Pyridones as herbicides

This invention relates to certain pyridones, their N-oxides, salts and compositions, and methods of their use for controlling undesirable vegetation.

The control of undesired vegetation is extremely important in achieving high crop efficiency. Achievement of selective control of the growth of weeds especially in such useful crops as rice, soybean, sugar beet, maize, potato, wheat, barley, tomato and plantation crops, among others, is very desirable. Unchecked weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of undesired vegetation in noncrop areas is also important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different sites of action.

This invention is directed to compounds of Formula 1 (including all stereoisomers), N-oxides, and salts thereof, agricultural compositions containing them and their use as herbicides:

wherein

A is phenyl optionally substituted with up to 4 R 2 ; or a 5- or 6-membered heteroaromatic ring, the ring bonded to the remainder of Formula 1 through a carbon atom, and optionally substituted with up to 4 R 2 ; Z is O or SO m ; R 1 is halogen, cyano, nitro, C 1 -C 4 alkoxy, C 1 -C 4 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, SO n R 3 or C 1 -C 4 haloalkyl; each R 2 is halogen, cyano, CHO, nitro, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 3 -C 4 alkenyloxy, C 3 -C 4 alkynyloxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alkylthioalkyl, SO n R 3 , C 2 -C 6 dialkylamino, C 1 -C 4 cyanoalkyl, C 1 -C 4 hydroxyalkyl, CH(═NOH), C 3 -C 6 cycloalkyl, phenyl or pyridyl; each R 3 is independently C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkylamino or C 2 -C 6 dialkylamino; each R 4 is independently halogen, cyano, hydroxy, nitro, amino, CHO, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C(═O)N(R 4A )(R 4B ), C(═NOR 4C )H, C(═N)(R 4D )H, C 1 -C 4 alkoxy, C 2 -C 4 cyanoalkoxy, C 2 -C 4 alkylcarbonyl, C 2 -C 4 alkoxycarbonyl, C 2 -C 4 alkylcarbonyloxy, C 2 -C 4 alkoxyalkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, SO n R 3 or C 3 -C 6 cycloalkyl; or phenyl optionally substituted with cyano, halogen or C 1 -C 4 alkyl; R 4A is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; R 4B is H, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; R 4C is H or C 1 -C 4 alkyl; R 4D is H or C 1 -C 4 alkyl; q is 0, 1, 2 or 3; m is 0, 1 or 2; and each n is independently 0, 1 or 2.

More particularly, this invention pertains to a compound of Formula 1 (including all stereoisomers), an N-oxide or a salt thereof. This invention also relates to a herbicidal composition comprising a compound of the invention (i.e. in a herbicidally effective amount) and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents. This invention further relates to a method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of the invention (e.g., as a composition described herein).

This invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, N-oxides, and salts thereof, and (b) at least one additional active ingredient selected from (b1) through (b16); and salts of compounds of (b1) through (b16), as described below.

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

The transitional phrase “consisting of” excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define a composition, method or apparatus that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term “consisting essentially of” occupies a middle ground between “comprising” and “consisting of”.

Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the terms “consisting essentially of” or “consisting of.”

Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

Also, the indefinite articles “a” and “an” preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore “a” or “an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.

As referred to herein, the term “seedling”, used either alone or in a combination of words means a young plant developing from the embryo of a seed.

As referred to herein, the term “broadleaf” used either alone or in words such as “broadleaf weed” means dicot or dicotyledon, a term used to describe a group of angiosperms characterized by embryos having two cotyledons.

In the above recitations, the term “alkyl”, used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl or hexyl isomers. “Alkenyl” includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. “Alkenyl” also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. “Alkynyl” includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. “Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.

“Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy isomers. “Alkoxyalkyl” denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 . “Alkenyloxy” includes straight-chain or branched alkenyloxy moieties. Examples of “alkenyloxy” include H 2 C═CHCH 2 O, (CH 3 ) 2 C═CHCH 2 O, (CH 3 )CH═CHCH 2 O and CH 2 ═CHCH 2 CH 2 O. “Alkynyloxy” includes straight-chain or branched alkynyloxy moieties. Examples of “alkynyloxy” include HC≡CCH 2 O and CH 3 C≡CCH 2 O. “Alkylthio” includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. “Alkylthioalkyl” denotes alkylthio substitution on alkyl. Examples of “alkylthioalkyl” include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 . “Cyanoalkyl” denotes an alkyl group substituted with one cyano group. Examples of “cyanoalkyl” include NCCH 2 , NCCH 2 CH 2 and CH 3 CH(CN)CH 2 . “Alkylamino”, “dialkylamino” and the like, are defined analogously to the above examples.

“Cycloalkyl” includes, for example, cyclopropyl. The term “halogen”, either alone or in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” or “alkyl substituted with halogen” include F 3 C, ClCH 2 , CF 3 CH 2 and CF 3 CCl 2 . Examples of “haloalkoxy” include CF 3 O—, CCl 3 CH 2 O—, HCF 2 CH 2 CH 2 O— and CF 3 CH 2 O—. “Alkylcarbonyl” denotes a straight-chain or branched alkyl moieties bonded to a C(═O) moiety. Examples of “alkylcarbonyl” include CH 3 C(═O)—, CH 3 CH 2 CH 2 C(═O)— and (CH 3 ) 2 CHC(═O)—. Examples of “alkoxycarbonyl” include CH 3 OC(═O)—, CH 3 CH 2 OC(═O)—, CH 3 CH 2 CH 2 OC(═O)—, (CH 3 ) 2 CHOC(═O)— and the different butoxycarbonyl isomers.

The total number of carbon atoms in a substituent group is indicated by the “C i -C j ” prefix where i and j are numbers from 1 to 6. For example, C 1 -C 4 alkyl designates methyl through butyl; C 2 alkoxyalkyl designates CH 3 OCH 2 —; C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 )—, CH 3 OCH 2 CH 2 — or CH 3 CH 2 OCH 2 —; and C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 — and CH 3 CH 2 OCH 2 CH 2 —.

When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents, e.g., [(R 4 ) q ], q is 0, 1, 2 or 3. When a variable group is shown to be optionally attached to a position, for example (R 4 ) q in Formula 1 wherein q may be 0, then hydrogen may be at the position even if not recited in the variable group definition. When one or more positions on a group are said to be “not substituted” or “unsubstituted”, then hydrogen atoms are attached to take up any free valency.

When a fully unsaturated carbocyclic ring satisfies Hückel's rule, then said ring is also called an “aromatic ring”.

The terms “heterocyclic ring”, “heterocycle” or “heterocyclic ring system” denote a ring or ring system in which at least one atom forming the ring backbone is not carbon, e.g., nitrogen, oxygen or sulfur. Typically a heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. Unless otherwise indicated, a heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies Hückel's rule, then said ring is also called a “heteroaromatic ring”. Unless otherwise indicated, heterocyclic rings and ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.

“Aromatic” indicates that each of the ring atoms is essentially in the same plane and has a p-orbital perpendicular to the ring plane, and that (4n+2) π electrons, where n is a positive integer, are associated with the ring to comply with Hückel's rule.

The term “optionally substituted” in connection with the heterocyclic rings refers to groups which are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the biological activity possessed by the unsubstituted analog. As used herein, the following definitions shall apply unless otherwise indicated. The term “optionally substituted” is used interchangeably with the phrase “substituted or unsubstituted” or with the term “(un)substituted.” Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and each substitution is independent of the other.

As noted above, A can be (among others) phenyl optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of the Invention. An example of phenyl optionally substituted with one to five substituents is the ring illustrated as U-1 in Exhibit 1, wherein R v is R 2 as defined in the Summary of the Invention for A and r is an integer (from 0 to 4).

As noted above, A can be (among others) 5- or 6-membered heteroaromatic ring, optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of the Invention. Examples of a 5- or 6-membered unsaturated aromatic heterocyclic ring optionally substituted with from one or more substituents include the rings U-2 through U-61 illustrated in Exhibit 1 wherein R v is any substituent as defined in the Summary of the Invention for A (i.e. R 2 ) and r is an integer from 0 to 4, limited by the number of available positions on each U group. As U-29, U-30, U-36, U-37, U-38, U-39, U-40, U-41, U-42 and U-43 have only one available position, for these U groups r is limited to the integers 0 or 1, and r being 0 means that the U group is unsubstituted and a hydrogen is present at the position indicated by (R v ) r .

Although R v groups are shown in the structures U-1 through U-61, it is noted that they do not need to be present since they are optional substituents. Note that when R v is H when attached to an atom, this is the same as if said atom is unsubstituted. The nitrogen atoms that require substitution to fill their valence are substituted with H or R v . Note that when the attachment point between (R v ) r and the U group is illustrated as floating, (R v ) r can be attached to any available carbon atom or nitrogen atom of the U group. Note that some U groups can only be substituted with less than 4 R v groups (e.g., U-2 through U-5, U-7 through U-48, and U-52 through U-61).

A wide variety of synthetic methods are known in the art to enable preparation of aromatic and nonaromatic heterocyclic rings and ring systems; for extensive reviews see the eight volume set of Comprehensive Heterocyclic Chemistry , A. R. Katritzky and C. W. Rees editors-in-chief, Pergamon Press, Oxford, 1984 and the twelve volume set of Comprehensive Heterocyclic Chemistry II , A. R. Katritzky, C. W. Rees and E. F. V. Scriven editors-in-chief, Pergamon Press, Oxford, 1996.

Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. Stereoisomers are isomers of identical constitution but differing in the arrangement of their atoms in space and include enantiomers, diastereomers, cis-trans isomers (also known as geometric isomers) and atropisomers. Atropisomers result from restricted rotation about single bonds where the rotational barrier is high enough to permit isolation of the isomeric species. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers or as an optically active form.

Compounds of Formula 1 typically exist in more than one form, and Formula 1 thus include all crystalline and non-crystalline forms of the compounds they represent. Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts. Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types). The term “polymorph” refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability. One skilled in the art will appreciate that a polymorph of a compound of Formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound of Formula 1. Preparation and isolation of a particular polymorph of a compound of Formula 1 can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures. For a comprehensive discussion of polymorphism see R. Hilfiker, Ed., Polymorphism in the Pharmaceutical Industry , Wiley-VCH, Weinheim, 2006.

One skilled in the art will appreciate that not all nitrogen-containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis , vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry , vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry , vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry , vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry , vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.

One skilled in the art recognizes that because in the environment and under physiological conditions salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms. Thus a wide variety of salts of a compound of Formula 1 are useful for control of undesired vegetation (i.e. are agriculturally suitable). The salts of a compound of Formula 1 include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. When a compound of Formula 1 contains an acidic moiety such as a carboxylic acid or phenol, salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention comprises compounds selected from Formula 1, N-oxides and agriculturally suitable salts thereof.

Embodiments of the present invention as described in the Summary of the Invention include (where Formula 1 as used in the following Embodiments includes N-oxides and salts thereof):

A compound of Formula 1 wherein A is a 5- or 6-membered nitrogen-containing heteroaromatic ring, the ring bonded to the remainder of Formula 1 through a carbon atom, and optionally substituted with up to 3 R 2 .

A compound of Embodiment 1 wherein A is selected from

and r is 0, 1, 2 or 3.

A compound of Embodiment 2 wherein A is selected from A-1 through A-13.

A compound of Embodiment 3 wherein A is selected from A-1, A-2, A-4, A-6, A-9, A-10, A-11 and A-12.

A compound of Embodiment 3 wherein A is selected from A-1, A-2 and A-6.

A compound of Embodiment 4 wherein A is A-1.

A compound of Embodiment 4 wherein A is A-2.

A compound of Embodiment 4 wherein A is A-6.

A compound of Embodiment 4 wherein A is selected from

A compound of Formula 1 wherein A is phenyl optionally substituted with up to 3 R 2 .

A compound of Embodiment 9 wherein A is phenyl optionally substituted with up to 2 R 2 .

A compound of Embodiment 10 wherein A is phenyl optionally substituted with one R 2 .

A compound of Formula 1 wherein Z is O.

A compound of Formula 1 or any one of Embodiments 1 through 11 wherein R 1 is halogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl.

A compound of Embodiment 12 wherein R 1 is halogen.

A compound of Embodiment 13 wherein R 1 is chlorine.

A compound of Formula 1 or any one of Embodiments 1 through 14 wherein each R 2 is independently halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl or C 1 -C 4 haloalkoxy.

A compound of Embodiment 15 wherein each R 2 is independently Cl, CF 3 or OCF 3 .

A compound of Formula 1 or any one of Embodiments 9 through 16 wherein A is substituted with one R 2 at the position meta or para to the connection of the phenyl ring to the remainder of Formula 1.

A compound of Embodiment 17 wherein R 2 is Cl, CF 3 or OCF 3 .

A compound of Embodiment 17 wherein A is substituted with one R 2 at the position para to the connection of the phenyl ring to the remainder of Formula 1.

A compound of Embodiment 19 wherein R 2 is halogen.

A compound of Embodiment 19 wherein R 2 is Cl.

A compound of Formula 1 or any one of Embodiments 1 through 21 wherein q is 0, 1 or 2.

A compound of Embodiment 22 wherein q is 0 or 1.

A compound of Embodiment 23 wherein q is 1.

A compound of Embodiment 23 wherein q is 0 (i.e. the 3-, 4- and 5-positions of the benzene ring are unsubstituted by R 4 ).

A compound of Formula 1 or any one of Embodiments 1 through 24 wherein each R 4 is independently halogen, cyano, hydroxy, nitro, amino, CHO, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C(═O)N(R 4A )(R 4B )C(═NOR 4 C)H, C(═N)(R 4D )H, C 1 -C 4 alkoxy, C 2 -C 4 cyanoalkoxy, C 2 -C 4 alkylcarbonyl, C 2 -C 4 alkoxycarbonyl, C 2 -C 4 alkylcarbonyloxy, C 2 -C 4 alkoxyalkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, SO n R 3 or C 3 -C 6 cycloalkyl.

A compound of Embodiment 26 wherein each R 4 is independently halogen, cyano, amino, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 2 -C 4 alkoxycarbonyl, C 2 -C 4 alkylcarbonyloxy, C 2 -C 4 alkoxyalkyl or C 1 -C 4 haloalkyl.

A compound of Embodiment 27 wherein each R 4 is independently halogen, cyano, amino or C 1 -C 4 alkyl.

A compound of Embodiment 28 wherein each R 4 is independently cyano.

A compound of Embodiment 26 wherein each R 4 is attached to the remainder of Formula 1 at the 3- or 4-position.

A compound of Embodiment 30 wherein R 4 is attached to the remainder of Formula 1 at the 3-position.

A compound of Embodiment 26 wherein R 4A is C 1 -C 4 alkyl.

A compound of Embodiment 26 wherein R 4B is C 1 -C 4 alkyl.

A compound of Embodiment 26 wherein R 4C is H or CH 3 .

A compound of Embodiment 26 wherein R 4D is H or CH 3 .

Embodiments of this invention, including Embodiments 1-35 above as well as any other embodiments described herein, can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula 1 but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1. In addition, embodiments of this invention, including Embodiments 1-35 above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present invention.

Combinations of Embodiments 1-35 are illustrated by:

A compound of the Summary of the Invention wherein

A is a 5- or 6-membered nitrogen-containing heteroaromatic ring, the ring bonded to the remainder of Formula 1 through a carbon atom, and optionally substituted with up to 3 R 2 ; or A is phenyl optionally substituted with up to 3 R 2 .

A compound of Embodiment A wherein

A is selected from A-1 through A-20;

Z is O;

R 1 is halogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; each R 2 is independently halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl or C 1 -C 4 haloalkoxy; q is 0, 1 or 2; and each R 4 is independently halogen, cyano, amino, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 2 -C 4 alkoxycarbonyl, C 2 -C 4 alkylcarbonyloxy, C 2 -C 4 alkoxyalkyl or C 1 -C 4 haloalkyl.

A compound of Embodiment B wherein

A is selected from A-1 through A-13; R 1 is halogen; each R 2 is independently Cl, CF 3 or OCF 3 ; q is 0 or 1; and R 4 is halogen, cyano, amino or C 1 -C 4 alkyl.

A compound of Embodiment C wherein

A is selected from A-1a, A-2a and A-6a; R 2 is halogen; and q is 0 (i.e. the 3-, 4- and 5-positions of the benzene ring are unsubstituted by R 4 ).

A compound of Embodiment A wherein

A is phenyl optionally substituted with up to 2 R 2 ; Z is O; R 1 is halogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; each R 2 is independently halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl or C 1 -C 4 haloalkoxy; q is 0, 1 or 2; and each R 4 is independently halogen, cyano, amino, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 2 -C 4 alkoxycarbonyl, C 2 -C 4 alkylcarbonyloxy, C 2 -C 4 alkoxyalkyl or C 1 -C 4 haloalkyl.

A compound of Embodiment E wherein

A is phenyl optionally substituted with one R 2 ; R 1 is halogen; R 2 is independently Cl, CF 3 or OCF 3 ; and q is 0 (i.e. the 3-, 4- and 5-positions of the benzene ring are unsubstituted by R 4 ).

A compound of Embodiment F wherein

R 1 is chlorine.

Specific embodiments include compounds of Formula 1 selected from the group consisting of:

1-(4-chlorophenyl)-6-[(5-chloro-2-pyrimidinyl)oxy]-2(1H)-pyridinone (Compound 1); 6-[(5-chloro-2-pyrimidinyl)oxy]-1-[3-(trifluoromethyl)phenyl]-2(1H)-pyridinone (Compound 2); 6-[(5-chloro-2-pyrimidinyl)oxy]-1-[3-(trifluoromethoxy)phenyl]-2(1H)-pyridinone (Compound 3);

This invention also relates to a method for controlling undesired vegetation comprising applying to the locus of the vegetation herbicidally effective amounts of the compounds of the invention (e.g., as a composition described herein). Of note as embodiments relating to methods of use are those involving the compounds of embodiments described above. Compounds of the invention are particularly useful for selective control of weeds in crops such as wheat, barley, maize, soybean, sunflower, cotton, oilseed rape and rice, and specialty crops such as sugarcane, citrus, fruit and nut crops.

Also noteworthy as embodiments are herbicidal compositions of the present invention comprising the compounds of embodiments described above.

This invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, N-oxides, and salts thereof, and (b) at least one additional active ingredient selected from (b1) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimics, (b5) 5-enol-pyruvylshikimate-3-phosphate (EPSP) synthase inhibitors, (b6) photosystem I electron diverters, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8) glutamine synthetase (GS) inhibitors, (b9) very long chain fatty acid (VLCFA) elongase inhibitors, (b10) auxin transport inhibitors, (b11) phytoene desaturase (PDS) inhibitors, (b12) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b13) homogentisate solenesyltransererase (HST) inhibitors, (b14) cellulose biosynthesis inhibitors, (b15) other herbicides including mitotic disruptors, organic arsenicals, asulam, bromobutide, cinmethylin, cumyluron, dazomet, difenzoquat, dymron, etobenzanid, flurenol, fosamine, fosamine-ammonium, metam, methyldymron, oleic acid, oxaziclomefone, pelargonic acid and pyributicarb, and (b16) herbicide safeners; and salts of compounds of (b1) through (b16).

