Herbicidal heterocycles

This application is a national phase entry under 35 U.S.C. 371 from International Application No. PCT/US01/43357, filed 20 Nov. 2001, which claims priority benefit from U.S. Provisional Application No. 60/250,678, filed 01 Dec. 2000, U.S. Provisional Application No. 60/273,469, filed 05 Mar. 2001, and U.S. Provisional Application No. 60/284,616, filed 18 Apr. 2001.

This, invention relates to certain pyrazoles and pyrazolines, their N-oxides, agriculturally suitable salts and compositions, and methods of their use for controlling undesired 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. Uncontrolled 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. For example, many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different modes of action.

World Patent Publication 95/33719 discloses compounds of Formula i as herbicides

This invention is directed to compounds of Formula 1 including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, agricultural compositions containing them and their use for controlling undesirable vegetation:

wherein:

A is an optionally substituted aryl or heteroaromatic ring, wherein the optional substituents are selected from halogen, cyano, C 1 –C 6 alkyl, C 1 –C 4 haloalkyl, C 2 –C 6 alkenyl, C 2 –C 6 alkynyl, OR 8 , —S(O) k R 9 , —C(O)R 10 , —C(O)OR 11 and —C(O)NR 12 R 13 ; two substituents of the group A may combine to form a fused 5- or 6-membered saturated or partially saturated carbocyclic or heterocyclic ring, and said fused ring system is optionally substituted with one or more R 7 ; Y is O or S; Z is O, S(O) n or CR 3 R 4 ; W is (CR 3 R 4 ) q ; R 1 is H, C 1 –C 12 alkyl, C 1 –C 12 haloalkyl, C 3 –C 12 cycloalkyl, C 3 –C 12 halocycloalkyl, C 4 –C 12 alkylcycloalkyl, C 4 –C 12 alkylhalocycloalkyl, C 1 –C 12 alkoxy, C 1 –C 12 alkylthio, di-(C 1 –C 2 alkyl)amino, Cl, Br, I, —C(O)R 5 , —C(O)OR 5 , —C(O)NR 5 R 6 or tri(C 1 –C 4 alkyl)silyl; R 2a is H, C 1 –C 4 alkyl or C 1 –C 4 haloalkyl; and R 2a only exists when the carbon atom to which it is connected is a quaternary carbon center in which case the dotted line in Formula 1, together with the parallel solid line, represents a single bond; R 2b is H, C 1 - 4 alkyl, C 1 –C 4 haloalkyl, C 1 –C 4 alkoxy, C 1 –C 4 haloalkoxy, F or Cl; or R 1 and R 2b are taken together as —C(R 3 R 4 )CH 2 CH 2 —, —C(R 3 R 4 )CH 2 CH 2 —or —(CH 2 ) m O(CH 2 ) t —; each R 3 and R 4 are independently H, C 1 –C 6 alkyl or C 1 –C 6 haloalkyl; R 5 is C 1 –C 6 alkyl, C 2 – 6 alkenyl, C 3 –C 6 cycloalkyl, C 3 –C 6 cycloalkyl or C 1 –C 6 haloalkyl; R 6 is H or C 1 –C 6 alkyl; each R 7 is independently C 1 –C 4 alkyl, C 1 –C 4 haloalkyl, C 1 –C 4 alkoxy, C 1 –C 4 haloalkoxy, C 1 –C 4 alkylthio, halogen, CN, NO 2 or hydroxy; each R 8 is independently C 1 –C 4 alkyl or C 1 –C 4 haloalkyl; each R 9 is independently C 1 –C 4 alkyl or C 1 –C 4 haloalkyl; each R 10 is independently C 1 –C 4 alkyl or C 1 –C 4 haloalkyl; each R 11 is independently C 1 –C 4 alkyl, C 1–hd 3 haloalkyl, C 2 –C 4 alkenyl, C 2 –C 3 haloalkenyl, C 2 –C 4 alkynyl, C 3 –C 6 cycloalkyl, C 3 –C 5 halocycloalkyl, C 3 –C 6 cycloalkenyl or C 4 –C 6 cycloalkylalkyl; each R 12 is independently H or C 1 –C 2 alkyl; each R 13 is independently C 1 –C 4 alkyl; or R 12 and R 13 are taken together as —(CH 2 ) 4 —, —(CH 2 ) 5 — or —(CH 2 ) 2 O(CH 2 ) 2 —; each k is independently 0, 1 or 2; n is 0, 1 or 2; q is 1 or 2; m is 0, 1 or 2; t is 0, 1 or 2; and m+t is 2 or 3; provided that: (a) each position on the aryl or heteroaromatic ring A vicinal (ortho) to the point of attachment of the aryl or heteroaromatic ring to the Formula 1 backbone is independently substituted with fluorine or not substituted; (b) when A is a phenyl ring with a fluorine substituent meta to the point of attachment of the phenyl ring to the remainder of the Formula 1 backbone, then attached at the other meta position of the phenyl ring is a substituent other than fluorine; (c) when A is a phenyl ring with at least one —C(O)NR 12 R 13 substituent, then the at least one —C(O)NR 12 R 13 substituent is at a position other than meta to the point of attachment of the phenyl ring to the remainder of the Formula 1 backbone; (d) when A is a phenyl ring, the position para to the point of attachment of the phenyl ring to the remainder of the Formula 1 backbone is unsubstituted or substituted by a substituent other than alkoxy; (e) when A is a phenyl ring with a —C(O)OR 11 substituent at the position para to the point of attachment of the phenyl ring to the remainder of the Formula 1 backbone, then a substituent is attached to a position on the phenyl ring meta to the point of attachment of the phenyl ring to the remainder of the Formula 1 backbone; (f) when A is a pyridine ring connected at the 2-position to the remainder of the Formula 1 backbone and methyl is at the 6-position of the pyridine ring, then the pyridine ring is substituted at the 4-position; (g) when A is a pyrimidine ring connected at the 2-position to the remainder of the Formula 1 backbone, and when the 4-position of the pyrimidine ring is unsubstituted or is substituted with methyl, then the substituent at the 6-position of the pyrimidine ring is other than methyl, and when a methoxy substituent is at the 4-position of the pyrimidine ring, then the substituent at the 6-position of the pyrimidine ring is other than methoxy, (h) when A is an isothiazole ring connected at the 5-position to the remainder of the Formula 1 backbone, then the isothiazole ring is substituted with a substituent other than alkyl; (i) when R 1 is a C 3 –C 12 alkoxy group, then the alkyl moiety of the alkoxy group is branched at the carbon atom attached to the oxygen atom; (j) when R 1 and R 2b are taken together as —C(R 3 R 4 )CH 2 CH 2 —, —C(R 3 R 4 )CH 2 CH 2 CH 2 —or —(CH 2 ) m O(CH 2 ) t — then Z is O or CR 3 R 4 ; and (k) when R 2b is connected to a quaternary carbon center, then R 2b is H, C 1 –C 4 alkyl or C 1 –C 4 haloalkyl.

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

In the above recitations the term “alkyl”, used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl or hexyl isomers. The term “1–2 alkyl” indicates that one or two of the available positions for that substituent may be alkyl. “Alkenyl” includes straight-chain or branched alkenes such as 1-propenyl, 2-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 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. “Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. “Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. “Alkoxyalkyl” denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH 3 OCH 2 , IH 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. “Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. “Saturated Carbocyclic” ring denotes a ring having a backbone consisting of carbon atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.

The term “halogen”, either alone or in compound words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F 3 C, ClCH 2 , CF 3 CH 2 and CF 3 CCl 2 . The terms “haloalkenyl”, “haloalkynyl”, “haloalkoxy”, and the like, are defined analogously to the term “haloalkyl”. Examples of “haloalkenyl” include (Cl) 2 C═CHCH 2 and CF 3 CH 2 CH═CHCH 2 . Examples of “haloalkynyl” include HC≡CCHCl, CF 3 C≡C, CCl 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

The total number of carbon atoms in a substituent group is indicated by the “C i –C j ” prefix where i and j are numbers from 1 to 12. For example, C 1 –C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C 2 alkoxyalkyl designates CH 3 OCH 2 ; C 3 alkoxy-alkyl 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 . In the above recitations, when a compound of Formula 1 contains a heterocyclic ring, all substituents are attached to this ring through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.

When a group contains a substituent which can be hydrogen, for example R 3 , then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. When a variable group is shown to be optionally attached to a position, for example (R 15 ) p 1 wherein p 1 may be 0, then hydrogen may be at the position even if not recited in the variable group definition. When a position on a group is said to be “not substituted” or “unsubstituted”, then hydrogen atoms are attached to take up any free valency.

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 1, 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.

According to commonly accepted definition, the terms “aryl” and “aryl ring” denote a phenyl or benzene ring subject to optional substitution. The term “carbocyclic ring” denotes a ring wherein the atoms forming the ring backbone are selected only from carbon. The term “heteroaromatic ring” denotes a heterocyclic ring wherein each of the ring atoms is essentially in the same plane and has a p-orbital perpendicular to the ring plane, and in which (4n+2) π electrons, where n is 0 or a positive integer, are associated with the ring to comply with Hückel's Rule. The term “heterocyclic ring” denotes a ring wherein the atoms forming the ring backbone are selected from not only carbon but also heteroatoms such as oxygen, sulfur and nitrogen. For sake of illustration, heteroaromatic rings include, but are not limited to, furan, thiophene, pyrrole, pyrazole, imidazole, oxazole, thiazole, isoxazole, isothiazole, pyridine, pyridazine, pyrimidine, pyrazine and 1,3,5-triazine. The heterocyclic ring can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.

The aryl or heteroaromatic ring of radical A of Formula 1 is optionally substituted by one or more substituents selected from halogen, cyano, C 1 –C 6 alkyl, C 1 –C 4 haloalkyl, C 2 –C 6 alkenyl, C 2 –C 6 alkynyl, OR 8 , —S(O) k R 9 , —C(O)R 10 , —C(O)OR 11 and —C(O)NR 12 R 13 . Furthermore for the purpose of defining the scope of the invention, by removing in effect one hydrogen radical from each of two substituent groups, the groups may be combined to form a saturated or partially saturated 5 or 6-membered ring fused to the aforementioned aryl or heteroaromatic ring, and said fused ring system is optionally substituted with one or more R 7 . For example, removing one hydrogen from each methyl of A-14 allows combination to form the fused dihydrofuran ring of A-56.

One skilled in the art will appreciate that not all nitrogen-containing heterocycles can form N-oxides, as oxidation to the oxide requires an available lone electron pair on the nitrogen atom; one skilled in the art will recognize those nitrogen-containing heterocycles which can form N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis , vol. 7, pp 748–750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry , vol. 3, pp 18–19, 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 139–151, 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 salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.

Preferred for reason of better activity and/or ease of synthesis are compounds of Formula 1 above, geometric and stereoisomers thereof, N-oxides thereof, and agriculturally suitable salts thereof, wherein the dotted line in Formula 1, together with the parallel solid line, represents a double bond.

For reason of better activity and/or ease of synthesis, certain substituent groups in Formula 1 are preferred. Y is preferably O. Z is preferably O, S or CH 2 . W is preferably CH 2 . R 1 is preferably C 1 – 12 alkyl or C 3 – 12 cycloalkyl. More preferably, R 1 is C 3 –C 12 alkyl, preferably branched, or C 3 –C 8 cycloalkyl. Even more preferably, R 1 is branched C 3 –C 6 alkyl or C 4 –C 6 cycloalkyl. Most preferably, R 1 is isopropyl, tert-butyl, sec-butyl (—CH(CH 3 )(CH 2 CH 3 )) or 3-pentyl (—CH(CH 2 CH 3 ) 2 ). R 2a is preferably H. R 2b is preferably H or C 1 –C 4 alkyl. More preferably, R 2b is H. A is preferably substituted phenyl or 5 or 6-membered heterocyclic ring comprising 0–3 nitrogen atoms, 0–1 oxygen atoms and 0–1 sulfur atoms in said ring. More preferably, A is A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 or A 8 as depicted:

wherein

R 14 is H, halogen, cyano, C 1 –C 6 alkyl, C 1 –C 4 haloalkyl, OR 8 , —S(O) k R 9 , —C(O)R 10 , —C(O)OR 11 or —C(O)NR 12 R 13 ; such that R 14 is bound to a ring atom joined through one intervening ring atom to the ring atom linking the ring to the remainder of Formula 1; each R 15 is independently halogen, cyano, C 1 –C 4 alkyl, C 1 –C 4 haloalkyl, C 1 –C 4 alkoxy, C 1 –C 4 alkylthio, C 1 –C 4 haloalkylthio or C 1 –C 4 haloalkoxy, or R 14 taken together with an adjacent R 15 is —(CH 2 ) 3 —, —(CH 2 ) 4 —, —O(CH 2 ) 2 —, —O(CH 2 ) —, —S(CH 2 ) 2 — or —S(CH 2 ) 3 —, each optionally substituted with 1–3 substituents selected from CH 3 , CH 2 CH 3 and F; Y 1 is O, S or N—H; such that when Y 1 is N—H, the H of N—H may be replaced by an R 14 or R 15 substituent selected from alkyl, or the H of N—H may be replaced by the bond linking the ring to the remainder of Formula 1; p 1 is 0, 1, 2 or 3; p 2 is 0, 1 or 2; p 3 is 0 or 1; provided that at least one R 14 or R 15 is other than H.

