Benzoxazine herbicide

Abstract

Disclosed are compounds of formula (I) (including all stereoisomers, N-oxides, and salts thereof), pesticidal compositions containing them, and their use as herbicides, wherein A is a 5- or 6-membered heterocyclic ring containing ring members selected from carbon atoms and up to four heteroatoms independently selected from up to two O, up to two S, and up to four N atoms, wherein one or two carbon or sulfur ring members of the heterocycle may optionally be present in the oxidized form of a carbonyl, sulfonyl, or sulfinyl moiety, said ring being bonded to the remainder of formula (I) through a carbon atom or heteroatom, and wherein one to four R 1 optionally replaced by R 1a , R 1b , R 2 , R 3a , R 3b , R 4a , R 4b , X 1 , X 2 , n, p and q are as defined in this disclosure. [Formula 1] TIFF2025525502000168.tif39170

Description

[Technical Field]

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

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

[0003] The present invention relates to compounds of formula 1, all stereoisomers, N-oxides and salts thereof, agricultural compositions containing them and their use as herbicides, [ka] During the ceremony, A is a 5- or 6-membered heterocyclic ring containing ring members selected from carbon atoms and up to four heteroatoms independently selected from up to two O, up to two S, and up to four N atoms, wherein one or two carbon or sulfur ring members of the heterocycle may optionally be present in the oxidized form of a carbonyl, thiocarbonyl, sulfonyl, or sulfinyl moiety, said ring being bonded to the remainder of Formula 1 through a carbon atom or heteroatom, and wherein one to four R1 optionally replaced by; R 1 are independently 1a , (R 1b ) m , R 1c or any combination thereof; R 1ais H, halogen, cyano, nitro, amino, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C1-C6 hydroxyalkyl, C3-C7 hydroxycycloalkyl, C1-C6 hydroxyhaloalkyl, C4-C8 alkoxycycloalkyl, C2-C7 alkoxyhaloalkyl, C2-C6 oxacycloalkyl, C3-C7 oxacycloalkylalkyl, C3-C7 alkyloxacycloalkyl alkyl, C2-C6 thiacycloalkyl, C3-C7 thiacycloalkylalkyl, C3-C7 alkylthiacycloalkyl, C2-C6(O-thia)cycloalkyl, C3-C7(O-thia)cycloalkylalkyl, C3-C7 alkyl(O-thia)cycloalkyl, C2-C6(O2thia)cycloalkyl, C3-C7(O2thia)cycloalkylalkyl, C3-C7 alkyl(O2thia)cycloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C7 halocycloalkyl, C4-C7 haloalkylcycloalkyl , C2-C7 alkoxyalkyl, C2-C7 haloalkoxyalkyl, C1-C7 alkoxy, C2-C5 alkenyloxy, C2-C5 alkynyloxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl, C1-C7 haloalkoxy, C1-C7 alkylthio, C2-C7 alkylthioalkyl, C1-C5 alkylsulfinyl, C1-C5 alkylsulfonyl, C1-C4 alkylsulfonate, C1-C5 haloalkylthio, C1-C5 haloalkylsulfinyl, C1-C5 haloalkylsulfonyl, C2-C7 alkenyloxy, C2-C5 alkynyloxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl, C1-C7 haloalkoxy, C1-C7 alkylthio, C2-C7 alkylthioalkyl, C1-C5 alkylsulfinyl, C1-C5 ... alkylsulfonylalkyl, C2-C7 alkylsulfonylalkyl, C2-C7 haloalkylthioalkyl, C2-C7 haloalkylsulfinylalkyl, C2-C7 haloalkylsulfonylalkyl, C4-C7 alkylthiocycloalkyl, C4-C7 alkylsulfinylcycloalkyl, C4-C7 alkylsulfonylcycloalkyl, C4-C7 haloalkylthiocycloalkyl, C2-C7 haloalkylsulfinylcycloalkyl, C2-C7 haloalkylsulfonylcycloalkyl, C2-C7 alkylsulfoximinoalkyl,C2-C5 cyanoalkyl, C4-C7 cyanocycloalkyl, C1-C4 nitroalkyl, C1-C7 alkylamino, C2-C7 dialkylamino, C3-C5 alkylcarbonyl(alkyl)amino, C3-C5 alkoxycarbonyl(alkyl)amino, C2-C4 alkylsulfonyl(alkyl)amino, C2-C6 alkylcarbonyl, C3-C6 alkylcarbonylalkyl, C2-C6 alkoxycarbonyl, C3-C6 alkoxycarbonylalkyl, C3-C6 trialkylsilyl, or C5-C8 trialkylsilylalkynyl; or phenyl optionally substituted with up to three substituents independently selected from the group consisting of halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, and C1-C2 haloalkoxy; R 1b is H, halogen, cyano, nitro, C1-C4 alkyl, C3-C5 cycloalkyl, C1-C4 haloalkyl, C3-C5 halocycloalkyl, C2-C4 alkoxyalkyl, C1-C4 alkoxy, C1-C4 alkylthio or C2-C4 alkoxycarbonyl; m is 0, 1 or 2; R 1c is H, C1-C7 alkyl, C3-C7 cycloalkyl, or C1-C7 haloalkyl; X 1 and X 2 are independently N or CR 2 and; n is 0, 1, 2 or 3; Each R 2are independently H, halogen, cyano, nitro, hydroxy, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C2-C5 alkenyloxy, C2-C5 alkynyloxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl, C3-C6 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C5 haloalkyl, C2-C5 haloalkenyl, C2-C5 haloalkynyl, C2-C5 alkoxyalkyl, C2-C5 haloalkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylsulfonate, C3-C5 cycloalkylsulfonate, C1-C4 haloalkylsulfonate, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C2-C5 cyanoalkyl, C4-C6 cyanocycloalkyl or C2-C5 alkoxycarbonyl; or Two adjacent R 2 may combine to form a saturated or unsaturated 5-8 membered ring containing carbon atoms and optionally 1-3 oxygen, sulfur or nitrogen atoms as ring members, wherein one or two carbon or sulfur ring members of the heterocycle may optionally be present in the oxidized form of a carbonyl, sulfonyl, sulfinyl moiety, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy; Y is O or S; R 3ais halogen, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C7 alkoxy, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C7 halocycloalkyl, C4-C7 haloalkylcycloalkyl, C2-C7 alkoxyalkyl, C2-C7 haloalkoxyalkyl, C2-C7 alkylthioalkyl, C2-C7 alkylsulfinylalkyl alkyl, C2-C7 alkylsulfonylalkyl, C2-C7 haloalkylthioalkyl, C2-C7 haloalkylsulfinylalkyl, C2-C7 haloalkylsulfonylalkyl, C2-C5 cyanoalkyl, C4-C6 cyanocycloalkyl, C1-C4 nitroalkyl, C3-C6 alkylcarbonylalkyl, C2-C6 oxacycloalkyl, C2-C6 oxacycloalkylalkyl, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl or C3-C6 alkoxycarbonylalkyl; Each R 3b are independently H, halogen, or C1-C3 alkyl; or R 3a and R 3b together with the carbon atoms to which they are attached form a 3- to 7-membered ring containing carbon atoms and ring members selected from one oxygen atom, one sulfur atom, and up to three heteroatoms independently selected from one nitrogen atom, wherein up to two carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring members are selected from S, S(O), or S(O)2; or The Two R's 3b together with the carbon atoms to which they are attached form a 3- to 7-membered ring containing carbon atoms and ring members selected from one oxygen atom, one sulfur atom, and up to three heteroatoms independently selected from one nitrogen atom, wherein up to two carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring members are selected from S, S(O), or S(O); p is 0, 1, 2 or 3; R 4ais H, halogen, cyano, nitro, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C1-C5 haloalkyl, C2-C5 haloalkenyl, C2-C5 haloalkynyl, C2-C5 alkoxyalkyl, C2-C5 haloalkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C3-C6 trialkylsilyl, C5-C8 trialkylsilylalkynyl, C1-C5 alkylthio, C1-C5 haloalkylthio or C2-C5 alkoxycarbonyl; q is 0, 1 or 2; Each R 4b are independently H, halogen, cyano, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, or C1-C4 alkylthio; The compound of formula 1 is [3-(5-cyclopropyl-1,2,4-oxadiazol-3-yl)phenyl](2-ethyl-2,3-dihydro-4H-1,4-benzoxazin-4-yl)-methanone (CAS Registry No. 1798020-19-5); (8-chloro-2-ethyl-2,3-dihydro-4H-1,4-benzoxazin-4-yl)[3-(1H-tetrazol-1-yl)phenyl]methanone (CAS Registry No. 2093742-48-2); (2-ethyl-2,3-dihydro-4H-1,4-benzoxazin-4-yl)[2-(1H-1,2,4-triazol-1-yl)-4-pyridinyl]-methanone (CAS Registration No. 1808378-56-4); (8-chloro-2-ethyl-2,3-dihydro-4H-1,4-benzoxazin-4-yl)[2-(1H-1,2,4-triazol-1-yl)-4-pyridinyl]-methanone (CAS Registration No. 1808849-41-3); (2,3-Dihydro-2,7-dimethyl-4H-1,4-benzoxazin-4-yl)[2-(1H-1,2,4-triazol-1-yl)-4-pyridinyl]-methanone (CAS Registration No. 1436224-65-5); (8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl)[2-(1H-pyrazol-1-yl)-4-pyridinyl]-methanone (CAS Registration No. 2224006-86-2); (2,3-Dihydro-2-methyl-4H-1,4-benzoxazin-4-yl)[3-(1-pyrrolidinyl)phenyl]methanone (CAS Registry No. 2733463-68-6); Methanone, (3,4-dihydrospiro[2H-1,4-benzoxazine-2,1'-cyclopropan]-4-yl)[3-(1-pyrrolidinyl)phenyl] (CAS Registry No. 2733410-16-5); (2,3-Dihydro-2-methyl-4H-1,4-benzoxazin-4-yl)[3-(1H-pyrrol-1-yl)phenyl]methanone (CAS Registry No. 2305402-15-5); (3,4-dihydrospiro[2H-1,4-benzoxazine-2,1'-cyclopropan]-4-yl)[3-(1H-pyrrol-1-yl)phenyl]methanone (CAS Registry No. 2305290-36-0); (8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl)[3-[5-(methoxymethyl)-1,3,4-oxadiazol-2-yl]phenyl]methanone (CAS Registry No. 2223792-20-7); (7-Fluoro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl)[2-(4-methyl-1-piperazinyl)-4-pyridinyl]methanone (CAS Registry No. 2212440-53-2); (7-Fluoro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl)[3-(1H-1,2,4-triazol-5-yl)phenyl]methanone (CAS Registration No. 2094921-82-9); (2-ethyl-2,3-dihydro-4H-1,4-benzoxazin-4-yl)[5-(4-morpholinyl)-3-pyridinyl]methanone (CAS Registry No. 1957585-10-2); (8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl)[5-(4-morpholinyl)-3-pyridinyl]methanone (CAS Registration No. 1957541-06-8); (8-chloro-2-ethyl-2,3-dihydro-4H-1,4-benzoxazin-4-yl)[5-(4-morpholinyl)-3-pyridinyl]methanone (CAS Registration No. 1956163-57-7); (2,3-Dihydro-2,6-dimethyl-4H-1,4-benzoxazin-4-yl)[5-(4-morpholinyl)-3-pyridinyl]methanone (CAS Registry No. 1955383-94-4); (2,3-Dihydro-2,2-dimethyl-4H-1,4-benzoxazin-4-yl)[5-(4-morpholinyl)-3-pyridinyl]methanone (CAS Registration No. 1955104-90-1); (6-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl)[5-(4-morpholinyl)-3-pyridinyl]methanone (CAS Registry No. 1954398-26-5); (2,3-Dihydro-6-methoxy-2-methyl-4H-1,4-benzoxazin-4-yl)[5-(4-morpholinyl)-3-pyridinyl]methanone (CAS Registry Number 1947266-43-4); and The condition is that it must be other than (2,3-dihydro-6-methoxy-2-methyl-4H-1,4-benzoxazin-4-yl)[3-(1H-imidazol-1-yl)phenyl]methanone (CAS Registration No. 1384688-76-9).

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

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

[0006] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," "characterized by," or any variation thereof, are intended to include a non-exclusive inclusion, subject to any limitations specified. For example, a composition, mixture, process, or method that includes a list of elements is not necessarily limited to only those elements and may include other elements not expressly listed or inherent to such composition, mixture, process, or method.

[0007] The transitional phrase "consisting of" excludes any unspecified element, step, or ingredient. In the case of a claim, such would close the claim to the inclusion of materials other than those recited, apart from impurities normally associated therewith. When the phrase "consisting of" appears within a clause in the body of a claim rather than immediately following a preamble, it limits only the elements set forth in that clause; other elements are not excluded from the claim as a whole.

[0008] The transitional phrase "consisting essentially of" is used to define a composition or method that includes materials, steps, features, components, or elements in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements materially affect the basic and novel characteristics of the claimed invention. The term "consisting essentially of" occupies a middle ground between "comprising" and "consisting of."

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

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

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

[0012] As referred to herein, the term "seedling", used alone or in combination, means a young plant developing from the germ of a seed.

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

[0014] As used herein, the term "alkylation" refers to a reaction in which a nucleophile displaces a leaving group, such as a halide or sulfonate, from a carbon-containing radical. Unless otherwise indicated, the term "alkylation" does not limit the carbon-containing radical to alkyl.

[0015] In the above description, the term "alkyl," used alone or in compound terms such as "alkylthio" or "haloalkyl," includes straight-chain or branched alkyls, such as methyl, ethyl, n-propyl, i-propyl, or the various butyl, pentyl, or hexyl isomers. "Alkenyl" includes straight-chain or branched alkenes, such as ethenyl, 1-propenyl, 2-propenyl, and the 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 the various butynyl, pentynyl, and hexynyl isomers. "Alkynyl" can also include moieties containing multiple triple bonds, such as 2,5-hexadiynyl.

[0016] "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy, and the various butoxy, pentoxy, and hexyloxy isomers. "Alkoxyalkyl" refers to alkoxy substitution on an alkyl. Examples of "alkoxyalkyl" include CHOCH, CHOCHCH, CHCHOCH, CHCHCHCHOCH, and CHCHOCHCH. "Hydroxyalkyl" refers to hydroxy substitution on an alkyl. "Hydroxycycloalkyl" refers to hydroxy substitution on a cycloalkyl. "Hydroxyhaloalkyl" refers to hydroxy substitution on a haloalkyl. "Alkoxycycloalkyl" refers to alkoxy substitution on a cycloalkyl. "Alkoxyhaloalkyl" refers to alkoxy substitution on an alkyl. Examples of "hydroxyalkyl," "hydroxycycloalkyl," "hydroxyhaloalkyl," "alkoxycycloalkyl," and "alkoxyhaloalkyl" include the following structures: [ka]

[0017] "Alkoxyalkoxy" refers to alkoxy substitution on alkoxy. "Alkylthio" includes branched or straight-chain alkylthio residues such as methylthio, ethylthio, and the various propylthio, butylthio, pentylthio, and hexylthio isomers. "Alkylthioalkyl" refers to alkylthio substitution on alkyl. Examples of "alkylthioalkyl" include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2, CH3CH2SCH2CH2 and their different isomers. "Alkylsulfinyl" includes both enantiomers of alkylsulfinyl groups. Examples of "alkylsulfinyl" include CH3S(O)-, CH3CH2S(O)-, CH3CH2CH2S(O)-, (CH3)2CHS(O)-, and the various butylsulfinyl, pentylsulfinyl, and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH3S(O)2-, CH3CH2S(O)2-, CH3CH2CH2S(O)2-, (CH3)2CHS(O)2-, and the various butylsulfonyl, pentylsulfonyl, and hexylsulfonyl isomers. Examples of "alkylsulfonate" include CH3S(O)2O-, CH3CH2S(O)2O-, CH3CH2CH2S(O)2O-, (CH3)2CHS(O)2O-, and the different butylsulfonate, pentylsulfonate, and hexylsulfonate isomers. "Cyanoalkyl" refers to an alkyl group substituted with one cyano group. Examples of "cyanoalkyl" include NCCH2 and NCCH2CH2 (alternatively identified as CH2CH2CN). "Nitroalkyl" refers to an alkyl group substituted with one nitro group. Examples of "nitroalkyl" include NO2CH2 and NO2CH2CH2 (alternatively identified as CH2CH2NO2). "Cyano" means NC- and "formyl" means HC(=O)-. "Alkylamino" includes an NH group substituted with a straight-chain or branched alkyl. Examples of "alkylamino" include CH3CH2NH, CH3CH2CH2NH, and (CH3)2CHCH2NH. Examples of "dialkylamino" include (CH3)2N, (CH3CH2CH2)2N, and CH3CH2(CH3)N."Alkylsilyl" includes a silyl group substituted with a linear or branched alkyl. "Trialkylsilyl" includes a silyl group substituted with three linear or branched alkyls. Examples of "trialkylsilyl" include (CH3)3Si- and (CH3CH2)3Si-. "Trialkylsilyalynyl" refers to a trialkylsilyl substitution on an alkynyl. Examples of "trialkylsilyalynyl" include (CH3)3SiC≡C- and (CH3CH2)3SiC≡C-.

[0018] Examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "cycloalkylalkyl" refers to cycloalkyl substitution on an alkyl moiety. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl residues bonded to a straight-chain or branched alkyl group. The term "alkylcycloalkyl" refers to an alkyl group bonded to a cycloalkyl moiety. The term "cycloalkoxy" refers to a cycloalkyl group bonded through an oxygen. Examples of "cycloalkoxy" include cyclopropoxy, cyclobutoxy, and cyclopentoxy. The term "cycloalkoxyalkyl" refers to cycloalkoxy substitution on an alkyl moiety. Examples of "cycloalkoxyalkyl" include cyclopropoxymethyl, cyclobutoxyethyl, and cyclopentoxymethyl, as well as other cycloalkoxy moieties bonded to a straight-chain or branched alkyl group. The term "oxycycloalkyl" refers to a cycloalkyl having one carbon ring member replaced with an oxygen atom. Examples of "oxycycloalkyl" include oxacyclopropyl, oxacyclobutyl, and oxacyclopentyl. The term "thiacycloalkyl" means a cycloalkyl having one carbon ring member replaced with a sulfur atom. Examples of "thiacycloalkyl" include thiacyclopropyl, thiacyclobutyl, and thiacyclopentyl. The term "(O-thia)cycloalkyl" means a cycloalkyl having one carbon ring member replaced with a -SO group. Examples of "(O-thia)cycloalkyl" include (O-thia)cyclopropyl, (O-thia)cyclobutyl, and (O-thia)cyclopentyl. The term "(O2thia)cycloalkyl" means a cycloalkyl having one carbon ring member replaced with a -SO2 group. Examples of "(O2thia)cycloalkyl" include (O2thia)cyclopropyl, (O2thia)cyclobutyl, and (O2thia)cyclopentyl.

[0019] The term "halogen," whether used alone or in compound words such as "haloalkyl," or in descriptions such as "alkyl substituted with halogen," includes fluorine, chlorine, bromine, or iodine. Furthermore, when used in compound words such as "haloalkyl" or in descriptions such as "alkyl substituted with halogen," the alkyl may be partially or fully substituted with halogen atoms, which may be the same or different. Examples of "haloalkyl" or "alkyl substituted with halogen" include F3C, ClCH2, CF3CH2, and CFC12. Terms such as "haloalkoxy," "haloalkoxyalkyl," "haloalkylthio," "haloalkenyl," "haloalkynyl," "halocycloalkyl," "haloalkylcycloalkyl," "haloalkylsulfinyl," and "haloalkylsulfonyl" are as defined analogously to the term "haloalkyl." Examples of "haloalkoxy" include CFO-, CCl3CHO-, HCF2CH2CHO-, and CF3CHO-. Examples of "haloalkoxyalkyl" include CF3OCH2-, CCl3CHOCH2-, HCF2CH2CHOCH2-, and CF3CHOCH2-. Examples of "haloalkylthio" include CCl3S-, CF3S-, CCl3CH2S-, and ClCH2CH2CH2S-. Examples of "haloalkenyl" include (Cl)2C=CH-(Cl)2C=CHCH2-, and CF3CH2CH=CHCH2-. Examples of "haloalkynyl" include HC≡CCHCl-, CF3C≡C-, CC13C≡C-, and FCH2C≡CCH2-. Examples of "halocycloalkyl" include 1-chlorocyclopropyl, 2-chlorocyclopropyl, 2-fluorocyclopropyl, 1-chlorocyclobutyl, 1-fluorocyclobutyl, and 2-fluorocyclobutyl. Examples of "haloalkylcycloalkyl" include 1-(chloromethyl)cyclopropyl, 2-(chloromethyl)cyclopropyl, 2-(fluoromethyl)cyclopropyl, 1-(chloromethyl)cyclobutyl, 2-(fluoroethyl)cyclobutyl, and 2-(fluoromethyl)cyclobutyl.

[0020] "Alkylcarbonyl" refers to a straight-chain or branched alkyl moiety attached to a C(=O) moiety. Examples of "alkylcarbonyl" include CH3C(=O)-, CH3CH2C(=O)-, CH3CH2CH2C(=O)-, (CH3)2CHC(=O)-, and different butyl- or pentylcarbonyl isomers. "Alkoxycarbonyl" refers to a straight-chain or branched alkoxy moiety attached to a C(=O) moiety. Examples of "alkoxycarbonyl" include CH3OC(=O)-, CH3CH2OC(=O)-, CH3CH2CH2OC(=O)-, (CH3)2CHOC(=O)-, and different butoxy- or pentoxycarbonyl isomers. C(=O) or C(O) represents a carbonyl. The term "alkoxycarbonylalkyl" refers to a straight-chain or branched alkoxycarbonyl moiety attached via an alkyl moiety. The term "alkylcarbonylalkyl" refers to a straight-chain or branched alkylcarbonyl moiety bonded via an alkyl moiety. The term "alkylcarbonyloxy" refers to an alkylcarbonyl moiety bonded via an oxygen. Examples of alkylcarbonyloxy include CHC(=O)O-, CHCHC(=O)O-, CHCHCHC(=O)O-, and (CH)CHC(=O)-. The term "alkenyloxy" refers to an alkenyl moiety bonded via an oxygen. Examples of "alkenyloxy" include CH=CHCHO-, 1-propenyloxy or CHCH=CHO-, 2-butenyloxy or CHCH=CHCHO-, and the different butenyloxy, pentenyloxy, and hexenyloxy isomers. Examples of "alkenyloxy" may also contain more than one double bond. The term "alkynyloxy" refers to an alkynyl moiety bonded via an oxygen. Examples of "alkynyloxy" include CHCCHO-, 1-propynyloxy or CHCCO-, 2-butynyloxy or CHCCCHO-, as well as the different butynyloxy, pentynyloxy, and hexynyloxy isomers. Examples of "alkynyloxy" may also contain more than one triple bond. The terms alkanediyl or alkenediyl refer to straight-chain or branched alkane or alkene linked chains, respectively.Examples of alkanediyl include -CH-, -CHCH(CH)-, or -CHCHCH-. Examples of alkenediyl include -CH=CH-, -CHC=CH-, or -CH=C(CH)-. The term "adjacent," in the context of positioning substituents, means "next to" or "immediately adjacent to."

[0021] "Alkylsulfoximinoalkyl" means an alkylsulfoximine or cycloalkylsulfoximine substitution on an alkyl or cycloalkyl. Examples of "alkylsulfoximinoalkyl" include the following structures: [ka]

[0022] The total number of carbon atoms in the substituent is "C i ~C j ", where i and j are numbers from 1 to 8. For example, C1-C4 alkylsulfonyl refers to methylsulfonyl through butylsulfonyl; C3-C8 alkylcarbonylalkyl refers to, for example, CH3COCH2-, CH3COCH2CH2-, or CH3CH2CH2COCH2CH2CH2-; C4-C7 alkylcycloalkyl can be, for example, methylcyclopropyl, methylcyclobutyl, ethylcyclopropyl, or propylcyclobutyl; C2 alkoxyalkyl refers to CHOCH2-; C3 alkoxyalkyl refers to, for example, CH3CH(OCH3)-, C3OCH2CH2-, or CH3CHOCH2-; and C4 alkoxyalkyl refers to the various isomers of an alkyl group substituted with an alkoxy group containing a total of 4 carbon atoms, examples include CH3CH2CH2OCH2- and CH3CHOCH2CH2-.

[0023] A group may have a substituent that can be hydrogen, e.g., R 2 or R 5

[0033] When a group contains a substituent, i.e., when the substituent is considered to be hydrogen, this is recognized as equivalent to the group being unsubstituted. When one or more positions on a group are described as "unsubstituted" or "unsubstituted," a hydrogen atom is bonded to occupy any free valence. Unless specifically indicated as optionally substituted, the term "phenyl" refers to unsubstituted phenyl. Unless specifically indicated as optionally substituted, the term "benzyl" refers to unsubstituted benzyl.

[0024] When a compound is substituted with a substituent bearing a subscript indicating that the number of said substituents can be more than one, said substituents (if they exceed one) can be independently selected from a defined group of substituents, e.g., ([(R 3b ) p ], n is 0, 1, 2, or 3). When p is 0, a hydrogen can be at a position not listed in the definition of a substituent. When a functional group or compound is indicated as being optionally substituted with a substituent, the functional group or compound can be unsubstituted or substituted. When one or more positions on a group are described as "unsubstituted" or "unsubstituted," a hydrogen atom is bonded to occupy any free valence.

[0025] (R 3b ) p The connection points of each R are shown as floating. 3b can be attached to any of the three available aromatic carbons by substitution of a hydrogen atom.

[0026] The term "ring system" means two or more fused rings. The term "bicyclic ring system" means a ring system consisting of two fused rings.

[0027] The compounds of the present invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers, and geometric isomers. Stereoisomers are isomers that have identical constitution but differ in the spatial arrangement of their atoms, including enantiomers, diastereomers, cis-trans isomers (also called geometric isomers), and atropisomers. Atropisomers result from restricted rotation around a single bond, and the high barrier to rotation allows for the isolation of these isomeric species. As will be appreciated by those skilled in the art, one stereoisomer may be more reactive and / or may exhibit advantageous effects when enriched or separated from other stereoisomers. Furthermore, those skilled in the art will recognize methods for separating, enriching, and / or selectively preparing such stereoisomers. The compounds of the present invention may exist as a mixture of stereoisomers, as individual stereoisomers, or as optically active forms.

[0028] Compounds of Formula 1 typically exist in more than one form, and therefore Formula 1 encompasses all crystalline and amorphous forms of the compounds represented therein. Amorphous forms include solid embodiments, such as waxes and rubbers, as well as liquid embodiments, such as solutions and melts. Crystalline forms include embodiments that exhibit a substantially single crystal type and embodiments that exhibit a mixture of polymorphs (i.e., multiple crystalline types). The term "polymorph" refers to a particular crystalline form of a compound that can crystallize in various crystalline forms, these forms having different molecular arrangements and / or conformations in the crystal lattice. Multiple polymorphs can have the same chemical composition, but they can also differ in composition due to the presence or absence of co-crystallized water or other molecules that may be weakly or strongly bound in the lattice. Polymorphs can differ in chemical, physical, and biological properties, such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspendability, dissolution rate, and bioavailability. As will be appreciated by those skilled in the art, polymorphs of the compound of Formula 1 may exhibit advantageous effects (e.g., suitability in preparing useful formulations, improved biological performance) compared to other polymorphs or mixtures of polymorphs of the same compound of Formula 1. The preparation and isolation of a particular polymorph of the compound of Formula 1 can be achieved by methods known to those skilled in the art, such as, for example, crystallization using selected solvents and temperatures. For a comprehensive discussion of polymorphism, see R. Hilfiker, Ed., Polymorphism in the Pharmaceutical Industry, Wiley-VCH, Weinheim, 2006.

[0029] Those skilled in the art will understand that not all nitrogen-containing heterocycles can form N-oxides because the nitrogen requires an available lone pair of electrons to be oxidized to the oxide. Those skilled in the art will recognize those nitrogen-containing heterocycles that can form N-oxides. Those skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for preparing N-oxides of heterocycles and tertiary amines are very well known to those skilled in the art, including the oxidation of heterocycles and tertiary amines using peroxyacids such as peracetic acid and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for preparing N-oxides have been widely described and reviewed in the literature, see, for example, the following references: T.L.G. Ilchrist, Comprehensive Organic Synthesis, vol. 7, pp. 748-750 (S.V. Ley, Ed., Pergamon Press); M. Tisler and B. Stanovnik, Comprehensive Heterocyclic Chemistry, vol. 3, pp. 18-20, A.J. Boulton and A. McKillop, Eds., Pergamon Press; M.R. Grimmett and B.R.T. Keene, Advances in Heterocyclic Chemistry, vol. 43, pp. 149-161, A.R.Katrittzky, Eds., Academic Press; M. Tisler and B. Stanovnik, Advances in Heterocyclic Chemistry, vol. 9, pp. 285-291, A.R.Katrittzky and A.J.Boulton, Eds., Academic Press. Press; and GWHCheeseman and ESGWerstiuk, Advances in Heterocyclic Chemistry, vol. 22, pp. 390-392, ARKatritzky and AJ Boulton, Eds., Academic Press.

[0030] Those skilled in the art recognize that salts of compounds share the biological utility of their corresponding non-salt forms because, under environmental and physiological conditions, salts of compounds are in equilibrium with their corresponding non-salt forms. Thus, a wide variety of salts of compounds of Formula 1 are useful for controlling undesirable vegetation (i.e., suitable as pesticides). Examples of salts of compounds of Formula 1 include acid addition salts with inorganic or organic acids, such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propynoic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid, or valeric acid. When compounds of Formula 1 contain an acidic residue, salts also include those formed with organic or inorganic bases, such as pyridine, triethylamine, or ammonia, or amides, hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium, or barium. Thus, the present invention includes compounds selected from Formula 1, their N-oxides, and salts suitable as pesticides.

[0031] As mentioned above, two adjacent R 2 may combine to form a 5-8 membered ring, which may be saturated or unsaturated (among other things) optionally substituted with one or more substituents selected from the group of substituents as defined in the Summary of the Invention. Examples of 5-8 membered unsaturated aromatic rings optionally substituted with one or more substituents include rings U-1 to U-60 shown in Exhibit 1, where R v are independently H, halogen, cyano, nitro, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, and C1-C4 haloalkoxy, and r is an integer from 0 to 2, limited by the number of available positions on each U group. The U groups may share any two available adjacent atoms with the connecting ring. [ka] [ka]

[0032] The 5- to 8-membered saturated or unsaturated non-aromatic heterocyclic ring is R 2 It should be noted that when optionally substituted with one or more substituents selected from the group of substituents as defined in the Summary of the Invention for, one or two carbon ring members of the heterocycle may optionally be present in the oxidized form of the carbonyl moiety.

[0033] containing ring members selected from up to two O atoms and up to two S atoms, and optionally up to four R v Examples of 5-8 membered heterocyclic rings that are saturated or non-aromatic unsaturated heterocyclic rings substituted on carbon atom ring members with include rings T-1 to T-35 as shown in Exhibit 2. Note that the T groups can share any two available adjacent atoms with the connecting ring. R v The optional substituents corresponding to can be attached to any available carbon or nitrogen by replacing a hydrogen atom. For these T rings, r is typically an integer from 0 to 4, limited by the number of available positions on each T group. The term "optionally substituted" means "substituted or unsubstituted." T 2 is N, the nitrogen atom may be H or R as defined in the Summary of the Invention. v It should be noted that the valence can be completed by substitution with any of the substituents corresponding to: [ka] [ka]

[0034] R v Note that although groups are shown in structures U-1 through U-60 and T1 through T35, they do not have to be present because they are optional substituents. vNote that if is H when attached to an atom, this is the same as if the atom were unsubstituted. Nitrogen atoms that require substitution to satisfy valence are H or R v It is replaced by (R v ) r When the point of attachment between the (R v ) r can be attached to any available carbon or nitrogen atom of the U group.

[0035] A wide variety of synthetic methods are known in the art that allow the preparation of aromatic and non-aromatic heterocyclic rings and ring systems. For detailed reviews, see the eight-volume set Comprehensive Heterocyclic Chemistry (A.R. Katrittzky and C.W. Rees, editors-in-chief, Pergamon Press, Oxford, 1984) and the twelve-volume set Comprehensive Heterocyclic Chemistry II (A.R. Katrittzky, C.W. Rees, and E.F.V. Scriven, editors-in-chief, Pergamon Press, Oxford, 1996).

[0036] Embodiments of the invention as described in the Summary of the Invention include those described below. In the following embodiments, Formula 1 includes its stereoisomers, N-oxides, and salts, and references to "compounds of Formula 1" include the definitions of the substituents defined in the Summary of the Invention, unless further defined in the embodiments.

[0037] Embodiment 1. Compounds of Formula 1, their stereoisomers, N-oxides, and salts, as described in the Summary of the Invention, agricultural compositions containing them, and their use as herbicides.

[0038] A Embodiment 2X.A is [ka] [ka] [ka] The compound of Formula 1 or Embodiment 1 selected from:

[0039] Embodiment 2. A compound of embodiment 2X wherein A is A-1, A-2, A-3, A-4, A-5, A-6, A-7, A-8, A-9, A-10, A-11, A-12 or A-13.

[0040] Embodiment 2a. A compound of embodiment 2 wherein A is A-1, A-2, A-3, A-4, A-5, A-7, A-8, A-9, A-10, A-11, A-12 or A-13.

[0041] Embodiment 2aa. A compound of embodiment 2a wherein A is A-1, A-3, A-4, A-5, A-12 or A-13.

[0042] Embodiment 2aaa. A compound of Embodiment 2aa wherein A is A-1, A-4 or A-5.

[0043] Embodiment 2b. A compound of embodiment 2a wherein A is A-1.

[0044] Embodiment 2c. A compound of Embodiment 2a wherein A is A-2.

[0045] Embodiment 2d. A compound of embodiment 2a wherein A is A-3.

[0046] Embodiment 2e. A compound of embodiment 2a wherein A is A-4.

[0047] Embodiment 2f. The compound of Embodiment 2a wherein A is A-5.

[0048] Embodiment 2g. A compound of embodiment 2a wherein A is A-7.

[0049] Embodiment 2h. A compound of Embodiment 2a wherein A is A-8.

[0050] Embodiment 2i. A compound of embodiment 2a wherein A is A-9.

[0051] Embodiment 2j. A compound of Embodiment 2a wherein A is A-10.

[0052] Embodiment 2k. A compound of Embodiment 2a wherein A is A-11.

[0053] Embodiment 2l. A compound of embodiment 2a wherein A is A-12.

