HERBICIDAL COMPOUNDS

Abstract

The present invention related to compounds of Formula (I) or an agronomically Macceptable salt thereof, wherein Q, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as described herein. The invention 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): ##STR00307## or an agronomically acceptable salt thereof, wherein: Q is Q.sup.1 or Q.sup.2; ##STR00308## R.sup.1a is selected from the group consisting of C.sub.1-C.sub.4alkyl-, C.sub.1-C.sub.4haloalkyl-, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl- and C.sub.1-C.sub.4haloalkoxy-C.sub.1-C.sub.4alkyl-; R.sup.1b is selected from the group consisting of C.sub.1-C.sub.4alkyl-, C.sub.1-C.sub.4haloalkyl-, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl- and C.sub.1-C.sub.4haloalkoxy-C.sub.1-C.sub.4alkyl-; R.sup.2 is selected from the group consisting of halogen, C.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.3alkoxy-, C.sub.1-C.sub.6 haloalkyl-, C.sub.1-C.sub.3haloalkoxy- and —S(O).sub.pC.sub.1-C.sub.6alkyl; R.sup.3 is C.sub.1-C.sub.6haloalkyl or C.sub.1-C.sub.6alkyl; R.sup.4 is selected from the group consisting of C.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.6 haloalkyl-, C.sub.1-C.sub.6alkyl-C(O)—, C.sub.1-C.sub.6haloalkyl-C(O)—, C.sub.3-C.sub.6cycloalkyl-, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6cycloalkyl-C(O)—, C.sub.1-C.sub.3alkoxy-C.sub.1-C.sub.3alkyl-, C.sub.1-C.sub.3alkoxy-C.sub.1-C.sub.3alkyl-C(O)—, —C(O)-phenyl and —C(O)-heteroaryl wherein the phenyl, heteroaryl or C.sub.3-C.sub.6cycloalkyl 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; R.sup.5 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.6haloalkyl and C.sub.1-C.sub.6cycloalkyl; or R.sup.4 and R.sup.5 together with the nitrogen atom to which they are attached form a 5- or 6-membered saturated heterocycle which is optionally oxo substituted; and pis0, 1 or2.

2. A compound according to claim 1, wherein R.sup.1a or R.sup.1b are selected from the group consisting of methyl, ethyl and n-propyl.

3. A compound according to any one of the previous claims claim 1, wherein Q is Q.sup.1 and R.sup.1ais methyl.

4. A compound according to claim 1, wherein Q is Q.sup.2 and R.sup.1b is methyl.

5. A 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.

6. A compound according to claim 5, wherein R.sup.2 is Cl.

7. A compound according to claim 1, wherein R.sup.3 is —CF.sub.3 or —CHF.sub.2.

8. A compound according to claim 1, wherein R.sup.4 is selected from the group consisting of C.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.6alkyl-C(O)— and C.sub.3.sup.-C.sub.6cycloalkyl-.

9. A compound according to claim 1, wherein R.sup.4 is —C(O)-heteroaryl wherein the heteroaryl 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.

10. A compound according to claim 1, wherein R.sup.5 is hydrogen or C.sub.1-C.sub.6alkyl-.

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 application to the locus of a weed controlling amount of a composition according to claim 11.

15. Use of a compound of Formula (I) as defined in claim 1 as a herbicide.

16. A compound of Formula (II) ##STR00309## wherein R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as defined in the compound of Formula (I) in claim 1.

17. A compound of Formula (V) ##STR00310## wherein R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as defined in the compound of Formula (I) in claim 1.

18. A compound of Formula (VIa) ##STR00311## wherein “Alk” is C.sub.1-C.sub.6 alkyl and R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as defined in the compound of Formula (I) claim 1.

Description

PREPARATIVE EXAMPLE 1

Compound 1.004

[0102] Step 1.

[0103] To a flask containing 5-bromo-2-(trifluoromethoxy)aniline (10 g, 39.1 mmol) was added toluene (100 mL) and diisopropylammonium chloride (1.08 g, 7.81 mmol). The reaction mixture was covered in foil to remove light. At 0° C., 1,3-dichloro-5,5-dimethyl-imidazolidine-2,4-dione (7.70 g, 39.1 mmol) was added and the reaction mixture was allowed to warm to room temperature and was stirred for 3 hours. The reaction mixture was quenched by the addition of saturated aqueous sodium bisulfite, then diluted with water and ethyl acetate, and the phases were separated. The organic phase was dried and concentrated in vacuo. The crude material was purified by normal phase flash chromatography (0 to 5% ethyl acetate in cyclohexane) to give 3-bromo-2-chloro-6-(trifluoromethoxy)aniline (7.07 g, 21.9 mmol, 56%) as a pale yellow oil. .sup.1H NMR (Methanol): 7.05 (m, 1H), 6.99 (d, 1H).

[0104] Step 2.

[0105] To a flask containing 3-bromo-2-chloro-6-(trifluoromethoxy)aniline (1.00 g, 3.40 mmol) was added acetonitrile (20 mL) and the reaction mixture was put under a nitrogen atmosphere. 5-Bromopentanoyl chloride (1.10 g, 0.79 mL, 5.90 mmol) was added. The reaction mixture was stirred at 50° C. for 6 hours. The reaction mixture was quenched by the addition of water and was concentrated in vacuo to remove the acetonitrile solvent. The reaction residue was taken up in ethyl acetate and water and the phases were separated. The aqueous phase was further extracted with ethyl acetate. The organic phases were combined, dried and concentrated in vacuo. The crude material was purified by normal phase flash chromatography (0 to 30% ethyl acetate in cyclohexane) to give impure product as a pale yellow solid. The crude material was taken up in ethyl acetate and washed with aqueous 2M sodium hydroxide solution. The organic phase was dried and concentrated in vacuo to give 5-bromo-N-[3-bromo-2-chloro-6-(trifluoromethoxy)phenyl]pentanamide (1.44 g, 2.92 mmol, 85%) as a pale yellow solid. .sup.1H NMR (chloroform): 7.62 (d, 1H), 7.16 (m, 1H), 6.90 (br s, 1H), 3.45 (t, 2H), 2.47 (br s, 2H), 2.02-1.87 (m, 4H).

[0106] Step 3.

[0107] To a flask containing N-[3-bromo-2-chloro-6-(trifluoromethoxy)phenyl]acetamide (1.44 g, 2.92 mmol) was added tetrahydrofuran (14 mL). The reaction mixture was stirred at 0° C. under nitrogen atmosphere for 10 min. To the reaction mixture was added sodium hydride in paraffin oil (60 mass %, 0.129 g, 3.21 mmol). The reaction mixture was stirred at room temperature for 4.5 hours. To the reaction mixture was added more sodium hydride in paraffin oil (60 mass %, 0.0818 g, 2.04 mmol). The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was quenched by the addition of water and was concentrated in vacuo to remove the tetrahydrofuran solvent. The residue was taken up in ethyl acetate and water, and the phases were separated. The aqueous phase was further extracted with ethyl acetate. The organic phases were combined, dried and concentrated in vacuo. The crude material was purified by normal phase flash chromatography (0 to 25% ethyl acetate in cyclohexane) to give 1-[3-bromo-2-chloro-6-(trifluoromethoxy)phenyl]piperidin-2-one (1.03 g, 2.43 mmol, 83%) as a colourless oil. .sup.1H NMR (chloroform): 7.64 (d, 1H), 7.17 (dq, 1H), 3.64-3.50 (m, 1H), 3.49-3.38 (m, 1H), 2.58 (dt, 2H), 2.07-1.88 (m, 4H).

[0108] Step 4.

[0109] To a vessel containing 1[3-bromo-2-chloro-6-(trifluoromethoxy)phenyl]piperidin-2-one (0.500 g, 1.34 mmol) was added palladium(II) acetate (0.0301 g, 0.134 mmol), XantPhos (0.160 g, 0.268 mmol), N-formylsaccharine (0.638 g, 3.02 mmol), 1-methyltetrazol-5-amine (1.20 g, 12.1 mmol) and 1-methyl-2-pyrrolidinone was added so the total volume of the vessel was 20 mL. To a second vessel containing triethylamine (0.611 g, 6.04 mmol, 0.842 mL) was added 1-methyl-2-pyrrolidinone so that the total volume of the vessel was 20 mL. The two solutions were injected into the sample loops pumped through a T-piece and then round a 20 mL stainless steel coil heated to 170° C. The flow rate was set so that the total residence time was 15 mins. The reaction mixture was concentrated in vacuo to remove the solvent 1-methyl-2-pyrrolidinone. The residue was taken up in dichloromethane and saturated aqueous sodium carbonate, and the phases were separated. The aqueous phase was further extracted with dichloromethane. The aqueous phase was acidified to pH 5 and was extracted with ethyl acetate. The organic phases were combined, dried and concentrated in vacuo. The crude material was purified by normal phase flash chromatography (0 to 10% dichloromethane in methanol) to give impure product as a glassy solid. The crude material was taken up in ethyl acetate and washed dilute aqueous HCl. The organic phase was dried and concentrated in vacuo to give 3-acetamido-2-chloro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-4-(trifluoromethoxy)benzamide (Compound 1.004) (0.0486 g, 0.116 mmol, 9%) as a foaming white solid. .sup.1H NMR (Methanol): 7.82 (d, 1H), 7.58 (m, 1H), 4.06 (s, 3H), 3.69-3.60 (m, 1H), 3.59-3.50 (m, 1H), 2.57 (m, 2H), 2.10-1.93 (dt, 4H)

PREPARATIVE EXAMPLE 2

Compound 1.006

[0110] 3-bromo-2-chloro-6-(trifluoromethoxy)aniline was prepared as described previously.

[0111] Step 1

[0112] An autoclave was charged with 3-bromo-2-chloro-6-(trifluoromethoxy)aniline (24 g, 76 mmol). Methanol (144 mL) was added. Triethylamine (23 g, 228 mmol) and then allylpalladium(II) chloride dimer (1.13 g, 3.10 mmol) and 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (2.44 g, 3.92 mmol) were added. The autoclave was flushed with nitrogen×3 and then with carbon monoxide×3. The reaction was pressurized to 20 bar CO and heated at 100° C. for 4 h. It was then cooled to RT and the atmosphere replaced with N.sub.2. The contents were discharged to a conical flask and the reaction mixture was filtered through celite and evaporated. Column chromatography gave methyl 3-amino-2-chloro-4-(trifluoromethoxy)benzoate (16 g, 59 mmol, 78%) as a white solid.

[0113] Step 2

[0114] To a flask containing methyl 3-amino-2-chloro-4-(trifluoromethoxy)benzoate (2.08 g, 7.70 mmol) was added acetonitrile (60 mL) and cyclopropanecarbonyl chloride (2.41 g, 23.1 mmol). The reaction mixture was stirred at 60° C. After the addition a white solid was formed that required vigorous stirring. After stirring for 2 h, the reaction mixture was cooled and the solvent was evaporated. The solid obtained was stirred was stirred in cyclohexane (100 ml) and filtered, then washed with cyclohexane to give methyl 2-chloro-3-(cyclopropanecarbonylamino)-4-(trifluoromethoxy)benzoate (2.40 g, 7.12 mmol, 92%) as white solid.

[0115] Step 3

[0116] To a solution of methyl 2-chloro-3-(cyclopropanecarbonylamino)-4-(trifluoromethoxy)benzoate (A, 0.35 g, 1.04 mmol) in THF (9 mL) and water (3 mL). Lithium hydroxide hydrate (87 mg, 2.1 mmol) was added and the reaction mixture was stirred for 16 h. The reaction was concentrated to remove THF. 2 M HCl was added to the solution until a white solid precipitated, which was isolated by filtration to give 2-chloro-3-(cyclopropanecarbonylamino)-4-(trifluoromethoxy)benzoic acid (0.296 g, 0.915 mmol, 88%) as a white solid. 1H NMR (400 MHz, methanol) δ ppm 7.87 (d, 1H) 7.43 (d, 1H) 1.85-1.96 (m, 1H) 0.84-1.02 (m, 4 H).

[0117] Step 4

[0118] 2-chloro-3-(cyclopropanecarbonylamino)-4-(trifluoromethoxy)benzoic acid (1.10 g, 3.4 mmol), 1-methyltetrazol-5-amine (400 mg, 4.1 mmol) in 2-methylpyridine (8 mL) was stirred for 10 min under a nitrogen atmosphere, then 1-methylimidazole (280 mg, 3.4 mmol) was added followed by triethylamine (520 mg, 5.1 mmol) and stirred at RT for 10 min. The reaction mass was then cooled to 0° C. and thionyl chloride (810 mg, 6.8 mmol) was added dropwise. The reaction mixture was stirred RT for 16 h. The reaction was diluted with 2N HCl and stirred for 30 min. A solid obtained was filtered, washed with ethanol and dried to obtain 2-chloro-3-(cyclopropanecarbonylamino)-N-(1-methyltetrazol-5-yl)-4-(trifluoromethoxy)benzamide as a white solid (820 mg, 2.08 mmol, 61%). 1H NMR (Methanol): 7.73 (d, 1H), 7.52 (br d, 1H), 4.06 (s, 3H), 1.91 (m, 1H), 1.01-0.88 (m, 4H).

