HERBICIDAL QUINOLINES

Abstract

The present invention relates to compounds of formula (I), or an agronomically acceptable salt of said compounds wherein A.sup.1a, A.sup.1b, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are as defined herein. The invention further relates to herbicidal compositions which comprise a compound of Formula (I), and to their use for controlling weeds, in particular in crops of useful plants.

##STR00001##

Claims

1. A compound of Formula (I): ##STR00035## or an agronomically acceptable salt thereof, wherein:— A.sup.1a and A.sup.1b are independently selected from CH and N, wherein A.sup.1a and A.sup.1b are not both CH; R.sup.1 is selected from the group consisting of C.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.3-alkyl-, C.sub.1-C.sub.6-haloalkoxy-C.sub.1-C.sub.3-alkyl-, C.sub.1-C.sub.6-haloalkyl-, C.sub.2-C.sub.6-alkenyl-, C.sub.2-C.sub.6-haloalkenyl-, C.sub.2-C.sub.6-alkynyl-, C.sub.2-C.sub.6-haloalkynyl-, heteroaryl-, (C.sub.3-C.sub.7)-cycloalkyl-, heterocyclyl- and phenyl-, wherein the heteroaryl-, (C.sub.3-C.sub.7)-cycloalkyl-, heterocyclyl- and phenyl- are optionally substituted by one or more substituents selected from the group consisting of halogen, nitro, cyano, C.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6-haloalkyl-, C.sub.3-C.sub.6-cycloalkyl-, C.sub.1-C.sub.6alkyl-S(O)p-, C.sub.1-C.sub.3-alkoxy- and C.sub.1-C.sub.6alkoxy-C.sub.1-C.sub.4alkyl-; R.sup.2 is selected form the group consisting of C.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.6alkoxy-, C.sub.1-C.sub.6 haloalkyl-, C.sub.1-C.sub.6haloalkoxy-, C.sub.1-C.sub.6alkoxy-C.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.3 alkoxy-C.sub.2-C.sub.3 alkoxy-C.sub.1-C.sub.3 alkyl-, C.sub.1-C.sub.3 alkoxy-C.sub.1-3-haloalkyl-, C.sub.1-C.sub.3-alkoxy-C.sub.1-C.sub.3-alkoxy-C.sub.1-C.sub.3-haloalkyl-, halogen, cyano, nitro, C.sub.1-C.sub.6alkyl-S(O)p-, C.sub.1-C.sub.6haloalkyl-S(O).sub.p—, C.sub.4-C.sub.6-oxasubstituted-cycloalkoxy-C.sub.1-C.sub.3-alkyl-, C.sub.4-C.sub.6-oxasubstituted-cycloalkoxy-C.sub.1-C.sub.3-haloalkyl-, (C.sub.1-C.sub.3-alkanesulfonyl-C.sub.1-C.sub.3 alkylamino)-C.sub.1-C.sub.3 alkyl- and (C.sub.1-C.sub.3 alkanesulfonyl-C.sub.3-C.sub.4cycloalkylamino)-C.sub.1-C.sub.3 alkyl-; R.sup.3 is aryl or a 5 or 6-membered heteroaryl, the heteroaryl containing one to three heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulphur, and wherein the aryl or heteroaryl component may be optionally substituted by one or more substituents selected from the group consisting of halogen, C.sub.1-C.sub.6alkyl-, C.sub.2-C.sub.6alkenyl-, C.sub.2-C.sub.6alkynyl-, C.sub.1-C.sub.6haloalkyl-, C.sub.1-C.sub.6alkoxy-, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.3 alkyl-, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.3 alkoxy-, C.sub.1-C.sub.6haloalkoxy-, C.sub.1-C.sub.6alkyl-S(O)p-, —NR.sup.7aR.sup.7b, cyano and nitro; R.sup.4 is selected from the group consisting of hydrogen, halogen, hydroxyl, sulfhydryl, C.sub.1-C.sub.6alkyl-, C.sub.3-C.sub.6cycloalkyl-, C.sub.1-C.sub.6haloalkyl-, C.sub.2-C.sub.6haloalkenyl-, C.sub.2-C.sub.6alkenyl, C.sub.3-C.sub.6alkynyl, C.sub.1-C.sub.6alkoxy, C.sub.4-C.sub.7cycloalkoxy-, C.sub.1-C.sub.6haloalkoxy-, C.sub.1-C.sub.6alkyl-S(O)p-, C.sub.1-C.sub.6alkoxy-C.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.6alkoxy-C.sub.2-C.sub.6alkoxy- and C.sub.1-C.sub.6alkoxy-C.sub.2-C.sub.6alkoxy-C.sub.1-C.sub.6-alkyl-; R.sup.5 is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.6alkyl- and C.sub.1-C.sub.6haloalkyl-; R.sup.6 is selected from the group consisting of hydrogen, methyl and halogen; R.sup.7a and R.sup.7b are independently selected from the group consisting of hydrogen and C.sub.1-C.sub.6alkyl or together form a C.sub.4-C.sub.5 alkylene chain; n=0 or 1; and p=0, 1 or 2.

2. The compound according to claim 1, wherein A.sup.1a and A.sup.1b are N.

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

4. The compound of claim 1, wherein R.sup.2 is selected form the group consisting of C.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.6alkoxy-, C.sub.1-C.sub.6 haloalkyl-, halogen and C.sub.1-C.sub.6alkyl-S(O)p-.

5. The compound of claim 1, wherein R.sup.3 is an aryl or heteroaryl selected from the group consisting of phenyl, furanyl, thiophenyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyrazolyl, isothiazolyl, pyridyl, pyridazinyl, pyrazinyl, pyrimidinyl and triazolyl.

6. The compound according to claim 5, wherein R.sup.3 is phenyl.

7. The compound of claim 1, wherein R.sup.4 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl- and C.sub.1-C.sub.6haloalkyl-.

8. The compound of claim 1, wherein R.sup.5 is hydrogen or halogen.

9. A herbicidal composition comprising a compound according to claim 1 and an agriculturally acceptable formulation adjuvant.

10. The herbicidal composition according to claim 9, further comprising at least one additional pesticide.

11. The herbicidal composition according to claim 10, wherein the additional pesticide is a herbicide.

12. The method of controlling weeds at a locus comprising application to the locus of a weed controlling amount of a composition according to claim 9.

13. (canceled)

Description

EXAMPLE P1: PREPARATION OF N-(1-METHYLTETRAZOL-5-YL)-8-PHENYL-7-(TRIFLUOROMETHYL)QUINOLINE-6-CARBOXAMIDE (COMPOUND 1.001)

Step 1: Preparation of ethyl 2-benzylpyridine-3-carboxylate

[0095] An oven dried 3-neck round bottom flask was charged with bis(triphenylphosphine)palladium(II) dichloride (0.80 g, 1.15 mmol) under nitrogen, followed by neat ethyl 2-chloropyridine-3-carboxylate (4.30 g, 23 mmol) and then a solution of benzyl(bromo)zinc in THF (50 mL, 25 mmol, 0.50 M). The mixture was stirred overnight at room temperature, when LCMS showed formation of the desired product. The mixture was dry loaded onto celite and purified by flash chromatography (silica) eluting with ethyl acetate in iso-hexane, to give ethyl 2-benzylpyridine-3-carboxylate (4.42 g, 80% Yield) as a pale-yellow oil.

[0096] 1H NMR (400 MHz, CDCl3) δ ppm 8.69 (dd, 1H), 8.16 (dd, 1H) 7.18-7.30 (m, 6H), 4.59 (s, 2H), 4.33 (q, 2H), 1.32 (t, 3H).

Step 2: Preparation (2-benzyl-3-pyridyl)methanol

[0097] A solution of ethyl 2-benzylpyridine-3-carboxylate (3.6 g, 15 mmol) in dry THF (70 mL) was cooled in an ice/water bath and treated with a solution of lithium aluminium hydride in THF (11 mL, 22 mmol, 2.0 M). Ten minutes after the addition, the cooling bath was removed and the mixture was stirred at room temperature for 2 hours, when LC showed formation of the desired product. The solution was re-cooled to 0° C. and quenched in succession by the slow addition of water (0.85 ml), 2M NaOH (0.85 ml), and more water (2.5 ml). The mixture was stirred for 15 min, then diethyl ether was added and the mixture was stirred for an additional 15 min. Magnesium sulphate was then added, and after 15 min the mixture was filtered, and the salts were washed with additional diethyl ether. The filtrate was evaporated to dryness—under reduced pressure to give (2-benzyl-3-pyridyl)methanol (2.81 g, 95% Yield) as an off-white solid.

[0098] 1H NMR (400 MHz, CDCl.sub.3) δ ppm 8.52 (dd, 1H), 7.74 (dd, 1H) 7.18-7.30 (m, 6H), 4.67 (d, 2H), 4.24 (s, 2H)

Step 3: Preparation of 2-benzylpyridine-3-carbaldehyde

[0099] A stirred mixture of (2-benzyl-3-pyridyl)methanol (2.81 g, 14.1 mmol) and manganese(IV)oxide (12.3 g, 141 mmol) in dichloromethane (28 mL) was heated under reflux for 3 hours, after which additional manganese(IV)oxide (2 g) was added and the mixture was heated for further hour. The reaction was cooled to room temperature, filtered through celite and washed with additional dichloromethane. The filtrate was evaporated under reduced pressure to leave 2-benzylpyridine-3-carbaldehyde (2.39 g, 86% Yield) as an orange oil.

