Substituted haloalkylsulfonylanilide herbicides

Abstract

Disclosed are compounds of Formula 1, all stereoisomers, N-oxides, and salts thereof, wherein G is CONR 5 R 6 or is selected from the group consisting of 1 R 18 Rf and G are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula 1, and methods for controlling undesirable vegetation comprising contacting the undesirable vegetation or its environment with an effective amount of a compound or composition of the invention.

Description

Technical Field

[0001] This invention relates to certain haloalkylsulfonylanilines, their N-oxides, salts and compositions, and methods for controlling unwanted vegetation. Background Technology

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

[0003] This invention relates to compounds of formula 1, all their stereoisomers, N-oxides and salts, agricultural compositions containing them, and their use as herbicides:

[0004]

[0005] in

[0006] G is CONR 5 R 6 Or selected from

[0007]

[0008] R 1 It 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;

[0009] R 2 It is H, C1-C7 alkyl, halogen, CN, C1-C7 haloalkyl, C1-C7 alkoxy, C3-C7 cycloalkyl or C1-C5 alkylthio;

[0010] R 3It 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;

[0011] R 4 It 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)2NR 19 R 20 S(OH)2NR 19 R 20 CH2OC(=O)OR 19 CH2OC(=O)NR 19 R 20 Or CH2OC(=O)R 19 ;

[0012] R 5 It 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;

[0013] R 6 It 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

[0014] R 5 and R 6Together with the nitrogen atoms attached to them, they form 3- to 7-membered rings, which contain carbon atoms and optionally 1 to 3 oxygen, sulfur, or nitrogen atoms as ring members, wherein at most 2 carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring member is selected from S, S(O), or S(O)2, wherein the ring is optionally composed of at most 5 independently selected from (R v ) r The substituents are substituted, and r is the number of substituents;

[0015] R v 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

[0016] When two R v When attached to the same carbon atom or to two adjacent carbon atoms, the two R atoms... v They can form 3- to 7-membered rings together with one or more carbon atoms attached to them, the ring containing carbon atoms and optionally one to three oxygen, sulfur, or nitrogen atoms as ring members, wherein at most two carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring member is selected from S, S(O) or S(O)2, the ring being unsubstituted or substituted by 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;

[0017] R 7 It is H, C1-C7 alkyl, halogen, CN, C1-C7 haloalkyl or C1-C7 alkoxy;

[0018] R 8 It is H, C1-C7 alkyl; or

[0019] R 7 and R 8 They can be combined to form 3- to 7-membered rings containing a carbon atom and optionally one or two oxygen, sulfur, or nitrogen atoms as ring members, wherein the ring is unsubstituted or substituted by 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;

[0020] R 9It 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;

[0021] R 7 and R 9 They can together form fused 3- to 7-membered rings, which contain a carbon atom and optionally one to two oxygen, sulfur, or nitrogen atoms as ring members, said ring being unsubstituted or substituted by 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;

[0022] R 10 It is H or C1-C7 alkyl; or

[0023] R 9 and R 10 Together with the carbon atoms to which they are attached, they can form 3- to 7-membered rings, the ring containing carbon atoms and optionally one or two oxygen, sulfur, or nitrogen atoms as ring members, wherein at most two carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring member is selected from S, S(O), or S(O)2, the ring optionally being composed of at most five independently selected from (R) v ) r The substituents are substituted, and r is the number of substituents; or

[0024] When two R v When attached to the same carbon atom or to two adjacent carbon atoms, the two R atoms... v They can form 3- to 7-membered rings together with one or more carbon atoms attached to them, the ring containing carbon atoms and optionally one or two oxygen, sulfur or nitrogen atoms as ring members, wherein the maximum two carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring member is selected from S, S(O) or S(O)2.

[0025] Q represents O, S, and CR. 11 R 12 or NR 13 ;

[0026] R 11 and R 12Together with the carbon atoms to which they are attached, they form 3- to 7-membered rings containing a carbon atom and optionally one or two oxygen, sulfur, or nitrogen atoms as ring members, said ring being unsubstituted or substituted by 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

[0027] R 9 and R 11 Together with the carbon atoms attached to them, they form a 6-membered aromatic ring, which is optionally composed of up to 4 independently selected from R w Substituents of the substituents;

[0028] R w It is a C1-C7 alkyl, halogen, C1-C7 haloalkyl, or C1-C7 alkoxy;

[0029] r is 0, 1, 2, 3, 4 or 5;

[0030] R 13 It 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;

[0031] R 14 It 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;

[0032] R 15 It is H, cyano, C1-C7 alkyl, halogen, C1-C7 haloalkyl or C1-C7 alkoxy;

[0033] R 16 It is H, cyano, C1-C7 alkyl, halogen, C1-C4 alkylthio, C1-C7 haloalkyl or C1-C7 alkoxy;

[0034] R 17It 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;

[0035] R 18 It is H, C1-C7 alkyl, halogen, C1-C7 haloalkyl or C1-C7 alkoxy;

[0036] R 19 It 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, C4-C7 alkylcycloalkyl;

[0037] R 20 It is an H or C1-C7 haloalkyl group; and

[0038] R f It is a C1-C7 haloalkyl group.

[0039] More specifically, the present invention relates to a compound of formula 1, all its stereoisomers, N-oxides, or salts. The invention also relates to a herbicidal composition comprising the compound disclosed herein (i.e., in a herbicidally effective amount) and at least one component selected from the group consisting of surfactants, solid diluents, and liquid diluents. The invention further relates to a method for controlling the growth of unwanted vegetation, the method comprising contacting vegetation or its environment with a herbicidally effective amount of the compound disclosed herein (e.g., the composition described herein).

[0040] The present invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, all its stereoisomers, N-oxides and salts, and (b) an additional active ingredient of at least one salt of a compound selected from (b1) to (b16) as described below. Detailed Implementation

[0041] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains,” “containing,” “characterized by,” or any other variation thereof, are intended to cover non-exclusive inclusion, subject to any expressly indicated limitations. For example, a composition, mixture, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or apparatus.

[0042] The connecting phrase "composed of..." excludes any unspecified element, step, or component. If in a claim, this phrase makes the claim closed, excluding materials other than those stated, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of a claim rather than immediately following the preamble, the phrase only limits the element set forth in that clause; the claim as a whole does not exclude other elements.

[0043] The connecting phrase "consistently composed of" is used to define a composition, method, or apparatus that includes materials, steps, features, components, or elements in addition to those explicitly disclosed, provided that such additional materials, steps, features, components, or elements do not materially affect the essential and novel features of the claimed invention. The term "consistently composed of" falls between "comprising" and "composed of".

[0044] When the applicant has defined the invention or a portion thereof using open-ended terms such as “comprising”, it should be readily understood (unless otherwise specified) that the specification should be interpreted as also using the terms “consistently made of” or “comprises of” to describe the invention.

[0045] Furthermore, unless explicitly stated to the contrary, "or" refers to an inclusive "or" rather than an exclusive "or". For example, conditions A or B are satisfied by any of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0046] Furthermore, the indefinite article "a / an" preceding an element or component of the invention is intended to be non-limiting in terms of the number of instances (i.e., occurrences) of that element or component. Therefore, "a / an" should be understood to include one / an or at least one / an, and the singular word form of an element or component also includes the plural, unless the number clearly indicates the singular.

[0047] As mentioned in this article, the term "seedling" used alone or in combination of words refers to a young plant that develops from the embryo of a seed.

[0048] As mentioned in this article, the term "broadleaf" used alone or in words such as "broadleaf weeds" refers to dicotyledonous or dicotyledonous plants, a term used to describe a class of angiosperms characterized by an embryo with two cotyledons.

[0049] In the above details, the term "alkyl," used alone or in compound terms such as "alkylthio" or "haloalkyl," includes straight-chain or branched alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, or various butyl, pentyl, or hexyl isomers. "Alkenyl" includes straight-chain or branched alkenes, such as vinyl, 1-propenyl, 2-propenyl, and various 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 various butynyl, pentynyl, and hexynyl isomers. "Alkynyl" may also include a moiety consisting of multiple triple bonds, such as 2,5-hexadiynyl. "Alkynylalkyl" indicates alkynyl substitution on an alkyl group. Examples of "alkynylalkyl" include CH≡CCH2, CH3C≡≡CCH2, CH≡CCH2CH2, CH≡CCH(CH3)CH2, and various alkynylalkyl isomers. "Alkylene" refers to a straight-chain or branched alkanediyl group. Examples of "alkylene" include CH2, CH2CH2, CH(CH3), CH2CH2CH2, CH2CH(CH3), and various butene isomers. "Alkenylene" refers to a straight-chain or branched alkenediyl group containing one alkene bond. Examples of "alkenylene" include CH=CH, CH2CH=CH, CH=C(CH3), and various butenylene isomers. "Alkynediylene" refers to a straight-chain or branched alkynyl group containing one triple bond. Examples of "ethynyl" include C≡C, CH2C≡C, C≡CCH2 and various butynyl isomers.

[0050] "Alkoxy" includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, and various butoxy, pentoxy, and hexoxy isomers. "Alkoxyalkyl" indicates alkoxy substitution on an alkyl group. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2, and CH3CH2OCH2CH2. "Alkoxyalkoxy" indicates alkoxy substitution on an alkoxy group. "Alkenoxy" includes a straight-chain or branched alkenoxy moiety. Examples of "alkenoxy" include H2C=CHCH2O, (CH3)2C=CHCH2O, (CH3)CH=CHCH2O, (CH3)CH=C(CH3)CH2O, and CH2=CHCH2CH2O. "Alkyneoxy" includes a straight-chain or branched alkyneoxy moiety. Examples of "alkyneoxy" include HC≡CCH2O, CH3C≡CCH2O, and CH3C≡CCH2CH2O. "Alkylthio" includes branched or straight-chain alkylthio groups, such as methylthio, ethylthio, and various propylthio, butylthio, pentylthio, and hexylthio isomers. "Alkylsulfinyl" includes two enantiomers of the alkylsulfinyl group. Examples of "alkylsulfinyl" include CH3S(O)-, CH3CH2S(O)-, CH3CH2CH2S(O)-, (CH3)2CHS(O)-, and various butylsulfinyl, pentylsulfinyl, and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH3S(O)2-, CH3CH2S(O)2-, CH3CH2CH2S(O)2-, (CH3)2CHS(O)2-, and various butylsulfonyl, pentylsulfonyl, and hexylsulfonyl isomers. "Alkylthioalkyl" indicates alkylthio substitution on the alkyl group. Examples of “alkylthioalkyl” include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2, and CH3CH2SCH2CH2. “Alkylthioalkoxy” indicates alkylthio substitution on an alkoxy group. “Alkyl dithio” indicates a branched or straight-chain alkyl dithio group. Examples of “alkyl dithio” include CH3SS-, CH3CH2SS-, CH3CH2CH2SS-, (CH3)2CHSS-, and various butyl dithio and pentyl dithio isomers. “Cyanoalkyl” indicates 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,” and “alkynylsulfonyl” are defined similarly to the examples above.

[0051] "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "alkylcycloalkyl" indicates alkyl substitution on the cycloalkyl moiety and includes, for example, ethylcyclopropyl, isopropylcyclobutyl, 3-methylcyclopentyl, and 4-methylcyclohexyl. The term "cycloalkylalkyl" indicates cycloalkyl substitution on the alkyl moiety. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moiety bonded to a straight-chain or branched alkyl group. The term "cycloalkoxy" indicates a cycloalkyl group linked by an oxygen atom, such as cyclopentoxy and cyclohexoxy. "Cycloalkylalkoxy" indicates a cycloalkylalkyl group linked by an oxygen atom attached to an alkyl chain. Examples of "cycloalkylalkoxy" include cyclopropylmethoxy, cyclopentylethoxy, and other cycloalkyl moiety bonded to a straight-chain or branched alkoxy group. "Cyanocycloalkyl" indicates 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 having more than one double bond, such as 1,3-cyclohexadienyl and 1,4-cyclohexadienyl.

[0052] The term "halogen," alone or in compound terms such as "halogenated alkyl," or when used in descriptions such as "halogen-substituted alkyl," includes fluorine, chlorine, bromine, or iodine. Furthermore, when used in compound terms such as "halogenated alkyl," or when used in descriptions such as "halogen-substituted alkyl," the alkyl group may be partially or completely substituted with halogen atoms (which may be the same or different). Examples of "halogenated alkyl" or "halogen-substituted alkyl" include F3C, ClCH2, CF3CH2, and CF3CCl2. The terms "halogenated cycloalkyl," "halogenated alkoxy," "halogenated alkylthio," "halogenated alkenyl," "halogenated alkynyl," etc., are defined similarly to the term "halogenated alkyl." Examples of "halogenated alkoxy" include CF3O-, CCl3CH2O-, HCF2CH2CH2O-, and CF3CH2O-. Examples of “haloalkylthiol” include CCl3S-, CF3S-, CCl3CH2S-, and ClCH2CH2CH2S-. Examples of “haloalkylsulfinyl” include CF3S(O)-, CCl3S(O)-, CF3CH2S(O)-, and CF3CF2S(O)-. Examples of “haloalkylsulfonyl” include CF3S(O)2-, CCl3S(O)2-, CF3CH2S(O)2-, and CF3CF2S(O)2-. Examples of “haloalkenyl” include (Cl)2C=CHCH2- and CF3CH2CH=CHCH2-. Examples of “haloalkynyl” include HC≡CCHCl-, CF3C≡C-, CCl3C≡C-, and FCH2C≡CCH2-. Examples of “haloalkoxyalkoxy” include CF3OCH2O-, ClCH2CH2OCH2CH2O-, Cl3CCH2OCH2O-, and branched alkyl derivatives.

[0053] "alkyl carbonyl" refers to a straight-chain or branched alkyl moiety bonded to a C(=O) portion. Examples of "alkyl carbonyl" include CH3C(=O)-, CH3CH2CH2C(=O)-, and (CH3)2CHC(=O)-. Examples of "alkoxy carbonyl" include CH3OC(=O)-, CH3CH2OC(=O)-, CH3CH2CH2OC(=O)-, (CH3)2CHOC(=O)-, and various butoxy- or pentoxy carbonyl isomers.

[0054] The total number of carbon atoms in the substituent groups is expressed as "C". i -C jThe prefix indicates that i and j are numbers from 1 to 7. For example, C1-C4 alkylsulfonyl groups specify methylsulfonyl to butylsulfonyl groups; C2 alkoxyalkyl groups specify CH3OCH2-; C3 alkoxyalkyl groups specify, for example, CH3CH(OCH3)-, CH3OCH2CH2-, or CH3CH2OCH2-; and C4 alkoxyalkyl groups specify various isomers of alkyl groups substituted with alkoxy groups containing a total of four carbon atoms, examples of which include CH3CH2CH2OCH2- and CH3CH2OCH2CH2-.

[0055] When the compound is unsubstituted or substituted with a substituent marked with a subscript (which indicates the number of the substituent), the substituent is independently selected from the defined substituents (e.g., [(R v ) r The group of substituents, r, is 0, 1, 2, 3, 4, or 5. For example, when r is 0, this indicates that the compound is unsubstituted, and hydrogen may be present at that position even if it is not listed in the definition of a variable group. As another example, when r is 2, this indicates that the compound is substituted by two independent R groups selected from the defined group of substituents. v replace.

[0056] When the group contains a substituent that can be hydrogen, such as R 1 Or R 2 When the substituent is considered to be hydrogen, it should be understood that this is equivalent to the group being unsubstituted. When one or more positions on a group are referred to as "unsubstituted" or "unreplaced," a hydrogen atom is attached to occupy any free valence.

[0057] Unless otherwise specified, the "ring" (e.g., two R's) that are components of Equation 1 v (Together with the carbon atoms to which they are attached, they form a ring) that is either carbocyclic or heterocyclic. The term “ring member” refers to the atoms or other parts that form the framework of a ring or ring system (e.g., C(=O), C(=S), S(O) or S(O)2).

[0058] The terms "carbocyclic," "carbocyclic," or "carbocyclic system" indicate that the atoms forming the ring skeleton are selected only from a ring or ring system of carbon. Unless otherwise specified, a carbocyclic ring can be saturated, partially unsaturated, or fully unsaturated. When a fully unsaturated carbocyclic ring satisfies Hückel's rule, the ring is also called an "aromatic ring." A "saturated carbocyclic ring" is a ring having a skeleton composed of carbon atoms connected to each other by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.

[0059] The terms "heterocyclic ring," "heterocycle," or "heterocyclic system" refer to a ring or ring system in which at least one atom forming the ring skeleton is not carbon (e.g., nitrogen, oxygen, or sulfur). Typically, a heterocycle contains no more than four nitrogen atoms, no more than two oxygen atoms, and no more than two sulfur atoms. Unless otherwise specified, a heterocycle can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocycle satisfies Hückel's rule, the ring is also called a "heteroaromatic ring" or "aromatic heterocycle." Unless otherwise specified, heterocycles and ring systems can be attached by any available carbon or nitrogen in place of hydrogen atoms.

[0060] "Aromatic" indicates that each ring atom is substantially in the same plane and has p-orbitals perpendicular to the plane of the ring, and (4n+2) π electrons (where n is a positive integer) are associated with the ring to conform to Hückel's rule. The term "aromatic ring system" means a system in which at least one ring is an aromatic carbon ring or heterocyclic system. The term "aromatic carbon ring system" means a system in which at least one ring is an aromatic carbon ring system. The term "aromatic heterocyclic system" means a system in which at least one ring is an aromatic heterocyclic system. The term "non-aromatic ring system" means a carbon ring or heterocyclic system that can be fully saturated, and partially or fully unsaturated, provided that none of the rings in the system are aromatic. The term "non-aromatic carbon ring system" (where there are no rings in the system) is aromatic. The term "non-aromatic heterocyclic system" means a heterocyclic system in which no ring is aromatic.

[0061] The term "optionally substituted" in relation to heterocycles refers to a group that is unsubstituted or has at least one non-hydrogen substituent that does not eliminate the biological activity of the unsubstituted analogue. As used herein, unless otherwise specified, the following definitions shall apply. The term "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted" or the term "(un)substituted." Unless otherwise specified, an optionally substituted group may have substituents at each substituted position of the group, and each substitution is independent of the others.

[0062] In Equation 1, when G is CONR 5 R 6 At that time, NR 5 R 6 It can be (especially) J. Some non-restrictive instances of J are shown in the table in Example 1, where each structure is associated with J-#, and # is a number.

[0063] Example 1

[0064]

[0065]

[0066]

[0067] *“a” indicates that the two CH3 moieties are in a cis configuration; and “b” indicates that the two CH3 moieties are in a trans configuration.

[0068] In Equation 1, when G is CONR 5 R 6 At that time, NR 5 R 6 It can also be (especially) K. Some non-restrictive instances of K are shown in the table in Example 2, where each structure is associated with K-#, and # is a number.

[0069] Example 2

[0070]

[0071]

[0072] In Equation 1, when G is G-1, some non-restrictive instances of G-1 are shown in the table of Example 3, where each structure is associated with G-1-# and # is a number.

[0073] Example 3

[0074]

[0075]

[0076]

[0077] *“a” indicates that both H's are in the cis configuration; and “b” indicates that both H's are in the trans configuration, except in the following compounds: for G-1-33a and G-1-33b, where “a” indicates that both Et's are in the cis configuration and “b” indicates that both Et's are in the trans configuration; for G-1-38a and G-1-38b, where “a” indicates that the H and Me shown are in the cis configuration and “b” indicates that the H and Me shown are in the trans configuration.

[0078] In Equation 1, when G is G-2, some non-restrictive instances of G-2 are shown in the table of Example 4, where each structure is associated with G-2-# and # is a number.

[0079] Example 4

[0080]

[0081] Various synthetic methods are known in this art for preparing aromatic and non-aromatic heterocyclic and cyclic systems; for a comprehensive review, see the eight-volume collection *Comprehensive Heterocyclic Chemistry*, edited by A.R. Katritzky and C.W., Pergamon Press, Oxford, 1984, and the twelve-volume collection *Comprehensive Heterocyclic Chemistry II*, edited by A.R. Katritzky, C.W. Rees and E.F. V. Criven, Pergamon Press, Oxford, 1996.

[0082] The compounds of the present invention can exist as one or more stereoisomers. Various stereoisomers include enantiomers, diastereomers, transisomers, and geometric isomers. Stereoisomers are isomers that have the same composition but whose atoms are arranged differently in space, and include enantiomers, diastereomers, cis-trans isomers (also called geometric isomers), and transisomers. Transisomers arise from restricted rotation around a single bond, where the rotation barrier is high enough to allow the separation of isomer species. Those skilled in the art will understand that a stereoisomer may be more active and / or may exhibit beneficial effects when enriched relative to one or more other stereoisomers, or when separated from one or more other stereoisomers. Furthermore, those skilled in the art know how to separate, enrich, and / or selectively prepare said stereoisomers. The compounds of the present invention can exist as mixtures of stereoisomers, individual stereoisomers, or as optically active forms.

[0083] For example, when G is G-1 and R7 and R9, together with the carbon atoms to which they are attached, form a cyclopentyl ring, the compound of Formula 1 can have at least two stereoisomers. These two stereoisomers are described as Formula 1' and Formula 1" and have chiral centers marked with 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.

[0084]

[0085] As another example, when G is CONR 5 R 6 At that time, R5 and R 6 Together with the nitrogen atoms to which they are attached, they form a piperidinyl ring having at least one chiral center. The compound of Formula 1 may have at least two stereoisomers having a chiral center marked with an asterisk (*).

[0086]

[0087] The molecular descriptions presented in this paper follow standard conventions for depicting stereochemistry. To indicate stereochemistry, bonds extending from the drawing plane toward the viewer are represented by solid wedges, with the wide end of the wedge connected to an atom extending from the drawing plane toward the viewer. Bonds extending below the drawing plane and away from the viewer are represented by dashed wedges, with the wide end of the wedge connected to an atom further away from the viewer. Lines of equal width indicate bonds with relative or neutral orientations to those shown with solid or dashed wedges; lines of equal width may also describe bonds in molecules or molecular portions not intended to indicate a specific stereochemistry.

[0088] This invention includes racemic mixtures, such as equal amounts of enantiomers of formula 1' and 1" or equal amounts of enantiomers of formula 1"' and 1"". Furthermore, this invention includes compounds enriched compared to racemic mixtures of enantiomers of formula 1. It also includes substantially pure enantiomers of compounds of formula 1 (e.g., formula 1' or formula 1").

[0089] When enantiomers are enriched, one enantiomer is present in a larger amount than the other, and the degree of enrichment can be defined by an expression of (2x-1)·100% enantiomer excess (“ee”), where x is the mole fraction of the dominant enantiomer in the mixture (e.g., 20% ee corresponds to an enantiomer ratio of 60:40).

[0090] Preferably, the composition of the present invention has an enantiomer excess of at least 50%; more preferably at least 75%; even more preferably at least 90%; and most preferably at least 94%. Particularly noteworthy are examples of enantiomer purity of more active isomers.

[0091] Compounds of Formula 1 may contain additional chiral centers. For example, substituents and other molecular components such as R v It may contain chiral centers. The present invention includes racemic mixtures and substantially pure stereochemical configurations enriched at these additional chiral centers.

[0092] The compounds of the present invention can exist as one or more conformational isomers due to any restricted bond rotation in Formula 1. The present invention includes mixtures of conformational isomers. Furthermore, the present invention includes compounds enriched in one conformational isomer relative to other conformational isomers.

[0093] Compounds of Formula 1 typically exist in more than one form, and therefore Formula 1 encompasses all crystalline and amorphous forms of the compounds they represent. Amorphous forms include examples that are solids such as waxes and gums, and examples that are liquids such as solutions and melts. Crystalline forms include examples representing substantially single-crystal types and examples representing mixtures of polymorphs (i.e., different crystal types). The term "polymorph" refers to a specific crystalline form of a compound that can crystallize in different crystal forms, having different molecular arrangements and / or conformations in the crystal lattice. While polymorphs may have the same chemical composition, they can also differ in composition due to the presence or absence of co-crystallization water or other molecules, which may be weakly or strongly bonded within the crystal lattice. Polymorphs can differ in such chemical, physical, and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspendability, dissolution rate, and bioavailability. Those skilled in the art will understand that, relative to another polymorph or mixture of polymorphs of the same compound of Formula 1, polymorphs of the compound of Formula 1 may exhibit beneficial effects (e.g., suitability for the preparation of useful formulations, improved biological properties). The preparation and separation of specific polymorphs of the compound of Formula 1 can be achieved by methods known to those skilled in the art, including, for example, crystallization using selected solvents and temperatures. For a comprehensive discussion of polymorphism, see R. Hilfiker (ed.), *Polymorphism in the Pharmaceutical Industry*, Wiley-VCH, Weinheim, 2006.

[0094] Those skilled in the art will understand that not all nitrogen-containing heterocycles can form N-oxides, because nitrogen requires a lone pair of electrons to be oxidized into an oxide; those skilled in the art will recognize which nitrogen-containing heterocycles can form N-oxides. Those skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for preparing N-oxides of heterocycles and tertiary amines are well known to those skilled in the art, including the oxidation of heterocycles and tertiary amines using peroxyacids such as peracetic acid and m-chloroperoxybenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as tert-butyl hydroperoxide, sodium perborate, and diethylene oxides such as dimethyldiethylene oxide. These methods for preparing N-oxides have been extensively described and reviewed in the literature, see, for example: T.L. Gilchrist in Comprehensive Organic Synthesis, Vol. 7, pp. 748-750, edited by S.V. Ley, Pergamon Press; M. Tisler and B. Stanovnik, Comprehensive Heterocyclic Chemistry, Vol. 3, pp. 18-20, edited by A.J. Boulton and A. McKillop, Pergamon Press; M.R. Grimemett and B.T. Keene, Advances in Heterocyclic Chemistry, Vol. 43, pp. 149-161, edited by A.R. Katritzky, Academic Press; M. Tisler and B. Stanovnik, Advances in Heterocyclic Chemistry. Chemistry, Vol. 9, pp. 285-291, edited by A.R. Katritzky and A.J. Boulton, Academic Press; and G.W. Heeseman and E.S. G.W. Gerstiuk, Advances in Heterocyclic Chemistry, Vol. 22, pp. 390-392, edited by A.R. Katritzky and A.J. Boulton, Academic Press.

