WO2015167795A1

WO2015167795A1 - Herbicidal substituted 3-phenyl-4-fluorobenzoyl pyrazoles

Info

Publication number: WO2015167795A1
Application number: PCT/US2015/025731
Authority: WO
Inventors: Thomas Paul Selby; David Andrew TRAVIS; Nicholas Ryan DEPREZ; Andrew Duncan Satterfield
Original assignee: E. I. Du Pont De Nemours And Company
Priority date: 2014-04-28
Filing date: 2015-04-14
Publication date: 2015-11-05
Also published as: TW201620879A; AR100192A1

Abstract

Disclosed are compounds of Formula 1, including all stereoisomers, N-oxides, and salts thereof, wherein X¹, X², X³, n and P are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling undesired vegetation comprising contacting the undesired vegetation or its environment with an effective amount of a compound or a composition of the invention.

Description

TITLE

HERBICIDAL SUBSTITUTED 3-PHENYL-4-FLUOROBENZOYL PYRAZOLES

FIELD OF THE INVENTION

This invention relates to certain 3-phenyl-4-fluorobenzoyl pyrazoles, their N-oxides, salts and compositions, and methods of their use for controlling undesirable vegetation.

BACKGROUND OF THE INVENTION

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. U.S. Pat. Nos. 5,939,559 and 6,030,926 disclose certain herbicidal pyrazoles. The 3-phenyl-4-fluorobenzoyl pyrazoles of the present invention are not disclosed in this publication.

SUMMARY OF THE INVENTION

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

1 wherein

X¹ is halogen, -CF₃, -CF₂H, -OCF₃, -OCF₂H, -SCHF₂ or -C≡CH;

X² is halogen, -CF₃, -CF₂H, -OCF₃, -OCF₂H, -SCHF₂ or -C≡CH;

X³ is H or halogen;

n is 1, 2, 3, 4 or 5; P is H, C1 -C7 alkyl, C3-C7 alkenyl, C3-C7 alkynyl, C3-C7 cycloalkyl, C -C haloalkyl, C2-C7 haloalkenyl, C3-C7 haloalkynyl, C2-C7 alkoxyalkyl, C4-C7

cycloalkylalkyl, C 1 -C7 alkoxy, C3-C7 alkoxyalkoxyalkyl, C3-C7

alkylcarbonylalkyl, C3-C7 alkoxycarbonylalkyl, C4-C7 halocycloalkylalkyl, C2-C7 haloalkoxyalkyl, C2-C7 alkylthioalkyl, C2-C7 alkylsulfonylalkyl, C2-C7 alkylsulfinylalkyl, C2-C7 haloalkylthioalkyl, C2-C7 haloalkylsulfonylalkyl, C2-C7 haloalkylsulfinylalkyl, C3-C7 haloalkoxycarbonylalkyl, C3-C7 haloalkylcarbonylalkyl, C2-C7 alkylaminoalkyl, C3-C7 dialkylaminoalkyl, C2-C7 cyanoalkyl, C_rC₇ nitroalkyl, amino, hydroxy, CH₂OH, C(=0)R¹, S0₂R², C(=0)NR³R⁴, S0₂NR³R⁴, C0₂R⁵, CH(OR⁶)₂, CH(C0₂CH₃)₂ or

CH(C0₂C₂H₅)2;

R¹ is H, C_rC₇ alkyl, C₂-C₇ alkenyl, C₂-C₇ alkynyl, C3-C7 cycloalkyl, C_rC₇ haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl or C4-C7 cycloalkylalkyl; or phenyl optionally substituted with R⁷; or benzyl optionally substituted on ring members with R⁷; or pyridyl optionally substituted with R⁷;

R² is H, C_rC₇ alkyl, C₂-C₇ alkenyl, C₂-C₇ alkynyl, C3-C7 cycloalkyl, C_rC₇ haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl or C4-C7 cycloalkylalkyl; or phenyl optionally substituted with R⁷; or benzyl optionally substituted on ring members with R⁷; or pyridyl optionally substituted with R⁷;

R³ is H, C_rC₇ alkyl, C₂-C₇ alkenyl, C₂-C₇ alkynyl, C3-C7 cycloalkyl, C_rC₇ haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl or C4-C7 cycloalkylalkyl; or phenyl optionally substituted with R⁷; or benzyl optionally substituted on ring members with R⁷; or pyridyl optionally substituted with R⁷;

R⁴ is H or C_rC₄ alkyl;

R⁵ is C -C alkyl, C3-C7 alkenyl, C3-C7 alkynyl, C3-C7 cycloalkyl, C2-C7 haloalkyl, C3-C7 haloalkenyl, C2-C7 alkoxyalkyl or C4-C7 cycloalkylalkyl; or phenyl optionally substituted with R⁷; or benzyl optionally substituted on ring members with R⁷; or pyridyl optionally substituted with R⁷;

R⁶ is C_rC₃ alkyl; or

two R⁶ are taken together as -(CH₂)2-, -(CH₂)3- or -CH₂CH(CH3)- to form a ring; and R⁷ is halogen, cyano, C1-C2 alkyl, C1-C3 haloalkyl, C1-C3 haloalkoxy or C1-C3 alkoxy.

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 (bl) through (bl6); and salts of compounds of (bl) through (bl6).

DETAILS OF THE INVENTION

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 or method 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 or method.

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, or method that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements 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 "broadlea ' 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. As used herein, the term "alkylating agent" refers to a chemical compound in which a carbon-containing radical is bound through a carbon atom to a leaving group such as halide or sulfonate, which is displaceable by bonding of a nucleophile to said carbon atom. Unless otherwise indicated, the term "alkylating" does not limit the carbon- containing radical to alkyl; the carbon-containing radicals in alkylating agents include the variety of carbon-bound substituent radicals specified for the fluorobenzoyl moiety on the pyrazole ring or nitrogen bound radicals specified for P.

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, /-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, pentoxy and hexyloxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂, CH₃CH₂CH₂CH₂OCH₂ and CH₃CH₂OCH₂CH₂. "Alkoxyalkoxy" denotes alkoxy substitution on alkoxy. "Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. "Alkylsulfinyl" includes both enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" include CH₃S(0)-, CH₃CH₂S(0)-, CH₃CH₂CH₂S(0)-, (CH₃)₂CHS(0)- and the different butylsulfmyl, pentylsulfmyl and hexylsulfmyl isomers. "Alkylthioalkyl" denotes alkylthio substitution on alkyl. Examples of "alkylthioalkyl" include CH₃SCH₂, CH₃SCH₂CH₂, CH₃CH₂SCH₂, CH₃CH₂CH₂CH₂SCH₂ and CH₃CH₂SCH₂CH₂. "Cyanoalkyl" denotes an alkyl group substituted with one cyano group. Examples of "cyanoalkyl" include NCCH₂, NCCH₂CH₂ and CH₃CH(CN)CH₂. "Alkylamino", "dialkylamino", "dialkylaminoalkyl", and the like, are defined analogously to the above examples.

"Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "cycloalkylalkyl" denotes cycloalkyl substitution on an alkyl moiety. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.

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 F₃C, C1CH₂, CF₃CH₂ and CF₃CC1₂. The terms "haloalkoxy", "haloalkylthio", "haloalkenyl", "haloalkynyl", and the like, areis defined analogously to the term "haloalkyl". Examples of "haloalkoxy" include CF3O-, CCI3CH2O-, HCF₂CH₂CH₂0- and CF₃CH₂0-. Examples of "haloalkylthio" include CCI3S-, CF3S-, CC1₃CH₂S- and C1CH₂CH₂CH₂S-. Examples of "haloalkylsulfmyl" include CF₃S(0)-, CC1₃S(0)-, CF₃CH₂S(0)- and CF₃CF₂S(0)-. Examples of "haloalkylsulfonyl" include CF₃S(0)₂-, CC1₃S(0)₂-, CF₃CH₂S(0)₂- and CF₃CF₂S(0)₂-. Examples of "haloalkenyl" include (C1)₂C=CHCH₂- and CF₃CH₂CH=CHCH₂-. Examples of "haloalkynyl" include HC≡CCHC1-, CF₃C≡C-, CC1₃C≡C- and FCH₂C≡CCH₂-. Examples of "haloalkoxyalkoxy" include CF₃OCH₂0-, C1CH₂CH₂0CH₂CH₂0-, Cl₃CCH₂OCH₂0- as well as branched alkyl derivatives. "Alkylcarbonyl" denotes a straight-chain or branched alkyl moieties bonded to a C(=0) moiety. Examples of "alkylcarbonyl" include CH₃C(=0)-, CH₃CH₂CH₂C(=0)- and (CH₃)₂CHC(=0)-. Examples of "alkoxycarbonyl" include CH₃OC(=0)-, CH₃CH₂OC(=0)-, CH₃CH₂CH₂OC(=0)-, (CH₃)₂CHOC(=0)- and the different butoxy- or pentoxycarbonyl isomers. When two variables are described as "taken together to form a ring" (e.g., two R⁶ in the variable CH(OR⁶)₂) the valencies of the two variables are connected by the listed radicals (e.g. -(CH₂)₂-, -(CH₂)₃- or -CH₂CH(CH₃)-) resulting in a ring comprising, in addition to the two oxygen atoms, the listed readicals as backbone members.

The total number of carbon atoms in a substituent group is indicated by the "C -Cj" prefix where i and j are numbers from 1 to 7. For example, C1-C4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl; C₂ alkoxyalkyl designates CH₃OCH₂-; C₃ alkoxyalkyl designates, for example, CH₃CH(OCH₃)-, CH₃OCH₂CH₂- or CH₃CH₂OCH₂-; and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH₃CH₂CH₂OCH₂- and CH₃CH₂OCH₂CH₂-.

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., F_n, n is 1, 2, 3, 4 or 5). When a group contains a substituent which can be hydrogen, for example X³, then when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. When a variable group is shown to be optionally attached to a position, for example R⁷, 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 "unsubstituted", then hydrogen atoms are attached to take up any free valency.

Unless otherwise indicated, the term "benzyl ring" is phenyl bonded to the remainder of Formula 1 through a methyl group, and is either unsubstituted or substituted on ring a member with a substituent selected from R⁷. The term "pyridyl" refers to a 6-memered ring containing ring members selected from carbon and 1 nitrogen atom. Examples of pyridyl include the following shown in Exhibit 1 where R^v refers to R⁷ in the Summary of the Invention.

Exhibit 1

U-l U-2 U-3

The term "optionally substituted" in connection with the term "benzyl" or "pyridyl" 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. Although R^v groups are shown in the structures U-l through U-3, it is noted that they do not need to be present since they are optional substituents. Note that the U groups are limited by the number of available valences on the ring and can only be substituted with up to 4 R^v groups.

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 (when P is H) can also as be isolated as the tautomeric mixture of Formuala 1A and 1A' under certain reaction conditions.

1A lA'

The Summary of the Invention and any Embodiments herein refer to either tautomer so long as the presence of the tautomer 1A' does not detract from the biological activity of the compound of the invention. When a compound of Formula 1A or 1A' are alkylated or capped with electrophiles, the predominant product is generally that from one or the other tautomer, however either "N-alkylated" tautomer isomer can be isolated using routing techniques known to one skilled in the art. In general, the tautomer represented by Formula 1A is known to impart the most biological activity.

Compounds of Formula 1 can comprise additional chiral centers. For example, substituents and other molecular constituents (such as P) may contain chiral centers. This invention comprises racemic mixtures as well as enriched and essentially pure stereoconfigurations at these additional chiral centers. Compounds of this invention can exist as one or more conformational isomers due to restricted rotation about the amide bond (e.g., -C(=0)(2- and/or 6-fluorophenyl) in Formula 1. This invention comprises mixtures of conformational isomers. In addition, this invention includes compounds that are enriched in one conformer relative to others.

Compounds of Formula 1 typically exist in more than one form, and thus a compound of Formula 1 includes 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):

Embodiment 1. The compound of Formula 1 as described in the Summary of the

Invention.

Embodiment 2. The compound of Embodiment 1 wherein X¹ is

halogen, -CF₃, -CF₂H, -OCF₃, or -OCF₂H.

Embodiment 3. The compound of Embodiment 2 wherein X¹ is halogen or -CF3.

Embodiment 4. The compound of Embodiment 3 wherein X¹ is halogen.

Embodiment 5. The compound of Embodiment 4 wherein X¹ is CI or Br.

Embodiment 6. The compound of Embodiment 5 wherein X¹ is CI.

Embodiment 7. The compound of any one of Embodiments 1 through 6 wherein X² is halogen, -CF₃, -CF₂H, -OCF3, or -OCF₂H.

Embodiment 8. The compound of Embodiment 7 wherein X² is halogen or -CF3.

Embodiment 9. The compound of Embodiment 8 wherein X² is halogen.

Embodiment 10. The compound of Embodiment 9 wherein X² is CI or Br.

Embodiment 11. The compound of Embodiment 10 wherein X² is CI.

Embodiment 12. The compound of any one of Embodiments 1 through 11 wherein X³ is H, F, CI or Br.

Embodiment 13. The compound of Embodiment 12 wherein X³ is H, F or CI.

Embodiment 14. The compound of Embodiment 13 wherein X³ is H or CI.

Embodiment 15. The compound of Embodiment 14 wherein X³ is H.

Embodiment 16. The compound of Embodiment 14 wherein X³ is CI.

Embodiment 17. The compound of any one of Embodiments 1 through 16 wherein n is 1, 2 or 3.

Embodiment 18. The compound of Embodiment 17 wherein n is 2 or 3.

Embodiment 19. The compound of Embodiment 18 wherein n is 2.

Embodiment 20. The compound of Embodiment 18 wherein n is 3. Embodiment 21. The compound of any one of Embodiments 1 through 20 wherein P is H, C_rC₇ alkyl, C₃-C₇ alkenyl, C₃-C₇ alkynyl, C₃-C₇ cycloalkyl, C_rC₇ haloalkyl, C2-C₇ haloalkenyl, C₃-C₇ haloalkynyl, C2-C₇ alkoxyalkyl, C4-C₇ cycloalkylalkyl, C 1 -C7 alkoxy, C₃-C₇ alkoxyalkoxyalkyl, C2-C₇ cyanoalkyl, C_rC₇ nitroalkyl, amino, hydroxy, CH₂OH, C(=0)R^!, S0₂R², C(=0)NR³R⁴,

S0₂NR³R⁴, C0₂R⁵, CH(OR⁶)₂, CH(C0₂CH₃)₂ or CH(C0₂C₂H₅)₂.

Embodiment 22. The compound of Embodiment 21 wherein P is H, Ci -C7 alkyl, C₃-C₇ alkenyl, C₃-C₇ alkynyl, C₂-C₇ alkoxyalkyl, CH₂OH, C(=0)R^! or S0₂R².

Embodiment 23. The compound of Embodiment 22 wherein P is H, Ci -C4 alkyl, C₃-C4 alkenyl, C₃-C₄ alkynyl, CH₂OCH₃, CH₂OC₂H₅, CH₂OH, C(=0)CH₃,

C(=0)C₂H₅, C(=0)CH₂OCH₃, C(=0)CH₂C≡CH, S0₂CH₃, S0₂C₂H₅ or S0₂CF₃.

Embodiment 24. The compound of Embodiment 23 wherein P is H, Ci -C4 alkyl,

CH₂C≡CH, CH₂OH, C(=0)CH₃, C(=0)C₂H₅, C(=0)CH₂C≡CH, S0₂CH₃ or S0₂CF₃.

Embodiment 25. The compound of Embodiment 24 wherein P is H, CH₃, CH₂CH₃,

CH₂C≡CH, CH₂OH, C(=0)CH₃ or C(=0)C₂H₅.

Embodiment 26. The compound of Embodiment 25 wherein P is H.

Embodiment 27. The compound of Embodiment 25 wherein P is CH₃.

Embodiment 28. The compound of Embodiment 25 wherein P is CH₂CH₃.

Embodiment 29. The compound of Embodiment 25 wherein P is CH₂C≡CH.

Embodiment 30. The compound of Embodiment 25 wherein P is CH₂OH.

Embodiment 31. The compound of Embodiment 25 wherein P is C(=0)CH₃.

Embodiment 32. The compound of Embodiment 25 wherein P is C(=0)C₂H5.

Embodiment 33. The compound of any one of Embodiments 1 through 32 wherein R¹ is

H, C_rC₇ alkyl, C₂-C₇ alkenyl, C₂-C₇ alkynyl, C_rC₇ haloalkyl or C₂-C₇ alkoxyalkyl; or benzyl optionally substituted on ring members with R⁷.

Embodiment 34. The compound of Embodiment 33 wherein R¹ is H, C1 -C4 alkyl,

C₂-C4 alkynyl, Ci -C4 haloalkyl or C₂-C4 alkoxyalkyl.

Embodiment 35. The compound of Embodiment 34 wherein R¹ is CH₃, CH₂CH₃,

CH₂C≡CH, -CF₃ or CH₂OCH₃.

Embodiment 36. The compound of Embodiment 35 wherein R¹ is CH₃ or -CF₃.

Embodiment 37. The compound of any one of Embodiments 1 through 36 wherein R² is

Embodiment 38. The compound of Embodiment 37 wherein R² is H, C1 -C4 alkyl,

C₂-C4 alkynyl, Ci -C4 haloalkyl or C₂-C4 alkoxyalkyl. Embodiment 39. The compound of Embodiment 38 wherein R² is CH3, CH2CH3,

CH₂C≡CH, -CF₃ or CH₂OCH₃.

Embodiment 40. The compound of Embodiment 39 wherein R² is CH₃ or -CF3.

Embodiment 41. The compound of any one of Embodiments 1 through 40 wherein R³ is

H, C_rC₇ alkyl, C₂-C₇ alkenyl, C₂-C₇ alkynyl, C_rC₇ haloalkyl or C₂-C₇ alkoxyalkyl; or benzyl optionally substituted on ring members with R⁷. Embodiment 42. The compound of Embodiment 41 wherein R³ is H, C1 -C4 alkyl,

C₂-C4 alkynyl, Ci -C4 haloalkyl or C₂-C4 alkoxyalkyl.

Embodiment 43. The compound of Embodiment 42 wherein R³ is CH3, CH₂CH3,

CH₂C≡CH, -CF₃ or CH₂OCH₃.

Embodiment 44. The compound of Embodiment 43 wherein R³ is CH3 or -CF3.

Embodiment 45. The compound of any one of Embodiments 1 through 44 wherein R⁴ is H or CH₃.

Embodiment 46. The compound of Embodiment 45 wherein R⁴ is CH3.

Embodiment 47. The compound of any one of Embodiments 1 through 46 wherein R⁵ is C1 -C4 alkyl.

Embodiment 48. The compound of Embodiment 47 wherein R⁵ is CH3 or CH₂CH3. Embodiment 49. The compound of any one of Embodiments 1 through 48 wherein R⁶ is CH₃ or CH₂CH₃.

Embodiment 50. The compound of Embodiment 49 wherein R⁶ is CH3.

Embodiment 51. The compound of any one of Embodiments 1 through 50 wherein two

R⁶ are taken together as -(CH₂)₂- or -(CH₂)3- to form a ring.

Embodiment 52. The compound of Embodiment 51 wherein two R⁶ are taken together as -(CH₂)₂- to form a ring.

Embodiment 53. The compound of any one of Embodiments 1 through 52 wherein R⁷ is halogen, cyano or C^-C₂ alkyl.

