TITLE HERBICIDAL TRIAZOLINONES

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of U.S. Serial No. 08,038,730 filed

March 26, 1993.

BACKGROUND OF THE INVENTION New compounds effective for controlling the growth of undesired vegetation are in constant demand. In the most common situation, such compounds are sought to selectively control the growth of weeds in useful crops such as cotton, rice, corn, wheat and soybeans, to name a few. Unchecked weed growth in such crops can cause significant losses, reducing profit to the farmer and increasing costs to the consumer. In other situations, herbicides are desired which will control all plant growth. Examples of areas in which complete control of all vegetation is desired are areas around railroad tracks, storage tanks and industrial storage areas. There are many products commercially available for these purposes, but the search continues for products which are more effective, less costly and environmentally safe.

U.S. 4,213,773 discloses herbicidal triazolinones which differ from the compounds of the present invention in that they lack a substituent on the left-hand ring. SUMMARY OF THE INVENTION

The crop protection chemical compounds of this invention are compounds of Formula I:

wherein the dashed line indicates that the left-hand ring contains only single bonds or one bond in the ring is a double bond; n is 1 or 2; ^{~~" ^} ^~ R ¹ is selected from the group H, halogen; hydroxy, C1-C3 alkoxy; Cj-C3 haloalkoxy; C2-C5 alkylcarbonyloxy; or C2-C5 haloalkylcarbonyloxy; R ² is selected from the group H, hydroxy, and halogen; or when R ¹ and R ² are bonded to the same carbon atom they can be taken together along with the carbon to which they are attached to form C=O; or

when R ¹ and R ² are bonded to adjacent carbon atoms they can be taken together along with the carbons to which they are attached to form

O / \ CH — CH _,

Q is selected from the group

Q-l Q-2 Q-3

Q4 Q-5 Q-6

R3 is selected from the group H and halogen;

R ⁴ is selected from the group H, Cj-Cg alkyl, C _j -Cg haloalkyl, halogen, OR ⁹ ,

S(O) _m R ⁹ , COR ⁹ , CO ₂ R ⁹ , C(O)SR ⁹ , CCOJNRUR ¹² , CHO,

CR ⁷ =CR ⁷ CO ₂ R ⁹ , CO ₂ N=CR ¹³ R ¹⁴ , NO ₂ , CN, NHSO ₂ R ¹⁵ and

NHSO ₂ NHR ¹⁵ ; m is 0, 1 or 2; R ⁵ is selected from the group C _r C ₂ alkyl, C _r C ₂ haloalkyl, OCH ₃ , SCH ₃ ,

OCHF ₂ , halogen, CN and NO ₂ ; R ⁶ is selected from the group H, Cj-C3 alkyl, C2-C3 alkynyl, C2-C3 haloalkynyl,

CO2(C _j -C4 alkyl), and halogen; R ⁷ is independently selected from the group H, C1-C3 alkyl and halogen; or when Q is Q-2 or Q-6, R ⁶ and R ⁷ together with the carbon to which they are attached can be C=O;

R ⁸ is selected from the group C _r C ₆ alkyl, C _r C ₆ haloalkyl, C ₂ -C ₆ alkoxyalkyl,

C3-C6 alkenyl and C3-C6 alkynyl; R ⁹ is selected from the group C _r C ₈ alkyl; C ₃ -C ₈ cycloalkyl; C ₃ -C ₈ alkenyl;

C ₃ -C ₈ alkynyl; C _r C ₈ haloalkyl; C ₂ -C ₈ alkoxyalkyl; C ₂ -C ₈ alkylthioalkyl; C ₂ -C ₈ alkylsulfinylalkyl; C ₂ -C ₈ alkylsulfonylalkyl; C _r C ₈ alkylsulfonyl; phenylsulfonyl optionally substituted on the phenyl ring with halogen or Cj- C4 alkyl; C4-C alkoxy alkox alkyl, C4-C ₈ cycloalkylalkyl; C4-C ₈ alkenoxyalkyl; C ₄ -C ₈ alkynoxyalkyl; C ₆ -C ₈ cycloalkoxyalkyl; C ₄ -C ₈ alkenyloxyalkyl; C4-C ₈ alkynyloxyalkyl; C3~C ₈ haloalkoxy alkyl; C4-C haloalkenoxyalkyl; C4-C ₈ haloalkynoxyalkyl; C ₆ -C ₈ cycloalkylthioalkyl;

C ₄ -C ₈ alkenylthioalkyl; C -C alkynylthioalkyl; C _r C4 alkyl substituted a substituent selected from phenoxy and benzyloxy, each ring optionally substituted with a substituent selected from halogen, C1-C3 alkyl and C1-C3 haloalkyl; C4-C ₈ trialkylsilylalkyl; C3-C ₈ cyanoalkyl; C3-C ₈ halocycloalkyl; C3-C ₈ haloalkenyl; C ₅ -C alkoxyalkenyl; C ₅ -C ₈ haloalkoxyalkenyl; C5-C alkylthioalkenyl; C3-C ₈ haloalkynyl; C5-C ₈ alkoxyalkynyl; C5-CJ5 haloalkoxyalkynyl; C5-C alkylthioalkynyl; C2-C alkyl carbonyl; benzyl optionally substituted with a substituent selected from the group halogen, C _r C ₃ alkyl and C _r C haloalkyl; CHR ¹⁶ COR ¹⁰ ; CHR ¹⁶ CO ₂ R ¹⁰ ; CHR ¹ 6p(O)(OR ¹⁰ ) ₂ ; CHR ¹⁶ P(S)(OR ¹ 0) ₂ ;

CHRl6c(O)NRllR ¹² ; and CHR ¹⁶ C(O)NH ₂ ; R ¹⁰ is selected from the group Cj-Cg alkyl, Cj-Cg alkenyl and C Cg alkynyl; R ¹¹ and R ¹³ are independently selected from the group H and C1-C4 alkyl; R ¹² and R ¹⁴ are independently selected from the group C1-C4 alkyl and phenyl optionally substituted with a substituent selected from the group halogen,

C _r C alkyl and C _r C ₃ haloalkyl; R ¹¹ and R ¹² may be taken together as -(CH ₂ )5-, -(CH^- or

-CH2CH2OCH2CH2-, each ring optionally substituted with a substituent selected from the group C _j -C3 alkyl, phenyl and benzyl; R ¹³ and R ¹⁴ may be taken together with the carbon to which they are attached to form C3-C ₈ cycloalkyl; R ¹⁵ is selected from the grou ^^ alkyl and C1-C4 haloalkyl; R ¹⁶ is selected from the group H and C1-C3 alkyl; and W is selected from the group O and S; provided that R ¹ is other than H when the left-hand ring contains only single bonds.

In the above definitions, the terms "alkyl", "alkenyl" and "alkynyl" include straight and branched chain groups. "Halogen" means fluorine, chlorine, bromine or

iodine. Further, when used in compound words such as "haloalkyl" said alkyl may be partially or fully saturated with halogen atoms, which may be the same or different.

The bonding in compounds of Formula I is such that the left-hand ring contains single bonds, except that at most one of the bonds may be a double bond. Examples of structures of Formula I are:

Preferred for reasons of better biological activity and/or ease of synthesis are: Preferred 1 : Compounds of Formula I wherein the left-hand ring contains only single bonds. Such compounds are compounds of Formula la:

la wherein n is 1 or 2;

R ¹ is selected from the group halogen; hydroxy, C1-C3 alkoxy; C _j -C^ haloalkoxy;

C2-C5 alkylcarbonyloxy; or C2-C5 haloalkylcarbonyloxy;

R ² is selected from the group H, hydroxy, and halogen; or when R ¹ and R ² are bonded to the same carbon atom they can be taken together along with the carbon to which they are attached to form C=O; or when R ¹ and R ² are bonded to adjacent carbon atoms they can be taken together along with the carbons to which they are attached to form

O

/ \ CH— CH

Q is selected from the group

Q-l Q-2 Q-3

Q4 Q-5 Q-6

R ³ is selected from the group H and halogen;

R ⁴ is selected from the group H, C _j -C ₈ alkyl, C _j -C haloalkyl, halogen, OR ⁹ ,

S(O) _m R ⁹ , COR ⁹ , CO ₂ R ⁹ , C(O)SR ⁹ , C(O)NR R ¹² , CHO,

CR ⁷ =CR ⁷ CO ₂ R ⁹ , CO ₂ N=CR ¹ Rl ⁴ , NO ₂ , CN, NHSO ₂ R ¹⁵ and

NHSOzNHR^; m is 0, 1 or 2; R ⁵ is selected from the group C _r C ₂ alkyl, C _r C ₂ haloalkyl, OCH ₃ , SCH ₃ ,

