WO1998035954A1 - Bicyclic hydrazone herbicides - Google Patents

Abstract

Compounds of Formula (I), and their N-oxides and agriculturally suitable salts, are disclosed which are useful for controlling undesired vegetation wherein Q is Q-1, Q-2, Q-3 or Q-4; and Q, Z, X, R1 through R20, m, n, and r are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula (I) and a method for controlling undesired vegetation which involves contacting the vegetation or its environment with an effective amount of a compound of Formula (I).

Description

TITLE

BICYCLIC HYDRAZONE HERBICIDES

BACKGROUND OF THE INVENTION

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

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

WO 94/08988 discloses oxime derivatives of Formula i as herbicides:

wherein, inter alia, R is lower alkyl; R ^! -R⁶ are H or lower alkyl ;

X¹ is lower alkyl; and X² is H or lower alkyl. The hydrazone compounds of the present invention are not disclosed in this publication. SUMMARY OF THE INVENTION

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

wherein Q is

Q-l Q-2

Q-3 Q-4

Z is selected from the group -CH₂CH₂CH₂-, -OCH₂CH₂-, -O-CH=CH-,

-NR¹³CH₂CH₂-, -NR¹³CH=CH-, -N=CHCH₂-, -OCH₂O-, -NR¹³CH₂NR¹³-, -N=CHNR¹³-, -CH₂OCH₂-, -CH₂NR¹³CH₂-, -CH₂S(O)_nCH₂-, -CH₂C(O)CH₂-, -CH=NCH₂-, -CH₂CH₂-, -OCH₂-, -SCH₂-, and -NRl³CH₂-, each group optionally substituted with one to four R⁵, and the directionality of the Z linkage is defined such that the moiety depicted on the left side of the linkage is bonded to the carbonyl carbon of Q-l;

X is O, S(O)_n, N(C_rC₂ alkyl) or CH₂ optionally substituted with 1-2 C_rC₂ alkyl; each R¹ is independently Cι-C₆ alkyl, Cj-C₆ haloalkyl, C_]-C₆ alkoxy, Cι-C₆ haloalkoxy, S(O)_nR¹⁷, SO₂N(R¹³)₂, halogen, cyano or nitro;

R² is NR¹⁸R¹⁹; or R² is a five-membered heterocyclic aromatic ring, or a five- or six- membered heterocyclic ring which may be partially or fully saturated, each ring containing 1 to 4 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, and containing at least one nitrogen and no more than one oxygen and no more than 2 sulfurs, and the ring is optionally substituted with one to three groups independently selected from the group C_j-C₃ alkyl, halogen, cyano, and nitro, provided that (a) said heterocyclic ring is bonded to the parent bicyclic structure through a ring nitrogen and (b) that when a nitrogen atom of the heterocyclic ring is substituted, then the nitrogen substituent is other than halogen; each R³ is independently Cι-C₂ alkyl;

R⁴ is OR¹⁴, SH, S(O)_nR¹⁷, halogen or NR¹⁵R¹⁶; or R⁴ is phenylthio or phenylsulfonyl, each optionally substituted with C1-C3 alkyl, halogen, cyano or nitro; each R⁵ is independently C1-C3 alkyl, C₃-Cg alkenyl, C3- alkynyl, C1-C3 alkoxy, formyl, C₂-C₆ alkoxycarbonyl, -CH (C_rC₃ alkoxy), -CH(C₁-C₃ alkoxy)₂, C1-C3 alkylthio, cyano or halogen; or when two R⁵ are attached to the same carbon atom, then they can be taken together to form -OCH₂CH₂O-, -OCH₂CH₂CH₂O-, -SCH₂CH₂S- or -SCH₂CH₂CH₂S-, each group optionally substituted with 1-4 CH₃;

R⁶ is H, C_rC₆ alkyl, C_rC₆ haloalkyl, C₂-C₆ alkoxyalkyl, formyl, C₂-C₆ alkylcarbonyl, C₂-Cg alkoxycarbonyl, C₂-Cg alkylaminocarbonyl, C3-C₇ dialkylaminocarbonyl or SO₂R¹⁷; or R⁶ is phenyl, benzyl, benzoyl, -CH₂C(O)phenyl or phenylsulfonyl, each optionally substituted on the phenyl ring with 1 to 3 groups selected from the group C1-C3 alkyl, halogen, cyano, and nitro;

R⁷ is H, C_rC₆ alkyl, C_rC₆ haloalkyl, C₃-C₆ alkenyl, C₃-C₆ alkynyl or

-CH₂CH₂OR¹³; or R⁷ is phenyl or benzyl, each optionally substituted on the phenyl ring with C1-C3 alkyl, halogen, cyano or nitro;

R⁸ is H, Ci-Cg alkyl, C Cg haloalkyl, Cj-Cg alkoxy, C Cg haloalkoxy, halogen, cyano or nitro;

R⁹ is H, Cι-C₆ alkyl, C_rC₆ haloalkyl, C3-C6 cycloalkyl or C3-C6 halocycloalkyl;

R¹⁰ is H, C₂-Cg alkoxycarbonyl, C₂-Cg haloalkoxy carbonyl, CO H or cyano; R¹1 is C_rC₆ alkyl, C_rC₆ haloalkyl, C₃-C₆ halocycloalkyl or C₃-C₆ cycloalkyl optionally substituted with 1-4 C1-C3 alkyl;

R¹² is cyano, C₂-C₆ alkoxycarbonyl, C₂-C₆ alkylcarbonyl, S(O)_nR¹⁶ or C(O)NR¹⁵R¹⁶; each R¹³ is independently H or Ci-Cg alkyl;

R¹⁴ is H, C_rC₆ alkyl, C_rC₆ haloalkyl, C₂-C₆ alkoxyalkyl, formyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C(O)NR¹⁵R¹⁶ or SO₂R¹⁷; or R¹⁴ is phenyl, benzyl, benzoyl, -CH₂C(O)phenyl or phenylsulfonyl, each optionally substituted on the phenyl ring with 1 to 3 groups selected from group C1-C₃ alkyl, halogen, cyano and nitro; R¹⁵ is H or C_rC₆ alkyl; R¹⁶ is C_rC₆ alkyl or C_rC₆ alkoxy; or

R¹⁵ and R¹⁶ can be taken together as -CH₂CH₂-, -CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂- , -CH₂CH₂CH₂CH₂CH₂- or -CH₂CH₂OCH₂CH₂-; R¹⁷ is C_rC₆ alkyl or C_rC₆ haloalkyl;

R¹⁸ is H or C_rC₆ alkyl;

R¹⁹ is H, C_j-Cg alkyl, C_j-Cg haloalkyl, C₂-Cg alkoxycarbonyl, C₂-Cg alkylcarbonyl, C(=O)R²⁰ or phenyl optionally substituted with one to three groups independently selected from the group C1-C3 alkyl, halogen, cyano, and nitro; or R¹⁸ and R¹⁹ can be taken together as =C(C_rC₃ alky_)₂;

R²⁰ is phenyl or a five- or six-membered aromatic heterocyclic ring, containing 1 to 4 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that the heterocyclic ring contains no more than one oxygen and no more than one sulfur, and the phenyl and heterocyclic ring are each optionally substituted with one to three groups independently selected from the group

C1-C3 alkyl, halogen, cyano, and nitro, provided that when a nitrogen atom of the heterocyclic ring is substituted, then the nitrogen substituent is other than halogen; m is 0, 1 or 2; n is 0, 1 or 2; p is 0, 1 , 2, 3 or 4; and r is 0, 1, 2 or 3.

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, «-propyl, -propyl, or the different butyl, pentyl or hexyl isomers. The term "1-2 alkyl" indicates that one or two of the available positions for that substituent may be alkyl which are independently selected. "Alkenyl" includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. "Alkenyl" also includes polyenes such as 1 ,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl" can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. "Alkoxy" includes, for example, methoxy, ethoxy, «-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂, CH₃CH₂CH₂CH₂OCH₂ and

CH₃CH₂OCH₂CH₂. "Alkoxyalkoxy" denotes alkoxy substitution on alkoxy. "Alkylamino", "dialkylamino", "alkenylthio", "alkenylsulfinyl", "alkenylsulfonyl", "alkynylthio", "alkynylsulfinyl", "alkynylsulfonyl", and the like, are defined analogously to the above examples. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "cycloalkoxy" includes the same groups linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy. The term "aromatic ring system" denotes fully unsaturated carbocycles and heterocycles in which the polycyclic ring system is aromatic (where aromatic indicates that the Hϋckel rule is satisfied for the ring system). The term "aromatic heterocyclic ring system" includes fully aromatic heterocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the Hϋckel rule is satisfied). The term "nonaromatic heterocyclic ring system" denotes fully saturated heterocycles as well as partially or fully unsaturated heterocycles where the Hϋckel rule is not satisfied by any of the rings in the ring system. The heterocyclic ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen. One skilled in the art will appreciate that not all nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and n-chloroperbenzoic acid (MCPB A), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.

The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. The term "1-2 halogen" indicates that one or two of the available positions for that substituent may be halogen which are independently selected. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" include F₃C, C1CH₂, CF₃CH₂ and CF₃CC1₂. The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", "haloalkylthio", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkenyl" include (C1)₂C=CHCH₂ and CF₃CH₂CH=CHCH₂. Examples of "haloalkynyl" include HC≡CCHCl, CF₃C≡C, CC1₃C≡C and FCH₂C≡CCH₂. Examples of "haloalkoxy" include CF₃O, CCl₃CH₂O, HCF₂CH₂CH₂O and CF₃CH₂O.

The total number of carbon atoms in a substituent group is indicated by the "Cj-C;" prefix where i and j are numbers from 1 to 6. For example, C1-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C alkoxyalkyl designates CH₃OCH₂; C3 alkoxyalkyl designates, for example, CH₃CH(OCH₃), CH₃OCH₂CH₂ or CH₃CH₂OCH₂; and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH₃CH₂CH₂OCH₂ and CH₃CH₂OCH₂CH₂. Examples of "alkylcarbonyl" include

C(O)CH₃, C(O)CH₂CH₂CH₃ and C(O)CH(CH₃)₂. Examples of "alkoxycarbonyl" include CH₃OC(=O), CH₃CH₂OC(=O), CH₃CH₂CH₂OC(=O), (CH₃)₂CHOC(=O) and the different butoxy- or pentoxycarbonyl isomers. In the above recitations, when a compound of Formula I is comprised of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.

When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R)i__j, then the number of substituents may be selected from the integers between i and j inclusive.

When a group contains a substituent which can be hydrogen, for example R⁶ or R⁷, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.

Some compounds of this invention can exist as one or more tautomers. One skilled in the art will recognize, for example, that compounds of Formula la (Formula I where Q is Q-l, R⁴ is OR¹⁴, and R¹⁴ is H) can also exist as the tautomers of Formulae lb and Ic as shown below. One skilled in the art will recognize that said tautomers often exist in equilibrium with each other. As these tautomers interconvert under environmental and physiological conditions, they provide the same useful biological effects. The present invention includes mixtures of such tautomers as well as the individual tautomers of compounds of Formula I.

lb ^Ic

The salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. The salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or phenol.

Preferred compounds for reasons of better activity and/or ease of synthesis are: Preferred 1. Compounds of Formula I above, and N-oxides and agriculturally suitable salts thereof, wherein: Q is Q-l. Preferred 2. Compounds of Preferred 1 wherein: X is SO₂. Preferred 3. Compounds of Preferred 1 wherein:

R² is ΝR¹⁸R!9. Preferred 4. Compounds of Formula I above, and N-oxides and agriculturally suitable salts thereof, wherein: Q is Q-2; Preferred 5. Compounds of Preferred 4 wherein:

X is SO₂. Preferred 6. Compounds of Preferred 5 wherein: R² is NR1SR1 . Most preferred is the compound of Preferred 3 selected from the group:

(a) 2,3-dihydro-6-[(2-hydroxy-6-oxo-l-cyclohexen-l-yl)carbonyl]-5,8-dimethyl-4H- l-benzothiopyran-4-one dimethylhydrazone 1,1 -dioxide;

(b) 2,3-dihydro-6-[(2-hydroxy-4-methyl-6-oxo- 1 -cyclohexen- 1 -yl)carbonyl]-5,8- dimethyl-4H-l-benzothiopyran-4-one dimethylhydrazone 1,1 -dioxide; (c) 6- [( 1 -ethyl-5-hydroxy- 1 H-pyrazol-4-yl)carbonyl] -2,3 -dihydro-5 ,8-dimethyl-4H-

1 -benzothiopyran-4-one dimethylhydrazone 1,1 -dioxide; and (d) 6-[[5-(benzoyloxy)- 1 -ethyl- l//-pyrazol-4-yl]carbonyl]-2,3-dihydro-5,8- dimethyl-4H-l-benzothiopyran-4-one dimethylhydrazone 1,1 -dioxide. This invention also relates to herbicidal compositions comprising herbicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent. The preferred compositions of the present invention are those which comprise the above preferred compounds.

