Herbicidal 3-azaspiro[5.5] undecane-8, 10-dione compounds

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) ##STR00070## wherein R.sup.1 is methyl; R.sup.2 is methyl or methoxy; R.sup.3 is methyl or methoxy; R.sup.4 is —C(═O)C.sub.1-C.sub.4alkyl or —C(═O)C.sub.1-C.sub.4haloalkyl; G is selected from the group consisting of hydrogen, —(CH.sub.2).sub.n—R.sup.a, —C(O)—R.sup.a, —C(O)—O—R.sup.d, —C(O)—S—R.sup.d, —C(O)NR.sup.aR.sup.a, —S(O).sub.2—C.sub.1-C.sub.8alkyl 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 and phenyl; R.sup.d 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 and phenyl; and n=0, 1 or 2; or an agriculturally acceptable salt thereof.

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

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

4. The compound according to claim 1, wherein R.sup.3 is methoxy.

5. The compound according to claim 1, wherein R.sup.4 is —C(═O)C.sub.1-C.sub.3alkyl.

6. The compound according to claim 1, wherein R.sup.4 is —C(═O)C.sub.1-C.sub.3haloalkyl.

7. The compound according to claim 1, wherein G is hydrogen.

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

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

10. A herbicidal composition comprising a compound of Formula (I) according to claim 1 and an agriculturally acceptable formulation adjuvant.

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

12. A herbicidal composition according to claim 11, wherein the additional pesticide is an herbicide or herbicide safener.

13. A method of controlling weeds at a locus comprising applying to the locus of a weed, a weed controlling amount of a composition according to claim 10.

14. A compound selected from the group consisting of: ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077##

15. The compound of claim 14, wherein the compound is Compound 2.

16. The compound of claim 14, wherein the compound is Compound 3.

17. The compound of claim 14, wherein the compound is Compound 5.

18. The compound of claim 14, wherein the compound is Compound 6.

19. The compound of claim 14, wherein the compound is selected from Compounds 11-30.

20. The compound of claim 14, wherein the compound is selected from Compounds 34-48.

Description

EXAMPLE 1: SYNTHESIS OF [3-ACETYL-9-(2,6-DIMETHYL-4-PROP-1-YNYL-PHENYL)-10-OXO-3-AZASPIRO[5.5]UNDEC-8-EN-8-YL] ACETATE (COMPOUND A2) AND [3-ACETYL-9-(2,6-DIMETHYL-4-PROP-1-YNYL-PHENYL)-10-OXO-3-AZASPIRO[5.5]UNDEC-8-EN-8-YL] ACETATE (COMPOUND P4)

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

(1) ##STR00015##

(2) 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

(3) ##STR00016##

(4) 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 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). 1H NMR (400 MHz, CDCl.sub.3, keto from only) 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

(5) ##STR00017##

(6) 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 aq layer was extracted with DCM. The combined organics were dried (MgSO4), 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). 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, 7H), 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

(7) ##STR00018##

(8) 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 chromatographyto give (gradient elution: 10-100% EtOAc in iso-hexane) tert-butyl 9-(2,6-d imethyl-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 followed by synthesis of [3-acetyl-9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-10-oxo-3-azaspiro[5.5]undec-8-en-8-yl] acetate (Compound P4)

(9) ##STR00019##

(10) 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.