[0095] Those skilled in the art recognize that salts of compounds share the bioutilization of their corresponding non-salt forms because the salts are in equilibrium with their corresponding non-salt forms in the environment and under physiological conditions. Therefore, salts of compounds of various Formula 1 can be used to control unwanted vegetation (i.e., are agriculturally suitable). Salts of compounds of Formula 1 include acid addition salts formed 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 portion such as formic acid or phenol, the 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. Therefore, the present invention includes compounds selected from Formula 1, their N-oxides, and agriculturally suitable salts.

[0096] As described in the summary of the invention, embodiments of the invention include compounds of formula 1, such as those described in any of the following embodiments:

[0097] Embodiment 1. A compound of Formula 1, its stereoisomers, N-oxides and salts, agricultural compositions containing them, and their use as herbicides, as described in the summary of the invention.

[0098] Embodiment 1a. The compound as described in Embodiment 1, wherein G is CONR 5 R 6 .

[0099] Implementation method 1b. The compound as described in Implementation Method 1, wherein G is G-1.

[0100] Implementation method 1c. The compound as described in Implementation Method 1, wherein G is G-2.

[0101] Embodiment 1d. The compound as described in Embodiment 1, wherein G is G-3.

[0102] Embodiment 1e. The compound as described in Embodiment 1, wherein G is G-4.

[0103] Embodiment 1f. The compound as described in Embodiment 1, wherein G is G-5.

[0104] Embodiment 2. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 1 It is H, C1-C7 alkyl, halogen, C2-C6 alkenyl, C2-C6 ynyl, C3-C7 cycloalkyl, or C1-C7 haloalkyl.

[0105] Embodiment 2a. The compound as described in Embodiment 2, wherein R 1It is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl;

[0106] Embodiment 2b. The compound as described in Embodiment 2a, wherein R 1 It is H, C1-C3 alkyl, halogen, or C3-C4 cycloalkyl.

[0107] Embodiment 2c. The compound as described in Embodiment 2b, wherein R 1 It is H, Me, halogen, or cyclopropyl.

[0108] Embodiment 2d. The compound as described in Embodiment 2c, wherein R 1 It is H, Me, F, Cl, Br or cyclopropyl.

[0109] Embodiment 2e. The compound as described in Embodiment 2d, wherein R 1 It is Me or Cl.

[0110] Embodiment 2f. The compound as described in Embodiment 2e, wherein R 1 It's me.

[0111] Example 2g. The compound as described in Example 2e, wherein R 1 It is Cl.

[0112] Embodiment 3. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 2 It is H, C1-C7 alkyl, halogen, -CN, C1-C7 haloalkyl, C1-C7 alkoxy, C3-C7 cycloalkyl or C1-C5 alkylthio.

[0113] Embodiment 3a. The compound as described in Embodiment 3, wherein R 2 It is H, C1-C7 alkyl, C3-C6 cycloalkyl, halogen, or CN.

[0114] Embodiment 3b. The compound as described in Embodiment 3a, wherein R 2 It is H, Me, F, Cl, or CN.

[0115] Embodiment 3c. The compound as described in Embodiment 3b, wherein R 2 It is H, Me, or F.

[0116] Embodiment 3d. The compound as described in Embodiment 3c, wherein R 2 It's H.

[0117] Embodiment 3e. The compound as described in Embodiment 3c, wherein R 2 It is F.

[0118] Embodiment 3f. The compound as described in Embodiment 3c, wherein R 2 It's me.

[0119] Embodiment 4. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 3 It 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.

[0120] Embodiment 4a. The compound as described in Embodiment 4, wherein R 3 It is H, C1-C7 alkyl, halogen, CN, C1-C7 alkoxy or C1-C7 haloalkyl.

[0121] Embodiment 4b. The compound as described in Embodiment 4a, wherein R 3 It is H, Me, F, Cl, -CN, OMe, or CF3.

[0122] Embodiment 4c. The compound as described in Embodiment 4b, wherein R 3 It is either Me or F.

[0123] Embodiment 4d. The compound as described in Embodiment 4c, wherein R 3 It's me.

[0124] Embodiment 4f. The compound as described in Embodiment 4c, wherein R 3 It is Cl.

[0125] Example 4g. The compound as described in Example 4c, wherein R 3 It is F.

[0126] Embodiment 5. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 4 It is 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)2NR 19 R 20 -S(OH)2NR 19 R 20 CH2OC(=O)OR19 CH2OC(=O)NR 19 R 20 Or CH2OC(=O)R 19 .

[0127] Embodiment 5a. The compound as described in Embodiment 5, wherein R 4 It is H, C(=O)R 19 CO2R 19 C(=O)SR 19 S(O)2R 19 or CH2OCOR 19 .

[0128] Embodiment 5b. The compound as described in Embodiment 5a, wherein R 4 It is H, SO2CF3, SO2CH3, CO2Me, COME, CH2OCO-t-Bu, CH2OCO-n-Bu, CH2OCO-cyclohexyl, CH2OCO-cyclopentyl, CH2OCOCH2CH3, COME, CH2OCOPh, CH2OCO-i-Bu, CH2OCOMe, CH2OCO-sec-Bu, or COSMe.

[0129] Embodiment 5c. The compound as described in Embodiment 5a, wherein R 4 It is H, CH2OCOR 19 or -S(O)2R 19 .

[0130] Embodiment 5d. The compound as described in Embodiment 5c, wherein R 4 It is H, CH2OCO-t-Bu or SO2CF3.

[0131] Embodiment 6. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 5 It 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.

[0132] Embodiment 6a. The compound as described in Embodiment 6, wherein R 5 It is H, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C3-C7 alkenylalkyl, C3-C7 ynylalkyl or C2-C3 cyanoalkyl.

[0133] Embodiment 6b. The compound as described in Embodiment 6a, wherein R 5 It 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.

[0134] Embodiment 6c. The compound as described in Embodiment 6b, wherein R 5 It is H, methyl, ethyl, propyl, cyanomethyl, CH2CCH or cyclopropylmethyl.

[0135] Embodiment 6d. The compound as described in Embodiment 6c, wherein R 5 It is H or methyl.

[0136] Embodiment 6e. The compound as described in Embodiment 6c, wherein R 5 It is a methyl group.

[0137] Embodiment 7. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 6 It 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.

[0138] Embodiment 7a. The compound as described in Embodiment 7, wherein R 6 It is H, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C3-C7 alkenylalkyl, C3-C7 ynylalkyl or C2-C3 cyanoalkyl.

[0139] Embodiment 7b. The compound as described in Embodiment 7a, wherein R 6 It 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.

[0140] Embodiment 7c. The compound as described in Embodiment 7b, wherein R 6 It is H, methyl, ethyl, propyl, cyanomethyl, CH2CCH or cyclopropylmethyl.

[0141] Embodiment 7d. The compound as described in Embodiment 7c, wherein R 6 It is H or methyl.

[0142] Embodiment 7e. The compound as described in Embodiment 7e, wherein R 6 It is a methyl group.

[0143] Embodiment 8. A compound as described in Formula 1 or any one of the embodiments, wherein R 5 and R 6 Together with the nitrogen atoms attached to them, they form 3- to 7-membered rings, which contain carbon atoms and optionally 1 to 3 oxygen, sulfur, or nitrogen atoms as ring members, wherein at most 2 carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring member is selected from S, S(O), or S(O)2, wherein the ring is optionally composed of at most 5 independently selected from (R v ) r The substituents are substituted, and r is the number of substituents.

[0144] Embodiment 8a. The compound as described in Embodiment 8, wherein the 3- to 7-membered rings are 5-membered rings.

[0145] Embodiment 8b. The compound as described in Embodiment 8a, wherein the 5-membered ring is not substituted.

[0146] Embodiment 8c. The compound as described in Embodiment 8a, wherein the 5-membered ring is substituted with at least one halogen, OMe, SMe or methyl group.

[0147] Embodiment 8d. The compound as described in any one of Embodiments 8a to 8c, wherein the 5-membered ring is a pyrrolidinyl or oxazolyl.

[0148] Embodiment 8e. The compound as described in Embodiment 8, wherein the 3- to 7-membered rings are 6-membered rings.

[0149] Embodiment 8f. The compound as described in Embodiment 8e, wherein the 6-membered ring is not substituted.

[0150] Example 8g. The compound as described in Example 8e, wherein the 6-membered ring is substituted with at least one halogen, OMe, SMe or methyl group.

[0151] Example 8h. The compound as described in Examples 8e to 8g, wherein the 6-membered ring is morpholino, thiomorpholino, piperidino, or piperazine.

[0152] Embodiment 8i. The compound as described in Embodiment 8, wherein the 3- to 7-membered rings are 4-membered rings.

[0153] Embodiment 8j. The compound as described in Embodiment 8i, wherein the 4-membered ring is not substituted.

[0154] Embodiment 8k. The compound as described in Embodiment 8i, wherein the 4-membered ring is substituted with at least one halogen, OMe, SMe or methyl.

[0155] Embodiment 81. The compound as described in any one of Embodiments 8i to 8k, wherein the 4-membered ring is a nitrogen-containing heterocyclic butyl group.

[0156] Embodiment 8m. The compound as described in Embodiment 8, wherein the 3- to 7-membered rings are 7-membered rings.

[0157] Embodiment 8n. The compound as described in Embodiment 8m, wherein the 7-membered ring is not substituted.

[0158] Embodiment 8o. The compound as described in Embodiment 8m, wherein the 7-membered ring is substituted with at least one halogen, OMe, SMe or methyl group.

[0159] Example 8p. The compound as described in any one of Examples 8m to 8o, wherein the 7-membered ring is azaheptyl or 1,4-oxazheptyl.

[0160] Embodiment 9. A compound as described in Formula 1 or any of the preceding embodiments, wherein R v 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.

[0161] Embodiment 9a. The compound as described in Embodiment 9, wherein R v Choose independently from the group consisting of: H, halogen, methyl, ethyl, propyl, cyclopropylmethyl, propargyl, OMe, or cyano.

[0162] Embodiment 9b. The compound as described in Embodiment 9a, wherein R v It is a methyl group.

[0163] Embodiment 9b1. The compound as described in Embodiment 9a, wherein R v It's OMe.

[0164] Embodiment 9b2. The compound as described in Embodiment 9a, wherein R v It's H.

[0165] Embodiment 9c. A compound as described in Formula 1 or any one of Embodiments 1 to 8p above, wherein two R v The two R atoms are attached to the same carbon atom or to two adjacent carbon atoms. vThey can form 3- to 7-membered rings together with one or more carbon atoms attached to them, the ring containing carbon atoms and optionally one to three oxygen, sulfur, or nitrogen atoms as ring members, wherein at most two carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring member is selected from S, S(O) or S(O)2, the ring being unsubstituted or substituted by 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.

[0166] Embodiment 9d. The compound as described in Embodiment 9c, wherein the two Rs v Attached to the same carbon atom, the two R v Together with the carbon atoms attached to them, they form 3- to 7-membered rings.

[0167] Embodiment 9e. The compound as described in Embodiment 9d, wherein the 3- to 7-membered rings are 5-membered rings.

[0168] Embodiment 9f. The compound as described in Embodiment 9e, wherein the 5-membered ring is 1,3-dioxolane or cyclopentyl.

[0169] Example 9g. The compound as described in Example 9d, wherein the 3- to 7-membered rings are 6-membered rings.

[0170] Example 9h. The compound as described in Example 9g, wherein the 6-membered ring is 1,3-dioxane or cyclohexyl.

[0171] Embodiment 9i. The compound as described in Embodiment 9c, wherein the two Rs v Attached to two adjacent carbon atoms, the two R v Together with the carbon atoms attached to them, they form 3- to 7-membered rings.

[0172] Embodiment 9j. The compound as described in Embodiment 9i, wherein the 3- to 7-membered rings are 5-membered rings.

[0173] Embodiment 9k. The compound as described in Embodiment 9j, wherein the 5-membered ring is 1,3-dioxolane or cyclopentyl.

[0174] Embodiment 91. The compound as described in Embodiment 9i, wherein the 3- to 7-membered rings are 6-membered rings.

[0175] Example 9m. The compound as described in Example 9l, wherein the 6-membered ring is 1,3-dioxane or cyclohexyl.

[0176] Embodiment 10. A compound as described in Formula 1 or any of the preceding embodiments, wherein R7 It is H, C1-C7 alkyl, halogen, -CN, C1-C7 haloalkyl or C1-C7 alkoxy.

[0177] Embodiment 10a. The compound as described in Embodiment 10, wherein R 7 It is H, methyl, F or Cl.

[0178] Embodiment 10b. The compound as described in Embodiment 10a, wherein R 7 It's H.

[0179] Embodiment 11. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 8 It is an H or C1-C7 alkyl group.

[0180] Embodiment 11a. The compound as described in Embodiment 11, wherein R 8 It is H or Me.

[0181] Embodiment 11b. The compound as described in Embodiment 11a, wherein R 8 It's H.

[0182] Embodiment 12. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 7 and R 8 They can form 3- to 7-membered rings, which contain a carbon atom and optionally one or two oxygen, sulfur, or nitrogen atoms as ring members.

[0183] Embodiment 12a. The compound as described in Embodiment 12, wherein the 3- to 7-membered rings are 5-membered rings.

[0184] Embodiment 12b. The compound as described in Embodiment 12, wherein the 3- to 7-membered rings are 6-membered rings.

[0185] Embodiment 13. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 9 It 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.

[0186] Embodiment 13a. The compound as described in Embodiment 13, wherein R 9 It is H, C1-C7 alkyl, C1-C7 haloalkyl or C2-C7 alkoxyalkyl.

[0187] Embodiment 13b. The compound as described in Embodiment 13a, wherein R 9 It is methyl, ethyl, tert-butyl, chloromethyl, or methoxymethyl.

[0188] Embodiment 15. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 7 and R 9 Together they form a fused 3- to 7-membered ring containing a carbon atom and optionally one or two oxygen, sulfur, or nitrogen atoms, said ring being unsubstituted or substituted by 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.

[0189] Embodiment 15a. The compound as described in Embodiment 15, wherein the 3- to 7-membered rings are 5- or 6-membered rings.

[0190] Embodiment 15b. The compound as described in Embodiment 15a, wherein the 5-membered ring is cyclopentyl.

[0191] Embodiment 15c. The compound as described in Embodiment 15, wherein the 3- to 7-membered rings are 6-membered rings.

[0192] Example 15d. A compound as described in Example 15c, wherein the 6-membered ring is cyclohexyl or tetrahydropyran.

[0193] Example 15e. The compound of any one of Examples 15 to 15d, wherein the ring is not substituted or is substituted by at least one substituent independently selected from H, halogen or C1-C4 alkyl.

[0194] Example 15f. The compound as described in Example 15e, wherein the ring is not substituted.

[0195] Embodiment 16. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 10 It is an H or C1-C7 alkyl group.

[0196] Embodiment 16a. The compound as described in Embodiment 16, wherein R 10 It is methyl or ethyl.

[0197] Embodiment 16b. The compound as described in Embodiment 16, wherein R 10 It's H.

[0198] Embodiment 17. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 9 and R 10Together with the carbon atoms to which they are attached, they form 3- to 7-membered rings, which contain carbon atoms and optionally one or two oxygen, sulfur, or nitrogen atoms as ring members, wherein at most two carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring member is selected from S, S(O), or S(O)2, wherein the ring is optionally composed of at most five independently selected from (R v ) r The substituents are substituted, and r is the number of substituents; or

[0199] When two R v When attached to the same carbon atom or to two adjacent carbon atoms, the two R atoms... v They can form 3- to 7-membered rings together with one or more carbon atoms attached to them, the ring containing carbon atoms and optionally one or two oxygen, sulfur or nitrogen atoms as ring members, wherein at most two carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring member is selected from S, S(O) or S(O)2.

[0200] Embodiment 17a. The compound as described in Embodiment 17, wherein the 3- to 7-membered rings are 5- or 6-membered rings.

[0201] Embodiment 17b. The compound as described in Embodiment 17a, wherein the 5-membered ring is cyclopentane.

[0202] Embodiment 17c. The compound as described in Embodiment 17, wherein the 3- to 7-membered rings are 6-membered rings.

[0203] Example 17d. A compound as described in Example 17c, wherein the 6-membered ring is cyclohexane, tetrahydro-2H-pyran, or tetrahydro-2H-thiaran.

[0204] Embodiment 17e. The compound as described in Embodiment 17d, wherein the 6-membered ring is cyclohexane.

[0205] Embodiment 17f. The compound as described in Embodiment 17, wherein the 3- to 7-membered rings are 4-membered rings.

[0206] Embodiment 17f. The compound as described in Embodiment 17, wherein the 3- to 7-membered rings are 7-membered rings.

[0207] Embodiment 18. A compound as described in Formula 1 or any of the preceding embodiments, wherein Q is O, S, or CR. 11 R 12 or NR 13 .

[0208] Embodiment 18a. The compound as described in Embodiment 18, wherein Q is O or S.

[0209] Embodiment 18b. The compound as described in Embodiment 18, wherein Q is O.

[0210] Embodiment 18c. The compound as described in Embodiment 18, wherein Q is CR 11 R 12 .

[0211] Embodiment 18d. The compound as described in Embodiment 18, wherein Q is NR. 13 .

[0212] Embodiment 18e. The compound as described in Embodiment 18, wherein Q is O, S, or CR. 11 R 12 .

[0213] Embodiment 18f. The compound as described in Embodiment 18, wherein Q is NR. 13 Other than substances.

[0214] Embodiment 19. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 11 and R 12 Together with the carbon atoms to which they are attached, they form fused 3- to 7-membered rings containing a carbon atom and optionally one or two oxygen, sulfur, or nitrogen atoms as ring members, said ring being unsubstituted or substituted by 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.

[0215] Embodiment 19a. The compound as described in Embodiment 19, wherein the 3- to 7-membered rings are 5-membered rings.

[0216] Embodiment 19b. The compound as described in Embodiment 19a, wherein the 5-membered ring is cyclopentane.

[0217] Embodiment 19c. The compound as described in Embodiment 19, wherein the 3- to 7-membered rings are 6-membered rings.

[0218] Example 19d. The compound as described in Example 19c, wherein the 6-membered ring is cyclohexane.

[0219] Embodiment 19e. The compound as described in Embodiment 19, wherein the ring is an unsubstituted 5- or 6-membered ring.

[0220] Embodiment 20. A compound as described in Formula 1 or any of the preceding embodiments, wherein r is 0, 1, 2 or 3.

[0221] Embodiment 20a. The compound as described in Embodiment 20, wherein r is 0.

[0222] Embodiment 20b. The compound as described in Embodiment 20, wherein r is 1 or 2.

[0223] Embodiment 20c. The compound as described in Embodiment 20, wherein r is 2.

[0224] Embodiment 20d. The compound as described in Embodiment 20, wherein r is 3.

[0225] Embodiment 20e. The compound as described in Embodiment 20, wherein r is 1.

[0226] Embodiment 21. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 13 It 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;

[0227] Embodiment 21a. The compound as described in Embodiment 21, wherein R 13 It is an H or C1-C7 alkyl group.

[0228] Embodiment 21b. The compound as described in Embodiment 21a, wherein R 13 It is either Me or Et.

[0229] Embodiment 21c. The compound as described in Embodiment 21b, wherein R 13 It's me.

[0230] Embodiment 21d. The compound as described in Embodiment 21d, wherein R 13 It is Et.

[0231] Embodiment 22. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 14 It 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.

[0232] Embodiment 22a. The compound as described in Embodiment 22, wherein R 14It is H, C1-C4 alkyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C4 haloalkyl, C1-C4 haloalkyl or C1-C7 alkoxy.

[0233] Embodiment 22b. The compound as described in Embodiment 22a, wherein R 14 It is a C1-C4 alkyl group.

[0234] Embodiment 22c. The compound as described in Embodiment 22b, wherein R 14 It's me.

[0235] Embodiment 22d. The compound as described in Embodiment 22b, wherein R 14 It is Et.

[0236] Embodiment 22e. The compound as described in Embodiment 22b, wherein R 14 It is CH2CF3.

[0237] Embodiment 23. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 15 It is H, C1-C7 alkyl, halogen, C1-C7 haloalkyl or C1-C7 alkoxy.

[0238] Embodiment 23a. The compound as described in Embodiment 23, wherein R 15 It is H, C1-C3 alkyl, or C1-C3 alkoxy.

[0239] Embodiment 23b. The compound as described in Embodiment 23a, wherein R 15 It is H or OMe.

[0240] Embodiment 23c. The compound as described in Embodiment 23b, wherein R 15 It's H.

[0241] Embodiment 23d. The compound as described in Embodiment 23b, wherein R 15 It's OMe.

[0242] Embodiment 24. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 16 It is H, cyano, C1-C7 alkyl, halogen, C1-C4 alkylthio, C1-C7 haloalkyl or C1-C7 alkoxy.

[0243] Embodiment 24a. The compound as described in Embodiment 24, wherein R 16 It is H, cyano, C1-C4 alkyl, halogen, C1-C4 alkylthio, C1-C4 haloalkyl or C1-C4 alkoxy.

[0244] Embodiment 24b. The compound as described in Embodiment 24a, wherein R 16 It is H or C1-C4 alkyl.

[0245] Embodiment 24c. The compound as described in Embodiment 24a, wherein R 16 It is H, cyano, methyl, ethyl, propyl, isopropyl, halogen, SMe, CF3, or OMe.

[0246] Embodiment 24d. The compound as described in Embodiment 24c, wherein R 16 It is H, cyano, methyl, F, SMe, CF3, or OMe.

[0247] Embodiment 25. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 17 It 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.

[0248] Embodiment 25a. The compound as described in Embodiment 25, wherein R 17 It is H, C1-C4 alkyl, halogen, or C1-C4 alkoxy.

[0249] Embodiment 25b. The compound as described in Embodiment 25a, wherein R 17 It is H, methyl, Cl, or OMe.

[0250] Embodiment 26. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 18 It is H, C1-C7 alkyl, halogen, C1-C7 haloalkyl or C1-C7 alkoxy;

[0251] Embodiment 26a. The compound as described in Embodiment 26, wherein R 18 It is an H or C1-C3 alkoxy group;

[0252] Embodiment 26b. The compound as described in Embodiment 26, wherein R 18 It is H, methyl, or OMe.

[0253] Embodiment 26c. The compound as described in Embodiment 26b, wherein R 18 It's H.

[0254] Embodiment 26d. The compound as described in Embodiment 26b, wherein R 18 It's OMe.

[0255] Embodiment 27. A compound as described in Formula 1 or any of the preceding embodiments, wherein R 19 It 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.

[0256] Embodiment 27a. The compound as described in Embodiment 27, wherein R 19 It is a C1-C7 alkyl or a C1-C7 haloalkyl.

[0257] Embodiment 27b. The compound as described in Embodiment 27a, wherein R 19 It is a C1-C7 alkyl group.

[0258] Embodiment 27c. The compound as described in Embodiment 27b, wherein R 19 It is methyl, ethyl, isopropyl, tert-butyl, n-butyl, sec-butyl, isobutyl, cyclopentyl, or cyclohexyl.

[0259] Embodiment 27d. The compound as described in Embodiment 27c, wherein R 19 It is tert-butyl.

[0260] Embodiment 27e. The compound as described in Embodiment 27a, wherein R 19 It is a C1-C3 haloalkyl group.

[0261] Embodiment 27f. The compound as described in Embodiment 27e, wherein R 19 It's CF3.

[0262] Embodiment 28. A compound as described in Formula 1 or any of the preceding embodiments, wherein R f It is a C1-C7 alkyl or a C1-C7 haloalkyl.

[0263] Embodiment 28a. The compound as described in Embodiment 28, wherein R f It is a C1-C3 haloalkyl group.

[0264] Embodiment 28b. The compound as described in Embodiment 28a, wherein R f It's CF3.

[0265] The embodiments of the present invention (including embodiments 1 to 28b described above and any other embodiments described herein) can be combined in any manner, and the description of variables in the embodiments relates not only to compounds of formula 1, but also to starting compounds and intermediate compounds that can be used to prepare compounds of formula 1. Furthermore, the embodiments of the present invention (including embodiments 1 to 28b described above and any other embodiments described herein) and any combination thereof relate to the compositions and methods of the present invention.

[0266] The combinations of implementation methods 1 to 28b are shown below:

[0267] Embodiment PA. A compound of Formula 1 as described in the invention, wherein Q is O, S, or CR. 11 R 12 .

[0268] Embodiment A. A compound of Formula 1 as described in the invention summary, wherein...

[0269] G is CONR 5 R 6 ;

[0270] R 1 It is H, C1-C7 alkyl, halogen, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl or C1-C7 haloalkyl;

[0271] R 2 It is H, C1-C7 alkyl, C3-C6 cycloalkyl, halogen or CN;

[0272] R 3 It is H, C1-C7 alkyl, halogen, CN, C1-C7 alkoxy or C1-C7 haloalkyl;

[0273] R 4 It is H, C(=O)R 19 CO2R 19 C(=O)SR 19 S(O)2R 19 or CH2OCOR 19 ;

[0274] R 5 It 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;

[0275] R 6It is H, C1-C3 alkyl, C2-C3 alkenyl, C2-C3 ynyl, C3-C6 cycloalkyl, C4-C7 cycloalkylalkyl, C3-C6 alkenylalkyl, C3-C6 ynylalkyl, or C2-C3 cyanoalkyl; and

[0276] R f It is a C1-C3 haloalkyl group.

[0277] Implementation method B. The compound as described in implementation method A, wherein...

[0278] R 1 It is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl;

[0279] R 2 It is H, Me, or F;

[0280] R 3 It is H, Me, F, Cl, CN, OMe, or CF3;

[0281] R 4 It is H, SO2CF3, SO2CH3, CO2Me, COME, CH2OCO-t-Bu, CH2OCO-n-Bu, CH2OCO-cyclohexyl, CH2OCO-cyclopentyl, CH2OCOCH2CH3, COME, CH2OCOPh, CH2OCO-i-Bu, CH2OCOMe, CH2OCO-sec-Bu, or COSMe;

[0282] R 5 It is H, methyl, ethyl, propyl, cyanomethyl, CH2CCH, or cyclopropylmethyl;

[0283] R 6 It is H, methyl, ethyl, propyl, cyanomethyl, CH2CCH, or cyclopropylmethyl; and

[0284] R f It's CF3.

[0285] Implementation method C. The compound as described in implementation method B, wherein

[0286] R 1 Is it Me or Cl;

[0287] R 3 It's me;

[0288] R 4 It is H, CH2OCO-t-Bu or SO2CF3;

[0289] R 5 It is methyl;

[0290] R 6It is a methyl group.

[0291] Embodiment D. A compound of Formula 1 as described in the invention summary, wherein...

