HERBICIDAL COMPOUNDS

Abstract

The present invention relates to compounds of Formula (I), or an agronomically acceptable salt of said compounds wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are as defined herein. The invention further relates to herbicidal compositions which comprise a compound of Formula (I) and to the use of compounds of Formula (I) for controlling weeds, in particular in crops of useful plants.

##STR00001##

Claims

1. A compound of Formula (I): ##STR00297## or an agronomically acceptable salt thereof, wherein X is CH or N, R.sup.1 is selected from the group consisting of hydrogen, C.sub.1-C.sub.10alkylC(O)—, C.sub.1-C.sub.10alkylOC(O)—, C.sub.1-C.sub.10alkylSC(O)—and R.sup.5R.sup.6NC(O)—; R.sup.2 is selected from the group consisting of halogen NO.sub.2, CN, C.sub.1-C.sub.6haloalkylS(O).sub.p—, C.sub.1-C.sub.6alkyl-S(O).sub.p—, C.sub.2-C.sub.4alkenyl-, C.sub.2-C.sub.4alkynyl-, C.sub.1-C.sub.4haloalkyl and C.sub.1-C.sub.4haloalkoxy-; R.sup.3 is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy- and C.sub.1-C.sub.4haloalkoxy-; R.sup.4 is phenyl or a five or six-membered heteroaryl, the heteroaryl containing from one to three heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the phenyl or heteroaryl may be optionally substituted by one or more substituents independently selected from the group consisting of halogen, C.sub.1-C.sub.6alkyl-, C.sub.2-C.sub.4alkenyl-, C.sub.2-C.sub.4alkynyl-, C.sub.1-C.sub.6haloaklkyl-, C.sub.1-C.sub.6alkoxy-, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.3alkyl-, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.3alkoxy-, C.sub.1-C.sub.6haloalkoxy-, C.sub.1-C.sub.6alkyl-S(O).sub.p—, C.sub.1-C.sub.6haloalkyl-S(O).sub.p—, C.sub.3-C.sub.6cycloalkyl- (optionally substituted by 1 or 2 halogen), cyano and nitro; or R.sup.4 is R.sup.4a ##STR00298## and R.sup.5 is hydrogen or C.sub.1-C.sub.10alkyl; R.sup.6 is hydrogen or C.sub.1-C.sub.10alkyl; R.sup.7 and R.sup.8 are independently selected from the group consisting of hydrogen and halogen; and p=0, 1 or 2; wherein said compound is not selected from the group consisting of 2-(3-bromo-5-cyano-2-hydroxyphenyl)pyridine, 3-chloro-2-ethoxy-4-hydroxy-5-phenyl-benzonitrile, 4-hydroxy-3-nitro-5-[3-(trifluoromethyl)phenyl]benzonitrile and 2′-fluoro-6-hydroxy-5-nitrobiphenyl-3-carbonitrile.

2. A compound according to claim 1, wherein R.sup.1 is hydrogen.

3. A compound according to claim 1 or claim 2, wherein R.sup.2 is selected from the group consisting of F, Cl, Br, —CF.sub.3 and —OCF.sub.3.

4. A compound according to claim 3, wherein R.sup.2 is CF.sub.3.

5. A compound according to any one of the previous claims, wherein R.sup.3 is hydrogen.

6. A compound according to any one of claims 1 to 5, wherein R.sup.4 is phenyl.

7. A compound according to any one of claims 1 to 5, wherein R.sup.4 is an optionally substituted five or six-membered heteroaryl selected from the group consisting of furanyl, thiophenyl, thiazolyl, oxazolyl, isoxazolyl, pyrazolyl, isothiazolyl, pyridyl, pyridazinyl, pyrazinyl, pyrimidinyl and triazolyl.

8. A compound according to claim 7, wherein R.sup.4 is an optionally substituted five or six-membered heteroaryl selected from the group consisting of pyrazolyl, thiazolyl and thiophenyl.

9. A compound according to claim 8, wherein R.sup.4 is pyridyl or pyrazolyl.

10. A compound according to any one of the previous claims, wherein X is CH.

11. A herbicidal composition comprising a compound according to any one of the previous claims and an agriculturally acceptable formulation adjuvant.

12. A herbicidal composition according to claim 11, further comprising at least one additional pesticide.

13. A herbicidal composition according to claim 12, wherein the additional pesticide is a herbicide or herbicide safener.

14. A method of controlling weeds at a locus comprising application to the locus a composition comprising a weed controlling amount of a compound of Formula (I): ##STR00299## or an agronomically acceptable salt thereof, wherein X is CH or N, R.sup.1 is selected from the group consisting of hydrogen, C.sub.1-C.sub.10alkylC(O)—, C.sub.1-C.sub.10alkylOC(O)—, C.sub.1-C.sub.10alkylSC(O)— and R.sup.5R.sup.6NC(O)—; R.sup.2 is selected from the group consisting of halogen NO.sub.2, CN, C.sub.1-C.sub.6haloalkylS(O).sub.p—, C.sub.1-C.sub.6alkyl-S(O).sub.p—, C.sub.2-C.sub.4alkenyl-, C.sub.2-C.sub.4alkynyl-, C.sub.1-C.sub.4haloalkyl and C.sub.1-C.sub.4haloalkoxy-; R.sup.3 is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy- and C.sub.1-C.sub.4haloalkoxy-; R.sup.4 is phenyl or a five or six-membered heteroaryl, the heteroaryl containing from one to three heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the phenyl or heteroaryl may be optionally substituted by one or more substituents selected from the group consisting of halogen, C.sub.1-C.sub.6alkyl-, C.sub.2-C.sub.4alkenyl-, C.sub.2-C.sub.4alkynyl-, C.sub.1-C.sub.6haloalkyl-, C.sub.1-C.sub.6alkoxy-, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.3alkyl-, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.3alkoxy-, C.sub.1-C.sub.6haloalkoxy-, C.sub.1-C.sub.6alkyl-S(O).sub.p—, C.sub.1-C.sub.6haloalkyl-S(O).sub.p—, C.sub.3-C.sub.6cycloalkyl- (optionally substituted by 1 or 2 halogen), cyano and nitro; or R.sup.4 is R.sup.4a ##STR00300## and R.sup.5 is hydrogen or C.sub.1-C.sub.10alkyl; R.sup.6 is hydrogen or C.sub.1-C.sub.10alkyl; R.sup.7 and R.sup.8 are independently selected from the group consisting of hydrogen and halogen; and p=0, 1 or 2.