This invention also relates to a method for controlling undesired vegetation comprising applying to the locus of the vegetation herbicidally effective amounts of the compounds of the invention (e.g., as a composition described herein). The preferred methods of use are those involving the above preferred compounds.

DETAILS OF THE INVENTION The compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-14. The definitions of Q, Rϊ-R²⁰, Z, X, m, n, p, and r in the compounds of Formulae 1-17 below are as defined above in the Summary of the Invention. Compounds of Formulae Ia-Ig are subsets of the compounds of Formula I, and all substituents for Formulae Ia-Ig are as defined above for Formula I. For example, compounds of Formula Id below are compounds of Formula I wherein Q is Q-l.

Id Scheme 1 illustrates the preparation of compounds of Formula Id whereby an enol ester of Formula 1 is reacted with a base such as triethylamine in the presence of a catalytic amount of a cyanide source (e.g., acetone cyanohydrin or potassium cyanide). This rearrangement is carried out by general methods known in the art; see for example, W. J. Michaely, EP 0369803-A1; D. Cartwright, et al., EP 0283261-B1.

Scheme 1

Enol esters of Formula 1 can be prepared by reacting the acid of Formula 2 with N- methyl-2-chloropyridinium iodide, followed by treatment of the formed intermediate with the dione of Formula 3 in the presence of a base such as triethylamine (Scheme 2). This coupling is carried out by methods known in the art (or by slight modification of these methods): for example, see E. Haslam Tetrahedron (1980), 36, 2409-2433.

Scheme 2

Et₃Ν

Compounds of Formula 2 can be readily prepared by treatment of ketones of Formula 4 with the appropriate amines (Scheme 3). This condensation is well known in the art: for example, see Lieberman et al., J. Heterocyclic Chem. (1988), 25, pp 827-830 and Yamazaki et al., Chem. Pharm. Bull. (1971), 19, p 159. The starting material amines are either commercially available or can be synthesized by methods known to those skilled in the art.

Scheme 3

Enol esters of Formula 1 can also be prepared by reacting a dione of Formula 3 with an acid chloride of Formula 17 in the presence of a slight excess of a base such as triethylamine in an inert organic solvent such as acetonitrile, dichloromethane or toluene at temperatures between 0 °C and 110 °C (Scheme 3a). This type of coupling is known in the art: for example, see W. J. Michaely, EP 369,803.

Scheme 3 a

base, e.g. Et3N

17

The acid chlorides of Formula 17 can be prepared by one skilled in the art by reacting an acid of Formula 2 with chlorinating agents such as oxalyl chloride or thionyl chloride and a catalytic amount of dimethylformamide (Scheme 3b). This chlorination is well known in the art: for example, see W. J. Michaely, EP 369,803. Scheme 3 b

oxalyl chloride (or thionyl chloride) »• 17 cat. amount of NN-dimethyl- formamide

Scheme 4 illustrates the preparation of compounds of Formula 4 whereby a compound of Formula 5 is stirred in a hydrochloric acid aqueous solution (O.lNto 12N) at temperatures between 0 °C and 100 °C for a period of time ranging from 30 minutes to 3 days. This conversion is carried out by methods known in the art (or by slight modification of these methods): for example; see P. A. Grieco, et al., J. Am. Chem. Soc. (1977), 99, p 5773; P. A. Grieco, et al., J. Org. Chem. (1978), 43, p 4178.

Scheme 4

Scheme 5 illustrates the preparation of acids of Formula 5 (X is S(O)_n and n is 1 or 2) whereby an acid of Formula 5 (X is S(O)_n and n is 0) is reacted with a oxidizing reagent such as peroxyacetic acid, -chloroperoxybenzoic acid, potassium peroxymonosulfate or hydrogen peroxide. The reaction may be buffered with a base such as sodium acetate or sodium carbonate. The oxidation is carried out by general methods known in the art (see for example, B. M. Trost, et al., J. Org. Chem. (1988), 53, 532; B. M. Trost, et al., Tetrahedron Lett. (1981), 21, 1287; S. Patai, et al., The Chemistry ofSulphones and Sulphoxides, John Wiley & Sons).

Scheme 5

5 (X is S(0)_n and n is 0) 5 (X is S(0)n and is l or 2) oxidizing agent Scheme 6 illustrates the preparation of acids of Formula 5 (n is 0 when X is S(O)_n) whereby a phenyl bromide of Formula 6 (n is 0 when X is S(O)_n) is treated with «-butyllithium (or magnesium), and the lithium salt (or the Grignard reagent) generated in situ is then reacted with carbon dioxide followed by acidification with an acid such as hydrochloric acid. This conversion is carried out by general methods known in the art; see for example, M. A. Ogliaruso et al., Synthesis of Carboxylic Acids, Esters and Their Derivatives, pp 27-28, John Wiley & Sons; A. J. Bridges, et al., J. Org. Chem. (1990), 55 (2), 773; C. Franke, et al., Angew. Chem. Int. Ed. (1969), 8, 68. In some instances, the incoφoration of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Green, T. W.; Wuts, P. G. M., Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991).

Scheme 6

(n is Owhen X is S(O)n)

Scheme 7 illustrates the preparation of phenyl bromides of Formula 6 (n is 0 when X is S(O)_n) whereby a ketone of Formula 7 (n is 0 when X is S(O)_n) is reacted with HO(CH₂)₂OH in the presence of a protic acid catalyst such as/?-toluenesulfonic acid (or a Lewis acid such as BF3) in an inert organic solvent such as toluene. This conversion is carried out by general methods known in the art; see for example, T. W. Greene, et al., Protective Groups in Organic Synthesis (Second Edition), pp 175-221, John Wiley & Sons, Inc. Scheme 7

7 (n is 0 hen X is S(O)n)

The ketones of Formula 7 can also be prepared by general methods known in the art (or by slight modification of these methods); see, for example, W. Flemming, et al., Chem. Ber. (1925), 58, 1612; I. W. J. Still, et al., Can. J. Chem. (1976), 54, 453-470; V. J. Traynelis, et al, J. Org. Chem. (1961), 26, 2728; I. Nasuno, et al., WO 94/08988; F. Camps, et al., J. Heterocycl. Chem. (1985), 22(5), p. 1421 ; T. S. Rao, et al, Indian J. Chem. B. (1985), 24(11), p. 1159; S. Ghosh, et al., Tetrahedron (1989), 45(5), p. 1441; A. Danan, et al., Synthesis-Stuttgart (1991), (10), p. 879; P. Magnus, et al., J. Chem. Soc. Chem. Comm. (1991), (7), p. 544; A. Padwa, et al., J. Org. Chem. (1989), 54(12), p. 2862; S. A. Ali, et al., J. Org. Chem. (1979), 44, p. 4213; J. Blake, et al., J. Am. Chem. Soc. (1966), 88, p. 4061; M. Mori, et al., J. Chem. Soc. Chem. Comm. (1990), (18), p. 1222; S. Kano, et al., J. Chem. Soc, Perkin. Trans. 1 (1980), p. 2105; A. F. Bekhli, et al., Khim Geterotsikl. Soedin. (1975), p. 1 118; W. S. Johnson, et al., J. Am. Chem. Soc. (1949), 71, p. 1901; J. A. Hirsch, et al., J. Org. Chem. (1974), 39(14), p. 2044; F. G. Mann, et al., J. Chem. Soc. (1957), p. 4166; A. C. Jain, et al., Indian. J. Chem. B (1987), 26(2), p. 136; G. Ariamala, et al, Tet. Lett. (1988), 29(28), p. 3487; B. Loubinoux, et al., Tet. Lett. (1992), 33(16), p. 2145; S. Cabiddu, et al., J. Organomet. Chem. (1989), 366(1-2), p. 1; R. HasenKamp, et al., Chem. Ber. (1980), 113, p. 1708; D. A. Pulman, et al., J. Chem. Soc. Perkin. Trans. 1 (1973), p. 410; W. C. Lumma, et al., J. Org. Chem. (1969), 34, p. 1566; P. D. Clark, et al., Can. J. Chem. (1982), 60(3), p. 243.

The dicarbonyl compounds of Formula 3 are either commercially available or can be prepared by general methods known in the art (or by slight modification of these methods): for example, see D. Cartwright, et al., EP 0283261-B1; J. Dangelo, et al., Tet. Lett. (1991), 32(26), p. 3063; T. Okado, et al., J. Org. Chem. (1977), 42, p. 1163; B. E. Maryanoff, et al., J. Am. Chem Soc. (1975), 97, p. 2718; E. Er, et al., Helv. Chim. Ada. (1992), 75(7), p. 2265; Y. D. Vankar, et al., Tet. Lett., (1987), 28(5), p. 551 ; C. S. Pak, et al., Tet. Lett. (1991), 32(42), p. 6011; I. Nishiguchi, et al., Chem. Lett. (1981), p. 551; B. Eistert, et al., Liebigs Ann. Chem. (1962), 659, p. 64; N. K. Hamer, Tet. Lett. (1986), 27(19), p. 2167; M. Sato, et al., Heterocycles (1987), 26(10), p. 2611; A. Murray, et al., Tet. Lett. (1995), 36(2), p. 291; K. S. Kochhar, et al., Tet. Lett. (1984), 25(18), p. 1871; M. Sato, et al., Tetrahedron (1991), 47(30), p. 5689; M. Sato, et al., Chem. Pharm. Bull. (1990), 38(1), p. 94; T. Meal, U.S. 4,931,570; T. Muel, et al., U.S. 5,093,503.

Compounds of General Formula Ie can be readily prepared by one skilled in the art by using the reactions and techniques described in Schemes 8 and 9 of this section.

Ie

Scheme 8 illustrates the preparation of compounds of Formula Ie (R⁶ = H). whereby an ester of Formula 8 or its isomer 8a is reacted with a base such as triethylamine in the presence of a catalytic amount of cyanide source (e.g., acetone cyanohydrin or potassium cyanide). This rearrangement is carried out by methods known in the art (or by slight modification of these methods): for example, see W. J. Michaely, EP 369,803.

Scheme 8

or (e.g., acetone cyanohydrin or potassium cyanide)

Compounds of Formula 8 or 8a can be prepared by reacting the acid of Formula 2 with N-methyl-2-chloropyridinium iodide, followed by treatment of the formed intermediate with the hydroxypyrazole of Formula 9 in the presence of a base such as triethylamine (Scheme 8a). This coupling is carried out by methods known in the art (or by slight modification of these methods): for example, see E. Haslam Tetrahedron (1980), 36, 2409-2433.

Scheme 8a

Et3N

8 or

Esters of Formula 8 or amides of Formula 8a can also be prepared by reacting a hydroxypyrazole of Formula 9 with an acid chloride of Formula 17 in the presence of a slight mole excess of a base such as triethylamine in an inert organic solvent such as acetonitrile, methylene chloride or toluene at temperatures between 0 °C and 110 °C (Scheme 9). This type of coupling is carried out by methods known in the art (or by slight modification of these methods): for example, see W. J. Michaely, EP 369,803.

Scheme 9

base (e.g., triethylamine)

17 + 9 8 or 8a

Compounds of General Formula If can be readily prepared by one skilled in the art by using the reactions and techniques described in Schemes 10-13 of this section.

Scheme 10 illustrates the preparation of compounds of Formula If whereby a compound of Formula 10 is reacted with a salt of hydroxylamine such as hydroxylamine hydrochloride in the presence of a base or acid acceptor such as triethylamine or sodium acetate. The substituents of the immediate products may be further modified if appropriate. This cyclization is carried out by methods known in the art (or by slight modification of these methods): for example, see P. A. Cain, et al., EP 560,483; C. J. Pearson, et al., EP 636,622.