Preferably, A is A 1 , A 2 , A 3 , A 4 or A 6 wherein Y l is O or S. More preferably, A is A 1 , A 2 or A 6 wherein Y 1 is O or S. Most preferably, A is A 1 , A 2 or A 6 wherein Y 1 is S. Preferably R 14 is halogen, cyano, C 1 –C 6 alkyl, C 1 –C 4 haloalkyl, OR 8 , —S(O) k R 9 , —C(O)R 10 or —C(O)OR 11 ; and R 15 is halogen, cyano, C 1 – 4 alkyl, C 1 –C 4 haloalkyl, C 1 –C 4 alkoxy, C 1 –C 4 alkylthio, C 1 –C 4 haloalkylthio or C 1 –C 4 haloalkoxy, or R 14 taken together with an adjacent R 15 is —(CH 2 ) 3 —, —(CH 2 ) 4 —, —O(CH 2 ) 2 —, —O(CH 2 ) 3 —S(CH 2 ) 2 — or —S(CH 2 ) 3 —, each optionally substituted with 1–3 substituents selected from CH 3 , CH 2 CH 3 and F; such that the left-hand bond is connected at the R 14 position and the right-hand bond is connected at the R 15 position. More preferably, R 14 is halogen, C 1 –C 6 alkyl, C 1 –C 4 haloalkyl, OR 8 , —S(O) k R 9 , —C(O)R 10 or —C(O)OR 11 . Even more preferably, R 14 is Br, C 1 –C 6 alkyl, CF 2 H, CF 3 , C 1 –C 4 alkoxy, OCF 3 , OCF 2 H, —C(O)R 10 or —C(O)OR 11 . Most preferably, R 14 is Br, C 1 –C 5 alkyl, CF 2 H, CF 3 , C 1 –C 4 alkoxy, OCF 3 , OCF 2 H or —C(O)OCH 3 . Preferably, p 1 is 0 or 1, p 2 is 0 or 1 and p 3 is 0 or 1. More preferably, R 15 is halogen, C 1 – 2 alkyl or C 1 –C 2 alkoxy. Even more preferably, R 15 is C 1 –C 6 alkyl or halogen. Most preferably, R 15 is CH 3 , F, Cl or Br, or p 1 is 0, p 2 is 0 and p 3 is 0, and when R 15 is CH 3 , Cl or Br, it is preferably bound to a ring atom joined through two intervening ring atoms to the ring atom linking the ring to the remainder of Formula 1; for example, when A is A 1 , R 15 being CH 3 is preferably in the para position. k is preferably 0. R 10 is preferably C 1 –C 2 alkyl, and most preferably CH 3 . R 11 is preferably C 1 –C 2 alkyl, and most preferably CH 3 . R 12 is preferably CH 3 . R 13 is preferably CH 3 .

Compounds of the invention illustrating groups preferred for reasons of better activity and/or ease of synthesis are:

Preferred A. A compound of Formula 1 above, geometric and stereoisomers thereof, N-oxides thereof, and agriculturally suitable salts thereof of, wherein the optional substituents on A are selected from halogen, C 1 –C 4 alkyl, C 1 –C 4 haloalkyl, C 1 –C 4 alkoxy, C 1 –C 4 alkylthio, C 1 –C 4 haloalkylthio or C 1 –C 4 haloalkoxy; two or more substituents of the group A may combine to form a fused 5 or 6-membered saturated or partially saturated carbocyclic or heterocyclic ring, and said ring system is optionally substituted with one or more R 7 ; and R 1 is H, C 1 –C 6 alkyl, C 1 –C 6 haloalkyl, C 3 –C 9 cycloalkyl, C 3 –C 9 halocycloalkyl, C 3 –C 12 alkylcycloalkyl, C 3 –C 12 alkylhalocycloalkyl, C 1 –C 6 alkoxy, C 1 –C 6 alkylthio, Cl, Br, I, —C(O)R 5 , —C(O)OR 5 , —C(O)NR 5 R 6 or tialkylsilane. Preferred B. A compound of Formula 1 above, geometric and stereoisomers thereof, N-oxides thereof, and agriculturally suitable salts thereof, wherein A is substituted phenyl or 5 or 6-membered heterocyclic ring comprising 0–3 nitrogen atoms, 0–1 oxygen atoms and 0–1 sulfur atoms in said ring. Preferred B1. A compound of Preferred B wherein

A is A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 or A 8 ; R 14 is H, halogen, cyano, C 1 –C 6 alkyl, C 1 –C 4 haloalkyl, OR 8 , —S(O) k R 9 , —C(O)R 10 or —C(O)OR 11 ; such that R 14 is bound to a ring atom joined through one intervening ring atom to the ring atom limiting the ring to the remainder of Formula 1; each R 15 is independently halogen, cyano, C 1 –C 4 alkyl, C 1 –C 4 haloalkyl, C 1 –C 4 alkoxy, C 1 –C 4 alkylthio, C 1 –C 4 haloalkylthio or C 1 –C 4 haloalkoxy; or R 14 taken together with an adjacent R 15 is —(CH 2 ) 3 —, —(CH 2 ) 4 —, —O(CH 2 ) 2 —, —O(CH 2 ) 3 —, —S(CH 2 ) 2 — or —S(CH 2 ) 3 —, each optionally substituted with 1–3 substituents selected from CH 3 , CH 2 CH 3 and F; Y 1 is O, S or N—H; such that when Y 1 is N—H, an alkyl R 14 or R 15 substituent or the linking bond may replace H of N—H; p 1 is 0, 1, 2 or 3; p 2 is 0, 1 or 2; p 3 is 0 or 1; provided that at least one R 14 or R 15 is other than H.

Preferred B2. A compound of Preferred B1 wherein

Y is O; Z is O, S or CH 2 ; W is CH 2 ; R 1 is C 1 –C 12 alkyl or C 3 –C 12 cycloalkyl; R 2a is H; and R 2b is H or C 1 –C 4 alkyl.

Preferred B3. A compound of Preferred B2 wherein

the dotted line in Formula 1, together with the parallel solid line, represents a double bond; and R 2b is H.

Preferred B4. A compound of Preferred B3 wherein

A is A 1 , A 2 or A 6 ; Y 1 is O or S; R 14 is halogen, C 1 –C 6 alkyl, C 1 –C 4 haloalkyl, OR 8 , —S(O) k R 9 , —C(O)R 10 or —C(O)OR 11 ; R 15 is halogen, C 1 –C 4 alkyl, C 1 –C 4 haloalkyl, C 1 –C 4 alkoxy, C 1 –C 4 alkylthio, C 1 –C 4 haloalkylthio or C 1 –C 4 haloalkoxy; or R 14 taken together with an adjacent R 15 is —(CH 2 ) 3 —, —(CH 2 ) 4 —, —O(CH 2 ) 2 —, —O(CH 2 ) 3 —, —S(CH 2 ) 2 —, —S(CH 2 ) 3 —, each optionally substituted with 1–2 CH 3 , CH 2 CH 3 or F; such that the left-hand bond is connected at the R 14 position and the right-hand bond is connected at the R 15 position; p 1 is 0 or 1; and p 2 is 0 or 1.

Preferred B5. A compound of Preferred B4 wherein

R 1 is branched C 3 –C 8 alkyl or C 4 –C 6 cycloalkyl.

Preferred B6. A compound of Preferred B5 wherein

R 1 is isopropyl, tert-butyl, sec-butyl or 3-pentyl.

Preferred B7. A compound of Preferred B4 wherein

Y 1 is S; R 14 is Br, C 1 –C 6 alkyl, CF 2 H, CF 3 , C 1 –C 4 alkoxy, OCF 3 , OCF 2 H, —C(O)R 10 or —C(O)OR 11 ; R 15 is halogen, C 1 –C 2 alkyl or C 1 –C 2 alkoxy; R 10 is C 1 –C 2 alkyl; and R 11 is C 1 –C 2 alkyl.

Preferred B8. A compound of Preferred B7 wherein

R 14 is Br, C 1 –C 5 alkyl, CF 2 H, CF 3 , C 1 –C 4 alkoxy, OCF 3 , OCF 2 H, or —C(O)OCH 3 ;

Preferred B9. A compound of Preferred B8 wherein

R 15 is C 1 –C 2 alkyl.

Preferred B10. A compound of Preferred B9 wherein

p 1 is 0 and p 2 is 0.

Preferred B11. A compound of Preferred B4 wherein

R 15 is CH 3 .

Preferred B12. A compound of Preferred B11 wherein

p 1 is 0; and p 2 is 0.

Preferred B13. A compound of Preferred B4 wherein

A is A 1 ; R 14 is C 1 –C 4 alkoxy; R 15 is CH 3 , F, Cl or Br and is in the para position relative to the bond connecting A to the remainder of Formula 1; and p 1 is 1.

Preferred B14. A compound of Preferred B5 wherein

A is selected from

R 14 is OCH 3 or OCH 2 CH 3 ;

R 15 is F, Cl or Br;

p 1 is 0 or 1; and

R 1 is CH(CH 3 ) 2 , CH(CH 3 )(C 2 H 5 ), C(CH 3 ) 3 , CH(C 2 H 5 ) 2 or CH(CH 3 )(CH 2 CH 2 CH 3 ).

Specifically preferred is a compound of Formula 1 selected from the group consisting of:

(a) 5-[3-(1,1-dimethylethyl)-1H-pyrazol-1-yl]-3-[3-(trifluoromethyl)phenyl]-4-thiazolidinone; (b) 3-[3-(1,1-dimethylethyl)-1H-pyrazol-1-yl]-1-[3-(trifluoromethyl)phenyl)]-2-pyrrolidinone; (c) 5-[3-(1,1-dimethylethyl)-1H-pyrazol-1-yl]-3-[3-(trifluoromethyl)phenyl]-4-oxazolidinone; (d) 3-[3-(1,1-dimethylethyl)-1H-pyrazol-1-yl]-1-(3-methoxy-4-methylphenyl)-2-pyrrolidinone; (e) 5-[3-(1-methylpropyl)-1H-pyrazol-1-yl]-3-[3-(trifluoromethyl)phenyl]-4-oxazolinone; and (f) 5-[(3-(1-ethylpropyl)-1H-pyrazol-1-yl]-3-[3-(trifluoromethyl)phenyl]-4-oxazolidinone; (g) 1-(4-chloro-3-methoxyphenyl)-3-[3-(1,1dimethylethyl)-1H-pyrazol-1-yl]-2-pyrrolidinone; and (h) 1-(4-chloro-3-methoxyphenyl)-3-[3-(1-ethylpropyl)-1H-pyrazol-1-yl]-2-pyrrolidinone.

The preferred compositions of the present invention and the preferred methods of use are those involving the above preferred compounds. Compounds of the invention are particularly useful for selective control of weeds in maize (corn) and/or rice crops.

Compounds of the Formula 1 can be readily prepared by one skilled in the art by using the reactions and techniques described in Scheme 1 to Scheme 4 below. In cases where a substituent of the starting material is not compatible with the reaction conditions described for any of the reaction schemes, the substituent can be converted to a protected form prior to the described reaction scheme and then deprotected after the reaction using commonly accepted protection/deprotection techniques (see Green, T. W and Wuts, P. G., Protecting Groups in Organic Transformations, 3rd Edition, John Wiley and Sons, New York, 1999). Otherwise, alternative approaches known to one skilled in the art are available. The definitions of A, R 1 , R 2a , R 2b , W, Y, and Z in compounds of Formulae 1–4 below are as defined in the Summary of the Invention.

As shown in Scheme 1, a compound of Formula 1 wherein Y is O can be prepared by contacting a compound of Formula 2 with 1–2 molar equivalents of a compound of Formula 3 in the presence of 1–1.5 molar equivalents of a dialkyl azodicarboxylate such as diethyl azodicarboxylate and 1–2 molar equivalents of a triarylphosphine such as triphenylphosphine.

