1,2-BENZOXATHIIN AND THIEPIN 2,2-DIOXIDE HERBICIDES

Abstract: Compounds of formula (I), and their N-oxides and agriculturally suitable salts, are disclosed which are useful for controlling undesired vegetation. In said formula (I) Q is (Q-1), (Q-2) or (Q-3); and A, R<1>-R<7>, and q 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 1 ,2-BENZOXATHΠN AND THEEPIN 2,2-DIOXLDE HERBICIDES BACKGROUND OF THE INVENTION This invention relates to certain 1 ,2-benzoxathiin and 1 ,2-benzothiepin 2,2-dioxides, their N-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. United States Patent 5,089,046 discloses ketones of Formula i as herbicides: wherein, inter alia one of Xj and X 2 represents CRι a R 2a and the other represents CR 3 R 4 ; Rj, R la , R , R 2a , 3, and R 4 are independently hydrogen or Ci-Cg alkyl; R 5 is C r C 8 alkyl, halogen, cyano, nitro, -(O) n S(O) rn R 12 or -ΝR 15 SO 2 R 12 ; R 6 and R 7 are independently hydrogen, Cι-C 8 alkyl, halogen, cyano, nitro, -(0)n S (°)m R 12 or " NR 15S0 2 R 12 ; provided that at least one of R 5 , R 6 or R 7 is a group -OS(O) 2 R 12 or -NR ]5 SO 2 R 12 ; Rg is hydrogen or a salt forming moiety; R J2 is C r C 8 alkyl optionally substituted with one to six halogens; R15 is hydrogen or C j -Cg alkyl; n is 0 or 1 ; and m is 0, 1 or 2. The 1 ,2-benzoxathiin and 1 ,2-benzothiepin 2,2-dioxides of the present invention are not disclosed in this patent. SUMMARY OF THE INVENTION This invention is directed to compounds of Formula I including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, agricultural compositions containing them and their use for controlling undesirable vegetation: wherein Q is Q-1 Q-2 Q-3 R 1 is OR 8 , SH, C r C 6 alkylthio, C r C 6 haloalkylthio, C r C 6 alkylsulfinyl, C r C 6 haloalkylsulfinyl, C Cg alkylsulfonyl, C j -Cg haloalkylsulfonyl, halogen or ΝR21a 2lb ; or Rl j s phenylthio, phenylsulfonyl or -SCH 2 C(O)Ph, each optionally substituted with C1-C3 alkyl, halogen, cyano or nitro; each R 2 is independently H, C j -C 3 alkyl, CyC 6 alkenyl, C 3 -C 6 alkynyl, C j -C 3 alkoxy, formyl, C 2 -Cg alkoxycarbonyl, -CH(C ] -C 3 alkoxy ) 2 , C1-C3 alkylthio, C 2 -C4 alkyl thioalkyl, cyano or halogen; or when two R 2 are attached to the same carbon atom, then said R 2 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 3 is H, Ct-Cg alkyl, C j -Cg haloalkyl, halogen, cyano or nitro; R 4 is H, C C 6 alkyl, C C 6 haloalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R * * is phenyl or benzyl, each optionally substituted on the phenyl ring with C J -C3 alkyl, halogen, cyano or nitro; R 5 is H, C,-C 6 alkyl, -Cg haloalkyl, C 2 -C 6 alkoxyalkyl, formyl, C 2 -C 6 alkylcarbonyl, C 2 -Cg alkoxycarbonyl, C 2 -C6 alkylaminocarbonyl, C3-C7 dialkylaminocarbonyl, C j -C 6 alkylsulfonyl or C j -Cg haloalkylsulfonyl; or R 5 is benzoyl or phenylsulfonyl, each optionally substituted with Cχ.-Cj alkyl, halogen, cyano or nitro; R 6 is H, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 haloalkoxycarbonyl, CO 2 H or cyano; R 7 is H, Cι-C 6 alkyl, C λ -C 6 haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl; R 8 is H, C,-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 21a R 21b , C,-C 6 alkylsulfonyl or C r C 6 haloalkylsulfonyl; or R 8 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; A-l A-2 A-3 A-4 A-5 A-6 R 9 and R 10 are independently H, C,-C 6 alkyl, C,-C 6 haloalkyl, C j -C 6 alkoxy, C j -Cg haloalkoxy, Cι-C 6 alkylthio, Cj-Cg haloalkylthio, Cι-C 6 alkyl sulfinyl, C l -C 6 haloalkylsulfmyl, Cι~C 6 alkylsulfonyl, C ] -C 6 haloalkylsulfonyl, aminosulfonyl, Cι~C 2 alkylaminosulfonyl, C 2 -C4 dialkylaminosulfonyl, halogen, cyano or nitro; R 1 1 , R 12 , R 13 , R 17 and R 18 are independently H, halogen, cyano, C j - alkyl, C,-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, Cj-C 6 alkoxy, Cj-C 6 haloalkoxy, C j -C 6 alkylthio or C j - haloalkylthio; R 14 is H, halogen, C,-C 6 alkyl or C,-C 6 haloalkyl; R 15 is H, halogen, cyano, Cj-C 6 alkyl, C j -Cg haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, - alkoxy, C ] -C 6 haloalkoxy, C^Cg alkylthio or Cι-C 6 haloalkylthio; R 16 is H, C ! -C 6 alkoxy, C 2 -C 6 haloalkoxy, C,-C 6 alkylthio, C 2 -C 6 haloalkylthio; or R 15 and R i 6 are taken together to form -X 1 -(CH 2 ) r -X 2 -, -(CH 2 ) S -X 3 -, -(CH 2 ) t -X 3 -CH 2 -, -(CH 2 ) V -X 3 -CH 2 CH 2 - or -(CH 2 ) W -, each group optionally substituted with at least one member selected from 1—6 halogen, 1-6 CH 3 and one C ] -C 3 alkoxy; or R 15 and R 16 are taken together to form -O-N(C , -C 3 alkyl)-CHR 20 -CH 2 - or -O-N=CHR 20 -CH 2 -, each group optionally substituted with at least one member selected from 1-2 halogen and 1-2 CH3; or R 15 and R 16 are taken together with the carbon to which they are attached to form C(=O), C(=S) or C(=NOR 2 l); X 1 and X 2 are each independently O, S or N(C j -C 3 alkyl); X 3 is O or S; G is O or CH 2 ; R 19 is H, C j -C 3 alkyl, C 3 -C 4 alkenyl or C 3 -C 4 alkynyl; R 20 is Cj-C alkyl; or R 20 is phenyl optionally substituted with Cι~C 3 alkyl, halogen, cyano or nitro; R 21 is H, C ] -C 3 alkyl, C 3 -C 4 alkenyl or C 3 -C 4 alkynyl; R 21 s H or C r C 6 alkyl; R 21b is C,-C 6 alkyl or C r C 6 alkoxy; or R 1a and R l t> 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 -; Y and Z together with the carbons to which they are attached form a fused lH-4,5- dihydropyrazole or pyridine ring optionally substituted with up to three groups independently selected from the group halogen and Cj-C alkyl, provided that when the nitrogen atom of the fused lH-4,5-dihydropyrazole ring is substituted, then the nitrogen substituent is C j -Cg alkyl; or Y and Z together with the carbons to which they are attached form a fused pyrazole, pyrimidine or thiophene ring, each optionally substituted with up to two groups independently selected from the group halogen and C j -Cg alkyl, provided that when the nitrogen atom of the fused pyrazole ring is substituted, then the nitrogen substituent is C j -Cg alkyl; or Y and Z together with the carbons to which they are attached form a fused isoxazole ring optionally substituted with halogen and Ci-Cg alkyl; k is O or 1; m is 0 or 1 ; n is 1 or 2; q is 0, 1, 2, 3 or 4; r is 2, 3 or 4; s is 2, 3, 4 or 5; t is 1, 2, 3 or 4; v is 2 or 3; and w is 2, 3, 4, 5 or 6; provided that: (i) k and m sum to 0 or 1 ; (ii) when R 16 is other than H, then R 15 is other than halogen and Cj haloalkoxy; and (iii) when A is A-l, A-2 or A-4, then Q is Q-1 or Q-2. In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers. The term "1-2 alkyl" indicates that one or two of the available positions for that substituent may be alkyl which are independently selected. "Alkenyl" includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. "Alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl" can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. "Alkoxy" includes, for example, methoxy, ethoxy, * ?-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. "Alkylthioalkyl" denotes alkylthio substitution on alkyl. Examples of "alkylthioalkyl" include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 . "Alkylthioalkoxy" denotes alkylthio substitution on alkoxy. "Alkylsulfinyl" includes both enantiomers of an alkylsulfmyl 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", "alkenylthio", "alkenylsulfinyl", "alkenylsulfonyl", "alkynylthio", "alkynylsulfinyl", "alkynylsulfonyl", and the like, are defined analogously to the above examples. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. One skilled in the art will appreciate that not all nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the preparation of /V-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press. The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. The term "1-2 halogen" indicates that one or two of the available positions for that substituent may be halogen which are independently selected. 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", "haloalkylthio", 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 HG≡CCHCl, CF 3 C=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 "haloalkylsulfinyl" include CF 3 S(O), CCl 3 S(O), CF 3 CH 2 S(O) and CF 3 CF 2 S(O). 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 "Cj-C j " prefix where i and j are numbers from 1 to 8. For example, C1-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C 2 alkoxyalkyl designates CH 3 OCH 2 ; C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2 ; and C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 . 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 compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R) j _ j , then the number of substituents may be selected from the integers between i and j inclusive. When a group contains a substituent which can be hydrogen, for example R 3 or R 12 , 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, N-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 Ia (Formula I where Q is Q- 1, R 1 is OR 8 , and R 8 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. The present invention includes mixtures of such tautomers as well as the individual tautomers of compounds of Formula I. lb 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, tartarie, 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 phenol. Preferred compounds for reasons of better activity and/or ease of synthesis are: Preferred 1. Compounds of Formula I above, and N-oxides and agriculturally suitable salts thereof, wherein A is selected from A-l, A-2 and A-6; R 9 and R 10 are independently H, halogen, nitro, C j -C 3 alkyl or Cj-C 3 alkoxy; R 11 and R 12 are independently H, halogen or C j -C 3 alkyl; R 13 and R 14 are independently H or C j -C 3 alkyl; R 15 and R 16 are independently H, C ] -C 3 alkyl , C j -C 3 alkoxy, C 2 -C 3 haloalkoxy, C j -C 3 alkylthio or C 2 -C 3 haloalkylthio; or R 15 and R 16 are taken together to form -X 1 -(CH 2 ) r -X 2 - optionally substituted with at least one member selected from 1-2 halogen and 1-3 CH 3 ; or R 15 and R 16 are taken together with the carbon to which they are attached to form C(=O) or C(=ΝOR l); r is 2 or 3; R 21 is H or C!-C 3 alkyl; A-6 is selected from A-6a, A-6b, A-6c, A-6d, A-6e and A-6f: A-6a A-6b A-6c A-6d A-6e A-6f wherein: R 22 , R 24 and R 30 are independently C]-C 6 alkyl; and R 23 , R 2 5, R 2 6, R 27 , R 28 and R 29 are independently H or C j -C 4 alkyl; and R 31 and R 32 are independently H or C j -C 2 alkyl. Preferred 2. Compounds of Preferred 1 wherein k is O; m is O; R 9 and R 10 are independently C } -C 3 alkyl or halogen; R 11 and R 12 are independently H or C j -C 3 alkyl; R 15 and R ] 6 are taken together as -OCH 2 CH 2 O- or -SCH 2 CH 2 S- ; or R 15 and R 16 with the carbon to which they are attached are taken together to form C(=O) or C(=NOR 21 ); R 21 is C!-C 2 alkyl; and R 22 , R 24 and R 30 are independently C j -C 3 alkyl; and R 23 , R 25 , R 26 , R 27 , R 28 and R 29 are independently H or C,-C 2 alkyl; and R 31 and R 32 are independently H or C ] -C 2 alkyl. Preferred 3. Compounds of Preferred 2 wherein Q is Q-1. Preferred 4. Compounds of Preferred 2 wherein Q is Q-2. Preferred 5. Compounds of Preferred 2 wherein Q is Q-3. Most preferred is the compound of Preferred 3 which is selected from the group: (a) 3-hydroxy-2-[(3,5,8-trimethyl- 1 ,2-benzoxathiin-6-yl)carbonyl]-2-cyclohexen- 1 - one 5,5-dioxide, which is alternatively named as its tautomer 2-[(3,5,8-trimethyl-l,2-benzoxathiin-6-yl)carbonyl]-l,3-cyclohexanedione S,S'- dioxide; (b) 3-hydroxy-2-[(2,6,9-trimethyl-4,4-dioxido-2H-[ 1 ,2]benzoxathiino[4,3- c]pyrazol-8-yl)carbonyl]-2-cyclohexen- 1 -one; and (c) 2-[(5,8-dimethyl-l,2-benzoxathiin-6-yl)carbonyl]-3-hydroxy-2-cyclohexen-l- one 5,5-dioxide. 