OCHF ₂ , halogen, CN and NO ₂ ; R ⁶ is selected from the group H, C1-C3 alkyl, C2-C3 alkynyl, C ₂ -C3 haloalkynyl,

CO (C _j -C4 alkyl), and halogen; R ⁷ is independently selected from the group H, C1-C3 alkyl and halogen; or when Q is Q-2 or Q-6, R ⁶ and R ⁷ together with the carbon to which they are attached can be C=O; R ⁸ is selected from the group ^^g alkyl, C _j -Cg haloalkyl, C ₂ -Cg alkoxyalkyl,

C3-C6 alkenyl and C3-C6 alkynyl; R ⁹ is selected from the group C _j -C ₈ alkyl; C3-C ₈ cycloalkyl; C3~C ₈ alkenyl;

C ₃ -C ₈ alkynyl; C _r C ₈ haloalkyl; C ₂ -C ₈ alkoxyalkyl; C ₂ -C ₈ alkylthioalkyl;

C ₂ -C alkylsulfinylalkyl; C ₂ -C ₈ alkylsulfonylalkyl; Cι-C alkylsulfonyl; phenylsulfonyl optionally substituted on the phenyl ring with halogen or C

C4 alkyl; C4~C alkoxyalkoxyalkyl, C4-C cycloalkylalkyl; C4-C

alkenoxyalkyl; C ₄ -Cg alkynoxyalkyl; C ₆ -Cg cycloalkoxy alkyl; C ₄ -Cg alkenyloxyalkyl; C -Cg alkynyloxyalkyl; C ₃ -Cg haloalkoxyalkyl; C -C ₈ haloalkenoxyalkyl; C -C ₈ haloalkynoxyalkyl; Cg-Cg cycloalkylthioalkyl; C4-Cg alkenylthioalkyl; C -C ₈ alkynylthioalkyl; C _r C4 alkyl substituted a substituent selected from phenoxy and benzyloxy, each ring optionally substituted with a substituent selected from halogen, C1-C3 alkyl and C1-C3 haloalkyl; C4-C ₈ trialkylsilylalkyl; C3-C ₈ cyanoalkyl; C3-C ₈ halocycloalkyl; C3-Cg haloalkenyl; C C% alkoxyalkenyl; Cs-Cg haloalkoxy alkenyl; C5~Cg alkylthioalkenyl; C3-C ₈ haloalkynyl; C5-C ₈ alkoxyalkynyl; C ₅ -C ₈ haloalkoxyalkynyl; CyC% alkylthioalkynyl; C ₂ -C ₈ alkyl carbonyl; benzyl optionally substituted with a substituent selected from the group halogen, C _r C ₃ alkyl and C _r C haloalkyl; CHR ¹⁶ COR ¹⁰ ; CHR ¹⁶ CO ₂ R ¹⁰ ; CHR ¹⁶ P(O)(OR ¹⁰ ) ₂ ; CHR ¹ 6p(S)(OR ¹⁰ ) ₂ ; CHR ¹⁶ C(O)NRURl ² ; and CHR ¹ 6C(O)NH ₂ ; R ¹⁰ is selected from d e group C _j -Cg alkyl, C _j -Cg alkenyl and C _j -Cg alkynyl;

R ¹¹ and R ¹³ are independently selected from the group H and C1-C4 alkyl; R ¹² and R ¹⁴ are independently selected from die group C1-C4 alkyl and phenyl optionally substituted with a substituent selected from the group halogen, C _r C ₃ alkyl and C _r C ₃ haloalkyl; R ¹¹ and R ¹² may be taken together as -(CH ₂ ) ₅ -, -(CH^- or

-CH ₂ CH ₂ OCH ₂ CH ₂ -, each ring optionally substituted with a substituent selected from the group 0^3 alkyl, phenyl and benzyl; R ¹³ and R ¹⁴ may be taken together with the carbon to which they are attached to form C3-C cycloalkyl; R ¹⁵ is selected from the group C C alkyl and C1-C4 haloalkyl;

R ¹⁶ is selected from the group H and C _j -03 alkyl; and W is selected from the group O and S. Preferred 2: Compounds of Formula I wherein: R ¹ is halogen; R ² is selected from the group H, and halogen;

Q is selected from the group consisting of Q-l, Q-2 and Q-6; R ³ is halogen;

R ⁵ is selected from the group C _r C ₂ haloalkyl, OCH ₃ , OCHF ₂ , CN, NO ₂ , and halogen; R ⁶ is selected from the group H, C _r C ₃ alkyl, C ₂ -C ₃ alkynyl, C ₂ -C ₃ haloalkynyl, and halogen; R ⁷ is H; and W is O.

Preferred 3: Compounds of Preferred 2 wherein:

R ⁴ is selected from the group halogen, OR ⁹ , S(O) _m R ⁹ , COR ⁹ , CO ₂ R ⁹ , C(O)NR ⁿ R ¹² , CH=CHCO ₂ R ⁹ , NHSO ₂ R ¹⁵ and NHSO ₂ NHR ¹⁵ ; R ⁵ is halogen; R ⁶ is selected from the group H and C1-C3 alkyl;

R ⁷ is H; and R ⁹ is selected from the group C _j -Cg alkyl; C3-Cg cycloalkyl; C3-Cg alkenyl;

C3-Cg alkynyl; C Cg haloalkyl; C2-Cg alkoxyalkyl; C1-C4 alkyl substituted with a substituent selected from phenoxy and benzyloxy, each ring optionally substituted with a substituent selected from halogen, C1-C3 alkyl and C _r C ₃ haloalkyl; C ₃ -C ₈ haloalkenyl; C ₃ -C ₈ haloalkynyl; C ₂ -C ₈ alkyl carbonyl; benzyl optionally substituted with a substituent selected from the group halogen, C _r C ₃ alkyl and C _r C ₃ haloalkyl; CHR ¹⁶ COR ¹⁰ ; CHR^CO^iO; CHR^PζOXOR ¹⁰ ^; CHR ¹ 6C(O)NR ¹¹ R ¹² ; and CHR ¹⁽ >C(O)NH ₂ .

Preferred compounds of the invention are:

2,5,6,7-tetrahydro-2-[2,4-dichloro-5-(2-propynyloxy)pheny l]-6-fluoro-3H- pyrrolo[2,l-c]-l,2,4-triazol-3-one; and 5,6,7,8-tetrahydro-2-[2,4-dichloro-5-(2-propynyloxy)phenyl]- 8-chloro-l,2,4- triazolo[4,3-Λ]pyridin-3(2H)-one.

Compounds of General Formula I can be readily prepared by one skilled in the art by using the reactions and techniques described in Schemes 1 to 11 below. The substituents Rϊ-R ¹⁶ , n, m, and Q for the compounds illustrated are as defined as for compounds of Formula I. Compounds prepared by Schemes 1 to 11 that include compounds numbered II to XVI are intermediates or reagents for the ultimate preparation of compounds of Formula I. Compounds of Formulae la-It are subsets of compounds of Formula I. In cases where the substituent of a starting material is not compatible with the reaction conditions described for any of the reaction schemes, it can be assumed that the substituent is converted to a protected form prior to the described reaction scheme and then deprotected after the reaction using commonly accepted protecting/ deprotecting techniques (as an example, see T. W. Greene and P. G. M. Wuts, "Protective GroupsjnJDrganic Synthesis", 2nd Edition, John Wiley and Sons, Inc., New York, 1991). Otherwise alternative approaches known to one skilled in the art are available. One skilled in the art will recognize that compounds of Formula I may exist as multiple stereoisomers. This invention therefore, comprises racemic mixtures, enriched mixtures, and pure enantiomers of compounds of Formula I.

The compounds of this invention are made by the following processes.

A retrosynthetic analysis of compounds of Formula lb (compounds of Formula I wherein n is 2) is shown below (Scheme 1). The formation of ring A can be accomplished by an intramolecular cyclization between the nitrogen in ring B and the terminal double bond of triazolinone of Formula II.

Scheme 1

The synthesis of the triazolinone ring B in compounds of Formula II is known in the art and can be prepared by methods such as those described in U.S. 4,818,275 and U.S. 4,818,276. Acidic condensation of α-ketoacids of Formula DI and phenyl hydrazine derivatives of Formula IV gives hydrazones of Formula V. Schmidt rearrangement of the acid of Formula V with diphenylphosphoryl azide followed by a ring cyclization gives triazolinones of Formula II as shown below (Scheme 2).