15. Use of a compound of a compound of Formula (I): ##STR00301## or an agronomically acceptable salt thereof, wherein X is CH or N, R.sup.1 is selected from the group consisting of hydrogen, C.sub.1-C.sub.10alkylC(O)—, C.sub.1-C.sub.10alkylOC(O)—, C.sub.1-C.sub.10alkylSC(O)—and R.sup.5R.sup.6NC(O)—; R.sup.2 is selected from the group consisting of halogen NO.sub.2, CN, C.sub.1-C.sub.6haloalkylS(O).sub.p—, C.sub.1-C.sub.6alkyl-S(O).sub.p—, C.sub.2-C.sub.4alkenyl-, C.sub.2-C.sub.4alkynyl-, C.sub.1-C.sub.4haloalkyl and C.sub.1-C.sub.4haloalkoxy-; R.sup.3 is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy- and C.sub.1-C.sub.4haloalkoxy-; R.sup.4 is phenyl or a five or six-membered heteroaryl, the heteroaryl containing from one to three heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the phenyl or heteroaryl may be optionally substituted by one or more substituents selected from the group consisting of halogen, C.sub.1-C.sub.6alkyl-, C.sub.2-C.sub.4alkenyl-, C.sub.2-C.sub.4alkynyl-, C.sub.1-C.sub.6haloalkyl-, C.sub.1-C.sub.6alkoxy-, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.3alkyl-, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.3alkoxy-, C.sub.1-C.sub.6haloalkoxy-, C.sub.1-C.sub.6alkyl-S(O).sub.p—, C.sub.1-C.sub.6haloalkyl-S(O).sub.p—, C.sub.3- C.sub.6cycloalkyl- (optionally substituted by 1 or 2 halogen), cyano and nitro; or R.sup.4 is R.sup.4a ##STR00302## and R.sup.5 is hydrogen or C.sub.1-C.sub.10alkyl; R.sup.6 is hydrogen or C.sub.1-C.sub.10alkyl; R.sup.7 and R.sup.8 are independently selected from the group consisting of hydrogen and halogen; and p=0, 1 or 2; as a herbicide.

Description

Example 1. Synthesis of 3-bromo-4-hydroxy-5-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile—Compound 1.007

Step 1 Synthesis of 4-methoxy-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile

[0112] ##STR00011##

[0113] A 25mL round bottomed flask was charged with a stirrer bar, (5-cyano-2-methoxy-phenyl)boronic acid (4.3 mmol, 0.76 g), 3-iodo-1-methyl-5-(trifluoromethyl)pyrazole (4 mmol, 1.10 g) and bis(triphenylphosphine)palladium dichloride (0.4 mmol, 0.28 g). Acetonitrile (10 mL) was added followed by and potassium carbonate (6 mmol, 0.82927 g) and mixture was heated at reflux. After 3 h, the reaction was diluted with dichloromethane (15 mL), washed with and brine (10 mL), dried with MgSO.sub.4 and concentrated. The crude product was then purified by chromatography (gradient elution EtOAc/Hexane) to afford 4-methoxy-3-[-1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile (665 mg, 60%) as an off white solid.

[0114] .sup.1HNMR (CDCl.sub.3) δ 8.28 (d, 1H), 7.51 (dd, 1H), 7.12 (s, 1H), 7.02 (1H, d), 5.04 (3H, s), 3.59 (3H, s).

Step 2 Synthesis of 4-hydroxy-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile

[0115] ##STR00012##

[0116] To a solution of 4-methoxy-3-[-1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile (0.65 g, 2.312 mmol) in anhydrous dichloromethane (20 mL) at 0° C. and under nitrogen was added boron tribromide (1M solution in DCM) (8.090 mL, 8.090 mmol) dropwise. Once addition was complete, the reaction mixture was allowed to warm to room temperature and stirred for a further 2 h. The reaction was carefully quenched with water and then extracted with dichloromethane (3×10 mL). The organics were combined, washed with brine, dried over magnesium sulfate and concentrated in vacuo to afford 4-hydroxy-3-[-1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile yellow solid (600 mg, 97%).

[0117] .sup.1HNMR (CDCl.sub.3) δ 10.80 (s, 1H), 7.82 (d, 1H), 7.51 (dd, 1H), 7.09 (1H, d), 7.01 (1H, s), 4.08 (3H, s).

Step 3 Synthesis of 3-bromo-4-hydroxy-5-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile—Compound 1.007

[0118] ##STR00013##

[0119] To a stirred solution of 4-hydroxy-3-[-1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile (0.580 g, 2.1706 mmol,) in acetonitrile (10 mL) was added 1-bromopyrrolidine-2,5-dione (0.579 g, 3.25 mmol), in one portion, and the mixture was heated at reflux for 2 h. The mixture was then diluted with EtOAc and washed with water (10 mL) and Brine (10), dried (MgSO4) and purified by chromatography to afford 3-bromo-4-hydroxy-5-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]benzonitrile (450 mg, 60%).