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 1-63. Unless otherwise specified, the definitions of Q, A, R'—R 32 , X -X 3 , G, Y, Z, k, m, n, q, r, s, t, v and w in the compounds of Formulae Id- If and Formulae 1-49 below are as described in the Summary of the Invention. Compounds of Formulae Id— If are various subsets of the compounds of Formula I. For example, compounds of Formula Id below are compounds of Formula I wherein Q is Q-1. Id Compounds of General Formula Id can be prepared by one skilled in the art by using the reactions and techniques described in Schemes 1-55 and 63 of this section as well as by following the specific procedures given in Examples 1, 2, and 3. Scheme 1 illustrates the preparation of compounds of Formula Id (A is A- 1 to A-6f, wherein for A-2, R 15 and R 16 are other than taken together with the carbon to which they are attached to form C(=O) and C(=S); R 1 is OR 33 and R 33 is the same as R 8 as described in the Summary of the Invention, but not H) whereby a compound of Formula Id (A is as defined above; R 1 is OH) is reacted with a reagent of Formula 1 (R 33 is as defined above; X 4 is chlorine, bromine, fluorine, trifluorosulfonyloxy (OTf) or acetyloxy (OAc)) in the presence of a base. The coupling is carried out by general methods known in the art (or by slight modification of these methods); see for example, K. Nakamura et al., WO 95/04054. Scheme 1 Id (Rl is OH) + R 33χ4 „ Id (Rl is OR 33 ) base Scheme 2 illustrates the preparation of compounds of Formula Id (A is as defined in Scheme 1; R 1 is S(O) x R 34 wherein x is 1 or 2, and R 34 is C j -C 6 alkyl or C C 6 haloalkyl) whereby a compound of Formula Id (A is as defined in Scheme 1; R 1 is SR 34 ) is reacted with an oxidizing reagent such as peroxyacetic acid, -chloroperoxybenzoic acid, potassium peroxymonosulfate (e.g., 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 ofSulphones and Sulphoxides, John Wiley & Sons, (1988); pp 205-213, 235-253. Protecting and deprotecting functional groups not compatible with the reaction conditions may be necessary for compounds with such a functional group (for procedures, see T. W. Greene et al., Protective Groups in Organic Synthesis, 2nd Edition, John Wiley & Sons). Scheme 2 Id (R ! is SR 34 ) »- Id (R J is S(0) χ R 34 ) oxidizing reagent Compounds of Formula Id (A is as defined in Scheme 1; R 1 is Nu; Nu is SR 34 or OR 35 wherein R 34 is as defined in Scheme 2 and R 35 is Cι-C 6 alkyl, Cι-C 6 haloalkyl or C 2 -C 6 alkoxyalkyl) can be prepared by one skilled in the art from a compound of Formula Id (A is as defined in Scheme 1 ; Rl is halogen) by treatment with a nucleophilic reagent of Formula 2 (Nu is SR 34 or OR 35 ; M is Na, K or Li) as shown in Scheme 3 using methods documented in the literature (or slight modification of these methods); for example, see S. Miyano et al., J. Chem. Soc, Perkin Trans. 1 (1976), 1 146. Scheme 3 Id (R ! is halogen) + MSR 34 or MOR 35 *■ Id (R l is SR 34 or OR 35 ) 2 Compounds of Formula Id (A is as defined in Scheme 1; R 1 is halogen) can be prepared by reacting a compound of Formula Id (A is as defined in Scheme 1; R l 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 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 (Rl is OH) Id (R is halogen) halogenating reagent (e.g., oxalyl bromide or oxalyl chloride) Scheme 5 illustrates the preparation of compounds of Formula Id (A is A-2 wherein Rl 5 and R 6 are taken together with the carbon to which they are attached to form C(=O)) whereby a compound of Formula Id (A is A-2 wherein R* 5 and R ϊ6 are independently Cι-C 6 alkoxy or R 15 and R 16 are taken together to form -O-(CH 2 ) r -O-) is stirred in aqueous hydrochloric or hydrobromic acid (0.1 to 12N) at temperatures between 0 and 100 °C for a period of time ranging from 30 minutes to 3 days. This conversion is carried out by methods known in the art (or slight modification of these methods); see for example, P. A. Grieco et al., J. Am. Chem. Soc. (1977), 99, 5773; P. A. Grieco et al, J. Org. Chem. (1978), 43, 4178. Scheme 5 , . HC1 H 2 0 Id (A is A-2 wherein R 1:> and R 10 ** ► Id (A is A-2 wherein R 15 and R* 6 are independently C j -C β alkoxy or HBr H 2 0 are taken together with the carbon to which they are attached to form C(=0)) or R!^ or Rl" are taken together with the carbon to which they are attached to form -0-(CH 2 ) r -0-) Scheme 6 illustrates the preparation of compounds of Formula Id (A is as defined in Scheme 1) whereby an enol ester of Formula 3 (A is as defined in Scheme 1) is reacted with a base such a triethylamine in the presence of a catalytic amount of a cyanide source (e.g., acetone cyanohydrin or potassium cyanide). This rearrangement is carried out by general methods known in the art; see for example, W. J. Michaely, EP 369,803. Scheme 6 2 cyanohydrin or potassium cyanide) Enol esters of Formula 3 (A is as defined in Scheme 1) can be prepared by reacting a dione of Formula 4 with an acid chloride of Formula 5 (A is as defined in Scheme 1 ) in the presence of a slight molar excess of a base such as triethylamine in an inert organic solvent such as acetonitrile, dichloromethane or toluene at temperatures between 0 and 110 °C (Scheme 7). This type of coupling is known in the art; see for example, W. J. Michaely, EP 369,803. Scheme 7 4 5 Acid chlorides of Formula 5 (A is as defined in Scheme 1) can be prepared by reacting an acid of Formula 6 (A is as defined in Scheme 1) with oxalyl chloride (or thionyl chloride) and a catalytic amount of N,N-dimethylformamide (DMF) (Scheme 8). This chlorination is well known in the art; see for example, W. J. Michaely, EP 369,803. Scheme 8 oxalyl chloride (optionally, a catalytic amount of DMF) As shown in Scheme 9, acids of Formula 6 can also be utilized to directly react with dione 4 in a direct ester formation reaction to provide esters of Formula 3. A promoter such as 1,3-dicyclohexyl carbodiimide, 1,1-carbonyl diimidazole, or 2-chloro-N-methylpyridinium iodide and other reagents known to couple acids and alcohols or phenols can be utilized together with an acid acceptor. The acid acceptor is usually an amine base such as triethylamine or pyridine; see for example, Larock, Comprehensive Organic Transformations, VCH publishing, New York (1989), pp. 978-979; K. Saigo et al., Bull. Chem. Soc. Jap. (1977), 50, 1863; L. Strekowski et al., Synthesis (1983), 493; S. G. Amin et al., Synthesis Commun. (1979), 210. Scheme 9 4 + 6 or other promoter Scheme 10 illustrates the preparation of compounds of Formula Id (A is A-2 wherein R' 5 and Rl 6 are taken together with the carbon to which they are attached to form C(=S)) whereby a compound of Formula Id (A is A-2 wherein R 15 and R 16 are taken together with the carbon to which they are attached to form C(=O)) is reacted with P 4 SJ Q or Lawesson's reagent (2,4-bis(4-methoxyphenyl)- 1 ,3-dithia-2,4-diphosphetane-2,4-disulfιde). This conversion is carried out by general methods known in the art (or slight modification of these methods); for example, see V. K. Lusis et al., Khim. Geterotsiklt. (1986), 5, 709; T. A. Chibisova et al., Zh. Org. Khim. (1986), 22 (9), 2019. Scheme 10 P 4 S 10 or Lawesson's reagent Id (A is A-2 wherein R ] 5 and R 16 Id (A is 2 wherein K ϊ5 and R ϊ 6 are taken together with the carbon are taken together with the carbon to which they are attached to form to which they are attached to C=0)) form C(=S)) The acids of Formula 6 can readily be prepared by one skilled in the art by using the reactions and techniques described in the following Schemes 11-55 and 63 (or by slight modification of these methods). For example, the preparation of acids of Formula 6a are described in Schemes 11-23 and 63. 6a Many acids of Formula 6a (m is 0; k is 0 or 1) can be prepared whereby an acid of Formula 7 (k is 0 or 1) is reacted with chlorosulfonic acid (Scheme 11). The chlorosulfonic acid is used in excess (at least 2 to 10 mole excess) and serves as both reactant and solvent. The reaction is carried out at a temperature between about 25 and 80 °C for a period of time ranging from 1 hour to about 72 hours. After quenching the reaction into excess ice, the mixture is filtered (if a solid is present) or extracted with a solvent such as dichloromethane and concentrated. The immediate residue (or solid from filtration) can be further purified by recrystallization or flash column chromatography procedures on silica gel by one skilled in the art. For an analogous reaction, see W. Werner, United States Patent 4,560,771 (published 1985). Scheme 11 7 (k is 0 or 1) wherein Rl ' is C 2 -C 6 alkyl, C λ -C β haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl or C 2 -C 6 haloalkynyl; and R l2 is R 1 as just defined and also H. Scheme 12 illustrates a method for preparing many acids of Formula 7 whereby a corresponding bromo compound of Formula 8 is reacted with n-butyllithium (or magnesium) and the lithium salt (or 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 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; pp. 27-28; A. J. Bridges et al., J. Org. Chem. (1990), 55, 773; C. Franke et al., Angew Chem. Int. Ed. (1969), 8, 68. Scheme 12 8 (L is Br, k is O or 1) wherein R l and R 12 are as defined in Scheme 11. Scheme 13 illustrates the preparation of many dihydrobenzofurans of Formula 8 (L is H or Br; k is 0) whereby an allyl phenyl ether of Formula 9 (L is H or Br) is heated under Claisen rearrangement conditions (e.g., about 200 °C optionally in the presence of a catalyst such as anhydrous magnesium bromide) by methods known in the art (or slight modification of these methods); see for example, J. March, Advanced Organic Chemistry, 3rd edition (1985), John Wiley & Sons, pp. 1028-1032 and references therein. The allyl phenyl ethers of Formula 9 can be prepared from corresponding phenols and allyl bromides or allyl chlorides by reaction in the presence of a base such as potassium carbonate by methods known in the art; see for example, M. P. Rorer, United States Patent 4,514,211 (published 1985). Also, bromination of dihydrobenzofurans of Formula 8 (L is H) by methods generally known in the art can also provide bromo compounds of Formula 8 (L is Br). Scheme 13 9 (L is H, Br) 8 (L is H) wherein R 1 la is H, Cj-C; alkyl or C^C ζ haloalkyl; Rl 1 is C,-C 6 alkyl or C,-C 6 haloalkyl; and Rl 2 is R π and also H. Chromanes of Formula 8 (k is 1) can be prepared by one skilled in the art also by methods known in the art; see for example, The Chemistry of Heterocyclic Compounds, G. P. Ellis, Ed. (1981), Volume 36, John Wiley & Sons, New York. Many acids of Formula 6a can also be readily prepared, as illustrated in Scheme 14, whereby an ester of Formula 10 (L is CO 2 CH 3 ) is saponified (e.g., potassium hydroxide in methanol, then acidified with an acid such as hydrochloric acid) or, alternatively, acid hydrolyzed (e.g., 5N HCl 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); pp. 5-7. Scheme 14 10 (L isCO 2 CH 3 ) wherein k, m, R 1 1 and Rl 2 are as originally defined. Alternatively, Scheme 15 illustrates many acids of Formula 6a can be prepared whereby an iodo compound of Formula 10 (L is I) is reacted with carbon monoxide (CO) in the presence of a palladium catalyst such as palladium acetate (Pd(OAc) 2 ), a phosphine catalyst such as l,3-bis(diphenylphosphino)propane (dppp), an excess of an alcohol such as methanol, and a base such as triethylamine to form the corresponding ester of Formula 10 (L is CO 2 CH 3 ). This reaction is carried out by methods known in the art (or by slight modification of these methods); see for example, Palladium Reagents in Organic Synthesis, R. F. Heck, Ed. (1985), Academic Press, New York. Subsequent saponifϊcation or acid hydrolysis by methods described in Scheme 14 can provide the acid of Formula 6a. Scheme 15 1) CO, CH 3 OH, N(C 2 H 5 ) 3 , Pd(OAcb, dppp 10 (L is I) l *- 6a 2) e.g., KOH in CH 3 OH, then H + wherein k, m, RU and R 2 are as originally defined. Scheme 16 illustrates the preparation of many esters of Formula 10 (L is CO 2 CH 3 ) or iodo compounds of Formula 10 (L is I) whereby a corresponding hydroxy compound of Formula 1 1 (L is CO 2 CH 3 or I) is reacted with appropriate reagents known in the art to cause water elimination (e.g., with phosphorus oxychloride (POCl 3 ) in pyridine). This reaction can be carried out by methods known in the art (or slight modification of these methods); see for example, J. Erhrenfreund et al, U.S. 4,589,911 (published 1986) and J. M. Clancy et al., Int. J. Sulfur Chem., A (1972), 2, 249. Scheme 16 Q H (L is C0 2 CH 3 or I) wherein R 1 1 and R ϊ 2 are as originally defined, except R 12 is not halogen, cyano, C j -Cg alkoxy, Cj-Cβ haloalkoxy, Ct-Cg alkylthio or C j -Cβ haloalkylthio. Scheme 17 illustrates the preparation of many hydroxy compounds of Formula 11 whereby a sulfonate of Formula 12 is reacted with a suitable base such as 5 l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) to cause cyclization. This reaction is carried out by methods known in the art (or slight modification of these methods); see for example, J. Erhrenfreund et al., U.S. 4,589,911 (published 1986); J. M. Clancy et al., Int. J. Sulfur Chem., A (1972), 