HERBICIDAL PYRIDINYL AND PYRAZOLYLPHENYL KETONES

Abstract: Compounds of Formula (I), and their N-oxides and agriculturally suitable salts, are disclosed which are useful for controlling undesired vegetation wherein Q is Q-1, Q-2, Q-3 or Q-4; and A, W, R<1>, R<3>-R<11>, and m are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula (I) and a method for controlling undesired vegetation which involves contacting the vegetation or its environment with an effective amount of a compound of Formula (I).

Description: TITLE HERBICIDAL PYRIDINYL, AND PYRAZOLYLPHENYL KETONES BACKGROUND OF THE INVENTION This invention relates to certain phenyl ketones, their JV-oxides, agriculturally suitable salts and compositions, and methods of their use for controlling undesirable vegetation. The control of undesired vegetation is extremely important in achieving high crop efficiency. Achievement of selective control of the growth of weeds especially in such useful crops as rice, soybean, sugar beet, corn (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 which are more effective, less costly, less toxic, environmentally safer or have different modes of action. WO 96/26200 discloses pyrazoles of Formula i as herbicides: wherein, inter alia Q represents a cyclohexane- 1,3-dione ring; L and M are hydrogen, C r C 6 alkyl, Cι-C 4 alkoxy, halogen or nitro; and Z represents a five to six-membered heterocyclic saturated or unsaturated group. The phenyl ketones of the present invention are not disclosed in this publication. SUMMARY OF THE INVENTION This invention is directed to compounds of Formula I including all geometric and stereoisomers, TV-oxides, and agriculturally suitable salts thereof, agricultural compositions containing them and their use for controlling undesirable vegetation: wherein Q is Q-l 0-2 Q-3 Q-4 A is a five- to ten-membered monocyclic or fused bicyclic ring system, which may be fully aromatic or partially saturated, containing 1 to 4 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 2 oxygens and no more than 2 sulfurs, and each ring system is optionally substituted with one to three R 2 , provided that when a nitrogen atom of a heterocyclic ring is substituted with R 2 , then R 2 is other than halogen; each R 1 is independently H, Cι-C 6 alkyl, C r C 6 haloalkyl, C r C 6 alkoxy, C r C 6 haloalkoxy, halogen, cyano, nitro, -(Y) r S(O) n R 15 or -(Y) t -C(O)R 15 ; W is N or CH; Y is O or NR 12 ; R 2 is C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C r C 6 alkoxy, C C 6 haloalkoxy, C 3 -C 6 alkenyloxy, C^-C^ alkynyloxy, mercapto, C j -C 6 alkylthio, C j -C 3 haloalkylthio, C 3 -C 6 alkenylthio, C 3 -C 6 haloalkenylthio, C 3 -C 6 alkynylthio, C 2 -C 5 alkoxyalkylthio, C 3 -C 5 acetylalkylthio, C 3 -C 6 alkoxycarbonylalkylthio, C2-C 4 cyanoalkylthio, C j -Cg alkylsulfinyl, Cj-C 6 haloalkylsulfinyl, C r C 6 alkylsulfonyl, C r C 6 haloalkylsulfonyl, aminosulfonyl, C 1 -C2 alkylaminosulfonyl, C2-C 4 dialkylaminosulfonyl, (CH 2 ) r R 16 , NR 12 R 13 , halogen, cyano or nitro; or R 2 is phenyl or benzylthio, each optionally substituted on the phenyl ring with C ] -C 3 alkyl, C r C 3 haloalkyl, Cι-C 3 alkoxy, C j -C 3 haloalkoxy, 1-2 halogen, cyano or nitro; R 3 is OR 14 , SH, C C 6 alkylthio, C,-C 6 haloalkylthio, C r C 6 alkylsulfinyl, C r C 6 haloalkylsulfinyl, C j -Cg alkylsulfonyl, C j -C 6 haloalkylsulfonyl, halogen or NR 12 R 13 ; or R 3 is phenylthio, phenylsulfonyl or -SCH 2 C(O)Ph, each optionally substituted with C ] -C 3 alkyl, halogen, cyano or nitro; each R 4 is independently C r C 3 alkyl, C j -C 3 alkoxy, C j -C 3 alkylthio or halogen; or when two R 4 are attached to the same carbon atom, then said R 4 pair can be taken together to form -OCH 2 CH 2 O-, -OCH 2 CH 2 CH 2 O-, -SCH 2 CH 2 S- or -SCH 2 CH 2 CH 2 S-, each group optionally substituted with 1-4 CH 3 ; R 5 is OR 14 , SH, C r C 6 alkylthio, C r C 6 haloalkylthio, C r C 6 alkylsulfinyl, C,-C 6 haloalkylsulfinyl, C r C 6 alkylsulfonyl, C j -C 6 haloalkylsulfonyl, halogen or NR 12 R 13 ; or R 5 is phenylthio, phenylsulfonyl or -SCH 2 C(O)Ph, each optionally substituted with Cι-C 3 alkyl, halogen, cyano or nitro; R 6 is H, C,-C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or -CH 2 CH 2 OR 12 ; or R 6 is phenyl or benzyl, each optionally substituted on the phenyl ring with Cj-C 3 alkyl, halogen, cyano or nitro; R 7 is H, C ] -C 6 alkyl, Cι-C 6 haloalkyl, C r C 6 alkoxy, C r C 6 haloalkoxy, halogen, cyano or nitro; R8 is H, C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl; R 9 is H, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 haloalkoxy carbonyl, CO 2 H or cyano; R 10 is C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 cycloalkyl optionally substituted with 1-4 C r C 3 alkyl or C 3 -C 6 halocycloalkyl; R 1 ! is cyano, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylcarbonyl, S(O) n R 13 or C(O)NR 12 R 13 ; each R 12 is independently H or C r C 6 alkyl; R 13 is C r C 6 alkyl or C r C 6 alkoxy; or R 12 and R 13 can be taken together as -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 CH 2 - or -CH 2 CH 2 OCH 2 CH 2 -; R 14 is H, C,-C 6 alkyl, C C 6 haloalkyl, C 2 -C 6 alkoxyalkyl, formyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C(O)NR 12 R 13 , C,-C 6 alkylsulfonyl or C j -C^ haloalkylsulfonyl; or R 14 is phenyl, benzyl, benzoyl, -CH 2 C(O)phenyl or phenylsulfonyl, each optionally substituted on the phenyl ring with C1-C3 alkyl, halogen, cyano or nitro; R 15 is NR 12 R 13 , C r C 6 alkoxy, C,-C 6 haloalkoxy, C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C£ alkenyl, C 3 -C6 haloalkenyl, C3-C6 alkynyl, C 3 -C 6 haloalkynyl or 3 -C<5 cycloalkyl; or R 15 is phenyl optionally substituted with C ] -C 3 alkyl, C j -C 3 haloalkyl, Cι-C 3 alkoxy, C C 3 haloalkoxy, 1-2 halogen, cyano or nitro; R 16 is C r C 3 alkoxy, C 2 -C alkoxycarbonyl, C r C 3 alkylthio, C j -C 3 alkylsulfinyl or C r C 3 alkylsulfonyl; or R 16 is phenyl optionally substituted with C r C 3 alkyl, Cj-C 3 haloalkyl, C1-C3 alkoxy, C r C 3 haloalkoxy, 1-2 halogen, cyano or nitro; m is O, 1, 2 or 3; n is 0, 1 or 2; p is O, 1, 2, 3 or 4; r is 1, 2 or 3; and t is 0 or 1 ; provided that when W is CH and A is in the meta position with respect to the group Q-C(O)- of Formula I, then m is 3 and R 1 is other than H. 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, H-propyl, -propyl, or the different butyl, pentyl or hexyl isomers. The term "1-2 alkyl" indicates that one or two of the available positions for that substituent may be alkyl. "Alkenyl" includes straight-chain or branched alkenes such as 1-propenyl, 2-proρenyl, 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 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 CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 . "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 CH 3 S(O), CH 3 CH 2 S(O), CH 3 CH 2 CH 2 S(O), (CH 3 ) 2 CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH 3 S(O) 2 , CH 3 CH 2 S(O) 2 , CH 3 CH 2 CH 2 S(O) 2 , (CH 3 ) 2 CHS(O) 2 and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. "Alkylamino", "dialkylamino", and the like, are defined analogously to the above examples. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 . The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkenyl" include (C1) 2 C=CHCH 2 and CF 3 CH 2 CH=CHCH 2 . Examples of "haloalkynyl" include HC≡CCHCl, CF 3 G≡C, CC1 3 C=C and FCH 2 C≡CCH 2 . Examples of "haloalkoxy" include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O. Examples of "haloalkylthio" include CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S. Examples of "haloalkylsulfonyl" include CF 3 S(O) 2 , CCl 3 S(O) 2 , CF 3 CH 2 S(O) 2 and CF 3 CF 2 S(O) 2 . The total number of carbon atoms in a substituent group is indicated by the "C j -Cj" prefix where i and j are numbers from 1 to 6. For example, C ] -C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C alkoxyalkyl designates CH 3 OCH 2 ; C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2 ; and C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 . Examples of "alkylcarbonyl" include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 . Examples of "alkoxycarbonyl" include CH 3 OC(=O), CH 3 CH 2 OC(=O), CH 3 CH 2 CH 2 OC(=O), (CH 3 ) 2 CHOC(=O) and the different butoxy- or pentoxycarbonyl isomers. In the above recitations, when a compound of Formula I is comprised of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen. When a group contains a substituent which can be hydrogen, for example R 1 or R 14 , then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. 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. Accordingly, the present invention comprises compounds selected from Formula I, /V-oxides and agriculturally suitable salts thereof. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form. Some compounds of this invention can exist as one or more tautomers. One skilled in the art will recognize, for example, that compounds of Formula la (Formula I where Q is Q-1, R 3 is OR 14 , and R 14 is H) can also exist as the tautomers of Formulae lb and Ic as shown below. One skilled in the art will recognize that said tautomers often exist in equilibrium with each other. As these tautomers interconvert under environmental and physiological conditions, they provide the same useful biological effects. The present invention includes mixtures of such tautomers as well as the individual tautomers of compounds of Formula I. Ib Ic The salts of the compounds of the invention 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. The salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or enol. Preferred salts include the lithium, sodium, potassium, triethylammonium, and quaternary ammonium salts of the compounds of the invention. Preferred compounds for reasons of better activity and/or ease of synthesis are: Preferred 1. Compounds of Formula I, and N-oxides and agriculturally-suitable salts thereof, wherein: A is selected from the group lH-pyrrolyl; furanyl; thienyl; lH-pyrazolyl; lH-imidazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; lH-l,2,3-triazolyl; 2H-l,2,3-triazolyl; lH-l,2,4-triazolyl; 4H-l,2,4-triazolyl; 1,2,3-oxadiazolyl; 1,2,4-oxadiazolyl; 1,2,5-oxadiazolyl; 1,3,4-oxadiazolyl; 1,2,3-thiadiazolyl; 1,2,4-thiadiazolyl; 1,2,5-thiadiazolyl; 1,3,4-thiadiazolyl; lH-tetrazolyl; 2H-tetrazolyl; pyridinyl; pyridazinyl; pyrimidinyl; pyrazinyl; 1,3,5-triazinyl; 1,2,4-triazinyl; and A may optionally be substituted by one to three R 2 , provided that when a nitrogen atom of a heterocyclic ring is substituted with R 2 , then R 2 is other than halogen; Preferred 2. Compounds of Preferred 1 wherein: Q is Q-1. Preferred 3. Compounds of Preferred 2 wherein: each R 1 is independently C ] -C 3 alkyl, C j -C 3 alkoxy, halogen or nitro; R3 is OR 14 ; and R 14 is Η or C j -C alkylsulfonyl; or R 14 is benzoyl or phenylsulfonyl, each optionally substituted with C C 3 alkyl, halogen, cyano or nitro. Preferred 4. Compounds of Preferred 3 wherein: A is pyridinyl, pyridazinyl, pyrimidinyl or lH-pyrazolyl; R 2 is -(Y) t -S(O) n R 15 , CF 3 , OCF 3 , OCF 2 Η or cyano; R15 is C r C 6 alkyl; t is 0; and n is 2. Preferred 5. Compounds of Preferred 1 wherein: Q is Q-2; Preferred 6. Compounds of Preferred 5 wherein: each R 1 is independently Cj-C 3 alkyl, C r C 3 alkoxy, halogen or nitro; R5 is OR 14 ; R 14 is H or C|-C 4 alkylsulfonyl; or R 14 is benzoyl or phenylsulfonyl, each optionally substituted with C r C 3 alkyl, halogen, cyano or nitro. R 6 is H, C r C 6 alkyl, or C 3 -C 6 alkenyl; and R7 is H; Preferred 7. Compounds of Preferred 6 wherein: A is pyridinyl, pyridazinyl, pyrimidinyl or lH-pyrazolyl; R 2 is -(Y) t -S(O) n R 15 , CF 3 , OCF 3 , OCF 2 Η or cyano; Rl5 is C r C 6 alkyl; t is 0; and n is 2. Preferred 8. Compounds of Preferred 1 wherein: Q is Q-3. Preferred 9. Compounds of Preferred 8 wherein: each R 1 is independently C j -C 3 alkyl, C j -C 3 alkoxy, halogen or nitro; R 8 is H, C.