Embodiment 54. The compound of Embodiment 53 wherein R⁷ is CI, Br, cyano or CH3. Embodiments of this invention, including Embodiments 1-54 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 1-54 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 1-54 are illustrated by:

Embodiment A. The compound of the Summary of the Invention wherein

X¹ is halogen, -CF₃, -CF₂H, -OCF3 or -OCF₂H;

X² is halogen, -CF₃, -CF₂H, -OCF3 or -OCF₂H; X³ is H, F, CI or Br;

P is H, C1 -C7 alkyl, C3-C7 alkenyl, C3-C7 alkynyl, C3-C7 cycloalkyl, C 1 -C7 haloalkyl, C2-C7 haloalkenyl, C3-C7 haloalkynyl, C2-C7 alkoxyalkyl, C4-C7 cycloalkylalkyl, C 1 -C7 alkoxy, C3-C7 alkoxyalkoxyalkyl, C2-C7 cyanoalkyl, C_rC₇ nitroalkyl, amino, hydroxy, CH₂OH, C(=0)R!, S0₂R², C(=0)NR³R⁴,

S0₂NR³R⁴, C0₂R⁵, CH(OR⁶)₂, CH(C0₂CH₃)₂ or CH(C0₂C₂H₅)2; R¹ is H, C_rC₇ alkyl, C₂-C₇ alkenyl, C₂-C₇ alkynyl, C_rC₇ haloalkyl or C₂-C₇

alkoxyalkyl; or benzyl optionally substituted on ring members with R⁷;

R² is H, C_rC₇ alkyl, C₂-C₇ alkenyl, C₂-C₇ alkynyl, C_rC₇ haloalkyl or C₂-C₇

alkoxyalkyl; or benzyl optionally substituted on ring members with R⁷;

R³ is H, C_rC₇ alkyl, C₂-C₇ alkenyl, C₂-C₇ alkynyl, C_rC₇ haloalkyl or C₂-C₇

alkoxyalkyl; or benzyl optionally substituted on ring members with R⁷;

R⁴ is H or CH₃;

R⁵ is C_rC₄ alkyl;

R⁶ is CH₃ or CH₂CH₃; or

two R⁶ are taken together as -(CH2)2- or -(CH2)3- to form a ring; and

R⁷ is CI, Br, cyano or CH₃.

Embodiment B. A compound of Embodiment A wherein

X¹ is halogen;

X² is halogen;

X³ is H, F, CI or Br;

n is 1, 2 or 3; and

P is H, C_rC₄ alkyl, C3-C4 alkenyl, C3-C4 alkynyl, CH₂OCH₃, CH₂OC₂H₅, CH₂OH, C(=0)CH₃, C(=0)C₂H₅, C(=0)CH₂OCH₃, C(=0)CH₂C≡CH, S0₂CH₃, S0₂C₂H₅ or S0₂CF₃.

Embodiment C. A compound of Embodiment B wherein

X¹ is CI or Br;

X² is CI or Br;

X³ is H, F or CI;

n is 2 or 3; and

P is H, C1-C₄ alkyl, CH₂C≡CH, CH₂OH, C(=0)CH₃, C(=0)C₂H₅, C(=0)CH₂C≡CH, S0₂CH₃ or S0₂CF₃.

Embodiment D. A compound of Embodiment C wherein

X¹ is CI;

X² is CI;

X³ is H or CI; and

P is H, CH₃, CH₂CH₃, CH₂C≡CH, CH₂OH, C(=0)CH₃ or C(=0)C₂H₅.

Embodiment E. A compound of Embodiment D wherein X³ is H;

n is 2; and

P is H.

Specific Embodiments of the Invention include a compound of Formula 1 selected from

[3-(3,5-dichlorophenyl)-lH-pyrazol-4-yl](2,5-difluorophenyl)methanone (Compound 1);

[3-(3,5-dibromophenyl)-lH-pyrazol-4-yl](2,5-difluorophenyl)methanone (Compound 2); (2,5-difluorophenyl)[3-(3,5-difluorophenyl)-lH-pyrazol-4-yl]methanone (Compuond 3);

[3 -(3 -chloro-5 -fluorophenyl)- lH-pyrazol-4-yl](3-fluorophenyl)methanone (Compound 4);

[3-(3,5-dichlorophenyl)-lH-pyrazol-4-yl](2,3,5-trifluorophenyl)methanone (Compound 5);

[3-(3,5-dichlorophenyl)-lH-pyrazol-4-yl](3-fluorophenyl)methanone (Compound 6);

[3-(3,5-dichlorophenyl)-lH-pyrazol-4-yl](3,5-difluorophenyl)methanone (Compound 7); l-[3-(3,5-dichlorophenyl)-4-(2,5-difluorobenzoyl)-lH-pyrazol-l-yl]ethanone (Compound 8); and

(3,5-difluorophenyl)[3-(3,5-difluorophenyl)-lH-pyrazol-4-yl]methanone (Compound 9).

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. Compounds of the invention are more particularly useful for selective control of weeds in crops such as maize and soybean. 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 (bl) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimics and (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, (blO) auxin transport inhibitors, (bl 1) phytoene desaturase (PDS) inhibitors, (bl2) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (bl3) homogentisate solenesyltransererase (HST) inhibitors, (bl4) cellulose biosynthesis inhibitors, (bl5) 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 (bl6) herbicide safeners; and salts of compounds of (bl) through (bl6).

"Photosystem II inhibitors" (bl) are chemical compounds that bind to the D-l protein at the Qfl-binding niche and thus block electron transport from to QB 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 QB-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 DNA 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-l,3,5-triazin-2- yl)amino]carbonyl]benzenesulfonamide), mesosulfuron-methyl, metazosulfuron (3-chloro-4- (5,6-dihydro-5-methyl-l,4,2-dioxazin-3-yl)-N-[[(4,6-dimethoxy-2- pyrimidinyl)amino]carbonyl]- 1 -methyl- lH-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 ,2-¾]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-l ,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, cyhalo fop-butyl, diclo fop-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 (5 -enol-pyruvylshikimate-3 -phosphate) 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]-l-oxopropyl]-P-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(lH,3H)-dione.

"GS (glutamine synthase) 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 ((25)-2-amino-4-(hydroxymethylphosphinyl)butanoic acid) and bilanaphos.

"VLCFA (very long chain fatty acid) 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-(l- naphthalenyloxy)propanamide), pethoxamid, piperophos, pretilachlor, propachlor, propisochlor, pyroxasulfone, and thenylchlor, including resolved forms such as S-metolachlor and chloroacetamides and oxyacetamides.

"Auxin transport inhibitors" (blO) 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-(l-naphthyl)phthalamic acid and 2-[(l-naphthalenylamino)carbonyl]benzoic acid). "PDS (phytoene desaturase inhibitors) (bl l) are chemical compounds that inhibit carotenoid biosynthesis pathway at the phytoene desaturase step. Examples of PDS inhibitors include beflubutamid, diflufenican, fiuridone, flurochloridone, flurtamone norflurzon and picolinafen.

"HPPD (4-hydroxyphenyl-pyruvate dioxygenase) inhibitors" (bl2) 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]-l ,3-cyclohexanedione),

isoxachlortole, isoxaflutole, mesotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, topramezone, 5-chloro-3-[(2-hydroxy-6-oxo-l- cyclohexen-l-yl)carbonyl]-l-(4-methoxyphenyl)-2(lH)-quinoxalinone, 4-(2,6-diethyl-4- methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone, 4-(4-fluorophenyl)-6-[(2- hydroxy-6-oxo-l-cyclohexen-l-yl)carbonyl]-2-methyl-l ,2,4-triazine-3,5(2H,4H)-dione, 5- [(2-hydroxy-6-oxo-l-cyclohexen-l-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-(l -methyl- lH-tetrazol-5-yl)- 4-(trifluoromethyl)benzamide.

HST (homogentisate solenesyltransererase) inhibitors (bl3) disrupt a plant's ability to convert homogentisate to 2-methyl-6-solanyl-l ,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( lH)-one, 7-(3 ,5 - dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-¾]pyrazin-6(5H)-one and 4- (2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone.

HST inhibitors also include com ounds of Formulae A and B.

B

wherein R^dl is H, CI or CF₃; R^d2 is H, CI or Br; R^d3 is H or CI; R^d4 is H, CI or CF₃; R^d5 is CH₃, CH₂CH₃ or CH₂CHF₂; and R^d6 is OH, or -OC(=0)-z-Pr; and R^el is H, F, CI, CH₃ or CH₂CH₃; R^e2 is H or CF₃; R^e3 is H, CH₃ or CH₂CH₃; R^e4 is H, F or Br; R^e5 is CI, CH₃, CF₃, OCF₃ or CH₂CH₃; R^e6 is H, CH₃, CH₂CHF₂ or C≡CH; R^e7 is OH, -OC(=0)Et, -OC(=0)-z-Pr or -OC(=0)-t-Bu; and A^e8 is N or CH.

Cellulose biosynthesis inhibitors (bl4) inhibit the biosynthesis of cellulose in certain plants. They are most effective when using a pre-aplication or early post-application on young or rapidly growing plants. Examples of cellulose biosynthesis inhibitors include chlorthiamid, dichlobenil, flupoxam, indaziflam (N²-[(li?,25)-2,3-dihydro-2,6-dimethyl-lH- inden-l-yl]-6-(l-fluoroethyl)-l ,3,5-triazine-2,4-diamine), isoxaben and triaziflam.

Other herbicides (bl5) 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 (bl) through (bl4) 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-l ,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" (bl6) 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-l ,3-dioxolane (MG 191), 4-(dichloroacetyl)-l-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 1-10 can be used to prepare compounds of Formula 1. The definitions of X¹, X², X³, n and P in the compounds of Formulae 1-17 below are as defined above in the Summary of the Invention unless otherwise noted. A compound of Formulae 1A, IB, and 1C are subsets of Formula 1, and all substituents for compounds of Formulae 1A, IB and 1C are as defined above for a compound of Formula 1 unless otherwise noted. A compound of Formulae 10A and 10B are subsets of Formula 10, and all substituents for compounds of Formulae 10A and 10B are as defined above for a compound of Formula 10 unless otherwise noted.

As shown in Scheme 1, pyrazoles of Formula 1A (a subset of compounds of Formula 1 where P is hydrogen) can be alkylated or allowed to react with a suitable electrophilic reagent in the presence of base in an appropriate solvent to afford compounds of Formulae IB where P is other than H as defined for compounds of Formulae 1 in the Summary of the Invention. Although shown as only one tautomer where the exchangeable ring hydrogen resides on the nitrogen with no adjacent substituents, pyrazoles of Formula 1A can exist in equilibrium with a tautomeric species where the ring hydrogen resides on the pyrazole nitrogen adjacent to the aryl substituent. Compounds of Formula IB are generally formed as the predominant product due to preferred alkylation at the less sterically hindered pyrazole ring nitrogen but some alkylation of the other pyrazole ring nitrogen adjacent to the aryl ring can take place through tautomerization to give the regioisomer pyrazole of Formula 2. However, isomeric pyrazoles of Formula 2 are generally obtained as minor products relative to pyrazoles of Formula IB. The relative amounts of regioisomeric pyrazoles of Formulae IB and 2 formed can vary depending on substituents present on pyrazoles of Formula 1 A and the specific alkylation method used. Pyrazoles of Formula 1 A can be treated initially with base to form a carbanionic species that is then allowed to react with the alkylating agent or electrophilic reagent. Alternatively, base and electrophile can be added simultaneously in some cases to compounds of Formula 1A previously dissolved in solvent. Examples of suitable bases for this reaction include but are not limited to potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, potassium t-butoxide and, depending on the specific base used, appropriate solvents can be protic or aprotic and used anhydrous or as an aqueous mixture. Some examples of solvents include acetonitrile, methanol, ethanol, tetrahydrofuran, diethyl ether, dioxane, dichloromethane or N,N-dimethylformamide. The reaction can be run at a range of temperatures, with temperatures typically ranging from 0 °C to the reflux temperature of the solvent. Scheme 1

A non-regioselective method for making pyrazoles of Formula 1A is outlined in Scheme 2. By the method taught in Example 2 of U.S. Pat. No. 5,939,559, or following the method described in J. Heterocyclic Chem. 1982, 19, 1355, hydrazine (anhydrous or the hydrate) can be cyclized with substituted 2-methylene-l,3-pentanediones of Formulae 3 (where A serves as a leaving group such as dimethylamino, ethoxy or methoxy) in a protic or aprotic solvent such as acetonitrile, methanol, ethanol or N,N-dimethylformamide to afford regioisomeric pyrazole mixtures of 1A and 4 that are separated via chromatography and/or fractional crystallization. Temperatures for this reaction typically range from 0 °C to the reflux temperature of the solvent. Pyrazoles of Formulae 1 A and 4 can exist as tautomeric species via isomerization where the exchangeable hydrogen can reside on either ring nitrogen, although this hydrogen is shown in the compounds of Formulae 1 A and 4 to reside of the ring nitrogen furthest from the aryl group. The ratio of pyrazoles of Formulae 1A and 4 formed in this reaction can vary depending on substitution on the substitution on the intermediate compound of Formula 3 and the reaction conditions employed. Scheme 2

4

A is NMe₂, OCH₃ or OCH₂CH₃

Substituted 2-methylene-l ,3-pentanediones of Formula 3, where A is a leaving group such dimethylamino, ethoxy or methoxy, can be made by reacting substituted diaryl-1 ,3- pentanediones of Formula 5 with N,N-dimethylformamide dimethylacetal or a trialkyl orthoformate such as HC(OMe)3 or HC(OEt)₃ neat or in a suitable solvent such as acetonitrile, methanol, ethanol, tetrahydrofuran, dioxane, toluene, dichloromethane or N,N-dimethylformamide. Temperatures for this reaction generally range from 25 °C to the reflux temperature of the neat mixture or solvent.

Methods to make substituted l ,3-diaryl-l ,3-pentanediones of Formula 5 are well established with many procedures documented in the literature. For example, see Synth. Comm. 2007, 57(23), 41 1 1-41 15, Org. Lett. 2005, 7(3), 455-458, U.S. 20130137688, Tetrahedron Lett. 2003, 44(5) 1067-1069 and Med. Chem. Res. 2012, 21(5), 584-589. A particularly useful method for making diones of Formula 5 involves base-catalyzed coupling of an appropriately substituted acetophenone with a substituted benzoate by the procedure described in Example 1 of U.S. Pat. No. 5,939,559. As outlined in Scheme 4, benzoates of Formula 6 (generally where R is ethyl or methyl) are allowed to react with a fluoroacetophenone of Formula 7 in the presence of a suitable base, i.e. sodium hydride, a sodium alkoxide or potassium t-butoxide in a solvent such as tetrahydrofuran, dioxane, N,N-dimethylformamide or a protic alcohol solvent such as methanol or ethanol at temperatures ranging from 0 °C to the reflux temperature of the solvent. Alternatively, substituted acetophenones of Formula 8 can undergo base-catalyzed coupling with a fluorobenzoate of Formula 9 under the same reaction conditions to provide diones of Formula 5.

Scheme 4

A regioselective route for making pyrazoles of Formula 1A entails a Grignard catalyzed coupling of an unprotected 3-phenyl-4-iodopyrazole of Formula 10A with a fluorobenzaldehyde of Formula 11. As shown in Scheme 5, this reaction can be performed in a suitable solvent such as tetrahydrofuran, dioxane or diethyl ether at temperatures ranging from 0 °C to the reflux temperature of the solvent. A preferred Grignard reagent used to generate the pyrazole Grignard compound of Formula 10A for coupling with an appropriate fluorobenzaldehyde is isopropylmagnesium bromide where over 2 equivalents are added to the compound of Formula 10A due to the exchangeable pyrazole ring proton present on the compound of Formula 10A. The formed alcohol adduct is oxidized directly with an appropriate oxidizing reagent such as Jones Reagent, magnesium dioxide or pyridinium chlorochromate, TEMPO or Fehling's solution, to afford pyrazole ketones of Formula 1A. The Grignard coupling described in Scheme 5 also works for 3-phenyl-4-bromopyrazoles but 3-phenyl-4-iodopyrazoles are generally preferred.

10A (X=I)

As shown in Scheme 6, iodopyrazoles of Formula 10A are readily made by iodination of pyrazoles of Formula 12 in the presence of an iodinating reagent such as N-iodosuccinimide or IC1 in a solvent such as acetonitrile, tetrahydrofuran, dioxane or N,N-dimethylformamide and at temperatures ranging from 0 °C to the reflux temperature of the solvent. Bromination of pyrazoles of Formula 12 with a brominating agent such as bromine or N-bromosuccinimide gives the corresponding 3-phenyl-4-bromopyrazols of Formula 10B.

Scheme 6

12 10A (X = I)

10B (X = Br)

Substituted 3-phenylpyrazoles of Formula 12 are readily made by the route outlined in Scheme 7. Stirrring substituted acetophenones of Formula 8 with N,N-dimethylformamide dimethylacetal or a trialkyl orthoformate such as HC(OMe)3 or HC(OEt)₃ neat or in a solvent such as acetonitrile, methanol, ethanol, tetrahydrofuran, dioxane, toluene, dichloromethane or N,N-dimethylformamide, at a temperature ranging from 25 °C to the reflux temperature of the neat mixture or solvent, gives enone intermediates of Formula 13 (where A is a leaving group that is generally dimethylamino, ethoxy or methoxy). Cyclization of a compound of Formula 13 with hydrazine (anhydrous or the hydrate) in a protic or aprotic solvent, i.e. acetonitrile, methanol, ethanol or N,N-dimethylformamide gives phenylpyrazoles of Formula 12. Temperatures for this reaction can range from 0 °C to the reflux temperature of the solvent. The chemistry methods described in Schemes 6 and 7 have literature precedence as illustrated in WO2013/062887 and Tetrahedron 2003, 59(4), 555-560.

Scheme 7

13 12

The ring nitrogen on 3-phenyl-4-iodopyrazoles of Formula 10A can also be protected with an appropriate capping group (e.g., N,N-dimethylsulfonyl (-S02N(CH₃)2), methoxymethyl (-CH2OCH3) or benzyl carbamate (cbz)) before generating the Grignard for addition to benzaldehydes of Formula 11 as shown in Scheme 8. For example, reaction of a compound of Formula 10A with N,N-dimethyl chlorosulfonylamine or bromomethylether in the presence of base (i.e. potassium carbonate or sodium hydride) in a solvent (tetrahydrofuran, dioxane, acetonitrile, toluene or N,N-dimethylformamide) affords N-protected pyrazoles 14 where P is S02N(CH₃) or CH2OCH3. Coupling of a compound of Formula 14 with isopropylmagnesium bromide gives the pyrazole Grignard that on reaction with fluorobenzaldehydes of Formula 11 in solvent, i.e. tetrahydrofuran, dioxane or diethyl ether, at temperatures ranging from 0 °C to the reflux temperature of the solvent gives alcohol intermediates that are oxidized to pyrazole ketones 1C (i.e. a subset of Formula 1 where P is S02N(CH₃) or CH2OCH3). The oxidation of alcohol to ketone is usually accomplished with Jones Reagent but other oxidants can be used. A preferred Grignard reagent for generating the N-protected pyrazole Grignard is isopropylmagnesium bromide where 1.1 to 1.2 equivalents are generally used. The N-protected 3-phenylpyrazole phenyl ketones of Formula 1C are sometimes the intended synthetic target as a further subset of IB but can also be converted to pyrazoles of Formula 1 A by removal of the N-protecting group with an appropriate reagent such as an acid. Trifluoroacetic acid works well for de- protection when PG is S0₂N(CH₃)₂. Scheme 8

1C

An alternative regioselective method for making 3-phenyl-4-flurobenzoyl pyrazoles of Formula 1A is summarized in Scheme 9. Nitrogen-protected 3-bromo-4-fluorobenzoyl pyrazoles of Formula 15 can be cross-coupled with aryl boronic acids of Formula 16 in the presence of a palladium catalyst such as tetrakis(triphenylphosphine)palladium or dichloro- bis-(triphenylphosphine)palladium, optionally with a base such as a metal carbonate or tertiary amine, in solvents solvents such as dioxane, N,N-dimethylformamide, tetrahydrofuran or toluene at temperatures normally ranging from 25 °C to the reflux temperature of the solvent to give N-protected 3-phenyl-4-fluorobenzoyl pyrazoles of Formula 1C that on de-protection provides compounds of Formula 1A. Protecting groups PG and de-protection conditions are the same as that described for Scheme 8.