The reaction is carried out in an inert solvent such as diethyl ether, tetrahydrofuran, methylene chloride, toluene or xylene at temperatures between −20 and 110° C., and preferably from −10° C. to ambient temperatures. The reaction time ranges from 1 hour to 4 days. The compound of Formula 1 is isolated using conventional purification methods such as extraction, concentration, chromatography and crystallization.

As shown in Scheme 2, a compound of Formula 1 wherein Y is O and Z is O or S can also be prepared by contacting a compound of Formula 2 wherein Z is O or S with a mixture prepared by mixing 1–2.5 molar equivalents of a compound of Formula 3, 1–2.5 molar equivalents of thionyl chloride and 2–5 molar equivalents of diisopropylethylamine in an inert solvent such as methylene chloride, tetrahydrofuran, diethyl ether, toluene or xylene.

The reaction is carried out at temperatures between −20 and 110° C. and preferably from 0° C. to ambient temperature. The reaction time ranges from 1 hour to 5 days. The compound of Formula 1 is isolated using conventional purification methods.

Alternatively as shown in Scheme 3, a compound of Formula 1 wherein Y is O is prepared by contacting a compound of Formula 4 with a compound of Formula 3 in the presence of a base such as N,N-diisopropylethylamine, NaH or KOC(CH 3 ) 3 or an excess of the compound of Formula 3.

The reaction is carried out by adding 1 molar equivalent of a compound of Formula 4 to a mixture of 1–2.5 molar equivalents of a compound of Formula 3 in an inert solvent such as diethyl ether, tetrahydrofuran, methylene chloride, NN-dimethylformamide or toluene under N 2 at ambient temperature. When less than about 2 molar equivalents of the Formula 3 compound is used, then about 0.5–2.5 molar equivalents of an additional base such as N,N-diisopropylethylamine, NaH or KOC(CH 3 ) 3 is optionally included in the Formula 3 mixture before addition of the Formula 4 compound. After the addition, the reaction mixture is stirred at temperatures between about −20 to 110° C., and preferably from about −10° C. to around 90° C. for a period of time ranging from 1 hour to 4 days. The reaction mixture is then poured into an excess amount of water and the aqueous layer is extracted with ethyl acetate between one to three times. The organic layers are separated from the aqueous layers, then combined and dried over a drying agent such as MgSO 4 or Na 2 SO 4 and subsequently concentrated. The residue is purified by conventional techniques such as column chromatography over silica gel with eluents such as solutions of ethyl acetate and hexanes in various ratios or solutions of methylene chloride and hexanes in various ratios to give the desired compounds of Formula 1 wherein Y is O.

As shown in Scheme 4, a compound of Formula 1 wherein Y is S is prepared by treating a compound of Formula 1 wherein Y is O with Lawesson's Reagent (2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide) or P 2 S 5 using methods or slight modification thereof taught in: Heterocycles 1995, 40(1), 271–8 ; J. Med. Chem. 1990, 33(10), 2697–706 ; Synthesis 1989, (5), 396–7 ; J. Chem. Soc., Perkin Trans. 1 1988, (7), 1663–8 ; Tetrahedron 1988, 44(10), 3025–36; and J. Org. Chem. 1988, 53(6), 1323–6.

Compounds of Formula 2 and Formula 4 are known in the art. Useful methods for their synthesis are compiled in European Patent Publication 0200415-A1 and World Patent Publications 94/13652, 95/33719, 97/19920, 97/20838, 97/28138 and 00/21928, and references cited therein.

Compounds of Formula 3 are either commercially available or can be prepared by one skilled in the art using literature methods or with slight modification thereof. Some examples of the above-mentioned literature methods are published in: A. R. Katritzky & C. W. Rees (editors), Comprehensive Heterocyclic Chemistry , (1984) Vol. 5, 167–304; Arnold Weissberger (editor), Heterocyclic Compounds , (1967), Vol. 22, 3–278 ; Chin. Chem. Lett. 1998, 9(9), 803–804 ; Synthesis 1998, (11), 1645–1654 ; Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 1995, 34B(9), 811–15; European Patent Number 546420 ; J. Indian Chem. Soc. 1991, 68(5), 281–4 ; J. Heterocycl. Chem. 1990, 27(2), 205–8 ; Synth. Commun. 1989, 19(18), 315–968 ; Synthesis 1989, (4), 320–1 ; J. Chem. Soc., Perkin Trans. 1 1987, (4), 885–97 ; J. Chem. Soc., Perkin Trans. 1 1985, (10), 2177–84 ; J. Org. Chem. 1986, 51(12), 2366–8 ; J. Chem. Soc., Perkin Trans. 1 1994, (4), 461–70 ; Heterocycles 1986, 24(2), 289–96 ; Tetrahedron Lett. 1998, 39(20), 3287–3290 ; Synthesis 1997, (3), 337–341 ; J. Am. Chem. Soc. 1993, 115(3), 1153–4 ; Heterocycles 1986, 24(4), 1075–8 ; Synthesis 1997, (10), 1140–1142 ; Tetrahedron Lett. 1996, 37(7), 1095–6 ; Synth. Commun. 1995, 25(5), 761–74 ; J. Org. Chem. 1988, 53(24), 5685–9 ; Heterocycles 1986, 24(4), 1075–8; and Synthesis 1985, (6–7), 690–1.

It is recognized that some reagents and reaction conditions described may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences into the synthesis will aid in obtaining the desired products. The use and choice of protecting groups will be apparent to one skilled in chemical synthesis.

One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula 1. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula 1.

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

Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. 1 H NMR spectra are reported in ppm downfield from tetramethylsilane, s=singlet, d=doublet, t=triplet, q=quartet, m=multiplet, dd=doublet of doublets, dt=doublet of triplets, br s=broad singlet.

To a stirred suspension of sodium methoxide (23.6 g, 0.437 mol) in diethyl ether (˜800 mL) was added dropwise a solution of 3-ethyl-2-pentanone (49.9 g, 0.437 mol) and ethyl formate (32.4 g, 0.437 mol) in diethyl ether (˜200 mL) at temperatures between 10° C. and 20° C. After the addition, the reaction mixture was allowed to warm up to room temperature, and stirred at room temperature for 2 hours. Additional diethyl ether (˜800 mL) was then added. The reaction mixture was stirred at room temperature for one additional hour and then concentrated. The residue was suspended in a solution of ethanol (950 mL) and acetic acid (30 mL). To this suspension was added hydrazine monohydrate (24 mL, 0.49 mol). The reaction mixture was heated at reflux for 60 hours and was then allowed to cool slowly to room temperature. The reaction mixture was then concentrated. To the residue was added 200 mL of 1N hydrochloric acid, followed by ˜75 mL of concentrated hydrochloric acid until pH ˜0. The acidic aqueous solution was then washed twice with diethyl ether (˜250 mL each). The pH of the aqueous solution was then adjusted to 9–10 by addition of aqueous 50% sodium hydroxide solution. The aqueous solution was then extracted twice with diethyl ether (˜300 mL each). The diethyl ether extracts were combined, dried over MgSO 4 and concentrated to give the title compound as a pale yellow oil (41 g).

1 H NMR (CDCl 3 ): δ 0.84 (t, 6H), 1.5–1.8 (m, 4H), 2.53–2.65 (m, 1H), 6.06 (d, 1H).

Step B: Preparation of 5-[3-(1-ethylpropyl)-1H-pyrazol-1-yl]-3-[3-(trifluoromethyl)phenyl]-4-oxazolidinone

To a stirred solution of thionyl chloride (5 mL, 68.55 mmol) in methylene chloride (100 mL) at ˜10° C. was slowly added 3-(1-ethylpropyl)-1H-pyrazole (11.74 g, 84.94 mmol). The resulting solution was stirred for ˜20 minutes and was then cooled to ˜0° C. To this solution was added N,N-diisopropylethylamine (24.7 mL, 141.8 mmol) dropwise and then 5-hydroxy-3-[3-(trifluoromethyl)phenyl]-4-oxazolidinone (14 g, 56.64 mmol), portionwise at temperatures between 0° C. and 15° C. After the addition, the reaction mixture was allowed to warm to room temperature, and then stirred at room temperature for 2 days. To the reaction mixture was then added concentrated aqueous sodium bicarbonate solution (100 mL). The methylene chloride layer was separated, and the aqueous layer was extracted twice with methylene chloride (˜100 mL each). The methylene chloride layers were combined, dried over MgSO 4 and then concentrated. The residue was loaded on silica gel in a column and eluted with methylene chloride to give a crude product. The crude product was further purified by trituration in hexanes followed by filtration to give the title compound, a compound of this invention, as a white solid (10.67 g) melting at 83–85° C.

1 H NMR (CDCl 3 ): δ 0.83 (t, 6H), 1.44–1.7 (m, 4H), 2.45–2.60 (m, 1H), 556 (m, 1H),580 (m, 1H), 6.08 (s, 1H), 6.15 (d, 1H), 7.5–7.6 (m, 3H), 7.85 (m, 2H).

To a stirred solution of 4-chloro-3-methoxybenzeneamine (4.7 g, 29.6 mmol) in methylene chloride (100 mL) at ˜0° C. was slowly added 2,4dibromobutyryl chloride (5.1 mL, 39 mmol). After the addition, the reaction mixture was stirred for ˜5 minutes and triethylamine (24.7 mL, 178 mmol) was then added. The resulting reaction mixture was allowed to warm up to room temperature and stirred at room temperature for 5 days. Water (˜100 mL) was then added to the reaction mixture. The organic layer was separated, dried over MgSO 4 and concentrated. The residue was purified by column chromatography (silica gel, ˜33% ethyl acetate/˜67% hexanes) to give the title compound as a yellow solid (3.9 g) melting at 113–115° C.

1 H NMR (CDCl 3 ): δ 2.3–2.53 (m, 1H), 2.6–2.8 (m, 1H), 3.78–4.1 (m, 5H), 4.5–4.6 (m, 1H), 6.8 (m, 1H), 7.34 (d, 1H), 7.77 (d, 1H).

Step B: Preparation of 1-(4-chloro-3-methoxyphenyl)-3-[3-(1,1-dimethylethyl)-1H-pyrazol-1-yl]-2-pyrrolidinone

To a solution of 3-(1,1-dimethylethyl)-1H-pyrazole (0.22 g, 1.8 mmol) in N,N-dimethylformamide (20 mL) under nitrogen at room temperature was added 60% sodium hydride in mineral oil (79 mg, 2.0 mmol). After the addition, the mixture was stirred at room temperature for ˜15 minutes, and then 3-bromo-1-(4-chloro-3-methoxyphenyl)-2-pyrrolidinone (0.5 g, 1.6 mmol) was added. The resulting reaction mixture was stirred at room temperature overnight and then poured into water (˜100 mL). The aqueous layer was extracted twice with ethyl acetate (˜50 mL each). The organic extracts were combined, washed twice with water (˜100 mL each), dried over MgSO 4 and filtered. The filtrate was concentrated. The residue was purified by medium pressure liquid chromatography (silica gel) using as eluant methylene chloride and then 10:1 (by volume) ethyl acetatemethylene chloride to give the title compound, a compound of this invention, as a solid (186 mg) melting at 128–130 ° C.

1 H NMR (CDCl 3 ): δ 1.29 (s, 9H), 2.7–2.98 (m, 2H), 3.84–4.17 (m, 5H), 5.04 (t,1H), 617 (d, 1H), 6.81–6.9 (m, 1H), 7.35 (d, 1H), 7.47 (d, 1H), 7.84 (d, 1H).

A mixture of N,N-dimethylformamide dimethyl acetal (67 mL, 503 mmol) and 2,2-dimethylcyclopentanone (10 g, 90 mmol) was heated at reflux for 2 days. The reaction mixture was then cooled down to room temperature and concentrated. Water (˜380 mL) was added to the residue, and the resulting solution was extracted with methylene chloride. The organic layer was separated, dried over MgSO 4 and concentrated to give the title compound (12.5 g) as a yellow-orange oil.

1 H NMR (CDCl 3 ): δ 1.03 (s, 6H), 1.68 (t, 2H), 2.74 (t, 2H), 3.06 (s, 6H), 7.19 (s, 1H).

To a solution of 2-[(dimethylamino)methylene]-5,5-dimethylcyclopentanone (12.5 g, 75 mmol) in ethanol (100 mL) at room temperature was added hydrazine hydrate (4 mL, 82.3 mmol). The reaction mixture was heated at reflux overnight. It was then cooled to room temperature and concentrated. Water (700 mL) was added to the residue, and the resulting solution was extracted twice with diethyl ether (2×250 mL). The organic extracts were combined, dried over MgSO 4 and concentrated to give the title compound as an oil (10.5 g). 1 H NMR indicated the oil to be ˜60% pure. It was used directly for Step C.

