HERBICIDAL COMPOUNDS

Abstract

The present invention relates to compounds of Formula (I), wherein R1, R2, R3, R4 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) ##STR00049## 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 —S(O).sub.2NR.sup.5R.sup.6 or —S(O)(═NR.sup.7)R.sup.8; R.sup.5 is hydrogen or C.sub.1-C.sub.6alkyl; and R.sup.6 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.5 and R.sup.6 together form —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2S(O).sub.2CH.sub.2CH.sub.2—; and R.sup.7 is hydrogen or C.sub.1-C.sub.6alkyl; 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.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.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.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-; 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 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.3 is methoxy.

6. A compound according to claim 1, wherein R.sup.4 is —S(O).sub.2NR.sup.5R.sup.6.

7. A compound according to claim 1, wherein R.sup.4 is —S(O)(═NR.sup.7)R.sup.8.

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. A method of controlling weeds by applying a compound of Formula (I) as defined in claim 1.

Description

EXAMPLE 1: SYNTHESIS OF 9-(2,6-DIMETHYL-4-PROP-1-YNYL-PHENYL)-3-(METHYLSULFONIMIDOYL)-3-AZASPIRO[5.5]UNDECANE-8,10-DIONE (COMPOUND A1)

[0102] ##STR00016##

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

[0103] ##STR00017##

[0104] 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

[0105] ##STR00018##

[0106] 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

[0107] ##STR00019##

[0108] 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 tert-butyl 9-(4-bromo-2,6-dimethyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (0.51 g, 1.1 mmol).

[0109] 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 tert-butyl 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (Compound A12)

[0110] ##STR00020##

[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 tert-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).

[0112] 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 tert-butyl 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8-methoxy-10-oxo-3-azaspiro[5.5]undec-8-ene-3-carboxylate

[0113] ##STR00021##

[0114] Tert-butyl9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (0.24 g, 0.56 mmol) was suspended in acetone (10 mL) at RT and then potassium carbonate (1.5 equiv., 0.83 mmol) was added followed by iodomethane (5 equiv., 2.77 mmol) and stirred at RT for 24 hours. The reaction mixture was concentrated in vacuo and then 2M HCl was added cautiously and the mixture extracted with EtOAc (×2). The combined organics were dried over sodium sulfate and concentrated in vacuo. The crude material was purified by flash column chromatography eluting with 5-100% EtOAc in iso-hexane to afford the title compound as an orange gum (0.18 g, 0.41 mmol, 74%).

[0115] .sup.1H NMR (400 MHz, chloroform) δ=7.10-7.02 (m, 2H), 3.64-3.52 (m, 5H), 3.39-3.29 (m, 2H), 2.64-2.47 (m, 4H), 2.02-1.97 (m, 9H), 1.74-1.55 (m, 4H), 1.48-1.39 (m, 9H)

Step 6: Synthesis of 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8-methoxy-3-azaspiro[5.5]undec-8-en-10-one

[0116] ##STR00022##

[0117] To a solution of tert-butyl 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8-methoxy-10-oxo-3-azaspiro[5.5]undec-8-ene-3-carboxylate (2.00 g, 4.57 mmol) in DCM (20 mL) at RT was added dropwise Hydrochloric Acid (HCl) (4M in Dioxane) (5.71 mL, 22.9 mmol). The resulting mixture was stirred at RT for 5 h before being evaporated under reduced pressure. The crude residue was diluted with ice-cold water (60 mL) and washed with DCM (20 mL). The aq layer was then rendered basic with 2M Na2CO3. The resulting solution was extracted with CHCl3:IPA (7:3, 3×20 mL). The combined organics were washed with brine and then passed through a phase-sep cartridge and the filtrate evaporated to afford 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8-methoxy-3-azaspiro[5.5]undec-8-en-10-one (1.40 g, 4.15 mmol, 90.8% Yield) as a pale yellow solid.