(11) The above solid was dissolved in dichloromethane (5 mL) and acetyl chloride (1.14 mmol) was added followed by N,N-diethylethanamine (0.912 mmol). After stirring at room temperature for 1 hour 30 minutes, a further portion of N,N-diethylethanamine (0.912 mmol) and acetyl chloride (1.14 mmol) was added and the reaction mixture was stirred for a further 3 hours. The reaction was diluted with 2 M HCl and extracted with DCM. The organics were dried and concentrated in vacuo to leave an orange gum which was purified by flash chromatography (gradient elution: 5-100% EtOAc:iso-hexane followed by 20% MeOH in DCM) to give [3-acetyl-9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-10-oxo-3-azaspiro[5.5]undec-8-en-8-yl] acetate (0.1637 g, 0.4017 mmol). 1H NMR (400 MHz, CDCl.sub.3) δ=7.10-7.03 (s, 2H), 3.80-3.66 (m, 1H), 3.62-3.45 (m, 3H), 2.75-2.70 (d, 2H), 2.62-2.58 (d, 2H), 2.13-2.10 (s, 3H), 2.04-2.02 (s, 3H), 2.03-2.01 (s, 6H), 1.88-1.86 (m, 3H), 1.85-1.77 (m, 1H), 1.76-1.61 (m, 3H)

Step 7: Synthesis of 3-acetyl-9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-azaspiro[5.5]undecane-8,10-dione (Compound A2)

(12) ##STR00020##

(13) [3-acetyl-9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-10-oxo-3-azaspiro[5.5]undec-8-en-8-yl] acetate (0.111 g, 0.272 mmol) was dissolved in methanol (3 mL) and treated with K.sub.2CO.sub.3 (76 mg, 0.545 mmol). The reaction mixture was stirred at room temperature for 1 hour 30 minutes, then poured into 2 M HCl and extracted with EtOAc. The organics were dried and concentrated in vacuo to give 3-acetyl-9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-azaspiro[5.5]undecane-8,10-dione (0.0669 g, 0.183 mmol). 1H NMR (400 MHz, Methanol-d4) δ=7.05-7.01 (s, 2H), 3.67-3.59 (m, 2H), 3.59-3.53 (m, 2H), 2.62-2.56 (s, 4H), 2.14-2.07 (s, 3H), 2.02-2.01 (s, 6H), 2.00-1.98 (s, 3H), 1.79-1.73 (m, 2H), 1.69-1.61 (m, 2H)

(14) Examples of herbicidal compounds of the present invention.