[0292] G is CONR 5 R 6 ;

[0293] R 1 It is H, C1-C7 alkyl, halogen, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl or C1-C7 haloalkyl;

[0294] R 2 It is H, C1-C7 alkyl, C3-C6 cycloalkyl, halogen or CN;

[0295] R 3 It is H, C1-C7 alkyl, halogen, CN, C1-C7 alkoxy or C1-C7 haloalkyl;

[0296] R 4 It is H, C(=O)R 19 CO2R 19 C(=O)SR 19 S(O)2R 19 or CH2OCOR 19 ;

[0297] R 5 and R 6 Together with the nitrogen atoms attached to them, they form 3- to 7-membered rings, which contain carbon atoms and optionally 1 to 3 oxygen, sulfur, or nitrogen atoms as ring members, wherein at most 2 carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring member is selected from S, S(O), or S(O)2, wherein the ring is optionally composed of at most 5 independently selected from (R v ) r The substituents are substituted, and r is the number of these substituents;

[0298] R v Independently selected from the group consisting of: H, methyl, ethyl, propyl, cyclopropylmethyl, propynyl, or cyanomethyl; and

[0299] r is 1 or 2.

[0300] Embodiment E. The compound as described in Embodiment D, wherein

[0301] R 1 It is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl;

[0302] R 2 It is H, Me, or F;

[0303] R 3 It is H, Me, F, Cl, CN, OMe, or CF3;

[0304] R 4 It is H, SO2CF3, SO2CH3, CO2Me, COME, CH2OCO-t-Bu, CH2OCO-n-Bu, CH2OCO-cyclohexyl, CH2OCO-cyclopentyl, CH2OCOCH2CH3, COME, CH2OCOPh, CH2OCO-i-Bu, CH2OCOMe, CH2OCO-sec-Bu, or COSMe;

[0305] R 5 and R 6 Together with the nitrogen atoms attached to them, they form 3- to 7-membered rings, wherein the rings are 5-membered rings; and

[0306] R f It's CF3.

[0307] Embodiment F. The compound as described in Embodiment D, wherein

[0308] R 1 It is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl;

[0309] R 2 It is H, Me, or F;

[0310] R 3 It is H, Me, F, Cl, CN, OMe, or CF3;

[0311] R 4 It is H, SO2CF3, SO2CH3, CO2Me, COME, CH2OCO-t-Bu, CH2OCO-n-Bu, CH2OCO-cyclohexyl, CH2OCO-cyclopentyl, CH2OCOCH2CH3, COME, CH2OCOPh, CH2OCO-i-Bu, CH2OCOMe, CH2OCO-sec-Bu, or COSMe;

[0312] R 5 and R 6 Together with the nitrogen atoms to which they are attached, they form 3- to 7-membered rings, wherein the rings are 6-membered rings; and

[0313] R f It's CF3.

[0314] Embodiment A1. A compound of Formula 1 as described in the invention summary, wherein

[0315] G is G-1;

[0316] R 1 It is H, C1-C7 alkyl, halogen, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl or C1-C7 haloalkyl;

[0317] R 2 It is H, C1-C7 alkyl, C3-C6 cycloalkyl, halogen or CN;

[0318] R 3 It is H, C1-C7 alkyl, halogen, CN, C1-C7 alkoxy or C1-C7 haloalkyl;

[0319] R 4 It is H, C(=O)R 19 CO2R 19 C(=O)SR 19 S(O)2R 19 or CH2OCOR 19 ;

[0320] R f It is a C1-C3 haloalkyl group.

[0321] Embodiment B1. The compound as described in Embodiment A1, wherein

[0322] R 1 It is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl;

[0323] R 2 It is H, Me, or F;

[0324] R 3 It is H, Me, F, Cl, CN, OMe, or CF3;

[0325] R 4 It is H, SO2CF3, SO2CH3, CO2Me, COME, CH2OCO-t-Bu, CH2OCO-n-Bu, CH2OCO-cyclohexyl, CH2OCO-cyclopentyl, CH2OCOCH2CH3, COME, CH2OCOPh, CH2OCO-i-Bu, CH2OCOMe, CH2OCO-sec-Bu, or COSMe;

[0326] R 7 It is H, C1-C7 alkyl, halogen, -CN, C1-C7 haloalkyl or C1-C7 alkoxy;

[0327] R 8 It is an H or C1-C7 alkyl group;

[0328] R 9It is H, C1-C7 alkyl, C1-C7 haloalkyl or C2-C7 alkoxyalkyl;

[0329] R 10 It is an H or C1-C7 alkyl group; and

[0330] R f It's CF3.

[0331] Embodiment C1. The compound as described in Embodiment B1, wherein

[0332] R 1 Is it Me or Cl;

[0333] R 3 It's me;

[0334] R 4 It is H, CH2OCO-t-Bu or SO2CF3.

[0335] R 7 It is H;

[0336] R 8 It is H;

[0337] R 9 It is methyl, ethyl, tert-butyl, chloromethyl, or methoxymethyl; and

[0338] R 10 It is methyl or ethyl.

[0339] Embodiment D1. The compound as described in Embodiment A1, wherein

[0340] R 7 and R 9 Together they form a fused 3- to 7-membered ring containing a carbon atom and optionally one or two oxygen, sulfur, or nitrogen atoms, said ring being unsubstituted or substituted by 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;

[0341] R 8 It is H; and

[0342] R 10 It is H;

[0343] Embodiment E1. The compound as described in Embodiment D1, wherein

[0344] R 1 It is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl;

[0345] R2 It is H, Me, or F;

[0346] R 3 It is H, Me, F, Cl, CN, OMe, or CF3;

[0347] R 4 It is H, SO2CF3, SO2CH3, CO2Me, COME, CH2OCO-t-Bu, CH2OCO-n-Bu, CH2OCO-cyclohexyl, CH2OCO-cyclopentyl, CH2OCOCH2CH3, COME, CH2OCOPh, CH2OCO-i-Bu, CH2OCOMe, CH2OCO-sec-Bu, or COSMe;

[0348] R 7 and R 9 Together they form fused 3- to 7-membered rings, wherein the 3- to 7-membered rings are 5- or 6-membered rings.

[0349] Embodiment F1. The compound as described in Embodiment E1, wherein

[0350] R 7 and R 9 Together they form a 5- or 6-membered ring of cyclopentyl, cyclohexyl, or tetrahydropyran, wherein the ring is unsubstituted or substituted by at least one substituent independently selected from H, halogen, or C1-C4 alkyl.

[0351] Implementation method G1. The compound as described in implementation method A1, wherein

[0352] R 9 and R 10 Together with the carbon atoms to which they are attached, they form 3- to 7-membered rings, which contain carbon atoms and optionally one or two oxygen, sulfur, or nitrogen atoms as ring members, wherein at most two carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring member is selected from S, S(O), or S(O)2, wherein the ring is optionally composed of at most five independently selected from (R v ) r The substituents are substituted, and r is the number of substituents; or

[0353] When two R v When attached to the same carbon atom or to two adjacent carbon atoms, the two R atoms... v They can form 3- to 7-membered rings together with one or more carbon atoms attached to them, the ring containing carbon atoms and optionally one or two oxygen, sulfur or nitrogen atoms as ring members, wherein at most two carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring member is selected from S, S(O) or S(O)2.

[0354] R 7 It is H; and

[0355] R 8 It is H;

[0356] Embodiment H1. The compound as described in Embodiment G1, wherein

[0357] R 1 It is H, C1-C3 alkyl, halogen, or C3-C4 cycloalkyl.

[0358] R 2 It is H, Me, or F;

[0359] R 3 It is H, Me, F, Cl, CN, OMe, or CF3;

[0360] R 4 It is H, SO2CF3, SO2CH3, CO2Me, COME, CH2OCO-t-Bu, CH2OCO-n-Bu, CH2OCO-cyclohexyl, CH2OCO-cyclopentyl, CH2OCOCH2CH3, COME, CH2OCOPh, CH2OCO-i-Bu, CH2OCOMe, CH2OCO-sec-Bu, or COSMe;

[0361] R 9 and R 10 Together with the carbon atoms to which they are attached, they form 3- to 7-membered rings, which are 5- or 6-membered rings.

[0362] R v Choose independently from the group consisting of: H, methyl, ethyl, propyl, cyclopropylmethyl, propyne, or cyanomethyl.

[0363] r is 1 or 2.

[0364] Embodiment I1. The compound as described in Embodiment H1, wherein

[0365] R 9 and R 10 Together with the carbon atoms attached to them, they form 3- to 7-membered rings, which are 5- or 6-membered rings of cyclopentane, cyclohexane, tetrahydro-2H-pyran, or tetrahydro-2H-thiaran.

[0366] Embodiment A2. The compound of Formula 1 as described in the invention summary, wherein

[0367] G is G-2;

[0368] R 1It is H, C1-C7 alkyl, halogen, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl or C1-C7 haloalkyl;

[0369] R 2 It is H, Me, or F;

[0370] R 3 It is H, Me, F, Cl, CN, OMe, or CF3;

[0371] R 4 It is H, SO2CF3, SO2CH3, CO2Me, COME, CH2OCO-t-Bu, CH2OCO-n-Bu, CH2OCO-cyclohexyl, CH2OCO-cyclopentyl, CH2OCOCH2CH3, COME, CH2OCOPh, CH2OCO-i-Bu, CH2OCOMe, CH2OCO-sec-Bu, or COSMe; and

[0372] R f It is a C1-C3 haloalkyl group.

[0373] Embodiment B2. The compound as described in Embodiment A2, wherein

[0374] Q is either O or S;

[0375] R 7 It is H;

[0376] R 8 It is H;

[0377] R f It's CF3.

[0378] R 9 and R 10 Together with the carbon atoms to which they are attached, they form 3- to 7-membered rings, wherein the rings are 5- or 6-membered rings;

[0379] R v Choose independently from the group consisting of: H, methyl, ethyl, propyl, cyclopropylmethyl, propyne, or cyanomethyl.

[0380] r is 1 or 2.

[0381] Embodiment C2. The compound as described in Embodiment B2, wherein

[0382] R 9 and R 10 Together with the carbon atoms attached to them, they form cyclopentane, cyclohexane, tetrahydro-2H-pyran, or tetrahydro-2H-thiaran; and

[0383] R v It's H.

[0384] Embodiment D2. The compound as described in Embodiment A2, wherein

[0385] Q is CR 11 R 12 ;

[0386] R 7 It is H;

[0387] R 8 It is H;

[0388] R 9 It is H;

[0389] R 10 It is H;

[0390] R 11 and R 12 Together with the carbon atoms to which they are attached, they form fused 3- to 7-membered rings, the rings containing a carbon atom and optionally one or two oxygen, sulfur, or nitrogen atoms as ring members, the rings being either unsubstituted or substituted by 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; and

[0391] R f It's CF3.

[0392] Embodiment E2. The compound as described in Embodiment D2, wherein

[0393] R 11 and R 12 Together with the carbon atoms to which they are attached, they form fused 3- to 7-membered rings, which are unsubstituted 5- or 6-membered rings.

[0394] Embodiment A3. The compound of Formula 1 as described in the invention summary, wherein...

[0395] G is G-3;

[0396] R 1 It is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl;

[0397] R 2 It is H, Me, or F;

[0398] R 3 It is H, Me, F, Cl, CN, OMe, or CF3;

[0399] R 4It is H, SO2CF3, SO2CH3, CO2Me, COME, CH2OCO-t-Bu, CH2OCO-n-Bu, CH2OCO-cyclohexyl, CH2OCO-cyclopentyl, CH2OCOCH2CH3, COME, CH2OCOPh, CH2OCO-i-Bu, CH2OCOMe, CH2OCO-sec-Bu, or COSMe;

[0400] R 13 It is a C1-C7 alkyl group;

[0401] R 14 It is a C1-C4 alkyl group;

[0402] R 15 It is H; and

[0403] R f It is a C1-C3 haloalkyl group.

[0404] Embodiment A4. The compound of Formula 1 as described in the invention summary, wherein...

[0405] G is G-4;

[0406] R 1 It is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl;

[0407] R 2 It is H, Me, or F;

[0408] R 3 It is H, Me, F, Cl, CN, OMe, or CF3;

[0409] R 4 It is H, SO2CF3, SO2CH3, CO2Me, COME, CH2OCO-t-Bu, CH2OCO-n-Bu, CH2OCO-cyclohexyl, CH2OCO-cyclopentyl, CH2OCOCH2CH3, COME, CH2OCOPh, CH2OCO-i-Bu, CH2OCOMe, CH2OCO-sec-Bu, or COSMe;

[0410] R 13 It is a C1-C7 alkyl group;

[0411] R f It is a C1-C3 haloalkyl;

[0412] R 15 It is H, C1-C3 alkyl, or C1-C3 alkoxy; and

[0413] R 16It is H, cyano, C1-C4 alkyl, halogen, C1-C4 alkylthio, C1-C4 haloalkyl or C1-C4 alkoxy.

[0414] Embodiment A5. A compound of Formula 1 as described in the invention, wherein

[0415] G is G-5;

[0416] R 1 It is H, C1-C7 alkyl, halogen, or C3-C7 cycloalkyl;

[0417] R 2 It is H, Me, or F;

[0418] R 3 It is H, Me, F, Cl, CN, OMe, or CF3;

[0419] R 4 It is H, SO2CF3, SO2CH3, CO2Me, COME, CH2OCO-t-Bu, CH2OCO-n-Bu, CH2OCO-cyclohexyl, CH2OCO-cyclopentyl, CH2OCOCH2CH3, COME, CH2OCOPh, CH2OCO-i-Bu, CH2OCOMe, CH2OCO-sec-Bu, or COSMe;

[0420] R f It is a C1-C3 haloalkyl;

[0421] R 16 It is an H or C1-C4 alkyl group;

[0422] R 17 It is H, C1-C4 alkyl, halogen, or C1-C4 alkoxy; and

[0423] R 18 It is an H or C1-C3 alkoxy group.

[0424] Specific embodiments include compounds of formula 1 selected from the group consisting of:

[0425] N-[2,4-dimethyl-5-(1-piperidinylcarbonyl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 260);

[0426] N-[2-chloro-4-methyl-5-(4-morpholinylcarbonyl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 16);

[0427] N-[2,4-dimethyl-5-(4-morpholinylcarbonyl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 6);

[0428] N-[2-chloro-4-methyl-5-(1-piperidinylcarbonyl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 18);

[0429] 3-Fluoro-N,N,2,4-Tetramethyl-5-[[(trifluoromethyl)sulfonyl]amino]benzamide (compound 128);

[0430] 1,1,1-Trifluoro-N-[3-fluoro-2,4-dimethyl-5-(4-morpholinylcarbonyl)phenyl]methanesulfonamide (compound 190);

[0431] N-[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.4]non-2-en-3-yl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 207);

[0432] N-[2,4-dimethyl-5-[(3aR,6aR)-3a,5,6,6a-tetrahydro-4H-cyclopentane[d]isoxazol-3-yl]phenyl]-1,1,1-trifluoromethanesulfonamide (compound 103);

[0433] N-[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.5]dec-2-en-3-yl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 197);

[0434] N-[2,4-dimethyl-5-(3a,4,7,7a-tetrahydro-5H-pyrano[4,3-d]isoxazo-3-yl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 121);

[0435] N-[2,4-dimethyl-5-(3a,6,7,7a-tetrahydro-4H-pyrano[3,4-d]isoxazo-3-yl)phenyl]-1,1,1-trifluoromethanesulfonamide (compound 120);

[0436] 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);

[0437] [[2,4-Dimethyl-5-(1-oxa-2-azaspiro[4.4]non-2-en-3-yl)phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropionate (compound 140);

[0438] [[2,4-Dimethyl-5-(1-oxa-2-azaspiro[4.5]dec-2-en-3-yl)phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropionate (compound 159);

[0439] [[2,4-Dimethyl-5-[(3aR,6aR)-3a,5,6,6a-tetrahydro-4H-cyclopentan[d]isoxazol-3-yl]phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropionate (compound 100);

[0440] [[2,4-Dimethyl-5-(1-oxo-2-azaspiro[4.5]dec-2-yl)phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropionate (compound 268);

[0441] Other specific embodiments include compounds of formula 1 selected from the group consisting of:

[0442] Specific embodiments include compounds of formula 1 selected from the group consisting of:

[0443] [[(trifluoromethyl)sulfonyl][2,3,4-trimethyl-5-(4-morpholinylcarbonyl)phenyl]amino]2,2-dimethylpropionate (compound 324);

[0444] N-[(trifluoromethyl)sulfonyl]-N-[2,3,4-trimethyl-5-(1-piperidinylcarbonyl)phenyl]carbamate (compound 330);

[0445] [[(trifluoromethyl)sulfonyl][2,3,4-trimethyl-5-(1-piperidinylcarbonyl)phenyl]amino]2,2-dimethylpropionate (compound 329);

[0446] 1,1,1-Trifluoro-N-[2,3,4-trimethyl-5-(4-morpholinylcarbonyl)phenyl]methanesulfonamide (compound 289); and

[0447] [[(trifluoromethyl)sulfonyl][2,3,4-trimethyl-5-[(3aR,6aR)-3a,5,6,6a-tetrahydro-4H-cyclopentan[d]isoxazol-3-yl]phenyl]amino]methyl 2,2-dimethylpropionate (compound 336);

[0448] Other specific embodiments include compounds of formula 1, wherein

[0449] G is CONR 5 R 6 And NR 5 R 6 It's J-3a, R 1 It's Me, R 2 It's Me, R 3 It's Me, R 4 It is CH2OCO-t-Bu, and R f It is CF3 (compound 331);

[0450] G is CONR 5 R 6 And NR 5 R 6 It's a J-4, R 1 It's Me, R 2 It's Me, R 3 It's Me, R 4 It is CO2Et and R f It is CF3 (compound 325).

[0451] The present invention also relates to a method for controlling unwanted vegetation, the method comprising applying a herbicidal amount of a compound of the present invention (e.g., as the composition described herein) to the site of the vegetation. It should be noted that the examples relating to the method of use pertain to those compounds described above. The compounds of the present invention are particularly useful for selectively controlling weeds in crops such as wheat, barley, corn, soybean, sunflower, cotton, oilseed rape, and rice, as well as specialty crops such as sugarcane, citrus, fruit, and nut crops.

[0452] It is also worth noting that the herbicidal composition of the present invention, which includes the compounds described in the above embodiments, is an example.

[0453] The present invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, its N-oxide and salt, and (b) at least one additional active ingredient selected from: (b1) a photosystem II inhibitor, (b2) an acetylhydroxy acid synthase (AHAS) inhibitor, (b3) an acetyl-CoA carboxylase (ACCase) inhibitor, (b4) an auxin mimic, (b5) a 5-enol-pyruvate-shikimate-3-phosphate (EPSP) synthase inhibitor, (b6) a photosystem I electron diverter, (b7) a protoporphyrinogen oxidase (PPO) inhibitor, (b8) a glutamine synthase (GS) inhibitor, (b9) a very long-chain fatty acid (VLCFA) elongation enzyme inhibitor, (b10) a photosystem II inhibitor, (b10) a photosystem III inhibitor, (b11) a photosystem II inhibitor, (b12) a photosystem II inhibitor, (b13) a photosystem II inhibitor, (b14) a photosystem II inhibitor, (b15) a photosystem II inhibitor, (b16) a photosystem II inhibitor, (b17) a photosystem II inhibitor, (b18) a photosystem II inhibitor, (b19) a photosystem II inhibitor, (b10 ... (b11) Auxin transport inhibitors, (b12) phytopenic oleate dehydrogenase (PDS) inhibitors, (b13) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b14) urosine solanyltransferase (HST) inhibitors, (b15) cellulose biosynthesis inhibitors, (b16) other herbicides, including mitosis disruptors, organoarsenic compounds, sulfadiazine, bromobutyroxyfen, cyclohexane, bensulfuron, dazomet, fenbendazim, oxychloride, ethoxybenzamide, chlorpyrifos, phosphonophosphorus-ammonium, hydantoin, methyl chlorpyrifos, oleic acid, oxadiazon, nonanoic acid and barnyardgrass, (b17) herbicide safeners and salts of compounds from (b1) to (b18).

[0454] "Optical System II inhibitor" (b1) is in QB - It binds to the D-1 protein at the binding site and thus blocks electrons from passing through the Q-cell membrane in the chloroplast. A Transmit to Q B Chemical compounds. Electrons blocked from passing through photosystem II are transferred through a series of reactions to form toxic compounds. These toxic compounds damage cell membranes, causing chloroplast swelling, membrane leakage, and ultimately cell rupture. Q B - The binding site has three different binding sites: binding site A binds triazine such as atrazine, triazinone such as cycloazinone, and uracil such as chlorpyrifos; binding site B binds phenylurea such as diuron; and binding site C binds benzothiadiazole such as metribuzin, nitrile such as bromobenzonitrile, and phenylpyridazine such as pyrazosulfuron. Examples of photosystem II inhibitors include atrazine, azoxystrobin, atrazine, bentazon, chlorpyrifos, bromofenac, chlorobromofenac, chlorpyrifos ...

[0455] "AHAS inhibitors" (b2) are chemical compounds that inhibit acetylhydroxy acid synthase (AHAS) (also known as acetyllactic acid synthase (ALS)), and thus kill plants by inhibiting the production of branched-chain aliphatic amino acids such as valine, leucine, and isoleucine, which are essential for protein synthesis and cell growth. Examples of AHAS inhibitors include pyrimisulfuron, tetrazolium-sulfuron, bensulfuron-methyl, bispyribac-sodium salt, chlorpyrifos, chlorpyrifos, chlorsulfuron, chlorpyrifos, chlorpyrifos, cyclopyrimisulfuron, dichlorvos, acesulfuron, ethoxysulfuron, pyrimisulfuron, flusulfuron-methyl, flusulfuron-methyl, pyrimisulfuron-methyl, flusulfuron-methyl sodium salt, formamide sulfuron, chlorpyrifos, imazalil, methoxysulfuron, methoxysulfuron, methoxysulfuron, metsulfuron-methyl, and fensulfuron-methyl. Metazolidinone, imazalil, azoxystrobin, mesosulfuron (including sodium salt), iofensulfuron (2-iodo-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide), sulfanilamide, iofensulfuron (3-chloro-4-(5,6-dihydro-5-methyl-1,4,2-dioxazin-3-yl)-N-[[(4-... (6-Dimethoxy-2-pyrimidinyl)amino]carbonyl]-1-methyl-1H-pyrazole-5-sulfonamide), sulfadiazine, mesosulfuron, nicosulfuron, cyclosulfuron, penoxsulam, flusulfuron, sodium propensulfuron, promethazine (2-chloro-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-6-propylimidazo[1,2-b]pyridazine-3-sulfonamide), flusulfuron, pyrimidinyl Sulfuron, pyrimisulfuron, cyclopyrimisulfuron, pyrimisulfuron sodium, sulfadiazine, mesosulfuron, sulfonylsulfuron, thiamethoxam, thifensulfuron, flufensulfuron (N-[2-[(4,6-dimethoxy-1,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-1,1-difluoro-N-methylmethanesulfonamide), etherbenzylsulfuron, benzylsulfuron, trifluridinesulfuron (including sodium salt), flumethanil, and trifluridinesulfuron.

[0456] "ACCase inhibitors" (b3) are chemical compounds that inhibit acetyl-CoA carboxylase, an enzyme responsible for catalyzing early steps in lipid and fatty acid synthesis in plants. Lipids are major components of cell membranes, and without lipids, new cells cannot be produced. Inhibition of acetyl-CoA carboxylase and the resulting lack of lipid production lead to a loss of cell membrane integrity, especially in actively growing areas such as meristems. Ultimately, seedling and rhizome growth ceases, and seedling meristems and rhizome buds begin to die. Examples of ACCase inhibitors include quizalofop-P-ethyl, clethodim, clodinafop-propargyl, thiamethoxam, cyhalofop-propargyl, quizalofop-P-ethyl, haloxyfop-propargyl, clodinafop-propargyl, cyclobenzanone, quizalofop-P-ethyl, quizalofop-P-ethyl, quizalofop-P-ethyl, and quizalofop-P-ethyl, including analytical forms such as quizalofop-P-ethyl, quizalofop-P-ethyl, quizalofop-P-ethyl, and quizalofop-P-ethyl, as well as ester forms such as clodinafop-propargyl, cyhalofop-propargyl, quizalofop-P-ethyl, and quizalofop-P-ethyl.

[0457] Auxins are plant hormones that regulate the growth of many plant tissues. "Auxin mimics" (b4) are compounds that mimic the plant growth hormone auxin, thus leading to uncontrolled and disordered growth, resulting in the death of susceptible species. Examples of auxin mimics include cyclopropylpyrimidine acid (6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid) and its methyl and ethyl esters and their sodium and potassium salts, chlorpyrifos, glyphosate-ethyl ester, glyphosate, chlorpyrifos, barnyardgrass, dichloropyridine acid, dicamba, 2,4-D, 2,4-DB, propionic acid, clopyralid, halauxifen (4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2- Methyl halauxifen-methyl (4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylate), MCPA, MCPB, 2-methyl-4-chloropropionic acid, doxycycline, dichloroquinoline acid, chloroquinoline acid, 2,3,6-TBA, chlorpyrifos, and methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate.

[0458] "EPSP synthase inhibitor" (b5) is a chemical compound that inhibits the enzyme 5-enol-pyruvate-shikimate-3-phosphate synthase, which is involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan, and phenylalanine. EPSP inhibitor herbicides are readily absorbed through plant leaves and translocated from the phloem to the growing point. Glyphosate is a relatively non-selective post-emergence herbicide belonging to this group. Glyphosate includes esters and salts such as ammonium salts, isopropylammonium salts, potassium salts, sodium salts (including sesquisodium salts), and trimethylsulfonium salts (alternatively known as glyphosate).

[0459] "Photosystem I electron diverters" (b6) are compounds that receive electrons from photosystem I and generate hydroxyl radicals after several cycles. These radicals are highly reactive and readily destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This disrupts cell membrane integrity, causing cells and organelles to "leak," leading to rapid leaf wilting and drying, and ultimately plant death. Examples of this second type of photosynthesis inhibitor include diquat and paraquat.