Scheme 10

wherein

L is a leaving group such as C _j-C jalkoxy (e.g., OC₂H5) or NN-dialkylamino (e.g., dimethyl amino)

RlOa j_s j^ C₂-Cg alkoxycarbonyl, C₂-Cg haloalkoxycarbonyl or CONH₂

Scheme 11 illustrates the preparation of compounds of Formula 10 whereby a compound of Formula 11 is reacted with a reagent of Formula 12 or Formula 13. This conversion is carried out by methods known in the art (or by slight modification of these methods): for example, see P. A. Cain, et al., EP 560,483; C. J. Pearson, et al., EP 636,622.

Scheme 11

Scheme 12 illustrates the preparation of compounds of Formula 11 whereby an ester of Formula 14 is decarboxylated in the presence of a catalyst, such as j-toluenesulfonic acid, in an inert solvent such as toluene. This conversion is carried out by methods known in the art (or by slight modification of these methods): for example, see P. A. Cain, et al., EP 560,483; C. J. Pearson, et al., EP 636,622. Scheme 12

14

Esters of Formula 14 can be prepared by reacting the metal salt of a compound of Formula 1 with an acid chloride of Formula 17 (Scheme 13). This type of coupling is known in the art: for example see P. A. Cain, et al., EP 560,483; C. J. Pearson, et al., EP 636,622.

Scheme 13

15

Scheme 14 illustrates the preparation of compounds of Formula Ig whereby a compound of Formula 17 is reacted with a compound of Formula 16 in the presence of a base such as triethylamine, potassium carbonate, sodium hydride or Mg(OEt)₂ in an inert organic solvent such as diethyl ether, tetrahydrofuran, NN-dimethylformamide, dichloromethane or acetonitrile.

This conversion is carried out by methods known in the art (or slight modification of these methods); for example, see J. W. Ashmore, EP 213,892 and P. A. Cain, EP 496,631 Al.

Scheme 14

16

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

One skilled in the art will also recognize that compounds of Formula I and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents. Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. ^lH NMR spectra are reported in ppm downfield from tetramethylsilane; s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd = doublet of doublets, dt = doublet of triplets, br s = broad singlet. EXAMPLE 1 Step A: Preparation of 3-|^"(2,5-dimethylphenyl)thio1propanoic acid

43.4 g (1.086 mol) of sodium hydroxide was added to 230 mL of water, 75.0 g (0.543 mol) of 2,5-dimethylthiophenol (purchased from Aldrich Chemical Company) was then added and the mixture was cooled to about 10 °C. 91.30 g (0.597 mol) of 3-bromopropionic acid (purchased from Aldrich Chemical Company) was added in portions while keeping the temperature below 25 °C. The mixture was warmed to room temperature, stirred for 2 h under nitrogen, and was then washed with diethyl ether (3 x 500 mL). The aqueous layer was acidified with 1NHC1 and filtered to yield 112.79 g of the title compound of Step A as a solid melting at 97-98 °C. *H ΝMR (CDC1₃): δ 2.3 (s,3H), 2.34 (s,3H), 2.68 (t,2H), 3.1 (t,2H), 6.9 (d,lH), 7.06-7.14 (2H). Step B: Preparation of 2,3-dihvdro-5,8-dimethyl-4_¹/- 1 -benzopyran-4-one

530 mL of concentrated sulfuric acid was added to 24.91 g (0.119 mol) of the title compound of Step A while being cooled with an acetone/ice bath. The ice bath was removed, the mixture was stirred for 1 h and was then poured over crushed ice. The aqueous mixture was extracted with a 1 : 9 mixture of diethyl ether : hexane (6 x 500 mL), dried (MgSO4), filtered, and evaporated to dryness to yield 11.75 g of the title compound of Step B as an oil. ^lU ΝMR (CDCI3): δ 2.3 (s,3H), 2.6 (s,3H), 2.97 (m,2H), 3.2 (m,2H), 6.9-7.1 (2H). Step C: Preparation of 6-bromo-2,3-dihydro-5,8-dimethyl-4H-l-benzothiopyran-4-one

A solution of 4.07 g (0.021 mol) of the title compound of Step B in 25 mL of methylene chloride was added dropwise to a mixture of 7.07 g (0.053 mol) of aluminum chloride (purchased from Aldrich Chemical Company) and 25 mL of methylene chloride. The suspension was stirred for approximately 15 minutes, 1.14 mL (0.022 mol) of bromine (purchased from Janssen) was added dropwise, and the mixture was refluxed for 10 minutes. The warm mixture was poured into 10 mL of concentrated hydrochloric acid containing 75 g of ice, stirred for 10 minutes, diluted with 50 mL of waiter, and then extracted with diethyl ether (2 x 200 mL). The combined organic layers were washed with water (2 x 200 mL), dried (Νa₂SU4), filtered, and evaporated to dryness. The crude product was chromatographed over silica gel eluting with a mixture of ethyl acetate : hexane (5% : 95%) to yield 2.62 g of the title compound of Step C as a solid melting at 87-88 °C. ^lH NMR (CDCI3): δ 2.3 (s,3H), 2.6 (s,3H), 3.0 (m,2H), 3.2 (m,2H), 7.45 (s,lH). Step D: Preparation of 6-bromo-2,3-dihvdro-5,8-dimethylspiror4/ -l-benzothiopyran-

4.2'-π.31dioxolanel 26.06 g (0.096 mol) of the title compound of Step C, 250 mL of ethylene glycol, 170 mL of trimethyl orthoformate (purchased from Aldrich Chemical Company), and 0.06 g of />-toluenesulfonic acid monohydrate were stirred together at 80 °C under nitrogen overnight. The mixture was diluted with 400 mL of diethyl ether. The resulting mixture was washed with a 1 : 1 mixture of IN sodium hydroxide: saturated aqueous ΝaCl (2 x 600 mL) and then with saturated aqueous ΝaCl (1 x 600 mL). The organic layer was dried (Νa₂S04), filtered, and evaporated to dryness. The crude product was chromatographed over silica gel eluting with a mixture of ethyl acetate : hexane (1 : 9) to yield 24.73 g of the title compound of Step D as a solid melting at 97 °C (dec). *H NMR (CDC1₃): δ 2.2 (s,3H), 2.3 (m,2H), 2.4 (s,3H), 3.0 (m,2H), 4.15 (m,2H), 4.3 (m,2H), 7.3 (s,lH).

Step E: Preparation of 2,3-dihydro-5, 8-dimethylspiror4H-l-beι_zothiopyran-4,2'-

[1 ,31dioxolanel-6-carboxylic acid 24.73 g (0.078 mol) of the title compound of Step D was added to 150 mL of tetrahydrofiiran. The solution was cooled to about -70 °C under nitrogen and 37.68 mL (0.094 mol) of 2.5M «-butyllithium in hexane was added dropwise while keeping the temperature below -65 °C. After stirring for 1 h, carbon dioxide was bubbled into the mixture for 2 h. The mixture was allowed to warm to room temperature, 300 mL of hexanes were added, and the resulting mixture was filtered. The resulting solid was added to a mixture of water : methylene chloride (400 mL : 400 mL), cooled to about 0 °C, and acidified to pH 1 with concentrated hydrochloric acid. The layers were separated and the aqueous layer was extracted with diethyl ether (2 x 300 mL). The combined organic layers were dried (MgSO₄), filtered, and evaporated to dryness to yield 4.73 g of the title compound of Step E as a solid melting at 207-208 °C. *H NMR ((CD₃)₂SO): δ 2.2 (m,5H), 2.4 (s,3H), 3.0 (m,2H), 4.1-4.2 (m,4H), 7.4 (s,lH).

Step F: Preparation of 2,3-dihydro-5.8-dimethylspiror4 _^"- 1 -benzothiopyran-4,2'- π,31dioxolanel-6-carboxylic acid 1,1 -dioxide 4.73 g (0.017 mol) of the title compound of Step E and 2.08 g (0.025 mol) of sodium acetate were added to 85 mL of methanol. The solution was cooled to about 0 °C, and a solution of 17.66 g (0.029 mol) of OXONE® (purchased from Aldrich Chemical Company) in 85 mL of water was added dropwise while keeping the temperature below 6 °C. The mixture was warmed to room temperature and stirred under nitrogen overnight. The mixture was diluted with 50 mL of water, cooled to about 0 °C, acidified to around pH 2 with concentrated hydrochloric acid, and then extracted with chloroform (3 x 150 mL). The combined organic layers were dried (MgSO4), filtered, and evaporated to dryness. The residue was triturated in diethyl ether : hexane (1 : 9) which was decanted to yield 4.18 g of the title compound of Step F as a solid melting at 185 °C (dec). *H NMR ((CD₃)₂SO): δ 2.35 (s,3H), 2.5 (m,2H), 2.6 (s,3H), 3.5 (m,2H), 4.16 (m,2H), 4.2 (m,2H), 7.6 (s,lH). Step G: Preparation of 3,4-dihvdro-5,8-dimethyl-4-oxo-2H-l-benzothiopyran-6- carboxylic acid 1,1 -dioxide

To 300 ml of IN hydrochloric acid was added 10.3 g (33 mmol) of the title compound of Step F. The reaction mixture was refluxed overnight and was then allowed to cool to room temperature. The precipitate was collected by filtration the next day and was then dissolved in ethyl acetate. The organic solution was dried over magnesium sulfate, filtered, and concentrated under reduced pressure to yield 5.97 g of the title compound of step G as a solid melting at 187-188 °C. Η NMR ((CD₃)₂SO): δ 14.65 (bs, IH), 7.79 (s, IH), 3.97 (t, 2H), 3.2 (t, 2H), 2.64 (s, 3H), 2.47 (s, 3H). Step H: Preparation of 4-(dimethylhydrazono)-3,4-dihydro-5,8-dimethyl-27 -l- benzothiopyran-6-carboxylic acid 1,1 -dioxide A mixture of 3.2 g of the title compound of step G, 50 ml of toluene, 3.0 ml of 1,1-dimethylhydrazine (purchased from Aldrich Chemical Company), and 60 mg ofp- toluenesulfonic acid monohydrate (purchased from Aldrich Chemical Company) was refluxed with a Dean Stark trap under nitrogen overnight. The reaction mixture was then allowed to cool to room temperature and was stirred at room temperature for 4 days. The dark precipitate was then collected by filtration. The solid was rinsed with 500 ml of methylene chloride and filtered. The methylene chloride filtrate was concentrated under reduced pressure to yield 2.41 g of the title compound of step H as a solid melting at 168— 170 °C. ^JH NMR ((CD₃)₂SO): δ 7.36 (s, IH), 3.56 (t, 2H), 3.25 (t, 2H), 2.45-2.6 (m, 9H), 2.4 (s, 3H).

Step I: Preparation of 3-oxo- 1 -cyclohexen- 1 -yl 4-(dimethylhydrazono)-3 ,4-dihydro-

5.8-dimethyl-2H- 1 -benzothiopyran-6-carboxylate 1 , 1 -dioxide To 30 ml of methylene chloride was added 2.3 ml of triethylamine, 2.25 g of the title compound of step H, and 2.22 g of 2-chloro-N-methylpyridinium iodide (purchased from Aldrich Chemical Company). The mixture was stirred at room temperature under nitrogen for 3 days. The reaction mixture was concentrated under reduced pressure and the residue was chromatographed over silica gel eluting with a mixture of ethyl acetate : hexane (2:1) to yield 0.42 g of the title compound of step I as a solid melting at 174-176 °C. *H ΝMR ((CD₃)₂SO) : δ 7.72 (s, IH), 6.03 (s, IH), 3.34- 5 (m, 4H), 2.37-2.77 (m, 14H), 2.47 (t, 2H), 2.07-2.2 (m, 2H). Step J: Preparation of 2-rr4-(dimethylhydrazono)-3,4-dihvdro-5,8-dimethyl-2 -^"-l- benzothiopyran-6-yllcarbonyll- 1 ,3-cvclohexanedione 5,S-dioxide To a mixture of 0.37 g of the title compound of step I, 20 ml of acetonitrile, 1 drop of acetone cyanohydrin (purchased from Aldrich Chemical Company) and 0.22 ml of triethylamine was added 0.06 g of potassium cyanide (purchased from Janssen) with stirring. The resulting solution was stirred at room temperature overnight and was then concentrated under reduced pressure. The residue was dissolved in water and the aqueous solution was acidified with concentrated hydrochloric acid. The precipitate was collected by filtration, washed with hexanes, and dried in a vacuum oven at 50 °C for 3 hours to yield 0.25 g of the title compound of step J, a compound of this invention, as a solid melting at 197—198 °C. ^lH ΝMR ((CD₃)₂SO): 7.05 (s, IH), 3.84 (br, 2H), 3.55 (br, 2H), 3.18 (br, 6H), 2.83 (m, 2H), 2.68 (s, 3H), 2.46 (m, 2H), 2.26 (s, 3H), 2.08 (m, 2H). By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 28 can be prepared. The following abbreviations are used in the Tables which follow: Ph = phenyl, CN = cyano, and NO₂ = nitro.