[0054] Embodiment 2m. A compound of Embodiment 2a wherein A is A-13.

[0055] Embodiment 2n. A compound of embodiment 2X wherein A is A-1, A-2, A-3, A-4, A-5, A-6, A-7, A-8, A-9, A-10, A-11, A-12, A-13, A-14, A-15, A-16 or A-17.

[0056] Embodiment 2o. A compound of embodiment 2n wherein A is A-1, A-3, A-4, A-5, A-11, A-12, A-13, A-14, A-15, A-16 or A-17.

[0057] Embodiment 2p. A compound of embodiment 2o wherein A is A-1, A-4, A-5, A-12, A-14, A-15 or A-17.

[0058] Embodiment 2q. A compound of Embodiment 2p wherein A is A-1, A-4 or A-15.

[0059] X 1 and X 2 Embodiment 3.X 1 and X 2 may be independently N or CR 2 a compound of Formula 1 or embodiment 1, wherein:

[0060] Embodiment 3a.X 1 and X 2 Both of these are CR 2 The compound of embodiment 3, wherein

[0061] Embodiment 3b.X 1 is N and X 2 but, CR 2 The compound of embodiment 3, wherein

[0062] Embodiment 3c.X 1 But, CR 2 and X 2 is N.

[0063] Embodiment 3d.X 1 and X 2 and R are N.

[0064] R 1a Embodiment 4.R 1a is H, halogen, cyano, nitro, amino, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C1-C6 hydroxyalkyl, C3-C7 hydroxycycloalkyl, C1-C6 hydroxyhaloalkyl, C4-C8 alkoxycycloalkyl, C2-C7 alkoxyhaloalkyl, C2-C6 oxacycloalkyl, C3-C7 oxacycloalkylalkyl, C2-C6 haloalkenyl, C2-C 6 haloalkynyl, C3-C7 halocycloalkyl, C4-C7 haloalkylcycloalkyl, C2-C7 alkoxyalkyl, C2-C7 haloalkoxyalkyl, C1-C7 alkoxy, C2-C5 alkenyloxy, C2-C5 alkynyloxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl, C1-C7 haloalkoxy, C1-C7 alkylthio, C2-C7 alkylthioalkyl, C1-C5 alkylsulfinyl, C1-C5 alkylsulfonyl, or C1-C5 haloalkylthio.

[0065] Embodiment 4a.R 1a is H, halogen, cyano, nitro, amino, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C1-C6 hydroxyalkyl, C3-C7 hydroxycycloalkyl, C1-C6 hydroxyhaloalkyl, C4-C8 alkoxycycloalkyl, C2-C7 alkoxyhaloalkyl, C2-C6 oxacycloalkyl The compound of embodiment 4, wherein the alkyl group is C-C oxacycloalkylalkyl, C-C haloalkenyl, C-C haloalkynyl, C-C halocycloalkyl, C-C haloalkylcycloalkyl, C-C alkoxyalkyl, C-C haloalkoxyalkyl, C-C alkoxy, C-C alkenyloxy, C-C alkynyloxy, C-C cycloalkoxy, C-C cycloalkoxyalkyl, or C-C haloalkoxy.

[0066] Embodiment 4b.R 1a is H, halogen, cyano, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C1-C6 hydroxyalkyl, C3-C7 hydroxycycloalkyl, C1-C6 hydroxyhaloalkyl, C4-C8 alkoxycycloalkyl, C2-C7 alkoxyhaloalkyl, C2-C6 oxacycloalkyl, C3- The compound of embodiment 4a, which is C7 oxacycloalkylalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C7 halocycloalkyl, C4-C7 haloalkylcycloalkyl, C2-C7 alkoxyalkyl, C2-C7 haloalkoxyalkyl, C1-C7 alkoxy, C2-C5 alkenyloxy, C2-C5 alkynyloxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl or C1-C7 haloalkoxy.

[0067] Embodiment 4c.R1a A compound of embodiment 4b wherein is H, halogen, cyano, C1-C7 alkyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C7 haloalkyl, C1-C6 hydroxyalkyl, C3-C7 hydroxycycloalkyl, C1-C6 hydroxyhaloalkyl, C4-C8 alkoxycycloalkyl, C2-C7 alkoxyhaloalkyl, C2-C6 oxacycloalkyl, C3-C7 oxacycloalkylalkyl, C3-C7 halocycloalkyl, C4-C7 haloalkylcycloalkyl, C2-C7 alkoxyalkyl, C2-C7 haloalkoxyalkyl, C1-C7 alkoxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl or C1-C7 haloalkoxy.

[0068] Embodiment 4d.R 1a A compound of embodiment 4c, wherein is H, halogen, cyano, C1-C7 alkyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C4 hydroxyalkyl, C3-C5 hydroxycycloalkyl, C2-C6 oxacycloalkyl, C3-C7 halocycloalkyl, C2-C7 alkoxyalkyl, C1-C7 alkoxy, C3-C7 cycloalkoxy, or C4-C7 cycloalkoxyalkyl.

[0069] Embodiment 4e.R 1a A compound of embodiment 4d, wherein is H, Me, Et, i-Pro, i-Bu, Bu, t-Bu, Br, cyano, c-Bu, c-Pen, c-Hex, HOCH2, HOC(Me)2, CHOMe, CHO-i-Pro, CHCHOMe, CH2-c-Hex, or 3-oxetanyl.

[0070] Embodiment 4f.R 1a The compound of embodiment 4d, wherein is H.

[0071] Embodiment 4g.R 1a The compound of embodiment 4d, wherein is C1-C7 alkyl.

[0072] Embodiment 4h.R 1aThe compound of embodiment 4g, wherein is Et,i-Pro or t-Bu.

[0073] Embodiment 4i.R 1a A compound of embodiment 4d, wherein is C3-C7 cycloalkyl.

[0074] Embodiment 4j.R 1a The compound of embodiment 4i, wherein is c-Bu.

[0075] Embodiment 4k.R 1a The compound of embodiment 4g, wherein is Me.

[0076] Embodiment 4l.R 1ais H, halogen, cyano, nitro, amino, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C1-C6 hydroxyalkyl, C3-C7 hydroxycycloalkyl, C1-C6 hydroxyhaloalkyl, C4-C8 alkoxycycloalkyl, C2-C7 alkoxyhaloalkyl, C2-C6 oxacycloalkyl, C3-C7 oxacycloalkylalkyl, C3-C7 alkyloxacycloalkyl alkyl, C2-C6 thiacycloalkyl, C3-C7 thiacycloalkylalkyl, C3-C7 alkylthiacycloalkyl, C2-C6(O-thia)cycloalkyl, C3-C7(O-thia)cycloalkylalkyl, C3-C7 alkyl(O-thia)cycloalkyl, C2-C6(O2thia)cycloalkyl, C3-C7(O2thia)cycloalkylalkyl, C3-C7 alkyl(O2thia)cycloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C7 halocycloalkyl, C4-C7 haloalkylcycloalkyl , C2-C7 alkoxyalkyl, C2-C7 haloalkoxyalkyl, C1-C7 alkoxy, C2-C5 alkenyloxy, C2-C5 alkynyloxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl, C1-C7 haloalkoxy, C1-C7 alkylthio, C2-C7 alkylthioalkyl, C1-C5 alkylsulfinyl, C1-C5 alkylsulfonyl, C1-C4 alkylsulfonate, C1-C5 haloalkylthio, C1-C5 haloalkylsulfinyl, C1-C5 haloalkylsulfonyl, C2-C7 alkenyloxy, C2-C5 alkynyloxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl, C1-C7 haloalkoxy, C1-C7 alkylthio, C2-C7 alkylthioalkyl, C1-C5 alkylsulfinyl, C1-C5 ... alkylsulfonylalkyl, C2-C7 alkylsulfonylalkyl, C2-C7 haloalkylthioalkyl, C2-C7 haloalkylsulfinylalkyl, C2-C7 haloalkylsulfonylalkyl, C4-C7 alkylthiocycloalkyl, C4-C7 alkylsulfinylcycloalkyl, C4-C7 alkylsulfonylcycloalkyl, C4-C7 haloalkylthiocycloalkyl, C2-C7 haloalkylsulfinylcycloalkyl, C2-C7 haloalkylsulfonylcycloalkyl, C2-C7 alkylsulfoximinoalkyl,or a compound of Formula 1 or embodiment 1 which is C2-C5 cyanoalkyl, C4-C7 cyanocycloalkyl, C1-C4 nitroalkyl, C1-C7 alkylamino, C2-C7 dialkylamino, C3-C5 alkylcarbonyl(alkyl)amino, C3-C5 alkoxycarbonyl(alkyl)amino, C2-C4 alkylsulfonyl(alkyl)amino, C2-C6 alkylcarbonyl, C3-C6 alkylcarbonylalkyl, C2-C6 alkoxycarbonyl, C3-C6 alkoxycarbonylalkyl, C3-C6 trialkylsilyl, or C5-C8 trialkylsilylalkynyl; or phenyl optionally substituted with up to three substituents independently selected from the group consisting of halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, and C1-C2 haloalkoxy.

[0077] R 1b Embodiment 5.R 1b is H, halogen, cyano, nitro, C1-C4 alkyl, C3-C5 cycloalkyl, C1-C4 haloalkyl, C3-C5 halocycloalkyl, C2-C4 alkoxyalkyl, C1-C4 alkoxy, C1-C4 alkylthio, or C2-C4 alkoxycarbonyl.

[0078] Embodiment 5a.R 1b The compound of embodiment 5, wherein is H, halogen, cyano, C1-C4 alkyl, C3-C5 cycloalkyl, C1-C4 haloalkyl, C3-C5 halocycloalkyl, C2-C4 alkoxyalkyl, C1-C4 alkoxy, or C2-C4 alkoxycarbonyl.

[0079] Embodiment 5b.R 1b A compound of embodiment 5a, wherein is H, halogen, cyano, C1-C4 alkyl, C3-C5 cycloalkyl, C1-C4 haloalkyl, C2-C4 alkoxyalkyl, or C2-C4 alkoxycarbonyl.

[0080] Embodiment 5c.R 1bA compound of embodiment 5b, wherein is H, Me, i-Pro, CN, CF3, F, or Cl.

[0081] Embodiment 5d.R 1b A compound of embodiment 5c, wherein is H.

[0082] m Embodiment 6. A compound of Formula 1 or Embodiment 1 wherein m is 0, 1, or 2.

[0083] The compound of embodiment 6, wherein a.m is 0.

[0084] The compound of embodiment 6, wherein b.m is 1.

[0085] The compound of embodiment 6, wherein c.m is 2.

[0086] R 1c Embodiment 7.R 1c is C1-C7 alkyl, C3-C7 cycloalkyl, or C1-C7 haloalkyl.

[0087] Embodiment 7a.R 1c The compound of embodiment 7, wherein is H or C1-C7 alkyl.

[0088] Embodiment 7b.R 1c A compound of embodiment 7a, wherein is H, Me or i-Pro.

[0089] Embodiment 7c.R 1c The compound of embodiment 7b, wherein is H.

[0090] Embodiment 7d.R 1c The compound of embodiment 7b, wherein is Me.

[0091] Embodiment 7e.R 1c The compound of embodiment 7b, wherein is i-Pro.

[0092] n Embodiment 8. A compound of Formula 1 or Embodiment 1 wherein n is 0, 1, 2 or 3.

[0093] Embodiment 8a. The compound of embodiment 8, wherein n is 0.

[0094] Embodiment 8b. The compound of embodiment 8, wherein n is 1.

[0095] Embodiment 8c. The compound of embodiment 8, wherein n is 2.

[0096] Embodiment 8d. The compound of embodiment 8, wherein n is 3.

[0097] R 2 Embodiment 9.R 2 are independently H, halogen, cyano, nitro, hydroxy, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C2-C5 alkenyloxy, C2-C5 alkynyloxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl, C3-C6 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C5 haloalkyl, C2-C5 haloalkenyl, C2-C5 haloalkynyl, C2-C5 alkoxyalkyl, C2-C5 haloalkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonate, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C2-C5 alkoxycarbonyl; or Two adjacent R 2 may combine to form a 5- or 6-membered ring containing carbon atoms and optionally 1-2 oxygen, sulfur, or nitrogen atoms as ring members, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, and C1-C4 haloalkoxy.

[0098] Embodiment 9a.R 2 are independently H, halogen, cyano, nitro, hydroxy, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C2-C5 alkenyloxy, C2-C5 alkynyloxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl, C3-C6 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C5 haloalkyl, C2-C5 haloalkenyl, C2-C5 haloalkynyl, C2- The compound of embodiment 9, which is C5 alkoxyalkyl, C2-C5 haloalkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfonate, or C2-C5 alkoxycarbonyl.

[0099] Embodiment 9a.R 2 are independently H, halogen, cyano, OH, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C2-C5 alkenyloxy, C2-C5 alkynyloxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl, C3-C6 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C5 haloalkyl, C2-C5 haloalkenyl, C2-C5 haloalkynyl, C2-C5 alkoxyalkyl, C2-C5 haloalkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy.

[0100] Embodiment 9b.R 2 are independently H, halogen, cyano, OH, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C5 haloalkyl, C2-C5 alkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy.

[0101] Embodiment 9c.R 2 A compound of embodiment 9a, wherein is independently H, halogen, cyano, OH, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C1-C5 haloalkyl, C1-C5 alkoxy, or C1-C5 haloalkoxy.

[0102] Embodiment 9d.R 2 A compound of embodiment 9c, wherein is independently H, C1-C5 alkyl, or C1-C5 alkoxy.

[0103] Embodiment 9d.R 2 is independently H, OH, CN, OEt, propargyl, allyl, c-Pro, F, Cl, Br, CN, Me, Et, OMe, CF3, OCF3, or CH2CF3.

[0104] Embodiment 9e.R 2 A compound of embodiment 9d, wherein is independently H, Me, or Et.

[0105] Embodiment 9f.R 2 is independently H. A compound of embodiment 9e.

[0106] Embodiment 9g.R 2 The compound of embodiment 9f, wherein is independently Me.

[0107] Embodiment 9h.R 2 The compound of embodiment 9g, wherein is independently Et.

[0108] Embodiment 9i. Two adjacent R 2 may combine to form a 5- or 6-membered ring containing carbon atoms and optionally 1-2 oxygen, sulfur, or nitrogen atoms as ring members, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, and C1-C4 haloalkoxy.

[0109] Embodiment 9j. Each R 2 are independently H, halogen, cyano, nitro, hydroxy, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C2-C5 alkenyloxy, C2-C5 alkynyloxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl, C3-C6 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C5 haloalkyl, C2-C5 haloalkenyl, C2-C5 haloalkynyl, C2-C5 alkoxyalkyl, C2-C5 haloalkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylsulfonate, C3-C5 cycloalkylsulfonate, C1-C4 haloalkylsulfonate, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C2-C5 cyanoalkyl, C4-C6 cyanocycloalkyl or C2-C5 alkoxycarbonyl; or Two adjacent R 2 may combine to form a saturated or unsaturated 5-8 membered ring containing carbon atoms and optionally 1-3 oxygen, sulfur, or nitrogen atoms as ring members, wherein one or two carbon or sulfur ring members of the heterocycle may optionally be present in the oxidized form of a carbonyl, sulfonyl, sulfinyl moiety, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, and C1-C4 haloalkoxy.

[0110] Embodiment 9k.R 2may combine to form a saturated or unsaturated 5-8 membered ring containing carbon atoms and optionally 1-3 oxygen, sulfur, or nitrogen atoms as ring members, wherein one or two carbon or sulfur ring members of the heterocycle may optionally be present in the oxidized form of a carbonyl, sulfonyl, sulfinyl moiety, and said ring is unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, and C1-C4 haloalkoxy.

[0111] Embodiment 9l.R 2 may combine to form a 5- or 6-membered ring containing up to two oxygen atoms as ring members.

[0112] Y Embodiment 10. A compound of Formula 1 or Embodiment 1 wherein Y is O or S.

[0113] Embodiment 10a. The compound of embodiment 10, wherein Y is O.

[0114] Embodiment 10b. The compound of Embodiment 10, wherein Y is S.

[0115] R 3a Embodiment 11.R 3ais halogen, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C7 alkoxy, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C7 halocycloalkyl, C4-C7 haloalkylcycloalkyl, C2-C7 alkoxyalkyl, C2-C7 haloalkoxyalkyl, C2-C7 alkylthioalkyl, C2-C7 haloalkylthioalkyl, C2-C5 cyanoalkyl, C4-C7 cyanocycloalkyl, C1-C4 nitroalkyl, C3-C6 alkylcarbonylalkyl, C2-C6 oxacycloalkyl, C3-C7 cycloalkoxy, or C3-C6 alkoxycarbonylalkyl.

[0116] Embodiment 11a.R 3a is halogen, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C7 alkoxy, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C7 halocycloalkyl, C4-C7 haloalkylcycloalkyl, C2-C7 alkoxyalkyl, or C2-C7 haloalkoxyalkyl.

[0117] Embodiment 11b.R 3a The compound of embodiment 11a, wherein is C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C7 alkoxy, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C3-C7 halocycloalkyl, C2-C7 alkoxyalkyl, or C2-C7 haloalkoxyalkyl.

[0118] Embodiment 11c.R 3a A compound of embodiment 11b, wherein is C1-C7 alkyl, C3-C7 cycloalkyl, C1-C7 haloalkyl, or C2-C7 alkoxyalkyl.

[0119] Embodiment 11d.R 3a A compound of embodiment 11c, wherein is Me, Et, Pro, i-Pro, CF3, CH2F or CH2OMe.

[0120] Embodiment 11e.R 3a The compound of embodiment 11d, wherein is Me.

[0121] Embodiment 11f.R 3a is halogen, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C7 alkoxy, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C7 halocycloalkyl, C4-C7 haloalkylcycloalkyl, C2-C7 alkoxyalkyl, C2-C7 haloalkoxyalkyl, C2-C7 alkylthioalkyl, C2-C7 alkylsulfinylalkyl, C2-C7 The compound of Formula 1 or Embodiment 1 is alkylsulfonylalkyl, C2-C7 haloalkylthioalkyl, C2-C7 haloalkylsulfinylalkyl, C2-C7 haloalkylsulfonylalkyl, C2-C5 cyanoalkyl, C4-C6 cyanocycloalkyl, C1-C4 nitroalkyl, C3-C6 alkylcarbonylalkyl, C2-C6 oxacycloalkyl, C2-C6 oxacycloalkylalkyl, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl, or C3-C6 alkoxycarbonylalkyl.

[0122] Embodiment 11g.R 3a A compound of embodiment 11f, wherein is halogen or C1-C7 alkyl.

[0123] Embodiment 11h.R 3a The compound of embodiment 11g, wherein is F, Cl or Me.

[0124] R 3b Embodiment 12.R 3bThe compound of Formula 1 or Embodiment 1, wherein is H or halogen.

[0125] Embodiment 12a.R 3b is H.

[0126] Embodiment 12b.R 3b 13. The compound of embodiment 12, wherein is halogen.

[0127] Embodiment 12c.R 3b are independently H, halogen, or C1-C3 alkyl; or R 3a and R 3b together with the carbon atoms to which they are attached form a 3- to 7-membered ring containing carbon atoms and ring members selected from one oxygen atom, one sulfur atom, and up to three heteroatoms independently selected from one nitrogen atom, wherein up to two carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring members are selected from S, S(O), or S(O)2; or The Two R's 3b together with the carbon atoms to which they are attached form a 3- to 7-membered ring containing ring members selected from carbon atoms and up to three heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to three nitrogen atoms, wherein up to two carbon atom ring members are independently selected from C(═O) and C(═S), and the sulfur atom ring members are selected from S, S(O), or S(O).

[0128] p Embodiment 13. A compound of Formula 1 or Embodiment 1 wherein p is 0, 1, 2 or 3.

[0129] Embodiment 13a. The compound of embodiment 13, wherein p is 0.

[0130] The compound of embodiment 13, wherein p is 1.

[0131] Embodiment 13c. The compound of embodiment 13, wherein p is 2.

[0132] Embodiment 13d. The compound of embodiment 13, wherein p is 3.

[0133] R 4a Embodiment 14.R 4a is H, halogen, cyano, nitro, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C1-C5 haloalkyl, C2-C5 haloalkenyl, C2-C5 haloalkynyl, C2-C5 alkoxyalkyl, C2-C5 haloalkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C3-C6 trialkylsilyl, C5-C8 trialkylsilylalkynyl, C1-C5 alkylthio, C1-C5 haloalkylthio, or C2-C5 alkoxycarbonyl.

[0134] Embodiment 14a.R 4a is H, halogen, cyano, nitro, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C1-C5 haloalkyl, C2-C5 haloalkenyl, C2-C5 haloalkynyl, C2-C5 alkoxyalkyl, C2-C5 haloalkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C3-C6 trialkylsilyl, or C5-C8 trialkylsilylalkynyl.

[0135] Embodiment 14b.R 4a The compound of embodiment 14a, wherein is H, halogen, cyano, nitro, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C1-C5 haloalkyl, C2-C5 haloalkenyl, C2-C5 haloalkynyl, C2-C5 alkoxyalkyl, C2-C5 haloalkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C3-C6 trialkylsilyl, or C5-C8 trialkylsilylalkynyl.

[0136] Embodiment 14c.R 4aThe compound of embodiment 14b, wherein is H, halogen, cyano, NO2, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C1-C5 haloalkyl, C2-C5 alkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C3-C6 trialkylsilyl, or C5-C8 trialkylsilylalkynyl.

[0137] Embodiment 14d.R 4a A compound of embodiment 14c, wherein is H, halogen, cyano, NO2, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, or C5-C8 trialkylsilylalkynyl.

[0138] Embodiment 14e.R 4a A compound of embodiment 14d, wherein is H, CN, NO2, F, Cl, Br, Me, Et, CF3, CH2F, OCF3, OMe, CHOMe, CH=CH2, C≡CSiMe3, C≡CH or c-Pro.

[0139] Embodiment 14f.R 4a A compound of embodiment 14e, wherein is H, F, Cl, Br, Me, Et, CF3, OCF3, OMe, CHOMe, CH=CH2, C≡CH, or c-Pro.

[0140] Embodiment 14g.R 4a A compound of embodiment 14e, wherein is Cl or Me.

[0141] R 4b Embodiment 15.R 4b A compound of Formula 1 or Embodiment 1, wherein is H, halogen, cyano, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, or C1-C4 alkylthio.

[0142] Embodiment 15a.R 4bThe compound of embodiment 15, wherein is H, halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy.

[0143] Embodiment 15b.R 4b A compound of embodiment 15a, wherein is H or halogen.

[0144] Embodiment 15c.R 4b A compound of embodiment 15b, wherein is H, F or Cl.

[0145] Embodiment 15d.R 4b is H. A compound of embodiment 15c.

[0146] Embodiment 15e.R 4b is F.

[0147] Embodiment 15f.R 4b The compound of embodiment 15c, wherein is Cl.

[0148] q Embodiment 16. A compound of Formula 1 or Embodiment 1 wherein q is 0, 1 or 2.

[0149] The compound of embodiment 16, wherein q is 0.

[0150] The compound of embodiment 16, wherein embodiment 16b.q is 1.

[0151] Embodiment 16c. The compound of embodiment 16, wherein q is 2.

[0152] Embodiment 17. A compound of Formula 1 or Embodiment 1, wherein the stereochemistry of the carbon atom bearing * is (1'), depicted below as Formula 1'. [ka]

[0153] Embodiment 18. A compound of Formula 1 or Embodiment 1, wherein the stereochemistry of the carbon atom bearing * is (1″), depicted below as Formula 1″. [ka]

[0154] Embodiment 19. A is A-1 and X 1 is CH and X 2 is CH and R 1a is H and R 1b is H, and (R 2 ) n is 2-Me, and R 3a is (1')-Me, and (R 3b ) p is H and R 4a is Cl, (R 4b ) q The compound of embodiment 1 other than a compound of formula 1 or formula 1, wherein is H (ie, compound 40).

[0155] Embodiment 20. A is A-1 and X 1 is CH and X 2 is CH and R 1a is H and R 1b is i-Pro, (R 2 ) n is H and R 3a is (1')-Me, and (R 3b ) p is H and R 4a is Me, and (R 4b ) q The compound of embodiment 1 other than a compound of formula 1 or formula 1, wherein is H (ie, compound 56).

[0156] Embodiment 21. A is A-1 and X 1 is CH and X 2 is CH and R 1a is CH2c-Hex, and R 1b is H, and (R 2 ) n is H and R3a is (1')-Me, and (R 3b ) p is H and R 4a is Cl, (R 4b ) q The compound of embodiment 1 other than a compound of formula 1 or formula 1, wherein is H (ie, compound 90).

[0157] Embodiments of the invention, including embodiments 1-21 above and any other embodiments described herein, can be combined in any manner, and the descriptions of the variables in the embodiments relate not only to compounds of Formula 1, but also to starting compounds and intermediate compounds useful for preparing compounds of Formula 1. Additionally, embodiments of the invention, including embodiments 1-12a above and any other embodiments described herein, and any combination thereof, relate to the compositions and methods of the invention.

[0158] Combinations of embodiments 1 to 21 are exemplified below.

[0159] Embodiment X. A compound of Formula 1 as described in the Summary of the Invention, A is A-1, A-2, A-3, A-4, A-5, A-7, A-8, A-9, A-10, A-11, A-12 or A-13; X 1 and X 2 may be independently N or CR 2 A compound.

[0160] Embodiment XX. A compound of Embodiment X wherein A is A-1.

[0161] Embodiment A. X 1 and X 2 Both of these are CR 2 and; R 1ais H, halogen, cyano, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C2-C6 oxacycloalkyl, C3-C7 oxacycloalkylalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C7 halocycloalkyl, C4-C7 haloalkylcycloalkyl, C2-C7 alkoxyalkyl, C2-C7 haloalkoxyalkyl, C1-C7 alkoxy, C2-C5 alkenyloxy, C2-C5 alkynyloxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl or C1-C7 haloalkoxy; R 1b is H, halogen, cyano, C1-C4 alkyl, C3-C5 cycloalkyl, C1-C4 haloalkyl, C3-C5 halocycloalkyl, C2-C4 alkoxyalkyl, C1-C4 alkoxy or C2-C4 alkoxycarbonyl; R 2 are independently H, halogen, cyano, nitro, hydroxy, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C2-C5 alkenyloxy, C2-C5 alkynyloxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl, C3-C6 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C5 haloalkyl, C2-C5 haloalkenyl, C2-C5 haloalkynyl, C2-C5 alkoxyalkyl, C2-C5 haloalkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonate, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C2-C5 alkoxycarbonyl; R 3ais halogen, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C7 alkoxy, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C7 halocycloalkyl, C4-C7 haloalkylcycloalkyl, C2-C7 alkoxyalkyl, C2-C7 haloalkoxyalkyl, C2-C7 alkylthioalkyl, C2-C7 haloalkylthioalkyl, C2-C5 cyanoalkyl, C1-C4 nitroalkyl, C3-C6 alkylcarbonylalkyl, C2-C6 oxacycloalkyl, C3-C7 cycloalkoxy or C3-C6 alkoxycarbonylalkyl; R 3b is H or a halogen; R 4a is H, halogen, cyano, nitro, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C1-C5 haloalkyl, C2-C5 haloalkenyl, C2-C5 haloalkynyl, C2-C5 alkoxyalkyl, C2-C5 haloalkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C3-C6 trialkylsilyl or C5-C8 trialkylsilylalkynyl; R 4b A compound of Embodiment XX wherein is H, halogen, cyano, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, or C1-C4 alkylthio.

[0162] Embodiment A1. R 1a is H, halogen, cyano, C1-C7 alkyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C7 haloalkyl, C2-C6 oxacycloalkyl, C3-C7 oxacycloalkylalkyl, C3-C7 halocycloalkyl, C4-C7 haloalkylcycloalkyl, C2-C7 alkoxyalkyl, C2-C7 haloalkoxyalkyl, C1-C7 alkoxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl or C1-C7 haloalkoxy; R 1b is H, halogen, cyano, C1-C4 alkyl, C3-C5 cycloalkyl, C1-C4 haloalkyl, C2-C4 alkoxyalkyl or C2-C4 alkoxycarbonyl; R 2 are independently H, halogen, cyano, OH, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C2-C5 alkenyloxy, C2-C5 alkynyloxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl, C3-C6 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C5 haloalkyl, C2-C5 haloalkenyl, C2-C5 haloalkynyl, C2-C5 alkoxyalkyl, C2-C5 haloalkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy; R 3a is halogen, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C7 alkoxy, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C7 halocycloalkyl, C4-C7 haloalkylcycloalkyl, C2-C7 alkoxyalkyl or C2-C7 haloalkoxyalkyl; R 4a is H, halogen, cyano, NO2, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, or C5-C8 trialkylsilylalkynyl; R 4b A compound of embodiment A wherein is H, halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy.

[0163] Embodiment A2. R 1ais H, halogen, cyano, C1-C7 alkyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C6 oxacycloalkyl, C3-C7 halocycloalkyl, C2-C7 alkoxyalkyl, C1-C7 alkoxy, C3-C7 cycloalkoxy or C4-C7 cycloalkoxyalkyl; R 1b is H, halogen, cyano, C1-C4 alkyl, C3-C5 cycloalkyl, C1-C4 haloalkyl, C2-C4 alkoxyalkyl or C2-C4 alkoxycarbonyl; R 2 are independently H, halogen, cyano, OH, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C1-C5 haloalkyl, C1-C5 alkoxy or C1-C5 haloalkoxy; R 3a is C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C7 alkoxy, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C3-C7 halocycloalkyl, C2-C7 alkoxyalkyl or C2-C7 haloalkoxyalkyl; R 4b A compound of embodiment A1, wherein is H or halogen.

[0164] Embodiment A3. R 1a is H, Me, Et, i-Pro, i-Bu, Bu, t-Bu, Br, cyano, c-Bu, c-Pen, c-Hex, CHOMe, CHO-i-Pro, CHCHOMe, CH-c-Hex or 3-oxetanyl; R 1b is H, Me, i-Pro, CN, CF3, F or Cl, R 2 are independently H, OH, CN, OEt, propargyl, allyl, c-Pro, F, Cl, Br, CN, Me, Et, OMe, CF3, OCF3, or CH2CF3; R 3ais Me, Et, Pro, i-Pro, CF3, CH2F or CHOMe, R 4a A compound of embodiment A2, wherein is H, CN, NO2, F, Cl, Br, Me, Et, CF3, CH2F, OCF3, OMe, CHOMe, CH=CH2, C≡CSiMe3, C≡CH or c-Pro.

[0165] Embodiment B. X 1 is N and X 2 But, CR 2 and R 1a is H, halogen, cyano, C1-C7 alkyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C6 oxacycloalkyl, C3-C7 halocycloalkyl, C2-C7 alkoxyalkyl, C1-C7 alkoxy, C3-C7 cycloalkoxy or C4-C7 cycloalkoxyalkyl; R 1b is H, halogen, cyano, C1-C4 alkyl, C3-C5 cycloalkyl, C1-C4 haloalkyl, C2-C4 alkoxyalkyl or C2-C4 alkoxycarbonyl; R 2 are independently H, halogen, cyano, OH, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C1-C5 haloalkyl, C1-C5 alkoxy or C1-C5 haloalkoxy; R 3a is C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C7 alkoxy, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C3-C7 halocycloalkyl, C2-C7 alkoxyalkyl or C2-C7 haloalkoxyalkyl; R 3b is H or a halogen; R 4ais H, halogen, cyano, NO2, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, or C5-C8 trialkylsilylalkynyl; R 4b A compound of Embodiment XX, wherein is H or halogen.

[0166] Embodiment B1. R 1a But H; R 1b But H; R 2 are independently H, C1-C5 alkyl, or C1-C5 alkoxy; R 3a is C1-C7 alkyl, C3-C7 cycloalkyl, C1-C7 haloalkyl or C2-C7 alkoxyalkyl, R 3b is H or a halogen, R 4a is H, halogen, cyano, NO2, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy or C5-C8 trialkylsilylalkynyl; R 4b A compound of embodiment B wherein is H, halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy.

[0167] Embodiment C. X 1 But, CR 2 and X 2 is N; R 1a is H, halogen, cyano, C1-C7 alkyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C6 oxacycloalkyl, C3-C7 halocycloalkyl, C2-C7 alkoxyalkyl, C1-C7 alkoxy, C3-C7 cycloalkoxy or C4-C7 cycloalkoxyalkyl; R 1bis H, halogen, cyano, C1-C4 alkyl, C3-C5 cycloalkyl, C1-C4 haloalkyl, C2-C4 alkoxyalkyl or C2-C4 alkoxycarbonyl; R 2 are independently H, halogen, cyano, OH, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C1-C5 haloalkyl, C1-C5 alkoxy or C1-C5 haloalkoxy; R 3a is C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C7 alkoxy, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C3-C7 halocycloalkyl, C2-C7 alkoxyalkyl or C2-C7 haloalkoxyalkyl; R 3b is H or a halogen; R 4a is H, halogen, cyano, NO2, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, or C5-C8 trialkylsilylalkynyl; R 4b A compound of Embodiment XX, wherein is H or halogen.

[0168] Certain embodiments include compounds of Formula 1 selected from the group consisting of: [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][2-methyl-5-[3-(1-methylethyl)-1H-1,2,4-triazol-1-yl]phenyl]methanone (compound 73); [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][5-[3-(1,1-dimethylethyl)-1H-1,2,4-triazol-1-yl]-2-methylphenyl]methanone (compound 76); [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][2-methoxy-5-[3-(1-methylethyl)-1H-1,2,4-triazol-1-yl]phenyl]methanone (compound 84); [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][5-(3-ethyl-1H-1,2,4-triazol-1-yl)-2-methoxyphenyl]methanone (compound 88); [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][2-ethyl-5-[3-(1-methylethyl)-1H-1,2,4-triazol-1-yl]phenyl]methanone (compound 94); [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][5-(3-cyclobutyl-1H-1,2,4-triazol-1-yl)-2-methylphenyl]methanone (compound 96); [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][3-(3-cyclobutyl-1H-1,2,4-triazol-1-yl)phenyl]methanone (compound 93); [(2S)-2,3-Dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl][2-methoxy-5-(1H-1,2,4-triazol-1-yl)phenyl]methanone (Compound 63)

[0169] Embodiment S. A compound of Formula 1 as described in the Summary of the Disclosure, A, [ka] [ka] [ka] A compound selected from:

[0170] Embodiment S1. The compound of embodiment S, wherein A is A-1, A-4, A-5, A-12, A-14, A-15, or A-17.

[0171] Embodiment S2. The compound of embodiment S, wherein A is A-1.