2, 249. Scheme 17 12 (L is C0 2 CH 3 or I; k is O or 1) 0 wherein Rl ] and R 12 are as defined in Scheme 16. Scheme 18 illustrates the preparation of many sulfonates of Formula 12 whereby a phenol of Formula 13 is reacted with a sulfonyl chloride of Formula 14 in the presence of a suitable base such as triethylamine by methods known in the art (or slight modification of these methods); see for example, the two references cited in Scheme 17 and J. F. King et al., J. Am. Chem. Soc. (1964), 86, 287. Scheme 18 wherein L, k, Rl l and R J2 are as defined in Scheme 17. Scheme 19 illustrates the preparation of many aldehydes of Formula 13 (k is 0; R i2 is H) whereby a phenol of Formula 15 is reacted with appropriate reagents to introduce an aldehyde group ortho to the phenyl hydroxy group. This reaction can be carried out by a variety of methods well known in the art (or slight modification of these methods); see for example, J. March, Advanced Organic Chemistry, 3rd edition (1985), John Wiley & Sons, pp. 487-491; G. Casiraghi et al., J. Chem. Soc. Perkin I (1980), 1862; R. X. Wang et al., Synthetic Commun. (1994), 24 (12), 1757. A preferred method is hexamethylenetetramine (HMT) in an acid such as polyphosphoric acid; see for example, Y. Suzuki et al., Chem. Pharm. Bull. (1983), 31, 1751. Scheme 19 13 (L is C0 2 CH 3 or I; k is 0; R 2 is H) 15 (L is C0 2 CH 3 or I) Scheme 20 illustrates the preparation of many ketones of Formula 13 whereby an ester of Formula 16 is heated under Fries rearrangement conditions (e.g., about 150 to 200 °C in the presence of a suitable Lewis catalyst such as aluminum chloride) by methods known in the art (or slight modification of these methods); see for example, F. Shawcross et al., J. Het. Chem. (1995), 32, 1393; J. March, Advanced Organic Chemistry (1985), 3rd edition, John Wiley & Sons, pp. 499-501. Scheme 20 13 (L is C0 2 CH 3 or I, k is 0) 16 (L is C0 2 CH 3 or I) wherein R ϊ2 is as defined in Scheme 18. Many iodo compounds of Formulae 13, 15, and 16 (wherein L is I) can be prepared by one skilled in the art by reacting corresponding compounds of Formulae 13, 15, and 16 (wherein L is H) with appropriate iodination reagents known in the art (e.g., with iodine monochloride in acetic acid, optionally with a base such as sodium acetate); see for example, K. M. Tramposch et al., J. Am. Chem. Soc. (1983), 26, 121; J. March, Advanced Organic Chemistry, 3rd Edition (1985), John Wiley & Sons, p. 478. Many aldo phenols of Formula 13 containing an ester group (i.e., L is CO 2 CH 3 ; k is 0; Rl 2 is H) can be prepared by one skilled in the art by a sequence of reactions illustrated in Scheme 21. These reactions can be carried out by methods known in the art whereby (a) a phenyl ether of Formula 17 is reacted with phosphorus oxychloride and DMF to form an aldehyde of Formula 17a (see for example, F. Balkau et al., Aust. J. Chem. (1969), 22, 2489; Buu-Hoi et al., Seanc. Acad. Sci., Paris (1955), 240, 2241 ; (b) deprotection of the aldehyde (e.g., aluminum chloride in benzene) to form a phenol of Formula 17b (see for example, T. W. Greene et al., Protective Groups in Organic Synthesis, 2nd Edition, John Wiley & Sons, pp. 145-174; (c) protection of the phenol by reaction with methanesulfonyl chloride and triethylamine to form a sulfonate of Formula 17c; (d) oxidation with a suitable reagent such as Jones reagent to form an acid of Formula 17d (see for example, S. Lee, United States Patent 5,089,046 (published 1992); (e) deprotection (e.g., aqueous sodium hydroxide) followed by esterification to form an ester of Formula 17e (see for example, T. W. Greene et al., Protective Groups in Organic Synthesis, 2nd edition, John Wiley & Sons, pp. 162 and 169); and (f) reacting the ester with a suitable reagent(s) known in the art for introducing an aldo group ortho to a phenyl hydroxy group, e.g., hexamethylenetetraamine (HMT) in an acid such as polyphosphonic acid (PPA); see for example, Y. Suzuki et al., Chem. Pharm. Bull. (1983), 31, 1751. Scheme 21 17 (L is H; R3 is a protecting (c) C,S ° 2CH3 ' N(C2H 5> 3 group; e.g., CH 3 ) ( d > Jones rea g ent (e) aqueous NaOH, then _ , CH 3 OH (H 2 S0 4 catalyst) 17a (L is CHO; R 3 is CH 3 ) (f) HMT in ppA 17b (L is CHO; R 36 is H) 17c (L is CHO, R 36 is S0 2 CH 3 ) 17d (L is C0 2 H; R 36 is S0 2 CH 3 ) 17e (L is C0 2 CH 3 ; R 36 is H) As illustrated in Scheme 22, many other compounds of Formula 10 (L is CO 2 CH3 or I; k is 0, m is 1) can be prepared whereby an allyl bromide of Formula 18 is reacted with sodium sulfite followed by phosphorus oxychloride by methods known in the art (or slight modification of these methods); see for example, J. M. Clancy, Int. J. Sulfur Chem., A (1972), 2, 249. Compounds of Formula 18 can be prepared by one skilled in the art by methods known in the art. Scheme 22 18 (L is C0 2 CH 3 or I) wherein Rl ' and R i2 are as originally defined. Also, as illustrated in Scheme 23, still other compounds of Formula 10 (R l l is Cl; R 12 is H, Cτ-C 6 alkyl or Cγ-Cf, haloalkyl; and L is CO 2 CH 3 or I) and Formula 10 (Rl * is Br; Rl 2 is H, CJ-CG alkyl or Cj-C 6 haloalkyl; and L is CO 2 CH or I) can be prepared whereby a corresponding compound of Formula 10 (R 1 1 is H; R i2 is H, C j -C 6 alkyl or Cj-C 6 haloalkyl; and L is CO 2 CH 3 or I) is halogenated by reaction with chlorine or bromine followed by dehydrohalogenation by reaction with a suitable base such as pyridine. These reactions can be carried out by methods known in the art (or slight modification of these methods); see for example, J. M. Clancy et al., Int. J. Sulfur Chem., A (1972), 2, 249. Scheme 23 10 (Rl l is H; » 10 (Rl l is Cl or Br; L is C0 2 CH 3 or I) l) Cl 2 or Br 2 L is C0 2 CH 3 or I) 2) e.g., C 5 H 5 N wherein R ϊ2 is H, C C 6 alkyl or Cj-C 6 haloalkyl. Acids of Formula 6b can be prepared by methods illustrated in Schemes 24-36 by one skilled in the art. 6b Scheme 24 illustrates the preparation of many acids of Formula 6b whereby corresponding acids of Formula 6a are catalytically hydrogenated by methods known in the art (or slight modification of these methods); see for example, W. Werner, United States Patent 4,560,771 (published 1985). Scheme 24 6a 6b H 2 , e.g., Pd/C As illustrated in Scheme 25, many acids of Formula 6b can also readily be prepared whereby corresponding esters of Formula 19 (L is CO 2 CH 3 ) are saponified or, alternatively, acid hydrolyzed. This reaction can be carried out by one skilled in the art using methods analogous to those described in Scheme 14. Scheme 25 19 (L is C0 2 CH 3 ) Alternatively, as illustrated in Scheme 26, many acids of Formula 6b can also be prepared from corresponding iodo compounds of Formula 19 (L is I). This reaction can be carried out by methods analogous to those described in Scheme 15 by one skilled in the art. Scheme 26 19 (L is I) «- 6b 1) CO, CH 3 OH, N(C 2 H 5 ) 3 , Pd(OAc) 2 , dppp 2) e.g., KOH in CH 3 OH, then H + Scheme 27 illustrates the preparation of many halogenated compounds of Formula 19 (L is I or CO 2 CH 3 ; R 15 is chlorine, bromine, or fluorine; R ϊ6 is H) whereby a hydroxy compound of Formula 11 is reacted with a suitable halogenating reagent such as thionyl chloride, thionyl bromide, or diethylaminosulfur trifluoride (DAST) by methods known in the art (or slight modification of these methods); see for example, J. March, Advanced Organic Chemistry (1985), 3rd edition, John Wiley & Sons, pp. 382-384; Larock, Comprehensive Organic Transformations, VCH publishing, New York, (1989), pp. 353- 360. Scheme 27 11 (L is C0 2 CH 3 or I) ** *- 19 (L is C0 2 CH 3 or I; SOCl or SOBr or DAST . L and Rl 5 is Cl, Br or F) wherein k is 0 or 1; m is 0; R 12 , R ϊ4 and Rl° are H; and R 3 is R 1 other than halogen. Scheme 28 illustrates the preparation of compounds of Formula 19 (L is I or CO 2 CH 3 ; Rl 5 is Cι-C 6 alkoxy, C j -C 6 haloalkoxy, C j -C 6 alkylthio, C j -Cg haloalkylthio or cyano; R 6 is H) whereby a halogenated compound of Formula 19 (L is I or CO 2 CH 3 ; R 15 is Cl or Br; R 16 is H) is reacted with a nucleophilic reagent of Formula 20 (R 37 is Cj-C 6 alkoxy, Cj- Cs haloalkoxy, Cι~C 6 alkylthio, Cι-C 6 haloalkylthio or cyano; M is Na, K or Li). The reaction is carried out in a suitable solvent such as methanol, DMF or tetrahydrofuran (preferably, methanol) at a temperature range between about 0 and 80 °C and for a time period of about 1 to 8 hours. Following concentration, the immediate residue can be further purified by flash column chromatography procedures on silica gel with mixed eluants such as ethyl acetate and hexanes by one skilled in the art. Scheme 28 19 (L is C0 2 CH 3 or I; *■ 19 (L is C0 2 CH 3 or I; Rl 5 is Cl orBr) R M R15 is C -C 6 alkoxy, C!-C 6 20 haloalkoxy, C j -Cg alkylthio, C j -Cg haloalkylthio or cyano) wherein k, m, R 2 -Rl 4 , R ]6 are as defined in Scheme 27. Scheme 29 illustrates the preparation of compounds of Formula 19 (L is I or CO 2 CH 3 ; R ] 5 and Rl 6 are independently C j -Cg alkoxy, C 2 -C 6 haloalkoxy, Cj-C 6 alkylthio or C 2 -C 6 haloalkylthio; or R 15 and R i6 are taken together to form -Xl-(CH 2 ) r -X 2 - optionally substituted with at least one member selected from 1-6 halogen, 1-6 CH 3 and one C!-C 3 alkoxy; and X J and X 2 are as defined in the Summary of the Invention) whereby a ketone of Formula 21 is reacted with an alcohol, an alkylthiol, or HXl-(CH 2 ) r -X 2 H (optionally substituted with at least one member selected from 1-6 halogen, 1-6 CH 3 and one Cj-C 3 alkoxy; X 1 , X 2 and r are as defined in the Summary of the Invention) in the presence of a protic acid catalyst such as ?-toluenesulfonic acid (or a Lewis acid such as BF 3 ) in an inert organic solvent such as toluene or in an alcohol (if the alcohol is the reagent). This conversion is carried out by general methods known in the art; see for example, T. W. Greene et al., Protective Groups in Organic Synthesis (Second Edition), pp. 175-221, John Wiley & Sons, Inc. Scheme 29 19 (L is I or C0 2 CH 3 ; R 15 and ) Rl" are independently C j -Cg alkoxy, C 2 -Cg haloalkoxy, C l -C 6 alkylthio or C 2 -C 6 21 (L is I or C0 2 CH 3 ) haloalkylthio; or R 15 and Rl *5 are taken together to form -X'^CH^ j .-X 2 -, optionally substituted with at least one member selected from 1-6 halogen, 1-6 CH 3 and one C j -C 3 alkoxy, X 1 , X 2 and r are as defined in the Summary of the Invention.) Scheme 30 illustrates the preparation of compounds of Formula 19 (L is I or CO 2 CH 3 ; R15 and Rl° are taken together to form -(CH 2 ) s -O-, -(CH 2 ) t -X 3 -CH 2 , -(CH 2 ) V -X 3 -CH 2 CH 2 - or -(CH 2 ) W -, each group optionally substituted with at least one member selected from 1-6 halogen, 1-6 CH 3 and one Cj-C 3 alkoxy) where a ketone of Formula 21 is reacted with a Grignard reagent, a sulfonium cycloalkylide, a lithium lithioalkoxide, an organopalladium reagent, a sulfonium ylide or other equivalent reagent in an inert organic solvent. Some of the immediate products from the reactions of Scheme 30 may be further modified to give the desired compounds of Formula 19. The above-mentioned reactions are carried out by methods known in the art (or by slight modification of these methods); for example, see S. Umio et al., J. Med. Chem. (1972), 15, 855; B. Mudryk et al., J. Org. Chem. (1989), 54 (24), 5657; Z. Paryzek et al., Can. J. Chem. (1987), 65 (1), 229; B. M. Trost et al., J. Am. Chem. Soc. (1972), 94, 4111; B. M. Trost et al., J. Am. Chem. Soc. (1985), 107, 1778; S. Fukuzawa et al., J. Chem. Soc. Chem. Comm. (1986), 8, 624; J. F. Gil et al., Tetrahedron (1994), 50 (11), 3437; T. J. Jenkins et al., J. Org. Chem. (1994), 59 (6), 1485; C. J. Li et al., Organometallics (1991), 10 (8), 2548; E. J. Corey et al., J. Am. Chem. Soc. (1965), 87 1353; K Okuma et al., J. Org. Chem. (1983), 48, 5133. Scheme 30 21 (L is I or C0 2 CH 3 ). 