenzyl alcohols of formula 8 are readily available from nitrobenzoic acids 4 by reduction with 2–3 equivalents of borane (e.g., BH3·THF) or lithium aluminum hydride in tetrahydrofuran, diethyl ether, or dioxane at temperatures typically ranging from −78 °C to ambient temperature, as shown in Scheme 8. [ka]

[0273] Benzoic acids of formula 9 can be nitrated in a mixture of nitric and sulfuric acids at temperatures ranging from 0° C. to ambient temperature to give nitrobenzoic acids of formula 4, as shown in Scheme 9. Other sources of nitronium ions for this nitration include nitronium tetrafluoroborate, acetyl nitrate, and guanidinium nitrate, which can also be used in a suitable solvent such as tetramethylene sulfone to accomplish this reaction. Benzoic acids of formula 9 are readily available commercially or are easily prepared by established methods from the literature. . [ka]

[0274] As shown in Scheme 10, compounds of formula 3c (i.e., compounds of formula 3 where G is G-2) can be converted to cyclic carbamates, cyclic thiocarbamates, cyclic lactams, or cyclic ureas of formula 11 (wherein Q is O, S, CR) of meta-bromo- or meta-iodo-substituted nitrobenzenes of formula 10a (i.e., compounds of formula 10 where X is bromine or iodine) in the presence of copper(I) iodide having a diamine ligand, such as trans-N,N'-dimethylcyclohexane-1,2-diamine or tetramethylethylenediamine (TMEDA), and potassium phosphate (KPO) in a suitable solvent, such as N,N-dimethylformamide, acetonitrile, tetrahydrofuran, or dioxane, optionally containing water as a co-solvent. 11 R 12 or NR 13(Figure 1). A similar copper-mediated coupling can also be performed under Chan-Lam conditions, in which a boronic acid of formula 10b (i.e., a compound of formula 10 where X is B(OH)) is coupled with a compound of formula 11 in the presence of copper(II) acetate and pyridine in dichloromethane. This cross-coupling can also be performed using 10a and a compound of formula 11 under the well-documented Buchwald-Hartwig amination protocol involving palladium mediated by an appropriate phosphine ligand as part of or as an additive to a precatalyst in a suitable solvent such as tetrahydrofuran, toluene, or dichloromethane. For most substrates, an auxiliary base, such as sodium tert-butoxide or cesium carbonate, is used in the reaction. Examples of palladium catalysts suitable for this transformation include, but are not limited to, tetrakis(triphenylphosphine)palladium(0) [Pd(PPh3)4], bis(triphenylphosphine)palladium chloride [PdCl2(PPh3)2], palladium(II) chloride-tris(2-methylphenyl)phosphine [PdCl2[P(o-Tol)3]2], or [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) [Pd(dppf)Cl2]. Finally, this cross-coupling can also be achieved with palladium acetate [Pd(OAc)2] or tris(dibenzylideneacetone)dipalladium(0) [Pd2(dba)3] used in combination with an appropriate dialkyldiarylphosphine ligand with a base such as sodium tert-butoxide in toluene or cesium carbonate in N,N-dimethylformamide.

[0275] Nitrobenzeneboronic acids of formula 10b can also be prepared by Suzuki coupling. [ka]

[0276] Uracil-substituted nitrobenzenes of formula 3d (i.e., compounds of formula 3 where G is G-3) and pyridazinone-substituted nitrobenzenes of formula 3e (i.e., compounds of formula 3 where G is G-4) can be prepared by palladium-mediated cross-coupling of nitrobenzene boronic acid pinacol esters of formula 12 with appropriately substituted 5-bromo- or 5-iodo-substituted uracils of formula 13 (wherein X is bromo or iodo) or pyridazinones of formula 14 (wherein X is bromo or iodo) in a suitable solvent such as aqueous dioxane, aqueous tetrahydrofuran, or N,N-dimethylformamide, with a suitable base such as sodium carbonate, potassium carbonate, or sodium bicarbonate, as outlined in Scheme 11. Examples of palladium catalysts useful for this transformation include, but are not limited to, tetrakis(triphenylphosphine)palladium(0) [Pd(PPh)] or bis(triphenylphosphine)palladium chloride [PdCl(PPh)].

[0277] Halogen-substituted uracils of formula 13 (where X is bromine or iodine) can be readily prepared by established methods by halogenating uracils of formula 13a (where X is hydrogen) with bromine, iodine, N-bromosuccinimide, or N-iodosuccinimide in a suitable solvent such as acetic acid, dichloromethane, carbon tetrachloride, chloroform, acetonitrile, or N,N-dimethylformamide. Pyridazinones of formula 14 (where X is iodine) can be prepared from pyridazinones of formula 14a (where X is hydrogen) by treatment with 2,2,6,6-tetramethylpiperidylzinc chloride-LiCl (TMPZnCl·LiCl) in tetrahydrofuran or dioxane, followed by the addition of iodine. [ka]

[0278] Nitrobenzeneboronic acid pinacol esters of formula 12 can be readily prepared from nitrobenzyl bromides or iodides of formula 15 by treatment with bis(pinacolato)diboron (Bpin2) in the presence of a palladium catalyst such as bistriphenylphosphinepalladium chloride [PdCl2(PPh3)2] in a solvent, i.e., dioxane or tetrahydrofuran, as shown in Scheme 12. [ka]

[0279] As shown in Scheme 13, N-linked pyridazinone nitrobenzenes of formula 3f (i.e., compounds of formula 3 where G is G-5) can be prepared by cross-coupling of a bromo- or iodo-substituted nitrobenzene of formula 10a (wherein X is bromine or iodine) with a pyridazinone of formula 15 in the presence of copper(I) iodide and KPO and a diamine ligand, i.e., trans-N,N'-dimethylcyclohexane-1,2-diamine or tetramethylethylenediamine (TMEDA), in a suitable solvent such as N,N-dimethylformamide, acetonitrile, tetrahydrofuran, or dioxane, optionally containing water as a co-solvent. Alternatively, a similar coupling can be achieved by cross-coupling an arylboronic acid of formula 10b (wherein X is B(OH)) with 15 under Buchwald-Hartwig amination conditions. [ka]

[0280] As shown in Scheme 14, R 4 is C(=O)R 19 , C(=S)R 19 , CO2R 9 , C(=O)SR 19 , S(O)2R 19 ,CONR 20 R 19 , S(O)NR 20 R 19 , S(OH)NR20 R 19 or CH2OCOR 19 The compound of formula 1, 4 is hydrogen, an appropriately substituted acyl halide, thioacyl halide, carbamoyl halide, sulfonyl halide, sulfamoyl halide, or acyloxymethyl halide (i.e., ClCHO(C=O)R 19 ) can be prepared by reaction with [ka]

[0281] It is recognized that some of the reagents and reaction conditions described above for preparing compounds of Formula 1 may be incompatible with certain functional groups present in the intermediates. In these instances, incorporating a series of protection / deprotection or functional group interconversions into the synthesis can aid in obtaining the desired product. The use and selection of protecting groups will be apparent to those skilled in the art of chemical synthesis (see, for example, Greene, TW; Wuts, PGM Protective Groups in Organic Synthesis, 2nd Ed.; Wiley: New York, 1991). Those skilled in the art will recognize that, in some cases, after introducing a given reagent as shown in any individual scheme, it may be necessary to perform additional conventional synthetic steps not specifically described to complete the synthesis of compounds of Formula 1. Those skilled in the art will also recognize that it may be necessary to perform combinations of the steps shown in the above schemes in an order other than that indicated by the specific order presented to prepare compounds of Formula 1.

[0282] Those skilled in the art will also recognize that compounds of Formula 1 and the intermediates described herein can be subjected to a variety of electrophilic, nucleophilic, radical organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.

[0283] It is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent without undue effort. The following non-limiting examples are illustrative of the present invention. The steps of the following examples show the sequence of each step in an overall synthetic transformation, and the starting material for each step may not necessarily have been prepared by the specific preparative procedure whose sequence is described in other examples or steps. Percentages are by weight unless the chromatographic solvent mixture or otherwise indicated. Parts and percentages of the chromatographic solvent mixture are by weight unless otherwise indicated. 1 H NMR spectra are reported in ppm downfield from tetramethylsilane, where "s" means singlet, "d" means doublet, "t" means triplet, "q" means quartet, "m" means multiplet, "dd" means doublet of doublets, "dt" means triplet of doublets, and "br s" means broad singlet. Mass spectra (MS) are reported as the molecular weight of the parent ion with the highest isotopically abundance, either formed by the addition of H+ (molecular weight 1) to the molecule (M+1), or formed by the loss of H+ (molecular weight 1) from the molecule (M-1), as observed using liquid chromatography coupled to a mass spectrometer (LCMS) using either atmospheric pressure chemical ionization (AP+), where "amu" stands for unified atomic mass unit.

[0284] The following non-limiting examples are intended to illustrate the processes of the present invention for preparing compounds of Formula 1 and corresponding intermediates. All NMR spectra are reported in CDCl3 at 500 MHz downfield from tetramethylsilane unless otherwise indicated.

[0285] Synthesis Example 1 Preparation of N-[5-[(4,4-difluoro-1-piperidinyl)carbonyl]-2,4-dimethylphenyl]-1,1,1-trifluoromethanesulfonamide (i.e., Compound 241) Step A: (4,4-difluoropiperidin-1-yl)(2,4-dimethyl-5- Preparation of (nitrophenyl)methanone To a stirred solution of 2,4-dimethyl-5-nitro-benzoic acid (0.30 g, 1.5 mmol), 4,4-difluoropiperidine (0.20 g, 1.7 mmol), and triethylamine (0.64 mL, 4.6 mmol) in dichloromethane (8 mL) was added propylphosphonic anhydride (50 wt% in ethyl acetate, 1.7 g, 2.7 mmol). The mixture was stirred at room temperature overnight, and then concentrated under reduced pressure. The mixture was diluted with 50% ethyl acetate in hexane and filtered through a pad of silica. The filtrate was concentrated under reduced pressure to give the title compound as a yellow solid (0.57 g), which was used in the next step without further purification. 1 H NMR(CDCl3)δ 7.87(s,1H),7.24(s,1H),4.11-3.97(m,1H),3.92-3.77(m,1H),3.43-3.3 6(m,2H),2.62(s,3H),2.36(s,3H),2.15-2.07(m,2H),1.99-1.86(m,2H).

[0286] Step B: (5-amino-2,4-dimethylphenyl)(4,4-difluoropiperidin) Preparation of di-(1-yl)methanone To a stirred solution of (4,4-difluoropiperidin-1-yl)(2,4-dimethyl-5-nitrophenyl)methanone (i.e., the product of Step A) (0.57 g) in ethanol (9 mL) and water (1 mL) was added ammonium chloride (0.10 g, 1.9 mmol) and iron powder (0.32 g, 5.7 mmol). The reaction mixture was stirred at 80° C. for 2 hours, then cooled to room temperature, diluted with ethyl acetate, and filtered through a pad of Celite® diatomaceous earth filter aid, followed by a pad of silica. The filtrate was concentrated under reduced pressure to give the title compound as an orange oil (0.40 g), which was used in the next step without further purification. 1 H NMR(CDCl3)δ 6.90(s,1H),6.48(s,1H),4.07-3.99(m,1H),3.81-3.73(m,1H),3.57(br s,2H),3.41-3.38(m,2H),2.15(sx 2,6H),2.11-2.02(m,2H),1.92-1.83(m,2H).

[0287] Step C: N-[5-[(4,4-difluoro-1-piperidinyl)carbonyl]- Preparation of 2,4-dimethylphenyl]-1,1,1-trifluoromethanesulfonamide To a stirred solution of (5-amino-2,4-dimethylphenyl)(4,4-difluoropiperidin-1-yl)methanone (i.e., the product of Step B) (0.40 g, 1.5 mmol) in dichloromethane (8 mL) at −40° C. was added triethylamine (0.27 mL, 1.9 mmol), followed by the dropwise addition of trifluoromethanesulfonic anhydride (0.27 mL, 1.6 mmol) over 5 minutes. The reaction mixture was stirred at −40° C. for 30 minutes and then poured into water. The layers were separated, the aqueous phase was extracted with ethyl acetate, and the combined organic extracts were concentrated under reduced pressure. The crude material was purified by column chromatography eluting with ethyl acetate / hexane (gradient of 0 to 60% ethyl acetate in hexane) to afford the title compound, a compound of the present disclosure, as a white solid (0.26 g). 1H NMR(CDCl3)δ 9.61(br s,1H),7.04(s,1H),6.55(s,1H),4.08-4.01(m,1H),3.84-3.76(m,1H) ,3.34-3.28(m,2H),2.25(s,6H),2.13-2.03(m,2H),1.92-1.82(m,2H).

[0288] Synthesis Example 2 Preparation of N-[2-chloro-5-[(4,4-difluoro-1-piperidinyl)carbonyl]-4-methylphenyl]-1,1,1-trifluoromethanesulfonamide (i.e., Compound 229) Step A: (4-chloro-2-methyl-5-nitrophenyl)(4,4-difluoro Preparation of (piperidin-1-yl)methanone To a stirred solution of 4-chloro-2-methyl-5-nitro-benzoic acid (0.30 g, 1.4 mmol), 4,4-difluoropiperidine (0.19 g, 1.6 mmol) and triethylamine (0.58 mL, 4.2 mmol) in dichloromethane (8 mL) was added propylphosphonic anhydride (50 wt% in ethyl acetate, 1.5 g, 2.4 mmol). The mixture was stirred at room temperature overnight, and then the mixture was concentrated under reduced pressure. The mixture was diluted with 50% ethyl acetate in hexane and filtered through a pad of silica. The filtrate was concentrated under reduced pressure to give the title compound as an off-white solid (0.39 g), which was used in the next step without further purification. 1 H NMR(CDCl3)δ 7.76(s,1H),7.44(s,1H),4.06-3.95(m,1H),3.86-3.74(m,1H),3.39-3.35(m,2H),2.36(s,3H),2.12-2.04(m,2H),1.98-1.85(m,2H).

[0289] Step B: (5-amino-4-chloro-2-methylphenyl)(4,4-difluoro Preparation of (piperidin-1-yl)methanone To a stirred solution of (4-chloro-2-methyl-5-nitrophenyl)(4,4-difluoropiperidin-1-yl)methanone (i.e., the product of Step A) (0.39 g, 1.2 mmol) in ethanol (9 mL) and water (1 mL) was added ammonium chloride (65 mg, 1.2 mmol) and iron powder (0.21 g, 3.8 mmol). The reaction mixture was stirred at 80° C. for 2 hours, then cooled to room temperature, diluted with ethyl acetate, and filtered through a pad of Celite® diatomaceous earth filter aid, followed by a pad of silica. The filtrate was concentrated under reduced pressure to give the title compound as an orange oil (0.40 g), which was used in the next step without further purification. 1 H NMR(CDCl3)δ 7.07(s,1H),6.53(s,1H),4.13-3.93(m,3H),3.76-3.68(m,1H),3.35-3.31(m,2H),2.11(s,3H),2.06-1.97(m,2H),1.87-1.79(m,2H).

[0290] Step C: N-[2-chloro-5-[(4,4-difluoro-1-piperidinyl)carbonyl] Preparation of [carbonyl]-4-methylphenyl]-1,1,1-trifluoromethanesulfonamide To a stirred solution of (5-amino-4-chloro-2-methylphenyl)(4,4-difluoropiperidin-1-yl)methanone (i.e., the product of Step B) (0.40 g) in dichloromethane (8 mL) at −10° C. was added triethylamine (0.25 mL, 1.8 mmol), followed by the dropwise addition of trifluoromethanesulfonic anhydride (0.25 mL, 1.5 mmol) over 5 minutes. The reaction mixture was stirred at −10° C. for 30 minutes and then poured into water. The layers were separated, the aqueous phase was extracted with ethyl acetate, and the combined organic extracts were concentrated under reduced pressure. The crude material was purified by trituration with diethyl ether to afford the title compound, a compound of the present disclosure, as a white solid (0.24 g). 1H NMR(CDCl3)δ 9.23(br s,1H),7.27(s,1H),6.97(s,1H),4.15-4.08(m,1H),3.80-3.72(m,1H) ,3.37-3.27(m,2H),2.30(s,3H),2.14-2.06(m,2H),1.96-1.86(m,2H).