[0172] Embodiment S3. X 1 and X 2 Both of these are CR 2 and; R 1a is H, halogen, cyano, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C1-C6 hydroxyalkyl, C3-C7 hydroxycycloalkyl, C1-C6 hydroxyhaloalkyl, C4-C8 alkoxycycloalkyl, C2-C7 alkoxyhaloalkyl, C2-C6 oxacycloalkenyl alkyl, C3-C7 oxacycloalkylalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C7 halocycloalkyl, C4-C7 haloalkylcycloalkyl, C2-C7 alkoxyalkyl, C2-C7 haloalkoxyalkyl, C1-C7 alkoxy, C2-C5 alkenyloxy, C2-C5 alkynyloxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl or C1-C7 haloalkoxy; R 1b is H, halogen, cyano, C1-C4 alkyl, C3-C5 cycloalkyl, C1-C4 haloalkyl, C3-C5 halocycloalkyl, C2-C4 alkoxyalkyl, C1-C4 alkoxy or C2-C4 alkoxycarbonyl; R 2are independently H, halogen, cyano, nitro, hydroxy, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C2-C5 alkenyloxy, C2-C5 alkynyloxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl, C3-C6 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C5 haloalkyl, C2-C5 haloalkenyl, C2-C5 haloalkynyl, C2-C5 alkoxyalkyl, C2-C5 haloalkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonate, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C2-C5 alkoxycarbonyl; R 3a is halogen, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C7 alkoxy, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C7 halocycloalkyl, C4-C7 haloalkylcycloalkyl, C2-C7 alkoxyalkyl, C2-C7 haloalkoxyalkyl, C2-C7 alkylthioalkyl, C2-C7 haloalkylthioalkyl, C2-C5 cyanoalkyl, C1-C4 nitroalkyl, C3-C6 alkylcarbonylalkyl, C2-C6 oxacycloalkyl, C3-C7 cycloalkoxy or C3-C6 alkoxycarbonylalkyl; R 3b is H or a halogen; R 4a is H, halogen, cyano, nitro, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C1-C5 haloalkyl, C2-C5 haloalkenyl, C2-C5 haloalkynyl, C2-C5 alkoxyalkyl, C2-C5 haloalkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C3-C6 trialkylsilyl or C5-C8 trialkylsilylalkynyl; R 4b The compound of embodiment S2, wherein is independently H, halogen, cyano, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, or C1-C4 alkylthio.

[0173] Embodiment S4. R 1a is H, halogen, cyano, C1-C7 alkyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C7 haloalkyl, C1-C6 hydroxyalkyl, C3-C7 hydroxycycloalkyl, C1-C6 hydroxyhaloalkyl, C4-C8 alkoxycycloalkyl, C2-C7 alkoxyhaloalkyl, C2-C6 oxacycloalkyl, C3-C7 oxacycloalkylalkyl, C3-C7 halocycloalkyl, C4-C7 haloalkylcycloalkyl, C2-C7 alkoxyalkyl, C2-C7 haloalkoxyalkyl, C1-C7 alkoxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl or C1-C7 haloalkoxy; R 1b is H, halogen, cyano, C1-C4 alkyl, C3-C5 cycloalkyl, C1-C4 haloalkyl, C2-C4 alkoxyalkyl or C2-C4 alkoxycarbonyl; R 2 are independently H, halogen, cyano, OH, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C2-C5 alkenyloxy, C2-C5 alkynyloxy, C3-C7 cycloalkoxy, C4-C7 cycloalkoxyalkyl, C3-C6 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C5 haloalkyl, C2-C5 haloalkenyl, C2-C5 haloalkynyl, C2-C5 alkoxyalkyl, C2-C5 haloalkoxyalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy; R 3ais halogen, C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C7 alkoxy, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C7 halocycloalkyl, C4-C7 haloalkylcycloalkyl, C2-C7 alkoxyalkyl or C2-C7 haloalkoxyalkyl; R 4a is H, halogen, cyano, NO2, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, or C5-C8 trialkylsilylalkynyl; R 4b The compound of embodiment S3, wherein is H, halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy.

[0174] Embodiment S5. R 1a is H, halogen, cyano, C1-C7 alkyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C6 hydroxyalkyl, C3-C7 hydroxycycloalkyl, C1-C6 hydroxyhaloalkyl, C4-C8 alkoxycycloalkyl, C2-C7 alkoxyhaloalkyl, C2-C6 oxacycloalkyl, C3-C7 halocycloalkyl, C2-C7 alkoxyalkyl, C1-C7 alkoxy, C3-C7 cycloalkoxy or C4-C7 cycloalkoxyalkyl; R 1b is H, halogen, cyano, C1-C4 alkyl, C3-C5 cycloalkyl, C1-C4 haloalkyl, C2-C4 alkoxyalkyl or C2-C4 alkoxycarbonyl; R 2 are independently H, halogen, cyano, OH, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C1-C5 haloalkyl, C1-C5 alkoxy or C1-C5 haloalkoxy; R3a is C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C7 alkoxy, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C3-C7 halocycloalkyl, C2-C7 alkoxyalkyl or C2-C7 haloalkoxyalkyl; R 4b The compound of embodiment S4, wherein is H or halogen.

[0175] Embodiment S6. R 1a is H, Me, Et, i-Pro, i-Bu, Bu, t-Bu, Br, cyano, c-Bu, c-Pen, c-Hex, HOCH2, HOC(Me)2, CHOMe, CHO-i-Pro, CHCHOMe, CH2-c-Hex or 3-oxetanyl; R 1b is H, Me, i-Pro, CN, CF3, F or Cl; R 2 are independently H, OH, CN, OEt, propargyl, allyl, c-Pro, F, Cl, Br, CN, Me, Et, OMe, CF3, OCF3, or CH2CF3; R 3a is Me, Et, Pro, i-Pro, CF3, CH2F or CHOMe; R 4a The compound of embodiment S5, wherein is H, CN, NO2, F, Cl, Br, Me, Et, CF3, CH2F, OCF3, OMe, CHOMe, CH=CH2, C≡CSiMe3, C≡CH, or c-Pro.

[0176] Embodiment S7. X 1 is N and X 2 But, CR 2 and R 1ais H, halogen, cyano, C1-C7 alkyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C6 oxacycloalkyl, C3-C7 halocycloalkyl, C2-C7 alkoxyalkyl, C1-C7 alkoxy, C3-C7 cycloalkoxy or C4-C7 cycloalkoxyalkyl; R 1b is H, halogen, cyano, C1-C4 alkyl, C3-C5 cycloalkyl, C1-C4 haloalkyl, C2-C4 alkoxyalkyl or C2-C4 alkoxycarbonyl; R 2 are independently H, halogen, cyano, OH, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C1-C5 haloalkyl, C1-C5 alkoxy or C1-C5 haloalkoxy; R 3a is C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C7 alkoxy, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C3-C7 halocycloalkyl, C2-C7 alkoxyalkyl or C2-C7 haloalkoxyalkyl; R 3b is H or a halogen; R 4a is H, halogen, cyano, NO2, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, or C5-C8 trialkylsilylalkynyl; R 4b The compound of embodiment S2, wherein is H or halogen.

[0177] Embodiment S8. R 1a But H; R 1b But H; R 2 are independently H, C1-C5 alkyl, or C1-C5 alkoxy; R 3ais C1-C7 alkyl, C3-C7 cycloalkyl, C1-C7 haloalkyl or C2-C7 alkoxyalkyl, R 3b is H or a halogen, R 4a is H, halogen, cyano, NO2, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy or C5-C8 trialkylsilylalkynyl; R 4b The compound of embodiment S7, wherein is H, halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy.

[0178] Embodiment S9. X 1 But, CR 2 and X 2 is N; R 1a is H, halogen, cyano, C1-C7 alkyl, C3-C7 cycloalkyl, C4-C7 cycloalkylalkyl, C2-C6 oxacycloalkyl, C3-C7 halocycloalkyl, C2-C7 alkoxyalkyl, C1-C7 alkoxy, C3-C7 cycloalkoxy or C4-C7 cycloalkoxyalkyl; R 1b is H, halogen, cyano, C1-C4 alkyl, C3-C5 cycloalkyl, C1-C4 haloalkyl, C2-C4 alkoxyalkyl or C2-C4 alkoxycarbonyl; R 2 are independently H, halogen, cyano, OH, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C1-C5 haloalkyl, C1-C5 alkoxy or C1-C5 haloalkoxy; R 3ais C1-C7 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C7 alkoxy, C4-C7 cycloalkylalkyl, C4-C7 alkylcycloalkyl, C1-C7 haloalkyl, C3-C7 halocycloalkyl, C2-C7 alkoxyalkyl or C2-C7 haloalkoxyalkyl; R 3b is H or a halogen; R 4a is H, halogen, cyano, NO2, C1-C5 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C3-C5 cycloalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, or C5-C8 trialkylsilylalkynyl; R 4b The compound of embodiment S2, wherein is H or halogen.

[0179] Embodiment S10. R 2 may combine to form a 5- or 6-membered ring containing up to two oxygen atoms as ring members.

[0180] Embodiment S11. Certain embodiments include a compound of Formula 1 selected from the group consisting of: [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][2-methyl-5-[3-(1-methylethyl)-1H-1,2,4-triazol-1-yl]phenyl]methanone; [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][5-[3-(1,1-dimethylethyl)-1H-1,2,4-triazol-1-yl]-2-methylphenyl]methanone; [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][2-methoxy-5-[3-(1-methylethyl)-1H-1,2,4-triazol-1-yl]phenyl]methanone; [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][5-(3-ethyl-1H-1,2,4-triazol-1-yl)-2-methoxyphenyl]methanone; [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][2-ethyl-5-[3-(1-methylethyl)-1H-1,2,4-triazol-1-yl]phenyl]methanone; [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][5-(3-cyclobutyl-1H-1,2,4-triazol-1-yl)-2-methylphenyl]methanone; [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][3-(3-cyclobutyl-1H-1,2,4-triazol-1-yl)phenyl]methanone; [(2S)-2,3-Dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl][2-methoxy-5-(1H-1,2,4-triazol-1-yl)phenyl]methanone; [ka]

[0181] The present invention also relates to a method for controlling undesirable vegetation, comprising applying an effective amount of the compound of the present invention as a herbicide (e.g., as a composition described herein).Notable embodiments related to the method of use include the compounds of the embodiments 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, rapeseed, and rice, and specialty crops such as sugarcane, citrus, fruit, and nut crops.

[0182] Also of note as an embodiment are herbicidal compositions of the present invention that include compounds of the previously described embodiments.

[0183] The present invention further includes herbicide mixtures comprising: (a) a compound selected from Formula 1, their N-oxides, and salts; and (b) (b1) a photosystem II inhibitor, (b2) an acetohydroxyacid synthase (AHAS) inhibitor, (b3) an acetyl-CoA carboxylase (ACCase) inhibitor, (b4) an auxin mimetic, (b5) a 5-enol-pyruvylshikimate-3-phosphate (EPSP) synthase inhibitor, (b6) a photosystem I electron diverter, (b7) a protoporphyrinogen oxidase (PPO) inhibitor, (b8) a glutamine synthetase (GS) inhibitor, (b9) a very long chain fatty acid (VLCFA) elongase inhibitor, (b10) an auxin transport inhibitor, (b11) a phytoene desaturase (PDS) inhibitor, (b12) a 4-hydroxybenzoate (4-hydroxybenzoate) synthase inhibitor, (b13) a 4-hydroxybenzoate (4-hydroxybenzoate) synthase inhibitor, (b14) a 4-hydroxybenzoate (4-hydroxybenzoate) synthase inhibitor, (b15) a 4-hydroxybenzoate (4-hydroxybenzoate) synthase inhibitor, (b16) a 4-hydroxybenzoate (4-hydroxybenzoate) synthase inhibitor, (b17) a 4-hydroxybenzoate (4-hydroxybenzoate) synthase inhibitor, (b18) a 4-hydroxybenzoate (4-hydroxybenzoate) synthase inhibitor, (b19) a 4-hydroxybenzoate (4-hydroxybenzoate) synthase inhibitor, (b20) a 4-hydroxybenzoate (4-hydroxybenzoate) synthase inhibitor, (b21) a 4-hydroxybenzoate (4-hydroxybenzoate) synthase inhibitor, (b22) a 4-hydroxybenzoate (4-hydroxybenzoate) synthase inhibitor, (b23) a 4-hydroxybenzoate (4- (b15) dehydroorotate dehydrogenase (DHODH) inhibitors; (b16) other herbicides including mitotic disruptors, organic arsenic compounds, asulam, bromobutide, cinmethylin, cumyluron, dazomet, difenzoquat, dymron, etobenzanide, flurenol, fosamine, fosamine-ammonium, hydantocidin, metam, methyldymron, oleic acid, oxaziclomefone, pelargonic acid, and pyributicarb; (b17) herbicide safeners; and at least one additional active ingredient selected from salts of the compounds of (b1) to (b17).

[0184] "Photosystem II inhibitor" (b1) is Q B Compounds that bind to the D-1 protein at the QB-binding niche, thereby inhibiting the QB binding in the thylakoid membrane of chloroplasts. A From Q B Blocking electron transport through photosystem II. Electrons blocked from the pathway through photosystem II are transported through a series of reactions to form toxic compounds that disrupt the cell membrane, leading to swelling of the chloroplast, membrane leakage, and ultimately cell destruction. BThe binding niche has three distinct binding sites. Binding site A binds triazines such as atrazine, triazinones such as hexazinone, and uracils such as bromacil; binding site B binds phenylureas such as diuron; and binding site C binds benzothiadiazoles such as bentazone, nitriles such as bromoxynil, and phenylpyridazines such as pyridate. Examples of photosystem II inhibitors include ametryn, amicarbazone, atrazine, bentazone, bromacil, bromofenoxime, bromoxynil, chlorbromuron, chloridazon, chlorotoluron, chloroxyuron, cumyluron, cyanazine, dymron, desmedipham, desmetrin, dimefuron, dimethamethrin, diuron, ethidimuron, fenuron, fluometuron, hexazinone, ioxynil, and methylpyridazine. le, isoproturon, isouron, lenacil, linuron, metamitron, methabenzthiazuron, metobromuron, methoxyuron, metribuzin, monolinuron, nebron, pentanochlor, phenmedipham, prometon, prometryn, propanil, propazine, pyridafol, pyridate, siduron, simazine, simetryn, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, and trietazine.

[0185] "AHAS inhibitors" (b2) are compounds that inhibit acetohydroxyacid synthase (AHAS), also known as acetolactate synthase (ALS), which kills plants by preventing the production of branched-chain aliphatic amino acids, such as valine, leucine, and isoleucine, which are required for protein synthesis and cell growth.Examples of AHAS inhibitors include: amidosulfuron, azimsulfuron, bensulfuron-methyl, bispyribac-sodium, cloransulam-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, diclosulam, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, florasulam, flucarbazone-sodium, flumetsulam, flupyrsulfuron-methyl, flupyrsulfuron-sodium, foramsulfuron, halosulfuron- Methyl, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron-methyl (including sodium salt), iofensulfuron (2-iodo-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide), mezosulfuron-methyl, metazosulfuron (3-chloro-4-(5,6-dihydro-5-methyl-1,4,2-dioxazin-3-yl)-N-[[(4,6-dimethoxy -2-pyrimidinyl)amino]carbonyl]-1-methyl-1H-pyrazole-5-sulfonamide), metsulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, penoxulam, primisulfuron-methyl, propoxycarbazone-sodium, propyrisulfuron (2-chloro-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-6-propylimidazo[1,2-b]pyridazine-3-sulfonamide), prosulfuron, pyrazosulfuron-ethyl, pyribenzoxime, pyrif Thalide, pyriminobac-methyl, pyrithiobac-sodium, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone, thifensulfuron-methyl, triafamone (N-[2-[(4,6-dimethoxy-1,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-1,1-difluoro-N-methylmethanesulfonamide), triasulfuron, tribenuron-methyl, trifloxysulfuron (including sodium salt), triflusulfuron-methyl, and tritosulfuron.

[0186] "ACCase inhibitors" (b3) are compounds that inhibit the enzyme acetyl-CoA carboxylase, which is responsible for catalyzing the initial steps in the synthesis of lipids and fatty acids in plants. Lipids are essential components of cell membranes, without which new cells cannot be produced. Inhibition of acetyl-CoA carboxylase and the subsequent lack of lipid production leads to a loss of cell membrane integrity, especially in areas of active growth, such as the meristem. Ultimately, shoot and root growth ceases, and shoot meristems and root buds begin to wither. Examples of ACCase inhibitors include alloxydim, butroxydim, clethodim, clodinafop, cycloxydim, cyhalofop, diclofop, fenoxaprop, fluazifop, haloxyfop, pinoxaden, profoxydim, propaquizafop, quizalofop, sethoxydim, tepraloxydim, and tralkoxydim (including resolved forms such as fenoxaprop-P, fluazifop-P, haloxyfop-P, and quizalofop-P, and ester forms such as clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl, and fenoxaprop-P-ethyl).

[0187] Auxin is a plant hormone that regulates growth in many plant tissues. "Auxin mimetics" (b4) are compounds that mimic the plant growth hormone auxin, resulting in uncontrolled and unregulated growth and plant death in sensitive species. Examples of auxin mimetics include aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid) and its methyl and ethyl esters and its sodium and potassium salts, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)-2-pyridinecarboxylic acid 2-propyn-1-yl ester (CAS No. 2251111-17-6), 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)-2-pyridinecarboxylic acid cyanomethyl ester (CAS No. 2251111-17-6), and 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)-2-pyridinecarboxylic acid cyanomethyl ester (CAS No. 2251111-17-6). No. 2251111-18-7), aminopyralid, benazolin-ethyl, chloramben, clasifos, clomeprop, clopyralid, dicamba, 2,4-D, 2,4-DB, dichlorprop, fluroxypyr, halauxifen (4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylic acid), halauxifen-methyl (methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylate), MCPA, MCPB, mecoprop, picloram, quinclorac, quinmerac, 2,3,6-TBA, triclopyr, and methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate.

[0188] "EPSP synthase inhibitors" (b5) are compounds that inhibit 5-enol-pyruvylshikimate-3-phosphate synthase, an enzyme involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan, and phenylalanine. EPSP-inhibiting herbicides are readily absorbed through plant leaves and translocated to the growing point through the phloem. Glyphosate is a relatively nonselective postemergence herbicide that belongs to this group. Glyphosate includes esters and salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium), and trimesium (also known as sulfosate).

[0189] "Photosystem I electron diverters" (b6) are compounds that accept electrons from photosystem I and, after several cycles, generate hydroxyl radicals. These radicals are highly reactive and readily destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This disrupts the integrity of cell membranes, resulting in "leakage" in cells and organelles, rapid wilting and drying of leaves, and ultimately plant death. Examples of this second type of photosynthesis inhibitor include diquat, paraquat, and 1-(2-carboxyethyl)-4-(2-pyrimidinyl)pyridazinium (CAS No. 2285384-11-2).

[0190] "PPO inhibitors" (b7) are compounds that inhibit the enzyme protoporphyrinogen oxidase, causing the rapid production of highly active compounds in plants that disrupt cell membranes and leak cell fluids. Examples of PPO inhibitors include acifluorfen-sodium, azafenidin, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlormethoxyfen, 3-[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenyl]-4,5-dihydro-5-methyl-5-isoxazolecarboxylic acid ethyl ester (CAS 60141-0001). No. 1949837-17-5), cinidon-ethyl, fluazolate, flufenoximacil, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazin, fluoroglycofen-ethyl, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazole, pyraclonil, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiadiamine, trifludimoxazine (dihydrazine) 1,5-dimethyl-6-thioxo-3-[2,2,7-trifluoro-3,4-dihydro-3-oxo-4-(2-propyn-1-yl)-2H-1,4-benzoxazin-6-yl]-1,3,5-triazine-2,4(1H,3H)-dione), and thiaphenacyl (methyl N-[2-[[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenyl]thio]-1-oxopropyl]-β-alaninate).

[0191] "GS inhibitors" (b8) are compounds that block the activity of the glutamine synthetase enzyme, which plants use to convert ammonia to glutamine. Thus, ammonia accumulates and glutamine levels decrease. Damage to the plant may result from the combined effects of ammonia toxicity and a lack of amino acids needed for other metabolic processes. GS inhibitors include glufosinate and its esters and salts, such as glufosinate-ammonium and other phosphinothricin derivatives, glufosinate-P ((2S)-2-amino-4-(hydroxymethylphosphinyl)butanoic acid), and viranaphos.

[0192] "VLCFA elongase inhibitors" (b9) are herbicides with a wide variety of chemical structures that inhibit elongase, an enzyme located in or near chloroplasts and involved in the biosynthesis of VLCFAs. In plants, very long-chain fatty acids are the main components of hydrophobic polymers that prevent desiccation on leaf surfaces and provide stability to pollen grains. Such herbicides include acetochlor, alachlor, anilophos, butachlor, cafenstrole, dimethachlor, dimethenamid, diphenamid, fenoxasulfone (3-[[(2,5-dichloro-4-ethoxyphenyl)methyl]sulfonyl]-4,5-dihydro-5,5-dimethylisoxazole), fentrazamide, flufenacet, indanofan, mefenacet, metazachlor, metolachlor, naproanilide, napropamide, napropamide-M ((2R)-N,N-diethyl-2-(1-naphthalenyloxy)propanamide), petoxamide, piperophos, pretilachlor, propachlor, propisochlor, pyroxasulfone, and thenylchlor (including resolved forms, such as S-metolachlor, and chloroacetamides and oxyacetamides).

[0193] "Auxin transport inhibitors" (b10) are chemical substances that inhibit the transport of auxin in plants, for example, by binding to auxin transport proteins. Examples of auxin transport inhibitors include diflufenzopyr and naptalam (also known as N-(1-naphthyl)phthalamic acid and 2-[(1-naphthalenylamino)carbonyl]benzoic acid).

[0194] "PDS inhibitors" (b11) are compounds that inhibit the carotenoid biosynthetic pathway at the phytoene desaturase step. Examples of PDS inhibitors include: beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurzone, and picolinafen.

[0195] "HPPD inhibitors" (b12) are chemical substances that inhibit the biosynthesis of 4-hydroxyphenyl-pyruvate dioxygenase. Examples of HPPD inhibitors include: benzobicyclone, benzofenap, bicyclopyrone (4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]bicyclo[3.2.1]oct-3-en-2-one), fenquinotrione (2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl]-1,3-cyclohe xanedione), flusulfinam, iptriazopyride, isoxaclortol, isoxaflutole, mesotrione, pyrasulfotole, pyrazolinate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate (1-[[1-ethyl-4-[3-(2-methoxyethoxy)-2-methyl-4-(methylsulfonyl)benzoyl]-1H-pyrazol-5-yl]oxy]ethyl methyl carbonate), topramezone, 5-chloro-3 -[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalinone, 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione, 5-[( 2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-(3-methoxyphenyl)-3-(3-methoxypropyl)-4(3H)-pyrimidinone, 2-methyl-(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.

[0196] "HST (homogentisic acid solanesyltransferase) inhibitors" (b13) disrupt the plant's ability to convert homogentisic acid to 2-methyl-6-solanyl-1,4-benzoquinone, thereby disrupting carotenoid biosynthesis. Examples of HST inhibitors include cyclopyrimorate (6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinyl 4-morpholinecarboxylate), haloxidine, pyrichlor, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridin-2(1H)-one, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-b]pyrazin-6(5H)-one, and 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone.

[0197] HST inhibitors also include compounds of formula A and B: [ka] In the formula, R d1 is H, Cl or CF; R d2 is H, Cl or Br; R d3 is H or Cl; R d4 is H, Cl or CF; R d5 is CH3, CH2CH3 or CH2CHF2; R d6 is OH or -OC(=O)-i-Pr; R e1 is H, F, Cl, CH3 or CH2CH3; R e2 is H or CF; R e3 is H, CH3 or CH2CH3; R e4 is H, F or Br; R e5 is Cl, CH3, CF3, OCF3 or CH2CH3; R e6 is H, CH, CHCHF or C≡CH; R e7 is OH, -OC(=O)Et, -OC(=O)-i-Pr, or -OC(=O)-t-Bu; A e8 is N or CH.

[0198] "Cellulose biosynthesis inhibitors" (b14) inhibit the biosynthesis of cellulose in certain plants. They are most effective when applied to young plants before or shortly after emergence, or to rapidly growing plants. Examples of cellulose biosynthesis inhibitors include: chlorthiamid, dichlobenil, furopoxam, indaziflam (N 2 -[(1R,2S)-2,3-dihydro-2,6-dimethyl-1H-inden-1-yl]-6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine), isoxaben, and triaziflam.

[0199] "DHODH (dihydroorotate dehydrogenase) inhibitors" (b15) act by inhibiting the catalysis of the fourth step in pyrimidine biosynthesis in plant systems. Inhibition of pyrimidine biosynthesis causes plant growth to cease. Examples of DHODH inhibitors include tetofurpirorimet ((3S,4S)-N-(2-fluorophenyl)-1-methyl-2-oxo-4-[3-(trifluoromethyl)phenyl]-3-pyrrolidinecarboxamide) and (3S,4R)-N-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-2-oxo-3-pyrrolidinecarboxamide.

[0200] "Other herbicides" (b16) include herbicides that function by a variety of different mechanisms, such as mitotic disruptors (e.g., flamprop-M-methyl and flamprop-M-isopropyl), organoarsenic compounds (e.g., DSMA and MSMA), 7,8-dihydropteroate synthase inhibitors, chloroplast isoprenoid synthesis inhibitors, and cell wall biosynthesis inhibitors. Other herbicides include herbicides with unknown mechanisms of action or that do not fall into the specific categories listed in (b1) through (b14), or that act by a combination of the mechanisms listed above. Examples of other herbicides include aclonifen, asulam, amitrole, bixlozone, brocorozone, bromobutide, cinmethylin, clomazone, cumylron, dymron, difenzoquat, dimesulfazate, epirifenacil, etobenzanid, fluometuron, flurenol, fosamine, fosamine-ammonium, dazomet, dimron, ipfencarbazone (1-(2,4-dichlorophenyl)-N-(2,4-difluorophenyl)- )-1,5-dihydro-N-(1-methylethyl)-5-oxo-4H-1,2,4-triazole-4-carboxamide), metam, methyl dimron, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, 2,5-anhydro-3,4-dideoxy-4-[[[(5S)-3-(3,5-difluorophenyl)-5-ethenyl-4,5-dihydro-5-isoxazolyl]carbonyl]amino]-threo-pentonic acid methyl ester (CAS No. 27499989-21-6) and 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole. "Other herbicides" (b16) also include compounds of formula (b16A): [ka] During the ceremony, R 12 is H, C1-C6 alkyl, C1-C6 haloalkyl, or C4-C8 cycloalkyl: R 13 is H, C1-C6 alkyl or C1-C6 alkoxy; Q 1is an optionally substituted ring system selected from the group consisting of phenyl, thienyl, pyridinyl, benzodioxolyl, naphthyl, naphthalenyl, benzofuranyl, furanyl, benzothiophenyl, and pyrazolyl, and when substituted, the ring system is substituted with 1 to 3 R 14 is replaced by; Q 2 is an optionally substituted ring system selected from the group consisting of phenyl, pyridinyl, benzodioxolyl, pyridinonyl, thiadiazolyl, thiazolyl, and oxazolyl, and when substituted, the ring system is 15 is replaced by; Each R 14 are independently halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C8 sialoalkyl, cyano, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, SF5, NHR 17 ; or 1 to 3 R 16 phenyl optionally substituted with 1 to 3 R 16 is pyrazolyl optionally substituted by Each R 15 are independently halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, cyano, nitro, C1-C6 alkylthio, C1-C6 alkylsulfinyl, or C1-C6 alkylsulfonyl; Each R 16 are independently halogen, C1-C6 alkyl, or C1-C6 haloalkyl; R 17 is a C1-C4 alkoxycarbonyl.

[0201] In one embodiment, where "other herbicides" (b16) also include compounds of formula (b16A), R 12 is preferably H or C1-C6 alkyl, and more preferably R 12 is H or methyl. Preferably, R 13 is H. Preferably, Q 1is either a phenyl ring or a pyridinyl ring, and each ring has 1 to 3 R 14 and more preferably, Q 1 is 1 to 2 R 14 Preferably, Q is a phenyl ring substituted with 2 is 1 to 3 R 15 and more preferably, Q 2 is 1 to 2 R 15 Preferably, each R 14 are independently halogen, C1-C4 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy or C1-C3 haloalkoxy, more preferably each R 14 are independently chloro, fluoro, bromo, C1-C2 haloalkyl, C1-C2 haloalkoxy, or C1-C2 alkoxy. Preferably, each R 15 are independently halogen, C1-C4 alkyl, C1-C3 haloalkoxy; more preferably, each R 15 are independently chloro, fluoro, bromo, C1-C2 haloalkyl, C1-C2 haloalkoxy, or C1-C2 alkoxy. Specific preferred examples of the "other herbicide" (b16) include any one of the following (b16A-1) to (b16A-15). [ka] [ka] [ka] [ka]

[0202] "Other herbicides" (b16) also include compounds of formula (b16B): [ka] During the ceremony, R 18is H, C1-C6 alkyl, C1-C6 haloalkyl, or C4-C8 cycloalkyl: Each R 19 are independently halogen, C1-C6 haloalkyl, or C1-C6 haloalkoxy; p is an integer of 0, 1, 2, or 3; Each R 20 are independently halogen, C1-C6 haloalkyl, or C1-C6 haloalkoxy; q is an integer of 0, 1, 2 or 3.

[0203] In one embodiment, where "other herbicides" (b16) also include compounds of formula (b16B), R 18 is preferably H, methyl, ethyl or propyl, more preferably R 18 is H or methyl, and most preferably R 18 is H. Preferably, each R 19 are independently chloro, fluoro, C1-C3 haloalkyl or C1-C3 haloalkoxy, more preferably each R 19 is independently chloro, fluoro, C1 fluoroalkyl (i.e., fluoromethyl, difluoromethyl, or trifluoromethyl), or C1 fluoroalkoxy (i.e., trifluoromethoxy, difluoromethoxy, or fluoromethoxy). Preferably, each R 20 are independently chloro, fluoro, C1 haloalkyl or C1 haloalkoxy, more preferably each R 20 are independently chloro, fluoro, C1 fluoroalkyl (i.e., fluoromethyl, difluoromethyl, or trifluoromethyl), or C1 fluoroalkoxy (i.e., trifluoromethoxy, difluoromethoxy, or fluoromethoxy). Specific preferred "other herbicides" (b16) include any one of the following (b16B-1) to (b16B-19). [ka] [ka] [ka]

[0204] Another embodiment in which "other herbicides" (b16) also include compounds of formula (b16C): [ka] In the formula, R 1 is Cl, Br or CN, and R 2 is C(=O)CH2CH2CF3, CH2CH2CH2CH2CF3 or 3-CHF2-isoxazol-5-yl.

[0205] "Herbicide safeners" (b17) are substances added to herbicide formulations to eliminate or reduce the phytotoxic effects of the herbicide on certain crops. These compounds protect the crop from herbicide damage but typically do not prevent the herbicide from controlling undesirable vegetation. Examples of herbicide safeners include, but are not limited to, benoxacor, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfamide, dymron, dichlormid, dicyclonone, dietholate, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, methoxyphenone, naphthalic anhydride, oxabetrinil, N-(aminocarbonyl)-2-methylbenzenesulfonamide, and N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene, 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), 4-(dichloroacetyl)-1-oxa-4-azospiro[4.5]decane (MON 4660), 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-ethanone, and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide.

[0206] For better control of undesirable vegetation (e.g., greater than additive effect, broader spectrum of weeds controlled, or reduced application rate due to improved crop safety) or prevention of the development of resistant weeds, preferred are combinations of the compounds of the present invention with 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)-2-pyridinecarboxylic acid 2-propyn-1-yl ester (CAS No. 2251111-17-6), 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)-2-pyridinecarboxylic acid cyanomethyl ester (CAS No. No. 2251111-18-7), 2,5-anhydro-3,4-dideoxy-4-[[[(5S)-3-(3,5-difluorophenyl)-5-ethenyl-4,5-dihydro-5-isoxazolyl]carbonyl]amino]-threo-pentonic acid methyl ester (CAS No. 27499989-21-6), atrazine, azimsulfuron, beflubutamid, beflubutamid-M, bixlozone, brocorozone, benzisothiazolinone, 1-(2-carboxyethyl)-4-(2-pyrimidinyl)pyridazinium (CAS No. 2285384-11-2) and its salts, carfentrazone-ethyl, chlorimuron-ethyl, 3-[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenyl]-4,5-dihydro-5-methyl-5-isoxazolecarboxylic acid ethyl ester (CAS No.1949837-17-5), chlorsulfuron-methyl, clomazone, clopyralid potassium, cloransulam-methyl, 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-isoxazolidinone, 2-[(2,5-dichlorophenyl)methyl]-4,4-dimethyl-isoxazolidinone, ethametsurron-methyl, flumetsulam, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl- and a herbicide selected from the group consisting of 1,2,4-triazine-3,5-(2H,4H)-dione, flupyrsulfuron-methyl, fluthiacet-methyl, fomesafen, imazethapyr, lenacil, mesotrione, metribuzin, metsulfuron-methyl, petoxamid, picloram, pyroxasulfone, quinclorac, rimsulfuron, S-metolachlor, sulfentrazone, thifensulfuron-methyl, triflusulfuron-methyl, and tribenuron-methyl.

[0207] To prepare compounds of formula 1, one or more of the following methods and variations as described in Schemes 1-16 can be used. 1a , R 1b , R 2 , R 3a , R 3b , R 4a , R 4b , X 1 , X 2 The definitions of n, p, and q are as defined above in the Summary of the Invention unless otherwise indicated. The compounds of Formulae 1a, 1b, 1c, 1d, 8a, 8b, 10a, 16a, and 16b are various subsets of the compounds of Formulae 1, 8, 10, and 16; all substituents of Formulae 1a, 1b, 1c, 1d, 8a, 8b, 10a, 16a, and 16b are as defined above for Formula 1 unless otherwise indicated in the disclosure, including the schemes.

