Amidine substituted benzoyl derivatives useful as herbicides

Abstract

The present invention related to compounds of Formula (I): or an agronomically acceptable salt thereof, wherein Q, X, Z, R.sup.2 and R.sup.3 areas described herein. The inventions further relates to compositions comprising said compounds, to methods of controlling weeds using said compositions, and to the use of Compounds of Formula (I) as a herbicide. ##STR00001##

Claims

1. A compound of Formula (I): ##STR00027## or an agronomically acceptable salt thereof, wherein: R.sup.2 is selected from the group consisting of halogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6 haloalkyl and —S(O).sub.pC.sub.1-C.sub.6 alkyl; R.sup.3 is selected from the group consisting of halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl and -S(O).sub.pC.sub.1-C.sub.6 alkyl; Q is selected from the group consisting of Q.sup.1, Q.sup.2 and Q.sup.3; ##STR00028## R.sup.1a is C.sub.1-C.sub.4alkyl- or C.sub.1-C.sub.3-alkoxy-C.sub.1-C.sub.3-alkyl-; R.sup.1b is selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl- and C.sub.1-C.sub.3-alkoxy-C.sub.1-C.sub.3-alkyl-; A.sup.1 is selected from the group consisting of O, C(O) and (CR.sup.eR.sup.f); R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e and R.sup.f are each independently selected from the group consisting of hydrogen and C.sub.1-C.sub.4alkyl wherein R.sup.a and R.sup.c may together form a C.sub.1-C.sub.3alkylene chain. X is —(CH.sub.2).sub.n- or —(CH.sub.2).sub.n- O—(CH.sub.2).sub.n-; n is independently selected from 0, 1 and 2; Z is Z.sup.1 or Z.sup.2 ##STR00029## R.sup.4 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl and C.sub.3-C.sub.6 cycloalkyl; R.sup.5 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl and C.sub.1-C.sub.6 haloalkyl; R.sup.6 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, cyano and phenyl wherein the phenyl is optionally substituted by 1, 2 or 3 substituents selected from the group consisting of halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl and C.sub.1-C.sub.6 alkoxy; or R.sup.5 and R.sup.6 together are —CH.sub.2CH.sub.2CH.sub.2CH.sub.2, —CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2- or —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2-; and R.sup.7 is selected from the group consisting of hydrogen and C.sub.1-C.sub.6 alkyl; R.sup.8 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6-haloalkyl and C.sub.3-C.sub.6-cycloalkyl; R.sup.9 is selected from the group consisting of hydrogen, cyano, C.sub.1-C.sub.6 alkyl and C.sub.1-C.sub.6alkoxy-; and p=0, 1 or 2.

2. The compound according to claim 1, wherein R.sup.2 is selected from the group consisting of methyl, Cl, —CF.sub.3 and —SO.sub.2methyl.

3. The compound according to claim 1, wherein R.sup.3 is selected from the group consisting of methyl, Cl, —CF.sub.3 and —SO.sub.2methyl.

4. The compound according to claim 1, wherein R.sup.1 is selected from the group consisting of methyl, ethyl and n-propyl.

5. The compound according to claim 1, wherein Q is Q.sup.1 and Z is Z.sup.1.

6. The compound according to claim 5, wherein X is —(CH.sub.2).sub.n- and n is 0.

7. The compound according to claim 1, wherein Q is Q.sup.2 and Z is Z.sup.1.

8. The compound according to claim 7, wherein X is —CH.sub.2O—.

9. The compound according to claim 1, wherein Q is Q.sup.3 and Z is Z.sup.1.

10. The compound according to claim 1, wherein Q is Q.sup.1 and Z is Z.sup.2.

11. A herbicidal composition comprising a compound according to claim 1 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 applying to the locus of a weed controlling amount of a composition according to claim 1.

Description

PREPARATIVE EXAMPLE 1: COMPOUND 1.025

(1) Oxalyl dichloride (1.20 g, 9.4 mmol) was added dropwise to a solution of DMF (0.34 g, 4.7 mmol) in DCM (25 mL) at 0° C. (vigorous effervescence then a white suspension formed). The reaction mixture was allowed to stir for 30 min at room temperature and was then concentrated to dryness giving an off-white solid. This was suspended in dichloromethane (25 mL) and then ethyl 3-amino-2-methyl-4-methylsulfonyl-benzoate (600 mg, 2.33 mmol) was added as a solution in DCM (2 mL). Within a few seconds a yellow solution formed, which was stirred for 10 min. The reaction mixture was added dropwise to stirring sat. NaHCO.sub.3 solution in an ice bath and stirred for 10 mins (care: effervescence). The organic layer was separated, extracted, with CHCl3:IPA (7:3 ratio, 2×10 mL) then dried and concentrated in vacuo. The material was loaded onto celite and purified by flash chromatography: Column: 40 g silica. Solvent A: Dichloromethane. Solvent B: Methanol. Gradient: 0-5% B in A over 15 min. Began to elute at 2% B in A. The fractions containing the product were combined and concentrated in vacuo and dried to give ethyl 3-[(E)-dimethylaminomethyleneamino]-2-methyl-4-methylsulfonyl-benzoate (665 mg, 2.13 mmol) as a yellow oil. 1H NMR (400 MHz, chloroform) 6=7.88 (d, J=8.3 Hz, 1H), 7.47 (d, J=8.3 Hz, 1H), 7.21 (s, 1H), 4.38 (q, J=7.1 Hz, 2H), 3.20 (s, 3H), 3.06 (br d, J=14.8 Hz, 6H), 2.33 (s, 3H), 1.40 (t, J=7.2 Hz, 3H).

(2) To ethyl 3-[(E)-dimethylaminomethyleneamino]-2-methyl-4-methylsulfonyl-benzoate (660 mg, 2.11 mmol) in ethanol (12 mL) and water (3.4 mL) was added lithium hydroxide monohydrate (222 mg, 5.28 mmol). After 2 h, the mixture was concentrated in vacuo to remove ethanol. The residue was taken up in water and the aqueous solution was adjusted to pH 10 by addition of excess ammonia solution (38% in water). This solution was purified directly by liquid injection to reversed phase flash chromatography using a C-18 aq 50 g column. Solvent A: Water+0.1% ammonia. Solvent B: acetonitrile+0.1% ammonia. Gradient: 0% for 3 column volumes, then 0-50% B in A over 10 column volumes. Eluted at 0% B in A. The fractions containing product were combined and concentrated in vacuo, then the material was dissolved in water and freeze-dryed overnight to give 3-[(E)-dimethylaminomethyleneamino]-2-methyl-4-methylsulfonyl-benzoic acid (496 mg, 1.75 mmol as a white solid). 1H NMR (400 MHz, DMSO-d6) δ=7.49 (d, J=8.1 Hz, 1H), 7.30 (s, 1H), 6.94 (d, J=8.1 Hz, 1H), 3.16 (s, 3H), 2.97 (s, 6H), 2.15-2.04 (m, 3H).

(3) To a flask containing 3-[(E)-dimethylaminomethyleneamino]-2-methyl-4-methylsulfonyl-benzoic acid (245 mg, 0.862 mmol) was added anhydrous 1,4-dioxane (5 mL) and N,N′-carbonyldiimidazole (210 mg, 1.29 mmol). The mixture was stirred at 100° C. for 16 h then cooled to RT. 1-methyltetrazol-5-amine (128 mg, 1.29 mmol) and DBU (0.132 mL, 0.862 mmol) was added and the reaction mixture was stirred at 100° C. for 3 days. A further portion of 1-methyltetrazol-5-amine (128 mg, 1.29 mmol) and DBU (0.132 mL, 0.862 mmol) were then added and the reaction mixture was stirred at 100° C. for 2 h. The reaction was allowed to cool and then concentrated in vacuo. Water (10 mL) was added to the residue and DCM (10 mL). The mixture was separated and the aqueous phase was extracted with CHCl.sub.3:IPA (7:3, 2×10 mL). The organic phases were combined, dried over MGSO.sub.4, filtered and concentrated in vacuo. The material was loaded onto celite and purified by flash chromatography (0 to 10% MeOH/DCM) to give 3-[(E)-dimethylaminomethyleneamino]-2-methyl-4-methylsulfonyl-N-(1-methyltetrazol-5-yl)benzamide (136 mg, 0.372 mmol) as a white solid. 1H NMR (400 MHz, DMSO-d6) δ=7.71 (d, J=8.2 Hz, 1H), 7.39 (s, 1H), 7.30 (d, J=8.2 Hz, 1H), 3.88 (s, 3H), 3.24 (s, 3H), 3.00 (s, 6H), 2.18 (s, 3H).

PREPARATIVE EXAMPLE 2: COMPOUND 1.130

(4) Added 2-[3-fluoro-4-(trifluoromethyl)phenyl]-4,4-dimethyl-5H-oxazole (14 g, 51 mmol) in 120 mL of dry THF to 500 mL 4-necked RBF equipped with a thermometer. Cooled the reaction mass to −74° C. and then added n-butyl lithium as a 2.0 M solution in hexane (36 mL, 71 mmol) drop-wise. Stirred the reaction mass at about −74° C. for another 1.5 h. To this solution then added the solution of hexachloroethane (8.8 mL, 77 mmol) in 40.3 mL of dry THF at −70° C. The mixture was stirred at about −70° C. for 30 min and then allowed to stand for 16 h, during which time TLC shows no starting material. The mixture was poured into ice-cold solution of 6N aq. HCl (40.30 mL) and extracted with EtOAc (750 ml×3). Combined organic phases then washed with brine, dried over Na.sub.2SO.sub.4, filtered and concentrated. The crude product was then purified by silica gel column chromatography and desired product was eluted with 4.0% EtOAc in Hexane to give 2-[2-chloro-3-fluoro-4-(trifluoromethyl)phenyl]-4,4-dimethyl-5H-oxazole (25 g, 28 mmol).

(5) To the solution of tBuOK (15.4 g) in N,N-dimethylacetamide (96 mL) in a RBF was added formamide (14.5 mL) dropwise and stirred. After 15 min, a solution of 2-[2-chloro-3-fluoro-4-(trifluoromethyl)phenyl]-4,4-dimethyl-5H-oxazole (16 g) in N,N-dimethylacetamide (38 mL) was added. The mixture was then warmed to 120° C. for 2 h. The reaction mass was then cooled to room temperature and then poured into ice water (160 mL) and extracted with 30% solution of EtOAc in MTBE (160 ml×4). The combined organic layers were washed with brine, dried over Na.sub.2SO.sub.4, filtered and concentrated under high vacuum. Finally, the crude product was triturated with 5% solution of Et2O in Hexane to afford desired product N-[2-chloro-3-(4,4-dimethyl-5H-oxazol-2-yl)-6-(trifluoromethyl)phenyl]formamide (16.8 g) as off white solid.

(6) N-[2-chloro-3-(4,4-dimethyl-5H-oxazol-2-yl)-6-(trifluoromethyl)phenyl]formamide (12 g, 37 mmol)) was taken in 52.2 mL of concentrated hydrochloric acid in an rbf, and the mixture was heated under reflux. After 4 h, the mixture was cooled on ice bath and resulting solid was filtered off and the residue was washed with cold water and then dried under high vacuum to give 3-amino-2-chloro-4-(trifluoromethyl)benzoic acid (9.0 g) as a solid. 1H NMR (d6-DMSO): 7.44 (1H, d), 6.92 (1H, d), 5.90 (2H, brs).

(7) To the solution of 3-amino-2-chloro-4-(trifluoromethyl)benzoic acid (16 g, 58 mmol) in 78 mL DMF in an RBF was added 8.36 potassium carbonate and stirred at RT for 15 min. To that was then added 23.4 mL iodoethane and stirred at RT for 2 h. TLC & HPLC checked and reaction was completed. Reaction mixture was diluted with 750 mL cold water and extracted with TBME (250 mL×2). The combined TBME layers were washed with aq. Na2S2O3 solution, then with rine, dried over Na.sub.2SO.sub.4, filtered and concentrated to give ethyl 3-amino-2-chloro-4-(trifluoromethyl)benzoate (8 g, 27 mmol) as a black liquid.

(8) Oxalyl dichloride (0.49 g, 0.34 mL, 3.8 mmol) was added dropwise to a colourless solution of N-methyl-N-(2,2,2-trifluoroethyl)formamide (268 mg, 1.9 mmol) in dichloromethane (12 mL). The reaction mixture was allowed to stir for 30 min (a yellow solution formed) and was then concentrated to dryness giving an orange oil. This was dissolved in dichloromethane (5 mL) and then ethyl 3-amino-2-chloro-4-(trifluoromethyl)benzoate (250 mg, 0.934 mmol) was added as a solution in DCM (1 ml). A yellow suspension formed. The reaction mixture was stirred for 5 min and LCMS analysis showed it to be complete. The reaction mixture was added dropwise to stirring sat. NaHCO.sub.3 solution (10 mL) in an ice bath and stirred for 5 mins (care: effervescence). The organic layer was separated, and the aqueous layer was extracted a second time with dichloromethane (10 mL). LCMS showed the product in the aqueous layer. Extraction with CHCl3:IPA (7:3, 10 mL) successfully extracted the product out of the aqueous layer. The material was purified by flash chromatography (0 to 100% EtOAc/isohexane) to give ethyl 2-chloro-3-[(E)-[methyl(2,2,2-trifluoroethyl)amino]methyleneamino]-4-(trifluoromethyl)benzoate (330 mg, 0.845 mmol) as a colourless oil. NMR shows two rotamers. 1H NMR (400 MHz, chloroform) 6=7.53 (br d, J=8.1 Hz, 2H), 7.45-7.30 (m, 4H), 4.41 (q, J=7.2 Hz, 4H), 4.20 (q, J=8.9 Hz, 2H), 3.77 (q, J=8.4 Hz, 2H), 3.24-3.18 (m, 1H), 3.18-3.11 (m, 1H), 3.18 (br d, J=16.1 Hz, 4H), 1.40 (t, J=7.2 Hz, 6H).