“Photosystem II inhibitors” (b1) are chemical compounds that bind to the D-1 protein at the Q B -binding niche and thus block electron transport from Q A to Q B in the chloroplast thylakoid membranes. The electrons blocked from passing through photosystem II are transferred through a series of reactions to form toxic compounds that disrupt cell membranes and cause chloroplast swelling, membrane leakage, and ultimately cellular destruction. The Q B -binding niche has three different binding sites: binding site A binds the triazines such as atrazine, triazinones such as hexazinone, and uracils such as bromacil, binding site B binds the phenylureas such as diuron, and binding site C binds benzothiadiazoles such as bentazon, nitriles such as bromoxynil and phenyl-pyridazines such as pyridate. Examples of photosystem II inhibitors include ametryn, amicarbazone, atrazine, bentazon, bromacil, bromofenoxim, bromoxynil, chlorbromuron, chloridazon, chlorotoluron, chloroxuron, cumyluron, cyanazine, daimuron, desmedipham, desmetryn, dimefuron, dimethametryn, diuron, ethidimuron, fenuron, fluometuron, hexazinone, ioxynil, isoproturon, isouron, lenacil, linuron, metamitron, methabenzthiazuron, metobromuron, metoxuron, metribuzin, monolinuron, neburon, pentanochlor, phenmedipham, prometon, prometryn, propanil, propazine, pyridafol, pyridate, siduron, simazine, simetryn, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn and trietazine.

“AHAS inhibitors” (b2) are chemical compounds that inhibit acetohydroxy acid synthase (AHAS), also known as acetolactate synthase (ALS), and thus kill plants by inhibiting the production of the 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), mesosulfuron-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), metosulam, metsulfuron-methyl, nicosulfuron, oxasulfuron, penoxsulam, 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, pyribenzoxim, pyriftalid, 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.

“ACCase inhibitors” (b3) are chemical compounds that inhibit the acetyl-CoA carboxylase enzyme, which is responsible for catalyzing an early step in lipid and fatty acid synthesis in plants. Lipids are essential components of cell membranes, and without them, new cells cannot be produced. The inhibition of acetyl CoA carboxylase and the subsequent lack of lipid production leads to losses in cell membrane integrity, especially in regions of active growth such as meristems. Eventually shoot and rhizome growth ceases, and shoot meristems and rhizome buds begin to die back. 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.

Auxin is a plant hormone that regulates growth in many plant tissues. “Auxin mimics” (b4) are chemical compounds mimicking the plant growth hormone auxin, thus causing uncontrolled and disorganized growth leading to plant death in susceptible species. Examples of auxin mimics include aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid) and its methyl and ethyl esters and its sodium and potassium salts, aminopyralid, benazolin-ethyl, chloramben, clacyfos, 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.

“EPSP synthase inhibitors” (b5) are chemical compounds that inhibit the enzyme, 5-enol-pyruvylshikimate-3-phosphate synthase, which is involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan and phenylalanine. EPSP inhibitor herbicides are readily absorbed through plant foliage and translocated in the phloem to the growing points. 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 (alternatively named sulfosate).

“Photosystem I electron diverters” (b6) are chemical compounds that accept electrons from Photosystem I, and after several cycles, generate hydroxyl radicals. These radicals are extremely reactive and readily destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This destroys cell membrane integrity, so that cells and organelles “leak”, leading to rapid leaf wilting and desiccation, and eventually to plant death. Examples of this second type of photosynthesis inhibitor include diquat and paraquat.

“PPO inhibitors” (b7) are chemical compounds that inhibit the enzyme protoporphyrinogen oxidase, quickly resulting in formation of highly reactive compounds in plants that rupture cell membranes, causing cell fluids to leak out. Examples of PPO inhibitors include acifluorfen-sodium, azafenidin, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, cinidon-ethyl, fluazolate, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazin, fluoroglycofen-ethyl, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, tiafenacil (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) and 3-[7-fluoro-3,4-dihydro-3-oxo-4-(2-propyn-1-yl)-2H-1,4-benzoxazin-6-yl]dihydro-1,5-dimethyl-6-thioxo-1,3,5-triazine-2,4(1H,3H)-dione.

“GS inhibitors” (b8) are chemical compounds that inhibit the activity of the glutamine synthetase enzyme, which plants use to convert ammonia into glutamine. Consequently, ammonia accumulates and glutamine levels decrease. Plant damage probably occurs due to the combined effects of ammonia toxicity and deficiency of amino acids required for other metabolic processes. The 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 bilanaphos.

“VLCFA elongase inhibitors” (b9) are herbicides having a wide variety of chemical structures, which inhibit the elongase. Elongase is one of the enzymes located in or near chloroplasts which are involved in biosynthesis of VLCFAs. In plants, very-long-chain fatty acids are the main constituents of hydrophobic polymers that prevent desiccation at the leaf surface and provide stability to pollen grains. Such herbicides include acetochlor, alachlor, anilofos, 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), pethoxamid, piperophos, pretilachlor, propachlor, propisochlor, pyroxasulfone, and thenylchlor, including resolved forms such as S-metolachlor and chloroacetamides and oxyacetamides.

“Auxin transport inhibitors” (b10) are chemical substances that inhibit auxin transport in plants, such as by binding with an auxin-carrier protein. Examples of auxin transport inhibitors include diflufenzopyr, naptalam (also known as N-(1-naphthyl)phthalamic acid and 2-[(1-naphthalenylamino)carbonyl]benzoic acid).

“PDS inhibitors” (b11) are chemical compounds that inhibit carotenoid biosynthesis pathway at the phytoene desaturase step. Examples of PDS inhibitors include beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone norflurzon and picolinafen.

“HPPD inhibitors” (b12) are chemical substances that inhibit the biosynthesis of synthesis of 4-hydroxyphenyl-pyruvate dioxygenase. Examples of HPPD inhibitors include benzobicyclon, benzofenap, bicyclopyrone (4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]bicyclo[3.2.1]oct-3-en-2-one), fenquinotrione (2-[ [8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl]-1,3-cyclohexanedione), isoxachlortole, isoxaflutole, mesotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, 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-N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide and 2-methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide.

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

HST inhibitors also include compounds of Formulae A and B.

wherein R d1 is H, Cl or CF 3 ; R d2 is H, Cl or Br; R d3 is H or Cl; R d4 is H, Cl or CF 3 ; R d5 is CH 3 , CH 2 CH 3 or CH 2 CHF 2 ; and R d6 is OH, or —OC(═O)-i-Pr; and E e1 is H, F, Cl, CH 3 or CH 2 CH 3 ; R e2 is H or CF 3 ; R e3 is H, CH 3 or CH 2 CH 3 ; R e4 is H, F or Br; R e5 is Cl, CH 3 , CF 3 , OCF 3 or CH 2 CH 3 ; R e6 is H, CH 3 , CH 2 CHF 2 or C≡CH; R e7 is OH, —OC(═O)Et, —OC(═O)-i-Pr or —OC(═O)-t-Bu; and A e8 is N or CH.

Cellulose biosynthesis inhibitors (b14) inhibit the biosynthesis of cellulose in certain plants. They are most effective when applied preemergence or early postemergence on young or rapidly growing plants. Examples of cellulose biosynthesis inhibitors include chlorthiamid, dichlobenil, flupoxam, 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.

Other herbicides (b15) include herbicides that act through a variety of different modes of action such as mitotic disruptors (e.g., flamprop-M-methyl and flamprop-M-isopropyl), organic arsenicals (e.g., DSMA, and MSMA), 7,8-dihydropteroate synthase inhibitors, chloroplast isoprenoid synthesis inhibitors and cell-wall biosynthesis inhibitors. Other herbicides include those herbicides having unknown modes of action or do not fall into a specific category listed in (b1) through (b14) or act through a combination of modes of action listed above. Examples of other herbicides include aclonifen, asulam, amitrole, bromobutide, cinmethylin, clomazone, cumyluron, cyclopyrimorate (6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinyl 4-morpholinecarboxylate), daimuron, difenzoquat, etobenzanid, fluometuron, flurenol, fosamine, fosamine-ammonium, dazomet, dymron, ipfencarbazone (1-(2,4-dichlorophenyl)-N-(2,4-difluorophenyl)-1,5-dihydro-N-(1-methylethyl)-5-oxo-4H-1,2,4-triazole-4-carboxamide), metam, methyldymron, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb and 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole.

“Herbicide safeners” (b16) are substances added to a herbicide formulation to eliminate or reduce phytotoxic effects of the herbicide to certain crops. These compounds protect crops from injury by herbicides but typically do not prevent the herbicide from controlling undesired vegetation. Examples of herbicide safeners include but are not limited to benoxacor, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfamide, daimuron, dichlormid, dicyclonon, 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).