[0460] "PPO inhibitors" (b7) are compounds that inhibit the enzyme protoporphyrinogen oxidase, rapidly leading to the formation of highly reactive compounds in plants that disrupt cell membranes, resulting in cell sap leakage. Examples of PPO inhibitors include trifluralin-sodium, pyrazosulfuron, pyrazosulfuron, methoxyfenozide, flufenoxuron, trifluralin, methoxyfenozide, indole-methyl, isopyrazosulfuron, flupyridaben, flumetsulam, propyzoxystrobin, ethoxysulfuron, fluthiamethoxam, flusulfanilamide, halosafen, quizalofop-P-ethyl, propyzoxystrobin, oxadiazon, ethoxysulfuron, cyclopentoxane, flupyrazosulfuron, pyrazosulfuron, pyrazosulfuron, mesotrione, thiamethoxam, trifluralin. udimoxazin (dihydro-1,5-dimethyl-6-thio-3-[2,2,7-trifluoro-3,4-dihydro-3-oxo-4-(2-propyl-1-yl)-2H-1,4-benzoxazin-6-yl]-1,3,5-triazin-2,4(1H,3H)-dione) and flupyrimisulfuron (N-[2-[[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxy-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenyl]thio]-1-oxopropyl]-β-alanine methyl ester).

[0461] "GS inhibitors" (b8) are compounds that inhibit the activity of glutamine synthase, an enzyme used by plants to convert ammonia into glutamine. As a result, ammonia accumulates and glutamine levels decrease. Plant damage can occur due to the combined effects of ammonia toxicity and the lack of amino acids required for other metabolic processes. GS inhibitors include glufosinate and its esters and salts, such as glufosinate and other glufosinate derivatives, glufosinate P ((2S)-2-amino-4-(hydroxymethylphosphono)butyric acid), and bilanaphos.

[0462] "VLCFA elongase inhibitor" (b9) is a herbicide with various chemical structures that inhibits elongation enzymes. Elongation enzymes are enzymes located in or near chloroplasts that are involved in the biosynthesis of VLCFAs. In plants, very long-chain fatty acids are major components of hydrophobic polymers that prevent drying at the leaf surface and provide stability to pollen grains. Such herbicides include acetochlor, metolachlor, sphagnum molybdate, butachlor, benzoyl sulfone, metolachlor, thifensulfonamide, fenoxasulfone (3-[[(2,5-dichloro-4-ethoxyphenyl)methyl]sulfonyl]-4,5-dihydro-5,5-dimethylisoxazole), tetrazolium-methyl, fluthiamethoxam, indicarb, bensulfuron-methyl, pyrazosulfuron, metolachlor, naphthylpropane, diltiazem, diltiazem-M ((2R)-N,N-diethyl-2-(1-naphthoxy)propamide), pethoxamid, piperazine, pretilachlor, doxycycline, pyroxasulfone, and methoxythiamethoxam, including analytical forms such as metolachlor and chloroacetamide and oxyacetamide.

[0463] Auxin transport inhibitors (b10) are chemicals that inhibit auxin transport in plants, such as by binding to auxin-carrier proteins. Examples of auxin transport inhibitors include flupyradifurone, naphthalenesulfonamide (also known as N-(1-naphthyl)-o-carbamoylbenzoic acid and 2-[(1-naphthylamino)carbonyl]benzoic acid).

[0464] "PDS inhibitors (b11)" are compounds that inhibit the carotenoid biosynthesis pathway during the phytoene desaturase step. Examples of PDS inhibitors include flubutyramide, pyrfluthrin, flupyridine, flurfluthrin, furazolidone, norflurzon, and flupyridine.

[0465] HPPD inhibitors (b12) are biosynthetic chemicals that inhibit the synthesis of 4-hydroxyphenylpyruvate dioxygenase. Examples of HPPD inhibitors include bicyclosulfonamide, pyrazinamide, flupyrazinamide (4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridyl]carbonyl]bicyclo[3.2.1]oct-3-en-2-one), fenquinolone (2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl]-1,3-cyclohexanedione), isoxachlor Sulphazoline, isoxazoline, mesotrione, sulfonylpyridinium, pyrazosulfuron, benzylpyrazol, sulfonylpyridinium, terbufos, cyclosulfonyl, tolpyralate (1-[[1-ethyl-4-[3-(2-methoxyethoxy)-2-methyl-4-(methylsulfonyl)benzoyl]-1H-pyrazol-5-yl]oxy]ethyl methyl carbonate), benzylpyridinium, 5-chloro-3-[(2-hydroxy-6-oxo-1 [-cyclohexen-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalone, 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione, 5-[(2-hydroxy-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione [-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-(3-methoxyphenyl)-3-(3-methoxypropyl)-4(3H)-pyrimidinone, 2-methyl-N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide and 2-methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide.

[0466] “HST inhibitors” (b13) disrupt the ability of plants to convert homogentisic acid to 2-methyl-6-solanyl-1,4-benzoquinone, thereby disrupting carotenoid biosynthesis. Examples of HST inhibitors include flupyradifurone, chlorpyrifos, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthidin-2(1H)-one, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrrolo[2,3-b]pyrazin-6(5H)-one, and 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone.

[0467] HST inhibitors also include compounds of formulas A and B.

[0468]

[0469] Where R d1 It is H, Cl, or CF3; R d2 It is H, Cl, or Br; R d3 It is H or Cl; R d4 It is H, Cl, or CF3; R d5 It is CH3, CH2CH3, or CH2CHF2; and R d6 It is OH, or -OC(=O)-i-Pr; and R e1 It is H, F, Cl, CH3 or CH2CH3; R e2 It is H or CF3; R e3 It is H, CH3, or CH2CH3; R e4 It is H, F, or Br; R e5 It is Cl, CH3, CF3, OCF3, or CH2CH3; R e6 It is H, CH3, CH2CHF2 or C≡CH; R e7 It is OH, -OC(=O)Et, -OC(=O)-i-Pr or -OC(=O)-t-Bu; and A e8 It is N or CH.

[0470] Cellulose biosynthesis inhibitors (b14) inhibit the biosynthesis of cellulose in certain plants. They are most effective when applied to young or rapidly growing plants before or early after emergence. Examples of cellulose biosynthesis inhibitors include glyphosate, fenpropathrin, flumetsulam, and triazinon (N... 2 -[(1R,2S)-2,3-dihydro-2,6-dimethyl-1H-indene-1-yl]-6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine), isoxaflutole and triazineflutole.

[0471] "Other herbicides" (b15) includes herbicides that act through a variety of different modes of action, such as mitosis disruptors (e.g., methyl methacrylate and isopropyl methacrylate), organoarsenic compounds (e.g., DSMA and MSMA), 7,8-dihydrofolate synthase inhibitors, chloroplast isoprene synthesis inhibitors, and cell wall biosynthesis inhibitors. Other herbicides include those with unknown modes of action, those not falling into the specific categories listed in (b1) to (b14), or those acting through a combination of the modes of action listed above. Other examples of herbicides include bensulfuron, sulfadiazine, chlorpyrifos, brobutyroxyfen, cyclohexane, isoxaflutole, bensulfuron, cyclopyrimisulfuron (6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinyl-4-morpholinocarboxylate), chlorpyrifos, fenvalerate, ethoxybenzamide, fenpyroximate, phosphonosulfuron-ammonium, dazomet, and triazolyl chlorpyrifos (1-(2,4-dioxane)). (Chlorophenyl)-N-(2,4-difluorophenyl)-1,5-dihydro-N-(1-methylethyl)-5-oxo-4H-1,2,4-triazole-4-carboxamide), methyl methoxyfenozide, oleic acid, oxadiazon, nonanoic acid, barnyardgrass and 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole.

[0472] "Other herbicides" (b15) also includes compounds of formula (b15A).

[0473]

[0474] in

[0475] R 12′ It is H, C1-C6 alkyl, C1-C6 haloalkyl or C4-C8 cycloalkyl;

[0476] R 13′ It is H, C1-C6 alkyl, or C1-C6 alkoxy;

[0477] Q 1 It is a ring system selected from the group consisting of optionally substituted groups of: phenyl, thiophene, pyridyl, benzodioxanepentenyl, naphthyl, benzofuranyl, furanyl, benzothiophene, and pyrazolyl, wherein when substituted, the ring system is formed by one to three R groups. 14′ replace;

[0478] Q 2 It is a ring system selected from the group consisting of optionally substituted groups of: phenyl, pyridinyl, benzodioxanepentenyl, pyridinonyl, thiadiazolyl, thiazolyl, and oxazolyl, wherein when substituted, the ring system is formed by one to three R groups. 15′ replace;

[0479] Each R 14′ Independently, it is halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C8 cycloalkyl, cyano, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, SF5, NHR 17 ; or optionally by 1 to 3 R 16 Substituted phenyl groups; or optionally with 1 to 3 R groups. 16 Substituted pyrazol group;

[0480] Each R 15′ Independently, it is halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, cyano, nitro, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl;

[0481] Each R 16′ It is independently a halogen, a C1-C6 alkyl group, or a C1-C6 haloalkyl group; and

[0482] R 17′ It is a C1-C4 alkoxycarbonyl group.

[0483] In one embodiment, the "other herbicides" (b15) further includes a compound of formula (b15A), preferably, R 12′ It is H or C1-C6 alkyl; more preferably, R 12′ It is H or methyl. Preferably, R 13′ It is H. Preferably, Q 1 It is a benzene ring or a pyridine ring, each ring being separated by 1 to 3 R... 14′ Replace; more preferably, Q 1 It is by 1 to 2 Rs 14′ Substituted benzene ring. Preferably, Q 2 It is by 1 to 3 Rs 15′ Substituted benzene ring; more preferably, Q 2 It is by 1 to 2 Rs 15′ Substituted benzene ring. Preferably, each R 14′ Independently, it is a halogen, a C1-C4 alkyl, a C1-C3 haloalkyl, a C1-C3 alkoxy, or a C1-C3 haloalkoxy; more preferably, each R 14′ Independently, it is chlorine, fluorine, bromine, C1-C2 haloalkyl, C1-C2 haloalkoxy, or C1-C2 alkoxy. Preferably, each R 15′ Independently, it is a halogen, a C1-C4 alkyl, or a C1-C3 haloalkoxy; more preferably, each R 15′Independently, it is chlorine, fluorine, bromine, C1-C2 haloalkyl, C1-C2 haloalkoxy, or C1-C2 alkoxy. Specifically, preferred "other herbicides" (b15) include any one of the following (b15A-1) to (b15A-19):

[0484]

[0485]

[0486]

[0487]

[0488] "Other herbicides" (b15) also includes compounds of formula (b15B).

[0489]

[0490] in

[0491] R 18′ It is H, C1-C6 alkyl, C1-C6 haloalkyl or C4-C8 cycloalkyl;

[0492] Each R 19′ It is independently a halogen, a C1-C6 haloalkyl, or a C1-C6 haloalkoxy;

[0493] p is an integer of 0, 1, 2 or 3;

[0494] Each R 20′ It is independently a halogen, a C1-C6 haloalkyl, or a C1-C6 haloalkoxy; and

[0495] q is an integer of 0, 1, 2 or 3.

[0496] In one embodiment, the "other herbicides" (b15) further includes a compound of formula (b15B), preferably, R 18 It is H, methyl, ethyl or propyl; more preferably, R 18 It is H or methyl; most preferably, R 18 It is H. Preferably, each R 19 Independently, it is chlorine, fluorine, C1-C3 haloalkyl, or C1-C3 haloalkoxy; more preferably, each R 19 Independently, it is chlorine, fluorine, C1 fluoroalkyl (i.e., fluoromethyl, difluoromethyl, or trifluoromethyl) or C1 fluoroalkoxy (i.e., trifluoromethoxy, difluoromethoxy, or fluoromethoxy). Preferably, each R 20 Independently, it is chlorine, fluorine, C1 haloalkyl, or C1 haloalkoxy; more preferably, each R 20Independently, it is chlorine, fluorine, C1 fluoroalkyl (i.e., fluoromethyl, difluoromethyl, or trifluoromethyl) or C1 fluoroalkoxy (i.e., trifluoromethoxy, difluoromethoxy, or fluoromethoxy). Specifically, preferred “other herbicides” (b15) include any one of the following (b15B-1) to (b15B-19):

[0497]

[0498]

[0499]

[0500] In another embodiment, "other herbicides" (b15) further includes compounds of formula (b15C).

[0501]

[0502] Where R 1′ It is Cl, Br, or CN; and R 2′ It is C(=O)CH2CH2CF3, CH2CH2CH2CH2CF3 or 3-CHF2-isoxazol-5-yl.

[0503] "Herbicide safeners" (B16) are substances added to herbicide formulations to eliminate or reduce the phytotoxic effects of herbicides on certain crops. These compounds protect crops from herbicide damage but generally do not prevent herbicide control of unwanted vegetation. Examples of herbicide safeners include, but are not limited to, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, dicyclonon, dietholate, piperazine, chlorpyrifos, chlorpyrifos, chlorpyrifos, fluroxypyr, chlorpyrifos, chlorpyrifos, pyrazosulfuron, mephenate, chlorpyrifos, naphthalenecarboxylic anhydride, chlorpyrifos, N-(aminocarbonyl)-2-methylbenzenesulfonamide and N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene, 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON 4660), 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-acetone and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]benzamide.

[0504] Compounds of Formula 1 can be prepared by general methods known in the field of synthetic organic chemistry. One or more of the following methods and variations as described in Schemes 1-14 can be used to prepare compounds of Formula 1. Unless otherwise indicated, G, R in the compounds of Formulas 1 to 15 below 1 To R 19 R v and R f The definitions are as defined in the above description of the invention. Compounds of formula 1a, 1b, 3a, 3b, 3b', 3c, 3d, 3e, and 3f are various subsets of compounds of formula 1 and 3; and all substituents for formula 1a, 1b, 3a, 3b, 3b', 3c, 3d, 3e, and 3f are as defined above for formula 1, unless otherwise indicated in this disclosure which includes such scheme.

[0505] As shown in Scheme 1, at temperatures typically ranging from -78°C to 0°C, the compound of Formula 1a (i.e., the compound of Formula 1, where R...) 4 (H) can be achieved by reacting a suitably substituted aniline of formula 2 with 1 equivalent (or slightly more than 1 equivalent) of R. f SO2Cl compounds or R f The corresponding anhydride of (SO2)2O is prepared by reacting it in a compatible solvent (including, but not limited to, tetrahydrofuran, acetonitrile, toluene, diethyl ether, dioxane, dichloromethane, or N,N-dimethylformamide) in the presence of a suitable base (such as pyridine, triethylamine, diisopropylethylamine, or potassium carbonate). Alternatively, compounds of formula 1b (i.e., compounds of formula 1, wherein R...) 4 It is SO2R 19 And R 19 It is R f This can be achieved by reacting aniline of formula 2 with 2 equivalents (or more than 2.0 equivalents) of formula R. f SO2Cl compounds or formula R f The corresponding anhydride of (SO2)2O is obtained by reacting under similar reaction conditions as described above. The corresponding monosulfonamide of formula 1a is readily obtained by treating the bissulfonamide of formula 1b with an excess of aqueous alkaline solution, followed by neutralization or acidification with acid. Preferred conditions for this hydrolysis are typically aqueous solutions of sodium hydroxide or potassium hydroxide, optionally with a co-solvent (such as methanol, ethanol, dioxane, or tetrahydrofuran), followed by neutralization or acidification with concentrated hydrochloric acid or an aqueous solution of hydrochloric acid.

[0506] Option 1

[0507]

[0508] As shown in Scheme 2, the substituted aniline of Formula 2 can be readily obtained by hydrogenation of nitrobenzene of Formula 3 under the following conditions: including but not limited to catalytic hydrogenation in a solvent (such as methanol, ethanol, or ethyl acetate) with 5% to 10% carbon-supported palladium or platinum oxide under a hydrogen atmosphere. This reaction can typically be carried out in a Parr hydrogenator. Alternatively, the reduction of the nitro group can be achieved in the presence of activated zinc in acetic acid, stannous chloride in an aqueous solution of hydrochloric acid, iron in an aqueous solution of acetic acid or alcohol or in a mixture of acetic acid or an aqueous solution of ammonium chloride (e.g., Fe in an aqueous solution of ethanol with 3 equivalents of ammonium chloride), or sodium borohydride in methanol in the presence of NiCl2·6H2O (see Journal of the American Chemical Society, Vol. 127, p. 119 (2005)).

[0509] Option 2

[0510]

[0511] As shown in Scheme 3, the amide-substituted nitrobenzene of Formula 3a (i.e., the compound of Formula 3, where G is CONR) 5 R 6 It can be prepared from the substituted nitrobenzoic acid of formula 4 by first forming an acyl chloride, and then allowing the acyl chloride to react with the acyl chloride of formula HNR. 5 R 6 The amine reaction. Alternatively, the compound of formula 3a can be reacted with the formic acid of formula 4 in the presence of a dehydrating amide coupling agent with formula HNR. 5 R 6 The amine reacts directly, optionally with a base in a suitable solvent, to prepare the acyl chloride. The formation of the acyl chloride from 4 can be achieved by reacting oxalyl chloride or thionyl chloride with a catalytic amount of N,N-dimethylformamide in a suitable solvent (such as dichloromethane, toluene, or dichloroethane). The resulting acyl chloride reacts with HNR... 5 R 6 The reaction of amines can be carried out in the presence of triethylamine, diisopropylethylamine (Hunig base), or pyridine in a solvent (such as tetrahydrofuran, dioxane, or dichloromethane). This is applicable to the reaction of formic acid 4 with amine HNR. 5 R 6Directly coupled dehydrating amide coupling agents include N,N'-dicyclohexylcarbodiimide (DCC), (benzotriazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate (BOP reagent), propylphosphonic anhydride (T3P reagent), or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC). Typically, a base (such as triethylamine, diisopropylethylamine, pyridine, or N,N-dimethylaminopyridine (DMAP)) is added to the dehydration coupling reaction in a solvent (such as N,N-dimethylformamide, acetonitrile, or dichloromethane). These reactions are typically carried out at temperatures ranging from 0°C to ambient temperature.

[0512] Option 3

[0513]

[0514] As shown in Scheme 4, at temperatures typically ranging from 0°C to ambient temperature, the isoxazoline-substituted nitrobenzene intermediate of Formula 3b (i.e., the compound of Formula 3, where G is an isoxazoline ring) can be reacted with nitrobenzene chlorooxime of Formula 5 and R. 7 R 8 C = CR 9 R 10 The olefin is prepared by cycloaddition in the presence of a suitable base (such as triethylamine, diisopropylethylamine, or pyridine) in a compatible solvent (such as chloroform, dichloromethane, acetonitrile, tetrahydrofuran, toluene, dioxane, or dichloroethane). When an asymmetric olefin R is used in this cycloaddition reaction... 7 R 8 C = CR 9 R 10 In this case, a mixture of positional isomers of isoxazoline nitrobenzene of formula 3b and 3b' can be obtained, in which case it may be necessary to separate the two positional isomers by silica gel chromatography.

[0515] Option 4

[0516]

[0517] At temperatures typically ranging from 0°C to ambient temperature, the chlorooxime of Formula 5 can be prepared by chlorinating the oxime of Formula 6 in a solvent (such as N,N-dimethylformamide, acetonitrile, dichloromethane, dichloroethane, or toluene) with a chlorinating agent (typically including but not limited to N-chlorosuccinimide, sodium hypochlorite, or chlorine) as shown in Scheme 5.

[0518] Option 5

[0519]

[0520] At temperatures typically ranging from 0°C to ambient temperature, the oxime of Formula 6 can be obtained from nitrobenzaldehyde of Formula 7 by reacting it with a base (such as sodium acetate, pyridine, or potassium carbonate) as a free base or as a hydrochloride or acetate salt in a compatible solvent (including, but not limited to, converting it to methanol, ethanol, acetonitrile, or dichloromethane), as shown in Scheme 6.

[0521] Option 6

[0522]

[0523] The compound of Formula 7 can be produced by using a suitable oxidizing agent (e.g., pyridinium chlorochromate (PCC), optionally with...). Nitrobenzyl alcohol of formula 8 is prepared by oxidizing diatomaceous earth (a filter aid), chromic acid, or manganese oxide (IV) in a suitable solvent (including, but not limited to, dichloromethane or dichloroethane), as shown in Scheme 7. Alternatively, oxidation can be performed under Swern conditions using oxalyl chloride, dimethyl sulfoxide, and triethylamine. The oxidation of benzyl alcohol to benzaldehyde is well documented in the field of synthetic organic chemistry.

[0524] Option 7

[0525]

[0526] At temperatures typically ranging from -78°C to ambient temperature, the nitrobenzyl alcohol of Formula 8 is readily obtained from nitrobenzoic acid 4 by reduction with 2 to 3 equivalents of borane (e.g., BH3·THF) or lithium aluminum hydride in tetrahydrofuran, diethyl ether, or dioxane, as shown in Scheme 8.

[0527] Option 8

[0528]

[0529] Benzoic acid of Formula 9 can be nitrated in a mixture of nitric acid and sulfuric acid at temperatures typically ranging from 0°C to ambient temperature to provide nitrobenzene of Formula 4, as shown in Scheme 9. Other sources of the nitronium ion used for this nitration include nitrofluoroborate, acetyl nitrate, and guanidine nitrate, and suitable solvents (such as tetramethylene sulfone) can also be used to complete the reaction. Benzoic acid of Formula 9 is readily commercially available or readily prepared by methods established in the literature.

[0530] Option 9

[0531]

[0532] As shown in Scheme 10, the compound of Formula 3c (i.e., the compound of Formula 3, wherein G is G-2) can be reacted with a nitrobenzene of Formula 10a that is substituted with m-bromine or m-iodine (i.e., the compound of Formula 10, wherein X is bromine or iodine) and a cyclic carbamate, cyclic thiocarbamate, cyclic lactam or cyclic urea of ​​Formula 11 (where Q is O, S, CR). 11 R 12 or NR 13 Copper-mediated coupling of cuprous iodide (I) with a diamine ligand (such as trans-N,N'-dimethylcyclohexane-1,2-diamine or tetramethylethylenediamine (TMEDA) and potassium phosphate (K3PO4)) in a suitable solvent (such as N,N-dimethylformamide, acetonitrile, tetrahydrofuran, or dioxane) is optionally carried out in the presence of a diamine ligand (such as trans-N,N'-dimethylformamide, acetonitrile, tetrahydrofuran, or dioxane) in a suitable solvent is also carried out. Similar copper-mediated coupling can also be carried out under Chan-Lam conditions, wherein boric acid of formula 10b (i.e., the compound of formula 10, where X is B(OH)2) is coupled with the compound of formula 11 in dichloromethane in the presence of copper acetate (II) and pyridine. Under the well-documented Buchwald-Hartwig amination scheme, this cross-coupling can also be carried out with compounds of formula 10a and 11, which involve palladium-mediated conversion with a suitable phosphine ligand, either as part of a pre-catalyst or as an additive 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 this reaction. Examples of palladium catalysts suitable for this conversion include, but are not limited to, tetra(triphenylphosphine)palladium(O)[Pd(PPh3)4], bis(triphenylphosphine)palladium chloride[PdCl2(PPh3)2], palladium(II)-tris(2-methylphenyl)phosphine[PdCl2[P(o-Tol)3]2], or [1,1'bis(diphenylphosphine)ferrocene]palladium(II) chloride[Pd(dppf)Cl2]. Finally, this cross-coupling can also be achieved using palladium acetate [Pd(OAc)2] or tris(dibenzylideneacetone)dipalladium(O) [Pd2(dba)3] in combination with a suitable dialkyl diarylphosphine ligand and a base (such as sodium tert-butoxide in toluene or cesium carbonate in N,N-dimethylformamide).

[0533] Nitrophenylboronic acid of formula 10b can also be prepared by Suzuki coupling.

[0534] Option 10

[0535]

[0536] The uracil-substituted nitrobenzene of Formula 3d (i.e., the compound of Formula 3, wherein G is G-3) and the pyridazinone-substituted nitrobenzene of Formula 3e (i.e., the compound of Formula 3, wherein G is G-4) can be prepared by palladium-mediated cross-coupling of pinacol nitrobenzeneborate of Formula 12 with a suitably substituted 5-bromo or 5-iodosubstituted uracil of Formula 13 (where X is bromo or iodo) or a pyridazinone of Formula 14 (where 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 that can be used for this conversion include, but are not limited to, tetra(triphenylphosphine)palladium(O)[Pd(PPh3)4] or bis(triphenylphosphine)palladium chloride [PdCl2(PPh3)2].

[0537] Halogenated uracil of Formula 13 (where X is bromine or iodine) can be readily prepared by halogenating uracil 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) by an established method. Pyridazinone of Formula 14 (where X is iodine) can be prepared from pyridazinone of Formula 14a (where X is hydrogen) by treating it with 2,2,6,6-tetramethylpiperidinyl zinc chloride-LiCl (TMPZnCl·LiCl) in tetrahydrofuran or dioxane followed by the addition of iodine.

[0538] Option 11

[0539]

[0540] The pinacol ester of Formula 12 can be readily prepared from the benzyl nitrobenzide or benzyl nitrobenzide of Formula 15 by treatment with bis(pinacolyl)diboron (B2pin2) in the presence of a palladium catalyst (such as bis(triphenylphosphine)palladium chloride [PdCl2(PPh3)2]) in a solvent (i.e. dioxane or tetrahydrofuran), as shown in Scheme 12.

[0541] Option 12

[0542]

[0543] As shown in Scheme 13, the N-linked pyridazinone nitrobenzene of Formula 3f (i.e., the compound of Formula 3, wherein G is G-5) can be prepared by cross-coupling of a bromine- or iodine-substituted nitrobenzene of Formula 10a (where X is bromine or iodine) with a pyridazinone of Formula 15 in the presence of cuprous iodide (I) and K3PO4 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 with water as a co-solvent). Alternatively, a similar coupling can be achieved by cross-coupling an arylboronic acid of Formula 10b (where X is B(OH)2 having 15 under Buchwald-Hartwig amination conditions).

[0544] Option 13

[0545]

[0546] As shown in Scheme 14, the compound of Formula 1 (where R) 4 It 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)2NR 20 R 19 S(OH)2NR 20 R 19 or CH2OCOR 19 ) can be obtained through sulfonylaniline of formula 1 (where R 4 (is hydrogen) and appropriately substituted acyl halides, thioacyl halides, carbamoyl halides, sulfonyl halides, or aminosulfonyl halides or acyloxymethyl halides (i.e., ClCH2O(C=O)R) 19 It is prepared by reacting a base (such as triethylamine, pyridine, or diisopropylethylamine (Hunig base) or potassium carbonate) in a solvent (including but not limited to tetrahydrofuran, dioxane, dichloromethane, acetonitrile, or N,N-dimethylformamide).