[0208] As shown in Scheme 1, compounds of formula 1a (i.e., compounds of formula 1 where Y is S) can be prepared by treatment of compounds of formula 1b (i.e., formula 1 where Y is O) with a sulfurizing reagent such as Lawesson's reagent, tetraphosphorus deca-sulfide, or diphosphorus pentasulfide in a suitable solvent (e.g., tetrahydrofuran or toluene) at a temperature typically ranging from 0° C. to the reflux temperature of the solvent. [ka]

[0209] Compounds of formula 1b (i.e., compounds of formula 1 where Y is O) can be prepared using standard cross-coupling reactions such as those described in Science of Synthesis: Cross Coupling and Heck-Type Reactions 1, Molander, GA (volume editor), Thieme (2013) and Science of Synthesis: Cross Coupling and Heck-Type Reactions 2, Wolfe, JP (volume editor), Thieme (2013); and references cited therein. For example, compounds of formula 1c (i.e., formula 1b where A is attached via a nitrogen ring member) can be prepared from compounds of formula 2 where Z is a halogen or pseudohalogen such as Cl, Br, I, or OTf via palladium- or copper-mediated coupling with a heterocycle of formula 3 where H is linked to the nitrogen ring member of A, as shown in Scheme 2. Ullmann-type coupling conditions, such as those described in J. Org. Chem. 2004, 69, 5578-5587, are often suitable and are typically catalyzed by a copper salt such as copper(I) iodide or copper(I) oxide in the presence of a base (e.g., potassium carbonate, cesium carbonate, or potassium phosphate) in a suitable solvent (e.g., N,N-dimethylformamide, dimethyl sulfoxide, N,N-dimethylacetamide, toluene, 1,4-dioxane, or acetonitrile) and a ligand such as trans-N,N'-dimethylcyclohexane-1,2-diamine, trans-1,2-diaminocyclohexane, N,N'-dimethylethylenediamine, 1,10-phenanthroline, 8-quinolinol, (S)-proline, or 2-picolinic acid. Temperatures between ambient temperature and 150 °C are generally suitable for the reaction. Palladium-catalyzed coupling conditions may also be suitable for some heterocycles.Suitable palladium catalysts include, but are not limited to, tetrakis(triphenylphosphine)palladium(0), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), bis(triphenylphosphine)palladium(II) dichloride, palladium(II) acetate, or tris(dibenzylideneacetone)dipalladium(0). In some cases, the addition of ligands is beneficial, including, but not limited to, 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene (BINAP), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos), 2-(di-tert-butylphosphino)biphenyl (JohnPhos), 2-dicyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl (RuPhos), or 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl-1,1'-biphenyl (Me4t-butylXphos). These reactions are typically carried out with a base (e.g., sodium tert-butoxide, lithium bis(trimethylsilyl)amide, cesium carbonate, potassium carbonate, or tripotassium phosphate) and a solvent (e.g., tetrahydrofuran, 1,4-dioxane, toluene, or tert-butanol) at temperatures generally ranging from ambient to 150° C. For reviews of these methods, see Chem. Rev. 2008, 108, 3054-3131; Chem. Sci. 2010, 1, 13-31; Beilstein J. Org. Chem. 2011, 7, 59-74; Chem. Rev. 2016, 116, 12564-12649; and Angew. Chem. Int. Ed. 2017, 56, 16136-16179 and Tetrahedron 2019, 75, 4199-4211.Those skilled in the art will recognize that when more than one nitrogen atom is present in the heterocycle of formula 3, the formation of regioisomers is possible and standard purification methods such as chromatography can generally be used to separate the mixtures. Heterocycles of formula 3 are generally commercially available or known in the literature.

[0210] Alternatively, when the aryl ring is sufficiently activated, e.g., X 1 is N or R 2 When Z is a suitably positioned electron-withdrawing group, compounds of formula 1c can generally be prepared without the addition of a metal catalyst. This is achieved by reacting a compound of formula 2 (where Z is a halogen, such as F or Cl) with a heterocycle of formula 3 in the presence of a base (e.g., potassium carbonate, sodium carbonate, cesium carbonate, potassium phosphate, sodium hydroxide, potassium tert-butoxide, sodium hydride, or potassium hydride) in a suitable solvent (e.g., N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, diglyme, acetonitrile, or toluene). Temperatures in the range of 0°C to 200°C are generally suitable for this reaction. For examples of this reaction in the literature, see WO 2012 / 054510; WO 2020 / 207941 and J. Med. Chem. 2014, 57, 10013-10030.

[0211] In some instances, the compound of formula 1c can be more easily obtained by using standard heterocyclic synthesis procedures known to those skilled in the art.For suitable methods, see Science of Synthesis, Volume 12-13, Neier, R., Storr, RC and Gilchrist, TL (volume editors), Thieme (2002-2003); Comprehensive Heterocyclic Chemistry IV, Volume 4-6, Black, DS, Cossy, J. and Stevens, CV (editors-in-chief), Elsevier (2022); WO 2015 / 160636 and WO 2017 / 205709; and the references cited therein. [ka]

[0212] As shown in Scheme 3, compounds of Formula 1d (i.e., compounds of Formula 1b, where A is attached via a carbon ring member) can be prepared by reacting a heterocycle of Formula 4, where Z is a halogen or pseudohalogen, such as Cl, Br, I, or OTf, linked to a carbon ring member, with an organometallic compound of Formula 5, where M is a boronic acid (e.g., M is B(OH)), a boronic acid ester (e.g., M is B(—O(CMe)O—), or an organotin reagent (e.g., M is Sn(n-Bu), SnMe). can be prepared by well-known metal-catalyzed cross-coupling reactions between tetrakis(triphenylphosphine)palladium(0), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), bis(triphenylphosphine)palladium(II) dichloride, palladium(II) acetate, or tris(dibenzylideneacetone)dipalladium(0). In some cases, the addition of a ligand, including but not limited to 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos), tricyclohexylphosphine, or tri(2-furyl)phosphine, is beneficial. Generally, these reactions are carried out in N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, toluene, 1,2-dimethoxyethane, 1,4-dioxane, tetrahydrofuran ... The reaction is generally carried out in a solvent such as dihydrofuran, acetonitrile, or ethanol at a temperature ranging from ambient temperature to 150°C. One skilled in the art will recognize that the reaction conditions will depend on the organometallic species used in the reaction; for example, when the compound of formula 5 is a boron reagent, a base, often an aqueous base, will be required. Suitable bases include potassium carbonate, sodium carbonate, cesium carbonate, sodium bicarbonate, or potassium phosphate. When the compound of formula 5 is a tin reagent, a base is not required.For reviews of transition metal-catalyzed cross-coupling reactions, see E. Negishi, Handbook of Organopalladium Chemistry for Organic Synthesis, John Wiley and Sons, Inc., New York, 2002; N. Miyaura, Cross-Coupling Reactions: A Practical Guide, Springer, New York, 2002; H. C. Brown et al., Organic Synthesis via Boranes, Vol. 3, Aldrich Chemical Co., Milwaukee, WI, 2002; Suzuki et al., Chem. Rev. 1995, 95, 2457-2483, and Molander et al., Acc. Chem. Res. 2007, 40, 275-286, and Chem. Soc. Rev. 2013, 42, 5270. For relevant examples of reactions in the literature using boron reagents, see WO 2012 / 137982, WO 2015 / 017610, WO 2016 / 040223 and WO 2020 / 182990. For relevant examples of reactions in the literature using tin reagents, see WO 2019 / 195810 and WO 2021 / 242677. Heterocycles of formula 4 are generally commercially available or known in the literature. [ka]

[0213] Those skilled in the art will recognize that in some instances, due to the availability or stability of the required reagents, it may be beneficial to invert the polarity of the coupling partners as shown in Scheme 4. In this scenario, a heterocycle of formula 6 (wherein M is a transmetallation group such as, but not limited to, B(OH) 2 , B(—O(CMe 2 ) 2 O—), BF 3 K, Sn(n-Bu) 3 or SnMe 3 or ZnBr, linked to a carbon ring member) is coupled with a compound of formula 2 (wherein Z is a halogen or pseudohalogen such as Cl, Br, I, or OTf). For relevant examples in the literature, see WO 2012 / 063207 and WO 2019 / 162323. For examples of cross-coupling of (hetero)aryl halides with alkyl coupling partners, see Chem. Rev. 2011, 111, 1417-1492; ACS Med. Chem. Lett. 2020, 11, 597-604 and J. Org. Chem. 2021, 86, 10380-10396; and references cited therein. Heterocycles of formula 6 are generally commercially available or known in the literature.

[0214] In some instances, compounds of formula 1d can be more easily obtained using standard heterocyclic synthesis procedures known to those skilled in the art.For suitable methods, see Science of Synthesis, Volumes 11-13 and 15, Schaumann, E., Neier, R., Storr, RC; Gilchrist, T. L. and Black, D. S. (volume editors), Thieme (2001-2004) and Comprehensive Heterocyclic Chemistry IV, Volumes 4-7, Black, D. S., Cossy, J. and Stevens, C. V. (editors-in-chief), Elsevier (2022); and the references cited therein. [ka]

[0215] As shown in Scheme 5, organometallic compounds of formula 5, where M is a transmetallation group such as, but not limited to, B(—O(CMe)O—), Sn(n-Bu) or SnMe, can be prepared from compounds of formula 2, where Z is a halogen or pseudohalogen such as Cl, Br, I or OTf, using well-known metal-catalyzed cross-coupling reactions. For example, pinacolboronic esters (where M = (BO(CMe2)2O-) can generally be prepared using palladium-catalyzed boronation conditions such as those described in J. Org. Chem. 1995, 60, 7508-7510 and J. Org. Chem. 2021, 86, 103-109; and references cited therein. Compounds of formula 2 are treated with bis(pinacolato)diboron in the presence of a palladium catalyst such as [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) and a base such as potassium acetate in a solvent such as dioxane or dimethyl sulfoxide at temperatures ranging from ambient temperature to the reflux temperature of the solvent. Similarly, trialkyltin reagents (e.g., M = SnMe3, SnBu3) can generally be prepared from compounds of Formula 2 by treatment with a stannane such as hexamethylditin or hexabutylditin in the presence of a palladium catalyst such as tetrakis(triphenylphosphine)palladium(0) in a solvent such as dioxane or toluene at temperatures ranging from ambient temperature to the reflux temperature of the solvent. For examples of this reaction in the literature, see WO 03 / 077918 and WO 2021 / 050964. For further details on the preparation and use of organoboron and organotin reagents, see Science of Synthesis, Volumes 5-6, Moloney, MG and Kaufmann, DE (volume editors), Thieme (2002-2004); and references cited therein. [ka]

[0216] As shown in Scheme 6, compounds of Formula 1 or 2 can be prepared by reacting a carboxylic acid of Formula 7 with a benzoxazine of Formula 8. The reaction proceeds via activation of the carboxylic acid of Formula 7 followed by reaction with the benzoxazine of Formula 8. The carboxylic acid can be activated with a coupling reagent or by conversion of the carboxylic acid to an acid halide, such as an acid chloride. For example, compounds of Formulas 7 and 8 can be reacted in the presence of a coupling reagent such as propylphosphonic anhydride (T3P), N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC), 1,1'-carbonyldiimidazole (CDI), or 2-chloro-1-methylpyridinium iodide (Mukaiyama's reagent). Polymer-supported reagents, such as polymer-supported cyclohexylcarbodiimide, are also suitable. These reactions are typically carried out in a suitable solvent (e.g., dichloromethane, 1,2-dichloroethane, ethyl acetate, acetonitrile, or N,N-dimethylformamide) in the presence of a base (e.g., triethylamine, N,N-diisopropylethylamine, or pyridine), optionally with a catalytic amount of 4-(dimethylamino)pyridine, at a temperature ranging from 0° C. to the reflux temperature of the solvent. Alternatively, the carboxylic acid of formula 7 can be converted to the acid chloride by treatment with a reagent such as thionyl chloride, oxalyl chloride, phosphoryl chloride, phosphorus trichloride, or phosphorus pentachloride, either neat or in a suitable solvent (e.g., dichloromethane, 1,2-dichloroethane, or toluene), optionally with a catalytic amount of N,N-dimethylformamide, at a temperature ranging from 0° C. to the reflux temperature of the solvent. The subsequent reaction of the acid chloride with the benzoxazine of formula 8 is generally carried out in the presence of a base (e.g., triethylamine, N,N-diisopropylethylamine or pyridine) optionally with a catalytic amount of 4-(dimethylamino)pyridine in a suitable solvent (e.g., tetrahydrofuran, dioxane, toluene, dichloromethane, chloroform, 1,2-dichloroethane or ethyl acetate) at a temperature ranging from 0°C to the reflux temperature of the solvent.For relevant examples of this reaction in the literature, see J.Med.Chem.2012,55,10475-10489; WO 2010 / 049302 and WO 2016 / 001631. Carboxylic acids of formula 7 are generally commercially available or known in the literature. In some cases, the corresponding acid chlorides are also commercially available. [ka]

[0217] Several methods useful for preparing benzoxazines of formula 8 are well known in the literature. In addition, some benzoxazines of formula 8 are commercially available. Benzoxazines of formula 8a (i.e., compounds of formula 8, where R b is H and p is 0 or 1) or a benzoxazine of formula 9, b is a suitable protecting group such as Bn or p-methoxybenzyl, and p is 0 or 1), one method for preparing benzoxazinones of formula 10 (wherein R is a suitable protecting group such as Bn or p-methoxybenzyl, and p is 0 or 1) is by the reduction of benzoxazinones of formula 10 (wherein R is a suitable protecting group such as Bn or p-methoxybenzyl, and p is 0 or 1) with a reducing agent such as borane or lithium aluminum hydride in a solvent such as tetrahydrofuran at a temperature ranging from 0° C. to the reflux temperature of the solvent. b is H or a suitable protecting group such as Bn or p-methoxybenzyl, where p is 0 or 1), as shown in Scheme 7 below. For relevant examples of this reaction in the literature, see WO 2015 / 095795. Several benzoxazinones of formula 10 are commercially available or known in the literature. [ka]

[0218] As shown in Scheme 8, a benzoxazine of formula 8b (i.e., a compound of formula 8, where R b is H, and R is α to the N atom 3bis F and p is 2 or 3) or a benzoxazine of formula 11 (wherein R b is a suitable protecting group such as Bn or p-methoxybenzyl, and R at the alpha position to the N atom 3b is F and p is 2 or 3) can be converted into a benzoxazinones of formula 10, where R b is H or a suitable protecting group such as Bn or p-methoxybenzyl, where p is 0 or 1. For example, α,α-difluoroamines can be prepared by first chlorinating an amide with a reagent such as oxalyl chloride in a suitable solvent (e.g., dichloromethane, carbon tetrachloride, tert-butyl methyl ether, or chloropentyl methyl ether) at temperatures generally between 0°C and the reflux temperature of the solvent. This is followed by fluorination with a reagent such as sodium fluoride, potassium fluoride, or triethylamine trihydrofluoride in a suitable solvent (e.g., acetonitrile, dichloromethane, or 1,3-dimethyl-2-imidazolidinone) at temperatures generally between 0°C and the reflux temperature of the solvent. Alternatively, amides can be first converted to thioamides by treatment with a sulfurizing reagent such as Lawesson's reagent or diphosphorus pentasulfide in a suitable solvent (e.g., toluene, xylene, dioxane, or tetrahydrofuran) at temperatures between ambient temperature and the reflux temperature of the solvent. In the second step, fluorination can be achieved using a reagent such as bis(2-methoxyethyl)aminosulfur trifluoride (Deoxo-Fluoro®) in a suitable solvent (e.g., dichloromethane) optionally in the presence of a Lewis acid catalyst (e.g., antimonyl chloride (III)), generally at temperatures between 0°C and ambient temperature. For relevant examples of this reaction in the literature, see EP 1437342; WO 2006 / 049014; Tetrahedron, 2013, 69, 8943-8951 and ChemMedChem, 2013, 8, 779-799; and the references cited therein. [ka]

[0219] As shown in Scheme 9, a benzoxazinone of formula 10a (i.e., a compound of formula 10, where R b is H) can be converted to compounds of formula 12 (wherein R a (C1-C4 alkyl, typically methyl or ethyl). This reaction is readily accomplished under a range of conditions, such as iron metal in the presence of an acid such as acetic acid, hydrochloric acid, or aqueous ammonium chloride, optionally with a solvent such as methanol, ethanol, ethyl acetate, or N,N-dimethylformamide, at temperatures ranging from ambient to the reflux temperature of the solvent. Other suitable conditions include zinc metal with acetic acid or aqueous ammonium chloride, and tin chloride in aqueous hydrochloric acid or ethanol. Alternatively, the reaction can be accomplished using a transition metal catalyst such as palladium on carbon, platinum oxide, or Raney nickel under an atmosphere of hydrogen in a suitable solvent (e.g., methanol, ethanol, ethyl acetate, or tetrahydrofuran). Temperatures typically range from ambient to 80°C. This reaction can generally be carried out in a Parr hydrogenation apparatus. For relevant examples of this reaction in the literature, see WO 2015 / 095795 and Angew. Chem. Int. Ed. 2014, 53, 6126-6130. [ka]

[0220] As shown in Scheme 10, compounds of formula 12 can be prepared by reacting an α-hydroxy ester of formula 14 (wherein R ais a C1-C4 alkyl, typically methyl or ethyl) by the Mitsunobu reaction of a nitrophenol of formula 13 with a C1-C4 alkyl, typically methyl or ethyl. Typical reaction conditions include triphenylphosphine and an azodicarboxylate ester, such as diethyl azodicarboxylate or diisopropyl azodicarboxylate, in a solvent such as tetrahydrofuran or dichloromethane at a temperature ranging from about -10°C to the reflux temperature of the solvent. Alternatively, a compound of formula 12 can be prepared by the Mitsunobu reaction of a nitrophenol of formula 13 with an α-haloester of formula 15 (where LG is a leaving group such as Cl or Br, and R is a methyl group, typically methyl or ethyl) in the presence of a base, such as potassium carbonate or cesium carbonate, in a solvent such as N,N-dimethylformamide, acetone, or 1,4-dioxane at a temperature ranging from about 0°C to the reflux temperature of the solvent. a can be prepared by reaction with a C1-C4 alkyl, typically methyl or ethyl. For relevant examples of these reactions in the literature, see Bioorg.Med.Chem. 2013, 23, 4501-4505; Bioorg.Med.Chem. 2007, 15, 5912-5949 and WO 2017 / 205536. Nitrophenols, α-hydroxyesters and α-haloesters of formulae 13, 14 and 15 are generally commercially available or known in the literature. [ka]

[0221] Alternatively, benzoxazines of formula 8 can be prepared according to the following sequence: As shown in Scheme 11, β-aminoalcohols of formula 16 (wherein R bA compound of formula 18 (wherein X is H or a suitable protecting group such as Ts or Bn, and X is a halogen or pseudohalogen such as F, Cl, Br, I, or OTs) can be prepared by ring-opening of an epoxide of formula 18 by nucleophilic attack of an aniline of formula 17. This reaction can generally be accomplished by heating the aniline and epoxide neat or in a suitable solvent (e.g., ethanol or N,N-dimethylformamide) at temperatures generally ranging from 40°C to 180°C. Optionally, a base (e.g., potassium carbonate or sodium hydride), a Lewis acid (e.g., ytterbium(III) trifluoromethanesulfonate or lithium bromide), or a phase transfer catalyst (e.g., benzyltriethylammonium chloride or tetrabutylammonium bromide) can be added to facilitate the reaction. Those skilled in the art will recognize that the epoxide substituents and reaction conditions affect the regioselectivity of the reaction; for example, acidic conditions may reverse the regioselectivity of the epoxide ring-opening. For relevant examples of these reactions in the literature, see Ind. Eng. Chem. Res. 2003, 42, 680-686; Eur. J. Org. Chem. 2004, 3597-3600; J. Het. Chem. 2010, 47, 1406-1410 and WO 2015 / 095792; and references cited therein. The anilines and epoxides of formulas 17 and 18 are generally commercially available or known in the literature. [ka]

[0222] As shown in Scheme 12, N-tosyl-protected benzoxazines of formula 20 can be converted to β-amino alcohols of formula 16a (i.e., compounds of formula 16, where R bis Ts, and X is usually F, but in some instances is OTs). For examples of this reaction in the literature, see Ind. Eng. Chem. Res. 2003, 42, 680-686; WO 2015 / 095792; and J. Mol. Catal. A Chem. 2008, 288, 28-32. Benzoxazines of formula 8 can be prepared by removal of the N-tosyl protecting group. This can be achieved under reducing conditions, for example, by treatment with magnesium metal in methanol at a temperature ranging from 0°C to the reflux temperature of the solvent, optionally with sonication. Alternatively, the reaction can be achieved using acidic hydrolysis conditions, for example, treatment with sulfuric acid, either neat or in a solvent such as dichloromethane, generally at a temperature ranging from 0°C to the reflux temperature of the solvent. For relevant examples of these reactions in the literature, see Chem. Commun. 1999, 2095-2096; WO 2015 / 095792 and J. Org. Chem. 2021, 86, 16573-16581; and references cited therein. [ka]

[0223] Alternatively, as shown in Scheme 13, benzoxazines of formula 8 (wherein R b is H) or a benzoxazine of formula 21 (wherein R b is a suitable protecting group such as Ts or Bn) can be converted by transition metal catalyzed O-arylation to a β-amino alcohol of formula 16b (i.e., a compound of formula 16, where R bis H or a suitable protecting group, and X is a halogen such as Cl, Br, or I. The reaction can be catalyzed by a copper salt such as copper(I) iodide and a ligand such as 1,10-phenanthroline, or by a palladium salt or complex such as palladium(II) acetate or tris(dibenzylideneacetone)dipalladium(0) and a phosphine ligand such as 2-di-tert-butylphosphino-2'-(N,N-dimethylamino)biphenyl (t-BuDavePhos) or rac-2-(di-tert-butylphosphino)-1,1'-binaphthyl (TrixiePhos). These reactions are generally carried out in a solvent such as dioxane or toluene in the presence of a base such as sodium tert-butoxide, cesium carbonate, or potassium phosphate at temperatures ranging from ambient temperature to the reflux temperature of the solvent. For examples of this reaction in the literature, see J. Am. Chem. Soc. 2000, 122, 12907-12908; J. Am. Chem. Soc. 2001, 123, 12202-12206; J. Mol. Catal. A Chem. 2008, 288, 28-32 and Tetrahedron Lett. 2009, 50, 3790-3793. When a protecting group is utilized, removal using standard procedures known to those skilled in the art provides the benzoxazine of formula 8. [ka]

[0224] In some instances, benzoxazines of formula 8 may be more readily accessible following the sequence shown in Scheme 14. Compounds of formula 22 may be prepared by ring-opening of an epoxide of formula 18 via nucleophilic attack of a phenol of formula 13. This reaction may generally be accomplished in the presence of a base (e.g., monosodium phosphate, sodium phosphate, potassium carbonate, sodium hydride, sodium hydroxide, cesium fluoride, or 1,8-diazabicyclo[5.4.0]undec-7-ene) in a suitable solvent (e.g., acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, dichloromethane, toluene, methanol, isopropanol, and / or water) at temperatures generally ranging from ambient to 180°C. Lewis acids (e.g., zinc chloride or boron trifluoride diethyl etherate) may also be used to promote the reaction. Those skilled in the art will recognize that the epoxide substituents and reaction conditions may affect the regioselectivity of the reaction; for example, acidic conditions may reverse the regioselectivity of the epoxide ring-opening. For relevant examples of this reaction in the literature, see WO 2000 / 010994; US Patent Application Publication No. 2007 / 0185097A1; WO 2009 / 009501; J.Med.Chem.2023,66,1583-1600 and Angew.Chem.Int.Ed.2023,62,e202217064.The compound of formula 23 can then be prepared by standard conditions (see scheme 9) as previously described, for example, nitro reduction, which can be achieved using palladium on carbon under an atmosphere of hydrogen in a suitable solvent such as methanol.For relevant examples of this reaction in the literature, see WO 2009 / 009501, WO 2010 / 047956 and WO 2019 / 162323. Benzoxazines of formula 8 can be prepared from compounds of formula 23 by treatment with an acid (e.g., phosphoric acid or p-toluenesulfonic acid) in a suitable solvent (e.g., xylene or toluene) at temperatures generally ranging from ambient temperature to the reflux temperature of the solvent.For relevant examples of this reaction in the literature, see WO 2017 / 108723 and Synth. Commun. 1998, 28, 4105-4121. In some instances, it may be advantageous to convert the alcohol to a leaving group (e.g., Cl or OMs) to facilitate the reaction, which can then proceed in the presence of a base (e.g., potassium carbonate) in a suitable solvent (e.g., N,N-dimethylformamide) at temperatures ranging from ambient temperature to the reflux temperature of the solvent. For relevant examples of this reaction in the literature, see WO 2002 / 070726. Alternatively, in some instances, the use of a suitable aniline protecting group (e.g., tosyl) allows for ring closure using Mitsunobu conditions (see Scheme 10) as previously described, e.g., triphenylphosphine and diethyl azodicarboxylate in a suitable solvent such as tetrahydrofuran. For relevant examples of this reaction in the literature see Org. Biomol. Chem. 2010, 8, 2823-2828 and J. Org. Chem. 2015, 80, 3815-3824. [ka]

[0225] As shown in Scheme 15, a benzoxazine of formula 8c (i.e., a compound of formula 8 (wherein one R 3b (i.e., α-amino R 3b ) is R c and the remaining α-amino R 3b is H;R c is H or C1-C3 alkyl; or R c is R 3a or α-oxo R 3b and can be combined to form a ring) can be converted to compounds of formula 24 (wherein R c is H or C1-C3 alkyl; or R c is R 3a or R 3band (which can combine to form a ring). This reaction can be accomplished using a transition metal catalyst such as, but not limited to, palladium on carbon, platinum on carbon, or Raney nickel under an atmosphere of hydrogen in a suitable solvent (e.g., methanol, ethanol, isopropanol, ethyl acetate, toluene, or tetrahydrofuran). Temperatures typically range from ambient to 80°C. This reaction can generally be carried out in a Parr hydrogenation apparatus, optionally above atmospheric pressure. Alternatively, the reaction can be accomplished in a stepwise manner. Nitro reduction can be accomplished under a range of conditions, such as iron metal in the presence of an acid such as acetic acid, hydrochloric acid, or aqueous ammonium chloride, optionally with a solvent such as methanol, ethanol, ethyl acetate, tetrahydrofuran, or N,N-dimethylformamide, at temperatures ranging from ambient to the reflux temperature of the solvent. Other suitable conditions include zinc metal with acetic acid or aqueous ammonium chloride, and tin chloride in aqueous hydrochloric acid or ethanol. The second step involves imine reduction, which can be accomplished using a reducing agent such as sodium borohydride, sodium cyanoborohydride, or lithium aluminum hydride in a suitable solvent (e.g., ethanol, methanol, tetrahydrofuran, or dichloromethane, optionally with a co-solvent or additive such as water or acetic acid) at a temperature generally between −78° C. and the reflux temperature of the solvent. Other suitable reducing conditions for this step include, but are not limited to, hydrogen and palladium on carbon in a solvent such as methanol, or triethylsilane and trifluoroacetic acid in a solvent such as dichloromethane. For relevant examples of this reaction in the literature, see J. Org. Chem. 2002, 67, 6097-6103; WO 2014 / 171527; J. Org. Chem. 2015, 80, 3815-3824; WO 2015 / 124868; WO 2017 / 172505 and WO 2022 / 035799. [ka]

[0226] As shown in Scheme 16, compounds of formula 24 can be prepared by reaction of compounds of formula 26 (LG is a leaving group such as Cl or Br, and R is a methyl group such as Cl or Br) in the presence of a base such as potassium carbonate, cesium carbonate, sodium bicarbonate, or sodium hydride, optionally with an additive such as sodium iodide, in a solvent such as N,N-dimethylformamide, acetone, or 1,4-dioxane at a temperature typically ranging from 0° C. to the reflux temperature of the solvent. c is H or C1-C3 alkyl; or R c is R 3a or R 3b Alternatively, the Mitsunobu reaction conditions may in some cases be used to prepare compounds of formula 25 (wherein R c is H or C1-C3 alkyl; or R c is R 3a or R 3b (which can be combined with the aryl group to form a ring). Typical reaction conditions include triphenylphosphine and an azodicarboxylic acid ester, such as diethyl azodicarboxylate or diisopropyl azodicarboxylate, in a solvent such as tetrahydrofuran or dichloromethane at a temperature ranging from about −10° C. to the reflux temperature of the solvent. For relevant examples of these reactions in the literature, see J. Med. Chem. 1988, 31, 1548-1558; WO 2001 / 090088; WO 2004 / 080973; and WO 2018 / 013770. Nitrophenols, α-hydroxycarbonyls, and α-halocarbonyls of formulas 13, 25, and 26 are generally commercially available or known in the literature. In some instances, compounds of formula 24 may be more readily accessible using a protecting group to mask the carbonyl group, such as an acetal group to mask the aldehyde, or via standard functional group interconversion of one carbonyl functionality to another. [ka]

[0227] Those skilled in the art will recognize that various functional groups can be converted into others to obtain different compounds of Formula 1. A valuable resource demonstrating simple and straightforward interconversion of functional groups can be found in Larock, R.C., Comprehensive Organic Transformations: A Guide to Functional Group Preparations, 2nd Ed., Wiley-VCH, New York, 1999. For example, intermediates for preparing compounds of Formula 1 may contain an aromatic nitro group, which can be reduced to an amino group and subsequently converted to various halides via reactions well known in the art, such as the Sandmeyer reaction, to obtain compounds of Formula 1. The reactions described above can often be performed in different orders.

[0228] It is recognized that some of the reagents and reaction conditions described above for preparing compounds of Formula 1 may be incompatible with certain functional groups present in those intermediates. In these cases, incorporating protection / deprotection sequences into the synthesis or functional group interconversions will aid in obtaining the desired reaction products. The use and selection of protecting groups will be apparent to those familiar with chemical synthesis (see, for example, Greene, TW; Wuts, PGM, Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). As those skilled in the art will recognize, in some cases, completing the synthesis of compounds of Formula 1 may require the performance of additional conventional synthetic steps not specifically described after the introduction of certain reagents as shown in the various individual schemes. As those skilled in the art will also recognize, it may be necessary to combine and perform the steps described in the above schemes in an order other than the specific order presented to prepare compounds of Formula 1.

[0229] Those skilled in the art will further recognize that the compounds of Formula 1 and intermediates described herein can also be subjected to a variety of electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.

[0230] Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following non-limiting examples illustrate the present invention. The steps in the following examples describe the procedure for each step in an overall synthetic transformation, and the starting material for each step does not necessarily have to be prepared by the specific preparative procedure whose procedure is described in another example or step. Percentages are by weight, except in the case of chromatographic solvent mixtures or unless otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise specified. Unless otherwise indicated, all NMR spectra are reported downfield in CDCl3 from tetramethylsilane at 500 MHz, where s means singlet, brs means broad singlet, d means doublet, t means triplet, q means quartet, p means quintet, and m means multiplet. [Example]

[0231] Synthesis Example 1 Preparation of [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-[5-(3-isopropyl-1,2,4-triazol-1-yl)-2-methoxy-phenyl]methanone (compound 84) Step A: Preparation of methyl (2S)-2-(2-chloro-6-nitro-phenoxy)propanoate To a stirred mixture of 2-chloro-6-nitrophenol (15 g, 86 mmol) and triphenylphosphine (29 g, 112 mmol) in anhydrous tetrahydrofuran (245 mL) was added (R)-(+)-methyl lactate (12.4 mL, 130 mmol). The mixture was cooled to 0 °C, and then a solution of diisopropyl azodicarboxylate (22 mL, 112 mmol) in anhydrous tetrahydrofuran (25 mL) was added over 20 minutes. The reaction mixture was stirred overnight at room temperature and then concentrated. A mixture of hexane and diethyl ether (1:1, 700 mL) was added, and the mixture was stirred for 2 hours, resulting in the formation of a precipitate. The mixture was filtered through a pad of Celite, rinsed with hexane / diethyl ether (1:1, 200 mL), and the filtrate was concentrated. The crude material was purified by column chromatography on silica gel (gradient of 10-25% ethyl acetate in hexanes) to give the title compound as a yellow oil (23 g). 1 H NMR(CDCl3)δ 7.71(dd,1H),7.60(dd,1H),7.19-7.16(m,1H),4.93(q,1H),3.71(s,3H),1.69(d,3H).

[0232] Step B: Preparation of (2S)-8-chloro-2-methyl-4H-1,4-benzoxazin-3-one To a stirred solution of methyl (2S)-2-(2-chloro-6-nitro-phenoxy)propanoate (i.e., the product of Step A) (22 g, 86 mmol) in ethanol (310 mL) was added a solution of ammonium chloride (9.2 g, 173 mmol) in water (35 mL) at 50°C. Iron powder (14.5 g, 259 mmol) was then added portionwise over 12 minutes, and the reaction mixture was heated to 50°C-70°C. After stirring at 70°C for 48 hours, the mixture was cooled to room temperature and filtered through a pad of Celite. The filtrate was concentrated, followed by the addition of ethyl acetate and water. The layers were separated, and the aqueous phase was extracted with ethyl acetate. The combined organic extracts were washed with saturated aqueous ammonium chloride, dried over anhydrous magnesium sulfate, filtered through a pad of Celite, and concentrated to afford the title compound (16.6 g) as a white solid, which was used without further purification. 1 H NMR(CDCl3)δ 8.47(br s,1H),7.06(dd,1H),6.91-6.88(m,1H),6.72(dd,1H),4.77(q,1H),1.63(d,3H).

[0233] Step C: Preparation of (2S)-8-chloro-2-methyl-3,4-dihydro-2H-1,4-benzoxazine To a stirred solution of (2S)-8-chloro-2-methyl-4H-1,4-benzoxazin-3-one (i.e., the product of Step B) (9.1 g, 46 mmol) in anhydrous tetrahydrofuran (100 mL) was added borane tetrahydrofuran complex (1 M in tetrahydrofuran, 92 mL, 92 mmol) over 30 minutes at 0°C. The reaction mixture was stirred at room temperature overnight, then cooled to 0°C, and methanol (70 mL) was added slowly. After stirring at room temperature for 1 hour, the mixture was concentrated and partitioned between ethyl acetate and water. The layers were separated, and the organic phase was washed with water, brine, dried over anhydrous magnesium sulfate, and concentrated to give the title compound (8.3 g) as a white solid, which was used without further purification. 1H NMR(CDCl3)δ 6.73(dd,1H),6.67 - 6.64(m,1H),6.49(dd,1H),4.34 - 4.28(m,1H),3.82(br s,1H),3.37(dd,1H),3.13(dd,1H),1.44(d,3H).