The compounds of Formula 1 can be prepared by general methods known in the art of synthetic organic chemistry. One or more of the following methods and variations as described in Schemes 1-6 can be used to prepare the compounds of Formula 1. The definitions of A, Z, R 1 , R 4 and q in the compounds of Formulae 1-9 below are as defined above in the Summary of the Invention unless otherwise noted. Compounds of Formulae 1a, 1b, 2a and 2b are various subsets of the compounds of Formula 1 and 2 and all substituents for Formulae 1, 1a, 1b, 2, 2a, 2b, 3, 5, 6, 7, 8, 9, 10 and 11 are as defined above for Formula 1 unless otherwise noted.

As shown in Scheme 1, a compound of Formula 1 can be prepared by nucleophilic substitution by heating a compound of Formula 2 in a suitable solvent such as acetonitrile, tetrahydrofuran or N,N-dimethylformamide in the presence of a base such as potassium or cesium carbonate, with a compound of Formula 3 (where LG is a nucleophilic reaction leaving group such as halogen or S(O) 2 Me). The reaction is typically conducted at temperatures ranging from 50 to 110° C.

As shown in Scheme 2, a compound of Formula 2 can be prepared by deprotection of a compound of Formula 2a (i.e. a compound of Formula 2 wherein Z is O and R a is CH 3 ) with a suitable deprotecting agent. Suitable methoxy deprotecting reagents such as BBr 3 , AlCl 3 and HBr in acetic acid can be used in the presence of solvents such as toluene, dichloromethane and dichloroethane at a temperature of from −80 to 120° C. Other useful phenolic protecting groups suitable for use in preparing the compound of Formula 2 can be found in Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 4th ed.; Wiley: Hoboken, N.J., 1991.

As shown in Scheme 3, a compound of Formula 5 or 6 can be coupled with an intermediate of Formula 4 under modified Chan-Lam conditions to give the compound of Formula 2a. Chan-Lam couplings typically are conducted in the presence of a copper salt, oxygen and a base at temperatures ranging from ambient to reflux for 24 to 72 h. Reactivity can be improved with additional additives. Examples of Cu(II) salts which can be used are Cu(OAc) 2 , CuBr 2 and CuI 2 . Suitable bases include pyridine, quinolone and triethylamine. Suitable additives include pyridine-N-oxide and 4 Å moleculuar sieves. Suitable solvents include dichloromethane, chloroform, diethyl ether and tetrahydrofuran. For representative conditions, see Eur. J. Med. Chem. 2013, 613-620 ; Tetrahedron Lett. 1998, 38, 2941 and PCT publication WO2003/072547. Boron intermediates of Formula 5 are commercially available or can be prepared from the corresponding halides or trifluoromethanesulfonates by methods known in the literature (see for example, PCT publication WO 2007/043278, U.S. Pat. No. 8,080,566 , Org. Lett. 2011, 13(6), 1366 and Org. Lett. 2012, 14(2), 600).

Alternatively, as shown in Scheme 4, a compound of Formula 7 can be coupled with an aryl halide of Formula 4 under Ullman conditions to give the compound of Formula 2a. Ullman couplings typically are conducted in the presence of a copper salt, a ligand and a base at a temperature ranging from ambient to reflux for 24 to 72 h. Examples of copper catalysts which can be used include CuI, CuBr, Cu 2 O or Copper powder. Suitable bases include potassium phosphate, potassium carbonate and cesium carbonate. Suitable ligands include N,N-dimethylcyclohexane-1,2-diamine and other N,N-dimethylethylenediamines. Suitable solvents include 1,4-dioxane, toluene, dimethyl formamide and dimethylsulfoxide. For representative conditions, see Chem. Pharm. Bull. 1997, 45, 719-721 , Tet. Lett. 2004, 45, 4257-4260 and Tetrahedron 2005, 61, 2931-2939. Halide intermediates of Formula 7 are commercially available or can be prepared by methods known in the literature.

As shown in Scheme 5, a compound of Formula 4 can be made by deprotection of a compound of Formula 8. The deprotection is typically conducted by hydrogenation in the presence of a metal catalyst in a solvent at a temperature ranging from ambient to reflux for 24 to 72 h. The pressure of hydrogen gas is ranges from atmospheric to 800 bar. An example of a metal catalyst which can be used is palladium on carbon. Suitable solvents include ethyl acetate, ethanol and methanol. For representative conditions see Chemical and Pharmaceutical Bulletin, 1986, 34, 3658-3671. For alternative deprotection conditions, see Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 4th ed.; Wiley: Hoboken, N.J., 1991.

As shown in Scheme 6, a compound of Formula 8 can be prepared by nucleophilic substitution by heating a compound of Formula 9 with benzyl alcohol in the presence of a base. Reactions are typically conducted in benzyl alcohol at reflux. Suitable bases include sodium benzoxide formed from reaction of sodium with benzyl alcohol. For representative conditions see Chemical and Pharmaceutical Bulletin, 1986, 34, 3658-3671. Compounds of Formula 9 are commercially available or can be prepared by methods known in the literature.

As shown in Scheme 7, Formula 1b (i.e. a compound of Formula 1 wherein Z is S) can be prepared by nucleophilic substitution by heating Formula 2b (i.e. a compound of Formula 2 wherein R a is H and Z is S) with a compound of Formula 3 using the method as described in Scheme 1.

As shown in Scheme 8, a compound of Formula 2b can be prepared by copper mediated cross-coupling reaction of a compound of Formula 10 with thiourea, followed by deprotection as described in Chin. J. Chem. 2010, 28, 1441-1443. Alternatively, Formula 2b can also be prepared by palladium coupling of a compound of Formula 10 with triisopropylsilane thiol (TIPS thiol), followed by deprotection as described in Angew. Chem. Int. Ed. 2012, 51, 3314-3322.

As shown in Scheme 9, a compound of Formula 5 or 6 can be coupled with an intermediate of Formula 11 using the method as described in Scheme 3 to give the compound of Formula 10. For representative conditions, see Eur. J. Med. Chem. 2013, 613-620 ; Tetrahedron Lett. 1998, 38, 2941 and PCT publication WO2003/072547.

As shown in Scheme 10, a compound of 1b can be converted into a compound of 1c (i.e a compound of Formula 1 wherein Z is SO) or 1d (i.e a compound of Formula 1 wherein Z is SO 2 ) using oxidizing conditions.

The compounds of Formula 11 are known in the literature and can be prepared easily from commercial materials. For representative methods, see Tetrahedron 1996, 52, 35, 11385-11404.

It is recognized by one skilled in the art that various functional groups can be converted into others to provide different compounds of Formula 1. For a valuable resource that illustrates the interconversion of functional groups in a simple and straightforward fashion, see Larock, R. C., Comprehensive Organic Transformations: A Guide to Functional Group Preparations, 2nd Ed., Wiley-VCH, New York, 1999. For example, intermediates for the preparation of compounds of Formula 1 may contain aromatic nitro groups, which can be reduced to amino groups, and then be converted via reactions well known in the art such as the Sandmeyer reaction, to various halides, providing compounds of Formula 1. The above reactions can also in many cases be performed in alternate order.

It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula 1 may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula 1. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular presented to prepare the compounds of Formula 1.

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

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 are illustrative of the invention. Steps in the following Examples illustrate a procedure for each step in an overall synthetic transformation, and the starting material for each step may not have necessarily been prepared by a particular preparative run whose procedure is described in other Examples or Steps. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. 1 H NMR spectra are reported in ppm downfield from tetramethylsilane in CDCl 3 unless otherwise noted; “s” means singlet, “d” means doublet, “t” means triplet, “m” means multiplet and “br s” means broad singlet.

Synthesis Example 1

Preparation of 1-(4-chlorophenyl)-6-[(5-chloro-2-pyrimidinyl)oxy]-2(1H)-pyridinone (Compound 1)

To a one liter three-neck round bottom flask containing benzyl alcohol (60.25 g, 557.2 mmol) was added sodium metal (3.56 g, 154.6 mmol) slowly in small pieces. The mixture was stirred for 1 h at room temperature. 2-Chloro-6-methoxy pyridine (20.0 g, 139.3 mmol) was added slowly and the reaction mixture was stirred and heated at 120° C. for 2 h, and monitored by TLC analysis. After completion, the reaction mixture was concentrated and the residue was diluted with water and extracted with EtOAc (3×300 mL). The combined organic layers were washed with water, dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure and the residue was purified by a short column. 1 HNMR showed residual peak of the title product along with a small trace of un-reacted benzyl alcohol. The product was used for the next reaction without further purification.

1 H NMR (400 MHz) δ 7.50-7.24 (m, 6H), 6.37-6.34 (m, 1H), 6.29 (d, 1H, J=8.0 Hz), 5.36 (s, 2H), 3.89 (s, 3H).

To a solution of 2-(benzyloxy)-6-methoxypyridine (i.e. the product of Step A) (6.3 g, 29.3 mmol) in MeOH (60 mL) was added 10% Pd/C (1.0 g) and the reaction mixture was stirred under a balloon of H 2 (gas) at ambient temperature for 2 h, monitored by TLC analysis. After completion, the reaction mixture was filtered through a bed of Celite® diatomaceous earth filter aid and washed with methanol (20 mL). The filtrate was concentrated under reduced pressure. The residue was purified by column chromatography, eluting with ethyl acetate in petroleum ether 1:19 to afford the title compound (800 mg) as an off white solid.

1 H NMR (300 MHz) δ 11.44 (br s, 1H), 7.43 (t, 1H, J=8.4 Hz), 6.23 (d, 1H, J=8.7 Hz), 5.70 (d, 1H, J=7.8 Hz), 3.86 (s, 3H).