TABLE 1

R___ R5b 2

H H -NHCH₃

H CH₃ -NHCH₃ CH₃ CH₃ -NHCH₃

H H -N(CH₃)₂

H CH₃ -N(CH₃)₂ CH₃ CH₃ -N(CH₃)₂

H H -N(CH₂CH₃)₂

H CH₃ -N(CH₂CH₃)₂ CH₃ CH₃ -N(CH₂CH₃)₂

H H -N(CH₃)(CH₂CH₂CH₃)

H CH₃ -N(CH₃)(CH₂CH₂CH₃) CH₃ CH₃ -N(CH₃)(CH₂CH₂CH₃)

H H -N(CH₃)(CH₂CF₃)

H CH₃ -N(CH₃)(CH₂CF₃) CH₃ CH₃ -N(CH₃)(CH₂CF₃)

H H -N(CH₃)Ph

H CH₃ -N(CH₃)Ph CH₃ CH₃ -N(CH₃)Ph

H H / \ N 0

\ /

H CH₃ / /—\ \

- NN 0 O

\ /

CH₃ CH₃ // \\ NN 0O

\ /

H CH₃ // \\ N N N _ vf —— C CH3

\ /

TABLE 2

R14 la Rib

H CH₃ H

H CH₃ CI

H CI H

H CI CH₃

PhC(=0) CH₃ CH₃

2-CH₃PhC(=0) CH₃ CH₃

4-CH₃PhC(=0) CH₃ CH₃

PhC(=0)CH₂ CH₃ CH₃

CH₃CH₂S(0)₂ CH₃ CH₃

PhS(0)₂ CH₃ CH₃ C(=0)N(C₂H₅)₂ CH₃ CH₃ C(=S)N(C₂H₅)₂ CH₃ CH₃

TABLE 3

CH₃ H -NHCH₃

CH₃ CH₃ -NHCH₃

CH₂CH₃ H -NI ICH₃ CH₃ H -N(CH₃)₂

CH₃ CH₃ -N(CH₃)₂

CH₂CH₃ H -N(CH₃)₂

CH₃ H -N(CH₂CH₃)₂

CH₃ CH₃ -N(CH₂CH₃)₂

CH₂CH₃ H -N(CH₂CH₃)₂

CH₃ H -N(CH₃)(CH₂CH₂CH₃)

CH₃ CH₃ -N(CH₃)(CH₂CH₂CH₃)

CH₂CH₃ H -N(CH₃)(CH₂CH₂CH₃)

CH₃ H -N(CH₃)(CH₂CF₃)

CH₃ CH₃ -N(CH₃)(CH₂CF₃)

CH₂CH₃ H -N(CH₃)(CH₂CF₃)

CH₃ H -N(CH₃)Ph

CH₃ CH₃ -N(CH₃)Ph

CH₂CH₃ H -N(CH₃)Ph

CH₃ H N XΛ

V

TABLE 4

R_. Rla Rib

H CH₃ H

H CH₃ CI

H CI H

H CI CH₃

PhC(=0) CH₃ CH₃

2-CH₃PhC(=0) CH₃ CH₃

4-CH₃PhC(=0) CH₃ CH₃

2-ClPhC(=0) CH₃ CH₃

4-ClPhC(=0) CH₃ CH₃

2-FPhC(=0) CH₃ CH₃ 2-BrPhC(=0) CH₃ CH₃

2-CH₃0PhC(=0) CH₃ CH₃

(CH₃)₂CHC(=0) CH₃ CH₃

(CH₃)₂CHCH₂C(=0) CH₃ CH₃

(CH₃)₃CC(=0) CH₃ CH₃ cyc/o-C₃H₅C(=0) CH₃ CH₃

CH₂=CCH₃C(=0) CH₃ CH₃

CH₂=CHC(=0) CH₃ CH₃

CH₃S(0)₂ CH₃ CH₃

CH₃CH₂S(0)₂ CH₃ CH₃

CH₃CH₂CH₂S(0)₂ CH₃ CH₃

CH₃CH₂CH₂CH₂S(0)₂ CH₃ CH₃

(CH₃)₂CHS(0)₂ CH₃ CH₃

PhS(0)₂ CH₃ CH₃

4-CH₃PhS(0)₂ CH₃ CH₃

CH₃OC(=0) CH₃ CH₃

CH₃CH₂OC(=0) CH₃ CH₃

CH₃CH₂CH₂OC(=0) CH₃ CH₃

(CH₃)₂CH0C(=0) CH₃ CH₃

CH₂=CHCH₂OC(=0) CH₃ CH₃

CH₃SC(=0) CH₃ CH₃

CH₃CH₂SC(=0) CH₃ CH₃

2-furanyl-C(=0) CH₃ CH₃

2-thienyl-C(=0) CH₃ CH₃

TABLE 5

R5a R5b Rla Rib ___:

H H CH₃ CH₃ -NHCH3 H CH₃ CH₃ CH₃ -NHCH3 CH₃ CH₃ CH₃ CH₃ -NHCH3

H H CH₃ CH₃ -N(CH₃)₂

H CH₃ CH₃ CH₃ -N(CH₃)₂

CH₃ CH₃ CH₃ CH₃ -N(CH₃)₂

H H CH₃ CH₃

— N

H H CH₃ H -NHCH3

H CH₃ CH₃ H -NHCH3

CH₃ CH₃ CH₃ H -NHCH3

H H CH₃ H -N(CH₃)₂

H CH₃ CH₃ H -N(CH₃)₂

CH₃ CH₃ CH₃ H -N(CH₃)₂

H H CI CH₃ -NHCH3

H CH₃ CI CH₃ -NHCH3

CH₃ CH₃ CI CH₃ -NHCH3

H H CI CH₃ -N(CH₃)₂

H CH₃ CI CH₃ -N(CH₃)₂

CH₃ CH₃ CI CH₃ -N(CH₃)₂

TABLE 6

R14 R18 El⁹

H CH₃ CH₃

PhC(=0) CH₃ CH₃

2-CH₃PhC(=0) CH₃ CH₃ 4-CH₃PhC(=0) CH₃ CH₃

PhC(=0)CH₂ CH₃ CH₃

CH₃CH₂S(0)₂ CH₃ CH₃

PhS(0)₂ CH₃ CH₃

C(=0)N(C₂H₅)₂ CH₃ CH₃

C(=S)N(C₂H₅)₂ CH₃ CH₃

H CH₂CH₃ CH₂CH₃

PhC(=0) CH₂CH₃ CH₂CH₃

2-CH₃PhC(=0) CH₂CH₃ CH₂CH₃

4-CH₃PhC(=0) CH₂CH₃ CH₂CH₃

PhC(=0)CH₂ CH₂CH₃ CH₂CH₃

CH₃CH₂S(0)₂ CH₂CH₃ CH₂CH₃

PhS(0)₂ CH₂CH₃ CH₂CH₃

C(=0)N(C₂H₅)₂ CH₂CH₃ CH₂CH₃

C(=S)N(C₂H₅)₂ CH₂CH₃ CH₂CH₃

TABLE 7

Rl^a Rl^b R^

CH₃ H N(CH₃)₂

CH₃ CH₃ N(CH₃)₂

CI H N(CH₃)₂

CI CH₃ N(CH₃)₂

CH₃ H NHCH₂CH₃

CH₃ CH₃ NHCH₂CH₃

CI H NHCH₂CH₃

CI CH₃ NHCH₂CH₃

CH₃ H N(CH₃)Ph

CH₃ CH₃ N(CH₃)Ph

CI H N(( _Η₃)Ph CI CH₃ N(CH₃)Ph

CH₃ H / \ N O

CH₃ CH₃ / N O

Cl CH₃ / \ N O

CI H

— N I

TABLE 8

Rl^a Rl^b 2

CH₃ H N(CH₃)₂

CH₃ CH₃ N(CH₃)₂

Cl H N(CH₃)₂

Cl CH₃ N(CH₃)₂

CH₃ H NHCH₂CH₃

CH₃ CH₃ NHCH₂CH₃

Cl H NHCH₂CH₃

Cl CH₃ NHCH₂CH₃

CH₃ H N(CH₃)Ph

CH₃ CH₃ ^' N(CH₃)Ph

Cl H N(CH₃)Ph

Cl CH₃ N(CH₃)Ph

CH₃ H / \

^■N 0

\ /

CH₃ CH₃ / \

^•N o

\ /

Cl H / \

^•N o

\ /

Cl CH₃ / \

^■N o

\ /

Formulation/Utility

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

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

Weight Percent

Active Ingredient Diluent Surfactant

Water-Dispersible and Water-soluble 5-90 0-94 1-15 Granules, Tablets and Powders.

Suspensions, Emulsions, Solutions 5-50 40-95 0-15 (including Emulsifiable Concentrates)

Dusts 1-25 70-99 0-5

Granules and Pellets 0.01-99 5-99.99 0-15

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

Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon 's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.

Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, NN-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, NN-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.

Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry 's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.

For further information regarding the art of formulation, see U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961 , pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.

In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Tables A and B.

Example A High Strength Concentrate

Compound 1 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%. Example B Wettable Powder

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

Example C Granule Compound 3 10.0% attapulgite granules (low volatile matter,

0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.

Example D Extruded Pellet Compound 10 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%. Test results indicate that the compounds of the present invention are highly active preemergent and postemergent herbicides or plant growth regulants. Many of them have utility for broad-spectrum pre- and/or postemergence weed control in areas where complete control of all vegetation is desired such as around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, air fields, river banks, irrigation and other waterways, around billboards and highway and railroad structures. Some of the compounds are useful for the control of selected grass and broadleaf weeds with tolerance to important agronomic crops which include but are not limited to alfalfa, barley, cotton, wheat, rape, sugar beets, corn (maize), sorghum, soybeans, rice, oats, peanuts, vegetables, tomato, potato, perennial plantation crops including coffee, cocoa, oil palm, rubber, sugarcane, citrus, grapes, fruit trees, nut trees, banana, plantain, pineapple, hops, tea and forests such as eucalyptus and conifers (e.g., loblolly pine), and turf species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue and Bermuda grass). Those skilled in the art will appreciate that not all compounds are equally effective against all weeds. Alternatively, the subject compounds are useful to modify plant growth. A herbicidally effective amount of the compounds of this invention is determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of compounds of this invention is 0.001 to 20 kg/ha with a preferred range of 0.004 to 1.0 kg/ha. One skilled in the art can easily determine the herbicidally effective amount necessary for the desired level of weed control.