[0120] .sup.1HNMR (CDCl.sub.3) δ 11.59 (s, 1H), 7.80 (s, 1H), 7.36 (s, 1H), 7.03 (s, 1H), 4.09 (3H, s).

Example 2. Synthesis of 4-bromo-6-(3-fluorophenyl)-5-hydroxy-pyridine-2-carbonitrile (Compound 1.040) and 6-bromo-4-(3-fluorophenyl)-5-hydroxy-pyridine-2-carbonitrile (Compound 1.039)

Step 1 Synthesis of (2,4-dibromo-6-cyano-3-pyridyl) acetate

[0121] ##STR00014##

[0122] 4,6-dibromo-5-hydroxy-pyridine-2-carbonitrile (1 g, 3.5984 mmol), dichloromethane (10 mL) N,N-diethylethanamine (1.2 equiv., 4.3181 mmol) were combined in a 50mL round bottomed flask and acetyl chloride (1.1 equiv., 3.9583 mmol) was added dropwise. After stirring at room temperature for 5 h, the mixture was washed with water (15 mL) and brine (15 mL), dried (MgSO4) and concentrated to afford a 2,4-dibromo-6-cyano-3-pyridyl) acetate 1.07g (93%).

[0123] .sup.1HNMR (CDCl.sub.3) δ 7.91 (s,1H), 2.46 (s, 3H).

Step 2 Synthesis of 4-bromo-6-(3-fluorophenyl)-5-hydroxy-pyridine-2-carbonitrile and 6-bromo-4-(3-fluorophenyl)-5-hydroxy-pyridine-2-carbonitrile

[0124] ##STR00015##

[0125] (2,4-dibromo-6-cyano-3-pyridyl) acetate (0.2 g, 0.625 mmol), (3-fluorophenyl)boronic acid (87 mg 0.625 mmol,) and bis(triphenylphosphine)palladium(II)dichloride (22 mg, 0.031 mmol) were weighed into a microwave vial. Acetonitrile (5 mL) was added followed by a stirrer bar and sodium carbonate (1.2502 mmol). The vial was sealed and heated for 10 min at 130° C. in the microwave. The mixture was diluted with EtOAc (15 mL) and washed with 2M HCl (10 mL), and brine (10 mL), dried with MgSO.sub.4 and concentrated. The resulting crude product was purified by RPHPLC (to afford the separated isomers 4-bromo-6-(3-fluorophenyl)-5-hydroxy-pyridine-2-carbonitrile (15 mg) and 6-bromo-4-(3-fluorophenyl)-5-hydroxy-pyridine-2-carbonitrile (10 mg).

[0126] 4-bromo-6-(3-fluorophenyl)-5-hydroxy-pyridine-2-carbonitrile .sup.1HNMR (DMSO-d.sub.6) δ 8.31 (s,1H), 7.73 (t, 2H), 7.53 (q, 1H), 7.29 (td, 1H).

[0127] 6-bromo-4-(3-fluorophenyl)-5-hydroxy-pyridine-2-carbonitrile .sup.1HNMR (DMSO-d.sub.6) δ 7.98 (s,1H), 7.58-7.48 (m, 3H), 7.28-7.24 (m,1H).

Example 3. Synthesis of 3-bromo-5-(3-fluorophenyl)-4-hydroxy-benzonitrile—Compound 1.046.

Step 1 Synthesis of (2,6-dibromo-4-cyano-phenyl) acetate

[0128] ##STR00016##

[0129] 3,5-dibromo-4-hydroxy-benzonitrile (5 g, 18.05 mmol) was weighed into a 250 ml round bottom flask and a stirrer bar added. Dichloromethane (100 mL) was added followed by triethylamine (1.1 equiv, 19.862 mmol) and the flask was cooled in an ice-bath. Acetyl chloride (1.1 equiv., 19.862 mmol) was added dropwise into the reaction mixture which was stirred for 1 h . The reaction mixture was washed with water (100ml×3) and the organic phase dried (MgSO4). The mixture was concentrated, in vacuo to afford the desired product (5.5 g, 96%).

[0130] .sup.1HNMR (CDCl.sub.3) δ 7.88 (s, 2H), 2.42 (s, 3H).

Step 2 Synthesis of 3-bromo-5-(3-fluorophenyl)-4-hydroxy-benzonitrile

[0131] ##STR00017##

[0132] To a microwave tube, charged with a stirrer bar, was added (3-fluorophenyl)boronic acid (91 mg, 0.65 mmol), bis(triphenylphosphine)palladium (II) dichloride) (0.05 equiv., 0.0325 mmol), and (2,6-dibromo-4-cyano-phenyl) acetate (207 mg, 0.65 mmol) in acetonitrile (5 mL). A 1 molar solution of Sodium carbonate (2 eq. 1.3 mmol, 1.3 mL), was added and the tube was capped and microwaved at 150° C. for 15 mins. The reaction mixture was passed through a SiTMT SPE cartridge. The mixture was then concentrated in vacuo and the residue re-dissolved in 10% MeOH in DMSO and purified by mass directed RPHPLC to afford the 3-bromo-5-(3-fluorophenyl)-4-hydroxy-benzonitrile (32 mg, 15%).

[0133] .sup.1HNMR (CDCl.sub.3) δ 7.85 (d, 1H), 7.53 (1H, d), 7.50-7.46 (1H, m), 7.27-7.18 (3H, m), 6.20 (1H, bs).