[0547] Option 14

[0548]

[0549] It should be recognized that some of the reagents and reaction conditions described above for the preparation of compounds of Formula 1 may not be compatible with certain functional groups present in the intermediates. In these cases, incorporating protecting / deprotecting sequences or functional group interconversions into the synthesis will facilitate obtaining the desired product. The use and selection of protecting groups will be readily apparent to those skilled in the art of chemical synthesis (see, for example, Greene, TW; Wuts, PGPMP, Protective Groups in Organic Synthesis, 2nd ed.; Wiley Publishers: New York, 1991). Those skilled in the art will recognize that in some cases, after the introduction of a given reagent as described in any individual scheme, additional conventional synthetic steps, not described in detail, may be necessary to complete the synthesis of compounds of Formula 1. Those skilled in the art will also recognize that it may be necessary to combine the steps shown in the above schemes in a different order than the specific sequence presented by the compounds of Formula 1.

[0550] Those skilled in the art will also recognize that the compounds and intermediates of Formula 1 described herein can undergo a variety of electrophilic, nucleophilic, free radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.

[0551] Without further detail, it is believed that those skilled in the art can utilize the invention to its fullest extent using the foregoing description. The following non-limiting examples are illustrative of the invention. The steps in the following examples illustrate the procedure for each step in the overall synthetic transformation, and the starting materials used for each step do not necessarily need to be prepared by the specific preparative experiments described in other examples or steps. Percentages are by weight, except for chromatographic solvent mixtures or otherwise specified. Unless otherwise specified, the parts and percentages of chromatographic solvent mixtures are by volume. 1 ¹H NMR spectra are reported in ppm at the low field of tetramethylsilane; “s” indicates a singlet, “d” indicates a doublet, “t” indicates a triplet, “q” indicates a quartet, “m” indicates a multiplet, “dd” indicates two doublets, “dt” indicates two triplets, and “br s” indicates a broad singlet. Mass spectrometry (MS) reports the molecular weight of the highest isotopic abundance precursor ion (M+1) formed by adding H+ (molecular weight 1) to the molecule or by losing H+ (molecular weight 1) from the molecule (M-1), which is observed by coupling liquid chromatography with mass spectrometry (LCMS) using atmospheric pressure chemical ionization (AP+), where “amu” represents the uniform atomic mass unit.

[0552] The following non-limiting examples are intended to illustrate the methods of the present invention for preparing compounds of Formula 1 and corresponding intermediates. Unless otherwise specified, all NMR spectra are reported as CDCl3 at a low field of 500 MHz from tetramethylsilane.

[0553] Synthesis Example 1

[0554] Preparation of N-[5-[(4,4-difluoro-1-piperidinyl)carbonyl]-2,4-dimethylphenyl]-1,1,1-trifluoromethanesulfonamide (i.e., compound 241)

[0555] Step A: Preparation of (4,4-difluoropiperidin-1-yl)(2,4-dimethyl-5-nitrophenyl) methyl ketone

[0556] Propylphosphine (1.7 g, 2.7 mmol, 50 wt% in ethyl acetate) was added to a stirred solution of 2,4-dimethyl-5-nitrobenzoic 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). The reaction mixture was stirred overnight at room temperature, and then concentrated under reduced pressure. The mixture was diluted with 50% ethyl acetate in hexane and filtered through a silica pad. The filtrate was concentrated under reduced pressure to provide the title compound (0.57 g) as a yellow solid, which was used in the next step without further purification.

[0557] 1 H NMR(CDCl3)δ7.87(s,1H),7.24(s,1H),4.11-3.97(m,1H),3.92-3.77(m,1H),3. 43-3.36(m,2H),2.62(s,3H),2.36(s,3H),2.15-2.07(m,2H),1.99-1.86(m,2H).

[0558] Step B: Preparation of (5-amino-2,4-dimethylphenyl)(4,4-difluoropiperidin-1-yl)methyl ketone

[0559] Ammonium chloride (0.10 g, 1.9 mmol) and iron powder (0.32 g, 5.7 mmol) were added to a stirred solution of (4,4-difluoropiperidin-1-yl)(2,4-dimethyl-5-nitrophenyl) ketone (i.e., the product of step A) (0.57 g) in ethanol (9 mL) and water (1 mL). The reaction mixture was stirred at 80 °C for 2 h, then cooled to room temperature, diluted with ethyl acetate, and analyzed by... The solution was filtered through a diatomaceous earth filter aid pad and then through a silica pad. The filtrate was concentrated under reduced pressure to provide the title compound (0.40 g) as an orange oil, which was used in the next step without further purification.

[0560] 1 H NMR(CDCl3)δ6.90(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).

[0561] Step C: Preparation of N-[5-[(4,4-difluoro-1-piperidinyl)carbonyl]-2,4-dimethylphenyl]-1,1,1-trifluoromethanesulfonamide

[0562] At -40°C, triethylamine (0.27 mL, 1.9 mmol) was added to a stirred solution of (5-amino-2,4-dimethylphenyl)(4,4-difluoropiperidin-1-yl) methyl ketone (i.e., the product of step B) (0.40 g, 1.5 mmol) in dichloromethane (8 mL), followed by dropwise addition of trifluoromethanesulfonic anhydride (0.27 mL, 1.6 mmol) over 5 minutes. The reaction mixture was stirred at -40°C for 30 min 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 (a gradient of 0% to 60% ethyl acetate in hexane) to provide the title compound (the compound disclosed herein) (0.26 g) as a white solid.

[0563] 1 H NMR(CDCl3)δ9.61(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).

[0564] Synthesis Example 2

[0565] Preparation of N-[2-chloro-5-[(4,4-difluoro-1-piperidinyl)carbonyl]-4-methylphenyl]-1,1,1-trifluoromethanesulfonamide (i.e., compound 229)

[0566] Step A: Preparation of (4-chloro-2-methyl-5-nitrophenyl)(4,4-difluoropiperidin-1-yl)methyl ketone

[0567] Propylphosphine (1.5 g, 2.4 mmol, 50 wt% in ethyl acetate) was added to a stirred solution of 4-chloro-2-methyl-5-nitrobenzoic 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). The reaction mixture was stirred overnight at room temperature, and then concentrated under reduced pressure. The mixture was diluted with 50% ethyl acetate in hexane and filtered through a silica pad. The filtrate was concentrated under reduced pressure to provide the title compound (0.39 g) as an off-white solid, which was used in the next step without further purification.

[0568] 1 H NMR(CDCl3)δ7.76(s,1H),7.44(s,1H),4.06-3.95(m,1H),3.86-3.74(m,1 H),3.39-3.35(m,2H),2.36(s,3H),2.12-2.04(m,2H),1.98-1.85(m,2H).

[0569] Step B: Preparation of (5-amino-4-chloro-2-methylphenyl)(4,4-difluoropiperidin-1-yl) methyl ketone

[0570] Ammonium chloride (65 mg, 1.2 mmol) and iron powder (0.21 g, 3.8 mmol) were added to a stirred solution of (4-chloro-2-methyl-5-nitrophenyl)(4,4-difluoropiperidin-1-yl) methyl ketone (i.e., the product of step A) (0.39 g, 1.2 mmol) in ethanol (9 mL) and water (1 mL). The reaction mixture was stirred at 80 °C for 2 h, then cooled to room temperature, diluted with ethyl acetate, and analyzed by... The solution was filtered through a diatomaceous earth filter aid pad and then through a silica pad. The filtrate was concentrated under reduced pressure to provide the title compound (0.40 g) as an orange oil, which was used in the next step without further purification.

[0571] 1 H NMR(CDCl3)δ7.07(s,1H),6.53(s,1H),4.13-3.93(m,3H),3.76-3.68(m,1 H),3.35-3.31(m,2H),2.11(s,3H),2.06-1.97(m,2H),1.87-1.79(m,2H).

[0572] Step C: Preparation of N-[2-chloro-5-[(4,4-difluoro-1-piperidinyl)carbonyl]-4-methylphenyl]-1,1,1-trifluoromethanesulfonamide

[0573] At -10°C, triethylamine (0.25 mL, 1.8 mmol) was added to a stirred solution of (5-amino-4-chloro-2-methylphenyl)(4,4-difluoropiperidin-1-yl) methyl ketone (i.e., the product of step B) (0.40 g) in dichloromethane (8 mL), followed by dropwise addition of trifluoromethanesulfonic anhydride (0.25 mL, 1.5 mmol) over 5 minutes. The reaction mixture was stirred at -10°C for 30 min 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 milling with diethyl ether to provide the title compound (the compound disclosed herein) (0.24 g) as a white solid.

[0574] 1 H NMR(CDCl3)δ9.23(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).

[0575] Synthesis Example 3

[0576] Preparation of 3-fluoro-N,N,2,4-tetramethyl-5-[[(trifluoromethyl)sulfonyl]amino]benzamide (i.e., compound 128)

[0577] Step A: Preparation of 3-fluoro-2,4-dimethylbenzoic acid

[0578] At 0 °C, 2,2,6,6-tetramethylpiperidine (4.9 mL, 29 mmol) was slowly added to a stirred solution of n-butyllithium (1.6 M solution in hexane, 18 mL, 29 mmol) in anhydrous tetrahydrofuran (40 mL). The mixture was stirred for 15 min, then cooled to -78 °C, and a solution of 3-fluoro-4-methylbenzoic 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 h, then warmed to -50 °C and stirred for another 45 min. Iodomethane (3.2 mL, 52 mmol) was then slowly added, and the reaction mixture was allowed to warm 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 (x2). The combined organic extracts were then washed with brine (x1), dried over sodium sulfate, and concentrated under reduced pressure to provide the title compound (2.18 g) as a pale yellow solid, which was used in the next step without further purification.

[0579] 1 H NMR(CDCl3)δ7.75(d,1H),7.10-7.07(m,1H),2.55(d,3H),2.33(d,3H).

[0580] Step B: Preparation of 3-fluoro-2,4-dimethyl-5-nitrobenzoic acid

[0581] At -20°C, concentrated nitric acid (0.5 mL) was added dropwise to a stirred mixture of 3-fluoro-2,4-dimethylbenzoic acid (i.e., the product of step A) (0.50 g, 3.0 mmol) in concentrated sulfuric acid (6 mL). The reaction mixture was stirred between -20°C and 0°C for 2 h, and then poured onto ice. The resulting solid was collected by filtration, washed with water (x1), and dried under vacuum to provide a 1:1 mixture (0.44 g) of the title compound and 3-fluoro-2,4-dimethyl-6-nitrobenzoic acid as a white solid, which was used in the next step without further purification.

[0582] 1 ¹H NMR (DMSO-d6, a 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).

[0583] Step C: Preparation of 3-fluoro-N,N,2,4-tetramethyl-5-nitro-benzamide

[0584] At 0 °C, propylphosphonic anhydride (3.8 g, 6 mmol, in ethyl acetate, 50 wt%) was slowly added to a stirred solution of 3-fluoro-2,4-dimethyl-5-nitrobenzoic acid (i.e., the product of step B) (a mixture of 0.86 g of positional isomers, including 2 mmol of the desired positional isomer), dimethylamine hydrochloride (0.20 g, 2.5 mmol), and triethylamine (0.97 mL, 7 mmol) in dichloromethane (10 mL). The reaction mixture was stirred overnight at room temperature, then washed with 1 N sodium hydroxide (x1), the aqueous phase was extracted with dichloromethane (x1), and the combined organic extracts were washed with brine (x1), dried over sodium sulfate, and concentrated under reduced pressure. The crude material was purified by column chromatography, eluting with ethyl acetate / hexane (a gradient of 20% to 50% ethyl acetate in hexane) to provide the title compound (0.39 g) as a pale yellow oil.

[0585] 1 H NMR(CDCl3)δ7.66(d,1H),3.15(s,3H),2.88(s,3H),2.50(d,3H),2.28(d,3H).

[0586] Step D: Preparation of 5-amino-3-fluoro-N,N,2,4-tetramethylbenzamide

[0587] At 70°C, a solution of ammonium chloride (1.36 g, 25.4 mmol) in water (5 mL) was added 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). Iron powder (2.17 g, 38.9 mmol) was then added in portions. After stirring for 1 h, additional iron powder (0.30 g, 5.4 mmol) was added, and the reaction mixture was stirred overnight at 70°C. The mixture was cooled to room temperature, diluted with ethyl acetate, and then... Diatomaceous earth filter aid. The mixture passes through... Filtration was performed using a diatomaceous earth filter aid pad. Ethyl acetate and water were added to the filtrate, the layers were separated, and the aqueous phase was extracted with ethyl acetate (x1). The combined organic extracts were washed with a saturated aqueous solution of ammonium chloride (x1), dried over sodium sulfate, filtered through a silica pad, and concentrated under reduced pressure to provide the title compound (2.68 g) as a pale orange solid, which was used in the next step without further purification.

[0588] 1 H NMR(CDCl3)δ6.32(d,1H),3.63(br s,2H),3.10(s,3H),2.84(s,3H),2.07-2.06(m,6H).

[0589] Step E: Preparation of 3-fluoro-N,N,2,4-tetramethyl-5-((1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methyl)sulfonylamino)benzamide

[0590] At -78 °C, triethylamine (5.3 mL, 38 mmol) was added to a stirred solution of 5-amino-3-fluoro-N,N,2,4-tetramethylbenzamide (i.e., the product of step D) (2.68 g, 12.7 mmol) in dichloromethane (30 mL), followed by dropwise addition of a solution of trifluoromethanesulfonic anhydride (5.1 mL, 30 mmol) in dichloromethane (10 mL) over 20 minutes. The reaction mixture was stirred at -20 °C for 1 h and then poured into water. The layers were separated, and the aqueous phase was extracted with dichloromethane (x1). The combined organic extracts were dried over sodium sulfate, filtered through a silica pad, and concentrated under reduced pressure. The crude material was purified by column chromatography (5% to 30% ethyl acetate in hexane gradient) to provide the title compound (4.48 g) as a white solid.

[0591] 1 H NMR(CDCl3) δ6.99(s,1H),3.14(s,3H),2.83(s,3H),2.33(d,3H),2.28(d,3H).

[0592] Step F: Preparation of 3-fluoro-N,N,2,4-tetramethyl-5-[[(trifluoromethyl)sulfonyl]amino]benzamide

[0593] 1N sodium hydroxide (20 mL, 20 mmol) was slowly added to a stirred solution of 5-[bis(trifluoromethanesulfonyl)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). 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 (x2), diethyl ether (x1), and hexane (x1). The obtained material was purified by crystallization from methanol / water to provide the title compound (the compound disclosed herein) (2.32 g) as a white solid.

[0594] 1 H NMR(CDCl3)δ10.50(br s,1H),6.40(s,1H),3.15(s,3H),2.79(s,3H),2.16(m,6H).

[0595] Synthesis Example 4

[0596] N-[2,4-Dimethyl-5-(1-oxa-2-azaspiro[4.5]dec-2-en-3-yl)phenyl]-1,1,1-trifluoromethanesulfonamide

[0597] (i.e., preparation of compound 197)

[0598] Step A: Preparation of (2,4-dimethyl-5-nitrophenyl)methanol

[0599] At -5°C, a borane-tetrahydrofuran complex (1M solution in tetrahydrofuran, 200 mL, 0.2 mol) was added to a stirred solution of 2,4-dimethyl-5-nitrobenzoic acid (21.5 g, 0.11 mol) in anhydrous tetrahydrofuran (275 mL). The reaction mixture was then allowed to warm to room temperature and stirred overnight. Methanol (12 mL) was added slowly, followed by a saturated aqueous solution of sodium bicarbonate (100 mL) and water (150 mL). The mixture was extracted with methyl tert-butyl ether (x2), and the combined organic extracts were washed with water (x1) and brine (x1), dried over magnesium sulfate, and concentrated under reduced pressure to provide the title compound (20.0 g) as a pale yellow solid, which was used in the next step without further purification.

[0600] 1 H NMR(CDCl3)δ8.07(s,1H),7.14(s,1H),4.73(d,2H),2.58(s,3H),2.37(s,3H).

[0601] Step B: Preparation of 2,4-dimethyl-5-nitrobenzaldehyde

[0602] Add 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) Diatomaceous earth filter aid (approximately 20 g) was added, followed by the addition of pyridinium chlorochromate (28 g, 0.13 mol) in portions over 1 hour. The reaction mixture was stirred overnight at room temperature and then filtered through a silica pad. The filtrate was concentrated under reduced pressure to provide the title compound (18.6 g) as a pale yellow solid, which was used in the next step without further purification.

[0603] 1 H NMR(CDCl3)δ10.23(s,1H),8.45(s,1H),7.27(s,1H),2.72(s,3H),2.67(s,3H).

[0604] Step C: Preparation of 2,4-dimethyl-5-nitro-benzaldehyde oxime

[0605] A solution of hydroxylamine (50 wt% in water, 13.2 g, 0.2 mol) in water (47 mL) was added dropwise to a stirred solution of 2,4-dimethyl-5-nitrobenzaldehyde (i.e., the product of step B) (29.0 g, 0.16 mol) in methanol (480 mL) for 25 min. The reaction mixture was stirred overnight at room temperature and then concentrated under reduced pressure to remove most of the methanol. Water was added, the mixture was stirred, and the solid material was collected by filtration, washed with water, and dried under vacuum to provide the title compound (30.5 g, 11:1 E / Z) as a white solid, which was used in the next step without further purification.

[0606] 1 ¹H 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).

[0607] Step D: Preparation of N-hydroxy-2,4-dimethyl-5-nitro-imine benzyl chloride

[0608] N-chlorosuccinimide (22.1 g, 0.166 mol) was added fractionally to a stirred solution of 2,4-dimethyl-5-nitrobenzaldehyde oxime (i.e., the product of step C) (30.5 g, 0.157 mol) in anhydrous N,N-dimethylformamide (160 mL) for 2 h, while maintaining the internal reaction temperature at 30 °C. The reaction mixture was stirred at room temperature for another 3 h, 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 (x2). The combined organic extracts were washed with water (x3), 1N hydrochloric acid, and a saturated aqueous solution of ammonium chloride, dried over magnesium sulfate, and concentrated under reduced pressure to provide the title compound (35.0 g) as a pale yellow solid, which was used in the next step without further purification.

[0609] 1 H NMR(CDCl3)δ8.20(s,1H),8.04-8.03(m,1H),7.23(s,1H),2.63(s,3H),2.49(s,3H).

[0610] Step E: Preparation of 3-(2,4-dimethyl-5-nitrophenyl)-1-oxa-2-azaspiro[4.5]dec-2-ene

[0611] Triethylamine (11.2 mL, 80 mmol) was added dropwise to a stirred solution of N-hydroxy-2,4-dimethyl-5-nitro-imine benzyl chloride (i.e., the product of step D) (11.5 g, 50 mmol) and methylenecyclohexane (5.8 g, 60 mmol) in chloroform (200 mL). The reaction mixture was stirred overnight at room temperature, then poured into water and the layers were separated. The aqueous phase was extracted with dichloromethane, and the combined organic extracts were washed with 1N hydrochloric acid (x1) and brine (x1), dried over magnesium sulfate, and concentrated under reduced pressure to provide the title compound (16.0 g) as a viscous yellow oil, which was used in the next step without further purification.

[0612] 1 H NMR(CDCl3)δ7.98(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).

[0613] Step F: Preparation of 2,4-dimethyl-5-(1-oxa-2-azaspiro[4.5]dec-2-en-3-yl)aniline

[0614] At 50°C, a solution of ammonium chloride (5.4 g, 0.10 mol) in water (20 mL) was added to a stirred solution of 16.0 g of 3-(2,4-dimethyl-5-nitro-phenyl)-1-oxa-2-azaspiro[4.5]dec-2-ene (i.e., the product of step E) in ethanol (180 mL). Then, iron powder (8.4 g, 0.15 mol) was added in portions over 25 min while the reaction mixture was heated from 50°C to 70°C. After stirring for another 30 min at 70°C, the mixture was cooled to room temperature and subjected to… The solution was filtered using a diatomaceous earth filter aid pad. The filtrate was concentrated under reduced pressure, and then ethyl acetate and water were added. The layers were separated, and the aqueous phase was extracted with ethyl acetate. The combined organic extracts were washed with a saturated aqueous solution of ammonium chloride, dried over magnesium sulfate, and concentrated under reduced pressure to provide the title compound (13.0 g) as a viscous amber oil, which was used in the next step without further purification.

[0615] 1 H NMR(CDCl3)δ6.93(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).

[0616] Step G: Preparation 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

[0617] Triethylamine (21 mL, 0.15 mol) was added 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). 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 minutes. The reaction mixture was stirred between 0 °C and 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 solution, saturated aqueous ammonium chloride solution, dried over magnesium sulfate, and concentrated under reduced pressure. The crude material was purified by column chromatography (0% to 10% methyl tert-butyl ether in hexane gradient) to provide the title compound (18.8 g) as a white solid.

[0618] 1 H NMR(CDCl3)δ7.27(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).

[0619] Step H: Preparation of N-[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.5]dec-2-en-3-yl)phenyl]-1,1,1-trifluoromethanesulfonamide

[0620] 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), 1 N sodium hydroxide (75 mL, 75 mmol) was added dropwise. 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 1 N hydrochloric acid and then extracted with dichloromethane (x2). The combined organic extracts were washed with a saturated aqueous solution of ammonium chloride, dried over magnesium sulfate, and concentrated under reduced pressure. The crude material was purified by grinding with hot cyclohexane to provide the title compound (the compound disclosed herein) (11.1 g) as a white solid.

[0621] 1 H NMR(CDCl3)δ7.30(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).

[0622] Synthesis Example 5

[0623] Preparation of [[2,4-dimethyl-5-(1-oxa-2-azaspiro[4.5]dec-2-en-3-yl)phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropionate (i.e., compound 159)

[0624] Triethylamine (0.14 mL, 1.0 mmol) was added 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-methanesulfonamide (i.e., the product of Synthetic Example 4) (0.20 g, 0.51 mmol) in dichloromethane (8 mL), followed by the addition of methyl tert-pivalate (0.11 mL, 0.76 mmol). The reaction mixture was stirred overnight at room temperature, followed by the addition of additional methyl tert-pivalate (0.15 mL, 1.0 mmol). The reaction mixture was stirred at 40 °C for 5 h, followed by overnight at room temperature. The mixture was concentrated under reduced pressure, and the crude material was purified by column chromatography (a gradient of 0% to 20% ethyl acetate in hexane) to provide the title compound (the compound disclosed herein) (0.19 g) as a clear, colorless oil.

[0625] 1 H NMR(CDCl3)δ7.22(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).

[0626] Synthesis Example 6

[0627] Preparation of N-[2,4-dimethyl-5-[(3aR,6aR)-3a,5,6,6a-tetrahydro-4H-cyclopentan[d]isoxazol-3-yl]phenyl]-1,1,1-trifluoromethanesulfonamide (i.e., compound 103)

[0628] Step A: Preparation of 3-(2,4-dimethyl-5-nitro-phenyl)-4,5,6,6a-tetrahydro-3aH-cyclopentadieno[d]isoxazole

[0629] Triethylamine (0.76 mL, 5.4 mmol) was added to a stirred solution of N-hydroxy-2,4-dimethyl-5-nitro-imine benzyl chloride (i.e., the product of step D in Synthetic Example 4) (0.50 g, 2.2 mmol) in chloroform (8 mL), followed by cyclopentene (0.29 mL, 3.3 mmol). The reaction mixture was stirred overnight at room temperature, then concentrated under reduced pressure, and the crude material was purified by column chromatography (a gradient of 0% to 20% ethyl acetate in hexane) to provide the title compound (0.41 g) as a white solid.

[0630] 1 H NMR(CDCl3)δ8.05(s,1H),7.25(s,1H),5.23-5.20(m,1H),4.16-4.12(m,1H),2. 62(s,3H),2.58(s,3H),2.23-2.19(m,1H),1.92-1.74(m,4H),1.58-1.47(m,1H).

[0631] Step B: Preparation of 5-(4,5,6,6a-tetrahydro-3aH-cyclopentadieno[d]isoxazol-3-yl)-2,4-dimethylaniline

[0632] Ammonium chloride (0.15 g, 2.8 mmol) and iron powder (0.26 g, 4.7 mmol) were added to a stirred solution of 3-(2,4-dimethyl-5-nitro-phenyl)-4,5,6,6a-tetrahydro-3aH-cyclopentadieno[d]isoxazole (i.e., the product of step A) (0.38 g, 1.5 mmol) in ethanol (9 mL) and water (1 mL). The reaction mixture was stirred at 80 °C for 1 h, then cooled to room temperature, diluted with ethyl acetate, and analyzed by... The solution was filtered through a diatomaceous earth filter aid pad and then through a silica pad. The filtrate was concentrated under reduced pressure to provide the title compound (0.35 g) as a brown oil, which was used in the next step without further purification.

[0633] 1 H NMR(CDCl3)δ6.92(s,1H),6.67(s,1H),5.11-5.09(m,1H),4.05-4.02(m,1H),3.57(br s,2H),2.35(s,3H),2.16-2.12(m,4H),1.82-1.66(m,4H),1.54-1.44(m,1H).

[0634] Step C: Preparation of N-[5-(4,5,6,6a-tetrahydro-3aH-cyclopentadieno[d]isoxazo-3-yl)-2,4-dimethyl-phenyl]-1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide

[0635] Triethylamine (0.59 mL, 4.2 mmol) was added to a stirred solution of 5-(4,5,6,6a-tetrahydro-3aH-cyclopentadieno[d]isoxazol-3-yl)-2,4-dimethylaniline (i.e., the product of step B) (0.33 g, 1.4 mmol) in dichloromethane (10 mL). The mixture was cooled to -10 °C, and then trifluoromethanesulfonic anhydride (0.59 mL, 3.5 mmol) was added dropwise over 5 minutes. The reaction mixture was stirred at -10 °C for 20 min 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% to 20% ethyl acetate in hexane gradient) to provide the title compound (0.48 g) as a white solid.

[0636] 1 H NMR(CDCl3)δ7.28(s,2H),5.21-5.18(m,1H),4.07-4.03(m,1H),2.57(s,3 H),2.42(s,3H),2.22-2.18(m,1H),1.88-1.73(m,4H),1.56-1.46(m,1H).

