HERBICIDAL CYCLOHEXANEDIONE DERIVATIVES

Abstract

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

##STR00001##

Claims

1. A compound of Formula (I) ##STR00090## wherein R.sup.1 is selected from methyl, ethynyl, 1-propynyl, phenyl and a 5 or 6 membered heteroaryl which comprises one or two nitrogen heteroatoms, said phenyl and heteroaryl optionally substituted by one or two R.sup.15 substituents; R.sup.2 is ethyl or chloro; R.sup.3 is selected from the group consisting of methyl, ethyl, methoxy and chloro; R.sup.4 is selected from the group consisting of C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy-, C.sub.1-C.sub.4haloalkyl, —C(═O)C.sub.1-C.sub.4alkyl, —C(═O)C.sub.1-C.sub.4haloalkyl, —S(O).sub.nC.sub.1-C.sub.6alkyl, —S(O).sub.nC.sub.1-C.sub.6haloalkyl, —S(O).sub.n—(CH.sub.2).sub.n—C.sub.3-C.sub.6cycloalkyl, —S(O).sub.1C(R.sup.11)R.sup.12R.sup.13, —C(O)H, —C(O)—(CH.sub.2).sub.n—C.sub.3-C.sub.6cycloalkyl, —C(O)C(R.sup.11)R.sup.12R.sup.13, —C(O)C.sub.2-C.sub.4alkenyl, —C(O)(CR.sup.9R.sup.10)CN, —C(O)(CR.sup.9R.sup.10)(CR.sup.9R.sup.10)CN, —C(O)CH.sub.2C(O)—C.sub.1-C.sub.6alkyl, —C(O)CH.sub.2OC(O)—C.sub.1-C.sub.6alkyl, —C(O)OC.sub.1-C.sub.6alkyl, —C(O)OC.sub.1-C.sub.6haloalkyl, —C(O)(CH.sub.2).sub.nS(O).sub.nC.sub.1-C.sub.6alkyl —C(O)C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.6alkyl, —C(O)C.sub.1-C.sub.3alkoxyC.sub.2-C.sub.6alkenyl, —C(O)C.sub.1-C.sub.3alkoxyC.sub.2-C.sub.6alkynyl, —C(O)C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.6haloalkyl, —C(O)C.sub.1-C.sub.3alkoxyC.sub.3-C.sub.6cycloalkyl, —C(O)OC.sub.1-C.sub.3alkoxyC.sub.1-C.sub.6alkyl, —C(O)C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkoxyC.sub.1-C.sub.6alkyl, —C(O)(CH.sub.2).sub.n—NR.sup.5R.sup.6, —C(O)—(CH.sub.2).sub.n—NR.sup.7C(O)R.sup.8, —C(O)—(CH.sub.2).sub.n—O—N═CR.sup.5R.sup.5, —CN, —S(O).sub.2NR.sup.16R.sup.17, —S(O)(═NR.sup.18)R.sup.19, —C(O)C(O)R.sup.20, —C(O)C(R.sup.23)═N—O—R.sup.24 or —C(O)C(R.sup.23)═N—NR.sup.25R.sup.26, —(CH.sub.2).sub.n-phenyl, —C(O)—(CH.sub.2).sub.n-phenyl, —S(O).sub.n—(CH.sub.2).sub.n-phenyl, -heterocyclyl, —C(O)—(CH.sub.2).sub.n-heterocyclyl, —C(O)(CH.sub.2).sub.n—(CH.sub.2).sub.n heterocyclyl, —S(O).sub.n—(CH.sub.2).sub.n-heterocyclyl, wherein each heterocyclyl is a 5- or 6-membered heterocyclyl which may be aromatic, saturated or partially saturated and can contain from 1 to 4 heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulphur, and wherein said heterocyclyl or phenyl groups are optionally substituted by one, two or three substituents independently selected from the group consisting of C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3alkoxy, C.sub.2-C.sub.3alkenyl, C.sub.2-C.sub.3alkynyl, halogen, cyano and nitro; R.sup.5 is independently selected from the group consisting of hydrogen and C.sub.1-C.sub.6 alkyl; R.sup.6 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.6haloalkyl, hydroxyl-, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6 cycloalkyl, —C.sub.1-C.sub.4alkoxyC.sub.1-C.sub.6alkyl, —C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.6haloalkyl, —(CR.sup.9R.sup.10)C.sub.1-C.sub.6haloalkyl, —(CR.sup.9R.sup.10)C(O)NR.sup.5R.sup.5, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally substituted by one, two or three substituents independently selected from the group consisting of C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.2-C.sub.3 alkenyl, C.sub.2-C.sub.3 alkynyl, halogen, cyano and nitro; or R.sup.5 and R.sup.6 together form —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2—; and R.sup.7 is selected from the group consisting of hydrogen and C.sub.1-C.sub.6 alkyl; R.sup.8 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 cycloalkyl, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally substituted by one, two or three substituents independently selected from the group consisting of C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.2-C.sub.3 alkenyl, C.sub.2-C.sub.3 alkynyl, halogen, cyano and nitro; R.sup.9 is hydrogen or methyl; R.sup.10 is hydrogen or methyl; or R.sup.9 and R.sup.10 together form —CH.sub.2CH.sub.2—; and R.sup.11 is hydrogen or methyl; R.sup.12 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl, hydroxyl and C.sub.1-C.sub.6 alkoxy-; R.sup.13 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl, hydroxyl and C.sub.1-C.sub.6 alkoxy; or R.sup.12 and R.sup.13 together form —CH.sub.2—X—CH.sub.2—; and X is selected from the group consisting of O, S and N—R.sup.14; R.sup.14 is selected from the group consisting of hydrogen, C.sub.1-C.sub.3 alkyl and C.sub.1-C.sub.3 alkoxy-; R.sup.15 is independently selected from the group consisting of C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, cyano and halogen; R.sup.16 is hydrogen or C.sub.1-C.sub.6alkyl; and R.sup.17 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6 alkoxy-C.sub.1-C.sub.3alkyl-, —C(O)C.sub.1-C.sub.6alkyl, —C(O)OC.sub.1-C.sub.6alkyl and CH.sub.2CN; or R.sup.16 and R.sup.17 together form —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2S(O).sub.2CH.sub.2CH.sub.2—; R.sup.18 is hydrogen or C.sub.1-C.sub.6alkyl; R.sup.19 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6cycloalkyl, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally substituted by one, two or three substituents independently selected from the group consisting of C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.2-C.sub.3 alkenyl, C.sub.2-C.sub.3 alkynyl, halogen, cyano and nitro; R.sup.20 is selected from the group consisting of C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy-, C.sub.1-C.sub.6haloalkoxy, —NR.sup.21R.sup.22, phenyl and -pyridyl, wherein the phenyl and pyridyl are optionally substituted by one, two or three substituents independently selected from the group consisting of C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.2-C.sub.3 alkenyl, C.sub.2-C.sub.3 alkynyl, halogen, cyano and nitro; R.sup.21 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6 cycloalkyl, C.sub.1-C.sub.6haloalkyl- and C.sub.1-C.sub.6haloalkoxy-, —C(O)C.sub.1-C.sub.6alkyl, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally substituted by one, two or three substituents independently selected from the group consisting of C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.2-C.sub.3 alkenyl, C.sub.2-C.sub.3 alkynyl, halogen, cyano and nitro; R.sup.22 is hydrogen or C.sub.1-C.sub.6alkyl; or R.sup.21 and R.sup.22 together form —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2—; R.sup.23 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy- and C.sub.1-C.sub.6haloalkoxy-; R.sup.24 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6cycloalkyl, —CH.sub.2CN, tetrahydropyranyl-, phenyl and -pyridyl, wherein the phenyl and pyridyl are optionally substituted by one, two or three substituents independently selected from the group consisting of C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3alkoxy, C.sub.2-C.sub.3alkenyl, C.sub.2-C.sub.3alkynyl, halogen, cyano and nitro; R.sup.25 is hydrogen or C.sub.1-C.sub.6 alkyl; R.sup.26 is hydrogen or C.sub.1-C.sub.6 alkyl; and G is selected from the group consisting of hydrogen, —(CH.sub.2).sub.n—R.sup.a, —C(O)—R.sup.a, —C(O)—(CR.sup.cR.sup.d).sub.n—O—R.sup.b, —C(O)—(CR.sup.cR.sup.d).sub.n—S—R.sup.b, —C(O)NR.sup.aR.sup.a, —S(O).sub.2—R.sup.a and C.sub.1-C.sub.3alkoxy-C.sub.1-C.sub.3alkyl-; R.sup.a is independently selected from the group consisting of hydrogen, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.2-C.sub.8alkenyl, C.sub.2-C.sub.8alkynyl, C.sub.3-C.sub.6cycloalkyl, heterocyclyl and phenyl wherein said heterocyclyl and phenyl groups are optionally substituted by one, two or three substituents independently selected from the group consisting of C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3alkoxy, C.sub.2-C.sub.3alkenyl, C.sub.2-C.sub.3alkynyl, halogen, cyano and nitro; R.sup.b is selected from the group consisting of C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.2-C.sub.8alkenyl, C.sub.2-C.sub.8alkynyl, C.sub.3-C.sub.6 cycloalkyl, heterocyclyl and phenyl wherein said heterocyclyl and phenyl groups are optionally substituted by one, two or three substituents independently selected from the group consisting of C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3alkoxy, C.sub.2-C.sub.3alkenyl, C.sub.2-C.sub.3alkynyl, halogen, cyano and nitro; R.sup.c is hydrogen or C.sub.1-C.sub.3 alkyl; R.sup.d is hydrogen or C.sub.1-C.sub.3 alkyl; and n is independently 0, 1 or 2; or an agriculturally acceptable salt thereof.

