HERBICIDAL COMPOUNDS

Abstract

The present invention relates to compounds Formula (I) wherein Q, R.sup.2, R.sup.3 and R.sup.4 are as defined herein. The invention further relates to compositions comprising said compounds, and methods of controlling weeds using said compounds and/or compositions.

Claims

1. A compound of Formula (I): ##STR00111## or an agronomically acceptable salt thereof, wherein: Q is selected from the group consisting of Q1 and Q2: ##STR00112## R.sup.1 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 selected from the group consisting of C.sub.1-C.sub.6alkyl-, C.sub.3-C.sub.6cycloalkyl- and C.sub.1-C.sub.6 haloalkyl-; R.sup.4 is C.sub.1-C.sub.6haloalkyl; and p is 0, 1 or 2.

2. A compound according to claim 1, wherein Q is Q1.

3. A compound according to claim 1, wherein Q is Q2.

4. A compound according to claim 1, wherein R.sup.1 is C.sub.1-C.sub.4alkyl-.

5. A compound according to claim 4, wherein R.sup.1 is methyl.

6. A compound according to claim 1, wherein R.sup.2 is selected from the group consisting of chlorine, methyl and CF.sub.3.

7. A compound according to claim 6, wherein R.sup.2 is chlorine.

8. A compound according to claim 1, wherein R.sup.3 is C.sub.1-C.sub.6alkyl-.

9. A compound according to claim 8, wherein R.sup.3 is methyl or ethyl.

10. A compound according to claim 1, wherein R.sup.4 is CF.sub.3 or CHF.sub.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 application to the locus of a weed controlling amount of a composition according to claim 1.

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

16. A compound of Formula (Va) ##STR00113## wherein R.sup.2, R.sup.3 and R.sup.4 are as defined in claim 1 above and R.sup.5 is hydrogen or C.sub.1-C.sub.4 alkyl.

Description

EXAMPLE 1. PREPARATION OF COMPOUND 1.001

[0093] Step 1

[0094] To a flask containing 4-bromo-3-chloro-phenol (8 g, 38.6 mmol) was added DCM (40 mL) and N,N-diisopropylethylamine (10 g, 13.5 mL, 77.1 mmol). At 0° C., 2-(chloromethoxy)ethyl-trimethyl-silane (7.07 g, 7.4 mL, 42.4 mmol) was added dropwise. The reaction was stirred at room temperature overnight. The reaction was quenched by addition of water, then saturated aqueous NaHCO.sub.3, The material was extracted with ethyl acetate and the organic phase was concentrated in vacuo to give 2-[(4-bromo-3-chloro-phenoxy)methoxy]ethyl-trimethyl-silane as an orange oil (14.8 g, quant %).sup.1H NMR (Chloroform): 7.47 (d, 1H), 7.18 (d, 1H), 6.83 (dd, 1H), 5.18 (s, 2H), 3.75 (m, 2H), 0.94 (m, 2H), 0.00 (m, 9H)

[0095] Step 2

[0096] To a 3 neck flask was added THE (280 mL) and the reaction mixture was purged and filled with N.sub.2. Diisopropylamine (6.78 g, 9.44 mL, 66.3 mmol) was added. The reaction was stirred at −78° C. for 30 min. N-butyllithium in hexane (16 g, 2.5 mol/L, 23 mL, 58.0 mmol) was added dropwise via syringe pump (10 mL/min). This was stirred for 1 h, then the mixture was allowed to warm to −40° C., then cooled to −78° C. again. A solution of 2-[(4-bromo-3-chloro-phenoxy)methoxy]ethyl-trimethyl-silane (14 g, 41.5 mmol) in 23 mL of THE was added via syringe pump (10 mL/min) and the reaction mixture was stirred at −78° C. for 3 h. Dimethyl disulfide (7.89 g, 7.54 mL, 82.9 mmol) in 16 mL THE was added dropwise (10 mL/min) and the mixture was stirred at −78° C. for 40 min. The reaction mixture was quenched by adding it cold into a stirred solution of water. 2M HCl was added until the mixture was acidic and the mixture was stirred for 15 min. The material was extracted with ethyl acetate and the organic phase was concentrated in vacuo to give 2-[(4-bromo-3-chloro-2-methylsulfanyl-phenoxy)methoxy]ethyl-trimethyl-silane (14.4 g, 31.1 mmol, 75%) as an orange oil. 1H NMR (Chloroform): 7.50 (d, 1H), 7.01 (d, 1H), 5.31 (s, 2H), 3.79 (m, 2H), 2.42 (s, 3H), 0.95 (m, 2H), 0.00 (s, 9H)

[0097] Step 3

[0098] To a flask containing 2-[(4-bromo-3-chloro-2-methylsulfanyl-phenoxy)methoxy]ethyl-trimethyl-silane (14.4 g, 37.5 mmol) was added THE (188 mL), MeOH (113 mL) and 2M aqueous HCl (113 mL). The reaction was stirred at 70° C. for 1 h. The reaction mixture was cooled to room temperature, then concentrated in vacuo. The crude material was diluted with water and extracted with ethyl acetate and the organic phase was concentrated in vacuo. The material was purified by flash chromatography (0 to 20% EtOAc in cyclohexane) to give 4-bromo-3-chloro-2-methylsulfanyl-phenol (8.28 g, 32.6 mmol, 87%) as white crystals. .sup.1H NMR (Chloroform): 7.50 (d, 1H), 7.09 (s, 1H), 6.85 (d, 1H), 2.34 (s, 3H)

[0099] Step 4

[0100] To a flask containing 4-bromo-3-chloro-2-methylsulfanyl-phenol (2 g, 7.89 mmol) was added DMF (20 mL). K.sub.2CO.sub.3 (1.38 g, 9.47 mmol) was added, followed by 2,2,2-trifluoroethyl trifluoromethanesulfonate (2.20 g, 1.36 mL, 9.47 mmol) and the reaction mixture was stirred at room temperature for 3.5 h. The reaction mixture was quenched by addition of water and the material was extracted with ethyl acetate. The organic phase was washed with water and concentrated in vacuo. The material was purified by flash chromatography (0 to 15% EtOAc in cyclohexane) to give 1-bromo-2-chloro-3-methylsulfanyl-4-(2,2,2-trifluoroethoxy)benzene (2.62 g, 7.81 mmol, 99%) as a colourless oil. 1H NMR (Chloroform): 7.54 (d, 1H), 6.73 (d, 1H), 4.42 (q, 2H), 2.45 (s, 3H)

[0101] Step 5

[0102] To a vessel containing NMP (101 mL) was added palladium(II) acetate (0.169 g, 0.751 mmol), XantPhos (0.896 g, 1.50 mmol), N-formylsaccharine (3.57 g, 16.9 mmol) and 1-bromo-2-chloro-3-methylsulfanyl-4-(2,2,2-trifluoroethoxy)benzene (2.52 g, 7.51 mmol). To a second vessel was added triethylamine (3.57 g, 4.71 mL, 33.8 mmol), NMP (101 mL) and water (5.04 mL). The reaction was carried out in a Uniqsis FlowSyn. The two solutions were 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 min. The reaction mixture was cooled to room temperature and was diluted with ethyl acetate. The organic phase was washed with 2M HCl, then with water. The organic phase was concentrated in vacuo. The material was purified by flash chromatography (0 to 100% EtOAc in cyclohexane) to give 2-chloro-3-methylsulfanyl-4-(2,2,2-trifluoroethoxy)benzoic acid (0.96 g, 2.87 mmol, 38%) as an orange solid. 1H NMR (Methanol): 7.78 (d, 1H), 7.09 (d, 1H), 4.71 (q, 2H), 2.40 (s, 3H)

[0103] Step 6

[0104] To a flask containing 2-chloro-3-methylsulfanyl-4-(2,2,2-trifluoroethoxy)benzoic acid (0.816 g, 2.71 mmol) was added 2,3,4,5,6-pentafluorophenol (0.750 g, 4.07 mmol) and DCM (16 mL). 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (0.602 g, 2.99 mmol) was added and the reaction was stirred at room temperature for 2 h. The reaction mixture was diluted with DCM and washed with saturated aqueous NaHCO.sub.3. The organic phase was concentrated in vacuo. The material was purified by flash chromatography (0 to 10% EtOAc in cyclohexane) to give (2,3,4,5,6-pentafluorophenyl) 2-chloro-3-methylsulfanyl-4-(2,2,2-trifluoroethoxy)benzoate (0.758 g, 1.62 mmol, 60%) as white needles. 1H NMR (Chloroform): 8.07 (d, 1H), 6.91 (d, 1H), 4.54 (q, 2H), 2.46 (s, 3H)

