HERBICIDAL COMPOUNDS

Abstract

The present invention relates to compounds of Formula (I), 5 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) ##STR00045## wherein R.sup.1 is selected from the group consisting of 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.9 substituents; R.sup.2 is selected from the group consisting of methyl, ethyl, methoxy and chloro; R.sup.3 is selected from the group consisting of methyl, ethyl, methoxy and chloro; R.sup.4 is —C(O)C(R.sup.5)═N—O—R.sup.6 or —C(O)C(R.sup.5)═N—NR.sup.7R.sup.8; R.sup.5 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.6 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.7 is hydrogen or C.sub.1-C.sub.6 alkyl; R.sup.8 is hydrogen or C.sub.1-C.sub.6 alkyl; R.sup.9 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; 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.8alkoxy-C.sub.1-C.sub.3alkyl-; Ra 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 of according to claim 1, wherein R.sup.1 is 1-propynyl, R.sup.2 is methyl or methoxy and R.sup.3 is methyl or methoxy.

3. A compound according to claim 1, wherein R.sup.2 is methyl.

4. A compound according to claim 1, wherein R.sup.3 is methyl.

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

6. A compound according to claim 1, wherein R.sup.4 is —C(O)C(R.sup.5)═N—O—R.sup.6.

7. A compound according to claim 1, wherein R.sup.6 is methyl.

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 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: Synthesis of 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-(2-methoxyiminopropanoyl)-3-azaspiro[5.5]undecane-8,10-dione (Compound A1).

[0103] ##STR00017##

Step 1: Synthesis of O3-tert-butyl O11-ethyl 8,10-dioxo-3-azaspiro[5.5]undecane-3,11-dicarboxylate

[0104] ##STR00018##

[0105] 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 room temperature for 3 hours then heated to reflux for 1 hour. Upon cooling the reaction mixture was concentrated in vacuo to give O3-tert-butyl O11-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

[0106] ##STR00019##

[0107] Crude O3-tert-butyl O11-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 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 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). 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-2,6-dimethyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate

[0108] ##STR00020##

[0109] Tert-Butyl 8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (0.5 g, 1.8 mmol) and DMAP (1.1 g, 8.9 mmol) were dissolved in chloroform (20 mL). The reaction mixture was stirred under nitrogen for 10 minutes and toluene (5 mL) was added followed by [diacetoxy-(4-bromo-2,6-dimethyl-phenyl)plumbyl] acetate (1.2 g, 2.1 mmol). The resulting suspension was heated under nitrogen at 75° C. for 3 hours and then allowed to cool to room temperature. The reaction mixture was treated with 2 M HCl (50 mL) and white precipitate formed on stirring. The mixture was filtered and the organic phase was separated and the aqueous layer was extracted with DCM. The combined organics were dried (MgSO.sub.4), evaporated and purified by flash column chromatography (gradient elution: 5-100% EtOAc:iso-hexane) to give tent-butyl 9-(4-bromo-2,6-dimethyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (0.51 g, 1.1 mmol). 1H NMR (400 MHz, CD.sub.3OD) 7.25-7.10 (m, 2H), 3.54-3.43 (m, 4H), 2.61-2.52 (m, 4H), 2.05-1.98 (m, 6H), 1.72-1.56 (m, 4H), 1.48-1.39 (m, 9H).

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

[0110] ##STR00021##

[0111] 4-diphenylphosphanylbutyl(diphenyl)phosphane (32 mg, 0.075 mmol), dichlorobis(triphenylphosphine)palladium(II) (26 mg, 0.0373 mmol) and but-2-ynoic acid (346 mg, 0.894 mmol) were placed into a microwave vial. A solution of tent-butyl 9-(4-bromo-2,6-dimethyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (0.346 g, 0.745 mmol) in DMSO (6 mL/mmol) was added followed by DBU (0.34 g, 2.24 mmol) and the reaction mixture was heated under microwave irradiation at 110° C. for 45 minutes. The reaction was diluted with 2M HCl and extracted with DCM. The organics were dried and concentrated in vacuo to leave an orange gum which purified by flash chromatography to give (gradient elution: 10-100% EtOAc in iso-hexane) tert-butyl 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (0.193 g, 0.456 mmol). 1H NMR (400 MHz, CD.sub.3OD) 7.07-6.93 (m, 2H), 3.52-3.45 (m, 4H), 2.62-2.53 (m, 4H), 2.02-1.98 (m, 9H), 1.70-1.60 (m, 4H), 1.51-1.42 (m, 9H).