Step C: Preparation of 3-(5,6-dihydro-4,4-dimethyl-2(4B)-cyclopentapyrazolyl)-1-[3-(trifluoromethyl)phenyl]-2-pyrrolidinone

To a solution of 2,4,5,6-tetrahydro-6,6-dimethylcyclopentapyrazole (0.41 g with 60% purity, 1.8 mmol) in N,N-dimethylformamide (20 mL) under nitrogen at room temperature was added sodium hydride (60% in mineral oil, 86 mg, 2.16 mmol). The mixture was stirred at room temperature under nitrogen for ˜15 minutes, and then 3-hydroxy-1-[3-(trifluoromethyl)phenyl]-2-pyrrolidinone methanesulfonate (0.5 g, 1.8 mmol) was added. The resulting reaction mixture was stirred at room temperature for 72 hours. The reaction mixture was then poured into water (˜100 mL) and the aqueous layer extracted with ethyl acetate (2×30 mL; brine solution was added to separate the layers). The organic extracts were combined and concentrated to give a crude product. This crude product was further purified by column chromatography (silica gel, ˜20% ethyl acetate/˜80% hexanes) to give the title compound, a compound of this invention, as an oil, which on standing crystallized to provide a solid (69 mg) melting at 123–126° C.

1 H NMR (CDCl 3 ): δ 1.3 (s, 6H), 2.21 (t, 2H), 2.61 (t, 2H), 2.7–2.87(m, 2H), 387–4.1(m, 2H), 5.04 (t, 1H), 7.13 (s, 1H), 7.4–7.55 (m, 2H) 7.9–8.0 (m, 2H).

By the procedures described herein together with methods known in the art, the following compounds of Tables 1A to 6 can be prepared.

The following tables use the following well-established abbreviations: n means normal, i means iso, s means secondary, t means tertiary and c means cyclo.

Formulation/Utility

Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible (“wettable”) or water-soluble. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or “overcoated”). Encapsulation can control or delay release of the active ingredient. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.

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

Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, N.J. 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, N.J., 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-alkylpyrolidone, ethylene glycol, polypropylene glycol, propylene carbonate, dibasic esters, 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-hydroxy4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol, benzyl 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. Pat. No. 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 , Dec. 4, 1967, pp 147–48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8–57 and following, and World Patent Publication 91/13546. Pellets can be prepared as described in U.S. Pat. No. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. Pat. No. 4,144,050, U.S. Pat. No. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. Pat. No. 5,180,587, U.S. Pat. No. 5,232,701 and U.S. Pat. No. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. Pat. No. 3,299,566.

For further information regarding the art of formulation, see T. S. Woods, “The Formulator's Toolbox—Product Forms for Modern Agriculture” in Pesticide Chemistry and Bioscience, The Food - Environment Challenge , T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120–133. See also U.S. Pat. No. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 101; U.S. Pat. No. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138–140, 162–164, 166, 167 and 169–182; U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1–4; Klingman, Weed Control as a Science , John Wiley and Sons, Inc., New York, 1961, pp 81–96; 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 A1–A5 below.

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. Many of the compounds of this invention, by virtue of selective metabolism in crops versus weeds, or by selective activity at the locus of physiological inhibition in crops and weeds, or by selective placement on or within the environment of a mixture of crops and weeds, are useful for the selective control of grass and broadleaf weeds within a crop/weed mixture. One skilled in the art will recognize that the preferred combination of these selectivity factors within a compound or group of compounds can readily be determined by performing routine biological and/or biochemical assays. Compounds of this invention may show tolerance to important agronomic crops including, but is not limited to, alfalfa, barley, cotton, wheat, rape, sugar beets, corn (maize), sorghum, soybeans, rice, oats, peanuts, vegetables, tomato, potato, perennial plantation crops including coffee, cocoa, oil palm, rubber, sugarcane, citrus, grapes, fruit trees, nut trees, banana, plantain, pineapple, hops, tea and forests such as eucalyptus and conifers (e.g., loblolly pine), and turf species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue and Bermuda grass). Those skilled in the art will appreciate that not all compounds are equally effective against all weeds. Alternatively, the subject compounds are useful to modify plant growth.

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

A herbicidally effective amount of the compounds of this invention is determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of compounds of this invention is about 0.001 to about 20 kg/ha with a preferred range of about 0.004 to about 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, properly formulated for application onto agricultural land or crops, are especially useful for prevention of weed growth in cultivated rice crops such as flooded paddy rice or dryland seeded or upland rice. These general groupings of rice crop cultivation methods include transplanted (i.e. transplanted into a flooded field (paddy)), water-seeded (i.e. seeded onto a flooded field so the seeds are positioned at or near the soil surface), broadcast dry-seeded (i.e. seeded onto the surface of the soil (typically prepared by cultivation) of a dry field, which is then flooded), and dry soil planted (i.e. seeded into the soil (so that the soil covers the seeds) of a dry field) with flood (i.e. the field is subsequently flooded) or without flood (i.e. the field is not subsequently flooded, and the rice crop relies instead on natural rainfall or non-flood irrigation).

The formulated compounds of the invention can be applied (i.e. contacted to the weeds or their environment) using a variety of methods, timings, or their combination(s), which allow the user to choose that which is most appropriate for the particular rice culture. The compounds can be applied: to soil or flood waters before transplants or seed are planted; at time of transplanting or seed planting; after transplanting or seed planting; after seed planting but before crop and/or weeds emerge; or after planting and the crop and/or weeds have emerged. The compounds can be applied, for example, as a treatment spray mixture, mixed with solid fertilizer or alone, or included in irrigation water. Applications to the soil can be enhanced by shallow mixing of the compounds into the soil with tillage equipment. The compound(s), alone or in mixture, can be applied directly to flood waters of the paddy as a liquid spray, suspension concentrate, or prepared granule or dispersible solid. The compounds can be applied over the top of the rice crop to emerged weed foliage and flood waters, or as a granule that can be broadcast-distributed onto the soil surface or into the flood, or they can incorporated in the soil before planting.

Applications of the compounds of the invention can be timed to coincide with specific stages of weed and/or crop growth dependent upon the rice culture practiced. The compounds can be applied to soil or flood waters: before crops are planted, at time of planting, after the crop is planted but before emergence, or after the crop emerges.

The compounds can be applied to the paddy by various means including, but not limited to: introduction or injection at the water source; manual or mechanical-equipment aided distribution from within or upon the levees; and dispersal or delivery by boat, airplane or helicopter.

Compounds of this invention, properly formulated for application onto agricultural land or crops, are also especially useful for prevention of weed growth in nonflooded crops such as maize when applied to the soil before weeds emerge or shortly after their emergence, either before or after the crop emerges. Applications to the soil can be made before, during, or after planting, and can be enhanced by shallow mixing of the compounds into the soil with tillage equipment. The formulated compounds can be applied to the soil, for example, as a treatment spray mixture, mixed with solid fertilizer or included in irrigation water.

Compounds of this invention can be used alone or in combination with other commercial herbicides, insecticides and fungicides, and other agricultural chemicals such as fertilizers. 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. Mixtures of the compounds of the invention with other herbicides can broaden the spectrum of activity against additional weed species, and suppress the proliferation of any resistant biotypes. A mixture of one or more of the following herbicides with a compound of this invention may be particularly useful for weed control: acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal), alachlor, alloxydim, ametr, amicarbazone, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, benzobicyclon, benzofenap, bifenox, bilanafos, bispyribac and its sodium salt, bromacil, bromobutide, bromoxynil, bromoxynil octanoate, butachlor, butafenacil, butamifos, butralin, butroxydim butylate, cafenstrole, caloxydim (QAS 620H), carbetamide, carfentrazone-ethyl, chlomethoxyfen, chloramben, chlorbromuron, chlorflurenol-methyl, chloridazon, chlorimuron-ethyl, chlornitrofen, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, clethodim, clodinafop-propargyl, clomazone, clomeprop, clopyralid, clopyralid-olamine, cloransulam-methyl, cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, 2,4-D and its butotyl, butyl, isoctyl and isopropyl esters and its dimethylammonium, diolamine and trolamine salts, daimuron, dalapon, dalapon-sodium, dazomet, 2,4-DB and its dimethylammonium, potassium and sodium salts, desmedipham, desmetryn, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, dichlobenil, dichilorprop, diclofop-methyl, diclosulam, difenzoquat metilsulfate, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethipin, dimethylarsinic acid and its sodium salt, dinitra ine, dinoterb, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethofumesate, ethoxysulfuron, etobenzanid, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fentrazamide, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, fluchloralin, flufenacet, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet-methyl, fomesafen, foramnsulfuron, fosamine-ammonium, glufosinate, glufosinate-ammonium, glyphosate, glyphosate-isopropylammonium, glyphosate-sesquisodium, glyphosate-trinmesium, halosulfuron-methyl, haloxyfop-etotyl, haloxyfop-methyl, hexazinone, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, iazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, indanofan, iodosulfuron-methyl, ioxynil, ioxynil octanoate, ioxynil-sodium, isoproturon, isouron, isoxaben, isoxaflutole, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its dimethyammonium, potassium and sodium salts, MCPA-isoctyl, MCPB and its sodium salt, MCPB-ethyl, mecoprop, mecoprop-P, mefenacet, mefluidide, mesosulfuron-methyl, mesotrione, metam-sodium, metamitron, metazachlor, methabenzthiazuron, methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyldymron, methyl [[[1-[5-[2-chloro4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2-methoxyethylidene]-amino]oxy]acetate (AKH-7088), methyl 5-[[[[(4,6 dimethyl-2-pyrimidinyl)amino]carbonyl]-amino]sulfonyl]-1-(2-pyridinyl)-1H-pyrazole-4-carboxylate (NC-330), metobenzuron, metobromuron, metolachlor, S-metholachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, naproanilide, napropamide, naptalam, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat dichloride, pebulate, pendimethalin, pentanochlor, pentoxazone, perfluidone, phenmedipham, picloram, picloram-potassium, picolinafen, piperofos, pretilachlor, primisulfuron-methyl, prodiamine, profoxydim (BAS625H, 2-[1-[[2-(4-cblorophenoxy)propoxy]imino]butyl]-3-hydroxy-5-(tetrahydro-2H-thiopyran-3-yl)-2-cyclohexen-1-one), prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen-ethyl, pyrazolynate, pyrazoxyfen, pyrazosulfuron-ethyl, pyribenzoxim, pyributicarb, pyridate, pynminobac-methyl, pyrithiobac, pyrithiobac-sodium, quinclorac, quinmerac, quinoclamine, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, sethoxydim, siduron, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron-methyl, sulfosulfuron, 2,3,6-TBA, TCA, TCA-sodium, tebutam, tebuthiuron, tepraloxydim, terbacil, terbumeton, terbuthylazine, terbutryn, thenylchlor, thiafluamide (BAY 11390), thiazopyr, thifeonmethyl, thiobencarb, tiocarbazil, tralkoxydim, tri-allate, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl, tdclopyr-triethylammonium, tridiphane, trietazine, trifloxysulfuron, trifluralin, triusulfuron-methyl, tritosulfuron and vernolate.

Especially useful herbicide mixture partners for the compounds of the invention in rice crops are the sulfonylurea herbicides azimsfuron, bensulfiron-methyl, metsulfuron-methyl, chlorimuron-ethyl, cinosulfuron, cyclosulfamuron, halosulfuron-methyl, imazosulfuron and pyrazosulfuron-ethyl, and the nonsulfonylurea herbicides bispyribac-sodium, carfentrazone-ethyl, molinate, propanil, quinchlorac, thiobencarb and triclopyr. Other herbicides useful in combination with the compounds of the invention for control of undesired vegetation in rice crops include, but are not limited to, anilofos, benfuresate, benzofenap, bispyribac-sodium, bromobutid, cafenstrole, copper(II) sulfate, cyhalofop-butyl, dimepiperate, epoprodan, etobenzanid, fenoxaprop-ethyl, fentrazamide, indanofan, mefenacet, pretilachlor, profoxydim, pyrazolate, pyributicarb and thenylchlor.

To achieve complete knockdown and residual weed control in maize crops, mixtures of the Formula 1 compounds of this invention with the following herbicides may be especially useful: acetochlor, atrazine, dicamba, dimethenamid, foramsulfuron, flufenacet, flumetsulam, glyphosate, isoxaflutole, mesotrione, metolachlor, metribuzin, nicosulfuron, rimsulfuron, simazine and sulcotrione.