Scheme 2

πia: R ² =H Va: R ² = _* H

For the synthesis of the triazolinones of Formula Ha (compounds of Formula II wherein R ² is H), 2-oxo-5-hexanoic acid IQa (compound of Formula III wherein R ² is H) can be used as the starting material (Scheme 3). 2-Oxo-5-hexanoic acid can be

made by hydrolysis of the methyl ester of Formula VI with base, preferably one equivalent of potassium hydroxide in an aqueous alcohol solvent. The ester of Formula VI is made from methyl pyruvate as described in /. Org. Chem., (1983), 48, 158 (Scheme 3).

Scheme 3

The triazolinone of Formula Ha can be made by the method described in Scheme 2. The hydrazone of Formula Va (compound of Formula V wherein R ² is H) is made by treating 2-oxo-5-hexanoic acid ula with a phenyl hydrazine of Formula IV under acidic conditions using hydrochloric acid in an organic solvent such as ethyl or methyl alcohol at a temperature between room temperature and about 100°C. Schmidt rearrangement of hydrazone of Formula Va using an azide such as diphenylphosphoryl azide followed by intramolecular cyclization at a temperature between about 0°C and about 100°C affords the intermediate of Formula Da.

Treatment of the olefin of Formula π with MCPBA ( -chloroperoxybenzoic acid) in an inert solvent such as dichloromethane at a temperature between about 0°C and about 100°C, preferably at room temperature, gives an epoxide of Formula VQ (Scheme 4). Intramolecular cyclization of the epoxide using a base such as potassium carbonate in an inert solvent such as acetonitrile or acetone gives the 6-membered ring product of Formula Ic (compound of Formula I wherein R ¹ is 6-OH). Fluorination of the alcohol of Formula Ic with DAST (diethylaminosulfur trifluoride) at a temperature between about -78°C and about 100°C in an inert solvent such as dichloromethane gives the fluorinated product of Formula Id.

Scheme 4

The alcohol of Formla Ic can also be prepared by hydroxybromination of the olefin of Formula II using N-bromosuccinimide (ΝBS) and water or N-bromoacetamide and water followed by cyclization of the resulting bromohydrin of Formula VIII using potassium carbonate in an inert solvent such as acetonitrile or acetone (Scheme 5).

Scheme 5

Ic

Compounds of Formula Ic can also be converted to the chloro-, bromo-, and iodo-R ¹ substituted bicyclic triazolinones of Formula I using methods known to those skilled in the art. The hydroxy grouplh compounds of Formula Ic can be acylated by known methods to prepare the alkylcarbonyloxy and haloalkylcarbonyloxy derivatives. In addition, the hydroxy or halo group can be converted by known methods to afford the R ¹ = alkoxy and haloalkoxy derivatives (March, J., Advanced Organic Chemistry, (1992), 4th Ed., John Wiley and Sons, Inc., pp 386-389). In fact all the R ¹ = OH or halogen compounds in the following Schemes can be functionalized as is known in the

art to prepare the other R ¹ substituted compounds. Compounds wherein R ¹ and R ² are taken together along with the carbon atom to which they are attached to form C=O can be prepared from the corresponding R ¹ = OH and R ² =H compounds by well-known methods for oxidizing secondary alcohols to ketones. Compounds of Formulae Ie and If (compounds of Formula I wherein n is 1) can be prepared as illustrated in Scheme 6. Oxidative cleavage of the olefin of Formula II using sodium periodate and a catalytic amount of osmium tetroxide in an inert solvent mixture such as tetrahydrofuran (THF) and water, or using ozone in dichloromethane followed by reductive workup using dimethyl sulfide (DMS), affords die aldehyde of Formula IX. Intramolecular cyclization of the aldehyde under basic conditions using potassium carbonate or sodium hydride gives the 5-membered ring alcohol of Formula Ie. Treatment of the alcohol of Formula Ie with DAST in an inert solvent such as dichloromethane at a temperature between about -80°C and about 60°C produces die fluoride of Formula If. The fluoride If can also be made by direct cyclization and fluorination using DAST at a temperature range between about -100°C and about 60°C.

Hydroboration of the olefin olEoπnula II with 9-borabicyclo[3.3.1]nonane (9-BBN) gives the alcohol of Formula X after oxidative workup (Scheme 7). Oxidation of alcohol X with oxidizing agents such as PDC (pyridinium dichlorochromate) produces the hemiaminal of Formula Ig presumably via the aldehyde intermediate of Formula XI. The fluoro compound of Formula Ih can be made by the treatment of the hemiaminal with DAST.

Scheme 7

Triazolinones of Formula XH can be made from 2-oxo-4-pentenoic acids and sustituted phenyl hydrazines of Formula IV by methods known to those skilled in the art and the methods taught herein (Scheme 8). The epoxide of Formula XDI can be prepared from the olefin of Formula XII using an oxidant such as MCPBA. Intramolecular cyclization of the epoxide with a base such as potassium carbonate affords the alcohol of Formula Ii. The fluoro compound of Formula Ij can be made from the alcohol using DAST at a temperature between about -70°C and about room temperature in an inert solvent such as dichloromethane.

Scheme 8

Ii

Compounds of Formula Iq can be prepared from the unsubstituted compounds of Formula XTV as illustrated in Scheme 9. Treatment of the bicyclic triazolinone of Formula XTV with N-bromosuccinimide (ΝBS) under allylic bromination conditions affords die mono-bromo derivative of Formula Io. One skilled in the art will recognize that bromination may also occur on Q if an electron-rich phenyl ring is present. When Q is Q-l, we have found tiiat bromination does not occur on the phenyl ring when R ³ and R ⁵ are Cl and R ⁴ is acetyloxy. The acetyl group can be removed by known methods, and die liberated phenolic hydroxyl group can be functionalized by known methods to prepare the desired OR ⁹ group. Hydrolysis of die bromide in hot aqueous dimethyl sulfoxide (DMSO) affords die alcohol of Formula Ip. The fluoro compound of Formula Iq can be prepared by treatment of die alcohol with diethylaminosulfiir trifluoride (DAST) as described above.

Scheme 9

Compounds of Formula I wherein the left-hand ring is unsaturated can be prepared by treating the hydroxy-, bromo, or chloro-substituted compound of Formula Ir with a base such as l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as illustrated in Scheme 10. The unsaturated compound is represented by Formula Is wherein the left- hand ring contains one double bond. Theliydroxy, bromo and chloro compounds of Formula Ir can be prepared by die methods described in the Schemes above. In some cases, the elimination results in a mixture of double bond isomers which can be separated by chromatography.

Compounds of Formula I wherein R ¹ and R ² are taken togedier along with the carbon atoms to which they are attached to form an epoxide can be prepared from the corresponding unsaturated ring compound of Formula Is by well known methods for epoxidizing double bonds, for example using MCPBA in CH2CI2.

Compounds of Formula It can be prepared as illustrated in Scheme 11. Allylic oxidation of die terminal alkene of Formula II with t-butyl hydroperoxide and catalytic selenium (IV) oxide in an inert solvent such as dichloromethane produces die allylic alcohol of Formula XV. Protection of the secondary alcohol as the t-butyldimethylsilyl (TBS) ether is accomplished using t-butylchlorodimethylsilane and a base, preferably triethylamine and catalytic 4-(dimethylamino)pyridine. The terminal olefin is converted to die primary alcohol to afford compounds of Formula XVI using 9-BBN followed by treatment with sodium perborate. Ring cyclization is accomplished using the Martin sulfurane dehydrating agent [CgH ₅ (CF3)2O]2S(CgH5)2. Removal of the TBS group and liberation of the alcohol can be accomplished using tetrabutylammonium fluoride. The alcohol can be converted to die corresponding fluoro compound using DAST, or to other R ¹ substituted compounds as described above.

Scheme 11

XV π 1)TBS-C3,base 2)9-BBN,NaB03

XVI

For some compounds of Formula I wherein R ² is other than hydrogen, die R ² substituent is more conveniendy introduced after cyclization to form the bicyclic triazolinone. This is especially the case when R ¹ and R ² are attached to die same carbon atom.