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

3. A compound according to claim 1, wherein R.sup.1 is a 5 or 6 membered heteroaryl which comprises one or two nitrogen heteroatoms, said phenyl and heteroaryl optionally substituted by one or two R.sup.15 substituents.

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

5. A compound according to claim 1, wherein R.sup.3 is methoxy.

6. A compound according to claim 1, wherein R.sup.3 is chloro.

7. A compound according to claim 1, wherein R.sup.4 is —C(═O)C.sub.1-C.sub.4alkyl.

8. A compound according to claim 1, wherein G is hydrogen.

9. A compound according to claim 1, wherein G is —C(O)C.sub.1-C.sub.6alkyl.

10. A compound according to claim 1, wherein G is —C(O)—O—C.sub.1-C.sub.6alkyl.

11. A herbicidal composition comprising a compound of Formula (I) 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.

Description

EXAMPLE 1

3-benzoyl-9-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-3-azaspiro[5.5]undecane-8,10-dione (Example A3)

[0139] ##STR00018##

Step 1: Synthesis of O3-tert-butyl 011-ethyl 8,10-dioxo-3-azaspiro[5.5]undecane-3,11-dicarboxylate

[0140] ##STR00019##

[0141] Tert-Butyl 4-acetonylidenepiperidine-1-carboxylate (12.9 g, 54.0 mmol) was dissolved in ethanol (100 mL) and diethyl propanedioate (54.12 mmol) was added. The reaction mixture was treated with a solution of sodium ethoxide which had been prepared by the addition of sodium (54.1 mmol) to ethanol (30 mL) at room temperature. The reaction mixture was stirred at RT for 3 hours then heated to reflux for 1 hour. Upon cooling the reaction mixture was concentrated in vacuo to give O3-tert-butyl 011-ethyl 8,10-dioxo-3-azaspiro[5.5]undecane-3,11-dicarboxylate as an oil, which was used in the next step without further purification.

Step 2: Synthesis of tert-butyl 8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate

[0142] ##STR00020##

[0143] Crude O3-tert-butyl 011-ethyl 8,10-dioxo-3-azaspiro[5.5]undecane-3,11-dicarboxylate from step 1 was dissolved in aqueous NaOH (12M, 5 mL) and stirred for 5 hours. The reaction mixture was acidified to pH 6 by the addition of conc HCl at 0° C., and extracted with EtOAc. The organics were dried and concentrated in vacuo to leave a yellow solid which on trituration yielded a pale pink powder of tert-butyl 8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate. The aqueous layer was further acidified to pH 2 by the addition of conc HCl and extracted with EtOAc. The organics were dried and concentrated in vacuo to leave a pale yellow solid which on trituration with ether gave a further batch of pale yellow powder of tert-butyl 8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (3.914 g, 13.91 mmol).

[0144] 1H NMR (400 MHz, CDCl.sub.3) 3.51-3.25 (m, 6H), 2.69-2.54 (m, 4H), 1.47-1.43 (m, 9H), 1.44-1.39 (m, 4H).