[0637] Step D: Preparation of N-[2,4-dimethyl-5-[(3aR,6aR)-3a,5,6,6a-tetrahydro-4H-cyclopentan[d]isoxazol-3-yl]phenyl]-1,1,1-trifluoromethanesulfonamide

[0638] 0.5N sodium hydroxide (5 mL, 2.5 mmol) was added to a stirred solution of N-[5-(4,5,6,6a-tetrahydro-3aH-cyclopentadieno[d]isoxazo-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). The reaction mixture was stirred at room temperature for 1 h and then concentrated under reduced pressure to remove most of the dioxane. The mixture was diluted with water, acidified with 1N hydrochloric acid, and then extracted with ethyl acetate (x2). The combined organic extracts were washed with water and brine, dried over magnesium sulfate, and concentrated under reduced pressure to provide the title compound (the compound disclosed herein) (0.33 g) as a white solid.

[0639] 1H NMR(CDCl3)δ7.55(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).

[0640] Synthesis Example 7

[0641] Preparation of [[2,4-dimethyl-5-[(3aR,6aR)-3a,5,6,6a-tetrahydro-4H-cyclopentan[d]isoxazol-3-yl]phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropionate (i.e., compound 100)

[0642] Triethylamine (0.10 mL, 0.72 mmol) was added to a stirred solution of N-[5-(4,5,6,6a-tetrahydro-3aH-cyclopentadieno[d]isoxazol-3-yl)-2,4-dimethyl-phenyl]-1,1,1-trifluoro-methanesulfonamide (i.e., the product of step D in Synthetic Example 6) (0.13 g, 0.36 mmol) in dichloromethane (8 mL), followed by methyl tert-pivalate (0.08 mL, 0.6 mmol). The reaction mixture was stirred overnight at room temperature, followed by the addition of additional triethylamine (0.10 mL, 0.72 mmol) and methyl tert-pivalate (0.10 mL, 0.69 mmol). The reaction mixture was stirred overnight at room temperature. The mixture was concentrated under reduced pressure, and the crude material was purified by column chromatography (a gradient of 0% to 20% ethyl acetate in hexane) to provide the title compound (the compound disclosed herein) (79 mg) as a clear, colorless oil.

[0643] 1 H NMR(CDCl3)δ7.28-7.22(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).

[0644] Synthesis Example 8

[0645] 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)

[0646] Step A: Preparation of 2-(2,4-dimethyl-5-nitro-phenyl)-2-azaspiro[4.5]dec-1-one

[0647] Cuprous iodide (0.148 g, 10.0 mmol), tripotassium phosphate (K3PO4) (3.5 g, 16.4 mmol), and 2-azaspiro[4.5]dec-1-one (1.0 g, 6.5 mmol) were added to a 25 mL scintillation flask with a diaphragm. The flask was evacuated and backfilled three times with nitrogen. Trans-(1R,2R)N,N'-dimethylcyclohexane-1,2-diamine (0.246 mL, 20.0 mol%) and 1-bromo-2,4-dimethyl-5-nitrobenzene (1.8 g, 7.8 mmol) were combined in toluene (10 mL) and added to the reaction mixture via syringe. The reaction mixture was stirred overnight under reflux at nitrogen, then diluted with ethyl acetate and passed through a syringe. The solution was filtered through a diatomaceous earth filter aid pad. The resulting filtrate was dried over magnesium sulfate and concentrated under reduced pressure to obtain a residue. The residue was purified by column chromatography (a gradient of 0% to 80% ethyl acetate in hexane, 40 g column) to provide the desired product (1.85 g) as a yellow solid.

[0648] 1 H NMR(CDCl3)δ7.85(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).

[0649] Step B: Preparation of 2-(5-amino-2,4-dimethyl-phenyl)-2-azaspiro[4.5]dec-1-one

[0650] A solution of ammonium chloride (0.728 g, 13.6 mmol) in water (2 mL) was added to a stirred solution of 2-(2,4-dimethyl-5-nitro-phenyl)-2-azaspiro[4.5]dec-1-one (i.e., the product of step A) (1.85 g, 6.8 mmol) in ethanol (20 mL). Iron powder (1.13 g, 20.3 mmol) was then added, and the mixture was stirred at 80 °C under nitrogen for 2 h. Thin-layer chromatography showed that the reaction was partially complete after this time. A second equivalent of ammonium chloride and iron powder was added, and stirring was continued overnight at 80 °C. The mixture was cooled to room temperature and analyzed by... Filtration using diatomaceous earth filter pads. A second filtration was performed using diatomaceous earth as a filter aid to remove turbidity. The filtrate was dried over magnesium sulfate and concentrated under reduced pressure to a yellow residue. The residue was purified by column chromatography (a gradient of 20% to 100% ethyl acetate in hexane, 40 g column) to provide the title compound (1.36 g) as a yellow solid.

[0651] 1 H NMR(CDCl3)δ6.92(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).

[0652] Step C: Preparation of N-[2,4-dimethyl-5-(1-oxo-2-azaspiro[4.5]dec-2-yl)phenyl]-1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide

[0653] Triethylamine (0.562 mL, 4.03 mmol) was added to a stirred solution of 2-(5-amino-2,4-dimethyl-phenyl)-2-azaspiro[4.5]dec-1-one (i.e., the product of step B) (0.500 g, 1.84 mmol) in dichloromethane (10 mL). The mixture was cooled to 0 °C, and then a solution of trifluoromethanesulfonic anhydride (0.677 mL, 4.03 mmol) in dichloromethane (10 mL) was added dropwise over 5 minutes. The reaction mixture was then stirred overnight at room temperature. The reaction mixture was concentrated under vacuum. The crude material was purified by column chromatography (gradient of 0% to 100% ethyl acetate in hexane, 40 g column) to provide the title compound (0.650 g) as an off-white solid.

[0654] 1 H NMR(CDCl3)δ7.25(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).

[0655] Step D: Preparation of N-[2,4-dimethyl-5-(1-oxo-2-azaspiro[4.5]dec-2-yl)phenyl]-1,1,1-trifluoromethanesulfonamide

[0656] A 1.0 N aqueous solution of sodium hydroxide (1 mL, 1.0 mmol) was added dropwise to a stirred solution of N-[2,4-dimethyl-5-(1-oxo-2-azaspiro[4.5]dec-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). 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 to form a white precipitate. The precipitate was then filtered and dried under vacuum overnight to provide the title compound (0.335 g).

[0657] 1 H NMR(CDCl3)δ6.93(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).

[0658] Synthesis Example 9

[0659] Preparation of [[2,4-dimethyl-5-(1-oxo-2-azaspiro[4.5]dec-2-yl)phenyl][(trifluoromethyl)sulfonyl]amino]methyl 2,2-dimethylpropionate (i.e., compound 268)

[0660] Triethylamine (0.103 mL, 0.740 mmol) and methyl tert-p-valerate (0.064 mL, 0.440 mmol) were added to a stirred solution of N-[2,4-dimethyl-5-(1-oxo-2-azaspiro[4.5]dec-2-yl)phenyl]-1,1,1-trifluoro-methanesulfonamide (i.e., the product of step D in Synthetic Example 8) (0.150 g, 0.370 mmol) in dichloromethane (15 mL). The reaction mixture was stirred overnight at room temperature. The reaction mixture was concentrated under vacuum. The residue was purified by column chromatography (gradient of 0% to 100% ethyl acetate in hexane, 12 g column) to provide the title compound (the compound disclosed herein) (0.092 g) as a clear oil.

[0661] 1H NMR(CDCl3)δ7.22(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).

[0662] Synthesis Example 10

[0663] Preparation of N-[5-(6-ethyl-2,3-dihydro-2-methyl-3-oxo-4-pyridazinyl)-2,4-dimethylphenyl]-1,1,1-trifluoromethanesulfonamide (i.e., compound 34)

[0664] Step A: Preparation of 2-(2,4-dimethyl-5-nitro-phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxane

[0665] To a stirred solution of 1-bromo-2,4-dimethyl-5-nitrobenzene (2.30 g, 10 mmol) in dioxane (20 mL), bis(pinacol)diboron (3.4 g, 14 mmol) was added, 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 heated to 110 °C and stirred overnight. The reaction mixture was then cooled to room temperature, diluted with ethyl acetate, and analyzed by... The mixture was filtered using a diatomaceous earth filter aid pad. The reaction mixture was concentrated under vacuum. The crude material was purified by column chromatography to provide the title compound (4.10 g).

[0666] 1 H NMR(CDCl3)δ8.40(s,1H),7.10(s,1H),2.57(s,3H),2.56(s,3H),1.35(s,12H).

[0667] Step B: Preparation of 6-ethyl-4-iodo-2-methyl-pyridazin-3-one

[0668] At 0 °C, TMP Zn·LiCl (14 mL, 9.6 mmol, 0.7 M in tetrahydrofuran) was added to a stirred solution of 6-ethyl-2-methylpyridazin-3-one (0.95 g, 6.9 mmol) in tetrahydrofuran (10 mL). The reaction mixture was warmed to room temperature and stirred for 1 hour. Iodine (2.7 g, 10.3 mmol) was then added, and the reaction mixture was stirred overnight at room temperature. A saturated aqueous solution of ammonium chloride was added, and the aqueous phase was extracted with ethyl acetate (x3). The combined organic layers were washed with Na2SO3 solution, followed by brine. The combined organic extracts were dried (MgSO4), filtered, and concentrated under vacuum. Purification by column chromatography (gradient of 0% to 100% ethyl acetate in hexane) yielded the title compound (290 mg).

[0669] 1 H NMR(CDCl3)δ7.81(d,1H),3.81(s,3H),2.62(m,2H),1.23(m,3H).

[0670] Step C: Preparation of 4-(2,4-dimethyl-5-nitro-phenyl)-6-ethyl-2-methyl-pyridazin-3-one

[0671] To a stirred solution of 6-ethyl-4-iodo-2-methylpyridazin-3-one benzamide (i.e., the product of step B) (0.26 g, 1 mmol) in dioxane (2 mL), 2-(2,4-dimethyl-5-nitro-phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxane (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 (in 2N H₂O, 1 mL) were added, and the reaction mixture was heated to 80 °C for 3 hours. The reaction mixture was then cooled to room temperature, diluted with ethyl acetate, and subjected to… The mixture was filtered using a diatomaceous earth filter aid pad. The reaction mixture was concentrated under vacuum. The crude material was purified by column chromatography to provide the title compound (0.28 g).

[0672] 1 H NMR(CDCl3)δ7.92(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).

[0673] Step D: Preparation of 4-(5-amino-2,4-dimethyl-phenyl)-6-ethyl-2-methyl-pyridazin-3-one

[0674] At 70°C, a solution of ammonium chloride (0.16 g, 3 mmol) in water (2 mL) was added 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). Iron powder (0.17 g, 3 mmol) was then added in portions, and the reaction mixture was stirred for 3 hours. The mixture was cooled to room temperature, diluted with ethyl acetate, and passed through… Filtration was performed using a diatomaceous earth filter aid pad. Ethyl acetate and water were added to the filtrate, the layers were separated, and the aqueous phase was extracted with ethyl acetate (x1). The combined organic extracts were washed with a saturated aqueous solution of ammonium chloride (x1), dried over sodium sulfate, filtered through a silica pad, and concentrated under reduced pressure to provide the title compound (0.21 g), which was used in the next step without further purification.

[0675] 1 H NMR(CDCl3)δ7.05(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).

[0676] Step E: Preparation of N-[5-(6-ethyl-2-methyl-3-oxo-pyridazin-4-yl)-2,4-dimethyl-phenyl]-1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide

[0677] At -78°C, triethylamine (0.13 mL, 0.9 mmol) was added 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), followed by dropwise addition of a solution of trifluoromethanesulfonic anhydride (0.11 mL, 0.9 mmol) in dichloromethane (2 mL) over 20 minutes. Silica gel was added to the reaction mixture, and the solvent was removed under vacuum. The crude material was purified by column chromatography (a gradient of 5% to 30% ethyl acetate in hexane) to provide 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-trifluoromethanesulfonamide (i.e., the product of step F in this synthetic example) (0.13 g).

[0678] 1H NMR(CDCl3)δ7.28(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).

[0679] Step F: Preparation of N-[5-(6-ethyl-2,3-dihydro-2-methyl-3-oxo-4-pyridazinyl)-2,4-dimethylphenyl]-1,1,1-trifluoromethanesulfonamide

[0680] Slowly add 1N sodium hydroxide (0.5 mL, 0.5 mmol) 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). Stir the reaction mixture overnight at room temperature, then concentrate under vacuum. Acidify, post-treat, and purify the crude material by column chromatography to provide the title compound (the compound disclosed herein) (0.025 g) as a white solid.

[0681] 1 H NMR(CDCl3)δ9.78(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).

[0682] Synthesis Example 11

[0683] 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)

[0684] Step A: Preparation of 5-(2,4-dimethyl-5-nitro-phenyl)-1,3-dimethyl-pyrimidine-2,4-dione

[0685] To a stirred solution of 5-bromo-1,3-dimethylpyrimidin-2,4-dione (0.65 g, 3 mmol) in dioxane (6 mL), 2-(2,4-dimethyl-5-nitro-phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxane (i.e., the product of step A in Synthetic Example 10) (1.1 g, 3.9 mmol), bis(triphenylphosphine)palladium(II) dichloride (0.11 mg, 0.15 mmol), and sodium carbonate (2N in H₂O, 3 mL) were added, and the reaction mixture was heated to 80 °C for 3 hours. The reaction mixture was then cooled to room temperature, diluted with ethyl acetate, and analyzed by... The mixture was filtered using a diatomaceous earth filter aid pad. The reaction mixture was concentrated under vacuum. The crude material was purified by column chromatography to provide the title compound (0.72 g).

[0686] 1 H NMR(CDCl3)δ7.84(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).

[0687] Step B: Preparation of 5-(5-amino-2,4-dimethyl-phenyl)-1,3-dimethyl-pyrimidine-2,4-dione

[0688] At 70°C, a solution of ammonium chloride (0.16 g, 3 mmol) in water (2 mL) was added to a stirred solution of 5-(2,4-dimethyl-5-nitro-phenyl)-1,3-dimethyl-pyrimidin-2,4-dione (i.e., the product of step A) (0.29 g, 1 mmol) in ethanol (18 mL). Iron powder (0.17 g, 3 mmol) was then added in portions, and the reaction mixture was stirred for 3 hours. The mixture was cooled to room temperature, diluted with ethyl acetate, and passed through… Filtration was performed using a diatomaceous earth filter aid pad. Ethyl acetate and water were added to the filtrate, the layers were separated, and the aqueous phase was extracted with ethyl acetate (x1). The combined organic extracts were washed with a saturated aqueous solution of ammonium chloride (x1), dried over sodium sulfate, filtered through a silica pad, and concentrated under reduced pressure to provide the title compound (0.21 g), which was used in the next step without further purification.

[0689] 1 H NMR(CDCl3)δ7.11(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).

[0690] Step C: 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

[0691] At -78°C, triethylamine (0.13 mL, 0.97 mmol) was added to a stirred solution of 5-(5-amino-2,4-dimethyl-phenyl)-1,3-dimethyl-pyrimidin-2,4-dione (i.e., the product of step B) (0.21 g, 0.81 mmol) in dichloromethane (3 mL), followed by dropwise addition of a solution of trifluoromethanesulfonic anhydride (0.11 mL, 0.9 mmol) in dichloromethane (2 mL) over 20 minutes. Silica gel was added to the reaction mixture, and the solvent was removed under vacuum. The crude material was purified by column chromatography (a gradient of 5% to 100% ethyl acetate in hexane) to provide the title compound (the compound disclosed herein) (0.11 g) as a white solid.

[0692] 1 H NMR(CDCl3)δ8.18(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).

[0693] Synthesis Example 12

[0694] Preparation of 1,1,1-trifluoro-N-[2,3,4-trimethyl-5-(4-morpholinylcarbonyl)phenyl]methanesulfonamide (i.e., compound 289)

[0695] Step A: Preparation of 2,3,4-trimethylbenzaldehyde

[0696] At 0 °C, 1,1-dichlorodimethyl ether (3.6 mL, 40 mmol) was added to a stirred solution of 1,2,3-trimethylbenzene (3 g, 25 mmol) in dichloromethane (35 mL), followed by dropwise addition of titanium tetrachloride (1 M solution in dichloromethane, 27.5 mL, 27.5 mmol). The reaction mixture was stirred at 0 °C for 2 h, then poured into ice water (300 mL). Dichloromethane (100 mL) was added, and the mixture was stirred vigorously for 10 min, then the layers were separated. The aqueous phase was extracted with dichloromethane (x1), and the combined organic extracts were washed with water and brine and concentrated under reduced pressure to provide the title compound (3.1 g) as a pale yellow oil, which was used in the next step without further purification.

[0697] 1H NMR(CDCl3)δ10.26(s,1H),7.56(d,1H),7.16(d,1H),2.61(s,3H),2.36(s,3H),2.24(s,3H).

[0698] Step B: Preparation of 2,3,4-trimethylbenzoic acid

[0699] At 0 °C, potassium permanganate (6.61 g, 41.8 mmol) was added fractionally to a stirred solution of 3.1 g of 2,3,4-trimethylbenzaldehyde (i.e., the product of step A) in acetone (20 mL) and water (10 mL). The reaction mixture was then allowed to warm to room temperature and stirred overnight. The mixture was filtered through a Celite pad, washed with water and acetone, and the filtrate was acidified to pH 2 with 1 N hydrochloric acid and extracted with ethyl acetate (x2). The combined organic extracts were washed with water and brine, dried over magnesium sulfate, and concentrated under reduced pressure to provide the title compound (2.6 g) as a white solid, which was used in the next step without further purification.

[0700] 1 H NMR(CDCl3)δ7.74(d,1H),7.08(d,1H),2.57(s,3H),2.35(s,3H),2.25(s,3H).

[0701] Step C: Preparation of 2,3,4-trimethyl-5-nitrobenzoic acid

[0702] At 0°C, concentrated nitric acid (0.8 mL) was added dropwise to concentrated sulfuric acid (0.7 mL), and the mixture was stirred for 5 min. Then, at 5°C, this mixture was 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). The reaction mixture was stirred between 0°C and 5°C for 2 h, 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 provide the title compound (1.82 g) as a brown solid, which was used in the next step without further purification.

[0703] 1 H NMR(CDCl3)δ8.24(s,1H),2.64(s,3H),2.46(s,3H),2.36(s,3H).

[0704] Step D: Preparation of morpholino-(2,3,4-trimethyl-5-nitro-phenyl) ketone

[0705] Triethylamine (0.4 mL, 2.9 mmol) and morpholine (0.1 mL, 1.1 mmol) were added to a stirred mixture of 0.20 g of 2,3,4-trimethyl-5-nitrobenzoic acid (i.e., the product of step C) in chloroform (8 mL), followed by the addition of propylphosphonic anhydride (1.2 g, 1.9 mmol, 50 wt% in ethyl acetate). The reaction mixture was stirred at 60 °C for 3 h, then cooled to room temperature and concentrated under reduced pressure. The crude material was purified by column chromatography (a gradient of 0% to 60% ethyl acetate in hexane) to provide the title compound (0.19 g) as a yellow oil.

[0706] 1 H NMR(CDCl3)δ7.43(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).

[0707] Step E: Preparation of (5-amino-2,3,4-trimethyl-phenyl)-morpholino-methyl ketone

[0708] Ammonium chloride (75 mg, 1.4 mmol) and iron powder (0.12 g, 2.1 mmol) were added to a stirred mixture of morpholino-(2,3,4-trimethyl-5-nitro-phenyl) ketone (i.e., the product of step D) (0.19 g, 0.70 mmol) in ethanol (9 mL) and water (1 mL). The reaction mixture was stirred at 80 °C for 2 h, then cooled to room temperature, diluted with ethyl acetate, and analyzed by... The solution was filtered through a pad, and then through a silica pad. The filtrate was concentrated under reduced pressure to provide the title compound (0.14 g) as a yellow oil, which was used in the next step without further purification.

[0709] 1 H NMR(CDCl3)δ6.26(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).

[0710] Step F: Preparation of 1,1,1-trifluoro-N-(trifluoromethylsulfonyl)-N-[2,3,4-trimethyl-5-(morpholin-4-carbonyl)phenyl]methanesulfonamide

[0711] At -10 °C, triethylamine (0.24 mL, 1.7 mmol) was added to a stirred solution of (5-amino-2,3,4-trimethyl-phenyl)-morpholino-methyl ketone (i.e., the product of step E) (0.14 g) in dichloromethane (8 mL), followed by dropwise addition of trifluoromethanesulfonic anhydride (0.19 mL, 1.1 mmol). The reaction mixture was stirred between 0 °C and 10 °C for 1 h, followed by the addition of water. The layers were separated and the organic phase was concentrated under reduced pressure. The crude material was purified by column chromatography (a gradient of 0% to 60% ethyl acetate in hexane) to provide the title compound (0.15 g) as a clear, colorless oil.

[0712] 1 H NMR(CDCl3)δ6.99(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).

[0713] Step G: Preparation of 1,1,1-trifluoro-N-[2,3,4-trimethyl-5-(morpholin-4-carbonyl)phenyl]methanesulfonamide

[0714] 0.5N sodium hydroxide (3.6 mL, 1.8 mmol) was added to a stirred solution of 1,1,1-trifluoro-N-(trifluoromethylsulfonyl)-N-[2,3,4-trimethyl-5-(morpholino-4-carbonyl)phenyl]methanesulfonamide (i.e., the product of step F) (0.15 g, 0.30 mmol) in dioxane (8 mL). The reaction mixture was stirred at room temperature for 2 h, and then concentrated under reduced pressure to remove dioxane. The mixture was diluted with water, acidified with 1N hydrochloric acid to pH about 2, and then extracted with ethyl acetate (x2). The combined organic extracts were washed with water and brine, dried over magnesium sulfate, and concentrated under reduced pressure to provide the title compound (the compound of the present invention) (0.10 g) as a white solid.

[0715] 1 H NMR(CDCl3)δ10.16(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).

[0716] Synthesis Example 13

[0717] Preparation of [[(trifluoromethyl)sulfonyl][2,3,4-trimethyl-5-(4-morpholinylcarbonyl)phenyl]amino]methyl 2,2-dimethylpropionate (i.e., compound 324)

[0718] Sodium bicarbonate (80 mg, 0.95 mmol), tetrabutylammonium bromide (87 mg, 0.27 mmol), and methyl terpentine (0.12 mL, 0.81 mmol) were added to a stirred solution of 1,1,1-trifluoro-N-[2,3,4-trimethyl-5-(4-morpholinylcarbonyl)phenyl]methanesulfonamide (i.e., the product of Synthetic Example 12, 0.10 g, 0.27 mmol) in acetonitrile (8 mL). The reaction mixture was stirred at 80 °C for 3 h, then cooled to room temperature and concentrated under reduced pressure. The crude material was purified by column chromatography (a gradient of 0% to 50% ethyl acetate in hexane) to provide the title compound (the compound of the present invention) (93 mg) as a clear, colorless oil.

[0719] 1 H NMR(CDCl3)δ6.97-6.93(m,1H),5.795.67(m,1H),5.455.37(m,1H),3.933.68(m,4 H),3.593.50(m,2H),3.253.16(m,2H),2.312.29(m,3H),2.25(s,6H),1.19(s,9H).

[0720] The following compounds listed in Tables 1 to 11 can be prepared using the procedures described herein in conjunction with methods known in the art. The following abbreviations are used in the subsequent tables: t signifies tert-, s signifies sec-, n signifies n-, i signifies iso-, c signifies cyclo-, Me signifies methyl, Et signifies ethyl, Pr signifies propyl, Bu signifies butyl, n-Pr signifies 1-propyl, i-Pr signifies isopropyl, Bu signifies butyl, c-Pr signifies cyclopropyl, c-Bu signifies cyclobutyl, i-Bu signifies isobutyl, Ph signifies phenyl, OMe signifies naphthyl, OEt signifies ethoxy, SMe signifies naphthio, SEt signifies ethylthio, NHMe signifies methylamino, -CN signifies cyano, Py signifies pyridinyl, -NO2 signifies nitro, TMS signifies trimethylsilyl, S(O)Me signifies methylsulfinyl, and S(O)2Me signifies methylsulfonyl.

[0721] Table 1

[0722]

[0723] G is CO-J and J is

[0724] J-6 J-7 J-8 J-9 J-10 J-11 J-12 J-13 J-14 J-15 J-16 J-17 J-18 J-19 J-20 J-21 J-22 J-23 J-24 J-25 J-26 J-27 J-28 J-29 J-30 J-31 J-32 J-33 J-34 J-35 J-36 J-37 J-38 J-39 J-40 J-41 J-42 J-43 J-44 J-45 J-46 J-47 J-48 J-49 J-50 J-51 J-52 J-53 J-54 J-3a* J-3b*

[0725] See Example 1 in J-1 through J-52.

[0726] Table 2

[0727]

[0728] G is CO-K and K is

[0729]

[0730] See Example 2 for K-1 through K-9.

[0731] Table 3

[0732]

[0733] G is either CO-J or CO-K; and J or K is...

[0734] J-6 J-7 J-8 J-9 J-10 J-11 J-12 J-13 J-14 J-15 J-16 J-17 J-18 J-19 J-20 J-21 J-22 J-23 J-24 J-25 J-26 J-27 J-28 J-29 J-30 J-31 J-32 J-33 J-34 J-35 J-36 J-37 J-38 J-39 J-40 J-41 J-42 J-43 J-44 J-45 J-46 J-47 J-48 J-49 J-50 J-51 J-52 J-53 J-54 J-3a* J-3b* K-2 K-3 K-4 K-5 K-6 K-7 K-8 K-9 K-1

[0735] See Example 1 for J-1 through J-52; and Example 2 for K-1 through K-9.

[0736] Table 4

[0737]

[0738] G is CO-J and J is

[0739]

[0740]

[0741] See Example 1 in J-1 through J-54.

[0742] Table 5

[0743]

[0744] G is CO-K and K is

[0745] K-6 K-7 K-8 K-9

[0746] See Example 2 for K-1 through K-9.

[0747] Table 6

[0748]

[0749] G is CO-J and J is

[0750]

[0751]

[0752] See Example 1 for J-1 through J-54; and Example 2 for K-1 through K-9.

[0753] Table 7

[0754]

[0755] G is

[0756] G-1-6 G-1-7 G-1-8 G-1-8a G-1-8b G-1-9 G-1-10 G-1-11 G-1-12 G-1-13 G-1-14 G-1-15 G-1-16 G-1-17 G-1-18 G-1-19 G-1-20 G-1-21 G-1-22 G-1-23 G-1-24 G-1-25 G-1-26 G-1-27 G-1-24a G-1-24b G-1-28a* G-1-28b* G-1-29 G-1-30 G-1-31 G-1-32 G-1-33 G-1-33a* G-1-33b* G-1-34 G-1-34a* G-1-34b* G-1-35 G-1-35a* G-1-35b* G-1-36 G-1-37 G-1-38 G-1-38a* G-1-38b* G-1-1aa G-1-1ab G-1-8aa G-1-8ab

[0757] See Example 3 in G-1-1 to G-1-27.