-C 3 alkyl, or cyclopropyl; and R 9 is H or C 2 -C 3 alkoxycarbonyl. Preferred 10. Compounds of Preferred 9 wherein: A is pyridinyl, pyridazinyl, pyrimidinyl or lH-pyrazolyl; R 2 is -(Y),-S(O) n R 15 , CF 3 , OCF 3 , OCF 2 Η or cyano; R15 is C,-C 6 alkyl; t is 0; and n is 2. Preferred 11. Compounds of Preferred 1 wherein: Q is Q-4. Preferred 12. Compounds of Preferred 11 wherein: each R 1 is independently C r C 3 alkyl, C C 3 alkoxy, halogen or nitro; R 10 is CyCf, cycloalkyl or C 3 -C6 halocycloalkyl, each optionally substituted with 1-4 C j -C 3 alkyl; and R 1 * is cyano or C 2 -Cg alkoxycarbonyl. Preferred 13. Compounds of Preferred 12 wherein: A is pyridinyl, pyridazinyl, pyrimidinyl or lH-pyrazolyl; R 2 is -(Y) r S(O) n R 15 , CF 3 , OCF 3 , OCF 2 Η or cyano; R'5 is C r C 6 alkyl; t is 0; and n is 2. Most preferred are compounds of Formula la above, and sodium, potassium, and quaternary ammonium salts thereof, selected from the group: a) 3-hydroxy-2-[[6-(trifluoromethyl)[2,4'-bipyridin]-3-yl]carbonyl]-2- cyclohexen-1-one; b) 2-[2-chloro-4-(4-pyridinyl)benzoyl]-3-hydroxy-2-cyclohexen- 1 -one; and c) 2-[2,5-dimethyl-3-( 1 -methyl- lH-pyrazol-3-yl)-4-(methylsulfonyl)benzoyl]- 3-hydroxy-2-cyclohexen-l-one. This invention also relates to herbicidal compositions comprising herbicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent. The preferred compositions of the present invention are those which comprise the above preferred compounds. 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). The preferred methods of use are those involving the above preferred compounds. DETAILS OF THE INVENTION The compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-22. The definitions of W, Y, A, R ! -R 16 , m, n, p, r, and t in the compounds of Formulae 1-22 below are as defined above in the Summary of the Invention. Compounds of Formulae Ia-Ig are various subsets of the compounds of Formula I, and all substituents for Formulae Ia-Ig are as defined above for Formula I. Compounds of General Formula Id can be readily prepared by one skilled in the art by using the reactions and techniques described in Schemes 1-14 of this section as well as by following the specific procedures given in Example 1. Id Scheme 1 illustrates the preparation of compounds of Formula Id (R 3 is OR 17 and R 17 is the same as R 14 as described in the Summary of the Invention excluding H) whereby a compound of Formula Id (R 3 is OH) is reacted with a reagent of Formula 1 in the presence of a base wherein X 1 is chlorine, bromine, fluorine, trifluorosulfonyloxy (OTf) or acetyloxy (OAc) and R 17 is as previously defined. The coupling is carried out by methods known in the art (or by slight modification of these methods): for example, see K. Nakamura, et al., WO 95/04054. Scheme 1 Id (R 3 is OH) + Rl7χl Id (R 3 is OR I 7 ) Base wherein R' 7 is the same as R' as described in the Summary of the Invention excluding H; X 1 is chlorine, bromine, fluorine, trifluorosulfonyloxy (OTf) or acetyloxy (OAc) Scheme 2 illustrates the preparation of compounds of Formula Id (R 3 is SO n R 18 ; n is 1 or 2; and R 18 is Cj-Cg alkyl or C]-C 6 haloalkyl) whereby a compound of Formula Id (R 3 is SR 18 ) is reacted with an oxidizing reagent such as peroxyacetic acid, m-chloroperoxybenzoic acid, potassium peroxymonosulfate (e.g., Oxone®, available from Aldrich Chemical Company), or hydrogen peroxide (the reaction may be buffered with a base such as sodium acetate or sodium carbonate). The oxidation is carried out by methods known in the art (or by slight modification of these methods): for example, see B. M. Trost, et al., J. Org. Chem. (1988), 53, 532; B. M. Trost, et al., Tetrahedron Lett. (1981), 21, 1287; S. Patai, et al., The Chemistry of Sulphones and Sulphoxides, John Wiley & Sons, Protecting and deprotecting functional groups not compatible with the reaction condition may be necessary for compounds with such a functional group (for procedures, see T. W. Greene, et al., Protective Groups in Organic Synthesis, Second Edition, John Wiley & Sons, Inc.). Scheme 2 Id (R 3 is SR 1 8 ) * • Id (R 3 is S(0) n R 1 ; n is 1 or 2) oxidizing agent wherein R^ is C1-C6 alkyl or C\-C(, haloalkyl Compounds of Formula Id (R 3 is Nu; Nu is SR 18 or OR 19 ; R 18 is as defined previously ; R 19 is C r C 6 alkyl, haloalkyl or C 2 -C 6 alkoxyalkyl) can be prepared by one skilled in the art from a compound of Formula Id (R 3 is halogen) by treatment with a nucleophile of Formula 2 (Nu is SR 18 or OR 19 ; M i s Na, K or Li) as shown in Scheme 3 using methods well documented in the literature (or slight modification of these methods): for example, see S. Miyano, et al., Chem. Soc, Perkin Trans. 1 (1976), 1 146. Scheme 3 Id (R 3 is halogen) + MNu >■ Id (R 3 is SR 18 or OR 19 ) 2 wherein Nu is SR 18 or OR 19 ; M is Na, K or Li; and R 19 is Cj-C6 alkyl, Cj-Cό haloalkyl or C -C6 alkoxyalkyl Compounds of Formula Id (R 3 is halogen) can be prepared by reacting a compound of Formula Id (R 3 is OH) with a halogenating reagent such as oxalyl bromide or oxalyl chloride (Scheme 4). This conversion is carried out by methods known in the art (or by slight modification of these methods): for example see S. Muller, et al., WO 94/13619; S. Muller, et al., DE 4,241,999. Scheme 4 Id (R 3 is OH) > ■ Id (R 3 is halogen) Halogenating reagent (e.g., oxalyl bromide, oxalyl chloride) Scheme 5 illustrates the preparation of compounds of Formula Id (R 3 is OH), whereby an enol ester of Formula 3 is reacted with a base such as triethylamine in the presence of a catalytic amount of cyanide source (e.g., acetone cyanohydrin or potassium cyanide). This rearrangement is carried out by methods known in the art (or by slight modification of these methods): for example see W. J. Michaely, EP 369,803. Scheme 5 3 Enol esters of Formula 3 can be prepared by reacting a dione of Formula 4 with an acid chloride of Formula 5 in the presence of a slight mole excess of a base such as triethylamine in an inert organic solvent such as acetonitrile, methylene chloride or toluene at temperatures between 0 °C and 110 °C (Scheme 6). This type of coupling is known in the art: for example, see W. J. Michaely, EP 369,803. Scheme 6 The acid chlorides of Formula 5 can be prepared by one skilled in the art by reacting an acid of Formula 6 with oxalyl chloride (or thionyl chloride) and a catalytic amount of dimethylformamide (Scheme 7). This chlorination is well known in the art: for example, see W. J. Michaely, EP 369,803. Scheme 7 Enol esters of Formula 3a can also be prepared by directly reacting the acid of Formula 6a with N-methyl-2-chloropyridinium iodide, followed by treatment of the formed intermediate with the dione of Formula 4 in the presence of a base such as triethylamine (Scheme 8). This coupling is carried out be methods known in the art (or by slight modification of these methods): for example, see E. Haslam Tetrahedron (1980), 36, 2409-2433. 530 13 Scheme 8 3a Scheme 9 illustrates the preparation of acids of Formula 6 (R 1 is S(O) n R 15 and n is 1 or 2) whereby an acid of Formula 6 (R 1 is SR 15 ) is reacted with an oxidizing reagent such as peroxyacetic acid, w-chloroperoxybenzoic acid, Oxone®, or hydrogen peroxide (the reaction may be buffered with a base such as sodium acetate or sodium carbonate). The oxidation is carried out by methods known in the art (or by slight modification of these methods): for example, see B. M. Trost, et al., J. Org. Chem. (1988), 53, 532; B. M. Trost, et al., Tetrahedron Lett. (1981), 21, 1287; S. Patai, et al., The Chemistry of Sulphones and Sulphoxides, John Wiley & Sons. For some acids of Formula 6 (R 1 is SR 15 ) with a functional group not compatible with the reaction conditions, the functional group may be protected before the oxidation and then be deprotected after the oxidation. The protecting and deprotecting procedures are well known in the literature: for example see T. W. Greene, et al., Protective Groups in Organic Synthesis (Second Edition), John Wiley & Sons, Inc. Scheme 9 oxidizing agent wherein R 1 is S(0) n R 15 and n is 0 wherein R 1 is S(0) n R 15 and n is 1 or 2 Scheme 10 illustrates the preparation of acids of Formula 6 (n is 0 if R 1 is S(O) n R 15 ) whereby a phenyl bromide of Formula 7 (n is 0 if R 1 is S(O) n R 15 ) is treated with n-butyllithium (or magnesium) and the lithium salt (or the Grignard reagent) generated in situ is then reacted with carbon dioxide followed by acidification with an acid such as hydrochloric acid. This conversion is carried out by methods known in the art (or by slight modification of these methods): for example, see M. A. Ogliaruso, et al., Synthesis of Carboxylic Acids, Esters and Their Derivatives, pp 27-28, John Wiley & Sons; A. J. Bridges, et al., J. Org. Chem. (1990), 55, 113; C. Franke, et al., Angew. Chem. Int. Ed. (1969), 8, 68. Protecting and deprotecting functional groups not compatible with the reaction conditions may be necessary for compounds with such a functional group. Scheme 10 wherein W is CH, and if R 1 is S(0) n Rl 5 , then n is 0 Many acids of Formula 6 can also be prepared, as shown in Scheme 1 1 , whereby an ester of