PREPARATIVE EXAMPLE 3

Compound 1.007

[0119] Methyl 3-amino-2-chloro-4-(trifluoromethoxy)benzoate was prepared as described previously.

[0120] Step 1

[0121] To a solution of methyl 3-amino-2-chloro-4-(trifluoromethoxy)benzoate (2.5 g, 9.3 mmol) in acetonitrile (60 mL) was added propanoyl chloride (2.6 g, 28 mmol). The reaction mixture was stirred at 60° C. for 2 h. After 2 h, the mixture was cooled to room temperature and the acetonitrile was removed under reduced pressure. The residue was taken up in ethyl acetate, then washed with sodium bicarbonate solution, dried (MgSO.sub.4) and concentrated under reduced pressure. Flash chromatography (0-30% EtOAc and cyclohexane) gave methyl 2-chloro-3-(propanoylamino)-4-(trifluoromethoxy)benzoate (2.28 g, 7.00 mmol, 76%) as a white solid. 1H NMR (400 MHz, d4-methanol): 7.87 (d, 1H) 7.45 (m, 1H) 3.93 (s, 3 H) 2.46 (q, 2 H) 1.24 (t, 3 H).

[0122] Step 2

[0123] To a stirred solution of methyl 2-chloro-3-(propanoylamino)-4-(trifluoromethoxy)benzoate (27.7 g, 85.1 mmol) in tetrahydrofuran (10 mL) and methanol (10 mL) was added lithium hydroxide (6.11 g, 255 mmol) in water (10 mL) and stirred for RT 12 hr. The reaction mass was concentrated under reduced pressure and partitioned between 1 N HCl and ethyl acetate. The organic layer was dried over sodium sulphate and concentrated to afford 2-chloro-3-(propanoylamino)-4-(trifluoromethoxy)benzoic acid (25.7 g, 78.3 mmol, 92%) as a white solid. 1H NMR (400 MHz, d6-DMSO): 13.70 (1H, s), 9.82 (1H, s), 7.79 (1H, d), 7.51 (1H, d), 2.35n (2H, q), 1.11 (H, t).

[0124] Step 3

[0125] A flask was charged with pyridine (50 mL) and 2-chloro-3-(propanoylamino)-4-(trifluoromethoxy)benzoic acid (5.00 g, 16.0 mmol) under N2 atmosphere at RT. 1-Methyltetrazol-5-amine (1.79 g, 17.7 mmol) and 1-methylimidazole (1.33 g, 16.0 mmol) were then added and the reaction mixture was cooled to 0° C. Thionyl chloride (3.94 g, 32.1 mmol) was added dropwise over 3 h maintaining the temperature at 0-10° C. using a syringe pump. After complete addition, the pH of the reaction mixture=5.7 and a brown precipitate appeared. The ice bath was removed and reaction was allowed to stir at RT, After a further 2 h, the reaction mixture became brown solution. After stirring for a further 2 h, the reaction mixture was cooled to 0° C. using an ice bath and then 25mL of water was added under stirring (pH=5.8-5.9). The reaction mixture was acidified using 2 N HCl to pH=1.5-2. During acidification a sticky solid precipitated. The suspension was extracted with ethyl acetate (50 mL×3). The combined organic layers were washed with cold water (25 mL), dried (Na.sub.2SO.sub.4) and concentrated under reduced pressure to get a light orange solid. This was purified by using chromatography (30-40% ethyl acetate in cyclohexane) to give 2-chloro-N-(1-methyltetrazol-5-yl)-3-(propanoylamino)-4-(trifluoromethoxy)benzamide (2.59 g, 6.61 mmol, 41%) as a white solid. 1H NMR (400 MHz, d6-DMSO): 11.92 (1H, s), 9.90 (1H, s), 7.80 (1H, d), 7.61 (1H, d), 4.00 (3H, s), 2.37 (2H, q), 1.12 (3H, t).

PREPARATIVE EXAMPLE 4

Compound 1.012

[0126] Methyl 3-amino-2-chloro-4-(trifluoromethoxy)benzoate was prepared as described previously.

[0127] Step 1

[0128] Methyl 3-amino-2-chloro-4-(trifluoromethoxy)benzoate (2.0 g, 7.4 mmol) and pyridine-2-carboxylic acid (1.1 g, 8.9 mmol) was dissolved in pyridine (10 mL) The solution was cooled to 0° C. by ice water. Phosphorous oxychloride (1.70 g, 11.1 mmol) was added dropwise over 4 min, and then the reaction was allowed to warm to RT and stirred for 3 h, whereupon a white precipitate appeared. The reaction mixture was quenched slowly into cold (0° C.) saturated aq sodium bicarbonate solution. After the addition, stirring was continued vigorously for 30 min. The white solid obtained was filtered and washed with water 3 times to give methyl 2-chloro-3-(pyridine-2-carbonylamino)-4-(trifluoromethoxy)benzoate (1.69 g, 4.51 mmol, 61%) as a white solid. 1H NMR (400 MHz, d6-DMSO): 10.69 (1H, s), 8.78 (1H, d), 8.15-8.06 (2H, m), 7.91 (1H, d), 7.73 (1H, ddd), 7.62 (1H, d), 3.90 (3H, s).

[0129] Step 2

[0130] To a solution of methyl 2-chloro-3-(pyridine-2-carbonylamino)-4-(trifluoromethoxy)benzoate (1.6 g, 4.3 mmol) in tetrahydrofuran (32 mL), a solution of hydroxylithium hydrate (0.54 g, 13 mmol) in water (8.0 mL) was added. The reaction mixture was stirred at RT for 16 h. The reaction was concentrated to remove THF. The aqueous solution was washed with cyclohexane, then cooled to 0° C. and adjusted pH to 3 with 10% aq. solution of Citric acid. The aqueous mixture was extracted with ethyl acetate×3 and the combined organic layers were dried over sodium sulphate and concentrated under reduced pressure to give 2-chloro-3-(pyridine-2-carbonylamino) (trifluoromethoxy)benzoic acid (1.6 g, 4.3 mmol, 100%) as a white solid. 1H NMR (400 MHz, d6-DMSO): 10.65 (1H, d), 8.77 (1H, d), 8.13 (1H, d), 8.05 (1H, t), 7.88 (1H, d), 7.69 (1H, m), 7.58 (1H, d).

[0131] Step 3

[0132] 2-chloro-3-(pyridine-2-carbonylamino)-4-(trifluoromethoxy)benzoic acid (1.5 g, 4.2 mmol), 1-methyltetrazol-5-amine (500 mg, 5.0 mmol) in 3-methylpyridine (15 mL) was stirred for 10 mins under a nitrogen atmosphere. Triethylamine (630 mg, 6.2 mmol) followed by 1-methylimidazole (340 mg, 4.2 mmol) was added and stirred at RT for 30 min. The reaction mass was then cooled to 0° C. and thionyl chloride (990 mg, 8.3 mmol) was added dropwise. After stirring at RT for 16 h, the reaction mixture was quenched with 2N HCl to pH 1-2 at 0° C. with vigorous stirring for 30 min. The aqueous layer was extracted with ethyl acetate×3, then concentrated under reduced pressure. The solid was recrystallized from ethyl acetate/n-pentane to obtain N-[2-chloro-3-[(1-methyltetrazol-5-yl)carbamoyl]-6-(trifluoromethoxy)phenyl]pyridine-2-carboxamide (1.45 g, 3.17 mmol, 76%) as a white solid. 1H NMR (400 MHz, d6-DMSO): 12.00 (1H, brs), 10.77 (1H, s), 8.78 (1H, d), 8.16-8.05 (2H, m), 7.88 (1H, d), 7.72 (1H, ddd), 7.67 (1H, dd), 4.00 (3H, s).

PREPARATIVE EXAMPLE 5

Compound 1.014

[0133] Step 1

[0134] To a 15 mL thick wall pressure vessel at room temperature, was added 2-amino-4-bromo-phenol (564 mg, 3.00 mmol), KOH (0.218 g, 3.90 mmol), DMSO (10 mL) and 1,2-dibromotetrafluoroethane (1.17 g, 4.50 mmol). The reaction flask was then closed and heated to 80° C. for 18 h. The reaction mixture was cooled to room temperature. The mixture is washed with H2O (200 mL) and extracted with ethyl acetate (100 mL×3). The layers are separated and dried over sodium sulfate. After evaporation of the solvent, the residue was purified by chromatography (petroleum ether/ethyl acetate=30:1) to afford 5-bromo-2-(2-bromo-1,1,2,2-tetrafluoro-ethoxy)aniline (0.215 g, 0.586 mmol, 19.5%) as a brown oil and 5-bromo-2-(1,1,2,2-tetrafluoroethoxy)aniline (0.206 g, 0.715 mmol, yield: 23.8%) as a brown oil. 1H NMR of 5-bromo-2-(1,1,2,2-tetrafluoroethoxy)aniline (400 MHz, d6-DMSO): 6.97-6.76 (3H, m), 6.65-6.62 (1H, m), 5.54 (2H, brs).

[0135] Step 2

[0136] Diisopropylamine (0.973 g, 9.63 mmol) is added to a mixture of ammonium chloride (0.511 g, 9.63 mmol) and ethanol (25 mL). The mixture was heated to reflux for 4 h. The reaction mixture was cooled and then concentrated to give a white solid that was washed with further ethanol, then dried under vacuum. To a 3 necked flask under nitrogen, is added 5-bromo-2-(1,1,2,2-tetrafluoroethoxy)aniline (18.5 g, 64.2 mmol), toluene (300 mL) and diisopropylammonium; chloride (1.4 g). The flask was covered in foil, then cooled to 0 deg C. 1,3-dichloro-5,5-dimethyl-imidazolidine-2,4-dione (11.4 g, 57.8 mmol) was added portionwise and the mixture was stirred at 0 deg C. for 2 h. The reaction mixture was quenched by addition of saturated aqueous sodium bisulfite solution, then diluted with water and ethyl acetate. The residue was purified by chromatography (eluent: petroleum ether/ethyl acetate=30:1) to afford 3-bromo-2-chloro-6-(1,1,2,2-tetrafluoroethoxy)aniline (9.00 g, 27.9 mmol, 43.5%) as a yellow oil. 1H NMR (400 MHz, d6-DMSO): 7.03 (1H, d), 3.92 (1H, d), 6.85 (1H, tt), 5.83 (2H, brs).

[0137] Step 3

[0138] Synthesis carried out in a Flow syn fitted with a 20 ml stainless steel loop. To loop A was added: palladium(II) acetate (694 mg., 3.10 mmol), XantPhos (3.59 g, 6.20 mmol), N-formylsaccharin (14.7 g, 69.8 mmol) and 3-bromo-2-chloro-6-(1,1,2,2-tetrafluoroethoxy)aniline (10 g, 31.0 mmol) in 1-methyl-2-pyrrolidinone (190 mL). To loop B was added triethylamine (19.4 mL, 139.54 mmol) and 1-methyl-2-pyrrolidinone (190 mL) and water (20.1 mL, 1116.3 mmol). The temperature was set to 170 mins and the time set to 15 mins. In a fixed vessel, to the output reaction mixure is added water (1000 ml) and 1M HCl (1000 ml), followed by the addition of ethyl acetate (1000 ml) was added and phases were separated. The organic layer was concentrated under reduced pressure. The crude material was purified by reversed phase chromatography: (50-70% MeCN in H2O gradient with 0.1% formic acid) to afford 3-amino-2-chloro-4-(1,1,2,2-tetrafluoroethoxy)benzoic acid (5.13 g, 17.8 mmol, 58%) as a white solid. 1H NMR (400 MHz, methanol) δ ppm 6.25-6.62 (m, 1H) 7.01-7.26 (m, 2 H).

[0139] Step 4

[0140] To a stirred suspension of 3-amino-2-chloro-4-(1,1,2,2-tetrafluoroethoxy)benzoic acid (5.13 g, 17.8 mmol) and 2,3,4,5,6-pentafluorophenol (3.61 g, 19.6 mmol) in dichloromethane (70 mL), at room temperature was added 3-(ethyliminomethyleneamino)-N,N-dimethyl-propan-1-amine hydrochloride (4.1 g, 21 mmol). The mixture was stirred at room temperature. Initially heterogeneous, within 5 minutes of adding EDC, the mixture was a homogeneous solution. The reaction mixture was stirred for 16 h at RT. The reaction was quenched by addition of sat. aq. NaHCO3 (100 mL). The mixture was stirred at room temperature for a further 5 min. The mixture filtered through a phase separation cartridge and the organics are collected. The filtrate was adsorbed onto silica and the crude product was purified by flash column chromatography (0-10% gradient of EtOAc in cyclohexane). Product-containing fractions were combined and concentrated in vacuo to afford (2,3,4,5,6-pentafluorophenyl) 3-amino-2-chloro-4-(1,1,2,2-tetrafluoroethoxy)benzoate (6.36 g, 14.0 mmol, 79%) as a colourless oil, which crystalised on standing. LCMS: M+H=452.1 in ES-.