EXAMPLE 1 Step 1: Preparation of 2-oxo-5-hexenoic acid. 2.4-dichloro-5-r(2-propynyl)oxyl- phenylhydrazone. To a solution of 2.0 g (14.1 mmol) of methyl 2-oxo-5-hexanoate prepared as described in /. Org. Chem., (1983), 48, 158, in 2.5 mL of ethyl alcohol was added a solution of 788 mg (14.1 mmol) of potassium hydroxide in 2.5 mL of water in an ice ba . After 10 min, a mixture of 20 mL of 10% aqueous hydrochloric acid and 20 mL of ethyl alcohol and 3.25 g (14.0 mmol) of 2,4-dichloro-5-[(2- propynyl)oxy]phenylhydrazine were added in sequence. The mixture was then warmed at 40°C for lh. The mixtue was cooled to room temperature and filtered to give 3.78 g of the tide product of Step 1 as a brown solid, m.p.: 152-153°C; *H NMR (DMSO-d ₆ , 400 MHz) δ 12.5 (s,lH), 7.6 (s,lH), 7.4 (s,lH), 5.9 (m,lH), 4.9-5.1 (m,2H), 4.9 (s,2H), 3.7 (s,lH), 2.6 (t,2H), 2.4 (q,2H). Step 2: Preparation of 2-r2.4-dichloro-5-(2-propynyloxy)phenvn-2.4-dihvdro-5-(3- butenyl)-3H- 1.2 ,4-triazol-3 -one To a solution of 7.34 g (21.6 mmol) of 2-oxo-5-hexenoic acid, 2,4-dichloro-5-[(2- propynyl)oxyl]phenylhydrazone in 100 mL of toluene was added 6.54 g (23.7 mmol) of diphenylphosphoryl azide and 3.6 mL of triethylamine (25.9 mmol) in sequence. The reaction mixture was then warmed at reflux for lh. The mixture was cooled to room

temperature and the excess toluene and triethylamine were evaporated in vacuo. The crude product was purified by flash chromatography over silica gel, eluting with 95:5 v:v mixture of dichloromethane and methanol to give 6.64 g of die tide compound of Step 2 as a brown solid, m.p.: 150-151°C; 1H NMR (CDC1 ₃ , 400 MHz) δ 11.7 (broad s,lH), 7.6 (s,lH), 7.2 (s,lH), 5.95-5.7 (m,lH), 5.2-5.0 (m,2H), 4.8 (s,2H), 2.7 (t,2H), 2.6 (t,lH), 2.5 (q,2H).

Step 3: Preparation of 2-r2.4-dicMoro-5-(2-propynyloxy)phenyl1-2.4-dihydro-5-(3.4- epoxybutyl)-3H- 1.2.4-triazol-3 -one To a solution of 500 mg (1.48 mmol) of 2-[2,4-dichloro-5-(2-propynyloxy)- phenyl]-2,4-dihydro-5-(3-butenyl)-3H- 1 ,2,4-triazol-3-one in 20 mL of dichloromethane was added 172 mg (1.63 mmol) of sodium carbonate and 970 mg of , m-chloroperoxybenzoic acid (50-60%, 2.81 mmol) in an ice bath. The reaction mixture was stirred at room temperature for 24h. The mixture was filtered and die filtrate was evaporated in vacuo to give 500 mg of the tide compound of Step 3 as yellow solid. The crude product was used in die following reaction witiiout further purification. ^J Η NMR (CDC1 ₃ , 400 MHz) δ 11.25 (s,lH), 7.55 (s,lH), 7.2 (s.lH), 4.8 (s,2H), 3.05 (m,lH), 2.8 (t,lH), 2.8 (t,2H), 2.6 (s,lH), 2.75 (d,lH), 2.2 (m,lH), 1.8 (m,lH). Step 4: Preparation of 5.6.7.8-tetrahydro-2-r2.4-dichloro-5-(2-propynyloxy)phenyn- 6-hydroxy- 1.2.4-triazolof 4.3-α]pyridin-3(2_ftπ-one A mixture of 500 mg ( 1.41 mmol) of 2-[2,4-dichloro-5-(2-propynyloxy)-phenyl]-

2,4-dihydro-5-(3,4-epoxybutyl)-3H-l,2,4-triazol-3-one and 563 mg (4.08 mmol) of potassium carbonate in 20 mL of acetonitrile was warmed at reflux for 2h. The mixture was cooled to room temperature and filtered. The filtrate was evaporated in vacuo. The crude product was purified by flash chromatography over silica gel, eluting with a 95:5 v:v mixture of dichloromethane and methanol to give 184 mg of the tide product of Step 4 as a pale yellow foam, *H NMR (CDC1 ₃ , 400 MHz) δ 7.5 (s,lH), 7.15 (s,lH), 4.8 (s,2H), 4.45 (broad t,lH), 3.8 (m,2H), 3.0 (m,lH), 2.8 (m,lH), 2.6 (s,lH), 2.2 (s,lH), 2.15 (m,lH), 1.95 (m,lH).

EXAMPLE 2 Step 1: Preparation of 2-f2.4-dicMoro-5-(2-propynyloxy)phenyl1-2.4-dihydro-5-(4- bromo-3-hydroxybutyl)-3H-1.2.4-triazol-3-one To a solution of 200 mg (0.592mmol) of 2-[2,4-dichloro-5-(2-propynyloxy)- phenyl]-2,4-dihydro-5-(3-butenyl)-3H-l,2,4-triazol-3-one in 1.8 mL of dimethyl sulfoxide was added 30 mL (1.67 mmol) of water and 211 mg (1.18 mmol) of N-bromosuccinimide, in sequence, at room temperature. The mixture was stirred at room temperature for 10 min. The mixture was then poured into cold water and extracted with dichloromethane. The organic layer was dried (MgSO4) and concentrated in vacuo. The crude product was purified by flash chromatography over

silica gel, eluting with a 97:3 v:v mixture of dichloromethane and methanol to-give 200 mg of the title product of Step 1 as a pale yellow foam. *H NMR (CDC1 ₃ , 400 MHz) δ 11.0 (s,lH), 7.55 (s,lH), 7.15 (s,lH), 4.8 (s,2H), 3.8 (m,lH), 3.4 (m,2H), 2.8 (m,2H), 2.6 (t,lH), 2.1-1.8 (m,2H). Step 2: Preparation of 5.6.7.8-tetrahydro-2-r2.4-dichloro-5-(2-propynyloxy)phenyl1- 6-hydroxy-1.2.4-triazolo|4.3-alpyridin-3(2H)-one A mixture of 200 mg (0.460 mmol) of 2-[2,4-dichloro-5-(2-propynyloxy)- phenyl]-2,4-dihydro-5-(4-bromo-3-hydroxybutyl)-3H-l,2,4-tria zol-3-one and 127 mg (0.920 mmol) of potassium carbonate in 10 mL of acetonitrile was warmed at reflux for 2h. The mixture was cooled to room temperature and filtered. The filtrate was evaporated in vacuo. The crude product was purified by flash chromatography over silica gel, eluting widi a 96:4 v:v mixture of dichloromethane and methanol to give 57 mg of die tide product as a pale yellow foam, The *Η NMR spectrum of the product was identical to tiiat obtained for die product of Step 4 in Example 1. EXAMPLE 3

Preparation of 5.6.7.8-tetrahydro-2-r2.4-dichloro-5-(2-propynyloxy)phenyn-6 -fluoro-

1.2.4-triazolor4.3-fllpyridin-3(2H)-one To a solution of 169 mg (0.477 mmol) of 5,6,7,8-tetrahydro-2-[2,4-dichloro-5-(2- propynyloxy)phenyl]-6-hydroxy-l,2,4-triazolo[4,3-α]pyridin- 3(2H)-one in 5 mL of dichloromethane was added 76 μl (0.573 mmol) of diediylaminosulfur trifluoride

(DAST) at 0°C. The reaction mixture was stirred at 0°C for lh. The mixture was then quenched widi ice and extracted with dichloromethane. The organic extracts were dried (MgSO ), and tiien concentrated in vacuo to give a pale red solid. The crude product was purified by flash chromatography over silica gel, eluting widi a 95:5 v:v mixture of dichloromethane and medianol to give 64 mg of the tide product as a pale yellow foam. ¹⁹ F NMR (CDC1 ₃ , 400 MHz) δ -188 ppm, *H NMR (CDC1 ₃ , 400 MHz) δ 7.5 (s,lH), 7.1 (s,lH), 5.2 (m,lH), 4.8 (s,2H), 4.2-3.6 (m,2H), 3.2-3.0 (m,lH), 3.0-2.6 (m,lH), 2.5 (s,lH), 2.3-1.8 (m,2H).