To a solution of 6-methoxy-2(1H)-pyridinone (i.e. the product of Step B) (1.0 g, 8.0 mmol) in dichloromethane (10 mL) was added 4-chlorophenylboronic acid (2.5 g, 16.0 mmol), Cu(OAc) 2 (160 mg, 0.88 mmol), pyridine (1.26 g, 16.0 mmol), pyridine N-oxide (840 mg, 8.80 mmol) and molecular sieves (150 mg) and the reaction mixture was stirred at room temperature for 12 h, and monitored by TLC analysis. After completion, the reaction mixture was diluted with dichloromethan (30 mL) and ammonium hydroxide (10 mL) was added. The resulting mixture was filtered through a bed of Celite® diatomaceous earth filter aid and washed with water (10 mL). From the filtrate, the organic layer was separated, dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure. The residue was purified by silica gel column chromatography, eluting with ethyl acetate in petroleum ether 1:9 to afford the title compound (320 mg) as a pale green liquid.

1 H NMR (400 MHz) δ 7.56 (t, 1H, J=8.0 Hz), 7.35-7.32 (m, 2H), 7.10-7.08 (m, 2H), 6.45 (d, 1H, J=8.0 Hz), 6.35 (d, 1H, J=8.0 Hz), 3.78 (s, 3H).

A solution of 1-(4-chlorophenyl)-6-methoxy-2(1H)-pyridinone (i.e. the product of Step C) (300 mg, 1.27 mmol) in 33% HBr in acetic acid (10 mL) was stirred at 80° C. for 12 h and monitored by TLC analysis. After completion, the reaction mixture was poured into saturated aqueous NaHCO 3 solution (15 mL) and extracted with dichloromethane (3×20 mL). The combined organic layers were dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure. The residue was purified by column chromatography, eluted with 1:9 of ethyl acetate in petroleum ether to afford the title compound (150 mg) as an off white solid.

1 H NMR (400 MHz, DMSO-d 6 ) δ 10.77 (br s, 1H), 7.66 (t, 1H, J=7.8 Hz), 7.46-7.43 (m, 2H), 7.16-7.12 (m, 2H), 6.41 (s, 1H), 6.36 (d, 1H, J=8.4 Hz).

Step E: Preparation of 1-(4-Chlorophenyl)-6-[(5-chloro-2-pyrimidinyl)oxy]-2(1H)-pyridinone (Compound 1)

To a solution of 1-(4-Chlorophenyl)-6-hydroxy-2-(1H)-pyridinone (i.e. the product of Step D) (120 mg, 0.541 mmol) in N,N-dimethylformamide (5 mL) was added 2,5-dichloropyrimidine (80 mg, 0.541 mmol) and K 2 CO 3 (225 mg, 1.62 mmol) and the reaction mixture was stirred at 80° C. for 2 h. After completion, the reaction mixture was poured into water (15 mL) and extracted with dicholormethane (3×10 mL). The combined organic layers were washed with water, followed by brine solution, dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure. The residue was purified by column chromatography, eluting with ethyl acetate in petroleum ether 1:4 to afford the title compound (100 mg) as an off white solid.

1 H NMR (300 MHz) δ 8.50 (s, 2H), 7.80 (t, 1H, J=7.8 Hz), 7.28 (m, 2H), 7.05-7.02 (m, 2H), 6.82 (d, 1H, J=7.5 Hz), 6.74 (d, 1H, J=8.1 Hz).

Synthesis Example 2

Preparation of 6-[(5-Chloro-2-pyrimidinyl)oxy]-1-[3-(trifluoromethyl)phenyl]-2(1H)-pyridinone (Compound 2)

To a solution of 6-methoxy-2(1H)-pyridinone (i.e. the product of Step B in Synthesis Example 1) (1.00 g, 8.0 mmol) in dichloromethane (20 mL) was added 3-(trifluoromethyl)phenylboronic acid (3.03 g, 16.0 mmol), Cu(OAc) 2 (160 mg, 0.88 mmol), pyridine (1.26 g, 16.0 mmol), pyridine N-oxide (840 mg, 8.80 mmol) and molecular sieves (150 mg) and the reaction mixture was stirred at room temperature for 12 h and monitored by TLC analysis. After completion, the reaction mixture was diluted with dichloromethane (20 mL) and ammonium hydroxide solution (10 mL) was added. Then the resulting mixture was filtered through a short celite bed and washed with water (10 mL). From the filtrate, the organic layer was separated, dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure. The residue was purified by column chromatography eluting with ethyl acetate in petroleum ether 1:19 to afford the title compound (630 mg) as a pale yellow liquid.

1 H NMR (400 MHz) δ7.59 (t, 1H, J=8.0 Hz), 7.51-7.42 (m, 3H), 7.33 (d, 1H, J=8.0 Hz), 6.48 (d, 1H, J=8.0 Hz), 6.43 (d, 1H, J=8.0 Hz), 3.74 (s, 3H).

A solution of 6-methoxy-1-[3-(trifluoromethyl)phenyl]-2(1H)-pyridinone (i.e. the product of Step A) (600 mg, 2.23 mmol) in 33% HBr in acetic acid (15 mL) was stirred at 80° C. for 12 h. The progress of the reaction was monitored by TLC analysis. After completion, the reaction mixture was poured into saturated aqueous NaHCO 3 solution (20 mL) and extracted with dichloromethane (3×25 mL). The combined organic layers were dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure. The residue was purified by column chromatography, eluting with ethyl acetate in petroleum ether 1:4 to afford the title compound (370 mg) as an off white solid.

1 H NMR (400 MHz) δ 10.70 (br s, 1H), 7.55-7.44 (m, 3H), 7.34 (t, 1H, J=2.0 Hz), 7.28 (t, 1H, J=2.0 Hz), 6.44 (d, 1H, J=8.3 Hz), 5.99 (d, 1H, J=7.9 Hz).

Step C: Preparation of 6-[(5-chloro-2-pyrimidinyl)oxy]-1-[3-(trifluoromethyl)phenyl]-2(1H)-pyridinone

To a solution of 6-hydroxy-1-[3-(trifluoromethyl)phenyl]-2(1H)-pyridinone (i.e. the product of Step B) (150 mg, 0.587 mmol) in N,N-dimethylformamide (8 mL) was added 2,5-dichloropyrimidine (87 mg, 0.587 mmol) and K 2 CO 3 (245 mg, 1.76 mmol) and the reaction was stirred at 80° C. for 2 h. The progress of the reaction was monitored by TLC analysis. After completion, the reaction mixture was poured into water (15 mL) and extracted with CH 2 Cl 2 (3×10 mL). The combined organic layers were washed with water, followed by brine solution, dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure. The residue was purified by column chromatography, eluting with ethyl acetate in petroleum ether 1:4 to afford the title compound (110 mg) as a pale yellow liquid.

1 H NMR (400 MHz) δ 8.48 (s, 2H), 7.84 (t, 1H, J=7.8 Hz), 7.43-7.37 (m, 3H), 7.28 (s, 1H), 6.86 (d, 1H, J=7.3 Hz), 6.82 (d, 1H, J=8.3 Hz).

Synthesis Example 3

Preparation of 6-[(5-Chloro-2-pyrimidinyl)oxy]-1-[3-(trifluoromethoxy)phenyl]-2(1H)-pyridinone (Compound 3)

To a solution of 6-methoxy-2(1H)-pyridinone (i.e. the product of Step B in Synthesis Example 1) (1.0 g, 8.0 mmol) in dichloromethane (20 mL) was added 3-(trifluoromethoxy)phenylboronic acid (3.29 g, 16.0 mmol), Cu(OAc) 2 (160 mg, 0.88 mmol), pyridine (1.26 g, 16.0 mmol), pyridine N-oxide (840 mg, 8.80 mmol) and molecular sieves (150 mg) and the reaction mixture was stirred at room temperature for 12 h, and monitored by TLC analysis. After completion, the reaction mixture was diluted with dichloromethane (20 mL) and ammonium hydroxide solution (10 mL) was added. Then the reaction mixture was filtered through a short celite bed and washed with water (10 mL). From the filtrate, the organic layer was separated, dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure. The resulting residue was purified by column chromatography, eluting with ethyl acetate in petroleum ether 1:9 to afford the title compound (450 mg) as a pale green liquid.

1 H NMR (400 MHz) δ7.58 (t, 1H, J=8.0 Hz), 7.38 (t, 1H, J=8.0 Hz), 7.10-7.03 (m, 3H), 6.48 (d, 1H, J=8.0 Hz), 6.42 (d, 1H, J=7.8 Hz), 3.76 (s, 3H).

A solution of 6-methoxy-1-[3-(trifluoromethoxy)phenyl]-2(1H)-pyridinone (i.e. the product of Step A) (500 mg, 1.27 mmol) in 33% HBr in acetic acid (10 mL) was stirred at 80° C. for 12 h and monitored by TLC analysis. After completion, the reaction mixture was poured into saturated aqueous NaHCO 3 solution (20 mL) and extracted with dichloromethane (3×20 mL). The combined organic layers were dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure. The resulting residue was purified by column chromatography, eluting with ethyl acetate in petroleum ether 1:9 to afford the title compound (250 mg) as an off white solid.

1 H NMR (400 MHz) δ9.64 (br s, 1H), 7.53 (t, 1H, J=8.0 Hz), 7.39 (t, 1H, J=8.3 Hz), 7.08-6.99 (m, 3H), 6.43 (d, 1H, J=8.0 Hz), 6.03 (d, 1H, J=8.0 Hz).