(15) TABLE-US-00001 TABLE 1 Compound Structure NMR or LCMS A1 DMSO-D6, 400 MHz: δ 10.26 (s, 1H), 6.79 (s, 1H), 6.73 (s, 1H), 3.58 (s, 3H), 3.41 (s, 3H), 3.10 (bs, 2H), 2.77-2.63 (m, 2H), 2.53 (bs, 2H), 2.32-2.22 (m, 2H), 2.02 (s, 3H), 1.92 (s, 4H), 1.75 (bs, 1H), 1.48 (bs, 2H) A2 1H NMR (400 MHz, Methanol- d4) δ = 7.05-7.01 (s, 2H), 3.67- 3.59 (m, 2H), 3.59-3.53 (m, 2H), 2.62-2.56 (s, 4H), 2.14-2.07 (s, 3H), 2.02-2.01 (s, 6H), 2.00-1.98 (s, 3H), 1.79-1.73 (m, 2H), 1.69- 1.61 (m, 2H) A3 1H NMR (400 MHz, Methanol- d4) δ = 7.03 (s, 2H), 3.63 (t, J = 5.5 Hz, 2H), 3.57 (t, J = 5.5 Hz, 2H), 2.60 (s, 4H), 2.41 (q, J = 7.5 Hz, 2H), 1.98-2.00 (9H), 1.73 (t, J = 5.5 Hz, 2H), 1.65 (t, J = 5.5 Hz, 2H), 1.11 (t, J = 7.5 Hz, 3H). A4 1H NMR (400 MHz, DMSO-D6) δ = 10.02 (s, 1H), 6.58 (s, 2H), 3.59 (s, 6H), 3.40 (s, 3H), 3.09 (bs, 2H), 2.58 (bs, 2H), 2.33 (bs, 2H), 2.16 (bs, 2H), 2.04 (s, 3H), 1.84-1.83 (m, 2H), 1.43-1.33 (m, 2H) A5 1H NMR (400 MHz, Methanol- d4) δ = 7.07-6.97 (m, 2H), 3.77- 3.67 (m, 4H), 2.67-2.59 (m, 4H), 2.02-1.97 (m, 9H), 1.82-1.72 (m, 4H) A6 1H NMR (400 MHz, Methanol- d4) δ = 7.05-7.01 (m, 2H), 6.47 (t, J = 1.0 Hz, 1H), 3.71-3.62 (m, 4H), 2.64-2.59 (m, 4H), 2.16- 2.14 (m, 4H), 2.02-2.01 (m, 6H), 2.00-1.99 (m, 3H), 1.81-1.70 (m, 4H) A7 1H NMR (400 MHz, Methanol- d4) δ = 7.04 (s, 2H), 3.72 (q, J = 9.5 Hz, 2H), 3.16 (br t, J = 5.4 Hz, 4H), 2.62 (s, 4H), 2.04-1.96 (m, 9H), 1.94-1.85 (m, 4H) A8 1H NMR (400 MHz, Methanol- d4) δ = 7.11-6.95 (m, 2H), 3.78- 3.68 (m, 3H), 3.59-3.44 (m, 2H), 3.22-3.07 (m, 2H), 2.71-2.67 (m, 2H), 2.61-2.49 (m, 2H), 2.12- 2.03 (m, 2H), 2.01-1.90 (m, 9H), 1.86-1.63 (m, 2H) A9 1H NMR (400 MHz, Methanol- d4) δ = 7.02-6.97 (m, 2H), 3.72- 3.67 (m, 3H), 3.29-3.25 (m, 4H), 3.00-2.92 (m, 2H), 2.70-2.60 (m, 2H), 2.08-2.03 (m, 2H), 2.03- 1.95 (m, 9H), 1.93-1.83 (m, 2H) A10 0 1H NMR (400 MHz, Methanol- d4) δ = 7.04-6.99 (m, 2H), 4.67- 4.61 (m, 4H), 2.72-2.68 (m, 3H), 2.46-2.40 (m, 4H), 2.07-2.02 (m, 6H), 2.00-1.96 (m, 3H), 1.93- 1.83 (m,4H) A11 1H NMR (400 MHz, Methanol- d4) δ = 7.08-6.90 (m, 2H), 3.67- 3.61 (m, 4H), 3.01-2.91 (m, 1H), 2.65-2.54 (m, 4H), 2.04-1.96 (m, 9H), 1.77-1.63 (m, 4H), 1.14- 1.06 (m, 4H) A12 1H NMR (400 MHz, Methanol- d4) δ = 7.05-6.98 (m, 2H), 3.74- 3.65 (m, 4H), 2.65-2.48 (m, 4H), 2.04-1.95 (m, 11H), 1.74-1.58 (m, 4H), 1.31-1.25 (m, 9H) A13 1H NMR (400 MHz, Methanol- d4) δ = 7.08-6.90 (m, 2H), 3.67- 3.61 (m, 4H), 3.01-2.91 (m, 1H), 2.65-2.54 (m, 