Compounds of this invention can be used alone or in combination with other commercial herbicides, insecticides or fungicides. Compounds of this invention can also be used in combination with commercial herbicide safeners such as benoxacor, dichlormid and furilazole to increase safety to certain crops. A mixture of one or more of the following herbicides with a compound of this invention may be particularly useful for weed control: acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal), alachlor, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, bifenox, bispyribac and its sodium salt, bromacil, bromoxynil, bromoxynil octanoate, butachlor, butralin, butroxydim (ICIA0500), butylate, caloxydim (BAS 620H), carfentrazone-ethyl, chlomethoxyfen, chloramben, chlorbromuron, chloridazon, chlorimuron-ethyl, chlornitrofen, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, cinmethylin, cinosulfuron, clethodim, clomazone, clopyralid, clopyralid-olamine, cyanazine, cycloate, cyclosulfamuron, 2,4-D and its butotyl, butyl, isoctyl and isopropyl esters and its dimethylammonium, diolamine and trolamine salts, daimuron, dalapon, dalapon-sodium, dazomet, 2,4-DB and its dimethylammonium, potassium and sodium salts, desmedipham, desmetryn, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, dichlobenil, dichlorprop, diclofop-methyl, 2-[4,5-dihydro-4-methyl-4-(l-methylethyl)-5-oxo-l_^t -imidazol-2-yl]-5-methyl-3- pyridinecarboxylic acid (AC 263,222), difenzoquat metilsulfate, diflufenican, dimepiperate, dimethenamid, dimethylarsinic acid and its sodium salt, dinitramine, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethofumesate, ethoxysulfuron, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, fluazifop-butyl, fluazifop-P-butyl, fluchloralin, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, fluridone, flurochloridone, fluroxypyr, fluthiacet-methyl, fomesafen, fosamine-ammonium, glufosinate, glufosinate-ammonium, glyphosate, glyphosate-isopropylammonium, glyphosate-sesquisodium, glyphosate-trimesium, halosulfuron-methyl, haloxyfop-etotyl, haloxyfop-methyl, hexazinone, imazamethabenz-methyl, imazamox, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfiiron, ioxynil, ioxynil octanoate, ioxynil-sodium, isoproturon, isouron, isoxaben, isoxaflutole, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its dimethylammonium, potassium and sodium salts, MCPA-isoctyl, mecoprop, mecoprop-P, mefenacet, mefluidide, metam-sodium, methabenzthiazuron, methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyl [[[l-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2- methoxyethylidene]amino]oxy]acetate (AKH-7088), methyl 5-[[[[(4,6-dimethyl-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]-l-(2-pyridinyl)-l/_^'-pyrazole-4-carboxylate (NC-330), metobenzuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, napropamide, naptalam, neburon, nicosulfuron, norflurazon, oryzalin, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pebulate, pendimethalin, pentoxazone (KPP-314), perfluidone, phenmedipham, picloram, picloram-potassium, pretilachlor, primisulfuron-methyl, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propyzamide, prosulfuron, pyrazolynate, pyrazosulfuron-ethyl, pyridate, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, quinclorac, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, sethoxydim, siduron, simazine, sulcotrione (ICIA0051), sulfentrazone, sulfometuron-methyl, TCA, TCA-sodium, tebuthiuron, terbacil, terbuthylazine, terbutryn, thenylchlor, thiafluamide (BAY 11390), thifensulfuron-methyl, thiobencarb, tralkoxydim, tri-allate, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tridiphane, trifluralin, triflusulfuron-methyl, and vernolate.

In certain instances, combinations with other herbicides having a similar spectrum of control but a different mode of action will be particularly advantageous for preventing the development of resistant weeds. The following Tests demonstrate the control efficacy of the compounds of this invention against specific weeds. The weed control afforded by the compounds is not limited, however, to these species. See Index Tables A-C for compound descriptions. The abbreviation "dec" indicates that the compound appeared to decompose on melting. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared.

INDEX TABLE A

Cmpd Rf R5a _R5b B mp (°C)

1 (Ex. 1) OH H H N(CH₃)₂ 197-198 *

2 OH CH₃ H N(CH₃)₂ 183-185

8 OΕt₃NH⁺ CH₃ CH₃ 160-163

OΕt₃NH⁺ CH₃ CH₃ >200 (dec)

N— CH₃

*See Index Table C for *H NMR data.

INDEX TABLE B

Cmpd R6 E^ mp (°C. 10 C(=0)Ph N(CH₃)₂ 60 (dec) 11 H N(CH₃)₂ 149-152

INDEX TABLE C Cmpd No. ^lH NMR Data (CDC1₃ solution unless indicated otherwise)³ 1 ((CD₃)₂SO): δ 7.05 (s, IH), 3.84 (br m, 2H), 3.55 (br m, 2H),

3.18 (br m, 6H), 2.83 (m, 2H), 2.68 (s, 3H), 2.46 (m, 2H), 2.26 (s, 3H), 2.08 (m, 2H).

^a lH NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (m)-multiplet, (br m)-broad multiplet.

BIOLOGICAL EXAMPLES OF THE INVENTION

Test A

Seeds of barley (Hordeum vulgar e), bamyardgrass (Echinochloa crus-galli), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium strumarium), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tedorum), giant foxtail (Setariafaberii), lambsquarters (Chenopodium album), morningglory (Ipomoea hederacea), rape (Brassica napus), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glycine max), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrastϊ), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), wild oat (Avenafatua) and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.

At the same time, these crop and weed species were also treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for twelve to sixteen days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table A, are based on a scale of 0 to 10 where 0 is no effect and 10 is complete control. A dash (-) response means no test result.

TABLE A COMPOUND TABLE A COMPOUND TABLE A COMPOUND

Rate 200 g/ha 1 Rate 200 g/ha 1 Rate 50 g/ha 1

POSTEMERGENCE PREEMERGENCE POSTEMERGENCE

Barley 9 Barley 0 Barley 7

Bamyardgrass 9 Bamyardgrass 9 Bamyardgrass 9

Bedstraw 9 Bedstraw 9 Bedstraw 9

Blackgrass 9 Blackgrass 5 Blackgrass 8

Chickweed 9 Chickweed 9 Chickweed 9

Cocklebur 10 Cocklebur 9 Cocklebur 10 Corn 1 Corn 0 Corn 0

Cotton 10 Cotton 6 Cotton 10

Crabgrass 9 Crabgrass 10 Crabgrass 9

Downy brome 9 Downy brome 2 Downy brome 9

Giant foxtail 9 Giant foxtail 4 Giant foxtail 9

Lambsquarters 9 Lambsquarters 9 Lambsquarters 9

Momingglory 10 Momingglory 9 Momingglory 10

Nutsedge 9 Nutsedge - Nutsedge 8

Rape 10 Rape 6 Rape 9

Rice 10 Rice 9 Rice 10

Sorghum 10 Sorghum 1 Sorghum 9

Soybean 10 Soybean 9 Soybean 10

Sugar beet 10 Sugar beet 10 Sugar beet 10

Velvetleaf 10 Velvetleaf 10 Velvetleaf 10

Wheat 9 Wheat 0 Wheat 9

Wild buckwheat 9 Wild buckwheat 3 Wild buckwheat 7

Wild oat 10 Wild oat 1 Wild oat 6

TABLE A COMPOUND TABLE A C0MP0UND TABLE A COMPOUND

Rate 50 g/ha 1 Rate 50 g/ha 1 Rate 50 g/ha 1

PREEMERGENCE PREEMERGENCE PREEMERGENCE

Barley 0 Crabgrass 3 Sorghum 0

Bamyardgrass 9 Downy brome 0 Soybean 3

Bedstraw 7 Giant foxtail 3 Sugar beet 10

Blackgrass 0 Lambsquarters 8 Velvetleaf 7

Chickweed 7 Momingglory 2 Wheat 0

Cocklebur 0 Nutsedge 0 Wild buckwheat 1

Corn 0 Rape 0 Wild oat 0

Cotton 2 Rice 4

Test B

Seeds of broadleaf signalgrass (Brachiaria decumbens), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), cocklebur (Xanthium strumarium), com (Zea mays), crabgrass (Digitaria sanguinalis), giant foxtail (Setariafaberii), momingglory (Ipomoea hederacea), rape (Brassica napus), redroot pigweed (Amaranthus retrofiexus), soybean (Glycine max), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild oat (Avenafatua) and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.

At the same time, these crop and weed species were also treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments. Plant species in the flood test consisted of rice (Oryza sativa), smallflower flatsedge (Cyperus difformis), duck salad (Heteranthera limosa) and bamyardgrass (Echinochloa crus-galli) grown to the 2-leaf stage for testing. Treated plants and controls were maintained in a greenhouse for twelve to sixteen days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table B, are based on a scale of 0 to 10 where 0 is no effect and 10 is complete control. A dash (-) response means no test result.