EXAMPLE 4 Step 1: Preparation of 2-r2.4-dicMoro-5-(2-propynyloxy)phenyl1-2.4-dihydro-5-(3- oxo-propyl)-3H- 1 ,2.4-triazol-3-one To a solution of 500 mg (1.48 mmol) of 2-[2,4-dichloro-5-(2-propynyloxy)- phenyl]-2,4-dihydro-5-(3-butenyl)-3H-l, 4-triazol-3-one in a mixture of 10 mL of tetrahydrofuran and 10 mL of water was added 696 mg (3.25 mmol) of sodium periodate and 167 mL of 0.18 M aqueous solution of osmium tetroxide at room temperature. The mixture was stirred at die room temperature for 2h, and then diluted widi water and extracted with ethyl acetate. The organic layer was dried (MgSO4) and concentrated in vacuo. The crude product was purified by flash chromatography over

silica gel, eluting with a 96:4 v:v mixture of dichloromethane and methanol to give 464 mg of the title product of Step 1 as a white foam. ^l H NMR (CDC1 ₃ , 400 MHz) δ 11.5 (broad s,lH), 9.8 (s,lH), 7.55 (s,lH), 7.2 (s,lH), 4.8 (s,2H), 2.9 (m,4H). Step 2: Preparation of 2.5.6.7-tetrahvdro-2-r2.4-dichloro-5-(2-propynyloxy)phenyll- 5-fluoro-3H-pyrrolo 2.1-c1-1.2.4-triazol-3-one

To a solution of 40 mg (0.117 mmol) of 2-[2,4-dichloro-5-(2-propynyloxy)- phenyl]-2,4-dihydro-5-(3-oxo-propyl)-3H-l,2,4-triazol-3-one in 5 mL of dichloromediane was added 22.7 mg (0.141 mmol) of diemylaminosulfur trifluoride at 0°C. The mixture was stirred at room temperature for 30 minutes, and tiien quenched with cold water and extracted with dichloromethane. The organic layer was washed with brine and water, dried (MgSO4) and concentrated in vacuo. The crude product was purified by flash chromatography over silica gel, eluting with a 95:5 v:v mixture of dichloromethane and methanol to give 18 mg of 2-[2,4-dichloro-5-(2- propynyloxy)phenyl]-2,4-dihydro-5-(3,3-difluoropropyl)-3H-l, 2,4-triazol-3-one as a white foam ^l U NMR (CDC1 ₃ , 400 MHz) δ 12.0 (s,lH), 7.55 (s,lH), 7.2 (s,lH), 5.95 (t,lH, J=55Hz), 4.8 (s,2H), 2.8 (t,2H), 2.6 (s,lH), 2.3 (m,2H), and 7 mg of the tide product as a solid, ^l H NMR (CDC1 ₃ , 400 MHz) δ 7.5 (s,lH), 7.2 (s,lH), 6.4 and 6.2 (q,lH, J=60 and 5Hz), 4.8 (s,2H), 3.15 (m,lH), 3.0-2.6 (m,3H), 2.6 (s,lH).

EXAMPLE 5 Step 1: Preparation of 5.6.7, 8-tetrahydro-2-(5-acetyloxy-2 _r 4-dichlorophenyl)-8- bromo-1.2.4-triazolof4.3-α]pyridin-3(2_ _f)-one To a solution of 3.55 g (10.4 mmol) of 5,6,7,8-tetrahydro-2-(5-acetyloxy~2,4- dichlorophenyl)-l,2,4-triazolo[4,3-α]pyridin-3(2H)-one in 100 mL of carbon tetrachloride was added 2.03 g (11.4 mmol) of N-bromosuccinimide at room temperature. The mixture was warmed under reflux by irradiating widi a sun lamp for 3h. The mixture was cooled to room temperature and concentrated under reduced pressure. The crude product was purified by flash chromatography over silica gel, eluting widi a 1:1 v:v mixture of ethyl acetate and n-hexane to give 4.10 g of the tide product of Step 1 as a white solid, m.p.: 75-83°C; *H ΝMR (CDCI3, 300 MHz) δ 7.6 (s,lH), 7.35 (S,1H), 5.25 (m,lH), 4.0 (m,lH), 3.6 (m,lH), 2.75 (s,3H), 2.5-1.9 (m,4H). Step 2: Preparation of 5.6.7.8-tetrahydro-2- ⁽ 2.4-dichloro-5-hvdroxyphenyl)-8- hydroxy- 1.2.4-triazolor4.3- 1pyridin-3(2H)-one A mixture of 4.10 g (9.74 mmol) of5,6,7,8-tetrahydro-2-(5-acetyloxy-2,4- dichlorophenyl)-8-bromo-l ,2,4-triazolo[4,3-α]pyridin-3(2H)-one, 50 mL of DMSO, and 50 mL of water was warmed at 90°C for 5h. The mixture was cooled to room temperature and diluted widi ethyl acetate. The organic layer was washed widi water, dried (MgSO4) and concentrated under reduced pressure. The crude product was purified by flash chromatography over silica gel, eluting with a 95:5 v:v mixture of

dichloromethane and methanol to give 1.70 g of the title product of Step 2 as a yellow oil. ^l U NMR (CD ₃ SO, 300 MHz) δ 7.65 (s,lH), 7.05 (s,lH), 5.85 (br s,lH), 4.60 (m,lH), 3.6-3.4 (m,2H), 2.2-1.8 (m,4H).

Step 3: Preparation of 5.6.7.8-tetrahydro-2-r2.4-dichloro-5-(2-propynyloxy)phenyn- 8-hydroxy-1.2.4-triazolor4.3-α1pyridin-3(2H)-one

A mixture of 1.7 g (5.38 mmol) of 5,6,7 ,8-tetrahydro-2-(2,4-dichloro-5- hydroxyphenyl)-8-hydroxy-l,2,4-ιriazolo[4,3-α]pyridin-3(2H )-one, 959 mL (10.7 mmol) of propargyl bromide (80% in toluene), and 1.48 g (10.7 mmol) of potassium carbonate in 20 mL of acetonitrile was warmed at reflux for 5h. The mixture was cooled to room temperature and filtered. The filtrate was evaporated under reduced pressure. The crude product was flash chromatographed over silica gel, eluting widi a 97:3 v:v mixture of dichloromethane and methanol to give 1.36 g of die tide product of Step 3 as a yellow solid, m.p. 168-170°C; ^l H NMR (CDCI3, 300 MHz) δ 7.55 (s,lH), 7.15 (s,lH), 4.85 (m,lH), 4.8 (d,2H), 3.8-3.6 (m,2H), 2.6 (m,lH), 2.55 (s,lH), 2.3-1.9 (m,4H).

Step 4: Preparation of 5.6.7.8-tetrahydro-2-r2.4-dichloro-5-(2-propynyloxy)phenyll- 8-fluoro-1.2.4-triazolor4.3-fl1pyridin-3(2H)-one To a solution of 300 mg (0.847 mmol) of 5,6,7,8-tetrahydro-2-[2,4-dichloro-5-(2- propynyloxy)phenyl]-8-hydroxy-l,2,4-triazolo[4,3-fl]pyridin- 3(2H)-one in 10 mL of dichloromethane was added 123 mL (0.930 mmol) of diethylaminosulfur trifluoride (DAST) at -78°C. The reaction mixture was stirred at -78°C for 4h. The mixture was warmed to room temperature, quenched widi ice, and extracted widi dichloromethane. The organic layers were dried (MgSO4), and concentrated under reduced pressure. The crude product was flash chromatographed over silica gel, eluting widi a 98:2 v:v mixture of dichloromethane and methanol to give 272 mg of the tide product of Step 4 as a yellow solid. ¹⁹ F NMR (CDC1 ₃ , 300 MHz) δ -172; lH NMR (CDCI3, 300 MHz) δ 7.55 (s,lH), 7.2 (s,lH), 5.6, 5.5 (2m, J=70Hz,lH), 4.8 (s,2H), 4.0 (m,lH), 3.55 (m,lH), 2.6 (m,lH), 2.5-1.8 (m,4H).

Using die procedures oudined in Schemes 1-11, the compounds of Tables 1-6 can be prepared.

The following abbreviations are used in the tables which follow.

n = normal Ph = phenyl Me = methyl i = iso Pr = propyl

TABLE 1

7-Cl 7-Cl F CH ₃ CH ₂ OCH 7-Cl 7-Cl F CH ₃ CH(CH ₃ )OCH 8-Cl 8-α F H CH ₂ OCH 8-Cl 8-Cl F H CH(CH ₃ )OCH

TABLE 4 Compounds of Formula Ik wherein Q = Q-1; R ¹ = 6-F; R ² = H; R ⁵ = O

TABLE 6

The compounds of this invention are useful as herbicides in agriculture. 5 Typically, such compound(s) can be formulated in an effective amount widi conventional additives including a carrier therefor (comprising a surfactant and/or a solid or liquid diluent) and applied by known methods to die locus to be protected.

Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent or an organic solvent. 0 Useful formulations include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and die like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture nd temperature. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several 5 hundred liters per hectare. High strengtii compositions are primarily used as intermediates for further formulation. The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within die following approximate ranges which add up 100 weight percent.

Typical solid diluents are described in Watitins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents and solvents 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, etc. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill. Water-dispersible granules can be produced by agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., (1988), pp 251-259. Suspensions are prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be made by spraying die 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), pp 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 also be prepared as taught in DE 3,246,493.

For further information regarding the art of formulation, see U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19_and Examρles 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 tiirough 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, 8tiι Ed., Blackwell Scientific Publications, Oxford, (1989).

In the following Examples, all percentages are by weight and all formulations are worked up in conventional ways. The compound number refers to die compound in Index Table A hereinafter.

Example A

High Strength Concentrate

Compound 12 98.5% silica aerogel 0.5% syndietic amorphous fine silica 1.0%. Example B

Wettable Powder

Compound 12 65.0% dodecylphenol polyetiiylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.

Example C Granule

Compound 12 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 12 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphdialenesulfonate 1.0% calcium/magnesium bentonite 59.0%. The compounds of the present invention are highly active preemergent and/or postemergent herbicides and/or plant growth regulants. Many of diem have utility for broad-spectrum pre- and/or postemergence weed control in areas where complete control of all vegetation is desired sucrTas around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, around billboards and highway and railroad strucmres. Some of die compounds are useful for die control of selected grass and broadleaf weeds widi tolerance to important agronomic crops which include but are not limited to barley, cotton, wheat, corn, soybeans, rice, citrus, peanut, and plantation crops such as sugarcane, coffee, banana, oil palm, rubber, grapes, fruit trees, nut trees,

turf, pineapple and loblolly pine. The compounds of the instant invention are particularly useful on plantation crops such as sugarcane, coffee, banana, oil palm, rubber, grapes, fruit trees, nut trees, turf, pineapple and loblolly pine. 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.

Compounds of this invention can be used alone or in combination widi otiier commercial herbicides, insecticides or fungicides. A mixture of one or more of the following herbicides with a compound of tiiis invention can be particularly useful for weed control: acetochlor, acifluorfen, acrolein, 2-propenal, alachlor, ametryn, amidosulfuron, ammonium sulfamate, amitrole, anilofos, asulam, atrazine, barban, benefin, bensulfuron methyl, bensulide, bentazon, benzofluor, benzoylprop, bifenox, bromacil, bromoxynil, bromoxynil heptanoate, bromoxynil octanoate, butachlor, buthidazole, butralin, butylate, cacodylic acid, 2-chloro-NN-di-2-propenyl-acetamide, 2-chloroallyl diediyldidiiocarbamate, chloramben, chlorbromuron, chloridazon, chlorimuron ethyl, chlormethoxynil, chlornitrofen, chloroxuron, chlorpropham, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clomazone, cloproxydim, clopyralid, calcium salt of methylarsonic acid, cyanazine, cycloate, cycluron, cyperquat, cyprazine, cyprazole, cypromid, dalapon, dazomet, dimethyl 2,3,5,6-tetrachloro-l,4-benzenedicarboxylate, desmedipham, desmetryn, dicamba, dichlobenil, dichlorprop, diclofop, diethatyl, difenzoquat, diflufenican, dimepiperate, dinitramine, dinoseb, diphenamid, dipropetryn, diquat, diuron, 2-methyl-4,6- dinitrophenol, disodium salt of methylarsonic acid, dymron, endothall, S-ethyl dipropylcarbamothioate, esprocarb, ethalfluralin, ethametsulfuron methyl, ethofumesate, fenac, fenoxaprop, fenuron, salt of fenuron and trichloroacetic acid, flamprop, fluazifop, fluazifop-P, fluchloralin, flumesulam, flumipropyn, fluometuron, fluorochloridone, fluorodifen, fluoroglycofen, flupoxam, fluridone, fluroxypyr, fluzasulfuron, fomesafen, fosamine, glyphosate, glyphosate salts, haloxyfop, hexaflurate, hexazinone, imazamethabenz, imazapyr, imazaquin, imazamethabenz methyl, imazethapyr, i azosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaben, karbutilate, lactofen, lenacil, linuron, metobenzuron, metsulfuron memyl, methylarsonic acid, monoammonium salt of methylarsonic acid, (4-chloro-2- methylphenoxy)acetic acid, S,S ^, -dimethyl-2-(difluoromedιyl)-4-(2-methylpropyl)-6- (trifluoromedιyl)-3,5-pyridinedicarbothioate, mecoprop, mefenacet, mefluidide, methalpropalin, methabenzdiiazuron, metham, methazole, methoxuron, metolachlor, metribuzin, 1 ,2-dihy dropyridazine-3 ,6-dione , molinate, monolinuron, monuron, monuron salt and trichloroacetic acid, monosodium salt of methylarsonic acid, napropamide, naptalam, neburon, nicosulfuron, nitralin, nitrofen, nitrofluorfen, norea, norflurazon, oryzalin, oxadiazon, oxyfluorfen, paraquat, pebulate, pendimethalin,

perfluidone, phenmedipham, picloram, 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2- nitroacetophenone oxime-O-acetic acid methyl ester, pretilachlor, primisulfuron, procyazine, profluralin, prometon, prometryn, pronamide, propachlor, propanil, propazine, propham, prosulfalin, prynachlor, pyrazolate, pyrazon, pyrazosulfuron ethyl, quinchlorac, quizalofop ethyl, rimsulfiiron, secbumeton, setiioxydim, siduron, simazine, l-(α,α-dimethylbenzyl)-3-(4-methylphenyl)urea, sulfometuron methyl, trichloroacetic acid, tebutiiiuron, terbacil, terbuchlor, terbuthylazine, terbutol, terbutryn, thifensulfuron methyl, thiobencarb, tri-allate, trialkoxydim, triasulfuron, tribenuron methyl, triclopyr, tridiphane, trifluralin, trimeturon, (2,4-dichlorophenoxy)acetic acid, 4-(2,4-dichloro- phenoxy )butanoic acid, vernolate, and xylachlor.

In certain instances, combinations with other herbicides having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management.

A herbicidally effective amount of die compounds of tiiis invention is determined by a number of factors. These factors include: formulation selected, metiiod of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of a compound(s) of this invention is applied at rates from about 0.005 to 5.0 kg/ha with a preferred rate range of 0.010 to 2.0 kg/ha. One skilled in die art can easily determine application rates necessary for the desired level of weed control.

The following Tests demonstrate die control efficacy of the compounds of this invention against specific weeds. The weed control afforded by die compounds is not limited, however, to tiiese species. See Index Tables A and B for compound descriptions. Index Table A

Im

Compounds of Formula Im wherein:

Index Table B

Compounds of Foπnula In wherein:

C φd 34: R ¹ = 5-F oil ¹ Cknpd35: R! =7-α oil ¹ Qnpd40: ιr_p l51-157 ^o C

¹ *H NMR data for oils and glass in Index Table C. d = decomposed

Index Table C Cmpd 'H NMR Data

No (solvent = CDθ3 unless otherwise indicated, in ppm downfield from tetramethylsilane) 1 7.55 (s,lH), 7.2 (s,lH), 4.8 (s,2H), 4.4 (m,lH), 3.75 (m,2H), 3.2 (s.lH), 3.0 (m,lH),

2.75 (m,lH), 2.6 (s,lH), 2.1 (mJH J^ (m.lH). 5 7.78 (d,2H), 7.55 (s,lH), 7.50 (s,lH), 7.35 (d,2H), 5.27 (t,lH), 4.0 (m,lH), 3.61 (m,lH), 2.45 (s,3H), 2.1-2.5 (m,4H).

7 7.6 (s,lH), 7.1 (S.1H), 4.8 (q,2H), 4.6 (m,lH), 4.0 (m,lH), 3.8 (m,lH), 3.2 (m,lH), 3.0 (m.lH), 2.6 (m.lH), 2.4 (m,2H).

8 7.55 (s,lH), 7.2 (s,lH), 5.4, 5.2 (2m, 1H), 4.8 (d,2H), 4.1 (m,lH), 3.8-3.6 (4d,lH), 2.95 (m,2H), 2.6 (m,lH), 2.5 (m,lH), 2.0 (m,lH).