[0291] Synthesis Example 3 Preparation of 3-fluoro-N,N,2,4-tetramethyl-5-[[(trifluoromethyl)sulfonyl]amino]benzamide (i.e., Compound 128) Step A: Preparation of 3-fluoro-2,4-dimethyl-benzoic acid To a stirred solution of n-butyllithium (1.6 M solution in hexane, 18 mL, 29 mmol) in anhydrous tetrahydrofuran (40 mL) at 0° C. was slowly added 2,2,6,6-tetramethylpiperidine (4.9 mL, 29 mmol). The mixture was stirred for 15 minutes, then cooled to −78° C., and a solution of 3-fluoro-4-methyl-benzoic acid (2.0 g, 13 mmol) in anhydrous tetrahydrofuran (10 mL) was added dropwise. The reaction mixture was stirred at −78° C. for 1.5 hours, then warmed to −50° C. and stirred for an additional 45 minutes. Iodine was then added to the resulting solution. C. The reaction mixture was warmed to room temperature and stirred overnight. Water was added and the mixture was washed with diethyl ether. The aqueous phase was acidified to pH 2 with 6N hydrochloric acid and extracted with diethyl ether (.times.2). The combined organic extracts were then washed with brine (.times.1), dried over sodium sulfate, and concentrated under reduced pressure to give the title compound as a pale yellow solid (2.18 g), which was used in the next step without further purification. 1 H NMR(CDCl3)δ 7.75(d,1H),7.10-7.07(m,1H),2.55(d,3H),2.33(d,3H).

[0292] Step B: Preparation of 3-fluoro-2,4-dimethyl-5-nitro-benzoic acid To a stirred mixture of 3-fluoro-2,4-dimethyl-benzoic acid (i.e., the product of Step A) (0.50 g, 3.0 mmol) in concentrated sulfuric acid (6 mL) at −20° C., concentrated nitric acid (0.5 mL) was added dropwise. The reaction mixture was stirred at −20° C. to 0° C. for 2 hours and poured onto ice. The resulting solid was collected by filtration, washed with water (×1), and dried under vacuum to afford a 1:1 mixture of the title compound and 3-fluoro-2,4-dimethyl-6-nitro-benzoic acid as a white solid (0.44 g), which was used in the next step without further purification. 1 H NMR (DMSO-d6, mixture of positional isomers) δ 8.24(d,1H),8.06(d,1H),2.52(d,3H),2.45(d,3H),2.34(d,3H),2.26(d,3H).

[0293] Step C: 3-Fluoro-N,N,2,4-tetramethyl-5-nitro-benzamine Preparation of the To a stirred solution of 3-fluoro-2,4-dimethyl-5-nitro-benzoic acid (i.e., the product of Step B) (0.86 g of a mixture of regioisomers, including 2 mmol of the required regioisomer), dimethylamine hydrochloride (0.20 g, 2.5 mmol), and triethylamine (0.97 mL, 7 mmol) in dichloromethane (10 mL) at 0 °C was slowly added propylphosphonic anhydride (50 wt% in ethyl acetate, 3.8 g, 6 mmol). The reaction mixture was stirred overnight at room temperature, then the mixture was washed with 1 N sodium hydroxide (×1), the aqueous phase was extracted with dichloromethane (×1), and the combined organic extracts were washed with brine (×1), dried over sodium sulfate, and concentrated under reduced pressure. The crude material was purified by column chromatography eluting with ethyl acetate / hexane (gradient of 20 to 50% ethyl acetate in hexane) to afford the title compound as a pale yellow oil (0.39 g). 1 H NMR(CDCl3)δ 7.66(d,1H),3.15(s,3H),2.88(s,3H),2.50(d,3H),2.28(d,3H).

[0294] Step D: 5-amino-3-fluoro-N,N,2,4-tetramethylbenzamide Preparation of To a stirred solution of 3-fluoro-N,N,2,4-tetramethyl-5-nitrobenzamide (i.e., the product of Step C) (3.10 g, 12.9 mmol) in ethanol (40 mL) at 70° C. was added a solution of ammonium chloride (1.36 g, 25.4 mmol) in water (5 mL). Iron powder (2.17 g, 38.9 mmol) was then added portionwise. After stirring for 1 hour, additional iron powder (0.30 g, 5.4 mmol) was added, and the reaction mixture was stirred at 70° C. overnight. The mixture was cooled to room temperature, diluted with ethyl acetate, and Celite® diatomaceous earth filter aid was added. The mixture was filtered through a pad of Celite® diatomaceous earth filter aid. Ethyl acetate and water were added to the filtrate, the layers were separated, and the aqueous phase was extracted with ethyl acetate (×1). The combined organic extracts were washed with saturated aqueous ammonium chloride (×1), dried over sodium sulfate, filtered through a pad of silica and concentrated under reduced pressure to give the title compound as a pale orange solid (2.68 g) which was used in the next step without further purification. 1 H NMR(CDCl3)δ 6.32(d,1H),3.63(br s,2H), 3.10(s,3H),2.84(s,3H),2.07-2.06(m,6H).

[0295] Step E: 3-Fluoro-N,N,2,4-tetramethyl-5-((1,1,1-tetramethyl)-N,N,N-tetramethyl ... Preparation of trifluoro-N-((trifluoromethyl)sulfonyl)methyl)sulfonamido)benzamide To a stirred solution of 5-amino-3-fluoro-N,N,2,4-tetramethyl-benzamide (i.e., the product of Step D) (2.68 g, 12.7 mmol) in dichloromethane (30 mL) at −78° C. was added triethylamine (5.3 mL, 38 mmol), followed by the dropwise addition of a solution of trifluoromethanesulfonic anhydride (5.1 mL, 30 mmol) in dichloromethane (10 mL) over 20 min. The reaction mixture was stirred at −20° C. for 1 h and then poured into water. The layers were separated, the aqueous phase was extracted with dichloromethane (×1), and the combined organic extracts were dried over sodium sulfate, filtered through a pad of silica, and concentrated under reduced pressure. The crude material was purified by column chromatography (gradient of 5 to 30% ethyl acetate in hexanes) to afford the title compound as a white solid (4.48 g). 1 H NMR(CDCl3)δ 6.99(s,1H),3.14(s,3H),2.83(s,3H),2.33(d,3H),2.28(d,3H).

[0296] Step F: 3-Fluoro-N,N,2,4-tetramethyl-5-[[(trifluoromethyl) Preparation of methyl)sulfonyl]amino]benzamide To a stirred solution of 5-[bis(trifluoromethylsulfonyl)amino]-3-fluoro-N,N,2,4-tetramethylbenzamide (i.e., the product of Step E) (4.48 g, 9.4 mmol) in dioxane (70 mL) was slowly added 1N sodium hydroxide (20 mL, 20 mmol). The reaction mixture was stirred overnight at room temperature and then concentrated under reduced pressure to remove most of the dioxane. The mixture was diluted with water and acidified with 1N hydrochloric acid, and the resulting precipitate was collected by filtration and washed with water (×2), diethyl ether (×1), and hexane (×1). The resulting material was purified by crystallization from methanol / water to yield the title compound, a compound of the present disclosure, as a white solid (2.32 g). 1 H NMR(CDCl3)δ 10.50(br s,1H),6.40(s,1H),3.15(s,3H),2.79(s,3H),2.16(m,6H).

[0297] Synthesis Example 4 Preparation of N-[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.5]dec-2-en-3-yl)phenyl]-1,1,1-trifluoromethanesulfonamide (i.e., Compound 197) Step A: Preparation of (2,4-dimethyl-5-nitrophenyl)methanol To a stirred solution of 2,4-dimethyl-5-nitrobenzoic acid (21.5 g, 0.11 mol) in anhydrous tetrahydrofuran (275 mL) at -5 °C was added borane-tetrahydrofuran complex (1 M solution in tetrahydrofuran, 200 mL, 0.2 mol). The reaction mixture was then warmed to room temperature and stirred overnight. Methanol (12 mL) was slowly added, followed by saturated aqueous sodium bicarbonate (100 mL) and water (150 mL). The mixture was extracted with methyl tert-butyl ether (×2), and the combined organic extracts were washed with water (×1) and brine (×1), dried over magnesium sulfate, and concentrated under reduced pressure to afford the title compound as a pale yellow solid (20.0 g), which was used in the next step without further purification. 1 H NMR(CDCl3)δ 8.07(s,1H),7.14(s,1H),4.73(d,2H),2.58(s,3H),2.37(s,3H).

[0298] Step B: Preparation of 2,4-dimethyl-5-nitro-benzaldehyde To a stirred solution of (2,4-dimethyl-5-nitrophenyl)methanol (i.e., the product of Step A) (20.0 g, 0.11 mol) in dichloromethane (330 mL), Celite® diatomaceous earth filter aid (approximately 20 g) was added, followed by pyridinium chlorochromate (28 g, 0.13 mol) in portions over 1 hour. The reaction mixture was stirred at room temperature overnight and then filtered through a pad of silica. The filtrate was concentrated under reduced pressure to give the title compound as a pale yellow solid (18.6 g), which was used in the next step without further purification. 1H NMR(CDCl3)δ 10.23(s,1H),8.45(s,1H),7.27(s,1H),2.72(s,3H),2.67(s,3H).

[0299] Step C: Preparation of 2,4-dimethyl-5-nitro-benzaldehyde oxime To a stirred solution of 2,4-dimethyl-5-nitro-benzaldehyde (i.e., the product of Step B) (29.0 g, 0.16 mol) in methanol (480 mL) was added a solution of hydroxylamine (50 wt % in water, 13.2 g, 0.2 mol) in water (47 mL) dropwise over 25 minutes. The reaction mixture was stirred at room temperature overnight and then concentrated under reduced pressure to remove most of the methanol. Water was added, the mixture was stirred, and the solid material was then collected by filtration, washed with water, and dried under vacuum to give the title compound as a white solid (30.5 g, 11:1). E / Z) which was used in the next step without further purification. 1 H NMR (CDCl3, E isomer) δ 8.34(s,1H),8.33(s,1H),7.51(m,1H),7.17(s,1H),2.59(s,3H),2.46(s,3H).

[0300] Step D: N-hydroxy-2,4-dimethyl-5-nitro-benzimidoyl chloride Preparation of Lido To a stirred solution of 2,4-dimethyl-5-nitro-benzaldehyde oxime (i.e., the product of Step C) (30.5 g, 0.157 mol) in anhydrous N,N-dimethylformamide (160 mL) was added N-chlorosuccinimide (22.1 g, 0.166 mol) in portions over 2 hours, maintaining the internal reaction temperature at 30 °C. The reaction mixture was stirred at room temperature for an additional 3 hours and then poured into ice water and diluted with methyl tert-butyl ether. The layers were then separated, and the aqueous phase was extracted with methyl tert-butyl ether (×2). The combined organic extracts were washed with water (×3), 1N hydrochloric acid, saturated aqueous ammonium chloride solution, dried over magnesium sulfate, and concentrated under reduced pressure to afford the title compound as a pale yellow solid (35.0 g), which was used in the next step without further purification. 1 H NMR(CDCl3)δ 8.20(s,1H),8.04-8.03(m,1H),7.23(s,1H),2.63(s,3H),2.49(s,3H).

[0301] Step E: 3-(2,4-dimethyl-5-nitrophenyl)-1-oxa-2-aza Preparation of spiro[4.5]dec-2-ene To a stirred solution of N-hydroxy-2,4-dimethyl-5-nitro-benzimidoyl chloride (i.e., the product of Step D) (11.5 g, 50 mmol) and methylenecyclohexane (5.8 g, 60 mmol) in chloroform (200 mL) was added triethylamine (11.2 mL, 80 mmol) dropwise over 5 minutes. The reaction mixture was stirred overnight at room temperature and then poured into water, and the layers were separated. The aqueous phase was extracted with dichloromethane, and the combined organic extracts were washed with 1 N hydrochloric acid (×1), brine (×1), dried over magnesium sulfate, and concentrated under reduced pressure to afford the title compound as a viscous yellow oil (16.0 g), which was used in the next step without further purification. 1H NMR(CDCl3)δ 7.98(s,1H),7.24(s,1H),3.13(s,2H),2.64(s,3H),2.63(s,3H),1.87-1.79(m,4H),1.71-1.67(m,2H),1.55-1.47(m,4H).

[0302] Step F: 2,4-dimethyl-5-(1-oxa-2-azaspiro[4.5]dec- Preparation of 2-en-3-yl)aniline To a stirred solution of 3-(2,4-dimethyl-5-nitrophenyl)-1-oxa-2-azaspiro[4.5]dec-2-ene (i.e., the product of Step E) (16.0 g) in ethanol (180 mL) was added a solution of ammonium chloride (5.4 g, 0.10 mol) in water (20 mL) at 50° C. Iron powder (8.4 g, 0.15 mol) was then added portionwise over 25 minutes while the reaction mixture was heated from 50 to 70° C. After stirring at 70° C. for an additional 30 minutes, the mixture was cooled to room temperature and filtered through a pad of Celite® diatomaceous earth filter aid. The filtrate was concentrated under reduced pressure, followed by the addition of ethyl acetate and water. The layers were separated, and the aqueous phase was extracted with ethyl acetate. The combined organic extracts were washed with saturated aqueous ammonium chloride, dried over magnesium sulfate and concentrated under reduced pressure to give the title compound as a viscous amber oil (13.0 g) which was used in the next step without further purification. 1 H NMR(CDCl3)δ 6.93(s,1H),6.67(s,1H),3.54(br s,2H),3.05(s,2H),2.41(s,3H),2.16(s,3H),1.85-1.78(m,4H),1.68-1.63(m,2H),1.51-1.42(m,4H).

[0303] Step G: N-[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.5] Preparation of [dec-2-en-3-yl]phenyl]-1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide To a stirred solution of 2,4-dimethyl-5-(1-oxa-2-azaspiro[4.5]dec-2-en-3-yl)aniline (i.e., the product of Step F) (13.0 g, 50 mmol) in dichloromethane (180 mL) was added triethylamine (21 mL, 0.15 mol). The mixture was cooled to -22 °C, and then a solution of trifluoromethanesulfonic anhydride (20 mL, 0.12 mol) in dichloromethane (20 mL) was added dropwise over 25 min. The reaction mixture was stirred at 0 °C to 10 °C for 1 h and then poured into water. The layers were separated, and the aqueous phase was extracted with dichloromethane. The combined organic extracts were washed with saturated aqueous sodium bicarbonate, saturated aqueous ammonium chloride, dried over magnesium sulfate, and concentrated under reduced pressure. The crude material was purified by column chromatography (gradient of 0-10% methyl tert-butyl ether in hexanes) to give the title compound as a white solid (18.8 g). 1 H NMR(CDCl3)δ 7.27(s,1H),7.19(s,1H),3.02(s,2H),2.59(s,3H),2.42(s,3H),1.89-1.78(m,4H),1.69-1.65(m,2H),1.55-1.42(m,4H).

[0304] Step H: N-[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.5] Preparation of [dec-2-en-3-yl]phenyl]-1,1,1-trifluoromethanesulfonamide To a stirred solution of N-[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.5]dec-2-en-3-yl)phenyl]-1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide (i.e., the product of Step G) (18.8 g, 36 mmol) in dioxane (250 mL) was added dropwise 1N sodium hydroxide (75 mL, 75 mmol). The reaction mixture was stirred overnight at room temperature and then concentrated under reduced pressure to remove most of the dioxane. Water was added, and the mixture was acidified with 1N hydrochloric acid and then extracted with dichloromethane (×2). The combined organic extracts were washed with saturated aqueous ammonium chloride, dried over magnesium sulfate, and concentrated under reduced pressure. The crude material was purified by trituration with hot cyclohexane to afford the title compound, a compound of the present disclosure, as a white solid (11.1 g). 1 H NMR(CDCl3)δ 7.30(s,1H),7.16(s,1H),6.46(s,1H),3.06(s,2H),2.54(s,3H),2.36(s,3H),1.87-1.78(m,4H),1.69-1.64(m,2H),1.54-1.43(m,4H).

[0305] Synthesis Example 5 Preparation of [[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.5]dec-2-en-3-yl)phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropanoate (i.e., Compound 159) To a stirred solution of N-[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.5]dec-2-en-3-yl)phenyl]-1,1,1-trifluoromethanesulfonamide (i.e., the product of Synthesis Example 4) (0.20 g, 0.51 mmol) in dichloromethane (8 mL) was added triethylamine (0.14 mL, 1.0 mmol), followed by chloromethyl pivalate (0.11 mL, 0.76 mmol). The reaction mixture was stirred at room temperature overnight, and then additional chloromethyl pivalate (0.15 mL, 1.0 mmol) was added. The reaction mixture was stirred at 40° C. for 5 hours and then at room temperature overnight. The mixture was concentrated under reduced pressure, and the crude material was purified by column chromatography (0-20% ethyl acetate in hexanes gradient) to afford the title compound, a clear, colorless oil (0.19 g). 1 H NMR(CDCl3)δ 7.22(s,2H),5.75(d,1H),5.41(d,1H),3.00(m,2H),2.54(s,3H),2.38(s, 3H), 1.86-1.76(m, 4H), 1.68-1.61(m, 2H), 1.53-1.42(m, 4H), 1.20(s, 9H).