[0141] Step 5

[0142] To a round bottom flask containing a solution of (2,3,4,5,6-pentafluorophenyl) 3-amino-2-chloro-4-(1,1,2,2-tetrafluoroethoxy)benzoate (3.18 g, 7.01 mmol) in acetonitrile (50 mL) at room temperature was added 1-methyltetrazol-5-amine (1.53 g, 15.4 mmol) followed by 2-tert-butylimino-N,N-diethyl-1,3-dimethyl-1,3,2λ.sup.5-diazaphosphinan-2-amine (4.4 g, 4.6 mL, 15 mmol). The mixture was stirred at room temperature overnight. The reaction was quenched by addition of 2 M aq. HCl (100 mL). The mixture was stirred at room temperature for a further 5 minutes. The mixture was transferred to a separating funnel and diluted with EtOAc (100 mL). The phases were separated. The aqueous phase was extracted with EtOAc (100 mL). The combined organic was adsorbed onto C18-silica and purified via reverse phase column chromatography (40-80% MeCN in H2O gradient with 0.1% formic acid) to give 3-amino-2-chloro-N-(1-methyltetrazol-5-yl)-4-(1,1,2,2-tetrafluoroethoxy)benzamide (1.88 g, 4.84 mmol, 69%) as a white solid. 1H NMR (400 MHz, methanol) δ ppm 4.05 (s, 3 H) 6.28-6.62 (m, 1H) 6.91-6.99 (m, 1 H) 7.22-7.30 (m, 1H).

[0143] Step 6

[0144] To a stirred solution of 3-amino-2-chloro-N-(1-methyltetrazol-5-yl)-4-(1,1,2,2-tetrafluoroethoxy)benzamide (0.3 g, 0.81 mmol) in acetonitrile (6 mL) at room temperature was added propanoyl chloride (0.23 g, 0.22 mL, 2.5 mmol). The stirred mixture was heated to 60° C. overnight. The reaction was cooled to room temperature and quenched by slow addition of water (2 mL). The mixture was stirred at room temperature for a further 5 minutes. The mixture was transferred to a separating funnel and diluted with EtOAc (20 mL) and water (20 mL). The phases were separated. The aqueous phase was extracted with EtOAc (20 mL). The combined organic phases were dried (MgSO.sub.4) and filtered. The filtrate was adsorbed onto C18-silica and purified via reverse phase column chromatography (30-60% MeCN in H.sub.2O gradient with 0.1% formic acid) to give 2-chloro-N-(1-methyltetrazol-5-yl)-3-(propanoylamino)-4-(1,1,2,2-tetrafluoroethoxy)benzamide (280 mg, 0.626 mmol, 77%) as a white solid. 1H NMR (400 MHz, d4-methanol): 1.16-1.28 (m, 3H) 2.41-2.53 (m, 2H) 4.06 (s, 3H) 6.21-6.53 (m, 1H) 7.49-7.57 (m, 1H) 7.73 (d, 1H).

PREPARATIVE EXAMPLE 6

Compound 1.016

[0145] Step 1.

[0146] To a flask containing 3-chloro-4-methyl-2-nitro-phenol (5.33 mmol, 1.00 g) was added acetone (20 mL), water (0.1 mL), potassium carbonate (10.7 mmol, 1.47 g) and 2,2,2-trifluoroethyl trifluoromethanesulfonate (8.00 mmol, 1.86 g). The reaction mixture was stirred at room temperature overnight. The reaction mixture was concentrated in vacuo to remove solvent. The residue was dissolved in water and ethyl acetate. The phases were separated then the aqueous phase was further extracted with ethyl acetate. The organic phases were combined, washed with water and concentrated in vacuo to give 2-chloro-1-methyl-3-nitro-4-(2,2,2-trifluoroethoxy)benzene (5.39 mmol, 1.450 g, quant %) as an orange solid, which required no further purification. .sup.1H NMR (chloroform): 7.32 (m, 1H), 6.91 (d, 1H), 4.42 (q, 2H), 2.39 (s, 3H).

[0147] Step 2.

[0148] To a flask containing 2-chloro-1-methyl-3-nitro-4-(2,2,2-trifluoroethoxy)benzene (10.0 mmol, 2.70 g) was added water (41 mL) and pyridine (41 mL). The reaction mixture was stirred at 100° C. until the reaction mixture was a solution. Potassium permanganate (40.0 mmol, 6.33 g) was added in 4 portions, one hour apart. The reaction mixture was stirred at 100° C. for 1 hour more, then left standing at room temperature overnight. The reaction mixture was cooled to room temperature and the solids were filtered off. The solution was washed with ethyl acetate. The aqueous phase was acidified with aqueous 2M HCl, and the material was extracted with ethyl acetate. The organic phases were combined and concentrated in vacuo to give 2-chloro-3-nitro-4-(2,2,2-trifluoroethoxy)benzoic acid (4.37 mmol, 1.31 g) as a white solid, which required no further purification. .sup.1H NMR (Methanol): 8.13 (d, 1H), 7.40 (d, 1H), 4.84 (m, 2H)

[0149] Step 3

[0150] To a flask containing 2-chloro-3-nitro-4-(2,2,2-trifluoroethoxy)benzoic acid (4.37 mmol, 1.31 g) was added triethyl orthoformate (60.1 mmol, 8.91 g, 10 mL). The reaction mixture was stirred at 140° C. for 1 hour. The reaction mixture was concentrated in vacuo to remove the triethyl orthoformate. The residue was triturated with ethyl acetate, and the solid was dried in vacuo to give ethyl 2-chloro-3-nitro-4-(2,2,2-trifluoroethoxy)benzoate (4.23 mmol, 1.39 g, 97%) as an orange solid, which required no further purification. .sup.1H NMR (chloroform): 8.05 (d, 1H), 7.02 (d, 1H), 4.52 (m, 2H), 4.42 (m, 2H), 1.41 (m, 3H)

[0151] Step 4

[0152] To a flask containing ethyl 2-chloro-3-nitro-4-(2,2,2-trifluoroethoxy)benzoate (2.44 mmol, 0.800 g) was added ethanol (8 mL), ammonium chloride (14.7 mmol, 0.784 g), water (8 mL) and iron (7.33 mmol, 0.409 g). The reaction mixture was stirred at 95° C. for 1 hour. The reaction mixture was cooled to room temperature and the solids were filtered through celite, then washed with water and ethyl acetate. The solution was further diluted with water and ethyl acetate. The phases were separated then the aqueous phase was further extracted with ethyl acetate. The organic phases were combined, washed with water, then brine, and concentrated in vacuo to give ethyl 3-amino-2-chloro-4-(2,2,2-trifluoroethoxy)benzoate (2.43 mmol, 0.723 g, 100%) as a pale orange solid, which required no further purification. .sup.1H NMR (chloroform): 7.27 (m, 1H), 6.70 (d, 1H), 4.46-4.40 (m, 4H), 4.37 (m, 2H), 1.39 (m, 3H)

[0153] Step 5

[0154] To a flask ethyl 3-amino-2-chloro-4-(2,2,2-trifluoroethoxy)benzoate (2.43 mmol, 0.723 g) was added ethanol (15 mL), sodium hydroxide (7.29 mmol, 0.291 g) and water (5 mL). The reaction mixture was stirred at room temperature for 6.5 hours. The reaction mixture was concentrated in vacuo to remove the ethanol solvent. The aqueous phase was acidified with concentrated HCl to pH 4, then concentrated in vacuo to remove the water. The residue was triturated with ethyl acetate and the resulting solid was dried in vacuo to give 3-amino-2-chloro-4-(2,2,2-trifluoroethoxy)benzoic acid (assumed 2.43 mmol, assumed quant %), which did not undergo further purification, and was taken on crude.

[0155] Step 6

[0156] To a flask containing 3-amino-2-chloro-4-(2,2,2-trifluoroethoxy)benzoic acid (2.43 mmol, 0.655 g) was added 2,3,4,5,6-pentafluorophenol (2.79 mmol, 0.514 g), dichloromethane (33 mL) and 1-3-(dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (2.79 mmol, 0.564 g). The reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was concentrated in vacuo to remove solvent. The reaction residue was dissolved in ethyl acetate and water. The phases were separated then the aqueous phase was further extracted with ethyl acetate. The organic phases were combined and concentrated in vacuo to give (2,3,4,5,6-pentafluorophenyl) 3-amino-2-chloro-4-(2,2,2-trifluoroethoxy)benzoate (assumed 2.43 mmol, assumed quant %) as a colourless oil, which did not undergo further purification and was taken on crude.

[0157] Step 7

[0158] To a flask containing (2,3,4,5,6-pentafluorophenyl) 3-amino-2-chloro-4-(2,2,2-trifluoroethoxy)benzoate (2.43 mmol, 1.06 g) was added 1-methyltetrazol-5-amine (2.68 mmol, 0.265 g), acetonitrile (21 mL) and 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (5.35 mmol, 1.51 g, 1.60 mL) was added. The reaction mixture was stirred at room temperature for 1.5 hours. The reaction mixture was quenched by the addition of aqueous 2M HCl, then extracted with ethyl acetate. The organic phases were combined, washed with water and concentrated in vacuo to give an off white solid. The crude material was triturated with dichloromethane, and the resulting solid was dried in vacuo to give 3-amino-2-chloro-N-(1-methyltetrazol-5-yl)-4-(2,2,2-trifluoroethoxy)benzamide (1.87 mmol, 0.655 g, 77%) as a white solid. .sup.1H NMR (Methanol): 7.01 (d, 2H), 4.69 (m, 2H), 4.04 (s, 3H)

[0159] Step 8

[0160] To a flask containing 3-amino-2-chloro-N-(1-methyltetrazol-5-yl)-4-(2,2,2-trifluoroethoxy)benzamide (0.570 mmol, 0.200 g) was added acetonitrile (4 mL) and 2-fluoropropanoyl chloride (1.43 mmol, 0.158 g). The reaction mixture was stirred at 60° C. for 1.5 hours. The reaction mixture was concentrated in vacuo to remove solvent. The crude material was purified by normal phase flash chromatography (0 to 5% methanol in dichloromethane) to give 2-chloro-3-(2-fluoropropanoylamino)-N-(1-methyltetrazol-5-yl)-4-(2,2,2-trifluoroethoxy)benzamide (Compound 1.016) (0.313 mmol, 0.133 g, 55%) as a white solid. 1H NMR (Methanol): 7.71 (d, 1H), 7.26 (d, 1H), 5.25 (m, 0.5H), 5.13 (m, 0.5H), 4.68 (m, 2H), 4.04 (s, 3H), 1.68 (d, 1.5H), 1.62 (d, 1.5H).

PREPARATIVE EXAMPLE 7

Compound 1.018

[0161] Step 1

[0162] 3-amino-2-chloro-N-(1-methyltetrazol-5-yl)-4-(2,2,2-trifluoroethoxy)benzamide is prepared as described above.

[0163] Step 2

[0164] To a flask containing 3-amino-2-chloro-N-(1-methyltetrazol-5-yl)-4-(2,2,2-trifluoroethoxy)benzamide (0.428 mmol, 0.150 g) was added acetonitrile (6 mL) and acetyl chloride (1.28 mmol, 0.101 g, 0.092 mL). The reaction mixture was stirred at 60° C. for 1.5 hours. The reaction mixture was concentrated in vacuo to remove solvent. The crude material was purified by normal phase flash chromatography (0 to 5% methanol in dichloromethane) to give 3-acetamido-2-chloro-N-(1-methyltetrazol-5-yl)-4-(2,2,2-trifluoroethoxy)benzamide (Compound 1.018) (0.357 mmol, 0.140 g, 83%) as a white solid. .sup.1H NMR (methanol): 7.67 (d, 1H), 7.25 (d, 1H), 4.67 (m, 2H), 4.04 (s, 3H), 2.18 (s, 3H).

PREPARATIVE EXAMPLE 8

Compound 1.028

[0165] Step 1

[0166] To a flask containing 3-chloro-4-methyl-2-nitro-phenol (5.33 mmol, 1.00 g) was added acetone (20 mL) and water (0.1 mL). Potassium carbonate (8.00 mmol, 1.11 g) and iodomethane (10.7 mmol, 1.51 g, 0.664 mL) were added. The reaction mixture was stirred at room temperature overnight. The reaction mixture was concentrated in vacuo to remove the acetone solvent. The residue was dissolved in water and ethyl acetate. The phases were separated then the aqueous phase was further extracted with ethyl acetate. The organic phases were combined and concentrated in vacuo to give 3-chloro-1-methoxy-4-methyl-2-nitro-benzene (4.98 mmol, 1.00 g, 93%) as a yellow solid, which required no further purification. .sup.1H NMR (chloroform): 7.28 (m, 1H), 6.87 (d, 1H), 3.88 (s, 3H), 2.36 (s, 3H).