Step 3: Synthesis of tert-butyl 9-(4-bromo-2-chloro-6-methoxy-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate

[0145] ##STR00021##

[0146] To a stirred solution of tert-butyl 8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (8.56 g, 30.4 mmol) in chloroform (320.0 mL) under nitrogen was added 4-Dimethylaminopyridine (23.2 g, 190 mmol). The reaction mixture was stirred for 15 mins at RT, then toluene (65.0 mL) was added followed by the addition of [diacetoxy-(4-bromo-2-chloro-6-methoxy-phenyl)plumbyl] acetate (for a synthesis see WO 2014096289) (23.0 g, 38.0 mmol). The reaction mixture was stirred at 80° C. for 4 h and then at RT overnight. The reaction mixture was cooled in an ice water bath, acidified with citric acid solution, filtered through celite pad. The filtrate was layer separated and the aqueous layer extracted with chloroform (×3). The combined organics were washed with brine, dried over Na.sub.2SO.sub.4, filtered and filtrate evaporated to obtained crude product, which was purified by flash column chromatography to give tert-butyl 9-(4-bromo-2-chloro-6-methoxy-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (6.2 g) as a brown foam.

[0147] LCMS(NH4OAc:ACN): M−H=500

Step 4: Synthesis of tert-butyl 9-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate

[0148] ##STR00022##

[0149] A mixture of tert-butyl 9-(4-bromo-2-chloro-6-methoxy-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (0.960 g, 1.92 mmol), and 4-diphenylphosphanylbutyl(diphenyl)phosphane (0.163 g, 0.383 mmol, and Bis(triphenylphosphine)palladium(II) chloride (0.135 g, 0.192 mmol) and 2-Butynoic acid (0.483 g, 5.75 mmol) was taken in a round bottomed flask. A vacuum/argon back fill cycle was repeated for two times, then treated with anhydrous DMSO (20 mL) and again vacuum/argon back fill cycle repeated for three times then 1,8-Diazabicyclo[5.4.0]undec-7-ene (1.75 g, 11.5 mmol) was added. The reaction mixture was stirred at 110° C. overnight and then the reaction mixture was allowed stand for the weekend at RT. The reaction mixture was acidified with 10% citric acid solution and extracted with EtOAc (×3). The combined organics were dried over Na.sub.2SO.sub.4, filtered and concentrated to obtain crude product as a brown gummy liquid.

[0150] LC-MS: (M+H=460, RT=2.87)

Step 5: Synthesis of 9-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-3-azoniaspiro[5.5]undecane-8,10-dione hydrochloride

[0151] ##STR00023##

[0152] A mixture of tert-butyl 9-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (4.60 g, 10.0 mmol) was stirred at RT in HCl in Dioxane (4M, 25.0 mL) for 2 h. The reaction mixture was concentrated and triturated with EtOAc to obtain 3.90 g of 9-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-3-azoniaspiro[5.5]undecane-8,10-dione hydrochloride as an off white solid LC-MS: M+H=360

Step 6: 3-benzoyl-9-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-3-azaspiro[5.5]undecane-8,10-dione (Example A3)

[0153] ##STR00024##

[0154] To a mixture of 9-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-3-azaspiro[5.5]undecane-8,10-dione hydrochloride (0.25 g, 0.5236 mmol), benzoic acid (0.06394 g, 0.5236 mmol) and HATU (0.220 g, 0.5760 mmol) in anhydrous DCM (3.46 g, 2.618 mL, 40.6 mmol) was added N,N-diisopropylethylamine (0.204 g, 0.270 mL, 1.571 mmol). The resulting mixture was stirred at RT overnight. The reaction mixture was poured into 2M HCl and extracted with DCM. The organics were passed through a phase-sep cartridge and the filtrate evaporated. The crude residue was submitted to FractionLynx reverse-phase HPLC purification (TFA method), product containing fractions were isolated and then freeze-dried overnight to give 3-benzoyl-9-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-3-azaspiro[5.5]undecane-8,10-dione (example A3) (113 mg, 47%) as a white solid.

[0155] 1H NMR (400 MHz, Methanol-d4) δ=7.50-7.38 (m, 5H), 7.00 (br s, 1H), 6.87 (br s, 1H), 3.87-3.60 (m, 5H), 3.47 (m, 2H), 2.61-2.60 (m, 4H), 2.02 (s, 3H), 1.85-1.65 (m, 4H)

EXAMPLE 2

6-[4-[3-(cyclopropanecarbonyl)-8,10-dioxo-3-azaspiro[5.5]undecan-9-yl]-3-ethyl-5-methyl-phenyl]pyridine-3-carbonitrile (Example A51)

[0156] ##STR00025##

Step 1: Synthesis of tert-butyl 8,10-dioxo-9-(phenyl-$I″{circumflex over ( )}{3}-iodanylidene)-3-azaspiro[5.5]undecane-3-carboxylate

[0157] ##STR00026##

[0158] A solution of tert-butyl 8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (915 mg, 3.252 mmol) and sodium carbonate (532 mg, 6.23 mmol) in water (11.8 mL) and ethanol (2.5 mL) was treated with (diacetoxyiodo)benzene (1.00 g, 2.961 mmol) and stirred at RT overnight. The precipitate was collected by filtration and washed with water and diethyl ether to give tert-butyl 8,10-dioxo-9-(phenyl-$1{3}-iodanylidene)-3-azaspiro[5.5]undecane-3-carboxylate (1.37 g, 91%) as a white solid.

[0159] 1H NMR (400 MHz, Methanol-d4) δ=7.85 (d, 2H), 7.55 (t, 1H), 7.40 (t, 2H), 3.46-3.34 (m, 4H), 2.58 (s, 4H), 1.52-1.46 (m, 4H), 1.44 (s, 9H)

Step 2: Synthesis of tert-butyl 9-(4-bromo-2-ethyl-6-methyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate

[0160] ##STR00027##

[0161] A mixture of (4-bromo-2-ethyl-6-methyl-phenyl)boronic acid (1.78 g, 5.869 mmol), tert-butyl 8,10-dioxo-9-(phenyl-$1{3}-iodanylidene)-3-azaspiro[5.5]undecane-3-carboxylate (1.374 g, 2.701 mmol), palladium(II) acetate (32 mg, 0.1425 mmol) and lithium hydroxide (377 mg, 15.7424 mmol) was treated with 1,2-dimethoxyethane (18 mL) and water (3 mL) The reaction vessel was evacuated and back-filled with nitrogen three times and the mixture was stirred at 50° C. overnight. The mixture was then allowed to cool to RT before being concentrated, taken up in water, acidified with aqueous ammonium chloride and extracted with dichloromethane. The organics were dried, concentrated and purified by flash column chromatography to give tert-butyl 9-(4-bromo-2-ethyl-6-methyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (808 mg, 53%) as a brown gum.