(9) To a stirred solution of ethyl 2-chloro-3-[(E)-[methyl(2,2,2-trifluoroethyl)amino]methyleneamino]-4-(trifluoromethyl)benzoate (320 mg, 0.819 mmol) in ethanol (5 mL) and water (1.5 mL) was added lithium hydroxide monohydrate (86 mg, 2.05 mmol) and the reaction mixture was stirred at room temperature for 30 min. The reaction mixture was concentrated in vacuo to remove EtOH. The mixture was diluted with DCM (10 mL) and then washed with 10% w/v citric acid in water (10 mL). The aqueous phase was extracted further with CHCl.sub.3:IPA (7:3 ratio, 10 mL). LCMS shows only trace amount of product present in the aqueous phase. The organic layer was dried over MgSO.sub.4, filtered and concentrated in vacuo to give 2-chloro-3-[(E)-[methyl(2,2,2-trifluoroethyl)amino]methyleneamino]-4-(trifluoromethyl)benzoic acid (250 mg, 0.689 mmol) as a yellow oil. 1H NMR (400 MHz, chloroform) 6=7.56 (d, J=4.2 Hz, 4H), 7.38 (br d, J=5.5 Hz, 2H), 4.21 (q, J=8.9 Hz, 2H), 3.85-3.75 (m, 2H), 3.19 (m, 6H).

(10) To a flask containing 2-chloro-3-[(E)-[methyl(2,2,2-trifluoroethyl)amino]methyleneamino]-4-(trifluoromethyl)benzoic acid (125 mg, 0.345 mmol) was added anhydrous 1,4-DIOXANE (3 mL) and CDI (84 mg, 0.52 mmol). The mixture was stirred at 100° C. for 45 min, then cooled to RT.

(11) To the reaction mixture was added 1-methyltetrazol-5-amine (51 mg, 0.52 mmol) and DBU (52 μL, 0.34 mmol). The reaction mixture was heated at 100° C. for 16 h. The reaction mixture was concentrated in vacuo. The crude material was diluted with CH.sub.2Cl.sub.2 (10 mL) and washed with aqueous sodium bicarbonate (10 mL). The aqueous phase was further extracted with CHCl.sub.3:IPA (10 mL, 7:3). The organic phases were combined and dried over MgSO.sub.4, filtered and concentrated in vacuo. The material was loaded onto celite and purified by flash chromatography (0 to 10% MeOH in CH.sub.2Cl.sub.2). The fractions containing the product were combined and concentrated in vacuo to give 2-chloro-N-(1-methyltetrazol-5-yl)-3-[(E)-[methyl(2,2,2-trifluoroethyl)amino]methylene amino]-4-(trifluoromethyl)benzamide (66 mg, 0.15 mmol) as a glassy solid. 1H NMR (400 MHz, chloroform) 6=11.21 (br s, 1H), 7.65-7.56 (m, 2H), 7.36 (br d, J=7.9 Hz, 1H), 4.21 (q, J=9.0 Hz, 0.9H), 4.12 (s, 3H), 3.84 (q, J=8.4 Hz, 1.1H), 3.21 (s, 3H) (note: rotamers present in NMR).

PREPARATIVE EXAMPLE 3: COMPOUND 1.132

(12) Oxalyl dichloride (0.49 g, 0.34 mL, 3.8 mmol) was added dropwise to a colourless solution of pyrrolidine-1-carbaldehyde (0.18 mL, 1.9 mmol) in dichloromethane (4 mL). The reaction mixture was allowed to stir for 30 min (a yellow solution formed) and was then concentrated to dryness giving an orange solid. This was dissolved in dichloromethane (5 mL) and then ethyl 3-amino-2-chloro-4-(trifluoromethyl)benzoate (250 mg, 0.934 mmol) was added as a solution in dichloromethane (1 ml). A yellow suspension formed. The reaction mixture was stirred for 10 min and LCMS analysis showed it to be complete. The reaction mixture was added dropwise to stirring saturated NaHCO.sub.3 solution (10 mL) in an ice bath and stirred for 5 mins. The organic layer was separated, and the aqueous layer was extracted a second time with dichloromethane (10 mL), then with CHCl.sub.3:IPA (7:3, 10 mL). The reaction mixture was dried over MgSO.sub.4, filtered and concentrated in vacuo. The material was purified by flash chromatography (0 to 20% EtOAc/isohexane) to give ethyl 2-chloro-3-[(E)-pyrrolidin-1-ylmethyleneamino]-4-(trifluoromethyl)benzoate (296 mg, 0.849 mmol) as a colourless oil. .sup.1H NMR (400 MHz, chloroform) 6=7.50 (d, J=8.3 Hz, 2H), 7.29 (dd, J=0.6, 8.1 Hz, 1H), 4.41 (q, J=7.2 Hz, 2H), 3.63-3.45 (m, 4H), 1.99 (br dd, J=5.9, 14.1 Hz, 4H), 1.40 (t, J=7.2 Hz, 3H)

(13) To a stirred solution ethyl 2-chloro-3-[(E)-pyrrolidin-1-ylmethyleneamino]-4-(trifluoromethyl)benzoate (296 mg, 0.849 mmol) in ethanol (4.8 mL) and water (1.4 mL) was added lithium hydroxide monohydrate (89 mg, 2.12 mmol) and the reaction mixture was stirred at room temperature for 2 h. The reaction mixture was concentrated in vacuo to remove ethanol. The mixture was diluted with water (2 mL), and ammonia solution (38% in water) was added dropwise until the aqueous solution was pH 10. The material was purified by reverse phase chromatography (0 to 12% acetonitrile+0.1% NH.sub.3/water+0.1% NH.sub.3). The fractions containing the product were combined and concentrated in vacuo to give 2-chloro-3-[(E)-pyrrolidin-1-ylmethyleneamino]-4-(trifluoromethyl)benzoic acid (242 mg, 0.755 mmol) as colourless crystals. .sup.1H NMR (400 MHz, DMSO-d.sub.6) δ=7.69 (s, 1H), 7.47 (d, J=8.2 Hz, 1H), 7.06 (d, J=7.9 Hz, 1H), 3.57-3.29 (m, 4H), 2.00-1.78 (m, 4H).

(14) To a flask containing 2-chloro-3-[(E)-pyrrolidin-1-ylmethyleneamino]-4-(trifluoromethyl)benzoic acid (110 mg, 0.343 mmol) was added anhydrous 1,4-dioxane (3 mL) and CDI (83 mg, 1.5 equiv., 0.515 mmol). The mixture was stirred at 100° C. for 1 h, then cooled to room temperature. To the reaction mixture was added a second batch of CDI (83 mg, 1.5 equiv., 0.515 mmol). The reaction mixture was stirred at 100° C. for 1 h.

(15) To the reaction mixture, DBU (52 mL, 1 equiv., 0.343 mmol) and 1-methyltetrazol-5-amine (51 mg, 1.5 equiv., 0.515 mmol) were added and the reaction mixture was stirred at 100° C. for 18 h. The reaction mixture was concentrated in vacuo. The crude material was diluted with CH.sub.2Cl.sub.2 (10 mL) and washed with aqueous sodium bicarbonate (10 mL). The aqueous phase was further extracted with CHCl.sub.3:IPA (10 mL, 7:3). The organic phases were combined and dried over MgSO.sub.4, filtered and concentrated in vacuo. The material was loaded onto celite and purified by flash chromatography (0 to 5% MeOH in CH.sub.2Cl.sub.2). The fractions containing the product were combined and concentrated in vacuo to give 2-chloro-N-(1-methyltetrazol-5-yl)-3-[(E)-pyrrolidin-1-ylmethyleneamino]-4-(trifluoromethyl)benzamide (47 mg, 0.12 mmol) as a white solid. .sup.1H NMR (400 MHz, chloroform) 6=10.46 (br s, 1H), 7.58 (d, J=8.2 Hz, 1H), 7.49 (s, 1H), 7.30 (d, J=7.8 Hz, 1H), 4.09 (s, 3H), 3.63 (br s, 2H), 3.53 (br t, J=6.4 Hz, 2H), 2.11-1.94 (m, 4H)

PREPARATIVE EXAMPLE 4: COMPOUND 4.033

Starting Material from Preparative Example 7

(16) To a solution of ethyl 2-chloro-3-[[ethanethioyl(methyl)amino]methyl]-4-methylsulfonyl-benzoate (100 mg, 0.275 mmol) in acetonitrile (5 mL) was added triethylamine (0.39 mL, 2.7 mmol), cyanamide (58 mg, 1.4 mmol) and silver tetrafluoroborate (270 mg, 1.37 mmol). The reaction mixture was stirred for 16 h overnight at RT. The solution was filtered and then concentrated in vacuo. The residue was dissolved in EtOAc (20 mL) and washed with postassium carbonate solution (20 mL), brine (20 mL), dried over magnesium sulfate and concentrated in vacuo. The product was purified by flash column chromatography (0-100% EtOAc/isohexane) to give ethyl 2-chloro-3-[[[N-cyano-C-methyl-carbonimidoyl]-methyl-amino]methyl]-4-methylsulfonyl-benzoate (77 mg, 0.21 mmol). NMR analysis showed the desired product exists as a mixture of isomers (˜1:7). .sup.1H NMR (500 MHz, Chloroform) d=8.16 (d, J=8.2 Hz, 1H), 7.83 (d, J=8.2 Hz, 1H), 5.29 (s, 2H), 4.46 (q, J=7.2 Hz, 2H), 3.20 (s, 2.65H), 3.10 (s, 0.35H), 2.91 (s, 2.65H), 2.79 (s, 0.35H), 2.66 (s, 0.35H), 2.45 (s, 2.65H), 1.43 (t, J=7.1 Hz, 3H).

(17) To a solution of ethyl 2-chloro-3-[[[N-cyano-C-methyl-carbonimidoyl]-methyl-amino]methyl]-4-methylsulfonyl-benzoate (77 mg, 0.19 mmol) in THF (2 mL) and water (2 mL) was added lithium hydroxide monohydrate (24 mg, 0.56 mmol). The reaction was stirred at room temperature for 30 min. The mixture was acidified with 2 N HCl to pH ˜2. The mixture was extracted with EtOAc (×3), reacidifying the aqueous layer on each occassion to maintain pH ˜2. The combined organics were dried by passing through a phase separator, and then concentrated in vacuo. 2-chloro-3-[[[N-cyano-C-methyl-carbonimidoyl]-methyl-amino]methyl]-4-methylsulfonyl-benzoic acid (51 mg, 0.14 mmol) as a solid.

(18) A solution of 2-chloro-3-[[[(Z)—N-cyano-C-methyl-carbonimidoyl]-methyl-amino]methyl]-4-methylsulfonyl-benzoic acid (54 mg, 0.16 mmol), 1-methyl-H-tetrazol-5-amine (0.20 mmol, 21 mg) and DMAP (0.47 mmol, 58 mg) in CH.sub.2Cl.sub.2 (1.5 mL) were stirred at RT for 1 h. Propylphosphonic anhydride (50% wt. in ethyl acetate, 0.94 mmol, 0.56 mL) was added to the reaction mixture, and was transferred to a microwave vial and heated in the microwave to 100° C. for 30 min. The reaction mixture was concentrated in vacuo to give an orange oil, and then was dissolved in EtOAc (25 mL). The organic was washed with water (carefully acidified to pH ˜4), and the aqueous further extracted with EtOAc (×2). The combined organics were washed with brine, dried over magnesium sulfate and concentrated in vacuo. The residue was purified by reversed-phase prep HPLC to give 2-chloro-3-[[[(Z)—N-cyano-C-methyl-carbonimidoyl]-methyl-amino]methyl]-4-methylsulfonyl-N-(1-methyltetrazol-5-yl)benzamide (8.5 mg, 0.018 mmol) as a colourless oil. NMR analysis showed the desired product exists as a mixture of isomers (˜2:1, not assigned). 1H NMR (400 MHz, Methanol) d=8.29-8.22 (m, 1H), 7.99-7.88 (m, 1H), 5.37 (s, 2H), 4.06 (s, 3H), 3.93 (s, 1H), 2.95 (s, 2H), 2.83-2.78 (m, 1H), 2.68-2.65 (m, 1H), 2.47 (s, 2H). NOTE: 2H not observed (masked by residual methanol peak at 3.30 ppm).

PREPARATIVE EXAMPLE 5: COMPOUND 2.049

(19) Oxalyl dichloride (0.67 g, 0.46 mL, 5.2 mmol) was added dropwise to a solution of N,N-dimethylformamide (0.20 mL, 2.6 mmol) in dichloromethane (3.8 mL) at 0° C. Vigorous effervescence was observed then a white suspension formed. The reaction mixture was allowed to stir for 30 min at room temperature and was then concentrated to dryness giving an off-white solid. This solid was suspended in dichloromethane (5 mL) and then ethyl 3-amino-2-chloro-4-(trifluoromethyl)benzoate (350 mg, 1.31 mmol) was added as a solution in dichloromethane (2 mL). Within a few seconds a yellow solution formed, which was stirred for 10 min. The reaction mixture was added dropwise to stirring sat. NaHCO.sub.3 solution in an ice bath and stirred for 10 mins (care: effervescence). The organic layer was separated, extracted again with dichloromethane (10 mL), then CHCl.sub.3:IPA (7:3 ratio, 10 mL) then the combined organic layers were dried (MgSO.sub.4) and concentrated in vacuo. The material was loaded onto celite and purified by flash chromatography. Column: 24 g silica. Solvent A: isohexane. Solvent B: Ethyl acetate. Gradient: 0-50% B in A over 15 min. The fractions containing the product were combined and concentrated in vacuo to give ethyl 2-chloro-3-[(E)-dimethylaminomethyleneamino]-4-(trifluoromethyl) benzoate (319 mg, 0.989 mmol) as a yellow oil. 1H NMR (400 MHz, chloroform) 6=7.50 (d, J=8.2 Hz, 1H), 7.34-7.28 (m, 2H), 4.41 (q, J=7.1 Hz, 2H), 3.05 (br d, J=8.8 Hz, 6H), 1.40 (t, J=7.2 Hz, 3H).