[0306] Synthesis Example 6 Preparation of N-[2,4-dimethyl-5-[(3aR,6aR)-3a,5,6,6a-tetrahydro-4H-cyclopento[d]isoxazol-3-yl]phenyl]-1,1,1-trifluoromethanesulfonamide (i.e., Compound 103) Step A: 3-(2,4-dimethyl-5-nitro-phenyl)-4,5,6,6a- Preparation of tetrahydro-3aH-cyclopenta[d]isoxazole To a stirred solution of N-hydroxy-2,4-dimethyl-5-nitro-benzimidoyl chloride (i.e., the product of Step D of Synthesis Example 4) (0.50 g, 2.2 mmol) in chloroform (8 mL) was added triethylamine (0.76 mL, 5.4 mmol), followed by cyclopentene (0.29 mL, 3.3 mmol). The reaction mixture was stirred at room temperature overnight, then concentrated under reduced pressure, and the crude material was purified by column chromatography (gradient of 0 to 20% ethyl acetate in hexanes) to afford the title compound as a white solid (0.41 g). 1 H NMR(CDCl3)δ 8.05(s,1H),7.25(s,1H),5.23-5.20(m,1H),4.16-4.12(m,1H),2.62(s,3 H),2.58(s,3H),2.23-2.19(m,1H),1.92-1.74(m,4H),1.58-1.47(m,1H).

[0307] Step B: 5-(4,5,6,6a-tetrahydro-3aH-cyclopenta[d]i) Preparation of (isoxazol-3-yl)-2,4-dimethyl-aniline To a stirred solution of 3-(2,4-dimethyl-5-nitrophenyl)-4,5,6,6a-tetrahydro-3aH-cyclopenta[d]isoxazole (i.e., the product of Step A) (0.38 g, 1.5 mmol) in ethanol (9 mL) and water (1 mL) was added ammonium chloride (0.15 g, 2.8 mmol) and iron powder (0.26 g, 4.7 mmol). The reaction mixture was stirred at 80° C. for 1 hour, then cooled to room temperature, diluted with ethyl acetate, and filtered through a pad of Celite® diatomaceous earth filter aid, followed by a pad of silica. The filtrate was concentrated under reduced pressure to give the title compound as a brown oil (0.35 g), which was used in the next step without further purification. 1 H NMR(CDCl3)δ 6.92(s,1H),6.67(s,1H),5.11-5.09(m,1H),4.05-4.02(m,1H),3.57(br s,2 H),2.35(s,3H),2.16-2.12(m,4H),1.82-1.66(m,4H),1.54-1.44(m,1H).

[0308] Step C: N-[5-(4,5,6,6a-tetrahydro-3aH-cyclopenta[ Preparation of [d]isoxazol-3-yl)-2,4-dimethyl-phenyl]-1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide To a stirred solution of 5-(4,5,6,6a-tetrahydro-3aH-cyclopenta[d]isoxazol-3-yl)-2,4-dimethyl-aniline (i.e., the product of Step B) (0.33 g, 1.4 mmol) in dichloromethane (10 mL) was added triethylamine (0.59 mL, 4.2 mmol). The mixture was cooled to -10 °C, and trifluoromethanesulfonic anhydride (0.59 mL, 3.5 mmol) was added dropwise over 5 minutes. The reaction mixture was stirred at -10 °C for 20 minutes and then poured into water. The layers were separated, the aqueous phase was extracted with dichloromethane, and the combined organic extracts were concentrated under reduced pressure. The crude material was purified by column chromatography (0-20% ethyl acetate in hexanes gradient) to afford the title compound as a white solid (0.48 g). 1 H NMR(CDCl3)δ 7.28(s,2H),5.21-5.18(m,1H),4.07-4.03(m,1H),2.57(s,3H),2.42(s,3H),2.22-2.18(m,1H),1.88-1.73(m,4H),1.56-1.46(m,1H).

[0309] Step D: N-[2,4-dimethyl-5-[(3aR,6aR)-3a,5,6,6 Preparation of a-tetrahydro-4H-cyclopent[d]isoxazol-3-yl]phenyl]-1,1,1-trifluoromethanesulfonamide To a stirred solution of N-[5-(4,5,6,6a-tetrahydro-3aH-cyclopenta[d]isoxazol-3-yl)-2,4-dimethyl-phenyl]-1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide (i.e., the product of Step C) (0.48 g, 0.97 mmol) in dioxane (10 mL) was added 0.5 N sodium hydroxide (5 mL, 2.5 mmol). The reaction mixture was stirred at room temperature for 1 hour and then concentrated under reduced pressure to remove most of the dioxane. The mixture was diluted with water, acidified with 1 N hydrochloric acid, and then extracted with ethyl acetate (×2). The combined organic extracts were washed with water, brine, dried over magnesium sulfate, and concentrated under reduced pressure to provide the title compound, a compound of the present disclosure, as a white solid (0.33 g). 1 H NMR(CDCl3)δ 7.55(br s,1H),7.22(s,1H),7.12(s,1H),5.18-5.15(m,1H),4.06-4.02(m,1H),2.42( s,3H),2.33(s,3H),2.17-2.14(m,1H),1.83-1.70(m,4H),1.52-1.42(m,1H).

[0310] Synthesis Example 7 Preparation of [[2,4-dimethyl-5-[(3aR,6aR)-3a,5,6,6a-tetrahydro-4H-cyclopento[d]isoxazol-3-yl]phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropanoate (i.e., Compound 100) To a stirred solution of N-[5-(4,5,6,6a-tetrahydro-3aH-cyclopenta[d]isoxazol-3-yl)-2,4-dimethyl-phenyl]-1,1,1-trifluoro-methanesulfonamide (i.e., the product of Step D of Synthesis Example 6) (0.13 g, 0.36 mmol) in dichloromethane (8 mL) was added triethylamine (0.10 mL, 0.72 mmol), followed by chloromethyl pivalate (0.08 mL, 0.6 mmol). The reaction mixture was stirred overnight at room temperature, and then additional triethylamine (0.10 mL, 0.72 mmol) and chloromethyl pivalate (0.10 mL, 0.69 mmol) were added. The reaction mixture was stirred overnight at room temperature. The mixture was concentrated under reduced pressure to give the crude product. The material was purified by column chromatography (gradient of 0-20% ethyl acetate in hexanes) to give the disclosed title compound as a clear, colorless oil (79 mg). 1 H NMR(CDCl3)δ 7.28-7.22(m,2H),5.80-5.76(m,1H),5.44-5.39(m,1H),5.20-5.14(m,1H),4.03-3.99(m,1H),2.53- 2.47(m,3H),2.39(m,3H),2.19-2.16(m,1H),1.81-1.71(m,4H),1.54-1.43(m,1H),1.21-1.20(m,9H).

[0311] Synthesis Example 8 Preparation of N-[2,4-dimethyl-5-(1-oxo-2-azaspiro[4.5]dec-2-yl)phenyl]-1,1,1-trifluoromethanesulfonamide (i.e., Compound 278) Step A: 2-(2,4-dimethyl-5-nitro-phenyl)-2-azaspiro[4 Preparation of .5]decan-1-one To a 25 mL scintillation vial with a septum was added copper iodide (0.148 g, 10.0 mmol), tripotassium phosphate (KPO) (3.5 g, 16.4 mmol), and 2-azaspiro[4.5]decan-1-one (1.0 g, 6.5 mmol). The reaction vial was evacuated and backfilled with nitrogen three times. Separately, trans-(1R,2R)N,N'-dimethyl-cyclohexane-1,2-diamine (0.246 mL, 20.0 mol%) and 1-bromo-2,4-dimethyl-5-nitro-benzene (1.8 g, 7.8 mmol) were combined in toluene (10 mL) and added to the reaction mixture vial via syringe. The reaction mixture was stirred at reflux under nitrogen overnight, then diluted with ethyl acetate and filtered through a pad of Celite® diatomaceous earth filter aid. The resulting filtrate was dried over magnesium sulfate and concentrated under reduced pressure to give a residue that was purified by column chromatography (0 to 80% ethyl acetate in hexanes gradient, 40 g column) to give the desired product as a yellow solid (1.85 g). 1 H NMR(CDCl3)δ 7.85(s,1H),7.23(s,1H),3.65(m,2H),2.59(s,3H),2.23(s,3H),2.14-2.18(m,2H),1.65-1.81(m,6H),1.31-1.44(m,4H).

[0312] Step B: 2-(5-amino-2,4-dimethyl-phenyl)-2-azaspiro[4 Preparation of .5]decan-1-one To a stirred solution of 2-(2,4-dimethyl-5-nitrophenyl)-2-azaspiro[4.5]decan-1-one (i.e., the product of Step A) (1.85 g, 6.8 mmol) in ethanol (20 mL) was added a solution of ammonium chloride (0.728 g, 13.6 mmol) in water (2 mL). Iron powder (1.13 g, 20.3 mmol) was then added and the mixture was stirred at 80°C under nitrogen for 2 hours. Thin layer chromatography indicated that the reaction was partially complete after this time. Two equivalents of ammonium chloride and iron powder were added, and stirring was continued at 80°C overnight. The mixture was cooled to room temperature and filtered through a pad of Celite® diatomaceous earth filter aid. A second filtration through Celite® diatomaceous earth filter aid was performed to remove turbidity. The filtrate was dried over magnesium sulfate and concentrated under reduced pressure to give a yellow residue. The residue was purified by column chromatography (20-100% ethyl acetate in hexanes gradient, 40 g column) to give the title compound as a yellow solid (1.36 g). 1 H NMR(CDCl3)δ 6.92(s,1H),6.46(s,1H),3.53-3.58(m,2H),2.12(s,3H),2.08(m,2H),2.05(s,3H),1.65-1.81(m,6H),1.29-1.44(m,4H).

[0313] Step C: N-[2,4-dimethyl-5-(1-oxo-2-azaspiro[4.5] decan-2-yl)phenyl]-1,1,1-trifluoro-N-(trifluoromethyl Preparation of sulfonylmethanesulfonamides To a stirred solution of 2-(5-amino-2,4-dimethyl-phenyl)-2-azaspiro[4.5]decan-1-one (i.e., the product of Step B) (0.500 g, 1.84 mmol) in dichloromethane (10 mL) was added triethylamine (0.562 mL, 4.03 mmol). The mixture was cooled to 0 °C, and then trifluoromethanesulfonic anhydride (0.677 mL, 4.03 mmol) in dichloromethane (10 mL) was added dropwise over 5 minutes. The reaction mixture was then stirred at room temperature overnight. The reaction mixture was concentrated in vacuo. The crude material was purified by column chromatography (0-100% ethyl acetate in hexanes gradient, 40 g column) to afford the title compound as an off-white solid (0.650 g). 1 H NMR(CDCl3)δ 7.25(s,1H),7.07(s,1H),3.61(m,2H),2.39(s,3H),2.21(s,3H),2.14(m,2H),1.58-1.81(m,6H),1.56-1.60,1.29-1.52(m,4H).

[0314] Step D: N-[2,4-dimethyl-5-(1-oxo-2-azaspiro[4.5] Preparation of [dec-2-yl]phenyl-1,1,1-trifluoromethanesulfonamide To a stirred solution of N-[2,4-dimethyl-5-(1-oxo-2-azaspiro[4.5]decan-2-yl)phenyl]-1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide (i.e., the product of Step C) (0.510 g, 0.951 mmol) in dioxane (15 mL) was added dropwise 1.0 N aqueous sodium hydroxide (1 mL, 1.0 mmol). The reaction mixture was stirred overnight at room temperature and then concentrated under reduced pressure to remove most of the dioxane and water. The mixture was acidified with a few drops of 6 N aqueous hydrochloric acid, forming a white precipitate. This precipitate was then filtered and dried under vacuum overnight to give the title compound (0.335 g). 1H NMR(CDCl3)δ 6.93(s,1H),6.79(s,1H),3.56(m,2H),2.08-2.16(m,8H),1.79(m,4H),1.56(m,3H),1.37(m,3H).

[0315] Synthesis Example 9 Preparation of [[2,4-dimethyl-5-(1-oxo-2-azaspiro[4.5]dec-2-yl)phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropanoate (i.e., Compound 268) To a stirred solution of N-[2,4-dimethyl-5-(1-oxo-2-azaspiro[4.5]decan-2-yl)phenyl]-1,1,1-trifluoromethanesulfonamide (i.e., Step D of Synthesis Example 8) (0.150 g, 0.370 mmol) in methylene chloride (15 mL) was added triethylamine (0.103 mL, 0.740 mmol) and chloromethyl pivalate (0.064 mL, 0.440 mmol). The reaction mixture was stirred overnight at room temperature. The reaction mixture was concentrated in vacuo. The residue was purified by column chromatography (0 to 100% ethyl acetate in hexanes gradient, 12 g column) to afford the disclosed compound, the title compound, as a clear oil (0.092 g). 1 H NMR(CDCl3)δ 7.22(s,1H),7.05(s,1H),5.71(d,1H),5.42(d,1H),3.53-3.63(m,2H),2.38(s,3H),2.19(s,3H),2. 10-2.15(m,2H),2.05(s,1H),1.57-1.82(m,4H),1.47-1.52(m,1H),1.30-1.51(m,3H),1.20(s,9H).

[0316] Synthesis Example 10 N-[5-(6-ethyl-2,3-dihydro-2-methyl-3-oxo-4-pyridazinyl)-2,4-dimethylphenyl]-1,1,1-trifluoromethanesulfonamide ( That is, preparation of compound 34) Step A: 2-(2,4-dimethyl-5-nitro-phenyl)-4,4,5,5-tetramethyl- Preparation of tetramethyl-1,3,2-dioxaborolane To a stirred solution of 1-bromo-2,4-dimethyl-5-nitro-benzene (2.30 g, 10 mmol) in dioxane (20 mL) was added bis(pinacolato)diboron (3.4 g, 14 mmol), followed by potassium acetate (2.84 g, 30 mmol) and bis(triphenylphosphine)palladium(II) dichloride (0.35 g, 0.5 mmol). The reaction mixture was warmed to 110° C. and stirred overnight. The reaction mixture was then cooled to room temperature, diluted with ethyl acetate, and filtered through a pad of Celite® diatomaceous earth filter aid. The reaction mixture was concentrated in vacuo. The crude material was purified by column chromatography to give the title compound (4.10 g). 1 H NMR(CDCl3)δ 8.40(s,1H),7.10(s,1H),2.57(s,3H),2.56(s,3H),1.35(s,12H).

[0317] Step B: Preparation of 6-ethyl-4-iodo-2-methyl-pyridazin-3-one To a stirred solution of 6-ethyl-2-methyl-pyridazin-3-one (0.95 g, 6.9 mmol) in tetrahydrofuran (10 mL) at 0 °C was added TMPZn·LiCl (14 mL, 9.6 mmol, 0.7 M in tetrahydrofuran). The reaction mixture was warmed to room temperature and stirred for 1 h. Iodine (2.7 g, 10.3 mmol) was then added, and the reaction mixture was stirred at room temperature overnight. Saturated aqueous ammonium chloride solution was added, and the aqueous phase was extracted with ethyl acetate (×3). The combined organic layers were washed with NaSO solution followed by brine. The combined organic extracts were dried (MgSO), filtered, and concentrated in vacuo. Purification by column chromatography (gradient of 0 to 100% ethyl acetate in hexanes) afforded the title compound (290 mg). 1 H NMR(CDCl3)δ 7.81(d,1H),3.81(s,3H),2.62(m,2H),1.23(m,3H).

[0318] Step C: 4-(2,4-dimethyl-5-nitro-phenyl)-6-ethyl-2-methyl Preparation of thyl-pyridazin-3-one To a stirred solution of 6-ethyl-4-iodo-2-methyl-pyridazin-3-one benzamide (i.e., the product of Step B) (0.26 g, 1 mmol) in dioxane (2 mL) was added 2-(2,4-dimethyl-5-nitro-phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (i.e., the product of Step A) (0.39 g, 1.4 mmol), bis(triphenylphosphine)palladium(II) dichloride (0.035 mg, 0.05 mmol), and sodium carbonate (2N in HO, 1 mL), and the reaction mixture was warmed to 80 °C for 3 hours. The reaction mixture was then cooled to room temperature, diluted with ethyl acetate, and filtered through a Celite® diatomaceous earth filter aid pad. The reaction mixture was concentrated in vacuo. The crude material was purified by column chromatography to give the title compound (0.28 g). 1 H NMR(CDCl3)δ 7.92(s,1H),7.25(s,1H),7.11(s,1H),3.86(s,3H),2.68(m,2H),2.63(s,3H),2.30(s,3H),1.26(m,3H).

[0319] Step D: 4-(5-amino-2,4-dimethyl-phenyl)-6-ethyl-2-methyl Preparation of thyl-pyridazin-3-one To a stirred solution of 4-(2,4-dimethyl-5-nitro-phenyl)-6-ethyl-2-methyl-pyridazin-3-one (i.e., the product of Step C) (0.28 g, 1 mmol) in ethanol (18 mL) was added a solution of ammonium chloride (0.16 g, 3 mmol) in water (2 mL) at 70 °C. Iron powder (0.17 g, 3 mmol) was then added portionwise, and the reaction mixture was stirred for 3 h. The mixture was cooled to room temperature, diluted with ethyl acetate, and The resulting mixture was filtered through a pad of Celite® diatomaceous earth filter aid. Ethyl acetate and water were added to the filtrate, the layers were separated, and the aqueous phase was extracted with ethyl acetate (×1). The combined organic extracts were washed with saturated aqueous ammonium chloride solution (×1), dried over sodium sulfate, filtered through a pad of silica, and concentrated under reduced pressure to give the title compound (0.21 g), which was used in the next step without further purification. 1 H NMR(CDCl3)δ 7.05(s,1H),6.97(s,1H),6.61(s,1H),3.81(s,3H),2.66(m,2H),2.19(s,3H),2.11(s,3H),1.25(m,3H).