Example 4. Synthesis of 3-chloro-4-hydroxy-5-[4-(trifluoromethyl)pyrazol-1-yl]benzonitrile—Compound 1.001

[0134] ##STR00018##

[0135] To a stirred solution of 3-bromo-5-chloro-4-hydroxy-benzonitrile (0.100 g, 0.430 mmol) in anhydrous N,N-dimethylformamide (3.00 mL) , 4-(trifluoromethyl)-1H-pyrazole (0.0820 g, 0.602 mmol), Cesium carbonate (0.280 g, 0.860 mmol) and Copper iodide (0.0164 g, 0.0860 mmol) were added at RT. The reaction mixture was purged with nitrogen for 15 min and then heated at 120° C. in a sealed tube for 24 hrs. Then the reaction mass was diluted with EtOAc and passed through the bed of silica gel and concentrated to afford the crude product. Purification by chromatography, eluting with 0 to 20% EtOAc in hexane, affords 3-chloro-4-hydroxy-5-[4-(trifluoromethyl)pyrazol-1-yl]benzonitrile (10 mg, 8%).

[0136] .sup.1HNMR (400MHz,DMSO): δ 8.93 (s, 1H), 8.27 (s, 1H), 8.11-8.10 (m, 2H).

Example 5. Synthesis of 4-hydroxy-3-thiazol-2-yl-5-(trifluoromethyl)benzonitrile

Step 1 Synthesis of 3-bromo-4-hydroxy-5-(trifluoromethyl)benzonitrile

[0137] ##STR00019##

[0138] To a stirred solution of 4-hydroxy-3-(trifluoromethyl)benzonitrile (4.5 g, 24 mmol,) in acetonitrile (30 mL) was added N-bromosuccinimide (4.3 g, 24 mmol), in one portion, and the mixture was heated at reflux for 1.5 h. The mixture was allowed to cool to room temperature and then dry-loaded on silica and purified by chromatography using a EtOAc/cyclohexane gradient elution to afford 3-bromo-4-hydroxy-5-(trifluoromethyl)benzonitrile (6.4 g).

[0139] .sup.1H NMR (400 MHz, chloroform) δ ppm 7.99 (d, J=1.83 Hz, 1H) 7.85 (d, J=1.34 Hz, 1H) 6.34-6.90 (br s, 1H).

Step 2 Synthesis of 3-bromo-4-[(4-methoxyphenyl)methoxy]-5-(trifluoromethyl)benzonitrile

[0140] ##STR00020##

[0141] To a solution of 3-bromo-4-hydroxy-5-(trifluoromethyl)benzonitrile (6.4 g, 24 mmol) in acetone (64 mL) were added potassium carbonate (6.7 g, 48 mmol), tetrabutylammonium iodide (1.8 g, 4.8 mmol) and 1-(chloromethyl)-4-methoxy-benzene (5.7 g, 36 mmol). The reaction was heated at reflux. After 4 h the reaction was worked up with water and ethyl acetate were added and the phases separated. The organic phase was dried over magnesium sulphate and concentrated in vacuo. Purification by column chromatography (10% ethyl acetate in cyclohexane) afforded 3-bromo-4-[(4-methoxyphenyl)methoxy]-5-(trifluoromethyl)benzonitrile (77%, 7.18 g)

[0142] .sup.1H NMR (400 MHz, chloroform) δ ppm 8.05-8.15 (m, 1H) 7.90 (d, J=1.59 Hz, 1H) 7.40-7.54 (m, 2H) 6.91-6.99 (m, 2H) 5.09 (s, 2H) 3.84 (s, 3H).

Step 3 Synthesis of 4-[(4-methoxyphenyl)methoxy]-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(trifluoromethyl)benzonitrile

[0143] ##STR00021##

[0144] To a stirring solution of 3-bromo-4-[(4-methoxyphenyl)methoxy]-5-(trifluoromethyl)benzonitrile (2.23 g, 5.77 mmol) and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.61 g, 8.66 mmol) in tetrahydrofuran (46.2 mL) at 0° C. was added isopropylmagnesium chloride Lithium chloride complex (1.3M in THF) (5.3 mL, 6.93 mmol) (added in a steady stream); after 45 min the reaction was quenched with sat. aq. ammonium chloride solution and extracted into ethyl acetate. The organic phase was dried over magnesium sulphate and concentrated in vacuo to afford a 3.4:1 ratio of 4-[(4-methoxyphenyl)methoxy]-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(trifluoromethyl)benzonitrile and deborylated 4-[(4-methoxyphenyl)methoxy]-3-(trifluoromethyl)benzonitrile (3.13 g).

[0145] .sup.1H NMR (400 MHz, chloroform) δ ppm 8.24-8.34 (m, 1H) 7.93-8.05 (m, 1H) 7.43-7.48 (m, 2H) 6.90-6.95 (m, 2H) 5.09 (s, 2H) 3.83 (s, 3H) 1.39 (s, 12H).

Step 4 Synthesis of 4-hydroxy-3-thiazol-2-yl-5-(trifluoromethyl) benzonitrile

[0146] ##STR00022##

[0147] 2-bromothiazole (0.046 g, 0.28 mmol), 4-[(4-methoxyphenyl)methoxy]-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(trifluoromethyl)benzonitrile (crude material, assumed ˜60% purity, 0.17 g, 0.24 mmol), SPhos Pd G3 (0.019 g, 0.024 mmol), tripotassium phosphate trihydrate (0.076 g, 0.35 mmol), cyclopentyl methyl ether (1.7 mL) and water (0.85 mL) were combined in a microwave vial. The vial was sealed and heated in the microwave at 120° C. for 10 mins. The sample was then diluted with water/ethyl acetate, the phases were separated, and the organic phase was dried over magnesium sulphate and concentrated in vacuo. 2,2,2-trifluoroacetic acid (0.5 mL) was added to the residue and the mixture was stirred for 5 min; water and ethyl acetate were added, the phases were separated and the organic phase was dried over magnesium sulphate and concentrated in vacuo. The cured mixture was purified by RPHPLC to afford 4-hydroxy-3-thiazol-2-yl-5-(trifluoromethyl)benzonitrile (0.0142 g, 22%).