(20) To a stirred solution of ethyl 2-chloro-3-[(E)-dimethylaminomethyleneamino]-4-(trifluoro methyl)benzoate (300 mg, 0.930 mmol), in ethanol (5 mL) and water (1.5 mL) was added lithium hydroxide monohydrate (98 mg, 2.3 mmol). After stirring at RT for 2 h, The mixture was concentrated in vacuo. The material was taken up in water (10 mL) and the aqueous solution was adjusted to pH 10 by addition of excess ammonia solution (38% in water). This was directly purified by reversed phase flash chromatography: Column: C-18 aq (50 g). Solvent A: Water+0.1% ammonia. Solvent B: acetonitrile+0.1% ammonia. Gradient: 0% for 3 column volumes, then 0-50% B in A over 10 column volumes. Eluted at 5% B in A. The desired fractions were concentrated and freeze-dried to afford 2-chloro-3-[(E)-dimethylaminomethyleneamino]-4-(trifluoromethyl)benzoic acid (280 mg, 274 mmol) as a white solid. 1H NMR (400 MHz, DMSO-d6) δ=7.42 (s, 1H), 7.34 (d, J=8.1 Hz, 1H), 6.85 (d, J=7.9 Hz, 1H), 3.05-2.87 (m, 6H).

(21) To a flask containing 2-chloro-3-[(E)-dimethylaminomethyleneamino]-4-(trifluoromethyl) benzoic acid (270 mg, 0.916 mmol) was added anhydrous 1,4-dioxane (8 mL) and N,N′-carbonyldiimidazole (223 mg, 1.37 mmol). DBU (0.140 mL, 0.916 mmol) and 5-methyl-1,3,4-oxadiazol-2-amine (136 mg, 1.37 mmol) were added and the mixture heated at 100° C. for 16 h. The material was cooled to RT and concentrated in vacuo. Saturated sodium bicarbomate (10 mL) and DCM (10 mL) were added and the layers were separated. The aqueous layer was extracted with DCM (10 mL) and CHCl.sub.3:IPA (7:3, 10 mL). The combined organic layers were dried over MgSO.sub.4, filtered and concentrated in vacuo. The material was loaded onto celite and purified by flash chromatography: 24 g silica. Solvent A: Dichloromethane. Solvent B: Methanol. Gradient: 0-10% B in A over 25 min. The fractions containing the product were combined and concentrated in vacuo to give 2-chloro-3-[(E)-dimethylaminomethyleneamino]-N-(5-methyl-1,3,4-oxadiazol-2-yl)-4-(trifluoromethyl)benzamide (75 mg, 0.20 mmol) as a white solid. .sup.1H NMR (400 MHz, DMSO-d.sub.6) δ=7.60-7.50 (m, 2H), 7.18-7.11 (m, 1H), 3.02 (s, 3H), 2.98-2.90 (m, 3H), 2.46-2.33 (m, 3H).

PREPARATIVE EXAMPLE 6: COMPOUND 3.129

(22) To a dry flask was added ethyl 3-(bromomethyl)-2-chloro-4-methylsulfonyl-benzoate (2.7 g, 7.6 mmol), potassium carbonate (1.g g, 9.1 mmol) and anhydrous acetonitrile (41 mL). The reaction mixture was purged and put under a nitrogen atmosphere. A suspension of N′-hydroxy-N,N-dimethyl-acetamidine (0.85 g, 8.4 mmol) in anhydrous acetonitrile (20 mL) was added to the reaction mixture dropwise and the reaction mixture was stirred at room temperature for 13 days. A further portion of N′-hydroxy-N,N-dimethyl-acetamidine (0.16 g, 1.5 mmol) and potassium carbonate (0.21 g, 1.5 mmol) were added and the reaction mixture was stirred at RT for a further day. The reaction mixture was diluted with dichloromethane (50 mL) and water (10 mL) was added to the reaction mixture. The phases were separated and the organic phase was passed through a phase separation cartridge and concentrated in vacuo to give a yellow oil. The crude material was purified by flash chromatography (Solvent A=hexane, Solvent B=ethyl acetate) gradient 0-50% ethyl acetate to give the desired product ethyl 2-chloro-3-[[(Z)-1-(dimethylamino)ethylideneamino]oxymethyl]-4-methylsulfonyl-benzoate (1.56 g, 4.13 mmol) as a yellow oil. 1H NMR (400 MHz, chloroform) 6=8.11 (d, J=8.3 Hz, 1H), 7.73 (d, J=8.3 Hz, 1H), 5.56 (s, 2H), 4.55-4.33 (m, 2H), 3.39 (s, 3H), 2.73 (s, 6H), 1.94 (s, 3H), 1.42 (t, J=7.2 Hz, 3H).

(23) To a stirred solution of ethyl 2-chloro-3-[[(Z)-1-(dimethylamino)ethylideneamino]oxymethyl]-4-methylsulfonyl-benzoate (1.5 g, 4.0 mmol) in ethanol (23 mL) and water (6.4 mL) was added lithium hydroxide monohydrate (0.42 g, 9.9 mmol) was added to the reaction mixture and it was stirred at room temperature for 16 h. The reaction mixture was concentrated in vacuo to remove the ethanol. The crude material was acidified with 2 N HCl to pH 3 and then aqueous ammonia was added until the pH was pH 10. This mixture was loaded onto a reverse phase column (high pH) that had been equilibrated with a solution of 0.1% ammonia in water and acetonitrile. The sample was loaded as a liquid onto the equilibrated column and was eluted using 0% acetonitrile in water (0.1% NH3) until solvent front came off, then a gradient from 0%-50% acetonitrile in water (0.1% NH3) until product eluted (approx 30%). The material was taken up in minimum amount of water and very small amount of acetonitrile and freeze dried overnight. The product 2-chloro-3-[[(Z)-1-(dimethylamino)ethylideneamino]oxymethyl]-4-methylsulfonyl-benzoic acid (1.31 g, 3.76 mmol) was obtained as an off-white solid. 1H NMR (400 MHz, DMSO-d6) δ=7.84 (d, J=8.1 Hz, 1H), 7.43 (d, J=8.1 Hz, 1H), 7.36-7.21 (m, 1H), 5.35 (s, 2H), 3.37 (s, 3H), 2.69 (s, 6H), 1.88 (s, 3H).

(24) To a solution of 2-chloro-3-[[(Z)-1-(dimethylamino)ethylideneamino]oxymethyl]-4-methyl sulfonyl-benzoic acid (500 mg, 1.43 mmol), in dichloromethane (7.5 mL) was added DMF (0.011 mL, 0.14 mmol). The reaction mixture was purged and put under a nitrogen atmosphere. Oxalyl chloride (0.24 mL, 0.96 mmol) was added dropwise; effervescence occurred on addition, and a red solid precipitate appeared. The reaction mixture was stirred at room temperature for 1 h and it became a pinkish red suspension. The reaction mixture was concentrated in vacuo to give a pink foaming solid, and the residue was dissolved in dichloromethane (7.5 mL). The reaction mixture was cooled to 0° C. under a nitrogen atmosphere and after 5 min, triethylamine (0.81 mL, 0.734 mmol) was added dropwise, followed by cyclohexane-1,3-dione (161 mg, 1.43 mmol) in a single portion. The reaction mixture was allowed to warm to RT over 1 h. Acetone cyanohydrin (0.33 mL, 0.36 mmol) was added to the reaction mixture. The reaction mixture was stirred at room temperature overnight. The reaction mixture was concentrated in vacuo and then the crude material was loaded onto celite and purified by flash chromatography using a solvent system of 10:4:2:2:0.5 toluene/1,4-dioxane/ethanoltriethylamine/water. The crude material (dark green oil) was diluted with dichloromethane (10 mL) and washed with 10% w/v citric acid solution (10 mL). The organic phase was dried over MgSO.sub.4, filtered and concentrated in vacuo to give N′-[[2-chloro-3-(2,6-dioxocyclohexanecarbonyl)-6-methylsulfonyl-phenyl]methoxy]-N,N-dimethyl-acetamidine (114 mg, 0.527 mmol) as a yellow oil (114 mg). 1H NMR (CDCl.sub.3): 8.12 (d, J=8.1 Hz, 1H), 5.54 (s, 2H), 3.37 (s, 3H), 2.81 (t, J=6.4 Hz, 2H), 2.73 (s, 6H), 2.44 (t, J=6.4 Hz, 2H), 2.13-2.02 (m, 2H), 1.92 (s, 3H).

PREPARATIVE EXAMPLE 7: COMPOUND 4.016

(25) To a solution of methylamine (2 M in THF, 55 mL, 109 mmol) was added dropwise ethyl 3-(bromomethyl)-2-chloro-4-methylsulfonyl-benzoate (2.43 g, 6.83 mmol) in acetonitrile (13.7 mL). The reaction was stirred at room temperature for 10 min. LCMS analysis showed formation of the product and no remaining starting material. The reaction was concentrated in vacuo and then diluted with DCM (250 mL). The organic was washed with sat. K2CO3 solution (100 mL), brine (100 mL), and concentrated in vacuo to give ethyl 2-chloro-3-(methylaminomethyl)-4-methylsulfonyl-benzoate (2.08 g, 6.46 mmol) as a colourless oil. .sup.1H NMR (400 MHz, chloroform) 6=8.10 (d, J=8.2 Hz, 1H), 7.71 (d, J=8.3 Hz, 1H), 4.44 (q, J=7.1 Hz, 2H), 4.33 (s, 2H), 3.37 (s, 3H), 2.55 (s, 3H), 1.42 (t, J=7.1 Hz, 3H).

(26) To a solution of ethyl 2-chloro-3-(methylaminomethyl)-4-methylsulfonyl-benzoate (500 mg, 1.55 mmol), 4-dimethylaminopyridine (19.4 mg, 0.155 mmol) and triethylamine (318 mg, 0.437 mL, 3.11 mmol) in tetrahydrofuran (13.8 g, 15.5 mL) was added dropwise ethyl dithioacetate (381 mg, 0.364 mL, 3.11 mmol). The reaction was equipped with a reflux condenser, stirred and heated to 50° C. for 10 days. LCMS analysis showed formation of product, but also remaining starting material. The reaction was cooled to room temperature, and then concentrated in vacuo to remove THF. The mixture was diluted with EtOAc (50 mL) and washed with water (50 mL×2), brine (50 mL) and concentrated in vacuo. The product was purified by flash column chromatography (0-60% EtOAc/isohexane) to give ethyl 2-chloro-3-[[ethanethioyl(methyl)amino]methyl]-4-methylsulfonyl-benzoate (217 mg, 0.596 mmol) as a brown gum. .sup.1H NMR (400 MHz, chloroform) 6=8.23-8.14 (m, 1H), 7.89-7.80 (m, 1H), 5.79 (br s, 2H), 4.46 (q, J=7.2 Hz, 2H), 3.20 (s, 2.6H), 3.15 (s, 0.4H), 3.10 (s, 0.4H), 2.99 (s, 2.6H), 2.94-2.91 (m, 0.4H), 2.71 (s, 2.6H), 1.42 (t, J=7.2 Hz, 3H).

(27) To a solution of ethyl 2-chloro-3-[[ethanethioyl(methyl)amino]methyl]-4-methylsulfonyl-benzoate (120 mg, 0.330 mmol) in acetonitrile (3.89 g, 4.95 mL, 94.2 mmol) was added triethylamine (337 mg, 0.464 mL, 3.30 mmol), o-methylhydroxylamine hydrochloride (141 mg, 1.65 mmol) and silver tetrafluoroborate (0.3242 g, 1.65 mmol). The reaction mixture was stirred overnight at room temperature. LCMS analysis showed formation of product and no remaining starting material. The solution was filtered through a plug of silica to remove the silver precipitate, and washed with MeCN (20 mL). The mixture was concentrated in vacuo to remove the MeCN. The residue was dissolved in EtOAc (20 mL) and washed with water (20 mL), brine (20 mL), dried over magnesium sulfate and concentrated in vacuo. The product was purified by flash column chromatography (0-50% EtOAc/isohexane) to give ethyl 2-chloro-3-[[[N-methoxy-C-methyl-carbonimidoyl]-methyl-amino]methyl]-4-methylsulfonyl-benzoate (90 mg, 0.239 mmol) as a brown gum. .sup.1H NMR (400 MHz, chloroform) 6=8.13 (d, J=8.2 Hz, 1H), 7.70 (d, J=8.2 Hz, 1H), 4.94 (s, 2H), 4.45 (q, J=7.2 Hz, 2H), 3.71 (s, 3H), 3.20 (s, 3H), 2.61 (s, 3H), 2.05 (s, 3H), 1.42 (t, J=7.2 Hz, 3H).