[0105] Step 7

[0106] To a flask containing the (2,3,4,5,6-pentafluorophenyl) 2-chloro-3-methylsulfanyl-4-(2,2,2-trifluoroethoxy)benzoate (0.379 g, 0.812 mmol) was added acetonitrile (7.6 mL) and the mixture was stirred at room temperature. 1-Methyltetrazol-5-amine (88.5 Mg, 0.893 mmol) was added, followed by 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (0.506 g, 0.533 mL, 1.79 mmol) and the reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with water and acidified with 2M HCl. The material was then extracted with ethyl acetate. The organic phase was concentrated in vacuo. The material was purified by flash chromatography (0 to 70% EtOAc in cyclohexane) to give a white solid. This material was crystallised from hot methanol to give 2-chloro-3-methylsulfanyl-N-(1-methyltetrazol-5-yl)-4-(2,2,2-trifluoroethoxy)benzamide (0.236 g, 0.544 mmol, 67%) as a white crystals. 1H NMR (Acetonitrile): 7.65 (d, 1H), 7.11 (d, 1H), 4.71 (q, 2H), 4.01 (s, 3H), 2.46 (s, 3H).

EXAMPLE 2. PREPARATION OF COMPOUND 1.005

[0107] Step 1

[0108] To a 3 necked flask was added THE (22 mL) and the reaction mixture was purged and filled with N.sub.2. Diisopropylamine (1.19 g, 1.65 mL, 11.6 mmol) was added. The reaction was stirred at −78° C. for 30 min. N-butyllithium in hexane (2.8 g, 2.5 mol/L, 4.1 mL, 10.2 mmol) was added dropwise. This was stirred for 1 h, then the mixture was allowed to warm to −40° C., then cooled to −78° C. again. A solution of 1-bromo-2-chloro-4-(trifluoromethoxy)benzene (2 g, 7.26 mmol) in 5 mL of THE was added and the reaction mixture was stirred at −78° C. for 1.5 h. Dimethyl disulfide (1.38 g, 1.32 mL, 14.5 mmol) was added dropwise and the mixture was stirred at −78° C. for 1 h. The reaction mixture was quenched by adding it cold into a stirred solution of water. 2M HCl was added until the mixture was acidic and the mixture was stirred for 15 min. The material was extracted with diethyl ether and the organic phase was concentrated in vacuo to give 1-bromo-2-chloro-3-methylsulfanyl-4-(trifluoromethoxy)benzene (2.09 g, 6.50 mmol, 90%) as a colourless oil. 1H NMR (Chloroform): 7.62 (d, 1H), 7.11 (d, 1H), 2.46 (s, 3H)

[0109] Step 2

[0110] To a vessel containing NMP (47 mL) was added palladium(II) acetate (0.082 g, 0.364 mmol), XantPhos (0.434 g, 0.728 mmol), N-formylsaccharin (1.73 g, 8.19 mmol) and 1-bromo-2-chloro-3-methylsulfanyl-4-(trifluoromethoxy)benzene (1.17 g, 3.64 mmol). To a second vessel was added triethylamine (1.66 g, 2.28 mL, 16.4 mmol), NMP (47 mL) and water (2.34 mL). The reaction was carried out in a Uniqsis FlowSyn. The two solutions were 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 cooled to room temperature and was diluted with ethyl acetate. The organic phase was washed with 2M HCl, then with water. The organic phase was concentrated in vacuo. The material was purified by flash chromatography (0 to 100% EtOAc in cyclohexane) to give 2-chloro-3-methylsulfanyl-4-(trifluoromethoxy)benzoic acid (0.691 g, 2.41 mmol, 66%) as a yellow solid. 1H NMR (Methanol): 7.82 (d, 1H), 7.44 (d, 1H), 2.46 (s, 3H)

[0111] Step 3

[0112] To a flask containing 2-chloro-3-methylsulfanyl-4-(trifluoromethoxy)benzoic acid (0.125 g, 0.436 mmol) was added 2,3,4,5,6-pentafluorophenol (88.2 mg, 0.480 mmol) and DCM (2.5 mL). 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (0.101 g, 0.501 mmol) was added and the reaction was stirred at room temperature for 1 h. The reaction mixture was diluted with DCM and washed with saturated aqueous NaHCO3. The organic phase was concentrated in vacuo to give (2,3,4,5,6-pentafluorophenyl) 2-chloro-3-methylsulfanyl-4-(trifluoromethoxy)benzoate (0.197 g, 0.436 mmol, 100%) as a pale yellow oil, which was used crude without further purification.

[0113] Step 4

[0114] To a flask containing the (2,3,4,5,6-pentafluorophenyl) 3-amino-2-chloro-4-(trifluoromethyl)benzoate (0.197 g, 0.436 mmol) was added DMF (2 mL). 1-Methyltetrazol-5-amine (47.5 mg, 0.480 mmol) was added, followed by 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (0.271 g, 0.286 mL, 0.959 mmol) and the reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with water, and acidified with 2M HCl. The material was then extracted with ethyl acetate. The organic phase was concentrated in vacuo. The material was purified by flash chromatography (0 to 100% EtOAc in cyclohexane) to give 2-chloro-3-methylsulfanyl-N-(1-methyltetrazol-5-yl)-4-(trifluoromethoxy)benzamide (76.6 mg, 0.208 mmol, 48%) as an off-white solid. 1H NMR (Methanol): 7.73 (d, 1H), 7.52 (d, 1H), 4.07 (s, 3H), 2.48 (s, 3H)

EXAMPLE 3. PREPARATION OF COMPOUND 2.001

[0115] The synthesis of the starting material phenol is described in the procedure above for Compound 1.001.

[0116] Step 1

[0117] To a flask containing 4-bromo-3-chloro-2-methylsulfanyl-phenol (2 g, 7.89 mmol) was added DMF (20 mL). K.sub.2CO.sub.3 (1.38 g, 9.47 mmol) was added, followed by sodium 2-chloro-2,2-difluoro-acetic acid (1.45 g, 9.47 mmol). The reaction mixture was stirred at 100° C. for 45 min, behind a blast shield. The mixture was cooled to room temperature. The reaction mixture was diluted with water and extracted with ethyl acetate. The organic phase was washed with water then concentrated in vacuo. The material was purified by flash chromatography (0 to 15% EtOAc in cyclohexane) to give a 1-bromo-2-chloro-4-(difluoromethoxy)-3-methylsulfanyl-benzene (1.46 g, 4.81 mmol, 61%) as a colourless oil. 1H NMR (Chloroform): 7.59 (d, 1H), 7.02 (d, 1H), 6.56 (t, 1H), 2.46 (s, 3H)

[0118] Step 2

[0119] To a vessel containing NMP (55 mL) was added palladium(II) acetate (0.101 g, 0.451 mmol), XantPhos (0.538 g, 0.903 mmol), N-formylsaccharine (2.15 g, 10.1 mmol) and 1-bromo-2-chloro-4-(difluoromethoxy)-3-methylsulfanyl-benzene (1.37 g, 4.51 mmol). To a second vessel was added triethylamine (2.06 g, 2.83 mL, 20.3 mmol), NMP (55 mL) and water (2.74 mL). The reaction was carried out in a Uniqsis FlowSyn. The two solutions were 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 min. The reaction mixture was cooled to room temperature and was diluted with ethyl acetate. The organic phase was washed with 2M HCl, then with water. The organic phase was concentrated in vacuo. The material was purified by flash chromatography (0 to 100% EtOAc in cyclohexane) to give 2-chloro-4-(difluoromethoxy)-3-methylsulfanyl-benzoic acid (0.953 g, 3.19 mmol, 70%) as a yellow solid. 1H NMR (Chloroform): 7.91 (d, 1H), 7.18 (d, 1H), 6.65 (t, 1H), 2.47 (s, 3H)

[0120] Step 3

[0121] To a flask containing 2-chloro-4-(difluoromethoxy)-3-methylsulfanyl-benzoic acid (0.65 g, 2.42 mmol) was added 2,3,4,5,6-pentafluorophenol (0.668 g, 3.63 mmol) and DCM (13 mL). 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (0.537 g, 2.66 mmol) was added and the reaction mixture was stirred at room temperature for 2 h. The reaction mixture was diluted with DCM and washed with saturated aqueous NaHCO.sub.3. The organic phase was concentrated in vacuo to give (2,3,4,5,6-pentafluorophenyl) 2-chloro-4-(difluoromethoxy)-3-methylsulfanyl-benzoate (1.3 g, 3.00 mmol, 1.sup.24%) as a green oil, which was used crude without further purification.