TABLE B COMPOUND TABLE B COMPOUND TABLE B COMPOUND

Rate 500 g/ha 5 6 Rate 500 g/ha 5 6 Rate 250 g/ha 5 6

Postemergence Preemergence Postemergence

B. signalgrass 5 7 B. signalgrass 6 8 B . signalgrass 4

Bamyardgrass 3 7 Blackgrass 4 3 Bamyardgrass 3

Blackgrass 4 9 Cocklebur 10 9 Blackgrass 4

Cocklebur 10 9 Corn 0 0 Cocklebur 10

Corn 6 4 Crabgrass 10 10 Corn 6

Crabgrass 10 9 Galium 8 9 Crabgrass 10

Ducksalad 7 8 Giant foxtail 4 8 Ducksalad 6

Galium 8 10 Momingglory 7 8 Galium 7 10

Giant foxtail 10 7 Nutsedge 2 2 Giant foxtail 10 7

Momingglory 10 10 Rape 6 10 Momingglory 10 10

Nutsedge - 2 Redroot pigweed 10 10 Nutsedge - 2

Rape 9 10 Soybean 8 6 Rape 9 10

Redroot pigweed 8 10 Sugarbeets 10 10 Redroot pigweed 8 10

Rice 5 6 Velvetleaf 10 10 Rice 4 4

S. Flatsedge 8 8 Wheat 1 0 S. Flatsedge 8 6

Soybean 10 10 Wild oats 1 1 Soybean 10 10

Sugarbeets 10 10 Sugarbeets 10 10

Velvetleaf 10 10 Velvetleaf 10 10

Wheat 9 10 Wheat 8 9

Wild oats 10 10 Wild oats 9 9 TABLE B COMPOUND TABLE B COMPOUND TABLE B COMPOUND

Rate 250 g/ha 5 6 Rate 125 g/ha 5 6 Rate 125 g/ha 5 6

Preemergence Postemergence Preemergence

B. signalgrass 4 6 B. si(gnalgrass 4 3 B. signalgrass 1 1 3 3

Blackgrass 3 1 Ba yardgrass 2 4 Blackgrass 0 0 1 1

Cocklebur 0 6 Blackgrass 4 3 Cocklebur 0 0 6 6

Corn 0 0 Cocklebur 10 9 Corn 0 0 0 0

Crabgrass 10 10 Corn 0 0 Crabgrass 1 1 9 9

Galium 7 8 Crabgrass 10 8 Galium 3 3 8 8

Giant foxtail 1 2 Ducksalad 3 7 Giant foxtail 1 1 1 1

Momingglory 3 6 Galium - 9 Momingglory 2 2 4 4

Nutsedge 1 - Giant foxtai 1 7 7 Nutsedge 0 0 0 0

Rape 4 10 Morni]ngglory 10 9 Rape 0 0 6 6

Redroot pigweed 3 10 Nutsedge - - Redroot pigweed 0 6

Soybean 3 1 Rape 3 10 Soybean 2 0

Sugarbeets 10 10 Redroot pigweed 8 10 Sugarbeets 10 10

Velvetleaf 10 10 Rice 1 2 Velvetleaf 10 10

Wheat 0 0 S. Flatsedge 7 4 Wheat 0 0

Wild oats 1 0 Soybean 10 10 Wild oats 0 0

Sugarbeets 10 10

Velvetleaf 10 10

Wheat 5 7

Wild < Dats 5 6

TABLE B COMPOUND

Rate 62 g/ha 3 4 5 6 7 8 11 12

Postemergence

B. signalgrass 10 2 2 3 3 2 - 2

Bamyardgrass 0 0 1 2 2 4 0 0

Blackgrass 10 5 3 3 4 7 3 0

Cocklebur 10 8 10 9 9 9 10 9

Corn 4 2 0 0 2 2 7 1

Crabgrass 8 6 8 8 8 8 10 4

Ducksalad 3 8 2 5 6 0 0 0

Galium 9 7 7 9 10 8 3 6

Giant foxtail 8 3 3 7 2 5 10 3

Momingglory 10 9 9 9 9 9^" 9 8 Nutsedge - - - 1 0 0 7 5

Rape 10 5 2 10 10 9 8 7

Redroot pigweed 8 7 8 9 9 9 9 8

Rice 0 0 0 0 2 0 0 0

S. Flatsedge 8 5 5 1 2 0 3 0

Soybean 9 9 10 10 10 9 10 7

Sugarbeets 10 10 10 10 10 10 10 10

Velvetleaf 10 10 10 9 10 9 10 8

Wheat 8 5 3 6 8 8 3 0

Wild oats 6 7 3 5 7 7 2 1

TABLE B COMPOUND

Rate 62 g/ha 3 4 5 6 7 8 11 12 Preemergence

B. signalgrass 0 0 0 0 1 3 5 0

Blackgrass 0 0 0 0 0 1 0 0

Cocklebur 0 0 0 - 0 - 0 0

Corn 0 0 0 0 0 0 0 0

Crabgrass 4 1 1 8 3 6 9 2

Galium 9 - 0 3 1 8 8 0

Giant foxtail 0 1 0 1 1 2 7 0

Momingglory 6 0 0 3 0 2 1 0

Nutsedge 0 0 0 0 0 0 - 0

Rape 7 1 0 3 1 6 0 1

Redroot pigweed 8 0 0 6 4 7 7 0

Soybean 3 3 0 0 0 0 2 0

Sugarbeets 10 8 0 10 10 10 9 8

Velvetleaf 10 10 10 10 10 10 9 0

Wheat 0 0 0 0 0 0 0 0

Wild oats 0 0 0 0 0 0 0 0

TABLE B COMPOUND

Rate 31 g/ha 2 3 4 7 8 10 11 12

Postemergence

B. signalgrass - 8 2 1 1 - - 2

Bamyardgrass 2 0 0 2 2 0 0 0

Blackgrass 5 4 5 2 5 6 3 0

Cocklebur 9 10 8 9 9 9 10 8 Corn 0 0 1 1 1 0 3 1

Crabgrass 9 8 6 8 3 10 10 -

Ducksalad 5 2 8 4 0 0 0 0

Galium 6 9 7 10 8 3 2 3

Giant foxtail 8 5 3 1 1 9 10 2

Momingglory 8 10 8 9 9 7 8 8

Nutsedge 4 0 - 0 0 0 4 0

Rape 8 8 2 10 9 7 8 4

Redroot pigweed 7 7 6 8 8 9 9 8

Rice 2 0 0 0 0 0 0 0

S. Flatsedge 3 6 3 1 0 0 2 0

Soybean 9 9 8 10 8 8 10 6

Sugarbeets 9 10 10 10 10 9 10 10

Velvetleaf 9 10 10 10 9 9 10 4

Wheat 7 8 5 3 6 1 1 0

Wild oats 7 5 3 4 6 2 2 1

TABLE B COMPOUNE )

Rate 31 g/ha 2 3 4 7 8 10 11 12

Preemergence

B. signalgrass - 0 0 0 0 - 0 0

Blackgrass 0 0 0 0 0 0 0 0

Cocklebur 0 0 - 0 - 0 - 0

Corn 0 0 0 0 0 0 0 0

Crabgrass 9 3 0 2 3 4 7 0

Galium 6 0 4 1 2 2 1 0

Giant foxtail 2 0 0 1 1 5 1 0

Momingglory 0 4 0 0 0 0 0 0

Nutsedge 0 - 0 0 0 0 0 0

Rape 1 3 0 0 3 0 0 1

Redroot pigweed 0 4 0 0 5 0 0 0

Soybean 1 0 0 0 0 0 0 0

Sugarbeets 4 10 1 9 10 4 7 0

Velvetleaf 9 10 6 10 10 3 0 0

Wheat 0 0 0 0 0 0 0 0

Wild oats 1 0 0 0 0 0 0 0 TABLE B COMPOUND

Rate 16 g/ha 2 3 4 7 8 10 11 12

Postemergence

B. signalgrass - 7 1 0 1 - - 1

Bamyardgrass 1 0 0 0 0 0 0 0

Blackgrass 4 4 3 1 4 2 1 0

Cocklebur 9 9 8 9 9 8 9 8

Corn 0 0 0 0 1 0 2 0

Crabgrass 9 8 4 5 2 9 7 4

Ducksalad 0 0 3 0 0 0 0 0

Galium 6 9 7 10 7 3 0 2

Giant foxtail 8 5 2 0 1 9 10 2

Momingglory 8 8 2 9 9 6 7 6

Nutsedge 2 0 0 0 0 0 1 0

Rape 7 8 1 10 8 7 7 2

Redroot pigweed 7 7 5 8 7 8 8 8

Rice 0 0 0 0 0 0 0 0

S. Flatsedge 2 2 3 0 0 0 2 0

Soybean 9 9 8 7 7 8 8 4

Sugarbeets 9 10 10 10 9 9 3 9

Velvetleaf 9 10 9 10 9 7 10 4

Wheat 3 4 3 0 3 0 1 0

Wild oats 6 4 2 0 5 0 2 0

TABLE B COMPOUND

Rate 16 g/ha 2 3 4 7 8 10 11 12

Preemergence

B. signalgrass - 0 0 0 0 - 0 0

Blackgrass 0 0 0 0 0 0 0 0

Cocklebur 0 - 0 0 0 0 0 0

Corn 0 0 0 0 0 0 0 0

Crabgrass 2 2 0 1 0 1 6 0

Galium 6 0 0 0 1 0 0 0

Giant foxtail 0 0 0 0 0 0 0 0

Momingglory 0 0 0 0 0 0 0 0

Nutsedge 0 0 - 0 0 0 0 0

Rape 0 0 0 0 0 0 0 0

Redroot pigweed 0 4 0 0 3 0 0 0 Soybean 0 0 0 0 0 0 0 0

Sugarbeets 1 8 0 1 5 0 0 0

Velvetleaf 7 7 4 8 5 0 0 0

Wheat 0 0 0 0 0 0 0 0

Wild oats 0 0 0 0 0 0 0 0

TABLE B COMPOUND

Rate 8 g/ha 2 3 4 7 8 10 11 12

Postemergence

B. signalgrass - 4 1 0 1 - - 0

Bamyardgrass 0 0 0 0 0 0 0 0

Blackgrass 3 3 3 0 2 0 1 0

Cocklebur 8 9 7 9 9 6 8 6

Corn 0 0 0 0 0 0 2 0

Crabgrass 7 8 3 3 0 8 4 3

Ducksalad 0 0 2 0 0 0 0 0

Galium 6 6 3 10 4 0 0 1

Giant foxtail 2 0 1 0 0 0 2 0

Momingglory 8 8 2 9 8 1 3 0

Nutsedge 1 - - 0 0 0 1 0

Rape 6 5 1 10 7 3 1 1

Redroot pigweed 6 7 5 7 6 5 8 7

Rice 0 0 0 0 0 0 0 0

S. Flatsedge 1 0 3 0 0 0 2 0

Soybean 9 8 8 5 6 6 7 3

Sugarbeets 9 10 10 9 8 7 2 7

Velvetleaf 9 10 9 10 9 7 9 1

Wheat 2 3 3 0 1 0 0 0

Wild oats 2 2 2 0 3 0 1 0

TABLE B COMPOUND TABLE B COMPOUND TABLE B COMPOUND

Rate 4 g/ha 2 10 Rate 4 : g/ha 2 10 Rate 4 g/ha 2 10

Postemergence Postemerς [ence Postemergence

B. signalgrass - - Galium 4 0 S. Flatsedge 0 0

Bamyardgrass 0 0 Giant foxtail 0 0 Soybean 9 4

Blackgrass 1 0 Momingglory 7 1 Sugarbeets 8 6

Cocklebur 8 6 Nutsedge 0 0 Velvetleaf 9 7

Corn 0 0 Rape 1 0 Wheat 2 0 Crabgrass 7 5 Redroot pigweed 5 5 Wild oats

Ducksalad 0 0 Rice 0 0

TestC

Seeds of bamyardgrass (Echinochloa crus-galli), bindweed (Concolculus arvensis), black nightshade (Solanum ptycanthum dunaϊ), cassia (Cassia obtusifolia), cocklebur (Xanthium strumarium), common ragweed (Ambrosia artemisiifolia), com (Zea mays designated 'Co 2', 'Com 4' and 'Com 5'), cotton (Gossypium hirsutam), crabgrass (Digitaria spp.), fall panicum (Panicum dichotomiflorum), giant foxtail (Setariafaberii), green foxtail (Setaria viridis), jimsonweed (Datura stramoni um), johnsongrass (Sorghum halepense), lambsquarter (Chenopodium album), momingglory (Ipomoea spp.), pigweed (Amaranthus retroflexus), prickly sida (Sida spinosa), shattercane (Sorghum vulgare), signalgrass (Brachiaria platyphylla), smartweed (Polygonum pensylvanicum), soybean (Glycine max designated 'Soybean 1 ' and 'Soybean 2'), sunflower (Helianthus annuus), velvetleaf (Abutilon theophrasti), wild proso (Pancium miliaceum), woolly cupgrass (Eriochloa villosa), yellow foxtail (Setaria lutescens) and purple nutsedge (Cyperus rotundus) tubers were planted into a clay loam soil. These crops and weeds were grown in the greenhouse until the plants ranged in height from two to eighteen cm (one- to four-leaf stage), then treated postemergence with the test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant. Pots receiving preemergence treatments were planted immediatley prior to test chemical application. Pots treated in this fashion were placed in the greenhouse and maintained according to routine greenhouse procedures.

Treated plants and untreated controls were maintained in the greenhouse approximately 14-21 days after application of the test compound. Visual evaluations of plant injury responses were then recorded. Plant response ratings, summarized in Table C, are reported on a 0 to 100 scale where 0 is no effect and 100 is complete control.

TABLE C COMPOUND TABLE C COMPOUND TABLE C COMPOUND

Rate 140 g/ha 1 Rate 140 g/ha 1 Rate 70 g/ha 1 POSTEMERGENCE PREEMERGENCE POSTEMERGENCE

Bamyardgrass 85 Bamyardgrass 20 Bamyardgrass 85

Bindweed 100 Bindweed 80 Bindweed 80

Blk nightshade 100 Blk nightshade 100 Blk nightshade 100

Cassia 80 Cassia 40 Cassia 75

Cocklebur 85 Cocklebur 0 Cocklebur 85

Corn 2 50 Corn 2 10 Corn 2 40

Cotton 100 Corn 4 10 Cotton 100

Crabgrass 100 Cotton 10 Crabgrass 75 CORN 5 35 Crabgrass 40 CORN 5 10

Fall panicum 100 CORN 5 0 Fall panicum 85

Giant foxtail 100 Fall panicum 15 Giant foxtail 100

Green foxtail 100 Giant foxtail 40 Green foxtail 100

Jimsonweed 100 Green foxtail 30 Jimsonweed 100

Johnsongrass 100 Jimsonweed 80 Johnsongrass 100

Lambsquarters 100 Lambsquarters 100 Lambsquarters 100

Momingglory 70 Momingglory 100 Momingglory 100

Nutsedge 75 Nutsedge 15 Nutsedge 60

Pigweed 100 Pigweed 80 Pigweed 100

Prickly sida 100 Ragweed 70 Prickly sida 100

Ragweed 100 Shattercane 15 Ragweed 100

Shattercane 85 Signalgrass 20 Shattercane 80

Signalgrass 100 Soybean 1 15 Signalgrass 100

Smartweed 100 Soybean 2 30 Smartweed 100

Soybean 1 100 Sunflower 30 Soybean 1 100

Soybean 2 100 Velvetleaf 100 Soybean 2 100

Sunflower 100 Wild proso 20 Sunflower 100

Velvetleaf 100 Woolly cupgrass 15 Velvetleaf 100

Wild proso 100 Yellow foxtail 40 Wild proso 85

Woolly cupgrass 75 Woolly cupgrass 70

Yellow foxtail 90 Yellow foxtail 85

TABLE C COMPOUND TABLE C COMPOUND TABLE C COMPOUND Rate 70 g/ha 1 Rate 35 g/ha 1 Rate 35 g/ha 1 PREEMERGENCE POSTEMERGENCE PREEMERGENCE Bamyardgrass 0 Bamyardgrass 85 Bamyardgrass 0 Bindweed 15 Bindweed 50 Bindweed 10 Blk nightshade 100 Blk nightshade 100 Blk nightshade 80