[0167] Step 2

[0168] To a flask containing 3-chloro-1-methoxy-4-methyl-2-nitro-benzene (3.97 mmol, 0.800 g) was added water (16 mL) and pyridine (16 mL). The reaction mixture was stirred at 100° C. until the reaction mixture was a solution. Potassium permanganate (11.9 mmol, 1.88 g) was added in 3 portions, one hour apart. The reaction mixture was stirred at 100° C. overnight. The reaction mixture was cooled to room temperature and the solids were filtered off. The solution was washed with TBME. The aqueous phase was acidified with aqueous 2M HCl, and the material was extracted with ethyl acetate. The organic phases were combined and concentrated in vacuo to give 2-chloro-4-methoxy-3-nitro-benzoic acid (2.20 mmol, 0.509 g, 55%) as a white solid, which required no further purification. .sup.1H NMR (methanol): 8.11 (d, 1H), 7.29 (d, 1H), 4.00 (s, 3H).

[0169] Step 3

[0170] To a flask containing 2-chloro-4-methoxy-3-nitro-benzoic acid (8.77 mmol, 2.03 g) was added triethyl orthoformate (120 mmol, 17.8 g, 20 mL). The reaction mixture was stirred at 140° C. for 3 hours. The reaction mixture was concentrated in vacuo to remove the triethyl orthoformate. The residue was triturated with ethyl acetate, and the solid was dried in vacuo to give ethyl 2-chloro-4-methoxy-3-nitro-benzoate (8.77 mmol, 2.28 g, quant %) as an orange solid, which required no further purification.

[0171] Step 4

[0172] To a flask containing ethyl 2-chloro-4-methoxy-3-nitro-benzoate (3.85 mmol, 1.00 g) was added ethanol (10 mL), ammonium chloride (23.1 mmol, 1.24 g), water (10 mL) and iron (11.6 mmol, 0.645 g). The reaction mixture was stirred at 95° C. for 1 hour. The reaction mixture was cooled to room temperature and the solids were filtered through celite, then washed with water and ethyl acetate. The solution was further diluted with water and ethyl acetate. The phases were separated then the aqueous phase was further extracted with ethyl acetate. The organic phases were combined, washed with water, then brine, and concentrated in vacuo to give ethyl 3-amino-2-chloro-4-methoxy-benzoate (3.76 mmol, 0.864 g, 98%) as an off white solid, which required no further purification.

[0173] Step 5

[0174] To a flask containing ethyl 3-amino-2-chloro-4-methoxy-benzoate (3.76 mmol, 0.864 g) was added ethanol (15 mL), sodium hydroxide (11.3 mmol, 0.451 g) and water (5 mL). The reaction mixture was stirred at room temperature overnight. The reaction mixture was concentrated in vacuo to remove the ethanol solvent. The aqueous phase was acidified with concentrated HCl to pH 4, then concentrated in vacuo to remove the water. The residue was dissolved in water and ethyl acetate and the phases were separated. The organic phase was concentrated in vacuo to give 3-amino-2-chloro-4-methoxy-benzoic acid (3.67 mmol, 0.740 g, 98%) as an off white solid, which required no further purification.

[0175] Step 6

[0176] To a flask containing 3-amino-2-chloro-4-methoxy-benzoic acid (3.70 mmol, 0.740 g) was added 2,3,4,5,6-pentafluorophenol (4.20 mmol, 0.780 g), dichloromethane (37 mL) and 1-3-(dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (4.20 mmol, 0.850 g). The reaction mixture was stirred at room temperature for 30 minutes. The reaction mixture was concentrated in vacuo to remove solvent. The reaction residue was dissolved in ethyl acetate and water. The phases were separated then the aqueous phase was further extracted with ethyl acetate. The organic phases were combined and concentrated in vacuo to give (2,3,4,5,6-pentafluorophenyl) 3-amino chloro-4-methoxy-benzoate (assumed 3.70 mmol, assumed quant %) as an orange oil, which did not undergo further purification and was taken on crude.

[0177] Step 7

[0178] To a flask containing (2,3,4,5,6-pentafluorophenyl) 3-amino-2-chloro-4-methoxy-benzoate (3.70 mmol, 1.36 g) was added 1-methyltetrazol-5-amine (4.07 mmol, 0.403 g), acetonitrile (27 mL), 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (8.14 mmol, 2.30 g, 2.43 mL). The reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was quenched by the addition of aqueous 2M HCl, then extracted with ethyl acetate. The organic phases were combined, washed with water and concentrated in vacuo to give an orange oil. The crude material was purified by normal phase flash chromatography (0 to 10% methanol in dichloromethane) to give 3-amino-2-chloro-4-methoxy-N-(1-methyltetrazol-5-yl)benzamide (2.21 mmol, 0.624 g, 60%) as a pale orange solid. .sup.1H NMR (Methanol): 7.04 (d, 1H), 6.91 (d, 1H), 4.03 (s, 3H), 3.94 (s, 3H).

[0179] Step 8

[0180] To a flask containing 2-fluoropropanoic acid (10.9 mmol, 1.00 g) was added thionyl chloride (23.5 mmol, 2.80 g, 1.68 mL). The reaction mixture was stirred at 60° C. for 4 hours. The product was distilled off to give 2-fluoropropanoyl chloride (6.81 mmol, 0.753 g, 63%) as a colourless oil. .sup.1H NMR (chloroform): 5.21 (m, 0.5H), 5.08 (m, 0.5H), 1.74 (d, 1.5H), 1.68 (d, 1.5H)

[0181] Step 9

[0182] To a flask containing 3-amino-2-chloro-4-methoxy-N-(1-methyltetrazol-5-yl)benzamide (0.707 mmol, 0.200 g) was added acetonitrile (8 mL) and 2-fluoropropanoyl chloride (1.41 mmol, 0.209 g). The reaction mixture was heated to 60° C. for 4 hours. The reaction mixture was concentrated in vacuo to remove solvent. The crude material was purified by normal phase flash chromatography (0 to 10% methanol in dichloromethane) to give 2-chloro-3-(2-fluoropropanoylamino)-4-methoxy-N-(1-methyltetrazol-5-yl)benzamide (Compound 1.031) (0.555 mmol, 0.198 g, 79%) as yellow solid. .sup.1H NMR (Methanol): 7.69 (d, 1H), 7.17 (d, 1H), 5.25 (m, 0.5H), 5.13 (m, 0.5H), 4.03 (s, 3H), 3.92 (s, 3H), 1.68 (d, 1.5H), 1.61 (d, 1.5H).

PREPARATIVE EXAMPLE 10

Compound 1.030

[0183] Step 1

[0184] 3-amino-2-chloro-4-methoxy-N-(1-methyltetrazol-5-yl)benzamide is prepared as described above.

[0185] Step 2

[0186] To a flask containing 3-amino-2-chloro-4-methoxy-N-(1-methyltetrazol-5-yl)benzamide (0.531 mmol, 0.150 g) was added acetonitrile (6 mL) and acetyl chloride (1.06 mmol, 0.0833 g). The reaction mixture was stirred at 60° C. for 2 hours. The reaction mixture was concentrated in vacuo to remove solvent. The crude material was triturated with ethyl acetate, and the solid was dried in vacuo to give 3-acetamido-2-chloro-4-methoxy-N-(1-methyltetrazol-5-yl)benzamide (Compound 1.033) (0.490 mmol, 0.159 g, 92%) as a white solid. .sup.1H NMR (Methanol): 7.66 (d, 1H), 7.16 (d, 1H), 4.04 (s, 3H), 3.92 (s, 3H), 2.17 (s, 3H).

PREPARATIVE EXAMPLE 11

Compound 2.001

[0187] Step 1

[0188] 3-bromo-2-chloro-6-(trifluoromethoxy)aniline is prepared as outlined previously.

[0189] Step 2

[0190] To a flask containing 3-bromo-2-chloro-6-(trifluoromethoxy)aniline (2.00 g, 6.89 mmol) was added tetrahydrofuran (30 mL). The reaction mixture was put under a nitrogen atmosphere and stirred at −78° C. for 30 minutes. To the reaction mixture, n-butyllithium (2.5 M in hexane, 7.57 mmol, 3.00 mL) was added dropwise. The reaction mixture was stirred at −78° C. for 1 hour. To the reaction mixture was added iodomethane (2.93 g, 20.7 mmol, 1.29 mL). The reaction mixture was allowed to warm to 0° C. and stirred for 3 hours. The reaction mixture was carefully quenched by slow addition of the reaction mixture into saturated aqueous ammonium chloride solution. The mixture was stirred at room temperature for 15 minutes, and the aqueous phase was extracted with ethyl acetate. The organic phases were combined, dried and concentrated in vacuo. The crude material was purified by normal phase flash chromatography (0 to 5% ethyl acetate in cyclohexane) to give impure product. The crude material was purified by reverse phase flash chromatography (60 to 100% (acetonitrile +0.1% formic acid) in (water +0.1% formic acid)) to give 3-bromo-2-chloro-N-methyl-6-(trifluoromethoxy)aniline (0.587 g, 1.93 mmol, 28%) as a brown oil. .sup.1H NMR (chloroform): 7.03-6.99 (m, 1H), 6.99-6.94 (m, 1H), 3.08 (s, 3H).

[0191] Step 3

[0192] To a flask containing 3-bromo-2-chloro-N-methyl-6-(trifluoromethoxy)aniline (1.36 g, 4.47 mmol) was added tetrahydrofuran (41 mL). The reaction mixture was put under a nitrogen atmosphere and stirred at −78° C. for 1 hour. To the reaction mixture, n-butyllithium (2.5 M in hexane, 4.91 mmol, 2.00 mL) was added dropwise. The reaction mixture was stirred at −78° C. for 45 minutes. To the reaction mixture was added iodomethane (1.90 g, 13.4 mmol, 0.834 mL). The reaction mixture was allowed to warm to 0° C. and stirred for 3.5 hours. The reaction mixture was carefully quenched by slow addition of the reaction mixture into ice cooled saturated aqueous ammonium chloride solution. The mixture was stirred at 0° C. for 15 minutes, and the aqueous phase was extracted with ethyl acetate. The organic phases were combined, dried and concentrated in vacuo. The crude material was purified by normal phase flash chromatography (0 to 1% ethyl acetate in cyclohexane) to give 3-bromo-2-chloro-N,N-dimethyl-6-(trifluoromethoxy)aniline (0.520 g, 1.63 mmol, 37%). .sup.1H NMR (chloroform): 7.35 (d, J=8.9 Hz, 1H), 7.01 (m, 1H), 2.87 (s, 6H).

[0193] Step 4

[0194] To a vessel containing 3-bromo-2-chloro-N,N-dimethyl-6-(trifluoromethoxy)aniline (0.520 g, 1.63 mmol) was added palladium(II) acetate (0.0367 g, 0.163 mmol), XantPhos (0.195 g, 0.327 mmol), N-formylsaccharine (0.776 g, 3.67 mmol), 5-methyl-1,3,4-oxadiazol-2-amine (1.46 g, 14.7 mmol) and 1-methyl-2-pyrrolidinone was added so the total volume of the vessel was 20 mL. To a second vessel containing triethylamine (0.743 g, 7.35 mmol, 1.02 mL) was added 1-methyl pyrrolidinone so that the total volume of the vessel was 20 mL. The reaction was carried out in a Uniqsis FlowSyn. The two solutions were injected into the sample loops pumped through a T-piece and then round a 20 mL stainless steel coil heated to 170° C. The flow rate was set so that the total residence time was 20 mins. The reaction mixture was concentrated in vacuo to remove the solvent 1-methyl-2-pyrrolidinone. The residue was purified by reverse phase HPLC to give impure product. The crude material was purified by normal phase flash chromatography (10 to 80% ethyl acetate in cyclohexane) to give 2-chloro-3-(dimethylamino)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-4-(trifluoromethoxy)benzamide (Compound 2.001) (0.174 g, 0.478 mmol, 29%) as a pale yellow solid. .sup.1H NMR (Methanol): 7.37-7.34 (m, 2H), 2.90 (s, 6H), 2.51 (s, 3H).