[0234] Step D: Preparation of [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-(5-iodo-2-methoxy-phenyl)methanone To a stirred solution of (2S)-8-chloro-2-methyl-3,4-dihydro-2H-1,4-benzoxazine (i.e., the product of Step C) (0.7 g, 3.8 mmol), 5-iodo-2-methoxybenzoic acid (1.06 g, 3.8 mmol), and triethylamine (1.6 mL, 11.4 mmol) in 1,2-dichloroethane (13 mL) was added propylphosphonic anhydride (50 wt.% in ethyl acetate, 4.9 mL, 8.2 mmol). The mixture was stirred at 70 °C for 24 h, then cooled to room temperature and concentrated. The crude material was purified by column chromatography on silica gel (0-30% ethyl acetate in hexanes gradient). The isolated material was dissolved in ethyl acetate, washed with 1N aqueous hydrochloric acid, 1N aqueous sodium hydroxide, brine, dried over anhydrous magnesium sulfate, concentrated, and then further purified by column chromatography on silica gel (gradient of 0 to 20% ethyl acetate in hexanes) to give the title compound (1.3 g) as a white foam. MS(ES + ) m / z Actual value: (M+H) + ,C 17 H 15 ClINO3, 444.2, theoretical value 444.0.

[0235] Step E: Preparation of [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-[5-(3-isopropyl-1,2,4-triazol-1-yl)-2-methoxy-phenyl]methanone A dry vial was charged with [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-(5-iodo-2-methoxyphenyl)methanone (i.e., the product of Step D) (1.03 g, 2.32 mmol), 3-isopropyl-1H-1,2,4-triazole (0.31 g, 2.79 mmol), potassium carbonate (0.64 g, 4.64 mmol), and copper(I) iodide (88 mg, 0.46 mmol), followed by purging with nitrogen gas for 10 minutes. Anhydrous N,N-dimethylformamide (8 mL) was added, and the mixture was aerated with nitrogen gas for 5 minutes, followed by the addition of trans-N,N'-dimethylcyclohexane-1,2-diamine (0.18 mL, 1.16 mmol). The mixture was stirred at 105° C. overnight, then cooled to room temperature and filtered through a pad of Celite. The filtrate was washed with water (×3), filtered through a plug of silica gel, and concentrated. The crude material was purified by reverse-phase chromatography on a C18 column (water / acetonitrile gradient) to give the title compound (630 mg) as a white solid. MS(ES + ) m / z Actual value: (M+H) + ,C 22 H 23 ClN4O3, 427.4, theoretical value 427.2.

[0236] Synthesis Example 2 Preparation of [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][2-methyl-5-(3-methyl-1H-1,2,4-triazol-1-yl)phenyl]methanone (Compound 74) and [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][2-methyl-5-(5-methyl-1H-1,2,4-triazol-1-yl)phenyl]methanone (Compound 126) Step A: Preparation of [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-(5-iodo-2-methyl-phenyl)methanone To a stirred solution of (2S)-8-chloro-2-methyl-3,4-dihydro-2H-1,4-benzoxazine (i.e., the product of Step C in Synthesis Example 1) (1.0 g, 5.4 mmol), 5-iodo-2-methyl-benzoic acid (1.4 g, 5.4 mmol), and N,N-diisopropylethylamine (2.4 mL, 13.6 mmol) in ethyl acetate (15 mL) was added propylphosphonic anhydride (50 wt. % in ethyl acetate, 5.2 mL, 8.7 mmol) at 0° C. The mixture was stirred at room temperature overnight and then heated at 70° C. for 24 hours. The mixture was cooled to room temperature, and additional N,N-diisopropylethylamine (2.4 mL, 13.6 mmol) and propylphosphonic anhydride (50 wt. % in ethyl acetate, 5.2 mL, 8.7 mmol) were added, followed by stirring the mixture at 70° C. for 22 hours. The mixture was cooled to room temperature and water was added. The layers were separated, the aqueous phase was extracted with ethyl acetate, and the combined organic extracts were washed with 1N aqueous hydrochloric acid, brine, dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (gradient of 0 to 20% ethyl acetate in hexanes) to give the title compound containing 5-iodo-2-methyl-benzoic acid. The material was dissolved in ethyl acetate and washed with 1N aqueous sodium hydroxide (x2), brine (x1), dried over anhydrous sodium sulfate, and concentrated to give the title compound (1.6 g) as a white foam. MS(ES + ) m / z Actual value: (M+H) + ,C 17 H 15 ClINO2, 428.1, theoretical value 428.0.

[0237] Step B: Preparation of [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][2-methyl-5-(3-methyl-1H-1,2,4-triazol-1-yl)phenyl]methanone (isomer 1) (Compound 74) and [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][2-methyl-5-(5-methyl-1H-1,2,4-triazol-1-yl)phenyl]methanone (isomer 2) (Compound 126) A dry vial was charged with [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-(5-iodo-2-methyl-phenyl)methanone (i.e., the product of Step A) (0.18 g, 0.42 mmol), 3-methyl-1H-1,2,4-triazole (42 mg, 0.50 mmol), potassium carbonate (0.12 g, 0.88 mmol), and copper(I) iodide (8.0 mg, 0.04 mmol), followed by purging with nitrogen gas for 10 minutes. Anhydrous N,N-dimethylformamide (3 mL) and trans-N,N'-dimethylcyclohexane-1,2-diamine (0.02 mL, 0.13 mmol) were added, and the mixture was stirred at 110 °C for 19 hours. The mixture was cooled to room temperature, diluted with ethyl acetate and saturated aqueous sodium bicarbonate, and stirred for 10 minutes. The layers were separated, the aqueous layer was extracted with ethyl acetate (x1), and the combined organic extracts were washed with brine (x2), dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (gradient of 0 to 100% ethyl acetate in hexanes) to afford the title compounds, Isomer 1 (90 mg) as a white solid and Isomer 2 (24 mg) as a yellow oil. Isomer 1: MS(ES + ) m / z Actual value: (M+H) + ,C 20 H 19 ClN4O2, 383.4, theoretical value 383.1. Isomer 2: MS(ES + ) m / z Actual value: (M+H) + ,C 20 H 19 ClN4O2, 383.4, theoretical value 383.1.

[0238] Synthesis Example 3 Preparation of [3-(3-bromo-1H-1,2,4-triazol-1-yl)phenyl][(2S)-2,3-dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl]methanone (compound 61) Step A: Preparation of methyl (2S)-2-(2-methyl-6-nitro-phenoxy)propanoate To a stirred mixture of 2-methyl-6-nitrophenol (10 g, 65 mmol) and triphenylphosphine (22 g, 85 mmol) in anhydrous tetrahydrofuran (100 mL) was added (R)-(+)-methyl lactate (9.4 mL, 98 mmol). The mixture was cooled to 0 °C, followed by the slow addition of a solution of isopropyl azodicarboxylate (17 mL, 85 mmol) in anhydrous tetrahydrofuran (20 mL). The reaction mixture was stirred overnight at room temperature and then concentrated. A mixture of hexane and diethyl ether (1:1, 350 mL) was added, and the mixture was stirred for 1 hour, resulting in the formation of a precipitate. The mixture was filtered through a pad of Celite, rinsed with hexane / diethyl ether (1:1, 150 mL), and the filtrate was concentrated. The crude material was purified by column chromatography on silica gel (0-30% ethyl acetate in hexane gradient) to give the title compound (14.5 g) as a yellow oil. 1 H NMR(CDCl3)δ 7.65-7.63(m,1H),7.41-7.39(m,1H),7.12-7.08(m,1H),4.56(q,1H),3.71(s,3H),2.38(s,3H),1.60(d,3H).

[0239] Step B: Preparation of (2S)-2,8-dimethyl-4H-1,4-benzoxazin-3-one To a stirred solution of methyl (2S)-2-(2-methyl-6-nitrophenoxy)propanoate (i.e., the product of Step A) (13.9 g, 58.2 mmol) in ethanol (210 mL) was added a solution of ammonium chloride (6.2 g, 116 mmol) in water (23 mL) at 50°C. Iron powder (9.7 g, 175 mmol) was then added portionwise over 15 minutes, and the reaction mixture was heated to 50°C-70°C. After stirring at 70°C for 23 hours, the mixture was cooled to room temperature and filtered through a pad of Celite. The filtrate was concentrated, followed by the addition of ethyl acetate and water. The layers were separated, and the aqueous phase was extracted with ethyl acetate (x1). The combined organic extracts were washed with saturated aqueous ammonium chloride solution (x1), dried over anhydrous magnesium sulfate, filtered through a pad of Celite, and concentrated to afford the title compound (9.2 g) as a white solid, which was used without further purification. 1 H NMR(CDCl3)δ 7.80(br s,1H),6.87-6.83(m,2H),6.64-6.60(m,1H),4.66(q,1H),2.25(s,3H),1.58(d,3H).

[0240] Step C: Preparation of (2S)-2,8-dimethyl-3,4-dihydro-2H-1,4-benzoxazine To a stirred solution of (2S)-2,8-dimethyl-4H-1,4-benzoxazin-3-one (i.e., the product of Step B) (10.3 g, 58 mmol) in anhydrous tetrahydrofuran (100 mL) was added borane tetrahydrofuran complex (1 M in tetrahydrofuran, 116 mL, 116 mmol) over 30 minutes at 0°C. The reaction mixture was stirred at room temperature overnight, then cooled to 0°C, and methanol (70 mL) was added slowly. After stirring at room temperature for 1 hour, the mixture was concentrated and partitioned between ethyl acetate and water. The layers were separated, and the organic phase was washed with water (x1), brine (x1), dried over anhydrous magnesium sulfate, and concentrated to give the title compound (9.4 g) as a light brown oil, which was used without further purification. 1H NMR(CDCl3)δ 6.68-6.65(m,1H),6.57-6.55(m,1H),6.48-6.46(m,1H),4.28-4.22(m,1H),3.68(br s,1H),3.34(dd,1H),3.10(dd,1H),2.20(s,3H),1.40(d,3H).

[0241] Step D: Preparation of [(2S)-2,8-dimethyl-2,3-dihydro-1,4-benzoxazin-4-yl]-(3-iodophenyl)methanone To a stirred solution of (2S)-2,8-dimethyl-3,4-dihydro-2H-1,4-benzoxazine (i.e., the product of Step C) (8.5 g, 52 mmol), 3-iodobenzoic acid (12.9 g, 52 mmol), and triethylamine (17 mL, 120 mmol) in 1,2-dichloroethane (125 mL) was slowly added propylphosphonic anhydride (50 wt.% in ethyl acetate, 50 mL, 84 mmol). The mixture was stirred at 60°C for 15 hours, then cooled to room temperature, and water was added. The layers were separated, the aqueous phase was extracted with dichloromethane (x1), and the combined organic extracts were washed with 1N aqueous hydrochloric acid (x1) and 1N aqueous sodium hydroxide (x1). The sodium hydroxide layer was extracted with dichloromethane (x1), and the combined organic extracts were washed with brine (x1), dried over anhydrous magnesium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (gradient of 0-20% ethyl acetate in hexanes) to give the title compound as a white foam (17.6 g). 1 H NMR(CDCl3)δ 7.88-7.87(m,1H),7.77-7.74(m,1H),7.38-7.37(m,1H),7.07-7.04(m,1H),6.88-6.87(m,1H),6 .81-6.47(m,2H),4.50-4.44(m,1H),4.37-4.23(m,1H),3.33(dd,1H),2.22(s,3H),1.43(d,3H).

[0242] Step E: Preparation of [3-(3-bromo-1H-1,2,4-triazol-1-yl)phenyl][(2S)-2,3-dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl]methanone A dry vial was charged with [(2S)-2,8-dimethyl-2,3-dihydro-1,4-benzoxazin-4-yl]-(3-iodophenyl)methanone (i.e., the product of Step D) (1.14 g, 2.89 mmol), 3-bromo-1H-1,2,4-triazole (0.51 g, 3.47 mmol), potassium carbonate (0.84 g, 6.1 mmol), and copper(I) iodide (55 mg, 0.29 mmol), followed by purging with nitrogen gas for 10 minutes. Anhydrous N,N-dimethylformamide (11 mL) and trans-N,N'-dimethylcyclohexane-1,2-diamine (0.14 mL, 0.87 mmol) were added, and the mixture was stirred at 110 °C for 17 hours. The mixture was cooled to room temperature and diluted with water and ethyl acetate. The layers were separated, the aqueous phase was extracted with ethyl acetate (x2), and the combined organic extracts were washed with water (x3), brine (x1), dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (gradient of 0 to 60% ethyl acetate in hexanes) to give the title compound as a pale green solid. The solid was dissolved in ethyl acetate, washed with saturated aqueous ammonium chloride solution (x3), dried over anhydrous sodium sulfate, and concentrated to give the title compound as a pale yellow solid (0.62 g). 1 H NMR(CDCl3)δ 8.33(s,1H),7.77-7.72(m,2H),7.50-7.47(m,2H),6.89-6.88(m,1H),6.69-6.37(m ,2H),4.55-4.48(m,1H),4.46-4.32(m,1H),3.36(dd,1H),2.23(s,3H),1.46(d,3H).

[0243] Synthesis Example 4 Preparation of [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][3-(1-methyl-1H-pyrazol-4-yl)phenyl]methanone (Compound 119) To a stirred solution of (2S)-8-chloro-2-methyl-3,4-dihydro-2H-1,4-benzoxazine (i.e., the product of Step C in Synthesis Example 1) (91 mg, 0.49 mmol), 3-(1-methylpyrazol-4-yl)benzoic acid (90 mg, 0.44 mmol), and triethylamine (0.21 mL, 1.5 mmol) in 1,2-dichloroethane (3 mL) was added propylphosphonic anhydride (50 wt.% in ethyl acetate, 0.63 mL, 1.1 mmol). The mixture was stirred at 70°C for 24 hours, then cooled to room temperature and concentrated. The crude material was purified by column chromatography on silica gel (0 to 50% ethyl acetate in hexanes gradient) to afford the title compound (124 mg) as a white foam. 1 H NMR(CDCl3)δ 7.72(s,1H),7.62-7.61(m,1H),7.58(s,1H),7.55-7.53(m,1H),7.36-7.32(m,1H),7.28-7.26(m,1H),7.11-7.09(m,1H) ),6.99-6.86(m,1H),6.62-6.59(m,1H),4.59-4.53(m,1H),4.32-4.29(m,1H),3.95(s,3H),3.44(dd,1H),1.48(d,3H).

[0244] Synthesis Example 5 Preparation of [3-(3-cyclopentyl-1H-1,2,4-triazol-1-yl)phenyl][(2S)-2,3-dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl]methanone (compound 80) A stirred solution of [3-(3-bromo-1H-1,2,4-triazol-1-yl)phenyl][(2S)-2,3-dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl]methanone (i.e., the product of Synthesis Example 3) (136 mg, 0.33 mmol) in anhydrous tetrahydrofuran (1 mL) was briefly purged with nitrogen gas (approximately 1 min), followed by the addition of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (24 mg, 0.03 mmol). Cyclopentylzinc bromide (0.5 M in tetrahydrofuran, 2.6 mL, 1.3 mmol) was added dropwise at room temperature, and the mixture was then stirred at 60°C for 1 hour. The mixture was cooled to room temperature, and saturated aqueous ammonium chloride solution was added. The mixture was extracted with ethyl acetate (x2), and the combined organic extracts were washed with brine (x1), dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (gradient of 0 to 100% ethyl acetate in hexanes) to give the title compound (53 mg) as a pale orange foam. 1 H NMR(CDCl3)δ 8.33(s,1H),7.80-7.73(m,2H),7.47-7.39(m,2H),6.89-6.87(m,1H),6.76-6.45(m,2H),4.55-4.47(m,1H),4.44-4.32(m,1H),3 .36(dd,1H),3.28(p,1H),2.23(s,3H),2.14-2.07(m,2H),1.95-1.88(m,2H),1.87-1.79(m,2H),1.74-1.67(m,2H),1.45(d,3H).

[0245] Synthesis Example 6 Preparation of [(2S)-2,3-dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl][3-(3-ethynyl-1H-1,2,4-triazol-1-yl)phenyl]methanone (compound 64) Step A: [(2S)-2,8-Dimethyl-2,3-dihydro-1,4-benzoxazin-4-yl]-[3-[3-(2-trimethylsilylethynyl)-1,2,4-triazol-1-yl]phenyl]methanone A dry vial was charged with [3-(3-bromo-1H-1,2,4-triazol-1-yl)phenyl][(2S)-2,3-dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl]methanone (i.e., the product of Synthesis Example 3) (134 mg, 0.32 mmol), copper(I) iodide (12 mg, 0.06 mmol), anhydrous N,N-dimethylformamide (3 mL), and triethylamine (0.09 mL, 0.65 mmol), and the mixture was purged with nitrogen gas for 4 minutes. Ethynyltrimethylsilane (0.23 mL, 1.6 mmol) was added, and the mixture was purged with nitrogen gas for 2 minutes. Tetrakis(triphenylphosphine)palladium(0) (70 mg, 0.06 mmol) was then added, and the mixture was stirred at 50 °C for 13 hours. The mixture was cooled to room temperature, then diluted with ethyl acetate, washed with saturated aqueous sodium bicarbonate (x2), brine (x1), dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (gradient of 0 to 60% ethyl acetate in hexanes) to give the title compound (98 mg) as a brown foam. 1 H NMR(CDCl3)δ 8.41(s,1H),7.81-7.75(m,2H),7.49-7.45(m,2H),6.89-6.87(m,1H),6.76-6.41(m,2H),4 .55-4.47(m,1H),4.44-4.32(m,1H),3.36(dd,1H),2.23(s,3H),1.45(d,3H),0.29(s,9H).

[0246] Step B: Preparation of [(2S)-2,3-dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl][3-(3-ethynyl-1H-1,2,4-triazol-1-yl)phenyl]methanone To a solution of [(2S)-2,8-dimethyl-2,3-dihydro-1,4-benzoxazin-4-yl]-[3-[3-(2-trimethylsilylethynyl)-1,2,4-triazol-1-yl]phenyl]methanone (i.e., the product of Step A) (81 mg, 0.19 mmol) in methanol (4 mL) was added potassium carbonate (30 mg, 0.22 mmol). The mixture was stirred at room temperature for 4.5 hours and then filtered through a pad of Celite, rinsing with ethyl acetate, and the filtrate was concentrated. The crude material was purified by column chromatography on silica gel (gradient of 0 to 50% ethyl acetate in hexanes) to afford the title compound (42 mg) as a pale yellow foam. 1 H NMR(CDCl3)δ 8.42(s,1H),7.81-7.76(m,2H),7.50-7.47(m,2H),6.89-6.88(m,1H),6.76-6.39(m,2H),4 .56-4.48(m,1H),4.45-4.33(m,1H),3.36(dd,1H),3.17(s,1H),2.23(s,3H),1.46(d,3H).

[0247] Synthesis Example 7 Preparation of [(2S)-2,3-dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl][3-[3-(methoxymethyl)-1H-1,2,4-triazol-1-yl]phenyl]methanone (Compound 101) A dry 40 mL vial was charged with [3-(3-bromo-1H-1,2,4-triazol-1-yl)phenyl][(2S)-2,3-dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl]methanone (i.e., the product of Synthesis Example 3) (104 mg, 0.25 mmol), potassium trifluoro(methoxymethyl)boranide (78 mg, 0.52 mmol), [Ir(dF(CF3)ppy)2(bpy)]PF6 (5.3 mg, 0.005 mmol), and [4,4'-bis(1,1-dimethylethyl)-2,2'-bipyridine]nickel(II) dichloride (5.3 mg, 0.013 mmol), followed by purging with nitrogen gas for 8 minutes. Anhydrous, degassed 1,4-dioxane (4.8 mL) was added, followed by 2,6-lutidine (0.10 mL, 0.88 mmol). The mixture was then stirred and irradiated with two blue Kessil LED lights (one 34 W and one 40 W, approximately 4 cm apart, with a cooling fan to keep the temperature from rising significantly) for 18 hours. The mixture was partitioned between water and ethyl acetate, the layers were separated, and the aqueous phase was extracted with ethyl acetate (x2). The combined organic extracts were washed with brine (x1), dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (gradient of 0 to 100% ethyl acetate in hexane) to give the title compound (45 mg) as a pale yellow foam. 1 H NMR(CDCl3)δ 8.42(s,1H),7.82-7.76(m,2H),7.48-7.43(m,2H),6.89-6.87(m,1H),6.76-6.41(m,2H),4.63(s ,2H),4.55-4.48(m,1H),4.44-4.31(m,1H),3.51(s,3H),3.36(dd,1H),2.23(s,3H),1.45(d,3H).

[0248] Synthesis Example 8 Preparation of [(2S)-2,3-dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl][3-[3-(3-oxetanyl)-1H-1,2,4-triazol-1-yl]phenyl]methanone (Compound 109) A dry 40 mL vial was charged with [3-(3-bromo-1H-1,2,4-triazol-1-yl)phenyl][(2S)-2,3-dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl]methanone (i.e., the product of Synthesis Example 3) (101 mg, 0.24 mmol), [Ir(dF(CF3)ppy)2(dtbbpy)]PF6 (3.5 mg, 0.003 mmol), and [4,4'-bis(1,1-dimethylethyl)-2,2'-bipyridine]nickel(II) dichloride (9.1 mg, 0.023 mmol), followed by purging with nitrogen gas for 7 minutes. Anhydrous, degassed 1,4-dioxane (3 mL) was added, followed by 2,6-lutidine (0.14 mL, 1.2 mmol), tris(trimethylsilyl)silane (0.11 mL, 0.36 mmol), and 3-bromooxetane (0.04 mL, 0.48 mmol), and the mixture was aerated with nitrogen gas for 6 minutes. The mixture was stirred and irradiated with two blue Kessil LED lights (one 34 W and one 40 W, approximately 6 cm apart, with a cooling fan to keep the temperature from rising significantly) for 18 hours. The mixture was diluted with saturated aqueous sodium bicarbonate (2 mL) and water (1 mL) and subsequently extracted with a 4:1 mixture of dichloromethane / isopropanol (x2) and dichloromethane (x1). The combined organic extracts were washed with brine (x1), dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (gradient of 0-80% ethyl acetate in hexanes) to give the title compound (33 mg) as a white foam. 1 H NMR(CDCl3)δ 8.42(s,1H),7.82-7.75(m,2H),7.48-7.43(m,2H),6.89-6.88(m,1H),6.78-6.44(m ,2H),5.06-5.02(m,4H),4.56-4.34(m,3H),3.37(dd,1H),2.24(s,3H),1.46(d,3H).

[0249] Synthesis Example 9 Preparation of [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][3-(2-methyl-2H-1,2,3-triazol-4-yl)phenyl]methanone (Compound 127) Step A: Preparation of [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-(3-iodophenyl)methanone To a stirred solution of (2S)-8-chloro-2-methyl-3,4-dihydro-2H-1,4-benzoxazine (i.e., the product of Step C in Synthesis Example 1) (1.5 g, 8.2 mmol) in dichloromethane (45 mL) was added N,N-diisopropylethylamine (2.1 mL, 12 mmol) at 0° C., followed by 3-iodobenzoyl chloride (2.3 g, 8.6 mmol). The mixture was stirred overnight at room temperature and then diluted with dichloromethane, washed with 1 N aqueous hydrochloric acid solution (×1), 1 N aqueous sodium hydroxide solution (×1), brine (×1), dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (0-30% ethyl acetate in hexanes gradient) to afford the title compound (3.27 g) as a white foam. 1 H NMR(CDCl3)δ 7.87(m,1H),7.80-7.78(m,1H),7.40-7.38(m,1H),7.12-7.08(m,2H),6.96-6 .61(m,2H),4.57-4.51(m,1H),4.30-4.22(m,1H),3.40(dd,1H),1.47(d,3H).

[0250] Step B: Preparation of [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]methanone A dry vial was charged with [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-(3-iodophenyl)methanone (i.e., the product of Step A) (204 mg, 0.49 mmol), bis(pinacolato)diboron (163 mg, 0.64 mmol), potassium acetate (145 mg, 1.48 mmol), and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (18 mg, 0.025 mmol), followed by purging with nitrogen gas. Anhydrous dimethyl sulfoxide (3 mL) was added, and the mixture was stirred at 80 °C overnight. The mixture was cooled to room temperature and diluted with water and ethyl acetate. The layers were separated, the aqueous phase was extracted with ethyl acetate (×1), and the combined organic extracts were washed with water (×1), brine (×1), dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (gradient of 0-100% ethyl acetate in hexanes) to give the title compound (187 mg) as a pale yellow foam. 1 H NMR(CDCl3)δ 7.98-7.97(m,1H),7.89-7.87(m,1H),7.52-7.49(m,1H),7.37-7.34(m,1H),7.09-6.90(m,2H),6.63 -6.59(m,1H),4.55-4.49(m,1H),4.29-4.20(m,1H),3.40(dd,1H),1.45(d,3H),1.35-1.33(m,12H).

[0251] Step C: Preparation of [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][3-(2-methyl-2H-1,2,3-triazol-4-yl)phenyl]methanone A microwave vial was charged with [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]methanone (i.e., the product of Step B) (174 mg, 0.42 mmol), 4-bromo-2-methyl-1,2,3-triazole (136 mg, 0.84 mmol), sodium carbonate (147 mg, 1.39 mmol), 1,2-dimethoxyethane (4 mL), and water (1.4 mL), and the mixture was then aerated with nitrogen gas for 5 minutes. Tetrakis(triphenylphosphine)palladium(0) (48 mg, 0.042 mmol) was added, and the vial was then sealed and stirred in a microwave at 140 °C for 25 minutes. The mixture was cooled to room temperature, diluted with dichloromethane, washed with saturated aqueous sodium bicarbonate (x2), brine (x1), dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (0-100% ethyl acetate in hexanes gradient) to give the title compound (107 mg) as a pale yellow foam. 1 H NMR(CDCl3)δ 7.94-7.93(m,1H),7.87-7.85(m,1H),7.80(s,1H),7.44-7.39(m,2H),7.11-6.87(m,2H),6.6 2-6.59(m,1H),4.59-4.53(m,1H),4.34-4.28(m,1H),4.24(s,3H),3.44(dd,1H),1.48(d,3H).

[0252] Synthesis Example 10 Preparation of 4-[3-[[(2S)-2,3-dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl]carbonyl]phenyl]-2,4-dihydro-3H-1,2,4-triazol-3-one (Compound 122) Step A: Preparation of 3-(5-oxo-1H-1,2,4-triazol-4-yl)benzoic acid To a stirred solution of methyl 3-aminobenzoate (2 g, 13 mmol) in methanol (20 mL), trimethyl orthoformate (1.4 mL, 12.6 mmol), methyl carbazate (1.13 g, 12.6 mmol), and p-toluenesulfonic acid monohydrate (50 mg, 0.26 mmol) were added, and the mixture was stirred at 65° C. for 48 hours. Sodium methoxide (25 wt.% in methanol, 8.58 g, 39.7 mmol) was added, and the mixture was stirred at 50° C. overnight, then cooled to room temperature and diluted with water. 1N aqueous sodium hydroxide solution was added, and the mixture was washed with diethyl ether (×3). The aqueous phase was acidified to a pH of approximately 2 with 1N aqueous hydrochloric acid and extracted with ethyl acetate (x2), and the combined organic extracts were subsequently washed with water (x1), brine (x1), dried over anhydrous magnesium sulfate and concentrated to give the title compound (396 mg) as a pale pink solid, which was used without further purification. 1 H NMR(CDCl3)δ 8.49-8.26(m,1H),8.06(s,1H),7.94(m,1H),7.73-7.70(m,1H),7.54-7.52(m,1H),7.14-7.10(m,1H).

[0253] Step B: Preparation of 4-[3-[[(2S)-2,3-dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl]carbonyl]phenyl]-2,4-dihydro-3H-1,2,4-triazol-3-one To a stirred solution of (2S)-2,8-dimethyl-3,4-dihydro-2H-1,4-benzoxazine (i.e., the product of Step C in Synthesis Example 3) (315 mg, 1.9 mmol), 3-(5-oxo-1H-1,2,4-triazol-4-yl)benzoic acid (i.e., the product of Step A) (396 mg, 1.9 mmol), and triethylamine (0.81 mL, 5.8 mmol) in ethyl acetate (10 mL) was added propylphosphonic anhydride (50 wt.% in ethyl acetate, 3.07 g, 4.8 mmol). The mixture was stirred at reflux overnight, then cooled to room temperature and diluted with ethyl acetate. The mixture was washed with 1 N aqueous hydrochloric acid solution (×1), 1 N aqueous sodium hydroxide solution (×1), water (×1), brine (×1), dried over anhydrous magnesium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (gradient of 0-40% ethyl acetate in hexanes) to give the title compound as a white solid (228 mg). 1 H NMR(CDCl3)δ 9.27(br s,1H),7.75-7.73(m,1H),7.63-7.60(m,2H),7.49-7.45(m,2H),6.90-6.88(m,1H),6.83-6 .41(m,2H),4.54-4.46(m,1H),4.42-4.30(m,1H),3.37(dd,1H),2.23(s,3H),1.44(d,3H).

[0254] Synthesis Example 11 Preparation of 4-[3-[[(2S)-2,3-dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl]carbonyl]phenyl]-2,4-dihydro-2-methyl-3H-1,2,4-triazol-3-one (Compound 117) To a stirred solution of 4-[3-[[(2S)-2,3-dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl]carbonyl]phenyl]-2,4-dihydro-3H-1,2,4-triazol-3-one (i.e., the product of Synthesis Example 10) (80 mg, 0.23 mmol) in N,N-dimethylformamide (4 mL) was added potassium carbonate (63 mg, 0.46 mmol) and iodomethane (0.04 mL, 0.69 mmol). The mixture was stirred overnight at room temperature, then water was added and the mixture was extracted with diethyl ether (×2). The combined organic extracts were washed with water (×1), brine (×1), dried over anhydrous magnesium sulfate, and concentrated to give the title compound (52 mg) as a light tan solid. 1 H NMR(CDCl3)δ 7.75-7.73(m,1H),7.61-7.59(m,2H),7.46-7.42(m,2H),6.88-6.86(m,1H),6.81-6 .36(m,2H),4.55-4.19(m,2H),3.52(s,3H),3.35(dd,1H),2.21(s,3H),1.42(d,3H).

[0255] Synthesis Example 12 Preparation of [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][3-(1H-1,2,4-triazol-1-yl)phenyl]methanone (compound 18) To a stirred solution of (2S)-8-chloro-2-methyl-3,4-dihydro-2H-1,4-benzoxazine (i.e., the product of Step C in Synthesis Example 1) (1 g, 5.4 mmol), 3-(1,2,4-triazol-1-yl)benzoic acid (i.e., the product of Step E in Synthesis Example 15) (1.03 g, 5.4 mmol), and triethylamine (1.9 mL, 13.6 mmol) in ethyl acetate (10 mL) was added propylphosphonic anhydride (50 wt. % in ethyl acetate, 5.2 g, 8.2 mmol). The mixture was stirred at 70° C. overnight and then at 60° C. for 2 days. The mixture was cooled to room temperature, diluted with water, and extracted with ethyl acetate. The organic extract was washed with 1 N aqueous hydrochloric acid solution (×1), 1 N aqueous sodium hydroxide solution (×1), water (×1), and brine (×1), dried over anhydrous magnesium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (gradient of 0-40% ethyl acetate in hexanes) to give the title compound as a white solid (1.48 g). 1 H NMR(CDCl3)δ 8.55(s,1H),8.05(s,1H),7.86-7.85(m,1H),7.78-7.75(m,1H),7.47-7.44(m,1H),7.41-7.38(m,1H),7.07-7.0 5(m,1H),6.97-6.70(m,1H),6.57-6.54(m,1H),4.55-4.50(m,1H),4.32-4.20(m,1H),3.40(dd,1H),1.43(d,3H).

[0256] Synthesis Example 13 Preparation of [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][3-(1H-1,2,4-triazol-1-yl)phenyl]methanethione (Compound 139) To a stirred solution of [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][3-(1H-1,2,4-triazol-1-yl)phenyl]methanone (i.e., the product of Synthesis Example 12) (200 mg, 0.56 mmol) in toluene (5 mL) was added Lawesson's reagent (228 mg, 0.56 mmol). The mixture was stirred at 90 °C overnight, then cooled to room temperature, diluted with water, extracted with ethyl acetate (x2), and concentrated. The crude material was purified by column chromatography on silica gel (0-50% ethyl acetate in hexanes gradient) to afford the title compound (200 mg) as a yellow solid. 1 H NMR(CDCl3)δ 8.50(br s,1H),8.07(s,1H),7.98-7.71(m,1H),7.65-7.63(m,1H),7.38-7.09(m,3H),6.47- 6.44(m,2H),5.44-5.08(m,1H),4.76-4.70(m,1H),4.04-3.67(m,1H),1.58(d,3H).

[0257] Synthesis Example 14 Preparation of [8-chloro-2,3-dihydro-2-(methoxymethyl)-4H-1,4-benzoxazin-4-yl][2-(1H-1,2,4-triazol-1-yl)-4-pyridinyl]methanone (compound 35) Step A: Preparation of N-(3-chloro-2-fluorophenyl)-4-methylbenzenesulfonamide To a stirred solution of 3-chloro-2-fluoroaniline (50 g, 345 mmol) in pyridine (300 mL) was added p-toluenesulfonyl chloride (72 g, 379 mmol) at 0 °C, and the mixture was stirred at room temperature for 16 hours. Ice-cold water (1000 mL) was added, and the mixture was extracted with ethyl acetate (1000 mL × 2). The combined organic extracts were washed with brine, dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by trituration with n-pentane to give the title compound (55 g) as an off-white solid. MS(ES + ) m / z Actual value: (MH) - ,C13 H 11 ClFNO2S, 298, theoretical value 298.0.

[0258] Step B: Preparation of N-(3-chloro-2-fluoro-phenyl)-N-(2,3-dihydroxypropyl)-4-methyl-benzenesulfonamide To a stirred mixture of N-(3-chloro-2-fluorophenyl)-4-methylbenzenesulfonamide (i.e., the product of Step A) (50 g, 167 mmol) and glycidol (13.6 g, 184 mmol), potassium carbonate (2.6 g, 17 mmol) and benzyltriethylammonium chloride (3.7 g, 17 mmol) were added, and the mixture was then stirred at 90° C. for 16 hours. Ice-cold water (1000 mL) was added, and the mixture was extracted with ethyl acetate (1000 mL × 2). The combined organic extracts were washed with brine, dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (20% ethyl acetate in hexane) to give the title compound (52 g) as a colorless liquid. MS(ES + ) m / z Actual value: (M+H) + ,C 16 H 17 ClFNO4S, 374, theoretical value 374.1.