[0122] Step 4

[0123] To a flask containing (2,3,4,5,6-pentafluorophenyl) 3-[dicyclopropylmethylcarbamoyl(methoxy)amino]-2-methyl-4-methylsulfonyl-benzoate (0.526 g, 1.21 mmol) was added acetonitrile (10 mL). 5-Methyl-1,3,4-oxadiazol-2-amine (0.132 g, 1.33 mmol) was added, followed by 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (0.821 g, 0.866 mL, 2.90 mmol) and the reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with water and acidified with 2M HCl. The material was then extracted with ethyl acetate. The organic phase was concentrated in vacuo.

[0124] The material was purified by flash chromatography (0 to 75% EtOAc in cyclohexane) to give 2-chloro-4-(difluoromethoxy)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-methylsulfanyl-benzamide (0.150 g, 0.399 mmol, 33%) as an off-white solid. 1H NMR (Methanol): 7.67 (d, 1H), 7.19 (d, 1H), 6.64 (t, 1H), 2.54 (s, 3H), 2.46 (s, 3H)

EXAMPLE 4. PREPARATION OF COMPOUND 1.002

[0125] The starting material is the product of Step 3 from Example 3.

[0126] Step 1

[0127] To a flask containing (2,3,4,5,6-pentafluorophenyl) 2-chloro-4-(difluoromethoxy)-3-methylsulfanyl-benzoate (0.23 g, 0.53 mmol) was added acetonitrile (4.6 mL), 1-methyltetrazol-5-amine (0.115 g, 1.16 mmol) and 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (0.35 mL, 1.2 mmol). The reaction mixture was stirred at RT for 30 min, then was concentrated in vacuo (room temp bath). The residue was diluted with water and washed with ethyl acetate. The aqueous phase was then acidified with 2M HCl and extracted with ethyl acetate×2. The combined organic phases were dried (MgSO.sub.4) and concentrated under reduced pressure. Flash chromatography (0 to 40% ethyl acetate in cyclohexane) gave 2-chloro-4-(difluoromethoxy)-3-methylsulfanyl-N-(1-methyltetrazol-5-yl)benzamide (0.115 g, 0.329 mmol, 62%) as a white solid.

EXAMPLE 5. PREPARATION OF COMPOUND 1.003

[0128] The starting material is compound 1.002, prepared in Example 4.

[0129] To a flask containing 2-chloro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-methylsulfanyl-4-(trifluoromethoxy)benzamide (0.15 g, 0.4289 mmol) was added DCM (6 mL) and 3-chloroperoxybenzoic acid (0.24 g, 1.1 mmol). The reaction was stirred at RT for 16 h. A further aliquot of 3-chloroperoxybenzoic acid (0.10 g, 0.44 mmol) was added. After stirring for a further 2.5 h, the reaction mixture was quenched with addition of saturated aqueous sodium metabisulfite and the phases were separated. The aqueous phase was extracted with DCM and the combined organic layers were dried (MgSO.sub.4) and concentrated under reduced pressure. Flash chromatography (0 to 80% ethyl acetate in cyclohexane) gave 2-chloro-4-(difluoromethoxy)-3-methylsulfonyl-N-(1-methyltetrazol-5-yl)benzamide (0.100 g, 0.263 mmol, 61%) as a white solid.

EXAMPLE 6. PREPARATION OF COMPOUND 1.009

[0130] The starting material was prepared in Step 3 from Example 1.

[0131] Steps 1 and 2

[0132] To a solution of 4-bromo-3-chloro-2-methylsulfanyl-phenol (5.10 g, 20.1 mmol) in DMSO (50 mL) was added 1,2-dibromo-1,1,2,2-tetrafluoro-ethane (7.84 g, 30.2 mmol) and KOH (1.46 g, 26.1 mmol). The mixture was stirred at 70 C for 16 h. The reaction mixture was cooled to room temperature, then concentrated in vacuo. The crude material was diluted with water and extracted with ethyl acetate and the organic phase was concentrated in vacuo. The material was purified by flash chromatography (PE) to afford a mixture of 1-bromo-4-(2-bromo-1,1,2,2-tetrafluoro-ethoxy)-2-chloro-3-methylsulfanyl-benzene and 1-bromo-2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzene (total 6.3 g) as a colorless oil.

[0133] This mixture was used crude in the following step:

[0134] To a mixture of 1-bromo-4-(2-bromo-1,1,2,2-tetrafluoro-ethoxy)-2-chloro-3-methylsulfanyl-benzene and 1-bromo-2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzene (total 6.3 g) in AcOH (15 mL) was added Zn (3.81 g, 58.3 mmol). The mixture was stirred at 70° C. for 3 h. After cooling to room temperature, the crude material was diluted with water (80 ml) and extracted with ethyl acetate (50 ml) and the organic phase was washed with sodium bicarbonate solution (20 ml×3) and concentrated in vacuo to afford 1-bromo-2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzene (3.90 g, 11.0 mmol, 2 steps yield: 55%) as a colorless oil.

[0135] Step 3

[0136] To a solution of 1-bromo-2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzene (10.2 g, 28.8 mmol) in ethanol (60 mL) was added Pd(OAc).sub.2 (0.130 g, 0.577 mmol) and 1,1′-bis(diphenylphosphino)ferrocene (0.800 g, 1.44 mmol). The mixture was charged with CO (2.0 MPa) and stirred at 120° C. for 6 h. After cooling to room temperature, the crude material was concentrated in vacuo and purified by flash chromatography (petroleum ether:ethyl acetate 40:1 to 20:1) to afford ethyl 2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzoate (8.00 g, 23.1 mmol, 80%) as a yellow liquid.

[0137] Step 4

[0138] To a solution of ethyl 2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzoate (15.0 g, 43.3 mmol) in THE (30 mL) and water (30 ml) was added LiOH H.sub.2O (5.45 g, 130 mmol). The mixture was stirred at room temperature and stirred for 16 h. Dilute hydrochloric acid was added to adjust pH to 2. The mixture was extracted with ethyl acetate (50 ml) and the organic phase was concentrated in vacuo and purified by flash chromatography (pet. Ether:ethyl acetate 2:1 to 1:1) to afford 2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzoic acid (11.5 g, 36.1 mmol, 83%) as a white solid.

[0139] Step 5

[0140] To a stirred suspension of 2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzoic acid (2.00 g, 6.28 mmol) and 2,3,4,5,6-pentafluorophenol (1.27 g, 6.90 mmol) in dichloromethane (30 mL) at room temperature was added 3-(ethyliminomethyleneamino)-N,N-dimethyl-propan-1-amine hydrochloride (1.44 g, 7.51 mmol). The mixture was stirred at room temperature. After 5 minutes of adding EDC, the mixture was a homogeneous solution.

[0141] The reaction mixture was stirred overnight at room temperature. The reaction was quenched by addition of sat. aq. NaHCO.sub.3 (100 mL). The mixture was stirred at room temperature for a further 5 minutes. 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) to afford (2,3,4,5,6-pentafluorophenyl) 2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzoate (3.42 g, 7.06 mmol) as a pale yellow oil, which crystallised on standing.