[0162] 1H NMR (400 MHz, CDCl.sub.3) δ=7.30 (s, 2H), 5.42 (s, 1H), 3.57-3.41 (m, 4H), 2.60 (s, 2H), 2.53 (s, 2H), 2.43-2.28 (m, 2H), 2.06 (s, 3H), 1.69-1.61 (m, 4H), 1.47 (s, 9H), 1.08 (t, 3H)

Step 3: Synthesis of tert-butyl 9-[2-ethyl-6-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate

[0163] ##STR00028##

[0164] A mixture of tert-butyl 9-(4-bromo-2-ethyl-6-methyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (300 mg, 0.533 mmol), bis(pinacolato)diboron (172 mg, 0.643 mmol), 1,1′-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (47 mg, 0.056 mmol) and potassium acetate (109 mg, 1.09 mmol) was treated with 1,4-dioxane (5.3 mL, 61 mmol, 99 mass %, 120). The vessel was evacuated and back-filled with nitrogen three times and the mixture was stirred at 100° C. for 4 hours. On cooling, the reaction mixture was concentrated and purified by flash column chromatography to give tert-butyl 9-[2-ethyl-6-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (338 mg, 84%) as an orange gum.

[0165] 1H NMR (400 MHz, CDCl.sub.3) δ=7.60 (d, 2H), 5.41-5.39 (m, 1H), 3.58-3.39 (m, 4H), 2.63-2.58 (m, 2H), 2.53 (s, 2H), 2.47-2.33 (m, 2H), 2.10 (s, 3H), 1.70-1.62 (m, 4H), 1.49-1.46 (m, 9H), 1.35 (s, 12H), 1.08 (t, 3H)

Step 4: Synthesis of tert-butyl 9-[4-(5-cyano-2-pyridyl)-2-ethyl-6-methyl-phenyl]-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate

[0166] ##STR00029##

[0167] A mixture of tert-butyl 9-[2-ethyl-6-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (338 mg, 0.450 mmol), 2-bromo-5-cyanopyridine (121 mg, 0.628 mmol), 1,1′-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (84 mg, 0.100 mmol) and potassium phosphate tribasic (383 mg, 1.804 mmol) was treated with 1,2-dimethoxyethane (4.5 mL) and water (2.3 mL). The reaction vessel was evacuated and back-filled with nitrogen three times and the mixture was stirred at 80° C. for an hour. On cooling, the mixture was diluted with 10% aqueous citric acid and extracted with dichloromethane. The organics were dried, concentrated and purified by flash column chromatography to give tert-butyl 9-[4-(5-cyano-2-pyridyl)-2-ethyl-6-methyl-phenyl]-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (213 mg, 85%) as a pale yellow solid.

[0168] 1H NMR (400 MHz, CDCl3) δ=8.93 (dd, 1H), 8.01 (dd, 1H), 7.84 (dd, 1H), 7.79 (d, 2H), 5.58-5.52 (m, 1H), 3.57-3.41 (m, 4H), 2.69-2.61 (m, 2H), 2.59-2.54 (m, 2H), 2.53-2.43 (m, 2H), 2.23-2.17 (m, 3H), 1.73-1.64 (m, 4H), 1.48 (s, 9H), 1.15 (t, 3H)

Step 5: Synthesis of 6-[4-(8,10-dioxo-3-azaspiro[5.5]undecan-9-yl)-3-ethyl-5-methyl-phenyl]pyridine-3-carbonitrile hydrochloride

[0169] ##STR00030##

[0170] A solution of tert-butyl 9-[4-(5-cyano-2-pyridyl)-2-ethyl-6-methyl-phenyl]-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (213 mg, 0.382 mmol) in dichloromethane (2.0 mL) was treated with 4M hydrogen chloride in dioxane (1.0 mL, 4.0 mmol) and was stirred at RT for 2.5 hours. The mixture was concentrated and the residues were triturated from diethyl ether to give 6-[4-(8,10-dioxo-3-azaspiro[5.5]undecan-9-yl)-3-ethyl-5-methyl-phenyl]pyridine-3-carbonitrile hydrochloride (260 mg, 100%) as a pale yellow solid.

[0171] 1H NMR (400 MHz, Methanol-d4) δ=9.00-8.94 (m, 1H), 8.23 (dd, 1H), 8.08 (d, 1H), 7.86-7.76 (m, 2H), 3.38-3.26 (m, 4H), 2.71 (s, 4H), 2.48 (q, 2H), 2.16 (s, 3H), 1.98-1.92 (m, 4H), 1.14 (t, 3H)

Step 6: Synthesis of 6-[4-[3-(cyclopropanecarbonyl)-8,10-dioxo-3-azaspiro[5.5]undecan-9-yl]-3-ethyl-5-methyl-phenyl]pyridine-3-carbonitrile (Example A51)

[0172] ##STR00031##

[0173] A suspension of 6-[4-(8,10-dioxo-3-azaspiro[5.5]undecan-9-yl)-3-ethyl-5-methyl-phenyl]pyridine-3-carbonitrile; dihydrochloride (260 mg, 0.382 mmol) and HATU (182 mg, 0.476 mmol) in dichloromethane (6.0 mL) was treated with triethyamine (260 μL, 1.93 mmol) and cyclopropanecarboxylic acid (50 μL, 0.628 mmol) and the mixture was stirred at RT for an hour. The mixture was concentrated, diluted with 0.5 M hydrochloric acid and extracted with dichloromethane. The organics were dried, concentrated and purified by flash column chromatography to give 6-[4-[3-(cyclopropanecarbonyl)-8,10-dioxo-3-azaspiro[5.5]undecan-9-yl]-3-ethyl-5-methyl-phenyl]pyridine-3-carbonitrile (156 mg, 82%) as a cream coloured solid.

[0174] 1H NMR (400 MHz, Methanol-d4) δ=8.93 (d, 1H), 8.17 (dd, 1H), 8.04 (d, 1H), 7.81 (s, 1H), 7.79 (s, 1H), 3.91-3.78 (m, 2H), 3.73-3.61 (m, 2H), 2.66 (s, 4H), 2.54-2.43 (q, 2H), 2.16 (s, 3H), 2.05-1.94 (m, 1H), 1.88-1.77 (m, 2H), 1.75-1.63 (m, 2H), 1.13 (t, 3H), 0.94-0.77 (m, 4H).

[0175] Examples of herbicidal compounds of the present invention.