(28) To a solution of ethyl 2-chloro-3-[[[N-methoxy-C-methyl-carbonimidoyl]-methyl-amino]methyl]-4-methylsulfonyl-benzoate (95 mg, 0.252 mmol) in tetrahydrofuran (1.69 g, 1.90 mL, 23.4 mmol) and water (1.9 g, 1.9 mL, 0.106 mmol) was added lithium hydroxide (53.9 mg, 2.25 mmol). The reaction was stirred at room temperature for 30 min. LCMS analysis showed formation of product. The mixture was partly concentrated in vacuo to remove tetrahydrofuran. The resulting aqueous solution was diluted with water (1 mL) and acidified with a few drops of 2 M HCl to pH 2. The mixture was then basified with aqueous NH.sub.3 until pH 9. The resulting solution was loaded on to a reverse phase column and purified using reverse phase chromatography (0-20% MeCN in H.sub.2O containing 0.1% NH.sub.3). The column fractions containing product were combined and concentrated using a freeze-dryer over the weekend to give 2-chloro-3-[[[N-methoxy-C-methyl-carbonimidoyl]-methyl-amino]methyl]-4-methylsulfonyl-benzoic acid (84 mg, 0.229 mmol) as a yellow gum.

(29) A solution of 2-chloro-3-[[[N-methoxy-C-methyl-carbonimidoyl]-methyl-amino]methyl]-4-methylsulfonyl-benzoic acid (65 mg, 0.186 mmol), 1-methyl-1H-tetrazol-5-amine (25.3 mg, 0.242 mmol) and 4-dimethylaminopyridine (69.0 mg, 0.559 mmol) in DCM (2.47 g, 1.86 mL, 29.0 mmol) were stirred at room temperature for 1 h. 1-propanephosphonic anhydride (0.712 g, 0.666 mL, 1.12 mmol) was added to the reaction mixture, and was transferred to a microwave vial and heated in the microwave to 100° C. for 30 min. LCMS analysis showed formation of product. The reaction mixture was concentrated in vacuo to give an orange oil. The solution was diluted in water (5 mL) and basified with conc. NH3 solution until pH ˜9/10. The product was purified by reverse phase column chromatography (0-50% MeCN in H.sub.2O containing 0.1% NH.sub.3). The product containing fractions were concentrated using the freeze-dryer to give 2-chloro-3-[[[N-methoxy-C-methyl-carbonimidoyl]-methyl-amino]methyl]-4-methylsulfonyl-N-(1-methyltetrazol-5-yl)benzamide (8.3 mg, 0.019 mmol) as a colourless gum. .sup.1H NMR (400 MHz, methanol) 6=8.20 (d, J=8.2 Hz, 1H), 7.83 (d, J=8.1 Hz, 1H), 4.95 (s, 2H), 4.06 (s, 3H), 3.68 (s, 3H), 3.27 (s, 3H), 2.60 (s, 3H), 2.06 (s, 3H).

PREPARATIVE EXAMPLE 8: COMPOUND 5.014

(30) To a solution of methylamine (2 M in THF, 40 g, 46 mL, 92.6 mmol) was added dropwise ethyl 3-(bromomethyl)-2-chloro-4-(trifluoromethyl)benzoate (2.0 g, 5.79 mmol) in acetonitrile (11.6 mL). The reaction was stirred at room temperature for 10 min. LCMS analysis showed formation of product and no remaining starting material. The reaction was concentrated in vacuo, then diluted with EtOAc (200 mL) and washed with sat. K.sub.2CO.sub.3 solution (100 mL), brine (100 mL) and concentrated in vacuo to give ethyl 2-chloro-3-(methylaminomethyl)-4-(trifluoromethyl)benzoate (1.80 g, 5.78 mmol) as a yellow oil. NMR analysis showed the desired product. .sup.1H NMR (400 MHz, chloroform) 6=7.73-7.53 (m, 2H), 4.43 (q, J=7.1 Hz, 2H), 4.01 (d, J=0.7 Hz, 2H), 2.51 (s, 3H), 1.41 (t, J=7.1 Hz, 3H) (N—H not observed). .sup.19F NMR (376 MHz, chloroform) δ= −58.94

(31) To a solution of ethyl 2-chloro-3-(methylaminomethyl)-4-(trifluoromethyl)benzoate (500 mg, 1.69 mmol), 4-dimethylaminopyridine (21.1 mg, 0.169 mmol) and triethylamine (346 mg, 0.476 mL, 3.38 mmol) in tetrahydrofuran (15.0 g, 16.9 mL) was added dropwise ethyl dithioacetate (415 mg, 0.396 mL, 3.38 mmol). The reaction was equipped with a reflux condenser, stirred and heated to 60° C. for 10 days. LCMS analysis showed formation of product, but also remaining starting material. The reaction was cooled to room temperature, and then concentrated in vacuo to remove tetrahydrofuran. The mixture was diluted with DCM (50 mL) and water (50 mL). The water was extracted with DCM (50 mL×2), and then the organics washed with brine (50 mL), and concentrated in vacuo. The product was purified by flash column chromatography (0-30% EtOAc/isohexane) to give ethyl 2-chloro-3-[[ethanethioyl(methyl)amino]methyl]-4-(trifluoromethyl)benzoate (370 mg, 0.941 mmol) as a brown gum. NMR shows two rotamers. .sup.1H NMR (400 MHz, chloroform) 6=7.87-7.71 (m, 2H), 5.54 (br s, 1.5H), 5.09 (s, 0.5H), 4.50-4.39 (m, 2H), 3.09 (s, 0.75H), 2.89 (s, 3H), 2.72 (s, 2.25H), 1.46-1.37 (m, 3H).

(32) To a solution of ethyl 2-chloro-3-[[ethanethioyl(methyl)amino]methyl]-4-(trifluoro methyl)benzoate (370 mg, 1.05 mmol) in acetonitrile (12.3 g, 15.7 mL) was added triethylamine (1.07 g, 1.47 mL, 10.46 mmol), O-methylhydroxylamine hydrochloride (446 mg, 5.23 mmol) and silver tetrafluoroborate (1.03 g, 5.23 mmol). The reaction mixture was stirred for 5 days at room temperature. LCMS analysis showed formation of product and no remaining starting material. The solution was filtered through a plug of silica to remove the silver precipitate, and washed with MeCN (20 mL). The mixture was concentrated in vacuo to remove the MeCN. The residue was dissolved in EtOAc (20 mL) and washed with water (20 mL), brine (20 mL), dried over magnesium sulfate and concentrated in vacuo. The product was purified by flash column chromatography (0-20% EtOAc/isohexane) to give ethyl 2-chloro-3-[[[(Z)—N-methoxy-C-methyl-carbonimidoyl]-methyl-amino]methyl]-4-(trifluoromethyl)benzoate (254 mg, 0.692 mmol) as a brown gum. .sup.1H NMR (400 MHz, chloroform) δ=7.67 (s, 2H), 4.66 (d, J=0.9 Hz, 2H), 4.44 (q, J=7.2 Hz, 2H), 3.74 (s, 3H), 2.48 (s, 3H), 2.04 (s, 3H), 1.41 (t, J=7.2 Hz, 3H). .sup.19F NMR (376 MHz, chloroform) d= −58.33 (s, 1F).

(33) To a solution of ethyl 2-chloro-3-[[[N-methoxy-C-methyl-carbonimidoyl]-methyl-amino]methyl]-4-(trifluoromethyl)benzoate (250 mg, 0.682 mmol) in tetrahydrofuran (4.45 g, 5.0 mL, 61.6 mmol) and water (5.0 g, 5.0 mL, 277 mmol) was added lithium hydroxide (87.4 mg, 2.05 mmol). The reaction was stirred at room temperature for 3 h. LCMS analysis showed formation of product. The resulting aqueous solution was diluted with water (1 mL) and acidified with a few drops of 2 M HCl to pH ˜2. The mixture was then concentrated in vacuo to remove THF and most of the water. The mixture was then diluted with water (2 mL total) and basified with aqueous NH.sub.3 until pH 9. The resulting solution was loaded on to a reverse phase column and purified using reverse phase chromatography (0-20% MeCN in H.sub.2O containing 0.1% NH.sub.3). The product containing fractions were concentrated using a freeze dryer overnight to give 2-chloro-3-[[[N-methoxy-C-methyl-carbonimidoyl]-methyl-amino]methyl]-4-(trifluoromethyl)benzoic acid (207 mg, 0.580 mmol).

(34) A solution of 2-chloro-3-[[[N-methoxy-C-methyl-carbonimidoyl]-methyl-amino]methyl]-4-(trifluoromethyl)benzoic acid (75 mg, 0.221 mmol), 5-methyl-1,3,4-oxadiazol-2-amine (29.4 mg, 0.287 mmol) and 4-dimethylaminopyridine (82.0 mg, 0.665 mmol) in DCM (2.93 g, 2.21 mL, 34.5 mmol) were stirred at room temperature for 1 h. 1-propanephosphonic anhydride (846 mg, 0.791 mL, 1.33 mmol) was added to the reaction mixture, and was transferred to a microwave vial and heated in the microwave to 80° C. for 1 h. LCMS analysis showed formation of product. The reaction mixture was concentrated in vacuo to give an orange oil. The mixture was dissolved in DCM (20 mL), and partitioned with dilute NaHCO.sub.3 (20 mL). The aqueous was washed with DCM (20 mL×5). The combined organics were washed with brine (20 mL) and concentrated in vacuo. The product was purified to give 2-chloro-3-[[[N-methoxy-C-methyl-carbonimidoyl]-methyl-amino]methyl]-N-(5-methyl-1,3,4-oxadiazol-2-yl)-4-(trifluoromethyl)benzamide (4.0 mg, 9.53 μmol) as a colourless gum. .sup.1H NMR (400 MHz, Methanol) 6=7.83 (d, J=8.1 Hz, 1H), 7.68 (d, J=8.1 Hz, 1H), 4.65 (s, 2H), 3.68 (s, 3H), 2.55-2.44 (m 6H), 2.04 (s, 3H).