[0142] Step 6

[0143] To a stirred solution of (2,3,4,5,6-pentafluorophenyl) 2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzoate (0.500 g, 1.03 mmol) in acetonitrile (10 mL) at room temperature was added 1-methyltetrazol-5-amine (0.225 g, 2.270 mmol) followed by 2-tert-butylimino-N,N-diethyl-1,3-dimethyl-1,3,2-diazaphosphinan-2-amine (0.64 g, 0.68 mL, 2.3 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 diluted with EtOAc (100 mL). The phases were separated. The aqueous phase was extracted with EtOAc (100 mL). The combined organic phases were washed with brine (100 mL), dried (MgSO4) and purified by reverse phase chromatography to give 2-chloro-3-methylsulfanyl-N-(1-methyltetrazol-5-yl)-4-(1,1,2,2-tetrafluoroethoxy)benzamide (295 mg, 0.701 mmol, 68%). 1H NMR (400 MHz, d4-methanol): 2.45 (s, 3H) 4.07 (s, 3H) 6.30-6.63 (m, 1H) 7.49-7.55 (m, 1H) 7.66-7.75 (m, 1H).

EXAMPLE 7: PREPARATION OF COMPOUND 1.010

[0144] The starting material is the same as produced in Step 4 of Example 6.

[0145] Step 1

[0146] To a flask containing 2-chloro-3-methylsulfanyl-4-(1,1,2,2-tetrafluoroethoxy)benzoic acid (3.00 g, 9.41 mmol) was added dichloromethane (90 mL) and 3-chloroperoxybenzoic acid (6.32 g, 28.2 mmol). The reaction was stirred for 16 h at RT. The reaction mixture was quenched with saturated aqueous sodium metabisulfite and the phases were separated. The aqueous layer was extracted with ethyl acetate. The combined organic phases were concentrated and purified by flash chromatography to give 2-chloro-3-methylsulfonyl-4-(1,1,2,2-tetrafluoroethoxy)benzoic acid (2.46 g, 75%) as a white solid.

[0147] Step 2

[0148] To a stirred suspension of 2-chloro-3-methylsulfonyl-4-(1,1,2,2-tetrafluoroethoxy)benzoic acid (2.5 g, 7.1 mmol) and 2,3,4,5,6-pentafluorophenol (1.4 g, 7.6 mmol) in dichloromethane (30 mL) at room temperature was added 3-(ethyliminomethyleneamino)-N,N-dimethyl-propan-1-amine hydrochloride (1.6 g, 8.3 mmol). Initially heterogeneous, however, within 5 minutes of adding EDC, the mixture was a homogeneous solution. The mixture was stirred at room temperature for 3 hours. The reaction was quenched by addition of sat. aq. NaHCO.sub.3 (100 mL). The mixture was stirred at room temperature for a further 5 minutes. The filtrate was adsorbed onto silica and the crude product was purified by flash column chromatography (0-10% gradient of EtOAc in cyclohexane) to give (2,3,4,5,6-pentafluorophenyl) 2-chloro-3-methylsulfonyl-4-(1,1,2,2-tetrafluoroethoxy) benzoate (3.42 g, 6.62 mmol, 93%) as a colourless oil.

[0149] Step 3

[0150] To a stirred solution of (2,3,4,5,6-pentafluorophenyl) 2-chloro-3-methylsulfonyl-4-(1,1,2,2-tetrafluoroethoxy)benzoate (A, 300 mg, 0.5806 mmol, 100 mass %) in acetonitrile (8 mL) at room temperature was added 1-methyltetrazol-5-amine (0.127 g, 1.28 mmol) followed by 2-tert-butylimino-N,N-diethyl-1,3-dimethyl-1,3,2-diazaphosphinan-2-amine (0.36 g, 0.38 mL, 1.3 mmol). The mixture was stirred at room temperature for 2 h. The reaction was quenched by addition of 2 M aq. HCl (10 mL). The mixture was stirred at room temperature for a further 5 minutes. The mixture was diluted with EtOAc (20 mL). The phases were separated. The aqueous phase was extracted with EtOAc (10 mL). The combined organic phases were adsorbed onto C18-silica and the crude product was purified by reverse phase chromatography. To give 2-chloro-3-methylsulfonyl-N-(1-methyltetrazol-5-yl)-4-(1,1,2,2-tetrafluoroethoxy)benzamide (170 mg, 0.374 mmol, 64%) as a white solid.

EXAMPLE 8: PREPARATION OF COMPOUND 1.007

[0151] The starting material is the product of Step 3 in Example 1.

[0152] Step 1

[0153] A solution of 4-bromo-3-chloro-2-methylsulfanyl-phenol (2.50 g, 9.86 mmol) in sodium hydroxide (5% solution in water) (8.87 mL) was added to a cooled (ice bath) solution of thiocarbonyl dichloride (9.86 mmol, 0.752 mL, 1.13 g) in chloroform (6 mL). The reaction mixture was scrubbed through bleach and stirred at 0° C. for 2.5 h. The phases were separated. The organic layer was washed (aq. 2M HCl then water), dried (MgSO4) and concentrated under vacuum to give O-(4-bromo-3-chloro-2-methylsulfanyl-phenyl) chloromethanethioate (3.07 g, 9.24 mmol, 94%) as a yellow liquid. 1H NMR (400 MHz, CDCl.sub.3) δ=7.69 (d, J=8.7 Hz, 1H), 6.98 (d, J=8.8 Hz, 1H), 2.44 (s, 3H).

[0154] Step 2

[0155] An oven dried flask was evacuated and purged with nitrogen (×3). A solution of O-(4-bromo-3-chloro-2-methylsulfanyl-phenyl) chloromethanethioate (3.00 g, 9.03 mmol) in THE (90 mL) was added followed by Copper(I) cyanide di(lithium chloride) complex solution (1M in THF, 9.94 mL, 9.94 mmol). It was cooled to −78° C. The methyl magnesium bromide (3M solution in THF) (9.94 mmol, 3.31 mL) was added slowly (the temperature was maintained below −70° C. during the addition). After the addition was complete it was stirred at −78° C. for 1 h. The reaction mixture was warmed to 0° C. and it was stirred at this temperature for 1 h. The reaction was quenched by the addition of sat. aq. NH.sub.4Cl. It was extracted with EtOAc (×3). The combined EtOAc extracts were dried (MgSO.sub.4) and concentrated under vacuum. The residue was purified by chromatography (0 to 10% EtOAc in cyclohexane) to give O-(4-bromo-3-chloro-2-methylsulfanyl-phenyl) ethanethioate (1.5 g, 4.8 mmol, 53%) as a yellow oil. 1H NMR (400 MHz, CDCl.sub.3) δ=7.65 (d, J=8.7 Hz, 1H), 6.86 (d, J=8.7 Hz, 1H), 2.38 (s, 3H)

[0156] Step 3

[0157] A solution of O-(4-bromo-3-chloro-2-methylsulfanyl-phenyl) ethanethioate (1.5 g, 4.8 mmol) in dichloromethane (19 mL) was stirred under nitrogen. This solution was treated with antimony(III) chloride (0.24 mmol, 0.055 g) then Deoxo-Fluor 50% solution in toluene (6.7 mmol, 3.4 mL). The reaction mixture was stirred at RT for 24 h under a blanket of nitrogen. The reaction mixture was quenched by the addition of aq. sat. NaHCO.sub.3. This was extracted with EtOAc (×3). The combined EtOAc extracts were dried (MgSO.sub.4) and concentrated under vacuum. The residue was purified by chromatography (0 to 10% EtOAc in cyclohexane) to give 1-bromo-2-chloro-4-(1,1-difluoroethoxy)-3-methylsulfanyl-benzene (0.867 g, 2.73 mmol, 57% yield). 1H NMR (400 MHz, CDCl3) δ=7.56 (d, J=8.9 Hz, 1H), 7.15 (td, J=1.3, 8.9 Hz, 1H), 2.42 (s, 3H), 2.00 (t, J=13.4 Hz, 3H).

[0158] Step 4

[0159] To a vessel containing NMP (20 mL) was added palladium(II) acetate (74 mg, 0.33 mmol), XantPhos (39 mg, 0.66 mmol), N-formylsaccharine (1.57 g, 7.44 mmol) and 1-bromo-2-chloro-4-(1,1-difluoroethoxy)-3-methylsulfanyl-benzene (1.05 g, 3.31 mmol). To a second vessel was added triethylamine (2.07 mL, 14.9 mmol), NMP (20 mL) and water (2.1 mL). The reaction was carried out in a Uniqsis FlowSyn. The two solutions were 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 min. The reaction mixture was cooled to room temperature and was diluted with ethyl acetate. The organic phase was washed with 2M HCl, then with water. The organic phase was concentrated in vacuo. The material was purified by reversed phase flash chromatography to give 2-chloro-4-(1,1-difluoroethoxy)-3-methylsulfanyl-benzoic acid (0.565 g, 2.00 mmol, 60%) as a yellow solid. 1H NMR (d4-methanol): 7.74 (d, 1H), 7.39 (m, 1H), 2.43 (s, 3H), 2.03 (m, 3H).