[0758] Table 8

[0759]

[0760] G is

[0761]

[0762] See Example 4 in G-2-1 to G-2-12.

[0763] Table 9

[0764]

[0765]

[0766] Table 10

[0767]

[0768]

[0769]

[0770] Table 11

[0771]

[0772]

[0773]

[0774] Table 12

[0775]

[0776] G is CO-J and J is

[0777] J-6 J-7 J-8 J-9 J-10 J-11 J-12 J-13 J-14 J-15 J-16 J-17 J-18 J-19 J-20 J-21 J-22 J-23 J-24 J-25 J-26 J-27 J-28 J-29 J-30 J-31 J-32 J-33 J-34 J-35 J-36 J-37 J-38 J-39 J-40 J-41 J-42 J-43 J-44 J-45 J-46 J-47 J-48 J-49 J-50 J-51 J-52 J-53 J-54 J-3a* J-3b*

[0778] See Example 1 in J-1 through J-54.

[0779] Table 13

[0780]

[0781] G is CO-K and K is

[0782] K-6 K-7 K-8 K-9

[0783] See Example 2 for K-1 through K-9.

[0784] Table 14

[0785]

[0786] G is either CO-J or CO-K; and J or K is...

[0787] J-6 J-7 J-8 J-9 J-10 J-11 J-12 J-13 J-14 J-15 J-16 J-17 J-18 J-19 J-20 J-21 J-22 J-23 J-24 J-25 J-26 J-27 J-28 J-29 J-30 J-31 J-32 J-33 J-34 J-35 J-36 J-37 J-38 J-39 J-40 J-41 J-42 J-43 J-44 J-45 J-46 J-47 J-48 J-49 J-50 J-51 J-52 J-53 J-54 J-3a* J-3b* K-2 K-3 K-4 K-5 K-6 K-7 K-8 K-9 K-1

[0788] See Example 1 for J-1 through J-54; and Example 2 for K-1 through K-9.

[0789] Table 15

[0790]

[0791] G is CO-J and J is

[0792] J-6 J-7 J-8 J-9 J-10 J-11 J-12 J-13 J-14 J-15 J-16 J-17 J-18 J-19 J-20 J-21 J-22 J-23 J-24 J-25 J-26 J-27 J-28 J-29 J-30 J-31 J-32 J-33 J-34 J-35 J-36 J-37 J-38 J-39 J-40 J-41 J-42 J-43 J-44 J-45 J-46 J-47 J-48 J-49 J-50 J-51 J-52 J-53 J-54 J-3a* J-3b*

[0793] See Example 1 of J-1 through J-54

[0794] Table 16

[0795]

[0796] G is CO-K and K is

[0797] K-6 K-7 K-8 K-9

[0798] See Example 2 for K-1 through K-9.

[0799] Table 17

[0800]

[0801] G is

[0802] G-1-6 G-1-7 G-1-8 G-1-8a G-1-8b G-1-9 G-1-10 G-1-11 G-1-12 G-1-13 G-1-14 G-1-15 G-1-16 G-1-17 G-1-18 G-1-19 G-1-20 G-1-21 G-1-22 G-1-23 G-1-24 G-1-25 G-1-26 G-1-27 G-1-24a G-1-24b G-1-28a* G-1-28b* G-1-29 G-1-30 G-1-31 G-1-32 G-1-33 G-1-33a* G-1-33b* G-1-34 G-1-34a* G-1-34b* G-1-35 G-1-35a* G-1-35b* G-1-36 G-1-37 G-1-38 G-1-38a* G-1-38b* G-1-1aa G-1-1ab G-1-8aa G-1-8ab

[0803] See Example 3 in G-1-1 to G-1-27.

[0804] Table 18

[0805]

[0806] G is

[0807] G-2-7 G-2-8 G-2-9 G-2-10 G-2-11 G-2-12 G-2-13 G-2-14 G-2-15 G-2-16 G-2-17

[0808] See Example 4 in G-2-1 to G-2-12.

[0809] Table 19

[0810]

[0811] Table 20

[0812]

[0813]

[0814]

[0815] Table 21

[0816]

[0817]

[0818] The compounds of the present invention are generally used as the herbicidal active ingredient in a composition (i.e., formulation), wherein at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents serves as a carrier. The formulation or composition components are selected to be consistent with the physical properties of the active ingredient, the application method, and environmental factors such as soil type, moisture, and temperature.

[0819] 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 suspension emulsions), which can optionally be thickened into gels. Common types of aqueous liquid compositions include soluble concentrates, suspensions, capsule suspensions, concentrated emulsions, microemulsions, oil-in-water emulsions, flowable concentrates, and suspension emulsions. Common types of non-aqueous liquid compositions include emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates, and oil dispersions.

[0820] Solid compositions are generally available in the form of powders, granules, pellets, beads, granules, lozenges, tablets, filler films (including seed coatings), etc., and can be water-dispersible (“wettable”) or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. Active ingredients can be (micro)encapsulated and further formulated as suspensions or solid formulations; alternatively, the entire formulation of the active ingredient can be encapsulated (or “coated”). Encapsulation can control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of emulsifiable concentrate formulations and dry granule formulations. High-strength compositions are primarily used as intermediates for further formulation.

[0821] Sprayable formulations are typically dispersed in a suitable medium before spraying. These liquid and solid formulations are formulated in a spraying medium, usually water, but occasionally another suitable medium that is easily diluted, such as aromatic hydrocarbons, paraffinic hydrocarbons, or vegetable oils. Spray volumes can range from about one liter to several thousand liters per hectare, but are more typically in the range of about ten to several hundred liters per hectare. Sprayable formulations can be mixed with water or another suitable medium for foliar application via air or ground application, or for application to the plant's growing medium. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into furrows during planting.

[0822] Formulations typically contain a total of up to 100% by weight of an effective amount of the active ingredient, diluent, and surfactant within the approximate range below.

[0823]

[0824]

[0825] 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, as well as 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.

[0826] Liquid diluents include, for example, water, N,N-dimethylalkanamide (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidone (e.g., N-methylpyrrolidone), alkyl phosphate esters (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butyl carbonate, paraffin (e.g., white mineral oil, n-alkanes, isoalkanes), alkylbenzenes, alkylnaphthalenes, glycerol, glycerol triacetate esters, sorbitol, aromatics, dearomatized aliphatic compounds, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, and isophorone. Ketones and 4-hydroxy-4-methyl-2-pentanone, acetate esters such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate, and isobornyl acetate, other esters such as alkyl lactates, diesters, alkyl and aryl benzoates, and γ-butyrolactone, and alcohols that can be straight-chain, branched, saturated, or unsaturated, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecanol, isoctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oily alcohols, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol, and benzyl alcohol. Liquid diluents also include saturated and unsaturated fatty acids (typically C6-C). 22 Oils containing plant seeds and fruits (e.g., olive oil, castor oil, flaxseed oil, sesame oil, corn oil, peanut oil, sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil, and palm kernel oil), animal fats (e.g., beef tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated (e.g., methylated, ethylated, butylated) fatty acids, wherein the fatty acids can be obtained by hydrolysis of glycerides from plant and animal sources and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Edition, Interscience, New York, 1950.

[0827] The solid and liquid compositions of the present invention typically contain one or more surfactants. When added to a liquid, a surfactant (also known as a "surfactant agent") typically alters, and most frequently reduces, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, the surfactant can be used as a wetting agent, dispersant, emulsifier, or defoamer.

[0828] Surfactants can be classified as nonionic, anionic, or cationic. Nonionic surfactants that can be used in the compositions of this invention include, but are not limited to: alcohol alkoxylates, such as those based on natural and synthetic alcohols (which may be branched or linear) and prepared from alcohols and ethylene oxide, propylene oxide, butane oxide, or mixtures thereof; amine ethoxylates, alkanolamides, and ethoxylated alkanolamides; alkoxylated triglycerides, such as ethoxylated soybean oil, castor oil, and rapeseed oil; alkylphenol alkoxylates, such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonylphenol ethoxylates, and dodecylphenol ethoxylates (prepared from phenol and ethylene oxide, propylene oxide, butane oxide, or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide, and trans-block polymers wherein the terminal blocks are prepared from propylene oxide; Ethoxylated fatty acids; ethoxylated fatty acid esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenols (including those prepared from ethylene oxide, propylene oxide, butane oxide, or mixtures thereof); fatty acid esters, glycerides, lanolin-based derivatives, polyethoxylated esters (such as polyethoxylated sorbitol fatty acid esters, polyethoxylated sorbitol fatty acid esters, and polyethoxylated glycerol fatty acid esters); other sorbitol derivatives such as sorbitol esters; polymer surfactants such as random copolymers, block copolymers, alkyd PEG (polyethylene glycol) resins, grafted or comb polymers, and star polymers; polyethylene glycol (PEG); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar derivatives such as sucrose esters, alkyl polyglycosides, and alkyl polysaccharides.

[0829] Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohols or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives, such as lignin sulfonates; maleic acid or succinic acid or their anhydrides; olefin sulfonates; phosphate esters, such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styrylphenol ethoxylates; protein-based surfactants; sarcosine derivatives; styrylphenol ether sulfates; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides, such as N,N-alkyl taurine; sulfonates of benzene, cumene, toluene, xylene, and dodecylbenzene and tridecylbenzene; sulfonates of condensed naphthalene; sulfonates of naphthalene and alkylnaphthalene; petroleum-grade sulfonates; sulfosuccinates; and sulfosuccinates and their derivatives, such as dialkyl sulfosuccinates.

[0830] Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkylpropylenediamine, tripropylenetriamine and dipropylenetetraamine, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butyl oxide or mixtures thereof); amine salts such as ammonium acetate and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

[0831] Also usable in the compositions of the present invention are mixtures of nonionic and anionic surfactants, or mixtures of nonionic and cationic surfactants. Nonionic surfactants, anionic surfactants, and cationic surfactants, and their recommended uses, are disclosed in several published references, including McCutcheon's Emulsifiers and Detergents, annual American and International Editions, published by The Manufacturing Confectioner Publishing Co., McCutcheon Division; Sisley and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A.S. Davidson and B. Milwidsky, Synthetic Detergents, 7th Edition, John Wiley and Sons, New York, 1987.

[0832] The compositions of the present invention may also contain formulation aids and additives known to those skilled in the art as adjuvants to formulation (some of which may also be considered as solid diluents, liquid diluents, or surfactants). Such formulation aids and additives can control: pH (buffers), foaming during processing (defoamers, such as polysiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), microbial growth within the container (antimicrobial agents), product freezing (antifreeze agents), color (dye / pigment dispersions), elution (film-forming agents or adhesives), evaporation (evaporation inhibitors), and other formulation properties. Film-forming agents include, for example, polyvinyl acetate, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol, polyvinyl alcohol copolymers, and waxes. Examples of formulation adjuvants and additives include those listed below: McCutcheon's Volume 2: Functional Materials, published by the McCutcheon division of Manufacturing Confectioner, annual International and North American editions; and PCT Publication WO 03 / 024222.

[0833] Typically, compounds of Formula 1 and any other active ingredients are incorporated into the compositions of the present invention by dissolving the active ingredient in a solvent or by milling in a liquid or dry diluent. Solutions comprising emulsifiable concentrates can be prepared by simply mixing these ingredients. If the solvent of the liquid composition intended to be used as an emulsifiable concentrate is immiscible with water, an emulsifier is typically added to emulsify the solvent containing the active ingredient when diluted with water. Active ingredient slurries with particle sizes up to 2,000 μm can be wet-milled using a media mill to obtain particles with an average particle size of less than 3 μm. Aqueous slurries can be formulated into finished suspensions (see, for example, US 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations typically require a dry milling process to produce an average particle size in the range of 2 to 10 μm. Powders and powders can be prepared by blending and typically by milling (e.g., using a hammer mill or kinetic mill). Granules and pellets can be prepared by spraying the active material onto a pre-formed granule carrier or by agglomeration techniques. See Browning, “Agglomeration,” Chemical Engineering, December 4, 1967, pp. 147-48; Perry’s Chemical Engineer’s Handbook, 4th edition, McGraw-Hill, New York, 1963, pp. 8-57 and following pages; and WO 91 / 13546. Pellets can be prepared as described in US4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in US4,144,050, US3,920,442, and DE 3,246,493. Tablets can be prepared as taught in US5,180,587, US5,232,701 and US5,208,030. Films can be prepared as taught in GB 2,095,558 and US3,299,566.

[0834] For further information on formulations, see “The Formulator’s Toolbox – Product Forms for Modern Agriculture” in T. Woods, Pesticide Chemistry and Bioscience, The Food-Environment Challenge, edited by T. Brooks and TR Roberts, Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120–133. See also US3,235,361, column 6, lines 16-7, line 19 and examples 10-41; US3,309,192, column 5, lines 43-7, line 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; US2,891,855, column 3, lines 66-5, line 17 and examples 1-4; Klingman, *Weed Control as a Science*, John Wiley and Sons, Inc., New York, 1961, pp. 81-96; Hance et al., *Weed Control Handbook*, 8th edition, Blackwell Scientific. Publications [Blackwell Science Publishing], Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

[0835] 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 Table AG. Without further exhaustive detail, it is believed that those skilled in the art can utilize the invention to its fullest extent using the foregoing description. Therefore, the following examples should be interpreted as illustrative only and do not limit this disclosure in any way. Unless otherwise stated, percentages are by weight.

[0836] Example A

[0837] High-strength concentrate

[0838] Compound 260 98.5%

[0839] 0.5% silica aerogel

[0840] Synthetic amorphous fine silica 1.0%

[0841] Example B

[0842] wettable powder

[0843]

[0844] Example C

[0845] Granules

[0846] Compound 260 10.0%

[0847] Attapulgite granules (low volatile matter, 0.71 / 0.30 mm; 90.0%)

[0848] USS size 25-50 sieve)

[0849] Example D

[0850] Extruded pellets

[0851]

[0852] Example E

[0853] Emulsifiable concentrate

[0854] Compound 260 10.0%

[0855] Polyoxyethylene sorbitan hexaoleate 20.0%

[0856] C6-C 10 Fatty acid methyl esters 70.0%

[0857] Example F

[0858] microemulsion

[0859]

[0860] Instance G

[0861] Suspension

[0862]

[0863]

[0864] Instance H

[0865] Emulsion in water

[0866]

[0867] Example I

[0868] oil dispersion

[0869]

[0870] Additional exemplary formulations include Examples A to I above, wherein in each of Examples A to I, “Compound 260” is replaced by the corresponding compound from Index Table A as shown below.

[0871]

[0872] Test results show that the compounds of this invention are highly active pre- and / or post-emergence herbicides and / or plant growth regulators. The compounds disclosed herein generally exhibit the highest activity for both post-emergence weed control (i.e., application after weeds have emerged from the soil) and pre-emergence weed control (i.e., application before weeds have emerged from the soil). Many of them are effective for broad-spectrum pre- and / or post-emergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, industrial storage areas, parking lots, drive-in cinemas, airports, riverbanks, irrigation and other waterways, billboards, and highway and railway structures. Many of the compounds of this invention can be used for selective control of grasses and broadleaf weeds in crop / weed mixed environments by means of selective metabolism in the crop-comparison weeds, selective activity at physiological inhibition sites in the crop and weeds, or selective application above or in the environment of crop-weed mixed environments. Those skilled in the art will recognize that preferred combinations of these selectivity factors within a compound or group of compounds can be readily determined by routine biological and / or biochemical assays. The compounds of the present invention can exhibit tolerance to important crops, including but not limited to alfalfa, barley, cotton, wheat, oilseed rape, sugar beets, corn, sorghum, soybean, rice, oats, peanuts, vegetables, tomatoes, potatoes, perennial crops including coffee, cocoa, oilseed palm, rubber, sugarcane, citrus, grapes, fruit trees, nut trees, bananas, plantain, pineapple, hops, tea, and trees such as eucalyptus and conifers (e.g., slash pine), as well as turfgrasses (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky yew, and Bermuda grass). The compounds of the present invention can be used in genetically modified or bred crops to incorporate herbicide resistance, express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxins), and / or express other useful traits. Those skilled in the art will understand that not all compounds are equally effective against all weeds. Instead, the subject compounds can be used to alter plant growth.

[0873] Since the compounds of the present invention have both pre-emergence and post-emergence herbicidal activities to control unwanted vegetation by killing or damaging it or slowing its growth, the compounds are typically applied effectively by a variety of methods. These methods involve contacting the leaves or other parts of the unwanted vegetation, or a composition comprising at least one of the compounds disclosed herein and a surfactant, a solid diluent, or a liquid diluent, with the leaves or other parts of the unwanted vegetation, or with the environment in which the unwanted vegetation grows, such as soil or water, or with the environment surrounding the seeds or other propagules of the unwanted vegetation.

[0874] The herbicidal effective amount of the compounds of the present invention is determined by many factors. These factors include: the selected formulation, the method of application, the quantity and type of vegetation present, and growing conditions. Typically, the herbicidal effective amount of the compounds of the present invention is from about 0.001 kg / ha to 20 kg / ha, with a preferred range of about 0.004 kg / ha to 1 kg / ha. Those skilled in the art can readily determine the herbicidal effective amount required for the desired level of weed control.

[0875] In a common embodiment, the compounds disclosed herein are typically applied as formulated compositions to a site comprising desired vegetation (e.g., crops) and undesirable vegetation (i.e., weeds), both of which may be seeds, seedlings, and / or larger plants in contact with a growing medium (e.g., soil). At this site, compositions comprising the compounds disclosed herein may be applied directly to the plants or portions thereof, particularly the undesirable vegetation, and / or to the growing medium in contact with the plants.

[0876] Plant varieties and cultivars of desired vegetation in locations treated with the compounds disclosed herein can be obtained through conventional propagation and breeding methods or through genetic engineering methods. Genetically modified plants (transgenic plants) are those in which a heterologous gene (transgenic gene) has been stably integrated into the plant genome. A transgene defined by a specific location of the transgene in the plant genome is called a transformation or transgenic event.

[0877] Genetically modified plant cultivars in the locations that can be treated according to the present invention include those cultivars resistant to one or more biotic stresses (pests, such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, low temperature, soil salinization, etc.), or those cultivars containing other desired characteristics. Plants can be genetically modified to exhibit traits such as herbicide tolerance, insect resistance, modified oil characteristics, or drought tolerance.

[0878] While the compounds of the present invention are most typically used to control undesirable vegetation, exposing desired vegetation to the compounds of the present invention in a treated location can result in an additive or synergistic effect with the genetic traits of the desired vegetation, including traits introduced through genetic modification. For example, resistance to herbivorous pests or plant diseases, tolerance to biotic / abiotic stresses, or storage stability may be greater than desired in the genetic traits of the desired vegetation.

[0879] The compounds of the present invention can also be mixed with one or more other biologically active compounds or reagents to form multi-component insecticides, thereby providing even broader agricultural protection. These biologically active compounds or reagents include herbicides, herbicide safeners, fungicides, insecticides, nematicides, fungicides, acaricides, growth regulators such as insect molting inhibitors and rooting stimulants, chemical sterilizers, chemical pheromones, insect repellents, attractants, pheromones, feeding stimulants, phytonutrients, other biologically active compounds, or insect pathogenic bacteria, viruses, or fungi. Mixtures of the compounds of the present invention with other herbicides can broaden the range of activity against additional weed species and inhibit the proliferation of any resistant organism type. Therefore, the present invention also relates to compositions comprising a compound of formula 1 (at a herbicidal effective amount) and at least one additional biologically active compound or reagent (at a biologically effective amount), and the composition may further comprise at least one of a surfactant, a solid diluent, or a liquid diluent. Other biologically active compounds or agents can be formulated into compositions comprising at least one of a surfactant, a solid or liquid diluent. For the mixtures of the present invention, one or more other biologically active compounds or agents may be formulated together with the compound of Formula 1 to form a premix, or one or more other biologically active compounds or agents may be formulated separately from the compound of Formula 1 and the formulations may be combined together (e.g., in a spray can) before application, or alternatively, applied sequentially.

[0880] Mixtures of one or more of the following herbicides with the compounds of the present invention are particularly useful for weed control: acetochlor, trifluralin and its sodium salt, bensulfuron, acrolein (2-acrylonitrile), metolachlor, quizalofop-P-ethyl, atrazine, azoxystrobin, pyrimisulfuron, cyclopropionic acid and its esters (e.g., methyl, ethyl) and salts (e.g., sodium, potassium), chlorpyrifos, glyphosate, ammonium aminosulfonate, sphagnum molybdate, sulfadiazine, atrazine, tetrazoxystrobin, flubutyroxyfen, glyphosate, ethyl glyphosate, bensulfuron-methyl, fluroxyfen, furazolidone, bensulfuron-methyl, dimethoate, bentazon, cyhalofop-P-ethyl, bispyribac-sodium, bispyribac-sodium and its sodium salt, chlorpyrifos, bromobutyroxyfen, bromophenol oxime. Bromobenzonitrile, bromobenzonitrile octanoate, butachlor, flupropargyl, chlorpyrifos, butachlor, butachlor, benzoyl sulfide, carbaryl, triadimefon, catechin, methoxyfen, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorfenapyr, chlorfenapyr, chlorpyrifos, dimethyl chlorphthalate, cypermethrin, indole-methyl, cyclohexane, chlorpyrifos, chlorpyrifos, cyclohexane, clethodim, clodinafop-propargyl, isoxaflutole, barnyardgrass, dichloropyridine, dichloropyridine ethanolamine, chlorpyrifos, bensulfuron-methyl, cyanazine, cyclohexane, cyclopyrimethanil, cyprofensulfuron-methyl, thiamethoxam, cyhalofop-butyl, 2,4-D and its butoxyesters, butyl ester, isooctyl ester and isopropyl ester and their dimethyl ammonium salts, diethanolamine salts and triethanolamine salts, chlorpyrifos, cogon grass The following herbicides are listed: calcined glyphosate, sodium calcinate, dazomet, 2,4-DB and its dimethyl ammonium salt, potassium and sodium salts, betaine, diquat, dicamba and its diethylene glycol ammonium salt, dimethyl ammonium salt, potassium and sodium salts, diquat, propionic acid, quizalofop-P-methyl, dimethyl sulfadiazine sulfate, pyrifluquinazon, flupyrazole, oxazolidinone, piperazine, metolachlor, isoamyl, thifensulfuron-methyl, thifensulfuron-P-methyl, thiamethoxam, dimethylarsine and its sodium salt, dichlorvos, terbuprofen, bispyribac-methyl, diquat, flusulfuron-methyl, diuron-methyl, DNOC, quizalofop-P-methyl, epoxam, ethylbutadiene, acesulfame K, ethoxysulfuron-methyl, ethoxysulfuron-methyl, ethoxysulfuron-methyl, oxazolidinone, fenquinolone, tetrazolium The following herbicides are listed: chlorpyrifos, feluroxime, feluroxime-TCA, methyl methacrylate, methyl methacrylate, chlorpyrifos, pyrazosulfuron, quizalofop-P-ethyl, quizalofop-P-ethyl, isopropylpyrazosulfuron, flufensulfuron, flupyrsulfuron, flupyrazosulfuron, flupyrazosulfuron, flupyrazosulfuron, flupyrazosulfuron, flupyrazosulfuron, fenpyrazosulfuron, flupyrazosulfuron and its sodium salt, chlorpyrifos, fluorenyl butyl ester, flupyridine, flupyrflupyr, clopyralid, furazolidone, flupyrazosulfuron, flupyrazosulfuron, formamide-sulfuron, phosphonium-ammonium, glufosinate, glufosinate-ammonium, chlorpyrifos, glyphosate and its salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimethylsulfonium (alternatively called glyphosate), flupyridine ester.Fluroxypyr, chlorpyrifos, fluroxypyr, fluroxypyr, cyclopyridazine, hydantoin, imazalil, methoxypyr, methyl methoxypyr, metribuzin, metribuzin ammonium, metribuzin, imazalil ammonium, pyrazosulfuron, indicarb, triazine indicarb, iodosulfuron, methyl iodosulfuron, iodobenzonitrile, iodobenzonitrile octanoate, iodobenzonitrile sodium, triazolyl chlorpyrifos, isoproturon, isoxaflutole, isoxaflutole, isoxaflutole, isoxaflutole, chlorpyrifos, quizalofop-p-ethyl, cyclopyridine, linuron, methyl methyl methacrylate, MCPA and its salts (e.g., MCPA-dimethylammonium, MCPA-potassium and MCPA-sodium), esters (e.g., MCPA-2-ethylhexyl ester, MCPA-butoxyethyl ester) and thioesters (e.g., MCPA-ethyl thioester), MCPB Its salts (e.g., sodium MCPB) and esters (e.g., ethyl MCPB), 2-methyl-4-chloropropionic acid, benzothiamethoxam, flusulfuron-methyl, mesosulfuron-methyl, methylsulfuron-methyl, oxazolidinyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, methylbenzyl, arsenopyr and its calcium salts, monoammonium salts, monosodium and disodium salts, methyl sulfadiazine, metolachlor, bromonazol, metolachlor, sulfadiazine, methoxysulfuron-methyl, methoxysulfuron-methyl, chlorpyrifos, nicosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl Paraquat dichlorvos, glyphosate, nonanoic acid, pendimethalin, penflusulfuron, metolachlor, cyclooxam, flusulfuron, pethoxamid, pethoxyamid, bendiclofen, chlorpyrifos, chlorpyrifos potassium, flupyridine, clodinafop-propargyl, piperazine, pretilachlor, flusulfuron-methyl, aminopropargyl, cyclobenzyl, propargyl, chlorpyrifos, propargyl, chlorpyrifos, propargyl, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos Pyrimisulfan, pyrimisulfuron, pyrimisulfuron sodium, sulfonyl sulfadiazine, metoxysulfuron, quinclorac, chlorpyrifos, quizalofop-P-ethyl, quizalofop-P-ethyl, sulfadiazine, pyrimisulfuron, haloxyfop-P-ethyl, cyclosulfuron, simazine, sulfadiazine, mesotrione, metsulfuron-methyl, sulfonylurea, 2,3,6-TBA, TCA, TCA-sodium, methoxysulfuron, terbufos, terbufos, terbufos, terbufos, terbufos, terbufos, methoxysulfuron, thiamethoxam, thiamethoxam, thiamethoxam, haloxyfop-P-ethyl, fluazinam, tolpyralate, pyrazosulfuron-methyl, pyrazosulfuron-P-ethyl, fluazinam, pyrazosulfuron-P-ethylBesulfanilamide, triazine flusulfanilamide, besulfanilamide, chlorpyrifos, trichloroisocyanurate, chlorpyrifos triethylammonium, metribuzin, chlorpyrifos trisulfuron, trifludimoxazin, trifluralin, flusulfanilamide, trifluralin, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthidine-2(1H)-one, 5-chloro-3-[(2-hydroxy-6-oxo-1-cyclohexane] [en-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalone, 2-chloro-N-(1-methyl-1H-tetrazol-5-yl)-6-(trifluoromethyl)-3-pyridinecarboxamide, 7-(3,5-dichloro-4-pyridyl)-5-(2,2-difluoroethyl)-8-hydroxypyridino[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 (the aforementioned is methioxolin), 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H) 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 include biological herbicides such as *Alternaria destruens* Simmons, *Colletotrichum gloeosporiodes* (Penz.) Penz. & Sacc., *Drechsiera monoceras* (MTB-951), *Myrothecium verrucaria* (Albertini & Schweinitz) Ditmar: Fries, *Phytophthorapalmivora* (Butl.) Butl., and *Puccinia thlaspeos* Schub.