[0100] 1H (400 MHz, CDCl.sub.3) δ ppm 10.34 (s, 1H), 8.77 (dd, 1H), 8.14 (dd, 1H) 7.37 (m, 1H), 7.28-7.19 (m, 5H), 4.61 (s, 2H)

Step 4: Preparation of ethyl 8-phenyl-7-(trifluoromethyl)quinoline-6-carboxylate

[0101] To a solution of 2-benzylpyridine-3-carbaldehyde (3.0 g, 15.2 mmol) in toluene (30 mL) was successively added ethyl trifluoroacetoacetate (4.45 mL, 30.4 mmol), pyridinium para-toluenesulfonic acid (PPTSA: 382 mg, 1.51 mmol) and the reaction mass was heated under reflux using a Dean-Stark apparatus for 48 h. The cooled reaction mixture was poured into saturated aqueous sodium bicarbonate solution (20 mL) and was extracted with ethyl acetate (20 mL×2). The combined organic layers were then washed with brine (20 mL), dried over sodium sulphate and evaporated to dryness under reduced pressure. The residue was purified by flash chromatography (silica), eluting with 0-30% ethyl acetate in isohexane, to give ethyl 8-phenyl-7-(trifluoromethyl)quinoline-6-carboxylate (3.71 g, 71% Yield) as a pale orange solid.

[0102] 1H NMR (400 MHz, CDCl.sub.3) δ ppm, 9.00 (dd, 1H), 8.25 (dd, 1H), 8.14 (s, 1H), 7.46-7.55 (m, 4H), 7.34-7.40 (m, 2H), 4.46 (q, 2H), 1.43 (t, 3H)

Step 5: Preparation of 8-phenyl-7-(trifluoromethyl)quinoline-6-carboxylic acid

[0103] Sodium hydroxide (3.5 g, 88 mmol) was added in one portion to a stirred suspension of ethyl 8-phenyl-7-(trifluoromethyl)quinoline-6-carboxylate (3.71 g, 10.8 mmol) in ethanol (90 mL) and water (30 mL). The reaction mixture was heated under reflux for 5 hours, then cooled to room temperature and left to stand overnight. The reaction was acidified (conc HCl) to pH 3, and the resultant precipitate was washed with water, then air dried to give 8-phenyl-7-(trifluoromethyl)quinoline-6-carboxylic acid (3.18 g, 93% Yield) as an orange solid.

[0104] 1H NMR (400 MHz, DMSO-d6) δ ppm 13.73 (br. s., 1H), 8.97 (dd, 1H), 8.61 (dd, 1H), 8.43 (s, 1H), 7.74 (dd, 1H), 7.42-7.49 (m, 3H), 7.27-7.33 (m, 2H)

Step 6: Preparation of N-(1-methyltetrazol-5-yl)-8-phenyl-7-(trifluoromethyl)-quinoline-6-carboxamide

[0105] Oxalyl chloride (0.80 g, 6.3 mmol) was added to a stirred solution of 8-phenyl-7-(trifluoromethyl)quinoline-6-carboxylic acid (500 mg, 1.58 mmol) and DMAP (ca. 5 mg) in dichloromethane (25 mL) at 0° C. The reaction was warmed to room temperature and stirred for 2 hours, then left to stand over the weekend. The mixture was heated to reflux for 2 hours, and was then concentrated in vacuo under reduced pressure. The residue was dissolved in dichloromethane (50 mL) and 1-methyltetrazol-5-amine (156 mg, 1.58 mmol) was added in one portion. The reaction was stirred for 10 minutes at room temperature then triethylamine (0.64 g, 6.30 mmol) was added. After 2 hours the mixture was transferred to a microwave vial and heated at 100° C. for 2 hours. The reaction mixture was diluted with dichloromethane, sequentially washed with water then brine. The organics was passed through a phase separating cartridge and concentrated under reduced pressure. The residue was purified by flash chromatography (12 g silica), eluting with 0-5% methanol in dichloromethane, to give N-(1-methyltetrazol-5-yl)-8-phenyl-7-(trifluoromethyl)quino line-6-carboxamide (191 mg, 30%).

[0106] 1H NMR (400 MHz, CDCl.sub.3) δ ppm 11.74 (br s, 1H), 9.05 (dd, 1H), 8.32-8.28 (m, 2H) 7.60-7.73 (m, 6H), 4.14 (s, 3H)

EXAMPLE P2. PREPARATION OF 7-METHOXY-N-(1-METHYLTETRAZOL-5-YL)-8-PHENYL-QUINOLINE-6-CARBOXAMIDE (COMPOUND 1.009)

Step 1: Preparation of dimethyl 2-[(2-benzyl-3-pyridyl)methylene]propanedioate

[0107] A solution of dimethyl malonate (1.22 g, 9.20 mmol), 2-benzylpyridine-3-carbaldehyde (1.65 g, 8.37 mmol) and piperidine (0.1 mL) in methanol (20 mL) was stirred at room temperature overnight, and then heated under reflux for 8 hours. The cooled mixture was concentrated under reduced pressure, and the residue was dry-loaded onto celite and purified by flash chromatography (silica), eluting with ethyl acetate in iso-hexane, to give dimethyl 2-[(2-benzyl-3-pyridyl)methylene]-propanedioate (2.25 g, 86.4% Yield) as a colourless oil.

[0108] 1H NMR (400 MHz, CDCl3) δ ppm 8.53 (dd, 1H), 7.95 (s, 1H) 7.61 (dd, 1H), 7.29-7.15 (m, 6H), 4.24 (s, 2H), 3.85 (s, 3H), 3.67 (s, 3H).

Step 2: Preparation of methyl 7-hydroxy-8-phenyl-quinoline-6-carboxylate

[0109] A oven dried microwave vial was charged with a solution of potassium tert-pentoxide in toluene (0.91 mL, 1.6 mmol, 1.7M), and then a solution of dimethyl 2-[(2-benzyl-3-pyridyl)methylene]propanedioate (0.44 g, 0.14 mmol) in dry tetrahydrofuran (5 mL) under nitrogen. The mixture was heated in a microwave oven at 100° C. for 30 min, then carefully acidified with 2M HCl, and concentrated to dryness under reduced pressure. The residue was dry loaded onto C18 silica and purified by reverse phase HPLC, eluting with 100% water to 100% acetonitrile, to give methyl 7-hydroxy-8-phenyl-quinoline-6-carboxylate (0.126 g, 32% Yield) as an off-white solid.

[0110] 1H NMR (400 MHz, CDCl.sub.3) δ ppm 10.91 (s, 1H) 8.91 (dd, 1H), 8.54 (s, 1H), 8.15 (dd, 1H) 7.55-7.41 (m, 5H), 7.27, (m, 1H), 4.07 (s, 3H)

Step 3: Preparation of methyl 7-methoxy-8-phenyl-quinoline-6-carboxylate

[0111] A solution of diazomethyl(trimethyl)silane in diethyl ether (0.67 mL, 1.35 mmol, 2.0 M) was added dropwise to a stirred suspension of methyl 7-hydroxy-8-phenyl-quinoline-6-carboxylate (188 mg, 0.67 mmol) in methanol (2 mL) at room temperature. The mixture was stirred overnight, when analysis showed that the reaction had not gone to completion. Toluene (ca. 5 mL) was added, followed by an additional solution of diazomethyl(trimethyl)silane in diethyl ether (0.67 mL, 1.35 mmol, 2.0 M). The solution was stirred overnight, quenched with acetic acid and concentrated under reduced pressure to leave methyl 7-methoxy-8-phenyl-quinoline-6-carboxylate (222 mg, 112% Yield) as a red solid.

[0112] 1H NMR (400 MHz, CDCl.sub.3) δ ppm 8.94 (dd, 1H), 8.32 (s, 1H), 8.20 (dd, 1H), 7.46-7.36 (m, 6H), 4.00 (s, 3H), 3.51 (s, 3H)

Step 4: Preparation of 7-methoxy-8-phenyl-quinoline-6-carboxylic acid

[0113] A solution of lithium hydroxide (34 mg, 1.43 mmol) in water (5 mL) was added to a solution of ethyl 7-methoxy-8-phenyl-quinoline-6-carboxylate (220 mg, 0.7159 mmol) in ethanol (5 mL), and the mixture was stirred at room temperature for 30 min. The ethanol was then removed in vacuo, ethyl acetate was added, and the mixture was acidified to pH7 and extracted 6 times with ethyl acetate. The aqueous layer was then lyophilised and triturated with hot ethyl acetate. The combined ethyl acetate layers were dried over magnesium sulfate, filtered and evaporated to dryness under reduced pressure to give 7-methoxy-8-phenyl-quinoline-6-carboxylic acid (167 mg, 84% Yield).