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

[0112] ##STR00022##

[0113] tent-Butyl 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (0.193 g, 0.456 mmol) was stirred for 1 hour at room temperature in 4 M HCl in 1,4-dioxane (4 mL, 16 mmol). The reaction mixture was concentrated in vacuo to leave 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-azaspiro[5.5]undecane-8,10-dione hydrochloride as a white solid which was used directly in the next reaction without further purification.

Step 6: Synthesis of 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-(2-oxopropanoyl)-3-azaspiro[5.5]undecane-8,10-dione

[0114] ##STR00023##

[0115] To a stirred solution of 2-oxopropanoic acid (0.049 g, 0.56 mmol) in DCM (3 mL), HATU (0.23 g, 0.61 mmol) was added at room temperature and the mixture was left to stir for 1 h. Then, 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-azaspiro[5.5]undecane-8,10-dione; hydrochloride (200 mg, 0.56 mmol) followed by N,N-diethylethanamine (0.15 mL, 1.11 mmol) were added to the mixture, which was left to stir at rt overnight. The reaction was diluted 2M HCl, extracted with dichloromethane and the organic layer directly loaded onto silica gel and purified using column chromatography (80-100% EtOAc in iso-hex) to afford 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-(2-oxopropanoyl)-3-azaspiro[5.5]undecane-8,10-dione (0.16 g, 60%) as a white solid.

[0116] .sup.1H NMR (400 MHz, methanol) δ=7.06-7.01 (m, 2H), 3.68-3.61 (m, 2H), 3.52-3.46 (m, 2H), 2.64 (br s, 4H), 2.40-2.37 (m, 3H), 2.01-2.00 (m, 6H), 2.00-1.98 (m, 3H), 1.77-1.70 (m, 4H)

Step 7: Synthesis of 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-(2-methoxyiminopropanoyl)-3-azaspiro[5.5]undecane-8,10-dione (Compound A1).

[0117] ##STR00024##

[0118] To a stirred solution of 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-(2-oxopropanoyl)-3-azaspiro[5.5]undecane-8,10-dione (39 mg, 0.101 mmol) in DCM (0.5 mL) at 0° C., pyridine (0.32 mL, 0.40 mmol) was added followed by O-methylhydroxylamine hydrochloride (9 mg 0.11 mmol) and the mixture was left to slowly warm to rt overnight. The reaction mixture was filtered through HyFlow, washed with DCM and the volatiles were removed in vacuo. The material was purified by flash column chromatography, eluting with 0-50% MeOH in DCM to afford 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-(2-methoxyiminopropanoyl)-3-azaspiro[5.5]undecane-8,10-dione (37 mg, 80%) as a white foam (2:1 ratio of oxime geometric isomers, E/Z unassigned).

[0119] .sup.1H NMR (400 MHz, Methanol) δ=7.07-7.00 (m, 2H), 3.93-3.89 (m, 1H), 3.86-3.80 (m, 2H), 3.76 -3.35 (m, 4H), 2.64-2.57 (m, 4H), 2.12-1.88 (m, 12H), 1.77-1.66(m, 4H)

[0120] Note on geometric isomers: Many of the following examples exist as a mixture of geometric isomers as observed by NMR and LC-MS. In these cases the compound is drawn with a cross bond for the oxime. In cases where the major isomer is >90%, these compounds are drawn as the major isomer.

Example 2: Synthesis of 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-[(2E)-2-methoxyiminoacetyl]-3-azaspiro[5.5]undecane-8,10-dione (Compound A3).

[0121] ##STR00025##

[0122] To a stirred solution of (2E)-2-methoxyiminoacetic acid (75 mg, 0.73 mmol) in DCM (3.5 mL), EDCI (0.126 g, 0.65 mmol) was added followed by 2,3,4,5,6-pentafluorophenol (0.121 g, 0.65 mmol) were added at 0° C. and the mixture was left to stir at rt overnight. 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-azaspiro[5.5]undecane-8,10-dione;hydrochloride (262 mg, 0.73 mmol) followed by N,N-diethylethanamine (0.15 mL, 1.09 mmol) were added to the mixture, which was left to stir at rt overnight. The reaction was directly dry-loaded on silica gel and purified using column chromatography (0-10% MeOH in DCM) to afford 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-[(2E)-2-methoxyiminoacetyl]-3-azaspiro[5.5]undecane-8,10-dione (216 mg, 73%) as a white solid.