[0118] .sup.1H NMR (400 MHz, methanol) δ ppm 1.71 (br t, J=5.50 Hz, 4H) 1.94-2.01 (m, 9H) 2.53 (s, 2H) 2.81 (s, 2H) 2.89 (br d, J=5.99 Hz, 4H) 3.75 (s, 3H) 7.00 (s, 2H).

Step 7: Synthesis of 3-[N-[tert-butyl(dimethyl)silyl]-S-methyl-sulfonimidoyl]-9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8-methoxy-3-azaspiro[5.5]undec-8-en-10-one

[0119] ##STR00023##

[0120] Triphenyl phosphine (0.34 g, 1.30 mmol) and hexachloroethane (0.31 g, 1.30 mmol) were suspended in chloroform (3 ml) and heated to 70° C. for 6 h. The mixture was cooled to rt, triethylamine (0.25 mL, 1.80 mmol) was added the mixture was stirred for 10 min at RT. The reaction mixture was cooled using an ice bath and N-[tert-butyl(dimethyl)silyl]methanesulfonamide (0.25 g, 1.20 mmol) was added in chloroform (1 ml). The reaction was stirred at 0° C. for 20 mins before 942,6-dimethyl-4-prop-1-ynyl-phenyl)-8-methoxy-3-azaspiro[5.5]undec-8-en-10-one (0.27 g, 0.80 mmol) and triethylamine (0.25 mL, 1.80 mmol) were and added the reaction stirred at RT overnight. The reaction mixture was directly purified by flash column chromatography (EtOAc in Cyclohexane 0-100%) to give 3-[N-[tert-butyl(dimethyl)silyl]-S-methyl-sulfonimidoyl]-9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8-methoxy-3-azaspiro[5.5]undec-8-en-10-one (220 mg, 0.42 mmol, 52%) as an off-white solid.

[0121] .sup.1H NMR (400 MHz, methanol) δ=7.00 (s, 2H), 3.76 (s, 3H), 3.42-3.32 (m, 2H), 3.22-3.09 (m, 2H), 2.83-2.82 (m, 2H), 2.81 (s, 3H), 2.55 (s, 2H), 1.99 (d, J=1.6 Hz, 9H), 1.82 (t, J=5.6 Hz, 4H), 0.93-0.89 (m, 9H), 0.10 (s, 3H), 0.09 (s, 3H)

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

[0122] ##STR00024##

[0123] To a solution of 3-[N-[tert-butyl(dimethyl)silyl]-S-methyl-sulfonimidoyl]-9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8-methoxy-3-azaspiro[5.5]undec-8-en-10-one (0.22 g, 0.418 mmol) in DCM (0.8 mL) at RT was added dropwise Hydrochloric Acid (HCl) (4M in Dioxane) (0.520 mL, 2.08 mmol). The resulting mixture was stirred at RT for 16 h. The mixture was extracted between DCM and H.sub.2O and the organic phase was dried and concentrated in vacuo. Purification via flash column chromatography (EtOAc in Hexane 10-30%) gave 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-(methylsulfonimidoyl)-3-azaspiro[5.5]undecane-8,10-dione (0.145 g, 87%) as an off-white solid.

[0124] .sup.1H NMR (400 MHz, Methanol) δ=7.04 (s, 2H), 3.41-3.36 (m, 4H), 3.05 (s, 3H), 2.61 (s, 4H), 2.01 (s, 6H), 1.99 (s, 3H), 1.88-1.78 (m, 4H).

EXAMPLE 2: SYNTHESIS OF [9-(2,6-DIMETHYL-4-PROP-1-YNYL-PHENYL)-3-(METHYLSULFONIMIDOYL)-10-OXO-3-AZASPIRO[5.5]UNDEC-8-EN-8-YL] METHYL CARBONATE (COMPOUND P3)

[0125] ##STR00025##

[0126] To a solution of 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-(methylsulfonimidoyl)-3-azaspiro[5.5]undecane-8,10-dione (0.15 g, 0.37 mmol) in anhydrous DCM (3 mL) at RT was added triethylamine (0.16 mL, 1.12 mmol) and methyl chloroformate (0.044 mL, 0.56 mmol). The resulting mixture was stirred at RT for 1 h. The mixture was then diluted with DCM and washed with 10% aq citric acid and brine and then passed through a phase-sep cartridge and the filtrate evaporated. The crude residue was purified by flash chromatography (50-100% EtOAc in hexanes) to afford [9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-(methylsulfonimidoyl)-10-oxo-3-azaspiro[5.5]undec-8-en-8-yl] methyl carbonate (0.144 g, 0.314 mmol, 83.84% Yield) as a white solid.