[0148] .sup.1H NMR (400 MHz, chloroform) δ ppm 8.11 (d, J=1.96 Hz, 1H) 7.92 (d, J=3.42 Hz, 1H) 7.89 (d, J=1.34 Hz, 1H) 7.50 (d, J=3.30 Hz, 1H)

[0149] The following tables provide examples of herbicidal compounds of the present invention. Mass spectrometry data was collected on a Waters Acquity UPLC-MS using a Sample Organizer with Sample Manager FTN, H-Class QSM, Column Manager, 2× Column Manager Aux, Photodiode Array (Wavelength range (nm): 210 to 400), ELSD and QDa mass spectrometer. Ionisation method: Electrospray positive and negative: Cone (V) 20.00, Source Temperature (° C.) 120, Cone Gas Flow (L/Hr.) 50. Mass range (Da): positive 100 to 800, negative 115 to 800.

[0150] Method 1) analysis was conducted using a four-minute run time, according to the following gradient table at 40° C.:

[0151] Waters Acquity UPLC HSS T3 (1.8 μm 2.1×50 mm).

TABLE-US-00001 Time (mins) Solvent A (%) Solvent B (%) Flow (ml/mn) 0.00 95.0 5.0 0.6 3.00 0.0 100 0.6 3.50 0.0 100 0.6 3.55 95.5 5.0 0.6 4.10 95.5 5.0 0.6

[0152] Solvent A: H.sub.2O with 0.05% TFA Solvent B: CH.sub.3CN with 0.05% TFA

[0153] Method 2) Analysis was conducted using a two-minute run time, according to the following gradient table at 40° C.:

[0154] Waters Acquity UPLC HSS T3 (1.8 μm 2.1×30 mm).

TABLE-US-00002 Time (mins) Solvent A (%) Solvent B (%) Flow (ml/mn) 0.00 95.0 5.0 0.7 1.75 0.0 100 0.7 1.76 0.0 100 0.7 2.00 0.0 100 0.7 2.01 95.5 5.0 0.7 2.11 95.5 5.0 0.7