[0123] .sup.1H NMR (400 MHz, methanol) 67 =7.86 (s, 1H), 7.03 (s, 2H), 3.95 (s, 3H), 3.76-3.64 (m, 4H), 2.61 (s, 4H), 2.02 (s, 6H), 1.99 (s, 3H), 1.78-1.67 (m, 4H).

Example 3: Synthesis of 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-[(2E)-2-(2-pyridyloxyimino)propanoyl]-3-azaspiro[5.5]undecane-8,10-dione (Compound A6)

[0124] ##STR00026##

[0125] 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-(2-oxopropanoyl)-3-azaspiro[5.5]undecane-8,10-dione (200 mg, 0.508 mmol) was suspended in ethanol (2 mL). Pyridine (126 μL, 1.53 mmol) was added and stirred for 5 mins. A solution of O-(2-pyridyl)hydroxylamine (112 mg, 1.0172 mmol) in ethanol (1 mL) was then added and stirred for 5 mins. DCM (2 mL) was added and the reaction heated to reflux for 3 hours, followed by microwave irradiation at 120 ° C. for 2 hours. The solvent was removed under vacuum and the residue was partitioned between water and DCM:MeOH (90:10) then the organic extract passed through a phase separating cartridge. The solvent was removed from the filtrate under vacuum. The residue was purified by flash chromatography, eluting with 1-15% (MeOH in DCM) to afford 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-[(2E)-2-(2-pyridyloxyimino)propanoyl]-3-azaspiro[5.5]undecane-8,10-dione (22 mg, 9%) as a white solid. .sup.1H NMR (400 MHz, methanol) δ ppm 1.65-1.91 (m, 4 H) 1.94-2.00 (m, 9 H) 2.00-2.04 (m, 4 H) 2.24 (s, 3 H) 2.55-2.70 (m, 4 H) 3.39-3.54 (m, 2 H) 3.61-3.72 (m, 1 H) 3.79-3.89 (m, 1 H) 7.02 (d, J=5.99 Hz, 2 H) 7.13 (ddd, J=7.21, 5.01, 0.73 Hz, 1 H) 7.33 (d, J=8.44 Hz, 1 H) 7.86 (ddd, J=8.62, 7.03, 1.96 Hz, 1 H) 8.17-8.20 (m, 1 H).

Example 4: Synthesis of 3-[2-(dimethylhydrazono)propanoyl]-9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-azaspiro[5.5]undecane-8,10-dione (Compound A8)

[0126] ##STR00027##

[0127] 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-(2-oxopropanoyl)-3-azaspiro[5.5]undecane-8,10-dione (31 mg, 0.080 mmol) was dissolved in MeOH (0.5 mL) and cooled to 0° C. 1,1-dimethylhydrazine (6.7 μL, 0.086 mmol) added in one portion and then the reaction stirred at rt for 48 hours. 4M HCl in dioxane (1.8 μL) was added and then the solvent was removed under vacuum. The residue was purified by flash chromatography (1-15% MeOH in DCM) to afford 3-[2-(dimethylhydrazono)propanoyl]-9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-azaspiro[5.5]undecane-8,10-dione (30 mg, 81%) as an off-white solid and an approximately 1:1 mixture of geometric isomers. .sup.1H NMR (400 MHz, methanol) δ ppm 1.73 (br d, J=3.91 Hz, 4 H) 1.97-2.04 (m, 9 H) 2.07-2.13 (m, 3 H), 2.47 (s, 3 H) 2.57 (s, 3 H), 2.61 (s, 4H), 3.33-3.42 (m, 1 H) 3.50-3.59 (m, 1 H) 3.62-3.74 (m, 2 H) 7.03 (s, 2 H).

[0128] Examples of herbicidal compounds of the present invention.