[0114] 1H NMR (400 Mz CD3OD) δ ppm 8.69 (m, 1H), 8.35 (m, 2H), 7.49-7.33 (m, 6H), 3.41 (s, 3H)

Step 5: Preparation of 7-methoxy-N-(1-methyltetrazol-5-yl)-8-phenyl-quinoline-6-carboxamide

[0115] To a suspension of 7-methoxy-8-phenyl-quinoline-6-carboxylic acid (167 mg, 0.60 mmol) in dichloromethane (5 mL), was added DMF (1 drop) and oxalyl chloride (0.21 mL, 2.4 mmol). The reaction was stirred for 5 minutes, when analysis showed complete consumption of the starting acid. The reaction mixture was concentrated to dryness under reduced pressure, and the residue was dissolved in dichloromethane (4 mL). 5-Amino-1-methyl-1H-tetrazole (129 mg, 1.290 mmol) and triethylamine (0.26 g, 2.58 mmol) were then added in one portion. The resultant mixture was heated in a microwave oven at 100° C. for 2 hours. The crude reaction mixture was then dry-loaded onto silica and purified by flash chromatography, eluting with methanol in dichloromethane (0-10%), to give 7-methoxy-N-(1-methyltetrazol-5-yl)-8-phenyl-quinoline-6-carboxamide (9 mg) as a pale brown solid.

[0116] 1H NMR (400 MHz, CDCl3) δ ppm 10.75 (br. S, 1H), 9.00 (dd, 1H), 8.80 (s, 1H), 8.32 (dd, 1H), 7.57-7.46 (m, 6H), 4.14 (s, 3H), 3.59 (s, 3H).

EXAMPLE P3. PREPARATION OF 3-FLUORO-N-(1-METHYLTETRAZOL-5-YL)-8-PHENYL-7-(TRIFLUOROMETHYL)QUINOLINE-6-CARBOXAMIDE (COMPOUND 1.007)

Step 1: Preparation of 2-benzyl-5-fluoro-pyridine-3-carbaldehyde

[0117] A 20 ml microwave vial was charged with 2-chloro-5-fluoro-pyridine-3-carbaldehyde (1.00 g, 6.27 mmol), 2-benzyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.1 equivalents, 6.89 mmol), [1,1′-Bis(diphenylphosphino)ferrocene]palladium(II) dichloride (PdCl.sub.2(dppf); 0.1 equivalents, 0.63 mmol) and powdered sodium carbonate (3 equivalents, 18.80 mmol). A mixture of 1,4-dioxane (9 mL) and water (5 mL) were added, the mixture was flushed with nitrogen, and then heated by microwave at 90° C. for three periods of 2 hours. The cooled mixture was then adsorbed directly onto silica and purified through a 40 g silica-gel column, eluting with isohexane:ethyl acetate (100:0% to 70:30%) to afford 2-benzyl-5-fluoro-pyridine-3-carbaldehyde (460 mg) as a colourless oil.

[0118] 1H NMR (400 MHz, CDCl3) δ ppm 10.35 (s, 1H), 8.64 (d, 1H), 7.84 M, 1H), 7.31-7.25 (m, 3H). 7.23-7.14 (m, 2H),

Step 2: Preparation of ethyl 3-fluoro-8-phenyl-7-(trifluoromethyl)quinoline-6-carboxylate

[0119] Using the method described in Preparative Example 1, Step 4, 2-benzyl-5-fluoro-pyridine-3-carbaldehyde was converted to ethyl 3-fluoro-8-phenyl-7-(trifluoro-methyl)quinoline-6-carboxylate.

[0120] 1H NMR (400 MHz, CDCl3) δ ppm 8.89 (d, 1H), 8.09 (s, 1H), 7.86 (m, 1H), 7.50-7.43 (m, 3H), 7.36-7.29 (m, 2H), 4.44 (q, 2H), 1.41 (t, 3H)

Step 3: Preparation of 3-fluoro-8-phenyl-7-(trifluoromethyl)quinoline-6-carboxylic acid

[0121] Using the method described in Preparative Example 2, Step 4, 3-fluoro-8-phenyl-7-(trifluoromethyl)quinoline-6-carboxylate was converted to 3-fluoro-8-phenyl-7-(trifluoromethyl)quinoline-6-carboxylic acid.

[0122] m/z 336.3 (M+H)

Step 4: Preparation of 3-fluoro-N-(1-methyltetrazol-5-yl)-8-phenyl-7-(trifluoro-methyl)quinoline-6-carboxamide

[0123] Using the method described in Preparative Example 2, Step 5, 3-fluoro-8-phenyl-7-(trifluoromethyl)quinoline-6-carboxylic acid was converted to 3-fluoro-N-(1-methyltetrazol-5-yl)-8-phenyl-7-(trifluoromethyl)quinoline-6-carboxamide.

[0124] 1H NMR (400 MHz, CD3CN) δ ppm 9.70 (br s, 1H), 8.90 (d, 1H), 8.39 (br, 1H), 8.20 (m, 1H), 7.55-7.49 (m, 3H), 7.40-7.34 (m, 2H), 4.03 (s, 3H)

EXAMPLE P4: PREPARATION OF 7-METHYL-8-(4-METHYLSULFANYLPHENYL)-N-(1-METHYLTETRAZOL-5-YL)QUINOLINE-6-CARBOXAMIDE (COMPOUND 1.030)

Step 1: Preparation of methyl 4-amino-3-bromo-2-methyl-benzoate

[0125] A stirred solution of methyl 4-amino-2-methyl-benzoate (500 mg, 3.03 mmol) in dimethylformamide (10 mL) was cooled in an ice-bath to 5° C., and N-bromosuccinimide (540 mg, 3.03 mmol) was added portion wise over 5 mins whilst maintaining the temperature between 5° C. and 7° C. The clear pale yellow reaction mixture was stirred in the ice-bath for a further 30 mins, and then poured into water. A dense white precipitate formed, which was extracted into diethyl ether. The ether extracts were separated, washed with water, dried over anhydrous magnesium sulphate, and the solvent was evaporated under reduced pressure to yield an inseparable 60:40 mixture of methyl 4-amino-3-bromo-2-methyl-benzoate and methyl 4-amino-5-bromo-2-methyl-benzoate, which was used directly in the next step.

[0126] 1H NMR (400 MHz, CDCl3) δ ppm inter alia 7.71 (d, 1H), 6.60 (d, 1H), 4.52 (br s, 2H), 3.84 (s, 3H), 2.71 (s, 3H)

Step 2: Preparation of methyl 8-bromo-7-methyl-quinoline-6-carboxylate

[0127] A stirred suspension of a 60:40 mixture of methyl 4-amino-3-bromo-2-methyl-benzoate and methyl 4-amino-5-bromo-2-methyl-benzoate (200 mg, 0.82 mmol) in n-butanol (5 mL, 55 mmol) was treated with conc. hydrochloric acid (0.2 mL) and p-chloranil (200 mg, 0.81 mmol). The resulting slurry was then heated to 100° C. and prop-2-enal (acrolein) (0.1 mL, 1 mmol) was added dropwise. Heating was continued for a further 30 mins, then the mixture was cooled and partitioned between water and dichloromethane. The dichloromethane layer was adsorbed on to silica-gel by evaporation under reduced pressure, and separated by flash chromatography (silica, eluting with an ethyl acetate/isohexane gradient) to afford an inseparable 60:40 mixture of methyl 8-bromo-7-methyl-quinoline-6-carboxylate and methyl 8-bromo-5-methyl-quinoline-6-carboxylate (155 mg) as a tan solid.

[0128] 1H NMR (400 MHz, CDCl3) δ ppm inter alia 9.11 (td, 1H), 8.28 (s, 1H), 8.20 (dd, 1H), 7.49 (dd, 1H), 3.99 (s, 3H), 2.90 (s, 3H)

Step 3: Preparation of methyl 8-(4-methylsulfanylphenyl)-7-methyl-quinoline-6-carboxylate

[0129] A stirred solution of a 60:40 mixture of methyl 8-bromo-7-methyl-quinoline-6-carboxylate and methyl 8-bromo-5-methyl-quinoline-6-carboxylate (310 mg, 1.14 mmol) in t-butanol (10.0 mL) was treated with potassium phosphate (610 mg, 2.79 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (S-Phos: 90 mg, 0.069 mmol), tris(dibenzylideneacetone)dipalladium(O) (50 mg, 0.053 mmol) and 4-methylsulfanylphenyl boronic acid (270 mg, 1.61 mmol) in a 20 ml microwave vial, blanketed with nitrogen. The vial was capped and the reaction mixture was heated by microwave to 100° C. for 45 mins. The cooled mixture was filtered through hyflo and washed with dichloromethane to yield a yellow filtrate, which was adsorbed on to silica-gel and purified by flash chromatography (silica, eluting with an ethyl acetate/isohexane gradient) to afford methyl 8-(4-methylsulfanylphenyl)-7-methyl-quinoline-6-carboxylate (190 mg) as a tan solid.