(35) TABLE-US-00001 TABLE 1 Examples of herbicidal compounds of the present invention. Compound 1H-NMR Number R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 X (in CDCl.sub.3 unless otherwise stated) 1.001 Me Me H Me Me — 1.002 Me Me H Me Me CH.sub.2 1.003 Me Me H Me Et — 1.004 Me Me H Me Et CH.sub.2 1.005 Me Me H Et Me — 1.006 Me Me H Et Me CH.sub.2 1.007 Me Me H Et Et — 1.008 Me Me H Et Et CH.sub.2 1.009 Me Cl H Me Me — 1.010 Me Cl H Me Me CH.sub.2 1.011 Me Cl H Me Et — 1.012 Me Cl H Me Et CH.sub.2 1.013 Me Cl H Et Me — 1.014 Me Cl H Et Me CH.sub.2 1.015 Me Cl H Et Et — 1.016 Me Cl H Et Et CH.sub.2 1.017 Me CF.sub.3 H Me Me — 1HNMR (400 MHz, d4- methanol) 7.57 (d, 1H), 7.36 (d, 1H), 7.29 (d, 1H), 4.05 (s, 3H), 3.05 (s, 6H), 2.27 (s, 3H) 1.018 Me CF.sub.3 H Me Me CH.sub.2 1.019 Me CF.sub.3 H Me Et — 1.020 Me CF.sub.3 H Me Et CH.sub.2 1.021 Me CF.sub.3 H Et Me — 1.022 Me CF.sub.3 H Et Me CH.sub.2 1.023 Me CF.sub.3 H Et Et — 1.024 Me CF.sub.3 H Et Et CH.sub.2 1.025 Me SO.sub.2Me H Me Me — 1H NMR (400 MHz, DMSO-d6) d = 7.71 (d, J = 8.2 Hz, 1H), 7.39 (s, 1H), 7.30 (d, J = 8.2 Hz, 1H), 3.88 (s, 3H), 3.24 (s, 3H), 3.00 (s, 6H), 2.18 (s, 3H) 1.026 Me SO.sub.2Me H Me Me CH.sub.2 1.027 Me SO.sub.2Me H Me Et — 1HNMR (400 MHz, chloroform): 10.76 (brs, 1H), 7.87 (d, 1H), 7.42- 7.31 (m, 1.7H), 4.10 (s, 3H), 3.61- 3.52 (m, 0.7H), 3.33 (q, 1.3H), 3.22 (s, 3H), 3.06 (s, 2H), 3.03 (s, 1H), 2.32 (s, 3H), 1.25 (q, 3H) 1.028 Me SO.sub.2Me H Me Et CH.sub.2 1.029 Me SO.sub.2Me H Et Me — 1.030 Me SO.sub.2Me H Et Me CH.sub.2 1.031 Me SO.sub.2Me H Et Et — 1HNMR (400 MHz, chloroform): 11.21-10.14 (m, 1H), 7.87 (d, 1H), 7.36 (d, 1H), 7.31 (s, 1H), 4.10 (s, 3H), 3.56 (q, 2H), 3.31 (q, 2H), 3.21 (s, 3H), 2.33 (s, 3H), 1.33-1.21 (m, 6H) 1.032 Me SO.sub.2Me H Et Et CH.sub.2 1.033 Cl Me H Me Me — 1.034 Cl Me H Me Me CH.sub.2 1.035 Cl Me H Me Et — 1.036 Cl Me H Me Et CH.sub.2 1.037 Cl Me H Et Me — 1.038 Cl Me H Et Me CH.sub.2 1.039 Cl Me H Et Et — 1.040 Cl Me H Et Et CH.sub.2 1.041 Cl Cl H Me Me — 1H NMR (400 MHz, DMSO-d6) δ = 12.13-11.48 (m, 1H), 7.59 (s, 1H), 7.51 (d, J = 8.3 Hz, 1H), 7.23 (d, J = 8.3 Hz, 1H), 3.97 (s, 3H), 3.06-2.96 (m, 6H) 1.042 Cl Cl H Me Me CH.sub.2 1.043 Cl Cl H Me Et — 1.044 Cl Cl H Me Et CH.sub.2 1.045 Cl Cl H Et Me — 1.046 Cl Cl H Et Me CH.sub.2 1.047 Cl Cl H Et Et — 1.048 Cl Cl H Et Et CH.sub.2 1.049 Cl CF.sub.3 H Me Me — 1H NMR (400 MHz, DMSO-d6) δ = 11.86 (br s, 1H), 7.83-7.59 (m, 2H), 7.55-7.33 (m, 1H), 4.00 (s, 3H), 3.07 (br s, 3H), 2.99 (br s, 3H) 1.050 Cl CF.sub.3 H Me Me CH.sub.2 1.051 Cl CF.sub.3 H Me Et — 1.052 Cl CF.sub.3 H Me Et CH.sub.2 1.053 Cl CF.sub.3 H Et Me — 1.054 Cl CF.sub.3 H Et Me CH.sub.2 1.055 Cl CF.sub.3 H Et Et — δ = 10.42 (br s, 1H), 7.60 (d, J = 8.2 Hz, 1H), 7.36 (s, 1H), 7.31 (d, J = 8.1 Hz, 1H), 4.12 (s, 3H), 3.54 (q, J = 7.1 Hz, 2H), 3.31 (q, J = 7.2 Hz, 2H), 1.29- 1.23 (m, 6H) 1.056 Cl CF.sub.3 H Et Et CH.sub.2 1.057 Cl SO.sub.2Me H Me Me — 1HNMR (400 MHz, DMSO-d6): 3.05 (d, 6H), 3.33 (s, 3H), 3.98 (s, 3H), 7.41 (d, 1H), 7.62 (s, 1H), 7.87 (d, 1H) 1.058 Cl SO.sub.2Me H Me Me CH.sub.2 1.059 Cl SO.sub.2Me H Me Et — 1.060 Cl SO.sub.2Me H Me Et CH.sub.2 1.061 Cl SO.sub.2Me H Et Me — 1.062 Cl SO.sub.2Me H Et Me CH.sub.2 1.063 Cl SO.sub.2Me H Et Et — 1.064 Cl SO.sub.2Me H Et Et CH.sub.2 1.065 CF.sub.3 Me H Me Me — 1.066 CF.sub.3 Me H Me Me CH.sub.2 1.067 CF.sub.3 Me H Me Et — 1.068 CF.sub.3 Me H Me Et CH.sub.2 1.069 CF.sub.3 Me H Et Me — 1.070 CF.sub.3 Me H Et Me CH.sub.2 1.071 CF.sub.3 Me H Et Et — 1.072 CF.sub.3 Me H Et Et CH.sub.2 1.073 CF.sub.3 Cl H Me Me — 1.074 CF.sub.3 Cl H Me Me CH.sub.2 1.075 CF.sub.3 Cl H Me Et — 1.076 CF.sub.3 Cl H Me Et CH.sub.2 1.077 CF.sub.3 Cl H Et Me — 1.078 CF.sub.3 Cl H Et Me CH.sub.2 1.079 CF.sub.3 Cl H Et Et — 1.080 CF.sub.3 Cl H Et Et CH.sub.2 1.081 CF.sub.3 CF.sub.3 H Me Me — 1.082 CF.sub.3 CF.sub.3 H Me Me CH.sub.2 1.083 CF.sub.3 CF.sub.3 H Me Et — 1.084 CF.sub.3 CF.sub.3 H Me Et CH.sub.2 1.085 CF.sub.3 CF.sub.3 H Et Me — 1.086 CF.sub.3 CF.sub.3 H Et Me CH.sub.2 1.087 CF.sub.3 CF.sub.3 H Et Et — 1.088 CF.sub.3 CF.sub.3 H Et Et CH.sub.2 1.089 CF.sub.3 SO.sub.2Me H Me Me — 1HNMR (500 MHz, Chloroform): 8.23 (d, 1H), 7.36 (s, 1H), 7.24 (d, 1H), 4.11 (s, 3H), 3.27 (s, 3H), 3.07 (d, 6H) 1.090 CF.sub.3 SO.sub.2Me H Me Me CH.sub.2 1.091 CF.sub.3 SO.sub.2Me H Me Et — 1.092 CF.sub.3 SO.sub.2Me H Me Et CH.sub.2 1.093 CF.sub.3 SO.sub.2Me H Et Me — 1.094 CF.sub.3 SO.sub.2Me H Et Me CH.sub.2 1.095 CF.sub.3 SO.sub.2Me H Et Et — 1.096 CF.sub.3 SO.sub.2Me H Et Et CH.sub.2 1.097 SO.sub.2Me Me H Me Me — 1.098 SO.sub.2Me Me H Me Me CH.sub.2 1.099 SO.sub.2Me Me H Me Et — 1.100 SO.sub.2Me Me H Me Et CH.sub.2 1.101 SO.sub.2Me Me H Et Me — 1.102 SO.sub.2Me Me H Et Me CH.sub.2 1.103 SO.sub.2Me Me H Et Et — 1.104 SO.sub.2Me Me H Et Et CH.sub.2 1.105 SO.sub.2Me Cl H Me Me — 1.106 SO.sub.2Me Cl H Me Me CH.sub.2 1.107 SO.sub.2Me Cl H Me Et — 1.108 SO.sub.2Me Cl H Me Et CH.sub.2 1.109 SO.sub.2Me Cl H Et Me — 1.110 SO.sub.2Me Cl H Et Me CH.sub.2 1.111 SO.sub.2Me Cl H Et Et — 1.112 SO.sub.2Me Cl H Et Et CH.sub.2 1.113 SO.sub.2Me CF.sub.3 H Me Me — 1.114 SO.sub.2Me CF.sub.3 H Me Me CH.sub.2 1.115 SO.sub.2Me CF.sub.3 H Me Et — 1.116 SO.sub.2Me CF.sub.3 H Me Et CH.sub.2 1.117 SO.sub.2Me CF.sub.3 H Et Me — 1.118 SO.sub.2Me CF.sub.3 H Et Me CH.sub.2 1.119 SO.sub.2Me CF.sub.3 H Et Et — 1.120 SO.sub.2Me CF.sub.3 H Et Et CH.sub.2 1.121 SO.sub.2Me SO.sub.2Me H Me Me — 1.122 SO.sub.2Me SO.sub.2Me H Me Me CH.sub.2 1.123 SO.sub.2Me SO.sub.2Me H Me Et — 1.124 SO.sub.2Me SO.sub.2Me H Me Et CH.sub.2 1.125 SO.sub.2Me SO.sub.2Me H Et Me — 1.126 SO.sub.2Me SO.sub.2Me H Et Me CH.sub.2 1.127 SO.sub.2Me SO.sub.2Me H Et Et — 1.128 SO.sub.2Me SO.sub.2Me H Et Et CH.sub.2 1.129 Cl SO.sub.2Me Me Me Me —CH.sub.2O— d = 8.15 (d, J = 8.2 Hz, 1H), 7.76 (d, J = 8.1 Hz, 1H), 5.54 (s, 2H), 4.14 (s, 3H), 3.41 (s, 3H), 2.72 (s, 6H), 1.94 (s, 3H) 1.130 Cl CF.sub.3 H CF.sub.3CH.sub.2— Me — δ = 11.21 (br s, 1H), 7.65-7.56 (m, 2H), 7.36 (br d, J = 7.9 Hz, 1H), 4.21 (q, J = 9.0 Hz, 0.9H), 4.12 (s, 3H), 3.84 (q, J = 8.4 Hz, 1.1H), 3.21 (s, 3H) 1.131 Cl CF.sub.3 H Me -phenyl — 1H NMR (400 MHz, chloroform) δ = 10.63 (br s, 1H), 7.98 (s, 1H), 7.66 (d, J = 8.2 Hz, 1H), 7.46-7.34 (m, 3H), 7.24-7.16 (m, 3H), 4.11 (s, 3H), 3.56 (s, 3H) 1.132 Cl CF.sub.3 H —CH.sub.2CH.sub.2CH.sub.2CH.sub.2— — δ = 10.46 (br s, 1H), 7.58 (d, J = 8.2 Hz, 1H), 7.49 (s, 1H), 7.30 (d, J = 7.8 Hz, 1H), 4.09 (s, 3H), 3.63 (br s, 2H), 3.53 (br t, J = 6.4 Hz, 2H), 2.11-1.94 (m, 4H) 1.133 Cl CF.sub.3 Me Me Et — 1.134 Cl CF.sub.3 H —CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2— — δ = 10.52 (br s, 1H), 7.59 (d, J = 8.1 Hz, 1H), 7.35 (s, 1H), 7.30 (d, J = 7.9 Hz, 1H), 4.11 (s, 3H), 3.67 (br s, 2H), 3.34 (br s, 2H), 1.72 (br d, J = 4.5 Hz, 2H), 1.64 (br s, 4H) 1.135 Cl CF.sub.3 H —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2— — δ = 11.86 (br s, 1H), 7.71 (d, J = 8.1 Hz, 1H), 7.66 (s, 1H), 7.41 (d, J = 7.9 Hz, 1H), 4.00 (s, 3H), 3.63 (br s, 6H), 3.46 (br s, 2H) 1.136 Cl CF.sub.3 H Me Et — δ = 10.46 (br s, 1H), 7.60 (d, J = 8.1 Hz, 1H), 7.40 (s, 0.6H), 7.35-7.28 (m, 1.4H), 4.11 (s, 3H), 3.56 (q, J = 6.8 Hz, 0.8H), 3.33 (q, J = 7.2 Hz, 1.2H), 3.08 (s, 1.8H), 3.04 (s, 1.2H), 1.24 (br t, J = 7.0 Hz, 3H) 1.137 Cl CF.sub.3 Me Me Me —CH.sub.2CH.sub.2— 1.138 Cl CF.sub.3 Me Me Me O 1.139 Cl CF.sub.3 CF.sub.3 Me Me — 7.59 (d, 1H), 7.31 (d, J = 8.1 Hz, 1H), 4.11 (s, 3H), 3.17 (s, 6H) 1.140 Cl CF.sub.3 H Me -iPr — 1HNMR (400 MHz, d4-methanol): 1.23-1.32 (m, 6H), 2.90-2.99 (m, 3H), 3.67-3.83 (m, 1H), 3.99-4.09 (m, 3H), 7.30-7.39 (m, 1H), 7.54 (s, 1H), 7.61- 7.72 (m, 1H) 1.141 Cl SO.sub.2Me H —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2— — 1HNMR (400 MHz, d4-methanol): 3.26-3.28 (m, 3H), 3.46-3.53 (m, 2H), 3.71-3.80 (m, 6H), 4.06 (s, 3H), 7.39 (d, 1H), 7.55 (s, 1H), 7.98 (d, 1H) 1.142 Cl SO.sub.2Me H Me —CH.sub.2CF.sub.3 — 1HNMR (400 MHz, chloroform): 8.04- 8.00 (m, 1H), 7.63 (d, 1H), 7.44- 7.39 (m, 1H), 4.23 (q, 1H), 4.13 (s, 3H), 3.86 (q, 1H), 3.29-3.17 (m, 6H) 1.143 Me SO.sub.2Me H Me —CH.sub.2CF.sub.3 — 1HNMR (400 MHz, d4-methanol): 7.92 (d, 1H), 7.49 (s, 1H), 7.42 (d, 1H), 4.41-4.29 (m, 1H), 4.14-4.03 (m, 4H), 3.25-3.13 (m, 6H), 2.27 (s, 3H) 1.144 Me SO.sub.2Me H Me -iPr — 1HNMR (400 MHz, chloroform): 7.89 (d, 1H), 7.43-7.31 (m, 1.8H), 7.24 (s, 0.2H), 4.80 (td, 0.2H), 4.10 (s, 3H), 3.64 (sepet, 0.8H), 3.25- 3.17 (m, 3H), 2.98 (s, 2.3H), 2.90 (s, 0.7H), 2.31 (s, 3H), 1.28 (d, 6H) 1.145 Cl SO.sub.2Me H Me -phenyl — 1HNMR (400 MHz, chloroform): 10.24 (brs, 1H), 7.97 (d, 1H), 7.84 (s, 1H), 7.43 (d, 1H), 7.39- 7.33 (m, 2H), 7.25-7.13 (m, 3H), 4.11 (s, 3H), 3.56 (s, 3H), 3.23 (s, 3H), 2.36 (s, 3H) 1.146 Me SO.sub.2Me H —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2— — 1HNMR (400 MHz, d4-methanol): 7.90 (d, 1H), 7.43-7.32 (m, 2H), 4.05 (s, 3H), 3.75 (brs, 6H), 3.45 (brd, 2H), 3.21 (s, 3H), 2.28 (s, 3H) 1.147 Me CF.sub.3 H —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2— — 1HNMR (400 MHz, d4-methanol): 7.58 (d, 1H), 7.39-7.31 (m, 2H), 4.05 (s, 3H), 3.72 (brs, 8H), 2.27 (s, 3H) 1.148 Cl CF.sub.3 Me Me Me — 1HNMR (400 MHz, d4-methanol) 7.67 (d, 1H), 7.31 (d, 1H), 4.06 (s, 3H), 3.11 (s, 6H), 1.81 (s, 3H) 1.149 Cl CHF.sub.2 H Me Me — 1.150 Cl CHF.sub.2 H Me Me CH.sub.2 1.151 Cl CHF.sub.2 H Me Et — 1.152 Cl CHF.sub.2 H Me Et CH.sub.2 1.153 Cl CHF.sub.2 H Et Me — 1.154 Cl CHF.sub.2 H Et Me CH.sub.2 1.155 Cl CHF.sub.2 H Et Et — 1.156 Cl CHF.sub.2 H Et Et CH.sub.2