[0155] Solvent A: H.sub.2O with 0.05% TFA Solvent B: CH.sub.3CN with 0.05% TFA

TABLE-US-00003 TABLE 1 Examples of herbicidal compounds of the present invention. Retention MH +/ M − H Compound Structure .sup.1HNMR Time (observed) 1.001 [00023] (DMSO-d.sub.6) δ 8.93 (s, 1H), 8.27 (s, 1H), 8.11-8.10 (m, 2H) 1.002 [00024] (DMSO-d.sub.6) δ 11.34 (s, 1H), 7.95 (s 1H), 7.84 (d, 1H), 7.53-7.49 (m, 1H), 7.44-7.41 (m, 2H), 7.27-7.22 (m, 1H). 1.003 [00025] (DMSO-d.sub.6) δ 11.16 (s, 1H), 7.85-7.82 (dd, 1H), 7.67 (s, 1H), 7.52-7.41 (m, 3H), 7.25-7.21 (m, 1H) 1.004 [00026] (DMSO-d.sub.6) δ 10.68 (s, 1H), 8.00 (d, 1H), 7.75 (d, 1H), 7.52-7.47 (q, 1H), 7.40-7.37 (m, 2H), 7.26-7.22 (m, 1H) 1.005 [00027] (DMSO-d.sub.6) δ 10.89 (s, 1H), 8.11-8.10 (d, 1H), 7.97-7.96 (d, 1H), 7.56-7.50 (m, 1H), 7.37-7.25 (m, 3H). 1.006 [00028] (DMSO-d.sub.6) 8.48 (d, 1H), 8.24 (d, 1H), 2.62 (s, 3H) 1.007 [00029] (CDCl.sub.3) δ 11.59 (s, 1H), 7.80 (s, 1H), 7.26 (s, 1H), 7.03 (s, 1H), 4.09 (3H, s). 1.008 [00030] 2.65 408.1 1.009 [00031] 2.49 371.1 1.010 [00032] 2.16 325.0 1.011 [00033] 2.06 345.0 1.012 [00034] 1.99 325.0 1.013 [00035] 2.08 309.9 1.014 [00036] 2.13 309.0 1.015 [00037] 2.47 338.1 1.016 [00038] 1.94 305.0 1.017 [00039] 1.12 274.99 1.018 [00040] 2.36 337.1 1.019 [00041] 2.34 351.0 1.020 [00042] 1.4 325.0 1.021 [00043] 1.85 310.0 1.022 [00044] 2.32 322.0 1.023 [00045] 1.64 278.0 1.024 [00046] 2.17 347.1 1.025 [00047] 2.45 318.1 1.026 [00048] 2.33 338.1 1.027 [00049] 2.51 358.1 1.028 [00050] 2.52 314.1 1.029 [00051] 2.31 339.0 1.030 [00052] 2.41 320.2 1.031 [00053] 2.39 288.6 1.032 [00054] 2.17 315.1 1.033 [00055] 2.09 297.1 1.034 [00056] 2.46 326.0 1.035 [00057] (DMSO-d.sub.6) δ 14.36 (s, 1H), 9.19 (s, 2H), 8.68 (d, 1H), 8.32 (d, 1H) 1.036 [00058] 1.037 [00059] 1.038 [00060] 1.039 [00061] (DMSO-d.sub.6) δ 7.98 (s,1H), 7.58-7.48 (m, 3H), 7.28-7.24 (m, 1H). 1.040 [00062] (DMSO-d.sub.6) δ 8.31 (s, 1H), 7.73 (t, 2H), 7.53 (q, 1H), 7.29 (td, 1H). 1.041 [00063] 1.42 386.4 1.042 [00064] 1.41 360.2 1.043 [00065] 1.35 352.1 1.044 [00066] 0.87 276.2 1.045 [00067] 1.37 326.1 1.046 [00068] (CDCl.sub.3) δ 7.85 (d, 1H), 7.53 (d, 1H), 7.50-7.46 (m, 1H), 7.27-7.18 (m 3H), 6.20 (bs, 1H). 1.047 [00069] 1.31 274.2 1.048 [00070] 2.27 292.2 1.049 [00071] 0.98 317.2 1.050 [00072] 2.5 323.2 1.051 [00073] 1.37 306.2 1.052 [00074] 2.26 293.1 1.053 [00075] 1.23 299.2 1.054 [00076] 1.41 308.2 1.055 [00077] 1.36 288.2 1.056 [00078] 2.73 352.1 1.057 [00079] 2.61 352.3 1.058 [00080] 1.45 342.2 1.059 [00081] 1.42 306.2 1.060 [00082] 1.44 342.2 1.061 [00083] 1.43 352.1 1.062 [00084] 1.28 292.2 1.063 [00085] 1.33 308.1 1.064 [00086] 1.38 338.2 1.065 [00087] 2.29 353.1 1.066 [00088] 1.39 358.2 1.067 [00089] 1.76 300.0 1.068 [00090] 1.34 324.2 1.069 [00091] 1.46 322.2 1.070 [00092] 0.93 293.1 1.071 [00093] 1.28 322.1 1.072 [00094] 1.3 391.2 1.073 [00095] 1.42 342.1 1.074 [00096] 1.44 302.1 1.075 [00097] 1.41 320.2 1.076 [00098] 1.39 318.2 1.077 [00099] 1.078 [00100] 1.98 307.0 1.079 [00101] 2.24 293.8 1.080 [00102] 2.39 306.1 1.081 [00103] 2.23 320.1 1.082 [00104] 2.53 322.0 1.083 [00105] 2.11 343.0 1.084 [00106] 2.50 302.0 1.085 [00107] 2.54 386.1 1.086 [00108] 2.08 323.0 1.087 [00109] 1.82 350.0 1.088 [00110] 2.14 321.0 1.089 [00111] 1.96 333.0 1.090 [00112] 2.20 317.1 1.091 [00113] 2.54 322.0 1.092 [00114] 1.82 352.0 1.093 [00115] 2.39 306.0 1.094 [00116] 1.90 303.0 1.095 [00117] 2.27 324.0 1.096 [00118] 2.47 359.98 1.097 [00119] 2.06 343.0 1.098 [00120] 1.82 300.1 1.099 [00121] 2.24 320.0 1.100 [00122] 2.17 316.1 1.101 [00123] 1.76 313.0 1.102 [00124] 2.37 320.9 1.103 [00125] 2.51 314.0 1.104 [00126] 2.35 327.9 1.105 [00127] 2.57 374.0 1.106 [00128] 2.60 374.0 1.107 [00129] 2.63 316.0 1.108 [00130] 2.49 332.0 1.109 [00131] 2.57 339.9 1.110 [00132] 2.49 356.0 1.111 [00133] 2.26 340.9 1.112 [00134] 2.29 310.0 1.113 [00135] 2.28 341.0 1.114 [00136] 2.60 388.0 1.115 [00137] 2.51 303.9 1.116 [00138] 2.34 365.1 1.117 [00139] 2.45 324.0 1.118 [00140] 1.80 292.0 1.119 [00141] 2.63 316.1 1.120 [00142] 2.38 338.0 1.121 [00143] 2.49 332.0 1.122 [00144] 2.44 370.1 1.123 [00145] 2.38 318.0 1.124 [00146] 2.45 358.0 1.125 [00147] 2.19 318.0 1.126 [00148] 2.31 367.0 1.127 [00149] 2.35 337.9 1.128 [00150] 2.23 303.9 1.129 [00151] 2.27 334.0 1.130 [00152] 2.29 309.9 1.131 [00153] 2.43 299.9 1.132 [00154] 2.73 330.2 1.133 [00155] 2.33 293.9 1.134 [00156] 2.15 279.9 1.135 [00157] 2.15 280.2 1.136 [00158] 2.26 313.9 1.137 [00159] 2.24 309.9 1.138 [00160] 2.36 313.9 1.139 [00161] 2.41 313.9 1.140 [00162] 2.17 299.1 1.141 [00163] 2.23 337.1 1.142 [00164] 2.36 282.1 1.143 [00165] 2.31 302.0 1.144 [00166] 2.21 305.1 1.145 [00167] 2.14 287.1 1.146 [00168] 2.34 312.1 1.147 [00169] 2.35 322.2 1.148 [00170] 2.45 314.1 1.149 [00171] 2.36 310.2 1.150 [00172] 2.30 310.1 1.151 [00173] 2.53 346.1 1.152 [00174] 2.05 293.2 1.153 [00175] 1.92 301.1 1.154 [00176] 1.96 340.1 1.155 [00177] 2.48 342.1 1.156 [00178] 2.34 331.1 1.157 [00179] (CDCl.sub.3) δ = 8.11 (d, 1 H) 7.92 (d, H) 7.89 (d, 1H) 7.50 (d, 1H) 1.61 269.0 1.158 [00180] 2.20 331.1 1.159 [00181] 2.21 311.1 1.160 [00182] 2.43 314.1 1.161 [00183] 2.38 355.2 1.162 [00184] 2.43 294.1 1.163 [00185] 2.31 310.1 1.164 [00186] 2.15 331.1 1.165 [00187] 2.51 346.2 1.166 [00188] 1.50 293.1 1.167 [00189] 2.26 315.1 1.168 [00190] 1.88 307.1 1.169 [00191] 2.33 282.1 1.170 [00192] 2.12 299.1 1.171 [00193] 2.13 332.1 1.172 [00194] 1.98 281.1 1.173 [00195] 1.91 280.1 1.174 [00196] 2.20 268.1 1.175 [00197] 2.08 311.1 1.176 [00198] 2.41 312.1 1.177 [00199] 2.35 341.1 1.178 [00200] 2.27 306.1 1.179 [00201] 2.07 297.1 1.180 [00202] 2.29 280.1 1.181 [00203] 2.24 334.2 1.182 [00204] (CDCl.sub.3) δ = 7.92- 7.86 (m, 1H), 7.69 (s, 1H), 7.17-7.11 (m, 2H) 1.183 [00205] (CDCl.sub.3) δ = 7.91 (d, 1H), 7.72 (d, 1H), 7.05- 6.94 (m, 3H) 1.184 [00206] (CDCl.sub.3) δ = 10.52 (bs, 1H), 8.89 (s, 1H), 8.05 (d, 1H), 7.98 (d, 1H) 1.185 [00207] (CDCl.sub.3) δ = 8.11 (d, 1H) 7.92 (d, H) 7.89 (d, 1H) 7.50 (d, 1H) 1.186 [00208] (CDCl.sub.3) δ = 7.69- 7.74 (m, 2 H) 7.79 (d, 1H) 7.96 (d, 1H) 12.79 (s, 1H). 1.187 [00209] (CDCl.sub.3) δ = 12.24 (s. 1H) 7.94 (s, 1H) 7.84 (s, 2H) 2.32 (s, 3H) 1.188 [00210] (CDCl.sub.3) δ = 12.68 (m, 1H), 8.07 (s, 1H), 7.82-7.80 (m, 1H), 7.78-7.77 (m, 2H) 1.189 [00211] (CDCl.sub.3) δ = 12.02 (bs, 1H), 8.16 (d, 1H), 7.92 (d, 1H), 7.88 (d, 1H), 6.94 (d, 1H). 1.190 [00212] (CDCl.sub.3) δ = 12.32 (s, 1H) 8.40 (s, 1H), 8.06 (s, 1H), 7.90 (d, 1H) 7.87 (d, 1H) 1.191 [00213] (DMSO-d6) δ = 8.53 (d, 1H) 8.11 (d, 1H), 7.53 (m, 1H), 7.40 (m, 2H) 7.28 (m, 1H) 1.192 [00214] (DMSO-d6) δ = 10.02 (s, 1H), 7.97- 8.00 (d, J = 8.0 HZ, 1H), 7.63-7.64 (d, J = 4.0 HZ, 1H), 7.46-7.52 (q, J = 4.0 HZ, 1H), 7.34-7.37 (m, J = 4.0 HZ, 2H), 7.20-7.25 (t, J = 4.0 HZ, 1H), 7.02-7.09 (dd, J = 72.0 HZ, 1H), 5.94-5.99 (d, J = 4.0 HZ, 1H), 5.40-5.43 (d, J = 4.0 HZ, 1H). 1.193 [00215] (DMSO-d6) δ = 10.66 (s, 1H), 7.93 (d, 1H), 7.87 (d, 1H), 7.49-7.55 (m, 1H), 7.33-7.38 (m, 2H), 7.05-7.28 (m, 2H) 1.194 [00216] (DMSO-d6) δ = 8.30 (d, 1H), 8.01 (d, 1H), 7.46-7.55 (q, J = 8.0 HZ, 1H), 7.36-7.42 (q, J = 8.0 HZ, 2H), 7.21- 7.29 (t, J = 8.0 HZ, 1H 1.195 [00217] (DMSO-d6) δ = 8.10-8.11 (d, J = 4.0 HZ, 1H), 8.00 (d, 1H), 7.50-7.55 (q, J = 4.0 HZ, 1H), 7.36-7.43 (q, J = 8.0 HZ, 2H), 7.24-7.29 (t, J = 4.0 HZ, 1H), 3.35 (s, 3H) 1.196 [00218] (DMSO-d6) δ = 10.02-9.98 (s, 1H), 7.60-7.59 (d, J = 4.0 HZ, 1H)7.54(d, 1H), 7.46-7.52 (q, J = 8.0 HZ, 1H), 7.33-7.36 (t, J = 4.0 HZ, 2H), 7.20-7.25 (t, J = 8.0 HZ, 1H), 2.47 (s, 3H) 1.197 [00219] 3.25 285.2 1.198 [00220] 1.199 [00221] 2.62 284.3 1.200 [00222] 1.201 [00223] 2.73 300.3 1.202 [00224] 1.203 [00225] 1.204 [00226] 1.205 [00227] 2.83 335.2 1.206 [00228] 3.15 284.3 1.207 [00229] 3.29 333.2 1.208 [00230] 2.73 265.2 1.209 [00231] 3.19 282.2 1.210 [00232] 1.211 [00233] 1.212 [00234] 1.213 [00235] 1.214 [00236] 2.81 335.2 1.215 [00237] 1.216 [00238] 1.217 [00239] 3.49 338.2 1.218 [00240] 1.219 [00241] 1.220 [00242] 1.221 [00243] 1.222 [00244] 2.60 303.2 1.223 [00245] 3.06 319.2 1.224 [00246] 1.225 [00247] 3.60 338.2 1.226 [00248] 2.79 294.3 1.227 [00249] 3.21 303.7 1.228 [00250] 2.44 270.2 1.229 [00251] 2.87 321.2 1.230 [00252] 2.92 268.2 1.231 [00253] 1.232 [00254] 3.48 321.2 1.233 [00255] 1.234 [00256] 2.74 294.3 1.235 [00257] 3.21 303.2 1.236 [00258] 1.237 [00259] 3.31 337.2 1.238 [00260] 1.239 [00261] 1.240 [00262] 1.241 [00263] 2.08 254.2 1.242 [00264] 1.243 [00265] 3.15 303.2 1.244 [00266] 2.37 268.2 1.245 [00267] 3.78 295.3 1.246 [00268] 3.60 301.7 1.247 [00269] 2.35 304.2 1.248 [00270] 3.06 297.2 1.249 [00271] 2.85 294.2 1.250 [00272] 3.26 337.6 1.251 [00273] 1.252 [00274] 3.04 292.2 1.253 [00275] 1.254 [00276] 3.12 308.3 1.255 [00277] 1.256 [00278] 1.257 [00279] 3.45 297.2 1.258 [00280] 2.21 298.2 1.259 [00281] 3.85 327.7 1.260 [00282] 3.06 253.2 1.261 [00283] 3.63 335.2 1.262 [00284] 1.263 [00285] 3.33 297.2 1.264 [00286] 2.25 331.0 1.265 [00287] δ = 7.56-7.43 (m, 2H), 7.28-7.12 (m, 3H), 6.34 (s, 1H) 1.266 [00288] δ = 7.61 (s, 1H), 7.45 (m, 1H), 7.26- 7.24 (m, 2H), 7.14 (m, 1H), 6.36 (s, 1H) 1.267 [00289] δ = 7.75 (s, 1H), 7.48 (m, 1H), 7.30 (m, 2H), 7.18 (m, 1H), 6.74 (s, 1H) 1.268 [00290] δ = 7.55 (s, 1H), 7.43 (m, 1H), 7.27- 7.25 (m, 2H), 7.11 (m, 1H), 6.28 (s, 1H), 2.68 (s, 3H)