[0127] 1H NMR (400 MHz, CDCl.sub.3) δ 7.08 (s, 2H), 3.69 (s, 3H), 3.41-3.27 (m, 4H), 2.83 (s, 3H), 2.77 (s, 2H), 2.62 (s, 2H), 2.03 (m, 9H), 1.93-1.75 (m, 4H)

EXAMPLE 3: SYNTHESIS OF 9-(2,6-DIMETHYL-4-PROP-1-YNYL-PHENYL)-N-METHYL-8,10-DIOXO-3-AZASPIRO[5.5]UNDECANE-3-SULFONAMIDE(COMPOUND A3)

[0128] ##STR00026##

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

[0129] ##STR00027##

[0130] 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) 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 2: Synthesis of 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-N-methyl-8,10-dioxo-3-azaspiro[5.5]undecane-3-sulfonamide(Compound A3)

[0131] ##STR00028##

[0132] 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-azaspiro[5.5]undecane-8,10-dione;hydrochloride (0.20 g, 0.56 mmol) was taken up into DCM (5 mL). Triethylamine (0.22 mL, 1.58 mmol) was added and the reaction mixture was stirred for a few minutes at RT before N-methylsulfamoyl chloride (0.073 g, 0.567 mmol) was added and then stirred at room temperature for 2 hours. The reaction mixture was poured into 2M HCl and extracted with DCM (×2). The combined organics were dried over sodium sulfate and concentrated in vacuo. The residue was purified by flash column chromatography using a gradient from 5-100% EtOAc in iHex to give 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-N-methyl-8,10-dioxo-3-azaspiro[5.5]undecane-3-sulfonamide (0.14 g, 0.34 mmol, 62%) as an off-white foam.

[0133] .sup.1H NMR (400 MHz, Methanol) 6=7.06-7.00 (m, 2H), 3.67-3.61 (m, 1H), 3.28-3.17 (m, 4H), 2.66-2.62 (m, 3H), 2.60-2.52 (m, 4H), 2.02-1.96 (m, 9H), 1.80-1.74 (m, 4H)

EXAMPLE 4: SYNTHESIS OF [9-(2,6-DIMETHYL-4-PROP-1-YNYL-PHENYL)-3-(METHYLSULFAMOYL)-10-OXO-3-AZASPIRO[5.5]UNDEC-8-EN-8-YL] METHYL CARBONATE (COMPOUND P2)

[0134] ##STR00029##

[0135] 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-N-methyl-8,10-dioxo-3-azaspiro[5.5]undecane-3-sulfonamide (0.065 g, 0.16 mmol) was dissolved in dichloromethane (1.3 mL) then N,N-diethylethanamine (0.033 mL, 0.23 mmol) was added followed by methyl carbonochloridate (0.014 mL, 0.19 mmol). After stirring at room temperature for 2 hours the reaction mixture was concentrated in vacuo. The residue was purified by flash column chromatography, eluting with 5-100% EtOAc in iso-hexane to afford [9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-(methylsulfamoyl)-10-oxo-3-azaspiro[5.5]undec-8-en-8-yl] methyl carbonate (0.040 g, 0.084 mmol, 54%) as a white solid. .sup.1H NMR (400 MHz, chloroform) δ=7.11-7.01 (m, 2H), 4.05-3.94 (m, 1H), 3.71-3.70 (m, 2H), 3.70-3.68 (m, 3H), 3.39-3.21 (m, 4H), 2.79-2.74 (m, 4H), 2.04-2.01 (m, 9H), 1.91-1.71 (m, 4H)

[0136] Examples of herbicidal compounds of the present invention.