Scheme 9

15 Scheme 10 outlines the preparation of N-protected 3-bromopyrazole ketone intermediates of Formula 15 where a protecting group is first placed on the ring nitrogen of 3,4-dibromopyrazole to give N-protected-3,4-dibromopyrazoles 17. Suitable protecting groups (PG) and reaction conditions are the same as that described in Scheme 8. Conditions for selective Grignard formation at the 4-pyrazole position, addition to fluorobenzaldehydes of Formula 11 to give alcohols that are oxidized to pyrazole ketones of Formual 16 is also the same as that in Scheme 8. Grignard formation at the 3-pyrazole position is generally not competitive with Grignard formation at the 4-positon which allows for limited side product formation. For literature methods to make N,N-dimethylsulfonyl pyrazoles of Formula 17 where PG is S0₂N(CH₃)₂, see WO2011/102399, WO2007/014290 and Synthesis 2006, (5), 793-798.

Scheme 10

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 it is 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 Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. 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. ¾ NMR spectra are reported in ppm downfield from tetramethylsilane in CDCI₃ at 500 MHz unless otherwise indicated; "s" means singlet, "d" means doublet, "t" means triplet, "td" means triplet of doublets, "m" means multiplet, "dd" means doublet of doublets, "ddd" means doublet of double doublets, and "br s" means broad singlet.

SYNTHESIS EXAMPLE 1

Preparation of [3-(3,5-dichlorophenyl)-lH-pyrazol-4-yl](3-fluorophenyl)methanone

(Compound 6)

Step A: Preparation of 3 ,4-dibromo-N,N-dimethyl- lH-pyrazole- 1 -sulfonamide

Triethylamine (8.0 mL, 57 mmol) was slowly added to a mixture of 3,4-dibromo-lH- pyrazole (10 g, 44 mmol) and dimethylsulfamoyl chloride (5.3 mL, 49 mmol) in dichloromethane (30 mL) at ambient temperature. After stirring for 24 h, water was added, and the reaction mixture was extracted with dichloromethane. The organic extract was dried over MgSC"4, filtered and concentrated. The concentrated material was filtered through a short pad of silica gel eluting with diethyl ether to give 15 g of a clear yellow oil.

!H NMR δ ppm 7.92 (s, 1H), 3.00 (s, 6H).

Step B: Preparation of 3-bromo-4-[(3-fluorophenyl)hydroxymethyl]-N,N-dimethyl- lH-pyrazole- 1 -sulfonamide

Isopropylmagnesium bromide (6.0 mL, 2.9 M in 2-methyltetrahydrofuran, 12 mmol) was added dropwise to a stirred solution of 3,4-dibromo-N,N-dimethyl-lH-pyrazole-l- sulfonamide (i.e. the product obtained in Step A above) (4.0 g, 12 mmol) in tetrahydrofuran (12 mL) at -5 °C. The reaction mixture was stirred at 0 °C for 1 h, then 3-fluorobenzaldehyde (3.8 mL, 36 mmol) was added, and the mixture was stirred for 16 h at ambient temperature. After cooling to 0 °C, the reaction was quenched with saturated aqueous ammonium chloride, and extracted with dichloromethane. The organic extract was dried over MgSC^, filtered, concentrated and purified by silica gel column chromatography, eluting with a 0 to 70% gradient of ethyl acetate in hexanes to give a yellow oil (0.23 g).

!H NMR δ ppm 7.72 (s, 1H), 7.35 (m, 1H), 7.15 (m, 2H), 7.00 (m, 1H), 5.78 (s, 1H), 2.98 (s, 6H).

Step C: Preparation of 3-bromo-4-(3-fluorobenzoyl)-N,N-dimethyl-lH-pyrazole-l- sulfonamide

To a solution of 3-bromo-4-[(3-fluorophenyl)hydroxymethyl]-N,N-dimethyl-lH- pyrazole-1 -sulfonamide (i.e. the product obtained in Step B above) (0.23 g, 0.61 mmol) in acetone (5.0 mL) at 0 °C was added Jones Reagent (0.6 mL, 2.7 M Cr0₃/H₂S0₄ in H₂0). The resulting solution was stirred at 0 °C for 1 h. Saturated aqueous NaHC0₃ was added and the mixture was then extracted with dichloromethane. The organic extract was dried over MgS0₄, filtered, and concentrated to give a yellow oil (0.22 g).

!H NMR δ ppm 8.19 (s, 1H), 7.60 (d, 1H), 7.50 (m, 2H), 7.30 (t, 1H), 3.05 (s, 6H).

Step D: Preparation of 3-(3,5-dichlorophenyl)-4-(3-fluorobenzoyl)-N,N-dimethyl-lH- pyrazole- 1 -sulfonamide

A solution of 3-bromo-4-(3-fluorobenzoyl)-N,N-dimethyl-lH-pyrazole-l- sulfonamide (i.e. the product obtained in Step C above) (1.1 g, 2.8 mmol) in dioxane (30 mL) was purged with N₂ for 15 min. After adding tetrakis(triphenylphosphine)palladium (0.23 g, 0.20 mmol), followed by 3,5-dichlorobenzene boronic acid (0.64 g, 3.3 mmol), potassium phosphate (0.89 g, 4.2 mmol) and water (5.0 mL), the mixture was heated to 100 °C for 16 h. The reaction was cooled to ambient temperature, water was added, and the reaction was then extracted with dichloromethane. The extract was dried over MgSC^ and filtered. The filtrate was concentrated onto Celite® diatomaceaous earth filter aid and purified by silica gel column chromatography, eluting with a 0 to 50% gradient of ethyl acetate in hexanes to yield a clear oil (0.60 g).

in NMR δ ppm 8.29 (s, 1H), 7.63 (d, J=1.89 Hz, 2H), 7.58 (m, 1H), 7.53 (dd, J=7.80, 1.18 Hz, 1H), 7.46 (m, 1H), 7.39 (m, 1H), 7.32 (m, 1 H), 3.08 (s, 6H).

Step E: Preparation of [3-(3,5-Dichlorophenyl)-lH-pyrazol-4-yl](3- fluorophenyl)methanone

Trifluoroacetic acid (3.0 mL) was added to 3-(3,5-dichlorophenyl)-4-(3- fluorobenzoyl)-N,N-dimethyl-lH-pyrazole-l -sulfonamide (i.e. the product obtained in Step D above) (0.60 g, 1.8 mmol) in dichloromethane (3.0 mL) and stirred at ambient temperature for 16 h. The reaction mixture was slowly poured into an ice-cooled aqueous solution of sodium bicarbonate and extracted with dichloromethane. The extract was dried over MgS04 and filtered. The filtrate was concentrated onto Celite® diatomaceaous earth filter aid and purified by silica gel column chromatography, eluting with a 0 to 40% gradient of ethyl acetate in hexanes to yield a white solid (98 mg). M.P. = 158-160 °C.

!H NMR δ ppm 10.5 (br s, 1H), 7.97 (s, 1H), 7.58 (m, 3H), 7.48 (m, 1H), 7.43 (m, 1H), 7.37 (s, 1H), 7.29 (m, 1H).

SYNTHESIS EXAMPLE 2

Preparation of (2-fluorophenyl)[3-(3,4,5-trichlorophenyl)-lH-pyrazol-4-yl]methanone

(Compound 19)

Step A: Preparation of 4-amino-3,5-dichlorobenzoic acid methyl ester

A solution of 4-amino-3,5-dichlorobenzoic acid (8.6 g, 42 mmol) in methanol

(140 mL) was cooled to 0 °C. While maintaining the temperature at 0 °C, thionyl chloride (6.4 mL, 88 mmol) was added dropwise to the reaction. The reaction was allowed to slowly warm to ambient temperature over 16 h. The reaction mixture was concentrated. Water was added, and the mixture was extracted with ethyl acetate. The organic extract was washed sequentially with aqueous saturated NaHC0₃, water, then saturated NaCl solution. The extract was dried over MgS0₄, filtered and the filtrate concentrated to give a brown solid (9-4 g).

!H NMR δ ppm 7.88 (s, 2H), 4.90 (br s, 2H), 3.87 (s, 3H).

Step B: Preparation of 3,4,5-trichlorobenzoic acid methyl ester

Isopentyl nitrite (3.7 mL, 27 mmol) was slowly added to a mixture of 4-amino-3,5- dichlorobenzoic acid methyl ester (i.e. the product obtained in Step A above) (2.0 g, 9.1 mmol) in acetonitrile (90 mL), containing copper(I) chloride (1.8 g, 18 mmol) and copper

(II) chloride (3.7 g, 27 mmol), at ambient temperature. The reaction was stirred for 1 h.

Thin layer chromatography confirmed consumption of the starting material. The reaction mixture was slowly poured into ice-water cooled 1 N aqueous hydrochloric acid and extracted with diethyl ether. The organic extract was dried over MgSOz_}, filtered and concentrated to give 2.3 g of a tan solid.

!H NMR δ ppm 8.03 (s, 2H), 3.94 (s, 3H).

Step C: Preparation of l-(2-fiuorophenyl)-3-(3,4,5-trichlorophenyl)-l,3-propanedione To a solution of tetrahydrofuran (20 mL) and sodium hydride (60% dispersion in mineral oil, 0.33 g, 8.3 mmol) was added 2'-fluoroacetophenone (0.56 mL, 4.6 mmol), followed by 3,4,5-trichlorobenzoic acid methyl ester (i.e. the product obtained in Step B above) (1.1 g, 4.6 mmol). The mixture was heated to reflux for 24 h. After cooling to ambient temperature, 1 N aqueous hydrochloric acid was added and the mixture was extracted three times with dichloromethane. The extracts were combined, dried over MgSC>4 and filtered. The filtrate was concentrated to give 1.7 g of a light brown solid, which was used without further purification. Step D: Preparation of 2-[(dimethylamino)methylene]-l-(2-fluorophenyl)-3-(3,4,5- trichlorophenyl)- 1 ,3-propanedione

To the product of Step C above (i.e. l-(2-fluorophenyl)-3-(3,4,5-trichlorophenyl)- 1,3-propanedione) (1.7 g) was added N,N-dimethylformamide dimethylacetal (20 mL). The solution was stirred for 3 d at ambient temperature. The reaction mixture was concentrated onto Celite® diatomaceaous earth filter aid and purified by silica gel column chromatography, eluting with a 0 to 100% gradient of ethyl acetate in hexanes to yield the desired product as a clear amber oil (0.24 g).

!H NMR δ ppm 7.62 (m, 2H), 7.40 (m, 1H), 7.28 (m, 2H), 7.05 (t, 1H), 6.90 (t, 1H), 3.34 (br s, 3H), 2.80 (br s, 3H).

Step E: Preparation of (2-fluorophenyl)[3-(3,4,5-trichlorophenyl)-lH-pyrazol-4- yljmethanone

To 2-[(dimethylamino)methylene]-l-(2-fluorophenyl)-3-(3,4,5-trichlorophenyl)-l,3- propanedione (i.e. the product obtained in Step D above) (0.24 g, 0.60 mmol) in ethanol (20 mL) was added hydrazine hydrate (68 μΐ,, 55% by weight in water, 1.2 mmol). The resulting mixture was stirred at ambient temperature for 24 h, then concentrated onto Celite and purified by silica gel column chromatography, eluting with a 0 to 40 % gradient of ethyl acetate in hexanes. After concentration, the product was crystallized from 1-chlorobutane to yield a light beige solid (0.18 g).M.P. = 187-189 °C.

!H NMR δ ppm 10.5 (br s, 1H), 7.95 (m, 1H), 7.78 (m, 2H), 7.58 (m, 1H), 7.50 (m, 1H), 7.24 (m, 1H), 7.06 (m, 1H).

SYNTHESIS EXAMPLE 3

Preparation of [3-(3,5-dichlorophenyl)-lH-pyrazol-4-yl](2-fluorophenyl)methanone

(Compound 18)

Step A: Preparation of l-(3,5-dichlorophenyl)-3-(2-fluorophenyl)-l,3-propanedione

To a solution of tetrahydrofuran (20 mL) and sodium hydride (60%> dispersion in mineral oil, 0.35 g, 8.7 mmol) was added 2'-fluoroacetophenone (0.59 mL, 4.9 mmol), followed by 3,5-dichlorobenzoic acid methyl ester (1.0 g, 4.9 mmol). The mixture was heated at reflux for 24 h. After cooling to ambient temperature, 1 N aqueous hydrochloric acid was added, and the mixture was extracted three times with dichloromethane. The extracts were combined, dried with MgSC^ and filtered. The filtrate was concentrated to give a tan solid (1.8 g), which was used without further purification.

Step B: Preparation of l-(3,5-dichlorophenyl)-2-[(dimethylamino)methylene]-3-(2- fluorophenyl)-l ,3-propanedione

To the crude sample obtained in Step A above (i.e. l-(3,5-dichlorophenyl)-3-(2- fluorophenyl)-l,3-propanedione) (1.8 g) was added N,N-dimethylformamide dimethylacetal (20 mL). The solution was stirred for 3 d at ambient temperature. The reaction mixture was concentrated onto Celite® diatomaceaous filter aid and purified by silica gel column chromatography, eluting with a 0 to 100 % gradient of ethyl acetate in hexanes to yield the desired product as a clear yellow oil (0.52 g).

1H NMR δ ppm 7.65 (s, IH), 7.47 (d, J=1.6 Hz, 2H), 7.40-7.34 (m, IH), 7.31-7.21 (m, 2H), 7.05 (td, J=7.5, 1.0 Hz, IH), 6.88 (ddd, J=9.9, 8.6, 0.8 Hz, IH), 3.38-3.31 (m, 3H), 2.87- 2.76 (m, 3H).

Step C: Preparation of [3-(3,5-dichlorophenyl)-lH-pyrazol-4-yl](2- fluorophenyl)methanone

To l-(3,5-dichlorophenyl)-2-[(dimethylamino)methylene]-3-(2-fluorophenyl)-l,3- propanedione (i.e. the product obtained in Step B above) (0.52 g, 1.4 mmol) in ethanol (20 mL) was added hydrazine hydrate (55 % by weight in water, 0.16 mL, 2.8 mmol). The reaction was stirred at ambient temperature for 24 h. The reaction mixture was concentrated onto Celite and purified by silica gel column chromatography, eluting with a 0 to 40 % gradient of ethyl acetate in hexanes to yield a white solid (0.17 g). m.p. = 149-151 °C.

1H NMR (CD₃OD) δ ppm 8.08 (s, 1Η), 7.63 (d, J=1.9 Hz, 2H), 7.59-7.50 (m, 2H), 7.44 (t, J=1.7 Hz, IH), 7.27 (t, J=7.8 Hz, IH), 7.14 (t, J=9.3 Hz, IH). A 3-bond NMR correlation was observed from the ortho proton (7.56 ppm) of the fluorinated phenyl ring to the carbonyl carbon (¹³C δ ppm 188.34).

SYNTHESIS EXAMPLE 4

Preparation of [3-(3,5-dichlorophenyl)-lH-pyrazol-4-yl](2,3,5-trifluorophenyl)methanone

(Compound 5)

Step A: Preparation of 3-(3,5-dichlorophenyl)-lH-pyrazole

To 3,5-dichloroacetophenone (9.90 g, 52.4 mmol, 1.0 eq.) was added N,N-dimethylformamide dimethylacetal (100 mL) and the resulting solution heated to 100 °C. After 18 h the reaction was cooled to ambient temperature and the solvent was removed under vacuum. The residue was dissolved in ethanol (100 mL) and hydrazine hydrate (3.81 mL, 78.6 mmol, 1.5 eq.) was added to the solution and the reaction mixture was stirred at ambient temperature for 18 h. The reaction mixture was concentrated under vacuum, and purified by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes to afford the title product (9.31 g).

in NMR δ ppm 7.69 (d, J=1.9 Hz, 2H), 7.64 (d, J=2.4 Hz, IH), 7.31 (t, J=1.9 Hz, IH), 7.26 (s, IH), 6.63 (d, J=2.5 Hz, IH).

Step B: Preparation of 3-(3,5-dichlorophenyl)-4-iodo-lH-pyrazole

To a solution of 3-(3,5-dichlorophenyl)-lH-pyrazole (i.e. the product obtained in Step A above) (9.31 g, 43.7 mmol, 1.0 eq.) in acetonitrile (200 mL) was added N-iodosuccinimide (10.8 g, 48.1 mmol, 1.1 eq.) and the reaction was heated to 60 °C for 18 h. The reaction mixture was cooled to ambient temperature and a saturated aqueous solution of sodium thiosulfate was added, followed by ethyl acetate. The phases were separated and the organic phase was further washed with a saturated aqueous solution of sodium thiosulfate followed by saturated aqueous NaCl. The organic phases were dried over MgS04, concentrated under vacuum, and purified by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes to afford the desired product (12.5g).

!H NMR δ ppm 7.75-7.69 (m, 3H), 7.39 (s, 1H).

Step C: Preparation of [3-(3,5-dichlorophenyl)-lH-pyrazol-4-yl](2,3,5- trifluorophenyl)methanone

To a solution of 3-(3,5-dichlorophenyl)-4-iodo-lH-pyrazole (300 mg, 0.885 mmol, 1.0 eq.) in tetrahydrofuran (5 mL) at 0 °C was added dropwise isopropylmagnesium bromide (2.9 M in 2-methyltetrahydrofuran, 0.67 mL, 2.2 eq.) and the reaction. After stirring for 30 min a solution of 2,3,5-trifluorobenzaldehyde (171 mg, 1.1 eq.) in tetrahydrofuran was added dropwise and the reaction was allowed to warm to ambient temperature over 18 h. The reaction was quenched by the addition of a saturated aqueous solution of ammonium chloride. The phases were separated and the aqueous phase was again washed with tetrahydrofuran. The organic phases were dried over MgS0₄, concentrated under vacuum, and purified by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes to afford the desired material which was then taken on to the next step as is. To a solution of this material in acetone (10 mL) at 0 °C was added Jones Reagent (1 mL, 2.7 M CrC^/^SC^ in H₂0) and the reaction was allowed to warm to ambient temperature over 5 h. The reaction was quenched by the addition of 2 drops of isopropyl alcohol and stirring for 5 min followed by the addition of a saturated solution of sodium bicarbonate and dichloromethane. The phases were separated and the organic layer was again washed with dichloromethane. The organic phases were dried over MgS0₄, concentrated under vacuum, and purified by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes to afford the desired product (123 mg).

lH NMR δ ppm 12.10-11.84 (br s, 1H), 7.92 (d, J=1.6 Hz, 1H), 7.54 (d, J=1.9 Hz, 2H), 7.37 (t, J=1.9 Hz, 1H), 7.11-7.02 (m, 2H).

SYNTHESIS EXAMPLE 5

Preparation of [3-(3,5-dichlorophenyl)-lH-pyrazol-4-yl](3,5-difluorophenyl)methanone

(Compound 7)

Step A: Preparation of 3-(3,5-dichlorophenyl)-a-(3,5-difluorophenyl)-lH-pyrazole-4- methanol

To a vial equipped with a septum was added 3-(3,5-dichlorophenyl)-4-iodo-lH- pyrazole (i.e. the product described in Example 4, Step A) (300 mg, 0.89 mmol) and anhydrous tetrahydrofuran (8 mL). The vial was purged under an N₂ atmosphere then cooled with an ice bath to 0 to 5 °C. Isopropylmagnesium bromide (2.9 M in 2-methyltetrahydrofuran, 0.71 mL, 2.04 mmol) was added dropwise via syringe. The reaction mixture was stirred at 0 °C for 30 min. A solution of 3,5-difluorobenzaldehyde (0.15 mL, 1.33 mmol) in anhydrous tetrahydrofuran (2 mL) was added dropwise. The stirring was continued at 0 °C for 30 min. The reaction was quenched by the addition of saturated aqueous ammonium chloride solution, extracted twice with ethyl acetate, washed with brine, dried over MgSC^ and filtered. The reaction was concentrated onto silica gel and purified by column chromatography eluting with 5% to 30% ethyl acetate in hexanes to provide the title product as a white solid (241 mg).