(36) TABLE-US-00002 TABLE 2 Examples of herbicidal compounds of the present invention. .sup.1H-NMR Compound (in CDCl.sub.3 unless Number R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 X otherwise stated) 2.001 Me Me H Me Me — 2.002 Me Me H Me Me CH.sub.2 2.003 Me Me H Me Et — 2.004 Me Me H Me Et CH.sub.2 2.005 Me Me H Et Me — 2.006 Me Me H Et Me CH.sub.2 2.007 Me Me H Et Et — 2.008 Me Me H Et Et CH.sub.2 2.009 Me Cl H Me Me — 2.010 Me Cl H Me Me CH.sub.2 2.011 Me Cl H Me Et — 2.012 Me Cl H Me Et CH.sub.2 2.013 Me Cl H Et Me — 2.014 Me Cl H Et Me CH.sub.2 2.015 Me Cl H Et Et — 2.016 Me Cl H Et Et CH.sub.2 2.017 Me CF.sub.3 H Me Me — .sup.1HNMR(400 MHz,d4- methano1)7.55(d,1H),7.2 9(d,1H),7.25(d,1H),3.04(s, 6H),2.51(s,3H),2.23(s,3H) 2.018 Me CF.sub.3 H Me Me CH.sub.2 2.019 Me CF.sub.3 H Me Et — 2.020 Me CF.sub.3 H Me Et CH.sub.2 2.021 Me CF.sub.3 H Et Me — 2.022 Me CF.sub.3 H Et Me CH.sub.2 2.023 Me CF.sub.3 H Et Et — 2.024 Me CF.sub.3 H Et Et CH.sub.2 2.025 Me SO.sub.2Me H Me Me — (DMSO) δ = 8.14-7.15 (m, 3H), 3.29 (s, 3H), 3.23- 3.05 (m, 6H), 2.49 (br s, 3H), 2.32-2.15 (m, 3H) 2.026 Me SO.sub.2Me H Me Me CH.sub.2 2.027 Me SO.sub.2Me H Me Et — δ = 10.88(brs,1H), 7.86(d,1H), 7.33(s,0.7H), 7.30(d,1H), 7.24(s,0.3H), 3.62-3.51(m,0.7H), 3.30(q,1.3H), 3.21(s,3H), 3.05(s,2H), 3.01(s,1H), 2.54(s,3H), 2.29(s,3H), 1.32-1.19(m,3H) 2.028 Me SO.sub.2Me H Me Et CH.sub.2 2.029 Me SO.sub.2Me H Et Me — 2.030 Me SO.sub.2Me H Et Me CH.sub.2 2.031 Me SO.sub.2Me H Et Et — δ = 7.91-7.82(m,1H), 7.31-7.27(m,2H), 3.55(q,2H), 3.28(q,2H), 3.20(s,3H), 2.54(s,3H), 2.29(s,3H), 1.26(td,6H) 2.032 Me SO.sub.2Me H Et Et CH.sub.2 2.033 Cl Me H Me Me — 2.034 Cl Me H Me Me CH.sub.2 2.035 Cl Me H Me Et — 2.036 Cl Me H Me Et CH.sub.2 2.037 Cl Me H Et Me — 2.038 Cl Me H Et Me CH.sub.2 2.039 Cl Me H Et Et — 2.040 Cl Me H Et Et CH.sub.2 2.041 Cl Cl H Me Me — 2.042 Cl Cl H Me Me CH.sub.2 2.043 Cl Cl H Me Et — 2.044 Cl Cl H Me Et CH.sub.2 2.045 Cl Cl H Et Me — 2.046 Cl Cl H Et Me CH.sub.2 2.047 Cl Cl H Et Et — 2.048 Cl Cl H Et Et CH.sub.2 2.049 Cl CF.sub.3 H Me Me — (DMSO) δ = 7.60-7.50 (m, 2H), 7.18-7.11 (m, 1H), 3.02 (s, 3H), 2.98- 2.90 (m, 3H), 2.46-2.33 (m, 3H) 2.050 Cl CF.sub.3 H Me Me CH.sub.2 2.051 Cl CF.sub.3 H Me Et — 2.052 Cl CF.sub.3 H Me Et CH.sub.2 2.053 Cl CF.sub.3 H Et Me — 2.054 Cl CF.sub.3 H Et Me CH.sub.2 2.055 Cl CF.sub.3 H Et Et — δ = 7.54 (d, J = 8.1 Hz, 1H), 7.29-7.26 (m, 2H), 3.52 (q, J = 7.1 Hz, 2H), 3.28 (q, J = 7.1 Hz, 2H), 2.54 (s, 3H), 1.28-1.21 (m, 6H) 2.056 Cl CF.sub.3 H Et Et CH.sub.2 2.057 Cl SO.sub.2Me H Me Me — δ = 7.95(d,1H), 7.51(s,1H), 7.28(d,1H), 3.30 (s, 3H), 3.10(s,6H), 2.51(s,3H) 2.058 Cl SO.sub.2Me H Me Me CH.sub.2 2.059 Cl SO.sub.2Me H Me Et — 2.060 Cl SO.sub.2Me H Me Et CH.sub.2 2.061 Cl SO.sub.2Me H Et Me — 2.062 Cl SO.sub.2Me H Et Me CH.sub.2 2.063 Cl SO.sub.2Me H Et Et — 2.064 Cl SO.sub.2Me H Et Et CH.sub.2 2.065 CF.sub.3 Me H Me Me — 2.066 CF.sub.3 Me H Me Me CH.sub.2 2.067 CF.sub.3 Me H Me Et — 2.068 CF.sub.3 Me H Me Et CH.sub.2 2.069 CF.sub.3 Me H Et Me — 2.070 CF.sub.3 Me H Et Me CH.sub.2 2.071 CF.sub.3 Me H Et Et — 2.072 CF.sub.3 Me H Et Et CH.sub.2 2.073 CF.sub.3 Cl H Me Me — 2.074 CF.sub.3 Cl H Me Me CH.sub.2 2.075 CF.sub.3 Cl H Me Et — 2.076 CF.sub.3 Cl H Me Et CH.sub.2 2.077 CF.sub.3 Cl H Et Me — 2.078 CF.sub.3 Cl H Et Me CH.sub.2 2.079 CF.sub.3 Cl H Et Et — 2.080 CF.sub.3 Cl H Et Et CH.sub.2 2.081 CF.sub.3 CF.sub.3 H Me Me — 2.082 CF.sub.3 CF.sub.3 H Me Me CH.sub.2 2.083 CF.sub.3 CF.sub.3 H Me Et — 2.084 CF.sub.3 CF.sub.3 H Me Et CH.sub.2 2.085 CF.sub.3 CF.sub.3 H Et Me — 2.086 CF.sub.3 CF.sub.3 H Et Me CH.sub.2 2.087 CF.sub.3 CF.sub.3 H Et Et — 2.088 CF.sub.3 CF.sub.3 H Et Et CH.sub.2 2.089 CF.sub.3 SO.sub.2Me H Me Me — 2.090 CF.sub.3 SO.sub.2Me H Me Me CH.sub.2 2.091 CF.sub.3 SO.sub.2Me H Me Et — 2.092 CF.sub.3 SO.sub.2Me H Me Et CH.sub.2 2.093 CF.sub.3 SO.sub.2Me H Et Me — 2.094 CF.sub.3 SO.sub.2Me H Et Me CH.sub.2 2.095 CF.sub.3 SO.sub.2Me H Et Et — 2.096 CF.sub.3 SO.sub.2Me H Et Et CH.sub.2 2.097 SO.sub.2Me Me H Me Me — 2.098 SO.sub.2Me Me H Me Me CH.sub.2 2.099 SO.sub.2Me Me H Me Et — 2.100 SO.sub.2Me Me H Me Et CH.sub.2 2.101 SO.sub.2Me Me H Et Me — 2.102 SO.sub.2Me Me H Et Me CH.sub.2 2.103 SO.sub.2Me Me H Et Et — 2.104 SO.sub.2Me Me H Et Et CH.sub.2 2.105 SO.sub.2Me Cl H Me Me — 2.106 SO.sub.2Me Cl H Me Me CH.sub.2 2.107 SO.sub.2Me Cl H Me Et — 2.108 SO.sub.2Me Cl H Me Et CH.sub.2 2.109 SO.sub.2Me Cl H Et Me — 2.110 SO.sub.2Me Cl H Et Me CH.sub.2 2.111 SO.sub.2Me Cl H Et Et — 2.112 SO.sub.2Me Cl H Et Et CH.sub.2 2.113 SO.sub.2Me CF.sub.3 H Me Me — 2.114 SO.sub.2Me CF.sub.3 H Me Me CH.sub.2 2.115 SO.sub.2Me CF.sub.3 H Me Et — 2.116 SO.sub.2Me CF.sub.3 H Me Et CH.sub.2 2.117 SO.sub.2Me CF.sub.3 H Et Me — 2.118 SO.sub.2Me CF.sub.3 H Et Me CH.sub.2 2.119 SO.sub.2Me CF.sub.3 H Et Et — 2.120 SO.sub.2Me CF.sub.3 H Et Et CH.sub.2 2.121 SO.sub.2Me SO.sub.2Me H Me Me — 2.122 SO.sub.2Me SO.sub.2Me H Me Me CH.sub.2 2.123 SO.sub.2Me SO.sub.2Me H Me Et — 2.124 SO.sub.2Me SO.sub.2Me H Me Et CH.sub.2 2.125 SO.sub.2Me SO.sub.2Me H Et Me — 2.126 SO.sub.2Me SO.sub.2Me H Et Me CH.sub.2 2.127 SO.sub.2Me SO.sub.2Me H Et Et — 2.128 SO.sub.2Me SO.sub.2Me H Et Et CH.sub.2 2.129 Cl SO.sub.2Me Me Me Me —CH.sub.2O— δ = 8.13 (d, J = 8.2 Hz, 1H), 7.75 (d, J = 8.2 Hz, 1H), 5.55 (s, 2H), 3.40 (s, 3H), 2.73 (s, 6H), 2.54 (s, 3H), 1.94 (s, 3H) 2.130 Cl CF.sub.3 H CF.sub.3CH.sub.2— Me — δ = 7.54 (m, 1H), 7.40 (m, 1H), 7.31 (m, 1H), 4.19 (q, J = 9.0 Hz, 0.9H), 3.78 (q, J = 8.4 Hz, 1.1H), 3.19 (s, 1.8H), 3.16 (s, 1.2H), 2.52 (s, 3H) 2.131 Cl CF.sub.3 H Me —phenyl — δ = 11.12 (br s, 1H), 7.97 (s, 1H), 7.60 (d, J = 8.1 Hz, 1H), 7.41-7.36 (m, 2H), 7.33 (d, J = 7.9 Hz, 1H), 7.22-7.13 (m, 3H), 3.54 (s, 3H), 2.38 (s, 3H) 2.132 Cl CF.sub.3 H —CH.sub.2CH.sub.2CH.sub.2CH.sub.2— — δ = 7.60-7.50 (m, 2H), 7.28 (d, J = 8.6 Hz, 1H), 3.60-3.49 (m, 4H), 2.54 (s, 3H), 2.05-1.94 (m, 4H) 2.133 Cl CF.sub.3 Me Me Et — 2.134 Cl CF.sub.3 H —CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2— — 2.135 Cl CF.sub.3 H —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2— — 2.136 Cl CF.sub.3 H Me Et — δ = 10.15 (br s, 1H), 7.55 (d, J = 8.2 Hz, 1H), 7.35 (s, 0.6H), 7.29 (d, J = 8.2 Hz, 1H), 7.26 (s, 0.4H), 3.54 (q, J = 6.9 Hz, 0.8H), 3.31 (q, J = 7.2 Hz, 1.2H), 3.04 (s, 1.8H), 3.01 (s, 1.2H), 2.54 (s, 3H), 1.26-1.20 (m, 3H) 2.137 Cl CF.sub.3 Me Me Me —CH.sub.2CH.sub.2— 2.138 Cl CF.sub.3 Me Me Me O 2.139 Cl CF.sub.3 CF.sub.3 Me Me — 2.140 Cl CF.sub.3 H Me —iPr — 1HNMR(400 MHz,d4- methanol)1.18- 1.34(m,6H), 2.45- 2.54(m,3H), 2.90- 3.00(m,3H), 3.68- 3.80(m,1H), 7.21- 7.31(m,1H), 7.36(d,1H), 7.53(s,1H), 7.58- 7.70(m,1H) 2.141 Cl SO.sub.2Me H —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2— — 2.142 Cl SO.sub.2Me H Me —CH.sub.2CF.sub.3 — δ = 8.01-7.96(m,1H), 7.56-7.40(m,2H), 4.27- 4.17(m,1H), 3.81(q, 1H), 3.26-3.14(m,6H), 2.55(s,3H) 2.143 Me SO.sub.2Me H Me —CH.sub.2CF.sub.3 — 1HNMR(400 MHz,d4- methanol): 7.89(d,1H), 7.48(s,1H), 7.31(d,1H), 4.34(q,0.7H), 4.08(q,1.3H), 3.26- 3.10(m,6H), 2.51(s,3H), 2.23(s,3H) 2.144 Me SO.sub.2Me H Me —iPr — 1H NMR(400MHz,d4- methanol): 7.87(d,1H), 7.43(s,0.8H), 7.27(d,1.2H), 3.72(td,1H), 3.22(s,3H), 3.00(s,2.4H), 2.92(s,0.6H), 2.51(s,3H), 2.24(s,3H), 1.28(d,6H) 2.145 Cl SO.sub.2Me H Me —phenyl — δ = 7.96(d,1H), 7.87(s,1H), 7.41- 7.34(m,3H), 7.25- 7.14(m,3H), 3.56(s,3H), 3.23(s,3H), 2.43(s,3H), 2.35(s,3H) 2.146 Me SO.sub.2Me H —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2— — 1HNMR(400 MHz,d4- methanol): 7.87(d,1H), 7.36(s,1H), 7.28(d,1H), 3.75(brs,6H), 3.54- 3.37(m,2H), 3.20(s,3H), 2.51(s,3H), 2.24(s,3H) 2.147 Me CF.sub.3 H —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2— — 1HNMR(400 MHz,d4- methanol): 7.55(d,1H), 7.34(d,1H), 7.25(d,1H), 3.81-3.36(m,8H), 2.51(s,3H), 2.23(s,3H) 2.148 Cl CF.sub.3 Me Me Me — 1HNMR(400 MHz,d4- methano1)7.64(d,1H),7.23 (d,1H),3.10(s,6H),2.50(s, 3H),1.80(s,3H) 2.149 Cl CHF.sub.2 H Me Me — 2.150 Cl CHF.sub.2 H Me Me CH.sub.2 2.151 Cl CHF.sub.2 H Me Et — 2.152 Cl CHF.sub.2 H Me Et CH.sub.2 2.153 Cl CHF.sub.2 H Et Me — 2.154 Cl CHF.sub.2 H Et Me CH.sub.2 2.155 Cl CHF.sub.2 H Et Et — 2.156 Cl CHF.sub.2 H Et Et CH.sub.2