TABLE-US-00001 TABLE 1 Compound Structure NMR A1 [00030] 1H NMR (400 MHz, Methanol-d4) δ = 7.13- 6.97 (m, 2H), 3.31 (br s, 4H), 3.08-2.97 (m, 3H), 2.69-2.54 (m, 4H), 2.09-1.95 (m, 9H), 1.89-1.77 (m, 4H). A2 [00031] 1H NMR (400 MHz, Methanol-d4) δ = 7.06- 7.01 (m, 2H), 3.45- 3.35 (m, 4H), 3.12 (d, J = 7.3 Hz, 2H), 2.60 (s, 4H), 2.01 (s, 6H), 1.99 (s, 3H), 1.79 (t, J = 5.6 Hz, 4H), 1.36 (t, J = 7.3 Hz, 3H). A3 [00032] 1H NMR (400 MHz, Methanol-d4) δ = 7.06- 7.00 (m, 2H), 3.67- 3.61 (m, 1H), 3.28- 3.17 (m, 4H), 2.66- 2.62 (m, 3H), 2.60- 2.52 (m, 4H), 2.02- 1.96(m, 9H), 1.80- 1.74 (m, 4H) A4 [00033] 1H NMR (400 MHz, Methanol-d4) δ = 1.77 (br t, J = 5.50 Hz, 4 H) 2.02-2.06 (m, 9 H) 2.49-2.65 (m, 4 H) 2.83 (s, 6 H) 3.33 (br d, J = 5.50 Hz, 4 H) 7.16 (s, 2 H). A5 [00034] [00035] 1H NMR (400 MHz, Methanol-d4/CDCl3 1:1) δ = 8.73 (br s, 1H), 8.13-7.97 (m, 2H), 7.62 (br s, 1H), 7.06 (s, 2H), 3.46- 3.36 (m, 4H), 2.49 (s, 4H), 2.00 (s, 10H), 1.78 (br t, J = 5.3 Hz, 4H) A6 [00036] 1H NMR (MeOD, 400 MHz): δ 7.03 (s, 2H), 3.23 (t, 4H), 3.04 (q, 2H), 2.58 (s, 4H), 2.0- 1.99 (9H), 1.77 (t, 4H), 1.16 (t, 3H). A7 [00037] 1H NMR (400 MHz, Methanol-d4) δ = 1.72- 1.80(m, 4 H) 2.00- 2.08 (m, 9 H) 2.55 (s, 4 H) 3.19-3.25 (m, 4 H) 3.31-3.39 (m, 4 H) 3.69-3.76 (m, 4 H) 7.15 (s, 2 H). A8 [00038] 1H NMR (MeOD, 400 MHz): δ 7.03 (s, 2H), 3.30 (t, 4H), 2.59 (s, 4H), 2.46-2.43 (m, 1H), 2.0-1.99 (9H), 1.78 (t, 4H), 0.64-0.61 (m, 4H). A9 [00039] 1H NMR (MeOD, 400 MHz): δ 7.02 (s, 2H), 3.47 (t, 2H), 3.36 (s, 3H), 3.24 (t, 4H), 3.17 (t, 2H), 2.57 (s, 4H), 2.0-1.99 (9H), 1.77 (t, 4H). A10 [00040] 1H NMR (400 MHz, Methanol-d4) δ = 7.02 (s, 2H), 3.67 (s, 2H), 3.45-3.40 (m, 2H), 2.72 (s, 2H), 2.68 (s, 2H), 2.04-1.90 (m, 19H) A11 [00041] 1H NMR (400 MHz, Methanol-d4) δ =7.01 (s, 2H), 4.26 (s, 2H), 3.34 (t, 4H), 2.95 (s, 3H), 2.54 (s, 4H), 2.0 (s, 6H), 1.98 (s, 3H), 1.78 (t, 4H). A12 [00042] 1H NMR (400 MHz, Methanol-d4) δ = 7.0 (s, 2H), 3.79 (t, 4H), 3.29 (4H, merged with MeOD), 3.18 (t, 4H), 2.49 (s, 4H), 2.0 (s, 6H), 1.98 (s, 3H), 1.76 (t, 4H) A13 [00043] 1H NMR (400 MHz, Methanol-d4) δ = 1.72- 1.84(m, 5 H) 1.96- 2.08(m, 13 H) 2.56 (s, 4 H) 3.36-3.47 (m, 5 H) 7.03 (s, 2 H).