TABLE-US-00001 TABLE 1 Examples of herbicidal compounds of the present invention. Time Solvent Solvent (mins) A (%) B (%) Flow (ml/mn) 0   95    5 0.6 3.3  0  100 0.6 3.5  0  100 0.6 3.55 95.5  5 0.6 4.1  95.5  5 0.6 Solvent A: H.sub.2O with 0.05% TFA Solvent B: CH.sub.3CN with 0.05% TFA Compound 1H-NMR or LCMS Number Structure (M.sup.+H; RT (min)) 1.001 [00019] 1H NMR (chloroform): 7.44 (d, 1H), 7.30-7.25 (m, 1H), 4.12 (s, 3H), 2.91 (s, 6H) 1.002 [00020] 1H NMR (Methanol): 7.75 (d, 1H), 7.53 (m, 1H), 4.06 (s, 3H), 2.20 (s, 3H) 1.003 [00021] 1H NMR (Methanol, rotameric): 7.89 (d, 0.8H), 7.81 (d, 0.2H), 7.67 (m, 0.8H), 7.57 (m, 0.2H), 4.11-4.02 (m, 3H), 3.36 (s, 0.6H), 3.17 (s, 2.4H), 2.32 (s, 0.6H), 1.84 (s, 2.4H) 1.004 [00022] 1H NMR (Methanol): 7.82 (d, 1H), 7.58 (m, 1H), 4.06 (s, 3H), 3.69-3.60 (m, 1H), 3.59-3.50 (m, 1H), 2.57 (m, 2H), 2.10-1.93 (m, 4H) 1.005 [00023] 1H NMR (Methanol): 7.29 (m, 1H), 7.00 (d, 1H), 4.05 (s, 3H), 3.07 (s, 3H) 1.006 [00024] 1H NMR (Methanol): 7.73 (d, 1H), 7.52 (br d, 1H), 4.06 (s, 3H), 1.91 (m, 1H), 1.01-0.88 (m, 4H) 1.007 [00025] 1H NMR (400 MHz, d6-DMSO): 11.92 (1H, s), 9.90 (1H, s), 7.80 (1H, d), 7.61 (1H, d), 4.00 (3H, s), 2.37 (2H, q), 1.12 (3H, t) 1.008 [00026] 1H NMR (400 MHz, methanol) 7.73 (d, 1H), 7.52 (m, 1H), 4.04 (s, 3H), 2.33 (d, 2H), 2.19 (m, 1H), 1.06 (d, 6H) 1.009 [00027] 1H NMR (400 MHz, methanol) δ = 7.79 (d, 1H), 7.59-7.54 (m, 1H), 5.22 (qd, 1H), 4.06 (s, 3H), 1.65 (dd, 3H) 1.010 [00028] 1H NMR (400 MHz, methanol) 8.39 (s, 1H), 7.84 (d, 1H), 7.62 (m, 1H), 4.09 (s, 3H), 2.80 (s, 3H) 1.011 [00029] 1H NMR (400 MHz, methanol) 7.85 (d, 1H), 7.62 (m, 1H), 6.59 (s, 1H), 4.09 (s, 3H), 2.56 (s, 3H) 1.012 [00030] 1H NMR (Methanol): 8.76 (m, 1H), 8.19 (m, 1H), 8.04 (m, 1H), 7.81 (d, 1H), 7.65 (m, 1H), 7.60 (m, 1H), 4.07 (s, 3H) 1.013 [00031] 1H NMR (400 MHz, methanol) 8.67 (d, 1H), 8.29 (m, 1H), 7.89-7.82 (m, 2H), 7.63 (m, 1H), 4.10 (s, 3H) 1.014 [00032] 1H NMR (400 MHz, methanol) 8.61 (d, 1H), 7.89-7.81 (m, 2H), 7.80-7.72 (m, 1H), 7.63 (m, 1H), 4.10 (s, 3H) 1.015 [00033] 1HNMR (Methanol): 7.77 (d, 1H), 7.57 (m, 1H), 4.45 (m, 2H), 2.23 (s, 3H), 1.60 (m, 3H) 1.016 [00034] 1H NMR (Methanol): 7.71 (d, 1H), 7.26 (d, 1H), 5.25-5.13 (m, 1H), 4.68 (m, 2H), 4.04 (s, 3H), 1.68-1.62 (m, 3H) 1.017 [00035] 1H NMR (Methanol): 7.66 (d, 1H), 7.24 (d, 1H), 4.66 (m, 2H), 4.05 (s, 3H), 1.90 (m, 1H), 1.02-0.84 (m, 4H) 1.018 [00036] 1H NMR (Methanol): 7.67 (d, 1H), 7.25 (d, 1H), 4.67 (m, 2H), 4.04 (s, 3H), 2.18 (s, 3H) 1.019 [00037] 1H NMR (DMSO- d6) δ ppm 11.85 (br s, 1H) 10.00 (s, 1H) 7.72-7.74 (d, 1H) 6.99-7.38 (m, 2H) 3.98 (s, 3H) 1.90 (br s, 1H) 0.77-0.82 (m, 4H) 1.020 [00038] 1H NMR (DMSO- d6) δ ppm 11.85 (br s, 1H) 9.67 (s, 1H) 7.74 (d, 1H) 7.35 (d, 1H) 7.15 (t, 1H) 3.98 (s, 3H) 2.68-2.72 (m, 1H) 1.14 (d, 6H) 1.021 [00039] 1.022 [00040] 1H NMR (DMSO- d6) δ ppm 11.89 (br s, 1H) 9.72 (br s, 1H) 7.74-7.76 (d, 1H) 6.91-7.49 (m, 2H) 3.99 (s, 3H) 2.34-2.40 (m, 2H) 1.10-1.14 (t, 3H) 1.023 [00041] 1H NMR (METHANOL-d4) δ ppm 7.79 (d, 1H) 7.44 (d, 1H) 6.97 (t, 1H) 4.08 (s, 3H) 3.58-3.61 (m, 2H) 2.59 (br t, 2H) 1.98-2.09 (m, 4H) 1.024 [00042] 1H NMR (400 MHz, CHLOROFORM-d, 60° C.) δ ppm 0.96 (t, 3H) 1.74-2.04 (m, 2H) 3.05 (s, 3H) 4.01 (s, 3H) 7.45 (t, 1H) 7.53 (d, 1H) 7.86 (d, 1H) 11.76 (br s, 1H) 1.025 [00043] 1H NMR (METHANOL-d4) δ ppm 7.76 (d, 1H), 7.42 (d, 1H) 6.92 (t, 1H) 5.15-5.33 (m, 1H) 4.08 (s, 3H) 1.62-1.74 (m, 3H) 1.026 [00044] 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.16-1.29 (m, 3H) 1.37-1.53 (m, 3H) 3.57-3.93 (m, 2H) 4.26 (s, 3H) 4.85-5.01 (m, 1H) 6.55-6.69 (m, 1H) 7.35-7.41 (m, 1H) 7.43-7.52 (m, 1H) 1.027 [00045] 1.028 [00046] 1H NMR (Methanol): 7.69 (d, 1H), 7.17 (d, 1H), 5.25-5.13 (m, 1H), 4.03 (s, 3H), 3.92 (s, 3H), 1.68-1.61 (m, 3H) 1.029 [00047] 1H NMR (Methanol): 7.64 (d, 1H), 7.15 (d, 1H), 4.04 (s, 3H), 3.92 (s, 3H), 1.87 (m, 1H), 1.00-0.83 (m, 4H) 1.030 [00048] 1H NMR (Methanol): 7.66 (d, 1H), 7.16 (d, 1H), 4.04 (s, 3H), 3.92 (s, 3H), 2.17 (s, 3H) 1.031 [00049] 1H NMR (d6- DMSO): 11.87 (1H, s), 9.83 (1H, s), 7.76 (1H, d), 7.52 (1H, d), 6.78 (1H, t), 3.98 (3H, s), 2.04 (3H, s) 1.032 [00050] 1H NMR (400 MHz, methanol) 7.76 (d, 1H), 7.55 (m, 1H), 4.06 (s, 3H), 2.83 (m, 1H), 2.10 (m, 1H), 1.98-1.83 (m, 1H) 1.033 [00051] 1H NMR (400 MHz, methanol) 7.75 (d, 1H), 7.52 (m, 1H), 4.06 (s, 3H), 1.49 (s, 3H), 1.23 (m, 2H), 0.77 (m, 2H) 1.034 [00052] 1H NMR (400 MHz, methanol) 7.76 (d, 1H), 7.55 (m, 1H), 4.06 (s, 3H), 2.35 (d, 2H), 1.16 (m, 1H), 0.61 (m, 2H), 0.30 (m, 2H) 1.035 [00053] 1H NMR (METHANOL-d4) δ ppm 7.60 (d, 1H) 7.28 (d, 1H) 6.76 (t, 1H), 3.94 ( s, 3H), 2.71-2.75 (m, 1H) 1.94-2.01 (m, 1H) 1.78-1.92 (m, 1H) 1.036 [00054] 1H NMR (400 MHz, METHANOL-d4): 0.31-0.36 (m, 2H), 0.60-0.65 (m, 2H), 1.18 (brs, 1H), 1.38 (s, 1H), 2.05 (s, 1H), 4.37 (d, 2H), 4.08 (s, 3H), 6.91 (t, 1H), 7.4O (d, 1H), 7.72 (d, 1H) 1.037 [00055] 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.01 (br d, 2H) 0.49 (br d, 2H) 0.97-1.05 (m, 1H) 1.91 (br d, 2H) 3.19 (s, 3H) 4.12 (s, 3H) 6.69 (t, 1H) 7.40 (d, 1H) 7.82 ( d,l H) 11.18 (s, 1H) 1.038 [00056] 1H NMR (400 MHz, DMSO-d6) δ ppm 11.92 (br s, 1H) 10.16 (s, 1H) 8.30 (s, 1H) 7.82 (d, 1H) 7.44 (d, 1H) 7.27 (t, 1H) 4.00 (s, 3H) 2.78 (s, 3H) 1.039 [00057] 1HNMR: 1H NMR (400 MHz, DMSO- d6) δ ppm 2.78 (s, 3H) 4.00 (s, 3H) 7.08 (s, 1H) 7.26 (s, 1H) 7.38-7.47 (m, 1H) 7.81 (d, J = 8.56 Hz, 1H) 8.29 (s, 1H) 10.16 (s, 1H) 11.92 (br s, 1H) 1.040 [00058] 1H NMR (400 MHz, CHLOROFORM- d): 2.56-2.62 (s, 3H), 4.06-4.17 (s, 3H), 6.63 (t, 1H), 7.00 (d, 1H), 7.29 (s, 1H), 7.43-7.49 (d, 2H), 7.73 (d, 1H), 10.42-10.80 (s, 1H) 1.041 [00059] 1H NMR (400 MHz, METHANOL-d4) δ ppm 7.67 (br d, 1H) 7.34 (br d, 1H) 7.20 (s, 1H) 6.84 (t, 1H) 4.00 (s, 3H) 1.042 [00060] 1H NMR (400 MHz, DMSO-d6): 2.58 (s, 3H), 2.67 (s, 3H), 4.06 (s, 3H), 7.36 (t, 1H), 7.44 (brd, 1H), 7.82 (brd, 1H), 10.00 (s, 1H), 11.60-12.25 (s, 1H) 1.043 [00061] 1H NMR (400 MHz, DMSO-d6) δ ppm 11.91 (br s, 1H) 10.47 (s, 1H) 7.90 (d, 1H) 7.71 (d, 1H) 7.48 (s, 1H) 4.01 (s, 3H) 1.044 [00062] 1H NMR (400 MHz, METHANOL-d4) δ ppm 7.67 (d, 1H) 7.33 (d, 1H) 6.82 (t, 1H) 6.46 (s, 1H) 3.96 (s, 3H) 2.43 (s, 3H) 1.045 [00063] 1H NMR (400 MHz, METHANOL-d4) δ ppm 8.21 (s, 1H) 7.70 (d, 1H) 7.48 (d, 1H) 7.07 (t, J = 54.10 Hz, 1H) 3.97 (s, 3H) 3.92 (s, 3H) 1.046 [00064] 1H NMR (d6- DMSO): 11.96 (1H, s), 10.02 (lH,s), 7.84 (1H, d), 7.63 (1H, d), 6.56 (1H, s), 4.01 (3H, s), 3.86 (3H, s), 2.32 (3H, s) 1.047 [00065] 1H NMR (400 MHz, DMSO-d6): 3.99 (s, 3H), 7.65 (d, 1H), 7.86 (d, 1H), 8.54 (d, 1H) 9.30 (d, 1H), 10.49 (s, 1H), 12.00 (brs, 1H) 1.048 [00066] 1HNMR (400 MHz, DMSO-d6): 1.02-1.08 (m, 1H), 2.99 (d, 6H), 3.99 (s, 3H), 7.17 (s, 1H), 7.34 (d, 1H), 7.65 (d, 1H) 11.40 (s, 1H), 11.83 (s, 1H) 1.049 [00067] 1H NMR (400 MHz, DMSO-d6): 1.17 (t, 1H), 1.99 (s, 1H), 3.98 (s, 3H), 4.03 (m, 1H), 7.26 (1H, t), 7.44 (1H, d), 7.80 (d.sub./lH).sub./ 8.52 (d, 1H), 9.29 (d, 1H), 10.26 (s, 1H), 11.90 (1H, brs) 1.050 [00068] 1H NMR (400 MHz, DMSO-d6) δ ppm 12.05 (brs, 1H) 10.55 (s, 1H) 8.75-8.82 (m, 1H) 8.21 (br dd, 1H) 7.99 (td, 1H) 7.83 (br d, 1H) 7.44 (br d, 1H) 7.09 (t, 1H) 4.03 (s, 1H) 1.051 [00069] 1H NMR (400 MHz, DMSO-d6) δ ppm 11.91 (s, 1H) 10.09 (s, 1H) 8.51 (s, 1H) 7.81 (d, 1H) 7.44 (d, 1H) 7.29 (t l H) 7.28 (t, 1H) 4.01 (s, 3H) 4.00 (s, 3H) 1.052 [00070] 1H NMR (400 MHz, DMSO-d6) δ ppm 11.91 (br s, 1H) 9.82 (s, 1H) 7.79 (d, 1H) 7.45 (d, 1H) 7.23 (t, 1H) 6.55 (s, 1H) 4.00 (s, 3H) 3.85 (s, 3H) 2.32 (s, 3H) 1.053 [00071] 1H NMR (400 MHz, DMSO-d6): 11.93 (br s, 1H) 10.80 (s, 1H) 9.08 (d, 1H) 8.32 (s, 1H) 8.15 (br d, 1H) 7.84 (d, 1H) 7.46 (d, 1H) 7.28 (t, 1H) 3.98 (s, 3H) 1.054 [00072] 421.3  1.7  1.055 [00073] 419.3  1.8  1.056 [00074] 469.3  1.98 1.057 [00075] 435.3  1.6  1.058 [00076] 435.3  1.49 1.059 [00077] 413.2  1.55 1.060 [00078] 441.2  1.8  1.061 [00079] 427.3  1.7  1.062 [00080] 435.3  1.84 1.063 [00081] 421.3  1.54 1.064 [00082] 435.3  1.8  1.065 [00083] 435.3  1.73 1.066 [00084] 421.3  1.62 1.067 [00085] 449.3  1.6  1.068 [00086] 459.2  1.81 1.069 [00087] 463.3  1.85 1.070 [00088] 449.3  1.93 1.071 [00089] 435.3  1.65 1.072 [00090] 449.3  1.9  1.073 [00091] 449.3  1.83 1.074 [00092] 435.3  1.73 1.075 [00093] 435.3  1.79 1.076 [00094] 433.3  1.89 1.077 [00095] 449.3  1.7  1.078 [00096] 1H NMR (400 MHz, methanol) δ ppm 7.70 (d, 1H) 7.35-7.43 (m, 1H) 4.05 (s, 3H) 2.48 (q, 2H) 2.38 (s, 3H) 1.26 (t, 3H) 1.079 [00097] 1H NMR (400 MHz, methanol) δ ppm 7.69 (d, 1H) 7.39 (dq, 1H) 4.41 (q, 2H) 2.48 (q, 2H) 2.38 (s, 3H) 1.58 (t, 3H) 1.26 (t, 3H) 1.080 [00098] 1H NMR (400 MHz, d6-DMSO): 11.92 (1H, brs, 10.51 (1H, s), 8.57 (1H, d), 7.81 (1H, d), 7.62 (1H, d), 7.46-7.06 (3H, m), 3.98 (3H, s), 3.94 (3H, s) 1.081 [00099] 1H NMR (400 MHz, DMSO-d6) δ ppm 4.01 (s, 3H) 7.37 (t, 1H), 7.49 (d, 1H) 7.85 (d, 1H) 8.71 (s, 1H) 9.12 (s, 1H) 10.74 (s, 1H) 11.92 (br s, 1H) 1.082 [00100] 1H NMR (400 MHz, methanol) δ ppm 7.83 (brs, 2H), 4.05 (s, 3H), 2.46 (q, 2H), 1.24 (t, 3H) 1.083 [00101] 1H NMR (400 MHz, DMSO-d6) δ ppm 12.12 (br s, 1H) 10.49 (s, 1H) 8.08-8.16 (m, 2H) 7.80-7.89 (m, 2H) 7.46 (d, 1H) 7.29 (t, 1H) 3.99 (s, 3H) 1.084 [00102] 1H NMR (400 MHz, DMSO-d6) δ ppm 11.94 (br s, 1H) 10.82 (s, 1H) 9.19 (s, 1H) 8.51 (dd, 1H) 8.33 (d, 1H) 7.86 (d, 1H) 7.50 (d, 1H) 7.23 (t, 1H) 4.01 (s, 3H) 1.085 [00103] 1H NMR (400 MHz, DMSO-d6) δ ppm 12.03 (br s, 1H) 10.22 (s, 1H) 7.95 (dd, 1H) 7.85 (d, 1H) 7.71 (d, 1H) 7.49 (d, 1H) 7.30 (t, 1H) 7.14 (d, 1H) 4.01 (s, 3H) 4.03 (s, 3H) 1.086 [00104] 1H NMR (400 MHz, DMSO-d6) 11.92 (br s, 1H) 10.66 (s, 1H) 8.77 (d, 1H) 8.13 (d, 1H) 7.90 (dd, 1H) 7.85 (d, 1H) 7.46 (d, 1H) 7.11 (t, 1H) 4.01 (s, 3H) 1.087 [00105] 1H NMR (400 MHz, DMSO-d6) δ ppm 11.92 (s, 1H) 10.62 (s, 1H) 8.79 (d, 1H) 8.46 (d, 1H) 7.84 (d, 1H) 7.46 (d, 1H) 7.16 (t, 1H) 4.01 (s, 3H) 1.088 [00106] 1H NMR (400 MHz, DMSO-d6) δ ppm 11.92 (br s, 1H) 10.67 (s, 1H) 8.21 (d, 1H) 7.85 (br d, 1H) 7.79 (d, 1H) 7.47 (br d, 1H) 7.36 (t, 1H) 4.02 (s, 3H) 1.089 [00107] 1H NMR (400 MHz, DMSO-d6) δ ppm 11.93 (br s, 1H) 10.52 (s, 1H) 8.71 (d, 1H) 8.19 (brt, 1H) 7.84 (d, 1H) 7.42 (d, 1H) 7.12 (t, 1H) 4.01 (s, 3H) 1.090 [00108] 1H NMR (400 MHz, METHANOL-d4) δ ppm 7.59 (br d, 1H) 7.26 (br d, 1H) 6.78 (t, 1H) 3.94 (s, 3H) 2.09 (s, 3H) 1.091 [00109] 1H NMR (CHLOROFORM- d) δ ppm 7.72 (d, 1H) 7.60 (d, 1H) 6.78 (t, 1H) 4.25 (s, 3H) 4.14-4.18 (m, 1H) 3.96-4.40 (m, 1H) 2.71 (q, 2H) 1.27 (t, 3H) 1.16 (t, 3H) 1.092 [00110] 1H NMR (400 MHz, DMSO-d6) δ ppm 11.92 (s, 1H) 10.57 (s, 1H) 8.68 (d, 1H) 8.13 (d, 1H) 7.83 (br d, 1H) 7.65 (dd, 1H) 7.46 (br d, 1H) 7.33 (t, 1H) 4.01 (s, 3H) 1.093 [00111] 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 11.00 (br s, 1H) 10.00 (s, 1H) 8.48 (br d, 1H) 7.72 (d, 1H) 7.64 (d, 1H) 7.39 (m, 1H) 7.25 (d, 1H) 6.63 (t, 1H) 4.01 (s, 3H) 2.71 (s, 3H) 1.094 [00112] 1HNMR (20-59780- 11HNMR, 400 MHz, methanol) 8.59 (d, J = 4.4 Hz, 1H), 7.87-7.78 (m, 2H), 7.76-7.70 (m, 1H), 7.63-7.58 (m, 1H), 4.44 (q, J = 7.3 Hz, 2H), 1.58 (t, J = 7.3 Hz, 3H) 1.095 [00113] 1H NMR (CHLOROFORM- d) δ ppm7.83 (d, 1H), 7.48 (d, 1H), 6.74 (t, 1H), 4.61 (q, 2H), 