Formula 8 is saponified (for example, potassium hydroxide in methanol, then acidification with an acid such as hydrochloric acid), or, alternatively, hydrolyzed in acid (for example, 5/V hydrochloric acid in acetic acid) by methods known in the art (or slight modification of these methods); see for example, M. A. Ogliaruso, et al., Synthesis of Carboxylic Acids, Esters and Their Derivatives, John Wiley & Sons, (1991), pages 5-7. Scheme 11 wherein R " is CH 3 or CH 2 CH 3 530 15 Esters of Formula 8 can be prepared using methods known in the art (or by slight modification of these methods): for example, see A. R. Katritzky, et al., Comprehensive Heterocyclic Chemistry, volumes 2-6, Pergamon Press. Esters of Formula 8a or 8b can also be prepared as shown in Scheme 12, whereby an ester of Formula 9a or 9b is contacted with an appropriate nucleophilic heterocycle Nu 1 and a suitable base in an inert solvent. This reaction can be carried out by a variety of well-known methods, preferably with potassium carbonate or potassium tert-butoxide as the base with N,N-dimethylfoimamide as the solvent and at a reaction temperature range of from approximately 0 to 100 °C. Scheme 12 wherein X 3 is Cl, F or CF 3 S0 0, wherein A l is 1 /-imidazole, l/Z-pyrazole, l -l,2,4-tπazole or 4/7-1,2,4-tπazole Nu ' is an imidazole, pyrazole or tπazole Esters of Formula 9a and 9b are commercially available or can be prepared using methods known in the art (or by slight modification of these methods). Scheme 13 illustrates the preparation of acids of Formula 6a whereby an aryl bromide of Formula 9c is treated with an aryl tin reagent in the presence of a palladium catalyst. This conversion is carried out by methods known in the art (or by slight modification of these methods): for example, see M. Fujta, et al., Tetrahedron Letters, (1995), 29, 5247-5250; Y. Yamamoto, et al., Heterocycles, (1996), 42, 189-194. Saponification of the ester with a base such as sodium hydroxide provides the acids of Formula 6a. Scheme 13 9c 6a Bromides of Formula 9c are either commercially available or can easily be prepared by methods known in the art (or by slight modification of these methods): for example, see T. Bryson, et al., J. Org. Chem., (1976), 41, 2066; Andrea, T. A. and Liang, P. H., U.S. 5,393,734. Aryl and heteroaryl organotin compounds can be prepared by methods known in the art (or by slight modification of these methods): for example, see D. Peters, et al., J. Heterocyclic Chem., (1990), 27, 2165. Bromides of Formula 7 (n is 0 if Rl is S(O) n R 15 ) can be prepared by one skilled in the art by using methods known in the art (or by slight modification of these methods): for example, see A. R. Katritzky, et al., Comprehensive Heterocyclic Chemistry, Volume 2-6, Pergamon Press; B. M. Lynch, et al., Tel. Lett. (1964), p. 617; M. A. ahn, et al., Rev. Latinoam. Quim. (1972), 3, p. 1 19; M. Kosugi, et al., Bull. Chem. Soc. Jpn. (1986), 59 (2), p. 677. Alternatively some of the bromides of Formula 7 (n is 0 if R 1 is S(O) n Rl 5 ) can also be prepared by bromination of the corresponding substituted benzenes of Formula 8 (n is 0 if Rl is S(O) n R l5 ) with the bromine or other equivalent reagent in an inert organic solvent as shown in Scheme 14. This bromination is carried out by general methods known in the art; see, for example, E. Campaigne, et al., J. Heterocycl. Chem. (1969), 6, p. 517; H. Gilman, J. Am. Chem. Soc. (1955), 77, p. 6059; Scheme 14 Br 2 or other equivalent brominating reagent The compounds of Formula 8 (n is 0 if R 1 is S(O) n R 15 ) can be prepared by one skilled in the art by using methods known in the art (or by slight modification of these methods): for example, see A. R. Katritzky, et. al., Comprehensive Heterocyclic Chemistry, Volume 2-6, Pergamon Press; B. M. Lynch, et al., Tet. Lett. (1964), p. 617; 530 17 M. A. Kahn, et al., Rev. Latinoam. Quim. (1972), 3, p. 119; M. Kosugi, et al., Bull. Chem. Soc. Jpn. (1986), 59, (2), p. 677. Compounds of General Formula le can be readily prepared by one skilled in the art by using the reactions and techniques described in Schemes 15-17 of this section. le Scheme 15 illustrates the preparation of compounds of Formula le (R 14 is R 14a and R ϊ4a is the same as R l as described in the Summary of the Invention excluding H) whereby a compound of Formula le ( R' 4 is H) is reacted with a reagent of Formula 9 in the presence of a base wherein X 2 is chlorine, bromine, fluorine, OTf or OAc and R , 4a is as previously defined. This coupling is carried out by methods known in the art (or by slight modification of these methods): for example, see K. Nakamura, et al., WO 95/04054. Scheme 15 le (Rl 4 is H) + R 14 ^ 2 — » ► le (R M is R' 4a ) 9 Scheme 16 illustrates the preparation of compounds of Formula le (R 14 is H). whereby an ester of Formula 10 is reacted with a base such as triethylamine in the presence of a catalytic amount of cyanide source (e.g., acetone cyanohydrin or potassium cyanide). This rearrangement is carried out by methods known in the art (or by slight modification of these methods): for example, see W. J. Michaely, EP 369,803. Scheme 16 or potassium cyanide) 10 Esters of Formula 10 can be prepared by reacting a hydroxypyrazole of Formula 11 with an acid chloride of Formula 5 in the presence of a slight mole excess of a base such as triethylamine in an inert organic solvent such as acetonitrile, methylene chloride or toluene at temperatures between 0 °C and 110 °C (Scheme 17). This type of coupling is carried out by methods known in the art (or by slight modification of these methods): for example, see W. J. Michaely, EP 369,803. Scheme 17 1 1 Compounds of General Formula If can be readily prepared by one skilled in the art by using the reactions and techniques described in Schemes 18-21 of this section. If Scheme 18 illustrates the preparation of compounds of Formula If whereby a compound of Formula 12 is reacted with a salt of hydroxylamine such as hydroxylamine hydrochloride in the presence of a base or acid acceptor such as triethylamine or sodium acetate. The substituents of the immediate products may be further modified if appropriate. This cyclization is carried out by methods known in the art (or by slight modification of these methods): for example, see P. A. Cain, et al., EP 560,483; C. J. Pearson, et al., EP 636,622. 530 19 Scheme 18 12 wherein L is a leaving group such as C ] -C 4 alkoxy (e.g. OC 2 H5) or V-dialkylamino (e.g. dimethyl amino) R 9 a is R 9 or CONH 2 Scheme 19 illustrates the preparation of compounds of Formula 12 whereby a compound of Formula 13 is reacted with a reagent of Formula 14 or Formula 15. This conversion is carried out by methods known in the art (or by slight modification of these methods): for example, see P. A. Cain, et al., EP 560,483; C. J. Pearson, et al., EP 636,622. Scheme 19 Scheme 20 illustrates the preparation of compounds of Formula 13 whereby a ester of Formula 16 is decarboxylated in the presence of a catalyst, such as -toluenesulfonic acid, in an inert solvent such as toluene. This conversion is carried out by methods known in the art (or by slight modification of these methods): for example, see P. A. Cain, et al., EP 560,483; C. J. Pearson, et al., EP 636,622. Scheme 20 16 Esters of Formula 16 can be prepared by reacting the metal salt of a compound of Formula 17 with an acid chloride of Formula 5 (Scheme 21). This type of coupling is known in the art: for example see P. A. Cain, et al., EP 560,483; C. J. Pearson, et al., EP 636,622. Scheme 21 17 Scheme 22 illustrates the preparation of compounds of Formula Ig whereby a compound of Formula 5 is reacted with a compound of Formula 18 in the presence of a base such as triethylamine, potassium carbonate, sodium hydride or Mg(OEt) 2 in an inert organic solvent such as diethyl ether, tetrahydrofuran, NN-dimethylformamide, dichloromethane or acetonitrile. Ig This conversion is carried out by methods known in the art (or slight modification of these methods); for example, see J. W. Ashmore, EP 213,892 and P. A. Cain, EP 496,631 Al. Scheme 22 It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group intercon versions 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 I. 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 sequence presented to prepare the compounds of Formula I. One skilled in the art will also recognize that compounds of Formula I 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. 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. •H NMR spectra are reported in ppm downfield from tetramethylsilane; s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd = doublet of doublets, dt = doublet of triplets, br s = broad singlet. EXAMPLE 1 Step A: Preparation of 3-r(2,5-dimethylphenyl)thiolpropanoic acid 43.4 g (1.086 mol) of sodium hydroxide was added to 230 mL of water, 75.0 g (0.543 mol) of 2,5-dimethylthiophenol (purchased from Aldrich Chemical Company) was then added and the mixture was cooled to about 10 C. 91.30 g (0.597 mol) of 3- bromopropionic acid (purchased from Aldrich Chemical Company) was added in portions keeping the temperature below 25 °C. The mixture was warmed to room temperature, stirred for 2 hr under nitrogen, and was then washed with diethyl ether (3 x 500 mL). The aqueous layer was acidified with IN HCl and filtered to yield 112.79 g of the title compound of step A as a solid, m.p. 97-98 °C. IH NMR (CDCI3): 52.3 (s, 3H), 2.34 (s, 3H), 2.68 (t, 2H), 3.1 (t, 2H), 6.9 (d, IH), 7.06-7.14 (2H). Step B: Preparation of 2,3-dihvdro-5,8-dimethyl-4H-l -benzopyran-4-one 530 mL of concentrated sulfuric acid was added to 24.91 g (0.1 19 mol) of the title compound of step A while being cooled with an acetone/ice bath. The ice bath was removed, the mixture was stirred for 1 hr and was then poured over crushed ice. The aqueous phase was extracted with a mixture of diethyl ether : hexane (1:9, 6 x 500 mL), dried (MgSO4), filtered, and evaporated to dryness to yield 11.75 g of the title compound of step B as an oil. IH NMR (CDCI3): δ 2.3 (s, 3H), 2.6 (s, 3H), 2.97 (m, 2H), 3.2 (m, 2H), 6.9-7.1 (2H). Step C: Preparation of 6-bromo-2,3-dihvdro-5,8-dimethyl-4H- 1 -benzothiopyran- 4-one A solution of 4.07 g (0.021 mol) of the title compound of step B in 25 mL of methylene chloride was added dropwise to a mixture of 7.07 g (0.053 mol) of aluminum chloride (purchased from Aldrich Chemical Company) in 25 mL of methylene chloride. The suspension was stirred for approximately 15 minutes, 1.14 mL (0.022 mol) of bromine (purchased from