!H NMR (400 MHz) δ ppm 7.43 (s, 2H), 7.26 (m, 1H), 7.17 (s, 1H), 6.87 (m, 2H), 6.70 (m, 1H), 5.82 (s, 1H).

Step B: Preparation of [3-(3,5-dichlorophenyl)-lH-pyrazol-4-yl](3,5- difluorophenyl)methanone

To a vial containing 3-(3,5-dichlorophenyl)-a-(3,5-difluorophenyl)-lH-pyrazole-4- methanol (i.e. the product obtained in Step A above) (205 mg, 0.58 mmol) and acetone (4 mL) stirring at 0 - 5° C was added Jones Reagent (0.1 mL, 2.8 M Cr0₃/H₂S0₄ in H₂0).

The reaction was stirred at 0 to 5° C for 1 h. Analysis by thin-layer chromatography revealed that starting material remained so additional Jones Reagent (0.1 mL) was added.

After 1 h of additional stirring, analysis by thin-layer chromatography showed complete consumption of starting material. The reaction was quenched by the addition of saturated aqueous sodium bicarbonate solution, extracted twice with ethyl acetate, washed with water, brine, dried over MgS0₄ and filtered. Excess solvent was evaporated to isolate the title compound as a white solid (169 mg).

!H NMR (400 MHz, acetone-<½) δ ppm 12.99 (br s, 1H), 8.35 (s, 1H), 7.81-7.86 (m, 2H), 7.41-7.49 (m, 3H), 7.28 (m, 1H).

By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 192 can be prepared.

Table 1 :

1

χΐ X2 X3 χΐ X2 X3 χΐ X2 X3

F Br I Br I I CF₃ SCF₂H

F I I Br CF₃ I CF₃ C≡CH

F CF₃ I Br CF₂H I CF₂H CF₂H

F CF₂H I Br OCF₃ I CF₂H OCF₃

F OCF₃ I Br OCF₂H I CF₂H OCF₂H

F OCF₂H I Br SCF₂H I CF₂H SCF₂H

F SCF₂H I Br C≡CH I CF₂H C≡CH

F C≡CH I I I I OCF₃ OCF₃

CI CI I I CF₃ I OCF₃ OCF₂H

CI Br I I CF₂H I OCF₃ SCF₂H

CI I I I OCF₃ I OCF₃ C≡CH

CI CF₃ I I OCF₂H I OCF₂H OCF₂H

CI CF₂H I I SCF₂H I OCF₂H SCF₂H

CI OCF3 I I C≡CH I OCF₂H C≡CH

CI OCF₂H I CF₃ CF₃ I SCF₂H SCF₂H

CI SCF₂H I CF₃ CF₂H I SCF₂H C≡CH

CI C≡CH I CF₃ OCF₃ I C≡CH C≡CH

Br Br I CF₃ OCF₂H I

The present disclosure also includes Tables 2 through 192, each of which is constructed the same as Table 1 above, except that the row heading in Table 1 (i.e. "F_n is 2-F; P is H") is replaced with the respective row heading shown below. For Example, in Table 2 the row heading is "F_n is 3-F; P is H" and X¹, X², and X³ are as defined in Table 1 above. Therefore, the first entry in Table A2 specifically discloses a comound of Formula 1 wherein X¹ is F, X² is F, X³ is H, P is H and F_n is 3-F. The remaining table entries are constructed in the same fashion.

Table Row Heading Table Row Heading

2 F_n is 3-F; P is H 13 F_n is 2,3,4,5-F; P is H

3 F_n is 4-F; P is H 14 F_n is 2,3,5,6-F; P is H

4 F_n is 2,3-F; P is H 15 F_n is 2,3,4,6-F; P is H

5 F_n is 2,4-F; P is H 16 F_n is 2,3,4,5,6-F; P is H

6 F_n is 2,5-F; P is H 17 F_n is 2-F; P is CH₃

7 F_n is 2,6-F; P is H 18 F_n is 3-F; P is CH₃

8 F_n is 2,3,4-F; P is H 19 F_n is 4-F; P is CH₃

9 F_n is 2,3,5-F; P is H 20 F_n is 2,3-F; P is CH₃

10 F_n is 2,3,6-F; P is H 21 F_n is 2,4-F; P is CH₃

11 F_n is 2,4,6-F; P is H 22 F_n is 2,5-F; P is CH₃

12 F_n is 2,4,5-F; P is H 23 F_n is 2,6-F; P is CH₃ Table Row Heading Table Row Heading

24 F_n is 2,3,4-F; P is CH₃ 61 F_n is 2,3,4,5-F; P is CH₂CH₂CH₃

25 F_n is 2,3,5-F; P is CH₃ 62 F_n is 2,3,5,6-F; P is CH₂CH₂CH₃

26 F_n is 2,3,6-F; P is CH₃ 63 F_n is 2,3,4,6-F; P is CH₂CH₂CH₃

27 F_n is 2,4,6-F; P is CH₃ 64 F_n is 2,3,4,5,6-F; P is CH₂CH₂CH₃

28 F_n is 2,4,5-F; P is CH₃ 65 F_n is 2-F; P is CH₂C≡CH

29 F_n is 2,3,4,5-F; P is CH₃ 66 F_n is 3-F; P is CH₂C≡CH

30 F_n is 2,3,5,6-F; P is CH₃ 67 F_n is 4-F; P is CH₂C≡CH

31 F_n is 2,3,4,6-F; P is CH₃ 68 F_n is 2,3-F; P is CH₂C≡CH

32 F_n is 2,3,4,5,6-F; P is CH₃ 69 F_n is 2,4-F; P is CH₂C≡CH

33 F_n is 2-F; P is CH₂CH₃ 70 F_n is 2,5-F; P is CH₂C≡CH

34 F_n is 3-F; P is CH₂CH₃ 71 F_n is 2,6-F; P is CH₂C≡CH

35 F_n is 4-F; P is CH₂CH₃ 72 F_n is 2,3,4-F; P is CH₂C≡CH

36 F_n is 2,3-F; P is CH₂CH₃ 73 F_n is 2,3,5-F; P is CH₂C≡CH

37 F_n is 2,4-F; P is CH₂CH₃ 74 F_n is 2,3,6-F; P is CH₂C≡CH

38 F_n is 2,5-F; P is CH₂CH₃ 75 F_n is 2,4,6-F; P is CH₂C≡CH

39 F_n is 2,6-F; P is CH₂CH₃ 76 F_n is 2,4,5-F; P is CH₂C≡CH

40 F_n is 2,3,4-F; P is CH₂CH₃ 77 F_n is 2,3,4,5-F; P is CH₂C≡CH

41 F_n is 2,3,5-F; P is CH₂CH₃ 78 F_n is 2,3,5,6-F; P is CH₂C≡CH

42 F_n is 2,3,6-F; P is CH₂CH₃ 79 F_n is 2,3,4,6-F; P is CH₂C≡CH

43 F_n is 2,4,6-F; P is CH₂CH₃ 80 F_n is 2,3,4,5,6-F; P is CH₂C≡CH

44 F_n is 2,4,5-F; P is CH₂CH₃ 81 F_n is 2-F; P is C(=0)CH₃

45 F_n is 2,3,4,5-F; P is CH₂CH₃ 82 F_n is 3-F; P is C(=0)CH₃

46 F_n is 2,3,5,6-F; P is CH₂CH₃ 83 F_n is 4-F; P is C(=0)CH₃

47 F_n is 2,3,4,6-F; P is CH₂CH₃ 84 F_n is 2,3-F; P is C(=0)CH₃

48 F_n is 2,3,4,5,6-F; P is CH₂CH₃ 85 F_n is 2,4-F; P is C(=0)CH₃

49 F_n is 2-F; P is CH₂CH₂CH₃ 86 F_n is 2,5-F; P is C(=0)CH₃

50 F_n is 3-F; P is CH₂CH₂CH₃ 87 F_n is 2,6-F; P is C(=0)CH₃

51 F_n is 4-F; P is CH₂CH₂CH₃ 88 F_n is 2,3,4-F; P is C(=0)CH₃

52 F_n is 2,3-F; P is CH₂CH₂CH₃ 89 F_n is 2,3,5-F; P is C(=0)CH₃

53 F_n is 2,4-F; P is CH₂CH₂CH₃ 90 F_n is 2,3,6-F; P is C(=0)CH₃

54 F_n is 2,5-F; P is CH₂CH₂CH₃ 91 F_n is 2,4,6-F; P is C(=0)CH₃

55 F_n is 2,6-F; P is CH₂CH₂CH₃ 92 F_n is 2,4,5-F; P is C(=0)CH₃

56 F_n is 2,3,4-F; P is CH₂CH₂CH₃ 93 F_n is 2,3,4,5-F; P is C(=0)CH₃

57 F_n is 2,3,5-F; P is CH₂CH₂CH₃ 94 F_n is 2,3,5,6-F; P is C(=0)CH₃

58 F_n is 2,3,6-F; P is CH₂CH₂CH₃ 95 F_n is 2,3,4,6-F; P is C(=0)CH₃

59 F_n is 2,4,6-F; P is CH₂CH₂CH₃ 96 F_n is 2,3,4,5,6-F; P is C(=0)CH₃

60 F_n is 2,4,5-F; P is CH₂CH₂CH₃ 97 F_n is 2-F; P is C(=0)CF₃ Table Row Heading Table Row Heading

98 F_n is 3-F; P is C(=0)CF₃ 135 F_n is 2,6-F; P is S0₂CF₃

99 F_n is 4-F; P is C(=0)CF₃ 136 F_n is 2,3,4-F; P is S0₂CF₃

100 F_n is 2,3-F; P is C(=0)CF₃ 137 F_n is 2,3,5-F; P is S0₂CF₃

101 F_n is 2,4-F; P is C(=0)CF₃ 138 F_n is 2,3,6-F; P is S0₂CF₃

102 F_n is 2,5-F; P is C(=0)CF₃ 139 F_n is 2,4,6-F; P is S0₂CF₃

103 F_n is 2,6-F; P is C(=0)CF₃ 140 F_n is 2,4,5-F; P is S0₂CF₃

104 F_n is 2,3,4-F; P is C(=0)CF₃ 141 F_n is 2,3,4,5-F; P is S0₂CF₃

105 F_n is 2,3,5-F; P is C(=0)CF₃ 142 F_n is 2,3,5,6-F; P is S0₂CF₃

106 F_n is 2,3,6-F; P is C(=0)CF₃ 143 F_n is 2,3,4,6-F; P is S0₂CF₃

107 F_n is 2,4,6-F; P is C(=0)CF₃ 144 F_n is 2,3,4,5,6-F; P is S0₂CF₃

108 F_n is 2,4,5-F; P is C(=0)CF₃ 145 F_n is 2-F; P is C(=0)CH₂OMe

109 F_n is 2,3,4,5-F; P is C(=0)CF₃ 146 F_n is 3-F; P is C(=0)CH₂OMe

110 F_n is 2,3,5,6-F; P is C(=0)CF₃ 147 F_n is 4-F; P is C(=0)CH₂OMe

111 F_n is 2,3,4,6-F; P is C(=0)CF₃ 148 F_n is 2,3-F; P is C(=0)CH₂OMe

112 F_n is 2,3,4,5,6-F; P is C(=0)CF₃ 149 F_n is 2,4-F; P is C(=0)CH₂OMe

113 F_n is 2-F; P is - CH₂OH 150 F_n is 2,5-F; P is C(=0)CH₂OMe

114 F_n is 3-F; P is CH₂OH 151 F_n is 2,6-F; P is C(=0)CH₂OMe

115 F_n is 4-F; P is CH₂OH 152 F_n is 2,3,4-F; P is C(=0)CH₂OMe

116 F_n is 2,3-F; P is CH₂OH 153 F_n is 2,3,5-F; P is C(=0)CH₂OMe

117 F_n is 2,4-F; P is CH₂OH 154 F_n is 2,3,6-F; P is C(=0)CH₂OMe

118 F_n is 2,5-F; P is CH₂OH 155 F_n is 2,4,6-F; P is C(=0)CH₂OMe

119 F_n is 2,6-F; P is CH₂OH 156 F_n is 2,4,5-F; P is C(=0)CH₂OMe

120 F_n is 2,3,4-F; P is CH₂OH 157 F_n is 2,3,4,5-F; P is C(=0)CH₂OMe

121 F_n is 2,3,5-F; P is CH₂OH 158 F_n is 2,3,5,6-F; P is C(=0)CH₂OMe

122 F_n is 2,3,6-F; P is CH₂OH 159 F_n is 2,3,4,6-F; P is C(=0)CH₂OMe

123 F_n is 2,4,6-F; P is CH₂OH 160 F_n is 2,3,4,5,6-F; P is C(=0)CH₂OMe

124 F_n is 2,4,5-F; P is CH₂OH 161 F_n is 2-F; P is SOoNMeo

125 F_n is 2,3,4,5-F; P is CH₂OH 162 F_n is 3-F; P is S0₂NMe₂

126 F_n is 2,3,5,6-F; P is CH₂OH 163 F_n is 4-F; P is S0₂NMe₂

127 F_n is 2,3,4,6-F; P is CH₂OH 164 F_n is 2,3-F; P is S0₂NMe₂

128 F_n is 2,3,4,5,6-F; P is CH₂OH 165 F_n is 2,4-F; P is S0₂NMe₂

129 F_n is 2-F; P is S0₂CF₃ 166 F_n is 2,5-F; P is S0₂NMe₂

130 F_n is 3-F; P is S0₂CF₃ 167 F_n is 2,6-F; P is S0₂NMe₂

131 F_n is 4-F; P is S0₂CF₃ 168 F_n is 2,3,4-F; P is S0₂NMe₂

132 F_n is 2,3-F; P is S0₂CF₃ 169 F_n is 2,3,5-F; P is SOoNMeo

133 F_n is 2,4-F; P is S0₂CF₃ 170 F_n is 2,3,6-F; P is S0₂NMe₂

134 F_n is 2,5-F; P is S0₂CF₃ 171 F_n is 2,4,6-F; P is S0₂NMe₂ Table Row Heading Table Row Heading

172 F_n is 2,4,5-F; P is S0₂NMe₂ 183 F_n is 2,6-F; P is CF₂H

173 F_n is 2,3 ,4,5-F; P is S0₂NMe₂ 184 F_n is 2,3,4-F; P is CF₂H

174 F_n is 2,3,5,6-F; P is S0₂NMe₂ 185 F_n is 2,3,5-F; P is CF₂H

175 F_n is 2,3,4,6-F; P is S0₂NMe₂ 186 F_n is 2,3,6-F; P is CF₂H

176 F_n is 2,3,4,5,6-F; P is S0₂NMe₂ 187 F_n is 2,4,6-F; P is CF₂H

177 F_n is 2-F; P is CF₂H 188 F_n is 2,4,5-F; P is CF₂H

178 F_n is 3-F; P is CF₂H 189 F_n is 2,3,4,5-F; P is CF₂H

179 F_n is 4-F; P is CF₂H 190 F_n is 2,3,5,6-F; P is CF₂H

180 F_n is 2,3-F; P is CF₂H 191 F_n is 2,3,4,6-F; P is CF₂H

181 F_n is 2,4-F; P is CF₂H 192 F_n is 2,3,4,5,6-F; P is CF₂H

182 F_n is 2,5-F; P is CF₂H

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 paraffmic 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.

Weight Percent

Active

Ingredient Diluent Surfactant

Water-Dispersible and Water-soluble Granules,

0.001-90 0-99.999 0-15 Tablets and Powders

Oil Dispersions, Suspensions, Emulsions, Solutions

1-50 40-99 0-50 (including Emulsifiable Concentrates)

Dusts 1-25 70-99 0-5

Granules and Pellets 0.001-99 5-99.999 0-15

High Strength Compositions 90-99 0-10 0-2

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

Liquid diluents include, for example, water, 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 C6-C22), 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 μιη can be wet milled using media mills to obtain particles with average diameters below 3 μιη. Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. 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 μιη 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, December 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. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 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. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 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. 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 Table 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.

Example A

High Strength Concentrate

Compound 1 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%

Example B

Wettable Powder

Compound 2 65.0% dodecylphenol polyethylene glycol ether 2.0%> sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%

Example C

Granule

Compound 3 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; 90.0%> U.S.S. No. 25-50 sieves)

Example D

Extruded Pellet

Compound 4 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0%> sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%

Example E

Emulsifiable Concentrate

Compound 5 10.0% polyoxyethylene sorbitol hexoleate 20.0%

C^-Cio fatty acid methyl ester 70.0%>

Example F

Microemulsion

Compound 6 5.0%> polyvinylpyrrolidone -vinyl acetate copolymer 30.0% alkylpolyglycoside 30.0%> glyceryl monooleate 15.0% water 20.0%

Example G

Suspension Concentrate

Compound 7 35% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0%> styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1 % l,2-benzisothiazolin-3-one 0.1% water 53.7%

Example H

Emulsion in Water

Compound 8 10.0% butyl polyoxyethylene/polypropylene block copolymer 4.0%> stearic acid/polyethylene glycol copolymer 1.0%) styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0%> silicone based defoamer 0.1 % l,2-benzisothiazolin-3-one 0.1% aromatic petroleum based hydrocarbon 20.0 water 58.7%

Example I

Oil Dispersion

Compound 9 25% polyoxy ethylene sorbitol hexaoleate 15% organically modified bentonite clay 2.5% fatty acid methyl ester 57.5%

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 mention 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.

As referred to herein Asteraceae is a plant family which includes the genera Ambrosia and Bidens; Brassicaceae is a plant family which includes the genera Brassica, Raphanus and Sinapis; Amaranthaceae is a plant family which includes the genera Amaranthus; Chenopodiaceae is a plant family which includes the genera Chenopodium and Kochia; Malvaceae is a plant family which includes the genera Abutilon and Sida; Papaveraceae is a plant family which includes the genera Papaver; Rubiaceae is a plant family which includes the genera Galium; Scrophulariaceae is a plant family which includes the genera Veronica; and Violaceae is a plant family which includes the genera Viola. As referred to herein, the term "pigweed" includes species of the genus Amaranthus. Species of pigweed for which control is often desired include A. retroflexus L. (redroot pigweed), A. palmeri (palmer pigweed), and A. rudis (common waterhemp). As referred to herein "chickweed" includes species of the genus Stellaria. Species of chickweed for which control is often desired include S. media (L.) Vill. (common chickweed). As referred to herein "velvetlea ' includes species of the genus Abutilon. Species of velvetleaf for which control is often desired include A. theophrasti Medik. (velvetleaf). As referred to herein "lambsquarters" includes species of the genus Chenopodium. Species of lambsquarters for which control is often desired include C. album L. (common lambsquarters). Therefore, one aspect of this invention includes a method of applying a compound of Formula 1 to control the growth of Amaranthus, Stellaria and Abutilon.

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.

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, Tl through T37, are used in Exhibit C for traits. A "-" means the entry is not available.

Trait Description Trait Description Trait Description

Tl Glyphosate tolerance T15 Cold tolerance T27 High tryptophan

T2 High lauric acid oil T16 Imidazolinone herb. tol. T28 Erect leaves semidwarf

T3 Glufosinate tolerance T17 Modified alpha-amylase T29 Semidwarf

T4 Phytate breakdown T18 Pollination control T30 Low iron tolerance

T5 Oxynil tolerance T19 2,4-D tolerance T31 Modified oil/fatty acid T6 Disease resistance T20 Increased lysine T32 HPPD tolerance

T7 Insect resistance T21 Drought tolerance T33 High oil

Τ9 Modi ied flower color T22 Delayed ripening/senescence T34 Aryloxyalkanoate tol.