19 (L is I or C0 2 CH 3 ; R 15 and Grignard reagent, sulfonium R 1 " are taken together to form cycloalkylide, lithium lithioalkoxide, organopalladium -(CH 2 ) x -0-, -(CH 2 ) t -X 3 -CH 2 -, reagent, sulfonium ylide or -(CH 2 ) V -X 3 -CH 2 CH 2 - or other equivalent reagent -(CH 2 ) W -, each group optionally substituted with at least one member selected from 1-6 halogen, 1-6 CH 3 and C1-C3 alkoxy) Scheme 31 illustrates the preparation of compounds of Formula 19 (L is I or CO CH 3 ; Rl 5 and Rl 6 are taken together to form -(CH 2 ) S -S- optionally substituted with at least one member selected from 1-6 halogen, 1-6 CH and one C ] -C alkoxy) whereby a thioketone of Formula 22 is reacted with a dibromo alkane of Formula 23 in the presence of an equimolar amount or more of ytterbium (Yb) metal in an inert organic solvent such as a mixture of benzene and hexamethylphosphoric triamide. This conversion is carried out by general methods known in the art; see for example, Y. Nakioka et al., Chem. Lett. (1994), (3), 611. Scheme 31 19 (L is I or C0 2 CH 3 ; R 15 and R1° are taken together to form -(CH 2 ) S -S-, optionally substituted with at least one 22 (L is I or C0 2 CH 3 ) member selected from 1-6 halogen, 1-6 CH 3 and one C1-C3 alkoxy) Scheme 32 illustrates the preparation of compounds of Formula 19 (R 5 and R 6 are taken together to form -CH 2 O- or -CH 2 -CH 2 -, each group optionally substituted with at least one member selected from 1-4 halogen, 1-4 CH 3 and one C ] -C 3 alkoxy; or R 15 and R l6 are taken together to form -O-N(C 1 -C 3 alkyl)-CHR 0 -CH 2 - or -O-N=CHR 20 -CH 2 -, each group optionally substituted with at least one member selected from 1-2 halogen and 1-2 CH 3 ) where an alkene of Formula 24 is reacted with a peracid, a Wittig reagent, a nitrone, a silyl nitronate, a nitrile oxide, or a Simmons-Smith reagent in an inert organic solvent. Some of the immediate products from the reactions of Scheme 32 may be further modified to give the desired compounds of Formula 19. The above mentioned reactions are carried out by methods known in the art (or by slight modification of these methods); for example, see M. Chini et al., J. Org. Chem. (1989), 54, 3930; B. Chenera et al., Tetrahedron (1986), 42 (13), 3443; R. Mechoulam et al., J. Am. Chem. Soc. (1958), 80, 4386; A. Hosomi et al., Chem. Lett. (1985), (7), 1049; S. Mzengeza et al., J. Chem. Soc. Chem. Commun. (1984), 9, 606; H. Mitsu et al, Tetrahedron Lett. (1983), 24 (10), 1049; J. E. Baldwin et al., J. Chem. Soc. Chem. Commun. (1968), 373; S. L. Ioffe et al., J. Gen. Chem. USSR (Engl. Transl.) (1973), 43, 1699; A. Brandi et al., Tetrahedron Lett. (1987), 28 (33), 3845; D. P. Curran et al., J. Org. Chem. (1984), 49 (19), 3474; R. J. Rawson et al., J. Org. Chem. (1970), 35 (6), 2057. Scheme 32 peracid, Wittig reagent, nitrone, silylnitronate ». 19 (L is I or C0 2 CH 3 ; R 15 and nitrile oxide or Simmons-Smith reagent R!6 re taken together to form -CH 2 0- or -CH 2 CH 2 -, each 24 (L is I or CC^CH^ R 38 and group optionally substituted from 1-4 halogen, 1-4 CH3 and R 9 are independently H, > 15 „nH p !6 halogen or CH 3 ) one C1-C3 alkoχ y or R and R are taken together to form -0-N(C r C 3 alkyl)-CHR 20 CH 2 - or O-N=CHR 20 -CH 2 -, each group optionally substituted with at least one member selected from 1-2 halogen and 1-2 CH3) Scheme 33 illustrates the preparation of many ketones of Formula 21 (R 15 and R 16 are taken together with the carbon to which they are attached to form C(=O)), whereby a hydroxy compound of Formula 11 is reacted with a suitable oxidizing reagent such as potassium permanganate, manganese dioxide, Jones reagent or, preferably, pyridinium chlorochromate (PCC) by methods known in the art (or slight modification of these methods); see for example, J. Marsh, Advanced Organic Chemistry, 3rd edition (1985), John Wiley & Sons, New York, pp. 1057-1058. Scheme 33 11 (L is I or C0 2 CH 3 ) +■ 21 (L is I or C0 2 CH 3 ) oxidizing agent (e.g., PCC) wherein k, m and R' 3 is as originally defined; and R ]4 is H. Many ketones of Formula 21 can also be prepared, as illustrated in Scheme 34, whereby a propionyl bromide of Formula 25 is reacted with sodium sulfite followed by phosphorus oxychloride. These reactions can be carried out by methods known in the art (or slight modification of these methods); see for example, J. M. Clancy, Int. J. Sulfur Chem., A (1972), 2, 249. Compounds of Formula 25 can be prepared by one skilled in the art by methods known in the art. Scheme 34 25 (L is C0 2 CH 3 or I) wherein k is 0, m is 1 and R* 3 and R' 4 are H. Alkene compounds of Formula 24 can be prepared from the ketones of Formula 21 by general methods known in the art; see for example, J. Hibino et al., Tetrahedron Lett. (1985), 26 (45), 5579; A. S. Rao, Synthetic Commun. (1989), 19 (5-6), 931-942; R. G. Gentles et al., J. Chem. Soc. Perkin Trans. 1 (1991), (6), 1423; F. A. Davis, Tetrahedron Lett. (1991), 32 (52), 7671. The thioketones of Formula 22 can be prepared from the ketones of Formula 21 by general methods known in the art (Scheme 35); see for example, V. K. Lusis et al., Khim. Geterotsiklt. (1986), (5), 709; T. A. Chibisova et al., Zh. Org. Khim. (1986), 22 (9), 2019. Scheme 35 P 4 S 10 or Lawesson's reagent 21 (L is I or C0 2 CH 3 ) * •► 22 (L is I or C0 2 CH 3 ) Scheme 36 illustrates the preparation of oximes of Formula 19 (L is I or CO 2 CH 3 ; R 15 and Rl 6 are taken together with the carbon to which they are attached to form C(=NOR 2J )) whereby a ketone of Formula 21 (L is I or CO 2 CH 3 ) is reacted with a hydroxylamine compound of Formula 26. Alternatively, an oxime of Formula 19 (R i is H) can be further O-alkylated by reaction with an alkylating reagent of Formula 27 (R 21 is Cj-C 3 alkyl, C 3 -C 4 alkenyl or C 3 -C alkynyl; and X 5 is Br, I or trifluorosulfonyloxy) in the presence of a suitable base such as sodium hydride or potassium carbonate and in a suitable solvent such as tetrahydrofuran or DMF. These reactions can be carried out by methods known in the art (or slight modification of these methods); see for example, Sandier and Karo, Organic Functional Group Preparations (1972), Vol. 3, Academic Press, New York, pp. 372-381; J. March, Advanced Organic Chemistry (1985), 3rd edition, John Wiley & Sons, New York, p. 805. Scheme 36 21 (L is I or C0 2 CH 3 ) »- 19 (L is I or C0 2 CH 3 ; R ϊ 5 and H 2 NOR R 16 are taken together with 26 the carbon to which they are attached to form C(=NOR 21 )) or R 2 lχ 5 27 Acids of Formula 6c can readily be prepared by one skilled in the art by using the reactions and techniques described in the following Schemes 37-40 (or by slight modification of these methods) by one skilled in the art. 6c As illustrated in Scheme 37, many acids of Formula 6c can readily be prepared whereby corresponding esters of Formula 28 (L is CO 2 CH 3 ) are saponified or, alternatively, acid hydrolyzed. This reaction can be carried out by methods analogous to those described in Scheme 14 by one skilled in the art. Scheme 37 28 (L is C0 2 CH 3 ) Alternatively, as illustrated in Scheme 38, acids of Formula 6c can be prepared from corresponding iodo compounds of Formula 28 (L is I) by methods analogous to those described in Scheme 15 by one skilled in the art. Scheme 38 1) CO, CH 3 OH, N(C 2 H 5 ) 3 , 2) e.g., KOH in CH 3 OH; then H + Scheme 39 illustrates the preparation of epoxides of Formula 28 (L is I or CO 2 CH 3 ; G is O) whereby a corresponding alkene compound of Formula 10 (L is I or CO CH 3 ) is reacted with a suitable oxidizing reagent such as aqueous hydrogen peroxide (preferably), or peroxytrifluoroacetic acid. This reaction is carried out by methods known in the art (or by slight modification of these methods); see for example, B. Z. Zwanenburg et al., Tetrahedron Lett. (1970), 935; G. B. Payne et al., J. Org. Chem. (1959), 24, 54; W. D. Emmons et al., J. Am. Chem. Soc. (1955), 77, 89. Analogously, acids of Formula 6a (Schemes 11, 14 and 15) can also be reacted to form corresponding epoxides of Formula 6c (L is CO 2 H). This reaction can be carried out by methods described above (or by slight modification of these methods) by one skilled in the art. Scheme 39 10 (L is I or C0 CH 3 ) ** ► 28 (L is I or C0 2 CH 3 ; G is O) oxidizing agent (e.g., H 2 0 2 ) Scheme 40 illustrates the preparation of cyclopropyl compounds of Formula 28 (L is I or CO 2 CH 3 , G is CH 2 ) whereby a corresponding alkene compound of Formula 10 (L is I or CO 2 CH 3 ) is reacted with a suitable sulfur ylide such as dimethylsulfonium methylide. This reaction is carried out by methods known in the art (or by slight modification of these methods); see for example, W. E. Truce et al., J. Org. Chem. (1964), 29, 3277. Scheme 40 10 (L is I or C0 2 CH 3 ) * *► 28 (L is I or C0 2 CH 3 ; G is CH 2 ) sulfur ylide (e.g., (CH 3 ) 2 S=CH 2 ) Acids of Formula 6d can readily be prepared by one skilled in the art by using the reactions and techniques described in the following Schemes 41—43 (or slight modification of these methods) by one skilled in the art. As illustrated in Scheme 41, many acids of Formula 6d can readily be prepared whereby corresponding esters of Formula 29 (L is CO 2 CH 3 ) are saponified or, alternatively, acid hydrolyzed. This reaction can be carried out by methods analogous to those described in Scheme 14 by one skilled in the art. Scheme 41 29 (L is C0 2 CH 3 ) Alternatively, as illustrated in Scheme 42, many acids of Formula 6d can also be prepared from corresponding iodo compounds of Formula 29 (L is I) by methods analogous to those described in Scheme 15 by one skilled in the art. Scheme 42 1) CO, CH 3 OH, N(C 2 H 5 ) 3 , Pd(OAc) 2 , dppp 29 (L is I) * ■ • 6d 2) e.g., KOH in CH 3 OH, then H+ Many compounds of Formula 29 (R !9 is H, k is 0 or 1 , m is 0) can be prepared by one skilled in the art by a sequence of reactions illustrated in Scheme 43. These reactions can be carried out by methods known in the art (or slight modification of these methods) whereby (a) an acid of Formula 30 (R 40 is CO 2 H; R 4Ϊ is benzyl) is reacted with fluorosulfonyl isocyanate (FSI); (b) the formed sulfamyl fluoride of Formula 30a (R 40 is C(=O)NHS(O) 2 F; R 4i is benzyl) is debenzylated by catalytic hydrogenation; and (c) the formed phenol of Formula 30b (R 40 is NHC(=O)S(O) 2 F; R 41 is H) is reacted with a suitable base such as aqueous sodium hydroxide to cause cyclization; see for example, K. Clauss et al., Angew. Chem. Int. Ed. Engl. (1973), 12, 869. Further, as also illustrated in Scheme 43, a compound of Formula 29 (wherein R 19 is H) may be N-alkylated by reaction with an alkylating reagent of Formula 31 (Rl9 is C j -C 3 alkyl, C 3 -C 4 alkenyl or C 3 -C 4 alkynyl; χ6 is Br or I) and a suitable base such as potassium carbonate to form a corresponding compound of Formula 29 (wherein R 19 is Cj-C 3 alkyl, C 3 -C 4 alkenyl or C 3 -C 4 alkynyl). The reaction is carried out in a suitable solvent such as acetonitrile and a temperature range of about -10 to 80 °C for a time range of about 1 to 8 hours. Following concentration, the immediate residue may be further purified by flash column chromatography on silica gel with mixed eluants such as ethyl acetate and hexanes by one skilled in the art. Compounds of Formula 30 can be prepared by one skilled in the art by methods known in the art. Scheme 43 CH 3 ; Rl9χ6 is 0) 31 30a (L is I or C0 2 CH 3 ; R 40 is C(=0)NHS0 2 F; 29 (L is I or C0 2 CH 3 ; R 4 is benzyl) R 19 is Cι-C 3 alkyl, C 3 -C alkenyl or 30b (L is I or C0 2 CH 3 ; C 3 -C 4 alkynyl; R 40 is C(=0)NHS0 2 F; k is 0 or 1 ; m is 0) R 4 is H) Acids of Formula 6e can readily be prepared by one skilled in the art by using the reactions and techniques described in the following Schemes 44—47 (or slight modification of these methods) by one skilled in the art. 6e As illustrated in Scheme 44, many acids of Formula 6e can readily be prepared whereby corresponding esters of Formula 32 (L is CO 2 CH 3 ) are saponified or, alternatively, acid hydrolyzed. This reaction can be carried out by methods analogous to those described in Scheme 14 by one skilled in the art. Scheme 44 32 (L is C0 2 CH 3 ) Alternatively, as illustrated in Scheme 45, many acids of Formula 6e can also be prepared from corresponding iodo compounds of Formula 32 (L is I). The reaction can be carried out by methods analogous to those described in Scheme 15 by one skilled in the art. Scheme 45 1) CO, CH 3 OH, N(C 2 H 5 ) 3 Pd(OAc) 2 , dppp 32 (L is I) 6e 2) e.g., KOH in CH 3 OH, then H + Scheme 46 illustrates the preparation of many compounds of Formula 32 (L is I or CO 2 CH 3 ) from corresponding compounds of Formula 33 (L is I or CO 2 CH 3 ). The reactions can be carried out by methods analogous to those described in Scheme 22 by one skilled in the art. Compounds of Formula 33 can be prepared by one skilled in the art by methods known in the art. Scheme 46 33 (L is I or C0 2 CH 3 ) In addition, Scheme 47 illustrates another method for the preparation of many acids of Formula 6e (k is 0 or 1; m is 0) whereby an acid of Formula 34 is reacted with chlorosulfonic acid. The reaction can be carried out by one skilled in the art following methods analogous to those described in Scheme 11. Acids of Formula 34 (k is 0 or 1) can be prepared by one skilled in the art by methods known in the art. Scheme 47 34 ( is 0 or l) Acids of Formula 6f can readily be prepared by one skilled in the art by using the reactions and techniques described in the following Schemes 48-55 and 63 (or slight modification of these methods). 