[0320] Step E: N-[5-(6-ethyl-2-methyl-3-oxo-pyridazin-4-yl] Preparation of [1,4-dimethyl-phenyl]-1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide To a stirred solution of 4-(5-amino-2,4-dimethyl-phenyl)-6-ethyl-2-methyl-pyridazin-3-one (i.e., the product of Step D) (0.2 g, 0.7 mmol) in dichloromethane (3 mL) was added triethylamine (0.13 mL, 0.9 mmol) at −78° C., followed by the dropwise addition of a solution of trifluoromethanesulfonic anhydride (0.11 mL, 0.9 mmol) in dichloromethane (2 mL) over 20 min. Silica gel was added to the reaction mixture, and the solvent was removed in vacuo. The crude material was purified by column chromatography (gradient of 5 to 30% ethyl acetate in hexanes) to give the title compound (0.08 g) and N-[5-(6-ethyl-2-methyl-3-oxo-pyridazin-4-yl)-2,4-dimethyl-phenyl]-1,1,1-trifluoro-methanesulfonamide (i.e., the product of Step F in this synthesis example) (0.13 g). 1 H NMR(CDCl3)δ 7.28(s,1H),7.20(s,1H),7.06(s,1H),3.83(s,3H),2.71(m,2H),2.43(s,3H),2.29(s,3H),1.27(m,3H).

[0321] Step F: N-[5-(6-ethyl-2,3-dihydro-2-methyl-3-oxo- Preparation of 4-pyridazinyl)-2,4-dimethylphenyl]-1,1,1-trifluoromethanesulfonamide To a stirred solution of N-[5-(6-ethyl-2-methyl-3-oxo-pyridazin-4-yl)-2,4-dimethyl-phenyl]-1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide (i.e., the product of Step E) (0.08 g) in dioxane (2 mL) was added 1N sodium hydroxide (0.5 mL, 0.5 mmol) slowly. The reaction mixture was stirred overnight at room temperature and then concentrated in vacuo. The crude material was acidified, worked up, and purified by column chromatography to give the title compound, a compound of the present disclosure, as a white solid (0.025 g). 1 H NMR(CDCl3)δ 9.78(s,1H),7.07(s,1H),6.92(s,1H),6.89(s,1H),3.90(s,3H),2.71(m,2H),2.16(s,3H),2.15(s,3H),1.27(m,3H).

[0322] Synthesis Example 11 Preparation of N-[2,4-dimethyl-5-(1,2,3,4-tetrahydro-1,3-dimethyl-2,4-dioxo-5-pyrimidinyl)phenyl]-1,1,1-trifluoromethanesulfonamide (i.e., Compound 49) Step A: 5-(2,4-dimethyl-5-nitro-phenyl)-1,3-dimethyl- Preparation of pyrimidine-2,4-diones To a stirred solution of 5-bromo-1,3-dimethyl-pyrimidine-2,4-dione (0.65 g, 3 mmol) in dioxane (6 mL) was added 2-(2,4-dimethyl-5-nitro-phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (i.e., the product of Step A of Synthesis Example 10) (1.1 g, 3.9 mmol), bis(triphenyl (Phosphine)palladium(II) dichloride (0.11 g, 0.15 mmol) and sodium carbonate (2N in HO, 3 mL) were added, and the reaction mixture was warmed to 80° C. for 3 h. The reaction mixture was then cooled to room temperature, diluted with ethyl acetate, and filtered through a pad of Celite® diatomaceous earth filter aid. The reaction mixture was concentrated in vacuo. The crude material was purified by column chromatography to give the title compound (0.72 g). 1 H NMR(CDCl3)δ 7.84(s,1H),7.29(s,1H),7.25(s,1H),3.49(s,3H),3.42(s,3H),2.62(s,3H),2.29(s,3H).

[0323] Step B: 5-(5-amino-2,4-dimethyl-phenyl)-1,3-dimethyl- Preparation of pyrimidine-2,4-diones To a stirred solution of 5-(2,4-dimethyl-5-nitro-phenyl)-1,3-dimethyl-pyrimidine-2,4-dione (i.e., the product of Step A) (0.29 g, 1 mmol) in ethanol (18 mL) at 70° C. was added a solution of ammonium chloride (0.16 g, 3 mmol) in water (2 mL). Iron powder (0.17 g, 3 mmol) was then added portionwise, and the reaction mixture was stirred for 3 hours. The mixture was cooled to room temperature, diluted with ethyl acetate, and filtered through a pad of Celite® diatomaceous earth filter aid. Ethyl acetate and water were added to the filtrate, the layers were separated, and the aqueous phase was extracted with ethyl acetate (×1). The combined organic extracts were washed with saturated aqueous ammonium chloride solution (×1), dried over sodium sulfate, filtered through a pad of silica, and concentrated under reduced pressure to give the title compound (0.21 g), which was used in the next step without further purification. 1 H NMR(CDCl3)δ 7.11(s,1H),6.92(s,1H),6.49(s,1H),3.44(s,3H),3.41(s,3H),2.15(s,3H),2.09(s,3H).

[0324] Step C: N-[2,4-dimethyl-5-(1,2,3,4-tetrahydro-1,3 Preparation of [(dimethyl-2,4-dioxo-5-pyrimidinyl)phenyl]-1,1,1-trifluoromethanesulfonamide To a stirred solution of 5-(5-amino-2,4-dimethyl-phenyl)-1,3-dimethyl-pyrimidine-2,4-dione (i.e., the product of Step B) (0.21 g, 0.81 mmol) in dichloromethane (3 mL) at −78° C. was added triethylamine (0.13 mL, 0.97 mmol), followed by the dropwise addition of a solution of trifluoromethanesulfonic anhydride (0.11 mL, 0.9 mmol) in dichloromethane (2 mL) over 20 min. Silica gel was added to the reaction mixture, and the solvent was removed in vacuo. The crude material was purified by column chromatography (gradient: 5 to 100% ethyl acetate in hexanes) to afford the title compound, a compound of the present disclosure, as a white solid (0.11 g). 1 H NMR(CDCl3)δ 8.18(s,1H),7.18(s,1H),7.01(s,1H),6.92(s,1H),3.47(s,3H),3.45(s,3H),2.18(s,3H),2.16(s,3H).

[0325] Synthesis Example 12 Preparation of 1,1,1-trifluoro-N-[2,3,4-trimethyl-5-(4-morpholinylcarbonyl)phenyl]methanesulfonamide (i.e., Compound 289) Step A: Preparation of 2,3,4-trimethylbenzaldehyde To a stirred solution of 1,2,3-trimethylbenzene (3 g, 25 mmol) in dichloromethane (35 mL) at 0 °C was added 1,1-dichlorodimethyl ether (3.6 mL, 40 mmol), followed by titanium tetrachloride (1 M solution in dichloromethane, 27.5 mL, 27.5 mmol). The reaction mixture was stirred at 0 °C for 2 h and then poured into ice-water (300 mL). Dichloromethane (100 mL) was added, the mixture was stirred vigorously for 10 min, and the layers were then separated. The aqueous phase was extracted with dichloromethane (×1), and the combined organic extracts were washed with water, brine, and hexane. and concentrated under reduced pressure to give the title compound as a pale yellow oil (3.1 g) which was used in the next step without further purification. 1 H NMR(CDCl3)δ 10.26(s,1H),7.56(d,1H),7.16(d,1H),2.61(s,3H),2.36(s,3H),2.24(s,3H).

[0326] Step B: Preparation of 2,3,4-trimethylbenzoic acid To a stirred solution of 2,3,4-trimethylbenzaldehyde (i.e., the product of Step A) (3.1 g) in acetone (20 mL) and water (10 mL) at 0° C. was added potassium permanganate (6.61 g, 41.8 mmol) in portions. The reaction mixture was then warmed to room temperature and stirred overnight. The mixture was filtered through a pad of Celite, rinsed with water and acetone, and the filtrate was then acidified to pH ∼2 with 1N hydrochloric acid and extracted with ethyl acetate (×2). The combined organic extracts were washed with water and brine, dried over magnesium sulfate, and concentrated under reduced pressure to afford the title compound as a white solid (2.6 g), which was used in the next step without further purification. 1 H NMR(CDCl3)δ 7.74(d,1H),7.08(d,1H),2.57(s,3H),2.35(s,3H),2.25(s,3H).

[0327] Step C: Preparation of 2,3,4-trimethyl-5-nitro-benzoic acid Concentrated nitric acid (0.8 mL) was added dropwise to concentrated sulfuric acid (0.7 mL) at 0°C, and the mixture was stirred for 5 minutes. This mixture was then added dropwise to a stirred mixture of 2,3,4-trimethylbenzoic acid (i.e., the product of Step B) (1.5 g) in concentrated sulfuric acid (8 mL) at 5°C. The reaction mixture was stirred at 0°C to 5°C for 2 hours and then poured into ice-water (200 mL). The mixture was extracted with ethyl acetate (x2), and the combined organic extracts were washed with water and brine, dried over magnesium sulfate, and concentrated under reduced pressure to afford the title compound as a tan solid (1.82 g), which was used in the next step without further purification. 1 H NMR(CDCl3)δ 8.24(s,1H),2.64(s,3H),2.46(s,3H),2.36(s,3H).

[0328] Step D: Morpholino-(2,3,4-trimethyl-5-nitro-phenyl)methano Preparation of To a stirred mixture of 2,3,4-trimethyl-5-nitrobenzoic acid (i.e., the product of Step C) (0.20 g) in chloroform (8 mL) was added triethylamine (0.4 mL, 2.9 mmol) and morpholine (0.1 mL, 1.1 mmol), followed by propylphosphonic anhydride (50 wt% in ethyl acetate, 1.2 g, 1.9 mmol). The reaction mixture was stirred at 60 °C for 3 h, then the mixture was cooled to room temperature and concentrated under reduced pressure. The crude material was purified by column chromatography (gradient of 0 to 60% ethyl acetate in hexanes) to afford the title compound as a yellow oil (0.19 g). 1 H NMR(CDCl3)δ 7.43(s,1H),3.803.73(m,4H),3.603.50(m,2H),3.263.16(m,2H),2.37(s,3H),2.27(s,6H).

[0329] Step E: (5-amino-2,3,4-trimethyl-phenyl)-morpholino-meth Preparation of NON To a stirred mixture of morpholino-(2,3,4-trimethyl-5-nitro-phenyl)methanone (i.e., the product of Step D) (0.19 g, 0.70 mmol) in ethanol (9 mL) and water (1 mL) was added ammonium chloride (75 mg, 1.4 mmol) and iron powder (0.12 g, 2.1 mmol). The reaction mixture was stirred at 80° C. for 2 hours, then cooled to room temperature, diluted with ethyl acetate, and filtered through a pad of Celite® followed by a pad of silica. The filtrate was concentrated under reduced pressure to give the title compound as a yellow oil ( 0.14 g), which was used in the next step without further purification. 1H NMR(CDCl3)δ 6.26(s,1H),3.793.55(m,6H),3.533.51(m,2H),3.233.20(m,2H),2.15(s,3H),2.09(s,3H),2.06(s,3H).

[0330] Step F: 1,1,1-trifluoro-N-(trifluoromethylsulfonyl)-N Preparation of -[2,3,4-trimethyl-5-(morpholine-4-carbonyl)phenyl]methanesulfonamide To a stirred solution of (5-amino-2,3,4-trimethyl-phenyl)-morpholino-methanone (i.e., the product of Step E) (0.14 g) in dichloromethane (8 mL) at -10 °C, triethylamine (0.24 mL, 1.7 mmol) was added, followed by the dropwise addition of trifluoromethanesulfonic anhydride (0.19 mL, 1.1 mmol). The reaction mixture was stirred at 0 °C to 10 °C for 1 h, and then water was added. The layers were separated, and the organic phase was concentrated under reduced pressure. The crude material was purified by column chromatography (gradient of 0 to 60% ethyl acetate in hexanes) to afford the title compound as a clear, colorless oil (0.15 g). 1 H NMR(CDCl3)δ 6.99(s,1H),3.83-3.73(m,4H),3.60-3.51(m,2H),3.24-3.15(m,2H),2.31(s,3H),2.29(s,3H),2.27(s,3H).

[0331] Step G: 1,1,1-trifluoro-N-[2,3,4-trimethyl-5-(methylamino)methyl] Preparation of [(4-carbonyl)phenyl]methanesulfonamide To a stirred solution of 1,1,1-trifluoro-N-(trifluoromethylsulfonyl)-N-[2,3,4-trimethyl-5-(morpholine-4-carbonyl)phenyl]methanesulfonamide (i.e., the product of Step F) (0.15 g, 0.30 mmol) in dioxane (8 mL) was added 0.5 N sodium hydroxide (3.6 mL, 1.8 mmol). The reaction mixture was stirred at room temperature for 2 hours and then concentrated under reduced pressure to remove the dioxane. The mixture was diluted with water, acidified to a pH of approximately 2 with 1 N hydrochloric acid, and then extracted with ethyl acetate (×2). The combined organic extracts were washed with water and brine, dried over magnesium sulfate, and concentrated under reduced pressure to provide the title compound, a compound of the present invention, as a white solid (0.10 g). 1 H NMR(CDCl3)δ 10.16(br s,1H),6.45(s,1H),3.853.82(s,2H),3.783.75(s,2H),3.57(m,2H),3.193.11(m,2H),2.19(s,3H),2.15(s,3H),2.13(s,3H).

[0332] Synthesis Example 13 Preparation of [[(trifluoromethyl)sulfonyl][2,3,4-trimethyl-5-(4-morpholinylcarbonyl)phenyl]amino]methyl 2,2-dimethylpropanoate (i.e., Compound 324) To a stirred solution of 1,1,1-trifluoro-N-[2,3,4-trimethyl-5-(4-morpholinylcarbonyl)phenyl]methanesulfonamide (i.e., the product of Synthesis Example 12, 0.10 g, 0.27 mmol) in acetonitrile (8 mL) was added sodium bicarbonate (80 mg, 0.95 mmol), tetrabutylammonium bromide (87 mg, 0.27 mmol), and chloromethyl pivalate (0.12 mL, 0.81 mmol). The reaction mixture was stirred at 80°C for 3 hours, then cooled to room temperature and concentrated under reduced pressure. The crude material was purified by column chromatography (gradient: 0 to 50% ethyl acetate in hexanes) to afford the title compound, a compound of the present invention, as a clear, colorless oil (93 mg). 1H NMR(CDCl3)δ 6.97-6.93(m,1H),5.79-5.67(m,1H),5.455.37(m,1H),3.933.68(m,4H),3.593.50(m,2H),3.253.16(m,2H),2.312.29(m,3H) ),2.25(s,6H),1.19(s,9H).

[0333] The compounds in Tables 1-11 below can be prepared by the procedures described herein and methods known in the art. In the following tables, the following abbreviations are used: t means tertiary, s means secondary, n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, Bu means butyl, n-Pr means 1-propyl, i-Pr means isopropyl, Bu means butyl, c-Pr means cyclopropyl, c-Bu means cyclobutyl, i-Bu means isobutyl, Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, SEt means ethylthio, NHMe means methylamino, -CN means cyano, Py means pyridinyl, -NO2 means nitro, TMS means trimethylsilyl, S(O)Me means methylsulfinyl, and S(O)2Me means methylsulfonyl.

[0334] [Table 1]

[0335] [Table 2]

[0336] [Table 3]

[0337] [Table 4]

[0338] Table 5

[0339] Table 6

[0340] Table 7

[0341] Table 8

[0342] Table 9

[0343] Table 10

[0344] Table 11

[0345] Table 12

[0346] Table 13

[0347] Table 14

[0348] [Table 15]

[0349] [Table 16]

[0350] [Table 17]

[0351] [Table 18]

[0352] [Table 19]

[0353] [Table 20]

[0354] [Table 21]

[0355] The compounds of the present invention are generally used as herbicidal active ingredients in compositions, i.e., formulations with at least one additional component (which serves as a carrier) selected from the group consisting of surfactants, solid excipients, and liquid excipients. The ingredients of the formulation or composition are selected to suit the physical properties of the active ingredient, the mode of application, and environmental factors such as soil type, moisture, and temperature.

[0356] Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, flowable concentrates, and / or suspoemulsions), which may optionally be thickened to form gels. Common types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions, oil-in-water emulsions, flowable concentrates, and suspoemulsions. Common types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates, and oil dispersions.