[0130] 1H NMR (400 MHz, CDCl3) δ ppm 8.92 (dd, 1H), 8.35 (s, 1H), 8.20 (dd, 1H), 7.44-7.35 (m, 3H), 7.24-7.16 (m, 2H), 3.99 (s, 3H), 2.56 (s, 3H), 2.45 (s, 3H)

Step 4: Preparation of 7-methyl-8-(4-methylsulfanylphenyl)quinoline-6-carboxylic acid

[0131] Using the method described in Preparative Example 2, Step 4, but using ethanol in place of methanol, methyl 8-(4-methylsulfanylphenyl)-7-methyl-quinoline-6-carboxylate was converted to 7-methyl-8-(4-methylsulfanylphenyl)quinoline-6-carboxylic acid.

[0132] 1H NMR (400 MHz, CDCl3/CD3OD) δ ppm 8.74 (dd, 1H), 8.17 (dd, 1H), 7.91 (s, 1H), 7.39 (d, 2H), 7.34-7.28 (m, 1H), 7.20 (d, 2H), 2.56 (s, 3H), 2.37 (s, 3H)

Step 5: Preparation of 7-methyl-8-(4-methylsulfanylphenyl)-N-(1-methyltetrazol-5-yl)quinoline-6-carboxamide

[0133] A stirred suspension of 7-methyl-8-(4-methylsulfanylphenyl)quinoline-6-carboxylic acid (0.59 mmol) in acetonitrile (5 mL) was treated with N,N′-carbonyldiimidazole (CDI: 140 mg, 0.86 mmol) in a single portion. The resultant suspension was heated to 90° C. for 4 hours, adding three further portions of CDI (3×140 mg) during this time. The reaction mixture was then cooled, filtered through hyflo, and evaporated under reduced pressure to afford the crude acyl imidazole. This was dissolved in 2-methyl tetrahydrofuran (10 mL) and treated with 5-amino-1-methyltetrazole (100 mg, 1.01 mmol) and 1,8-diazabicyclo[5,4,0]-7-undecene (DBU) (0.25 mL, 1.7 mmol). The stirred mixture was heated to 90° C. for 3 hours, adding a further portion of 5-amino-1-methyltetrazole (100 mg, 1.01 mmol) after 1 hour. The mixture was then cooled and the solvent was evaporated under reduced pressure. The residue was partitioned between dichloromethane and water, and the dichloromethane layer was washed with water and brine before being dried by passing through a phase-separating cartridge. The filtrate was adsorbed on to silica-gel and separated by chromatography (Silica, eluting with an methanol/dichloromethane gradient) to afford the crude product as a yellow solid. Trituration with diethyl ether afforded 7-methyl-8-(4-methylsulfanylphenyl)-N-(1-methyltetrazol-5-yl)quinoline-6-carboxamide (35 mg) as a cream solid.

[0134] 1H NMR (400 MHz, CD3OD) δ ppm 8.92-8.82 (m, 1H), 8.29 (d, 1H), 8.18 (s, 1H), 7.47 (dd, 1H), 7.42 (d, 2H), 7.22 (d, 2H), 4.14 (s, 3H), 2.58 (s, 3H), 2.41 (s, 3H)

EXAMPLE P5: PREPARATION OF 7-METHYL-8-(4-METHYLSULFONYLPHENYL)-N-(1-METHYLTETRAZOL-5-YL)QUINOLINE-6-CARBOXAMIDE (COMPOUND 1.031)

[0135] A stirred solution of 7-methyl-8-(4-methylsulfanylphenyl)-N-(1-methyltetrazol-5-yl)quinoline-6-carboxamide (25 mg, 0.064 mmol) in dichloromethane (2 mL) and methanol (2 mL) was treated dropwise with peracetic acid (0.15 mL) at room temperature. The mixture was stirred for 1 hour, then carefully evaporated to dryness under reduced pressure to afford 7-methyl-8-(4-methylsulfonylphenyl)-N-(1-methyltetrazol-5-yl)quinoline-6-carboxamide (27 mg) as a cream solid.

[0136] 1H NMR (400 MHz, CD3OD) δ ppm 8.96 (d, 1H), 8.73 (d, 1H), 8.42 (s, 1H), 8.17 (d, 2H), 7.76 (dd, 1H), 7.59 (d2H), 4.15 (s, 3H), 3.24 (s, 3H), 2.43 (s, 3H)

EXAMPLE P6: PREPARATION OF 7-CHLORO-N-(1-METHYLTETRAZOL-5-YL)-8-PHENYL-QUINOLINE-6-CARBOXAMIDE (COMPOUND 1.011)

Step 1: Preparation of methyl 7-chloro-8-phenyl-quinoline-6-carboxylate and 7-chloro-8-phenyl-quinoline-6-carboxylic acid

[0137] A stirred suspension of methyl 7-hydroxy-8-phenyl-quinoline-6-carboxylate (2.0 g, 7.16 mmol) in phosphorus oxychloride (10 mL) was heated by microwave to 120° C. for 8 hours, then to 200° C. for 7 mins. The cooled mixture was added dropwise to aqueous sodium bicarbonate solution, and extracted with ethyl acetate. The ethyl acetate extract was extracted with aqueous sodium bicarbonate, dried and evaporated under reduced pressure to afford crude methyl 7-chloro-8-phenyl-quinoline-6-carboxylate, which was purified by flash chromatography (Silica, eluting with an ethyl acetate/isohexane gradient) to afford the pure compound (212 mg).

[0138] 1H NMR (400 MHz, CDCl3) δ ppm 8.96 (d, 1H), 8.27 (s, 1H), 8.21 (m, 1H), 7.58-7.40 (m, 4H), 7.32 (m, 2H), 4.01 (s, 3H)

[0139] The bicarbonate extracts were combined with the original bicarbonate reaction quench and carefully acidified using c. hydrochloric acid, and this was extracted with ethyl acetate (3×). These combined ethyl acetate extracts were dried and the solvent was removed under reduced pressure to afford 7-chloro-8-phenyl-quinoline-6-carboxylic acid (626 mg).

[0140] 1H NMR (400 MHz, CD3OD) δ ppm 8.92 (m, 1H), 8.45 (m, 1H), 8.38 (s, 1H), 7.60-7.38 (m, 4H), 7.29 (m, 2H)

Step 2: Preparation of 7-chloro-N-(1-methyltetrazol-5-yl)-8-phenyl-quinoline-6-carboxamide

[0141] A stirred solution of 7-chloro-8-phenyl-quinoline-6-carboxylic acid (168 mg, 0.44 mmol) and 5-amino-1-methyltetrazole (1.2 equivalents, 0.53 mmol) in dichloromethane (3 mL) was treated with 4-(dimethylamino) pyridine (DMAP: 3 equivalents, 1.33 mmol), and the reaction mixture was stirred for 1 hour. 1-propanephosphonic acid cyclic anhydride (PPAA: (50 mass % in ethyl acetate); 6 equivalents, 2.66 mmol) was added, and the reaction mixture was transferred to a microwave vial and heated 120° C. for 10 mins. The mixture was cooled and the solvent was removed under reduced pressure. The residue was dissolved in ethyl acetate, which was washed with water (3×), brine, dried over magnesium sulphate, and the solvent was removed under reduced pressure. The residue was adsorbed on to silica-gel and purified by flash chromatography (Silica, eluting with a methanol/dichloromethane gradient) to afford 7-chloro-N-(1-methyltetrazol-5-yl)-8-phenyl-quinoline-6-carboxamide (42 mg).

[0142] 1H NMR (400 MHz, CD3CN) δ ppm 9.61 (br s, 1H), 8.91 (d, 1H), 8.45 (dd, 1H), 8.32 (s, 1H), 7.63-7.45 (m, 4H), 7.39 (m, 2H), 4.05 (s, 3H).

EXAMPLE P7: PREPARATION OF 7-METHYLSULFANYL-N-(1-METHYLTETRAZOL-5-YL)-8-PHENYL-QUINOLINE-6-CARBOXAMIDE (COMPOUND 1.032)

Step 1: Preparation of 7-methylsulfanyl-8-phenyl-quinoline-6-carboxylic acid

[0143] A stirred solution of methyl 7-chloro-8-phenyl-quinoline-6-carboxylate (130 mg, 0.437 mmol) was dissolved in dimethylformamide (3 mL) and sodium thiomethoxide (2 equivalents, 0.874 mmol) was added. The mixture was stirred at room temperature for 1 hour, then heated by microwave to 100° C. for 35 mins. A further 2 equivalents of sodium thiomethoxide was added and the mixture was heated by microwave at 140° C. for 1 hour. A further 2 equivalents of sodium thiomethoxide was added and the mixture was heated by microwave at 140° C. for a further 2 hours, followed by heating to 160° C. for 30 mins. The cooled reaction mixture was diluted with water and washed with ether (2×). The aqueous layer was then acidified, and extracted with diethyl ether (6×). The combined ether extracts were dried over magnesium sulphate, then concentrated under reduced pressure to afford very crude 7-methylsulfanyl-8-phenyl-quinoline-6-carboxylic acid, which was used in the next step without further purification.