TABLE-US-00004 TABLE 2 Examples of herbicidal compounds of the present invention. Compound Structure .sup.1HNMR 2.001 [00291] (DMSO-d.sub.6) δ 8.15 − 8.13 (d, 1H), 7.95 (s, 1H), 7.58 − 7.53 (q, 1H), 7.35 − 7.29 (m, 3H), 2.24 (s, 3H) 2.002 [00292] (DMSO-d.sub.6) δ 8.46 (s, 1H), 8.39 (s, 1H), 7.58 − 7.52 (q, 1H), 7.40 − 7.30 (m, 3H), 2.10 (s, 3H). 2.003 [00293] (DMSO-d.sub.6) δ 8.47 (s, 1H), 8.38 (s, 1H), 7.57 − 7.52 (q, 1H), 7.35 − 7.29 (m, 3H), 2.66 − 2.50 (m, 1H), 0.96 (brs, 6H). 2.004 [00294] (DMSO-d.sub.6) δ 8.47 (s, 1H), 8.35 (d, 1H), 7.57 − 7.52 (q, 1H), 7.34 − 7.25 (m, 3H), 1.02 (s, 9H). 2.005 [00295] (DMSO-d.sub.6) δ 8.30 (d, 1H), 8.02 (d, 1H), 7.56 − 7.50 (q, 1H), 7.33 − 7.23 (m, 3H), 1.12 (s, 9H). 2.006 [00296] (DMSO-d.sub.6) δ 8.30 (d, 1H), 8.03 (d, 1H), 7.56 − 7.51 (q, 1H), 7.33 − 7.25 (m, 3H), 2.77 − 2.67 (m, 1H), 1.06 − 1.04 (d, 6H)