[0357] Common types of solid compositions include dusts, powders, granules, pellets, prills, pastilles, tablets, and fill films (including seed coatings), which may be water-dispersible ("wettable") or water-soluble. Films and coatings formed from film-forming solutions or fluid suspensions are particularly useful for seed treatments. Active ingredients can be (micro)encapsulated or further processed into suspension or solid formulations; alternatively, the entire active ingredient formulation can be encapsulated (or "overcoated"). Encapsulation can control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsion and dry granular formulations. High-strength compositions are primarily used as intermediates for further formulation.

[0358] Sprayable formulations are typically diluted in a suitable vehicle before spraying. Such liquid and solid formulations are formulated to be easily diluted in the spray vehicle, usually water, but sometimes other suitable vehicles, such as aromatic or paraffinic hydrocarbons or vegetable oils. Spray volumes can range from about 1 liter to several thousand liters per hectare, but more typically range from about 10 liters to several hundred liters per hectare. Sprayable formulations can be tank-mixed with water or other suitable vehicles for foliar treatment by aerial or ground application, or for application to the plant growing medium. Liquid and dry formulations can be metered directly into drip irrigation systems or into the furrow at planting time.

[0359] The formulations typically contain effective amounts of active ingredient, diluent, and surfactant within the general ranges below, the total of which adds up to 100 weight percent.

[0360] [Table 22]

[0361] Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite, and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and sodium bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.

[0362] Examples of liquid diluents include water, N,N-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), alkyl phosphates (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oil, normal paraffin, isoparaffin), alkylbenzenes, alkylnaphthalenes, glycerin, glycerol, glycerol, methylparaben ... esters such as alkyl lactate, dibasic esters, alkyl and aryl benzoates, γ-butyrolactone, and alcohols which may be linear, branched, saturated, or unsaturated, e.g., methyl methyl acrylate, methyl methyl acrylate, methyl methyl meth ... Liquid diluents include, for example, methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol, and benzyl alcohol. Liquid diluents also include saturated and unsaturated fatty acids (typically C6-C8 22glycerol esters of vegetable oils, such as vegetable seed and fruit oils (e.g., olive oil, castor oil, linseed oil, sesame oil, corn oil (maize oil), peanut oil, sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil, and palm kernel oil), fats of animal origin (e.g., beef tallow, pork fat, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated), which can be obtained by hydrolysis of vegetable and animal-derived glycerol esters and purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.

[0363] The solid and liquid compositions of the present invention often contain one or more surfactants. When added to a liquid, a surfactant (also known as a "surface-active agent") generally modifies, and in most cases reduces, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, surfactants can be useful as wetting agents, dispersants, emulsifiers, or antifoaming agents.

[0364] Surfactants can be classified as nonionic, anionic, or cationic. Nonionic surfactants useful in the compositions of the present invention include, but are not limited to, alcohol alkoxylates, such as those based on natural and synthetic alcohols (which may be branched or linear) and prepared from alcohols with ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof; amine ethoxylates, alkanolamides, and ethoxylated alkanolamides; alkoxylated triglycerides, such as ethoxylated soybean oil, linseed oil, and rapeseed oil; alkylphenol alkoxylates, such as octylphenol ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate, and dodecylphenol ethoxylate (prepared from phenol and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide, and the end blocks of which are propylene oxide. reverse block polymers prepared from ethylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenols (including those prepared from ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters, and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd PEG (polyethylene glycol) resins, graft or comb polymers, and star polymers; polyethylene glycol (PEG); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar derivatives such as sucrose esters, alkyl polyglycosides, and alkyl polysaccharides.

[0365] Useful anionic surfactants include, but are not limited to, alkylarylsulfonic acids and their salts; carboxylate alcohols, or alkylphenol ethoxylates; diphenylsulfonate derivatives; lignin and lignin derivatives, such as lignosulfonates; maleic or succinic acid, or their anhydrides; olefin sulfonates; phosphate esters, such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates, and phosphate esters of styrylphenol ethoxylates; protein-based surfactants; and sarcosine. derivatives; styrylphenol ether sulfates; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides, such as N,N-alkyl taurates; sulfonates of benzene, cumene, toluene, xylene, and dodecylbenzene and tridecylbenzene; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkylnaphthalenes; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their derivatives, such as the salts of dialkyl sulfosuccinates.

[0366] Useful cationic surfactants include, but are not limited to, amides and ethoxylated amides; amines such as N-alkylpropanediamines, tripropylenetriamine, and dipropylenetetramine, and ethoxylated amines, ethoxylated diamines, and propoxylated amines (prepared from amines with ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); amine salts such as acetate salts of amines and salts of diamines; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts, and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

[0367] Also useful in the compositions of the present invention are mixtures of nonionic and anionic surfactants, or mixtures of nonionic and cationic surfactants. Nonionic, anionic, and cationic surfactants, and their recommended uses, are disclosed in various published references, such as McCutcheon's Emulsifiers and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publishein Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and AS Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.

[0368] The compositions of the present invention may further include formulation aids and additives known to those skilled in the art as formulation aids, some of which may also be considered to function as solid diluents, liquid diluents, or surfactants. Such formulation aids and additives can adjust: pH (buffers), foaming during processing (defoamers, e.g., polyorganosiloxanes), active ingredient settling (suspending agents), viscosity (thixotropic thickeners), microbial growth in the container (antimicrobial agents), product freezing (antifreeze), color (dye / pigment dispersions), wash-off (film formers, or stickers), evaporation (evaporation inhibitors), and other formulation attributes. Film formers include, for example, polyvinyl acetate, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol, polyvinyl alcohol copolymers, and waxes. Examples of formulation aids and additives include those listed in McCutcheon's Vol. 1, No. 1, pp. 111-114, 1997. me 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and WO 03 / 024222 pamphlet.

[0369] The compound of Formula 1 and various other active ingredients are typically incorporated into the compositions of the present invention by dissolving the active ingredient in a solvent or by milling it in a liquid or dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. When the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added and diluted with water to emulsify the active ingredient-containing solvent. Slurries of active ingredients having particle diameters up to 2,000 μm can be wet-milled using a media mill to obtain particles with an average diameter of less than 3 μm. Aqueous slurries can be made into final suspension concentrates (see, e.g., U.S. Pat. No. 3,060,084) or can be further processed by spray drying to form water-dispersible granules. Dry formulations typically require a dry milling process, resulting in average particle diameters in the range of 2 to 10 μm. Dusts and powders can be prepared by blending and, usually, grinding (e.g., using a hammer mill or fluid energy mill). Granules and pellets can be prepared by spraying the active material onto a preformed granular carrier or by agglomeration techniques. See Browning, "Agglomeration," Chemical Engineering, December 4, 1967, pp. 147-48; Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57; and WO 91 / 13546. Pellets can be prepared as described in U.S. Pat. No. 4,172,714. Water-dispersible and water-soluble granules can be prepared according to the teachings of U.S. Pat. No. 4,144,050, U.S. Pat. No. 3,920,442, and German Patent No. 3,246,493. Tablets can be prepared according to the teachings of US Pat. Nos. 5,180,587, 5,232,701, and 5,208,030.Films can be prepared according to the teachings of British Patent No. 2,095,558 and US Pat. No. 3,299,566.

[0370] For more information on formulation techniques, see T. S. Woods, "The Formulator's Toolbox - Product Forms for Modern Agriculture," in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also the following: U.S. Pat. No. 3,235,361, column 6, line 16 to column 7, line 19, and Examples 10-41; U.S. Pat. No. 3,309,192, column 5, line 43 to column 7, line 62, and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, and 169-182; U.S. Pat. No. 2,891,855, column 3, line 66 to column 5, line 17, and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientif ic Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

[0371] In the following examples, all percentages are by weight and all formulations are prepared in a conventional manner. Compound numbers refer to compounds in Index Tables A-G. It is believed that one skilled in the art using the preceding description will be able, without undue effort, to utilize the present invention to its fullest extent. Accordingly, the following examples are to be construed as merely illustrative and not limiting of the disclosure in any way. Percentages are by weight unless otherwise indicated. [Example]

[0372] Example A high strength concentrate Compound 260 98.5% Silica aerogel 0.5% Synthetic amorphous fine silica 1.0%

[0373] Example B Wettable powder Compound 260 65.0% Dodecylphenol polyethylene glycol ether 2.0% Sodium lignosulfonate 4.0% Sodium silicoaluminate 6.0% Montmorillonite (calcined) 23.0%

[0374] Example C 0B granule Compound 260 10.0% Attapulgite Granules (Low Volatility, 0.71 / 0.30 mm; USS No. 25-50 Sieve) 90.0%

[0375] Example D Extrusion processed pellets Compound 260 25.0% Anhydrous sodium sulfate 10.0% Crude calcium lignosulfonate 5.0% Sodium alkylnaphthalene sulfonate 1.0% Calcium / Magnesium Bentonite 59.0%

[0376] Example E emulsifiable concentrate Compound 260 10.0% Polyoxyethylene sorbitol hexaoleate 20.0% C6~C 10 Fatty acid methyl ester 70.0%

[0377] Example F Microemulsion Compound 260 5.0% Polyvinylpyrrolidone-vinyl acetate copolymer 30.0% Alkyl polyglycoside 30.0% Glyceryl monooleate 15.0% Water 20.0%

[0378] Example G Suspension concentrate Compound 260 35% Butyl polyoxyethylene / polypropylene block copolymer 4.0% Stearic acid / polyethylene glycol copolymer 1.0% Styrene acrylic polymer 1.0% Xanthan gum 0.1% Propylene glycol 5.0% Silicone-based antifoam agent 0.1% 1,2-benzisothiazolin-3-one 0.1% Water 53.7%

[0379] Example H Emulsion in water Compound 260 10.0% Butyl polyoxyethylene / polypropylene block copolymer 4.0% Stearic acid / polyethylene glycol copolymer 1.0% Styrene acrylic polymer 1.0% Xanthan gum 0.1% Propylene glycol 5.0% Silicone-based antifoam agent 0.1% 1,2-benzisothiazolin-3-one 0.1% Aromatic Petroleum-Based Hydrocarbons 20.0 Water 58.7%

[0380] Example I Oil dispersion Compound 260 25% Polyoxyethylene sorbitol hexaoleate 15% Organically modified bentonite clay 2.5% Fatty acid methyl esters 57.5%

[0381] Additional example formulations include Examples A-I above, where "Compound 260" is replaced in each of Examples A-I with the respective compound from Index Table A, as shown below.

[0382] [Table 23]

[0383] The test results show that the compounds of the present invention are highly active pre-emergence and / or post-emergence herbicides and / or plant growth inhibitors.The compounds of the present disclosure generally show the highest activity for post-emergence weed control (i.e., applied after weed seedlings emerge from the soil) and pre-emergence weed control (i.e., applied before weed seedlings emerge from the soil).Many of them are useful for broad-spectrum pre-emergence and / or post-emergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, airports, riverbanks, irrigation and other waterways, around large billboards, and railroad facilities. Many of the compounds of the present invention are useful for the selective control of grasses and broadleaf weeds in crop / weed mixtures because they have selective crop versus weed metabolism, or selective activity in areas of physiological inhibition in crops and weeds, or selective placement on or in the mixed crop and weed environment. As will be recognized by those skilled in the art, suitable combinations of selectivity factors within a single compound or group of compounds can be readily determined by routine biological and / or biochemical assays.

[0384] The compounds of the invention may exhibit resistance to important agricultural crops such as, but not limited to, alfalfa, barley, cotton, wheat, oilseed rape, sugar beet, corn (maize), sorghum, soybean, rice, oats, peas, vegetables, tomatoes, potatoes, perennial plantation crops (including coffee, cocoa, oil palm, rubber), sugarcane, citrus, grapeseed, fruit trees, nut trees, bananas, plantains, pineapples, hops, tea plants, and woodlands such as eucalyptus and conifers (e.g., loblolly pine), and turf species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue, and cypress). The compounds of the present invention may be useful in genetically transformed crops, or crops bred to incorporate herbicide resistance, express proteins toxic to invertebrate pests (e.g., Bacillus thuringiensis toxins), and / or express other useful traits. As one of ordinary skill in the art will recognize, not all compounds are equally effective against all weeds. However, the compounds that are the subject of the present invention are useful for regulating plant growth.

[0385] Because the compounds of the present invention have both pre- and post-emergence herbicidal activity and control undesirable vegetation by killing or damaging the vegetation or inhibiting its growth, they can be usefully applied by a variety of methods, including contacting a herbicidally effective amount of a compound of the present disclosure, or a composition comprising said compound and at least one surfactant, solid diluent, or liquid diluent, with the foliage or other parts of the undesirable vegetation, or with the environment of the undesirable vegetation, e.g., soil or water, in which the undesirable vegetation is growing or surrounding the seeds or other propagules of the undesirable vegetation.

[0386] The herbicidally effective amount of the compounds of the present invention depends on several factors, including the formulation selected, the method of application, the amount and type of vegetation present, and growing conditions. Generally, the herbicidally effective amount of the compounds of the present invention ranges from about 0.001 to 20 kg / ha, preferably from about 0.004 to 1 kg / ha. Those skilled in the art can readily determine the herbicidally effective amount required to achieve the desired level of weed control.

[0387] In one general embodiment, a compound of the present disclosure, typically in the form of a formulated composition, is applied to an area containing desirable vegetation (e.g., crops) and undesirable vegetation (i.e., weeds), both of which may be seeds, seedlings, and / or more mature plants, in contact with a growing medium (e.g., soil). In this area, a composition containing a compound of the present disclosure can be applied directly to the plants or parts thereof of the undesirable vegetation, and / or to the growing medium in contact with the plants.

[0388] Plant varieties and cultivars of the desired vegetation in the habitat treated with the compounds of the present disclosure can be obtained by conventional propagation and breeding methods or by genetic engineering methods. A genetically modified plant (transgenic plant) is one in which a heterologous gene (transgene) is stably integrated into the plant's genome. A transgene, defined by its specific location in the plant genome, is called a transformation or transgenic event.

[0389] Genetically modified plant varieties at loci that can be treated according to the present invention include those that are resistant to one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, low temperatures, soil salinity, etc.), or contain other desirable traits. Plants can be genetically modified to exhibit traits such as herbicide tolerance, insect resistance, altered oil profile, or drought tolerance, for example.

[0390] Although compounds of the invention are most typically used to control undesirable vegetation, contacting desirable vegetation with a compound of the invention in a treated area may result in superadditive or synergistic effects with the genetic traits in the desirable vegetation, including traits acquired through genetic modification. For example, resistance to herbivorous pests or plant diseases, resistance to biotic / abiotic stresses, or storage stability may be greater than would be expected from the genetic traits in the desirable vegetation.

[0391] The compounds of the present invention can also be mixed with one or more other biologically active compounds or agents, including herbicides, herbicide safeners, fungicides, insecticides, nematicides, bactericides, acaricides, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, signal chemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds, or entomopathogenic bacteria, viruses, or fungi, to form multi-component biocides that provide an even broader agricultural protection spectrum. Mixtures of the compounds of the present invention with other herbicides can extend the spectrum of activity against additional weed species and suppress the growth of various resistant biotypes. Thus, The present invention also relates to compositions comprising a compound of Formula 1 (in a herbicidally effective amount) and at least one additional biologically active compound or agent (in a biologically effective amount), and may further comprise at least one surfactant, solid diluent, or liquid diluent. The other biologically active compound or agent can be formulated in a composition comprising at least one surfactant, solid diluent, or liquid diluent. For the mixtures of the present invention, one or more other biologically active compounds or agents can be formulated with the compound of Formula 1 to form a premix, or one or more other biologically active compounds or agents can be formulated separately from the compound of Formula 1, and the formulations can be combined (e.g., in a spray tank) before application, or alternatively, applied sequentially.