Combination of these companion herbicides with the novel herbicidal compounds of the invention may provide reduction of injury (i.e. safening) on crops and greater control of weeds than expected from additive effects (i.e. synergism). Daimuron and quinoclamine are examples of companion herbicides safening the novel compounds of the invention on crops and also providing greater than expected control of certain weeds. Particularly preferred are mixtures of Index Table A Compound 1 with daimuron and mixtures of Index Table A Compound 1 with quinoclamine.

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 A1 to B for compound descriptions. The abbreviation “Ex.” stands for “Example” and is followed by a number indicating in which example the compound is prepared.

Seeds of barnyardgrass ( Echinochloa crus - galli ), crabgrass ( Digitaria spp.), giant foxtail ( Setaria viridis ), morning glory ( Ipomoea spp.), redroot pigweed ( Amaranthus retroflexus ) and velvetleaf ( Abutilon theophrasti ) were planted into a sandy loam soil and treated preemergence by soil drench with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant. At the same time, these crop and weed species were also treated postemergence sprayed to runoff with test chemicals formulated in the same manner.

Plants ranged in height from two to eighteen cm and were in the one- to two-leaf stage for the postemergence treatment. Treated plants and untreated controls were maintained in a greenhouse for approximately eleven days, after which time all treated plants were compared to untreated controls and visually evaluated for injury. Plant response ratings, summarized in Table A, are based on a 0 to 10 scale where 0 is no effect and 10 is complete control. A dash (-) response means no test results.

TABLE A Postemergence Rate 2000 g/ha Rate 1000 g/ha COMPOUND COMPOUND 1 4 5 6 7 9 10 11 12 13 14 15 16 26 27 28 88 3 Barnyardgrass 90 0 90 90 90 90 10 40 0 0 0 10 10 90 80 60 80 10 Crabgrass 10 0 10 20 20 10 10 10 0 0 0 10 20 20 60 40 40 0 Giant foxtail 30 0 20 90 100 100 10 50 0 0 0 10 30 100 90 90 90 10 Morningglory 90 0 10 10 10 10 20 10 0 0 0 20 20 50 20 20 30 10 Pigweed 90 30 80 70 80 80 100 90 0 70 20 0 0 80 80 80 100 10 Velvetleaf 30 0 40 0 30 40 50 0 0 0 0 10 20 10 20 50 0 0 Rate 500 g/ha Rate 250 g/ha COMPOUND COMPOUND 1 4 5 6 7 9 10 11 12 13 14 15 16 26 27 28 88 3 Barnyardgrass 60 0 90 90 90 80 20 20 0 0 0 10 0 90 70 60 30 20 Crabgrass 10 0 10 10 10 20 10 0 0 0 0 10 10 30 20 20 20 0 Giant foxtail 30 0 20 60 80 30 10 0 0 0 0 10 0 50 50 80 40 0 Morningglory 90 0 10 0 10 10 10 10 0 0 0 30 20 20 0 10 10 10 Pigweed 20 20 10 40 10 20 20 70 0 20 0 0 0 40 20 20 80 60 Velvetleaf 10 0 0 0 30 0 0 0 0 0 0 0 0 10 0 0 0 0 Preemergence Rate 2000 g/ha COMPOUND 1 4 5 6 7 9 10 11 12 13 14 15 16 26 27 28 Barnyardgrass 100 80 100 100 100 100 100 100 0 10 0 10 70 100 100 100 Crabgrass 100 70 100 100 100 100 100 100 60 80 0 100 100 100 90 100 Giant foxtail 100 100 100 100 100 100 100 100 30 90 0 100 90 100 100 100 Morningglory 80 0 0 0 10 0 20 0 0 20 0 0 20 30 20 0 Pigweed 100 80 100 100 100 100 100 100 40 100 70 100 100 100 100 100 Velvetleaf 70 0 30 20 0 10 10 20 0 0 0 100 100 40 10 10 Rate 2000 g/ha Rate 1000 g/ha Rate 500 g/ha COMPOUND COMPOUND COMPOUND 88 3 1 4 5 6 7 9 10 11 12 13 14 15 Barnyardgrass 100 100 90 10 100 100 100 100 100 100 0 0 0 10 Crabgrass 100 100 90 50 100 100 100 90 90 100 0 0 0 80 Giant foxtail 100 100 90 10 100 100 100 100 90 100 0 20 0 50 Morningglory 30 0 10 0 0 0 0 0 0 0 0 0 0 0 Pigweed 100 100 100 70 100 100 100 100 100 100 0 80 40 30 Velvetleaf 30 0 10 0 20 20 20 20 20 0 0 0 0 30 Rate 500 g/ha Rate 250 g/ha COMPOUND COMPOUND 16 26 27 28 88 3 Barnyardgrass 10 100 100 100 40 100 Crabgrass 100 100 100 90 80 100 Giant foxtail 80 100 100 100 70 100 Morningglory 0 0 0 0 0 0 Pigweed 80 100 100 100 100 100 Velvetleaf 10 50 20 10 0 0

Seeds selected from barnyardgrass ( Echinochloa crus - galli ), Surinam grass ( Brachiaria decumbens ), cocklebur ( Xanthium strumarium ), corn ( Zea mays ), crabgrass ( Digitaria sanguinalis ), giant foxtail ( Setaria faberii ), lambsquarters ( Chenopodium album ), morning glory ( Ipomoea hederacea ), pigweed ( Amaranthus retroflexus ), rice ( Oryza saliva ) and velvetleaf ( Abutilon theophrasti ) were planted and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.

At the same time, plants selected from these crop and weed species and also blackgrass ( Alopecurus myosuroides ), wheat ( Triticum aestivum ) and wild oat ( Avena fatua ) were treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments. Plant species in the flooded paddy test consisted of rice ( Oryza saliva ), smallflower flatsedge ( Cyperus difformis ), duck salad ( Heteranthera limosa ) and barnyardgrass ( Echinochloa crus - galli ) grown to the 2-leaf stage for testing. Treated plants and controls were maintained in a greenhouse for 13 to 15 days, after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table B, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (-) response means no test result.