[0259] Step C: Preparation of N-[3-[tert-butyl(dimethyl)silyl]oxy-2-hydroxy-propyl]-N-(3-chloro-2-fluoro-phenyl)-4-methyl-benzenesulfonamide To a stirred solution of N-(3-chloro-2-fluoro-phenyl)-N-(2,3-dihydroxypropyl)-4-methyl-benzenesulfonamide (i.e., the product of Step B) (52 g, 139 mmol) in dichloromethane (500 mL) was added imidazole (10.4 g, 153 mmol) and tert-butyldimethylsilyl chloride (23.0 g, 153 mmol) at 0° C. The mixture was stirred at room temperature for 16 hours, ice-cold water (1000 mL) was added, and the mixture was extracted with ethyl acetate (1000 mL × 2). The combined organic extracts were washed with brine, dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (10% ethyl acetate in hexane) to give the title compound (50 g) as a colorless liquid. MS(ES + ) m / z Actual value: (M+H) + ,C 22 H 31 ClFNO4SSi, 488, theoretical value 488.1.

[0260] Step D: Preparation of [8-chloro-4-(p-tolylsulfonyl)-2,3-dihydro-1,4-benzoxazin-2-yl]methanol To a stirred solution of N-[3-[tert-butyl(dimethyl)silyl]oxy-2-hydroxypropyl]-N-(3-chloro-2-fluoro-phenyl)-4-methyl-benzenesulfonamide (i.e., the product of Step C) (20 g, 41 mmol) in tetrahydrofuran (20 mL) was added sodium hydroxide (6.5 g, 164 mmol) and tetrabutylammonium bromide (1.32 g, 4.10 mmol), followed by stirring the mixture at 70° C. for 1 hour. Ice-cold water (500 mL) was added, and the mixture was extracted with ethyl acetate (500 mL×2). The combined organic extracts were washed with brine, dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (10% ethyl acetate in hexane) to give the title compound (4.5 g) as an off-white solid. Additionally, tert-butyl-[[8-chloro-4-(p-tolylsulfonyl)-2,3-dihydro-1,4-benzoxazin-2-yl]methoxy]-dimethyl-silane (5 g) was also isolated. MS(ES + ) m / z Actual value: (M+H) + ,C 16 H 16 ClNO4S, 354, theoretical value 354.1.

[0261] Step E: Preparation of 8-chloro-2-(methoxymethyl)-4-(p-tolylsulfonyl)-2,3-dihydro-1,4-benzoxazine To a stirred solution of [8-chloro-4-(p-tolylsulfonyl)-2,3-dihydro-1,4-benzoxazin-2-yl]methanol (i.e., the product of Step D) (2 g, 5.7 mmol) in tetrahydrofuran (20 mL) was added sodium hydride (60% dispersion in mineral oil, 0.26 g, 6.5 mmol) at 0° C. The mixture was stirred at this temperature for 15 minutes, followed by the addition of iodomethane (1.2 g, 8.5 mmol). The mixture was stirred at room temperature for 3 hours, followed by the addition of ice-cold water (100 mL). The mixture was extracted with ethyl acetate (100 mL × 2), and the combined organic extracts were washed with brine, dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (10% ethyl acetate in hexane) to afford the title compound (1 g) as an off-white solid. MS(ES + ) m / z Actual value: (M+H) + ,C 17 H 18 ClNO4S, 368, theoretical value 368.1.

[0262] Step F: Preparation of 8-chloro-2-(methoxymethyl)-3,4-dihydro-2H-1,4-benzoxazine To a stirred solution of 8-chloro-2-(methoxymethyl)-4-(p-tolylsulfonyl)-2,3-dihydro-1,4-benzoxazine (i.e., the product of Step E) (1 g, 2.7 mmol) in dichloromethane (10 mL) was added sulfuric acid (2.6 mL) at 0° C. The mixture was stirred at room temperature for 16 hours and then quenched with solid sodium bicarbonate. Ethyl acetate (50 mL) was added, and the mixture was filtered through a pad of Celite and rinsed with ethyl acetate (50 mL). The filtrate was concentrated, and the crude material was purified by column chromatography on silica gel (20% ethyl acetate in hexanes) to afford the title compound (0.3 g) as a colorless liquid. MS(ES + ) m / z Actual value: (M+H) + ,C 10 H 12 ClNO2,214, theoretical value 214.1.

[0263] Step G: Preparation of 2-(1,2,4-triazol-1-yl)pyridine-4-carboxylic acid To a mixture of ethyl 2-bromoisonicotinate (5 g, 21.7 mmol) and 1,2,4-triazole (1.79 g, 25.9 mmol) in N,N-dimethylformamide (50 mL) was added cesium carbonate (14.1 g, 43.5 mmol) and copper(I) iodide (1.65 g, 8.69 mmol), and the mixture was then stirred at 120 °C for 16 h. The mixture was filtered through a pad of Celite and rinsed with N,N-dimethylformamide (50 mL). The filtrate was diluted with water (100 mL) and acidified with 1 N aqueous hydrochloric acid. The resulting precipitate was collected by filtration, washed with ice-cold water, and dried under vacuum to give the title compound (3 g) as an off-white solid. 1 H NMR(DMSO-d6)δ 14.06(br s,1H),9.44(s,1H),8.74-8.72(m,1H),8.36(s,1H),8.22(s,1H),7.89-7.88(m,1H).

[0264] Step H: [8-chloro-2,3-dihydro-2-(methoxymethyl)-4H-1,4-benzoxazin-4-yl][2-(1H-1,2,4-triazol-1-yl)-4-pyridinyl]methanone Thionyl chloride (2.4 mL) was added to 2-(1,2,4-triazol-1-yl)pyridine-4-carboxylic acid (i.e., the product of Step G) (0.2 g, 1.05 mmol), and the mixture was stirred at 100° C. for 2 hours. The mixture was concentrated, followed by the addition of dichloromethane (10 mL), and the solution was cooled to 0° C. 8-Chloro-2-(methoxymethyl)-3,4-dihydro-2H-1,4-benzoxazine (i.e., the product of Step F) (0.26 g, 1.22 mmol) and triethylamine (0.31 g, 3.06 mmol) were added, and the mixture was stirred at room temperature for 16 hours. Ice-cold water (100 mL) was added, and the mixture was extracted with dichloromethane (100 mL × 2). The combined organic extracts were washed with brine (×1), dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (50% ethyl acetate in hexanes) to give the title compound (80 mg) as an off-white solid. 1 H NMR(DMSO-d6,100℃)δ 9.28(s,1H),8.61-8.60(m,1H),8.22-8.18(m,1H),7.93(s,1H),7.53-7.52(m,1H),7.30-7.28(m,1H),7. 20-7.18(m,1H),6.78-6.74(m,1H),4.69-4.67(m,1H),4.09-4.05(m,1H),3.74-3.58(m,3H),3.32(s,3H).

[0265] Synthesis Example 15 Preparation of (+)-[(2S)-2,3-dihydro-8-methyl-2-(trifluoromethyl)-4H-1,4-benzoxazin-4-yl][3-(1H-1,2,4-triazol-1-yl)phenyl]methanone (Compound 58) and (-)-[(2R)-2,3-dihydro-8-methyl-2-(trifluoromethyl)-4H-1,4-benzoxazin-4-yl][3-(1H-1,2,4-triazol-1-yl)phenyl]methanone (Compound 68) Step A: Preparation of N-(3-chloro-2-fluoro-phenyl)-4-methyl-N-(3,3,3-trifluoro-2-hydroxy-propyl)benzenesulfonamide To a stirred mixture of N-(3-chloro-2-fluorophenyl)-4-methylbenzenesulfonamide (i.e., the product of Step A in Synthesis Example 14) (20 g, 67 mmol) and 2-(trifluoromethyl)oxirane (8.2 g, 74 mmol), potassium carbonate (0.92 g, 6.7 mmol) and benzyltriethylammonium chloride (1.51 g, 6.7 mmol) were added, and the mixture was then allowed to stir at 90° C. for 24 hours. Ice-cold water (500 mL) was added, and the mixture was extracted with ethyl acetate (500 mL × 2). The combined organic extracts were washed with brine, dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (20% ethyl acetate in hexane) to give the title compound (10 g) as an off-white solid. MS(ES + ) m / z Actual value: (M+H) + ,C 16 H 14 ClF4NO3S, 412, theoretical value 412.0.

[0266] Step B: Preparation of 8-chloro-4-(p-tolylsulfonyl)-2-(trifluoromethyl)-2,3-dihydro-1,4-benzoxazine To a stirred solution of N-(3-chloro-2-fluoro-phenyl)-4-methyl-N-(3,3,3-trifluoro-2-hydroxy-propyl)benzenesulfonamide (i.e., the product of Step A) (3 g, 7.3 mmol) in tetrahydrofuran (2 mL) was added sodium hydroxide (1.16 g, 29.7 mmol) and tetrabutylammonium bromide (0.22 g, 0.7 mmol), and the mixture was then stirred at 70° C. for 1 hour. Ice-cold water (100 mL) was added, and the mixture was extracted with ethyl acetate (100 mL × 2). The combined organic extracts were washed with brine, dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (10% ethyl acetate in hexane) to give the title compound (2.2 g) as an off-white solid. MS(ES + ) m / z Actual value: (M+H) + ,C16 H 13 ClF3NO3S, 392, theoretical value 392.0.

[0267] Step C: Preparation of 8-methyl-4-(p-tolylsulfonyl)-2-(trifluoromethyl)-2,3-dihydro-1,4-benzoxazine A sealed tube was charged with 8-chloro-4-(p-tolylsulfonyl)-2-(trifluoromethyl)-2,3-dihydro-1,4-benzoxazine (i.e., the product of Step B) (1 g, 2.55 mmol), toluene (5 mL), methylboronic acid (1.5 g, 25 mmol), and potassium phosphate (1.0 g, 4.7 mmol), and the mixture was then aerated with argon gas for 10 minutes. Palladium(II) acetate (57 mg, 0.25 mmol) and SPhos (0.2 g, 0.48 mmol) were added, the tube was then sealed, and the mixture was stirred at 120 °C for 16 hours. This reaction was carried out four times, and the four reaction mixtures were subsequently combined, worked up, and purified. Ice-cold water was added, and the mixture was extracted with ethyl acetate (x2). The combined organic extracts were washed with brine, dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (5% ethyl acetate in hexanes) to give the title compound (1.1 g) as an off-white solid. MS(ES + ) m / z Actual value: (M+H) + ,C 17 H 16 F3NO3S, 372, theoretical value 372.1.

[0268] Step D: Preparation of 8-methyl-2-(trifluoromethyl)-3,4-dihydro-2H-1,4-benzoxazine To a solution of 8-methyl-4-(p-tolylsulfonyl)-2-(trifluoromethyl)-2,3-dihydro-1,4-benzoxazine (i.e., the product of Step C) (1.5 g, 4.0 mmol) in methanol (10 mL) was added magnesium powder (1 g, 40 mmol) at 0 °C, and the mixture was sonicated at room temperature for 2 hours. Ethyl acetate (100 mL) was added, the mixture was filtered through a pad of Celite, and the filtrate was concentrated. The crude material was purified by column chromatography on silica gel (10% ethyl acetate in hexanes) to give the title compound (0.7 g) as a yellow oil. MS(ES + ) m / z Actual value: (M+H) + ,C 10 H 10 F3NO,218,Theoretical value 218.1.

[0269] Step E: Preparation of 3-(1,2,4-triazol-1-yl)benzoic acid To a mixture of ethyl 3-iodobenzoate (20 g, 87 mmol) and 1,2,4-triazole (7.1 g, 103 mmol) in N,N-dimethylformamide (100 mL) was added cesium carbonate (56.5 g, 172 mmol) and copper(I) iodide (6.65 g, 34.8 mmol), and the mixture was then stirred at 120 °C for 16 h. The mixture was filtered through a pad of Celite and rinsed with N,N-dimethylformamide (50 mL). The filtrate was diluted with water (100 mL) and acidified with 1 N aqueous hydrochloric acid. The resulting precipitate was collected by filtration, washed with ice-cold water, and dried under vacuum to give the title compound (10 g) as an off-white solid. MS(ES + ) m / z Actual value: (M+H) + ,C9H7N3O2,190,Theoretical value 190.1.

[0270] Step F: Preparation of (+)-[(2S)-2,3-dihydro-8-methyl-2-(trifluoromethyl)-4H-1,4-benzoxazin-4-yl][3-(1H-1,2,4-triazol-1-yl)phenyl]methanone (Isomer 1) and (−)-[(2R)-2,3-dihydro-8-methyl-2-(trifluoromethyl)-4H-1,4-benzoxazin-4-yl][3-(1H-1,2,4-triazol-1-yl)phenyl]methanone (Isomer 2) To a mixture of 8-methyl-2-(trifluoromethyl)-3,4-dihydro-2H-1,4-benzoxazine (i.e., the product of Step D) (0.75 g, 3.45 mmol) and 3-(1,2,4-triazol-1-yl)benzoic acid (i.e., the product of Step E) (0.78 g, 4.14 mmol) in pyridine (20 mL) was added phosphoryl chloride (1.5 g, 10.4 mmol) at 0° C. The mixture was stirred at 0° C. for 2 hours, followed by the addition of ice-cold water (200 mL). The mixture was extracted with ethyl acetate (200 mL × 2), and the combined organic extracts were washed with brine, dried over anhydrous sodium sulfate, and concentrated. The crude material was purified by column chromatography on silica gel (5% ethyl acetate in hexane) to give [8-methyl-2-(trifluoromethyl)-2,3-dihydro-1,4-benzoxazin-4-yl]-[3-(1,2,4-triazol-1-yl)phenyl]methanone (0.52 g) as a pale yellow solid. 1 H NMR(CDCl3)δ 8.45(s,1H),8.10(s,1H),7.81-7.79(m,2H),7.48-7.40(m,2H),6.94-6.92(m,1H),6.60-6.56(m,1H),6.44(br s,1H),4.88-4.85(m,1H),4.36-4.32(m,1H),4.20-4.16(m,1H),2.29(s,3H).

[0271] The enantiomers were separated by chiral supercritical fluid chromatography to give the title compounds. Isomer 1: [α] 25 D = +17.2° (c = 0.1% in CHCl3) Isomer 2: [α] 25 D = -13.8° (c = 0.1% in CHCl3)

[0272] Synthesis Example 16 Preparation of (8-chloro-2-cyclopropyl-2,3-dihydro-4H-1,4-benzoxazin-4-yl)[3-(1H-1,2,4-triazol-1-yl)phenyl]methanone (compound 22) Step A: Preparation of 8-chloro-2-cyclopropyl-4H-1,4-benzoxazin-3-one A microwave vial was charged with 2-amino-6-chlorophenol (0.5 g, 3.5 mmol), 2-bromo-2-cyclopropyl-ethyl acetate (0.6 g, 2.9 mmol), 1,8-diazabicyclo[5.4.0]undec-7-ene (0.49 g, 3.2 mmol), and N-methyl-2-pyrrolidone (8 mL). The vial was sealed and stirred in a microwave at 180 °C for 4 min. The mixture was cooled to room temperature, diluted with ethyl acetate, and filtered through a pad of Celite. The filtrate was washed with brine (x2) and concentrated. The crude material was purified by column chromatography on silica gel (0-50% ethyl acetate in hexanes gradient) to give the title compound (0.51 g) as an orange solid. 1 H NMR(CDCl3)δ 8.45(br s,1H),7.06-7.05(m,1H),6.91-6.87(m,1H),6.73-6.71(m,1H),4.20(d,1H),1.33-1.26(m,1H),0.75-0.58(m,4H).

[0273] Step B: Preparation of 8-chloro-2-cyclopropyl-3,4-dihydro-2H-1,4-benzoxazine To a stirred solution of 8-chloro-2-cyclopropyl-4H-1,4-benzoxazin-3-one (i.e., the product of Step A) (0.42 g, 1.9 mmol) in anhydrous tetrahydrofuran (10 mL) was added borane tetrahydrofuran complex (1 M in tetrahydrofuran, 3.2 mL, 3.2 mmol) dropwise at 0 °C. The reaction mixture was stirred at room temperature for 3 hours and then at 50 °C overnight. The mixture was cooled to room temperature, and methanol (5 mL) was slowly added. After stirring for 20 minutes, the mixture was concentrated, then dissolved in ethyl acetate, washed with saturated aqueous sodium bicarbonate (x1), water (x1), brine (x1), dried over anhydrous magnesium sulfate, and concentrated to give the title compound (0.37 g) as a light brown oil, which was used without further purification. 1 H NMR(CDCl3)δ 6.73-6.71(m,1H),6.66-6.63(m,1H),6.49-6.47(m,1H),3.83(br s,1H),3.52-3.46(m,2H),3.32-3.29(m,1H),1.14-1.08(m,1H),0.72-0.66(m,1H),0.64-0.57(m,2H),0.43-0.37(m,1H).

[0274] Step C: Preparation of (8-chloro-2-cyclopropyl-2,3-dihydro-4H-1,4-benzoxazin-4-yl)[3-(1H-1,2,4-triazol-1-yl)phenyl]methanone To a stirred solution of 8-chloro-2-cyclopropyl-3,4-dihydro-2H-1,4-benzoxazine (i.e., the product of Step B) (0.11 g, 0.52 mmol), 3-(1,2,4-triazol-1-yl)benzoic acid (i.e., the product of Step E in Synthesis Example 15) (0.12 g, 0.63 mmol), and triethylamine (0.22 mL, 1.6 mmol) in dichloromethane (8 mL) was added propylphosphonic anhydride (50 wt.% in ethyl acetate, 0.57 g, 0.90 mmol). The mixture was stirred at 40 °C overnight, then cooled to room temperature and concentrated. The crude material was purified by column chromatography on silica gel (gradient of 0 to 70% ethyl acetate in hexanes). The isolated material was further purified by column chromatography on silica gel (gradient of 0-20% ethyl acetate in dichloromethane) to give the title compound as a colourless oil (39 mg). 1 H NMR(CDCl3)δ 8.53(s,1H),8.10(s,1H),7.87-7.86(m,1H),7.80-7.78(m,1H),7.51-7.48(m,1H),7.44-7.42(m,1H),7.11-7.10(m,1H),6.82(br s,1H),6.60-6.57(m,1H),4.40-4.38(m,1H),3.87-3.83(m,1H),3.60(dd,1H) ,1.13-1.06(m,1H),0.74-0.68(m,1H),0.66-0.58(m,2H),0.47-0.41(m,1H).

[0275] Synthesis Example 17 Preparation of [(2R)-8-chloro-2-(ethoxymethyl)-2,3-dihydro-1,4-benzoxazin-4-yl]-[5-(3-isopropyl-1,2,4-triazol-1-yl)-2-methyl-phenyl]methanone (compound 340) Step A: Preparation of [(2R)-8-chloro-3,4-dihydro-2H-1,4-benzoxazin-2-yl]methanol To a stirred solution of 2-amino-6-chlorophenol (10 g, 70 mmol) in water (100 mL) was added (S)-(+)-epichlorohydrin (7.7 g, 83 mmol) and sodium hydroxide (3.9 g, 98 mmol). The reaction mixture was stirred at room temperature for 20 minutes, then diluted with water and extracted with ethyl acetate (x2). The combined organic extracts were dried over anhydrous sodium sulfate and concentrated. The crude material was purified by column chromatography on silica gel (25% ethyl acetate in hexane) to give the title compound (7 g) as a colorless liquid. 1 H NMR(CDCl3)δ 6.74(dd,1H),6.70-6.66(m,1H),6.50(dd,1H),4.32-4.28(m,1H),3.91-3.82(m,2H),3.42-3.39(m,1H),3.35-3.31(m,1H). MS(ES + ) m / z Actual value: (M+H) + ,C9H 10 ClNO2,200, theoretical value 200.0.

[0276] Step B: Preparation of (2R)-8-chloro-2-(ethoxymethyl)-3,4-dihydro-2H-1,4-benzoxazine To a stirred solution of [(2R)-8-chloro-3,4-dihydro-2H-1,4-benzoxazin-2-yl]methanol (i.e., the product of Step A) (2 g, 10 mmol) in anhydrous tetrahydrofuran (20 mL) was added sodium hydride (60% dispersion in mineral oil, 0.8 g, 20 mmol) and iodoethane (2.3 g, 15 mmol) at 0° C. The reaction mixture was stirred at room temperature for 1 hour, then diluted with water and extracted with ethyl acetate (×2). The combined organic extracts were dried over anhydrous sodium sulfate and concentrated. The crude material was purified by column chromatography on silica gel (15% ethyl acetate in hexanes) to afford the title compound (1.5 g) as a colorless liquid. 1H NMR(CDCl3)δ 6.72(dd,1H),6.68-6.65(m,1H),6.49(dd,1H),4.39-4.35(m,1H),3.75(dd,1H),3.66-3.55(m,3H),3.48(dd,1H),3.28(dd,1H),1.22(t,3H). MS(ES + ) m / z Actual value: (M+H) + ,C 11 H 14 ClNO2,228, theoretical value 228.1.

[0277] Step C: Preparation of methyl 5-(3-isopropyl-1,2,4-triazol-1-yl)-2-methyl-benzoate A microwave vial was charged with methyl 5-bromo-2-methylbenzoate (2.5 g, 11 mmol), anhydrous N,N-dimethylformamide (15 mL), and 3-isopropyl-1H-1,2,4-triazole (1.83 g, 16.5 mmol), and the mixture was then aerated with nitrogen gas for 10 minutes. Potassium carbonate (4.55 g, 33 mmol), copper(I) iodide (418 mg, 2.2 mmol), and trans-N,N'-dimethylcyclohexane-1,2-diamine (0.86 mL, 5.5 mmol) were added, and the mixture was then stirred in a microwave at 110 °C for 3 hours. The mixture was cooled to room temperature, diluted with water, and extracted with ethyl acetate (x2). The combined organic extracts were filtered through a pad of Celite, rinsed with ethyl acetate (25 mL), and the filtrate was washed with brine (x1) and concentrated. The crude material was purified by column chromatography on silica gel (20% ethyl acetate in hexanes) to give the title compound as an off-white solid (2.4 g). MS(ES + ) m / z Actual value: (M+H) + ,C 14 H 17 N3O2, 260, theoretical value 260.1.

[0278] Step D: Preparation of 5-(3-isopropyl-1,2,4-triazol-1-yl)-2-methyl-benzoic acid To a stirred solution of methyl 5-(3-isopropyl-1,2,4-triazol-1-yl)-2-methylbenzoate (i.e., the product of Step C) (2.4 g, 9.3 mmol) in tetrahydrofuran (7 mL) and water (3 mL) was added lithium hydroxide monohydrate (583 mg, 13.9 mmol). The reaction mixture was stirred at room temperature for 16 hours. The mixture was concentrated, then diluted with water (20 mL) and acidified with citric acid. The resulting precipitate was collected by filtration and dried under vacuum to give the title compound (1.6 g) as an off-white solid. MS(ES + ) m / z Actual value: (M+H) + ,C 13 H 15 N3O2, 246, theoretical value 246.1.

[0279] Step E: Preparation of [(2R)-8-chloro-2-(ethoxymethyl)-2,3-dihydro-1,4-benzoxazin-4-yl]-[5-(3-isopropyl-1,2,4-triazol-1-yl)-2-methyl-phenyl]methanone To a stirred solution of 5-(3-isopropyl-1,2,4-triazol-1-yl)-2-methyl-benzoic acid (i.e., product of Step D) (600 mg, 2.4 mmol) in pyridine (6 mL) was added (2R)-8-chloro-2-(ethoxymethyl)-3,4-dihydro-2H-1,4-benzoxazine (i.e., product of Step B) (555 mg, 2.4 mmol) and phosphoryl chloride (0.68 mL, 7.3 mmol) at 0° C. The reaction mixture was stirred at room temperature for 16 hours and then concentrated. The crude material was purified by column chromatography on silica gel (25% ethyl acetate in hexane) to give the title compound (232 mg) as a brown foam. 1H NMR(DMSO-d6,90℃)δ 8.96(s,1H),7.79-7.76(m,2H),7.43-7.41(m,2H),7.18-7.16(m,1H),6.79-6.76(m,1H),4.59-4.57(m,1H),4.0 9-4.06(m,1H),3.67-3.58(m,2H),3.54-3.47(m,3H),3.07-3.01(m,1H),2.28(s,3H),1.29(d,6H),1.03(t,3H). MS(ES + ) m / z Actual value: (M+H) + ,C 24 H 27 ClN4O3, 455.3, theoretical value 455.2.

[0280] Synthesis Example 18 Preparation of [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-[5-(3-isopropyl-1,2,4-triazol-1-yl)-2,3-dimethoxy-phenyl]methanone (compound 194) Step A: Preparation of (5-bromo-2,3-dimethoxy-phenyl)-[(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]methanone To a stirred solution of 5-bromo-2,3-dimethoxybenzoic acid (1 g, 3.8 mmol) and a few drops of N,N-dimethylformamide in chloroform (10 mL) was added thionyl chloride (1.3 mL, 18 mmol) at 0° C. The reaction mixture was stirred at 60° C. for 3 hours, then cooled to room temperature and concentrated. The crude acid chloride was then dissolved in dichloromethane (10 mL) and added to a solution of (2S)-8-chloro-2-methyl-3,4-dihydro-2H-1,4-benzoxazine (i.e., the product of Step C in Synthesis Example 1) (697 mg, 3.8 mmol) and pyridine (1 mL, 12 mmol) in dichloromethane (10 mL) at 0° C. The mixture was stirred at room temperature for 16 hours, then diluted with water and extracted with dichloromethane (×2), and the combined organic extracts were dried over anhydrous sodium sulfate and concentrated. The crude material was purified by column chromatography on silica gel (30% ethyl acetate in hexanes) to give the title compound (1.3 g) as a colorless liquid. MS(ES + ) m / z Actual value: (M+H) + ,C 18 H 17 BrClNO4, 426.1, theoretical value 426.0.

[0281] Step B: Preparation of [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-[5-(3-isopropyl-1,2,4-triazol-1-yl)-2,3-dimethoxy-phenyl]methanone A solution of (5-bromo-2,3-dimethoxy-phenyl)-[(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]methanone (i.e., the product of Step A) (400 mg, 0.94 mmol) in N,N-dimethylformamide (4 mL) was aerated with nitrogen, followed by the addition of potassium carbonate (389 mg, 2.8 mmol), copper(I) iodide (89 mg, 0.47 mmol), and trans-N,N'-dimethylcyclohexane-1,2-diamine (0.074 mL, 0.47 mmol). The reaction mixture was stirred in a sealed tube at 120 °C for 16 h. The mixture was cooled to room temperature, diluted with water, and extracted with ethyl acetate (x2). The combined organic extracts were dried over anhydrous sodium sulfate and concentrated. The crude material was purified by column chromatography on silica gel (35% ethyl acetate in hexanes) to give the title compound (270 mg) as an off-white semi-solid. 1 H NMR(DMSO-d6,90℃)δ 8.99(s,1H),7.56-7.38(m,3H),7.16-7.14(m,1H),6.74(m,1H),4.52(m,1H),4.05(m,1H), 3.91(s,3H),3.67(m,3H),3.41-3.37(m,1H),3.07-3.03(m,1H),1.36(d,3H),1.30(d,6H). MS(ES + ) m / z Actual value: (M+H) + ,C 23 H 25 ClN4O4, 457.27, theoretical value 457.16.

[0282] Synthesis Example 19 Preparation of [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-[2,3-dihydroxy-5-(3-isopropyl-1,2,4-triazol-1-yl)phenyl]methanone (compound 272) To a stirred solution of [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-[5-(3-isopropyl-1,2,4-triazol-1-yl)-2,3-dimethoxy-phenyl]methanone (i.e., the product of Synthesis Example 18) (3 g, 6.6 mmol) in dichloromethane (60 mL) was added dropwise boron tribromide (1 M in dichloromethane, 39.5 ml, 39.5 mmol) at −30° C. The mixture was stirred at room temperature for 1 hour, then cooled to 0° C., and methanol (100 mL) was added. The mixture was concentrated, then diluted with water (25 mL), extracted with ethyl acetate (×2), and the combined organic extracts were dried over anhydrous sodium sulfate and concentrated. The crude material was purified by trituration with n-pentane to give the title compound (2.55 g) as a brown solid. 1 H NMR(DMSO-d6,90℃)δ 8.83(m,1H),7.51-7.49(m,1H),7.30-7.29(m,1H),7.18(m,1H),7.13-7.11(m,1H),6.76-6.71(m,1 H),4.55-4.51(m,1H),4.07-4.03(m,1H),3.40-3.35(m,1H),3.05-3.02(m,1H),1.35-1.25(m,9H). MS(ES + ) m / z Actual value: (M+H) + ,C 21 H 21 ClN4O4, 429.09, theoretical value 429.13.

[0283] Synthesis Example 20 Preparation of [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-[6-(3-isopropyl-1,2,4-triazol-1-yl)-1,3-benzodioxol-4-yl]methanone (compound 258) To a stirred solution of [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-[2,3-dihydroxy-5-(3-isopropyl-1,2,4-triazol-1-yl)phenyl]methanone (i.e., the product of Synthesis Example 19) (300 mg, 0.7 mmol) in anhydrous N,N-dimethylformamide (5 mL) was added cesium carbonate (1.8 g, 5.5 mmol) and bromochloromethane (0.45 g, 3.5 mmol). The mixture was stirred at 90° C. for 6 hours, then cooled to room temperature, and ice-cold water (10 mL) was added. The solid material was collected by filtration and dried to give the crude product. Purification by column chromatography on silica gel (30% ethyl acetate in hexane) afforded the title compound (100 mg) as a white solid. 1 H NMR(CDCl3)δ 8.36(s,1H),7.34(d,1H),7.23(d,1H),7.10-7.08(m,1H),7.02-6.40(m,2H),5.92-5.40(m,2 H),4.63-4.13(m,2H),3.55-3.30(m,1H),3.16-3.08(m,1H),1.48-1.43(m,3H),1.36(d,6H). MS(ES + ) m / z Actual value: (M+H) + ,C 22 H 21 ClN4O4, 441.21, theoretical value 441.13.

[0284] Synthesis Example 21 Preparation of [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-[7-(3-isopropyl-1,2,4-triazol-1-yl)-2,3-dihydro-1,4-benzodioxin-5-yl]methanone (compound 217) A microwave vial was charged with [(2S)-8-chloro-2-methyl-2,3-dihydro-1,4-benzoxazin-4-yl]-[2,3-dihydroxy-5-(3-isopropyl-1,2,4-triazol-1-yl)phenyl]methanone (i.e., the product of Synthesis Example 19) (400 mg, 0.93 mmol), acetone (8 mL), cesium carbonate (2.4 g, 7.4 mmol), and dibromoethane (0.8 mL, 9.3 mmol). The mixture was stirred in a microwave at 90° C. for 30 minutes. The mixture was cooled to room temperature, and the solid was removed by filtration and rinsed with acetone (10 mL). The filtrate was concentrated, and the resulting crude material was purified by preparative HPLC to afford the title compound (170 mg) as a light brown solid. 1 H NMR(DMSO-d6,90℃)δ 8.93(s,1H),7.41-7.14(m,4H),6.74-6.70(m,1H),4.53(m,1H),4.22-3.9 5(m,5H),3.47-3.40(m,1H),3.07-2.98(m,1H),1.37(d,3H),1.29(d,6H). MS(ES + ) m / z Actual value: (M+H) + ,C 23 H 23 ClN4O4, 455.27, theoretical value 455.15

[0285] The compounds in Tables 1-236 below can be prepared by the procedures described herein and methods known in the art. The following abbreviations are used in the tables: t means tertiary, s means secondary, n means straight chain, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, Bu means butyl, i-Pro means isopropyl, c-Pro means cyclopropyl, t-Bu means tertiary butyl, Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, -CN means cyano, -NO means nitro, TMS means trimethylsilyl, SOMe means methylsulfinyl, CF means CF, and SOMe means methylsulfonyl.

[0286] [ka] R 1b is H and X 1 is CH and X 2 is CH, (R 2 ) n is 6-OMe, Y is O, (R 3b ) p is H and R 3a is Me and R 4a is Cl, (R 4b ) q is H.

[0287] [Table 1]

[0288] Some of the J groups in the table are defined below. [ka] [ka] [ka]

[0289] Table 2 is organized by the row heading "R 1b is H and X 1 is CH and X 2 is CH, (R 2 ) n is 6-OMe, Y is O, and (R 3b ) p is H and R 3a is Me and R 4a is Cl and (R 4b ) q is H.' is listed with respect to Table 2 below in the row heading (i.e., 'R 1b is H and X 1 is CH and X 2 is CH, (R 2 ) n is H, Y is O, and (R 3b ) p is H and R 3a is Me and R 4a is Cl and (R 4b ) q is H."). Thus, the first entry in Table 2 is a compound of Formula 1, where R 1b is H and X 1 is CH and X 2 is CH, (R 2 ) n is H, Y is O, and (R 3b ) p is H and R 3a is Me and R 4a is Cl, (R 4b ) q is H and R 1a is H). Tables 3 to 230 are similarly constructed.

[0290] [Table 2]

[0291]

Table 3

[0292]

Table 4

[0293]

Table 5

[0294]

Table 6

[0295]

Table 7

[0296]

Table 8

[0297]

Table 9

[0298]

Table 10

[0299]

Table 11

[0300]

Table 12

[0301]

Table 13

[0302] [Table 14]

[0303] [Table 15]

[0304] [Table 16]

[0305] [Table 17]

[0306] [Table 18]

[0307] Table 232 shows the row heading "R 1b is H and X 1 is CH and X 2 is CH, (R 2 ) n is 6-OMe, Y is O, and (R 3b ) p is H and R 3a is Me and R 4a is Cl and (R 4b ) q is H.' is listed in the row heading for Table 232 below (i.e., 'R 1b is H and X 1 is CH and X 2 combines with C6 to form J-34, Y is O, and (R 3b ) p is H and R 3a is Me and R 4a is Cl and (R 4b ) qis H."). Thus, the first entry in Table 232 is a compound of Formula 1, where R 1b is H and X 1 is CH and X 2 combines with C6 to form J-34, Y is O, and (R 3b ) p is H and R 3a is Me and R 4a is Cl, (R 4b ) q is H and R 1a is H). Tables 233 to 236 are similarly constructed.

[0308] [Table 19]

[0309] Formulation / Practical Use The compounds of the present invention will generally be used as the herbicidal active ingredient in a composition, i.e., a formulation, along with at least one additional ingredient selected from the group consisting of surfactants, solid diluents, and liquid diluents, which acts as a carrier. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, the mode of application, and environmental factors such as soil type, moisture, and temperature.

[0310] Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, flowable concentrates, and / or suspoemulsions), which may optionally be thickened to form gels. Common types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions, oil-in-water emulsions, flowable concentrates, and suspoemulsions. Common types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates, and oil dispersions.

[0311] Common types of solid compositions include dusts, powders, granules, pellets, prills, pastilles, tablets, and fill films (including seed coatings), which can be water-dispersible ("wettable") or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatments. Active ingredients can be (micro)encapsulated and further processed into suspensions or solid formulations; alternatively, entire formulations of active ingredients can be encapsulated (or "overcoated"). Encapsulation can control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsifiable concentrate and dry granule formulations. High-strength compositions are primarily used as intermediates for further formulation.