[0392] Mixtures of the compounds of the invention with one or more of the following herbicides may be particularly useful for weed control: acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal), alachlor, alloxydim, ametryn, amicarbazone, amidosulfuron, aminocyclopyrachlor and its esters (e.g., methyl, ethyl) and salts (e.g., sodium, potassium), aminopyralid, amitrole, ammonium sulfamate. , Anilofos, Ashlam, Atrazine, Azimsulfuron, Beflubutamid, Benazolin, Benazolin-ethyl, Bencarbazone, Benfluralin, Benfuresate, Bensulfuron-methyl, Bensulide, Bentazon, Benzobicyclon, Benzofenap, Bicyclopyrone, Bifenox, Biranaphos, Bispyribac and its sodium salt, Bromacil, Bromobutide, Bromofenoxime, Bromoxynil, Bromoxynil octanoate, Butachlor, Butafena Sil, butamifos, butralin, butroquidizime, butyrate, cafenstrole, carbetamide, carfentrazone-ethyl, catechin, chlormethoxyfen, chloramben, chlorbromuron, chlorflurenol-methyl, chloridazon, chlorimuron-ethyl, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, clasifos, clefoxydim, clethodim, Clodinafop-propargyl, clomazone, clomeprop, clopyralid, clopyralid-olamine, chloransulam-methyl, cumyluron, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, 2,4-D and its butotyl, butyl, isoctyl and isopropyl esters and its dimethylammonium, diolamine and trolamine salts, dymron, dalapon, dalapon sodium, dazomet, 2,4-DB and its dimethylammonium, potassium and sodium salts, desmedipham, desmetrin, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, dichlobenil, dichlorprop, diclofop-methyl, diclosulam, difenzoquat methylsulfate, diflufenican, diflufenzopyr, dimefron, dimepiperate, dimethachlor, dimethametrin, dimethenamid, dimethenamid-P, dimethipine, dimethylarsinic acid and its sodium salt, dinitramine, dinoterb, diphenamide, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsurfuron-methyl, ethiozin, ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanide, fenoxaprop-e methyl, fenoxaprop-P-ethyl, fenoxasulfone, fenquinotrione, fentrazamide, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, flurenol, flurenol-butyl, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet-methyl, fomesafen, foramsulfuron, fosamine- Ammonium, glufosinate, glufosinate ammonium, glufosinate-P, glyphosate and its salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (also known as sulfosate), haloxifen, haloxifen methyl, halosulfuron-methyl, haloxyfop-ethotyl, haloxyfop-methyl, hexazinone, hydantocidin, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr ... tapyr-ammonium, imazosulfuron, indanofan, indaziflam, iofensulfuron, iodosulfuron-methyl, ioxynil, ioxynil octanoate, ioxynil-sodium, ifencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, isoxachlorthole, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its salts (e.g., MCPA-dimethylammonium, MCPA-potassium and MCPA-sodium), esters (e.g., MCPA-2-ethylhexyl, MCPA-butotyl) and thioesters (e.g., MCPA-thioethyl), MCPB and its salts (e.g., MCPB-sodium) and esters (e.g., MCPB-ethyl), mecoprop, mecoprop-P, mefenacet, mefluidide, mesosulfuron-methyl, mesotrione, metam-sodium, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyldimuron, metobenzuron, metobromuron, Metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron methyl, molinate, monolinuron, naproanilide, napropamide, napropamide-M, naptalam, nevron, nicosulfuron, norflurazon orbencarb or tosulfamuron oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat dichloride, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentanochlor, pentoxazone, perfluidone, petoxamid,Petoxyamide, phenmedipham, picloram, picloram-potassium, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron-methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazogyl, pyrazolinate, pyrazoxyfen, pyrazosulf ron-ethyl, pyribenzoxim, pyributicarb, pyridate, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, piroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop-ethyl, quizalofop-p-ethyl, quizalofop-p-tefuryl, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron-methyl, sulfosulfuron, 2,3,6-TBA, TCA , TCA-sodium, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbumeton, terbuthylazine, terbutryn, thenylchlor, thiazopyr, thiencarbazone, thifensulfuron-methyl, thiobencarb, thiafenacil, thiocarbazil, tolpyralate, topramezone, traalkoxydim, triallate, triafamone, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tridiphane, Trietazine, trifloxysulfuron, trifludimoxadine, trifluralin, triflusulfuron-methyl, tritosulfuron, vernolate, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridin-2(1H)-one, 5-chloro-3-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalinone, 2-chloro-N-(1-methyl-1H-tetrazol-5-yl)-6-(trifluoromethyl)-3-pyridinone, azinecarboxamide, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-b]pyrazin-6(5H)-one), 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone), 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole (formerly methioxoline), 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexyl)-1-methyl-2-methyl-3-methyl-2-thienyl]isoxazole (formerly methioxoline),

[0033] -2-methyl-1,2,4-triazine-3,5(2H,4H)-dione, methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate, 2-methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide, and 2-methyl-N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide. Other herbicides also include Alternaria destruens Simmons, Colletotrichum gloeosporiodes (Penz.) Penz. & Sacc., Drechsiera monoceras (MTB-951), Myrothecium verrucaria (Albertini & Schweinitz) Ditmar:Fries, Phytophthora palmivora (Butl.) Butl., and Puccinia thlaspeos Schub.

[0393] The compounds of the invention may also be used in combination with plant growth regulators such as aviglycin, N-(phenylmethyl)-1H-purin-6-amine, epocholeon, gibberellic acid, gibberellins A4 and A7, harpin proteins, mepiquat chloride, prohexadione calcium, prohydrojasmone, nitrophenol sodium, and trinexapac-methyl, and plant growth-modifying organisms such as Bacillus cereus strain BP01.

[0394] General references for agricultural protectants (i.e., herbicides, herbicide safeners, insecticides, fungicides, nematicides, acaricides, and biological agents) include: The Pesticide Manual, 13th Edition, CDS Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2003, and The BioPesticide Manual, 2nd Edition, L.G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2001.

[0395] In embodiments in which one or more of these various mixing partners are used, the mixing partners are typically used in amounts comparable to those customarily used when the mixing partners are used alone. More specifically, in mixtures, the active ingredient is often applied at a rate between half and all of the rate prescribed on the product label for the active ingredient used alone. These amounts are described, for example, in the following references: The Pesticide Manual and The BioPesticide Manual. The weight ratio of these various mixing partners (combined) to the compound of Formula 1 is typically between about 1:3000 and about 3000:1. Of note are weight ratios between about 1:300 and about 300:1 (e.g., ratios between about 1:30 and about 30:1). Those skilled in the art can easily determine by simple experimentation the biologically effective amount of the active ingredient required to obtain the desired spectrum of biological activity. These additional components are also useful. It will be apparent that the inclusion of a compound of formula 1 makes it possible to extend the spectrum of weeds controlled beyond that controlled by the compound of formula 1 alone.

[0396] In certain cases, the compounds of the present invention may be combined with other biologically active (especially herbicidal) compounds or agents (i.e., active ingredients) to achieve greater than additive (i.e., synergistic) effects against weeds and / or less than additive (i.e., safening) results for crops or other desirable plants. Reducing the amount of active ingredient released into the environment while still effectively controlling pests is always desirable. The ability to use greater amounts of active ingredient for more effective weed control without excessive crop damage is also desirable. If synergistic effects of herbicidal active ingredients occur with weeds at application rates that provide agronomically satisfactory levels of weed control, such combinations may be advantageous for reducing crop production costs and reducing environmental impact. If safening of herbicidal active ingredients occurs with crops, such combinations may be advantageous for reducing weed competition and enhancing crop protection.

[0397] Of note is the combination of the compound of the present disclosure with at least one other herbicidal active ingredient. Particularly noteworthy is the combination in which the other herbicidal active ingredient has a different site of action from the compound of the present invention. In some cases, the combination with at least one other herbicidal active ingredient having a similar control spectrum but a different site of action may be particularly advantageous for resistance management. Therefore, the composition of the present invention may further comprise at least one additional herbicidal active ingredient (in a herbicidally effective amount) having a similar control spectrum but a different site of action.

[0398] The compounds of the invention can also be used in combination with herbicide safeners to increase safety in certain crops, such as, for example, allidochlor, benoxacor, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfonamide, dymron, dichlormid, dicyclonone, dietholate, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, methoxyphenone, naphthalic anhydride (1,8-naphthalic anhydride), oxabetrinil, N-(aminocarbonyl)-2-methylbenzenesulfonamide, N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene (BCS), 4-(dichloroacetyl)-1-oxa-4-azospiro[4.5]decane (MON). 4660), 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), ethyl 1,6-dihydro-1-(2-methoxyphenyl)-6-oxo-2-phenyl-5-pyrimidinecarboxylate, 2-hydroxy-N,N-dimethyl-6-(trifluoromethyl)pyridine-3-carboxamide, and 3-oxo-1-cyclohexan-1-yl 1-(3,4-dimethylphenyl)-1,6-dihydro-6-oxo-2-phenyl-5-pyrimidinecarboxylate, 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-ethanone, and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide. An additional effective amount of a herbicide safener can be applied simultaneously with the compound of the invention or as a seed treatment. Thus, an embodiment of the invention relates to herbicide mixtures comprising a compound of the invention and an antidotal effective amount of a herbicide safener. Seed treatments are particularly useful for selective weed control because they limit the antidote effect to the crop. Thus, a particularly useful embodiment of the present invention is a method for selectively controlling the growth of undesirable vegetation in a crop, comprising contacting a locus of the crop with a herbicidally effective amount of a compound of the present disclosure, wherein the seeds from which the crop grows are treated with an antidote-effective amount of a safener. The antidote-effective amount of the safener can be determined by one of ordinary skill in the art using simple methods. This can be easily determined by experiment.

[0399] The compounds of the present invention can also be mixed with: (1) polynucleotides, including but not limited to, DNA, RNA, and / or chemically modified nucleotides that affect the abundance of specific targets through, for example, downregulation, interference, suppression, or silencing of engineered transcripts to confer a herbicidal effect; or (2) polynucleotides, including but not limited to, DNA, RNA, and / or chemically modified nucleotides that affect the abundance of specific targets through, for example, downregulation, interference, suppression, or silencing of engineered transcripts to confer a safening effect.

[0400] Of note are compositions comprising a compound of the present disclosure (in a herbicidally effective amount), at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners (in an effective amount), and at least one component selected from the group consisting of surfactants, solid excipients, and liquid excipients.

[0401] For better control of undesirable vegetation (e.g., lower application rates due to additive effects, a broader spectrum of weeds controlled, or improved crop safety) or to prevent the development of resistant weeds, preferred are combinations of the compounds of the present invention with atrazine, azimsulfuron, beflubutamid, S-beflubutamid, benzisothiazolinone, carfentrazone-ethyl, chlorimuron-ethyl, chlorsulfuron-methyl, clomazone, clopyralid potassium, cloransulam-methyl, 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-3-isoxazolidinone (CA No. 81777-95-9), and 2-[(2,5-dichlorophenyl)methyl]-4,4-dimethyl-3-isoxazolidinone. and a herbicide selected from the group consisting of ethametsulfuron-methyl, flumetsulam, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5-(2H,4H)-dione, flupyrsulfuron-methyl, fluthiacet-methyl, fomesafen, imazethapyr, lenacil, mesotrione, metribuzin, metsulfuron-methyl, petoxamid, picloram, pyroxasulfone, quinclorac, rimsulfuron, rinzucor, S-metolachlor, sulfentrazone, thifensulfuron-methyl, triflusulfuron-methyl, and tribenuron-methyl. Table A1 lists specific combinations of component (a) and component (b) that are illustrative of the mixtures, compositions, and methods of the present invention. The compound numbers in the component (a) column are identified in Index Table A. The second column of Table A1 lists specific component (b) compounds (e.g., "2,4-D" in the first row). The third, fourth, and fifth columns of Table A1 list a series of weight ratios for the rate at which component (a) compounds relative to component (b) are typically applied to field-grown crops (i.e., (a):(b)). Thus, for example, the first row of Table A1 specifically discloses that combinations of component (a) (i.e., compound 45 in Index Table A) and 2,4-D are typically applied in weight ratios of 1:192 to 6:1. The remaining rows of Table A1 are interpreted similarly.

[0402] [Table 24]

[0403] [Table 25]

[0404] [Table 26]

[0405] [Table 27]

[0406] [Table 28]

[0407] [Table 29]

[0408] [Table 30]

[0409] Table A2 is structured the same as Table A1 above, except that the contents under the "Component (a) (Compound Number)" column heading are replaced with the contents of the respective Component (a) column shown below. Compound 16 in the Component (a) column is identified in Index Table A. Thus, for example, in Table A2, the contents under the "Component (a)" column heading all list "Compound 16" (i.e., Compound 16 as identified in Index Table A), and the first row under the column heading in Table A2 specifically discloses a mixture of Compound Number 16 and 2,4-D. Tables A3-A16 are structured similarly.

[0410] [Table 31]

[0411] The following tests demonstrate the effectiveness of the compounds of the present invention against specific weeds. However, the weed control provided by the compounds is not limited to these species. See Index Tables A-G for compound descriptions. In the following Index Tables, the following abbreviations are used: t is tertiary, s is secondary, n is normal, i is iso, c is cyclo, Me is methyl, Et is ethyl, Pr is propyl, i-Pr is isopropyl, Bu is butyl, c-Pr is cyclopropyl, t-Bu is tert-butyl, Ph is phenyl, OMe is methoxy, OEt is ethoxy, SMe is methylthio, SEt is ethylthio, -CN is cyano, -NO is nitro, TMS is trimethylsilyl, and naphthyl means naphthalenyl. (R) or (S) denotes the absolute chirality of the asymmetric carbon center. The abbreviation "(d)" indicates that the compound appeared to decompose upon melting. The abbreviation "Cmpd.#" stands for "Compound Number." The abbreviation "Ex." stands for "Example," followed by a number indicating the example in which the compound was prepared. Mass spectra are based on the parent ion with the highest isotopically abundant ion, H + Reported with an estimated accuracy within ±0.5 Da as the molecular weight of (M+1) formed by the addition of (Mw1), observed using atmospheric pressure chemical ionization (AP+).

[0412] [Table 32]

[0413] [Table 33]

[0414] [Table 34]

[0415] Table 35

[0416] Table 36

[0417] Table 37

[0418] Table 38

[0419] Table 39

[0420] Table 40

[0421] Table 41

[0422] Table 42

[0423] Table 43

[0424] Table 44

[0425] [Table 45]

[0426] [Table 46]

[0427] [Table 47]

[0428] [Table 48]

[0429] Biological Examples of the Invention Test A Seeds of plant species selected from barnyard grass (Echinochloa crus-galli), kochia (Bassia scoparia), common ragweed (Ambrosia artemisiifolia), ryegrass (Italian ryegrass, Lolium multiflorum), foxtail (Setaria faberii), and pigweed (Amaranthus retroflexus) were planted in a blend of loam soil and sand and pre-emergence treated with a directional soil application of test chemicals formulated in a non-phytotoxic solvent mixture containing a surfactant.

[0430] Concurrently, plants selected from these weed species, as well as wheat (Triticum aestivum), corn (Zea mays), blackgrass (Alopecurus myosuroides), and cleaver (Galium aparine), were planted in pots containing the same blend of loam soil and sand and treated with postemergence applications of the formulated test chemicals in the same manner. Plants ranged in height from 2 to 10 cm and were at the one- to two-leaf stage for postemergence treatment. Treated plants and untreated controls were maintained in the greenhouse for approximately 10 days, after which time all treated plants were compared to untreated controls and visually evaluated for injury. Plant response ratings, summarized in Table A, were based on a 0 to 100 scale, where 0 was no effect and 100 was complete control. A dash (-) response indicates no test result.

[0431] [Table 49]

[0432] [Table 50]

[0433] [Table 51]

[0434] [Table 52]

[0435] [Table 53]

[0436] [Table 54]

[0437] Table 55

[0438] Table 56

[0439] Table 57

[0440] Table 58

[0441] Table 59

[0442] Table 60

[0443] Table 61

[0444] Table 62

[0445] Table 63

[0446] Table 64

[0447] [Table 65]

[0448] [Table 66]

[0449] [Table 67]

[0450] [Table 68]

[0451] [Table 69]

[0452] [Table 70]

[0453] [Table 71]

[0454] [Table 72]

[0455] Test A1 Seeds of plant species selected from blackgrass (Alopecurus myosuroides), corn (Zea mays), giant foxtail (Setaria faberi), goosegrass (Eleusine indica), broomwood (Bassia scoparia), wild oat (Avena fatua), palmer amaranth (Amaranthus palmeri), common ragweed (Ambrosia artemisiifolia), ryegrass (Italian ryegrass, Lolium multiflorum), soybean (Glycine max), and wheat (Triticum aestivum) were planted in a blend of loam soil and sand and pre-emergence treated with a directional soil application of test chemicals formulated in a non-phytotoxic solvent mixture containing a surfactant.

[0456] Simultaneously, plants selected from these crop and weed species, as well as catchweed bedstraw (Galium aparine) and dwarf artemisia (Erigeron canadensis), were planted in pots containing the same blend of loam soil and sand and treated with postemergence applications of the formulated test chemicals in the same manner. Plants ranged in height from 2 to 10 cm and were at the one- to two-leaf stage for postemergence treatment. Treated plants and untreated controls were maintained in the greenhouse for 10 days, after which time all treated plants were compared to untreated controls and visually evaluated for injury. Plant response ratings, summarized in Table A, were based on a 0 to 100 scale, where 0 is no effect and 100 is complete control. A dash (-) response indicates no test result.