[0144] m/z 296.1 (M+H)

Step 2: Preparation of 7-methylsulfanyl-N-(1-methyltetrazol-5-yl)-8-phenyl-quinoline-6-carboxamide

[0145] Using the method described in Preparative Example 6, Step 2, 7-methylsulfanyl-8-phenyl-quinoline-6-carboxylic acid was converted to 7-methylsulfanyl-N-(1-methyltetrazol-5-yl)-8-phenyl-quinoline-6-carboxamide.

[0146] 1H NMR (400 MHz, CD3CN) δ ppm 9.70 (br s, 1H), 8.88 (m, 1H), 8.39 (m, 1H), 8.21 (s, 1H), 7.60-7.42 (m, 4H), 7.40-7.35 (m, 2H), 4.10 (s, 3H), 2.13 (s, 3H)

EXAMPLE P8: PREPARATION OF 7-METHYLSULFONYL-N-(1-METHYLTETRAZOL-5-YL)-8-PHENYL-QUINOLINE-6-CARBOXAMIDE (COMPOUND 1.010)

[0147] A stirred solution of 7-methylsulfanyl-N-(1-methyltetrazol-5-yl)-8-phenyl-quinoline-6-carboxamide (147 mg, 0.39 mmol) in acetic acid (10 mL) was treated with a catalytic amount of sodium tungstate dihydrate (100 mass %) followed by the dropwise addition of hydrogen peroxide (1 mL). The mixture was heated to 65° C., and a further 3 mL of hydrogen peroxide was added in 1 mL amounts. The mixture was cooled and quenched with sodium metabisulfite. This was extracted with ethyl acetate, and the extracts were dried over magnesium sulphate, then adsorbed onto silica-gel under reduced pressure. Separation by flash chromatography (Silica (20-40 micron), eluting with a methanol/dichloromethane gradient) afforded 7-methylsulfonyl-N-(1-methyltetrazol-5-yl)-8-phenyl-quino line-6-carboxamide (29 mg).

[0148] 1H NMR (400 MHz, CDCl3) δ ppm 10.30 (br s, 1H), 9.08 (m, 1H), 8.88-8.78 (m, 2H), 7.67-7.48 (m, 4H), 7.45-7.38 (m, 2H), 4.25 (s, 3H), 3.06 (s, 3H).

TABLE-US-00001 TABLE 1 Examples of herbicidal compounds of the present invention. [00021] Compound A.sup.1a A.sup.1b R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 NMR 1.001 N N Me CF.sub.3 phenyl H H H 1H NMR (400 MHz, CDCl.sub.3) δ ppm 11.74 (br s, 1H), 9.05 (dd, 1H), 8.32-8.28 (m, 2H) 7.60-7.73 (m, 6H), 4.14 (s, 3H) 1.002 N N Et CF.sub.3 phenyl H H H 1H NMR (400 MHz, CDCl.sub.3) δ ppm 11.50 (br s, 1H), 9.04 (m, 1H), 8.31-8.24 (m, 2H), 7.55 (m, 1H), 7.53-7.42 (m, 3H0, 7.40 (m, 2H), 4.49 (q, 2H), 1.61 (t, 3H) 1.003 N N nPr CF.sub.3 phenyl H H H m/z = 427.2 (M + H) 1.004 N N Me CF.sub.3 phenyl Me H H 1.005 N N Me CF.sub.3 phenyl CF.sub.3 H H 1.006 N N Me CF.sub.3 phenyl Me F H 1.007 N N Me CF.sub.3 phenyl H F H 1H NMR (400 MHz, CD3CN) δ ppm 9.70 (br s, 1H), 8.90 (d, 1H), 8.39 (br, 1H), 8.20 (m, 1H), 7.55-7.49 (m, 3H), 7.40-7.34 (m, 2H), 4.03 (s, 3H) 1.008 N N Me Me phenyl H H H 1.009 N N Me MeO— phenyl H H H 1H NMR (400 MHz, CDCl3) δ ppm 10.75 (br. S, 1H), 9.00 (dd, 1H), 8.80 (s, 1H), 8.32 (dd, 1H), 7.57-7.46 (m, 6H), 4.14 (s, 3H), 3.59 (s, 3H). 1.010 N N Me —S(O).sub.2Me phenyl H H H 1H NMR (400 MHz, CDCl3) δ ppm 10.30 (br s, 1H), 9.08 (m, 1H), 8.88- 8.78 (m, 2H), 7.67- 7.48 (m, 4H), 7.45- 7.38 (m, 2H), 4.25 (s, 3H), 3.06 (s, 3H) 1.011 N N Me Cl phenyl H H H 1H NMR (400 MHz, CD3CN) δ ppm 9.61 (br s, 1H), 8.91 (d, 1H), 8.45 (dd, 1H), 8.32 (s, 1H), 7.63-7.45 (m, 4H), 7.39 (m, 2H), 4.05 (s, 3H). 1.012 N N Me CF.sub.3 phenyl H H Cl 1.013 CH N Me CF.sub.3 phenyl H H H 1.014 N CH Me CF.sub.3 phenyl H H H 1.015 N N Me CF.sub.3 4-Cl- H H H phenyl- 1.016 N N Me CF.sub.3 4-MeO- H H H phenyl- 1.017 N N Me CF.sub.3 4-Me- H H H 1H NMR (400 MHz, phenyl- CD3CN) δ ppm 9.78 (br s, 1H), 8.94 (m, 1H), 8.45 (m, 1H), 8.37 (br, 1H), 7.66 (m, 1H), 7.31 (d, 2H), 7.25 (d, 2H), 4.04 (s, 3H), 2.44 (s, 3H) 1.018 N N Me CF.sub.3 4-CF.sub.3- H H H phenyl 1.019 N N Me CF.sub.3 4-NO.sub.2- H H H phenyl- 1.020 N N Me CF.sub.3 4-MeS(O).sub.2- H H H phenyl- 1.021 N N Me CF.sub.3 4-CN- H H H phenyl- 1.022 N N Me CF.sub.3 4-CF.sub.3O- H H H phenyl 1.023 N N Me CF.sub.3 [00022] H H H 1.024 N N Me CF.sub.3 [00023] H H H 1.025 N N Me CF.sub.3 3-Me- H H H phenyl- 1.026 N N Me CF.sub.3 3,4-diMe- H H H phenyl- 1.027 N N Me CF.sub.3 3-Cl- H H H phenyl- 1.028 N N Me CF.sub.3 3-MeO- H H H phenyl- 1.029 N N Me CF.sub.3 2F-phenyl- H H H 1.030 N N Me Me 4-MeS- H H H 1H NMR (400 MHz, phenyl- CD3OD) δ ppm 8.92-8.82 (m, 1H), 8.29 (d, 1H), 8.18 (s, 1H), 7.47 (dd, 1H), 7.42 (d, 2H), 7.22 (d, 2H), 4.14 (s, 3H), 2.58 (s, 3H), 2.41 (s, 3H) 1.031 N N Me Me 4-MeS(O).sub.2- H H H 1H NMR (400 MHz, phenyl- CD3OD) δ ppm 8.96 (d, 1H), 8.73 (d, 1H), 8.42 (s, 1H), 8.17 (d, 2H), 7.76 (dd, 1H), 7.59 (d2H), 4.15 (s, 3H), 3.24 (s, 3H), 2.43 (s, 3H) 1.032 N N Me MeS— phenyl H H H 1H NMR (400 MHz, CD3CN) δ ppm 9.70 (br s, 1H), 8.88 (m, 1H), 8.39 (m, 1H), 8.21 (s, 1H), 7.60-7.42 (m, 4H), 7.40-7.35 (m, 2H), 4.10 (s, 3H), 2.13 (s, 3H) 1.033 N N phenyl CF.sub.3 phenyl H H H 1H NMR (400 MHz, CDCl3) δ ppm 11.01 (br s, 1H), 8.94 (m, 1H), 8.27- 8.05 (m, 2H), 7.62- 7.35 (m, 9H), 7.30- 7.20 (m, 2H) 1.034 N N Me Me 4-MeO- H H H 1H NMR (400 MHz, phenyl- CDCl3) δ ppm 8.91 (dd, 1H), 8.26 (dd, 1H), 8.15 (s, 1H), 7.44 (dd, 1H), 7.25- 7.18 (m, 2H), 7.12- 7.04 (m, 2H), 4.14 (s, 3H), 3.91 (s, 3H), 2.42 (s, 3H) 1.035 N N Me Me 4-F-phenyl- H H H 1H NMR (400 MHz, CDCl3) δ ppm 8.91 (dd, 1H), 8.27 (dd, 1H), 8.19 (s, 1H), 7.46 (dd, 1H), 7.29- 7.18 (m, 4H), 4.15 (s, 3H), 2.40 (s, 3H) 1.036 N N Me Me 4-Cl- H H H 1H NMR (400 MHz, phenyl- CDCl3) δ ppm 11.24 (br. s., 1H), 8.95 (dd, 1H), 8.47 (s, 1H), 8.35 (dd1H), 7.52-7.47 (m, 2H), 7.45 (dd, 1H), 7.26- 7.22 (m, 2H), 4.16 (s, 3H), 2.43 (s, 3H) 1.037 N N Me Me 4-MeO- Me H H 1H NMR (400 MHz, phenyl- CDCl3) δ ppm 11.99 (br.s, 1H), 8.74 (d, 1H), 8.53 (s, 1H), 7.56 (d, 1H), 7.12 (d, 2H), 6.99 (d, 2H), 4.10 (s, 3H), 3.84 (s, 3H), 2.86 (s, 3H), 2.27 (s, 3H) 1.038 N N Me Me 4-MeS(O).sub.2- Me H H 1H NMR (400 MHz, phenyl- CD3OD) δ ppm 8.21 (s, 1H), 8.20 (d1H), 8.08 (d2H), 7.55 (d, 2H), 7.38 (d, 1H), 4.14 (s, 3H), 3.23 (s, 3H), 2.60 (s, 3H), 2.39 (s, 3H) 1.039 N N Me Me [00024] H H H 1H NMR (400 MHz, CD3OD) δ ppm 8.92 (dd, 1H), 8.26 (dd, 1H), 8.15 (s, 1H), 7.53 (dd1H), 7.46 (dd, 1H), 7.27 (dd, 1H), 7.12 (dd, 1H), 4.14 (s, 3H), 2.47 (s, 3H) 1.040 N N Me Me [00025] H H H 1H NMR (400 MHz, CD3OD) δ ppm 8.84 (dd, 1H), 8.65 (dd, 1H), 8.49 (dd, 1H), 8.42 (dd, 1H), 8.33 (s, 1H), 7.80 (td, 1H), 7.61 (ddd, 1H), 7.56 (dd, 1H), 4.14 (s, 3H), 2.44 (s, 3H) 1.041 N N Me Me [00026] H H H 1H NMR (400 MHz, CD3OD) δ ppm 9.28 (s, 1H), 8.88 (dd, 1H), 8.78 (s, 2H), 8.38 (dd, 1H), 8.33 (s, 1H), 7.56 (dd, 1H), 4.15 (s, 3H), 2.52 (s, 3H) 1.042 N N Me Me [00027] H H H 1H NMR (400 MHz, d6-DMSO) δ ppm 11.76 (s, 1H), 8.94 (br d, 1H), 8.45 (d, 1H), 8.27 (s, 1H), 7.90 (s, 1H), 7.58 (m, 2H), 4.05 (s, 3H), 3.96 (s, 3H), 2.50 (s, 3H) 1.043 N N Me Me [00028] H H H 1H NMR (400 MHz, d6-DMSO) δ ppm 11.83 (s, 1H), 8.94 (dd, 1H), 8.52 (dd, 1H), 8.45 (s, 1H), 7.63 (dd, 1H), 4.06 (s, 3H), 2.39 (s, 3H), 2.15 (s, 3H), 1.92 (s, 3H) 1.044 N N Me Me [00029] H H H 1H NMR (400 MHz, d6-DMSO) δ ppm 11.78 (s, 1H), 8.94 (dd, 1H), 8.47 (dd, 1H), 8.34 (s, 1H), 7.84 (t, 1H), 7.81 (m, 1H), 7.59 (dd, 1H), 6.66 (dd, 1H), 4.05 (s, 3H), 2.49 (s, 3H) 1.045 N N Me —S(O)Me phenyl H H H 1.046 N N Me Cl 4-MeS(O).sub.2- H H H phenyl- 1.047 N N Et CF.sub.3 4-MeS(O).sub.2- H H H phenyl- 1.048 N N Et Cl 4-MeS(O).sub.2- H H H phenyl- 1.049 N N Me CF.sub.3 [00030] H H H 1H NMR (400 MHz, CD3CN) δ ppm 9.05 (dd, 1H), 8.59- 8.47 (m, 2H), 7.95 (d, 1H), 7.82 (d, 1H), 7.79 (dd, 1H), 6.61 (dd, 1H), 4.04 (s, 3H) 1.050 N N Me CF.sub.3 [00031] H H H 1.051 N N Me CF.sub.3 [00032] H H H 1.052 N N Et CF.sub.3 [00033] H H H