(37) TABLE-US-00003 TABLE 3 Examples of herbicidal compounds of the present invention. 0 1H-NMR Compound (in CDCl.sub.3 unless otherwise Number R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 X stated) 3.001 Me Me H Me Me — 3.002 Me Me H Me Me CH.sub.2 3.003 Me Me H Me Et — 3.004 Me Me H Me Et CH.sub.2 3.005 Me Me H Et Me — 3.006 Me Me H Et Me CH.sub.2 3.007 Me Me H Et Et — 3.008 Me Me H Et Et CH.sub.2 3.009 Me Cl H Me Me — 3.010 Me Cl H Me Me CH.sub.2 3.011 Me Cl H Me Et — 3.012 Me Cl H Me Et CH.sub.2 3.013 Me Cl H Et Me — 3.014 Me Cl H Et Me CH.sub.2 3.015 Me Cl H Et Et — 3.016 Me Cl H Et Et CH.sub.2 3.017 Me CF.sub.3 H Me Me — 1HNMR(400 MHz,d4-methanol) 7.75(brs,1H),7.51(d,1H),7.05(d,1H), 3.18(brd,6H),2.49(t,4H),2.11(s,3H),1.97 (quin, 2H) 3.018 Me CF.sub.3 H Me Me CH.sub.2 3.019 Me CF.sub.3 H Me Et — 3.020 Me CF.sub.3 H Me Et CH.sub.2 3.021 Me CF.sub.3 H Et Me — 3.022 Me CF.sub.3 H Et Me CH.sub.2 3.023 Me CF.sub.3 H Et Et — 3.024 Me CF.sub.3 H Et Et CH.sub.2 3.025 Me SO.sub.2Me H Me Me — (DMSO) δ = 7.66 (d, J = 8.1 Hz, 1H), 7.40 (s, 1H), 6.90 (d, J = 8.2 Hz, 1H), 3.24 (s, 3H), 3.00 (br d, J = 4.6 Hz, 6H), 2.64-2.51 (m, 4H), 1.99-1.91 (m, 5H) 3.026 Me SO.sub.2Me H Me Me CH.sub.2 3.027 Me SO.sub.2Me H Me Et — 3.028 Me SO.sub.2Me H Me Et CH.sub.2 3.029 Me SO.sub.2Me H Et Me — 3.030 Me SO.sub.2Me H Et Me CH.sub.2 3.031 Me SO.sub.2Me H Et Et — 3.032 Me SO.sub.2Me H Et Et CH.sub.2 3.033 Cl Me H Me Me — 3.034 Cl Me H Me Me CH.sub.2 3.035 Cl Me H Me Et — 3.036 Cl Me H Me Et CH.sub.2 3.037 Cl Me H Et Me — 3.038 Cl Me H Et Me CH.sub.2 3.039 Cl Me H Et Et — 3.040 Cl Me H Et Et CH.sub.2 3.041 Cl Cl H Me Me — 3.042 Cl Cl H Me Me CH.sub.2 3.043 Cl Cl H Me Et — 3.044 Cl Cl H Me Et CH.sub.2 3.045 Cl Cl H Et Me — 3.046 Cl Cl H Et Me CH.sub.2 3.047 Cl Cl H Et Et — 3.048 Cl Cl H Et Et CH.sub.2 3.049 Cl CF.sub.3 H Me Me — (DMSO): 7.59-7.49 (m, 2H), 6.94 (d, J = 8.1 Hz, 1H), 3.01 (s, 3H), 2.97- 2.90 (m, 3H), 2.70-2.51 (m, 4H), 1.93 (quin, J = 6.3 Hz, 2H) 3.050 Cl CF.sub.3 H Me Me CH.sub.2 3.051 Cl CF.sub.3 H Me Et — 3.052 Cl CF.sub.3 H Me Et CH.sub.2 3.053 Cl CF.sub.3 H Et Me — 3.054 Cl CF.sub.3 H Et Me CH.sub.2 3.055 Cl CF.sub.3 H Et Et — 3.056 Cl CF.sub.3 H Et Et CH.sub.2 3.057 Cl SO.sub.2Me H Me Me — 1HNMR(400 MHz,chloroform): 7.95(d,1H), 7.42(s,1H), 6.87(d,1H), 3.29(s,3H), 3.06(d,6H), 2.80(t,2H), 2.45(t, 2H), 2.06(quin,2H) 3.058 Cl SO.sub.2Me H Me Me CH.sub.2 3.059 Cl SO.sub.2Me H Me Et — 3.060 Cl SO.sub.2Me H Me Et CH.sub.2 3.061 Cl SO.sub.2Me H Et Me — 3.062 Cl SO.sub.2Me H Et Me CH.sub.2 3.063 Cl SO.sub.2Me H Et Et — 3.064 Cl SO.sub.2Me H Et Et CH.sub.2 3.065 CF.sub.3 Me H Me Me — 3.066 CF.sub.3 Me H Me Me CH.sub.2 3.067 CF.sub.3 Me H Me Et — 3.068 CF.sub.3 Me H Me Et CH.sub.2 3.069 CF.sub.3 Me H Et Me — 3.070 CF.sub.3 Me H Et Me CH.sub.2 3.071 CF.sub.3 Me H Et Et — 3.072 CF.sub.3 Me H Et Et CH.sub.2 3.073 CF.sub.3 Cl H Me Me — 3.074 CF.sub.3 Cl H Me Me CH.sub.2 3.075 CF.sub.3 Cl H Me Et — 3.076 CF.sub.3 Cl H Me Et CH.sub.2 3.077 CF.sub.3 Cl H Et Me — 3.078 CF.sub.3 Cl H Et Me CH.sub.2 3.079 CF.sub.3 Cl H Et Et — 3.080 CF.sub.3 Cl H Et Et CH.sub.2 3.081 CF.sub.3 CF.sub.3 H Me Me — 3.082 CF.sub.3 CF.sub.3 H Me Me CH.sub.2 3.083 CF.sub.3 CF.sub.3 H Me Et — 3.084 CF.sub.3 CF.sub.3 H Me Et CH.sub.2 3.085 CF.sub.3 CF.sub.3 H Et Me — 3.086 CF.sub.3 CF.sub.3 H Et Me CH.sub.2 3.087 CF.sub.3 CF.sub.3 H Et Et — 3.088 CF.sub.3 CF.sub.3 H Et Et CH.sub.2 3.089 CF.sub.3 SO.sub.2Me H Me Me — 3.090 CF.sub.3 SO.sub.2Me H Me Me CH.sub.2 3.091 CF.sub.3 SO.sub.2Me H Me Et — 3.092 CF.sub.3 SO.sub.2Me H Me Et CH.sub.2 3.093 CF.sub.3 SO.sub.2Me H Et Me — 3.094 CF.sub.3 SO.sub.2Me H Et Me CH.sub.2 3.095 CF.sub.3 SO.sub.2Me H Et Et — 3.096 CF.sub.3 SO.sub.2Me H Et Et CH.sub.2 3.097 SO.sub.2Me Me H Me Me — 3.098 SO.sub.2Me Me H Me Me CH.sub.2 3.099 SO.sub.2Me Me H Me Et — 3.100 SO.sub.2Me Me H Me Et CH.sub.2 3.101 SO.sub.2Me Me H Et Me — 3.102 SO.sub.2Me Me H Et Me CH.sub.2 3.103 SO.sub.2Me Me H Et Et — 3.104 SO.sub.2Me Me H Et Et CH.sub.2 3.105 SO.sub.2Me Cl H Me Me — 3.106 SO.sub.2Me Cl H Me Me CH.sub.2 3.107 SO.sub.2Me Cl H Me Et — 3.108 SO.sub.2Me Cl H Me Et CH.sub.2 3.109 SO.sub.2Me Cl H Et Me — 3.110 SO.sub.2Me Cl H Et Me CH.sub.2 3.111 SO.sub.2Me Cl H Et Et — 3.112 SO.sub.2Me Cl H Et Et CH.sub.2 3.113 SO.sub.2Me CF.sub.3 H Me Me — 3.114 SO.sub.2Me CF.sub.3 H Me Me CH.sub.2 3.115 SO.sub.2Me CF.sub.3 H Me Et — 3.116 SO.sub.2Me CF.sub.3 H Me Et CH.sub.2 3.117 SO.sub.2Me CF.sub.3 H Et Me — 3.118 SO.sub.2Me CF.sub.3 H Et Me CH.sub.2 3.119 SO.sub.2Me CF.sub.3 H Et Et — 3.120 SO.sub.2Me CF.sub.3 H Et Et CH.sub.2 3.121 SO.sub.2Me SO.sub.2Me H Me Me — 3.122 SO.sub.2Me SO.sub.2Me H Me Me CH.sub.2 3.123 SO.sub.2Me SO.sub.2Me H Me Et — 3.124 SO.sub.2Me SO.sub.2Me H Me Et CH.sub.2 3.125 SO.sub.2Me SO.sub.2Me H Et Me — 3.126 SO.sub.2Me SO.sub.2Me H Et Me CH.sub.2 3.127 SO.sub.2Me SO.sub.2Me H Et Et — 3.128 SO.sub.2Me SO.sub.2Me H Et Et CH.sub.2 3.129 Cl SO.sub.2Me Me Me Me —CH.sub.2O— δ = 8.12 (d, J = 8.1 Hz, 1H), 5.54 (s, 2H), 3.37 (s, 3H), 2.81 (t, J = 6.4 Hz, 2H), 2.73 (s, 6H), 2.44 (t, J = 6.4 Hz, 2H), 2.13-2.02 (m, 2H), 1.92 (s, 3H) 3.130 Cl CF.sub.3 H CF.sub.3CH.sub.2— Me — 1H NMR(400 MHz,d4-methanol): 7.69-7.54(m,2H), 7.06-6.93(m,1H), 4.27(q, 0.6H), 4.11(q, 1.4H), 3.17(s,3H), 2.87-2.40(m,4H), 2.04(quin,2H) 3.131 Cl CF.sub.3 H Me —phenyl — 3.132 Cl CF.sub.3 H —CH.sub.2CH.sub.2CH.sub.2CH.sub.2— — 3.133 Cl CF.sub.3 Me Me Et — 3.134 Cl CF.sub.3 H —CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2— — 3.135 Cl CF.sub.3 H —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2— — 3.136 Cl CF.sub.3 H Me Et — 3.137 Cl CF.sub.3 Me Me Me —CH.sub.2CH.sub.2— 3.138 Cl CF.sub.3 Me Me Me O 3.139 Cl CF.sub.3 CF.sub.3 Me Me — 3.140 Cl CF.sub.3 H Me —iPr — 3.141 Cl SO.sub.2Me H —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2— — 3.142 Cl SO.sub.2Me H Me —CH.sub.2CF.sub.3 — 3.143 Me SO.sub.2Me H Me —CH.sub.2CF.sub.3 — 3.144 Me SO.sub.2Me H Me —iPr — 3.145 Cl SO.sub.2Me H Me —phenyl — 3.146 Me SO.sub.2Me H —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2— — 3.147 Me CF.sub.3 H —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2— — 3.148 Cl CF.sub.3 Me Me Me — 3.149 Cl CHF.sub.2 H Me Me — 3.150 Cl CHF.sub.2 H Me Me CH.sub.2 3.151 Cl CHF.sub.2 H Me Et — 3.152 Cl CHF.sub.2 H Me Et CH.sub.2 3.153 Cl CHF.sub.2 H Et Me — 3.154 Cl CHF.sub.2 H Et Me CH.sub.2 3.155 Cl CHF.sub.2 H Et Et — 3.156 Cl CHF.sub.2 H Et Et CH.sub.2