TABLE B Postemergence Rate 500 g/ha COMPOUND 1 2 3 4 5 6 7 8 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 Barnyardgrass 50 0 70 0 90 60 100 0 0 0 0 0 0 0 0 0 0 0 100 100 80 90 100 Blackgrass 0 0 0 0 0 0 0 0 0 0 0 0 0 30 0 0 0 0 0 0 0 20 0 Surinam grass 0 0 20 0 0 0 20 0 0 0 0 0 0 0 0 0 0 10 0 0 20 20 50 Cocklebur 80 60 30 0 20 0 0 10 0 0 0 0 0 0 0 0 20 20 90 80 20 80 40 Corn 60 0 0 0 20 0 0 0 0 0 0 0 0 0 0 0 0 0 20 0 0 50 50 Crabgrass 40 0 40 0 50 30 70 0 0 0 0 60 70 50 60 0 0 20 80 70 40 40 90 Foxtail, Giant 60 0 30 0 70 0 70 0 0 0 0 0 30 30 30 0 0 0 90 60 0 80 80 Lambsquarters 100 80 100 80 90 60 80 50 0 0 0 0 0 0 0 80 70 70 90 100 90 100 100 Morningglory 100 0 30 0 10 0 70 0 0 0 0 70 80 0 0 0 10 30 60 80 30 80 40 Pigweed 100 100 90 50 80 90 80 10 0 0 0 — — — — 0 0 0 90 90 90 100 100 Velvetleaf 60 0 0 40 10 20 50 0 0 0 0 0 0 0 0 0 20 20 20 60 30 30 0 Wheat 30 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Wild Oat 0 0 0 0 0 0 0 0 0 0 0 20 0 50 50 0 0 0 0 0 0 0 0 Rate 500 g/ha COMPOUND 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 Barnyardgrass 100 80 60 60 0 100 100 90 0 0 40 100 100 100 100 100 70 100 70 100 100 Blackgrass 0 0 0 0 0 20 0 0 0 0 0 0 0 0 0 0 0 50 0 0 0 Surinam grass 40 20 20 0 0 20 0 10 0 0 0 50 0 0 0 0 0 0 0 0 0 Cocklebur 70 60 30 0 0 70 70 60 10 0 40 60 30 80 0 50 0 60 0 70 40 Corn 60 70 10 0 0 0 0 0 0 0 0 70 20 0 10 50 0 40 0 20 0 Crabgrass 90 20 40 30 50 100 40 100 0 0 0 100 100 100 70 90 40 80 50 40 0 Foxtail, Giant 80 50 30 30 0 80 20 60 20 0 0 90 80 80 0 90 0 70 0 60 0 Lambsquarters 100 80 90 70 20 90 80 90 80 100 80 100 90 90 90 90 60 100 80 60 0 Morningglory 100 10 50 0 0 90 30 20 10 0 20 40 40 20 0 20 20 100 0 0 0 Pigweed 100 60 60 30 30 100 60 60 80 90 90 100 90 80 90 80 80 100 80 0 0 Velvetleaf 20 20 0 0 20 0 0 0 0 0 0 60 0 70 0 0 0 80 0 0 0 Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Wild Oat 0 0 0 0 0 0 0 0 0 0 0 20 0 0 0 0 0 40 0 0 0 Rate 500 g/ha COMPOUND 46 47 48 49 50 51 52 53 54 55 56 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 Barnyardgrass 0 0 0 80 90 0 0 0 0 0 0 0 0 0 0 0 60 50 100 100 100 100 90 0 0 70 Blackgrass 0 0 0 60 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 70 0 0 0 Surinam grass 0 0 0 90 0 0 0 0 0 0 0 0 0 0 0 0 0 40 40 30 30 30 0 0 30 0 Cocklebur 0 0 0 30 50 0 0 0 20 10 0 0 0 0 0 0 50 70 30 20 60 80 20 0 20 90 Corn 0 0 0 0 0 0 20 10 0 0 0 0 0 0 0 0 0 20 0 0 0 0 0 0 0 0 Crabgrass 0 0 0 40 50 20 0 0 0 0 0 0 0 0 0 0 60 50 100 100 100 100 30 0 30 30 Foxtail, Giant 0 0 0 0 50 0 0 0 0 0 0 0 0 0 0 0 50 30 0 60 40 40 0 0 20 50 Lambsquarters 70 90 80 50 80 90 0 80 30 0 90 0 0 0 0 60 80 80 70 90 100 100 80 0 50 0 Morningglory 0 0 0 30 0 0 0 10 20 30 10 0 0 0 0 0 40 60 0 0 0 0 0 30 20 50 Pigweed 0 50 0 30 0 80 0 90 0 0 90 0 0 0 0 40 70 70 0 0 0 0 0 0 60 60 Velvetleaf 0 0 0 40 0 0 0 0 0 0 0 0 0 0 0 0 50 30 0 20 20 20 0 0 20 60 Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Wild Oat 0 0 0 30 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Rate 500 g/ha COMPOUND 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 Barnyardgrass 90 0 0 90 0 0 0 10 0 0 0 80 50 0 30 90 80 80 90 70 0 0 30 90 Blackgrass 0 0 0 0 0 0 0 0 0 0 0 0 20 0 0 0 0 0 0 0 0 0 0 0 Surinam grass 0 0 0 10 0 0 0 0 10 0 0 10 0 0 0 0 0 30 10 10 0 0 0 0 Cocklebur 90 0 0 20 20 20 30 80 100 20 10 20 100 0 0 30 30 60 80 80 50 0 20 20 Corn 40 0 0 0 0 0 0 0 10 0 0 0 30 0 0 10 0 10 10 10 0 0 0 0 Crabgrass 50 0 0 40 0 0 0 40 30 10 0 10 50 0 0 0 60 50 90 50 0 0 20 70 Foxtail, Giant 50 0 0 30 0 0 0 0 0 0 0 10 20 0 0 60 70 40 40 30 0 0 0 40 Lambsquarters 70 0 80 40 20 10 10 90 90 70 60 60 90 50 50 100 100 100 100 90 80 20 90 90 Morningglory 20 0 60 20 0 0 40 90 100 10 10 30 80 0 0 70 40 70 80 50 10 0 20 50 Pigweed 90 90 90 80 80 80 70 80 90 10 10 70 90 0 40 100 90 90 90 60 20 10 60 90 Velvetleaf 70 0 50 0 0 0 0 70 90 0 0 10 50 0 0 40 0 40 30 20 10 0 0 10 Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 30 0 0 0 0 0 0 0 0 Wild Oat 0 0 0 0 0 0 0 0 0 0 0 10 20 0 0 0 0 20 0 0 0 0 0 0 Rate 500 g/ha COMPOUND 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 Barnyardgrass 0 0 0 0 0 0 0 0 0 0 0 0 0 0 20 0 20 0 20 Blackgrass 0 0 0 0 0 0 0 0 0 0 0 0 0 20 0 0 0 0 60 Surinam grass 0 0 0 0 0 0 0 0 0 0 20 0 0 40 100 0 30 100 20 Cocklebur — — — — — — — — 90 100 40 90 30 0 0 70 60 70 50 Corn 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 20 20 Crabgrass 20 0 0 0 0 0 0 0 0 0 0 0 0 30 30 40 30 30 40 Foxtail, Giant 20 0 0 0 0 0 0 0 0 0 0 0 0 0 0 20 0 0 0 Lambsquarters 80 70 80 0 0 50 0 0 100 100 80 90 90 20 30 100 100 0 90 Morningglory 0 0 0 0 0 0 0 0 100 70 70 100 60 0 50 30 60 0 30 Pigweed 100 0 0 0 0 0 0 0 90 90 40 90 70 0 80 100 100 60 70 Velvetleaf 20 0 0 0 0 0 0 0 80 70 60 80 70 0 0 0 0 0 30 Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 20 40 30 30 50 20 Wild Oat 0 0 0 0 0 0 0 0 0 0 0 0 0 60 60 40 50 60 50 Rate 500 g/ha COMPOUND 117 118 119 120 121 122 123 124 126 127 128 129 130 131 132 133 134 136 Barnyardgrass 90 90 100 60 90 0 0 0 80 0 80 60 90 100 30 100 100 0 Blackgrass 0 0 0 0 0 — 0 — 0 0 0 0 20 0 0 0 0 0 Surinam grass 40 40 50 40 40 0 0 0 0 0 100 0 40 30 0 40 60 0 Cocklebur 100 100 100 100 100 90 80 90 70 60 50 30 50 70 0 30 30 0 Corn 0 20 0 20 30 0 0 0 0 0 0 0 0 20 0 0 20 0 Crabgrass 40 40 100 70 60 0 0 0 0 0 60 0 30 90 90 80 90 0 Foxtail, Giant 20 0 0 50 0 0 0 0 60 0 60 0 40 50 0 50 60 0 Lambsquarters 100 100 100 90 90 100 20 40 100 50 0 100 100 100 80 100 100 0 Morningglory 100 60 80 90 70 100 0 30 50 0 0 0 80 80 0 30 40 0 Pigweed 100 70 80 80 90 70 0 30 100 0 100 60 100 90 30 100 80 0 Velvetleaf 70 70 60 50 30 0 0 20 0 0 0 0 30 30 0 30 10 0 Wheat 30 20 40 20 50 0 0 0 0 0 0 0 0 0 0 10 0 0 Wild Oat 70 60 50 60 50 0 0 0 0 0 0 0 0 30 0 0 0 0 Rate 500 g/ha Rate 250 g/ha Rate 125 g/ha COMPOUND COMPOUND COMPOUND 137 138 139 140 141 142 143 144 145 146 9 10 109 125 1 2 3 4 5 6 7 8 Barnyard- 0 0 0 80 80 60 70 0 90 90 60 0 0 80 0 0 0 0 50 0 20 0 grass Blackgrass 0 0 0 0 40 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Surinam 0 0 0 0 0 0 0 0 0 0 0 0 20 0 0 0 0 0 0 0 0 0 grass Cocklebur 0 0 0 90 100 90 100 30 0 0 20 0 70 70 60 20 0 0 20 0 0 0 Corn 0 0 0 0 0 30 0 0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 Crabgrass 0 0 0 80 40 60 80 40 0 60 0 0 0 0 0 0 0 0 50 0 0 0 Foxtail, 90 0 0 70 50 90 80 40 40 70 0 0 20 0 30 0 0 0 20 0 0 0 Giant Lambs- 0 0 0 100 100 100 100 100 100 100 80 100 90 100 90 80 80 50 80 0 30 30 quarters Morning- 0 30 0 100 70 100 100 30 0 0 10 0 100 100 50 — 0 0 0 0 0 0 glory Pigweed 0 30 0 90 100 80 90 100 80 70 80 0 60 70 90 0 70 20 10 0 20 0 Velvetleaf 0 0 0 60 70 70 70 0 30 0 0 0 80 0 50 0 0 20 0 0 0 0 Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Wild Oat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Rate 125 g/ha COMPOUND 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 Barnyardgrass 0 0 0 0 0 0 0 0 0 0 60 90 0 20 70 100 0 20 0 0 100 100 80 0 0 Blackgrass 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Surinam grass 0 0 0 0 0 0 0 0 0 0 0 0 200 20 0 0 20 0 0 0 0 0 0 0 0 Cocklebur 0 0 0 0 0 0 0 0 0 20 80 70 20 40 20 60 50 0 0 0 70 60 60 0 0 Corn 0 0 0 0 0 0 0 0 0 0 0 0 0 20 0 0 0 0 0 0 0 0 0 0 0 Crabgrass 0 0 0 60 50 20 0 0 0 0 20 30 40 20 60 60 0 20 20 0 50 0 80 0 0 Foxtail, Giant 0 0 0 0 20 0 0 0 0 0 50 20 0 20 20 20 20 0 0 0 10 0 0 0 0 Lambsquarters 0 0 0 0 0 0 0 80 60 10 90 100 90 80 90 100 80 50 60 0 90 70 80 70 90 Morningglory 0 0 0 0 30 0 0 0 10 20 60 70 30 20 0 90 0 0 0 0 40 10 20 0 0 Pigweed 0 0 0 — — — — 0 0 0 90 70 80 70 80 70 0 40 30 30 100 20 40 70 90 Velvetleaf 0 0 0 0 0 0 0 0 0 10 10 20 20 20 0 0 20 0 0 0 0 0 0 0 0 Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Wild Oat 0 0 0 20 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Rate 125 g/ha COMPOUND 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 58 59 60 61 62 Barnyard- 0 90 80 100 0 90 0 60 0 40 30 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 grass Blackgrass 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Surinam 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 grass Cocklebur 40 20 10 40 0 30 0 40 0 20 20 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0 0 Corn 0 0 0 0 0 0 — 0 0 0 0 0 0 0 0 0 0 20 0 0 0 0 0 0 0 0 0 Crabgrass 0 80 0 60 0 60 0 50 0 0 0 0 0 0 0 30 0 0 0 0 0 0 0 0 0 0 0 Foxtail, 0 60 60 30 0 70 0 50 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Giant Lambs- 0 90 0 80 70 70 0 70 50 20 0 0 70 0 30 70 80 0 40 0 0 80 0 0 0 0 0 quarters Morning- 0 30 20 10 0 10 0 60 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 glory Pigweed 90 90 20 60 60 40 0 80 50 0 0 0 50 0 30 0 0 0 80 0 0 90 0 0 0 0 0 Velvetleaf 0 0 0 0 0 0 0 50 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Wild Oat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Rate 125 g/ha COMPOUND 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 Barnyardgrass 0 0 0 100 90 90 0 0 0 30 30 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Blackgrass 0 0 0 0 0 0 70 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Surinam grass 0 0 20 0 30 20 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Cocklebur 0 70 20 0 0 50 0 0 0 80 20 0 0 0 0 0 30 70 90 0 10 10 40 0 0 20 Corn 0 0 0 0 0 0 0 0 0 0 30 0 0 0 0 0 0 0 10 0 0 0 0 0 0 0 Crabgrass 0 0 0 30 50 90 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 20 0 0 0 Foxtail, Giant 0 0 0 0 20 20 0 0 0 0 20 0 0 0 0 0 0 0 0 0 0 0 0 0 0 20 Lambsquarters 60 70 60 90 90 100 80 0 0 0 0 0 70 0 0 0 0 10 20 20 10 50 30 0 0 100 Morningglory 0 0 0 0 0 0 0 30 20 20 20 0 20 0 0 0 30 40 80 0 0 10 0 0 0 20 Pigweed 50 40 0 0 0 0 0 0 30 20 20 80 50 30 70 70 70 70 70 0 0 60 60 0 0 90 Velvetleaf 0 0 0 20 0 0 0 0 0 30 50 0 0 0 0 0 0 40 80 0 0 0 20 0 0 0 Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Wild Oat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Rate 125 g/ha COMPOUND 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 Barnyardgrass 0 20 50 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Blackgrass 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Surinam grass 0 0 10 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Cocklebur 0 20 20 20 30 0 0 10 — — — — — — — — — 90 70 20 40 30 Corn 30 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Crabgrass 0 20 40 10 0 0 0 20 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Foxtail, Giant 90 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Lambsquarters 0 90 90 80 80 0 80 80 80 30 0 20 0 0 0 0 0 100 90 30 90 100 Morningglory 60 40 0 50 10 0 10 0 0 0 0 0 0 0 0 0 0 90 50 0 100 30 Pigweed 0 60 80 20 0 0 20 90 0 80 0 0 0 0 0 0 0 60 20 0 70 90 Velvetleaf 0 10 0 0 10 0 0 0 0 0 0 0 0 0 0 0 0 50 0 0 50 50 Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Wild Oat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Rate 125 g/ha COMPOUND 111 112 113 114 115 116 117 118 119 120 121 122 123 124 126 127 128 129 Barnyardgrass 0 0 0 0 0 0 40 0 30 0 0 0 0 0 0 0 0 0 Blackgrass 0 0 0 0 0 0 0 0 0 0 0 — — 0 0 0 0 0 Surinam grass 0 0 0 30 20 0 30 30 20 20 30 0 0 0 0 0 70 0 Cocklebur 0 0 0 50 20 30 90 60 90 90 70 30 30 20 0 0 0 0 Corn 0 0 0 0 20 20 0 20 0 0 20 0 0 0 0 0 0 0 Crabgrass 0 30 40 20 20 20 30 40 40 30 30 — 0 0 0 0 0 0 Foxtail,Giant 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Lambsquarters 0 30 30 90 0 70 90 90 90 60 80 90 0 20 100 30 0 100 Morningglory 0 20 0 30 0 30 70 40 30 50 50 20 0 0 0 0 0 0 Pigweed 0 60 100 90 50 50 80 70 60 60 50 30 0 0 30 0 0 0 Velvetleaf 0 0 0 0 0 20 70 40 30 20 30 0 0 0 0 0 0 0 Wheat 20 40 30 20 40 20 30 20 20 10 50 0 0 0 0 0 0 0 Wild Oat 0 30 40 30 30 30 40 30 0 30 30 0 0 0 0 0 0 0 Rate 125 g/ha Rate 62 g/ha COMPOUND COMPOUND 130 131 132 133 134 136 137 138 139 140 141 142 143 144 145 146 9 109 125 Barnyardgrass 0 80 0 80 90 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Blackgrass 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Surinam grass 0 0 0 0 20 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Cocklebur 20 30 0 10 30 0 0 0 0 60 40 60 0 0 0 0 10 60 30 Corn 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Crabgrass 0 0 0 40 20 0 0 0 0 20 20 40 0 0 0 0 0 0 0 Foxtail, Giant 0 20 0 0 30 0 0 0 0 0 30 30 30 20 0 0 0 0 0 Lambsquarters 90 90 70 100 100 0 0 0 0 70 90 70 80 100 80 80 70 80 100 Morningglory 70 20 0 0 10 0 0 10 0 0 0 70 30 0 0 0 0 90 50 Pigweed 80 80 0 80 60 0 0 0 0 60 80 60 70 50 0 0 70 50 30 Velvetleaf 0 0 0 0 0 0 0 0 0 0 50 40 50 0 0 0 0 0 0 Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Wild Oat 0 20 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Preemergence Rate 500 g/ha COMPOUND 1 2 3 4 5 6 7 8 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Barnyardgrass 100 0 100 0 100 100 100 70 0 0 0 0 0 0 0 0 0 0 100 100 80 100 Surinam grass 0 0 70 0 20 30 20 70 0 0 0 0 0 20 0 0 0 20 0 20 50 20 Cocklebur 40 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 20 Corn 20 0 30 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Crabgrass 100 0 100 0 100 100 100 100 0 0 0 0 0 0 0 0 0 0 — 100 100 100 Foxtail, Giant 100 0 80 0 100 100 100 90 0 0 0 0 0 0 0 0 0 0 100 100 100 50 Lambsquarters 100 90 100 0 100 100 100 100 0 0 0 0 0 60 0 0 — 60 — — 100 100 Morningglory 40 0 0 0 0 0 0 0 0 0 0 0 0 30 0 0 0 0 0 100 0 60 Pigweed 100 80 100 0 100 100 100 100 0 0 0 0 0 0 0 0 0 0 100 90 100 100 Rice — — — — 0 0 20 0 0 0 0 0 0 0 0 0 0 0 0 0 0 30 Velvetleaf 30 0 0 0 0 0 0 0 0 0 0 0 0 70 20 0 — 0 0 0 0 0 Rate 500 g/ha COMPOUND 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 Barnyardgrass 100 100 100 100 100 20 100 100 100 80 60 60 100 100 100 100 100 100 Surinam grass 80 80 70 0 70 0 60 70 60 60 20 0 100 0 60 20 90 0 Cocklebur 0 0 0 0 100 0 90 0 0 — 0 0 0 — 0 0 0 0 Corn 20 0 70 0 0 0 0 0 0 0 0 0 0 0 0 0 60 0 Crabgrass 100 100 100 90 100 0 100 100 100 100 — 100 100 100 100 100 100 0 Foxtail, Giant 100 100 100 90 100 0 100 90 100 80 70 0 100 100 100 100 100 60 Lambsquarters 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Morningglory 0 90 0 0 0 30 90 0 0 0 0 0 0 0 0 0 60 0 Pigweed 100 100 100 100 100 70 100 100 100 100 100 100 100 100 100 100 100 100 Rice 0 0 80 40 40 0 0 0 0 0 0 0 90 0 10 0 100 0 Velvetleaf 0 0 0 0 0 20 40 0 0 0 100 0 0 0 0 0 0 0 Rate 500 g/ha COMPOUND 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 58 59 60 61 62 Barnyardgrass 100 100 100 100 80 0 0 100 90 80 100 90 0 0 50 70 90 0 0 90 Surinam grass 100 20 100 80 0 0 0 0 30 20 0 0 0 0 30 0 80 0 0 0 Cocklebur 70 0 — 0 0 0 0 0 0 0 0 0 0 — — 0 0 0 0 0 Corn 20 0 20 0 0 0 0 0 0 0 20 0 0 0 0 0 0 0 0 0 Crabgrass 100 90 100 100 0 0 80 0 100 100 100 0 0 0 100 80 90 0 0 90 Foxtail, Giant 100 100 100 100 0 0 0 90 100 50 100 0 0 0 90 70 70 0 0 80 Lambsquarters 100 100 100 100 100 100 100 100 90 100 100 100 0 0 100 0 100 0 — 100 Morningglory 100 0 0 0 — 0 0 30 0 0 0 0 0 0 0 0 0 0 0 0 Pigweed 100 100 100 100 100 100 0 100 0 100 30 100 0 0 100 0 0 100 0 100 Rice 100 70 100 60 0 20 0 20 0 0 0 0 0 0 0 0 50 0 0 30 Velvetleaf 90 0 0 0 0 0 0 0 100 0 0 0 0 0 0 0 0 0 0 0 Rate 500 g/ha COMPOUND 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 Barnyardgrass 90 90 100 100 100 100 40 — 90 100 100 90 100 100 100 90 100 100 Surinam grass 30 60 20 20 50 0 20 0 40 70 90 20 100 100 40 0 90 90 Cocklebur 0 10 20 0 0 0 20 0 0 60 90 0 70 0 0 0 0 0 Corn 0 20 0 0 20 20 0 — 20 0 30 0 20 70 0 0 0 20 Crabgrass 100 100 70 40 80 20 0 100 100 100 100 70 100 100 90 30 100 100 Foxtail, Giant 90 90 70 40 40 20 0 100 100 100 100 60 100 100 0 10 60 100 Lambsquarters 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Morningglory 0 10 0 20 0 0 0 80 0 90 100 0 0 100 0 0 100 100 Pigweed 100 100 100 100 100 100 90 100 100 100 100 90 100 100 100 100 100 100 Rice 0 0 20 20 40 30 0 30 40 0 40 0 70 90 0 0 90 90 Velvetleaf 0 0 20 20 0 0 0 0 30 90 100 0 70 0 0 0 90 70 Rate 500 g/ha COMPOUND 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 98 99 Barnyardgrass 100 100 100 100 100 100 100 100 100 100 100 100 100 0 100 100 90 100 Surinam grass 100 100 90 100 90 60 100 100 100 80 80 70 70 0 90 80 0 20 Cocklebur 90 0 0 0 90 0 0 0 0 0 0 0 0 0 60 30 0 0 Corn 30 20 20 20 30 20 60 20 0 20 30 0 0 0 50 20 0 30 Crabgrass 100 100 100 100 100 100 100 100 100 100 100 100 100 30 100 100 100 100 Foxtail, Giant 100 100 100 100 100 100 100 100 100 100 100 100 90 0 100 100 90 100 Lambsquarters 100 100 100 — 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Morningglory 100 0 — 0 100 0 0 0 0 0 0 0 0 0 60 80 0 0 Pigweed 100 100 100 100 100 100 100 100 100 100 100 100 80 0 100 100 40 100 Rice 90 100 100 100 100 0 100 100 10 0 0 0 0 20 100 100 30 20 Velvetleaf 80 0 0 0 100 0 0 0 0 0 0 0 0 70 50 50 0 0 Rate 500 g/ha COMPOUND 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 Barnyardgrass 100 100 0 0 0 0 100 30 0 100 0 100 100 0 0 0 0 100 Surinam grass 20 80 0 0 0 0 100 70 30 100 40 0 30 0 0 0 0 100 Cocklebur 0 0 0 0 0 0 100 20 0 0 70 0 0 0 0 0 0 100 Corn 20 70 0 0 0 0 30 0 0 0 0 30 30 0 30 0 0 30 Crabgrass 100 100 90 60 0 30 100 100 0 100 100 100 100 0 0 0 0 100 Foxtail, Giant 70 100 0 0 0 20 60 40 20 50 50 0 100 0 0 0 0 100 Lambsquarters 100 100 0 100 100 100 100 100 100 100 100 100 100 0 100 0 0 100 Morningglory 0 0 0 0 0 0 100 100 0 0 0 0 30 0 30 0 0 100 Pigweed 100 100 0 0 100 100 100 100 60 100 100 100 100 0 100 0 0 100 Rice 20 — 0 0 0 0 100 0 0 0 0 0 100 0 0 0 0 70 Velvetleaf 0 0 0 0 0 0 100 0 0 70 80 0 0 0 0 0 0 100 Rate 500 g/ha COMPOUND 118 119 120 121 122 123 124 126 127 128 129 130 131 132 133 134 136 137 138 Barnyard- 100 100 100 100 100 0 100 100 100 100 100 100 100 100 100 100 0 40 100 grass Surinam 90 100 100 40 70 0 40 100 70 100 100 100 100 100 100 100 0 50 100 grass Cocklebur 0 30 40 30 0 0 0 70 0 60 0 50 30 30 0 0 0 80 100 Corn 30 40 50 50 0 0 0 50 0 60 30 70 50 0 90 90 0 0 20 Crabgrass 100 100 100 100 100 60 100 100 100 100 100 100 100 100 100 100 70 80 100 Foxtail, 100 100 100 100 30 0 100 100 100 100 100 100 100 100 100 100 0 0 100 Giant Lambs- 100 100 100 100 100 60 100 100 100 100 100 100 100 100 100 100 100 0 100 quarters Morning- 100 70 100 30 0 0 60 100 0 90 0 100 90 0 0 0 0 0 100 glory Pigweed 100 100 100 100 100 70 100 100 100 100 100 100 100 100 100 100 60 0 100 Rice 0 20 30 0 0 0 0 100 50 100 50 100 100 50 100 100 0 70 100 Velvetleaf 90 70 40 20 0 0 0 60 0 50 0 50 40 30 — 0 0 80 0 Rate 500 g/ha Rate 250 g/ha Rate 125 g/ha COMPOUND COMPOUND COMPOUND 139 140 141 142 143 144 145 146 9 10 109 125 1 2 3 4 5 6 7 Barnyardgrass 0 100 100 100 100 100 100 100 60 100 50 100 50 0 80 0 60 100 100 Surinam grass 0 100 100 100 90 70 60 100 70 30 90 100 0 0 40 0 0 0 0 Cocklebur 0 60 100 60 30 0 0 0 0 0 0 50 0 0 0 0 0 0 0 Corn 0 20 20 20 20 20 0 0 0 30 0 40 0 0 0 0 0 0 0 Crabgrass 0 100 100 100 100 100 100 100 100 100 100 100 0 0 70 0 90 70 70 Foxtail, Giant 0 100 100 100 100 100 100 100 90 100 100 100 50 0 40 0 80 20 70 Lambsquarters 100 100 100 100 100 100 100 100 100 100 100 100 100 80 100 0 100 100 100 Morningglory 0 100 100 50 70 0 0 40 0 0 0 80 20 0 0 0 0 0 0 Pigweed 100 100 100 100 100 100 100 100 100 100 100 100 100 20 100 0 80 100 100 Rice 0 40 50 40 30 0 80 0 0 0 0 100 — — — — 0 0 0 Velvetleaf 0 80 100 90 80 0 0 20 0 0 60 40 0 0 0 0 0 0 0 Rate 125 g/ha COMPOUND 8 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 Barnyardgrass 0 0 0 0 0 0 0 0 0 0 0 0 60 0 0 20 100 100 30 Surinam grass 20 0 0 0 0 0 0 0 0 0 0 0 20 30 0 20 80 40 0 Cocklebur 0 0 0 0 0 0 0 0 — 0 0 0 — 0 0 0 0 0 0 Corn 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 10 0 Crabgrass 30 0 0 0 0 0 0 0 0 0 0 0 100 0 70 100 100 100 0 Foxtail, Giant 40 0 0 0 0 0 0 0 0 0 0 70 70 30 50 90 100 100 0 Lambsquarters 0 0 0 0 0 0 0 0 — 0 0 — — 100 100 100 100 100 100 Morningglory 0 0 0 0 0 0 0 0 — 0 0 0 90 0 0 0 0 0 0 Pigweed 20 0 0 0 0 0 0 0 0 0 0 0 0 90 100 100 100 100 100 Rice 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 40 0 Velvetleaf 0 0 0 0 0 0 50 0 — — 0 0 0 0 0 0 0 0 0 Rate 125 g/ha COMPOUND 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 Barnyardgrass 50 0 40 100 80 30 0 0 100 0 70 50 100 40 100 60 80 80 Surinam grass 0 0 40 30 40 30 0 0 70 0 0 20 60 0 90 0 0 70 Cocklebur 0 0 0 0 — 0 0 0 0 0 — 0 0 0 0 — 0 0 Corn 0 0 0 0 0 0 0 0 0 0 0 0 0 0 20 0 0 0 Crabgrass 20 0 20 100 60 0 100 0 100 0 0 0 100 0 100 0 0 30 Foxtail, Giant 20 0 70 30 70 20 0 0 100 40 0 30 70 0 100 0 10 100 Lambsquarters 100 0 100 100 100 90 20 0 100 100 100 100 100 100 100 100 100 100 Morningglory 0 0 0 0 0 0 0 0 0 0 0 0 0 0 80 0 0 0 Pigweed 100 0 100 100 100 100 30 — 100 100 100 100 100 100 100 100 100 0 Rice 0 0 0 0 0 0 0 0 90 0 0 0 40 0 90 0 30 60 Velvetleaf 0 0 0 0 0 0 0 0 0 0 0 0 0 0 70 0 0 0 Rate 125 g/ha COMPOUND 46 47 48 49 50 51 52 53 54 55 56 58 59 60 61 62 63 64 Barnyardgrass 0 0 0 100 0 80 0 0 0 0 0 0 0 0 0 0 50 50 Surinam grass 0 0 0 0 0 0 0 0 0 0 30 0 60 0 0 0 0 30 Cocklebur 0 0 0 0 0 0 0 — 0 0 0 0 0 0 0 0 0 0 Corn 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Crabgrass 0 0 0 0 100 100 100 0 0 0 30 0 20 — 0 0 0 40 Foxtail, Giant 0 0 0 0 20 0 90 0 0 0 50 0 0 0 0 0 50 0 Lambsquarters 100 0 100 100 0 100 100 100 0 0 100 0 0 0 — 100 100 100 Morningglory 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Pigweed 100 100 0 100 0 0 0 100 0 — 100 0 0 0 0 100 100 100 Rice 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Velvetleaf 0 0 0 0 100 0 — 0 0 0 0 — 0 0 0 0 0 0 Rate 125 g/ha COMPOUND 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 Barnyardgrass 90 100 60 100 20 — 10 100 100 30 100 100 20 0 70 0 100 100 Surinam grass 0 20 20 0 20 0 40 0 50 0 60 80 0 0 70 80 90 90 Cocklebur 0 — 0 0 0 0 0 0 0 0 30 0 0 0 0 0 0 0 Corn 0 0 0 0 0 — 0 0 0 0 0 0 0 0 0 0 0 0 Crabgrass 20 0 20 — 0 90 50 100 100 20 100 100 60 0 100 100 100 100 Foxtail, Giant 20 20 40 — 0 90 90 100 100 0 100 100 0 0 0 100 100 100 Lambsquarters 100 100 100 100 90 100 100 100 100 100 100 100 90 100 100 100 100 100 Morningglory 0 — 0 0 0 20 0 0 0 0 0 0 0 0 0 60 30 0 Pigweed 100 100 100 100 60 100 100 100 100 80 100 100 90 80 100 100 100 100 Rice 0 0 40 0 0 30 20 0 30 0 50 70 0 0 50 60 50 70 Velvetleaf 0 0 0 0 0 0 0 0 90 0 50 0 0 0 0 0 70 0 Rate 125 g/ha COMPOUND 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 Barnyardgrass 100 100 100 0 100 100 80 50 100 30 0 0 90 100 30 0 0 0 Surinam grass 70 80 60 0 80 70 60 20 70 0 0 0 60 50 0 0 0 0 Cocklebur 0 0 40 0 0 0 0 0 0 0 0 0 0 20 0 0 0 0 Corn 20 0 20 0 30 20 0 0 0 0 0 0 20 0 0 0 0 0 Crabgrass 100 100 100 0 100 100 90 90 100 50 20 0 100 100 20 0 0 0 Foxtail, Giant 100 100 80 80 100 100 90 80 90 50 20 0 100 100 20 0 0 0 Lambsquarters 100 — 100 100 100 100 100 100 100 100 60 0 100 100 20 60 100 100 Morningglory 0 0 90 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Pigweed 100 100 100 100 100 100 90 80 90 80 0 0 100 100 0 0 0 70 Rice 20 0 100 0 70 0 0 0 0 0 0 0 90 70 0 0 0 0 Velvetleaf 0 0 20 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Rate 125 g/ha COMPOUND 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 Barnyardgrass 30 0 0 0 0 90 0 0 30 30 0 90 0 0 0 0 100 100 Surinam grass 0 0 0 0 0 100 0 0 50 0 0 10 0 0 0 0 100 0 Cocklebur 0 0 0 0 0 30 0 0 0 0 0 0 0 0 0 0 70 0 Corn 0 0 0 0 0 30 0 0 0 0 0 0 0 20 0 0 20 30 Crabgrass 90 0 0 0 0 100 0 0 100 100 70 100 0 0 0 0 100 100 Foxtail, Giant 0 0 0 0 0 40 0 0 0 0 0 100 0 0 0 0 100 40 Lambsquarters 100 0 100 100 60 100 100 100 100 0 30 100 0 30 0 0 100 100 Morningglory 0 0 0 0 0 100 0 0 0 0 0 30 0 0 0 0 80 40 Pigweed 40 0 0 70 0 100 80 20 100 100 0 100 0 30 0 0 100 100 Rice 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Velvetleaf 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 40 20 Rate 125 g/ha COMPOUND 119 120 121 122 123 124 126 127 128 129 130 131 132 133 134 136 137 138 Barnyardgrass 100 100 40 0 0 70 100 0 100 100 100 100 100 100 100 0 0 0 Surinam grass 100 40 0 50 0 0 100 0 100 90 100 100 80 100 90 0 0 70 Cocklebur 30 20 10 0 0 0 50 0 0 0 0 0 0 0 0 0 0 0 Corn 0 20 20 0 0 0 30 0 30 20 50 40 0 0 20 0 0 0 Crabgrass 100 100 10 100 0 30 100 100 100 100 100 100 100 100 100 0 0 100 Foxtail, Giant 100 100 0 20 0 50 100 70 100 100 100 100 100 100 100 0 0 80 Lambsquarters 100 100 100 100 0 100 100 90 100 100 100 100 100 100 100 100 0 100 Morningglory 50 70 20 0 0 0 70 0 70 0 50 0 0 0 0 0 0 90 Pigweed 100 100 100 100 0 80 100 0 100 100 100 100 70 100 100 0 0 100 Rice 10 20 0 0 0 0 70 0 100 30 100 70 0 90 100 0 30 0 Velvetleaf 30 20 10 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Rate 125 g/ha Rate 62 g/ha COMPOUND COMPOUND 139 140 141 142 143 144 145 146 9 10 109 125 Barnyardgrass 0 100 100 100 100 80 70 90 0 0 0 100 Surinam grass 0 100 100 100 80 0 0 40 0 20 20 70 Cocklebur — 20 70 0 0 0 0 0 0 — 0 0 Corn 0 0 0 0 0 0 0 0 0 0 0 20 Crabgrass 0 100 100 100 100 100 100 100 0 100 100 100 Foxtail, Giant 0 100 100 100 100 100 100 100 30 80 20 100 Lambsquarters 100 100 100 100 100 100 100 100 90 100 100 100 Morningglory 0 0 90 20 20 0 0 0 0 0 0 50 Pigweed 0 100 100 100 100 100 100 100 80 90 100 100 Rice 0 20 30 20 0 0 0 0 0 0 0 50 Velvetleaf 0 60 70 20 60 0 0 0 0 0 0 0 Flooded Paddy Rate 1000 g/ha COMPOUND 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 Barnyardgrass 100 100 70 100 100 100 100 100 100 60 0 0 0 0 0 80 0 60 100 100 100 Ducksalad 90 100 50 100 100 100 80 100 100 90 0 0 0 0 0 60 0 80 100 100 100 Rice 40 90 0 50 90 90 90 100 60 40 0 0 0 0 0 40 0 0 100 90 90 Flatsedge 90 100 90 100 100 100 100 100 100 100 30 0 0 0 0 90 0 90 100 100 100 Rate 1000 g/ha COMPOUND 23 24 25 26 27 28 29 30 31 32 33 34 35 41 42 46 47 50 51 Barnyardgrass 0 100 100 0 90 100 0 100 100 100 0 100 60 70 100 100 70 100 100 Ducksalad 100 100 100 0 100 100 0 100 100 100 0 100 0 70 100 70 20 100 100 Rice 0 90 90 0 50 50 0 90 90 100 0 30 0 40 100 90 70 60 30 Flatsedge 0 100 100 0 100 100 30 100 100 100 0 100 100 100 100 — 100 100 100 Rate 1000 g/ha COMPOUND 52 53 54 55 56 57 58 59 60 61 93 94 138 139 Barnyardgrass 100 100 80 100 80 100 90 100 0 0 100 0 100 20 Ducksalad 100 30 30 80 20 100 70 70 50 30 100 0 90 0 Rice 50 20 0 0 0 90 20 20 0 0 50 0 90 0 Flatsedge 100 90 90 100 90 100 80 90 0 20 100 0 90 70