TABLE-US-00002 TABLE 2 Examples of herbicidal compounds of the present invention. [00034] Compound R.sup.1 R.sup.2 R.sup.3 R.sup.4 2.001 Et CF.sub.3 4-Cl-phenyl H 2.002 n-Pr CF.sub.3 4-Cl-phenyl H 2.003 Et CF.sub.3 4-F-phenyl H 2.004 Me CF.sub.3 4-F-phenyl H 2.005 n-Pr CF.sub.3 4-F-phenyl H 2.006 n-Pr CF.sub.3 4-MeS(O).sub.2-phenyl H 2.007 Et CF.sub.3 4-MeS-phenyl H 2.008 Me CF.sub.3 4-MeS-phenyl H 2.009 n-Pr CF.sub.3 4-MeS-phenyl H 2.010 Et CF.sub.3 4-Me-phenyl H 2.011 n-Pr CF.sub.3 4-Me-phenyl H 2.012 n-Pr CF.sub.3 pyrazol-1-yl H 2.013 Et CF.sub.3 furan-3-yl H 2.014 Me CF.sub.3 furan-3-yl H 2.015 n-Pr CF.sub.3 furan-3-yl H 2.016 Et CF.sub.3 3,5-dimethyl-isoxazol-4-yl H 2.017 Me CF.sub.3 3,5-dimethyl-isoxazol-4-yl H 2.018 n-Pr CF.sub.3 3,5-dimethyl-isoxazol-4-yl H 2.019 Et CF.sub.3 thien-2-yl H 2.020 n-Pr CF.sub.3 thien-2-yl H 2.021 Et CF.sub.3 1-methyl-pyrazol-4-yl H 2.022 Me CF.sub.3 1-methyl-pyrazol-4-yl H 2.023 n-Pr CF.sub.3 1-methyl-pyrazol-4-yl H 2.024 Et CF.sub.3 pyrimidin-5-yl H 2.025 Me CF.sub.3 pyrimidin-5-yl H 2.026 n-Pr CF.sub.3 pyrimidin-5-yl H 2.027 Et CF.sub.3 pyridin-3-yl H 2.028 Me CF.sub.3 pyridin-3-yl H 2.029 n-Pr CF.sub.3 pyridin-3-yl H 2.030 Et Cl phenyl H 2.031 n-Pr Cl phenyl H 2.032 Et Cl 4-Cl-phenyl H 2.033 Me Cl 4-Cl-phenyl H 2.034 n-Pr Cl 4-Cl-phenyl H 2.035 Et Cl 4-F-phenyl H 2.036 Me Cl 4-F-phenyl H 2.037 n-Pr Cl 4-F-phenyl H 2.038 n-Pr Cl 4-MeS(O).sub.2-phenyl H 2.039 Et Cl 4-MeS-phenyl H 2.040 Me Cl 4-MeS-phenyl H 2.041 n-Pr Cl 4-MeS-phenyl H 2.042 Et Cl 4-Me-phenyl H 2.043 Me Cl 4-Me-phenyl H 2.044 n-Pr Cl 4-Me-phenyl H 2.045 Et Cl pyrazol-1-yl H 2.046 Me Cl pyrazol-1-yl H 2.047 n-Pr Cl pyrazol-1-yl H 2.048 Et Cl furan-3-yl H 2.049 Me Cl furan-3-yl H 2.050 n-Pr Cl furan-3-yl H 2.051 Et Cl 3,5-dimethyl-isoxazol-4-yl H 2.052 Me Cl 3,5-dimethyl-isoxazol-4-yl H 2.053 n-Pr Cl 3,5-dimethyl-isoxazol-4-yl H 2.054 Et Cl thien-2-yl H 2.055 Me Cl thien-2-yl H 2.056 n-Pr Cl thien-2-yl H 2.057 Et Cl 1-methyl-pyrazol-4-yl H 2.058 Me Cl 1-methyl-pyrazol-4-yl H 2.059 n-Pr Cl 1-methyl-pyrazol-4-yl H 2.060 Et Cl pyrimidin-5-yl H 2.061 Me Cl pyrimidin-5-yl H 2.062 n-Pr Cl pyrimidin-5-yl H 2.063 Et Cl pyridin-3-yl H 2.064 Me Cl pyridin-3-yl H 2.065 n-Pr Cl pyridin-3-yl H 2.066 Et —SMe phenyl H 2.067 n-Pr —SMe phenyl H 2.068 Et —SMe 4-Cl-phenyl H 2.069 Me —SMe 4-Cl-phenyl H 2.070 n-Pr —SMe 4-Cl-phenyl H 2.071 Et —SMe 4-F-phenyl H 2.072 Me —SMe 4-F-phenyl H 2.073 n-Pr —SMe 4-F-phenyl H 2.074 Et —SMe 4-MeS(O).sub.2-phenyl H 2.075 Me —SMe 4-MeS(O).sub.2-phenyl H 2.076 n-Pr —SMe 4-MeS(O).sub.2-phenyl H 2.077 Et —SMe 4-MeS-phenyl H 2.078 Me —SMe 4-MeS-phenyl H 2.079 n-Pr —SMe 4-MeS-phenyl H 2.080 Et —SMe 4-Me-phenyl H 2.081 Me —SMe 4-Me-phenyl H 2.082 n-Pr —SMe 4-Me-phenyl H 2.083 Et —SMe pyrazol-1-yl H 2.084 Me —SMe pyrazol-1-yl H 2.085 n-Pr —SMe pyrazol-1-yl H 2.086 Et —SMe furan-3-yl H 2.087 Me —SMe furan-3-yl H 2.088 n-Pr —SMe furan-3-yl H 2.089 Et —SMe 3,5-dimethyl-isoxazol-4-yl H 2.090 Me —SMe 3,5-dimethyl-isoxazol-4-yl H 2.091 n-Pr —SMe 3,5-dimethyl-isoxazol-4-yl H 2.092 Et —SMe thien-2-yl H 2.093 Me —SMe thien-2-yl H 2.094 n-Pr —SMe thien-2-yl H 2.095 Et —SMe 1-methyl-pyrazol-4-yl H 2.096 Me —SMe 1-methyl-pyrazol-4-yl H 2.097 n-Pr —SMe 1-methyl-pyrazol-4-yl H 2.098 Et —SMe pyrimidin-5-yl H 2.099 Me —SMe pyrimidin-5-yl H 2.100 n-Pr —SMe pyrimidin-5-yl H 2.101 Et —SMe pyridin-3-yl H 2.102 Me —SMe pyridin-3-yl H 2.103 n-Pr —SMe pyridin-3-yl H 2.104 Et —S(O).sub.2Me phenyl H 2.105 n-Pr —S(O).sub.2Me phenyl H 2.106 Et —S(O).sub.2Me 4-Cl-phenyl H 2.107 Me —S(O).sub.2Me 4-Cl-phenyl H 2.108 n-Pr —S(O).sub.2Me 4-Cl-phenyl H 2.109 Et —S(O).sub.2Me 4-F-phenyl H 2.110 Me —S(O).sub.2Me 4-F-phenyl H 2.111 n-Pr —S(O).sub.2Me 4-F-phenyl H 2.112 Et —S(O).sub.2Me 4-MeS(O).sub.2-phenyl H 2.113 Me —S(O).sub.2Me 4-MeS(O).sub.2-phenyl H 2.114 n-Pr —S(O).sub.2Me 4-MeS(O).sub.2-phenyl H 2.115 Et —S(O).sub.2Me 4-MeS-phenyl H 2.116 Me —S(O).sub.2Me 4-MeS-phenyl H 2.117 n-Pr —S(O).sub.2Me 4-MeS-phenyl H 2.118 Et —S(O).sub.2Me 4-Me-phenyl H 2.119 Me —S(O).sub.2Me 4-Me-phenyl H 2.120 n-Pr —S(O).sub.2Me 4-Me-phenyl H 2.121 Et —S(O).sub.2Me pyrazol-1-yl H 2.122 Me —S(O).sub.2Me pyrazol-1-yl H 2.123 n-Pr —S(O).sub.2Me pyrazol-1-yl H 2.124 Et —S(O).sub.2Me furan-3-yl H 2.125 Me —S(O).sub.2Me furan-3-yl H 2.126 n-Pr —S(O).sub.2Me furan-3-yl H 2.127 Et —S(O).sub.2Me 3,5-dimethyl-isoxazol-4-yl H 2.128 Me —S(O).sub.2Me 3,5-dimethyl-isoxazol-4-yl H 2.129 n-Pr —S(O).sub.2Me 3,5-dimethyl-isoxazol-4-yl H 2.130 Et —S(O).sub.2Me thien-2-yl H 2.131 Me —S(O).sub.2Me thien-2-yl H 2.132 n-Pr —S(O).sub.2Me thien-2-yl H 2.133 Et —S(O).sub.2Me 1-methyl-pyrazol-4-yl H 2.134 Me —S(O).sub.2Me 1-methyl-pyrazol-4-yl H 2.135 n-Pr —S(O).sub.2Me 1-methyl-pyrazol-4-yl H 2.136 Et —S(O).sub.2Me pyrimidin-5-yl H 2.137 Me —S(O).sub.2Me pyrimidin-5-yl H 2.138 n-Pr —S(O).sub.2Me pyrimidin-5-yl H 2.139 Et —S(O).sub.2Me pyridin-3-yl H 2.140 Me —S(O).sub.2Me pyridin-3-yl H 2.141 n-Pr —S(O).sub.2Me pyridin-3-yl H 2.142 Et CF.sub.3 phenyl Me 2.143 n-Pr CF.sub.3 phenyl Me 2.144 Et CF.sub.3 4-Cl-phenyl Me 2.145 Me CF.sub.3 4-Cl-phenyl Me 2.146 n-Pr CF.sub.3 4-Cl-phenyl Me 2.147 Et CF.sub.3 4-F-phenyl Me 2.148 Me CF.sub.3 4-F-phenyl Me 2.149 n-Pr