Janssen) was added dropwise, and the mixture was then refluxed for 10 minutes. The warm mixture was poured into 10 mL of concentrated hydrochloric acid containing 75 g of ice, stirred for 10 minutes, diluted with 50 mL of water, and extracted with diethyl ether (2 x 200 mL). The combined organic layers were washed with water (2 x 200 mL), dried (Na2SO4), filtered, and evaporated to dryness. The crude product was chromatographed over silica gel eluting with a mixture of ethyl acetate : hexane (5:95) to yield 2.62 g of the title compound of step C as a solid, m.p. 87-88 °C. lΗ NMR (CDCI3): δ 2.3 (s, 3Η), 2.6 (s, 3H), 3.0 (m, 2H), 3.2 (m, 2H), 7.45 (s, IH). Step D: Preparation of 6-bromo-5,8-dimethyl-4H- 1 -benzothiopyran-4-one 30 g (0.11 mol) of the title compound of step C and 8.95 mL (0.1 1 mol) of pyridine were added to 250 mL of methylene chloride. The solution was cooled to about 0 °C and 14.76 g (0.11 mol) of N-chlorosuccinimide was added. The mixture was stirred overnight under nitrogen while warming to room temperature and then refluxed for 12 h. The reaction was evaporated to dryness, the residue was stirred in diethyl ether, and filtered. The filtrate was dried (MgSO4), filtered, and evaporated to dryness to yield 13.25 g of the title compound of step D as a solid, m.p. 123-124 °C. 1H NMR (CDCI3): δ 2.5 (s, 3Η), 2.9 (s, 3H), 7.0 (d, IH), 7.7 (m, 2H). Step E: Preparation of 3-[3-bromo-2,5-dimethyl-6-(methylthio)phenvn- 1-methyl- lH-pyrazole 13.25 g (0.049 mol) of the title compound of step D and 2.88 mL (0.054 mol) of methylhydrazine (purchased from Aldrich Chemical Company) was added to 150 mL of absolute ethanol. After stirring at reflux under nitrogen for 5 hr the mixture was allowed to warm to room temperature and stir for 2.5 days. The mixture was refluxed for 3 hr after which time 0.5 mL of acetic acid was added and the reaction was refluxed overnight. After cooling to room temperature, 12.35 mL (0.054 mol) of sodium methoxide (25% in methanol) and 3.66 mL (0.059 mol) of iodomethane were added and the reaction stirred for 2 hr. The mixture was evaporated to dryness. The residue was stirred in water, extracted with methylene chloride (250 mL), dried (MgSO4), filtered, and evaporated to dryness. The crude product was chromatographed over silica gel eluting with methylene chloride to yield 5.97 g of the title compound of step E as an oil. 1H NMR (CDCI3): δ 2.0 (s, 3H), 2.1 (s, 3H), 2.5 (s, 3H), 3.6 (s, 3H), 6.2 (s, IH), 7.6 (m, 2H). Step F: Preparation of 2,5-dimethyl-3-(l -methyl- lH-pyrazol-3-yl)-4- (methylthio)benzoic acid 5.9 g (0.019 mol) of the title compound of step E was added to 100 mL of tetrahydrofuran and cooled to -70 °C. 9.1 mL (0.023 mol) of 2.5M Η-butyllithium (purchased from Aldrich Chemical Company) was added dropwise keeping the temperature below -65 C. Solid carbon dioxide was added in one portion and the mixture warmed to room temperature. 200 mL of hexane was added and the mixture was filtered. The solid collected was added to water and acidified to about pΗ 1 with concentrated hydrochloric acid. The aqueous was extracted with methylene chloride (3 x 100 mL), dried (MgSO4), filtered, and evaporated to dryness to yield 3.13 g of the title compound of step F as a semi-solid. ! Η NMR (CDCI3): δ 2.1 (s, 3Η), 2.3 (s, 3H), 2.6 (s, 3H), 3.6 (s, 3H), 6.2 (m, IH), 7.6 (d, lH), 7.97 (s, lH). Step G: Preparation of 2,5-dimethyl-3-(l -methyl- lH-pyrazol-3-yl)-4- (methylsulfonyl)benzoic acid 4.5 mL (0.046 mol) of hydrogen peroxide (35%) was added to 25 mL of trifluoroacetic acid. The mixture was allowed to stir for 30 min under nitrogen and was then cooled to 0 C. A solution of 3.1 g (0.011 mol) of the title compound of step F in 25 mL of trifluoroacetic acid was added dropwise keeping the temperature below 10 °C. The mixture was warmed to room temperature and stirred for 3 days. 2 mL of dimethylsulfide was added and the reaction stirred for 30 min. The mixture was then evaporated to dryness, and the residue was triturated with water and filtered. The collected solid was dissolved in methylene chloride, dried (MgSO4), filtered, and evaporated to dryness to yield 1.41 g of the title compound of step G as a solid, m.p. 60t°C (dec). lΗ NMR (CDCI3): δ 2.2 (s, 3Η), 2.8 (s, 3H), 3.0 (s, 3H), 3.7 (s, 3H), 6.2 (m, lH), 7.7 (m, lH), 8.0 (s, IH). Step H: Preparation of 3-oxo-l-cylcohexen-l-yl 2,5-dimethyl-3-(l-methyl-lH- pyrazol-3-yl)-4-(methylsulfonyl)benzoate 1.39 g (0.0045 mol) of the title compound of step G, 1.18 mL (0.0135 mol) of oxalyl chloride (purchased from Janssen), and 2 drops of N,N-dimethylformamide were added to 50 mL of methylene chloride. The mixture was refluxed under nitrogen for 2.5 hr and was then evaporated to dryness. 50 mL of methylene chloride was added to the residue and the solution was again evaporated to dryness. Another 50 mL of methylene chloride was added to the residue, and the solution was cooled to about 0 °C. 0.56 g (0.0049 mol) of 1,3-cyclohexanedione (purchased from Aldrich Chemical Company) was added followed by 1.94 mL (0.0139 mol) of triethylamine, and the mixture was stirred overnight while warming to room temperature. The mixture was evaporated to dryness and the crude product was chromatographed over silica gel eluting with a mixture of ethyl acetate:hexane (6:4, then 7:3) to yield 0.47 g of the title compound of step Η as a solid, m.p. 165 - 167 C. 2 Η NMR (CDCI3): 6 2.1 - 2.2 (m, 5Η), 2.5 (m, 2H), 2.7 (m, 2H), 2.8 (s, 3H), 2.98 (s, 3H), 3.6 (s, 3H), 6.0 (s, IH), 6.1 (m, IH), 7.6 (m, IH), 7.9 (s, IH). Step I: Preparation of 2-r2,5-dimethyl-3-(l-methyl-lH-pyrazol-3-yl)-4- (methylsulfonyl)benzoyll-l,3-cvcIohexanedione 0.47 g (0.0012 mol) of the title compound of step Η, 1 drop of acetone cyanohydrin (purchased from Aldrich Chemical Company), and 0.29 mL (0.0020 mol) of triethylamine were added to 25 mL of acetonitrile and allowed to stir overnight at room temperature under nitrogen. The mixture was evaporated to dryness, water was added to the residue, and the solution was acidified to pΗ 1 with concentrated hydrochloric acid. The aqueous was extracted with methylene chloride, dried (MgSO4), filtered, and evaporated to dryness to yield 0.27 g of the title compound of example 1 , a compound of the invention, as a solid, m.p. 93 C (decomposed). lΗ NMR (CDCI3): δ 1.8 (s, 3Η), 2.1 (m, 2H), 2.4 (m, 2H), 2.7 (s, 3H), 2.8 (m, 2H), 2.98 (s, 3H), 3.7 (s, 3H), 6.2 (s, IH), 7.1 (s, IH), 7.6 (s, IH). EXAMPLE 2 Step A: Preparation of 2-r3-(trifluoromethyl)-lH-pyrazol-l-yllbenzoic acid To 100 mL of dimethylformamide was added sequentially 19.3 g (0.125 mol) of methyl 2-fluorobenzoate, 18.7 g (0.138 mol) of 3-(trifluoromethyl)pyrazole (purchased from Maybridge Chemical Company), and 19.0 g (0.138 mol) of potassium carbonate. The suspension was stirred and heated at about 100 °C for 16 hours, then cooled to 25 °C and poured into excess water. The aqueous suspension was extracted three times with 75 mL of diethyl ether and the combined ether layers were dried over magnesium sulfate and concentrated under reduced pressure. The residual oil was chromatographed over silica gel eluting with hexane:ethyl acetate (9.6:0.4, then 100% ethyl acetate) to yield 15.3 g of crude methyl 2-[3-(trifluoromethyl)-lH-pyrazol-l-yl]benzoate as an oil. 14 g (0.052 mol) of this oil was added to a solution of 3.8 g (0.057 mol) of potassium hydroxide (85%) dissolved in 60 mL of methanol. The solution was stirred at 25 °C for one hour, refluxed for 5 hours, stirred at 25 °C for 48 hours, and finally concentrated under reduced pressure. 100 mL of water was added to the residue and the cloudy solution was extracted twice with 40 mL of diethyl ether. The clear aqueous layer was acidified with concentrated ΗC1 and filtered. The collected solid was dissolved in dichloromethane, dried over magnesium sulfate, and the solvent was removed under reduced pressure to yield 5.0 g of the title compound of Step A as a solid melting at 138-144 °C. lΗ NMR (CDC13): δ 6.95 (d, 1Η), 7.65 (m, 2Η), 7.7 (m, IH), 7.85 (m, IH), 8.35 (d, IH), 13.15 (s, IH). Step B: Preparation of 3-oxo- 1 -cyclohexen- 1 -yl 2-r3-(trifluoromethyl)- 1 H- pyrazol- 1 -yllbenzoate To 20 mL of oxalyl chloride was added portionwise 4.0 g of the title compound of Step A. The suspension was refluxed for about 3 hours and then concentrated under reduced pressure. The residue was azeotroped with dichloromethane (two times with 20 mL at 60 °C) to yield an oil which solidified upon cooling and melted at 64-68 °C. 2.0 g (0.0073 mol) of this acid chloride was added to 20 mL of dichloromethane, followed by the addition of 0.99 g (0.0088 mol) of 1,3-cyclohexanedione, and 2.2 g (0.022 mol) of triethylamine. The suspension was stirred overnight and then concentrated under reduced pressure. The residue was dissolved in diethyl ether and the solution was then extracted with water, dried over magnesium sulfate, and concentrated under reduced pressure to yield 2.0 g of the title compound of Step B as an oil. *Η NMR (CDCI3): δ 2.0 (m, 2H), 2.35 (m, 2H), 2.5 (m, 2H), 5.85 (s, IH), 6.75 (d, IH), 7.5 (m, IH), 7.6 (m, IH), 7.7 (m, IH), 7.8 (d, IH), 8.0 (m, IH). Step C: Preparation of 3-hvdroxy-2-r2-f3-(trifluoromethyl)-lH-pyrazol- l- yllbenzovn-2-cvclohexen-l-one To 20 mL of acetonitrile was added sequentially 1.8 g (0.005 mol) of the title compound of Step B, 1.0 g (0.01 mol) of triethylamine, and 8 drops of acetone cyanohydrin. The solution was stirred under a nitrogen atmosphere at 25 °C overnight, and then diluted with 40 mL of water and acidified by the addition of concentrated hydrochloric acid (red to litmus paper). The suspension was filtered, and the collected solid was washed three times with 20 mL of water, suction dried, and then recrystallized from 2-propanol to yield 0.97 g of the title compound of Step C, a compound of this invention, as a solid melting at 141-143 °C. *Η NMR (CDCI3): δ 1.8 (m, 2Η), 2.1 (m, 2H), 2.6 (m, 2H), 6.6 (d, IH), 7.4-7.6 (m, 4H), 7.75 (d, IH), 16.6 (s, IH). EXAMPLE 3 Step A: Preparation of methyl 6-(trifluoromethyl)[2,4'-bipyridinel-3-carboxylate To a stirred solution of 8.49 g (0.03 mol) of methyl 2-bromo-6-(trifluoromethyl)- 3-ρyridine carboxylate (prepared as described by Andrea T. A. and Liang P. H., U.S. Patent 5,393,734) in 25 mL of N,/V-dimethylformamide under a nitrogen atmosphere was added 0.5 g of tetrakis(triphenylphosphine)palladium(0) and the mixture was heated at 100 °C for 30 minutes. 