Seeds of plant species selected from bermudagrass ( Cynodon dactylon ), Surinam grass ( Brachiaria decumbens ), cocklebur ( Xanthium strumarium ), corn ( Zea mays ), crabgrass ( Digitaria sanguinalis ), woolly cupgrass ( Eriochloa villosa ), giant foxtail ( Setaria faberii ), goosegrass ( Eleusine indica ), johnsongrass ( Sorghum halepense ), kochia ( Kochia scoparia ), lambsquarters ( Chenopodium album ), morningglory ( Ipomoea hederacea ), yellow nutsedge ( Cyperus esculentus ), pigweed ( Amaranthus retroflexus ), common ragweed ( Ambrosia elatior ), soybean ( Glycine max ) and velvetleaf ( Abutilon theophrasti ) were planted and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.

At the same time, plants selected from these crop and weed species and also winter barley ( Hordeum vulgare ), blackgrass ( Alopecurus myosuroides ), canary grass ( Phalaris minor ), chickweed ( Stellaria media ), downy brome ( Bromus tectorum ), green foxtail ( Setaria viridis ), Italian ryegrass ( Lolium multiflorum ), wheat ( Triticum aestivum ), wild oat ( Avena fatua ) and windgrass ( Apera spica - venti ) were treated with postemergence applications of some of the test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments. Plant species in the flooded paddy test consisted of rice ( Oryza saliva ), smallflower flatsedge ( Cyperus difformis ), duck salad ( Heteranthera limosa ) and barnyardgrass ( Echinochloa crus - galli ) grown to the 2-leaf stage for testing. Treated plants and controls were maintained in a greenhouse for 12 to 14 days, after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table C, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (-) response means no test result.

Four plastic pots (ca. 16-cm diameter) per rate were partially filled with sterilized Tama silt loam soil comprised of a 35:50:15 ratio of sand, silt and clay and 2.6% organic matter. Separate plantings for each of the four pots were as follows. Seeds from the U.S. of Heteranthera limosa (Hl), Monochoria vaginalis (Mv), Ammania auriculata (Aa), and Sphenoclea zeylanica (Sz) were planted into one 16-cm pot for each rate. Seeds from the U.S. of Cyperus iria (Ci), Leptochloa fascicularis (Li), one stand of 9 or 10 direct-seeded rice seedlings ( Oryza saliva cv. ‘Japonica—M202’; Oss), and one stand of 6 transplanted rice seedlings ( Oryza sativa cv. ‘Japonica—M202’; Ost) were planted into one 16-cm pot for each rate. Seeds from the U.S. of Cyperus difformis (Cd), Alisma plantago - aquatica (Ap), and Scirpus mucronatus (Sm) were planted into one 16-cm pot for each rate. Seeds from the U.S. of Echinochloa crus - galli (Ecg), Echinochloa oryzicola (Eor), Echinochloa oryzoides (Eoz) and Echinochloa colonum (Ecc) were planted into one 16-cm pot for each rate. Plantings were sequential so that crop and weed species were at the 2.0 to 2.5-leaf stage at time of treatment.

Potted plants were grown in a greenhouse with day/night temperature settings of 29.5/26.7° C., and supplemental balanced lighting was provided to maintain a 16-hour photoperiod. Test pots were maintained in the greenhouse until test completion.

Chemical treatments consisting of Compound 1 of Index Table A (Cmpd 1), daimuron (Cmpd D), quinoclamine (Cmpd Q) and combinations thereof were formulated in acetone. At time of treatment, test pots were flooded to 3 cm above the soil surface, treated by application of test compounds directly to the paddy water, and then maintained at that water depth for the duration of the test. Effects of treatments on rice and weeds were visually evaluated by comparison to untreated controls after 21 days. Plant response ratings are reported on a 0 to 100 scale; where 0 is no effect and 100 is complete control. ND means no data.

Colby's equation was used to calculate the expected additive herbicidal effect of the mixtures of Compound 1 with daimuron (Cmpd D) and quinoclamine (Cmpd Q). Colby's equation (Colby, S. R “Calculating Synergistic and Antagonistic Responses of Herbicide Combinations,” Weeds, 15(1), pp 20–22 (1967)) calculates the expected additive effect of herbicidal mixtures, and for two active ingredients is of the form:

P a+b =P a +P b −( P a P b /100)

wherein P a+b is the percentage effect of the mixture expected from additive contribution of the individual components,

P a is the observed percentage effect of the first active ingredient at the same use rate as in the mixture, and P b is the observed percentage effect of the second active ingredient at the same use rate as in the mixture.

Plant response ratings and additive effects expected from the Colby Equation are shown in Table D.

As can be seen from the results listed in Table C for this test, mixtures of daimuron and quinoclamine with Compound 1 reduced phytotoxicity on direct-seeded rice (Oss), daimuron being more effective than quinoclamine in this regard. In contrast to the safening on rice, these combinations generally retain excellent effect for controlling weeds. The results suggest some synergism of mixtures of Compound 1 with daimuron on Ammania auniculata (Aa) and mixtures of Compound 1 with quinoclamine on Ammania auriculata (Aa) and Scirpus mucronatus (Sm). Mixtures of Compound 1 with daimuron showed synergism on all four Echinochloa species, E. crus - galli (Ecg), E. oryzicola (Eor), E. oryzoides (Eoz) and E. colonum (Ecc), while mixtures of Compound 1 with quinoclamine show synergism on two species, E. crus - galli (Ecg) and E. oryzoides (Eoz). The synergism on Echinochloa species with safening on direct-seeded rice is particularly surprising, as both Echinochloa species and rice are grasses.