TABLE-US-00001 TABLE 1 CMP Structure NMR A1 [00032] 1H NMR (400 MHz, CDCl.sub.3) 7.11 (s, 1H), 6.84 (s, 1H), 3.73 (s, 3H), 3.69-3.55 (m, 2H), 3.49 (s, 2H), 2.57 (s, 4H), 2.12 (s, 3H), 2.06 (s, 3H), 1.82-1.62 (m, 4H) A2 [00033] 1H NMR (400 MHz, Methanol-d4) δ = 6.99 (s, 1H), 6.85 (s, 1H), 3.69 (s, 3H), 3.34-3.30 (4H), 3.07-3.02 (q, 2H), 2.51 (s, 4H), 2.01 (s, 3H), 1.81-1.75 (m, 4H), 1.34-1.28 (m, 3H) A3 [00034] 1H NMR (400 MHz, Methanol-d4) δ = 7.50- 7.38 (m, 5H), 7.00 (br s, 1H), 6.87 (br s, 1H), 3.87-3.60 (m, 5H), 3.47 (m, 2H), 2.61- 2.60 (m, 4H), 2.02 (s, 3H), 1.85-1.65 (m, 4H) A4 [00035] 1H NMR (400 MHz, Methanol-d4) δ = 8.58- 8.57 (d, 1H), 7.89 (t, 1H), 7.55-7.49 (d, 1H), 7.43 (t, 1H), 6.96 (s, 1H), 6.86 (s, 1H), 3.65 (s, 3H), 3.54-3.44 (m, 4H), 2.45 (s, 4H), 2.04 (s, 3H), 1.66 (bs, 4H) A5 [00036] 1H NMR (400 MHz, Methanol-d4) δ = 6.99 (s, 1H), 6.86 (s, 1H), 4.15 (s, 2H), 3.69 (s, 3H), 3.62-3.60 (m, 2H), 3.49 (m, 2H), 3.39 (s, 3H), 2.55 (s, 4H), 2.01 (s, 3H), 1.78-1.66 (m, 4H) A6 [00037] 1H NMR (400 MHz, Methanol-d4) δ = 6.99 (s, 1H), 6.86 (s, 1H), 3.69 (s, 3H), 3.38 (m, 4H), 2.51 (s, 4H), 2.01 (s, 3H), 1.70-1.63 (m, 4H), 1.32 (s, 9H) A7 [00038] 1H NMR (400 MHz, Methanol-d4) δ = 6.99 (s, 1H), 6.85 (s, 1H), 3.69 (s, 3H), 3.51 (bs, 4H), 2.54 (s, 4H), 2.01 (s, 3H), 1.78-1.72 (m, 4H), 1.22 (s, 9H) A8 [00039] 1H NMR (400 MHz, Methanol-d4) δ = 7.00 (s, 1H), 6.86 (s, 1H), 3.79 (bs, 2H), 3.69 (s, 3H), 3.62 (bs, 2H), 2.56 (s, 4H), 2.01 (s, 3H), 1.97-1.96 (m, 1H), 1.80- 1.76 (m, 2H), 1.68-1.65 (m, 2H), 0.86-0.85 (ill.res.d, 2H), 0.81- 0.79 (d, 2H) A9 [00040] 1H NMR (400 MHz, Methanol-d4) δ = 7.00 (s, 1H), 6.87 (s, 1H), 6.47 (t, 1H), 3.70-3.62 (m, 7H), 2.57 (s, 4H), 2.01 (s, 3H), 1.81-1.71 (m, 4H) A10 [00041] 1H NMR (400 MHz, Methanol-d4) δ = 6.99 (s, 1H), 6.86 (s, 1H), 3.70-3.66 (m, 7H), 2.54 (s, 4H), 2.01 (s, 3H), 1.73-1.66 (m, 4H), 1.27 (s, 9H) A11 [00042] 1H NMR (400 MHz, Methanol-d4) δ = 8.68- 8.67 (d, 1H), 8.19-8.17 (d, 1H), 8.03-7.99 (m, 1H), 7.64-7.61 (m, 1H), 6.99 (s, 1H), 6.86 (s, 1H), 3.69 (s, 3H), 3.64 (m, 4H), 2.57 (s, 4H), 2.01 (s, 3H), 1.84-1.77 (m, 4H) A12 [00043] 1H NMR (400 MHz, Methanol-d4) δ = 6.98 (s, 1H), 6.86 (s, 1H), 3.61 (s, 3H), 3.45 (bs, 2H), 3.31 (bs, 2H), 2.42 (s, 4H), 2.02 (s, 3H), 1.61 (m, 2H), 1.52 (m, 2H) A13 [00044] 1H NMR (400 MHz, Methanol-d4) δ = 8.96- 8.95 (ill.res.d, 1H), 8.22- 8.19 (dd, 1H), 8.11-8.09 (d, 1H), 7.78 (s, 1H), 7.66 (s, 1H), 3.83 (s, 3H), 3.63 (t, 2H), 3.57 (t, 2H), 2.57 (s, 4H), 2.11-2.10 (3H), 1.81-1.77 (m, 2H), 1.70 (t, 2H) A14 [00045] 1H NMR (400 MHz, Methanol-d4) δ = 7.34 (s, 2H), 3.62 (t, 2H), 3.56 (t, 2H), 2.60 (s, 4H), 2.09 (s, 3H), 2.03 (s, 3H), 1.78 (t, 2H), 1.68 (t, 2H) (m, 4H) A15 [00046] 1H NMR (400 MHz, Methanol-d4) δ = 7.34 (s, 2H), 3.88 (s, 2H), 3.64 (t, 2H), 3.49 (t, 2H), 2.61 (s, 4H), 2.03 (s, 3H), 1.80 (t, 2H), 1.72 (t, 2H) A16 [00047] 1H NMR (400 MHz, Methanol-d4) δ = 7.34 (s, 2H), 6.46 (t, 1H), 3.69-3.62 (m, 4H), 2.63 (s, 4H), 2.03 (s, 3H), 1.82-1.74 (m, 4H) A17 [00048] 1H NMR (400 MHz, Methanol-d4) δ = 8.67 (d, 1H), 8.18 (d, 1H), 8.02 (t, 1H), 7.64-7.63 (m, 1H), 7.34 (s, 2H), 3.65 (t, 4H), 2.63 (s, 4H), 2.03 (s, 3H), 1.83 (t, 4H) A18 [00049] 1H NMR (400 MHz, Methanol-d4) δ = 7.30 (s, 2H), 6.48 (t, 1H), 4.62 (s, 2H), 3.68-3.57 (m, 2H), 3.51-3.43 (m, 2H), 2.49 (s, 4H), 2.02 (s, 3H), 1.78-1.70 (m, 4H) A19 [00050] 1H NMR (400 MHz, Methanol-d4) δ = 8.93 (s, 1H), 8.26 (d, 1H), 7.78 (d, 1H), 6.99 (d, 1H), 6.86 (d, 1H), 3.83- 3.81 (m, 2H), 3.69 (d, 3H), 3.46-3.45 (m, 2H), 2.64-2.60 (m, 4H), 2.02 (s, 3H), 1.87-1.81 (m, 2H), 1.77-1.72 (m, 2H) A20 [00051] 1H NMR (400 MHz, Methanol-d4) δ = 8.65 (br s, 2H), 7.45 (d, 2H), 6.99 (d, 1H), 6.86 (d, 1H), 3.83-3.77 (m, 2H), 3.68 (d, 3H), 3.42-3.33 (m, 2H), 2.67-2.52 (m, 4H), 2.02 (s, 3H), 1.88- 1.78 (m, 2H), 1.72-1.69 (m, 2H) A21 [00052] 1H NMR (400 MHz, Methanol-d4) δ = 8.63 (s, 2H), 7.90 (d, 1H), 7.52 (t, 1H), 6.99 (s, 1H), 6.86 (s, 1H), 3.82 (br s, 2H), 3.70-3.66 (br d, 3H), 3.47 (br s, 2H), 2.60 (s, 4H), 2.02 (s, 3H), 1.82-1.72 (m, 4H) A22 [00053] 1H NMR (400 MHz, Methanol-d4) δ = 9.27- 9.23 (m, 1H), 7.91-7.83 (m, 2H), 6.99 (d, 1H), 6.86 (d, 1H), 3.90-3.82 (m, 2H), 3.69 (d, 3H), 3.56-3.43 (m, 2H), 2.66- 2.57 (m, 4H), 2.02 (s, 3H), 1.86-1.77 (m, 4H) A23 [00054] 1H NMR (400 MHz, Methanol-d4) δ = 8.17 (t, 1H), 7.90-7.84 (m, 2H), 6.99 (d, 1H), 6.86 (d, 1H), 3.84-3.82 (m, 2H), 3.69 (d, 3H), 3.54-3.45 (m, 2H), 2.64-2.56 (m, 4H), 2.02 (s, 3H), 1.88- 1.80 (m, 2H), 1.78-1.75 (m, 2H) A24 [00055] 1H NMR (400 MHz, Methanol-d4) δ = 7.77 (t, 1H), 7.14 (d, 1H), 7.00 (d, 1H), 6.87 (d, 2H), 3.92 (d, 3H), 3.83-3.78 (m, 2H), 3.69 (d, 3H), 3.60-3.54 (m, 2H), 2.64- 2.54 (m, 4H), 2.02 (s, 3H), 1.82-1.78 (m, 4H) A25 [00056] 1H NMR (400 MHz, Methanol-d4) δ = 8.26 (d, 1H), 7.58 (d, 1H), 7.51-7.45 (m, 1H), 6.99 (br s, 1H), 6.86 (br s, 1H), 3.91 (s, 3H), 3.79 (br s, 2H), 3.69 (d, 3H), 3.54 (br s, 2H), 2.98 (s, 4H), 2.02 (s, 3H), 1.85- 1.68 (m, 4H) A26 [00057] 1H NMR (400 MHz, Methanol-d4) δ = 8.38 (d, 1H), 7.12 (s, 1H), 7.05 (d, 1H), 6.99 (d, 1H), 6.86 (d, 1H), 3.92 (s, 3H), 3.83-3.76 (m, 2H), 3.69 (d, 3H), 3.45- 3.37 (m, 2H), 2.64-2.55 (m, 4H), 2.02 (s, 3H), 1.86-1.79 (m, 2H), 1.78- 1.66 (m, 2H) A27 [00058] 1H NMR (400 MHz, Methanol-d4) δ = 8.31 (d, 1H), 7.33 (d, 1H), 7.14 (s, 1H), 7.00 (d, 1H), 6.86 (d, 1H), 3.83- 3.77 (m, 2H), 3.69 (d, 3H), 3.42-3.36 (m, 2H), 2.64-2.55 (m, 4H), 2.02 (s, 3H), 1.88-1.68 (m, 4H) A28 [00059] 1H NMR (400 MHz, Methanol-d4) δ = 8.69 (s, 1H), 8.54 (s, 1H), 6.99 (d, 1H), 6.86 (d, 1H), 3.85-3.79 (m, 2H), 3.69 (d, 3H), 3.60-3.53 (m, 2H), 2.64-2.55 (m, 7H), 2.01 (s, 3H), 1.87- 1.71 (m, 4H) A29 [00060] 1H NMR (400 MHz, Methanol-d4) δ = 7.76 (d, 1H), 7.27 (d, 1H), 7.00 (d, 1H), 6.87 (d, 1H), 4.14 (s, 3H), 3.88- 3.80 (m, 2H), 3.69 (d, 3H), 3.62-3.55 (m, 2H), 2.65-2.56 (m, 4H), 2.02 (s, 3H), 1.89-1.74 (m, 4H) A30 [00061] 1H NMR (400 MHz, DMSO-d6) δ = 8.58 (br s, 1H), 8.47 (br s, 1H), 6.97 (d, 1H), 6.86 (d, 1H), 3.69 (br s, 2H), 3.61 (d, 3H), 3.15 (br s, 2H), 2.50-2.40 (m, 7H), 2.05 (s, 3H), 1.72-1.50 (m, 4H) A31 [00062] 1H NMR (400 MHz, Methanol-d4) δ = 7.52- 7.45 (m, 1H), 7.42-7.36 (m, 1H), 7.31-7.25 (m, 1H), 7.23-7.16 (m, 1H), 6.99 (d, 1H), 6.85 (d, 1H), 3.89-3.80 (m, 2H), 3.68 (d, 3H), 3.41-3.33 (m, 2H), 2.64-2.52 (m, 4H), 2.03-2.00 (m, 3H), 1.88-1.65 (m, 4H) A32 [00063] 1H NMR (400 MHz, Methanol-d4) δ = 7.69- 7.61 (m, 2H), 7.50-7.39 (m, 5H), 7.23 (br s, 1H), 7.17 (t, 2H), 7.07 (br s, 1H), 3.88-3.70 (m, 5H), 3.48 (br s, 2H), 2.63 (s, 4H), 1.90-1.66 (m, 4H) A33 [00064] 1H NMR (400 MHz, Methanol-d4) δ = 8.78 (s, 2H), 8.06 (s, 1H), 7.94 (s, 1H), 7.49-7.40 (m, 5H), 3.89-3.75 (m, 5H), 3.48 (br s, 2H), 2.63 (s, 4H), 1.90-1.67 (m, 4H) A34 [00065] 1H NMR (400 MHz, Methanol-d4) δ = 8.96 (d, 1H), 8.20 (dd, 1H), 8.10 (d, 1H), 7.78 (s, 1H), 7.66 (s, 1H), 7.48- 7.39 (m, 5H), 3.88-3.76 (m, 5H), 3.48 (br s, 2H), 2.70-2.55 (m, 4H), 1.90- 1.67 (m, 4H) A35 [00066] 1H NMR (400 MHz, Methanol-d4) δ = 8.98- 8.97 (m, 1H), 8.22 (dd, 1H), 8.12 (dd, 1H), 7.80 (d, 1H), 7.68 (d, 1H), 3.85 (s, 3H), 3.85-3.80 (m, 2H), 3.68-3.61 (m, 2H), 2.63 (s, 4H), 2.03- 1.95 (m, 1H), 1.86-1.66 (m, 4H), 0.92-0.74 (m, 4H) A36 [00067] 1H NMR (400 MHz, Methanol-d4) δ = 6.99 (s, 1H), 6.85 (s, 1H), 5.97-5.89 (m, 1H), 5.30 (d, 1H), 5.19 (d, 1H), 4.20 (s, 2H), 4.04 (d, 2H), 3.69 (s, 3H), 3.66- 3.59 (m, 2H), 3.55-3.47 (m, 2H), 2.53 (s, 4H), 2.02 (s, 3H), 1.79-1.64 (m, 4H) A37 [00068] 1H NMR (400 MHz, Methanol-d4) δ = 7.00 (s, 1H), 6.86 (s, 1H), 3.70 (s, 3H), 3.66-3.59 (m, 2H), 3.58-3.52 (m, 2H), 2.79-2.71 (m, 1H), 2.57 (s, 4H), 2.02 (s, 3H), 1.81-1.69 (m, 4H), 0.81-0.75 (m, 2H), 0.59- 0.54 (m, 2H) A38 [00069] 1H NMR (400 MHz, Methanol-d4) δ = 7.00 (s, 1H), 6.87 (s, 1H), 4.18 (s, 2H), 3.70 (s, 3H), 3.65-3.59 (m, 2H), 3.58-3.50 (m, 2H), 3.45 (t, 2H), 2.56 (s, 4H), 2.02 (s, 3H), 1.80-1.59 (m, 6H), 0.94 (t, 3H) A39 [00070] 1H NMR (400 MHz, Methanol-d4) δ = 7.00 (s, 1H), 7.87 (s, 1H), 3.70 (s, 3H), 3.66-3.63 (m, 2H), 3.59-3.54 (m, 2H), 3.49 (q, 2H), 2.56 (s, 4H), 2.02 (s, 3H), 1.82-1.64 (m, 4H) A40 [00071] 1H NMR (400 MHz, Methanol-d4) δ = 7.38 (d, 2H), 7.02-6.96 (m, 3H), 6.86 (s, 1H), 3.83 (s, 3H), 3.80-3.48 (m, 7H), 2.58 (s, 4H), 2.01 (s, 3H), 1.75 (br s, 4H) A41 [00072] 1H NMR (400 MHz, Methanol-d4) δ = 7.36 (t, 1H), 7.05-6.93 (m, 4H), 6.85 (s, 1H), 3.82 (s, 3H), 3.78 (br s, 2H), 3.72-3.63 (m, 3H), 3.46 (br s, 2H), 2.57 (s, 4H), 2.01 (s, 3H), 1.87-1.78 (m, 2H), 1.76-1.63 (m, 2H) A42 [00073] 1H NMR (400 MHz, Methanol-d4) δ = 7.41 (t, 1H), 7.21 (d, 1H), 7.09- 6.96 (m, 3H), 6.85 (d, 1H), 3.85 (s, 3H), 3.79 (t, 2H), 3.68 (d, 3H), 3.33 (m, 2H), 2.62-2.48 (m, 4H), 2.01 (s, 3H), 1.82-1.56 (m, 4H) A43 [00074] 1H NMR (400 MHz, Methanol-d4) δ = 7.94 (d, 1H), 7.81 (d, 1H), 7.00 (s, 1H), 6.87 (s, 1H), 4.32 (br s, 2H), 3.81 (br s, 2H), 3.70 (s, 3H), 2.60 (s, 4H), 2.02 (s, 3H), 1.86-1.78 (m, 4H) A44 [00075] 1H NMR (400 MHz, Methanol-d4) δ = 7.48 (d, 1H), 7.00 (d, 1H), 6.87 (d, 1H), 6.47 (d, 1H), 3.90 (s, 3H), 3.84- 3.56 (m, 7H), 2.60 (s, 4H), 2.02 (s, 3H), 1.86- 1.68 (m, 4H) A45 [00076] 1H NMR (400 MHz, Methanol-d4) δ = 8.78 (s, 1H), 7.00 (d, 1H), 6.86 (s, 1H), 6.69 (s, 1H), 3.85-3.79 (m, 2H), 3.74-3.65 (m, 5H), 2.59 (s, 4H), 2.02 (s, 3H), 1.86-1.63 (m, 4H) A46 [00077] 1H NMR (400 MHz, Methanol-d4) δ = 6.99 (s, 1H), 6.87 (s, 1H), 3.69 (s, 3H), 3.33-3.24 (m, 4H), 2.83 (s, 6H), 2.54 (s, 4H), 2.02 (s, 3H), 1.75-1.67 (m, 4H) A47 [00078] 1H NMR (400 MHz, Methanol-d4) δ = 7.05 (d, 2H), 3.69-3.53 (m, 4H), 2.60 (s, 4H), 2.38- 2.29 (q, 2H), 2.11 (s, 3H), 2.03-1.97 (m, 6H), 1.79-1.71 (m, 2H), 1.71- 1.62 (m, 2H), 1.04 (t, 3H) A48 [00079] 1H NMR (400 MHz, Methanol-d4) δ = 7.07 (s, 2H), 3.66-3.54 (m, 4H), 2.60 (s, 4H), 2.34 (q, 4H), 2.11 (s, 3H), 2.01 (s, 3H), 1.78-1.71 (m, 2H), 1.70-1.62 (m, 2H), 1.04 (t, 6H) A49 [00080] 1H NMR (400 MHz, Methanol-d4) δ = 7.23 (s, 1H), 7.16 (s, 1H), 3.68-3.53 (m, 4H), 2.60 (s, 4H), 2.39 (q, 2H), 2.10 (s, 3H), 2.02 (s, 3H), 1.87-1.79 (m, 1H), 1.77-1.69 (m, 2H), 1.68- 1.61 (m, 1H), 1.06 (t, 3H) A50 [00081] 1H NMR (400 MHz, Methanol-d4) δ = 6.87 (s, 1H), 6.78 (d, 1H), 3.67 (d, 3H), 3.65-3.59 (m, 2H), 3.59-3.53 (m, 2H), 2.58 (s, 4H), 2.33 (q, 2H), 2.11 (s, 3H), 2.01 (s, 3H), 1.82-1.76 (m, 1H), 1.75-1.67 (m, 2H), 1.66-1.59 (m, 1H), 1.04 (t, 3H) A51 [00082] 1H NMR (400 MHz, Methanol-d4) δ = 8.93 (d, 1H), 8.17 (dd, 1H), 8.04 (d, 1H), 7.81 (s, 1H), 7.79 (s, 1H), 3.91- 3.78 (m, 2H), 3.73-3.61 (m, 2H), 2.66 (s, 4H), 2.54-2.43 (q, 2H), 2.16 (s, 3H), 2.05-1.94 (m, 1H), 1.88-1.77 (m, 2H), 1.75-1.63 (m, 2H), 1.13 (t, 3H), 0.94-0.77 (m, 4H) A52 [00083] 1H NMR (400 MHz, Methanol-d4) δ = 8.94 (dd, 1H), 8.18 (dd, 1H), 8.06 (dd, 1H), 7.82 (s, 2H), 3.90-3.79 (m, 2H), 3.73-3.61 (m, 2H), 2.67 (s, 4H), 2.48 (q, 4H), 2.05-1.95 (m, 1H), 1.85- 1.76 (m, 2H), 1.74-1.66 (m, 2H), 1.14 (t, 6H), 0.92-0.76 (m, 4H) A53 [00084] 1H NMR (400 MHz, Methanol-d4) δ = 8.96 (dd, 1H), 8.21 (dd, 1H), 8.09 (d, 1H), 8.03 (d, 1H), 7.93 (d, 1H), 3.88- 3.79 (m, 2H), 3.72-3.61 (m, 2H), 2.66 (s, 4H), 2.53 (q, 2H), 2.05-1.95 (m, 1H), 1.93-1.85 (m, 1H), 1.83-1.73 (m, 2H), 1.72-1.62 (m, 1H), 1.14 (t, 3H), 0.93-0.76 (m, 4H) A54 [00085] 1H NMR (400 MHz, Methanol-d4) δ = 8.94 (d, 1H), 8.18 (dd, 1H), 8.08 (d, 1H), 7.60 (d, 1H), 7.56 (d, 1H), 3.88- 3.74 (m, 5H), 3.72-3.61 (m, 2H), 2.63 (s, 4H), 2.49 (q, 2H), 2.04-1.95 (m, 1H), 1.90-1.82 (m, 1H), 1.81-1.70 (m, 2H), 1.70-1.62 (m, 1H), 1.14 (t, 3H), 0.92-0.77 (m, 4H) A55 [00086] 1H NMR (400 MHz, DMSO-d6) δ = 7.22 (s, 1H), 7.17 (s, 1H), 3.50- 3.39 (m, 4H), 2.04 (s, 3H), 2.01-1.98 (m, 6H), 1.70-1.63 (m, 1H), 1.62- 1.52 (m, 2H), 1.51-1.45 (m, 1H) A56 [00087] 1H NMR (400 MHz, DMSO-d6) δ = 9.11 (d, 1H), 8.41 (dd, 1H), 8.25 (d, 1H), 8.03 (d, 1H), 7.97 (d, 1H), 3.51-3.39 (m, 4H), 2.55 (br s, 4H), 2.14 (s, 3H), 2.00 (s, 3H), 1.74-1.66 (m, 1H), 1.65-1.56 (m, 2H), 1.55- 1.47 (m, 1H) A57 [00088] 1H NMR (400 MHz, DMSO-d6) δ = 9.11 (s, 1H), 8.42 (d, 1H), 8.26 (d, 1H), 8.03 (s, 1H), 7.97 (s, 1H), 3.81-3.64 (m, 2H), 3.60-3.44 (m, 2H), 2.68-2.54 (m, 4H), 2.16 (s, 3H), 2.05-1.90 (m, 1H), 1.81-1.42 (m, 4H), 0.77-0.62 (m, 4H) A58 [00089] 1H NMR (400 MHz, Methanol-d4) δ = 8.52 (s, 1H), 7.97-7.90 (m, 1H), 7.87 (d, 1H), 7.75 (d, 1H), 7.72-7.62 (m, 1H), 3.88-3.79 (m, 2H), 3.69-3.60 (m, 2H), 2.66 (s, 4H), 2.20 (s, 3H), 2.05-1.94 (m, 1H), 1.93- 1.84 (m, 1H), 1.83-1.73 (m, 2H), 1.70-1.61 (m, 1H), 0.92-0.77 (m, 4H)