[0312] Sprayable formulations are typically spread in a suitable medium before spraying. Such liquid and solid formulations are formulated to be easily diluted in the spray medium, usually water, but sometimes another suitable medium, such as an aromatic or paraffinic hydrocarbon or vegetable oil. Spray volumes can range from about 1 liter to several thousand liters per hectare, but more typically range from about 10 liters to several hundred liters per hectare. Sprayable formulations can be tank-mixed with water or other suitable medium for foliar treatment by aerial or ground application, or for application to the plant growing medium. Liquid and dry formulations can be injected directly into drip irrigation systems or metered into the furrow at planting time.

[0313] The formulations will typically contain active ingredients, diluents, and surfactants within the following approximate ranges, which add up to 100 weight percent:

[0314] [Table 20]

[0315] Examples of solid diluents include clays such as bentonite, montmorillonite, attapulgite, kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and sodium bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.

[0316] Examples of liquid diluents include water, N,N-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), alkyl phosphates (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oil, normal paraffin, isoparaffin), alkylbenzenes, alkylnaphthalenes, glycerin, glycerin triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatic hydrocarbons, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone, and 4-hydroxy-4-methyl-2-pentanone. Liquid diluents include glycerol esters of saturated and unsaturated fatty acids (typically C6-C8), glycerol esters of saturated and unsaturated fatty acids (typically C6-C8). 22Liquid diluents also include glycerol esters of vegetable oils (e.g., olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut, and palm kernel oils), fats of animal origin (e.g., beef tallow, pork fat, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated), where the fatty acids can be obtained by hydrolysis of glycerol esters from vegetable and animal sources and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.

[0317] The solid and liquid compositions of the present invention often contain one or more surfactants. Surfactants (also known as "surface active agents"), when added to a liquid, generally modify, and in most cases reduce, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, surfactants can be useful as wetting agents, dispersants, emulsifiers, or antifoaming agents.

[0318] Surfactants can be classified as nonionic, anionic, or cationic. Nonionic surfactants useful for the present compositions 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, butylene 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 ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate, and dodecylphenol ethoxylate (prepared from phenol and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide, and the end blocks of which are prepared from propylene oxide. , reverse block polymers; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenols (including those prepared from ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters, and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd PEG (polyethylene glycol) resins, graft or comb polymers, and star polymers; polyethylene glycol (PEG); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar derivatives such as sucrose esters, alkyl polyglycosides, and alkyl polysaccharides.

[0319] Useful anionic surfactants include, but are not limited to, alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonic acid derivatives; lignin and lignin derivatives such as lignosulfonates; maleic acid or succinic acid or 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 sulfonates; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides such as N,N-alkyl taurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecyl benzene; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkyl naphthalenes; sulfonates of fractionated petroleum oils; sulfosuccinamates; and sulfosuccinates and their derivatives, such as dialkyl sulfosuccinate salts.

[0320] Useful cationic surfactants include, but are not limited to, amides and ethoxylated amides; amines such as N-alkylpropanediamines, tripropylenetriamine, and dipropylenetetramine; and ethoxylated amines, ethoxylated diamines, and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts, and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

[0321] Also useful in the compositions of the present invention are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic, and cationic surfactants and their recommended uses are disclosed in various published references, including McCutcheon's Emulsifiers and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A.S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.

[0322] The compositions of the present invention may further contain formulation aids and additives known to those skilled in the art as formulation aids, some of which may also function as solid diluents, liquid diluents, or surfactants. Such formulation aids and additives may control pH (buffering agents), foaming during processing (antifoaming agents such as polyorganosiloxanes), active ingredient settling (suspending agents), viscosity (thixotropic thickeners), microbial growth in the container (antimicrobial agents), product freezing (antifreeze agents), color (dye / pigment dispersions), wash-off (film formers or spreading agents), evaporation (evaporation retardants), and other formulation properties. Film formers include, for example, polyvinyl acetate, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol, polyvinyl alcohol copolymers, and waxes. Examples of formulation aids and additives include those described in McCutcheon's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03 / 024222.

[0323] The compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredients in a solvent or milling them in a liquid or dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is not miscible with water, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water. Active ingredient slurries with particle sizes up to 2,000 μm can be wet-milled using a media mill to obtain particles with an average particle size of less than 3 μm. Aqueous slurries can be made into finished suspension concentrates (see, e.g., U.S. Pat. No. 3,060,084) or can be further processed by spray drying to form water-dispersible granules. Dry formulations typically require a dry milling process that results in an average particle size in the range of 2 to 10 μm. Dusts and powders can be prepared by blending and typically milling (such as with a hammer mill or fluid energy mill). Granules and pellets can be prepared by spraying the active material onto a preformed granular carrier or by agglomeration techniques. See Browning, "Agglomeration," Chemical Engineering, December 4, 1967, pp. 147-48; Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57; and International Publication No. WO 91 / 13546. Pellets can be prepared as described in U.S. Pat. No. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. Pat. No. 4,144,050, U.S. Pat. No. 3,920,442, and German Patent No. 3,246,493. Tablets can be prepared as taught in U.S. Patent Nos. 5,180,587, 5,232,701, and 5,208,030. Films can be prepared as taught in British Patent No. 2,095,558 and U.S. Patent No. 3,299,566.

[0324] For further information on formulation techniques, see T. Swoods, "The Formulator's Toolbox - Product Forms for Modern Agriculture," in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also the following references: U.S. Pat. No. 3,235,361, column 6, line 16 to column 7, line 19, and Examples 10-41; U.S. Pat. No. 3,309,192, column 5, line 43 to column 7, line 62, and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, and 169-182; U.S. Pat. No. 2,891,855, column 3, line 66 to column 5, line 17, and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp. 81-96; Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

[0325] In the following examples, all percentages are by weight, and all formulations are prepared by conventional methods. Compound numbers refer to compounds in Index Tables A-F. Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. Accordingly, the following examples are intended to be merely illustrative and not limiting of the present disclosure in any way. Percentages are by weight unless otherwise specified.

[0326] Example A high strength concentrate Compound 1 98.5% Silica gel aerosol 0.5% Synthetic amorphous fine silica 1.0%

[0327] Example B hydratable powder Compound 1 65.0% Dodecylphenol polyethylene glycol ether 2.0% Sodium lignosulfonate 4.0% Sodium aluminosilicate 6.0% Montmorillonite (calcined) 23.0%

[0328] Example C granules Compound 1 10.0% Attapulgite Granules (Low Volatility, 0.71 / 0.30 mm; USS No. 25-50 Sieve) 90.0%

[0329] Example D Extruded pellets Compound 1 25.0% Anhydrous sodium sulfate 10.0% Crude calcium lignosulfonate 5.0% Sodium alkylnaphthalene sulfonate 1.0% Calcium / Magnesium Bentonite 59.0%

[0330] Example E emulsifiable concentrate Compound 1 10.0% Polyoxyethylene sorbitol hexolate 20.0% C6~C 10 Fatty acid methyl ester 70.0%

[0331] Example F Microemulsion Compound 1 5.0% Polyvinylpyrrolidone-vinyl acetate copolymer 30.0% Alkyl polyglycoside 30.0% Glyceryl monooleate 15.0% Water 20.0%

[0332] Example G Suspension concentrate Compound 1 35% Butyl polyoxyethylene / polypropylene block copolymer 4.0% Stearic acid / polyethylene glycol copolymer 1.0% Styrene acrylic acid polymer 1.0% Xanthan gum 0.1% Propylene glycol 5.0% Silicone-based antifoam agent 0.1% 1,2-benzisothiazolin-3-one 0.1% Water 53.7%

[0333] Example H Emulsion in water Compound 1 10.0% Butyl polyoxyethylene / polypropylene block copolymer 4.0% Stearic acid / polyethylene glycol copolymer 1.0% Styrene acrylic acid polymer 1.0% Xanthan gum 0.1% Propylene glycol 5.0% Silicone-based antifoam agent 0.1% 1,2-benzisothiazolin-3-one 0.1% Aromatic Petroleum-Based Hydrocarbons 20.0 Water 58.7%

[0334] Example I oil dispersion system Compound 1 25% Polyoxyethylene sorbitol hexaoleate 15% Organically modified bentonite clay 2.5% Fatty acid methyl esters 57.5%

[0335] The present disclosure also includes Examples A to I above, except that "Compound 1" is replaced with any one of "Compound 2" to "Compound 144" and "Compound 145" to "Compound 414".

[0336] The test results show that the compounds of the present invention are highly active pre-emergence and / or post-emergence herbicides and / or plant growth regulators.The compounds of the present invention generally show the best activity in post-emergence weed control (i.e., application after weed seedlings emerge from the soil) and pre-emergence weed control (i.e., application before weed seedlings emerge from the soil).Many of them are useful for broad-spectrum pre-emergence and / or post-emergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, airports, riverbanks, irrigation and other waterways, around large billboards, and railroad facilities. Many of the compounds of the present invention are useful for the selective control of grasses and broadleaf weeds in crop / weed mixtures because they have selective crop versus weed metabolism, or selective activity in areas of physiological inhibition in crops and weeds, or selective placement on or in the mixed crop and weed environment. As will be recognized by those skilled in the art, suitable combinations of selectivity factors within a single compound or group of compounds can be readily determined by routine biological and / or biochemical assays. The compounds of the invention may exhibit resistance to important agricultural crops such as, but not limited to, alfalfa, barley, cotton, wheat, rapeseed, sugar beet, corn (maize), sorghum, soybean, rice, oats, peas, vegetables, tomatoes, potatoes, perennial plantation crops (including coffee, cocoa, oil palm, rubber), sugarcane, citrus, grapeseed, fruit trees, nut trees, bananas, plantains, pineapples, hops, tea plants, and woodlands such as eucalyptus and conifers (e.g., loblolly pine), and turf species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue, and cypress).The compounds of the present invention may be useful in genetically transformed crops, or crops bred to incorporate herbicide resistance, express proteins toxic to invertebrate pests (e.g., Bacillus thuringiensis toxins), and / or express other useful traits. As one of ordinary skill in the art will recognize, not all compounds are equally effective against all weeds. However, the compounds that are the subject of the present invention are useful for regulating plant growth.

[0337] Because the compounds of the present invention have both pre- and post-emergence herbicidal activity and control undesirable vegetation by killing or damaging the vegetation or inhibiting its growth, they can be usefully applied by a variety of methods, including contacting a herbicidally effective amount of a compound of the present invention or a composition comprising a compound of the present invention and at least one surfactant, solid diluent, or liquid diluent with the foliage or other parts of the undesirable vegetation, or with the environment of the undesirable vegetation, such as soil or water, in which the undesirable vegetation is growing or surrounding the seeds or other propagules of the undesirable vegetation. The undesirable vegetation can include at least one species selected from the group consisting of grass weeds and broadleaf weeds. Unwanted vegetation includes annual bluegrass, spotted daygrass, blackgrass, black nightshade, broadleaf signalgrass, foxglove, bromegrass, cocklebur (Xanthium pensylvanicum), ragweed, corn poppy, field violet, foxtail, goosegrass, green foxtail, guineagrass, burdock, herbicide-resistant blackgrass, dwarf artemisia, Italian ryegrass, morning glory, Pennsylvania willow weed, morning glory, pea weed, quackgrass, red ragweed, sedge, shepherd's purse, and silky windgrass. windgrass, sunflower (as potato species), bindweed (Polygonum convolvulus), wild mustard (Brassica kaber), wild oat (Avena fatua), wild poinsettia, golden foxtail, and tiger berry (Cyperus esculentus).

[0338] The herbicidally effective amount of the compounds of the present invention depends on several factors, including the formulation selected, the method of application, the amount and type of vegetation present, etc. In general, the herbicidally effective amount of the compounds of the present invention is about 0.001 to 20 kg / ha, with a preferred range being about 0.004 to 1 kg / ha. One skilled in the art can readily determine the herbicidally effective amount required to achieve the desired level of weed control.

[0339] In one general embodiment, the compounds of the invention, typically in the form of a formulated composition, are applied to an area containing desirable vegetation (e.g., crops) and undesirable vegetation (i.e., weeds), both of which may be seeds, seedlings, and / or more mature plants, in contact with the growing medium (e.g., soil). In this area, compositions containing the compounds of the invention can be applied directly to the plants or parts thereof of the undesirable vegetation and / or to the growing medium in contact with the plants.

[0340] Although compounds of the invention are most typically used to control undesirable vegetation, contacting desirable vegetation with a compound of the invention in a treated area may result in superadditive or enhanced effects, including those derived from the genetic traits of the desirable vegetation and traits acquired through genetic modification. For example, resistance to herbivorous pests or plant diseases, resistance to biotic / abiotic stresses, or storage stability may be greater than would be expected from the genetic traits of the desirable vegetation.

[0341] The compounds of the present invention can also be mixed with one or more other biologically active compounds or agents, including herbicides, herbicide safeners, fungicides, insecticides, nematicides, bactericides, acaricides, growth regulators (e.g., insect molting inhibitors and root stimulators), chemosterilants, signal chemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds, or insect pathogenic bacteria, viruses, or fungi, to form multi-component biocides that provide even broader agricultural protection. Mixtures of the compounds of the present invention with other herbicides can extend the spectrum of activity against additional weed species and suppress the growth of various resistant biotypes. Thus, the present invention also relates to compositions comprising a compound of Formula 1 (in a herbicidally effective amount) and at least one additional biologically active compound or agent (in a biologically effective amount), and can further comprise at least one surfactant, solid diluent, or liquid diluent. Other biologically active compounds or agents can be formulated in compositions that include at least one of a surfactant, a solid diluent, or a liquid diluent. With respect to the mixtures of the present invention, one or more other biologically active compounds or agents can be formulated with the compound of Formula 1 to form a premix, or one or more other biologically active compounds or agents can be formulated separately from the compound of Formula 1, and the formulations can be combined together (e.g., in a spray tank) prior to application or alternatively applied sequentially.

[0342] Mixtures of the compounds of the present invention with one or more of the following herbicides may be particularly useful for weed control: acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal), alachlor, alloxydim, ametryn, amicarbazone, amidosulfuron, aminocyclopyrachlor and its esters (e.g., methyl, ethyl) and salts (e.g., sodium, potassium), 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)-2-pyridinecarboxylic acid 2-propyn-1-yl ester (CAS No. 2251111-17-6), 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)-2-pyridinecarboxylic acid cyanomethyl ester (CAS No. 2251111-18-7), aminopyralid, amitrole, ammonium sulfamate, 2,5-anhydro-3,4-dideoxy-4-[[[(5S)-3-(3,5-difluorophenyl)-5-ethenyl-4,5-dihydro-5-isoxazolyl]carbonyl]amino]-threo-pentonic acid methyl ester (CAS No. 27499989-21-6), anilofos, anicifluprine, asulam, atrazine, azimsulfuron, bixlozone, beflubutamid, beflubutamid-M, benazolin, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, benquitrione, bensulfuron-methyl, bensulide, bentazon, benzobicyclon, benzofenap, bicyclopyrone, bifenox, viranaphos, bispyribac and its sodium salt, bromacil, bromobutide, bromofenoxime, bromoxynil, bromoxynil octanoate, butachlor, butafenacil, butamifos, butralin, butroxydim, butyrate, bipyrazone, cafenstrole, carbetamide, 1-(2-carboxyethyl)-4-(2-pyrimidinyl)pyridazinium (CAS No.2285384-11-2) and its salts, carfentrazone-ethyl, catechin, chlormethoxyfen, chloramben, chlorbromuron, chlorflurenol-methyl, chloridazon, chlorimuron-ethyl, 3-[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenyl]-4,5-dihydro-5-methyl-5-isoxazolecarboxylic acid ethyl ester (CAS No. 1949837-17-5), chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, clasifos, clefoxydim, clethodim, clodinafop-propargyl, clomazone, clomeprop, clopyralid, clopyralid-olamine, chloransulam-methyl, cumyluron, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, 2,4-D and its butotyl, butyl, isoctyl and isopropyl esters and its dimethylammonium, diolamine and trolamine salts, cipirafluon, dymron, dalapon, dalapon-sodium, dazo Met, 2,4-DB and its dimethylammonium, potassium and sodium salts, desmedipham, desmetrin, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, dichlobenil, dichlorprop, diclofop-methyl, diclosulam, difenzoquat methylsulfate, diflufenican, diflufenzopyr, dimefurone, dimepiperate, dimesulfazate, dimethachlor, dimethametrin, dimethenamid, dimethenamid-P, dimethipine, dimethylarsinic acid and its sodium salt, dinitramine, dinoterb, dioxopyritrone, diphenamide, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC. Epirifenacil, esprocarb, ethalfluralin, ethametsulfuron-methyl, etiodin, ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanide, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenpyrazone, fenquinotrione, fentrazamide, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop-butyl, fluazifop-P-butyl , fluazolate, flucarbazone, flucetosulfuron, fluchloralin, fluchloraminopyr, flufenacet, flufenoximacil, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, flurenol, flurenol-butyl, fluridone, flurochloridone, fluroxypyr, flurtamone, flusulfinam, fluthiacet-methyl, fomesafen, foramsul Furono, fosamine-ammonium, glufosinate, glufosinate-ammonium, glufosinate-P, glyphosate and its salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (also named sulfosate), haloxifen, haloxifen-methyl, halosulfuron-methyl, haloxyfop-ethotyl, haloxyfop-methyl, hexazinone, hydantocidin, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, ibuprofen, imibuprofen, imibuprofen-methyl ... Mazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, indanofan, indaziflam, iofensulfuron, iodosulfuron-methyl, ioxynil, ioxynil octanoate, ioxynil-sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, isoxachlorthole, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its salts (e.g., MCPA-dimethylammonium, MCPA-potassium and MCPA-sodium,Esters (e.g., MCPA-2-ethylhexyl, MCPA-butotyl) and thioesters (e.g., MCPA-thioethyl), MCPB and its salts (e.g., MCPB-sodium) and esters (e.g., MCPB-ethyl), mecoprop, mecoprop-P, mefenacet, mefluidide, mesosulfuron-methyl, mesotrione, metam-sodium, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts Salt, methyldaimron, metobenzuron, metobromuron, metolachlor, S-metolachlor, metoslam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, naproanilide, napropamide, napropamide-M, naptalam, nebron, nicosulfuron, norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxiflufen, paraquat dichloride, pebulate, pelargonic acid, pendimethalin, penoxox Sulam, pentanochlor, pentoxazone, perfluidone, petoxamide, petoxyamide, phenmedipham, picloram, picloram-potassium, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron-methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen-ethyl, Pyrasulfotole, pyrazogyl, pyrazolinate, pyrazoxifen, pyrazosulfuron-ethyl, pyribenzoxim, pyributicarb, pyridate, pyriflubenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimisoxafen, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine,Simetryne, Sulcotrione, Sulfentrazone, Sulfometuron-methyl, Sulfosulfuron, 2,3,6-TBA, TCA, TCA-sodium, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbumeton, terbuthylazine, terbutryn, tetflupyrrolimet, thenylchlor, thiazopyr, thiencarbazone, thifensulfuron-methyl, thiobencarb, thiafenacil, thiocarbazil, tolpyralate, topramezone, tralkoxydim, triallate, triafamone, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-buty , triclopyr-triethylammonium, tridiphan, trietazine, trifloxysulfuron, trifludimoxazine, trifluralin, triflusulfuron-methyl, tripyrasulfone, tritosulfuron, vernalate, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridin-2(1H)-one, 5-chloro-3-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalinone, 2-chloro-N -(1-Methyl-1H-tetrazol-5-yl)-6-(trifluoromethyl)-3-pyridinecarboxamide, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-b]pyrazin-6(5H)-one), 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone), 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole (hereinafter Previously, methioxoline), 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione, methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate, 2-methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide, and 2-methyl-N-(4-methyl-1,2,5-Oxadiazol-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide. Other herbicides include bioherbicides such as Alternaria destruens Simmons, Colletotrichum gloeosporiodes (Penz.) Penz. & Sacc., Drechsiera monoceras (MTB-951), Myrothecium verrucaria (Albertini & Schweinitz) Ditmar:Fries, Phytophthora palmivora (Butl.) Butl., and Puccinia thlaspeos Schub.

[0343] Preferred for better control of undesirable vegetation (e.g., reduced application rates due to increased efficacy, increased spectrum of weed control, or increased crop safety) or to prevent the development of resistant weeds are mixtures of the compounds of the present invention with herbicides selected from the group consisting of atrazine, azimsulfuron, S-beflubutamid, benzisothiazolinone, carfentrazone-ethyl, chlorimuron-ethyl, chlorsulfuron-methyl, clomazone, clopyralid potassium, chloransulam-methyl, 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-3-isoxazolidinone, 2-[(2,5-dichlorophenyl)methyl]-4, 4-Dimethyl-3-isoxazolidinone, ethametsulfuron-methyl, flumetoslam, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5-(2H,4H)-dione, flupyrsulfuron-methyl, fluthiacet-methyl, fomesafen, imazethapyr, lenacil, mesotrione, metribuzin, metsulfuron-methyl, petoxamide, picloram, pyroxasulfone, quinclorac, rimsulfuron, S-metolachlor, sulfentrazone, thifensulfuron-methyl, triflusulfuron-methyl, and tribenuron-methyl.

[0344] The compounds of the invention may also be used in combination with plant growth regulators such as aviglycin, N-(phenylmethyl)-1H-purin-6-amine, epocholeon, gibberellic acid, gibberellins A4 and A7, harpin proteins, mepiquat chloride, prohexadione calcium, prohydrojasmone, sodium nitrophenolate, and trinexapac-methyl, and plant growth-regulating organisms such as Bacillus cereus strain BP01.

[0345] General references for agricultural protectants (i.e., herbicides, herbicide safeners, insecticides, fungicides, nematicides, acaricides, and biological agents) include: The Pesticide Manual, 13th Edition, CDS Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2003 and The BioPesticide Manual, 2nd Edition, L.G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2001.

[0346] In embodiments in which one or more of these various mixing partners are used, the mixing partners are typically used in amounts similar to those customarily used when the mixing partners are used alone. More specifically, in mixtures, the active ingredients are often applied at application rates between half and full of the application rate for the active ingredient alone as specified on the product label. These amounts are described, for example, in the following references: The Pesticide Manual and The BioPesticide Manual. The weight ratio of these various mixing partners (combined) to the compound of Formula 1 is typically between about 1:3000 and about 3000:1. Of note are weight ratios of about 1:300 to about 300:1 (e.g., ratios of about 1:30 to about 30:1). Those skilled in the art can easily determine by simple experimentation the biologically effective amount of the active ingredient required to achieve the desired spectrum of biological activity. It will be apparent that the inclusion of these additional components can broaden the spectrum of weeds controlled beyond that controlled by the compound of Formula 1 alone.

[0347] In certain cases, the compounds of the present invention can be combined with other biologically active (especially herbicidal) compounds or agents (i.e., active ingredients) to achieve greater than additive (i.e., enhanced) effects on weeds and / or less than additive (i.e., safer) results on crops or other desirable plants. Reducing the amount of active ingredient released into the environment while still ensuring effective pest control is always desirable. The ability to use greater amounts of active ingredient to achieve more effective weed control without excessive crop damage is also desirable. When the enhanced effect of a herbicidal mixture of active ingredients occurs on weeds at application rates that provide an agronomically satisfactory level of weed control, such combinations can be advantageous for reducing crop production costs and reducing environmental impact. When detoxification of the herbicidal active ingredient occurs on the crop, such combinations can be advantageous for increasing crop protection by reducing weed competition.

[0348] Of note is the combination of the compound of the present invention with at least one other herbicidal active ingredient. Particularly noteworthy is the combination in which the other herbicidal active ingredient has a different site of action from the compound of the present invention. In some cases, the combination with at least one other herbicidal active ingredient with a similar control spectrum but a different site of action will be particularly advantageous for resistance management. Therefore, the composition of the present invention can further contain at least one additional herbicidal active ingredient (in a herbicidally effective amount) with a similar control spectrum but a different site of action.

[0349] The compounds of the invention can also be used in combination with herbicide safeners to increase safety in certain crops, such as, for example, allidochlor, benoxacor, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfonamide, dymron, dichlormid, dicyclonone, dietholate, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, methoxyphenone, naphthalic anhydride (1,8-naphthalic anhydride), oxabetrinil, N-(aminocarbonyl)-2-methylbenzenesulfonamide, N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene (BCS), 4-(dichloroacetyl)-1-oxa-4-azospiro[4.5]decane (MON). 4660), 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), ethyl 1,6-dihydro-1-(2-methoxyphenyl)-6-oxo-2-phenyl-5-pyrimidinecarboxylate, 2-hydroxy-N,N-dimethyl-6-(trifluoromethyl)pyridine-3-carboxamide, and 3-oxo-1-cyclohexen-1-yl,1-(3,4-dimethylphenyl)-1,6-dihydro-6-oxo-2-phenyl-5-pyrimidinecarboxylate, 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-ethanone, and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide. An additional effective amount of a herbicide safener can be applied simultaneously with the compounds of the invention or as a seed treatment. Thus, an aspect of the invention relates to herbicidal mixtures comprising a compound of the invention and an antidotal effective amount of a herbicide safener. Seed treatments are particularly useful for selective weed control because they have limited antidotal effect on the crop.Thus, a particularly useful embodiment of the present invention is a method for selectively controlling the growth of undesirable vegetation in a crop, comprising contacting a locus of the crop with a herbicidally effective amount of a compound of the present invention, wherein the seeds from which the crop grows are treated with an antidote-effective amount of a safener, which antidote-effective amount can be readily determined by one skilled in the art by simple experimentation.

[0350] 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 that affect the abundance of specific targets through, for example, downregulation, interference, suppression, or silencing of engineered transcripts to confer a herbicidal effect; or (2) polynucleotides, including but not limited to, DNA, RNA, and / or chemically modified nucleotides that affect the abundance of specific targets through, for example, downregulation, interference, suppression, or silencing of engineered transcripts to confer a safening effect.

[0351] Of note are compositions comprising a herbicidally effective amount of a compound of the present invention, an effective amount of at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners, and at least one ingredient selected from the group consisting of surfactants, solid diluents, and liquid diluents.

[0352] Table A1 lists specific combinations of components (a) and (b) that illustrate the mixtures, compositions, and methods of the present invention. The compound numbers in the component (a) column (i.e., Compound 1) are identified in Index Table A. The second column of Table A1 lists specific component (b) compounds (e.g., "2,4-D" in the first row). The third, fourth, and fifth columns of Table A1 list the weight ratio ranges at which component (a) compounds are typically applied to field-grown crops relative to component (b) (i.e., (a):(b)). Thus, for example, the first row of Table A1 specifically discloses that a combination of component (a) (i.e., Compound 1 in Index Table A) and 2,4-D is typically applied in a weight ratio between 1:384 and 6:1. The remaining rows of Table A1 are similarly organized.

[0353] [Table 21]

[0354] [Table 22]

[0355] [Table 23]

[0356] [Table 24]

[0357] [Table 25]

[0358] [Table 26]

[0359] [Table 27]

[0360] Table A2 is structured the same as Table A1 above, except that the entries under the "Component (a)" column heading are replaced with the respective component (a) column headings shown below. The compound numbers in the component (a) column are identified in Index Table A. Thus, for example, in Table A2, all content under the "Component (a)" column heading represents "Compound 2" (i.e., Compound 2 as identified in Index Table A), and the first row under the column heading in Table A2 specifically discloses a mixture of Compound 2 with 2,4-D. Tables A3-A414 are structured similarly.

[0361] [Table 28]

[0362] [Table 29]

[0363] [Table 30]

[0364] [Table 31]

[0365] [Table 32]

[0366] Preferred for better control of undesirable vegetation (e.g., reduced application rate due to increased efficacy, increased spectrum of weeds controlled, or increased crop safety) or prevention of the emergence of resistant weeds are mixtures of a compound of the invention with a herbicide selected from the group consisting of chlorimuron ethyl, nicosulfuron, mesotrione, thifensulfuron methyl, flupyrsulfuron methyl, tribenuron, pyroxasulfone, pinoxaden, tembotrione, pyroxsulam, metolachlor and S-metolachlor.

[0367] The following tests demonstrate the control efficacy of the compounds of the present invention against specific weeds. However, the weed control achieved by these compounds is not limited to these species. See Index Tables A-F for compound descriptions. The following abbreviations are used in the Index Tables below: t is tertiary, s is secondary, n is linear, i is iso, c is cyclo, Me is methyl, Et is ethyl, Pro is propyl, i-Pro is isopropyl, Bu is butyl, c-Pro is cyclopropyl, c-Bu is cyclobutyl, c-Pen is cyclopentyl, t-Bu is tert-butyl, i-Bu is isobutyl, s-Bu is sec-butyl, Ph is phenyl, OMe is methoxy, OEt is ethoxy, SMe is methylthio, SEt is ethylthio, -CN is cyano, -NO is nitrile, TMS is trimethylsilyl, allyl is CHCH=CH, propargyl is CHC≡CH, and naphthyl means naphthalenyl. Some other structures are defined in the table below.

[0368] [Table 33]

[0369] (1') or (1'') refers to the absolute chirality of the asymmetric carbon center (*). (1') and (1'') are defined as follows: [ka]

[0370] The abbreviation "(d)" indicates that the compound appears to decompose upon melting. The abbreviation "Cmpd.#" stands for "Compound Number." The abbreviation "Ex." stands for "Example," followed by a number indicating the example in which the compound was prepared. Mass spectra are reported, within an estimated accuracy of ±0.5 Da, as the molecular weight of the parent ion of highest isotopic abundance (M+1) formed by adding H+ (molecular weight, 1) to the molecule, observed using atmospheric pressure chemical ionization (AP+).

[0371] [Table 34]

[0372] [Table 35]

[0373] [Table 36]

[0374] [Table 37]

[0375] [Table 38]

[0376] [Table 39]

[0377] [Table 40]

[0378] Table 41

[0379] Table 42

[0380] Table 43

[0381] Table 44

[0382] Table 45

[0383] Table 46

[0384] Table 47

[0385] Table 48

[0386] Table 49

[0387]

Table 50

[0388] [Table 51]

[0389] [Table 52]

[0390] [Table 53]

[0391] [Table 54]

[0392] [Table 55]

[0393] [Table 56]

[0394] [Table 57]

[0395] [Table 58]

[0396] Biological Examples of the Invention Test A Barnyard grass (Echinochloa crus-galli), blackgrass (Alopecurus myosuroides), corn (Zea mays), foxtail (giant foxtail), Japanese foxtail (Setaria faberi), goosegrass (Eleusine indica), kochia (Bassia scoparia), oats (Avena fatua), amaranth (Palmer amaranth), palmer pigweed (Amaranthus palmeri), redroot pigweed (Amaranthus retroflexus), common ragweed (Ambrosia artemisiifolia), Italian ryegrass (Italian Seeds of plant species selected from ryegrass (Lolium multiflorum), soybean (Glycine max), and wheat (Triticum aestivum) were planted in a blend of loam soil and sand and pre-emergence treated with a directional soil spray using test chemicals formulated in a non-phytotoxic solvent mixture containing a surfactant.

[0397] Simultaneously, plants selected from these crop and weed species, as well as catchweed bedstraw (Galium aparine) and dwarf artemisia (Erigeron canadensis), were planted in pots containing the same blend of loam soil and sand and treated with postemergence applications of identically formulated test chemicals. Plant heights ranged from 2 cm to 10 cm and were at the one- to two-leaf stage for postemergence treatment. Treated plants and untreated controls were maintained in the greenhouse for 10 days, after which all treated plants were compared to untreated controls and visually evaluated for damage. Plant response ratings, summarized in Table A, are based on a scale of 0 to 100, where 0 is no effect and 100 is complete control. A dash (-) response indicates no test result.

[0398] Table 59

[0399] Table 60

[0400] Table 61

[0401] Table 62

[0402] Table 63

[0403] Table 64

[0404] Table 65

[0405] Table 66

[0406] Table 67

[0407] Table 68

[0408] Table 69

[0409] [Table 70]

[0410] [Table 71]

[0411] [Table 72]

[0412] [Table 73]

[0413] [Table 74]

[0414] [Table 75]

[0415] [Table 76]

[0416] Test B Flooded rice test plant species selected from barnyard grass (Echinochloa crus-galli), American whitegrass (Heteranthera limosa), rice (Oryza sativa), and small-flower umbrella sedge (Cyperus difformis) were grown to the two-leaf stage for testing. At the time of treatment, test pots were flooded to 3 cm above the soil surface and treated by applying the test compound directly to the paddy water, then maintained at that water depth for the duration of the test. Treated plants and controls were held in the greenhouse for 13 days, after which all species were visually evaluated compared to the control. Plant response ratings, summarized in Table B, are based on a scale of 0 to 100, where 0 is no effect and 100 is complete control. A dash (-) response means there was no test result.

[0417] [Table 77]

[0418] [Table 78]

[0419] [Table 79]

[0420] Test C Barnyardgrass (Echinochloa crus-galli), black-grass (Alopecurus myosuroides), corn (Zea mays), foxtail (giant foxtail), Japanese kittel (Setaria faberi), cattail (Setaria viridis), goosegrass (Eleusine indica), kochia (Bassia scoparia), oats (Avena fatua), amaranth (Palmer amaranth), palmer pigweed (Amaranthus palmeri), redroot pigweed (Amaranthus retroflexus), common ragweed (Ambrosia Seeds of plant species selected from (artemisiifolia), Italian ryegrass (µallium ryegrass, Lolium multiflorum), soybean (Glycine max), and wheat (Triticum aestivum) were planted in a blend of loam soil and sand and pre-emergence treated with a directional soil spray using test chemicals formulated in a non-phytotoxic solvent mixture containing a surfactant.

[0421] Simultaneously, plants selected from these crop and weed species, as well as catchweed bedstraw (Galium aparine) and dwarf artemisia (Erigeron canadensis), were planted in pots containing the same blend of loam soil and sand and treated with postemergence applications of identically formulated test chemicals. Plant heights ranged from 2 cm to 10 cm and were at the one- to two-leaf stage for postemergence treatment. Treated plants and untreated controls were maintained in the greenhouse for 10 days, after which all treated plants were compared to untreated controls and visually evaluated for damage. Plant response ratings, summarized in Table C, are based on a scale of 0 to 100, where 0 is no effect and 100 is complete control. A dash (-) response indicates no test result.