[0160] Step 5

[0161] To a flask containing 2-chloro-4-(1,1-difluoroethoxy)-3-methylsulfanyl-benzoic acid (0.565 g, 2.00 mmol) was added: dichloromethane (11 mL) and 2,3,4,5,6-pentafluorophenol (0.405 g, 2.20 mmol). 3-(ethyliminomethyleneamino)-N,N-dimethyl-propan-1-amine hydrochloride (0.464 g, 2.30 mmol) was added and the reaction was stirred for 1 h. The reaction mixture was quenched by addition of saturated aqueous saturated aqueous sodium bicarbonate and the phases were separated and extracted with ethyl acetate×2. The organic phase were combined dried (MgSO.sub.4) and concentrated in vacuo. The crude material was purified by flash chromatography (0 to 10% ethyl acetate in cyclohexane) to give (2,3,4,5,6-pentafluorophenyl) 2-chloro-4-(1,1-difluoroethoxy)-3-methylsulfanyl-benzoate (604 mg, 1.23 mmol, 63%) as a yellow solid. 1H NMR (CDCl.sub.3): 8.01 (d, 1H), 7.45 (m, 1H), 2.45 (s, 3H), 2.06 (m, 3H).

[0162] Step 6

[0163] To a flask containing (2,3,4,5,6-pentafluorophenyl) 2-chloro-4-(1,1-difluoroethoxy)-3-methylsulfanyl-benzoate (0.400 g, 0.892 mmol) was added DCM (4 mL) and 3-chlorobenzenecarboperoxoic acid (0.528 g, 2.14 mmol). After stirring for 5 h, a further portion of 3-chlorobenzenecarboperoxoic acid (0.220 g, 0.892 mmol) was added. After stirring for 24 h, the reaction mixture was quenched by the addition of saturated aqueous sodium metabisulfite. The phases were separated, and the aqueous layer was extracted with DCM. The combined organic layers were washed with saturated aqueous sodium carbonate×2, then dried (MgSO.sub.4) and concentrated in vacuo to give (2,3,4,5,6-pentafluorophenyl) 2-chloro-4-(1,1-difluoroethoxy)-3-methylsulfonyl-benzoate (0.411 g, 0.8550 mmol, 96%) as pale yellow crystals. .sup.1H NMR (CDCl.sub.3): 8.14 (d, 1H), 7.58 (m, 1H), 3.36 (s, 3H), 2.08 (m, 3H).

[0164] Step 7

[0165] To a flask containing (2,3,4,5,6-pentafluorophenyl) 2-chloro-4-(1,1-difluoroethoxy)-3-methylsulfanyl-benzoate (0.21 g, 0.4369 mmol) was added acetonitrile (4.2 mL), 1-methyltetrazol-5-amine (0.09524 g, 0.9611 mmol) and 2-tert-butylimino-N,N-diethyl-1,3-dimethyl-1,3,2-diazaphosphinan-2-amine (0.272 g, 0.287 mL, 0.961 mmol) were then added and stirred at RT for 1 h. The reaction mixture was concentrated in vacuo, then diluted with 2M aq HCl and extracted with ethyl acetate. The organic phase was dried (MgSO.sub.4).sub.4, concentrated and purified by reversed phase chromatography to give 2-chloro-3-methylsulfonyl-N-(1-methyltetrazol-5-yl)-4-(1,1,2,2-tetrafluoroethoxy)benzamide (170 mg, 0.374 mmol, 64%) as a white solid.