BIOLOGICAL EXAMPLES

[0176] Seeds of a variety of test species are sown in standard soil in pots (Lolium perenne (LOLPE), Setaria faberi (SETFA), Alopecurus myosuroides (ALOMY), Echinochloa crus-galli (ECHCG), Avena fatua (AVEFA)). 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 250 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-00002 TABLE B1 LOLPE SETFA ALOMY ECHCG AVEFA Compound PRE POST PRE POST PRE POST PRE POST PRE POST A1  5 5 5 5 NT NT 5 5 5 5 A2  5 5 5 5 5 5 5 5 5 5 A3  5 5 5 5 5 5 5 5 5 5 A4  5 5 5 5 5 5 5 5 5 5 A5  5 5 5 5 5 5 5 5 5 5 A6  5 5 5 5 5 5 5 5 5 5 A7  5 5 5 5 5 5 5 5 5 5 A8  5 5 5 5 5 5 5 5 5 5 A9  5 5 5 5 5 5 5 5 5 5 A10 5 5 5 5 5 5 5 5 5 5 A11 5 5 5 5 5 5 5 5 3 5 A12 5 5 5 5 5 5 5 5 5 5 A13 1 5 2 5 3 5 5 5 2 5 A14 5 5 5 5 5 5 5 5 5 5 A15 5 5 5 5 5 5 5 5 5 5 A16 5 5 5 5 5 5 5 5 5 5 A17 2 5 4 5 2 2 3 5 2 5 A18 5 5 5 5 5 5 5 5 5 5 A35 5 5 5 5 5 5 5 5 5 5 A47 5 5 5 5 5 5 5 5 5 5 A48 5 5 5 5 5 5 4 5 5 5 A49 5 5 5 5 5 5 5 5 5 5 A51 5 5 5 5 5 5 4 5 5 5 A52 5 5 5 5 5 5 5 5 5 5 A53 5 5 5 5 5 5 5 5 5 5 A55 5 5 5 5 5 5 5 5 5 5 A56 5 5 5 5 3 5 4 5 3 5 A57 5 5 5 5 5 5 5 5 5 5 A58 5 5 5 5 5 5 5 5 5 5 NT = not tested.