TABLE-US-00001 TABLE 1 CMP Structure NMR A1  [00028] 1H NMR (400 MHz, Methanol-d4) δ = 7.07- 7.00 (m, 2H), 3.93-3.89 (m, 1H), 3.86-3.80 (m, 2H), 3.76-3.35 (m, 4H), 2.64-2.57 (m, 4H), 2.12- 1.88 (m, 12H), 1.77-1.66 (m, 4H) A2  [00029] 1H NMR (400 MHz, Methanol-d4) δ 7.06- 7.00 (m, 2H), 4.20-4.04 (m, 2H), 3.83-3.37 (m, 4H), 2.66-2.56 (m, 4H), 2.00 (br s, 9H), 2.00-1.98 (m, 3H), 1.80-1.67 (m, 4H), 1.30-1.20 (m, 3H) A3  [00030] 1H NMR (400 MHz, Methanol-d4) δ = 7.86 (s, 1H), 7.03 (s, 2H), 3.95 (s, 3H), 3.76-3.64 (m, 4H), 2.61 (s, 4H), 2.02 (s, 6H), 1.99 (s, 3H), 1.78-1.67 (m, 4H) A4  [00031] 1H NMR (400 MHz, Methanol-d4) δ = 1.67- 1.76 (m, 4H) 1.96-2.03 (m, 12H) 2.61 (s, 4H) 3.59-3.73 (m, 4H) 7.03 (s, 2H) A5  [00032] 1H NMR (400 MHz, Methanol-d4) δ = 1.67- 1.81 (m, 4H) 1.95-2.05 (m, 12H) 2.60 (s, 4H) 3.37-3.47 (m, 2H) 3.67 (br s, 2H) 7.04 (s, 2H) A6  [00033] 1H NMR (400 MHz, Methanol-d4) δ = 1.65- 1.91 (m, 4H) 1.94-2.00 (m, 9H) 2.00-2.04 (m, 4H) 2.24 (s, 3H) 2.55-2.70 (m, 4H) 3.39-3.54 (m, 2H) 3.61-3.72 (m, 1H) 3.79-3.89 (m, 1H) 7.02 (d, J = 5.99 Hz, 2H) 7.13 (ddd, J = 7.21, 5.01, 0.73 Hz, 1H) 7.33 (d, J = 8.44 Hz, 1H) 7.86 (ddd, J = 8.62, 7.03, 1.96 Hz, 1H) 8.17-8.20 (m, 1H) A7  [00034] 1H NMR (400 MHz, Methanol-d4) δ = 1.20 (s, 9H) 1.66-1.76 (m, 4H) 2.00 (d, J = 8.56 Hz, 9H) 2.55-2.66 (m, 4H) 3.35- 3.39 (m, 1H) 3.49-3.58 (m, 1H) 3.75-3.82 (m, 1H) 3.82 (s, 3H) 7.04 (s, 2H) A8  [00035] .sup.1H NMR (400 MHz, methanol) δ ppm 1.73 (br d, J = 3.91 Hz, 4H) 1.97- 2.04 (m, 9H) 2.07-2.13 (m, 3H), 2.47 (s, 3H) 2.57 (s, 3H), 2.61 (s, 4H), 3.33- 3.42 (m, 1H) 3.50-3.59 (m, 1H) 3.62-3.74 (m, 2H) 7.03 (s, 2H). A9  [00036] 1H NMR (400 MHz, Methanol-d4) δ = 1.64- 1.76 (m, 5H) 1.94-2.06 (m, 13H) 1.98-2.05 (m, 1H) 2.62 (s, 4H) 3.53 (ddd, J = 11.77, 9.08, 3.00 Hz, 2H) 3.60-3.74 (m, 3H) 3.91 (dt, J = 11.74, 4.58 Hz, 2H) 4.32 (tt, J = 8.65, 4.19 Hz, 1H) 7.03 (s, 2H) A10 [00037] 1H NMR (400 MHz, Methanol-d4) δ = 1.65- 1.81 (m, 4H) 1.97-2.03 (m, 9H) 2.08 (s, 2H) 2.09 (s, 1H) 2.59-2.65 (m, 4H) 3.39-3.45 (m, 1H) 3.53-3.81 (m, 3H), 4.83 (s, 1H) 4.90 (s, 1H) 7.04 (s, 2H) A11 [00038] 1H NMR (400 MHz, Methanol-d4) δ = 1.61- 1.80 (m, 4H) 1.88 (d, J = 3.06 Hz, 1H) 2.00- 2.08 (m, 12H) 2.62 (s, 4H) 3.34-3.39 (m, 4H) 3.40-3.55 (m, 1H) 3.65 (br dd, J = 5.32, 4.10 Hz, 5H) 3.88 (s, 1H) 4.09-4.23 (m, 1H) 4.27 (dd, J = 5.32, 4.10 Hz, 1H) 7.07 (s, 2H) A12 [00039] 1H NMR (400 MHz, Methanol-d4) δ = 1.74 (dt, J = 11.71, 5.82 Hz, 4H) 2.00 (d, J = 8.31 Hz, 9H) 2.62 (s, 4H) 3.36 (s, 3H) 3.61-3.66 (m, 2H) 3.67- 3.78 (m, 4H) 4.25-4.33 (m, 2H) 7.04 (s, 2H) 7.89 (s, 1H) A13 [00040] 1H NMR (400 MHz, Methanol-d4) δ = 1.77 (dt, J = 15.47, 5.72 Hz, 4H) 1.96-2.05 (m, 9H) 2.63 (s, 4H) 3.73 (dt, J = 7.55, 3.87 Hz, 4H) 4.95 (s, 2H) 7.03 (s, 2H) 8.00 (s, 1H) A14 [00041] 1H NMR (400 MHz, Methanol-d4) δ = 1.59- 1.82 (m, 6H) 1.96-2.04 (m, 11H) 2.62 (s, 4H) 3.44-3.57 (m, 3H) 3.65- 3.76 (m, 3H) 3.85-3.95 (m, 2H) 4.38 (td, J = 8.96, 4.59 Hz, 1H) 7.04 (s, 2H) 7.23 (s, 1H) 7.91 (s, 1H) A15 [00042] 1H NMR (400 MHz, Methanol-d4) δ = 7.84 (s, 1H), 7.03 (s, 2H), 3.79- 3.68 (m, 4H), 2.62 (s, 4H), 2.01 (d, J = 2.0 Hz, 6H), 1.99 (s, 3H), 1.78-1.70 (m, 4H) A16 [00043] 1H NMR (400 MHz, Methanol-d4) δ = 1.73 (br s, 4H) 1.97-2.04 (m, 9H) 2.62 (s, 4H) 3.08 (s, 6H) 3.65-3.86 (m, 4H) 6.83 (s, 1H) 7.04 (s, 2H)