Ti l ALS Herbicide Tol. T23 Modified product quality T35 Mesotrione tolerance

T12 Dicamba Tolerance T24 High cellulose T36 Reduced nicotine

T13 Anti- allergy T25 Modified starch/carbohydrate T37 Modified product

T14 Salt tolerance T26 Insect & disease resist.

Crop Gene(s)

Alfalfa cp4 epsps (aroA:CP4)

Canola* te

Canola* gat4621

Canola* cp4 epsps (aroA:CP4); goxv247

Canola* bar

Canola* pat (syn)

Canola* bar

Canola* cp4 epsps (aroA:CP4)

Canola* phyA

Canola* bar

Canola* bxn

Canola* bar

Bean

acl (sense and antisense) Brinjal # cry 1 Ac

Cotton S4-HrA

Cotton pat (syn); crylF

Cotton pat (syn); crylAc

Cotton bxn; crylAc

Cotton crylAc

Cotton bxn; crylAc

Cotton vip3A(a)

Cotton crylAb

Cotton vip3A

Cotton crylAc

Cotton crylAb-Ac

Cotton cry2Ae

Cotton 2mepsps

Cotton crylAb-Ac

Cotton bar

Cotton crylC

Cotton crylAc

Cotton cp4 epsps (aroA:CP4)

Cotton crylAc; cry2Ab2

Cotton cp4 epsps (aroA:CP4)

Cotton ci lAc

Cotton crylAc

Cotton cp4 epsps (aroA:CP4)

Cotton -

Cotton crylA; CpTI

Cotton crylAb; bar

Cotton crylAb

Cotton

crylAb Cotton

Cotton

Flax

Lentil

Maize

at at at at

7 7 7

Soybean MON89788 cp4 epsps (aroA:CP4)

Soybean W62 bar

Soybean W98 bar

Soybean MON87754 dgat2A

Soybean DAS21606 Modified aad-12; pat

Soybean DAS44406 Modified aad-12; 2mepsps; pat

Soybean SYHT04R Modified avhppd

Soybean 9582.814.19.1 crylAc; crylF; pat

Squash CZW3 cmv cp; zymv cp; wmv cp

Squash ZW20 zymv cp; wmv cp

Sugar Beet GTSB77 (T9100152) cp4 epsps (aroA:CP4); goxv247

Sugar Beet H7-1 cp4 epsps (aroA:CP4)

Sugar Beet T120-7 pat

Sugar Beet T227-1 cp4 epsps (aroA:CP4)

Sugarcane NXI-1T EcbetA

Sunflower X81359 als

Pepper PK-SP01 cmv cp

Tobacco C/F/93/08-02 bxn

Tobacco Vector 21-41 NtQPTl (antisense)

Sunflower X81359 als

Wheat MON71800 cp4 epsps (aroA:CP4)

* Argentine (Brassica napus), ** Polish (B. rapa), # Eggplant

Treatment of genetically modified plants with compounds of the invention may result in super-additive or synergistic effects. For example, reduction in application rates, broadening of the activity spectrum, increased tolerance to biotic/abiotic stresses or enhanced storage stability may be greater than expected from just simple additive effects of the application of compounds of the invention on genetically modified plants.

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-isopropyl, flamprop-M -methyl, flazasulfuron, florasulam, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, flurenol, flurenol-butyl, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet-methyl, fomesafen, foramsulfuron, fosamine-ammonium, glufosinate, glufosinate-ammonium, glufosinate-P, glyphosate and its salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (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, oxyfiuorfen, 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, pyrafiufen-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, safiufenacil, 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, trifiuralin, triflusulfuron-methyl, tritosulfuron, vernolate, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-l- methyl- 1 ,5-naphthyridin-2(lH)-one, 5-chloro-3-[(2-hydroxy-6-oxo- 1 -cyclohexen- 1 - yl)carbonyl]- 1 -(4-methoxyphenyl)-2( lH)-quinoxalinone, 2-chloro-N-( 1 -methyl- lH-tetrazol- 5-yl)-6-(trifluoromethyl)-3-pyridinecarboxamide, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2- difluoroethyl)-8-hydroxypyrido[2,3-¾]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(lH,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-(l -methyl- lH-tetrazol-5-yl)-4-(trifluoromethyl)benzamide and 2-methyl- N-(4-methyl-l,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)-lH-purin-6-amine, epocholeone, gibberellic acid, gibberellin A₄ and A₇, 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, l-bromo-4-[(chloromethyl)sulfonyl]benzene (BCS), 4- (dichloroacetyl)-l-oxa-4-azospiro[4.5]decane (MON 4660), 2-(dichloromethyl)-2-methyl- 1,3-dioxolane (MG 191), ethyl l,6-dihydro-l-(2-methoxyphenyl)-6-oxo-2-phenyl-5- pyrimidinecarboxylate, 2-hydroxy-N,N-dimethyl-6-(trifluoromethyl)pyridine-3- carboxamide, and 3-oxo-l-cyclohexen-l-yl l-(3,4-dimethylphenyl)-l,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 Al lists specific combinations of a Component (a) with Component (b) illustrative of the mixtures, compositions and methods of the present invention. Compound 1 in the Component (a) column is identified in Index Table A. The second column of Table Al lists the specific Component (b) compound (e.g., "2,4-D" in the first line). The third, fourth and fifth columns of Table Al 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 Al 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 Al are to be construed similarly.

TABLE Al

Component (a) Typical More Typical Most Typical (Compound) Component (b Weiaht Ratio Weiaht Ratio Weiaht Ratio

1 2,4-D 1:192-6:1 1:64-2:1 1:24-1:3

1 Acetochlor 1:768-2:1 1:256- 1:2 1:96-1:11

1 Acifluorfen 1:96-12:1 1:32-4:1 1:12-1:2

1 Aclonifen 1:857-2:1 1:285 - 1:3 1:107-1:12

1 Alachlor 1:768-2:1 1:256- 1:2 1:96-1:11

1 Ametryn 1:384- 3:1 1:128-1:1 1:48-1:6

1 Amicarbazone 1:192-6:1 1:64-2:1 1:24-1:3

1 Amidosulfuron 1:6-168:1 1:2-56:1 1:1 - 11:1

1 Aminocyclopyrachlor 1:48-24:1 1:16-8:1 1:6-2:1

1 Aminopyralid 1:20-56:1 1:6-19:1 1:2-4:1

1 Amitrole 1:768-2:1 1:256- 1:2 1:96-1:11

1 Anilofos 1:96-12:1 1:32-4:1 1:12-1:2

1 Asulam 1:960-2:1 1:320- 1:3 1:120-1:14

1 Atrazine 1:192-6:1 1:64-2:1 1:24-1:3

1 Azimsulfuron 1:6-168:1 1:2-56:1 1:1 - 11:1

1 Beflubutamid 1:342-4:1 1:114-2:1 1:42-1:5

1 Benfuresate 1:617-2:1 1:205- 1:2 1:77-1:9

1 Bensulfuron-methyl 1:25 -45:1 1:8-15:1 1:3-3:1

1 Bentazone 1:192-6:1 1:64-2:1 1:24-1:3 Component (a) Typical More Typical Most Typical (Compound) Component (b Weiaht Ratio Weiaht Ratio Weiaht Ratio

1 Benzobicyclon 1:85-14:1 1:28-5:1 1:10-1:2

1 Benzofenap 1:257-5:1 1:85-2:1 1:32-1:4

1 Bicyclopyrone 1:42-27:1 1:14-9:1 1:5-2:1

1 Bifenox 1:257-5:1 1:85-2:1 1:32-1:4

1 Bispyribac-sodium 1:10-112:1 1:3-38:1 1:1-7:1

1 Bromacil 1:384- 3:1 1:128-1:1 1:48-1:6

1 Bromobutide 1:384 -3:1 1:128-1:1 1:48-1:6

1 Bromoxynil 1:96-12:1 1:32-4:1 1:12-1:2

1 Butachlor 1:768-2:1 1:256- 1:2 1:96-1:11

1 Butafenacil 1:42-27:1 1:14-9:1 1:5-2:1

1 Butylate 1:1542- 1:2 1:514-1:5 1:192-1:22

1 Carfenstrole 1:192-6:1 1:64-2:1 1:24-1:3

1 Carfentrazone-ethyl 1:128-9:1 1:42-3:1 1:16-1:2

1 Chlorimuron-ethyl 1:8-135:1 1:2-45:1 1:1-9:1

1 Chlorotoluron 1:768-2:1 1:256- 1:2 1:96-1:11

1 Chlorsulfuron 1:6-168:1 1:2-56:1 1:1 - 11:1

1 Cincosulfuron 1:17-68:1 1:5-23:1 1:2-5:1

1 Cinidon-ethyl 1:384 -3:1 1:128-1:1 1:48-1:6

1 Cinmethylin 1:34-34:1 1:11 - 12:1 1:4-3:1

1 Clacyfos 1:34-34:1 1:11 - 12:1 1:4-3:1

1 Clethodim 1:48-24:1 1:16-8:1 1:6-2:1

1 Clodinafop-propargyl 1:20-56:1 1:6-19:1 1:2-4:1

1 Clomazone 1:384- 3:1 1:128-1:1 1:48-1:6

1 Clomeprop 1:171-7:1 1:57-3:1 1:21 - 1:3

1 Clopyralid 1:192-6:1 1:64-2:1 1:24-1:3

1 Cloransulam-methyl 1:12-96:1 1:4-32:1 1:1-6:1

1 Cumyluron 1:384- 3:1 1:128-1:1 1:48-1:6

1 Cyanazine 1:384- 3:1 1:128-1:1 1:48-1:6

1 Cyclopyrimorate 1:17-68:1 1:5-23:1 1:2-5:1

1 Cyclosulfamuron 1:17-68:1 1:5-23:1 1:2-5:1

1 Cycloxydim 1:96-12:1 1:32-4:1 1:12-1:2

1 Cyhalofop 1:25 -45:1 1:8-15:1 1:3-3:1

1 Daimuron 1:192-6:1 1:64-2:1 1:24-1:3

1 Desmedipham 1:322-4:1 1:107-2:1 1:40-1:5

1 Dicamba 1:192-6:1 1:64-2:1 1:24-1:3 Component (a) Typical More Typical Most Typical (Compound) Component (b Weiaht Ratio Weiaht Ratio Weiaht Ratio

1 Dichlobenil 1:1371 - 1:2 1:457- 1:4 1:171 - 1:20

1 Dichlorprop 1:925-2:1 1:308 - 1:3 1:115-1:13

1 Diclofop-methyl 1:384- 3:1 1:128-1:1 1:48-1:6

1 Diclosulam 1:10-112:1 1:3-38:1 1:1-7:1

1 Difenzoquat 1:288-4:1 1:96-2:1 1:36-1:4

1 Diflufenican 1:857-2:1 1:285 - 1:3 1:107-1:12

1 Diflufenzopyr 1:12-96:1 1:4-32:1 1:1-6:1

1 Dimethachlor 1:768-2:1 1:256- 1:2 1:96-1:11

1 Dimethametryn 1:192-6:1 1:64-2:1 1:24-1:3

1 Dimethenamid-P 1:384- 3:1 1:128-1:1 1:48-1:6

1 Dithiopyr 1:192-6:1 1:64-2:1 1:24-1:3

1 Diuron 1:384- 3:1 1:128-1:1 1:48-1:6

1 EPTC 1:768-2:1 1:256- 1:2 1:96-1:11

1 Esprocarb 1:1371 - 1:2 1:457- 1:4 1:171 - 1:20

1 Ethalfluralin 1:384- 3:1 1:128-1:1 1:48-1:6

1 Ethametsulfuron-methyl 1:17-68:1 1:5-23:1 1:2-5:1

1 Ethoxyfen 1:8-135:1 1:2-45:1 1:1-9:1

1 Ethoxysulfuron 1:20-56:1 1:6-19:1 1:2-4:1

1 Etobenzanid 1:257-5:1 1:85-2:1 1:32-1:4

1 Fenoxaprop-ethyl 1:120-10:1 1:40-4:1 1:15-1:2

1 Fenoxasulfone 1:85-14:1 1:28-5:1 1:10-1:2

1 Fenquinotrione 1:17-68:1 1:5-23:1 1:2-5:1

1 Fentrazamide 1:17-68:1 1:5-23:1 1:2-5:1

1 Flazasulfuron 1:17-68:1 1:5-23:1 1:2-5:1

1 Florasulam 1:2-420:1 1:1 - 140:1 2:1-27:1

1 Fluazifop-butyl 1:192-6:1 1:64-2:1 1:24-1:3

1 Flucarbazone 1:8-135:1 1:2-45:1 1:1-9:1

1 Flucetosulfuron 1:8-135:1 1:2-45:1 1:1-9:1

1 Flufenacet 1:257-5:1 1:85-2:1 1:32-1:4

1 Flumetsulam 1:24-48:1 1:8-16:1 1:3-3:1

1 F lumiclorac -pentyl 1:10-112:1 1:3-38:1 1:1-7:1

1 Flumioxazin 1:25 -45:1 1:8-15:1 1:3-3:1

1 Fluometuron 1:384- 3:1 1:128-1:1 1:48-1:6

1 Flupyrsulfuron-methyl 1:3 -336:1 1:1 - 112:1 2:1-21:1

1 Fluridone 1:384- 3:1 1:128-1:1 1:48-1:6 Component (a) Typical More Typical Most Typical (Compound) Component (b Weiaht Ratio Weiaht Ratio Weiaht Ratio

1 Fluroxypyr 1:96-12:1 1:32-4:1 1:12-1:2

1 Flurtamone 1:857-2:1 1:285- 1:3 1:107-1:12

1 Fluthiacet-methyl 1:48-42:1 1:16-14:1 1:3-3:1

1 Fomesafen 1:96-12:1 1:32-4:1 1:12-1:2

1 Foramsulfuron 1:13-84:1 1:4-28:1 1:1-6:1

1 Glufosinate 1:288-4:1 1:96-2:1 1:36-1:4

1 Glyphosate 1:288-4:1 1:96-2:1 1:36-1:4

1 Halosulfuron-methyl 1:17-68:1 1:5-23:1 1:2-5:1

1 Halauxifen 1:20-56:1 1:6-19:1 1:2-4:1

1 Halauxifen methyl 1:20-56:1 1:6-19:1 1:2-4:1

1 Haloxyfop-methyl 1:34-34:1 1:11 - 12:1 1:4-3:1

1 Hexazinone 1:192-6:1 1:64-2:1 1:24-1:3

1 Imazamox 1:13-84:1 1:4-28:1 1:1-6:1

1 Imazapic 1:20-56:1 1:6-19:1 1:2-4:1

1 Imazapyr 1:85-14:1 1:28-5:1 1:10-1:2

1 Imazaquin 1:34-34:1 1:11 - 12:1 1:4-3:1

1 Imazethabenz -methyl 1:171-7:1 1:57-3:1 1:21 - 1:3

1 Imazethapyr 1:24-48:1 1:8-16:1 1:3-3:1

1 Imazosulfuron 1:27-42:1 1:9-14:1 1:3-3:1

1 Indanofan 1:342-4:1 1:114-2:1 1:42-1:5

1 Indaziflam 1:25-45:1 1:8-15:1 1:3-3:1

1 Iodosulfuron-methyl 1:3 -336:1 1:1 - 112:1 2:1-21:1

1 Ioxynil 1:192-6:1 1:64-2:1 1:24-1:3

1 Ipfencarbazone 1:85-14:1 1:28-5:1 1:10-1:2

1 Isoproturon 1:384 -3:1 1:128-1:1 1:48-1:6

1 Isoxaben 1:288-4:1 1:96-2:1 1:36-1:4

1 Isoxaflutole 1:60-20:1 1:20-7:1 1:7-2:1

1 Lactofen 1:42-27:1 1:14-9:1 1:5-2:1

1 Lenacil 1:384- 3:1 1:128-1:1 1:48-1:6

1 Linuron 1:384- 3:1 1:128-1:1 1:48-1:6

1 MCPA 1:192-6:1 1:64-2:1 1:24-1:3

1 MCPB 1:288-4:1 1:96-2:1 1:36-1:4

1 Mecoprop 1:768-2:1 1:256- 1:2 1:96-1:11

1 Mefenacet 1:384- 3:1 1:128-1:1 1:48-1:6

1 Mefluidide 1:192-6:1 1:64-2:1 1:24-1:3 Component (a) Typical More Typical Most Typical (Compound) Component (b Weiaht Ratio Weiaht Ratio Weiaht Ratio

1 Mesosulfuron-methyl 1:5-224:1 1:1-75:1 1:1 - 14:1

1 Mesotrione 1:42-27:1 1:14-9:1 1:5-2:1

1 Metamifop 1:42-27:1 1:14-9:1 1:5-2:1

1 Metazachlor 1:384 -3:1 1:128-1:1 1:48-1:6

1 Metazosulfuron 1:25-45:1 1:8-15:1 1:3-3:1

1 Methabenzthiazuron 1:768-2:1 1:256- 1:2 1:96-1:11

1 Metolachlor 1:768-2:1 1:256- 1:2 1:96-1:11

1 Metosulam 1:8-135:1 1:2-45:1 1:1-9:1

1 Metribuzin 1:192-6:1 1:64-2:1 1:24-1:3

1 Metsulfuron-methyl 1:2-560:1 1:1 - 187:1 3:1-35:1

1 Molinate 1:1028-2:1 1:342- 1:3 1:128-1:15

1 Napropamide 1:384 -3:1 1:128-1:1 1:48-1:6

1 Napropamide-M 1:192-6:1 1:64-2:1 1:24-1:3

1 Naptalam 1:192-6:1 1:64-2:1 1:24-1:3

1 Nicosulfuron 1:12-96:1 1:4-32:1 1:1-6:1

1 Norflurazon 1:1152-1:1 1:384 - 1:3 1:144-1:16

1 Orbencarb 1:1371 - 1:2 1:457- 1:4 1:171 - 1:20

1 Orthosulfamuron 1:20-56:1 1:6-19:1 1:2-4:1

1 Oryzalin 1:514-3:1 1:171 - 1:2 1:64-1:8

1 Oxadiargyl 1:384 -3:1 1:128-1:1 1:48-1:6

1 Oxadiazon 1:548- 3:1 1:182-1:2 1:68-1:8

1 Oxasulfuron 1:27-42:1 1:9-14:1 1:3-3:1

1 Oxaziclomefone 1:42-27:1 1:14-9:1 1:5-2:1

1 Oxyfluorfen 1:384- 3:1 1:128-1:1 1:48-1:6

1 Paraquat 1:192-6:1 1:64-2:1 1:24-1:3

1 Pendimethalin 1:384- 3:1 1:128-1:1 1:48-1:6

1 Penoxsulam 1:10-112:1 1:3-38:1 1:1-7:1

1 Penthoxamid 1:384- 3:1 1:128-1:1 1:48-1:6

1 Pentoxazone 1:102-12:1 1:34-4:1 1:12-1:2

1 Phenmedipham 1:102-12:1 1:34-4:1 1:12-1:2

1 Picloram 1:96-12:1 1:32-4:1 1:12-1:2

1 Picolinafen 1:34-34:1 1:11 - 12:1 1:4-3:1

1 Pinoxaden 1:25 -45:1 1:8-15:1 1:3-3:1

1 Pretilachlor 1:192-6:1 1:64-2:1 1:24-1:3

1 Primisulfuron-methyl 1:8-135:1 1:2-45:1 1:1-9:1 Component (a) Typical More Typical Most Typical (Compound) Component (b Weiaht Ratio Weiaht Ratio Weiaht Ratio