Biological Examples

[0156] Seeds of a variety of test species are sown in standard soil in pots (Ipomoea hederacea (IPOHE), Abutilon theophrasti (ABUTH), Amaranthus retoflexus (AMARE), Echinochloa crus-galli (ECHCG), Setaria faberi (SETFA)). After 8 days cultivation under controlled conditions in a glasshouse (at 24/16° C., day/night; 14 hours light; 65% humidity), the plants are sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5). Compounds are applied at 1000 g/ha unless otherwise stated. The test plants are then grown in a glasshouse under controlled conditions in a glasshouse (at 24/16° C., day/night; 14 hours light; 65% humidity) and watered twice daily. After 13 days the test is evaluated for the percentage damage caused to the plant. The biological activities are shown in the following table on a five-point scale (5=81-100%; 4=61-80%; 3=41-60%; 2=21-40%; 1=0-20%).

TABLE-US-00005 TABLE B1 Post-emergence Test Compound IPOHE ABUTH AMARE ECHCG SETFA 1.001 1 5 4 — 4 1.002 5 4 5 3 2 1.004 1 5 5 3 3 1.005 5 5 4 4 1 1.007 3 2 5 — 1 1.008 2 2 5 — 4 1.009 2 2 4 — 2 1.027 3 4 5 — 4 1.032 3 4 5 — 4 1.034 — 4 4 — — 1.036 3 2 5 3 4 1.044 1 5 5 2 3 1.045 1 3 5 1 1 1.046 3 5 5 2 3 1.047 3 5 5 1 2 1.048 2 5 5 2 2 1.052 1 5 5 1 3 1.053 3 2 5 1 1 1.054 2 5 5 3 2 1.058 2 1 5 2 3 1.060 2 4 5 1 1 1.061 3 3 5 1 1 1.067 2 3 1 2 2 1.130 2 5 5 1 1 1.134 4 4 4 1 1 1.135 5 5 2 1 1 1.145* 3 1 1 1 1 1.148* 4 1 3 1 1 1.151 3 1 5 1 1 1.158 2 1 4 1 1 1.160 2 1 5 1 1 1.162 3 1 2 1 1 1.165 4 1 3 1 1 1.180 3 3 1 1 1 1.182 5 4 5 1 1 1.183 2 4 5 2 2 1.186 4 5 2 1 1 1.187 1 1 5 1 1 1.190 1 1 3 1 1 1.191 3 4 5 2 2 1.194 3 3 2 1 2 1.225 — — 5 — — 1.250 5 2 5 2 2 1.259 5 3 5 2 2 2.002 5 5 5 4 1 2.006 1 4 3 1 1 *Applied at 500 gai/ha