TABLE-US-00001 TABLE 1 Examples of herbicidal compounds of the present invention. COMPOUND STRUCTURE NMR 1.001 [00017] .sup.1H NMR (d-MeCN): 7.65 (d, 1H), 7.11 (d, 1H), 4.71 (q, 2H), 4.01 (s, 3H), 2.46 (s, 3H) 1.002 [00018] .sup.1H NMR (CDCl.sub.3): 10.19-11.00 (m, 1H), 7.69 (d, 1H), 7.25 (d, 1H), 6.67 (t, 1H), 4.12 (s, 3H), 2.49 (s, 3H) 1.003 [00019] .sup.1H NMR (d4-MeOD): 7.95 (d, 1H), 7.53 (d, 1H), 7.01 (t, 1H), 4.07 (s, 3H), 3.41 (s, 3H) 1.004 [00020] .sup.1H NMR (CDCl.sub.3): 7.87 (d, 1H), 7.53 (m, 1H), 4.15 (s, 3H), 3.40 (s, 3H) 1.005 [00021] .sup.1H NMR (d4-MeOD): 7.73 (d, 1H), 7.52 (m, 1H), 4.07 (s, 3H), 2.48 (s, 3H) 1.006 [00022] .sup.1H NMR (Acetonitrile): 7.86 (d, 1H), 7.30 (d, 1H), 4.78 (q, 2H), 4.02 (s, 3H), 3.36 (s, 3H) 1.007 [00023] .sup.1H NMR (d4- MeOD): 7.97 (d, 1H), 7.67 (d, 1H), 4.10 (s, 3H), 3.40 (s, 3H), 2.07 (m, 3H) 1.008 [00024] .sup.1H NMR (d4-MeOD) 7.67 (d, 1H), 7.49 (m, 1H), 4.09 (s, 3H), 2.46 (s, 3H), 2.06 (m, 3H) 1.009 [00025] .sup.1H NMR (d4-MeOD) δ ppm 2.45 (s, 3 H) 4.07 (s, 3 H) 6.30-6.63 (m, 1 H) 7.49-7.55 (m, 1 H) 7.66-7.75 (m, 1 H) 1.010 [00026] .sup.1H NMR (400 MHz, methanol) δ ppm 3.40 (s, 3 H) 4.08 (s, 3 H) 6.23-6.56 (m, 1 H) 7.65- 7.74 (m, 1H) 7.98-8.07 (m, 1 H) 1.011 [00027] 1.012 [00028] 1.013 [00029] .sup.1H NMR (d-MeCN): 7.90 (d, 1H), 7.55 (d, 1H), 4.01 (s, 3H), 3.30 (s, 3H), 2.81 (s, 3H) 1.014 [00030] .sup.1H NMR (d4-MeOD): 7.68 (d, 1H), 7.37 (d, 1H), 4.05 (s, 3H), 2.72 (s, 3H), 2.36 (s, 3H) 1.015 [00031] .sup.1HNMR (Acetonitrile): 7.81 (d, 1H), 7.22 (d, 1H), 4.69-4.82 (m, 2H), 4.00 (s, 3H), 3.08 (s, 3H) 1.016 [00032] .sup.1H NMR (Methanol): 7.90 (d, 1H), 7.49 (d, 1H), 7.23-6.87 (m, 1H), 4.05 (s, 3H), 3.18 (s, 3H) 1.017 [00033] .sup.1HNMR (d4-MeOD): 7.96 (d, 1H), 7.59-7.70 (m, 1H), 4.07 (s, 3H), 3.17 (s, 3H) 1.018 [00034] .sup.1H NMR (400 MHz, methanol) δ ppm 2.81 (s, 3 H) 4.04-4.08 (m, 3 H) 6.24-6.58 (m, 1 H) 7.57-7.62 (m, 1 H) 7.89-7.98 (m, 1 H) 1.019 [00035] .sup.1H NMR (400 MHz, methanol) δ ppm 1.58 (t, 3 H) 2.77-2.86 (m, 3 H) 4.40 (q, J = 7.30 Hz, 2 H) 6.25-6.58 (m, 1 H) 7.54-7.62 (m, 1 H) 7.88- 7.95 (m, 1 H) 1.020 [00036] .sup.1H NMR (DMSO-d6) 11.95 (brs, 1H) 8.07 (brd, 1H) 7.73 (brd, 1H) 4.01 (s, 3H) 3.37- 3.45 (m, 1H) 3.28-3.31 (m, 1H) 1.14-1.30 (m, 3H) 1.021 [00037] .sup.1H NMR (DMSO-d6) δ ppm 1.11-1.18 (m, 3 H), 2.97 (q, 2 H) 4.01 (s, 3 H) 7.66 (br d, J = 7.53 Hz, 1 H) 7.89 (br d, J = 8.78 Hz, 1 H) 11.88 (br s, 1 H). 1.022 [00038] .sup.1H NMR (DMSO-d6): 12.00 (br s, 1 H), 8.21 (d, 1 H), 7.82 (d, 1 H), 4.02 (s, 3 H), 3.65-3.55 (m, 2H), 1.23 (t, 3 H) 1.023 [00039] .sup.1H NMR (DMSO-d6): 11.76 (s, 1 H), 7.92 (d, 1 H), 7.54 (d, 1 H), 4.01 (s, 3 H), 3.42-3.30 (m, 1 H), 3.23-3.10 (m, 1 H), 2.69 (s, 3 H), 1.21 (t, 3 H) 1.024 [00040] .sup.1H NMR (DMSO-d6): 11.80 (br s, 1 H), 8.05 (d, 1 H), 7.66 (d, 1 H), 4.02 (s, 3 H), 3.51-3.42 (m, 2 H), 2.73 (s, 3 H), 2.21 (t, 3 H) 1.025 [00041] .sup.1H NMR (DMSO-d6): 11.96 (br s, 1 H), 8.12 (d, 1 H), 7.60-7.22 (m, 2 H), 4.02 (s, 3 H), 3.59- 3.49 (m, 2 H), 1.28-1.19 (m, 3 H) 1.026 [00042] .sup.1H NMR (DMSO-d6): 11.92 (br s, 1 H), 8.00 (d, 1 H), 7.60-7.15 (m, 2 H), 4.01 (s, 3 H), 3.50- 3.25 (m, 2 H), 1.19 (t, 3 H) 1.027 [00043] .sup.1H NMR (DMSO-d6): 11.83 (br s, 1 H), 7.81 (d, 1 H), 7.62-7.26 (m, 2 H), 4.01 (s, 3 H), 3.00- 2.90 (m, 2 H), 1.14 (t, 3H) 1.028 [00044] .sup.1H NMR (DMSO-d6): 11.58 (br s, 1 H), 7.70 (d, 1 H), 7.57-7.20 (m, 2 H), 3.99 (s, 3 H), 2.88- 2.80 (m, 2 H), 2.61 (s, 3 H), 1.12 (t, 3 H) 1.029 [00045] .sup.1H NMR (DMSO-d6): 11.69 (brs, 1H) 7.85 (brd, 1H) 7.54-7.17 (m, 2H) 4.00 (s, 3H) 3.19 (m, 1H) 3.17 (m, 1H) 2.68 (s, 3H) 1.20 (brt, 3H) 1.030 [00046] .sup.1H NMR (DMSO-d6): 11.67 (s, 1H), 7.77 (d, 1H), 7.49 (brd, 1H), 4.01 (s, 3H), 2.84 (q, 2H), 2.64 (s, 3H), 1.13 (t, 3H) 1.031 [00047] .sup.1H NMR (d6-DMSO): 11.76 (1H, s), 7.98 (1H, d), 7.44 (1H, d), 7.37 (1H, t), 4.01 (3H, s), 3.47 (2H, q), 2.70 (3H, s), 1.21 (3H, t). 1.032 [00048] .sup.1H NMR (Methanol): 7.61 (d, 1H), 7.15 (d, 1H), 6.14-6.46 (m, 1H), 4.41 (td, 2H), 4.05 (s, 3H), 2.43 (s, 3H) 1.033 [00049] .sup.1H NMR (Methanol): 7.86 (d, 1H), 7.41 (d, 1H), 6.16-6.53 (m, 1H), 4.54 (td, 2H), 4.06 (s, 3H), 3.39 (s, 3H) 1.034 [00050] .sup.1H NMR (Methanol): 7.85 (d, 1H), 7.36 (d, 1H), 6.18-6.52 (m, 1H), 4.46-4.57 (m, 3H), 4.04 (s, 3H), 3.18 (s, 3H) 1.035 [00051] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 1.19 (t, 3 H) 3.48 (q, 2 H) 4.00 (s, 3 H) 5.07 (q, 2 H) 7.50 (d, 1 H) 8.03 (d, 1 H) 11.85 (br s, 1 H) 1.036 [00052] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 1.14 (t, 3 H) 3.41 (q, 2H) 3.99 (s, 3 H) 5.07 (q, 2 H) 7.43 (d, 1 H) 7.93 (d, 1 H), 11.80 (br s, 1H) 1.037 [00053] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 1.10 (t, 3 H) 2.91 (q, 2 H) 3.99 (s, 3 H) 4.98 (q, 2 H) 7.30 (d, 1 H) 7.74 (d, 1 H) 11.70 (s, 1 H) 1.038 [00054] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 1.07 (t, 3 H) 2.58 (s, 3 H) 2.82 (q, 2 H) 3.97 (s, 3 H) 4.92 (q, 2 H) 7.15 (d, 1 H) 7.67 (d, 1 H) 11.47 (s, 1 H) 1.039 [00055] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 1.16 (t, 3 H) 2.68 (s, 3 H) 3.10-3.30 (m, 2 H) 3.98 (s, 3 H) 4.96 (q, 2 H) 7.25 (d, 1 H) 7.80 (d, 1 H) 11.59 (br s, 1 H) 1.040 [00056] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 1.17 (t, 3 H) 2.67 (s, 3 H) 3.41 (q, 2 H) 4.00 (s, 3 H) 5.03 (q, 2 H) 7.37 (d, 1 H) 7.91 (d, 1 H) 11.66 (br s, 1 H) 1.041 [00057] .sup.1H NMR (Methanol) δ: 1.58 (t, 3H), 3.41 (s, 3H), 4.43 (q, 2H), 7.01 (t, 1H), 7.53 (d, 1H), 7.94 (d, 1H) 1.042 [00058] .sup.1H NMR (Methanol): 7.94 (d, 1H), 7.54 (d, 1H), 6.80-7.22 (m, 1H), 4.37 (t, 2H), 3.41 (s, 3H), 1.92-2.07 (m, 2H), 0.98 (t, 3H) 1.043 [00059] .sup.1H NMR (Methanol): 7.96 (d, 1H), 7.54 (d, 1H), 6.77-7.28 (m, 1H), 4.81 (m, 1H), 3.41 (s, 3H), 1.62 (d, 6H) 1.044 [00060] .sup.1H NMR (Methanol): 7.93 (d, 1H), 7.54 (d, 1H), 6.80-7.24 (m, 1H), 4.41 (t, 2H), 3.41 (s, 3H), 1.89-2.02 (m, 2H), 1.28-1.50 (m, 2H), 0.98 (t, 3H) 1.045 [00061] .sup.1H NMR (Acetonitrile): 7.89 (d, 1H), 7.47 (d, 1H), 6.61-7.24 (m, 1H), 4.56 (t, 2H), 3.81 (t, 2H), 3.38 (s, 3H), 3.31 (s, 3H) 1.046 [00062] .sup.1H NMR (400 MHz, DMSO-d6): 11.73 (brs, 1H), 8.04 (d, 1H), 7.65 (d, 1H), 4.36 (q, 2H), 3.43- 3.50 (m, 2H), 2.73 (s, 3H), 1.48 (t, 3H), 1.21 (t, 3H) 1.047 [00063] .sup.1H NMR (DMSO-d6): 1.24 (t, 3 H), 1.48 (t, 3 H), 3.60 (q, 2 H), 4.38 (q, 2 H), 7.82 (d, 1 H), 8.21 (d, 1 H), 11.90 (brs, 1 H) 1.048 [00064] .sup.1H NMR (400 MHz, DMSO-d6): 1.21 (t, 3 H), 1.48 (t, 3 H), 2.70 (s, 3 H), 3.38-3.51 (m, 2 H), 4.35 (q, 2 H), 7.36 (t, 1 H), 7.43 (d, 1 H), 7.96 (d, 1 H), 11.50-11.78 (br s, 1 H) 1.049 [00065] .sup.1H NMR (400 MHz, DMSO-d6): 1.23 (t, 3 H), 1.48 (t, 3 H), 3.50-3.59 (m, 2 H), 4.38 (q, 2 H), 7.53-7.63 (m, 1 H), 7.88-7.94 (m, 1 H), 8.11 (br d, 1 H), 11.74-11.99 (br s, 1 H) 1.050 [00066] .sup.1H NMR (400 MHz, DMSO-d6): 0.99 (t, 3 H), 1.70 (m, 2 H), 3.49-3.56 (m, 2 H), 4.02 (s, 3 H), 7.40 (s, 1 H), 7.53-7.63 (m, 1 H), 8.11 (br d, 1 H), 11.94 (br s, 1 H) 1.051 [00067] .sup.1H NMR (400 MHz, DMSO-d6): 0.99 (t, 3 H), 1.48 (t, 3 H), 1.63-1.76 (m, 2 H), 3.49-3.56 (m, 2 H), 4.38 (q, 2 H),7.22 (s, 1 H), 7.53-7.63 (m, 1 H), 8.11 (br d, 1 H), 11.84 (br s, 1 H) 1.052 [00068] .sup.1H NMR (400 MHz, DMSO-d6): 0.99 (t, 3 H), 1.48 (t, 3 H), 1.63-1.76 (m, 2 H), 3.49-3.56 (m, 2 H), 4.38 (q, 2 H), 7.22 (s, 1 H), 7.53-7.63 (m, 1 H), 8.11 (br d, 1 H), 11.84 (br s, 1 H) 1.053 [00069] .sup.1H NMR (d6-DMSO): 8.08 (1H, d), 7.60-7.19 (2H, m), 4.36 (2H, q), 3.47 (2H, d), 2.16 (1H, m), 1.47 (3H, t), 1.03 (6H, d) 1.054 [00070] .sup.1H NMR (400 MHz, CDCl3): 1.39-1.44 (m, 6 H), 3.68-3.74 (m, 1 H), 4.14 (s, 3 H), 6.42-6.82 (m, 1 H), 7.42-7.50 (m, 1 H), 7.81-7.88 (m, 1 H) 1.055 [00071] .sup.1H NMR, (d4-methanol): 8.05 (br d, 1H), 7.71 (d, 1H), 4.44 (q, 2H), 3.78 (m, 1H), 1.59 (t, 3H), 1.36 (d, 6H) 1.056 [00072] .sup.1H NMR (d4-methanol): 8.07 (br d, 1H), 7.73 (br d, 1H), 4.10 (s, 3H), 3.80 (m, 1H), 1.38 (d, 6H) 1.057 [00073] .sup.1H NMR, (d4-methanol): 8.03 (d, 1H), 7.74- 7.66 (m, 1H), 4.43 (q, 2H), 3.43 (d, 2H), 2.39- 2.27 (m, 1H), 1.58 (t, 3H), 1.12 (d, 6H) 1.058 [00074] .sup.1H NMR, (d4-methanol): 8.04 (d, 1H), 7.74- 7.65 (m, 1H), 4.08 (s, 3H), 3.43 (d, 2H), 2.41- 2.25 (m, 1H), 1.12 (d, 6H) 1.059 [00075] .sup.1H NMR (d4-methanol): 8.04 (d, 1H), 7.72 (m, 1H), 4.10 (s, 3H), 3.24 (m, 1H), 1.42-1.35 (m, 2H), 1.23-1.15 (m, 2H) 1.060 [00076] .sup.1H NMR (400 MHz, CDCl3): 7.86 (d, 1H), 7.49 (br d, 1H), 4.49 (q, 2H), 3.46-3.38 (m, 2H), 1.98-1.79 (m, 2H), 1.61 (t, 3H), 1.09 (t, 3H) 1.061 [00077] .sup.1H NMR (d4-Methanol): 8.04 (d, 1H), 7.72 (m, 1H), 4.46 (m, 2H), 3.24 (m, 1H), 1.61 (m, 3H), 1.43-1.34 (m, 2H), 1.24-1.15 (m, 2H) 1.062 [00078] .sup.1H NMR (400 MHz, CDCl3): 7.90-7.86 (m, 1H), 7.54-7.49 (m, 1H), 4.13 (s, 3H), 3.44-3.38 (m, 2H), 1.95-1.85 (m, 2H), 1.10 (t, 3H) 1.063 [00079] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 1.17 (t, 3 H) 1.47 (t, 3 H) 2.67 (s, 3 H) 3.43 (q, 2 H) 4.34 (q, 2H) 5.03 (q, 2 H) 7.37 (d, 1 H) 7.90 (d, 1 H) 11.56 (br s, 1 H) 1.064 [00080] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 1.10 (t, 3 H) 1.47 (t, 3 H) 2.91 (q, 2 H) 4.35 (q, 2 H) 4.99 (q, 2 H) 7.29 (d, 1 H) 7.73 (d, 1 H) 11.60 (br s, 1 H) 1.065 [00081] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 1.19 (t, 3 H) 1.47 (t, 3 H) 3.48 (q, 2 H) 4.36 (q, 2 H) 5.08 (q, 2 H) 7.50 (d,l H) 8.03 (d, 1 H) 11.76 (br s, 1 H) 1.066 [00082] .sup.1H NMR (400 MHz, CDCl3): 11.06 (s, 1H), 7.70 (d, 1H), 7.29-7.25 (m, 1H), 6.68 (t, 1H), 4.14 (s, 3H), 2.94 (t, 2H), 1.64-1.53 (m, 2H), 1.03 (t, 3H) 1.067 [00083] .sup.1H NMR (d6-DMSO): 11.84 (1H, s), 8.11 (1H, d), 7.59-7.22 (2H, m), 4.38 (2H, q), 3.53 (2H, t), 1.70 (2H, m), 1.48 (3H, t), 0.99 (3H, t) 1.068 [00084] .sup.1H NMR (400 MHz, methanol) δ ppm 1.50- 1.70 (m, 3 H) 3.42 (s, 3 H) 4.39-4.51 (m, 2 H) 6.22-6.60 (m, 1 H) 7.66-7.75 (m, 1 H) 7.97- 8.06 (m, 1 H) 1.069 [00085] .sup.1H NMR (d4-Methanol): 8.01 (d, 1H), 7.69 (d, 1H), 4.17-4.08 (m, 5H), 3.43 (s, 3H) 1.070 [00086] .sup.1H NMR (d4- Methanol): 7.66 (d, 1H), 7.49 (m, 1H), 4.45 (q, 2H), 2.47 (s, 3H), 2.06 (t, 3H), 1.60 (t, 3H) 1.071 [00087] .sup.1H NMR (Methanol): 7.94 (d, 1H), 7.65 (d, 1H), 4.43 (m, 2H), 3.38 (s, 3H), 2.05 (m, 3H), 1.58 (m, 3H) 1.072 [00088] .sup.1H NMR (400 MHz, methanol) δ ppm 1.58 (t, 3 H) 2.39-2.49 (m, 3 H) 4.44 (q, 2 H) 6.30-6.64 (m, 1 H) 7.52 (d, 1 H) 7.65-7.74 (m, 1 H)