1 Prodiamine 1:384- 3:1 1:128-1:1 1:48-1:6

1 Profoxydim 1:42-27:1 1:14-9:1 1:5-2:1

1 Prometryn 1:384- 3:1 1:128-1:1 1:48-1:6

1 Propachlor 1:1152-1:1 1:384 - 1:3 1:144-1:16

1 Propanil 1:384- 3:1 1:128-1:1 1:48-1:6

1 Propaquizafop 1:48-24:1 1:16-8:1 1:6-2:1

1 Propoxycarbazone 1:17-68:1 1:5-23:1 1:2-5:1

1 Propyrisulfuron 1:17-68:1 1:5-23:1 1:2-5:1

1 Propyzamide 1:384- 3:1 1:128-1:1 1:48-1:6

1 Prosulfocarb 1:1200- 1:2 1:400- 1:4 1:150-1:17

1 Prosulfuron 1:6-168:1 1:2-56:1 1:1 - 11:1

1 Pyraclonil 1:42-27:1 1:14-9:1 1:5-2:1

1 Pyraflufen-ethyl 1:5-224:1 1:1-75:1 1:1 - 14:1

1 Pyrasulfotole 1:13-84:1 1:4-28:1 1:1-6:1

1 Pyrazolynate 1:857-2:1 1:285 - 1:3 1:107-1:12

1 Pyrazosulfuron-ethyl 1:10-112:1 1:3-38:1 1:1-7:1

1 Pyrazoxyfen 1:5-224:1 1:1-75:1 1:1 - 14:1

1 Pyribenzoxim 1:10-112:1 1:3-38:1 1:1-7:1

1 Pyributicarb 1:384- 3:1 1:128-1:1 1:48-1:6

1 Pyridate 1:288-4:1 1:96-2:1 1:36-1:4

1 Pyriftalid 1:10-112:1 1:3-38:1 1:1-7:1

1 Pyriminobac -methyl 1:20-56:1 1:6-19:1 1:2-4:1

1 Pyrimisulfan 1:17-68:1 1:5-23:1 1:2-5:1

1 Pyrithiobac 1:24-48:1 1:8-16:1 1:3-3:1

1 Pyroxasulfone 1:85-14:1 1:28-5:1 1:10-1:2

1 Pyroxsulam 1:5-224:1 1:1-75:1 1:1 - 14:1

1 Quinclorac 1:192-6:1 1:64-2:1 1:24-1:3

1 Quizalofop-ethyl 1:42-27:1 1:14-9:1 1:5-2:1

1 Rimsulfuron 1:13-84:1 1:4-28:1 1:1-6:1

1 Saflufenacil 1:25-45:1 1:8-15:1 1:3-3:1

1 Sethoxydim 1:96-12:1 1:32-4:1 1:12-1:2

1 Simazine 1:384- 3:1 1:128-1:1 1:48-1:6

1 Sulcotrione 1:120-10:1 1:40-4:1 1:15-1:2

1 Sulfentrazone 1:147-8:1 1:49-3:1 1:18-1:3

1 Sulfometuron-methyl 1:34-34:1 1:11 - 12:1 1:4-3:1 Component (a) Typical More Typical Most Typical (Compound) Component (b Weiaht Ratio Weiaht Ratio Weiaht Ratio

1 Sulfosulfuron 1:8-135:1 1:2-45:1 1:1-9:1

1 Tebuthiuron 1:384- 3:1 1:128-1:1 1:48-1:6

1 Tefuryltrione 1:42-27:1 1:14-9:1 1:5-2:1

1 Tembotrione 1:31-37:1 1:10-13:1 1:3-3:1

1 Tepraloxydim 1:25-45:1 1:8-15:1 1:3-3:1

1 Terbacil 1:288-4:1 1:96-2:1 1:36-1:4

1 Terbuthylazine 1:857-2:1 1:285- 1:3 1:107-1:12

1 Terbutryn 1:192-6:1 1:64-2:1 1:24-1:3

1 Thenylchlor 1:85-14:1 1:28-5:1 1:10-1:2

1 Thiazopyr 1:384- 3:1 1:128-1:1 1:48-1:6

1 Thiencarbazone 1:3 -336:1 1:1 - 112:1 2:1-21:1

1 Thifensulfuron-methyl 1:5-224:1 1:1-75:1 1:1 - 14:1

1 Tiafenacil 1:17-68:1 1:5-23:1 1:2-5:1

1 Thiobencarb 1:768-2:1 1:256- 1:2 1:96-1:11

1 Topramzone 1:6-168:1 1:2-56:1 1:1 - 11:1

1 Tralkoxydim 1:68-17:1 1:22-6:1 1:8-2:1

1 Triallate 1:768-2:1 1:256- 1:2 1:96-1:11

1 Triasulfuron 1:5-224:1 1:1-75:1 1:1 - 14:1

1 Triaziflam 1:171-7:1 1:57-3:1 1:21 - 1:3

1 Tribenuron-methyl 1:3 -336:1 1:1 - 112:1 2:1-21:1

1 Triclopyr 1:192-6:1 1:64-2:1 1:24-1:3

1 Trifloxysulfuron 1:2-420:1 1:1 - 140:1 2:1-27:1

1 Trifluralin 1:288-4:1 1:96-2:1 1:36-1:4

1 Triflusulfuron-methyl 1:17-68:1 1:5-23:1 1:2-5:1

1 Tritosulfuron 1:13-84:1 1:4-28:1 1:1-6:1

Table A2 is constructed the same as Table Al above except that entries below the "Component (a)" column heading are replaced with the respective Component (a) Column Entry shown below. Compound 1 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. Tables A3 through A7 are constructed similarly.

Table Number Component (a) Column Entries Table Number Component (a) Column Entries

A2 Compound 2 A3 Compound 3 Table Number Component (a) Column Entries Table Number Component (a) Column Entries A4 Compound 4 A7 Compound 7

A5 Compound 5 A8 Compound 8

A6 Compound 6 A9 Compound 9

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 chlorimuron-ethyl, nicosulfuron, mesotrione, thifensulfuron-methyl, flupyrsulfuron-methyl, tribenuron, pyroxasulfone, pinoxaden, tembotrione, pyroxsulam, metolachlor and ^-metolachlor. More prererred are mixtures of a compound of this invention with a herbicide selected from the group consisting of indaziflam and isoxaben.

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 Tables A for compound descriptions. The following abbreviations are used in the Index Table which follow: "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared, "Cmpd. No." means compound number. M.S. is reported as M+H unless otherwise indicated.

Cmpd. No. χΐ X2 X3 Fn P m.p. (°C) M.S.

1 CI CI H 2,5-di-F H 355

2 Br Br H 2,5-di-F H 441

3 F F H 2,5-di-F H 321

4 F CI H 3-F H 319

**

5 (Ex. 4) CI CI H 2,3,5-tri-F H 371

**

6 (Ex. 1) CI CI H 3-F H 158-160 7 (Ex. 5) CI CI H 3,5-di-F H 353

8 CI CI H 2,5-di-F C(=0)CH₃ 394*

9 F F H 3,5-di-F H 321

10 CI CI H 2,3,6-tri-F H 371

11 CI CI H 3,4-di-F H 353

12 CI CI H 2,3-di-F H 353

13 CI CI H 4-F H 158-163

14 F F H 2,3-di-F H 321

15 Br Br F 3-F H 457*

16 Br Br H 3-F H 425

17 Br Br H 3,5-di-F H 443

18 (Ex. 3) CI CI H 2-F H 149-151 **

19 (Ex. 2) CI CI CI 2-F H 187-189 **

20 CI CF₃ H 3-F H 369

21 CF₃ CF₃ H 3-F H 403

***

22 Br OCHF₂ H 3-F H

23 CI CI F 2,5-di-F H 60-88

24 CI CI H 2,6-di-F H 353

25 CI CI H 2,3,5,6-tetra-F H 387

26 CI CI CI 2,5-di-F H 168-171

* See Index Table B for NMR data.

See Synthesis Example for ⁱH NMR data.

INDEX TABLE B

Cmpd. No. NMR Data (CDC1₃ solution unless indicated otherwise)^a

22 !H NMR (500MHz) δ ppm 8.04-7.92 (br s, 1H), 7.73-7.67 (m, 1H), 7.59-7.54 (m, 1H),

7.52-7.46 (m, 1H), 7.46-7.38 (m, 2H), 7.33-7.23 (m, 3H), 6.50 (t, J= 22.5 Hz, 1H) a NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (t)-triplet, (m) -multiple t, (br s)-broad singlet.

BIOLOGICAL EXAMPLES OF THE INVENTION

TEST A

Seeds of plant species selected from barnyardgrass {Echinochloa crus-galli), kochia (Kochia scoparia), ragweed (common ragweed, Ambrosia elatior), Italian ryegrass (Lolium multiflorum), foxtail, giant (giant foxtail Setaria faberii), pigweed (Amaranthus retroflexus), crabgrass, large (large crabgrass, Digitaria sanguinalis), morningglory (Ipomoea spp.), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), and corn (Zea mays) 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 crop and weed species and also 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 Compounds

1000 g ai/ha 1 6 7 8 9 11 12 13 14 15 16 17 18 19 Postemergence

Barnyardgrass 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Corn 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Crabgrass, Large 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Foxtail, Giant 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Morningglory 0 0 0 0 0 30 30 10 0 0 0 0 10 10

Pigweed 100 100 100 90 70 60 80 80 80 80 100 90 90 80

Velvetleaf 100 100 90 90 90 70 90 80 80 80 90 90 80 80

Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Table A Compounds Table A Compounds

1000 g ai/ha 20 21 22 1000 g ai/ha 20 21 22

Postemergence Postemergence

Barnyardgrass 0 0 0 Morningglory 0 0 0

Corn 0 0 0 Pigweed 80 0 70

Crabgrass, Large 0 0 0 Velvetleaf 70 0 70

Foxtail, Giant 0 0 0 Wheat 0 0 0

Table A impounds

500 g ai/ha 2 3 4 5 10 23 24 25 26

Postemergence

Barnyardgrass 0 0 0 10 0 0 0 0 0

Blackgrass - - - 0 - - - Corn 0 0 0 0 0 0 0 0 0

Crabgrass, Large 0 0 0 0 0 - 0 0 0

Foxtail, Giant 0 0 0 0 0 0 0 0 0 Galium - - - - - 60 - - -

Kochia - - - - - 90 - - -

Morningglory 0 0 0 0 0 - 0 0 0

Pigweed 90 70 90 100 100 90 90 100 90

Ragweed - - - - - 80 - - -

Ryegrass, Italian - - - - - 0 - - -

Velvetleaf 90 80 90 90 80 - 80 90 90

Wheat 0 0 0 0 0 0 0 0 0

Table A Compounds

125 g ai/ha 2 3 4 5 10 23 24 25 26

Postemergence

Barnyardgrass 0 0 0 0 0 0 0 0 0

Blackgrass - - - - - 0 - - -

Corn 0 0 0 0 0 0 0 0 0

Crabgrass, Large 0 0 0 0 0 - 0 0 0

Foxtail, Giant 0 0 0 0 0 0 0 0 0

Galium - - - - - 10 - - -

Kochia - - - - - 50 - - -

Morningglory 0 0 0 0 0 - 0 0 0

Pigweed 80 60 80 80 70 80 50 70 80

Ragweed - - - - - 20 - - -

Ryegrass, Italian - - - - - 0 - - -

Velvetleaf 80 70 90 60 60 - 50 80 50

Wheat 0 0 0 0 0 0 0 0 0

Table A Compounds

1000 g ai/ha 1 6 7 8 9 11 12 13 14 15 16 17 18 19

Preemergence

Barnyardgrass 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Corn 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Crabgrass, Large 0 0 0 0 0 0 0 0 0 0 0 0 0 -

Foxtail, Giant 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Morningglory 0 0 0 0 0 0 0 0 0 0 0 0 10 0

Pigweed 100 100 90 80 100 80 70 70 100 70 70 70 80 80

Velvetleaf 50 80 60 80 90 0 70 70 80 60 70 60 60 30

Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Table A Compounds Table A Compounds

1000 g ai/ha 20 21 22 1000 g ai/ha 20 21 22

Preemergence Preemergence Table A Compounds Table A Compounds

1000 g ai/ha 20 21 22 1000 g ai/ha 20 21 22

Preemergence Preemergence

Barnyardgrass 0 0 0 Morningglory 0 0 0

Corn 0 0 0 Pigweed 60 0 40

Crabgrass, Large 0 0 0 Velvetleaf 20 0 40

Foxtail, Giant 0 0 0 Wheat 0 0 0

Table A Compounds

500 g ai/ha 2 3 4 5 10 23 24 25 26

Preemergence

Barnyardgrass 0 0 0 0 0 0 0 0 0

Corn 0 0 0 0 0 - 0 0 0

Crabgrass, Large 0 0 0 0 0 - 0 0 0

Foxtail, Giant 0 0 0 0 0 0 0 0 0

Kochia - - - - - 70 - - -

Morningglory 0 0 0 0 0 - 0 0 0

Pigweed 100 100 100 100 90 100 80 70 90

Ragweed - - - - - 90 - - -

Ryegrass, Italian - - - - - 0 - - -

Velvetleaf 50 90 80 70 30 - 20 70 20

Wheat 0 0 0 0 0 - 0 0 0

Table A Compounds

125 g ai/ha 2 3 4 5 10 23 24 25 26

Preemergence

Barnyardgrass 0 0 0 0 0 0 0 0 0

Corn 0 0 0 0 0 - 0 0 0

Crabgrass, Large 0 0 0 0 0 - 0 0 0

Foxtail, Giant 0 0 0 0 0 0 0 0 0

Kochia - - - - - 20 - - -

Morningglory 0 0 0 0 0 - 0 0 0

Pigweed 60 100 40 80 10 30 30 50 30

Ragweed - - - - - 20 - - -

Ryegrass, Italian - - - - - 0 - - -

Velvetleaf 0 60 60 30 0 - 0 0 0

Wheat 0 0 0 0 0 - 0 0 0 TEST B

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 8 10 23 24 25 26

Flood

Barnyardgrass 0 0 0 0 0 0 0 0 0 0 0

Ducksalad 0 0 0 0 0 0 0 0 0 0 0

Rice 0 0 0 0 0 0 0 0 30 0 0

Sedge, Umbrella 65 0 0 0 0 0 0 0 40 0 0

TEST C

Seeds of plant species selected from blackgrass (Alopecurus myosuroides), ryegrass, Italian (Italian ryegrass, Lolium multiflorum), wheat (winter wheat, Triticum aestivum), Galium (catchweed bedstraw, Galium aparine), corn (Zea mays), crabgrass, large (large crabgrass, Digitaria sanguinalis), foxtail, giant (giant foxtail, Setaria faberii), lambsquarters (Chenopodium album), morningglory (Ipomoea coccinea), nutsedge, yellow (yellow nutsedge, Cyperus esculentus), pigweed (Amaranthus retroflexus), johnsongrass (Sorghum halepense), 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 barley (winter barley, Hordeum vulgare), canarygrass (Phalaris minor), chickweed (common chickweed, Stellaria media), windgrass (Apera spica-venti), bromegrass, downy (downy bromegrass, Bromus tectorum), foxtail, green (green foxtail, Setaria viridis), oat, wild (wild oat, Avena fatua), bermudagrass (Cynodon dactylon), Surinam grass (Brachiaria decumbens), cocklebur (common cocklebur, Xanthium strumarium), cupgrass, woolly (woolly cupgrass, Eriochloa villosa), goosegrass (Eleusine indica), johnsongrass (Sorghum halepense), Kochia (Kochia scoparia), and deadnettle (henbit deadnettle, Lamium amplexicaule) were planted in pots containing Redi-Earth^® planting medium (Scotts Company, 14111 Scottslawn Road, Marysville, Ohio 43041) comprising spaghnum peat moss, vermiculite, wetting agent and starter nutrients 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.

Table C Compounds Table C Compounds

500 g ai/ha 1 2 3 4 500 g ai/ha 1 2 3 4

Postemergence Postemergence

Barnyardgrass 0 5 0 5 Nutsedge, Yellow 0 0 0 0

Blackgrass 0 0 0 5 Oat, Wild 0 0 0 0

Chickweed 100 98 100 100 Oilseed Rape 85 60 90 95

Corn 0 0 0 0 Pigweed 100 98 90 80

Crabgrass, Large 0 0 0 0 Ragweed 70 80 85 90

Foxtail, Giant 0 0 10 0 Ryegrass, Italian 5 0 0 0

Galium 30 30 20 40 Soybean 0 0 0 0

Johnsongrass 0 0 0 0 Velvetleaf 85 65 70 90

Kochia 90 85 85 95 Waterhemp 98 100 90 85

Lambsquarters 90 100 85 98 Wheat 0 0 0 0

Morningglory 0 0 0 0

Table C Compounds

250 g ai/ha 1 2 3 4 6 7 10

Postemergence

Barley - - - - 0 -

Barnyardgrass 0 0 0 0 - 0 0

Bermudagrass - - - - 0 -

Blackgrass 0 0 0 0 0 10 0

Bromegrass, Downy - - - - 0 -

Canarygrass - - - - 0 -

Chickweed 100 98 100 100 100 100 70

Cocklebur - - - - ί 55 - - Corn 0 0 0 0 0 0 0

Crabgrass, Large 0 0 0 0 0 10 0

Cupgrass, Woolly - - - - 0 - -

Deadnettle - - - - 0 - -

Foxtail, Giant 0 0 0 0 0 0 0

Foxtail, Green - - - - 0 - -

Galium 45 10 5 45 5 55 15

Goosegrass - - - - 0 - -

Johnsongrass 0 0 0 0 0 0 0

Kochia 90 90 80 85 65 85 80

Lambsquarters 98 98 85 95 98 85 95

Morningglory 0 10 10 0 0 0 0

Nutsedge, Yellow 0 0 0 0 0 5 0

Oat, Wild 0 0 0 0 0 0 0

Oilseed Rape 70 65 90 70 - 70 60

Pigweed 100 85 85 80 80 95 98

Ragweed 85 40 90 85 60 80 50

Ryegrass, Italian 5 0 0 0 0 0 0

Soybean 0 0 0 0 - 0 0

Surinam Grass - - - - 0 - -

Velvetleaf 80 65 60 85 85 85 55

Waterhemp 90 95 80 75 - 98 100

Wheat 5 0 0 0 0 0 0

Windgrass - - - - 0 - -

Table C Compounds

125 g ai/ha 1 2 3 4 6 7 10

Postemergence

Barley - - - - 0 - -

Barnyardgrass 0 0 0 0 - 0 0

Bermudagrass - - - - 0 - -

Blackgrass 0 0 0 0 0 0 0

Bromegrass, Downy - - - - 0 - -

Canarygrass - - - - 0 - -

Chickweed 95 100 100 100 98 100 85

Cocklebur - - - - 75 - -

Corn 0 0 0 0 0 0 0

Crabgrass, Large 0 0 0 0 0 0 0

Cupgrass, Woolly - - - - 0 - - Deadnettle - - - - 0 - -

Foxtail, Giant 0 0 0 0 0 0 0

Foxtail, Green - - - - 0 - -

Galium 40 0 0 10 0 50 5

Goosegrass - - - - 0 - -

Johnsongrass 0 0 0 0 0 0 0

Kochia 90 85 80 85 65 85 75

Lambsquarters 98 70 45 75 95 98 75

Morningglory 0 0 15 0 0 0 0

Nutsedge, Yellow 0 0 0 0 0 0 10

Oat, Wild 0 0 0 0 0 0 0

Oilseed Rape 70 30 0 70 - 85 60

Pigweed 100 90 70 80 60 95 80

Ragweed 60 60 80 70 50 75 50

Ryegrass, Italian 0 0 0 0 0 0 0

Soybean 0 0 0 0 - 0 0

Surinam Grass - - - - 0 - -

Velvetleaf 75 55 55 70 80 75 40

Waterhemp 100 90 60 75 - 98 90

Wheat 0 0 0 0 0 0 0

Windgrass - - - - 0 - -

Table C Compounds

62 g ai/ha 1 2 3 4 6 7 10

Postemergence

Barley - - - - 0 - -

Barnyardgrass 0 0 0 0 - 5 0

Bermudagrass - - - - 0 - -

Blackgrass 0 0 0 0 0 0 0

Bromegrass, Downy - - - - 0 - -

Canarygrass - - - - 0 - -

Chickweed 95 85 100 98 80 100 85

Cocklebur - - - - 20 - -

Corn 0 0 0 0 0 0 0

Crabgrass, Large 0 0 0 0 0 0 0

Cupgrass, Woolly - - - - 0 - -

Deadnettle - - - - 0 - -

Foxtail, Giant 0 10 0 0 0 0 0

Foxtail, Green - - - - 0 - - Galium 35 0 0 5 0 30 0

Goosegrass - - - - 0 - -

Johnsongrass 0 0 0 0 0 0 0

Kochia 85 75 75 80 60 80 50

Lambsquarters 95 30 50 40 60 75 75

Morningglory 0 0 0 0 0 0 5

Nutsedge, Yellow 0 0 10 0 0 0 10

Oat, Wild 0 0 0 0 0 0 0

Oilseed Rape 45 55 0 80 - 30 0

Pigweed 98 85 65 60 60 90 75

Ragweed 75 60 55 70 45 60 30

Ryegrass, Italian 0 0 0 0 0 0 0

Soybean 0 0 0 0 0 0 0

Surinam Grass - - - - 0 - -

Velvetleaf 70 45 25 70 70 60 20

Waterhemp 90 90 55 60 - 95 95

Wheat 0 0 0 0 0 0 0

Windgrass - - - - 0 - -

Table C Compounds

31 g ai/ha 6 7 10

Postemergence

Table C Compounds Table C Compounds

31 g ai/ha 6 7 10 31 g ai/ha 6 7 10

Postemergence Postemergence

Barley 0 - - Johnsongrass 0 0 0

Barnyardgrass - 0 0 Kochia 35 70 10

Bermudagrass 0 - - Lambsquarters 0 45 55

Blackgrass 0 0 0 Morningglory 0 0 0

Bromegrass, Downy 0 - - Nutsedge, Yellow 0 10 0

Canarygrass 0 - - Oat, Wild 0 0 0

Chickweed 70 98 60 Oilseed Rape - 15 0

Cocklebur 10 - - Pigweed 25 80 70

Corn 0 0 0 Ragweed 25 15 0

Crabgrass, Large 0 0 0 Ryegrass, Italian 0 0 0

Cupgrass, Woolly 0 - - Soybean 0 0 0

Deadnettle 0 - - Surinam Grass 0 - -

Foxtail, Giant 0 0 0 Velvetleaf 70 45 20

Foxtail, Green 0 - - Waterhemp - 80 70 Table C Compounds Table C Compounds 31 g ai/ha 6 7 10 31 g ai/ha 6 7 10 Postemergence Postemergence