[0422] Table 80

[0423] Table 81

[0424] Table 82

[0425] Table 83

[0426] Table 84

[0427] Table 85

[0428] Table 86

[0429] Table 87

[0430] Table 88

[0431] Table 89

[0432] Table 90

[0433]

Table 91

[0434] Table 92

[0435] Table 93

[0436] Table 94

[0437] Table 95

[0438] Table 96

[0439] Table 97

[0440] Table 98

[0441]

Table 99

[0442]

Table 100

[0443] [Table 101]

[0444] [Table 102]

[0445] [Table 103]

[0446] [Table 104]

[0447] [Table 105]

[0448] [Table 106]

[0449] [Table 107]

[0450] [Table 108]

[0451] [Table 109]

[0452] Test D Flooded rice test plant species selected from barnyard grass (Echinochloa crus-galli), American whitegrass (Heteranthera limosa), rice (Oryza sativa), and small-flower umbrella sedge (Cyperus difformis) were grown to the two-leaf stage for testing. At the time of treatment, test pots were flooded to 3 cm above the soil surface and treated by applying test compounds directly to the paddy water, then maintained at that water depth for the duration of the test. Treated plants and controls were held in the greenhouse for 13-14 days, after which all species were visually evaluated compared to the control. Plant response ratings, summarized in Table D, are based on a scale of 0 to 100, where 0 is no effect and 100 is complete control. A dash (-) response indicates no test result.

[0453] [Table 110]

[0454] [Table 111]

[0455] [Table 112]

[0456] [Table 113]

Claims

1. Compounds of Formula 1, all stereoisomers, N-oxides, and salts thereof 【Chemical 1】 (In the formula, A is a 5- or 6-membered heterocyclic ring containing ring members selected from carbon atoms and up to four heteroatoms independently selected from up to two O, up to two S, and up to four N atoms, wherein one or two carbon or sulfur ring members of the heterocycle may optionally be present in the oxidized form of a carbonyl, sulfonyl, or sulfinyl moiety, said ring being bonded to the remainder of Formula 1 through a carbon atom or heteroatom, and wherein one to four R １ optionally replaced by; R １ are independently R １ａ , (R １ｂ ) ｍ Or R １ｃ or any combination thereof; R １ａ is H, halogen, cyano, nitro, amino, C １ ~C ７ Alkyl, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl, C ４ ~C ７ Cycloalkylalkyl, C ４ ~C ７ Alkylcycloalkyl, C １ ~C ７ Haloalkyl, C １ ~C ６ Hydroxyalkyl, C ３ ~C ７ Hydroxycycloalkyl, C １ ~C ６ Hydroxyhaloalkyl, C ４ ~C ８ Alkoxycycloalkyl, C ２ ~C ７ Alkoxyhaloalkyl, C ２ ~C ６ Oxacycloalkyl, C ３ ~C ７ Oxacycloalkylalkyl, C ３ ~C ７ Alkyloxacycloalkyl, C ２ ~C ６ Thiacycloalkyl, C ３ ~C ７ Thiacycloalkylalkyl, C ３ ~C ７ Alkylthiacycloalkyl, C ２ ~C ６ (O-thia)cycloalkyl, C ３ ~C ７ (O-thia)cycloalkylalkyl, C ３ ~C ７ Alkyl(O-thia)cycloalkyl, C ２ ~C ６ (O ２ thia)cycloalkyl, C ３ ~C ７ (O ２ Thia)cycloalkylalkyl, C ３ ~C ７ Alkyl (O ２ thia)cycloalkyl, C ２ ~C ６ Haloalkenyl, C ２ ~C ６ Haloalkynyl, C ３ ~C ７ Halocycloalkyl, C ４ ~C ７ Haloalkylcycloalkyl, C ２ ~C ７ Alkoxyalkyl, C ２ ~C ７ Haloalkoxyalkyl, C １ ~C ７ Alkoxy, C ２ ~C ５ Alkenyloxy, C ２ ~C ５ Alkynyloxy, C ３ ~C ７ Cycloalkoxy, C ４ ~C ７ Cycloalkoxyalkyl, C １ ~C ７ Haloalkoxy, C １ ~C ７ Alkylthio, C ２ ~C ７ Alkylthioalkyl, C １ ~C ５ Alkylsulfinyl, C １ ~C ５ Alkylsulfonyl, C １ ~C ４ Alkyl sulfonates, C １ ~C ５ Haloalkylthio, C １ ~C ５ Haloalkylsulfinyl, C １ ~C ５ Haloalkylsulfonyl, C ２ ~C ７ Alkylsulfinylalkyl, C ２ ~C ７ Alkylsulfonylalkyl, C ２ ~C ７ Haloalkylthioalkyl, C ２ ~C ７ Haloalkylsulfinylalkyl, C ２ ~C ７ Haloalkylsulfonylalkyl, C ２ ~C ７ Alkylthiocycloalkyl, C ４ ~C ７ Alkylsulfinylcycloalkyl, C ４ ~C ７ Alkylsulfonylcycloalkyl, C ４ ~C ７ Haloalkylthiocycloalkyl, C ２ ~C ７ Haloalkylsulfinylcycloalkyl, C ２ ~C ７ Haloalkylsulfonylcycloalkyl, C2-C7 alkylsulfoximinoalkyl, C ２ ~C ５ Cyanoalkyl, C ４ ~C ７ Cyanocycloalkyl, C １ ~C ４ Nitroalkyl, C １ ~C ７ Alkylamino, C ２ ~C ７ Dialkylamino, C ３ ~C ５ Alkylcarbonyl(alkyl)amino, C ３ ~C ５ Alkoxycarbonyl(alkyl)amino, C2-C4 alkoxysulfonyl(alkyl)amino, C ２ ~C ６ Alkylcarbonyl, C ３ ~C ６ Alkylcarbonylalkyl, C ２ ~C ６ Alkoxycarbonyl, C ３ ~C ６ Alkoxycarbonylalkyl, C ３ ~C ６ Trialkylsilyl or C ５ ~C ８ trialkylsilylalkynyl; or Halogen, cyano, C １ ~C ２ Alkyl, C １ ~C ２ Haloalkyl, C １ ~C ２ Alkoxy and C １ ~C ２ phenyl optionally substituted with up to 3 substituents independently selected from the group consisting of haloalkoxy; R １ｂ is H, halogen, cyano, nitro, C １ ~C ４ Alkyl, C ３ ~C ５ Cycloalkyl, C １ ~C ４ Haloalkyl, C ３ ~C ５ Halocycloalkyl, C ２ ~C ４ Alkoxyalkyl, C １ ~C ４ Alkoxy, C １ ~C ４ Alkylthio or C ２ ~C ４ is alkoxycarbonyl; m is 0, 1 or 2; R １ｃ is H, C １ ~C ７ Alkyl, C ３ ~C ７ Cycloalkyl or C １ ~C ７ haloalkyl; X １ and X ２ are independently N or CR ２ and n is 0, 1, 2 or 3; Each R ２ are independently H, halogen, cyano, nitro, hydroxy, C １ ~C ５ Alkyl, C ２ ~C ５ Alkenyl, C ２ ~C ５ Alkynyl, C ２ ~C ５ Alkenyloxy, C ２ ~C ５ Alkynyloxy, C ３ ~C ７ Cycloalkoxy, C ４ ~C ７ Cycloalkoxyalkyl, C ３ ~C ６ Cycloalkyl, C ４ ~C ７ Cycloalkylalkyl, C １ ~C ５ Haloalkyl, C ２ ~C ５ Haloalkenyl, C ２ ~C ５ Haloalkynyl, C ２ ~C ５ Alkoxyalkyl, C ２ ~C ５ Haloalkoxyalkyl, C １ ~C ５ Alkoxy, C １ ~C ５ Haloalkoxy, C １ ~C ５ Alkylthio, C １ ~C ４ Alkylsulfinyl, C １ ~C ４ Alkylsulfonyl, C １ ~C ４ Alkyl sulfonates, C ３ ~C ５ Cycloalkylsulfonates, C １ ~C ４ Haloalkylsulfonates, C １ ~C ４ Haloalkylthio, C １ ~C ４ Haloalkylsulfinyl, C １ ~C ４ Haloalkylsulfonyl, C ２ ~C ５ Cyanoalkyl, C ４ ~C ６ Cyanocycloalkyl or C ２ ~C ５ Is alkoxycarbonyl; or Two adjacent R ２ may combine to form a saturated or unsaturated 5- to 8-membered ring containing carbon atoms and optionally 1 to 3 oxygen, sulfur or nitrogen atoms as ring members, wherein one or two carbon or sulfur ring members of the heterocycle may optionally be present in the oxidized form of a carbonyl, sulfonyl, sulfinyl moiety, and the ring may be unsubstituted or substituted with halogen, cyano, nitro, C １ ~C ４ Alkyl, C ３ ~C ６ Cycloalkyl, C １ ~C ４ Haloalkyl, C １ ~C ４ Alkoxy and C １ ~C ４ substituted with at least one substituent independently selected from the group consisting of haloalkoxy; Y is O or S; R ３ａ is a halogen, C １ ~C ７ Alkyl, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl, C １ ~C ７ Alkoxy, C ４ ~C ７ Cycloalkylalkyl, C ４ ~C ７ Alkylcycloalkyl, C １ ~C ７ Haloalkyl, C ２ ~C ６ Haloalkenyl, C ２ ~C ６ Haloalkynyl, C ３ ~C ７ Halocycloalkyl, C ４ ~C ７ Haloalkylcycloalkyl, C ２ ~C ７ Alkoxyalkyl, C ２ ~C ７ Haloalkoxyalkyl, C ２ ~C ７ Alkylthioalkyl, C ２ ~C ７ Alkylsulfinylalkyl, C ２ ~C ７ Alkylsulfonylalkyl, C ２ ~C ７ Haloalkylthioalkyl, C ２ ~C ７ Haloalkylsulfinylalkyl, C ２ ~C ７ Haloalkylsulfonylalkyl, C ２ ~C ５ Cyanoalkyl, C ４ ~C ６ Cyanocycloalkyl, C １ ~C ４ Nitroalkyl, C ３ ~C ６ Alkylcarbonylalkyl, C ２ ~C ６ Oxacycloalkyl, C ２ ~C ６ Oxacycloalkylalkyl, C ３ ~C ７ Cycloalkoxy, C ４ ~C ７ Cycloalkoxyalkyl or C ３ ~C ６ alkoxycarbonylalkyl; Each R ３ｂ are independently H, halogen, or C １ ~C ３ is alkyl; or R ３ａ and R ３ｂ together with the carbon atoms to which they are attached form a 3- to 7-membered ring containing carbon atoms and ring members selected from one oxygen atom, one sulfur atom, and up to three heteroatoms independently selected from one nitrogen atom, wherein up to two carbon atom ring members are independently selected from C(═O) and C(═S), and the sulfur atom ring member is S, S(O), or S(O) ２ or Two R's ３ｂ together with the carbon atoms to which they are attached form a 3- to 7-membered ring containing carbon atoms and ring members selected from one oxygen atom, one sulfur atom, and up to three heteroatoms independently selected from one nitrogen atom, wherein up to two carbon atom ring members are independently selected from C(═O) and C(═S), and the sulfur atom ring member is S, S(O), or S(O) ２ Selected from: p is 0, 1, 2 or 3; R ４ａ is H, halogen, cyano, nitro, C １ ~C ５ Alkyl, C ２ ~C ５ Alkenyl, C ２ ~C ５ Alkynyl, C ３ ~C ５ Cycloalkyl, C １ ~C ５ Haloalkyl, C ２ ~C ５ Haloalkenyl, C ２ ~C ５ Haloalkynyl, C ２ ~C ５ Alkoxyalkyl, C ２ ~C ５ Haloalkoxyalkyl, C １ ~C ５ Alkoxy, C １ ~C ５ Haloalkoxy, C ３ ~C ６ Trialkylsilyl, C ５ ~C ８ Trialkylsilylalkynyl, C １ ~C ５ Alkylthio, C １ ~C ５ Haloalkylthio or C ２ ~C ５ is alkoxycarbonyl; q is 0, 1 or 2; Each R ４ｂ are independently H, halogen, cyano, nitro, C １ ~C ４ Alkyl, C １ ~C ４ Haloalkyl, C １ ~C ４ Alkoxy or C １ ~C ４ alkylthio; The compound of formula 1 is [3-(5-cyclopropyl-1,2,4-oxadiazol-3-yl)phenyl](2-ethyl-2,3-dihydro-4H-1,4-benzoxazin-4-yl)-methanone (CAS Registration No. 1798020-19-5); (8-chloro-2-ethyl-2,3-dihydro-4H-1,4-benzoxazin-4-yl)[3-(1H-tetrazol-1-yl)phenyl]methanone (CAS Registration No. 2093742-48-2); (2-ethyl-2,3-dihydro-4H-1,4-benzoxazin-4-yl)[2-(1H-1,2,4-triazol-1-yl)-4-pyridinyl]-methanone (CAS Registration No. 1808378-56-4); (8-chloro-2-ethyl-2,3-dihydro-4H-1,4-benzoxazin-4-yl)[2-(1H-1,2,4-triazol-1-yl)-4-pyridinyl]-methanone (CAS Registration No. 1808849-41-3); (2,3-Dihydro-2,7-dimethyl-4H-1,4-benzoxazin-4-yl)[2-(1H-1,2,4-triazol-1-yl)-4-pyridinyl]-methanone (CAS Registration No. 1436224-65-5); (8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl)[2-(1H-pyrazol-1-yl)-4-pyridinyl]-methanone (CAS Registration No. 2224006-86-2); (2,3-Dihydro-2-methyl-4H-1,4-benzoxazin-4-yl)[3-(1-pyrrolidinyl)phenyl]methanone (CAS Registration No. 2733463-68-6); Methanone, (3,4-dihydrospiro[2H-1,4-benzoxazine-2,1′-cyclopropan]-4-yl)[3-(1-pyrrolidinyl)phenyl] (CAS Registration No. 2733410-16-5); (2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl)[3-(1H-pyrrol-1-yl)phenyl]methanone (CAS Registration No. 2305402-15-5); (3,4-dihydrospiro[2H-1,4-benzoxazin-2,1′-cyclopropan]-4-yl)[3-(1H-pyrrol-1-yl)phenyl]methanone (CAS Registration No. 2305290-36-0); (8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl)[3-[5-(methoxymethyl)-1,3,4-oxadiazol-2-yl]phenyl]methanone (CAS Registration No. 2223792-20-7); (7-fluoro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl)[2-(4-methyl-1-piperazinyl)-4-pyridinyl]methanone (CAS Registration No. 2212440-53-2); (7-fluoro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl)[3-(1H-1,2,4-triazol-5-yl)phenyl]methanone (CAS Registration No. 2094921-82-9); (2-ethyl-2,3-dihydro-4H-1,4-benzoxazin-4-yl)[5-(4-morpholinyl)-3-pyridinyl]methanone (CAS Registration No. 1957585-10-2); (8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl)[5-(4-morpholinyl)-3-pyridinyl]methanone (CAS Registration No. 1957541-06-8); (8-chloro-2-ethyl-2,3-dihydro-4H-1,4-benzoxazin-4-yl)[5-(4-morpholinyl)-3-pyridinyl]methanone (CAS Registration No. 1956163-57-7); (2,3-Dihydro-2,6-dimethyl-4H-1,4-benzoxazin-4-yl)[5-(4-morpholinyl)-3-pyridinyl]methanone (CAS Registration No. 1955383-94-4); (2,3-Dihydro-2,2-dimethyl-4H-1,4-benzoxazin-4-yl)[5-(4-morpholinyl)-3-pyridinyl]methanone (CAS Registration No. 1955104-90-1); (6-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl)[5-(4-morpholinyl)-3-pyridinyl]methanone (CAS Registration No. 1954398-26-5); (2,3-dihydro-6-methoxy-2-methyl-4H-1,4-benzoxazin-4-yl)[5-(4-morpholinyl)-3-pyridinyl]methanone (CAS Registry No. 1947266-43-4); and provided that the compound is other than (2,3-dihydro-6-methoxy-2-methyl-4H-1,4-benzoxazin-4-yl)[3-(1H-imidazol-1-yl)phenyl]methanone (CAS Registration No. 1384688-76-9).

2. A is, 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 2. The compound of claim 1 selected from:

3. The compound according to claim 1, wherein A is A-1, A-4, A-5, A-12, A-14, A-15, or A-17.

4. The compound of claim 3, wherein A is A-1.

5. X １ and X ２ Both of these are CR ２ and R １ａ H, halogen, cyano, C １ ~C ７ Alkyl, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl, C ４ ~C ７ Cycloalkylalkyl, C ４ ~C ７ Alkylcycloalkyl, C １ ~C ７ Haloalkyl, C １ ~C ６ Hydroxyalkyl, C ３ ~C ７ Hydroxycycloalkyl, C １ ~C ６ Hydroxyhaloalkyl, C ４ ~C ８ Alkoxycycloalkyl, C ２ ~C ７ Alkoxyhaloalkyl, C ２ ~C ６ Oxacycloalkyl, C ３ ~C ７ Oxacycloalkylalkyl, C ２ ~C ６ Haloalkenyl, C ２ ~C ６ Haloalkynyl, C ３ ~C ７ Halocycloalkyl, C ４ ~C ７ Haloalkylcycloalkyl, C ２ ~C ７ Alkoxyalkyl, C ２ ~C ７ Haloalkoxyalkyl, C １ ~C ７ Alkoxy, C ２ ~C ５ Alkenyloxy, C ２ ~C ５ Alkynyloxy, C ３ ~C ７ Cycloalkoxy, C ４ ~C ７ Cycloalkoxyalkyl or C １ ~C ７ haloalkoxy; R １ｂ H, halogen, cyano, C １ ~C ４ Alkyl, C ３ ~C ５ Cycloalkyl, C １ ~C ４ Haloalkyl, C ３ ~C ５ Halocycloalkyl, C ２ ~C ４ Alkoxyalkyl, C １ ~C ４ Alkoxy or C ２ ~C ４ is alkoxycarbonyl; R ２ are independently H, halogen, cyano, nitro, hydroxy, C １ ~C ５ Alkyl, C ２ ~C ５ Alkenyl, C ２ ~C ５ Alkynyl, C ２ ~C ５ Alkenyloxy, C ２ ~C ５ Alkynyloxy, C ３ ~C ７ Cycloalkoxy, C ４ ~C ７ Cycloalkoxyalkyl, C ３ ~C ６ Cycloalkyl, C ４ ~C ７ Cycloalkylalkyl, C １ ~C ５ Haloalkyl, C ２ ~C ５ Haloalkenyl, C ２ ~C ５ Haloalkynyl, C ２ ~C ５ Alkoxyalkyl, C ２ ~C ５ Haloalkoxyalkyl, C １ ~C ５ Alkoxy, C １ ~C ５ Haloalkoxy, C １ ~C ５ Alkylthio, C １ ~C ４ Alkylsulfinyl, C １ ~C ４ Alkylsulfonyl, C １ ~C ４ Alkyl sulfonates, C １ ~C ４ Haloalkylthio, C １ ~C ４ Haloalkylsulfinyl, C １ ~C ４ Haloalkylsulfonyl or C ２ ~C ５ alkoxycarbonyl; or R ２ may be taken together to form a 5- or 6-membered ring containing up to two oxygen atoms as ring members, R ３ａ But halogen, C １ ~C ７ Alkyl, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl, C １ ~C ７ Alkoxy, C ４ ~C ７ Cycloalkylalkyl, C ４ ~C ７ Alkylcycloalkyl, C １ ~C ７ Haloalkyl, C ２ ~C ６ Haloalkenyl, C ２ ~C ６ Haloalkynyl, C ３ ~C ７ Halocycloalkyl, C ４ ~C ７ Haloalkylcycloalkyl, C ２ ~C ７ Alkoxyalkyl, C ２ ~C ７ Haloalkoxyalkyl, C ２ ~C ７ Alkylthioalkyl, C ２ ~C ７ Haloalkylthioalkyl, C ２ ~C ５ Cyanoalkyl, C １ ~C ４ Nitroalkyl, C ３ ~C ６ Alkylcarbonylalkyl, C ２ ~C ６ Oxacycloalkyl, C ３ ~C ７ Cycloalkoxy or C ３ ~C ６ alkoxycarbonylalkyl; R ３ｂ is H or halogen; R ４ａ H, halogen, cyano, nitro, C １ ~C ５ Alkyl, C ２ ~C ５ Alkenyl, C ２ ~C ５ Alkynyl, C ３ ~C ５ Cycloalkyl, C １ ~C ５ Haloalkyl, C ２ ~C ５ Haloalkenyl, C ２ ~C ５ Haloalkynyl, C ２ ~C ５ Alkoxyalkyl, C ２ ~C ５ Haloalkoxyalkyl, C １ ~C ５ Alkoxy, C １ ~C ５ Haloalkoxy, C ３ ~C ６ Trialkylsilyl or C ５ ~C ８ trialkylsilylalkynyl; R ４ｂ are independently H, halogen, cyano, nitro, C １ ~C ４ Alkyl, C １ ~C ４ Haloalkyl, C １ ~C ４ Alkoxy or C １ ~C ４ The compound of claim 4 which is alkylthio.

6. R １ａ H, halogen, cyano, C １ ~C ７ Alkyl, C ３ ~C ７ Cycloalkyl, C ４ ~C ７ Cycloalkylalkyl, C １ ~C ７ Haloalkyl, C １ ~C ６ Hydroxyalkyl, C ３ ~C ７ Hydroxycycloalkyl, C １ ~C ６ Hydroxyhaloalkyl, C ４ ~C ８ Alkoxycycloalkyl, C ２ ~C ７ Alkoxyhaloalkyl, C ２ ~C ６ Oxacycloalkyl, C ３ ~C ７ Oxacycloalkylalkyl, C ３ ~C ７ Halocycloalkyl, C ４ ~C ７ Haloalkylcycloalkyl, C ２ ~C ７ Alkoxyalkyl, C ２ ~C ７ Haloalkoxyalkyl, C １ ~C ７ Alkoxy, C ３ ~C ７ Cycloalkoxy, C ４ ~C ７ Cycloalkoxyalkyl or C １ ~C ７ haloalkoxy; R １ｂ H, halogen, cyano, C １ ~C ４ Alkyl, C ３ ~C ５ Cycloalkyl, C １ ~C ４ Haloalkyl, C ２ ~C ４ Alkoxyalkyl or C ２ ~C ４ is alkoxycarbonyl; R ２ are independently H, halogen, cyano, OH, C １ ~C ５ Alkyl, C ２ ~C ５ Alkenyl, C ２ ~C ５ Alkynyl, C ２ ~C ５ Alkenyloxy, C ２ ~C ５ Alkynyloxy, C ３ ~C ７ Cycloalkoxy, C ４ ~C ７ Cycloalkoxyalkyl, C ３ ~C ６ Cycloalkyl, C ４ ~C ７ Cycloalkylalkyl, C １ ~C ５ Haloalkyl, C ２ ~C ５ Haloalkenyl, C ２ ~C ５ Haloalkynyl, C ２ ~C ５ Alkoxyalkyl, C ２ ~C ５ Haloalkoxyalkyl, C １ ~C ５ Alkoxy, C １ ~C ５ haloalkoxy; R ３ａ But halogen, C １ ~C ７ Alkyl, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl, C １ ~C ７ Alkoxy, C ４ ~C ７ Cycloalkylalkyl, C ４ ~C ７ Alkylcycloalkyl, C １ ~C ７ Haloalkyl, C ２ ~C ６ Haloalkenyl, C ２ ~C ６ Haloalkynyl, C ３ ~C ７ Halocycloalkyl, C ４ ~C ７ Haloalkylcycloalkyl, C ２ ~C ７ Alkoxyalkyl or C ２ ~C ７ haloalkoxyalkyl; R ４ａ H, halogen, cyano, NO ２ , C １ ~C ５ Alkyl, C ２ ~C ５ Alkenyl, C ２ ~C ５ Alkynyl, C ３ ~C ５ Cycloalkyl, C １ ~C ５ Alkoxy, C １ ~C ５ haloalkoxy or C ５ ~C ８ trialkylsilylalkynyl; R ４ｂ H, halogen, cyano, C １ ~C ４ Alkyl, C １ ~C ４ Haloalkyl or C １ ~C ４ The compound of claim 5 which is alkoxy.

7. R １ａ H, halogen, cyano, C １ ~C ７ Alkyl, C ３ ~C ７ Cycloalkyl, C ４ ~C ７ Cycloalkylalkyl, C １ ~C ６ Hydroxyalkyl, C ３ ~C ７ Hydroxycycloalkyl, C １ ~C ６ Hydroxyhaloalkyl, C ４ ~C ８ Alkoxycycloalkyl, C ２ ~C ７ Alkoxyhaloalkyl, C ２ ~C ６ Oxacycloalkyl, C ３ ~C ７ Halocycloalkyl, C ２ ~C ７ Alkoxyalkyl, C １ ~C ７ Alkoxy, C ３ ~C ７ Cycloalkoxy or C ４ ~C ７ cycloalkoxyalkyl; R １ｂ H, halogen, cyano, C １ ~C ４ Alkyl, C ３ ~C ５ Cycloalkyl, C １ ~C ４ Haloalkyl, C ２ ~C ４ Alkoxyalkyl or C ２ ~C ４ is alkoxycarbonyl; R ２ are independently H, halogen, cyano, OH, C １ ~C ５ Alkyl, C ２ ~C ５ Alkenyl, C ２ ~C ５ Alkynyl, C ３ ~C ６ Cycloalkyl, C １ ~C ５ Haloalkyl, C １ ~C ５ Alkoxy or C １ ~C ５ haloalkoxy; R ３ａ But C １ ~C ７ Alkyl, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl, C １ ~C ７ Alkoxy, C ４ ~C ７ Cycloalkylalkyl, C ４ ~C ７ Alkylcycloalkyl, C １ ~C ７ Haloalkyl, C ３ ~C ７ Halocycloalkyl, C ２ ~C ７ Alkoxyalkyl or C ２ ~C ７ haloalkoxyalkyl; R ４ｂ The compound of claim 6, wherein is H or a halogen.

8. R １ａ is H, Me, Et, i-Pro, i-Bu, Bu, t-Bu, Br, cyano, c-Bu, c-Pen, c-Hex, HOCH ２ , HOC(Me) ２ , C.H. ２ OMe, CH ２ O-i-Pro, C.H. ２ CH ２ OMe, CH ２ -c-Hex or 3-oxetanyl; R １ｂ But, H, Me, i-Pro, CN, CF ３ , F or Cl; R ２ are independently H, OH, CN, OEt, propargyl, allyl, c-Pro, F, Cl, Br, CN, Me, Et, OMe, CF ３ , OCF ３ or CH ２ CF ３ and R ３ａ But, Me, Et, Pro, i-Pro, CF ３ , C.H. ２ F or CH ２ OMe; R ４ａ But H, CN, NO ２ , F, Cl, Br, Me, Et, CF ３ , C.H. ２ F, OCF ３ , OMe, C.H. ２ OMe, CH=CH ２ , C≡CSiMe ３ 8. The compound of claim 7, wherein C≡CH or c-Pro.

9. X １ is N and X ２ But, CR ２ and R １ａ H, halogen, cyano, C １ ~C ７ Alkyl, C ３ ~C ７ Cycloalkyl, C ４ ~C ７ Cycloalkylalkyl, C ２ ~C ６ Oxacycloalkyl, C ３ ~C ７ Halocycloalkyl, C ２ ~C ７ Alkoxyalkyl, C １ ~C ７ Alkoxy, C ３ ~C ７ Cycloalkoxy or C ４ ~C ７ cycloalkoxyalkyl; R １ｂ H, halogen, cyano, C １ ~C ４ Alkyl, C ３ ~C ５ Cycloalkyl, C １ ~C ４ Haloalkyl, C ２ ~C ４ Alkoxyalkyl or C ２ ~C ４ is alkoxycarbonyl; R ２ are independently H, halogen, cyano, OH, C １ ~C ５ Alkyl, C ２ ~C ５ Alkenyl, C ２ ~C ５ Alkynyl, C ３ ~C ６ Cycloalkyl, C １ ~C ５ Haloalkyl, C １ ~C ５ Alkoxy or C １ ~C ５ haloalkoxy; R ３ａ But C １ ~C ７ Alkyl, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl, C １ ~C ７ Alkoxy, C ４ ~C ７ Cycloalkylalkyl, C ４ ~C ７ Alkylcycloalkyl, C １ ~C ７ Haloalkyl, C ３ ~C ７ Halocycloalkyl, C ２ ~C ７ Alkoxyalkyl or C ２ ~C ７ haloalkoxyalkyl; R ３ｂ is H or halogen; R ４ａ H, halogen, cyano, NO ２ , C １ ~C ５ Alkyl, C ２ ~C ５ Alkenyl, C ２ ~C ５ Alkynyl, C ３ ~C ５ Cycloalkyl, C １ ~C ５ Alkoxy, C １ ~C ５ haloalkoxy or C ５ ~C ８ trialkylsilylalkynyl; R ４ｂ The compound of claim 4, wherein is H or a halogen.

10. R １ａ is H; R １ｂ is H; R ２ However, independently, H, C １ ~C ５ Alkyl or C １ ~C ５ is alkoxy; R ３ａ But C １ ~C ７ Alkyl, C ３ ~C ７ Cycloalkyl, C １ ~C ７ Haloalkyl or C ２ ~C ７ is an alkoxyalkyl; R ３ｂ is H or a halogen; R ４ａ H, halogen, cyano, NO ２ , C １ ~C ５ Alkyl, C ２ ~C ５ Alkenyl, C ２ ~C ５ Alkynyl, C ３ ~C ５ Cycloalkyl, C １ ~C ５ Alkoxy, C １ ~C ５ haloalkoxy or C ５ ~C ８ trialkylsilylalkynyl, R ４ｂ H, halogen, cyano, C １ ~C ４ Alkyl, C １ ~C ４ Haloalkyl or C １ ~C ４ 10. The compound of claim 9 which is alkoxy.

11. X １ But, CR ２ and X ２ is N; R １ａ H, halogen, cyano, C １ ~C ７ Alkyl, C ３ ~C ７ Cycloalkyl, C ４ ~C ７ Cycloalkylalkyl, C ２ ~C ６ Oxacycloalkyl, C ３ ~C ７ Halocycloalkyl, C ２ ~C ７ Alkoxyalkyl, C １ ~C ７ Alkoxy, C ３ ~C ７ Cycloalkoxy or C ４ ~C ７ cycloalkoxyalkyl; R １ｂ H, halogen, cyano, C １ ~C ４ Alkyl, C ３ ~C ５ Cycloalkyl, C １ ~C ４ Haloalkyl, C ２ ~C ４ Alkoxyalkyl or C ２ ~C ４ is alkoxycarbonyl; R ２ are independently H, halogen, cyano, OH, C １ ~C ５ Alkyl, C ２ ~C ５ Alkenyl, C ２ ~C ５ Alkynyl, C ３ ~C ６ Cycloalkyl, C １ ~C ５ Haloalkyl, C １ ~C ５ Alkoxy or C １ ~C ５ haloalkoxy; R ３ａ But C １ ~C ７ Alkyl, C ２ ~C ６ Alkenyl, C ２ ~C ６ Alkynyl, C ３ ~C ７ Cycloalkyl, C １ ~C ７ Alkoxy, C ４ ~C ７ Cycloalkylalkyl, C ４ ~C ７ Alkylcycloalkyl, C １ ~C ７ Haloalkyl, C ３ ~C ７ Halocycloalkyl, C ２ ~C ７ Alkoxyalkyl or C ２ ~C ７ haloalkoxyalkyl; R ３ｂ is H or halogen; R ４ａ H, halogen, cyano, NO ２ , C １ ~C ５ Alkyl, C ２ ~C ５ Alkenyl, C ２ ~C ５ Alkynyl, C ３ ~C ５ Cycloalkyl, C １ ~C ５ Alkoxy, C １ ~C ５ haloalkoxy or C ５ ~C ８ trialkylsilylalkynyl; R ４ｂ The compound of claim 4, wherein is H or a halogen.

12. R ２ may be taken together to form a 5- or 6-membered ring containing up to two oxygen atoms as ring members.

13. [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][2-methyl-5-[3-(1-methylethyl)-1H-1,2,4-triazol-1-yl]phenyl]methanone; [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][5-[3-(1,1-dimethylethyl)-1H-1,2,4-triazol-1-yl]-2-methylphenyl]methanone; [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][2-methoxy-5-[3-(1-methylethyl)-1H-1,2,4-triazol-1-yl]phenyl]methanone; [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][5-(3-ethyl-1H-1,2,4-triazol-1-yl)-2-methoxyphenyl]methanone; [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][2-ethyl-5-[3-(1-methylethyl)-1H-1,2,4-triazol-1-yl]phenyl]methanone; [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][5-(3-cyclobutyl-1H-1,2,4-triazol-1-yl)-2-methylphenyl]methanone; [(2S)-8-chloro-2,3-dihydro-2-methyl-4H-1,4-benzoxazin-4-yl][3-(3-cyclobutyl-1H-1,2,4-triazol-1-yl)phenyl]methanone; [(2S)-2,3-dihydro-2,8-dimethyl-4H-1,4-benzoxazin-4-yl][2-methoxy-5-(1H-1,2,4-triazol-1-yl)phenyl]methanone; 【Chemistry 5】 2. The compound of claim 1 selected from the group consisting of:

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

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

16. 1. A herbicidal mixture comprising: (a) the compound of claim 1; and (b) (b1) a photosystem II inhibitor, (b2) an acetohydroxyacid synthase (AHAS) inhibitor, (b3) an acetyl-CoA carboxylase (ACCase) inhibitor, (b4) an auxin mimetic, (b5) a 5-enol-pyruvylshikimate-3-phosphate (EPSP) synthase inhibitor, (b6) a photosystem I electron diverter, (b7) a protoporphyrinogen oxidase (PPO) inhibitor, (b8) a glutamine synthetase (GS) inhibitor, (b9) a very long chain fatty acid (VLCFA) elongase inhibitor, (b10) an auxin transport inhibitor, (b11) a phytoene desaturase (PDS) inhibitor, (b12) a 4-hydroxybenzoate (4-hydroxybenzoate) (b13) a homogentisate solanesyltransferase (HST) inhibitor, (b14) a cellulose biosynthesis inhibitor, (b16) other herbicides including mitotic disruptors, organic arsenic compounds, asulam, bromobutide, cinmethylin, cumyluron, dazomet, difenzoquat, dymron, etobenzanide, flurenol, fosamine, fosamine-ammonium, hydantocidin, metam, methyldymron, oleic acid, oxaziclomefone, pelargonic acid, and biributicarb, (b16) a herbicide safener, and a salt of a compound of (b1) to (b16).

17. 10. A method for controlling the growth of undesirable vegetation comprising contacting said vegetation or its environment with a herbicidally effective amount of a compound of claim 1.

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