Step C: Preparation of 6-[(5-Chloro-2-pyrimidinyl)oxy]-1-[3-(trifluoromethoxy)phenyl]-2(1H)-pyridinone

To a solution of 6-hydroxy-1-[3-(trifluoromethoxy)phenyl]-2(1H)-pyridinone (i.e. the product of Step B) (70 mg, 0.26 mmol) in N,N-dimethylformamide (5 mL) was added 2.5-dichloropyrimidine (38 mg, 0.26 mmol) and K 2 CO 3 (107 mg, 0.774 mmol) and the reaction was stirred at 80° C. for 2 h and monitored by TLC analysis. After the reaction was completed, the reaction mixture was poured into water (10 mL) and extracted with CH 2 Cl 2 (3×10 mL). The combined organic layers were washed with water, followed by brine solution, dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure. The residue was purified by column chromatography, eluted with 1:9 of ethyl acetate in petroleum ether to afford the title compound (70 mg) as a pale green liquid.

1 H NMR (300 MHz) δ 8.50 (s, 2H), 7.83 (t, 1H, J=8.0 Hz), 7.31 (t, 1H, J=8.0 Hz), 7.05-6.98 (m, 3H), 6.86 (t, 1H, J=8.0 Hz), 6.80 (d, 1H, J=8.0 Hz).

By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 13,712 can be prepared. The following abbreviations are used in the Tables which follow: Ph means phenyl, OTFE means OCH 2 CF 3 , ODFM means OCF 2 H, DFM means CF 2 H, TFE means CH 2 CF 3 , OEt means ethoxy, CN means cyano, NO 2 means nitro, TMS means trimethylsilyl, S(O)Me means methylsulfinyl, and S(O) 2 Me means methylsulfonyl.

The present disclosure also includes Tables 2 through 319, each of which is constructed the same as Table 1 above, except that the row heading in Table 1 (i.e. “Z═O, R 1 ═Cl, R 4a ═H, R 4b ═H R 4c ═H”) is replaced with the respective row heading shown below. For Example, in Table 2 the row heading is “Z═O, R 1 ═F, R 4a ═H, R 4b ═H R 4c ═H” and R 2a , R 2b , and W are as defined in Table 1 above.

Table 320

Table 320 is constructed the same way as Table 1 above except that the structure is replaced with the structure below.

The disclosure also includes Tables 321-638 which are constructed the same as Table 320 except that the header row is replaced with the header row shown in Tables 2-319.

Table 639

Table 639 is constructed the same way as Table 1 except that the structure is replaced with the structure below.

The disclosure also includes Tables 640-958 which are constructed the same as Table 639 except that the header row is replaced with the header row shown in Tables 2-319.

Table 959

Table 959 is constructed the same way as Table 1 except that the structure is replaced with the structure below.

The disclosure also includes Tables 960-1278 which are constructed the same as Table 959 except that the header row is replaced with the header row shown in Tables 2-319.

Table 1279

Table 1279 is constructed the same way as Table 1 except that the structure is replaced with the structure below.

The disclosure also includes Tables 1280-1598 which are constructed the same as Table 1279 except that the header row is replaced with the header row shown in Tables 2-319.

Table 1599

Table 1599 is constructed the same way as Table 1 except that the structure is replaced with the structure below.

The disclosure also includes Tables 1600-1918 which are constructed the same as Table 1599 except that the header row is replaced with the header row shown in Tables 2-319.

The disclosure also includes Tables 1920-2238 which are constructed the same as Table 1919 except that the header row is replaced with the header row shown in Tables 2-319.

Table 2239

Table 2239 is constructed the same way as Table 1919 except that the structure is replaced with the structure below.

The disclosure also includes Tables 2400-2718 which are constructed the same as Table 2239 except that the header row is replaced with the header row shown in Tables 2-319.

Table 2719

Table 2719 is constructed the same way as Table 1919 except that the structure is replaced with the structure below.

The disclosure also includes Tables 2720-3038 which are constructed the same as Table 2719 except that the header row is replaced with the header row shown in Tables 2-319.

Table 3039

Table 3039 is constructed the same way as Table 1919 except that the structure is replaced with the structure below.

The disclosure also includes Tables 3040-3358 which are constructed the same as Table 3039 except that the header row is replaced with the header row shown in Tables 2-319.

Table 3359

Table 3359 is constructed the same way as Table 1919 except that the structure is replaced with the structure below.

The disclosure also includes Tables 3360-3678 which are constructed the same as Table 3359 except that the header row is replaced with the header row shown in Tables 2-319.

Table 3679

Table 3679 is constructed the same way as Table 1919 except that the structure is replaced with the structure below.

The disclosure also includes Tables 3680-3998 which are constructed the same as Table 3679 except that the header row is replaced with the header row shown in Tables 2-319.

TABLE 3999

R2a

CF 2 H

CF 3

CH 2 CF 3

H

Me

The disclosure also includes Tables 4000-4318 which are constructed the same as Table 3999 except that the header row is replaced with the header row shown in Tables 2-319.

Table 4319

Table 4319 is constructed the same way as Table 3999 except that the structure is replaced with the structure below.

The disclosure also includes Tables 4320-4638 which are constructed the same as Table 4319 except that the header row is replaced with the header row shown in Tables 2-319.

The present disclosure also includes Tables 4640-6389, each of which is constructed the same as Table 4639 above, except that the row heading in Table 4639 (i.e. “Z═O, R 1 ═Cl, R 2c ═H, R 4a ═H, R 4b ═H R 4c ═H”) is replaced with the respective row heading shown below. For Example, in Table 4640 the row heading is “Z═O, R 1 ═F, R 2c ═H, R 4a ═H, R 4b ═H R 4c ═H” and Z and R 1 are as defined in Table 4639 above.

Table 6390

Table 6390 is constructed the same way as Table 4639 except that the structure is replaced with the structure below.

The disclosure also includes Tables 6391-8140 which are constructed the same as Table 6390 except that the header row is replaced with the header row shown in Tables 4640-6389.

The disclosure also includes Tables 8142-9891 which are constructed the same as Table 8141 except that the header row is replaced with the header row shown in Tables 4640-6389.

Table 9892

Table 9892 is constructed the same way as Table 4639 except that the structure is replaced with the structure below.

The disclosure also includes Tables 9893-11642 which are constructed the same as Table 9892 except that the header row is replaced with the header row shown in Tables 4640-6389.

Table 11643

Table 11643 is constructed the same way as Table 4639 except that the structure is replaced with the structure below.

The disclosure also includes Tables 11644-13393 which are constructed the same as Table 11643 except that the header row is replaced with the header row shown in Tables 4640-6389.

The disclosure also includes Tables 13395-13712 which are constructed the same as Table 13394 except that the header row is replaced with the header row shown in Tables 2-319.

Formulation/Utility

A compound of this invention will generally be used as a herbicidal active ingredient in a composition, i.e. formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serves as a carrier. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.

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) and the like, which optionally can be thickened into gels. The general types of aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion, oil-in-water emulsion, flowable concentrate and suspo-emulsion. The general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.

The general types of solid compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, 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 treatment. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or “overcoated”). Encapsulation can control or delay release of the active ingredient. An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.

Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water, but occasionally another suitable medium like an aromatic or paraffinic hydrocarbon or vegetable oil. Spray volumes can range from about from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into the furrow during planting.

The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.

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

Liquid diluents include, for example, 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 oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactate esters, dibasic esters, alkyl and aryl benzoates and γ-butyrolactone, and alcohols, which can be linear, branched, saturated or unsaturated, such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol and benzyl alcohol. Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C 6 -C 22 ), such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.

The solid and liquid compositions of the present invention often include one or more surfactants. When added to a liquid, surfactants (also known as “surface-active agents”) generally modify, most often reduce, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in a surfactant molecule, surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.

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 alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenol (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 glycols (pegs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar-derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.

Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides such as N,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkyl naphthalene; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their derivatives such as dialkyl sulfosuccinate salts.

Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

Also useful for the present compositions are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon's Emulsifiers and Detergents , 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.

Compositions of this invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants). Such formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes. Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of formulation auxiliaries and additives include those listed 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.

The compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding 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 water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water. Active ingredient slurries, with particle diameters of up to 2,000 μm can be wet milled using media mills to obtain particles with average diameters below 3 μm. Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. Pat. No. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 μm range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, “Agglomeration”, Chemical Engineering , Dec. 4, 1967, pp 147-48 , Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. Pat. No. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. Pat. No. 4,144,050, U.S. Pat. No. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. Pat. No. 5,180,587, U.S. Pat. No. 5,232,701 and U.S. Pat. No. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. Pat. No. 3,299,566.

For further information regarding the art of formulation, see T. S. Woods, “The Formulator's Toolbox—Product Forms for Modern Agriculture” in Pesticide Chemistry and Bioscience, The Food—Environment Challenge , T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. Pat. No. 3,309,192, Col. 5, line 43 through Col. 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, Col. 3, line 66 through Col. 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.

In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Tables A. 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 Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except where otherwise indicated.