TABLE-US-00002 TABLE 2 Compound Structure NMR P1 [00044] 1H NMR (400 MHz, CDCl3) δ = 7.08 (s, 2H), 3.69 (s, 3H), 3.46-3.31 (m, 4H), 3.03 (d, J = 7.5 Hz, 1H), 2.99- 2.88 (m, 1H), 2.76 (s, 2H), 2.65-2.57 (m, 2H), 2.03 (s, 3H), 2.02 (s, 6H), 1.89- 1.70 (m, 4H), 1.41 (t, J = 7.5 Hz, 3H). P2 [00045] 1H NMR (400 MHz, CDCl3) δ = 7.11-7.01 (m, 2H), 4.05-3.94 (m, 1H), 3.71- 3.70 (m, 2H), 3.70-3.68 (m, 3H), 3.39-3.21 (m, 4H), 2.79-2.74 (m, 4H), 2.04- 2.01 (m, 9H), 1.91-1.71 (m, 4H) P3 [00046] 1H NMR (400 MHz, CDCl3) δ = 7.08 (s, 2H), 3.69 (s, 3H), 3.41-3.27 (m, 4H), 2.83 (s, 3H), 2.77 (s, 2H), 2.62 (s, 2H), 2.03 (m, 9H), 1.93-1.75 (m, 4H) P4 [00047] .sup.1H NMR (400 MHz, chloroform) δ = 7.12-7.05 (m, 2H), 3.86-3.78 (m, 3H), 3.74-3.64 (m, 3H), 3.48- 3.39 (m, 4H), 3.31-3.22 (m, 3H), 2.79-2.73 (m, 2H), 2.64- 2.54 (m, 2H), 2.05- 1.99 (m, 9H), 1.91-1.72 (m, 4H)

Biological Examples

[0137] 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-00003 TABLE B1 Application pre-emergence Com- Rate pound (g/Ha) ECHCG SETFA LOLPE AVEFA ALOMY 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 NT A6 250 5 5 4 4 3 A7 250 5 5 5 1 2 A11 250 5 5 4 2 1 A12 250 5 5 4 5 5 A13 250 5 5 5 5 5 P1 250 5 5 5 5 5 P2 250 5 5 5 5 5 P3 250 5 5 5 5 5 P4 250 5 5 5 5 5

TABLE-US-00004 TABLE B2 Application post-emergence Com- Rate pound (g/Ha) LOLPE AVEFA ALOMY ECHCG 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 NT 5 5 A6 250 5 5 5 5 5 A7 250 5 5 5 5 5 A11 250 5 5 5 5 5 A12 250 4 5 5 5 5 A13 250 5 5 5 5 5 P1 250 5 5 5 5 5 P2 250 5 5 5 5 5 P3 250 5 5 5 NT 5 P4 250 5 5 5 5 5

Comparison

[0138] Using procedures outlines above, wheat and barley crop plants are treated, post-emergence with compounds A1 or A3 of the present invention or comparator compound C.sub.1 (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-00005 TABLE B3 Compound Rate g/ha Wheat Barley A1 30 0 0 60 0 0 60 + CQC 0 — A3 30 0 0 60 0 0 60 + CQC 0 — C1 30 40 80 60 70 90 60 + CQC 60 —

[0139] The results outlined in Table B3 above show % phytotoxicity observed and that compounds A1 and A3 of the present invention is significantly less damaging to the wheat and barley crops compared to prior art compound C1.

TABLE-US-00006 Compound Structure Cl (Compound A-38 from W02014/096289) [00048]