3.81-3.88 (m, 2H), 2.07-2.13 (m, 2H), 1.70 (t, 3H), 1.31 (t, 3H), 1.08 (t, 3H) 1.096 [00114] 1H NMR (DMSO- d6) δ ppm 11.98 (br s, 1H), 9.70 (s, 1H), 7.85 (brd, 1H), 7.70 (br d, 1H), 7.23 (t, 1H), 3.99 (s, 3H), 2.35 (q, 2H), 1.11 (t, 3H) 1.097 [00115] 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.08 (t, 3H) 1.63 (t, 3H) 1.96-2.01 (m, 2H) 3.19 (s, 3H) 4.49 (q, 2H) 6.68 (t, 1H) 7.40 (d, 1H), 7.82 (d, 1H), 11.13 (s, 1H) 1.098 [00116] 1H NMR (400 MHz, METHANOL-d4) δ ppm 2.22 (s, 3H) 2.26 (s, 3H) 3.87 (s, 3H) 4.07 (s, 3H) 6.90 (t, 1H) 7.40 (d, 1H) 7.72 (d, 1H) 1.099 [00117] 1H NMR (METHANOL-d4) δ ppm 8.06 (br dd, 2H), 7.76 (d, 1H), 7.42 (dd, 1H) 7.28 (br t, 2H), 6.90 (t, 1H), 4.61 (s, 3H) 1.100 [00118] 1H NMR (400 MHz, DMSO-d6) δ ppm 3.98 (s, 3H) 1.T1 (t, 1H) 7.45 (d, 1H) 7.76 (m, 2H) 7.96 (t, 1H) 8.61 (d, 1H) 10.50 (s, 1H) 11.91 ( s, 1H) 1.101 [00119] 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 3.91 (s, 3H) 4.10 (s, 3H) 6.61 (t, 1H) 7.02 (d, 2H) 7.28-7.36 (m, 1H) 7.73 (br s, 2H) 7.91 (d, 2H) 10.40 (s, 1H) 1.102 [00120] 1H NMR (400 MHz, methanol): 0.84-1.01 (m, 4H), 1.57 (tJ = 7.34 Hz, 3H), 1.82-1.94 (m, 1H), 4.37-4.49 (m, 2H), 6.17-6.51 (m, 1H), 7.50-7.57 (m, 1H), 7.67-7.74 (m, 1H) 1.103 [00121] 1H NMR (400 MHz, methanol): 1.23 (t, 3H), 1.48-1.63 (m, 3H), 2.39-2.54 (m, 2H), 4.35-4.48 (m, 2H), 6.18-6.54 (m, 1H), 7.54 (d, 1H), 7.67-7.76 (m, 1H) 1.104 [00122] 1H NMR (400 MHz, DMSO-d6) 11.93 (s, 1H), 9.92 (s, 1H), 7.81 (d, 1H), 7.62 (d, 1H), 4.00 (s, 3H), 2.34 (m, 1H), 1.42-1.65 (m, 4H), 0.93 (t, 6H) 1.105 [00123] 1H NMR (400 MHz, methanol) δ ppm 7.75 (d, 1H), 7.56 (dq, 1H), 4.43 (q, 2H), 2.40 (tt, 1H), 1.66-1.77 (m, 2H), 1.53-1.65 (m, 5H), 1.04 (t, 6H) 1.106 [00124] 1H NMR (400 MHz, chloroform) δ ppm 7.67 (d, 1H), 7.31-7.35 (m, 2H), 4.44 (q, 2H), 1.60 (t, 3H), 1.35 (s, 9H) 1.107 [00125] 1H NMR (400 MHz, chloroform) δ ppm 7.68 (d, 1H), 7.31-7.37 (m, 2H), 4.08 (s, 3H), 1.35 (s, 9H) 1.108 [00126] 1H NMR (METHANOL-d4) δ ppm 8.74 (d, 1H) 8.30 (d, 1H) 8.20-8.25 (m, 1H) 7.78 (dd, 1H) 7.70 (d, 1H) 7.37 (d, 1H) 6.86 (t, 1H) 3.98 (s, 3H) 1.109 [00127] 1H NMR (400 MHz, methanol): 1.16-1.28 (m, 3H), 2.41-2.53 (m, 2H), 4.06 (s, 3H), 6.21-6.53 (m, 1H), 7.49-7.57 (m, 1H), 7.73 (d, 1H) 1.110 [00128] 1H NMR (400 MHz, methanol): 0.85-1.03 (m, 4H), 1.82-1.95 (m, 1H), 4.06 (s, 3H), 6.18-6.51 (m, 1H), 7.48-7.57 (m, 1H), 7.67-7.75 (m, 1H) 1.111 [00129] 1H NMR (400 MHz, methanol) δ ppm 7.74 (d, 1H), 7.54 (dq, 1H), 4.43 (q, 2H), 3.41 (quin, 1H), 2.33-2.46 (m, 2H), 2.23-2.33 (m, 2H), 2.01-2.15 (m, 1H), 1.89-2.00 (m, 1H), 1.58 (t, 3H) 1.112 [00130] 1H NMR (400 MHz, methanol) δ ppm 7.75 (d, 1H), 7.54 (d, 1H), 4.07 (s, 3H), 3.41 (quin, 1H), 2.22-2.47 (m, 4H), 2.01-2.15 (m, 1H), 1.88-2.00 (m, 1H) 1.113 [00131] 1H NMR (400 MHz, methanol) 7.75 (d, 1H), 7.58-7.51 (m, 1H), 4.43 (q, 2H), 3.75 (t, 2H), 3.38 (s, 3H), 2.71 (t, 2H), 1.58 (t, 3H) 1.114 [00132] 1H NMR (400 MHz, methanol) 7.75 (d, 1H), 7.57-7.52 (m, 1H), 4.43 (q, 2H), 2.45 (t, 2H), 1.78 (sxt, 2H), 1.58 (t, 3H), 1.05 (t, 3H) 1.115 [00133] 1H NMR (400 MHz, methanol) δ ppm 7.66 (d, 1H), 7.50 (dq, 1H), 2.51 (s, 3H), 1.86-1.95 (m, 1H), 0.89-1.00 (m, 4H) 1.116 [00134] 1H NMR (400 MHz, methanol) 7.78 (d, 1H), 7.59-7.53 (m, 1H), 4.43 (q, 2H), 4.14 (s, 2H), 3.54 (s, 3H), 1.58 (t, 3H) 1.117 [00135] 1H NMR (400 MHz, methanol) δ ppm 7.73 (d, 1H), 7.53 (dq, 1H), 4.43 (q, 2H), 1.86-1.97 (m, 1H), 1.58 (t, 3H), 0.86-1.03 (m, 4H) 1.118 [00136] 1H NMR (400 MHz, methanol): 7.74 (d, 1H), 7.57-7.52 (m, 1H), 4.43 (q, 2H), 2.77 (septet, 1H), 1.58 (t, 3H), 1.26 (d, 6H) 1.119 [00137] 1H NMR (400 MHz, methanol) 7.74 (d, 1H), 7.54 (m, 1H), 4.42 (q, 2H), 2.48 (q, 2H), 1.57 (t, 3H), 1.25 (t, 3H) 1.120 [00138] 1H NMR (400 MHz, methanol) 7.75 (d, 1H), 7.57-7.51 (m, 1H), 4.06 (s, 3H), 3.75 (t, 2H), 3.38 (s, 3H), 2.71 (t, 2H) 1.121 [00139] 1H NMR (400 MHz, methanol) 7.75 (d, 1H), 7.57-7.52 (m, 1H), 4.07 (s, 3H), 2.45 (t, 2H), 1.77 (sxt, 2H), 1.05 (t, 3H) 1.122 [00140] 1H NMR (400 MHz, methanol): 1.52-1.63 (m, 3H), 4.35-4.49 (m, 2H), 6.11-6.48 (m, 1H), 7.56-7.63 (m, 1H), 7.76-7.87 (m, 1H) 1.123 [00141] 1H NMR (400 MHz, methanol): 1.49-1.65 (m, 3H), 4.05 (s, 3H), 4.44 (m, 2H), 7.12 (t, 1H), 7.24 (d, 1H), 7.58 (d, 2H), 7.78 (d, 1H), 7.93-8.02 (m, 1H) 1.124 [00142] 1H NMR (400 MHz, methanol) 7.75 (d, 1H), 7.56-7.51 (m, 1H), 4.06 (s, 3H), 2.77 (spt, 1H), 1.25 (d, 6H) 1.125 [00143] 1H NMR (400 MHz, methanol) 7.79 (d, 1H), 7.57 (m, 1H), 4.08 (s, 3H), 3.45 (s, 3H), 1.50 (s, 6H) 1.126 [00144] 1H NMR (400 MHz, DMSO-d6) δ ppm 11.61 (br s, 1H) 9.45 (s, 1H) 7.65 (br d, 1H) 7.21 (br d, 1H) 7.13 (t, 1H) 3.97 (s, 3H) 2.35 (q, 2H) 2.26 (s, 3H) 1.12 (t, 3H) 1.127 [00145] 1H NMR (400 MHz, acetonitrile) 8.54 (br s, 1H), 7.78 (d, 1H), 7.56 (m, 1H), 5.26 (m, 1H), 4.37 (m, 2H), 1.65 (m, 3H), 1.56 (m, 3H) 1.128 [00146] 1H NMR (400 MHz, methanol) 8.78 (m, 1H), 8.22 (m, 1H), 8.07 (m, 1H), 7.83 (d, 1H), 7.68 (m, 1H), 7.63 (m, 1H), 4.46 (m, 2H), 1.60 (m, 3H) 1.129 [00147] 1H NMR (400 MHz, methanol) 7.73 (d, 1H), 7.54 (m, 1H), 4.36 (m, 2H), 2.20 (s, 3H), 1.99 (m, 2H), 0.97 (m, 3H) 1.130 [00148] 1H NMR (400 MHz, methanol) 7.78 (d, 1H), 7.59-7.53 (m, 1H), 4.14 (s, 2H), 4.06 (s, 3H), 3.54 (s, 3H) 1.131 [00149] 1H NMR (Methanol): 7.69 (d, 1H), 7.38 (d, 1H), 6.89 (m, 1H), 4.42 (m, 2H), 2.35 (d, 2H), 1.57 (m, 3H), 1.21-1.09 (m, 1H), 0.65-0.56 (m, 2H), 0.34-0.27 (m, 2H) 1.132 [00150] 1H NMR (400 MHz, methanol): 8.76 (dd, 1H), 8.20 (d, 1H), 8.05 (dt, 1H), 7.80 (d, 1H), 7.66 (ddd, 1H), 7.64-7.59 (m, 1H), 4.38 (t, 2H), 2.06-1.95 (m, 2H), 0.98 (t, 3H) 1.133 [00151] 1H NMR (400 MHz, acetonitrile): 9.80 (brs, 1H), 8.71 (d, 1H), 8.18 (d, 1H), 8.03 (dt, 1H), 7.75 (d, 1H), 7.65 (ddd, 1H), 7.60-7.54 (m, 1H), 4.55 (t, 2H), 3.83-3.75 (m, 2H), 3.29 (s, 3H) 1.134 [00152] 1H NMR (400 MHz, METHANOL-d4) δ ppm 9.56 (s, 1H) 9.39 (dd, 1H) 8.10 (br d, 1H) 7.71 (d, 1H) 7.37 (d, 1H) 6.87 (t, 1H) 3.97 (s, 3H) 1.135 [00153] 1H NMR (400 MHz, METHANOL-d4): 7.68 (d, 1H) 7.35 (d, 1H) 6.86 (t, 1H) 6.26 (s, 1H) 3.98 (s, 3H) 3.97 (s, 6H) 1.136 [00154] 1H NMR (400 MHz, DMSO-d6) δ ppm 9.56 (s, 1H) 9.39 (dd, 1H) 8.10 (dd, 1H) 7.71 (d, 1H) 7.37 (d, 1H) 6.87 (t, 1H) 3.97 (s, 3H) 1.137 [00155] 1H NMR (400 MHz, DMSO-d6): 3.98 (s, 3H), 7.30 (d, 1H), 7.46 (t, 1H), 7.85 (d, 1H), 9.11 (s, 1H), 9.23 (d, 1H), 10.74 (s, 1H), 11.92 (s, 1H) 1.138 [00156] 1H NMR (400 MHz, DMSO-d6) δ ppm 11.98 (br s, 1H) 11.14 (s, 1H) 9.53 (dd, 1H) 8.32 (dd, 1H) 8.01 (dd, 1H) 7.86 (d, 1H) 7.49 (d, 1H) 7.31 (t, 1H) 4.01 (s, 3H) 1.139 [00157] 1H NMR (400 MHz, DMSO-d6) δ ppm 11.94 (br s, 1H) 10.94 (br s, 1H) 8.24 (s, 1H), 7.88 (d, 1H) 7.51 (d, 1H) 7.41 (t, lH)4.02 (s, 3H) 1.140 [00158] 455.2  1.92 1.141 [00159] 473.2  2.04 1.142 [00160] 457.2  1.88 1.143 [00161] 421.2  1.69 1.144 [00162] 453.2  1.96 1.145 [00163] 453.2  1.97 1.146 [00164] 435.3  1.85 1.147 [00165] 435.3  1.84 1.148 [00166] 455.2  1.91 1.149 [00167] 473.2  2.04 1.150 [00168] 435.3  1.79 1.151 [00169] 453.2  1.91 1.152 [00170] 457.2  1.86 1.153 [00171] 439.2  1.73 1.154 [00172] 455.2  1.75 1.155 [00173] 473.2  1.88 1.156 [00174] 439.2  1.77 1.157 [00175] 457.2  1.9  1.158 [00176] 507.1  2.23 1.159 [00177] 489.2  2.1  1.160 [00178] 489.1  1.81 1.161 [00179] 507.1  2.28 1.162 [00180] 489.1  2.15 1.163 [00181] 469.2  1.87 1.164 [00182] 451.2  1.75 1.165 [00183] 469.2  1.84 1.166 [00184] 475.2  1.81 1.167 [00185] 457.2  1.67 1.168 [00186] 475.2  1.92 1.169 [00187] 457.2  1.8  1.170 [00188] 475.2  1.92 1.171 [00189] 457.2  1.78 1.172 [00190] 475.2  1.99 1.173 [00191] 489.2  1.93 1.174 [00192] 457.2  1.86 1.175 [00193] 507.1  2.05 1.176 [00194] 1H NMR (400 MHz, DMSO-d6) δ ppm 7.66 (d, 2H) 11.99 (br s, 1H) 10.04 (s, 1H) 7.88 (d, 1H) 4.01 (s, 3H) 2.47 (s, 3H) 1.177 [00195] 1HNMR (400 MHz, DMSO-d6): 4.01 (s, 3H), 7.68-7.72 (d, 1H), 7.92 (d, 1H), 9.08 (d, 1H), 9.16 (d, 1H), 11.06 (s, 1H), 12.01 (brs, 1H) 1.178 [00196] 1H NMR (400 MHz, DMSO-d6) δ ppm 12.05 (br s, 1H) 11.33 (br s, 1H) 9.54 (dd,l H) 8.33 (dd, 1H) 8.01 (dd, 1H) 7.89 (d, 1H) 7.68 (br d, 1H) 3.99 (s, 3H) 1.179 [00197] 1H NMR (400 MHz, DMSO-d6): 12.03 (br s, 1H) 10.59 (s, 1H) 7.90 (br d, 1H), 7.69 (br d, 1H), 6.52 (s, 1H), 4.06 (s, 3H), 4.04 (s, 6H) 1.180 [00198] 1H NMR (400 MHz, DMSO-d6): 3.93 (s, 3H) 7.48-7.76 (m, 1H) 7.68 (br s, 1H) 7.86 (br d, 1H) 8.16 (br s, 1H) 9.57 (br d, 1H) 9.67 (br s, 1H) 10.63-11.20 (m 1.181 [00199] 1H NMR (400 MHz, DMSO-d6, 80 ° C.): 10.35 (br s, 1H) 9.30 (s, 1H) 8.67 (s, 1H) 7.82 (br d, 1H) 7.52 (d, 1H) 3.87 (s, 3H) 1.182 [00200] 1HNMR (400 MHz, methanol): 9.18 (d, 1H), 8.70 (d, 1H), 7.83 (d,H), 7.61 (qd, 1H), 4.07 (s, 3H), 2.70 (s, 3H) 1.183 [00201] 1H NMR (400 MHz, DMSO-d6) δ ppm 12.01 (br s, 1H) 11.15 (br s, 1H) 8.27 (s, 1H) 7.95 (d, 1H) 7.75 (d, 1H) 4.03 (s, 3H) 1.184 [00202] 507.1  2.1  1.185 [00203] 489.1  1.98 1.186 [00204] 489.1  1.81 1.187 [00205] 507.1  1.94 1.188 [00206] 1H NMR (400 MHz, methanol) 8.03-7.95 (m, 2H), 7.81 (d, 1H), 7.68-7.62 (m, 1H), 7.62-7.52 (m, 3H), 4.07 (s, 3H) 1.189 [00207] 461.1  1.81 1.190 [00208] 508.6  2.15 1.191 [00209] 454.2  1.22 1.192 [00210] 443.2  1.38 1.193 [00211] 431.2  1.73 1.194 [00212] 447.1  1.71 1.195 [00213] 474.1  2.05 1.196 [00214] 458.1  1.54 1.197 [00215] 509.2  1.72 1.198 [00216] 522.1  2.01 1.199 [00217] 508   1.73 1.200 [00218] 454.2  1.19 1.201 [00219] 461.1  1.88 1.202 [00220] 511.1  2.07 1.203 [00221] 488.1  1.88 1.204 [00222] 510.1  2   1.205 [00223] 510.0  2.09 1.206 [00224] 513.1  1.78 1.207 [00225] 455.2  1.67 1.208 [00226] 456.1  1.96 1.209 [00227] 443.2  1.56 1.210 [00228] 508.0  1.74 1.211 [00229] 441.8  1.25 1.212 [00230] 459.1  1.45 1.213 [00231] 474.0  1.78 1.214 [00232] 474.0  1.58 1.215 [00233] 508.0  1.94 1.216 [00234] 447.1  1.68 1.217 [00235] 510.1  2.09 1.218 [00236] 508.0  1.94 1.219 [00237] 445.1  1.85 1.220 [00238] 444.2  1.32 1.221 [00239] 542.0  2.13 1.222 [00240] 457.1  1.64 1.223 [00241] 431.1  1.44 1.224 [00242] 492.1  1.96 1.225 [00243] 443.1  1.65 1.226 [00244] 436.1  1.08 1.227 [00245] 429.1  1.35 1.228 [00246] 425.2  1.24 1.229 [00247] 429.1  1.46 1.230 [00248] 507.8  2.06 1.231 [00249] 413.1  1.56 1.232 [00250] 429.1  1.55 1.233 [00251] 456.1  1.91 1.234 [00252] 440.2  1.39 1.235 [00253] 492.1  1.58 1.236 [00254] 505.6  1.88 1.237 [00255] 491.9  1.59 1.238 [00256] 436.2  1.07 1.239 [00257] 443.1  1.72 1.240 [00258] 495.2  1.94 1.241 [00259] 450.2  1.1  1.242 [00260] 470.1  1.74 1.243 [00261] 490.0  1.96 1.244 [00262] 493.1  1.66 1.245 [00263] 438.2  1.8  1.246 [00264] 437.2  1.52 1.247 [00265] 425.2  1.42 1.248 [00266] 491.8  1.6  1.249 [00267] 439.2  1.33 1.250 [00268] 456.1  1.64 1.251 [00269] 456.1  1.44 1.252 [00270] 490.1  1.82 1.253 [00271] 429.1  1.54 1.254 [00272] 492.  1.97 1.255 [00273] 492.01 1.83 1.256 [00274] 427.2  1.72 1.257 [00275] 426.2  1.2  1.258 [00276] 439.2  1.51 1.259 [00277] 413.1  1.28 1.260 [00278] 474.1  1.83 1.261 [00279] 1.262 [00280] 1.263 [00281] 1.264 [00282] 1.265 [00283] 1.266 [00284] 1.267 [00285] 1.268 [00286] 1.269 [00287] 1.270 [00288] 1.271 [00289] 1.272 [00290] 1.273 [00291] 1.274 [00292] 1.275 [00293] 1.276 [00294] 1.277 [00295]