7.55 (s.lH), 7.2 (s,lH), 4.8 (s,2H), 4.4 (s,2H), 3.15 (m,2H), 2.8 (m,2H), 2.6 (s,lH). 7.55 (s,lH), 7.2 (s.lH), 5.4 (m,lH), 4.8 (s,2H), 3.95 (m,lH), 3.8 (dd,lH), 2.9 (m,2H), 2.6 (s,lH), 2.3 (m,lH), 2.1 (s,3H), 2.0 (m,lH). 7.55 (s,lH), 7.2 (s.lH), 5.6, 5.5 (2m,lH), 4.8 (s,2H), 4.0 (m,lH), 3.55 (m,lH), 2.6 (m,lH), 2.5-1.8 (m,4H). 7.55 (s,lH), 7.2 (s,lH), 5.15 (t,lH), 4.8 (s,2H), 3.95 (m,lH), 3.6 (m,lH), 2.6 (m,lH), 2.5-2.0 (m,4H). 7.81 (d,2H), 7.63 (s.lH), 7.50 (s.lH), 7.35 (d,2H), 4.62 (dd,lH), 4.15 (m.lH), 3.89 (m.lH), 3.71 (m,lH), 3.55 (d,lH), 2.77 (d,lH), 2.46 (s,3H), 2.36 (m,lH), 2.1 (m,lH). 7.55 (s,lH), 7.15 (m,lH), 5.95 (m,lH), 4.8 (s,2H), 3.85 (m,lH), 3.6 (m,lH), 2.6 (S,1H), 2.2-2.0 (m,4H), 2.15 (s,3H). (solvent = (CD ₃ ) ₂ SO) 7.85 (s.lH), 7.35 (s.lH), 6.13 (d,lH), 5.44 (d,lH), 4.97 (d, 2H), 4.35 (m,lH), 3.95 (m,lH), 3.70 (t,lH), 3.65 (m,lH), 3.5 (m,lH), 2.15 (m,lH), 1.9 (m.lH). 7.78 (d,2H), 7.60 (s.lH), 7.50 (s.lH), 7.34 (d,2H), 4.85 (m,lH), 2.78 (d,lH), 2.45 (s,3H), 2.25 (m.lH), 2.0 (m,3H). 7.77 (d,2H), 7.60 (s,lH), 7.53 (s,lH), 7.30 (d,2H), 4.00 (m,2H), 2.86 (m,2H), 2.46 (s,3H), 2.42 (m,2H). (solvent = (CD ₃ ) ₂ SO) 7.92 (s.lH), 7.42 (s,lH), 4.98 (d,2H), 3.8 (t,2H), 3.70 (t,lH), 2.75 (t,2H), 2.25 (m,2H). 7.54 (s,lH), 7.16 (s,lH), 4.77 (d,2H), 4.40 (m,lH), 3.75-3.90 (m,2H), 3.6 (t,lH), 2.9- 3.0 (m,2H), 2.6 (m.lH), 2.0-2.2 (m,2H). 7.9 (m,2H), 7.1 (m,2H), 4.5 (m.lH), 3.8 (m,2H), 3.0 (m.lH), 2.8 (m,lH), 2.2 (m.lH), 1.9 (m,lH), 1.6 (br s,lH). 7.55 (S.1H), 7.2 (s,lH), 4.8 (s,2H), 4.6 (m,lH), 4.0 (m,2H), 3.15 (m,lH), 2.9 (m.lH), 2.6 (m,lH), 2.3 (m,2H). 7.55 (S.1H), 7.2 (s,lH), 6.3, 6.15 (2t,lH), 4.8 (d,2H), 3.0 (m,lH), 2.7 (m,lH), 2.6 (m,lH), 2.5 (m,lH), 2.2-1.8 (m,3H). 7.55 (S,1H), 7.2 (s,lH), 6.2 (m.lH), 4.8 (t,2H), 3.0 (m.lH), 2.8 (m,lH), 2.6 (m,lH), 2.6-2.0 (m,4H) 7.55 (s,lH), 7.2 (s,lH), 4.8 (d,2H), 4.6 (m,lH), 4.0-3.8 (m,2H), 3.2 (m,2H), 2.65 (m,lH), 2.6 (m.lH), 2.4 (m.lHJ ^ 7.6 (S,1H), 7.2 (s,lH), 5.4, 5.2 (2q,lH), 4.8 (d,2H), 4.0-3.75 (m,2H), 3.3-2.8 (m,2H), 2.6 (m,lH), 2.5 (m,lH), 2.2-2.0 (m,lH). (solvent = (CD ₃ ) ₂ SO) 10.9 (s,lH), 7.65 (s,lH), 7.02 (s.lH), 5.22 (d,lH), 4.17 (m.lH), 3.55 (m,2H), 2.80 (m.lH), 2.59 (dd,lH), 1.95 (m,2H). (solvent = (CD ₃ ) ₂ SO) 11.1 (s,lH), 7.75 (s.lH), 7.09 (s,lH), 3.78 (t,2H), 2.74 (d,2H), 2.25 (m,2H).

34 7.55 (s,lH), 7.2 (s,lH), 6.4, 6.2 (2d,lH), 4.8 (s,2H), 3.2-2.6 (m,4H), 2.6 (s,lH).

35 7.55 (s,lH), 7.2 (s.lH), 5.2 (d,lH), 4.8 (d,2H), 4.0 (m,2H), 2.8 (m,2H), 2.6 (m,lH).

36 7.80 (d,2H), 7.62 (s,lH), 7.48 (s,lH), 7.34 (d,2H), 6.43 (m,2H), 3.89 (t,2H), 2.69 (dt,2H), 2.45 (s,3H).

37 7.46 (S,1H), 7.10 (s,lH), 6.4 (m,2H), 3.89 (t,2H), 2.65 (m,2H).

39 7.6 (S,1H), 7.35 (s,lH), 6.7 (t,lH), 3.9 (t,2H), 2.7 (q,2H), 2.35 (s,3H).

TEST A Seeds of barley (Hordeum vulgare), barnyardgrass (Echinochloa crus-gallϊ), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), cheatgrass (Bromus secalinus), chickweed (Stellaria media), cocklebur (Xanthium pensylvanicum), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria spp.), downy brome (Bromus tectorum), giant foxtail (Setaria faberii), lambsquarters (Chenopodium album), morninggloiy (Ipomoea hederacea), rape (Brassica napus), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glycine max), sugar beet (Beta vulgaris), velvedeaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), wild oat (Avenafatua) and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence widi test chemicals dissolved in a non-phytotoxic solvent. At die same time, these crop and weed species were also treated with postemergence applications of test chemicals. Plants ranged in height from two to eighteen cm (one to four leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for twelve to sixteen days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table A, are based on a scale of 0 to 10 where 0 is no effect and 10 is complete control. A dash (-) response means no test result.

TEST B Seeds of barnyardgrass (EchinochJoa crus-galli), cheatgrass (Bromus secalinus), cocklebur (Xanthium pensylvanicum), crabgrass (Digitaria spp.), giant foxtail (Setaria faberiϊ), morningglory (lpomoea spp.), sorghum (Sorghum bicolor), velvedeaf (Abutilon theophrasti), and wild oat (Avenafatua) were planted into a sandy loam soil and treated preemergence, or with a soil drench(PDRN), with test chemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species were also treated postemergence, or sprayed to runoff(STRO), with test chemicals. Plants ranged in height from two to eighteen cm and were in die two to three 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 B, 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.

TEST C The compounds evaluated in this test were formulated in a non- phytoxic solvent and applied to die soil surface before plant seedlings emerged (preemergence application), to water that covered the soil surface (flood application), and to plants diat were in the one-to-four leaf stage (postemergence application). A sandy loam soil was used for the preemergence and postemergence tests, while a silt loam soil was used in the flood test. Water depdi was approximately 2.5 cm for the flood test and was maintained at this level for the duration of the test.

Plant species in the preemergence and postemergence tests consisted of barnyardgrass (Echinochloa crus-galli), barley (Hordeum vulgare), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium pensylvanicum), com (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setaria faberii), johnsongrass (Sorghum halpense), lambsquarters (Chenopodium album), morningglory (Ipomoea hederacea), pigweed (Amaranthus retroflexus), rape (Brassica napus), ryegrass (Lolium multiflorum), sorghum (Sorghum bicolor), soybean (Glycine max), speedwell (Veronica persica), sugar beet (Beta vulgaris), velvedeaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), and wild oat (Avenafatua). All plant species were planted one day before application of die compound for die preemergence portion of this test. Plantings of these species were adjusted to produce plants of appropriate size for the postemergence portion of die test. Plant species in die flood test consisted of rice (Oryza sativa), umbrella sedge (Cyperus difformis), duck salad (Heteranthera limosa), barnyardgrass (Echinochloa crus-galli) and Late watergrass (Echinocloa oryzicola) grown to die 1 and 2 leaf stage for testing. All plant species were grown using normal greenhouse practices. Visual evaluations of injury expressed on treated plants, when compared to untreated controls, were recorded approximately fourteen to twenty one days after application of die test compound. Plant response ratings, summarized in Table C, were recorded on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result.