11 g (0.03 mol) of 4-tributylstannylpyridine (prepared by a modification of the procedure described by A. Lee and W. Dai, Tetrahedron Letters (1996), 37, 495-498) was added and heating was continued at 100 °C for 24 hours. The reaction mixture was cooled to room temperature and N,N-dimethylformamide was removed by distillation under high vacuum. The residue was purified by flash chromatography over silica gel utilizing dichloromethane:ethyl acetate (8:2) to provide 4.0 g of the title compound of Step A as a red oil. J H NMR (CDCI3): δ 8.76 (d, 2H), 8.4 (d, IH), 7.8 (d, IH), 7.47 (m, 2H), 3.76 (s, 3H). Step B: Preparation of 6-(trifluoromethvDf2,4'-bipyridinel-3-carboxylic acid To a solution of 1.7 g of the title compound of Step A in 20 mL of methanol was added 2 mL of 50% aqueous sodium hydroxide and the reaction was stirred at room temperature for 24 hours. The mixture was concentrated and acidified with 6Λ aqueous hydrochloric acid to pH 3 and extracted three times with 20 mL of ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure to provide 1.6 g of title compound of Step B as a crude solid. iH NMR (CD 3 ) 2 SO): δ 9.02 (d, 2H), 8.26 (d, IH), 8.22 (m, IH), 8.14 (d, 2H). Step C: Preparation of 3-oxo-l-cvclohexen-l-yl 6-(trifluoromethyl)[2,4'- bipyridinel-3-carboxylate To a suspension of 1.6 g (6 mmol) of the title compound of Step B in 100 mL of dichloromethane was added 0.78 g (7 mmol) of 1,3-cyclohexanedione followed by 2.4 mL (16 mmol) of triethylamine and 1.8 g (7 mmol) of 2-chloro-l-methylpyridinium iodide. The mixture was stirred at room temperature under nitrogen for 24 hours and then applied directly to a silica gel column and purified by flash chromatography using ethyl acetate/dichloromethane (2:8) to afford 1.34 g of the title compound of Step C as a tan solid melting at 49-56 °C. IH NMR (CDCI3): δ 8.78 (d, 2H), 8.6 (d, IH), 7.51 (d, 2H), 5.93 (s, IH), 2.2 (m, 2H), 2.1 (m, 2H), 2.0 (m, 2H). Step D: Preparation of 3-hvdroxy-2-f[6-(trifluoromethyl)f2,4'-bipyridin1-3- yllcarbonvn-2-cvclohexen- 1 -one To a solution of 1.22 g (3.5 mmol) of the title compound of Step C in 25 mL of acetonitrile was added 1.16 mL (8.36 mmol) of triethylamine, followed by 2 drops of acetonecyanohydrin. The mixture was stirred under nitrogen for 18 hours. The mixture was then concentrated under reduced pressure, and the residual oil was acidified with aqueous IN hydrochloric acid and extracted three times with 20 mL of dichloromethane. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure to afford 0.4 g of the title compound of Step D, a compound of this invention, as a white solid melting at 137-145 °C. IH NMR (CDC13): δ 8.66 (m, 2H), 7.79 (m, 2H), 7.45 (m, 2H), 2.8 (m, 2H), 2.0 (m, 2H), 1.8 (m, 2H). By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 20 can be prepared. The following abbreviations are used in the Tables which follow: NO 2 = nitro and Ph = phenyl. The following notations have been used in Tables 1-20: A-51 = (5-methyl-l,2,3-oxadιazol-4-yl)- A-77 = (3-pyπdazmyl)- A-52 = (l,2,3-oxadιazol-4-yl)- A-78 = (4,6-dιmethyl-2-pyrιmιdmyl)- A-53 = (3-methyl- l,2,4-oxadιazol-5-yl)- A-79 = (4-methyl-2-pyπmιdιnyl)- A-54 = (5-methyl-l,2,4-oxadιazol-3-yl)- A-80 = (2-pyπmιdιnyl)- A-55 = (4-methyl-3-furazanyl)- A-81 = (2-methyl-4-pyπmιdιnyl)- A-56 = (3-furazanyl)- A-82 = (2-chloro-4-pyπmιdιnyl)- A-57 = (5-methyl-l,3,4-oxadιazol-2-yl)- A-83 = (2,6-dιmethyl-4-pyπmιdιnyl)- A-58 = (5-methyl-l,2,3-thιadιazol-4-yl)- A-84 = (4-pyπmιdιnyl)- A-59 = (l,2,3-thιadιazol-4-yl)- A-85 = (2-methyl-5-pyπmιdιnyl) A-60 = (3-methyl l ,2,4-thιadιazol-5-yl)- A-86 = (6-methyl-2-pyrazmyl)- A-61 = (5-methyl-l ,2,4-thιadιazol-3-yl)- A-87 = (2-pyrazιnyl)- A-62 = (4-methyl- l ,2,5-thιadιazol-3-yl)- A-88 = (4,6-dιmethyl- I ,3,5-tπazιn-2-yl)- A-63 = (5-methyl- l ,3,4-thιadιazol-2-yl)- A-89 = (4,6-dιchloro- l,3,5-tπazιn-2-yl)- A-64 = (l-methyl-l/7-tetrazol-5-yl)- A-90 = (l ,3,5-tπazιn-2-yl)- A-65 = (l//-tetrazol-5-yl)- A-91 = (4-methyl- 1,3,5-tπazιn- 2-yl)- A-66 = (5-methyl-l /-tetrazol-l-yI)- A-92 = (3-methyl- l ,2,4-tπazιn-5-yl)- A-67 = (2-methyl-2/ -tetrazol-5-yl)- A-93 = (3-methyl- l,2,4-tπazιn-6-yl)- A-68 = (2-ethyl-2/ -tetrazol-5-yl)- A-69 = (5-methyl-2 /-tetrazol-2-yl)- A-70 = (2 -tetrazol-2-yl)- A-71 = (2-pyπdιnyl)- A-72 = (6-methyl-2-pyπdιnyl)- A-73 = (4-pyπdιnyl)- A-74 = (3-pyπdιnyl)- A-75 = (6-methyl-3-pyπdazιnyl)- A-76 = (5-methyl -3-pyπdazιnyl)- 97/46530 30 TABLE 1 O 97/46530 31 TABLE 2 TABLE 3 97/46530 33 R 15 is CT and R 6 is CH 2 CH 3 TABLE 4 TABLE 5 O 97/46530 37 TABLE 6 TABLE 7 a Rib CH, CH 3 Cl CH, Cl O 97/46530 39 O 97/46530 41 CH 3 Cl CH 3 CH, Cl A-24 S0 2 CH 3 Cl Cl A-33 S0 2 CH 3 Cl Cl A-24 S0 2 CH 2 CH 3 Cl CH 3 A-33 S0 2 CH 2 CH 3 Cl CH 3 A-24 S0 2 CH 2 CH 3 Cl Cl A-33 S0 2 CH 2 CH 3 Cl Cl A-24 S0 2 CH 2 CH 2 CH 3 Cl CH 3 A-33 S0 2 CH 2 CH 2 CH 3 Cl CH 3 A-24 S0 2 CH 2 CH 2 CH 3 Cl Cl A-33 S0 2 CH 2 CH 2 CH 3 Cl Cl A-24 S0 2 N(CH 3 ) 2 CH 3 CH 3 A-33 S0 2 N(CH 3 ) 2 CH 3 CH 3 A-24 S0 2 N(CH 3 ) 2 Cl CH 3 A-33 S0 2 N(CH 3 ) 2 Cl CH 3 A-24 S0 2 N(CH 3 ) 2 Cl Cl A-33 S0 2 N(CH 3 ) 2 Cl Cl A-24 S0 2 CF 3 CH 3 CH 3 A-33 S0 2 CF 3 CH 3 CH 3 A-24 S0 2 CF 3 Cl CH 3 A-33 S0 2 CF 3 Cl CH 3 A-24 S0 2 CF 3 Cl Cl A-33 S0 2 CF 3 Cl Cl A-24 S0 2 OCH 2 CF CH CH 3 A-33 S0 2 OCH 2 CF 3 CH 3 CH 3 A-24 S0 2 OCH 2 CF Cl CH 3 A-33 S0 2 OCH 2 CF 3 Cl CH 3 A-24 S0 2 OCH 2 CF 3 Cl Cl A-33 S0 2 OCH 2 CF 3 Cl Cl A-24 CF 3 CH 3 CH 3 A-33 CF 3 CH 3 CH 3 A-24 CF 3 Cl CH 3 A-33 CF 3 Cl CH 3 A-24 CF 3 Cl Cl A-33 CF 3 Cl Cl A-24 OCH 3 CH 3 CH 3 A-33 OCH 3 CH 3 CH 3 A-24 OCH Cl CH 3 A-33 OCH 3 Cl CH 3 A-24 OCH 3 Cl Cl A-33 OCH 3 Cl Cl A-24 N0 2 CH 3 CH 3 A-33 N0 2 CH 3 CH 3 A-24 N0 2 Cl CH 3 A-33 N0 2 Cl CH 3 A-24 N0 2 Cl Cl A-33 N0 2 Cl Cl A-42 S0 2 CH 3 N0 2 CH 3 A-44 S0 2 CH 3 N0 2 CH 3 A-42 S0 2 CH 3 Cl CH 3 A-44 SO,CH 3 Cl CH 3 A-42 S0 2 CH 3 Cl Cl A-44 S0 2 CH 3 Cl Cl A-42 S0 2 CH 2 CH 3 Cl CH 3 A-44 S0 2 CH 2 CH 3 Cl CH 3 A-42 S0 2 CH 2 CH 3 Cl Cl A-44 S0 2 CH 2 CH 3 Cl Cl A-42 S0 2 CH 2 CH 2 CH 3 Cl CH 3 A-44 S0 2 CH 2 CH 2 CH 3 Cl CH 3 A-42 S0 2 CH 2 CH 2 CH 3 Cl Cl A-44 S0 2 CH 2 CH 2 CH 3 Cl Cl A-42 S0 2 N(CH 3 ) 2 CH 3 CH 3 A-44 S0 2 N(CH 3 ) 2 CH 3 CH 3 A-42 S0 2 N(CH 3 ) 2 Cl CH 3 A-44 S0 2 N(CH 3 ) 2 Cl CH 3 A-42 S0 2 N(CH 3 ) 2 Cl Cl A-44 S0 2 N(CH 3 ) 2 Cl Cl A-42 S0 2 CF 3 CH 3 CH 3 A-44 S0 2 CF 3 CH 3 CH 3 A-42 S0 2 CF 3 Cl CH 3 A-44 S0 2 CF 3 Cl CH 3 A-42 S0 2 CF 3 Cl Cl A-44 S0 2 CF 3 Cl Cl A-42 S0 2 OCH 2 CF 3 CH 3 CH 3 A-44 S0 2 OCH 2 CF 3 CH 3 CH 3 A-42 S0 2 OCH 2 CF 3 Cl CH, A-44 S0 2 OCH 2 CF 3 Cl CH, O 97/46530 53 CH 3 CH 3 A-91 CF 3 CH 3 CH 3 Cl CH 3 A-91 CF 3 Cl CH 3 Cl Cl A-91 CF 3 Cl Cl CH 3 CH 3 A-91 OCH 3 CH 3 CH 3 Cl CH 3 A-91 OCH 3 Cl CH 3 Cl Cl A-91 OCH 3 Cl Cl CH 3 CH 3 A-91 N0 2 CH 3 CH 3 Cl CH 3 A-91 N0 2 Cl CH 3 Cl Cl A-91 NO, Cl Cl TABLE 10 O 97/4653 59 TABLE 11 o TABLE 13 la is isN R la is CH,, R lb is CN, and W is N Rla IS Rla is Cl. R lb is Cl. and W is CH Rla is CH . R lb is SO 2 CH ? . and W is N TABLE 14 R ϊa is CH , R b is H, and W is N Rla IS RiaisCl.R lb isCl.andWisN Rl a isCl.R lb isCl.andWisCH Rla IS TABLE 15 Rl jsCl.RlbisCl.andWisN TABLE 16 Rla is isCH Rlais Rla is Cl. R l b is Cl. and W is N Rla is Cl. R lb is Cl. and W is CH TABLE 17 TABLE 18 WisCH WisN TABLE 19 WisCH TABLE 20 W is N Formulation/Utility Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. 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 liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible ("wettable") or water-soluble. 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. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation. 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 5-90 0-94 1-15 Granules, Tablets and Powders. Suspensions, Emulsions, Solutions 5-50 40-95 0-15 (including Emulsifiable Concentrates) Dusts 1-25 70-99 0-5 Granules and Pellets 0.01-99 5-99.99 0-15 High Strength Compositions 90-99 0-10 0-2 Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity. Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, Λ/,/V-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-mefhyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. 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 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; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989. In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Tables A-C. Example A High Strength Concentrate Compound 1 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%. Example B Wettable Powder Compound 15 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%. Example C Granule Compound 25 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%. Example D Extruded Pellet Compound 26 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%. Test results indicate that the compounds of the present invention are highly active preemergent and postemergent herbicides or plant growth regulants. 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. Some of the compounds are useful for the control of selected grass and broadleaf weeds with tolerance to important agronomic crops which include but are 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). 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. 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 0.001 to 20 kg/ha with a preferred range of 0.004 to 1.0 kg/ha. One skilled in the art can easily determine the herbicidally effective amount necessary for the desired level of weed control. Compounds of this invention can be used alone or in combination with other commercial herbicides, insecticides or fungicides. Compounds of this invention can also be used in combination with commercial herbicide safeners such as benoxacor, dichlormid and furilazole to increase safety to certain crops. 