6f As illustrated in Scheme 48, many acids of Formula 6f can readily be prepared whereby corresponding esters of Formula 35 (L is CO 2 CH 3 ) are saponified or, alternatively, acid hydrolyzed. This reaction can be carried out by methods analogous to those described in Scheme 14 by one skilled in the art. Scheme 48 35 (L is C0 2 CH 3 ) Alternatively, as illustrated in Scheme 49, many acids of Formula 6f can also be prepared from corresponding iodo compounds of Formula 35 (L is I). The reaction can be carried out by one skilled in the art following methods analogous to those described in Scheme 15. Scheme 49 1) CO, CH 3 OH, N(C 2 H 5 ) 3 , Pd(OAc) 2 , dppp 35 (L is I) 6f 2) e.g., KOH in CH 3 OH, then H + Scheme 50 illustrates the preparation of compounds of Formula 35a (L is I or CO CH 3 ) and Formula 35b (L is I or CO 2 CH 3 ) whereby a ketone of Formula 36 (L is I or CO 2 CH 3 ) is reacted with hydrazine of Formula 37 in an inert organic acidic solvent such as glacial acetic acid at a temperature between about 15 and 120 °C for a period of time ranging from about 1 to 24 hours. The reaction is quenched with excess water and filtered if a solid is formed. Alternatively, the suspension can be extracted with a suitable inert organic solvent such as dichloromethane, dried (e.g., over magnesium sulfate) and concentrated. The solid from the filtration or the residue from the concentration can be further purified if needed by recrystallization from an inert organic solvent such as acetonitrile or 1-chlorobutane, or can be flash column chromatographed over silica gel with eluants such as mixtures of ethyl acetate and hexanes to give compounds of Formula 35a and 35b. Compounds of Formula 35a (R 22 is H) or Formula 35b (R 24 is H) may be further N-alkylated by reaction with an alkylating reagent such as ethyl bromide and a suitable base such as potassium t-butoxide to give compounds of Formula 35a (R 22 is Cj-C 3 alkyl) and Formula 35b (R 24 is C j -C 3 alkyl). The reaction is carried out in a suitable inert inorganic solvent such as DMF and the isolation and purification procedures are similar to those just described. Scheme 50 36 (L is C0 2 CH 3 or I) 35a (L is C0 2 CH 3 or I) 35b (L is C0 2 CH 3 or I) wherein R 40 is H or alkyl; R i is H or Cι-C 3 alkyl. Similarly, as illustrated in Scheme 51, compounds of Formula 35c (L is CO 2 CH 3 or I) and Formula 35d (L is CO CH 3 or I) can be prepared by reacting a ketone of Formula 36 with hydroxylamine or hydroxylamine hydrochloride in an inert organic solvent such as ethanol or glacial acetic acid. The reaction can be carried out by methods known in the art (or slight modification of these methods); see for example, A. R. Katritzky et al., Comprehensive Heterocyclic Chemistry, Volume 6 (1984), Pergamon Press, pp. 61-64 and p 118; H. Boshagen, Chem. Ber. (1967), 100, 3326. Scheme 51 35c (L is C0 2 CH 3 or I) 35d (L is C0 2 CH 3 or I) Scheme 52 illustrates the preparation of compounds of Formula 35e (L is I or CO 2 CH 3 ) whereby a ketone of Formula 36 (L is I or CO 2 CH 3 ) is reacted with an amidine of Formula 38. The reaction can be carried out by methods known in the art (or slight modification of these methods); see for example, A. R. Katritzky et al., Comprehensive Heterocyclic Chemistry, Volume 3 (1984), Pergamon Press, pp. 112-114; D. J. Brown et al., J. Chem. Soc. C. (1967), 1922; I. Kogon et al., Org. Synth. (1963), IN, 182. Scheme 53 illustrates the preparation of compounds of Formula 35f whereby a ketone of Formula 39 is reacted with a hydrazine of Formula 40. This conversion is carried out by methods known in the art (or by slight modification of these methods); see for example, A. R. Katritzky et al., Comprehensive Heterocyclic Chemistry (1984), Volume 5, pp. 278- 279, Pergamon Press. Scheme 53 39 (L i C0 2 CH 3 or I) 35f (L is CH 2 CH 3 or I) The ketones of Formula 36 can be prepared by one skilled in the art by reacting a ketone of Formula 21 with an amide dimethyl acetal of Formula 41 (Scheme 54). The reaction can be carried out by methods well known in the art (or slight modification of these methods); see for example, G. Litkei et al., Org. Prep. Proced. Int. (1990), 22, 47-56; N. Dereu et al., J. Organomet. Chem. (1981), 208, 11; B. Gammill, Synthesis (1979), 901. Scheme 54 21 (L is C0 2 CH 3 or I) 36 (L is C0 2 CH 3 or I) 41 The ketones of Formula 39 can be prepared by one skilled in the art by reacting a ketone of Formula 21 with an aldehyde or a ketone of Formula 42 (or its equivalent) in the presence of an acid or a base (Scheme 55). This conversion is well known in the art; see for example, J. L. Gras, Tetrahedron Lett. (1978), 2111; L. Engman et al., Tetrahedron Lett. (1981), 5251; A. Roedig et al., Chem. Ber. (1960), 2294; T. Girija et al., J. Chem. Soc. Perk. Trans. 1 (1991), 1467; A. J. Laurent et al., Tetrahedron Lett. (1992), 8091. Scheme 55 21 ( is I or C0 2 CH 3 )- 39 (L is I or C0 2 CH 3 ) 42 Compounds of General Formula le can be readily prepared by one skilled in the art by using the reactions and techniques illustrated in Schemes 56-58 of this section. le Scheme 56 illustrates the preparation of compounds of Formula le (R 5 is R 5a , R 5a is the same as R 5 as described in the Summary of the Invention excluding H) whereby a compound of Formula le (R 5 is H) is reacted with a reagent of Formula 43 in the presence of a base wherein X 7 is chlorine, bromine, fluorine, OTf, OAc and R 5a is as previously defined. This coupling is carried out by methods known in the art (or by slight modification of these methods); see for example, K. Nakamura et al., WO 95/04054. Scheme 56 le (R 5 is H) + R 5a X 7 *► le (R 5 is R 5a ) 43 Scheme 57 illustrates the preparation of compounds of Formula le (R 5 is H) whereby an ester of Formula 44 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); see for example, W. J. Michaely, EP 369,803. Scheme 57 Λ potassium cyanide) Esters of Formula 44 can be prepared by reacting a hydroxypyrazole of Formula 45 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, dichloromethane or toluene at temperatures between 0 and 110 °C (Scheme 58). This type of coupling is carried out by methods known in the art (or by slight modification of these methods); see for example, W. J. Michaely, EP 369,803. Scheme 58 45 Compounds of General Formula If can be readily prepared by one skilled in the art by using the reactions and techniques described in Schemes 59-62 of this section. If Scheme 59 illustrates the preparation of compounds of Formula If whereby a compound of Formula 46 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); see for example, P. A. Cain et al., EP 560,483; C. J. Pearson et al., EP 636,622. Scheme 59 46 wherein L 1 is a leaving group such as C j -C alkoxy (e.g., OC 2 H 5 ) or N,N-dialkylamino (e.g., dimethylamino), R°a i s R6 0 r COΝH 2 . Scheme 60 illustrates the preparation of compounds of Formula 46 whereby a compound of Formula 47 is reacted with a reagent of Formula 48 or Formula 49. This conversion is carried out by methods known in the art (or by slight modification of these methods); see for example P. A. Cain et al., EP 560,483; C. J. Pearson et al., EP 636,622. Scheme 60 49 wherein R 42 is C j - alkyl. Scheme 61 illustrates the preparation of compounds of Formula 47 whereby an ester of Formula 48 is decarboxylated in the presence of a catalyst, such as p-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); see for example, P. A. Cain et al., EP 560,483; C. J. Pearson et al., EP 636,622. Scheme 61 48 Esters of Formula 48 can be prepared by reacting the metal salt of a compound of Formula 49 with an acid chloride of Formula 5 (Scheme 62). This type of coupling is known in the art; see for example, P. A. Cain et al., EP 560,483; C. J. Pearson et al., EP 636,622. Scheme 62 49 In addition, many intermediate carboxylic acids of Formula 6a and Formula 6f can be prepared by one skilled in the art by a sequence of reactions illustrated in Scheme 63. These reactions can be carried out by methods known in the art (or slight modification of these methods) whereby (a) a bromo or iodo compound of Formula 10 (L is Br or I) or Formula 35 (L is Br or I) is reacted with cuprous cyanide in an inert solvent such as refluxing dimethylforma ide; (b) the formed corresponding cyano derivative is hydrolyzed with an appropriate reagent such as polyphosphoric acid or sulfuric acid to provide the corresponding amide of Formula 10 (L is C(O)NH 2 ) or Formula 35 (L is C(O)NH 2 ); see, for example, Larock, Comprehensive Organic Transformations; VCH Publishing: New York, 1989; p 994; and (c) treatment of the formed amide with an appropriate nitrous acid reagent such as nitrosonium tetrafluoroborate in acetonitrile provides the corresponding carboxylic acid of Formula 6a or Formula 6f; see, for example, Olah, G. et al. J. Org. Chem. (1965), 30, 2386. Scheme 63 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 interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula 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. l 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 l,4-dimethyl-2-(2-propenyloxy)benzene To a suspension of 2,5-dimethylphenol (purchased from Aldrich Chemical Company, 50.0 g, 0.41 mol) and anhydrous potassium carbonate (66.3 g, 0.48 mol) in acetone (350 mL) was added dropwise rapidly 3-bromo-l-propene (purchased from Janssen Chemical Company, 58.5 g). The suspension was heated at reflux overnight (ca. 22 h), cooled to room temperature, filtered, and the filtrate evaporated to dryness to give an oil. The oil was dissolved in hexanes, extracted three times with IN ΝaOH, dried (MgSO 4 ) and concentrated under reduced pressure to yield 51.9 g of the title compound of Step A as an oil. H ΝMR (CDC1 3 ): δ 2.2 (s, 3H), 2.3 (s, 3H), 4.5 (m, 2H), 5.25 (m, IH), 5.4 (m, IH), 6.0-6.1 (m, IH), 6.6 (s, IH), 6.65 (m, IH), 7.0 (m, IH). Step B: Preparation of 3,6-dimethyl-2-(2-propenyl)phenol A 100-mL two-neck round-bottom flask equipped with a thermometer and magnetic stirring bar and containing the title compound of Step A (31.7 g, 0.195 mol) was lowered into an oil bath preheated to 200 °C. The oil in the flask was stirred and heated under nitrogen at 200 °C for 2 h, then the flask was removed from the oil bath and the oil was allowed to cool to room temperature. The oil residue was dissolved in hexane (about 100 mL) and the solution was extracted with aqueous IN ΝaOH (four times with 50 mL each). The aqueous extracts were combined, made acidic to pH 1 by addition of concentrated hydrochloric acid, then extracted with dichloromethane. The organic layer was dried (MgSO ) and concentrated under reduced pressure to yield 24.8 g of the title compound of Step B as an oil. 1ΝMR (CDC1 3 ): δ 2.2 (s, 3H), 2.25 (s, 3H), 3.45 (m, 2H), 4.85 (s, IH), 5.0-5.1 (m, 2H), 5.9-6.0 (m, IH), 6.7 (d, IH), 6.9 (d, IH). Step C: Preparation of 2.3-dihvdro-2.4.7-trimethylbenzofuran To a solution of 23.9 g (0.147 mol) of the title compound of Step B in 60 mL of glacial acetic acid was added 30 mL of 48.5 percent aqueous hydrobromic acid. The suspension was stirred and refluxed for 2 h, then cooled to room temperature and poured over crushed ice (500 g). The aqueous suspension was extracted with hexane (three times with 75 mL each). The hexane extractions were combined and extracted with saturated aqueous sodium bicarbonate (three times with 50 mL each) followed by aqueous IN ΝaOH (50 mL), then dried (MgSO ) and concentrated under reduced pressure to give 21.1 g of oil. The oil was flash chromatographed on silica gel with hexane initially, then with a mixture of hexane and ethyl acetate (8:2 ratio) to yield 14.4 g of the title compound of Step C as an oil. l H ΝMR (CDCI3): δ 1.45 (d, 3H), 2.15 (d, 6H), 2.7 (q, IH), 3.2 (q, IH), 4.9 (m, IH), 6.55 (d, IH), 6.85 (d, IH). Step D: Preparation of 5-bromo-2.3-dihvdro-2.4.7-trimethylbenzofuran To a suspension containing 10.0 g (0.062 mol) of the title compound of Step C and 5.18 g (0.062 mol) of sodium bicarbonate in 40 mL of dichloromethane