High Strength Concentrate

Wettable Powder

(i) Granule

Extruded Pellet

Emulsifiable Concentrate

Microemulsion

Suspension Concentrate

Emulsion in Water

Oil Dispersion

Test results indicate that the compounds of the present invention are highly active preemergent and/or postemergent herbicides and/or plant growth regulants. The compounds of the inention generally show highest activity for postemergence weed control (i.e. applied after weed seedlings emerge from the soil) and preemergence weed control (i.e. applied before weed seedlings emerge from the soil). Many of them have utility for broad-spectrum pre- and/or postemergence 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, air fields, river banks, irrigation and other waterways, around billboards and highway and railroad structures. Many of the compounds of this invention, by virtue of selective metabolism in crops versus weeds, or by selective activity at the locus of physiological inhibition in crops and weeds, or by selective placement on or within the environment of a mixture of crops and weeds, are useful for the selective control of grass and broadleaf weeds within a crop/weed mixture. One skilled in the art will recognize that the preferred combination of these selectivity factors within a compound or group of compounds can readily be determined by performing routine biological and/or biochemical assays. Compounds of this invention may show tolerance to important agronomic crops including, but is not limited to, alfalfa, barley, cotton, wheat, rape, sugar beets, corn (maize), sorghum , soybeans, rice, oats, peanuts, vegetables, tomato, potato, perennial plantation crops including coffee, cocoa, oil palm, rubber, sugarcane, citrus, grapes, fruit trees, nut trees, banana, plantain, pineapple, hops, tea and forests such as eucalyptus and conifers (e.g., loblolly pine), and turf species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue and Bermuda grass). Compounds of this invention can be used in crops genetically transformed or bred to incorporate resistance to herbicides, express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxin), and/or express other useful traits. Those skilled in the art will appreciate that not all compounds are equally effective against all weeds. Alternatively, the subject compounds are useful to modify plant growth.

As the compounds of the invention have (both preemergent and postemergent herbicidal) activity, to control undesired vegetation by killing or injuring the vegetation or reducing its growth, the compounds can be usefully applied by a variety of methods involving contacting a herbicidally effective amount of a compound of the invention, or a composition comprising said compound and at least one of a surfactant, a solid diluent or a liquid diluent, to the foliage or other part of the undesired vegetation or to the environment of the undesired vegetation such as the soil or water in which the undesired vegetation is growing or which surrounds the seed or other propagule of the undesired vegetation.

A herbicidally effective amount of the compounds of this invention is determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of compounds of this invention is about 0.001 to 20 kg/ha with a preferred range of about 0.004 to 1 kg/ha. One skilled in the art can easily determine the herbicidally effective amount necessary for the desired level of weed control.

In one common embodiment, a compound of the invention is applied, typically in a formulated composition, to a locus comprising desired vegetation (e.g., crops) and undesired vegetation (i.e. weeds), both of which may be seeds, seedlings and/or larger plants, in contact with a growth medium (e.g., soil). In this locus, a composition comprising a compound of the invention can be directly applied to a plant or a part thereof, particularly of the undesired vegetation, and/or to the growth medium in contact with the plant.

Compounds of the invention are useful in treating all plants and plant parts. Plant varieties and cultivars can be obtained by conventional propagation and breeding methods or by genetic engineering methods. Genetically modified plants (transgenic plants) are those in which a heterologous gene (transgene) has been stably integrated into the plant's genome. A transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.

Genetically modified plant cultivars which can be treated according to the invention include those that are resistant against one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, cold temperature, soil salinity, etc.), or that contain other desirable characteristics. Plants can be genetically modified to exhibit traits of, for example, herbicide tolerance, insect-resistance, modified oil profiles or drought tolerance. Useful genetically modified plants containing single gene transformation events or combinations of transformation events are listed in Exhibit C. Additional information for the genetic modifications listed in Exhibit C can be obtained from publicly available databases maintained, for example, by the U.S. Department of Agriculture.

The following abbreviations, T1 through T37, are used in Exhibit C for traits. A “-” means the entry is not available. “tol.” means tolerance.

Although most typically, compounds of the invention are used to control undesired vegetation, contact of desired vegetation in the treated locus with compounds of the invention may result in super-additive or synergistic effects with genetic traits in the desired vegetation, including traits incorporated through genetic modification. For example, resistance to phytophagous insect pests or plant diseases, tolerance to biotic/abiotic stresses or storage stability may be greater than expected from the genetic traits in the desired vegetation.

Compounds of this invention can also be mixed with one or more other biologically active compounds or agents including herbicides, herbicide safeners, fungicides, insecticides, nematocides, bactericides, acaricides, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Mixtures of the compounds of the invention with other herbicides can broaden the spectrum of activity against additional weed species, and suppress the proliferation of any resistant biotypes. Thus the present invention also pertains to a composition 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 of a surfactant, a solid diluent or a liquid diluent. The other biologically active compounds or agents can be formulated in compositions comprising at least one of a surfactant, solid or liquid diluent. For mixtures of the present invention, one or more other biologically active compounds or agents can be formulated together with a 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 combined together before application (e.g., in a spray tank) or, alternatively, applied in succession.

A mixture of one or more of the following herbicides with a compound of this invention may be particularly useful for weed control: acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal), alachlor, alloxydim, ametryn, amicarbazone, amidosulfuron, aminocyclopyrachlor and its esters (e.g., methyl, ethyl) and salts (e.g., sodium, potassium), aminopyralid, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azimsulfuron, beflubutamid, benazolin, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, benzobicyclon, benzofenap, bicyclopyrone, bifenox, bilanafos, bispyribac and its sodium salt, bromacil, bromobutide, bromofenoxim, bromoxynil, bromoxynil octanoate, butachlor, butafenacil, butamifos, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone-ethyl, catechin, chlomethoxyfen, chloramben, chlorbromuron, chlorflurenol-methyl, chloridazon, chlorimuron-ethyl, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, clacyfos, clefoxydim, clethodim, clodinafop-propargyl, clomazone, clomeprop, clopyralid, clopyralid-olamine, cloransulam-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, daimuron, dalapon, dalapon-sodium, dazomet, 2,4-DB and its dimethylammonium, potassium and sodium salts, desmedipham, desmetryn, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, dichlobenil, dichlorprop, diclofop-methyl, diclosulam, difenzoquat metilsulfate, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin, dimethylarsinic acid and its sodium salt, dinitramine, dinoterb, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenquinotrione, fentrazamide, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-i sopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, flurenol, flurenol-butyl, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet-methyl, fomesafen, foramsulfuron, fosamine-ammonium, glufosinate, glufosinate-ammonium, glufosinate-P, glyphosate and its salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively named sulfosate), halauxifen, halauxifen-methyl, halosulfuron-methyl, haloxyfop-etotyl, haloxyfop-methyl, hexazinone, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, indanofan, indaziflam, iofensulfuron, iodosulfuron-methyl, ioxynil, ioxynil octanoate, ioxynil-sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, isoxachlortole, 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, methyldymron, metobenzuron, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, naproanilide, napropamide, napropamide-M, naptalam, neburon, nicosulfuron, norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat dichloride, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentanochlor, pentoxazone, perfluidone, pethoxamid, pethoxyamid, 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, pyrazolynate, pyrazoxyfen, pyrazosulfuron-ethyl, pyribenzoxim, pyributicarb, pyridate, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron-methyl, sulfosulfuron, 2,3,6-TBA, TCA, TCA-sodium, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbumeton, terbuthylazine, terbutryn, thenylchlor, thiazopyr, thiencarbazone, thifensulfuron-methyl, thiobencarb, tiafenacil, tiocarbazil, topramezone, tralkoxydim, tri-allate, triafamone, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tridiphane, trietazine, trifloxysulfuron, trifluralin, triflusulfuron-methyl, tritosulfuron, vernolate, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridin-2(1H)-one, 5-chloro-3-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalinone, 2-chloro-N-(1-methyl-1H-tetrazol-5-yl)-6-(trifluoromethyl)-3-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 (previously methioxolin), 3-[7-fluoro-3,4-dihydro-3-oxo-4-(2-propyn-1-yl)-2H-1,4-benzoxazin-6-yl]dihydro-1,5-dimethyl-6-thioxo-1,3,5-triazine-2,4(1H,3H)-dione, 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 also 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.

Compounds of this invention can also be used in combination with plant growth regulators such as aviglycine, N-(phenylmethyl)-1H-purin-6-amine, epocholeone, gibberellic acid, gibberellin A 4 and A 7 , harpin protein, mepiquat chloride, prohexadione calcium, prohydrojasmon, sodium nitrophenolate and trinexapac-methyl, and plant growth modifying organisms such as Bacillus cereus strain BP01.

General references for agricultural protectants (i.e. herbicides, herbicide safeners, insecticides, fungicides, nematocides, acaricides and biological agents) include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U. K., 2003 and The BioPesticide Manual, 2nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, U. K., 2001.

For embodiments where one or more of these various mixing partners are used, the weight ratio of these various mixing partners (in total) to the compound of Formula 1 is typically between about 1:3000 and about 3000:1. Of note are weight ratios between about 1:300 and about 300:1 (for example ratios between about 1:30 and about 30:1). One skilled in the art can easily determine through simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity. It will be evident that including these additional components may expand the spectrum of weeds controlled beyond the spectrum controlled by the compound of Formula 1 alone.

In certain instances, combinations of a compound of this invention with other biologically active (particularly herbicidal) compounds or agents (i.e. active ingredients) can result in a greater-than-additive (i.e. synergistic) effect on weeds and/or a less-than-additive effect (i.e. safening) on crops or other desirable plants. Reducing the quantity of active ingredients released in the environment while ensuring effective pest control is always desirable. Ability to use greater amounts of active ingredients to provide more effective weed control without excessive crop injury is also desirable. When synergism of herbicidal active ingredients occurs on weeds at application rates giving agronomically satisfactory levels of weed control, such combinations can be advantageous for reducing crop production cost and decreasing environmental load. When safening of herbicidal active ingredients occurs on crops, such combinations can be advantageous for increasing crop protection by reducing weed competition.