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, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, bifenox, bispyribac and its sodium salt, bromacil, bromoxynil, bromoxynil octanoate, butachlor, butralin, butroxydim (ICIA0500), butylate, caloxydim (BAS 620H), carfentrazone-ethyl, chlomethoxyfen, chloramben, chlorbromuron, chloridazon, chlorimuron-ethyl, chlornitrofen, chlorotoluron, chlorpropham, chlorsulfuron, chlorfhal-dimethyl, cinmethylin, cinosulfuron, clethodim, clomazone, clopyralid, clopyralid-olamine, cyanazine, cycloate, cyclosulfamuron, 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, 2-[4,5-dihydro-4-methyl-4-(l-methylethyl)-5-oxo-lH-imidazol-2-yl]-5-methyl-3- pyridinecarboxylic acid (AC 263,222), difenzoquat metilsulfate, diflufenican, dimepiperate, dimefhenamid, dimethylarsinic acid and its sodium salt, dinitramine, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethofumesate, ethoxysulfuron, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, fluazifop-butyl, fluazifop-P-butyl, fluchloralin, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, fluridone, flurochloridone, fluroxypyr, fluthiacet-methyl, fomesafen, fosamine-ammonium, glufosinate, glufosinate-ammonium, glyphosate, glyphosate-isopropylammonium, glyphosate-sesquisodium, glyphosate-trimesium, halosulfuron-methyl, haloxyfop-etotyl, haloxy fop-methyl, hexazinone, imazamethabenz-methyl, imazamox, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, ioxynil, ioxynil octanoate, ioxynil-sodium, isoproturon, isouron, isoxaben, isoxaflutole, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its dimethylammonium, potassium and sodium salts, MCPA-isoctyl, mecoprop, mecoprop-P, mefenacet, mefluidide, metam-sodium, methabenzthiazuron, methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyl [[[l-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2- methoxyethylidene]amino]oxy]acetate (AKH-7088), methyl 5-[[[[(4,6-dimethyl-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]-l-(2-pyridinyl)-lH-pyrazole-4-carboxylate (NC-330), metobenzuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, napropamide, naptalam, neburon, nicosulfuron, norflurazon, oryzalin, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pebulate, pendimethalin, pentoxazone (KPP-314), perfluidone, phenmedipham, picloram, picloram-potassium, pretilachlor, primisulfuron-methyl, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propyzamide, prosulfuron, pyrazolynate, pyrazosulfuron-ethyl, pyridate, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, quinclorac, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, sethoxydim, siduron, simazine, sulcotrione (ICIA0051), sulfentrazone, sulfometuron-methyl, TCA, TCA-sodium, tebuthiuron, terbacil, terbuthylazine, terbutryn, thenylchlor, thiafluamidc (BAY 1 1390), thifensulfuron-methyl, thiobencarb, tralkoxydim, iri-allate, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tridiphane, trifluralin, triflusulfuron-methyl, and vernolate. In certain instances, combinations with other herbicides having a similar spectrum of control but a different mode of action will be particularly advantageous for preventing the development of resistant weeds. Preferred for better control of undesired vegetation (e.g., lower use rate, 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 nicosulfuron, rimsulfuron, nicosulfuron in combination with rimsulfuron, imazethapyr, sethoxydim, glyphosate, and glufosinate. 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-D for compound descriptions. The abbreviation "dec." indicates that the compound appeared to decompose on melting. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared. INDEX TABLE A *See Index Table D for Η NMR data. INDEX TABLE B Cmod R 4a R 4b R3 Rl W m.p. f°α 14 H H N 4-pyridyl oil* 15 (Ex. 3) H H N 4-pyridyl 137-145 19 H H N 4-pyridyl oil* 20 H H N 2-pyridyl 126-131 21 CH 3 CH 3 N 2-pyridyl oil* 22 H H N 3-pyridyl oil* 23 (Ex. 2) H H CH 3-CF3-I 7- 141-143 pyrazol- 1 -yl 24 H H OH CF 3 CH 3-CF3- I//- 123- 126 ρyrazol-1-yl *See Index Table D for l H NMR data. INDEX TABLE C Cmpd No. Structure m.p. (°C) 25 (Ex. 1) 93 (dec.) *See Index Table D for *H NMR data. INDEX TABLE D Cmpd No. J H NMR Data (CDCI 3 solution unless indicated otherwise) 3 1 δ 9.7 (m, 2H), 7.63 (m, 2H), 7.62 (m, IH), 7.6 (s, IH), 7.37 (m, IH), 2.8 (m, 2H), 2.5 ( , 2H), 2.08 (m, 2H). 2 δ 8.65 (d, 2H), 7.6 (d, IH), 7.5 (m, 3H), 7.27 (m, IH), 3.13 (m, 6H), 2.32 (s, 4H), 1.3 (m, 9H), 1.04 (s, 6H). 3 δ 8.8 (m, 2H), 7.84 ( , 2H), 7.69 (m, 2H), 7.38 (d, IH), 2.4 (m, 2H), 1.2 (m, 2H), 1.04 (d, 6H). 4 δ 8.62 (d, 2H), 7.6 (s, IH), 7.5 (m, 3H), 7.28 (d, IH), 3.17 (m, 6H), 2.5 (d, 2H), 2.2 (d, IH), 1.7 (m, IH), 1.31 (m, 9H), 1.03 (d, 3H). 5 δ 8.72 ( , 2H), 7.65 (m, 3H), 7.5 (d. IH), 7.3 (d, IH), 2.6-2.0 (m, 4H), 1.6 (m, IH), 1.13 (d, 6H). 6 δ 7.9 (s, IH), 7.7 (s, IH), 7.5 (d, IH), 7.28 (d, lH), 6.8 (s, IH), 3.18 (m, 6H), 2.42 (m, 4H), 1.98 (m, 2H), 1.29 (m, 9H). 8 δ 8.63 (d, 2H), 7.48 (s, IH), 7.46 (m, 3H), 7.2 (d, IH), 3.15 (m, 6H), 2.43 (m, 4H), 1.98 (m, 2H), 1.29 ( , 9H). 9 δ 8.7 (m, IH), 8.0 (s, !H), 7.8 (d, lH), 7.72 (m, IH), 7.70 (m, I H), 7.26 (m, IH), 3.14 (m, 6H), 2.45 (m, 4H), 1.99 (m, 2H), 1.26 (m, 9H). 10 δ 7.8 (d, I H), 7.77 (s, IH), 7.6 (d, I H), 7.3 (m, IH), 7.18 (d, IH), 3.09 (m, 6H), 2.45 (m, 4H), 2.34 (s, 3H), 1.99 (m, 2H), 1.26 (m, 9H). 1 1 δ 7.88 (m, 2H), 7.85 (m, IH), 7.33 (s, IH), 7.16 (d, IH), 2.71 (m, 2H), 2.4 (m, 2H), 2.33 (s, 3H), 2.0 (m, 2H). 12 δ 8.8 (s, IH), 8.6 (d, IH), 7.8 (dd, IH), 7.5 (s, IH), 7.4 (d, I H), 7.35 (m, IH), 7.24 (d, IH), 3.21 (m, 6H), 2.45 (m, 4H), 1.99 (m, 2H), 1.28 (m, 9H). 14 δ 8.6 (d, IH), 8.55 (d, IH), 7.8 (d, IH), 7.5 (m, 3H), 3.0 (m, 6H), 2.33 (m, 4H), 1.8 (m, 2H), 1.16 (m, 9H). 19 δ 8.6 ( , 2H), 7.7 (m, IH), 7.65 (m, IH), 7.5 (m, IH), 7.2 (m, IH), 2.95 (m, 6H), 2.9 (m, IH), 2.3 (m, 2H), 1.6 (m, 2H), 1.13 (m, 9H), 0.95 (m, 6H). 21 δ 8.47 (m, IH), 8.44 (m, IH), 7.8 (m, IH), 7.73 (m, IH), 7.7 (m, IH), 7.25 (m, I H), 2.6 (m, IH), 2.02 (m, 2H), 0.92 (m, 6H). 22 δ 8.6 (m, 2H), 8.0 (m, IH), 7.77 (m, I H), 7.6 (m, IH), 7.4 (m, IH), 3.2-1.8 (m, 6H). 26 6 7.57 (d. lH), 7.1 (s, 1H), 6.1 (d, IH), 3.67 (s, 3H), 3.2-2.1 (m, 10H), 1.73 (s, 3H), 1.29 (t, 3H), 1.13 (d. 3H). 27 67.56 (d, IH), 7.1 (s, IH), 6.1 1 (d, IH), 3.67 (s, 3H), 3.2-3.0 (m, 2H), 2.82 (t, 2H), 2.74 (s, 3H), 2.42 (t, 2H), 2.14-2.0 (m, 2H), 1.74 (s, 3H), 1.29 (t, 3H). 29 δ 8.7 (m, 2H), 7.7-7.4 (m, 5H), 7.09 (s, IH), 3.9 (q, 2H), 3.24 (m, 6H), 1.35 (m, 12H). a ] H NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (dd)-doublet of doublets, (t)-triplet, (q)-quartet, (m)-multiplet. BIOLOGICAL EXAMPLES OF THE INVENTION TEST A Seeds of barley (Hordeum vulgare), barnyardgrass (Echinochloa crus-gallϊ), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium strumarium), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setaria faberii), lambsquarters (Chenopodium album), morningglory (ϊpomoea hederacea), rape (Brassica napus), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glycine max), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), wild oat (Avenafatua) and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which includes a surfactant. At the same time, these crop and weed species were also treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from two to eighteen cm (one to four leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for twelve to sixteen days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table A, are based on a scale of 0 to 10 where 0 is no effect and 10 is complete control. A dash (-) response means no test result. TEST B The compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which includes a surfactant and applied to the soil surface before plant seedlings emerged (preemergence application), to water that covered the soil surface (flood application), and to plants that were in the one-to-four leaf stage (postemergence application). A sandy loam soil was used for the preemergence and postemergence tests, while a silt loam soil was used in the flood test. Water depth was approximately 2.5 cm for the flood test and was maintained at this level for the duration of the test. Plant species in the preemergence and postemergence tests consisted of barnyardgrass (Echinochloa crus-galli), barley (Hordeum vulgare), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium strumarium), corn (Zea mays v. Pioneer 3394), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setaria faberii), johnsongrass (Sorghum halpense), lambsquarters (Chenopodium album), morningglory (Ipomoea hederacea), pigweed (Amaranthus retroflexus), rape (Brassica napus), ryegrass (Lolium multiflorum), soybean (Glycine max), speedwell (Veronica persica), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), and wild oat (Avenafatua). Additionally, two 10.3 cm pots each containing two plant of corn (Zea mays) of the varieties M17 and B73 were treated in addition to the normal compliment of crop species. All plant species were planted one day before application of the compound for the preemergence portion of this test. Plantings of these species were adjusted to produce plants of appropriate size for the postemergence portion of the test. Plant species in the flood test consisted of rice (Oryza sativa), umbrella sedge (Cyperus difformis), duck salad (Heteranthera limosa), barnyardgrass2 (Echinochloa crus-galli) and Late watergrass (Echinochloa oryzicola grown to the 2 leaf stage for testing. All plant species were grown using normal greenhouse practices. Visual evaluations of injury expressed on treated plants, when compared to untreated controls, were recorded approximately fourteen to twenty one days after application of the test compound. Plant response ratings, summarized in Table B, were recorded on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result. Table B COMPOUND Rate 31 g/ha 1 5 6 12 13 14 15 22 23 24 25 26 POSTEMERGENCE Barley Igri Barnyard 2 Barnyardgrass Bedstraw Blackgrass Chickweed Cocklebur Corn Corn (B73) Corn (M17) Cotton Crabgrass Downy Brome Duck salad Giant foxtail Italn. Rygrass Johnsongrass Lambsquarter Morningglory Rape Redroot Pigweed Rice Japonica Soybean Speedwell Sugar beet Umbrella sedge Velvetleaf Wheat Wild buckwheat Wild oat TEST C Plastic pots were partially filled with silt loam soil. The soil was then saturated with water. Indica Rice (Oryza saliva) seed or seedlings at the 2.0 to 3.5 leaf stage; seeds, tubers or plant parts selected from arrowhead (Sagittaria rigida), barnyardgrass (Echinochloa crus- galli), ducksalad (Heteranthera limosa), early watergrass (Echinochloa oryzoides), junglerice (Echinochloa colonum), late watergrass (Echinochloa oryzicola), redstem (Ammonia species), rice flatsedge (Cyperus iria), smallflower flatsedge (Cyperus difformis) and tighthead sprangletop (Leptochloafasicularis), were planted into this soil. Plantings and waterings of these crops and weed species were adjusted to produce plants of appropriate size for the test. At the two leaf stage, water levels were raised to 3 cm above the soil surface and maintained at this level throughout the test. Chemical treatments were formulated in a non-phytotoxic solvent mixture which includes a surfactant and applied directly to the paddy water, by pipette, or to the plant foliage, by an air-pressure assisted, calibrated belt-conveyer spray system. Treated plants and controls were maintained in a greenhouse for approximately 21 days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table C, are reported