and 100 mL of water was added dropwise a solution containing 9.85 g (0.062 mol) of bromine in 10 mL of dichloromethane while maintaining the reaction temperature at 0 to 5 °C with external cooling. After completion of addition, the external cooling was removed and the reaction mixture was allowed to stir at room temperature for about 1.25 h. The organic layer was separated, washed with water, dried (MgSO 4 ) and concentrated under reduced pressure to yield 14.4 g of the title compound of Step D as an oil. NMR (CDC1 3 ): δ 1.45 (d, 3H), 2.15 (s, 3H), 2.25 (s, 3H), 2.75 (q, IH), 3.25 (q, IH), 4.9 (m, IH), 7.1 (s, IH). Step E: Preparation of 2,3-dihvdro-2 7-trimethvI-5-benzofurancarboxylic acid To 160 mL of tetrahydrofuran cooled under nitrogen at -70 °C was added n-butyllithium in hexanes (purchased from Aldrich Chemical Company, 2.5N, 18.4 mL, 0.046 mol). To this solution under nitrogen was added dropwise a solution containing the title compound of Step D (10.0 g, 0.042 mol) dissolved in 40 mL of tetrahydrofuran while maintaining the reaction temperature at about -72 to -60 °C. The suspension was stirred at about -65 to -72 °C for 1 hour, then crushed solid carbon dioxide (about 7.0 g, 0.16 mol) was added portionwise at -72 to -60 C C. The suspension was stirred 1 hour at about -75 °C, then the cooling was removed and 120 mL of aqueous IN ΝaOH was added dropwise as the reaction temperature was allowed to rise. After reaching about 10 °C, the suspension was concentrated under reduced pressure until most of the tetrahydrofuran was removed. The aqueous residue was diluted with 200 mL of water, extracted with diethyl ether (twice with 40 mL each), acidified to pH 1 by addition of concentrated hydrochloric acid, then filtered. The isolated solid was washed with water, then dissolved in dichloromethane, dried (MgSO ) and the solution concentrated under reduced pressure to give 5.7 g of the title compound of Step E as a solid melting at 155-158 °C. 1ΝMR (CDC1 3 ): δ 1.5 (d, 3H), 2.2 (s, 3H), 2.5 (s, 3H), 2.7-2.85 (q, IH), 3.3-3.4 (q, IH), 5.0 (m, IH), 7.8 (s, IH); IR (nujol): 1679 cm- l . Step F: Preparation of 3,5,8-trimethyl-l,2-benzoxathiin-6-carboxylic acid 2,2-dioxide To chlorosulfonic acid (60 mL) was added portionwise the title compound of Step E (9.5 g, 0.046 mol) to give a black suspension with some exothermicity (to 29 °C). The suspension was stirred and heated under nitrogen at 60 °C for 3.5 h then at 80 °C for about 42 h. The black suspension was cooled to room temperature and poured slowly and cautiously onto excess crushed ice. The obtained light tan suspension was filtered, the isolated solid was dissolved in aqueous IN ΝaOH and extracted with ethyl acetate (twice with 30 mL each), and then the aqueous layer was acidified to pH 1 with concentrated hydrochloric acid and filtered. The isolated solid was dissolved in dichloromethane and a small amount of tetrahydrofuran. The solution was dried (MgSO 4 ) and then concentrated under reduced pressure to yield 4.4 g of the title compound of Step F as a light tan solid with a melting point of 208-210 °C. iH NMR ((CD 3 ) 2 SO): δ 2.3 (s, 3H), 2.35 (s, 3H), 2.6 (s, 3H), 7.65 (s, IH), 7.75 (s, IH), 13.1-13.3 (br s, IH). Step G: Preparation of 3-oxo-l-cvclohexen-l-yl 3,5.8-trimethyI-L2-benzoxathiin-6- carboxylate 2,2-dioxide To oxalyl chloride (about 15 mL) was added the title compound of Step F (2.0 g, 0.0075 mol). The suspension was heated at reflux under nitrogen for about 2.5 h (giving a solution) then concentrated under reduced pressure. The residue was twice taken up in dichloromethane (30 mL) and concentrated under reduced pressure. Another portion of dichloromethane (25 mL) was added to the residual gum and the solution was cooled to about 5 °C. 1,3-Cyclohexanedione (purchased from Aldrich Chemical Company, 0.84 g, 0.0075 mol) was added, followed by triethylamine (1.52 g, 0.015 mol), and the suspension was stirred overnight while warming to room temperature. The solution was concentrated under reduced pressure and the residue was dissolved in ethyl acetate (30 mL). The ethyl acetate solution was extracted with water (30 mL), dilute aqueous sodium bicarbonate (IN, 30 mL), aqueous sodium hydroxide (IN, 20 mL) and then water again (30 mL). The ethyl acetate solution was dried (MgSO 4 ) and concentrated under reduced pressure to yield 1.4 g of the title compound of Step G as a solid with a melting point of 199-203 °C. 'ΝMR (CDC1 3 ): δ 2.15 (m, 2H), 2.4-2.5 (m, 8H), 2.7 (m, 5H), 6.0 (s, IH), 7.2 (s, IH), 7.85 (s, IH). Step H: Preparation of 3-hvdroxy-2-f(3,5.8-trimethyl- 1 ,2-benzoxathiin-6-yl)carbonyl1- 2-cvclohexen-l-one 5. -dioxide The title compound of Step G (2.16 g, 0.006 mol), triethylamine (1.2 g, 0.012 mol) and acetone cyanohydrin (purchased from Aldrich Chemical Company, 6 drops) was added to acetonitrile (100 mL) and the suspension was allowed to stir at room temperature under nitrogen overnight. The resultant solution was evaporated to dryness, and ethyl acetate (100 mL) and aqueous sodium hydroxide (IN, 200 mL) were added to the residue. The aqueous layer was separated, extracted twice more with ethyl acetate (75 mL each), then acidified to pH 1 by addition of concentrated hydrochloric acid. The suspension was filtered, the solid was washed with water and suction-dried to yield 1.2 g of a solid which was about 85% of the title compound of Step H, a compound of the invention, melting at 205-230 °C, and about 15% of the title compound of Step F. iH ΝMR (CDC1 3 ): δ 2.05 (m, 2H), 2.25- 2.5 (m, I IH), 2.8 (m, IH), 6.95 (s, IH), 7.1 (s, IH), 17.4-17.7 (br s, IH). EXAMPLE 2 Step A: Preparation of 2-hvdroxy-3.6-dimethylbenzaldehvde By the procedure of G. Casiraghi et al. J. Chem. Soc. Perk. Trans. 1 (1980), p 1862, 2,5-dimethylphenol (purchased from Aldrich Chemical Company, 30.6 g, 0.25 mol) was reacted with paraformaldehyde (17.4 g, 0.55 mol), tributylamine (18.6 g, 0.1 mol) and tin tetrachloride (2.92 mL, 0.025 mol) in about 50 mL of refluxing toluene. Following workup by the procedure described in the above reference, the crude oil was further purified by flash chromatography on silica gel eluting with a mixture of hexane:ethyl acetate (9.7:0.3, then 9.5:0.5) to yield 16.9 g of the title compound of Step A as a solid melting at 47-50 °C. 1NMR (CDC1 3 ): δ 2.2 (s, 3H), 2.55 (s, 3H), 6.6 (d, IH), 7.2 (d, IH), 10.35 (s, IH), 12.1 (s, IH). Step B: Preparation of 3-bromo-6-hvdroxy-2.5-dimethylbenzaldehyde To a suspension containing 30.0 g (0.2 mol) of the title compound of Step A and 17.2 g (0.21 mol) of anhydrous sodium acetate in 250 mL of acetic acid was added dropwise a solution containing 33.6 g (0.21 mol) of bromine in 35 mL of acetic acid while maintaining the reaction temperature between 25 and 40 °C with external cooling. The suspension was stirred about 1 h at room temperature then poured into excess water (500 mL). The aqueous mixture was filtered, and the isolated solid was washed with water then suction dried to yield 44.3 g of the title compound of Step B as a solid melting at 72-76 °C. H NMR (CDC1 3 ): δ 2.2 (s, 3H), 2.6 (s, 3H), 7.3 (s, IH), 10.35 (s, IH), 12.35 (s, IH). Step C: Preparation of 3-bromo-2,5-dimethyl-6-f(methylsulfonyl)oxy1benzaldehvde To a solution containing 44.0 g (0.19 mol) of the title compound of Step B and 29.1 g (0.29 mol) of triethylamine in 290 mL of dichloromethane was added dropwise a solution containing 24.2 g (0.21 mol) of methanesulfonyl chloride in 30 mL of dichloromethane while maintaining the reaction temperature between 0 and 5 °C with external cooling. The suspension was stirred at 0 °C for 0.7 h, and then an additional 1.0 g of methanesulfonyl chloride was added to complete the reaction. After stirring an additional 0.15 h at 0 to 5 °C the suspension was added to aqueous IN HCl (300 mL). The organic layer was separated, extracted with aqueous IN HCl (twice with 100 mL), dried (MgSO 4 ), then concentrated under reduced pressure to yield 57.8 g of the title compound of Step C as a solid melting at 101-105 °C. iH ΝMR (CDC1 3 ): δ 2.35 (s, 3H), 2.6 (s, 3H), 3.35 (s, 3H), 7.7 (s, IH), 10.35 (s, IH). Step D: Preparation of 6-bromo-5.8-dimethyl-l,2-benzoxathiin-4(3H)-one 2.2-dioxide To a solution containing 36.7 g (0.12 mol) of the title compound of Step C in 188 mL of dichloromethane was added dropwise a solution containing 18.2 g (0.12 mol) of 1,8- diazabicyclo[5.4.0]undec-7-ene (DBU) in 20 mL of dichloromethane while maintaining the reaction temperature between 0 and 5 °C with external cooling. After stirring at 0 to 5°C for 1 h the solution was diluted with 200 mL of dichloromethane, extracted with aqueous IN ΗC1 (twice with 75 mL) and then with water, then dried (MgSO ) and concentrated under reduced pressure to yield 39.9 g of crude solid. In similar fashion, this reaction was repeated using 60.2 g (0.196 mol) of the title compound of Step C and 29.8 g (0.194 mol) of DBU in 307 mL of dichloromethane to yield 71.7 g of crude solid. The above crude solids were combined. A solution containing 97.0 g of the combined solids in 1.67 L of dichloromethane was added portionwise at room temperature to a suspension containing 102.5 g (0.475 mol) of pyridinium chlorochromate and 114.3 g of Celite® in 1.34 L of dichloromethane which had stirred about 0.25 h prior to addition of the crude solid solution. The suspension was stirred at 25 °C overnight (ca. 16 h) and was then filtered through a thick pad of Celite®. The filtrate was concentrated under reduced pressure. The residue was dissolved in dichloromethane and flashed chromatographed over silica gel with dichloromethane to yield 68.9 g a crude solid. The solid was dissolved in aqueous IN NaOH (300 mL). The aqueous solution was extracted with diethyl ether (twice with 100 mL) and then acidified with concentrated hydrochloric acid and filtered. The isolated solid was dissolved in dichloromethane, dried (MgSO 4 ), and the solution was concentrated under reduced pressure to yield 49.5 g the title compound of Step D as a solid melting at 132-135 °C. i NMR (CDC1 3 ): δ 2.35 (s, 3H), 2.7 (s, 3H), 4.45 (s, 2H), 7.75 (s, IH). IR (nujol): 1698 cm *1 . Step E: Preparation of 6-bromo-3-r(dimethylamino)methylenel-5.8-dimethyl- 1 ,2- benzoxathiin-4(3H)-one 2.2-dioxide 4.9 g (0.04) of 94% dimethylformamide dimethyl acetal (Aldrich Chemical Company) was added to a suspension containing 10.0 g (0.033 mol) of the title compound of Step D in 38 mL of toluene. The suspension was refluxed for 2.5 h and then cooled to 15 °C and filtered. The residue was washed with hexane and suction dried to yield 10 g of the title compound of Step E as a solid melting at 145-148 °C. J Η NMR (CDC1 3 ): δ 2.3 (m, 3H), 2.65 (m, 3H), 3.4 (m, 6H), 7.6 (s, IH), 8.1 (s, IH). Step F: Preparation of 8-bromo-2,6,9-trimethyl-2H-f 1 ,21benzoxathiinor4,3-clpyrazole 4.4-dioxide 1.8 g (0.036 mol) of hydrazine monohydrate was added to a suspension containing 10.0 g (0.028 mol) of the title compound of Step E in about 80 mL of acetic acid. The suspension was stirred at 25 °C overnight (ca. 16 h), refluxed for 2 h, then cooled to room temperature and poured into excess ice/water. The mixture was filtered and the isolated solid was dissolved in dichloromethane and a small amount of tetrahydrofuran. The solution was dried (MgSO ) and the filtrate was concentrated under reduced pressure to yield 9.0 g of a solid melting at 233-237 °C. 8.05 g of this solid was dissolved in 50 mL of dimethylformamide and to it was added 2.9 g (0.0245 mol) of 95% potassium tert-butoxide (Aldrich). After stirring under nitrogen for 1 h, 6.95 g (0.049 mol) of methyl iodide was added. The suspension was stirred at room temperature for 3 h then poured into excess ice/water. After stirring for about 0.25 h, the suspension was filtered, and the isolated solid was suction dried to yield 7.8 g of the title compound of Step F as a solid melting at 214-217 °C. 1Η NMR (CDCI3): δ 2.4 (s, 3Η), 2.85 (s, 3H), 7.5 (s, IH), 7.95 (s, IH). Step G: Preparation of 2.6.9-trimethyl-2H-r 1.21benzoxathiinof4.3-clpyrazole-8- carbonitrile 4.4-dioxide A suspension containing 5.6 g (0.016 mol) of the title compound of Step F and 2.1 g (0.023 mol) of copper (I) cyanide in about 70 mL of dimethylformamide was refluxed under nitrogen for 21 h then cooled to 25 °C and poured into excess water. The mixture was filtered and the isolated solid was flash chromatographed on silica gel with a mixture of hexane:ethyl acetate (1:1, then 