4H), 2.04-1.96 (m, 9H), 1.77-1.63 (m, 4H), 1.14- 1.06 (m, 4H) A14 1H NMR (400 MHz, Methanol- d4) δ = 6.63 (s, 2H), 3.68 (s, 6H), 3.61 (t, 2H), 3.55 (t, 2H), 2.54 (s, 4H), 2.09 (s, 3H), 2.01 (s, 3H), 1.74 (t, 2H), 1.65 (t, 2H) A15 1H NMR (400 MHz, Methanol- d4) δ = 6.84 (s, 1H), 6.77 (s, 1H), 3.66 (s, 3H), 3.62-3.54 (m, 4H), 2.57 (s, 4H), 2.10 (s, 3H), 2.01- 1.99 (6H), 1.79-1.63 (m, 4H) A16 1H NMR (400 MHz, CDCl3) δ = 7.04-6.98 (m, 2H), 5.06- 4.82 (m, 3H), 3.63-3.55 (m, 2H), 3.45-3.38 (m, 2H), 2.88-2.74 (m, 2H), 2.42-2.31 (m, 4H), 2.11- 2.06 (m, 3H), 2.04-1.98 (m, 9H), 1.67-1.55 (m, 4H), 1.06-0.88 (m, 12H) A17 1H NMR (400 MHz, CDCl3) δ = δ = 7.08-7.03 (m, 2H), 4.48- 4.37 (m, 3H), 3.63-3.55 (m, 2H), 3.47-3.39 (m, 2H), 2.52-2.42 (m, 6H), 2.40-2.36 (m, 4H), 2.10- 2.07 (m, 3H), 2.05-2.03 (m, 6H), 2.02-2.01 (m, 3H), 1.67-1.57 (m, 4H), 1.09-0.96 (m, 9H) A18 1H NMR (400 MHz, CDCl3) δ = 7.10-7.04 (m, 2H), 3.64- 3.57 (m, 2H), 3.52-3.45 (m, 2H), 2.45-2.38 (m, 4H), 2.12-2.07 (m, 3H), 2.05-2.00 (m, 9H), 1.72- 1.60 (m, 4H) A19 1H NMR (400 MHz, Methanol- d4) δ = 6.83 (s, 1H), 6.74 (s, 1H), 6.47 (t, 1H), 3.65-3.62 (7H), 2.52-2.49 (m, 4H), 2.01- 1.99 (6H), 1.82-1.67 (m, 4H) A20 0 1H NMR (400 MHz, Methanol- d4) δ = 6.83 (s, 1H), 6.75 (s, 1H), 3.68-3.66 (7H), 2.55 (s, 4H), 2.01-1.99 (6H), 1.72 (t, 2H), 1.66 (t, 2H), 1.28 (s, 9H) A21 1H NMR (400 MHz, Methanol- d4) δ = 7.04 (s, 2H), 5.46 (qd, J = 6.6, 47.4 Hz, 1H), 3.78-3.52 (m, 4H), 2.62 (d, J = 6.8 Hz, 4H), 2.01 (s, 6H), 1.99 (s, 3H), 1.79- 1.66 (m, 4H), 1.50 (dd, J = 6.6, 24.8 Hz, 3H) A22 1H NMR (400 MHz, Methanol- d4) δ = 7.04 (s, 2H), 3.77 (br d, J = 5.4 Hz, 2H), 3.73-3.65 (m, 2H), 2.63 (s, 4H), 2.01 (s, 6H), 2.00-1.98 (m, 3H), 1.81 (t, J = 19.9 Hz, 3H), 1.78-1.70 (m, 4H) A23 1H NMR (400 MHz, Methanol- d4) δ = 7.03 (s, 2H), 3.93-3.77 (m, 2H), 3.75-3.58 (m, 2H), 2.62 (s, 4H), 2.01 (s, 6H), 1.99 (s, 3H), 1.73 (br s, 4H), 1.59 (d, J = 21.5 Hz, 6H) A24 1H NMR (400 MHz, Methanol- d4) δ = 7.04 (s, 2H), 3.91 (td, J = 7.6, 15.2 Hz, 1H), 3.78-3.57 (m, 4H), 2.61 (d, J = 1.6 Hz, 4H), 2.01 (d, J = 1.6 Hz, 6H), 1.99 (s, 3H), 1.78-1.62 (m, 4H), 1.34 (d, J = 6.8 Hz, 3H) A25 1H NMR (400 MHz, Methanol- d4) δ = 7.03 (s, 2H), 3.70-3.64 (m, 2H), 3.61-3.56 (m, 2H), 3.51 (q, J = 10.5 Hz, 2H), 2.61 (s, 4H), 2.01 (s, 6H), 1.99 (s, 3H), 1.78- 1.73 (m, 2H), 1.72-1.66 (m, 2H) A26 LCMS M + H: 470 A27 LCMS M + H: 448 A28 LCMS M + H: 434 A29 LCMS M + H: 452 A30 0 LCMS M + H: 436