Of note is a combination of a compound of the invention with at least one other herbicidal active ingredient. Of particular note is such a combination where the other herbicidal active ingredient has different site of action from the compound of the invention. In certain instances, a combination with at least one other herbicidal active ingredient having a similar spectrum of control but a different site of action will be particularly advantageous for resistance management. Thus, a composition of the present invention can further comprise (in a herbicidally effective amount) at least one additional herbicidal active ingredient having a similar spectrum of control but a different site of action.

Compounds of this invention can also be used in combination with herbicide safeners such as allidochlor, benoxacor, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfonamide, daimuron, dichlormid, dicyclonon, 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 to increase safety to certain crops. Antidotally effective amounts of the herbicide safeners can be applied at the same time as the compounds of this invention, or applied as seed treatments. Therefore an aspect of the present invention relates to a herbicidal mixture comprising a compound of this invention and an antidotally effective amount of a herbicide safener. Seed treatment is particularly useful for selective weed control, because it physically restricts antidoting to the crop plants. Therefore a particularly useful embodiment of the present invention is a method for selectively controlling the growth of undesired vegetation in a crop comprising contacting the locus of the crop with a herbicidally effective amount of a compound of this invention wherein seed from which the crop is grown is treated with an antidotally effective amount of safener. Antidotally effective amounts of safeners can be easily determined by one skilled in the art through simple experimentation.

Of note is a composition comprising a compound of the invention (in a herbicidally effective amount), at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners (in an effective amount), and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.

Table A1 lists specific combinations of a Component (a) with Component (b) illustrative of the mixtures, compositions and methods of the present invention. Compound No. (Compound Number) (i.e. Compound 1) in the Component (a) column is identified in Index Table A. The second column of Table A1 lists the specific Component (b) compound (e.g., “2,4-D” in the first line). The third, fourth and fifth columns of Table A1 lists ranges of weight ratios for rates at which the Component (a) compound is typically applied to a field-grown crop relative to Component (b) (i.e. (a):(b)). Thus, for example, the first line of Table A1 specifically discloses the combination of Component (a) (i.e. Compound 1 in Index Table A) with 2,4-D is typically applied in a weight ratio between 1:192-6:1. The remaining lines of Table A1 are to be construed similarly.

Table A2 is constructed the same as Table A1 above except that entries below the “Component (a)” column heading are replaced with the respective Component (a) Column Entry shown below. Compound No. in the Component (a) column is identified in Index Table A. Thus, for example, in Table A2 the entries below the “Component (a)” column heading all recite “Compound 2” (i.e. Compound 2 identified in Index Table A), and the first line below the column headings in Table A2 specifically discloses a mixture of Compound 2 with 2,4-D. Table A3 is constructed similarly.

Preferred for better control of undesired vegetation (e.g., lower use rate such as from synergism, broader spectrum of weeds controlled, or enhanced crop safety) or for preventing the development of resistant weeds are mixtures of a compound of this invention with a herbicide selected from the group consisting of aminocyclopyrachlor, chlorimuron-ethyl, diuron, hexazinone, mesotrione, S-metolachlor, metsulfuron-methyl, nicosulfuron, thifensulfuron-methyl and tribenuron-methyl.

The following Tests demonstrate the control efficacy of the compounds of this invention against specific weeds. The weed control afforded by the compounds is not limited, however, to these species. See Index Table A for compound descriptions. The following abbreviations are used in the Index Table which follow: Ph is phenyl, CF 3 is trifluoromethyl and OCF 3 is trifluoromethoxy. The abbreviation “Ex.” stands for “Example” and is followed by a number indicating in which example the compound is prepared.

Seeds of plant species selected from barnyardgrass ( Echinochloa crus - galli ), kochia ( Kochia scoparia ), ragweed (common ragweed, Ambrosia elatior ), Italian ryegrass ( Lolium multiflorum ), giant foxtail ( Setaria faberii ), and pigweed ( Amaranthus retroflexus ) were planted into a blend of loam soil and sand and treated preemergence with a directed soil spray using test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.

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

TABLE A Compound 1000 g ai/ha 3 500 g ai/ha 1 2 Postemergence Barnyardgrass 70 Barnyardgrass 100 0 Blackgrass 40 Blackgrass 90 0 Corn 20 Corn 30 20 Foxtail, Giant 100 Foxtail, Giant 100 60 Galium 100 Galium 100 60 Kochia 90 Kochia 100 90 Pigweed 90 Pigweed 100 80 Ragweed 30 Ragweed 20 0 Ryegrass, Italian 30 Ryegrass, Italian 70 0 Wheat 30 Wheat 40 20 Compounds 125 g ai/ha 1 2 4 5 6 7 8 9 10 Postemergence Barnyardgrass 20 0 0 20 30 50 30 10 90 Blackgrass 20 0 20 50 50 30 20 10 50 Corn 30 0 10 10 20 20 20 10 30 Foxtail, Giant 70 0 0 80 60 50 70 20 90 Galium 50 20 50 90 90 90 70 60 80 Kochia 90 30 80 60 90 90 90 90 90 Pigweed 100 30 70 90 90 90 90 80 90 Ragweed 20 0 20 80 50 60 70 40 20 Ryegrass, Italian 0 0 0 30 20 20 20 20 60 Wheat 30 0 0 0 0 20 0 0 10 Compounds 31 g ai/ha 4 5 6 7 8 9 10 Postemergence Barnyardgrass 0 0 10 20 10 0 40 Blackgrass 20 30 10 10 10 0 30 Corn 0 0 0 10 10 10 20 Foxtail, Giant 0 10 10 20 20 0 50 Galium 30 50 60 50 60 30 30 Kochia 40 40 80 80 70 70 80 Pigweed 50 70 80 70 80 50 70 Ragweed 10 30 30 30 30 20 10 Ryegrass, Italian 0 0 0 0 10 0 0 Wheat 0 0 0 0 0 0 0 Compound Compounds 1000 g ai/ha 3 500 g ai/ha 1 2 Preemergence Barnyardgrass 80 Barnyardgrass 100 0 Foxtail, Giant 100 Foxtail, Giant 100 90 Kochia 40 Kochia 100 30 Pigweed 70 Pigweed 100 20 Ragweed 20 Ragweed 20 0 Ryegrass, Italian 50 Ryegrass, Italian 20 0 Compounds 125 g ai/ha 1 2 4 5 6 7 8 9 10 Preemergence Barnyardgrass 30 0 0 80 70 70 30 0 90 Foxtail, Giant 90 0 20 100 100 100 80 70 100 Kochia 40 0 70 100 100 70 100 50 60 Pigweed 40 0 70 100 100 100 100 80 100 Ragweed 0 0 0 80 80 70 20 70 10 Ryegrass, Italian 0 0 0 0 10 60 10 0 50 Compounds 31 g ai/ha 4 5 6 7 8 9 10 Preemergence Barnyardgrass 0 0 20 20 0 0 50 Foxtail, Giant 0 70 60 60 40 10 70 Kochia 0 0 60 30 30 20 30 Pigweed 70 90 80 100 70 50 50 Ragweed 0 0 70 10 0 — 0 Ryegrass, Italian 0 0 0 10 0 0 10

Plant species in the flooded paddy test selected from rice ( Oryza sativa ), sedge, umbrella (small-flower umbrella sedge, Cyperus difformis ), ducksalad ( Heteranthera limosa ), and barnyardgrass ( Echinochloa crus - galli ) were grown to the 2-leaf stage for testing. At time of treatment, test pots were flooded to 3 cm above the soil surface, treated by application of test compounds directly to the paddy water, and then maintained at that water depth for the duration of the test. Treated plants and controls were maintained in a greenhouse for 13 to 15 days, after which time all species were compared to controls and visually evaluated. 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 no test result.

TABLE B Compounds 250 g ai/ha 1 2 3 4 5 6 7 8 9 10 Flood Barnyardgrass 20 0 0 0 0 0 0 0 0 30 Ducksalad 45 0 0 0 85 80 100 75 60 65 Rice 10 0 0 0 0 0 0 0 0 20 Sedge, Umbrella 65 0 0 0 75 85 90 65 40 90

Seeds of plant species selected from blackgrass ( Alopecurus myosuroides ), Italian ryegrass ( Lolium multiflorum ), winter wheat ( Triticum aestivum ), galium (catchweed bedstraw, Galium aparine ), corn ( Zea mays ), large (Lg) crabgrass ( Digitaria sanguinalis ), giant foxtail ( Setaria faberii ), johnsongrass ( Sorghum halepense ), lambsquarters ( Chenopodium album ), morningglory ( Ipomoea coccinea ), yellow nutsedge ( Cyperus esculentus ), pigweed ( Amaranthus retroflexus ), ragweed (common ragweed, Ambrosia elatior ), soybean ( Glycine max ), barnyardgrass ( Echinochloa crus - galli ), oilseed rape ( Brassica napus ), waterhemp (common waterhemp, Amaranthus rudis ), and velvetleaf ( Abutilon theophrasti ) were planted into a blend of loam soil and sand and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.

At the same time, plants selected from these crop and weed species and also chickweed (common chickweed, Stellaria media ), kochia ( Kochia scoparia ), and wild oat ( Avena fatua ), were planted in pots containing Sunshine Redi-Earth® planting medium comprising spaghnum peat moss, vermiculite, starter nutrients and dolomitic limestone and treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for 13 to 15 days, after which time all species were compared to controls and visually evaluated. 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 means no test result.