Cassia 20 Cassia 50 Cassia -

Cocklebur 0 Cocklebur 85 Cocklebur 0

Corn 2 0 Corn 2 30 Corn 2 0

Corn 4 0 Cotton 100 Corn 4 0

Cotton 10 Crabgrass 70 Cotton 10

Crabgrass 20 CORN 5 0 Crabgrass 20

CORN 5 0 Fall panicum 85 CORN 5 0

Fall panicum 15 Giant foxtail 100 Fall panicum -

Giant foxtail 40 Green foxtail 100 Giant foxtail 30 Green foxtail 15 Jimsonweed 100 Green foxtail 10

Jimsonweed 60 Johnsongrass 85 Jimsonweed 35

Lambsquarters 100 Lambsquarters 100 Lambsquarters 100

Momingglory 25 Momingglory 100 Momingglory 0

Nutsedge 0 Nutsedge 55 Nutsedge 0

Pigweed 60 Pigweed 100 Pigweed 55

Ragweed 50 Prickly sida 85 Ragweed 20

Shattercane 10 Ragweed 100 Shattercane 10

Signalgrass 0 Shattercane 80 Signalgrass 0

Soybean 1 15 Signalgrass 100 Soybean 1 15

Soybean 2 30 Smartweed 100 Soybean 2 25

Sunflower 0 Soybean 1 100 Sunflower 0

Velvetleaf 100 Soybean 2 100 Velvetleaf 60

Wild proso 15 Sunflower 100 Wild proso 10

Woolly cupgrass 15 Velvetleaf 100 Woolly cupgrass 10

Yellow foxtail 40 Wild proso 80 Yellow foxtail 40 Woolly cupgrass 65 Yellow foxtail 85

TABLE C COMPOUND TABLE C COMPOUND TABLE C COMPOUND Rate 17 g/ha 1 Rate 17 g/ha 1 Rate 8 g/ha 1 POSTEMERGENCE PREEMERGENCE POSTEMERGENCE

Barnyardgrass 80 Bamyardgrass 0 Bamyardgrass 75

Bindweed 45 Bindweed 10 Bindweed 40

Blk nightshade 85 Blk nightshade 75 Blk nightshade 85

Cassia 40 Cassia - Cassia 35

Cocklebur 80 Cocklebur 0 Cocklebur 80

Corn 2 10 Corn 2 0 Corn 2 0

Cotton 85 Corn 4 0 Cotton 80

Crabgrass 65 Cotton 10 Crabgrass 65

CORN 5 0 Crabgrass 30 CORN 5 0

Fall panicum 70 CORN 5 0 Fall panicum 70

Giant foxtail 75 Fall panicum 30 Giant foxtail 75

Green foxtail 85 Giant foxtail 30 Green foxtail 60

Jimsonweed 100 Green foxtail 0 Jimsonweed 100

Johnsongrass 65 Jimsonweed 45 Johnsongrass 45

Lambsquarters 100 Lambsquarters 0 Lambsquarters 100

Momingglory 100 Momingglory 0 Momingglory 100 Nutsedge 45 Nutsedge 0 Nutsedge 40

Pigweed 85 Pigweed 55 Pigweed 80

Prickly sida 70 Ragweed 25 Prickly sida 60

Ragweed 100 Shattercane 0 Ragweed 100

Shattercane 75 Signalgrass 0 Shattercane 75

Signalgrass 100 Soybean 1 15 Signalgrass 85

Smartweed 100 Soybean 2 20 Smartweed 100

Soybean 1 85 Sunflower 0 Soybean 1 85

Soybean 2 85 Velvetleaf 20 Soybean 2 85

Sunflower 100 Wild proso 0 Sunflower 100

Velvetleaf 100 Woolly cupgrass 0 Velvetleaf 100

Wild proso 80 Yellow foxtail 25 Wild proso 75

Woolly cupgrass 60 Woolly cupgrass 55

Yellow foxtail 80 Yellow foxtail 80

TestD

The compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied to the soil surface before plant seedlings emerged (preemergence application), to water that covered the soil surface (flood application), and to plants that were in the one- to four-leaf stage (postemergence application). A sandy loam soil was used for the preemergence and postemergence tests, while a silt loam soil was used in the flood application. Water depth was approximately 2.5 cm for the flood application and was maintained at this level for the duration of the test. Plant species in the preemergence and postemergence tests consisted of bamyardgrass

(Echinochloa crus-galli), winter barley (Hordeum vulgare), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium strumarium), varieties of com (Zea mays designated 'Com 1 ', 'Com 2' and 'Com 3'), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tedorum), giant foxtail (Setariafaberii), johnsongrass (Sorghum halpense), lambsquarters

(Chenopodium album), momingglory (Ipomoea hederacea), pigweed (Amaranthus retroflexus), rape (Brassica napus), Italian ryegrass (Lolium multiflorum), soybean (Glycine max), speedwell (Veronica persica), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), and wild oat (Avenafatua). All plant species were planted one day before application of the compound for the preemergence portion of this test. Plantings of these species were adjusted to produce plants of appropriate size for the postemergence portion of the test. Plant species in the flood test consisted of rice (Oryza sativa), umbrella sedge (Cyperus difformis), duck salad (Heteranthera limosa) and bamyardgrass 1 (Echinochloa crus-galli). All plant species were grown using normal greenhouse practices. Visual evaluations of injury expressed on treated plants, when compared to untreated controls, were recorded approximately fourteen to twenty one days after application of the test compound. Plant response to the test compound is summarized in Table D, recorded on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result.

TABLE D COMPOUND TABLE D COMPOUND TABLE D COMPOUND

Rate 62 g/ha 1 Rate 62 g/ha 1 Rate 31 g/ha 1 POSTEMERGENCE PREEMERGENCE POSTEMERGENCE

Barley (winter ) 35 Barley (winter ) 0 Barley (winter ) 30

Bamyardgrass 90 Bamyardgrass 30 Bamyardgras s 90

Bamyardgrass 1 20 Bedstraw 70 Bamyardgrass 1 10

Beds traw 80 Blackgrass 0 Beds traw 80

Blackgrass 60 Chickweed 75 Blackgrass 40

Chickweed 95 Cocklebur 40 Chickweed 90

Cocklebur 100 Corn 1 0 Cocklebur 100

Corn 1 0 Cotton 10 Corn 1 0

Corn 2 30 Crabgrass 100 Corn 2 20

Corn 3 70 Downy brome 10 Corn 3 60

Cotton 100 Giant foxtai l 40 Cotton 100

Crabgrass 90 I tain , ryegrass 0 Crabgrass 90

Downy brome 30 Johnsongrass 0 Downy brome 20

Ducksalad 70 Lambsquarter 95 Ducksalad 40

Giant foxtai l 90 Mo ingglory 100 Giant foxtai l 90

I tain , ryegras s 30 Rape 15 I taln . ryegrass 20

Johnsongrass 100 Redroot pigweed 50 Johnsongrass 90

Lambsquarter 100 Soybean 0 Lambsquarter 100

Momingglory 90 Speedwell 100 Momingglory 90

Rape 80 Sugar beet 90 Rape 60

Redroot pigweed 90 Velvetleaf 100 Redroot pigweed 90

Rice j aponica 30 Wheat 0 Rice j aponica 20

Soybean 90 Wild buckwheat 0 Soybean 90

Speedwel l 100 Wild oat 0 Speedwel l 100

Sugar beet 100 Sugar beet 100

Umbrella sedge 80 Umbrel la sedge 60

Velvetleaf 100 Velvetleaf 100

Wheat 40 Wheat 30

Wild buckwheat 90 Wi ld buckwheat 50 Wi ld oat 80 Wi ld oat 60

TABLE D COMPOUND TABLE D COMPOUND TABLE D COMPOUND

Rate 31 g/ha 1 Rate 16 g/ha 1 Rate 16 g/ha 1

PREEMERGENCE POSTEMERGENCE PREEMERGENCE

Barley (winter) 0 Barley (winter) 20 Barley (winter) 0

Bamyardgrass 0 Bamyardgrass 90 Bamyardgrass 0

Bedstraw 50 Bamyardgrass 1 0 Bedstraw 50

Blackgrass 0 Bedstraw 60 Blackgrass 0

Chickweed 35 Blackgrass 30 Chickweed 10

Cocklebur 20 Chickweed 80 Cocklebur 0

Corn 1 0 Cocklebur 90 Corn 1 0

Cotton - Corn 1 0 Cotton 0

Crabgrass 100 Corn 2 0 Crabgrass 30

Downy brome 0 Corn 3 35 Downy brome 0

Giant foxtail 10 Cotton 100 Giant foxtail 0

Italn. ryegrass 0 Crabgrass 80 Italn. ryegrass 0

Johnsongrass 0 Downy brome 0 Johnsongrass 0

Lambsquarter 95 Ducksalad 20 Lambsquarter 85

Momingglory 30 Giant foxtail 70 Momingglory -

Rape 10 Italn. ryegrass 0 Rape 0

Redroot pigweed 40 Johnsongrass 60 Redroot pigweed 10

Soybean 0 Lambsquarter 95 Soybean 0

Speedwell 70 Momingglory 90 Speedwell 70

Sugar beet 70 Rape 30 Sugar beet 50

Velvetleaf 100 Redroot pigweed 70 Velvetleaf 30

Wheat 0 Rice japonica 5 Wheat 0

Wild buckwheat 0 Soybean 90 Wild buckwheat 0

Wild oat 0 Speedwell 90 Wild oat 0

Sugar beet 95

Umbrella sedge 30

Velvetleaf 100

Wheat 10

Wild buckwheat 30

Wild oat 10 TABLE D COMPOUND TABLE D COMPOUND

Rate 8 g/ha 1 Rate 8 g/ha 1

POSTEMERGENCE PREEMERGENCE

Barley (winter) 10 Barley (winter) 0

Barnyardgrass 90 Bamyardgrass 0

Bamyardgrass 1 0 Bedstraw 0

Bedstraw 50 Blackgrass 0

Blackgrass 20 Chickweed -

Chickweed 70 Cocklebur 0

Cocklebur 90 Corn 1 0

Corn 1 0 Cotton 0

Corn 2 0 Crabgrass 20

Corn 3 30 Downy brome 0

Cotton 95 Giant foxtail 0

Crabgrass 70 Italn. ryegrass 0

Downy brome 0 Johnsongrass 0

Ducksalad 10 Lambsquarter 80

Giant foxtail 50 Momingglory 0

Italn. ryegrass 0 Rape 0

Johnsongrass 60 Redroot pigweed 0

Lambsquarter 90 Soybean 0

Momingglory 90 Speedwell -

Rape 20 Sugar beet 50

Redroot pigweed 70 Velvetleaf 20

Rice japonica 0 Wheat 0

Soybean 70 Wild buckwheat 0

Speedwell 70 Wild oat 0

Sugar beet 90

Umbrella sedge 10

Velvetleaf 100

Wheat 0

Wild buckwheat 30

Wild oat 0

Test E

Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied to plants that were grown for various periods of time before treatment (postemergence application). A mixture of sandy loam soil and greenhouse potting mix in a 60:40 ratio was used for the postemergence test.

Plantings of these crops and weed species were adjusted to produce plants of appropriate size for the postemergence test. All plant species were grown using normal greenhouse practices. Crop and weed species include arrowleaf sida (Sida rhombifolia), bamyardgrass (Echinochloa crus-galli), cocklebur (Xanthium strumarium), common ragweed (Ambrosia elatior), com 1 (Zea mays), cotton (Gossypium hirsutum), eastern black nightshade (Solanum ptycanthum), fall panicum (Panicum dichotomiflorum), field bindweed (Convolvulus arvensis), giant foxtail (Setariafaberii), hairy beggarticks (Bidens pilosa), ivyleaf momingglory (Ipomoea hederacea), johnsongrass (Sorghum halepense), ladysthumb smartweed (Polygonum per sicar i ), lambsquarters (Chenopodium album), large crabgrass (Digitaria sanguinalis), purple nutsedge (Cyperus rotundus), redroot pigweed (Amaranthus retroflexus), soybean \(Glycine max), Surinam grass (Brachiaria decumbens), velvetleaf (Abutilon theophrasti) and wild poinsettia (Euphorbia heterophylla).