(16) TABLE-US-00002 TABLE 2 Compound Structure NMR P1 1H NMR (400 MHz, CDCl.sub.3) δ = 7.09-7.02 (m, 2H), 3.54 (s, 3H), 3.34-3.10 (m, 2H), 2.82-2.39 (m, 6H), 2.04-1.86 (m, 11H), 1.81- 1.62 (m, 2H), 0.89 (s, 9H) P2 1H NMR (400 MHz, CDCl.sub.3) δ = 7.14-7.01 (m, 2H), 3.53 (s, 3H), 3.31-3.11 (m, 2H), 2.83-2.40 (m, 6H), 2.04-1.99 (m, 9H), 1.98- 1.83 (m, 5H), 1.77-1.60 (m, 2H) P3 1H NMR (400 MHz, CDCl.sub.3) δ = 7.10-7.04 (m, 2H), 3.68 (s, 3H), 3.54 (s, 3H), 3.31-3.13 (m, 2H), 2.85-2.43 (m, 6H), 2.04-2.00 (m, 9H), 1.99-1.83 (m, 2H), 1.80- 1.61 (m, 2H) P4 1H NMR (400 MHz, CDCl.sub.3) δ = 7.10-7.03 (s, 2H), 3.80-3.66 (m, 1H), 3.62-3.45 (m, 3H), 2.75- 2.70 (d, 2H), 2.62-2.58 (d, 2H), 2.13-2.10 (s, 3H), 2.04-2.02 (s, 3H), 2.03-2.01 (s, 6H), 1.88-1.86 (m, 3H), 1.85-1.77 (m, 1H), 1.76- 1.61 (m, 3H) P5 1H NMR (400 MHz, CDCl.sub.3) δ = 7.11-7.05 (s, 2H), 3.76-3.71 (m, 1H), 3.69-3.63 (s, 3H), 3.62-3.53 (m, 1H), 3.52-3.44 (m, 2H), 2.82- 2.75 (m, 2H), 2.68-2.56 (m, 2H), 2.14-2.08 (m, 3H) 2.04-2.03 (m, 6H) 2.02-2.02 (m, 3H), 1.87-1.78 (m, 1H) 1.75-1.61 (m, 3H) P6 1H NMR (400 MHz, CDCl.sub.3) δ = 7.10-7.02 (m, 2H), 3.80-3.69 (m, 2H), 3.64-3.52 (m, 2H), 2.78-2.67 (m, 2H), 2.64-2.50 (m, 2H), 2.05- 1.97 (m, 9H), 1.82-1.73 (m, 2H), 1.71-1.64 (m, 2H), 1.33-1.26 (m, 9H), 0.92-0.84 (m, 9H) P7 1H NMR (400 MHz, Methanol- d4) δ = 7.04-6.89 (m, 2H), 3.92- 3.44 (m, 4H), 3.01-2.92 (m, 1H), 2.88-2.80 (m, 2H), 2.69-2.59 (m, 2H), 2.45-2.33 (m, 1H), 2.03- 1.96 (m, 9H), 1.94-1.60 (m, 4H), 1.14-1.05 (m, 6H), 0.86-0.70 (m, 6H) P8 1H NMR (400 MHz, Methanol- d4) δ = 7.04-6.93 (m, 2H), 4.30- 4.21 (m, 2H), 4.07-3.98 (m, 2H), 3.89-3.42 (m, 4H), 2.95-2.88 (m, 2H), 2.71-2.63 (m, 2H), 2.03- 2.00 (m, 9H), 1.95-1.62 (m, 4H) P9 1H NMR (400 MHz, CDCl.sub.3) δ = 7.35-7.29 (m, 2H), 7.24-7.20 (m, 1H), 7.14-7.09 (m, 2H), 6.89-6.76 (m, 2H), 3.78-3.68 (m, 1H), 3.63- 3.53 (m, 1H), 