CF.sub.3 4-F-phenyl Me 2.150 Et CF.sub.3 4-MeS(O).sub.2-phenyl Me 2.151 Me CF.sub.3 4-MeS(O).sub.2-phenyl Me 2.152 n-Pr CF.sub.3 4-MeS(O).sub.2-phenyl Me 2.153 Et CF.sub.3 4-MeS-phenyl Me 2.154 Me CF.sub.3 4-MeS-phenyl Me 2.155 n-Pr CF.sub.3 4-MeS-phenyl Me 2.156 Et CF.sub.3 4-Me-phenyl Me 2.157 Me CF.sub.3 4-Me-phenyl Me 2.158 n-Pr CF.sub.3 4-Me-phenyl Me 2.159 Et CF.sub.3 pyrazol-1-yl Me 2.160 Me CF.sub.3 pyrazol-1-yl Me 2.161 n-Pr CF.sub.3 pyrazol-1-yl Me 2.162 Et CF.sub.3 furan-3-yl Me 2.163 Me CF.sub.3 furan-3-yl Me 2.164 n-Pr CF.sub.3 furan-3-yl Me 2.165 Et CF.sub.3 3,5-dimethyl-isoxazol-4-yl Me 2.166 Me CF.sub.3 3,5-dimethyl-isoxazol-4-yl Me 2.167 n-Pr CF.sub.3 3,5-dimethyl-isoxazol-4-yl Me 2.168 Et CF.sub.3 thien-2-yl Me 2.169 Me CF.sub.3 thien-2-yl Me 2.170 n-Pr CF.sub.3 thien-2-yl Me 2.171 Et CF.sub.3 1-methyl-pyrazol-4-yl Me 2.172 Me CF.sub.3 1-methyl-pyrazol-4-yl Me 2.173 n-Pr CF.sub.3 1-methyl-pyrazol-4-yl Me 2.174 Et CF.sub.3 pyrimidin-5-yl Me 2.175 Me CF.sub.3 pyrimidin-5-yl Me 2.176 n-Pr CF.sub.3 pyrimidin-5-yl Me 2.177 Et CF.sub.3 pyridin-3-yl Me 2.178 Me CF.sub.3 pyridin-3-yl Me 2.179 n-Pr CF.sub.3 pyridin-3-yl Me 2.180 Et Cl phenyl Me 2.181 Me Cl phenyl Me 2.182 n-Pr Cl phenyl Me 2.183 Et Cl 4-Cl-phenyl Me 2.184 Me Cl 4-Cl-phenyl Me 2.185 n-Pr Cl 4-Cl-phenyl Me 2.186 Et Cl 4-F-phenyl Me 2.187 Me Cl 4-F-phenyl Me 2.188 n-Pr Cl 4-F-phenyl Me 2.189 Et Cl 4-MeS(O).sub.2-phenyl Me 2.190 Me Cl 4-MeS(O).sub.2-phenyl Me 2.191 n-Pr Cl 4-MeS(O).sub.2-phenyl Me 2.192 Et Cl 4-MeS-phenyl Me 2.193 Me Cl 4-MeS-phenyl Me 2.194 n-Pr Cl 4-MeS-phenyl Me 2.195 Et Cl 4-Me-phenyl Me 2.196 Me Cl 4-Me-phenyl Me 2.197 n-Pr Cl 4-Me-phenyl Me 2.198 Et Cl pyrazol-1-yl Me 2.199 Me Cl pyrazol-1-yl Me 2.200 n-Pr Cl pyrazol-1-yl Me 2.201 Et Cl furan-3-yl Me 2.202 Me Cl furan-3-yl Me 2.203 n-Pr Cl furan-3-yl Me 2.204 Et Cl 3,5-dimethyl-isoxazol-4-yl Me 2.205 Me Cl 3,5-dimethyl-isoxazol-4-yl Me 2.206 n-Pr Cl 3,5-dimethyl-isoxazol-4-yl Me 2.207 Et Cl thien-2-yl Me 2.208 Me Cl thien-2-yl Me 2.209 n-Pr Cl thien-2-yl Me 2.210 Et Cl 1-methyl-pyrazol-4-yl Me 2.211 Me Cl 1-methyl-pyrazol-4-yl Me 2.212 n-Pr Cl 1-methyl-pyrazol-4-yl Me 2.213 Et Cl pyrimidin-5-yl Me 2.214 Me Cl pyrimidin-5-yl Me 2.215 n-Pr Cl pyrimidin-5-yl Me 2.216 Et Cl pyridin-3-yl Me 2.217 Me Cl pyridin-3-yl Me 2.218 n-Pr Cl pyridin-3-yl Me 2.219 Et —SMe phenyl Me 2.220 Me —SMe phenyl Me 2.221 n-Pr —SMe phenyl Me 2.222 Et —SMe 4-Cl-phenyl Me 2.223 Me —SMe 4-Cl-phenyl Me 2.224 n-Pr —SMe 4-Cl-phenyl Me 2.225 Et —SMe 4-F-phenyl Me 2.226 Me —SMe 4-F-phenyl Me 2.227 n-Pr —SMe 4-F-phenyl Me 2.228 Et —SMe 4-MeS(O).sub.2-phenyl Me 2.229 Me —SMe 4-MeS(O).sub.2-phenyl Me 2.230 n-Pr —SMe 4-MeS(O).sub.2-phenyl Me 2.231 Et —SMe 4-MeS-phenyl Me 2.232 Me —SMe 4-MeS-phenyl Me 2.233 n-Pr —SMe 4-MeS-phenyl Me 2.234 Et —SMe 4-Me-phenyl Me 2.235 Me —SMe 4-Me-phenyl Me 2.236 n-Pr —SMe 4-Me-phenyl Me 2.237 Et —SMe pyrazol-1-yl Me 2.238 Me —SMe pyrazol-1-yl Me 2.239 n-Pr —SMe pyrazol-1-yl Me 2.240 Et —SMe furan-3-yl Me 2.241 Me —SMe furan-3-yl Me 2.242 n-Pr —SMe furan-3-yl Me 2.243 Et —SMe 3,5-dimethyl-isoxazol-4-yl Me 2.244 Me —SMe 3,5-dimethyl-isoxazol-4-yl Me 2.245 n-Pr —SMe 3,5-dimethyl-isoxazol-4-yl Me 2.246 Et —SMe thien-2-yl Me 2.247 Me —SMe thien-2-yl Me 2.248 n-Pr —SMe thien-2-yl Me 2.249 Et —SMe 1-methyl-pyrazol-4-yl Me 2.250 Me —SMe 1-methyl-pyrazol-4-yl Me 2.251 n-Pr —SMe 1-methyl-pyrazol-4-yl Me 2.252 Et —SMe pyrimidin-5-yl Me 2.253 Me —SMe pyrimidin-5-yl Me 2.254 n-Pr —SMe pyrimidin-5-yl Me 2.255 Et —SMe pyridin-3-yl Me 2.256 Me —SMe pyridin-3-yl Me 2.257 n-Pr —SMe pyridin-3-yl Me 2.258 Et —S(O).sub.2Me phenyl Me 2.259 Me —S(O).sub.2Me phenyl Me 2.260 n-Pr —S(O).sub.2Me phenyl Me 2.261 Et —S(O).sub.2Me 4-Cl-phenyl Me 2.262 Me —S(O).sub.2Me 4-Cl-phenyl Me 2.263 n-Pr —S(O).sub.2Me 4-Cl-phenyl Me 2.264 Et —S(O).sub.2Me 4-F-phenyl Me 2.265 Me —S(O).sub.2Me 4-F-phenyl Me 2.266 n-Pr —S(O).sub.2Me 4-F-phenyl Me 2.267 Et —S(O).sub.2Me 4-MeS(O).sub.2-phenyl Me 2.268 Me —S(O).sub.2Me 4-MeS(O).sub.2-phenyl Me 2.269 n-Pr —S(O).sub.2Me 4-MeS(O).sub.2-phenyl Me 2.270 Et —S(O).sub.2Me 4-MeS-phenyl Me 2.271 Me —S(O).sub.2Me 4-MeS-phenyl Me 2.272 n-Pr —S(O).sub.2Me 4-MeS-phenyl Me 2.273 Et —S(O).sub.2Me 4-Me-phenyl Me 2.274 Me —S(O).sub.2Me 4-Me-phenyl Me 2.275 n-Pr —S(O).sub.2Me 4-Me-phenyl Me 2.276 Et —S(O).sub.2Me pyrazol-1-yl Me 2.277 Me —S(O).sub.2Me pyrazol-1-yl Me 2.278 n-Pr —S(O).sub.2Me pyrazol-1-yl Me 2.279 Et —S(O).sub.2Me furan-3-yl Me 2.280 Me —S(O).sub.2Me furan-3-yl Me 2.281 n-Pr —S(O).sub.2Me furan-3-yl Me 2.282 Et —S(O).sub.2Me 3,5-dimethyl-isoxazol-4-yl Me 2.283 Me —S(O).sub.2Me 3,5-dimethyl-isoxazol-4-yl Me 2.284 n-Pr —S(O).sub.2Me 3,5-dimethyl-isoxazol-4-yl Me 2.285 Et —S(O).sub.2Me thien-2-yl Me 2.286 Me —S(O).sub.2Me thien-2-yl Me 2.287 n-Pr —S(O).sub.2Me thien-2-yl Me 2.288 Et —S(O).sub.2Me 1-methyl-pyrazol-4-yl Me 2.289 Me —S(O).sub.2Me 1-methyl-pyrazol-4-yl Me 2.290 n-Pr —S(O).sub.2Me 1-methyl-pyrazol-4-yl Me 2.291 Et —S(O).sub.2Me pyrimidin-5-yl Me 2.292 Me —S(O).sub.2Me pyrimidin-5-yl Me 2.293 n-Pr —S(O).sub.2Me pyrimidin-5-yl Me 2.294 Et —S(O).sub.2Me pyridin-3-yl Me 2.295 Me —S(O).sub.2Me pyridin-3-yl Me 2.296 n-Pr —S(O).sub.2Me pyridin-3-yl Me