1:9, then 100% ethyl acetate) to yield 4.0 g of the title compound of Step G as a solid melting at 227-230 °C. iH NMR ((CD 3 ) 2 SO): δ 2.35 (s, 3H), 2.85 (s, 3H), 4.1 (s, 3H), 7.9 (s, IH), 8.9 (s, IH); IR (nujol): 2229 cm " l. Step H: Preparation of 2.6.9-trimethyl-2H-r 1 ,21benzoxathiinor4,3-clpyrazole-8- carboxamide 4.4-dioxide To about 37 mL of polyphosphoric acid being stirred and heated in an oil bath at 115 °C was added portionwise 1.95 g (0.0068 mol) of the title compound of Step G. The suspension was stirred and heated at about 120 °C for 6.5 h then cooled to 25 °C. Excess ice water was added to the suspension. The resulting mixture was filtered and the isolated solid was washed with water then suction dried to yield 1.5 g of the title compound of Step Η as a solid melting at 240-243 °C (decomp). lΗ NMR ((CD 3 ) 2 SO): 2.35 (s, 3Η), 2.7 (s, 3H), 4.1 (s, 3H), 7.4 (s, IH), 7.6 (s, IH), 7.9 (s, IH), 8.85 (s, IH). Step I: Preparation of 2,6.9-trimethyl-2H-r 1.21benzoxathiino[4,3-clpyrazole-8- carboxylic acid 4.4-dioxide To a suspension containing 1.68 g (0.0055 mol) of the title compound of Step Η in 30 mL of acetonitrile under nitrogen was added portionwise 1.28 g (0.011 mol) of nitrosonium tetrafluoroborate (Aldrich Chemical Company) while maintaining the reaction temperature between 20 to 27 °C with external cooling. The suspension was stirred at 25 °C for 1.5 h, heated at 50 °C in an oil bath for 4 h, then cooled to 25 °C. After adding 5 mL of water and stirring several minutes, the suspension was concentrated under reduced pressure at 30 °C. Water was added to the residue and the mixture was filtered. The isolated solid was washed with water, then slurried in warm acetonitrile (15 mL). The slurry was cooled to 25 °C and filtered to yield 0.96 g of the title compound as a solid melting at 287 °C (decomp). J Η NMR ((CD 3 ) 2 SO): δ 2.35 (s, 3H), 2.95 (s, 3H), 4.1 (s, 3H), 7.85 (s, IH), 8.9 (s, IH), 13.3 (s, IH). Step J: Preparation of 5.5-dimethyl-3-oxo-l-cvclohexen-l-yl 2.6.9-trimethyl-2H- T 1.21benzoxathiinor4.3-clpyrazole-8-carboxylate 4.4-dioxide To 20 mL of oxalyl chloride was added 1.5 g (0.0049 mol) of the title compound of Step I. The suspension was heated at reflux for 3 h (giving a solution) and concentrated under reduced pressure. The residue was twice taken up in dichloromethane (20 mL) and concentrated under reduced pressure to yield 1.59 g of solid. The solid was added to 30 mL of dichloromethane and the solution was cooled to 10 °C. 0.86 g (0.0058 mol) of 5,5- dimethylcyclohexanedione (Aldrich Chemical Company) was added followed by 1.76 g (0.0174 mol) of triethylamine. The suspension was stirred at room temperature overnight and then concentrated under reduced pressure. The residue was diluted with water (30 mL) and the suspension was filtered. The residue was added to 75 mL aqueous IN ΝaOΗ, stirred several minutes, then the suspension was filtered. The residue was washed with water (20 mL) and suction dried to yield 1.87 g of the title compound of Step J as a solid melting at 199-202 °C. IH NMR ((CD 3 ) 2 SO): δ 1.1 (s, 6H), 2.3 (s, 2H), 2.35 (s, 3H), 2.6 (s, 2H), 2.9 (s, 3H), 4.1 (s, 3H), 6.05 (s, IH), 8.0 (s, IH), 8.9 (s, IH). Step K: Preparation of 3-hvdroxy-5.5-dimethyl-2-r(2.6.9-trimethyl-4.4-dioxido-2H- T 1.21benzoxathiinof4,3-clpyrazol-8-yl)carbonyll-2-cvclohexen- 1 -one 1.72 g (0.004 mol) of the title compound of Step J, 0.81 g (0.008 mol) of triethylamine and 10 drops of acetone cyanohydrin were added sequentially to 75 mL acetonitrile and the suspension was stirred under nitrogen overnight (ca. 24 h). The resultant solution was added to 125 mL water to afford a solution. The solution was acidified with concentrated hydrochloric acid, then filtered, and the isolated solid was washed with water. The solid was further purified by stirring in hot acetonitrile (5-10 mL), cooling to 25 °C and filtering to yield 1.26 g of the title compound of Step K, a compound of this invention, as a solid melting at 256-259 °C. lΗ NMR ((CD 3 ) 2 SO): δ 1.05 (s, 6Η), 2.35 (s, 3H), 2.4-2.65 (m, 7H), 4.05 (s, 3H), 7.25 (s, IH), 8.85 (s, IH), 16.8 (br s, IH). EXAMPLE 3 Step A: Preparation of l-ethyl-lH-pyrazol-5-yl 2.6.9-trimethyl-2H- π .21benzoxathiinof4.3-c1pyrazole-8-carboxylate 4,4-dioxide To 20 mL of oxalyl chloride was added 1.5 g (0.0049 mol) of the title compound of Step I of Example 2. The suspension was heated at reflux for 3 h (giving a solution) then concentrated under reduced pressure. The residue was twice taken up in dichloromethane (20 mL) and concentrated under reduced pressure to yield 1.59 g of solid. The solid was added to 25 mL of dichloromethane and cooled to 10 °C. 0.66 g (0.00584 mol) of 1 -ethyl- lH-pyrazol-5-ol was added followed by 1.5 g (0.015 mol) of triethylamine. The suspension was stirred at room temperature about 48 h then evaporated to dryness. Water (30 mL) was added to the residue and the suspension was filtered. The isolated solid was further purified by flash chromatography on silica gel using a mixture of hexane:ethyl acetate (6:4) to yield 1.2 g of the title compound of Step A as a solid melting at 202-205 °C. Η NMR ((CD 3 ) 2 SO): δ 1.3 (m, 3Η), 2.4 (s, 3H), 3.0 (s, 3H), 4.05 (m, 5H), 6.25 (s, IH), 7.5 (s, IH), 8.15 (s, IH), 8.9 (s, IH). Step B: Preparation of ( l-ethyl-5-hvdroxy- lH-pyrazol-4-yl)(2.6.9-trimethyl-4.4- dioxido-2H-r 1.21benzoxathiinor4.3-c1pyrazol-8-yl)methanone 1.1 g (0.0027 mol) of the title compound of Step A, 0.55 g (0.0055 mol) of triethylamine and 7 drops of acetone cyanohydrin were added sequentially to 50 mL of acetonitrile and the suspension was stirred under nitrogen overnight (ca. 16 h). A few crystals of potassium cyanide were added and the solution was stirred an additional 3 h and then concentrated under reduced pressure. Water (40 mL) was added to the residue and the formed cloudy solution was acidified with concentrated hydrochloric acid. The resultant mixture was filtered. The isolated solid was washed with water (twice with 20 mL), then recrystallized from acetonitrile to yield 0.72 g of the title compound of Step B, a compound of this invention, as a solid melting at 155 °C (decomp). iH NMR (CDC1 3 ): δ 1.5 (m, 3H), 2.4 (s, 3H), 2.75 (s, 3H), 4.1 (m, 5H), 5.8 (br s, 2H), 7.35 (s, IH), 7.4 (s, IH), 8.0 (s, IH). By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 36 can be prepared. The following abbreviations are used in the Tables which follow: t = tertiary, s - secondary, n = normal, i = iso, c = cyclo, Me = methyl, Et = ethyl, Pr = propyl, i-Pr = isopropyl, Bu = butyl, Ph = phenyl, OMe = methoxy, OEt = ethoxy, SMe = methylthio, SEt = ethylthio, CN = cyano, NO 2 = nitro, TMS = trimethylsilyl, S(O)Me = methylsulfinyl, and S(O) Me = methylsulfonyl. q is O k m R 1 R 9 .10 .11 R 12 0 0 OH 0 0 OH 0 0 OH 0 0 OH 0 0 OH 0 0 OH 0 0 OH 0 0 OH 0 0 OH 0 0 OH 0 0 OH 0 0 OH 0 0 OH 0 0 OH 0 0 OH 0 0 OH qisO m Rl R 9 RlO R 13 R 14 R 15 R 16 0 0 OH CH 3 4-CH 3 H H -CH 2 (CH 2 ) 2 CH 2 - 0 0 OH CH 3 4-CH 3 H H -CH 2 (CH 2 ) 3 CH 2 - 0 0 OH CH 3 4-CH 3 H H -CH 2 CH 2 CH 2 0- 0 0 OH CH 3 4-CH 3 H H -SCH 2 CH 2 S- 0 0 OH CH 3 4-CH 3 H H -SCH 2 CH 2 0- 0 OH CH 3 4-CH 3 H H -SCH 2 CH 2 CH 2 S- 0 OH CH 3 4-CH3 H H =0 0 OH Cl 4-C1 H H =0 0 OH CH 3 4-CH3 H H =N(OH) 0 OH CH 3 4-CH3 H H =N(OCH 3 ) 1 0 OH CH 3 4-CH 3 H H =0 1 0 OH CH 3 4-CH 3 H H -OCH 2 CH 2 0- 1 0 OH CH 3 4-CH 3 H H =N(OCH 3 ) 1 OH CH 3 4-CH 3 H H =0 1 OH CH 3 4-CH 3 H H -OCH 2 CH 2 0- 1 OH CH 3 4-CH 3 H H =N(OCH 3 ) Rl is OH, R 9 is CH 3 , R 10 is 4-CH 3 m R 2 »13 -14 R 15 R 16 H H CN H H H CH 3 H Et H n-Pr H -Pr H R 1 R 2 R 9 R 10 Rl7 TABLE 6 R 2 R 9 R 10 R 19 m R l R 2 R 9 .10 TABLE 8 R 1 R 2 R 9 R 10 R 22 R 23 .1 R 2 R 9 R 10 R 24 R 25 0 0 OH CH 3 4-CH 3 CH 3 H 0 0 OH CH 3 4-CH 3 CH 3 CH 3 0 0 OH CH 3 4-CH 3 Et H 0 0 OH CH 3 4-CH 3 n-Pr H TABLE 10 R R 2 R 9 R 10 R 26 0 0 OH CH 3 4-CH 3 H 0 0 OH CH 3 H H 0 0 OH CH 3 4-CH 3 CH 3 0 1 OH 5-CH3 CH 3 4-CH 3 H 0 2 OH 5,5-di-CH 3 CH 3 4-CH 3 H TABLE 11 m R' R 2 R 9 R 10 R 27 m R 1 R 2 R 9 .10 R 28 R 29 R 2 R 9 R 10 R 30 R 31 R 32 R 5 isH m R3 R 4 R 9 R 10 R 11 R12 0 H Et 4-F CH 3 H in R3 R 4 R 9 R 10 R 1 1 R 12 Et CH 3 4-CH 3 CH 3 H Et CH 3 4-CH 3 CH 3 H H CH 3 4-CH 3 CH 3 H CH 3 CH 3 4-CH 3 CH 3 H n-Pr CH 3 4-CH 3 CH 3 H i-Pr CH 3 4-CH 3 CH 3 H CH 2 CF 3 CH 3 4-CH 3 CH 3 H phenyl CH 3 4-CH 3 CH 3 H benzyl CH 3 4-CH 3 CH 3 H Et CH 3 4-CH 3 CH 3 H Et CH 3 4-CH 3 CH 3 H m R 3 R 4 R 5 R 9 ' 10 R 13 R 14 R 15 R 16 R 3 is H, R 4 is Et, R 5 is H m R 9 R 10 R 13 R 14 .15 R 16 0 CH 3 4-CH 3 H n-Pr H H m G R R 4 R5 R 9 .10 Rl7 R 18 TABLE 19 _k_ R 3 R 4 _R R9 RlO Rl9 0 0 H Et H CH 3 4-CH 3 H 0 0 H Et H CH 3 4-CH 3 CH 3 0 0 H Et H CH 3 4-CH 3 Et 0 0 H Et H CH 3 4-CH 3 n-Pr 0 H Et H CH 3 4-CH 3 i-Pr TABLE 20 m R3 R 4 R5 R 9 RlO m R 3 R 4 R^ R 9 (10 R 22 R 23 m R R 4 R5 R9 RIO R 24 R25 TABLE 23 m R3 R 4 R5 R 9 r-10 R 26 m R3 R5 R 9 R 10 R 27 R3 R 4 R5 R 9 R 10 R 28 R 29 0 H Et H CH 3 H 0 H Et H Cl H 0 H Et H CH 3 H 0 H Et H N0 2 H 0 H Et H CH 3 H m R 3 R 4 R5 R 9 R 10 R 30 R 31 R 32 7 R 6 R 7 R 9 R 10 R 17 R 18 0 CH 2 H cyclopropyl CH 3 4-CH 3 H H 0 CH 2 H cyclopropyl CH 3 4-CH 3 CH 3 H 0 CH 2 H cyclopropyl CH 3 4-CH 3 H CH 3 0 CH 2 H cyclopropyl CH 3 4-CH 3 CH 3 CH 3 H cyclopropyl CH 3 4-CH 3 H H H cyclopropyl CH 3 4-CH 3 CH 3 H H cyclopropyl CH 3 4-CH 3 H CH 3 H cyclopropyl CH 3 4-CH 3 H H 2 H cyclopropyl CH 3 4-CH 3 H H H cyclopropyl CH 3 4-CH 3 H H H cyclopropyl CH 3 4-CH 3 H H TABLE 28 m R6 R7 R 9 RlO R6 R7 R 9 R 10 R 22 R 23 TABLE 30 m R6 R 9 R 10 R 24 R 25 R c R7 R 9 (10 R 26 ι * n R 6 R 7 R 9 R 10 R30 R 31 R 2 0 H cyclopropyl CH 3 4-CH 3 H H 0 H cyclopropyl CH 3 4-CH 3 CH 3 H 0 H cyclopropyl CH 3 4-CH 3 Et H 0 H cyclopropyl CH 3 4-CH 3 n-Pr H 0 H cyclopropyl CH 3 4-CH 3 H CH 3 0 H cyclopropyl CH 3 4-CH 3 i-Pr H m R6 R 9 R 10 R 13 R14 ( 15 R 16 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. Water-Dispersible and Water-soluble 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, N,N-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-methyl-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 4 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%. Example B Wettable Powder Compound 5 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%. Example C Granule Compound 6 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%. 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, chlo ropham, chlorsulfuron, chlorthal-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, dichloφrop, diclofop-methyl, 2-[4,5-dihydro-4-methyl-4-( 1 -methylethyl)-5-oxo- lH-imidazol-2-yl]-5-methyl-3- pyridinecarboxylic acid (AC 263,222), difenzoquat metilsulfate, diflufenican, dimepiperate, dimethenamid, 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-mefhyl, 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 (AKΗ-7088), methyl 5-[[[[(4,6-dimethyl-2- pyri * rmdinyl)an-ύno]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, thiafluamide (BAY 11390), thifensulfuron-methyl, thiobencarb, tralkoxydim, tri-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. 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-C 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 Cmpd R2a 2b Rli mp TO 1 (Ex. 1) H H CH 3 205-230 2 H H H 181-184 3 H CH 3 H 196-199 INDEX TABLE B Cmpd 4 5 INDEX TABLE C Cmpd Structure mp (°C) BIOLOGICAL EXAMPLES OF THE INVENTION TEST A Seeds of barley (Hordeum vulgare), barnyardgrass (Echinochloa crus-galli), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium strumarium), corn (xZea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setaria faberii), lambsquarters (Chenopodium album), morningglory (Ipomoea 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 included a surfactant and were 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 barley (Hordeum vulgare), barnyardgrass (Echinochloa crus-galli), 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 (Setariafaberii), ryegrass (Lolium multiflorum), johnsongrass (Sorghum halpense), lambsquarters (Chenopodium album), morningglory (Ipomoea hederacea), rape (Brassica napus), pigweed (Amaranthus retroβexus), soybean (Glycine max), speedwell (Veronica persica), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), and wild oat (Avenafatua). 