Blackgrass 100 40 50 45

Chickweed 85 45 30 35

Cocklebur 55 65 65 70

Corn 50 65 35 50

Cotton 100 100 100 100

Crabgrass 35 65 80 90

Downy Brome 90 55 45 90

Duck salad 35 20 50 90

Galium 100 60 65 70

Giant foxtail 95 95 80 95 Italn. Rygrass 100 90 80 100

Italn. Rygrass 100 55 75 100 Johnsongrass 100 95 100 100

Johnsongrass 100 95 100 100 Lambsquarters 100 100 100 100

Lambsquarters 100 100 100 95 Morningglory 85 30 65 95

Morningglory 100 100 100 95 Rape 100 95 95 100

Rape 100 100 100 100 Redroot Pigweed 100 100 90 100 Redroot Pigweed 100 90 100 100 Soybean 60 25 40 90

Rice Japonica 95 80 95 90 Speedwell 100 55 100 100

Soybean 85 75 90 90 Sugar beet 100 100 100 100

Speedwell 100 100 100 Velvetleaf 100 100 100 100

Sugar beet 100 100 100 100 Wheat 80 45 35 95

Umbrella sedge 100 60 45 90 Wild buckwheat 100 100 100 100

Velvetleaf 100 100 100 100 Wild oat 100 55 60 70

Watergrass 2 100 100 90 95

Wheat 100 35 45 100

Wild buckwheat 100 100 100 100

Wild oat 100 60 65 95

2 Leaf BYG 100 100 100 95

Table C COMPOUND Table C COMPOUND

Rate 125 g/ha 11 12 14 20 Rate 125 g/ha 11 12 14 20

POSTEMERGENCE PREEMERGENCE

Barley Igri 65 35 45 85 Barley Igri 70 15 25 55

Barnyardgrass 100 95 85 80 Barnyardgrass 95 100 100 100

Blackgrass 100 40 50 45 Blackgrass 100 80 60 95

Chickweed 85 45 30 35 Chickweed 100 0 25 60

Cocklebur 55 65 65 70 Cocklebur 35 0 85 65

Corn 50 65 35 50 Corn 65 0 85 70

Cotton 100 100 100 100 Cotton 95 0 90 85

Crabgrass 35 65 80 90 Crabgrass 100 95 100 100

Downy Brome 90 55 45 90 Downy Brome 90 10 30 55

Duck salad 35 20 50 90 Galium 100 80 90 30

Galium 100 60 65 70 Giant foxtail 100 100 100 100

Giant foxtail 95 95 80 95 Italn. Rygrass 100 90 80 100

Italn. Rygrass 100 55 75 100 Johnsongrass 100 95 100 100

Johnsongrass 100 95 100 100 Lambsquarters 100 100 100 100

Lambsquarters 100 100 100 95 Morningglory 85 30 65 95

Morningglory 100 100 100 95 Rape 100 95 95 100

Rape 100 100 100 100 Redroot Pigweed 100 100 90 100

Redroot Pigweed 100 90 100 100 Soybean 60 25 40 90

Rice Japonica 95 80 95 90 Speedwell 100 55 100 100

Soybean 85 75 90 90 Sugar beet 100 100 100 100

Speedwell 100 100 100 Velvetleaf 100 100 100 100

Sugar beet 100 100 100 100 Wheat 80 45 35 95

Umbrella sedge 100 60 45 90 Wild buckwheat 100 100 100 100

Velvetleaf 100 100 100 100 Wild oat 100 55 60 70

Watergrass 2 100 100 90 95

Wheat 100 35 45 100

Wild buckwheat 100 100 100 100

Wild oat 100 60 65 95

2 Leaf BYG 100 100 100__-55^

Table C COMPOUND

Rate 62 g/ha 11 12 14 20 22

POSTEMERGENCE

Barley Igri 65 35 45 85 0

Barnyardgrass 100 65 45 80 95

Blackgrass 95 40 50 35 65

Chickweed 80 30 30 20 95

Cocklebur 50 45 45 45 95

Corn 35 30 35 50 60

Cotton 100 100 100 100 100

Crabgrass 35 35

Downy Brome 85 50

Duck salad 30 0

Galium 100 55

Giant foxtail 95 90

Italn. Rygrass 95 50

Johnsongrass 90 95

Lambsquarters 100 100

Morningglory 100 95

Rape 100 100

Redroot Pigweed 100 90

Rice Japonica 95 70

Soybean 80 75

Speedwell 100 95

Sugar beet 100 100

Umbrella sedge 95 30

Velvetleaf 100 90

Watergrass 2 100 100

Wheat 95 30

Wild buckwheat 100 95

Wild oat 95 60

2 Leaf BYG 100 100

Table C COMPOUND

Rate 31 g/ha 11 12 14 20 22

PREEMERGENCE

Barley Igri

Barnyardgrass

Blackgrass

Chickweed

Cocklebur Corn

Wild buckwheat 45 Wild oat 0

TEST D Seeds of barnyardgrass (Echinochloa crus-galli), bindweed (Convolvulus erubescens), black nightshade (Solanum ptycanthum dunal), cassia (Cassia unifloria), 5 cocklebur (Xanthium pensylvanicum), common ragweed (Ambrosia artemisiifolia), com (Zea mays), cotton (Gossypium hirsutam), crabgrass (Digitaria spp.), fall panicum (Panicum dichotomiflorum), giant foxtail (Setaria faberii), green foxtail (Setaria viridis), jimsonweed (Datura stramonium), Johnson grass (Sorghum halepense), lambsquarter (Chenpopdium album), morningglory (Ipomoea spp.), pigweed 0 (Amaranthus retroflexus), prickly sida (Sida spinosa), shattercane (Sorghum vulgare), signalgrass (Brachiaria platyphylla), smartweed (Polygonum persicaria), soybean (Glycine max), sunflower (Helianthus annuus), velvedeaf (Abutilon theophrasti), wild proso (Pancium miliaceum), wooly cup grass (Eriochloa villosa), yellow foxtail (Setaria lutescens) and purple nutsedge (Cyperus rotundus) tubers were planted into a 5 matapeake sandy loam soil. These crops and weeds were grown in die greenhouse until die plants ranged in height from two to eighteen cm (one to four leaf stage), then treated postemergence widi die test chemicals dissolved in a non-phytotoxic solvent. Pots receiving tiiese postemergence treatments were placed in the greenhouse and maintained according to routine greenhouse procedures. Treated plants and 0 untreated controls were maintained in the greenhouse approximately 14-21 days after application of die test compound. Visual evaluations of plant injury responses were tiien recorded. Plant response ratings, summarized in Table D, are reported on a 0 to 100 scale where 0 is no effect and 100 is complete control.

Table D COMPOUND Rate 140 g/ha 12 PREEMERGENCE Barnyardgrass 100 Bindweed 100 Blk Nightshade 100

Seeds, rhizomes, or plant parts of alfalfa (Medicago sativa), annual bluegrass (Poa annua), bermudagrass (Cynodon dactylon), broadleaf signalgrass (Brachiaria platyphylia), common purslane (Portulaca oleracea), common ragweed (Ambrosia artemisiifolia), dallisgrass (Paspalum dilatatum), goosegrass (Eleusine indica), guineagrass (Panicum maximum), itchgrass (Rottboellia cochinchinensis), johnsongrass

(Sorghum halepense), large crabgrass (Digitaria sanguinalis), peanut (Arachis hypoagaea), pitted morningglory (Ipomoea lacunosa), purple nutsedge (Cyperus rotundus), sandbur (Southern sandbur), smooth crabgrass (Digitaria ischaemum) were planted into greenhouse pots containing greenhouse planting medium. Each pot contained only one plant species.

The test compound was dissolved in a non-phytotoxic solvent and applied preemergence and/or postemergence to die plants. Preemergence applications were made widiin one day of planting die seeds or plant parts. Postemergence applications were applied when the plants were in die two to four leaf stage (three to twenty cm). Untreated control plants and treated plants were placed in die greenhouse and visually evaluated for injury at 14 to 28 days after herbicide application. Plant response ratings, summarized in Table E, are based on a 0 to 100 scale where 0 is no injury and 100 is complete control. A dash (-) response indicates no test result.