Galium 0 0 0 Wheat 0 0 0 Goosegrass 0 - - Windgrass 0 - -

Table C Compounds Table C Compounds

500 g ai/ha 1 2 3 4 500 g ai/ha 1 2 3 4

Preemergence Preemergence

Barnyardgrass 0 0 0 0 Nutsedge, Yell 80 0 0 0

Blackgrass 0 0 60 30 Oilseed Rape 90 50 100 98

Corn 0 0 0 0 Pigweed 100 100 100 100

Crabgrass, Large 0 0 0 0 Ragweed 98 80 100 100

Foxtail, Giant 0 0 0 0 Ryegrass, Ital 0 0 0 0

Galium 80 35 98 100 Soybean 0 0 0 0

Johnsongrass 10 0 0 0 Velvetleaf 55 80 100 100

Lambsquarters 100 100 - 100 Waterhemp 100 100 100 100

Morningglory 0 0 10 0

Table C Compounds

250 g ai/ha 1 2 3 4 7 10

Preemergence

Barnyardgrass 0 0 0 0 0 0

Blackgrass 10 0 0 0 30 0

Corn 0 0 0 0 5 0

Crabgrass, Large 0 0 0 0 0 0

Foxtail, Giant 0 0 0 0 0 0

Galium 60 30 98 85 90 0

Johnsongrass 0 0 0 0 0 0

Lambsquarters 100 100 - 100 100 -

Morningglory 0 15 10 0 20 0

Nutsedge, Yellow 30 0 0 0 0 0

Oilseed Rape 60 80 30 100 90 10

Pigweed 100 90 100 100 100 100

Ragweed 100 40 100 90 95 50

Ryegrass, Italian 0 0 0 0 10 0

Soybean 0 0 0 0 0 0

Velvetleaf 75 50 100 95 75 20

Waterhemp 100 98 100 100 100 100 Wheat 0 0 0 0 0 0

Table C Compounds

125 g ai/ha 1 2 3 4 7 10

Preemergence

Barnyardgrass 0 0 0 0 0 0

Blackgrass 50 0 0 45 10 0

Corn 0 0 0 10 5 0

Crabgrass, Large 0 0 20 0 0 0

Foxtail, Giant 0 0 0 0 0 0

Galium 0 0 0 90 90 10

Johnsongrass 10 0 0 0 0 0

Lambsquarters 100 85 - 100 100 -

Morningglory 0 0 0 0 0 0

Nutsedge, Yellow 0 0 0 20 0 0

Oilseed Rape 40 0 80 98 40 0

Pigweed 100 85 100 100 100 100

Ragweed 100 30 100 90 100 60

Ryegrass, Italian 0 0 0 0 0 0

Soybean 0 0 0 0 0 0

Velvetleaf 75 60 90 85 80 10

Waterhemp 100 90 100 100 100 100

Wheat 0 0 0 0 0 0

Table C Compounds

62 g ai/ha 1 2 3 4 7 10

Preemergence

Barnyardgrass 0 0 0 0 0 0

Blackgrass 10 0 0 0 10 0

Corn 0 0 0 0 0 0

Crabgrass, Large 0 0 0 0 0 15

Foxtail, Giant 0 0 0 0 0 0

Galium 80 0 50 100 0 80

Johnsongrass 0 0 0 0 0 0

Lambsquarters 98 100 - 100 80 -

Morningglory 0 0 0 0 0 0

Nutsedge, Yellow 0 0 0 0 0 0

Oilseed Rape 10 0 0 0 0 0

Pigweed 85 50 100 55 65 55

Ragweed 55 40 100 35 100 50 Ryegrass, Italian 0 0 0 35 30 0

Soybean 0 0 0 0 10 5

Velvetleaf 55 15 40 50 20 0

Waterhemp 100 85 100 100 80 65

Wheat 0 0 0 0 10 0

Table C Compounds Table C Compounds

31 g ai/ha 7 10 31 g ai/ha 7 10

Preemergence Preemergence

Barnyardgrass 0 0 Nutsedge, Yellow 0 0

Blackgrass 0 0 Oilseed Rape 0 0

Corn 5 0 Pigweed 20 10

Crabgrass, Large 0 0 Ragweed 45 0

Foxtail, Giant 0 0 Ryegrass, Italian 0 0

Galium 0 0 Soybean 0 0

Johnsongrass 0 0 Velvetleaf 15 20

Lambsquarters 0 - Waterhemp 75 40

Morningglory 0 0 Wheat 0 0

TEST D

Seeds of plant species selected from bluegrass (annual bluegrass, Poa annua), blackgrass (Alopecurus myosuroides), canarygrass (Phalaris minor), chickweed (common chickweed, Stellaria media), Galium (catchweed bedstraw, Galium aparine), bromegrass, downy (downy bromegrass, Bromus tectorum), field poppy (Papaver rhoeas), field violet {Viola arvensis), foxtail, green (green foxtail, Setaria viridis), deadnettle (henbit deadnettle, Lamium amplexicaule), ryegrass, Italian (Italian ryegrass, Lolium multiflorum), Kochia (Kochia scoparia), lambsquarters (Chenopodium album), oilseed rape (Brassica napus), pigweed (Amaranthus retroflexus), chamomile (scentless chamomile, Matricaria inodora), speedwell (bird's-eye speedwell, Veronica persica), barley, spring (spring barley, Hordeum vulgare), wheat, spring (spring wheat, Triticum aestivum), buckwheat, wild (wild buckwheat, Polygonum convolvulus), mustard, wild (wild mustard, Sinapis arvensis), oat, wild (wild oat, Avena fatua), radish, wild (wild radish, Raphanus raphanistrum), windgrass (Apera spica-venti), barley, winter (winter barley, Hordeum vulgare), and wheat, winter (winter wheat, Triticum aestivum) were planted into a silt loam soil and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant. At the same time, these species were planted in pots containing Redi- Earth^® planting medium (Scotts Company, 14111 Scottslawn Road, Marysville, Ohio 43041) comprising spaghnum peat moss, vermiculite, wetting agent and starter nutrients and treated with postemergence applications of the test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage). Treated plants and controls were maintained in a controlled growth environment for 14 to 21 days after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table D, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (-) response means no test result.

Table D Compounds Table D Compounds

500 g ai/ha 1 7 250 g ai/ha 1 7

Postemergence Postemergence

Barley, Spring 0 0 Barley, Spring 0 0

Barley, Winter 0 0 Barley, Winter 0 0

Blackgrass 0 0 Blackgrass 0 0

Bluegrass 0 0 Bluegrass 0 0

Bromegrass, Downy 0 0 Bromegrass, Downy 0 0

Buckwheat, Wild 60 60 Buckwheat, Wild 70 50

Canarygrass 0 0 Canarygrass 0 0

Chamomile 65 60 Chamomile 60 50

Chickweed 100 80 Chickweed 75 100

Deadnettle 10 20 Deadnettle 5 10

Field Poppy 80 50 Field Poppy 70 50

Field Violet 90 90 Field Violet 90 75

Foxtail, Green 0 0 Foxtail, Green 0 0

Galium 20 40 Galium 20 50

Kochia 75 70 Kochia 70 60

Lambsquarters 90 85 Lambsquarters 85 75

Mustard, Wild 95 100 Mustard, Wild 85 90

Oat, Wild 0 0 Oat, Wild 0 0

Oilseed Rape 75 60 Oilseed Rape 75 70

Pigweed 100 100 Pigweed 100 95

Radish, Wild 75 70 Radish, Wild 75 80

Ryegrass, Italian 0 0 Ryegrass, Italian 0 0

Speedwell 25 20 Speedwell 20 45

Wheat, Spring 0 0 Wheat, Spring 0 0

Wheat, Winter 0 0 Wheat, Winter 0 0

Windgrass 0 0 Windgrass 0 0

Table D Compounds Table D Compounds

250 g ai/ha 1 7 125 g ai/ha 1 7

Postemergence Postemergence Table D Compounds Table D Compounds

250 g ai/ha 1 7 125 g ai/ha 1 7

Postemergence Postemergence

Barley, Spring 0 0 Barley, Spring 0 0

Barley, Winter 0 0 Barley, Winter 0 0

Blackgrass 0 0 Blackgrass 0 0

Bluegrass 0 0 Bluegrass 0 0

Bromegrass, Downy 0 0 Bromegrass, Downy 0 0

Buckwheat, Wild 70 50 Buckwheat, Wild 60 30

Canarygrass 0 0 Canarygrass 0 0

Chamomile 60 50 Chamomile 55 30

Chickweed 75 100 Chickweed 85 75

Deadnettle 5 10 Deadnettle 0 10

Field Poppy 70 50 Field Poppy 50 30

Field Violet 90 75 Field Violet 80 75

Foxtail, Green 0 0 Foxtail, Green 0 0

Galium 20 50 Galium 10 35

Kochia 70 60 Kochia 60 55

Lambsquarters 85 75 Lambsquarters 75 70

Mustard, Wild 85 90 Mustard, Wild 80 80

Oat, Wild 0 0 Oat, Wild 0 0

Oilseed Rape 75 70 Oilseed Rape 65 55

Pigweed 100 95 Pigweed 85 75

Radish, Wild 75 80 Radish, Wild 70 65

Ryegrass, Italian 0 0 Ryegrass, Italian 0 0

Speedwell 20 45 Speedwell 15 10

Wheat, Spring 0 0 Wheat, Spring 0 0

Wheat, Winter 0 0 Wheat, Winter 0 0

Windgrass 0 0 Windgrass 0 0

Table D Compounds Table D Compounds

62 g ai/ha 1 7 500 g ai/ha 1 7

Postemergence Preemergence

Barley, Spring 0 0 Barley, Spring 0 0

Barley, Winter 0 0 Barley, Winter 0 0

Blackgrass 0 0 Blackgrass 0 0

Bluegrass 0 0 Bluegrass 0 0

Bromegrass, Downy 0 0 Bromegrass, Downy 0 0 Table D Compounds Table D Compounds

62 g ai/ha 1 7 500 g ai/ha 1 7

Postemergence Preemergence

Buckwheat, Wild 15 20 Buckwheat, Wild 50 10

Canarygrass 0 0 Canarygrass 0 0

Chamomile 30 15 Chamomile - 55

Chickweed 75 75 Chickweed 100 100

Deadnettle 0 10 Deadnettle 5 0

Field Poppy 35 20 Field Poppy - 100

Field Violet 90 60 Field Violet 0 100

Foxtail, Green 0 0 Foxtail, Green 0 0

Galium 5 25 Galium 0 5

Kochia 55 50 Kochia 70 60

Lambsquarters 70 55 Lambsquarters 100 100

Mustard, Wild 80 80 Mustard, Wild 100 55

Oat, Wild 0 0 Oat, Wild 0 0

Oilseed Rape 60 40 Oilseed Rape 65 10

Pigweed 75 70 Pigweed 100 80

Radish, Wild 70 60 Radish, Wild 65 0

Ryegrass, Italian 0 0 Ryegrass, Italian 0 0

Speedwell 10 5 Speedwell - 20

Wheat, Spring 0 0 Wheat, Spring 0 0

Wheat, Winter 0 0 Wheat, Winter 0 0

Windgrass 0 0 Windgrass 0 0

Table D Compounds Table D Compounds

250 g ai/ha 1 7 125 g ai/ha 1 7

Preemergence Preemergence

Barley, Spring 0 0 Barley, Spring 0 0

Barley, Winter 0 0 Barley, Winter 0 0

Blackgrass 0 0 Blackgrass 0 0

Bluegrass 0 0 Bluegrass 0 0

Bromegrass, Downy 0 0 Bromegrass, Downy 0 0

Buckwheat, Wild 0 10 Buckwheat, Wild 5 5

Canarygrass 0 0 Canarygrass 0 0

Chamomile 65 - Chickweed 100 100

Chickweed 100 100 Deadnettle 0 0

Deadnettle 0 0 Field Poppy - 100 Table D Compounds Table D Compounds

250 g ai/ha 1 7 125 g ai/ha 1 7

Preemergence Preemergence

Field Poppy - 100 Field Violet 0 35

Field Violet 0 60 Foxtail, Green 0 0

Foxtail, Green 0 0 Galium 0 0

Galium 0 5 Kochia 50 10

Kochia 60 25 Lambsquarters 100 25

Lambsquarters 100 80 Mustard, Wild 60 0

Mustard, Wild 85 10 Oat, Wild 0 0

Oat, Wild 0 0 Oilseed Rape 10 0

Oilseed Rape 20 5 Pigweed 95 40

Pigweed 100 60 Radish, Wild 0 0

Radish, Wild 75 0 Ryegrass, Italian 0 0

Ryegrass, Italian 0 0 Speedwell - 0

Speedwell - 0 Wheat, Spring 0 0

Wheat, Spring 0 0 Wheat, Winter 0 0

Wheat, Winter 0 0 Windgrass 0 0

Windgrass 0 0

Table D Compounds Table D Compounds

62 g ai/ha 1 7 62 g ai/ha 1 7

Preemergence Preemergence

Barley, Spring 0 0 Galium 0 0

Barley, Winter 0 0 Kochia 55 10

Blackgrass 0 0 Lambsquarters 60 25

Bluegrass 0 0 Mustard, Wild 40 0

Bromegrass, Downy 0 0 Oat, Wild 0 0

Buckwheat, Wild 0 5 Oilseed Rape 10 0

Canarygrass 0 0 Pigweed 80 35

Chamomile 0 0 Radish, Wild 0 0

Chickweed 100 100 Ryegrass, Italian 0 0

Deadnettle 0 0 Speedwell - 0

Field Poppy - 0 Wheat, Spring 0 0

Field Violet 0 - Wheat, Winter 0 0

Foxtail, Green 0 0 Windgrass 0 0 TEST E

Seeds of plant species selected from corn (Zea mays), soybean (Glycine max), velvetleaf (Abutilon theophrasti), lambsquarters (Chenopodium album), poinsettia, wild (wild poinsettia, Euphorbia heterophylla), pigweed, palmer (palmer pigweed, Amaranthus palmeri), waterhemp (common waterhemp, Amaranthus rudis), Surinam grass (Brachiaria decumbens), crabgrass, large (large crabgrass, Digitaria sanguinalis), crabgrass, Brazil (Brazilian crabgrass, Digitaria horizontalis), panicum, fall (fall panicum, Panicum dichotomiflorum), foxtail, giant (giant foxtail Setaria faberii), foxtail, green (green foxtail, Setaria viridis), goosegrass (Eleusine indica), johnsongrass (Sorghum halepense), ragweed (common ragweed, Ambrosia elatior), barnyardgrass (Echinochloa crus-galli), sandbur (southern sandbur, Cenchrus echinatus), arrowleaf sida (Sida rhombifolia), ryegrass, Italian (Italian ryegrass, Lolium multiflorum), dayflower, VA (Virginia dayflower, Commelina virginica), field bindweed (Convolvulus arvensis), cocklebur (common cocklebur, Xanthium strumarium), morningglory (Ipomoea coccinea), nightshade (eastern black nightshade, Solanum ptycanthum), Kochia (Kochia scoparia), nutsedge, yellow (yellow nutsedge, Cyperus esculentus), smartweed (ladysthumb smartweed, Polygonum persicaria), and beggarticks (hairy beggarticks, Bidens pilosa), were planted into a silt loam soil and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant. At the same time, plants from these crop and weed species and also waterhemp RES 1 , (ALS & Triazine resistant common waterhemp, Amaranthus rudis), and waterhemp_RES2, (ALS & HPPD resistant common waterhemp, Amaranthus rudis) were treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm for postemergence treatments (1- to 4-leaf stage). Treated plants and controls were maintained in a greenhouse for 14 to 21 days, after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table E, 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 E Compounds