[0457] [Table 73]

[0458] [Table 74]

[0459] Table 75

[0460] Table 76

[0461] Table 77

[0462] Table 78

[0463] Table 79

[0464] Table 80

[0465] Table 81

[0466] Table 82

[0467] Table 83

[0468] Table 84

[0469] [Table 85]

[0470] [Table 86]

[0471] [Table 87]

[0472] [Table 88]

[0473] [Table 89]

[0474] Test B Flooded paddy test plant species selected from rice (Oryza sativa), sedge (small-flower umbrella sedge, Cyperus difformis), American barnyard grass (Heteranthera limosa), and barnyardgrass (Echinochloa crus-galli) were grown to the two-leaf stage for testing. At the time of treatment, test pots were flooded to 3 cm above the soil surface, and test compounds were treated by applying them directly to the paddy water and then maintained at that water depth for the duration of the test. Treated plants and controls were maintained in the greenhouse for 13 to 15 days, after which all species were visually evaluated compared to the control. Plant response ratings, summarized in Table B, were based on a 0 to 100 scale, where 0 is no effect and 100 is complete control. A dash (-) response indicates no test result.

[0475] [Table 90]

[0476] [Table 91]

[0477] [Table 92]

[0478] [Table 93]

[0479] Exam B1 Barnyardgrass (Echinochloa crus-galli), American barnyardgrass (Heteranthera limosa), rice (Oryza sativa), and small-flower umbrella sedge (Cyperus Flooded paddy test plant species selected from the group consisting of P. difformis (L.) were grown to the two-leaf stage for testing. At the time of treatment, test pots were flooded to 3 cm above the soil surface, and test compounds were treated by applying them directly to the paddy water, then maintained at that water depth for the duration of the test. Treated plants and controls were maintained in the greenhouse for 10-14 days, after which all species were visually evaluated compared to the control. Plant response ratings, summarized in Table B, were based on a 0-100 scale, where 0 is no effect and 100 is complete control. A dash (-) response indicates no test result.

[0480] [Table 94]

[0481] [Table 95]

[0482] [Table 96]

Claims

1. A compound selected from formula 1, its stereoisomers, N-oxides, and salts, 【Chemistry 1】 During the ceremony, G is CONR ５ R ６ or 【Chemistry 2】 is selected from R １ But H, C １ ~C ７ Alkyl, halogen, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl or C １ ~C ７ haloalkyl; R ２ But H, C １ ~C ７ Alkyl, halogen, CN, C １ ~C ７ Haloalkyl, C １ ~C ７ Alkoxy, C ３ ~C ７ cycloalkyl, or C １ ~C ５ alkylthio; R ３ But H, C １ ~C ７ Alkyl, halogen, CN, C ２ ~C ６ Alkenyl, C ３ ~C ７ Alkynyl, C ３ ~C ７ Cycloalkyl, C ２ ~C ３ Cyanoalkyl, C １ ~C ７ Haloalkyl, C ３ ~C ７ Haloalkenyl, C ３ ~C ７ Haloalkynyl, C ２ ~C ７ Alkoxyalkyl, C １ ~C ７ Alkoxy, C １ ~C ５ Alkylthio, C ２ ~C ３ Alkoxycarbonyl or C ２ ~C ７ haloalkoxyalkyl; R ４ H, C(=O)R １９ , -C(=S)R １９ , -CO ２ R １９ , -C(=O)SR １９ , -S(O) ２ R １９ , C(═O)NR １９ R ２０ , -S(O) ２ NR １９ R ２０ , S(OH) ２ NR １９ R ２０ or CH ２ OC(=O)R １９ and R ５ But H, C １ ~C ７ Alkyl, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl, C ４ ~C ７ Cycloalkylalkyl, C ３ ~C ７ Alkenylalkenyl Kill, C ３ ~C ７ Alkynylalkyl, C ２ ~C ３ Cyanoalkyl, C １ ~C ７ Haloalkyl, C ３ ~C ７ Haloalkenyl, C ２ ~C ７ Alkoxyalkyl, C ３ ~C ７ Alkylthioalkyl, C １ ~C ７ Alkoxy; C ２ ~C ７ Alkoxyalkyl or C ４ ~C ７ alkylcycloalkyl; R ６ But H, C １ ~C ７ Alkyl, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl, C ４ ~C ７ Cycloalkylalkyl, C ３ ~C ７ Alkenyl alkyl, C ３ ~C ７ Alkynylalkyl, C ２ ~C ３ Cyanoalkyl, C １ ~C ７ Haloalkyl, C ３ ~C ７ Haloalkenyl, C ２ ~C ７ Alkoxyalkyl, C ３ ~C ７ Alkylthioalkyl, C １ ~C ７ Alkoxy; C ２ ~C ７ Alkoxyalkyl or C ４ ~C ７ alkylcycloalkyl; or R ５ and R ６ together with the nitrogen atom to which they are attached form a 3- to 7-membered ring containing carbon atoms and optionally 1-3 oxygen, sulfur or nitrogen atom ring members, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring members are S, S(O) or S(O) ２ wherein the rings are independently selected from (R ｖ ) ｒ optionally substituted with up to 5 substituents selected from: R ｖ are independently H, halogen, cyano, nitro, C １ ~C ４ Alkyl, C ３ ~C ６ Cycloalkyl, C １ ~C ４ Haloalkyl, C １ ~C ４ Alkoxy and C １ ~C ４ haloalkoxy; or Two R's ｖ are bonded to the same carbon atom or to two adjacent carbon atoms, the two R ｖ together with the carbon atom or atoms to which they are attached form a 3- to 7-membered ring containing carbon atoms and optionally 1-3 oxygen, sulfur, or nitrogen atoms as ring members, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring members are S, S(O), or S(O) ２ wherein the ring is unsubstituted or is selected from halogen, cyano, nitro, C １ ~C ４ Alkyl, C ３ ~C ６ Cycloalkyl, C １ ~C ４ Haloalkyl, C １ ~C ４ Alkoxy and C １ ~C ４ substituted with at least one substituent independently selected from the group consisting of haloalkoxy; R ７ But H, C １ ~C ７ Alkyl, halogen, CN, C １ ~C ７ Haloalkyl or C １ ~C ７ is alkoxy; R ８ But H, C １ ~C ７ is alkyl; or R ７ and R ８ may be taken together to form a 3- to 7-membered ring containing carbon atoms and optionally 1 to 2 oxygen, sulfur or nitrogen atoms as ring members, said ring being unsubstituted or substituted with halogen, cyano, nitro, C １ ~C ４ Alkyl, C ３ ~C ６ Cycloalkyl, C １ ~C ４ Haloalkyl, C １ ~C ４ Alkoxy and C １ ~C ４ substituted with at least one substituent independently selected from the group consisting of haloalkoxy; R ９ But H, C １ ~C ７ Alkyl, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl, C ４ ~C ７ Cycloalkylalkyl, C ２ ~C ３ Cyanoalkyl, C １ ~C ７ Haloalkyl, C ３ ~C ７ Haloalkenyl, C ２ ~C ７ Alkoxyalkyl, C ３ ~C ７ Alkylthioalkyl, C １ ~C ７ Alkoxy; C ２ ~C ７ Alkoxyalkyl or C ４ ~C ７ alkylcycloalkyl; R ７ and R ９ may be taken together to form a fused 3- to 7-membered ring containing carbon atoms and optionally 1 to 2 oxygen, sulfur or nitrogen atoms as ring members, said ring being unsubstituted or substituted with halogen, cyano, nitro, C １ ~C ４ Alkyl, C ３ ~C ６ Cycloalkyl, C １ ~C ４ Haloalkyl, C １ ~C ４ Alkoxy and C １ ~C ４ substituted with at least one substituent independently selected from the group consisting of haloalkoxy; R １０ is H or C １ ~C ７ is alkyl; or R ９ and R １０ may be taken together with the carbon atoms to which they are attached to form a 3- to 7-membered ring containing carbon atoms and optionally 1-2 oxygen, sulfur, or nitrogen atoms as ring members, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring member is S, S(O), or S(O) ２ wherein the rings are independently selected from (R ｖ ) ｒ where r is the number of substituents; or teeth Two R's ｖ are bonded to the same carbon atom or to two adjacent carbon atoms, the two R ｖ are taken together with the carbon atom or atoms to which they are attached to form a 3- to 7-membered ring containing carbon atoms and optionally 1-2 oxygen, sulfur, or nitrogen atoms as ring members, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring member is S, S(O), or S(O) ２ Selected from: Q is O, S, CR １１ R １２ or NR １３ and R １１ and R １２ together with the carbon atoms to which they are attached form a fused 3- to 7-membered ring containing carbon atoms and optionally 1 to 2 oxygen, sulfur or nitrogen atoms as ring members, said ring being unsubstituted or substituted with halogen, cyano, nitro, C １ ~C ４ Alkyl, C ３ ~C ６ Cycloalkyl, C １ ~C ４ Haloalkyl, C １ ~C ４ Alkoxy and C １ ~C ４ substituted with at least one substituent independently selected from the group consisting of haloalkoxy; or R ９ and R １１ together with the carbon atoms to which they are attached form a six-membered aromatic ring, said ring being independently selected from R ｗ optionally substituted with up to four substituents selected from: R ｗ But C １ ~C ７ Alkyl, halogen, C １ ~C ７ Haloalkyl or C １ ~C ７ is alkoxy; r is 0, 1, 2, 3, 4 or 5; s is 0, 1, 2, 3, or 4; R １３ But H, C １ ~C ７ Alkyl, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl, C ４ ~C ７ Cycloalkylalkyl, C ２ ~C ３ Cyanoalkyl, C １ ~C ７ Haloalkyl, C ３ ~C ７ Haloalkenyl, C ２ ~C ７ Alkoxyalkyl, C ３ ~C ７ Alkylthioalkyl, C １ ~C ７ Alkoxy; C ２ ~C ７ Alkoxyalkyl or C ４ ~C ７ alkylcycloalkyl; R １４ But H, C １ ~C ７ Alkyl, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl, C ４ ~C ７ Cycloalkylalkyl, C ２ ~C ３ Cyanoalkyl, C １ ~C ７ Haloalkyl, C １ ~C ７ Thioalkyl, C ３ ~C ７ Haloalkenyl, C ２ ~C ７ Alkoxyalkyl, C ３ ~C ７ Alkylthioalkyl, C １ ~C ７ Alkoxy; C ２ ~C ７ Alkoxyalkyl or C ４ ~C ７ alkylcycloalkyl; R １５ But H, C １ ~C ７ Alkyl, halogen, C １ ~C ７ Haloalkyl or C １ ~C ７ is alkoxy; R １６ But H, cyano, C １ ~C ７ Alkyl, halogen, C １ ~C ４ Alkylthio, C １ ~C ７ Haloalkyl or C １ ~C ７ is alkoxy; R １７ But H, C １ ~C ７ Alkyl, halogen, CN, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl, C ２ ~C ３ Cyanoalkyl, C １ ~C ７ Haloalkyl, C ３ ~C ７ Haloalkenyl, C ３ ~C ７ Haloalkynyl, C ２ ~C ７ Alkoxyalkyl, C １ ~C ７ Alkoxy, C １ ~C ５ Alkylthio, C ２ ~C ３ Alkoxycarbonyl or C ２ ~C ７ haloalkoxyalkyl; R １８ But H, C １ ~C ７ Alkyl, halogen, C １ ~C ７ Haloalkyl or C １ ~C ７ is alkoxy; R １９ But C １ ~C ７ Alkyl, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl, C ４ ~C ７ Cycloalkylalkyl, C ２ ~C ３ Cyanoalkyl, C １ ~C ７ Haloalkyl, C ３ ~C ７ Haloalkenyl, C ２ ~C ７ Alkoxyalkyl, C ３ ~C ７ Alkylthioalkyl, C １ ~C ７ Alkoxy; C ２ ~C ７ Alkoxyalkyl, C ４ ~C ７ alkylcycloalkyl; R ２０ is H or C １ ~C ７ haloalkyl; R ｆ But C １ ~C ７ A compound that is a haloalkyl.

2. Q is O, S or CR １１ R １２ 2. The compound of claim 1, wherein:

3. G is CONR ５ R ６ and R １ But H, C １ ~C ７ Alkyl, halogen, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl or C １ ~C ７ haloalkyl; R ２ But H, C １ ~C ７ Alkyl, C ３ ~C ６ cycloalkyl, halogen or CN; R ３ But H, C １ ~C ７ Alkyl, halogen, CN, C １ ~C ７ Alkoxy or C １ ~C ７ haloalkyl; R ４ H, C(=O)R １９ , CO ２ R １９ , C(=O)SR １９ , S(O) ２ R １９ or CH ２ OCOR １９ and R ５ But H, C １ ~C ３ Alkyl, C ２ ~C ３ Alkenyl, C ２ ~C ３ Alkynyl, C ３ ~C ６ Cycloalkyl, C ４ ~C ７ Cycloalkylalkyl, C ３ ~C ６ Alkenyl alkyl, C ３ ~C ６ Alkynylalkyl or C ２ ~C ３ is cyanoalkyl; R ６ But H, C １ ~C ３ Alkyl, C ２ ~C ３ Alkenyl, C ２ ~C ３ Alkynyl, C ３ ~C ６ Cycloalkyl, C ４ ~C ７ Cycloalkylalkyl, C ３ ~C ６ Alkenyl alkyl, C ３ ~C ６ Alkynylalkyl or C ２ ~C ３ is cyanoalkyl; R ｆ But C １ ~C ３ The compound of claim 1 which is a haloalkyl.

4. R １ But H, C １ ~C ７ Alkyl, halogen or C ３ ~C ７ is cycloalkyl; R ２ is H, Me or F; R ３ is H, Me, F, Cl, CN, OMe or CF ３ and R ４ But, H, SO ２ CF ３ , S.O. ２ CH ３ , CO ２ Me, COMe, CH ２ OCO-t-Bu, CH ２ OCO-n-Bu, CH ２ OCO-c-hexyl, CH ２ OCO-c-pentyl, CH ２ OCOCH ２ CH ３ ,COMe,CH ２ OCOPh, CH ２ OCO-i-Bu, CH ２ OCOMe, CH ２ OCO-sec-Bu or COSMe; R ５ is H, methyl, ethyl, propyl, cyanomethyl, CH ２ CCH or c-propylmethyl; R ６ is H, methyl, ethyl, propyl, cyanomethyl, CH ２ CCH or c-propylmethyl; R ｆ But CF ３ 4. The compound of claim 3, wherein:

5. R １ is Me or Cl; R ３ is Me; R ４ But H, CH ２ OCO-t-Bu or SO ２ CF ３ and R ５ is methyl; R ６ The compound of claim 4, wherein is methyl.

6. Q is CONR ５ R ６ and R １ But H, C １ ~C ７ Alkyl, halogen, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl or C １ ~C ７ haloalkyl; R ２ But H, C １ ~C ７ Alkyl, C ３ ~C ６ cycloalkyl, halogen or CN; R ３ But H, C １ ~C ７ Alkyl, halogen, CN, C １ ~C ７ Alkoxy or C １ ~C ７ haloalkyl; R ４ H, C(=O)R １９ , CO ２ R １９ , C(=O)SR １９ , S(O) ２ R １９ or CH ２ OCOR １９ and R ５ and R ６ together with the nitrogen atom to which they are attached form a 3- to 7-membered ring containing carbon atoms and optionally 1-3 oxygen, sulfur or nitrogen atom ring members, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring members are S, S(O) or S(O) ２ wherein the rings are independently selected from (R ｖ ) ｒ optionally substituted with up to 5 substituents selected from: R ｖ is independently selected from the group consisting of H, methyl, ethyl, propyl, c-propylmethyl, propargyl, or cyanomethyl; 2. The compound of claim 1, wherein r is 1 or 2.

7. R １ But H, C １ ~C ７ Alkyl, halogen or C ３ ~C ７ is cycloalkyl; R ２ is H or F; R ３ is H, Me, F, Cl, CN, OMe or CF ３ and R ４ But, H, SO ２ CF ３ , S.O. ２ CH ３ , CO ２ Me, COMe, CH ２ OCO-t-Bu, CH ２ OCO-n-Bu, CH ２ OCO-c-hexyl, CH ２ OCO-c-pentyl, CH ２ OCOCH ２ CH ３ ,COMe,CH ２ OCOPh, CH ２ OCO-i-Bu, CH ２ OCOMe, CH ２ OCO-sec-Bu or COSMe; R ５ and R ６ together with the nitrogen atom to which they are attached form a 3- to 7-membered ring, said ring being a 5-membered ring; R ｆ But CF ３ 7. The compound of claim 6, wherein:

8. R １ But H, C １ ~C ７ Alkyl, halogen or C ３ ~C ７ is cycloalkyl; R ２ is H or F; R ３ is H, Me, F, Cl, CN, OMe or CF ３ and R ４ But, H, SO ２ CF ３ , S.O. ２ CH ３ , CO ２ Me, COMe, CH ２ OCO-t-Bu, CH ２ OCO-n-Bu, CH ２ OCO-c-hexyl, CH ２ OCO-c-pentyl, CH ２ OCOCH ２ CH ３ ,COMe,CH ２ OCOPh, CH ２ OCO-i-Bu, CH ２ OCOMe, CH ２ OCO-sec-Bu or COSMe; R ５ and R ６ together with the nitrogen atom to which they are attached form a 3- to 7-membered ring, said ring being a 6-membered ring; R ｆ But CF ３ 7. The compound of claim 6, wherein:

9. G is G-1; R １ But H, C １ ~C ７ Alkyl, halogen, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl or C １ ~C ７ haloalkyl; R ２ But H, C １ ~C ７ Alkyl, C ３ ~C ６ cycloalkyl, halogen or CN; R ３ But H, C １ ~C ７ Alkyl, halogen, CN, C １ ~C ７ Alkoxy or C １ ~C ７ haloalkyl; R ４ H, C(=O)R １９ , CO ２ R １９ , C(=O)SR １９ , S(O) ２ R １９ or CH ２ OCOR １９ and R ｆ But C １ ~C ３ The compound of claim 1 which is a haloalkyl.