[0881] The compounds of the present invention can also be used in combination with plant growth regulators such as ivermectin, N-(phenylmethyl)-1H-purine-6-amine, propionyl brassinolide, gibberellic acid, gibberellin A4 and A7, hypersensitive protein, mepiquat, calcium cyclohexane, jasmone, sodium nitrophenolate and anti-rot ester-methyl, as well as plant growth modifying organisms such as Bacillus cereus strain BP01.

[0882] General references for agricultural protectants (i.e., herbicides, herbicide safeners, insecticides, fungicides, nematicides, acaricides, and biological agents) include The Pesticide Manual, 13th edition, edited by CDSTomlin, British Crop Protection Council, Farnham, Surrey, UK, 2003, and The BioPesticide Manual, 2nd edition, edited by LGCopping, British Crop Protection Council, Farnham, Surrey, UK, 2001.

[0883] In embodiments where one or more of these different blending components are used, these blending components are typically used in amounts similar to those conventionally used when the blending components are used alone. More specifically, in the blend, the active ingredient is typically applied at an amount between half and the total amount of the active ingredient specified on the product label. These amounts are listed in references such as The Pesticide Manual and The BioPesticide Manual. The weight ratio of these different blending components (total) to the compound of Formula 1 is typically between about 1:3000 and about 3000:1. It is noteworthy that weight ratios between about 1:300 and about 300:1 (e.g., ratios between about 1:30 and about 30:1) are also possible. Those skilled in the art can readily determine, through simple experiments, the bioeffective amount of the active ingredient necessary for the desired biological activity spectrum. It will be apparent that including these additional components allows the controlled weed spectrum to be extended beyond the control spectrum provided by the compound of Formula 1 alone.

[0884] In certain circumstances, the combination of the compounds of the present invention with other bioactive (particularly herbicidal) compounds or agents (i.e., active ingredients) can result in a greater-than-additive (i.e., synergistic) effect on weeds and / or a less-than-additive (i.e., safetyation) effect on crops or other desired plants. Reducing the amount of active ingredient released into the environment while ensuring effective pest control has always been desirable. The ability to use larger amounts of active ingredient to provide more effective weed control without excessive crop damage is also desirable. Such combinations can be advantageously used to reduce crop production costs and environmental impact when the application rate of the herbicidal active ingredient synergizes with weeds to achieve agronomically satisfactory weed control levels. When the safetyation of the herbicidal active ingredient occurs on crops, such combinations can be advantageously used to increase crop protection by reducing weed competition.

[0885] It is noteworthy that the disclosed compounds are combined with at least one other herbicidal active ingredient. Particularly noteworthy are combinations of other herbicidal active ingredients with compounds of the present invention that have different sites of action. In some cases, combinations with at least one other herbicidal active ingredient having a similar range of control but a different site of action will be particularly advantageous for resistance management. Therefore, the compositions of the present invention may further comprise (at a herbicidally effective amount) at least one additional herbicidal active ingredient having a similar range of control but a different site of action.

[0886] The compounds of the present invention can also be used in combination with herbicide safeners such as those listed below to increase safety for certain crops: dipropionylamine, cyproconazole, cyproconazole ester, bensulfuron-methyl, cyproconazole nitrile, propanesulfonamide, cyproconazole, dichloropropionylamine, cyproconazole, cyproconazole nitrile, cyproconazole nitrile, fluroxypyr, cyproconazole nitrile, pyrazole nitrile, mefenoxam, cyproconazole nitrile, 1,8-naphthalenecarboxylic anhydride, cyproconazole nitrile, N-(aminocarbonyl)-2-methylbenzenesulfonamide, N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene (BCS), 4-(dichloroacetyl)-1-oxa-4-azaspiro[4,5]decane (MON) 4660), 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG191), ethyl 1,6-dihydro-1-(2-methoxyphenyl)-6-oxy-2-phenyl-5-pyrimidinecarboxylate, 2-hydroxy-N,N-dimethyl-6-(trifluoromethyl)pyridine-3-carboxamide, and 3-oxy-1-cyclohexen-1-yl-1-(3,4-dimethylphenyl)-1,6-dihydro-6-oxy-2-phenyl-5-pyrimidinecarboxylate, 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolyl)-acetone and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]benzamide. An effective amount of the herbicide safener can be applied simultaneously with the compounds of this invention or as a seed treatment. Therefore, one aspect of the invention relates to a herbicidal mixture comprising the compound of the invention and an effective amount of a herbicide safener. Seed treatment is particularly useful for selective weed control because it physically restricts the detoxification effect to the crop plant. Therefore, a particularly useful embodiment of the invention is a method for selectively controlling unwanted vegetation growth in a crop, comprising contacting the site of the crop with an effective amount of the herbicide compound of the invention, wherein the crop, from its seed, has been treated with an effective amount of the safener. The effective amount of the safener can be readily determined by those skilled in the art through simple experiments.

[0887] The compounds of the present invention may also be mixed with: (1) polynucleotides, including but not limited to DNA, RNA and / or chemically modified nucleotides, which affect the amount of a specific target by modulating, interfering with, inhibiting or silencing gene-derived transcripts that exhibit herbicidal effects; or (2) polynucleotides, including but not limited to DNA, RNA and / or chemically modified nucleotides, which affect the amount of a specific target by modulating, interfering with, inhibiting or silencing gene-derived transcripts that exhibit safety effects.

[0888] It is noteworthy that a composition comprises the compound disclosed herein (in an effective amount for weed control), 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 diluents and liquid diluents.

[0889] Preferred for better control of unwanted vegetation (e.g., lower application rates, such as from synergistic effects, broader-spectrum weed control, or enhanced crop safety) or for preventing the development of resistant weeds, is a mixture of the compounds of the present invention with a herbicide selected from the group consisting of: atrazine, tetrazolium-sulfuron, flubutyramide, S-flubutyramide, benzisothiazolinone, pyrazosulfuron, chlorpyrifos, chlorsulfuron-methyl, isoxaflutole, potassium dichloropyridinate, chlorpyrifos-sulfuron, 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 (CA No. 81778-66-7), benzylsulfuron, pyrazosulfuron, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5-(2H,4H)-dione, flupyrimisulfuron, fluthiamethoxam, flusulfanilamide, imazalil, cyclosporine, mesotrione, methamidophos, metsulfuron, clethodim, sulfadiazine, sulfonamide, sulfadiazine, quinclorac, pyrazosulfuron, linsyl, succinate, metolachlor, mesotrione, thifensulfuron, flusulfanilamide, and benzylsulfuron. Table A1 lists specific combinations of components (a) and (b), illustrating the mixtures, compositions, and methods of the present invention. The compounds in column (a) are identified by the # symbol in Index Table A. The second column of Table A1 lists specific compounds of component (b) (e.g., “2,4-D” in the first row). Columns three, four, and five of Table A1 list the range of weight ratios (i.e., (a):(b)) at which compound (a) is typically applied to field-grown crops. Thus, for example, the first row of Table A1 specifically discloses that the combination of component (a) (i.e., compound 45 in Index Table A) and 2,4-D is typically applied at a weight ratio between 1:192 and 6:1. The remaining rows of Table A1 will be constructed similarly.

[0890] Table A1

[0891]

[0892]

[0893]

[0894]

[0895]

[0896]

[0897]

[0898]

[0899]

[0900] Table A2 is constructed similarly to Table A1 above, except that the entries under the “Component(a)(Compound#)” column heading are replaced by the corresponding Component(a) column entries as shown below. Compound 16 in the Component(a) column is identified in Index Table A. Therefore, for example, in Table A2, all entries under the “Component(a)” column heading list “Compound 16” (i.e., Compound 16 identified in Index Table A), and the first row under the column heading in Table A2 specifically discloses the mixture of Compound 16 and 2,4-D. Tables A3 through A16 are constructed similarly.

[0901]

[0902] The following tests demonstrate the efficacy of the compounds of this invention in controlling specific weeds. However, the weed control provided by the compounds is not limited to these species. See Index Table AG for a description of the compounds. The following abbreviations are used in the subsequent index table: t for tert-, s for secondary-, n for normal-, i for iso-, c for cyclic, Me for methyl, Et for ethyl, Pr for propyl, i-Pr for isopropyl, Bu for butyl, c-Pr for cyclopropyl, t-Bu for tert-butyl, Ph for phenyl, OMe for methoxy, OEt for ethoxy, SMe for methylthio, SEt for ethylthio, -CN for cyano, -NO2 for nitro, TMS for trimethylsilyl, and naphthyl means naphthalenyl. (R) or (S) indicates the absolute chirality of the asymmetric carbon center. The abbreviation "(d)" indicates that the compound appears to decompose upon melting. The abbreviation "Cmpd.#" represents the "compound number". The abbreviation "Ex." stands for "Example," followed by a number indicating in which instance the compound was prepared. This is as observed through atmospheric pressure chemical ionization (AP+) via H+. + The molecular weight of the highest isotopic abundance precursor ion (M+1) formed by adding to the molecule (molecular weight 1) is reported by mass spectrometry with an estimation accuracy within ±0.5 Da.

[0903] Index Table A

[0904]

[0905] G is CONR 5 R 6 ; and NR 5 R 6 It is J or K.

[0906]

[0907]

[0908]

[0909]

[0910]

[0911]

[0912]

[0913] @ See Examples 1 and 2 for J-1 to J-52 and K-1 to K-9. Index Table B

[0914]

[0915]

[0916]

[0917]

[0918]

[0919]

[0920]

[0921] See Example 3 in G-1-1 to G-1-27.

[0922] *Indicates that the compound is a trans or cis isomer of the two methyl groups on the six-membered ring.

[0923] **This indicates that the compound is an enantiomer.

[0924] Index Table C

[0925]

[0926]

[0927]

[0928] **for 1 See index table G for H NMR data.

[0929] See Example 4 in G-2-1 to G-2-12.

[0930] Index Table D

[0931]

[0932]

[0933] Index Table E

[0934]

[0935]

[0936]

[0937] Index table F

[0938]

[0939]

[0940]

[0941] Index table G

[0942]

[0943]

[0944] Index table H

[0945]

[0946] a 1 1H NMR data are expressed in ppm at the low field of tetramethylsilane. Coupling is specified by (s)-single and (m)-multiplex.

[0947] Biological Examples of the Invention

[0948] Test A

[0949] Seeds of the following plant species were planted in a mixture of fertile soil and sand and pre-emergence treated by targeted soil spraying with a test chemical formulated in a mixture of non-phytotoxic solvents containing surfactants: barnyard grass (Echinochloa crus-galli), kochia (Bassia scoparia), ragweed (Ambrosia artemisiifolia), Italian ryegrass (Lolium multiflorum), giant foxtail (Setaria faberi), and wild amaranth (Amaranthus retroflexus).

[0950] Simultaneously, plants selected from these weed species, along with wheat (Triticum aestivum), corn (Zeamays), black grass (Alopecurus myosuroides), and cleavers (Galium aparine), were planted in pots with the same mixture of fertile soil and sand, and post-emergence treated with test chemicals formulated in the same manner. For post-emergence treatment, the plants ranged in height from 2 to 10 cm and were at the one- to two-leaf stage. The treated plants and untreated controls were kept in a greenhouse for approximately 10 days, after which all treated plants were compared with the untreated controls, and damage was visually assessed. Plant response ratings summarized in Table A are based on a scale of 0 to 100, where 0 represents no effect and 100 represents complete control. A dash (-) response indicates no test result.

[0951]

[0952]

[0953]

[0954]

[0955]

[0956]

[0957]

[0958]

[0959]

[0960]

[0961]

[0962]

[0963]

[0964]

[0965]

[0966]

[0967]

[0968]

[0969]

[0970]

[0971]

[0972]

[0973]

[0974]

[0975]

[0976]

[0977]

[0978]

[0979]

[0980]

[0981]

[0982]

[0983]

[0984]

[0985]

[0986]

[0987]

[0988]

[0989]

[0990]

[0991]

[0992]

[0993]

[0994]

[0995]

[0996]

[0997]

[0998]

[0999]

[1000]

[1001]

[1002]

[1003]

[1004]

[1005]

[1006]

[1007]

[1008]

[1009]

[1010]

[1011]

[1012]

[1013]

[1014]

[1015]

[1016]

[1017]

[1018]

[1019]

[1020]

[1021]

[1022]

[1023]

[1024]

[1025]

[1026]

[1027]

[1028]

[1029]

[1030]

[1031]

[1032]

[1033]

[1034]

[1035]

[1036]

[1037]

[1038]

[1039]

[1040]

[1041]

[1042]

[1043]

[1044]

[1045]

[1046]

[1047]

[1048]

[1049]

[1050]

[1051]

[1052]

[1053] Test A1

[1054] Seeds of the following plant species were planted in a mixture of fertile soil and sand and pre-emergence treated by targeted soil spraying with a test chemical formulated in a mixture of non-phytotoxic solvents containing surfactants: black grass (Alopecurus myosuroides), corn (Zea mays), giant foxtail (Setariafaberi), goosegrass (Eleusine indica), kochia (Bassia scoparia), wild oat (Avenafatua), palmer pigweed (Amaranthus palmeri), ragweed (Ambrosia artemisiifolia), Italian ryegrass (Lolium multiflorum), soybean (Glycine max), and wheat (Triticum aestivum).

[1055] Simultaneously, plants selected from these crops and weed species, along with Galiumaparine and Erigeron canadensis, were planted in pots containing the same mixture of fertile soil and sand, and post-emergence treated with test chemicals formulated in the same manner. For post-emergence treatment, plants ranged in height from 2 to 10 cm and were at the one- to two-leaf stage. The treated plants and untreated controls were kept in a greenhouse for 10 days, after which all treated plants were compared to the untreated controls, and damage was visually assessed. Plant response ratings summarized in Table A are based on a scale of 0 to 100, where 0 represents no effect and 100 represents complete control. A dash (-) response indicates no test result.

[1056]

[1057]

[1058]

[1059]

[1060]

[1061]

[1062]

[1063]

[1064]

[1065]

[1066]

[1067]

[1068]

[1069]

[1070]

[1071]

[1072]

[1073]

[1074]

[1075]

[1076]

[1077]

[1078]

[1079]

[1080]

[1081]

[1082]

[1083]

[1084]

[1085]

[1086]

[1087]

[1088]

[1089]

[1090]

[1091]

[1092]

[1093]

[1094]

[1095]

[1096]

[1097]

[1098]

[1099]

[1100]

[1101]

[1102]

[1103]

[1104]

[1105]

[1106]

[1107]

[1108]

[1109]

[1110] Test B

[1111] Plant species selected from flooded paddy fields for testing—Oryza sativa, Cyperus difformis, Heteranthera limosa, and Echinochloa crus-galli—were grown to the 2-leaf stage for testing. During treatment, test pots were submerged 3 cm above the soil surface, and the test compound was applied directly to the paddy field water, maintaining this water depth throughout the test. The treated plants and controls were kept in a greenhouse for 13 to 15 days, after which all species were compared to the controls and visually evaluated. Plant response ratings summarized in Table B are based on a scale of 0 to 100, where 0 represents no effect and 100 represents complete control. A dash (-) response indicates no test result.

[1112]

[1113]

[1114]

[1115]

[1116]

[1117]

[1118]

[1119]

[1120]

[1121]

[1122]

[1123]

[1124]

[1125]

[1126]

[1127]

[1128]

[1129]

[1130]

[1131]

[1132]

[1133]

[1134]

[1135] Test B1

[1136] Plant species selected from flooded paddy field tests, including *Echinochloa crus-galli*, *Heteranthera limosa*, rice (*Oryza sativa*), and *Cyperus difformis*, were grown to the 2-leaf stage for testing. During treatment, test pots were submerged 3 cm above the soil surface, and the test compound was applied directly to the paddy field water, maintaining this water depth throughout the test. Treated plants and controls were kept in a greenhouse for 10 to 14 days, after which all species were compared to the controls and visually evaluated. Plant response ratings summarized in Table B are based on a scale of 0 to 100, where 0 represents no effect and 100 represents complete control. A dash (-) response indicates no test result.

[1137]

[1138]

[1139]

[1140]

[1141]

[1142]

[1143]

[1144]

[1145]

[1146]

[1147]

Claims

1. A compound selected from Formula 1, in G is CONR 5 R 6 ; R 1 It is a C1 alkyl, halogen, C3 cycloalkyl, or C1 haloalkyl; R 2 It is H, C1 alkyl, or halogen; R 3 It is H, C1 alkyl, halogen, CN, C1 haloalkyl or C1 alkoxy; R 4 It is H, C(=O)R 19 -CO2R 19 -S(O)2R 19 Or CH2OC(=O)R 19 ; R 5 It is H, C1-C2 alkyl, C4 cycloalkylalkyl, or C3 alkynylalkyl; R 6 It is H or C1-C2 alkyl; or R 5 and R 6 Together with the nitrogen atoms to which they are attached, they form 4- to 7-membered rings, which contain carbon atoms and optionally 1 to 3 oxygen, sulfur, or nitrogen atoms as ring members, said rings optionally being composed of up to 5 independently selected from (R... v ) r The substituents are substituted, and r is the number of these substituents; R v Independently selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, and C1-C4 alkoxy; or When two R v When attached to the same carbon atom, the two Rs v Together with the carbon atom to which they are attached, they can form a 5- or 6-membered ring containing a carbon atom and two optional oxygen atoms as ring members. r is 0, 1, or 2; R 19 It is a C1-C7 alkyl, C1-C7 haloalkyl, or C1-C7 alkoxy; and R f It's CF3.

2. The compound of claim 1, wherein... R 2 It is H, C1 alkyl, or halogen; R 3 It is H, C1 alkyl, halogen, CN, C1 alkoxy, or C1 haloalkyl; R 4 It is H, C(=O)R 19 CO2R 19 S(O)2R 19 or CH2OCOR 19 ; R 5 It is H, C1-C2 alkyl, C4 cycloalkylalkyl, or C3 alkynylalkyl; R 6 It is an H or C1-C2 alkyl group; and R f It's CF3.

3. The compound of claim 2, wherein... R 1 It is a C1 alkyl, halogen, or C3 cycloalkyl; R 2 It is H, Me, or F; R 3 It is H, Me, F, Cl, CN, OMe, or CF3; R 4 It is H, SO2CF3, CO2Me, COME, CH2OCO- t -Bu, CH2OCOCH2CH3 or CH2OCOMe; R 5 It is H, methyl, ethyl, CH2CCH or ring propylmethyl; R 6 It is H, methyl, or ethyl; and R f It's CF3.

4. The compound of claim 3, wherein R 1 Is it Me or Cl; R 3 It's me; R 4 It is H, CH2OCO- t -Bu or SO2CF3; R 5 It is methyl; and R 6 It is a methyl group.

5. The compound of claim 1, wherein... R 2 It is H, C1 alkyl, or halogen; R 3 It is H, C1 alkyl, halogen, CN, C1 alkoxy, or C1 haloalkyl; R 4 It is H, C(=O)R 19 CO2R 19 S(O)2R 19 or CH2OCOR 19 ; R 5 and R 6 Together with the nitrogen atoms to which they are attached, they form 4- to 7-membered rings, which contain carbon atoms and optionally 1 to 3 oxygen, sulfur, or nitrogen atoms as ring members, said rings optionally being composed of up to 5 independently selected from (R... v ) r The substituents are substituted, and r is the number of these substituents; R v Independently selected from the group consisting of: methyl, ethyl, or propyl; and r is 1 or 2.

6. The compound of claim 5, wherein... R 1 It is a C1 alkyl, halogen, or C3 cycloalkyl; R 2 It is H or F; R 3 It is H, Me, F, Cl, CN, OMe, or CF3; R 4 It is H, SO2CF3, CO2Me, COME, CH2OCO- t -Bu, CH2OCOCH2CH3 or CH2OCOMe; R 5 and R 6 Together with the nitrogen atom to which they are attached, they form a 5-membered ring; and R f It's CF3.

7. The compound of claim 5, wherein... R 1 It is a C1 alkyl, halogen, or C3 cycloalkyl; R 2 It is H or F; R 3 It is H, Me, F, Cl, CN, OMe, or CF3; R 4 It is H, SO2CF3, CO2Me, COME, CH2OCO- t -Bu, CH2OCOCH2CH3 or CH2OCOMe; R 5 and R 6 Together with the nitrogen atom to which they are attached, they form a 6-membered ring; and R f It's CF3.

8. The compound of claim 1, wherein the compound is selected from the group consisting of: N -[2,4-Dimethyl-5-(1-piperidinylcarbonyl)phenyl]-1,1,1-trifluoromethanesulfonamide; N -[2-chloro-4-methyl-5-(4-morpholinylcarbonyl)phenyl]-1,1,1-trifluoromethanesulfonamide; N -[2,4-Dimethyl-5-(4-morpholinylcarbonyl)phenyl]-1,1,1-trifluoromethanesulfonamide; N -[2-chloro-4-methyl-5-(1-piperidinylcarbonyl)phenyl]-1,1,1-trifluoromethanesulfonamide; 3-Fluoro- N,N 2,4-Tetramethyl-5-[[(trifluoromethyl)sulfonyl]amino]benzamide; and 1,1,1-trifluoro- N -[3-fluoro-2,4-dimethyl-5-(4-morpholinylcarbonyl)phenyl]methanesulfonamide.

9. The compound of claim 1, wherein the compound is selected from the group consisting of: Methyl [[(trifluoromethyl)sulfonyl][2,3,4-trimethyl-5-(4-morpholinylcarbonyl)phenyl]amino]2,2-dimethylpropionate; N -[(trifluoromethyl)sulfonyl]- N ethyl [2,3,4-trimethyl-5-(1-piperidinylcarbonyl)phenyl]carbamate; Methyl [[(trifluoromethyl)sulfonyl][2,3,4-trimethyl-5-(1-piperidinylcarbonyl)phenyl]amino]2,2-dimethylpropionate; and 1,1,1-trifluoro- N -[2,3,4-trimethyl-5-(4-morpholinylcarbonyl)phenyl]methanesulfonamide.

10. The compound of claim 1, wherein... G is CONR 5 R 6 And NR 5 R 6 It's J-3a, R 1 It's Me, R 2 It's Me, R 3 It's Me, R 4 It is CH2OCO- t -Bu, and R f It is CF3, where J-3a is ;or G is CONR 5 R 6 And NR 5 R 6 It's a J-4, R 1 It's Me, R 2 It's Me, R 3 It's Me, R 4 It is CO2Et and R f It is CF3, of which J-4 is .

11. A weed-control composition comprising the compound of claim 1 and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.

12. A weed control 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 diluents and liquid diluents.

13. A herbicidal mixture comprising (a) the compound of claim 1 and (b) at least one additional active ingredient selected from the group consisting of: (b1) a photosystem II inhibitor, (b2) an acetylhydroxy acid synthase inhibitor, (b3) an acetyl-CoA carboxylase inhibitor, (b4) an auxin mimic, (b5) a 5-enol-pyruvate-shikimate-3-phosphate synthase inhibitor, (b6) a photosystem I electron diverter, (b7) a protoporphyrinogen oxidase inhibitor, (b8) a glutamine synthase inhibitor, (b9) a very long-chain fatty acid elongation enzyme inhibitor, (b10) an auxin transport inhibitor, (b11) a phytopenic oleoresin dehydrogenase inhibitor, (b12) a 4-hydroxyphenyl-pyruvate dioxygenase inhibitor, (b13) a solanyltransferase inhibitor, (b14) a cellulose biosynthesis inhibitor, and (b15) a phytopenic oleoresin inhibitor. Other herbicides, including mitotic disruptors, organoarsenic compounds, sulfadiazine, bromobutyrazoline, cyclohexane, bensulfuron, dazomet, fenbendazim, oxybenzamide, succinate, phosphonium-ammonium, hydantoin, methyl succinate, oleic acid, oxadiazon, nonanoic acid and barnyardgrass, (b16) herbicide safeners, and salts of compounds (b1) to (b16).

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

15. The method of claim 14, further comprising contacting the vegetation or its environment with an effective amount of at least one additional active ingredient selected from the group consisting of: (b1) a photosystem II inhibitor, (b2) an acetylhydroxy acid synthase inhibitor, (b3) an acetyl-CoA carboxylase inhibitor, (b4) an auxin mimic, (b5) a 5-enol-pyruvate-shikimate-3-phosphate synthase inhibitor, (b6) a photosystem I electron diverter, (b7) a protoporphyrinogen oxidase inhibitor, (b8) a glutamine synthase inhibitor, (b9) a very long-chain fatty acid elongation enzyme inhibitor, (b10) an auxin transport inhibitor, (b11) a phytopenic oleoresin dehydrogenase inhibitor, (b12) a 4-hydroxyphenyl-pyruvate dioxygenase inhibitor, (b13) a solanyltransferase inhibitor, (b14) a cellulose biosynthesis inhibitor, and (b15) a phytopenic oleoresin inhibitor. Other herbicides, including mitotic disruptors, organoarsenic compounds, sulfadiazine, bromobutyrazoline, cyclohexane, bensulfuron, dazomet, fenbendazim, oxybenzamide, succinate, phosphonium-ammonium, hydantoin, methyl succinate, oleic acid, oxadiazon, nonanoic acid and barnyardgrass, (b16) herbicide safeners, and salts of compounds (b1) to (b16).

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