[0195] Compounds are characterised using NMR as indicated or LCMS using the following conditions. Waters Aquity UPLC-MS using a Sample Organizer with Sample Manager FTN, H-class QSM, Column Manager, 2×Column Manager Aux, photodiode array, ELSD and a QDA SQD 2 equipped with a Waters HSS C18 column (column length 50 mm, internal diameter of column 2.3 mm, particle size 1.8 micron). The analysis was conducted using a four minute run time, according to the following gradient table:

TABLE-US-00002 TABLE 2 Examples of herbicidal compounds of the present invention. Compound Number Structure .sup.1H-NMR 2.001 [00296] 1H NMR (Methanol): 7.37-7.34 (m, 2H), 2.90 (s, 6H), 2.51 (s, 3H) 2.002 [00297] 1H NMR (Methanol): 7.67 (d, 1H), 7.51 (m, 1H), 2.51 (s, 3H), 2.19 (s,3H) 2.003 [00298] 1H NMR (Methanol, rotameric): 7.79 (d, 0.8H), 7.72 (d, 0.2H), 7.61 (m, 0.8H), 7.54 (m, 0.2H), 3.35 (s, 0.6H), 3.15 (s, 2.4H), 2.58-2.45 (m, 3H), 2.31 (s, 0.6H), 1.83 (s, 2.4H) 2.004 [00299] 1H NMR (Methanol): 7.74 (d, 1H), 7.55 (m, 1H), 3.68-3.59 (m, 1H), 3.57-3.49 (m, 1H), 2.57 (m, 2H), 2.51 (s, 3H), 2.08-1.93 (m, 3H) 2.005 [00300] 2.006 [00301] 1H NMR (400 MHz, methanol) δ ppm 7.67 (d, 1H), 7.51 (dq, 1 H), 2.51 (s, 3 H), 2.43 - 2.50 (m, 2 H), 1.25 (t, 3 H)