TABLE-US-00002 TABLE 2 Examples of herbicidal compounds of the present invention. COMPOUND STRUCTURE NMR 2.001 [00089] .sup.1H NMR (d4-MeOD): 7.67 (d, 1H), 7.19 (d, 1H), 6.64 (t, 1H), 2.54 (s, 3H), 2.46 (s, 3H) 2.002 [00090] .sup.1H NMR (d4-MeOD): 7.87 (d, 1H), 7.50 (d, 1H), 6.99 (t, 1H), 3.39 (s, 3H) 2.51 (s, 3H) 2.003 [00091] .sup.1H NMR (d4-MeOD): 7.54 (d, 1H), 7.15 (d, 1H), 4.73 (q, 2H), 2.51 (s, 3H), 2.42 (s, 3H) 2.004 [00092] .sup.1H NMR (d-MeCN): 7.77 (d, 1H), 7.24 (d, 1H), 4.73 (q, 2H), 3.31 (s, 3H), 2.45 (s, 3H) 2.005 [00093] .sup.1H NMR (d4-MeOD): 7.98 (d, 1H), 7.69 (m, 1H), 3.42 (s, 3H), 2.54 (s, 3H) 2.006 [00094] .sup.1H NMR(CDCl.sub.3): 7.66 (d, 1H), 7.31 (m, 1H), 2.52 (s, 3H), 2.46 (s, 3H) 2.007 [00095] .sup.1H NMR (d-MeCN): 7.82 (d, 1H), 7.51 (d, 1H), 3.29 (s, 3H), 2.77 (s, 3H), 2.48 (s, 3H) 2.008 [00096] .sup.1H NMR (d4-MeOD): 7.57 (d, 1H), 7.34 (d, 1H), 2.67 (s, 3H), 2.51 (s, 3H), 2.35 (s, 3H) 2.009 [00097] .sup.1H NMR (DMSO-d6) δ ppm 12.38-12.55 (m, 1 H) 8.10 (br d, 1 H) 7.78 (br d, 1 H) 4.03 (q, 1 H) 3.58 (q, 2 H) 3.40-3.48 (m, 1 H) 3.30 (br s, 1 H) 2.57-2.60 (m, 1 H) 2.48-2.50 (m, 3 H) 2.42 (br s, 1 H) 1.99 (s, 1 H) 1.89 (s, 1 H) 1.34 (s, 1 H) 1.14-1.28 (m, 1H) 2.010 [00098] .sup.1H NMR (DMSO-d6): 12.35 (br s, 1 H), 7.76 (d, 1 H), 7.65-7.55 (m, 1 H), 3.00-2.90 (m, 2 H), 2.48 (s, 3H), 1.14 (t, 3H) 2.011 [00099] .sup.1H NMR (d4-methanol): 7.89 (1H, d), 7.57 (1H, d), 3.50-3.26 (5H, m), 2.79 (3H, s), 2.54 (3H, s), 1.32 (3H, t). 2.012 [00100] .sup.1H NMR (DMSO-d6): 12.23 (br s, 1 H), 7.69 (d, 1 H), 7.42-7.24 (m, 2 H), 2.98-2.89 (m, 2 H), 2.48 (s, 3H), 1.13 (t, 3H) 2.013 [00101] .sup.1H NMR (DMSO-d6): 12.39 (br s, 1 H), 8.00 (d, 1 H), 7.59-7.17 (m, 2 H), 3.57-3.49 (m, 2 H), 2.48 (s, 3H), 1.22 (t, 3H) 2.014 [00102] .sup.1H NMR (DMSO-d6): 12.19 (br s, 1 H), 7.85 (d, 1 H), 7.52-7.16 (m, 2 H), 3.50-3.41 (m, 2 H), 2.64 (s, 3 H), 2.49 (s, 3 H), 1.20 (t, 3 H) 2.015 [00103] .sup.1H NMR (Methanol): 7.83 (d, 1H), 7.47 (d, 1H), 6.84-7.26 (m, 1H), 3.17 (s, 3H), 2.51 (s, 3H) 2.016 [00104] .sup.1H NMR (Methanol): 7.52 (d, 1H), 7.12 (d, 1H), 6.12-6.47 (m, 1H), 4.40 (td, 2H), 2.50 (s, 3H), 2.41(s, 3H) 2.017 [00105] .sup.1H NMR (Methanol): 7.78 (d, 1H), 7.37 (d, 1H), 6.15-6.53 (m, 1H), 4.52 (td, 2H), 3.38 (s, 3H), 2.50 (s, 3H) 2.018 [00106] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 1.16 (t, 3 H) 2.47 (s, 3 H) 2.62 (s, 3 H) 3.41 (q, 2 H) 5.00 (q, 2 H) 7.32 (d, 1 H) 7.78 (d, 1 H) 11.97 (br s, 1 H) 2.019 [00107] .sup.1H NMR (d6-DMSO): 7.76 (1H, d), 7.58 (1H, d), 6.94 (1H, tt), 2.43 (3H, s), 2.21 (3H, s).