Treated plants and untreated controls were maintained in a greenhouse for approximately 14 to 21 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table E, were based upon a 0 to 100 scale where 0 was no effect and 100 was complete control. A dash response (-) means no test result.

TABLE E COMPOUND TABLE E COMPOUND TABLE E COMPOUND

Rate 140 g/ha 1 Rate 70 g/ha 1 Rate 35 g/ha 1

POSTEMERGENCE POSTEMERGENCE POSTEMERGENCE Arrowleaf sida 85 Arrowleaf sida 85 Arrowleaf sida 70 Bamyardgrass 95 Bamyardgrass 95 Bamyardgrass 90

Cocklebur 100 Cocklebur 100 Cocklebur 100

Common ragweed 100 Common ragweed 100 Common ragweed 95 Corn 1 0 Corn 1 0 Corn 1 0

Cotton 100 Cotton 100 Cotton 100

E . blacknightsh 100 E . blacknightsh 100 E . blacknightsh 100 Fal l panicum 95 Fal l panicum 95 Fal l panicum 95

Field bindweed 85 Field bindweed 95 Field bindweed 95 Giant foxtai l 100 Giant foxtai l 95 Giant foxtai l 90 H . beggarticks 85 H . beggarticks 80 H . beggarticks 70 I . momingglory 100 I . momingglory 100 I . momingglory 100 Johnsongrass 90 Johnsongrass 75 Johnsongrass 50

Ladysthumb 100 Ladys thumb 100 Ladysthumb 95

Lambsquarters 100 Lambsquarters 100 Lambsquarters 100 Large crabgrass 100 Large crabgrass 95 Large crabgrass 95 Purple nutsedge 70 Purple nutsedge 50 Purple nutsedge 50 Redroot pigweed 95 Redroot pigweed 90 Redroot pigweed 95 Soybean 1 100 Soybean 1 100 Soybean 1 100 Surinam grass 95 Surinam grass 95 Surinam grass 80 Velvetleaf 100 Velvetleaf 100 Velvetleaf 100 Wild poinsettia 100 Wild poinsettia 100 Wild poinsettia 100

TABLE E COMPOUND TABLE E COMPOUND Rate 17 g/ha 1 Rate 8 g/ha 1 POSTEMERGENCE POSTEMERGENCE Arrowleaf sida 70 Arrowleaf sida 65 Ba yardgrass 85 Bamyardgrass 80 Cocklebur 95 Cocklebur 85 Common ragweed 95 Common ragweed 90 Corn 1 0 Corn 1 0

Cotton 100 Cotton 80

E. blacknightsh 100 E. blacknightsh 100 Fall panicum 95 Fall panicum 75 Field bindweed 90 Field bindweed 75 Giant foxtail 80 Giant foxtail 35 H. beggarticks 50 H. beggarticks 20 I. momingglory 95 I. momingglory 85 Johnsongrass 20 Johnsongrass 10 Ladysthumb 95 Ladysthumb 90 Lambsquarters 100 Lambsquarters 25 Large crabgrass 85 Large crabgrass 75 Purple nutsedge 20 Purple nutsedge 10 Redroot pigweed 70 Redroot pigweed 65 Soybean 1 90 Soybean 1 80 Surinam grass 75 Surinam grass 50 Velvetleaf 100 Velvetleaf 100 Wild poinsettia 95 Wild poinsettia 85

Test F

Seeds of bamyardgrass (Echinochloa crus-galli), crabgrass (Digitaria spp.), momingglory (Ipomoea spp.), 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 all treated plants were compared to untreated controls and visually evaluated for injury. Plant response ratings, summarized in Table F, 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 F COMPOUND TABLE F COMPOUND

Rate 2000 g/ha 3 7 8 9 Rate 1000 g/ha 3 7 8 9

PREEMERGENCE POSTEMERGENCE

Bamyardgrass 10 10 10 9 Bamyardgrass 10 9 10 9

Crabgrass 10 9 10 9 Crabgrass 10 9 10 9

Momingglory 9 10 9 8 Momingglory 9 9 9 8

Velvetleaf 10 10 10 9 Velvetleaf 10 10 10 9

Claims

CLAIMS What is claimed is:

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

wherein Q is

Q-l Q-2

Q-3 Q-4

Z is selected from the group -CH₂CH₂CH₂-, -OCH₂CH₂-, -O-CH=CH-,

-╬¥R13CH₂CH₂-, -NR!3CH=CH-, -N=CHCH₂-, -OCH₂O-, -NRl3CH₂NRl3-, -N=CHNR13-, -CH₂OCH₂-, -CH₂NR¹³CH₂-, -CH₂S(O)_nCH₂-, -CH₂C(O)CH₂-, -CH=NCH₂-, -CH₂CH₂-, -OCH₂-, -SCH₂-, and -NR^l3CH₂-, each group optionally substituted with one to four R⁵, and the directionality of the Z linkage is defined such that the moiety depicted on the left side of the linkage is bonded to the carbonyl carbon of Q-l;

X is O, S(O)_n, N(C_rC₂ alkyl) or CH₂ optionally substituted with 1-2 C_rC₂ alkyl; each R¹ is independently Cj-Cg alkyl, C1-C6 haloalkyl, Ci-Cg alkoxy, C_j-Cg haloalkoxy, S(O)_nR¹⁷, SO₂N(Rl3)₂, halogen, cyano or nitro; R² is NR^l┬░\R^l9; or R² is a five-membered heterocyclic aromatic ring, or a five- or six- membered heterocyclic ring which may be partially or fully saturated, each ring containing 1 to 4 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, and containing at least one nitrogen and no more than one oxygen and no more than 2 sulfurs, and the ring is optionally substituted with one to three groups independently selected from the group C_j-C3 alkyl, halogen, cyano, and nitro, provided that (a) said heterocyclic ring is bonded to the parent bicyclic structure through a ring nitrogen and (b) that when a nitrogen atom of the heterocyclic ring is substituted, then the nitrogen substituent is other than halogen; each R³ is independently C╬╣-C₂ alkyl;

R⁴ is ORl⁴, SH, S(O)_nRl⁷, halogen or NRl⁵Rl⁶; or R⁴ is phenylthio or phenylsulfonyl, each optionally substituted with C_j-C3 alkyl, halogen, cyano or nitro; each R⁵ is independently C1-C3 alkyl, C3-C6 alkenyl, C3-C6 alkynyl, C1-C3 alkoxy, formyl, C₂-CG alkoxycarbonyl, -CH₂(Cj-C3 alkoxy), -CH(C_j-C3 alkoxy)₂, C_]-C₃ alkylthio, cyano or halogen; or when two R⁵ are attached to the same carbon atom, then they can be taken together to form -OCH₂CH₂O-, -OCH₂CH₂CH₂O-, -SCH₂CH₂S- or -SCH₂CH₂CH₂S-, each group optionally substituted with 1 -4 CH₃;

R⁶ is H, C_rC₆ alkyl, C_rC₆ haloalkyl, C₂-C₆ alkoxyalkyl, formyl, C₂-C₆ alkylcarbonyl, C₂-Cg alkoxycarbonyl, C₂-C6 alkylaminocarbonyl, C3~C₇ dialkylaminocarbonyl or SO R¹⁷; or R⁶ is phenyl, benzyl, benzoyl, -CH₂C(O)phenyl or phenylsulfonyl, each optionally substituted on the phenyl ring with 1 to 3 groups selected from the group C1-C3 alkyl, halogen, cyano, and nitro;

R⁷ is H, C_rC₆ alkyl, C_rC₆ haloalkyl, C₃-C₆ alkenyl, C₃-C₆ alkynyl or

-CH₂CH₂ORl3; or R⁷ is phenyl or benzyl, each optionally substituted on the phenyl ring with C1-C3 alkyl, halogen, cyano or nitro; R⁸ is H, C╬╣-C₆ alkyl, C_rC₆ haloalkyl, C╬╣-C₆ alkoxy, C_rC₆ haloalkoxy, halogen, cyano or nitro;

R⁹ is H, C_rC₆ alkyl, C_rC₆ haloalkyl, C₃-C₆ cycloalkyl or C₃-C₆ halocycloalkyl;

Rⁱ┬░ is H, C₂-C_╬▓ alkoxycarbonyl, C₂-Cg haloalkoxycarbonyl, CO₂H or cyano;

R^{1 1} is C_rC₆ alkyl, C_rC₆ haloalkyl, C₃-C₆ halocycloalkyl or C₃-C₆ cycloalkyl optionally substituted with 1-4 C1-C3 alkyl;

R¹² is cyano, C₂-C₆ alkoxycarbonyl, C₂-C₆ alkylcarbonyl, S(O)_nR¹⁶ or C(O)NR^l5Rl6_; each R 3 is independently H or C_j^ alkyl; Rl is H, C_rC₆ alkyl, C_rC₆ haloalkyl, C₂-C₆ alkoxyalkyl, formyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C(O)NR^{! 5}R^l6 or SO₂Rl⁷; or Rⁱ is phenyl, benzyl, benzoyl, -CH₂C(O)phenyl or phenylsulfonyl, each optionally substituted on the phenyl ring with 1 to 3 groups selected from group C1-C3 alkyl, halogen, cyano and nitro;

R^l5 is H or C_rC₆ alkyl;

R^l6 is C_rC₆ alkyl or C_rC₆ alkoxy; or

R^l5 and R^l6 can be taken together as -CH₂CH₂-, -CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂- , -CH₂CH₂CH₂CH₂CH₂- or -CH₂CH₂OCH₂CH₂-; RI⁷ is C_rC₆ alkyl or C_rC₆ haloalkyl;

R^lS is H or C_j-Cg alkyl;

Rl9 is H, C1-C5 alkyl, C_j-C₆ haloalkyl, C₂-Cg alkoxycarbonyl, C₂-Cg alkylcarbonyl, C(=O)R²⁰ or phenyl optionally substituted with one to three groups independently selected from the group C₁-C3 alkyl, halogen, cyano, and nitro; or R¹⁸ and R¹⁹ can be taken together as =C(C_rC₃ alkyl)₂;

R²⁰ is phenyl or a five- or six-membered aromatic heterocyclic ring, containing 1 to 4 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that the heterocyclic ring contains no more than one oxygen and no more than one sulfur, and the phenyl and heterocyclic ring are each optionally substituted with one to three groups independently selected from the group

C1-C3 alkyl, halogen, cyano, and nitro, provided that when a nitrogen atom of the heterocyclic ring is substituted, then the nitrogen substituent is other than halogen; m is 0, 1 or 2; n is 0, 1 or 2; p is O, 1, 2, 3 or 4; and r is 0, 1, 2 or 3.

2. A compound of Claim 1 wherein Q is Q-l.

3. A compound of Claim 2 wherein X is SO₂.

4. A compound of Claim 3 wherein

R² is NRl⁸Rl9.

5. A compound of Claim 1 wherein Q is Q-2.

6. A compound of Claim 5 wherein X is SO₂.

7. A compound of Claim 6 wherein R² is NRl⁸R 9.

8. The compound of Claim 1 which is selected from the group:

(a) 2,3-dihydro-6-[(2-hydroxy-6-oxo- 1 -cyclohexen- 1 -yl)carbonyl]-5,8-dimethyl-4/_^"- 1 -benzothiopyran-4-one dimethylhydrazone 1,1 -dioxide;

(b) 2,3-dihydro-6-[(2-hydroxy-4-methyl-6-oxo- 1 -cyclohexen- 1 -yl)carbonyl]-5,8- dimethyl-4H- 1 -benzothiopyran-4-one dimethylhydrazone 1 , 1 -dioxide; (c) 6-[(l -ethyl-5-hydroxy-lH-pyrazol-4-yl)carbonyl]-2,3-dihydro-5,8-dimethyl-4H-

1 -benzothiopyran-4-one dimethylhydrazone 1,1 -dioxide; and (d) 6-[[5-(benzoyloxy)- 1 -ethyl- lH-pyrazol-4-yl]carbonyl]-2,3-dihydro-5,8- dimethyl-4/ - 1 -benzothiopyran-4-one dimethylhydrazone 1 , 1 -dioxide.

9. A herbicidal composition comprising a herbicidally effective amount of a compound of Claim 1 and at least one of a surfactant, a solid diluent or a liquid diluent.

10. A method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of Claim 1.