(38) TABLE-US-00004 TABLE 4 Examples of herbicidal compounds of the present invention. 1H-NNIR Compound (in CDCl.sub.3 unless otherwise Number R.sup.2 R.sup.3 R.sup.7 R.sup.8 R.sup.9 X stated) 4.001 Me Me Me Me MeO — 4.002 Me Me Me Me MeO CH.sub.2 4.003 Me Cl Me Me MeO — 4.004 Me Cl Me Me MeO CH.sub.2 4.005 Me CF.sub.3 Me Me MeO — 4.006 Me CF.sub.3 Me Me MeO CH.sub.2 4.007 Me SO.sub.2Me Me Me MeO — 4.008 Me SO.sub.2Me Me Me MeO CH.sub.2 4.009 Cl Me Me Me MeO — 4.010 Cl Me Me Me MeO CH.sub.2 4.011 Cl Cl Me Me MeO — 4.012 Cl Cl Me Me MeO CH.sub.2 4.013 Cl CF.sub.3 Me Me MeO — 4.014 Cl CF.sub.3 Me Me MeO CH.sub.2 (Methanol) δ = 7.94-7.84 (m, 1H), 7.79 (d, J = 8.1 Hz, 1H), 4.67 (s, 2H), 4.08 (s, 3H), 3.68 (s, 3H), 2.51 (s, 3H), 2.05 (s, 3H) 4.015 Cl SO.sub.2Me Me Me MeO — 4.016 Cl SO.sub.2Me Me Me MeO CH.sub.2 (Methanol) δ = 8.20 (d, J = 8.2 Hz, 1H), 7.83 (d, J = 8.1 Hz, 1H), 4.95 (s, 2H), 4.06 (s, 3H), 3.68 (s, 3H), 3.27 (s, 3H), 2.60 (s, 3H), 2.06 (s, 3H) 4.017 CF.sub.3 Me Me Me MeO — 4.018 CF.sub.3 Me Me Me MeO CH.sub.2 4.019 CF.sub.3 Cl Me Me MeO — 4.020 CF.sub.3 Cl Me Me MeO CH.sub.2 4.021 CF.sub.3 CF.sub.3 Me Me MeO — 4.022 CF.sub.3 CF.sub.3 Me Me MeO CH.sub.2 4.023 CF.sub.3 SO.sub.2Me Me Me MeO — 4.024 CF.sub.3 SO.sub.2Me Me Me MeO CH.sub.2 4.025 SO.sub.2Me Me Me Me MeO — 4.026 SO.sub.2Me Me Me Me MeO CH.sub.2 4.027 SO.sub.2Me Cl Me Me MeO — 4.028 SO.sub.2Me Cl Me Me MeO CH.sub.2 4.029 SO.sub.2Me CF.sub.3 Me Me MeO — 4.030 SO.sub.2Me CF.sub.3 Me Me MeO CH.sub.2 4.031 SO.sub.2Me SO.sub.2Me Me Me MeO — 4.032 SO.sub.2Me SO.sub.2Me Me Me MeO CH.sub.2 4.033 Cl SO.sub.2Me Me Me CN CH.sub.2 1H NMR (400 MHz, Methanol) d = 8.29-8.22 (m, 1H), 7.99-7.88 (m, 1H), 5.37 (s, 2H), 4.06 (s, 3H), 3.93 (s, 1H), 2.95 (s, 2H), 2.83-2.78 (m, 1H), 2.68-2.65 (m, 1H), 2.47 (s, 2H). 4.034 Cl CF.sub.3 Me Me CN CH.sub.2 1H NMR (400 MHz, Methanol) d = 7.90 (d, J = 8.1 Hz, 1H), 7.83 (s, 1H), 5.09 (s, 2H), 4.06-3.95 (m, 3H), 2.84 (s, 2.25H), 2.74 (s, 0.75H), 2.64 (s, 0.75H), 2.47 (s, 2.25H)

(39) TABLE-US-00005 TABLE 5 Examples of herbicidal compounds of the present invention. 1H-NMR Compound (in CDCl.sub.3 unless otherwise Number R.sup.2 R.sup.3 R.sup.7 R.sup.8 R.sup.9 X stated) 5.001 Me Me Me Me MeO — 5.002 Me Me Me Me MeO CH.sub.2 5.003 Me Cl Me Me MeO — 5.004 Me Cl Me Me MeO CH.sub.2 5.005 Me CF.sub.3 Me Me MeO — 5.006 Me CF.sub.3 Me Me MeO CH.sub.2 5.007 Me SO.sub.2Me Me Me MeO — 5.008 Me SO.sub.2Me Me Me MeO CH.sub.2 5.009 Cl Me Me Me MeO — 5.010 Cl Me Me Me MeO CH.sub.2 5.011 Cl Cl Me Me MeO — 5.012 Cl Cl Me Me MeO CH.sub.2 5.013 Cl CF.sub.3 Me Me MeO — 5.014 Cl CF.sub.3 Me Me MeO CH.sub.2 (Methanol) δ = 7.83 (d, J = 8.1 Hz, 1H), 7.68 (d, J = 8.1 Hz, 1H), 4.65 (s, 2H), 3.68 (s, 3H), 2.55-2.44 (m, 6H), 2.04 (s, 3H) 5.015 Cl SO.sub.2Me Me Me MeO — 5.016 Cl SO.sub.2Me Me Me MeO CH.sub.2 (Methanol) δ = 8.18 (d, J = 8.2 Hz, 1H), 7.75 (d, J = 8.2 Hz, 1H), 4.94 (s, 2H), 3.67 (s, 3H), 3.27 (s, 3H), 2.59 (s, 3H), 2.51 (s, 3H), 2.06 (s, 3H) 5.017 CF.sub.3 Me Me Me MeO — 5.018 CF.sub.3 Me Me Me MeO CH.sub.2 5.019 CF.sub.3 Cl Me Me MeO — 5.020 CF.sub.3 Cl Me Me MeO CH.sub.2 5.021 CF.sub.3 CF.sub.3 Me Me MeO — 5.022 CF.sub.3 CF.sub.3 Me Me MeO CH.sub.2 5.023 CF.sub.3 SO.sub.2Me Me Me MeO — 5.024 CF.sub.3 SO.sub.2Me Me Me MeO CH.sub.2 5.025 SO.sub.2Me Me Me Me MeO — 5.026 SO.sub.2Me Me Me Me MeO CH.sub.2 5.027 SO.sub.2Me Cl Me Me MeO — 5.028 SO.sub.2Me Cl Me Me MeO CH.sub.2 5.029 SO.sub.2Me CF.sub.3 Me Me MeO — 5.030 SO.sub.2Me CF.sub.3 Me Me MeO CH.sub.2 5.031 SO.sub.2Me SO.sub.2Me Me Me MeO — 5.032 SO.sub.2Me SO.sub.2Me Me Me MeO CH.sub.2 5.033 Cl SO.sub.2Me Me Me CN CH.sub.2 5.034 Cl CF.sub.3 Me Me CN CH.sub.2

(40) TABLE-US-00006 TABLE 6 Examples of herbicidal compounds of the present invention. 1H-NMR (in CDCl.sub.3 Compound unless otherwise Number R.sup.2 R.sup.3 R.sup.7 R.sup.8 R.sup.9 X stated) 6.001 Me Me Me Me MeO — 6.002 Me Me Me Me MeO CH.sub.2 6.003 Me Cl Me Me MeO — 6.004 Me Cl Me Me MeO CH.sub.2 6.005 Me CF.sub.3 Me Me MeO — 6.006 Me CF.sub.3 Me Me MeO CH.sub.2 6.007 Me SO.sub.2Me Me Me MeO — 6.008 Me SO.sub.2Me Me Me MeO CH.sub.2 6.009 Cl Me Me Me MeO — 6.010 Cl Me Me Me MeO CH.sub.2 6.011 Cl Cl Me Me MeO — 6.012 Cl Cl Me Me MeO CH.sub.2 6.013 Cl CF.sub.3 Me Me MeO — 6.014 Cl CF.sub.3 Me Me MeO CH.sub.2 6.015 Cl SO.sub.2Me Me Me MeO — 6.016 Cl SO.sub.2Me Me Me MeO CH.sub.2 6.017 CF.sub.3 Me Me Me MeO — 6.018 CF.sub.3 Me Me Me MeO CH.sub.2 6.019 CF.sub.3 Cl Me Me MeO — 6.020 CF.sub.3 Cl Me Me MeO CH.sub.2 6.021 CF.sub.3 CF.sub.3 Me Me MeO — 6.022 CF.sub.3 CF.sub.3 Me Me MeO CH.sub.2 6.023 CF.sub.3 SO.sub.2Me Me Me MeO — 6.024 CF.sub.3 SO.sub.2Me Me Me MeO CH.sub.2 6.025 SO.sub.2Me Me Me Me MeO — 6.026 SO.sub.2Me Me Me Me MeO CH.sub.2 6.027 SO.sub.2Me Cl Me Me MeO — 6.028 SO.sub.2Me Cl Me Me MeO CH.sub.2 6.029 SO.sub.2Me CF.sub.3 Me Me MeO — 6.030 SO.sub.2Me CF.sub.3 Me Me MeO CH.sub.2 6.031 SO.sub.2Me SO.sub.2Me Me Me MeO — 6.032 SO.sub.2Me SO.sub.2Me Me Me MeO CH.sub.2 6.033 Cl SO.sub.2Me Me Me CN CH.sub.2 6.034 Cl CF.sub.3 Me Me CN CH.sub.2

(41) TABLE-US-00007 TABLE 7 Examples of herbicidal compounds of the present invention. Compound 1H-NMR Number R.sup.1a R.sup.2 R.sup.3 (in CDCl.sub.3 unless otherwise stated) 7.001 Et Me SO.sub.2Me 7.95 (d, 1H), 7.33 (d, 1H), 7.27 (s, 1H), 4.47 (q, J = 7.3 Hz, 2H), 3.22 (s, 3H), 3.07 (br d, 6H), 2.31 (s, 3H), 2.08 (s, 3H), 1.64 (t, J = 7.3 Hz, 4H) 7.002 nPr Me SO.sub.2Me 1H NMR(400 MHz,d4-methano1)7.89(d,1H),7.38- 7.30(m,2H), 5.49(s,1H), 4.34(t,2H), 3.23(s,3H), 3.08(brd,6H), 2.28(s,3H), 2.08-1.93(m,2H), 0.98(t,3H) 7.003 —CH.sub.2CH.sub.2OCH.sub.3 Me SO.sub.2Me 9.74-9.22(m,1H), 7.94(d,1H), 7.26-7.23 (m, 2H), 4.62(t,2H), 3.84(t,2H), 3.37(s,3H), 3.22(s,3H), 3.07(d,6H), 2.33(s,3H)

BIOLOGICAL EXAMPLES

(42) Seeds of a variety of test species are sown in standard soil in pots (Lolium perenne (LOLPE), Amaranthus retoflexus (AMARE), Abutilon theophrasti (ABUTH), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE)). After cultivation for one day (pre-emergence) or after 8 days cultivation (post-emergence) 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 500 g/h unless otherwise indicated. 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 for pre and post-emergence, 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=80-100%; 4=60-79%; 3=40-59%; 2=20-39%; 1=0-19%).

(43) TABLE-US-00008 TABLE B1 POST Application PRE Application Compound AMARE ABUTH SETFA ECHCG IPOHE AMARE ABUTH SETFA ECHCG IPOHE 1.017 5 5 5 5 5 5 5 5 5 5 1.025 5 5 5 5 5 5 5 5 5 5 1.027 5 5 5 5 5 5 5 5 5 5 1.031 5 5 5 5 5 5 5 5 5 4 1.041 5 5 5 5 5 5 5 — 5 5 1.049 5 5 5 5 5 5 5 5 5 5 1.055 5 5 5 5 5 5 5 5 5 5 1.057** 5 5 5 5 5 5 5 5 5 5 1.129 5 5 5 5 5 5 5 5 5 5 1.130 5 5 5 5 5 5 5 5 5 5 1.131 5 5 5 5 5 5 5 5 5 5 1.132 5 5 5 5 5 5 5 5 5 5 1.135* 5 5 5 3 5 5 5 5 5 5 1.139 5 5 5 5 4 5 5 5 5 5 1.140 5 5 5 5 5 5 5 5 5 5 1.142* 5 5 5 5 5 5 5 5 5 4 1.144 5 5 5 5 5 5 5 5 5 5 1.145 4 3 5 5 4 5 5 5 5 4 1.148 5 4 5 5 4 5 5 5 5 5 2.017 5 4 5 5 4 5 5 4 5 5 2.025 5 5 5 5 5 5 5 5 5 3 2.027 5 5 5 5 5 5 5 5 5 4 2.031 5 5 5 5 4 5 4 5 5 4 2.049 5 5 5 5 5 5 5 5 5 5 2.055 5 4 5 5 4 5 5 5 5 5 2.129 5 5 5 5 5 5 5 3 3 2 2.131 5 4 5 5 3 5 3 5 5 2 2.132 5 5 5 5 5 5 5 5 5 5 2.140 5 5 5 5 4 5 5 5 5 4 2.142* 5 5 5 5 5 5 3 5 5 1 2.143 5 5 5 5 5 5 5 5 5 5 2.144 5 5 5 5 4 5 5 5 5 3 2.148 5 5 5 5 3 5 5 5 5 5 3.017 3 5 5 5 5 5 5 4 5 5 3.025 5 5 5 5 5 5 5 4 5 4 3.049 5 5 5 5 5 5 5 5 5 5 3.057 5 5 5 5 5 5 5 5 5 5 3.130 5 5 5 5 4 5 5 5 5 5 4.014 5 5 5 5 5 5 5 5 5 5 4.016 4 3 5 5 4 5 5 5 5 5 5.016 4 3 5 5 4 5 5 5 5 5 7.002 5 5 5 5 4 5 5 5 5 5 7.003 5 5 5 5 5 5 5 5 5 5 — = No Data. *Applied at 250 g/ha. **Applied at 125 g/ha.

(44) TABLE-US-00009 TABLE B2 A comparative experiment is conducted to show the advantage provided by the compounds of the present invention. Thus the biological performance of compound 1.049 of the present invention is compared with Compound C1, which is an aniline compound of the type referred to in WO2012/028579. Results are given as (%) phytotoxicity observed. The result demonstrates that compounds of the present invention provide much improved control of problematic weed species, exemplified using Echinochloa crus-galli (ECHCG) and Setaria faberi (SETFA), at similar application rates. Compound Rate g/ha POST Application PRE Application ECHCG SETFA ECHCG SETFA 1.049 31 90 90 90 90 Cl 31 0 20 0 0