10. R １ But H, C １ ~C ７ Alkyl, halogen or C ３ ~C ７ is cycloalkyl; R ２ is H, Me or F; R ３ is H, Me, F, Cl, CN, OMe or CF ３ and R ４ But, H, SO ２ CF ３ , S.O. ２ CH ３ , CO ２ Me, COMe, CH ２ OCO-t-Bu, CH ２ OCO-n-Bu, CH ２ OCO-c-hexyl, CH ２ OCO-c-pentyl, CH ２ OCOCH ２ CH ３ ,COMe,CH ２ OCOPh, CH ２ OCO-i-Bu, CH ２ OCOMe, CH ２ OCO-sec-Bu or COSMe; R ７ But H, C １ ~C ７ Alkyl, halogen, -CN, C １ ~C ７ Haloalkyl or C １ ~C ７ is alkoxy; R ８ is H or C １ ~C ７ is alkyl; R ９ But H, C １ ~C ７ Alkyl, C １ ~C ７ Haloalkyl or C ２ ~C ７ is alkoxyalkyl; R １０ is H or C １ ~C ７ is alkyl; R ｆ But CF ３ 10. The compound of claim 9, wherein:

11. R １ is Me or Cl; R ３ is Me; R ４ But H, CH ２ OCO-t-Bu or SO ２ CF ３ and R ７ is H; R ８ is H; R ９ is methyl, ethyl, t-butyl, chloromethyl, or methoxymethyl; R １０ The compound of claim 10, wherein is methyl or ethyl.

12. R ７ and R ９ together with a carbon atom and optionally one to two oxygen, sulfur or Forms a fused 3- to 7-membered ring containing a nitrogen atom as a ring member, said ring being unsubstituted or substituted with halogen, cyano, nitro, C １ ~C ４ Alkyl, C ３ ~C ６ Cycloalkyl, C １ ~C ４ Haloalkyl, C １ ~C ４ Alkoxy and C １ ~C ４ substituted with at least one substituent independently selected from the group consisting of haloalkoxy; R ８ is H; R １０ The compound of claim 9 , wherein is H.

13. R １ But H, C １ ~C ７ Alkyl, halogen or C ３ ~C ７ is cycloalkyl; R ２ is H, Me or F; R ３ is H, Me, F, Cl, CN, OMe or CF ３ and R ４ But, H, SO ２ CF ３ , S.O. ２ CH ３ , CO ２ Me, COMe, CH ２ OCO-t-Bu, CH ２ OCO-n-Bu, CH ２ OCO-c-hexyl, CH ２ OCO-c-pentyl, CH ２ OCOCH ２ CH ３ ,COMe,CH ２ OCOPh, CH ２ OCO-i-Bu, CH ２ OCOMe, CH ２ OCO-sec-Bu or COSMe; R ７ and R ９ are taken together to form a fused 3- to 7-membered ring, and the 3- to 7-membered ring is a 5- or 6-membered ring.

14. R ７ and R ９ together form c-pentyl, c-hexyl or tetrahydropyridine. and forming a 5- or 6-membered ring of the alkyl group, said ring being unsubstituted or substituted with H, halogen or C. １ ~C ４ 14. The compound of claim 13, substituted with at least one substituent independently selected from alkyl.

15. R ９ and R １０ together with the carbon atoms to which they are attached, form a carbon atom and any optionally forming a 3-7 membered ring containing 1-2 oxygen, sulfur, or nitrogen atoms as ring members, wherein up to two carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring members are S, S(O), or S(O) ２ wherein the rings are independently selected from (R ｖ ) ｒ optionally substituted with up to five substituents selected from: Two R's ｖ are bonded to the same carbon atom or to two adjacent carbon atoms, the two R ｖ are taken together with the carbon atom or atoms to which they are attached to form a 3- to 7-membered ring containing carbon atoms and optionally 1-2 oxygen, sulfur, or nitrogen atoms as ring members, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring member is S, S(O), or S(O) ２ Selected from: R ７ is H; R ８ The compound of claim 9 , wherein is H.

16. R １ But H, C １ ~C ３ Alkyl, halogen or C ３ ~C ４ is cycloalkyl; R ２ is H, Me or F; R ３ is H, Me, F, Cl, CN, OMe or CF ３ and R ４ But, H, SO ２ CF ３ , S.O. ２ CH ３ , CO ２ Me, COMe, CH ２ OCO-t-Bu, CH ２ OCO-n-Bu, CH ２ OCO-c-hexyl, CH ２ OCO-c-pentyl, CH ２ OCOCH ２ CH ３ ,COMe,CH ２ OCOPh, CH ２ OCO-i-Bu, CH ２ OCOMe, CH ２ OCO-sec-Bu or COSMe; R ９ and R １０ together with the carbon atoms to which they are attached form a 3- to 7-membered ring, said ring being 5- or 6-membered; R ｖ is independently selected from the group consisting of H, methyl, ethyl, propyl, c-propylmethyl, propargyl, or cyanomethyl; 16. The compound of claim 15, wherein r is 1 or 2.

17. R ９ and R １０ form a 3- to 7-membered ring together with the carbon atoms to which they are attached.

17. The compound according to claim 16, wherein the ring is a 5- or 6-membered ring of cyclopentane, cyclohexane, tetrahydro-2H-pyran, or tetrahydro-2H-thiopyran.

18. G is G-2; R １ But H, C １ ~C ７ Alkyl, halogen, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl or C １ ~C ７ haloalkyl; R ２ is H, Me or F; R ３ is H, Me, F, Cl, CN, OMe or CF ３ and R ４ But, H, SO ２ CF ３ , S.O. ２ CH ３ , CO ２ Me, COMe, CH ２ OCO-t-Bu, CH ２ OCO-n-Bu, CH ２ OCO-c-hexyl, CH ２ OCO-c-pentyl, CH ２ OCOCH ２ CH ３ ,COMe,CH ２ OCOPh, CH ２ OCO-i-Bu, CH ２ OCOMe, CH ２ OCO-sec-Bu or COSMe; R ｆ But C １ ~C ３ The compound of claim 1 which is a haloalkyl.

19. Q is O or S; R ７ is H; R ８ is H; R ｆ But CF ３ and R ９ and R １０ together with the carbon atoms to which they are attached form a 3- to 7-membered ring, said ring being 5- or 6-membered; R ｖ is independently selected from the group consisting of H, methyl, ethyl, propyl, c-propylmethyl, propargyl, or cyanomethyl; 19. The compound of claim 18, wherein r is 1 or 2.

20. R ９ and R １０ together with the carbon atoms to which they are attached to form cyclopentane , forming cyclohexane, tetrahydro-2H-pyran or tetrahydro-2H-thiopyran; R ｖ 20. The compound of claim 19, wherein is H.

21. Q is CR １１ R １２ and R ７ is H; R ８ is H; R ９ is H; R １０ is H; R １１ and R １２ together with the carbon atoms to which they are attached form a fused 3- to 7-membered ring containing carbon atoms and optionally 1 to 2 oxygen, sulfur or nitrogen atoms as ring members, said ring being unsubstituted or substituted with halogen, cyano, nitro, C １ ~C ４ Alkyl, C ３ ~C ６ Cycloalkyl, C １ ~C ４ Haloalkyl, C １ ~C ４ Alkoxy and C １ ~C ４ substituted with at least one substituent independently selected from the group consisting of haloalkoxy; and R ｆ But CF ３ 19. The compound of claim 18, wherein:

22. R １１ and R １２ together with the carbon atoms to which they are attached form a fused 3- to 7-membered 22. The compound of claim 21, wherein the ring forms a 5- or 6-membered ring that is unsubstituted.

23. G is G-3; R １ But H, C １ ~C ７ Alkyl, halogen or C ３ ~C ７ is cycloalkyl; R ２ is H, Me or F; R ３ is H, Me, F, Cl, CN, OMe or CF ３ and R ４ But, H, SO ２ CF ３ , S.O. ２ CH ３ , CO ２ Me, COMe, CH ２ OCO-t-Bu, CH ２ OCO-n-Bu, CH ２ OCO-c-hexyl, CH ２ OCO-c-pentyl, CH ２ OCOCH ２ CH ３ ,COMe,CH ２ OCOPh, CH ２ OCO-i-Bu, CH ２ OCOMe, CH ２ OCO-sec-Bu or COSMe; R １３ But C １ ~C ７ is alkyl; R １４ But C １ ~C ４ is alkyl; R １５ is H; R ｆ But C １ ~C ３ The compound of claim 1 which is a haloalkyl.

24. G is G-4; R １ But H, C １ ~C ７ Alkyl, halogen or C ３ ~C ７ is cycloalkyl; R ２ is H, Me or F; R ３ is H, Me, F, Cl, CN, OMe or CF ３ and R ４ But, H, SO ２ CF ３ , S.O. ２ CH ３ , CO ２ Me, COMe, CH ２ OCO-t-Bu, CH ２ OCO-n-Bu, CH ２ OCO-c-hexyl, CH ２ OCO-c-pentyl, CH ２ OCOCH ２ CH ３ ,COMe,CH ２ OCOPh, CH ２ OCO-i-Bu, CH ２ OCOMe, CH ２ OCO-sec-Bu or COSMe; R １３ But C １ ~C ７ is alkyl; R ｆ But C １ ~C ３ haloalkyl; R １５ But H, C １ ~C ３ Alkyl or C １ ~C ３ is alkoxy; R １６ But H, cyano, C １ ~C ４ Alkyl, halogen, C １ ~C ４ Alkylthio, C １ ~C ４ Haloalkyl or C １ ~C ４ The compound of claim 1 which is alkoxy.

25. G is G-5; R １ But H, C １ ~C ７ Alkyl, halogen or C ３ ~C ７ is cycloalkyl; R ２ is H, Me or F; R ３ is H, Me, F, Cl, CN, OMe or CF ３ and R ４ But, H, SO ２ CF ３ , S.O. ２ CH ３ , CO ２ Me, COMe, CH ２ OCO-t-Bu, CH ２ OCO-n-Bu, CH ２ OCO-c-hexyl, CH ２ OCO-c-pentyl, CH ２ OCOCH ２ CH ３ ,COMe,CH ２ OCOPh, CH ２ OCO-i-Bu, CH ２ OCOMe, CH ２ OCO-sec-Bu or COSMe; R ｆ But C １ ~C ３ haloalkyl; R １６ is H or C １ ~C ４ is alkyl; R １７ But H, C １ ~C ４ Alkyl, halogen or C １ ~C ４ is alkoxy; R １８ is H or C １ ~C ３ The compound of claim 1 which is alkoxy.

26. N-[2,4-dimethyl-5-(1-piperidinylcarbonyl)phenyl]-1,1 , 1-trifluoromethanesulfonamide (compound 260); N-[2-chloro-4-methyl-5-(4-morpholinylcarbonyl)phenyl]-1, 1,1-trifluoromethanesulfonamide (compound 16); N-[2,4-dimethyl-5-(4-morpholinylcarbonyl)phenyl]-1,1,1-trifluoromethanesulfonamide (Compound 6); N-[2-chloro-4-methyl-5-(1-piperidinylcarbonyl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 18); 3-Fluoro-N,N,2,4-tetramethyl-5-[[(trifluoromethyl)sulfonyl]amino]benzamide (Compound 128); 1,1,1-trifluoro-N-[3-fluoro-2,4-dimethyl-5-(4-morpholinylcarbonyl)phenyl]methanesulfonamide (compound 190); N-[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.4]non-2-en-3-yl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 207); N-[2,4-dimethyl-5-[(3aR,6aR)-3a,5,6,6a-tetrahydro-4H-cyclopenta[d]isoxazol-3-yl]phenyl]-1,1,1-trifluoromethanesulfonamide (compound 103); N-[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.5]dec-2-en-3-yl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 197); N-[2,4-dimethyl-5-(3a,4,7,7a-tetrahydro-5H-pyrano[4,3-d]isoxazol-3-yl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 121); N-[2,4-dimethyl-5-(3a,6,7,7a-tetrahydro-4H-pyrano[3,4-d]isoxazol-3-yl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 120); N-[2,4-dimethyl-5-(1-oxo-2-azaspiro[4.5]dec-2-yl)phenyl]-1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide (Compound 267); [[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.4]non-2-en-3-yl)phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropanoate (compound 140); [[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.5]dec-2-en-3-yl)phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropanoate (compound 159); [[2,4-dimethyl-5-[(3aR,6aR)-3a,5,6,6a-tetrahydro-4H-cyclopenta[d]isoxazol-3-yl]phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropanoate (Compound 100); and [[2,4-dimethyl-5-(1-oxo-2-azaspiro[4.5]dec-2-yl)phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropanoate (Compound 268) 2. The compound of claim 1 selected from the group consisting of:

27. [[(trifluoromethyl)sulfonyl][2,3,4-trimethyl-5-(4-mo (amino)methyl 2,2-dimethylpropanoate; Ethyl N-[(trifluoromethyl)sulfonyl]-N-[2,3,4-trimethyl-5-(1-piperidinylcarbonyl)phenyl]carbamate; [[(trifluoromethyl)sulfonyl][2,3,4-trimethyl-5-(1-piperidinylcarbonyl)phenyl]amino]methyl 2,2-dimethylpropanoate; 1,1,1-trifluoro-N-[2,3,4-trimethyl-5-(4-morpholinylcarbonyl)phenyl]methanesulfonamide; and [[(Trifluoromethyl)sulfonyl][2,3,4-trimethyl-5-[(3aR,6aR)-3a,5,6,6a-tetrahydro-4H-cyclopent[d]isoxazol-3-yl]phenyl]amino]methyl 2,2-dimethylpropanoate 2. The compound of claim 1 selected from the group consisting of:

28. G is CONR ５ R ６ and NR ５ R ６ is J-3a, and R １ is Me and R ２ is Me and R ３ is Me and R ４ is CH ２ OCO-t-Bu, and R ｆ is CF ３ is; G is CONR ５ R ６ and NR ５ R ６ is J-4 and R １ is Me and R ２ is Me and R ３ is Me and R ４ is CO ２ Et and R ｆ is CF ３ That is, The compound of claim 1.

29. 10. A herbicidal composition comprising the compound of claim 1 and at least one component selected from the group consisting of a surfactant, a solid excipient, and a liquid excipient.

30. 10. A herbicidal composition comprising the compound of claim 1, at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners, and at least one component selected from the group consisting of surfactants, solid excipients, and liquid excipients.

31. (a) the compound of claim 1; (b) (b1) a photosystem II inhibitor; (b2) acetonitrile; (b10) auxin transport inhibitors, (b11) phytoene desaturase (PDS) inhibitors, (b12) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b13) hydroxylic acid synthase (AHAS) inhibitors, (b14) acetyl-CoA carboxylase (ACCase) inhibitors, (b15) auxin mimics, (b16) 5-enol-pyruvylshikimate-3-phosphate (EPSP) synthase inhibitors, (b17) photosystem I electron diverters, (b18) protoporphyrinogen oxidase (PPO) inhibitors, (b19) glutamine synthetase (GS) inhibitors, (b20) very long chain fatty acid (VLCFA) elongase inhibitors, (b21) auxin transport inhibitors, (b22) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b23) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b24) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b25) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b26) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b27) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b28) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b29) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b30) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b31) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b32) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitor (b13) a homogentisic acid solanesyltransferase (HST) inhibitor, (b14) a cellulose biosynthesis inhibitor, (b15) other herbicides (including mitotic disruptors, organic arsenic compounds, asulam, bromobutide, cinmethylin, cumyluron, dazomet, difenzoquat, dymron, etobenzanide, flurenol, fosamine, fosamine-ammonium, hydantocidin, metam, methyldymron, oleic acid, oxaziclomefone, pelargonic acid, and biributicarb), (b16) a herbicide safener, and at least one further active ingredient selected from salts of the compounds of (b1) to (b16).

32. 10. A method for controlling the growth of undesired vegetation which comprises contacting said undesired vegetation or its environment with a herbicidally effective amount of a compound of claim 1.

33. Unwanted vegetation or its environment and (b1) to (b16) and (b1) to (b16) 33. The method of claim 32, further comprising contacting with a herbicidally effective amount of at least one additional active ingredient selected from a salt of a compound.

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