BIOLOGICAL EXAMPLES

[0196] 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-galh (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%).

TABLE-US-00003 TABLE B1 POST Application PRE Application Compound AMARE ABUTH SETFA ECHCG IPOHE AMARE ABUTH SETFA ECHCG IPOHE 1.001 5 5 5 5 5 5 5 5 5 5 1.002 5 5 5 5 5 5 5 2 5 1 1.003 5 5 — 5 5 5 5 5 5 1 1.004 5 5 5 5 5 5 5 4 3 1 1.005 5 5 5 5 5 5 5 5 5 5 1.006 5 5 5 5 5 5 5 5 5 2 1.007* 5 — 5 5 4 5 5 5 5 5 1.008 5 5 5 5 5 5 5 4 5 3 1.009 5 5 5 5 5 5 5 5 1 4 1.010 — 5 5 5 5 5 5 2 1 2 1.011 5 5 4 5 5 5 4 1 1 4 1.012* 4 4 4 3 4 5 5 5 5 4 1.014* 4 5 4 4 4 5 5 5 4 5 1.015 5 5 5 5 5 5 5 2 4 1 1.016 5 5 5 5 5 5 5 5 5 5 1.017 5 4 5 5 5 5 5 5 5 5 1.018 5 5 5 5 4 5 4 3 3 3 1.019* 5 5 5 5 5 5 5 5 5 5 1.020* 5 5 5 5 5 5 5 5 5 5 1.021* 3 4 4 4 3 3 5 3 3 3 1.022* 5 5 5 5 4 5 5 5 5 4 1.023* 5 5 5 5 5 5 5 5 5 2 1.024* 3 4 4 4 4 5 5 4 4 4 1.025* 5 4 4 5 2 5 5 3 3 4 1.026* 4 4 4 5 4 5 5 5 5 4 1.028 5 5 4 3 4 5 5 3 4 3 1.029 5 5 5 5 5 5 5 5 5 4 1.030 5 5 5 5 4 5 5 3 3 3 1.031* 4 4 4 4 4 5 4 3 4 3 1.032 5 5 5 5 5 5 5 5 5 3 1.033 5 5 5 5 5 5 5 5 5 5 1.034 5 5 5 5 5 5 5 5 5 4 1.035* 4 4 4 4 4 5 5 4 3 3 1.036* 5 5 5 5 4 5 5 5 5 4 1.037* 5 5 5 5 4 5 5 4 5 4 1.038* 4 — 4 — 4 5 5 4 5 5 1.041* 3 — 3 — 3 2 5 2 3 2 1.042* 5 — 5 5 5 5 4 5 5 5 1.044* 5 3 3 2 4 4 4 2 2 1 1.045* 5 — 5 5 4 5 5 5 5 4 1.046* 5 — 5 5 5 5 5 5 5 5 1.052* 5 — 5 4 4 5 5 5 5 4 1.053* 5 — 5 3 4 5 5 4 4 4 1.054* 5 5 5 — 5 5 5 5 5 4 1.055* 5 5 5 5 4 5 5 — 5 4 1.056* 4 — 4 4 4 3 5 3 1 — 1.057* 5 — 5 5 4 5 5 4 5 5 1.058* 4 — 4 5 4 5 5 3 5 5 1.059* 5 — 4 5 3 5 5 1 4 3 1.060* 5 — 5 4 4 5 5 4 4 3 1.061* 5 — 5 4 4 5 — 3 3 3 1.062* 5 — 5 4 4 5 — 3 2 4 1.063* 5 5 5 5 4 5 5 5 5 5 1.064* 4 — 4 — 4 5 5 4 3 4 1.065* 5 5 5 5 5 5 5 5 5 5 1.066* 4 — 4 — 4 5 5 4 5 5 1.067* 5 — 5 5 4 5 5 5 5 5 1.068* 4 — 5 — 4 5 5 5 5 3 1.069* 4 — 5 5 4 5 5 5 5 4 1.070* 4 — 4 4 4 5 5 4 4 4 1.071* 4 — 5 5 4 5 5 5 5 5 1.072* 4 — 5 5 4 5 5 4 5 5 1.073* 5 — 5 5 4 5 5 5 5 5 1.074* 5 — 5 5 5 5 5 4 4 5 1.075* 4 — 5 4 4 5 5 5 5 5 1.076* 4 — 4 5 4 5 5 5 5 5 1.077* 5 — 5 5 4 5 5 3 5 5 1.078* 5 — 5 5 4 5 5 4 5 4 1.079* 4 — 4 5 4 5 5 4 5 4 1.080* 4 — 4 — 4 4 1 1 1 2 1.081* 4 — 3 3 4 5 5 1 1 1 1.082* 4 4 4 3 4 5 5 4 5 3 1.083* 4 4 4 2 4 5 5 4 — 3 1.084* 4 5 3 3 3 5 4 1 1 1 1.085* 4 4 4 4 4 4 5 3 — 3 1.086* 5 4 4 4 5 5 5 4 — 4 1.087* 4 4 4 — 4 5 4 4 1 4 1.088* 4 4 4 3 4 5 4 5 — 4 1.089* 4 3 4 2 3 5 2 3 — 3 1.090* 4 4 4 4 4 5 5 4 5 4 1.091* 4 — 4 5 3 5 5 4 5 3 1.092* 3 — 4 — 4 5 5 5 — 3 1.093* 4 4 4 5 4 5 5 4 5 4 1.094 5 — 5 5 5 5 1 1 1 1 1.095* 5 — 5 5 4 5 5 4 5 4 1.096* 4 — 3 4 3 4 3 1 1 3 1.097* 4 — 5 4 4 5 5 4 5 5 1.098* 4 4 4 4 4 3 4 4 1 4 1.099* 4 4 3 4 4 5 4 1 1 3 1.100* 4 4 4 4 4 5 5 3 1 2 1.102 5 5 5 5 5 5 4 4 5 1 1.101* 4 4 4 5 4 4 4 4 1 2 1.103 5 5 5 5 5 5 4 1 3 1 1.104 5 5 5 5 5 5 4 3 5 2 1.105 5 5 5 5 5 5 5 3 5 2 1.106 5 5 5 5 5 5 5 5 5 — 1.107 5 5 5 5 5 5 5 5 5 4 1.108* 5 4 4 5 4 5 4 3 2 2 1.109 5 — 5 — 5 5 5 4 4 5 1.110 5 — 5 5 5 5 3 5 5 1 1.111 5 5 1 5 5 5 4 1 4 1 1.112 5 5 5 5 5 5 4 1 5 1 1.113 5 5 5 5 5 5 5 2 5 1 1.114 5 5 5 5 5 5 5 2 5 3 1.115* 3 4 4 4 4 4 4 4 5 2 1.116 5 5 5 5 5 5 5 1 3 1 1.117 5 5 5 5 5 5 5 4 5 4 1.118* 4 4 4 4 4 4 4 4 5 2 1.119 5 5 5 5 5 5 5 2 5 4 1.120 5 5 5 5 5 5 4 1 5 1 1.121 5 5 5 5 5 5 4 1 5 2 1.122* 5 4 3 4 2 5 3 3 4 1 1.123* 4 4 4 4 5 3 3 4 3 2 1.124 5 5 5 5 5 5 4 4 5 1 1.125 5 5 5 5 5 5 5 1 5 4 1.126* 5 5 5 5 4 5 5 2 5 3 1.127 5 5 5 5 5 5 5 3 5 2 1.128 5 5 5 5 5 5 4 1 3 1 1.129 5 5 5 5 5 5 5 1 4 2 1.130 5 5 5 5 4 5 4 1 2 1 1.131 5 5 4 5 5 5 5 1 3 1 1.132 5 5 5 5 5 5 4 1 3 4 2.001 5 4 5 5 5 5 4 5 5 3 2.002 5 5 5 5 5 1 3 1 1 1 2.003 5 5 5 5 5 5 5 5 5 4 2.004 5 5 5 5 5 5 4 5 5 1 *Applied at 125 g/ha

[0197] TABLE B2—COMPARATIVE TEST

[0198] Seeds of test species were sown in standard soil in pots. After cultivation for one day under controlled conditions in a glasshouse (at 24/16° C., day/night; 14 hours light; 65% humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in 0.6 ml acetone and 45 ml formulation solution containing 10.6% Emulsogen EL (Registry number 61791-12-6), 42.2% N-methyl pyrrolidone, 42.2% dipropylene glycol monomethyl ether (CAS RN 34590-94-8) and 0.2% X-77 (CAS RN 11097-66-8). The test plants were 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 14 days, the test was evaluated (100=total damage to plant; 0=no damage to plant).

[0199] Test species: ABUTH (Abutilon theophrasti); BRO′I′L (Bromus tectorum); ECHCG (Echinochloa crus-galli); SINAR (Sinapis arvensis).

TABLE-US-00004 Compound PRE Application Cl [00302] Rate g/ha ABUTH BROTE ECHCG SINAR 250 0 0 20 30 130 0 0 30 0 30 0 0 10 0 1.002 [00303] Rate g/ha ABUTH BROTE ECHCG SINAR 250 80 70 80 80 130 10 10 30 30 30 0 0 20 10 1.007 [00304] Rate g/ha ABUTH BROTE ECHCG SINAR 250 90 20 90 100 130 60 0 70 60 30 0 0 20 10 1.012 [00305] Rate g/ha ABUTH BROTE ECHCG SINAR 250 10 70 30 80 130 0 0 30 70 30 0 0 10 0 1.014 [00306] Rate g/ha ABUTH BROTE ECHCG SINAR 250 60 30 30 80 130 0 10 40 80 30 0 0 20 20

[0200] C1 is compound 4-659 disclosed in WO2012/028579. As can be seen, the replacement of the 4-chloro substituent on the phenyl ring with the haloalkoxy group of the present invention provides an unexpected improvement in the weed control observed.