BIOLOGICAL EXAMPLES

[0166] 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 125 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 Pre-Emergence Application Compound IPOHE ECHCG SETFA ABUTH AMARE 1.003 1 5 5 5 5 1.004* 1 5 5 5 5 1.005* 1 1 1 2 4 1.009 3 5 5 4 5 1.013 5 5 5 5 5 1.014 3 5 5 5 5 1.020 5 5 5 5 5 1.021 3 5 5 4 5 1.022 5 5 5 5 5 1.023 5 5 5 5 5 1.024 5 5 5 5 5 1.025 4 5 5 5 5 1.026 5 5 5 5 5 1.027 3 5 5 5 5 1.028 3 5 5 5 5 1.029 4 5 5 5 5 1.030 3 5 5 5 5 1.031 5 5 5 5 5 1.034 2 4 4 3 4 1.035 5 5 5 5 5 1.036 4 5 5 5 5 1.037 1 4 3 3 5 1.038 2 2 2 4 5 1.039 4 4 4 5 5 1.040 5 5 5 5 5 1.046 5 5 5 5 5 1.047 5 5 5 5 5 1.048 5 5 5 5 5 1.049 5 5 5 5 5 1.050 3 5 5 5 5 1.051 4 5 5 5 5 1.052 5 5 5 5 5 1.053 4 5 5 5 5 1.054 4 5 5 5 5 1.063 4 5 5 5 5 1.064 1 5 2 4 5 1.065 3 5 5 5 5 1.066 3 5 5 5 5 1.067 2 5 4 4 5 2.005* 1 5 5 5 5 2.006* 1 1 1 2 5 2.009 2 5 5 5 5 2.010 1 5 5 4 5 2.011 5 5 5 5 5 2.012 3 5 5 4 5 2.013 4 5 5 5 5 2.014 5 5 5 5 5 2.018 4 5 5 5 5

TABLE-US-00004 TABLE B2 Post-Emergence Application Compound IPOHE ECHCG SETFA ABUTH AMARE 1.003 5 5 5 5 5 1.004* 5 5 5 5 5 1.005* 5 5 5 5 5 1.009 4 4 4 4 4 1.013 5 5 5 5 5 1.014 5 5 5 5 5 1.020 5 5 5 5 5 1.021 5 5 5 5 4 1.022 5 5 5 5 4 1.023 5 5 5 5 5 1.024 5 5 5 5 5 1.025 5 5 5 5 5 1.026 5 5 5 5 5 1.027 4 5 5 5 5 1.028 5 5 5 5 5 1.029 5 5 5 5 5 1.030 5 5 5 5 5 1.031 5 5 5 5 5 1.034 3 5 4 4 4 1.035 5 5 5 5 5 1.036 5 5 5 5 5 1.037 3 5 5 5 5 1.038 4 5 5 5 5 1.039 4 5 5 5 5 1.040 5 5 5 5 5 1.046 5 5 5 5 5 1.047 5 5 5 5 5 1.048 5 5 5 5 5 1.049 4 5 5 5 5 1.050 4 5 5 5 5 1.051 4 5 5 5 5 1.052 5 4 4 5 4 1.053 5 5 5 5 5 1.054 4 4 4 4 4 1.063 3 5 5 5 5 1.064 4 5 5 5 5 1.065 4 5 5 5 5 1.066 5 4 4 5 5 1.067 4 4 4 5 5 2.005* 5 5 5 5 5 2.006* 5 5 5 5 5 2.009 4 5 5 4 5 2.010 4 5 5 5 5 2.011 4 5 5 5 5 2.012 4 5 5 5 5 2.013 4 5 5 5 5 2.014 4 5 5 5 5 2.018 5 5 5 5 5 *Applied at 250 g/ha

[0167] A comparative experiment is conducted to show the advantage provided by the compounds of the present invention. Thus the biological performance of representative compounds 1.004 and with Compound 4-460 of the type referred to in WO2012/028579. Results are given as (%) phytotoxicity observed. The result demonstrates that compounds of the present invention exhibit much improved crop (ZEAMX/maize) selectivity—that is they provide improved control of problematic weed species, whilst exhibiting little if any crop damage at like-for-like application rates.

TABLE-US-00005 TABLE B3 Comparative Experiment Rate POST Application Compound g/ha ZEAMX IPOHE ECHCG SETFA ABUTH DIGSA AMARE 1.003   [00108] 30 15  0  0 100 100  90  90  90  80 100  90  80  80 100 100 1.004   [00109] 30 15 30  0 100  90 100  90 100 100 100  90 100  80 100 100 Compound 4-640 30 70  90  90  90  90  80  90 WO2012/028579   [00110] 15 40  90  80  90  90  80  90