on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result. Seeds, tubers, or plant parts of alexandergrass (Brachiaria plantaginea), bermudagrass (Cynodon dactylon), broadleaf signalgrass (Brachiaria platyphylla), common purslane (Portulaca oleracea), common ragweed (Ambrosia elatior), cotton (Gossypium hirsutum), dallisgrass (Paspalum dilatatum), goosegrass (Eleusine indica), guineagrass (Panicum maximum), itchgrass (Rottboellia exaltatά), Johnson grass (Sorghum halepense), large crabgrass (Digitaria sanguinalis), peanuts (Arachis hypogaea), pitted morningglory (Ipomoea lacunosa), purple nutsedge (Cyperus rotundus), sandbur (Cenchrus echinatus), sourgrass (Trichachne insularis), and Surinam grass (Brachiaria decumbens) were planted into greenhouse pots of flats containing greenhouse planting medium. Plant species were grown in separate pots or individual compartments. Preemergence applications were made within one day of planting the seed or plant part. Postemergence applications were applied when the plants were in the two to four leaf stage (three to twenty cm). Test chemicals were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied preemergence and postemergence to the plants. Untreated control plants and treated plants were placed in the greenhouse and visually evaluated for injury 13 to 21 days after herbicide application. Plant response ratings, summarized in Table D, are based on a 0 to 100 scale where 0 is no injury and 100 is complete control. A dash (-) response means no test result. Table D COMPOUND Rate 125 g/ha 22 23 25 POSTEMERGENCE Alexandergrass 80 75 95 Bermudagrass 85 60 85 Brdlf Sgnlgrass 80 98 100 Cmn Purslane 70 30 75 Cmn Ragweed 50 Cotton 95 35 0 Dallisgrass 85 75 0 Goosegrass 85 35 Guineagrass 80 95 75 Itchgrass 5 35 0 Johnson grass 80 90 100 Large Crabgrass 70 100 Peanuts 65 50 90 Pit Morninglory 80 90 30 Purple Nutsedge 75 30 10 Sandbur 40 75 20 Sourgrass 80 60 20 Surinam grass 90 75 90 Table D COMPOUND Rate 64 g/ha 22 23 25 POSTEMERGENCE Alexandergrass 80 65 100 Bermudagrass 75 50 75 Brdlf Sgnlgrass 95 95 80 Cmn Purslane 65 30 75 Cmn Ragweed Cotton 90 35 0 Dallisgrass 85 75 0 Goosegrass 70 35 90 Guineagrass 75 80 35 Itchgrass 0 0 0 Johnson grass 80 80 100 Large Crabgrass 60 50 0 Peanuts 35 65 75 Pit Morninglory 75 90 30 Purple Nutsedge 75 20 10 Sandbur 20 0 20 Sourgrass 70 40 20 Surinam grass 80 65 Large Crabgrass 65 40 Peanuts 100 5 Pit Morninglory 65 100 Purple Nutsedge - 0 Sandbur 0 0 Sourgrass 98 85 Surinam grass 0 0 Table D COMPOUND Rate 16 g/ha 22 POSTEMERGENCE Alexandergrass 35 Bermudagrass 50 Brdlf Sgnlgrass 40 Cmn Purslane 30 Cmn Ragweed Cotton 70 Dallisgrass 35 Goosegrass 30 Guineagrass 35 Itchgrass 20 Johnson grass 35 Large Crabgrass 50 Peanuts 0 Pit Morninglory 65 Purple Nutsedge 5 Sandbur 0 Sourgrass 35 Surinam grass 35 Table D COMPOUND Rate 8 g/ha 22 POSTEMERGENCE Alexandergrass 35 Bermudagrass 40 Brdlf Sgnlgrass 70 Cmn Purslane 35 Cmn Ragweed Cotton 0 Dallisgrass 20 Goosegrass 30 Guineagrass 35 Itchgrass 0 Johnson grass 35 Large Crabgrass 35 Peanuts 0 Pit Morninglory 35 Purple Nutsedge 0 Sandbur 0 Sourgrass 35 Surinam grass 35 TEST E Seeds of barnyardgrass (Echinochloa crus-galli), bindweed (Concolculus arvensis), black nightshade (Solanum ptycanthum dunal), cassia (Cassia obtusifolia), cocklebur (Xanthium strumarium), common ragweed (Ambrosia artemisiifoliά), corn (Zea mays v. Pioneer 3394), corn2 (Zea mays v. IMR Ciba 4393), cotton (Gossypium hirsutam), crabgrass (Digitaria spp.), fall panicum (Panicum dichotomiflorum), giant foxtail (Setaria faberii), green foxtail (Setaria viridis), jimsonweed (Datura stramonium), johnsongrass (Sorghum halepense), lambsquarter (Chenopodium album), morningglory (Ipomoea spp.), pigweed (Amaranthus retroflexus), prickly sida (Sida spinosa), shattercane (Sorghum vulgare), signalgrass (Brachiaria platyphylla), smartweed (Polygonum pensylvanicum), soybean (Glycine max v. Williams 95) and soybean2 (Glycine max v. Asgrow 3304), sunflower (Helianthus annuus), velvetleaf (Abutilon theophrasti), wild proso (Pancium miliaceum), woolly cupgrass (Eriochloa villosa), yellow foxtail (Setaria lutescens) and purple nutsedge (Cyperus rotundus) tubers were planted into a sandy loam or clay loam soil. These crops and weeds were grown in the greenhouse until the plants ranged in height from two to eighteen cm (one to four leaf stage), then treated postemergence with the test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant. Pots treated in this fashion were placed in the greenhouse and maintained according to routine greenhouse procedures. Treated plants and untreated controls were maintained in the greenhouse approximately 14-21 days after application of the test compound. Visual evaluations of plant injury responses were then recorded. Plant response ratings, summarized in Table E, are reported on a 0 to 100 scale where 0 is no effect and 100 is complete control. Table E COMPOUND TEST F Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied to plants that were grown for various periods of time before treatment (postemergence application). A mixture of sandy loam soil and greenhouse potting mix in a 60:40 ratio was used for the postemergence test. Plantings of these crops and weed species were adjusted to produce plants of appropriate size for the postemergence test. All plant species were grown using normal greenhouse practices. Crop and weed species include arrowleaf sida (Sida rhombifoliά), barnyardgrass (Echinochloa crus-galli), cocklebur (Xanthium strumarium), common lambsquarters (Chenopodium album), corn (Zea mays), cotton (Gossypium hirsutum), eastern black nightshade (Solanum ptycanthum), fall panicum (Panicum dichotomiflorum), field bindweed (Convolvulus arvensis), Florida beggarweed (Desmodium purpureum), giant foxtail (Setaria faberii), hairy beggarticks (Bidens pilosa), ivyleaf morningglory (Ipomoea hederacea), johnsongrass (Sorghum halepense), ladysthumb (Polygonum persicaria), large crabgrass (Digitaria sanguinalis), purple nutsedge (Cyperus rotundus), redroot pigweed (Amaranthus retroflexus), soybean (Glycine max), Surinam grass (Brachiaria decumbens), velvetleaf (Abutilon theophrasti) and wild poinsettia (Euphorbia heterophylla). Treated plants and untreated controls were maintained in a greenhouse for approximately 14 to 21 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table F, were based upon a 0 to 100 scale where 0 was no effect and 100 was complete control. A dash response (-) means no test result. TEST G Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which includes a surfactant and applied to plants that were grown for various periods of time before treatment (postemergence application). A mixture of sandy loam soil and greenhouse potting mix in a 60:40 ratio was used for the postemergence test. Test compounds were applied 13 days after the last postemergence planting. Plantings of these crops and weed species were adjusted to produce plants of appropriate size for the postemergence test. All plant species were grown using normal greenhouse practices. Crop and weed species include bristly starbur (Acanthospermun hispidum) alexandergrass (Brachiaria plantaginea), american black nightshade (Solanum americanum), apple-of-Peru (Nicandra physaloides), arrowleaf sida (Sida rhombifolia), Brazilian sicklepod (Cassia tora Brazilian), Surinam grass (Brachiaria decumbens), capim- colchao (Digitaria horizontalis), Crist, soybean (Glycine max v. Cristalina), florida beggarweed (Desmodium purpureum), hairy beggarticks (Bidens pilosa), slender amaranth (Amaranthus viridis), southern sandbur (Cenchrus echinatus), tall morningglory (Ipomoea purpurea), tropical spiderwort (Commelina benghalensis), W20 Soybean (Glycine max v. W20), W4-4 Soybean (Glycine max v. W4-4), corn (Zea mays v. Pioneer 3394) and wild pointsettia (Eupohorbia heterophylla). Treated plants and untreated controls were maintained in a greenhouse for approximately 13 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table G, are based upon a 0 to 100 scale where 0 is no effect and 100 is complete control. Table G COMPOUND Rate 70 g/ha 23 POSTEMERGENCE Acanthospermum 100 Alexandergrass 100 Apple-of-Peru 80 Arrowleaf Sida 70 Surinam grass 100 Bl. Nightshade 100 Braz Sicklepod 65 Capim-Colch 100 Corn 15 Crist. Soybean 100 Crist. Soybean 100 Fl . Beggarweed 100 Fl. Beggarweed 85 H. Beggarticks 85 H. Beggarticks 75 Morningglory 90 Morningglory 80 SI. Amaranth 100 SI. Amaranth 90 Southern Sandur 85 Southern Sandur 80 Tr. Spiderwort 100 Tr. Spiderwort 90 Wld Pointsettia 100 Wld Pointsettia 85 W20 Soybean 100 W20 Soybean 100 W4-4 Soybean 100 W4-4 Soybean 100 Table G COMPOUND Table G COMPOUND Table G COMPOUND Rate 35 g/ha 23 Rate 17 g/ha 23 Rate 8 g/ha 23 POSTEMERGENCE POSTEMERGENCE POSTEMERGENCE Acanthospermum 100 Acanthospermum 100 Acanthospermum 55 Alexandergrass 100 Alexandergrass 100 Alexandergrass 85 Apple-of-Peru 80 Apple-of-Peru 75 Apple-of-Peru 65 Arrowleaf Sida 65 Arrowleaf Sida 60 Arrowleaf Sida 40 Surinam grass 100 Surinam grass 90 Surinam grass 80 Bl . Nightshade 100 Bl . Nightshade 100 Bl . Nightshade 85 Braz Sicklepod 60 Braz Sicklepod 35 Braz Sicklepod 10 Capim-Colch 100 Capim-Colch 65 Capim-Colch 60 Corn 0 Corn 0 Corn 0 Crist. Soybean 100 Crist. Soybean 90 Crist. Soybean 85 Fl. Beggarweed 85 Fl. Beggarweed 85 Fl. Beggarweed 100 H. Beggarticks 70 H. Beggarticks 80 H. Beggarticks 75 Morningglory 70 Morningglory 65 Morningglory 60 Si. Amaranth 80 SI. Amaranth 80 SI. Amaranth 75 Southern Sandur 50 Southern Sandur 45 Southern Sandur 45 Tr. Spiderwort 80 Tr. Spiderwort 70 Tr. Spiderwort 65 Wld Pointsettia 85 Wld Pointsettia 70 Wld Pointsettia 70 W20 Soybean 90 W20 Soybean 80 W20 Soybean 75 W4-4 Soybean 100 W4-4 Soybean 100 W4-4 Soybean 90 TEST H Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which includes a surfactant and applied to plants that were in the one-to four leaf stage (postemergence application). A mixture of sandy loam soil and greenhouse potting mix in a 60:40 ratio was used for the postemergence test. Plantings of these crops and weed species were adjusted to produce plants of appropriate size for the postemergence test. All plant species were grown using normal greenhouse practices. Crop and weed species include annual bluegrass (Poa annuά), blackgrass (Alopecurus myosuroides), black nightshade (Solanum nigra), chickweed (Stellaria media), common poppy (Papaver rhoeas), deadnettle (Lamium amplexicaule), downy brome (Bromus tectorum), field violet (Viola arvensis), galium (Galium aparine), green foxtail (Setaria