500 g ai/ha 2 3 4 7 1 0

Postemergence

Arrowleaf Sida 80 90 90 65 60

Barnyardgrass 0 0 0 0 0

Beggarticks 80 95 1 00 90 7 0

Corn 0 0 0 0 0

Crabgrass, Brazil 0 2 0 0 1 0 0

Dayflower, VA 0 0 0 0 0

Field Bindweed 0 0 0 0 0

Panicum, Fall 0 0 0 0 0 Pigweed, Palmer 95 70 85 95 75

Poinsettia, Wild 0 20 15 30 0

Ryegrass, Italian 0 0 0 0 0

Sandbur 0 0 0 0 0

Soybean 0 0 0 0 0

Waterhemp 100 90 90 100 95

Waterhemp RESl 100 95 95 98 100

Waterhemp RES2 100 75 90 100 95

Table E Compounds

250 g ai/ha 1 2 3 4 7 10

Postemergence

Arrowleaf Sida 80 70 80 90 60 40

Barnyardgrass 10 0 0 0 0 0

Beggarticks 80 80 90 100 75 60

Corn 0 0 0 0 0 0

Crabgrass, Brazil 0 0 0 0 10 0

Dayflower, VA 0 0 0 0 0 0

Field Bindweed 0 0 0 0 0 0

Panicum, Fall - 0 0 0 0 0

Pigweed, Palmer 95 95 30 70 100 60

Poinsettia, Wild 30 0 0 0 0 0

Ryegrass, Italian 0 0 0 0 0 0

Sandbur 0 0 0 0 0 0

Smartweed 30 - - - - -

Soybean 0 0 0 0 0 0

Waterhemp 95 100 75 95 95 85

Waterhemp RESl 100 100 75 85 90 100

Waterhemp RES2 90 100 60 85 100 80

Table E Compounds

125 g ai/ha 1 2 3 4 7 10

Postemergence

Arrowleaf Sida 75 65 50 85 75 60

Barnyardgrass 20 0 0 0 0 0

Beggarticks 60 70 80 95 80 50

Corn 0 0 0 0 0 0

Crabgrass, Brazil 0 0 0 0 0 0

Dayflower, VA 0 0 0 0 0 0

Field Bindweed 0 0 0 0 0 0 Panicura, Fall - 0 0 0 0 0

Pigweed, Palmer 90 100 20 50 70 50

Poinsettia, Wild 20 0 0 0 0 0

Ryegrass, Italian 10 0 0 0 0 0

Sandbur 0 0 0 0 0 0

Smartweed 20 - - - - -

Soybean 0 0 0 0 0 0

Waterhemp 95 100 60 80 98 80

Waterhemp RESl 100 100 70 80 100 90

Waterhemp RES2 80 98 50 80 90 65

Table E Compounds

62 g ai/ha 1 2 3 4 7 10

Postemergence

Arrowleaf Sida 60 50 50 75 50 50

Barnyardgrass 10 0 0 0 0 0

Beggarticks 60 50 50 85 70 60

Corn 0 0 0 0 0 0

Crabgrass, Brazil 0 0 0 0 0 0

Dayflower, VA 0 0 0 0 0 0

Field Bindweed 0 0 0 0 0 0

Panicum, Fall - 0 0 0 0 0

Pigweed, Palmer 60 80 20 40 60 40

Poinsettia, Wild 30 0 0 0 0 0

Ryegrass, Italian 10 0 0 0 0 0

Sandbur 10 0 0 0 0 0

Smartweed 0 - - - - -

Soybean 0 0 0 0 0 0

Waterhemp 85 95 40 50 90 75

Waterhemp RESl 95 95 50 70 90 85

Waterhemp RES2 85 75 70 40 90 40

Table E Compounds

31 g ai/ha 1 2 3 4 7 10

Postemergence

Arrowleaf Sida 60 65 60 70 40 40

Barnyardgrass 0 0 0 0 0 0

Beggarticks 40 25 40 80 60 40

Corn 0 0 0 0 0 0

Crabgrass, Brazil 0 0 0 0 0 0 Dayflower, VA 0 0 0 0 0 0

Field Bindweed 0 0 0 0 0 0

Panicura, Fall - 0 0 0 0 0

Pigweed, Palmer 40 85 10 30 70 40

Poinsettia, Wild 0 0 0 0 0 0

Ryegrass, Italian 0 0 0 0 0 0

Sandbur 0 0 0 0 0 0

Smartweed 0 - - - - -

Soybean 0 0 0 0 0 0

Waterhemp 90 80 30 60 75 70

Waterhemp RESl 80 80 50 70 90 80

Waterhemp RES2 0 65 50 40 95 60

Table E Compound Table E Compound

16 g ai/ha 1 16 g ai/ha 1

Postemergence Postemergence

Arrowleaf Sida 50 Poinsettia, Wild 0

Barnyardgrass 0 Ryegrass, Italian 0

Beggarticks 40 Sandbur 0

Corn 20 Smartweed 0

Crabgrass, Brazil 0 Soybean 0

Dayflower, VA 0 Waterhemp 80

Field Bindweed 0 Waterhemp RESl 70

Pigweed, Palmer 50 Waterhemp RES2 0

Table E Compounds

500 g ai/ha 2 3 4 7 10

Preemergence

Arrowleaf Sida 35 100 100 90 40

Barnyardgrass 0 0 0 0 0

Beggarticks 15 35 60 40 0

Cocklebur - - - 0 -

Corn 35 0 20 0 0

Crabgrass, Brazil 35 0 35 0 -

Crabgrass, Large 0 0 0 0 0

Dayflower, VA 0 0 25 0 0

Field Bindweed 0 0 35 0 30

Foxtail, Giant 0 0 15 0 10

Foxtail, Green 20 0 0 0 0

Goosegrass 0 0 35 0 35 Johnsongrass 20 0 0 0 0

Kochia 0 60 75 60 30

Lambsquarters 98 100 100 98 80

Morningglory 50 0 0 0 0

Nightshade 0 0 25 0 20

Nutsedge, Yellow 0 0 0 0 0

Panicum, Fall 0 0 0 0 0

Pigweed, Palmer 35 - 65 35 -

Poinsettia, Wild 20 0 35 0 0

Ragweed 35 100 98 90 65

Ryegrass, Italian 0 0 35 0 0

Sandbur 0 0 20 0 0

Soybean 25 0 50 0 0

Surinam Grass 0 0 0 0 0

Velvetleaf 35 100 100 50 25

Waterhemp 90 100 90 100 75

Table E Compounds

250 g ai/ha 1 2 3 4 7 10

Preemergence

Arrowleaf Sida 90 0 100 95 90 40

Barnyardgrass 0 0 0 0 0 0

Beggarticks 20 15 20 60 30 0

Cocklebur 0 - - - - -

Corn 0 35 0 20 0 0

Crabgrass, Brazil 0 0 0 50 0 -

Crabgrass, Large 0 0 0 0 0 0

Dayflower, VA 0 0 0 0 0 0

Field Bindweed 0 0 25 10 0 0

Foxtail, Giant 0 0 0 0 0 10

Foxtail, Green 0 0 0 0 0 0

Goosegrass 0 0 0 65 0 20

Johnsongrass 65 0 0 0 0 -

Kochia 30 0 25 75 75 15

Lambsquarters 98 0 100 100 95 70

Morningglory 0 20 0 0 0 0

Nightshade 0 0 0 65 0 20

Nutsedge, Yellow 0 0 0 0 0 0

Panicum, Fall 0 0 0 0 0 0 Pigweed, Palmer 100 30 - 0 0 -

Poinsettia, Wild 20 20 25 15 0 0

Ragweed 20 20 100 65 65 40

Ryegrass, Italian 0 0 0 20 0 0

Sandbur 0 0 0 20 0 0

Smartweed 0 - - - - -

Soybean 35 0 0 0 0 0

Surinam Grass 0 0 0 20 0 0

Velvetleaf 98 25 35 95 35 0

Waterhemp 100 90 90 60 80 60

Table E Compounds

125 g ai/ha 1 2 3 4 7 10

Preemergence

Arrowleaf Sida 50 0 100 70 50 10

Barnyardgrass 0 0 0 0 0 0

Beggarticks 20 0 15 35 0 0

Cocklebur 0 - 0 0 - -

Corn 0 0 0 0 0 0

Crabgrass, Brazil 0 0 0 - 0 0

Crabgrass, Large 0 0 0 0 0 0

Dayflower, VA 0 0 0 0 0 0

Field Bindweed 0 0 30 0 0 30

Foxtail, Giant 0 0 0 0 0 0

Foxtail, Green 0 0 0 0 0 0

Goosegrass 0 0 0 0 0 0

Johnsongrass 0 0 0 0 0 0

Kochia 20 0 20 0 40 0

Lambsquarters 85 - 80 100 90 0

Morningglory 0 0 0 0 0 0

Nightshade 0 0 0 25 0 0

Nutsedge, Yellow 0 0 0 0 0 0

Panicum, Fall 0 0 0 0 0 0

Pigweed, Palmer 0 30 - 0 20 -

Poinsettia, Wild 20 0 10 0 0 0

Ragweed 15 0 60 75 40 35

Ryegrass, Italian 0 0 10 20 0 0

Sandbur 0 0 0 0 0 0

Soybean 0 0 0 0 0 0 Surinam Grass 0 0 0 0 0 0

Velvetleaf 35 15 20 75 20 0

Waterhemp 80 65 50 0 40 20

Table E Compounds

62 g ai/ha 1 2 3 4 7 10

Preemergence

Arrowleaf Sida 10 0 0 50 20 0

Barnyardgrass 0 0 0 0 0 0

Beggarticks 20 0 0 35 0 0

Cocklebur - - - - 0 -

Corn 0 0 0 0 0 0

Crabgrass, Brazil 0 0 - - 0 -

Crabgrass, Large 0 0 0 0 0 0

Dayflower, VA 0 0 0 0 0 0

Field Bindweed 0 0 0 0 0 35

Foxtail, Giant 0 0 0 0 - 0

Foxtail, Green 0 0 0 0 0 0

Goosegrass 0 0 0 0 0 0

Johnsongrass 0 0 0 0 0 0

Kochia 20 0 0 0 0 0

Lambsquarters 30 - 100 98 65 -

Morningglory 0 0 0 0 0 0

Nightshade 0 0 0 0 0 0

Nutsedge, Yellow 0 0 0 0 0 0

Panicum, Fall 0 0 0 0 0 0

Pigweed, Palmer - 20 - 0 20 -

Poinsettia, Wild 0 0 0 0 0 0

Ragweed 0 0 0 0 65 0

Ryegrass, Italian 0 0 0 0 0 0

Sandbur 0 0 0 0 0 0

Soybean 0 0 0 0 0 0

Surinam Grass 0 0 0 0 0 0

Velvetleaf 0 20 20 0 0 0

Waterhemp 35 40 0 0 30 15

Table E Compounds

31 g ai/ha 1 2 3 4 7 10

Preemergence

Arrowleaf Sida 10 0 0 65 20 30 Barnyardgrass 0 0 0 0 0 0

Beggarticks 0 0 0 0 0 0

Cocklebur 0 - 0 0 - 0

Corn 0 0 0 0 0 0

Crabgrass, Brazil 0 0 - 0 0 0

Crabgrass, Large 0 0 0 0 0 0

Dayflower, VA 0 0 0 0 0 0

Field Bindweed 0 0 0 0 0 0

Foxtail, Giant 0 0 0 0 0 0

Foxtail, Green 0 0 0 0 0 0

Goosegrass 0 0 0 0 0 0

Johnsongrass 0 0 0 0 0 0

Kochia 35 0 0 0 0 0

Lambsquarters 40 0 95 0 0 0

Morningglory 0 0 0 0 0 0

Nightshade 0 0 0 0 0 0

Nutsedge, Yellow 0 0 0 0 0 0

Panicura, Fall 0 0 0 0 0 0

Pigweed, Palmer 30 0 - 0 0 -

Poinsettia, Wild 20 0 15 0 0 0

Ragweed 0 0 0 0 35 0

Ryegrass, Italian 0 0 0 0 0 0

Sandbur 0 0 0 0 0 0

Soybean 0 0 0 0 0 0

Surinam Grass 0 0 0 0 0 0

Velvetleaf 0 0 0 0 0 0

Waterhemp 65 0 0 0 0 0

Table E Compound Table E Compound

16 g ai/ha 1 16 g ai/ha 1

Preemergence Preemergence

Arrowleaf Sida 0 Lambsquarters 70

Barnyardgrass 0 Morningglory 0

Beggarticks 0 Nightshade 0

Waterhemp 0 Nutsedge, Yellow 0

Corn 0 Panicum, Fall 0

Crabgrass, Brazil 0 Pigweed, Palmer 0

Crabgrass, Large 0 Poinsettia, Wild 0

Dayflower, VA 0 Ragweed 0 Field Bindweed 0 Ryegrass, Italian 0

Foxtail, Giant 0 Sandbur 0

Foxtail, Green 0 Smartweed 0

Goosegrass 0 Soybean 0

Johnsongrass 0 Surinam Grass 0

Kochia 0 Velvetleaf 0

Waterhemp 0

Claims

CLAIMS What is claimed is:

1. A compound selected from Formula 1, N-oxides and salts thereof,

1 wherein

X¹ is halogen, -CF₃, -CF₂H, -OCF₃, -OCF₂H, -SCHF₂ or -C≡CH;

X² is halogen, -CF₃, -CF₂H, -OCF₃, -OCF₂H, -SCHF₂ or -C≡CH;

X³ is H or halogen;

n is 1 , 2, 3, 4 or 5;

P is H, C1-C7 alkyl, C₃-C₇ alkenyl, C₃-C₇ alkynyl, C₃-C₇ cycloalkyl, C -C haloalkyl, C₂-C₇ haloalkenyl, C₃-C₇ haloalkynyl, C₂-C₇ alkoxyalkyl, C4-C₇

cycloalkylalkyl, C^-C₇ alkoxy, C₃-C₇ alkoxyalkoxyalkyl, C₃-C₇

alkylcarbonylalkyl, C₃-C₇ alkoxycarbonylalkyl, C4-C₇ halocycloalkylalkyl, C₂-C₇ haloalkoxyalkyl, C₂-C₇ alkylthioalkyl, C₂-C₇ alkylsulfonylalkyl, C₂-C₇ alkylsulfinylalkyl, C₂-C₇ haloalkylthioalkyl, C₂-C₇ haloalkylsulfonylalkyl, C₂-C₇ haloalkylsulfmylalkyl, C₃-C₇ haloalkoxycarbonylalkyl, C₃-C₇ haloalkylcarbonylalkyl, C₂-C₇ alkylaminoalkyl, C₃-C₇ dialkylaminoalkyl, C₂-C₇ cyanoalkyl, C_}-C₇ nitroalkyl, amino, hydroxy, CH₂OH, C(=0)R¹, S0₂R², C(=0)NR³R⁴, S0₂NR³R⁴, C0₂R⁵, CH(OR⁶)₂, CH(C0₂CH₃)₂ or

CH(C0₂C₂H₅)₂;

R¹ is H, C_rC₇ alkyl, C₂-C₇ alkenyl, C₂-C₇ alkynyl, C₃-C₇ cycloalkyl, C_rC₇ haloalkyl, C₃-C₇ haloalkenyl, C₂-C₇ alkoxyalkyl or C4-C₇ cycloalkylalkyl; or phenyl optionally substituted with R⁷; or benzyl optionally substituted on ring members with R⁷; or pyridyl optionally substituted with R⁷;

R² is H, C_rC₇ alkyl, C₂-C₇ alkenyl, C₂-C₇ alkynyl, C₃-C₇ cycloalkyl, C_rC₇ haloalkyl, C₃-C₇ haloalkenyl, C₂-C₇ alkoxyalkyl or C4-C₇ cycloalkylalkyl; or phenyl optionally substituted with R⁷; or benzyl optionally substituted on ring members with R⁷; or pyridyl optionally substituted with R⁷; R³ is H, C_rC₇ alkyl, C₂-C₇ alkenyl, C₂-C₇ alkynyl, C₃-C₇ cycloalkyl, C_rC₇ haloalkyl, C3"C₇ haloalkenyl, C2-C₇ alkoxyalkyl or C4-C₇ cycloalkylalkyl; or phenyl optionally substituted with R⁷; or benzyl optionally substituted on ring members with R⁷; or pyridyl optionally substituted with R⁷;

R⁴ is H or C_rC₄ alkyl;

R⁵ is C -C alkyl, C3-C₇ alkenyl, C3-C₇ alkynyl, C3-C₇ cycloalkyl, C2-C₇ haloalkyl, C3"C₇ haloalkenyl, C2-C₇ alkoxyalkyl or C4-C₇ cycloalkylalkyl; or phenyl optionally substituted with R⁷; or benzyl optionally substituted on ring members with R⁷; or pyridyl optionally substituted with R⁷;

R⁶ is C_rC₃ alkyl; or

two R⁶ are taken together as -(CH₂)2-, -(CH₂)3- or -CH₂CH(CH3)- to form a ring; and

R⁷ is halogen, cyano, C1-C2 alkyl, C1-C3 haloalkyl, C1-C3 haloalkoxy or C1-C3 alkoxy.

2. The compound of Claim 1 wherein

X¹ is halogen, -CF₃, -CF₂H, -OCF3 or -OCF₂H;

X² is halogen, -CF₃ , -CF₂H, -OCF3 or -OCF₂H ;

X³ is H, F, CI or Br;

P is H, C -C alkyl, C3-C₇ alkenyl, C3-C₇ alkynyl, C3-C₇ cycloalkyl, C -C haloalkyl, C2"C₇ haloalkenyl, C3-C₇ haloalkynyl, C2-C₇ alkoxyalkyl, C4-C₇

cycloalkylalkyl, C 1 -C7 alkoxy, C3-C₇ alkoxyalkoxyalkyl, C2-C7 cyanoalkyl, C_rC₇ nitroalkyl, amino, hydroxy, CH₂OH, C(=0)R!, S0₂R², C(=0)NR³R⁴,

S0₂NR³R⁴, C0₂R⁵, CH(OR⁶)₂, CH(C0₂CH₃)₂ or CH(C0₂C₂H₅)2;

R¹ is H, C_rC₇ alkyl, C₂-C₇ alkenyl, C₂-C₇ alkynyl, C_rC₇ haloalkyl or C₂-C₇

alkoxyalkyl; or benzyl optionally substituted on ring members with R⁷;

R⁴ is H or CH₃;

R⁵ is C_rC₄ alkyl;

R⁶ is CH₃ or CH₂CH₃; or

two R⁶ are taken together as -(CH2)2- or -(CH2)3- to form a ring; and

R⁷ is CI, Br, cyano or CH₃.

3. The compound of Claim 2 wherein

X¹ is halogen;

X² is halogen;

X³ is H, F, CI or Br;

n is 1 , 2 or 3; and P is H, C_rC₄ alkyl, C3-C4 alkenyl, C3-C4 alkynyl, CH₂OCH₃, CH₂OC₂H₅, CH₂OH, C(=0)CH₃, C(=0)C₂H₅, C(=0)CH₂OCH₃, C(=0)CH₂C≡CH, S0₂CH₃, S0₂C₂H₅ or S0₂CF₃.

4. The compound of Claim 3 wherein

X¹ is CI or Br;

X² is CI or Br;

X³ is H, F or CI;

n is 2 or 3; and

P is H, C1-C4 alkyl, CH₂C≡CH, CH₂OH, C(=0)CH₃, C(=0)C₂H₅, C(=0)CH₂C≡CH, S0₂CH₃ or S0₂CF₃ or.

5. The compound of Claim 4 wherein

X¹ is CI;

X² is CI;

X³ is H or CI; and

P is H, CH₃ , CH₂CH₃ , CH₂C≡CH, CH₂OH, C(=0)CH₃ or C(=0)C₂H₅.

6. The compound of Claim 1 wherein

X³ is H;

n is 2; and

P is H.

7. The compound of Claim 1 selected from

[3-(3,5-dichlorophenyl)-lH-pyrazol-4-yl](2,5-difluorophenyl)methanone;

[3-(3,5-dibromophenyl)-lH-pyrazol-4-yl](2,5-difluorophenyl)methanone;

(2,5-difluorophenyl)[3-(3,5-difluorophenyl)-lH-pyrazol-4-yl]methanone;

[3 -(3 -chloro-5 -fluorophenyl)- lH-pyrazol-4-yl] (3 -fluorophenyl)methanone;

[3 -(3 ,5 -dichlorophenyl)- 1 H-pyrazol-4-yl] (2,3 ,5 -trifluorophenyl)methanone;

[3 -(3 ,5 -dichlorophenyl)- 1 H-pyrazol-4-yl] (3 -fluorophenyl)methanone;

[3 -(3 ,5 -dichlorophenyl)- 1 H-pyrazol-4-yl](3 ,5 -difluorophenyl)methanone;

1 -[3-(3,5-dichlorophenyl)-4-(2,5-difluorobenzoyl)- lH-pyrazol- 1 -yljethanone; and

(3,5-difluorophenyl)[3-(3,5-difluorophenyl)-lH-pyrazol-4-yl]methanone.

8. A herbicidal composition comprising a compound of Claim 1 and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.

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

10. A herbicidal mixture comprising (a) a compound of Claim 1, and (b) at least one additional active ingredient selected from (bl) through (bl6) and salts of compounds of (bl) through (bl6).

1 1. 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 Claim 1.