Biological Examples

[0129] 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%). NT=not tested.

TABLE-US-00002 TABLE B1 Application pre-emergence Rate Compound (g/Ha) ALOMY AVEFA ECHCG LOLPE SETFA A1 250 5 5 5 5 5 A2 250 5 5 5 5 5 A3 250 4 5 5 5 5 A4 250 5 5 5 5 5 A5 250 4 5 5 5 5 A6 250 5 5 5 5 5 A7 250 4 2 5 5 5 A8 250 5 5 5 5 5 A9 250 5 2 3 3 4  A10 250 4 1 4 1 4  A11 250 5 3 5 5 5

TABLE-US-00003 TABLE B2 Application post-emergence Rate Compound (g/Ha) ALOMY AVEFA ECHCG LOLPE SETFA A1 250 5 5 5 5 5 A2 250 5 5 5 5 5 A3 250 5 5 5 5 5 A4 250 5 5 5 5 5 A5 250 5 5 5 5 5 A6 250 5 5 5 5 5 A7 250 4 3 5 5 5 A8 250 5 5 5 5 5 A9 250 5 5 5 4 5  A10 250 5 5 5 5 5  A11 250 5 5 5 5 5

Comparison

[0130] Using procedures outlines above, wheat and barley crop plants are treated, post- emergence with compounds A1, A3 or A8 of the present invention or comparator compound C1 (Compound A-38 from WO2014/096289) at the application rates indicated. The compounds were also applied in conjunction with the safener compound cloquintocet-mexyl (CQC) at 50 g/ha.

TABLE-US-00004 Compound Structure Cl (Compound A-38 from WO2014/096289) [00044]

TABLE-US-00005 TABLE B3 Compound Rate g/ha Wheat Barley A1 30 10 20 60 20 40 60 + CQC 0 — A3 30 0  0 60 20 30 60 + CQC 0 — A8 30 0  0 60 10  0 60 + CQC 10 — C1 30 40 80 60 70 90 60 + CQC 60 —

[0131] The results outlined in Table B3 above show % phytotoxicity observed and that compounds A1, A3 & A8 of the present invention are significantly less damaging to the wheat and barley crops compared to prior art compound C1.