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 500 g/ha 8 POSTEMERGENCE Barley Igri Barnyard 2 70 Barnyardgrass Bedstraw Blackgrass Chickweed Cocklebur Corn Cotton Crabgrass Downy Brome Duck salad 90 Giant foxtail Itain. Rygrass Johnsongrass Lambsquarter Morningglory Rape Redroot Pigweed Rice Japonica 75 Soybean Speedwell Sugar beet Umbrella sedge 80 Velvetleaf Watergrass 2 Wheat Wild buckwheat Wild oat Table B COMPOUND Rate 250 g/ha 1 PREEMERGENCE TEST C Plastic pots were partially filled with silt loam soil. The soil was then saturated with water. Indica Rice (Oryza sativa) seed or seedlings at the 2.0 leaf stage; seeds, tubers or plant parts selected from barnyardgrass (Echinochloa crus-galli), at a two leaf stage ducksalad (Heteranthera limosa), junglerice (Echinochloa colonum), late watergrass (Echinochloa oryzicola), redstem (Ammonia species), rice flatsedge (Cyperus iria), smallflower flatsedge (Cyperus difformis) and tighthead sprangletop (Leptochloa fasicularis), 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. Table C COMPOUND Table C COMPOUND Table C COMPOUND Rate 125 g/ha 7 Rate 64 g/ha 4 7 Rate 50 g/ha 4 PD/TA PD/TA PD/TA ducksalad 50 ducksalad 80 50 ducksalad 70 junglerice 100 junglerice 70 80 junglerice 20 late watergrass 20 late watergrass 0 20 late watergrass 0 redstem 75 redstem 98 40 redstem 95 rice flatsedge 90 rice flatsedge 75 85 rice flatsedge 65 smallflower fla 75 smallflower fla 75 25 smallflower fla 70 tighthead spran tighthead spran 95 tighthead spran 85 2 LF barnyard g 35 2 LF barnyard g 25 10 2 LF barnyard g 10 2 LF direct see 70 2 LF direct see 15 20 2 LF direct see 15 2 LF transp. in 65 2 LF transp. in 15 25 2 LF transp. in 15 Table C Table C COMPOUND COMPOUND Rate 25 g/ha 4 Rate 32 g/ha 4 7 PD/TA PD/TA ducksalad 40 ducksalad 65 50 junglerice 15 junglerice 20 30 late watergrass 0 late watergrass 0 0 redstem 85 redstem 95 45 rice flatsedge 50 rice flatsedge 65 50 smallflower fla 30 smallflower fla 30 0 tighthead spran 60 tighthead spran 80 2 LF barnyard g 10 2 LF barnyard g 10 5 2 LF direct see 10 2 LF direct see 15 15 2 LF transp. in 10 2 LF transp. in 15 20 Table C COMPOUND Rate 8 g/ha 7 PD/TA ducksalad 30 junglerice 0 late watergrass 0 redstem 25 rice flatsedge 25 smallflower fla 0 tighthead spran 2 LF barnyard g 0 2 LF direct see 10 2 LF transp. in 5 TEST D Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture and applied to the surface of the water which was contained in each pot. Individual containers of barnyardgrass (Echinochloa oryzicola), small flower umbrella sedge (Cyperus difformis), common falsepimpernel (Lindemia procumbens), monochoria (Monochoria vaginalis) and bulrush (Scirpus juncoides) were seeded and allowed to grow until the 1.5 (early) and 2.5 (late) leaf stage of development. A clay loam soil was used for this propagation. Japonica rice (Oryza sativa) was transplanted at 0 and 2 cm depth five days before application of the test compound to the water surface. Treated plants and untreated controls were maintained under greenhouse conditions for twenty to thirty days at which time treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table D, are based upon a 0 to 100 scale where 0 is no effect and 100 is complete control. Table D COMPOUND Table D COMPOUND Table D COMPOUND Rate 250 g/ha 1 Rate 125 g/ha 1 Rate 64 g/ha 1 Flood Saita soi Flood Saita soi Flood Saita soi barnyard early 90 barnyard early 95 barnyard early 70 barnyard late 90 barnyard late 60 barnyard late 50 C. difformis ea 100 C. difformis ea 60 C. difformis ea 40 C. difformis la 60 C. difformis la 40 C. difformis la 20 Japoni rice 0cm 100 Japoni rice 0cm 60 Japoni rice 0cm 40 Japoni rice 2cm 50 Japoni rice 2cm 20 Japoni rice 2cm 15 L. procumben ea 100 L. procumben ea 100 L. procumben ea 100 L. procumben la 100 L. procumben la 100 L. procumben la 100 M. vaginalis ea 75 M. vaginalis ea 65 M. vaginalis ea 65 M. vaginalis la 65 M. vaginalis la 65 M. vaginalis la 40 S. juncoides 1. 65 S. juncoides 1. 60 S. juncoides 1. 40 S. juncoides 2. 65 S. juncoides 2. 50 S. juncoides 2. 40 Table D COMPOUND Rate 32 g/ha 1 Flood Saita soi barnyard early 40 barnyard late 40 C. difformis ea 20 C. difformis la 30 Japoni rice Ocm 25 Japoni rice 2cm 10 L. procumben ea 80 L. procumben la 100 M. vaginalis ea 40 M. vaginalis la 35 S. juncoides 1. 35 S. juncoides 2. 40 TEST E 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. A preemergence planting of these test species was prepared immediately before compound application using a sandy loam soil as the planting media. 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 annua), 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 m ltiflorum), 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 (Sinapsis arvensis), wild oat (Avenafatua) at a 3 to 4 leaf (2) and a 1 to 2 leaf (1) stage, 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 E, 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. Redroot Pigweed 35 Russian Thistle 10 Ryegrass 10 Scentless Chamo 85 Spring Barley 10 Sugar beet 10 Sunflower 50 Veronica hedera 60 Wheat (Spring) 30 Wheat (Winter) 0 Wild buckwheat 20 Wild mustard 30 Wild oat (1) 0 Windgrass 10 Winter Barley 20

Claims: CLAIMS What is claimed is: 1. A compound selected from Formula I, N-oxides and agriculturally suitable salts thereof, wherein Q is Q-1 Q-2 Q-3 R 1 is OR 8 , SH, C r C 6 alkylthio, C r C 6 haloalkylthio, C r C 6 alkylsulfinyl, C r C 6 haloalkylsulfinyl, Cj-C 6 alkylsulfonyl, C r C 6 haloalkylsulfonyl, halogen or ΝR2ia 2ib ; or Rl i s phenylthio, phenylsulfonyl or -SCH 2 C(O)Ph, each optionally substituted with C j -C 3 alkyl, halogen, cyano or nitro; each R 2 is independently H, C r C 3 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C r C 3 alkoxy, formyl, C 2 -C 6 alkoxycarbonyl, -CH(C r C 3 alkoxy) 2 , C r C 3 alkylthio, C 2 -C 4 alkylthioalkyl, cyano or halogen; or when two R 2 are attached to the same carbon atom, then said R 2 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 3 is H, Cj- alkyl, -Cg haloalkyl, halogen, cyano or nitro; R 4 is H, Cj-C 6 alkyl, C,-C 6 haloalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 4 is phenyl or benzyl, each optionally substituted on the phenyl ring with C j -C 3 alkyl, halogen, cyano or nitro; R 5 is H, Cj-C 6 alkyl, Cj-C 6 haloalkyl, C 2 -C 6 alkoxyalkyl, formyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 -C 7 dialkylaminocarbonyl, Cj-C 6 alkylsulfonyl or C l -C 6 haloalkylsulfonyl; or R 5 is benzoyl or phenylsulfonyl, each optionally substituted with Cγ-C 3 alkyl, halogen, cyano or nitro; R 6 is H, C 2 -C6 alkoxycarbonyl, C 2 -C 6 haloalkoxycarbonyl, CO 2 H or cyano; R 7 is H, C,-C 6 alkyl, Cj-Cg haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl; R 8 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 21a R 211 > ) C r C 6 alkylsulfonyl or Cj-C 6 haloalkylsulfonyl; or R 8 is phenyl, benzyl, benzoyl, -CH 2 C(O)phenyl or phenylsulfonyl, each optionally substituted on the phenyl ring with C r C 3 alkyl, halogen, cyano or nitro; A-l A-2 A-3 A-4 A-5 A-6 R 9 and R 10 are independently H, C j -C 6 alkyl, C - 6 haloalkyl, C j -C 6 alkoxy, C j -^ haloalkoxy, Cj-C 6 alkylthio, C j -Cg haloalkylthio, C j -Cg alkylsulfinyl, C j -Cg haloalkylsulfinyl, C j -C 6 alkylsulfonyl, C j -Cg haloalkylsulfonyl, aminosulfonyl, C!-C 2 alkylaminosulfonyl, C 2 -C4 dialkylaminosulfonyl, halogen, cyano or nitro; R u , R 12 , R 13 , R 17 and R 18 are independently H, halogen, cyano, C j -C 6 alkyl, C j -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, Cj-Cg alkoxy, C^Cg haloalkoxy, C j -Cg alkylthio or Cj-C 6 haloalkylthio; R 14 is H, halogen, C ] -C 6 alkyl or C^Cg haloalkyl; R 15 is H, halogen, cyano, Cι~C 6 alkyl, Cι-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -Cg haloalkynyl, C j - alkoxy, C ] -C 6 haloalkoxy, Cj-Cg alkylthio or CJ-CG haloalkylthio; R 16 is H, C!-C 6 alkoxy, C 2 -C 6 haloalkoxy, C j - alkylthio, C 2 -C 6 haloalkylthio; or Rl5 and Rl6 are taken together to form -X l -(CH 2 ) T -X 2 -, -(CH 2 ) S -X 3 -, -(CH 2 ) t -χ3-CH 2 -, -(CH 2 ) V -X3-CH 2 CH 2 - or -(CH 2 ) W -, each group optionally substituted with at least one member selected from 1-6 halogen, 1-6 CH 3 and one C ! -C 3 alkoxy; or R 15 and R 16 are taken together to form -O-N(C r C 3 alkyl)-CHR20-CH or -O-N=CHR 20 -CH 2 -, each group optionally substituted with at least one member selected from 1-2 halogen and 1-2 CH ; or R 15 and R 16 are taken together with the carbon to which they are attached to form C(=O), C(=S) or C(=NOR 21 ); X 1 and X 2 are each independently O, S or N(Cι~C 3 alkyl); X 3 is O or S; G is O or CH 2 ; R 19 is H, C j -C 3 alkyl, C 3 -C 4 alkenyl or C^^ alkynyl; R 20 is C j -C 3 alkyl; or R 20 is phenyl optionally substituted with C ] -C 3 alkyl, halogen, cyano or nitro; R 21 is H, C C 3 alkyl, C 3 -C 4 alkenyl or C 3 -C 4 alkynyl; R2la is H or C,-C 6 alkyl; R 21b is C r C 6 alkyl or C r C 6 alkoxy; or R 21a and R 21b 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 -; Y and Z together with the carbons to which they are attached form a fused lH-4,5- dihydropyrazole or pyridine ring optionally substituted with up to three groups independently selected from the group halogen and C j -C 8 alkyl, provided that when the nitrogen atom of the fused lH-4,5-dihydropyrazole ring is substituted, then the nitrogen substituent is C j -Cg alkyl; or Y and Z together with the carbons to which they are attached form a fused pyrazole, pyrimidine or thiophene ring, each optionally substituted with up to two groups independently selected from the group halogen and C j -Cg alkyl, provided that when the nitrogen atom of the fused pyrazole ring is substituted, then the nitrogen substituent is Cj-C 8 alkyl; or Y and Z together with the carbons to which they are attached form a fused isoxazole ring optionally substituted with halogen and C!-C 8 alkyl; k is O or 1; m is O or l; n is 1 or 2; q is O, 1, 2, 3 or 4; r is 2, 3 or 4; s is 2, 3, 4 or 5; t is 1, 2, 3 or 4; v is 2 or 3; and w is 2, 3, 4, 5 or 6; provided that: (i) k and m sum to 0 or 1 ; (ii) when Rl 6 is other than H, then R !5 is other than halogen and C j haloalkoxy; and (iii) when A is A-l, A-2 or A-4, then Q is Q-1 or Q-2. 2. A compound of Claim 1 wherein A is selected from A-l, A-2 and A-6; R 9 and R 10 are independently H, halogen, nitro, C j -C 3 alkyl or C j -C 3 alkoxy; Rl l and R ϊ2 are independently H, halogen or C ] -C 3 alkyl; R l3 and RI 4 are independently H or C ! -C 3 alkyl; R l5 and R 16 are independently H, C j -C 3 alkyl , C j -C 3 alkoxy, C 2 -C 3 haloalkoxy, C}-C 3 alkylthio or C 2 -C 3 haloalkylthio; or R i5 and R 6 are taken together to form -X l -(CH 2 ) r -X 2 - optionally substituted with at least one member selected from 1-2 halogen and 1-3 CH 3 ; or R ϊ5 and R ]6 are taken together with the carbon to which they are attached to form C(=O) or C(=NOR21); r is 2 or 3; R21 is H or C!-C 3 alkyl; A-6 is selected from A-6a, A-6b, A-6c, A-6d, A-6e and A-6f: A-6a A-6b A-6c A-6d A-6e A-6f wherein R 22 , R 24 and R 30 are independently C j -Cg alkyl; and R 23 , R ^, R26, R27 } R28 and R 29 ^ independently H or C,-C 4 alkyl; and R 31 and R 32 are independently H or Cι-C 2 alkyl. 3. A compound of Claim 2 wherein k is O; m is 0; R 9 and Rl° are independently C j -C 3 alkyl or halogen; R 1 1 and R 12 are independently H or Cι~C 3 alkyl; R i5 and Rl- 3 are taken together as -OCH 2 CH 2 O- or -SCH 2 CH 2 S-; or R 15 and R 16 with the carbon to which they are attached are taken together to form C(=O), C(=NOR21); R2 i is C j -C 2 alkyl; and R 22 , R24 a nd R ° are independently C j -C 3 alkyl; and R 23 , R 25 , R 26 , R 27 , R28 ^d R 2 9 ^ independently H or C j - alkyl; and R 31 and R 32 are independently H or C j -C 2 alkyl. 4. A compound of Claim 3 wherein Q is Q-1. 5. A compound of Claim 3 wherein Q is Q-2. 6. A compound of Claim 3 wherein Q is Q-3. 7. The compound of Claim 4 which is selected from the group: (a) 3-hydroxy-2-[(3,5,8-trimethyl-l,2-benzoxathiin-6-yl)carbonyl]-2-cyclohexen-l- one 5,5-dioxide, which is alternatively named as its tautomer 2-[(3,5,8-trimethyl-l,2-benzoxathiin-6-yl)carbonyl]-l,3-cyclohexanedione 5,5- dioxide; (b) 3-hydroxy-2-[(2,6,9-trimethyl-4,4-dioxido-2H-[ 1 ,2]benzoxathiino[4,3- c]pyrazol-8-yl)carbonyl]-2-cyclohexen- 1-one; and (c) 2-[(5,8-dimethyI- 1 ,2-benzoxathiin-6-yl)carbonyl]-3-hydroxy-2-cyclohexen- 1 - one S,.?-dioxide. 8. 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. 9. 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: RORER MORRIS PADGETT, RORER, MORRIS, PADGETT
Applicants: DU PONT, RORER MORRIS PADGETT, E.I. DU PONT DE NEMOURS AND COMPANY, RORER, MORRIS, PADGETT
Application year: 1997
Main classification: C07D327
IPC codes: A01N43, C07D291, C07D327, C07D411, C07D419, C07D497