viridis), jointed goatgrass (Aegilops cylindrica), kochia (Kochia scoparia), lambsquarters (Chenopodium album), littleseed canarygrass (Phalaris minor), rape (Brassica napus), redroot pigweed (Amaranthus retroflexus), Russian thistle (Salsola kali), ryegrass (Lolium multiflorum), scentless chamomile (Matricaria inodora), spring barley (Hordeum vulgare), sugar beet (Beta vulgaris), sunflower (Helianthus annuus), ivyleaf speedwell (Veronica hederaefolia), spring wheat (Triticum aestivum), winter wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), wild mustard (Sinapis arvensis), wild oat (Avenafatua), windgrass (Apera spica-venti) and winter barley (Hordeum vulgare). Treated plants and untreated controls were maintained in a greenhouse for approximately 21 to 28 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table H, are based upon a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash response (-) means no test result. Table H COMPOUND Table H Rate 125 g/ha 15 Rate 62 g/ha POSTEMERGENCE POSTEMERGENCE Annual Bluegras 0 Annual Bluegras Blackgrass 0 Blackgrass Blk Nightshade 75 Blk Nightshade Chickweed 85 Chickweed Common poppy 55 Common poppy Deadnettle 75 Deadnettle Downy brome 0 Downy brome Field violet 75 Field violet Galium 30 Galium Green foxtail 30 Green foxtail Jointed Goatgra 0 Jointed Goatgra Kochia 85 Kochia Lambsquarters 75 Lambsquarters LS Canarygrass 0 LS Canarygrass Rape 85 Rape Redroot Pigweed 75 Redroot Pigweed Russian Thistle 10 Russian Thistle Ryegrass 0 Ryegrass Scentless Chamo 60 Scentless Chamo Spring Barley 0 Spring Barley Sugar beet 100 Sugar beet Sunflower 55 Sunflower Veronica hedera 40 Veronica hedera Wheat (Spring) 0 Wheat (Spring) Wheat (Winter) 0 Wheat (Winter) Wild buckwheat 75 Wild buckwheat Wild mustard 95 Wild mustard Wild oat 0 Wild oat Windgrass 0 Windgrass Winter Barley 0 Winter Barley Table H COMPOUND Rate 8 g/ha 25 POSTEMERGENCE Annual Bluegras 30 Blackgrass 10 Blk Nightshade 75 Chickweed 60 Common poppy 50 Deadnettle 60 Downy brome 15 Field violet 50 Galium 50 Green foxtail 50 Jointed Goatgra 0 Kochia 45 Lambsquarters 100 LS Canarygrass 50 Rape 60 Redroot Pigweed 70 Russian Thistle 10 Ryegrass 2 Scentless Chamo 50 Spring Barley 0 Sugar beet 50 Sunflower 60 Veronica hedera 50 Wheat (Spring) 10 Wheat (Winter) 20 Wild buckwheat 0 Wild mustard 70 Wild oat 10 Windgrass 30 Winter Barley 2

Claims: CLAIMS What is claimed is: 1. A compound selected from the formula and N-oxides and agriculturally suitable salts thereof, wherein Q is Q-1 Q-2 Q-3 Q-4 A is a five- to ten-membered monocyclic or fused bicyclic ring system, which may be fully aromatic or partially saturated, containing 1 to 4 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 2 oxygens and no more than 2 sulfurs, and each ring system is optionally substituted with one to three R 2 , provided that when a nitrogen atom of a heterocyclic ring is substituted with R 2 , then R 2 is other than halogen; each R 1 is independently H, C r C 6 alkyl, C r C 6 haloalkyl, C r C 6 alkoxy, C r C 6 haloalkoxy, halogen, cyano, nitro, -(Y) t -S(O) n R 15 or -(Y) t -C(O)R 15 ; W is N or CH; Y is O or NR 12 ; R 2 is C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C6 haloalkynyl, C j -C 6 alkoxy, Ci-Cg haloalkoxy, C 3 -Cg alkenyloxy, C 3 -C 6 alkynyloxy, mercapto, Ci-Cfc alkylthio, C j -C 3 haloalkylthio, C 3 -C 6 alkenylthio, C 3 -C 6 haloalkenylthio, yCf, alkynylthio, C 2 -C 5 alkoxyalkylthio, C 3 -C 5 acetylalkylthio, alkylsulfinyl, C r C 6 haloalkylsulfinyl, C r C 6 alkylsulfonyl, C r C 6 haloalkylsulfonyl, aminosulfonyl, Cι-C 2 alkylaminosulfonyl, C2-C4 dialkylaminosulfonyl, (CH 2 ) r R 16 , NR 12 R 13 , halogen, cyano or nitro; or R 2 is phenyl or benzylthio, each optionally substituted on the phenyl ring with C j -C 3 alkyl, C r C 3 haloalkyl, Cj-C 3 alkoxy, C j -C 3 haloalkoxy, 1-2 halogen, cyano or nitro; R 3 is OR 14 , SH, C,-C 6 alkylthio, C,-C 6 haloalkylthio, C j -C 6 alkylsulfinyl, C r C 6 haloalkylsulfinyl, C ] -C6 alkylsulfonyl, C j -Cg haloalkylsulfonyl, halogen or NR 12 R 13 ; or R 3 is phenylthio, phenylsulfonyl or -SCH 2 C(O)Ph, each optionally substituted with C]-C 3 alkyl, halogen, cyano or nitro; each R 4 is independently C j -C 3 alkyl, C j -C 3 alkoxy, C ] -C 3 alkylthio or halogen; or when two R 4 are attached to the same carbon atom, then said R 4 pair can be taken together to form -OCH 2 CH 2 O-, -OCH 2 CH 2 CH 2 O-, -SCH 2 CH 2 S- or -SCH 2 CH 2 CH 2 S-, each group optionally substituted with 1 -4 CH 3 ; R 5 is OR 14 , SH, C r C 6 alkylthio, C,-C 6 haloalkylthio, C r C 6 alkylsulfinyl, C r C 6 haloalkylsulfinyl, C j -C^ alkylsulfonyl, Ci-Cg haloalkylsulfonyl, halogen or NR 12 R 13 ; or R 5 is phenylthio, phenylsulfonyl or -SCH 2 C(O)Ph, each optionally substituted with Cj-C 3 alkyl, halogen, cyano or nitro; R6 is H, C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or -CH 2 CH 2 OR 12 ; or R 6 is phenyl or benzyl, each optionally substituted on the phenyl ring with C1-C3 alkyl, halogen, cyano or nitro; R 7 is H, Cj-Cg alkyl, C r C 6 haloalkyl, C r C 6 alkoxy, C r C 6 haloalkoxy, halogen, cyano or nitro; R 8 is H, C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 cycloalkyl or C r C 6 halocycloalkyl; R 9 is H, C2- 6 alkoxycarbonyl, C 2 -C6 haloalkoxycarbonyl, CO 2 H or cyano; R 10 is C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 cycloalkyl optionally substituted with 1-4 C ] -C 3 alkyl or C 3 -C6 halocycloalkyl; R ] I is cyano, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylcarbonyl, S(O) n R 13 or C(O)NR 12 R 13 ; each R 12 is independently H or C j -C 6 alkyl ; R 13 is C r C 6 alkyl or C r C 6 alkoxy; or R 12 and R 13 can be taken together as -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 CH 2 - or -CH 2 CH 2 OCH 2 CH 2 -; R 14 is H, C r C 6 alkyl, C r C 6 haloalkyl, C 2 -C 6 alkoxyalkyl, formyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C(O)NR 12 R 13 , C r C 6 alkylsulfonyl or C j -Cg haloalkylsulfonyl; or R 14 is phenyl, benzyl, benzoyl, -CH 2 C(O)phenyl or phenylsulfonyl, each optionally substituted on the phenyl ring with C j -C 3 alkyl, halogen, cyano or nitro; R 15 is NR 12 R 13 , C r C 6 alkoxy, C r C 6 haloalkoxy, C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl or C -C 6 cycloalkyl; or R 15 is phenyl optionally substituted with C r C 3 alkyl, C r C 3 haloalkyl, Cι-C 3 alkoxy, C 1 -C3 haloalkoxy, 1-2 halogen, cyano or nitro; R 16 is C r C 3 alkoxy, 2 -C 4 alkoxycarbonyl, C r C 3 alkylthio, C r C 3 alkylsulfinyl or Cι-C 3 alkylsulfonyl; or R 16 is phenyl optionally substituted with C1-C3 alkyl, C ] -C 3 haloalkyl, C r C 3 alkoxy, C r C 3 haloalkoxy, 1-2 halogen, cyano or nitro; m is 0, 1, 2 or 3; n is 0, 1 or 2; p is O, 1, 2, 3 or 4; r is 1, 2 or 3; and t is 0 or 1 ; provided that when W is CH and A is in the meta position with respect to the group Q- C(O)- of Formula I, then m is 3 and R 1 is other than H. 2. A compound of Claim 1 wherein A is selected from the group lH-pyrrolyl; furanyl; thienyl; lH-pyrazolyl; lH-imidazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; lH-l,2,3-triazolyl; 2H-l,2,3-triazolyl; lH-l,2,4-triazolyl; 4H-l,2,4-triazolyl; 1,2,3-oxadiazolyl; 1,2,4-oxadiazolyl; 1,2,5-oxadiazolyl; 1,3,4-oxadiazolyl; 1,2,3-thiadiazolyl; 1,2,4-thiadiazolyl; 1,2,5-thiadiazolyl; 1,3,4-thiadiazolyl; lH-tetrazolyl; 2H-tetrazolyl; pyridinyl; pyridazinyl; pyrimidinyl; pyrazinyl; 1,3,5-triazinyl; 1,2,4-triazinyl; and A may optionally be substituted by one to three R 2 , provided that when a nitrogen atom of a heterocyclic ring is substituted with R 2 , then R 2 is other than halogen. 3. A compound of Claim 2 wherein Q is Q-1. 4. A compound of Claim 3 wherein each R 1 is independently C j -C 3 alkyl, Cι-C 3 alkoxy, halogen or nitro; R 3 is OR 14 ; and R 14 is H or C1-C4 alkylsulfonyl; or R 14 is benzoyl or phenylsulfonyl, each optionally substituted with C 1 -C3 alkyl, halogen, cyano or nitro. 5. A compound of Claim 4 wherein A is pyridinyl, pyridazinyl, pyrimidinyl or lH-pyrazolyl; R 2 is -(Y) t -S(O) n R 15 , CF 3 , OCF 3 , OCF 2 Η or cyano; R 15 is C r C 6 alkyl; t is 0; and n is 2. 6. A compound of Claim 2 wherein: Q is Q-2. 7. A compound of Claim 6 wherein: each R 1 is independently C r C 3 alkyl, C C 3 alkoxy, halogen or nitro; R 5 is OR 14 ; R 14 is H or C r C 4 alkylsulfonyl; or R 14 is benzoyl or phenylsulfonyl, each optionally substituted with Cj-C 3 alkyl, halogen, cyano or nitro. R 6 is H, C r C 6 alkyl, or C 3 -C 6 alkenyl; and R 7 is H. 8. A compound of Claim 7 wherein A is pyridinyl, pyridazinyl, pyrimidinyl or lH-pyrazolyl; R 2 is -(Y) t -S(O) n R 15 , CF 3 , OCF 3 , OCF 2 Η or cyano; R 15 is C r C 6 alkyl; t is 0; and n is 2. 9. A compound of Claim 2 wherein Q is Q-3. 10. A compound of Claim 9 wherein each R 1 is independently C ] -C alkyl, C ] -C 3 alkoxy, halogen or nitro; R 8 is H, i-C^ alkyl, or cyclopropyl; and R 9 is H or C 2 -C 3 alkoxycarbonyl. 11. A compound of Claim 10 wherein A is pyridinyl, pyridazinyl, pyrimidinyl or lH-pyrazolyl; R 2 is -(Y) t -S(O) n R 15 , CF 3 , OCF 3 , OCF 2 H or cyano; Ri5 is C,-C 6 alkyl; t is 0; and n is 2. 12. A compound of Claim 2 wherein Q is Q-4. 13. A compound of Claim 12 wherein each R 1 is independently Cι-C 3 alkyl, C r C 3 alkoxy, halogen or nitro; R 10 is C 3 -C6 cycloalkyl or C 3 -C6 halocycloalkyl, each optionally substituted with 1-4 C j -C 3 alkyl; and R 1 ! is cyano or C -C 6 alkoxycarbonyl. 14. A compound of Claim 13 wherein A is pyridinyl, pyridazinyl, pyrimidinyl or lH-pyrazolyl; R 2 is -(Y) t -S(O) n R 15 , CF 3 , OCF 3 , OCF 2 Η or cyano; R 15 is C,-C 6 alkyl; t is 0; and n is 2. 15. The compound of Claim 5 which is selected from the group a) 3-hydroxy-2-[[6-(trifluoromethyl)[2,4'-bipyridin]-3-yl]carbonyl]-2-cyclohexen- 1-one; b) 2-[2-chloro-4-(4-pyridinyl)benzoyl]-3-hydroxy-2-cyclohexen-l-one; and c) 2-[2,5-dimethyl-3-(l-methyl-lH-pyrazol-3-yl)-4-(methylsulfonyl)benzoyl]-3- hydroxy-2-cyclohexen- 1 -one. 16. A herbicidal composition comprising a herbicidally effective amount of a compound of Claim 1 and at least one of a surfactant, a solid diluent or a liquid diluent. 17. 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.

Inventors: PATEL KANU MAGANBHAI, RORER MORRIS PADGETT, TSENG CHI-PING, PATEL, KANU, MAGANBHAI, RORER, MORRIS, PADGETT, TSENG, CHI-PING
Applicants: DU PONT, PATEL KANU MAGANBHAI, RORER MORRIS PADGETT, TSENG CHI PING, E.I. DU PONT DE NEMOURS AND COMPANY, PATEL, KANU, MAGANBHAI, RORER, MORRIS, PADGETT, TSENG, CHI-PING
Application year: 1997
Main classification: C07D213
IPC codes: A01N43, C07D213, C07D231, C07D277, C07D401