BIOLOGICAL EXAMPLES

Experiment B1

[0149] Seeds of a variety of test species are sown in standard soil in pots (Lolium perenne (LOLPE), Solanum nigrum (SOLNI), Amaranthus retoflexus (AMARE), 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 1000 g/h. 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 POST Application PRE Application Compound LOLPE SOLNI AMARE SETFA ECHCG IPOHE LOLPE SOLNI AMARE SETFA ECHCG IPOHE 1.001 5 5 5 5 5 5 5 5 5 5 5 5 1.002 5 5 5 5 5 5 5 5 5 5 5 5 1.003 1 5 5 2 3 4 1 5 5 1 5 2 1.007 5 5 5 5 5 5 5 5 5 5 5 5 1.009 4 5 5 5 5 5 5 5 5 5 5 5 1.010* 4 5 5 5 5 5 2 5 5 2 5 4 1.011 5 5 5 5 5 5 5 5 5 5 5 5 1.017 4 5 5 5 5 5 4 5 5 5 5 5 1.030 4 5 5 5 5 5 4 5 5 5 5 4 1.031 5 5 5 5 5 5 5 5 5 5 5 5 1.032 5 5 5 5 5 5 5 5 5 5 5 5 1.033 1 5 5 2 2 5 1 4 5 1 1 3 1.034 4 5 5 5 5 5 5 5 5 5 5 5 1.035 4 5 5 5 5 5 5 5 5 5 5 5 1.036 4 5 5 5 5 5 4 5 5 5 5 5 1.037 5 5 5 5 5 5 3 5 5 5 5 4 1.038 5 5 5 5 5 5 4 5 5 5 5 4 1.045* 3 5 5 5 5 5 1 4 4 1 4 2 *Applied at 250 g/ha

Experiment B2

[0150] A comparative test is performed to compare the efficacy of quinoline compounds of the present invention with quinoline compounds taught in WO2014/037342 and napthyridines taught in WO2013/092834. Seeds of a variety of test species were sown in standard soil in pots. After cultivation for one day (pre-emergence) or after 10 days cultivation (post-emergence) 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).

[0151] 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 for post-emergence and 21 days for pre-emergence and phytotoxicity evaluated using a five point scale (5=80-100%; 4=60-79%; 3=40-59%; 2=20-39%; 1=0-19%). Test Plants:—Eriochloa villosa (ERBVI), Panicum miliaceum (PANMI).

TABLE-US-00004 POST PRE Application Application (60 g/ha) (250 g/ha) Compound ERBVI PANMI ERBVI PANMI Compound 5 5 3 5 1.001 Compound 2.002 1 2 1 1 WO2013/092834 Compound 43-3 1 1 1 2 WO2014/037342

[0152] This result shows that the quinoline compounds of the present invention exhibit a surprisingly improved herbicidal effect, when applied either pre- or post-emergence, compared to known, structurally similar compounds.