3.54-3.40 (m, 2H), 2.86-2.81 (m, 2H), 2.71-2.56 (m, 2H), 2.12-2.07 (m, 3H), 2.07-1.92 (m, 9H), 1.88-1.78 (m, 1H), 1.78- 1.63 (m, 3H) P10 0 1H NMR (400 MHz, CDCl.sub.3) δ = 7.11-7.05 (m, 2H), 4.76-4.65 (m, 1H), 3.80-3.69 (m, 1H), 3.63-3.56 (m, 1H), 3.55-3.41 (m, 2H), 2.79- 2.71 (m, 2H), 2.63-2.52 (m, 2H), 2.13-2.08 (m, 3H), 2.06-1.96 (m, 9H), 1.84-1.76 (m, 1H), 1.75-1.61 (m, 3H), 1.19-1.09 (m, 6H) P11 1H NMR (400 MHz, CDCl.sub.3) δ = 7.09-7.04 (m, 2H), 3.81-3.68 (m, 1H), 3.64-3.42 (m, 3H), 2.75-2.65 (m, 2H), 2.64-2.55 (m, 2H), 2.12- 2.07 (m, 3H), 2.05-1.96 (m, 9H), 1.89-1.79 (m, 1H), 1.75-1.60 (m, 3H), 0.94-0.87 (m, 9H) P12 1H NMR (400 MHz, CDCl3) δ = 7.09-7.04 (m, 2H), 3.81-3.68 (m, 1H), 3.64-3.42 (m, 3H), 2.75-2.65 (m, 2H), 2.64-2.55 (m, 2H), 2.12- 2.07 (m, 3H), 2.05-1.96 (m, 9H), 1.89-1.79 (m, 1H), 1.75-1.60 (m, 3H), 0.94-0.87 (m, 9H) P13 P14 1H NMR (400 MHz, CDCl3) δ = 7.10-7.03 (m, 2H), 3.76-3.65 (m, 1H), 3.64-3.54 (m, 1H), 3.53-3.43 (m, 2H), 3.39-3.27 (m, 1H), 2.80- 2.72 (m, 2H), 2.64-2.56 (m, 2H), 2.14-2.08 (m, 3H), 2.05-1.98 (m, 9H), 1.87-1.77 (m, 1H), 1.75-1.62 P15 1H NMR (400 MHz, CDCl3) δ = 7.10-7.01 (m, 2H), 3.80-3.68 (m, 1H), 3.59-3.43 (m, 3H), 2.79-2.72 (m, 2H), 2.64-2.54 (m, 2H), 2.13- 2.05 (m, 3H), 2.04-2.03 (m, 3H), 2.02-1.97 (m, 6H), 1.87-1.77 (m, 1H), 1.76-1.63 (m, 3H), 1.43-1.38 P16 1H NMR (400 MHz, CDCl3) δ = 7.11-7.04 (m, 2H), 6.28-5.94 (m, 1H), 3.79-3.58 (m, 7H), 2.86-2.75 (m, 2H), 2.69-2.60 (m, 2H), 2.09- 1.99 (m, 9H), 1.92-1.66 (m, 5H) P17 1H NMR (400 MHz, CDCl3) δ = 7.14-7.04 (m, 2H), 4.48-4.35 (m, 2H), 3.90-3.79 (m, 1H), 3.59-3.41 (m, 3H), 2.80-2.72 (m, 2H), 2.60- 2.53 (m, 3H), 2.14-2.08 (m, 3H), 2.07-1.98 (m, 9H), 1.80-1.66 (m, 4H) P18 1H NMR (400 MHz, Methanol- d4) δ = 6.81-6.75 (2H), 3.78- 3.75 (m, 1H), 3.68-3.65 (6H), 3.60-3.46 (m, 3H), 2.89 (s, 2H), 2.59 (s, 2H), 2.14 (s, 3H), 2.00- 1.98(6H), 1.93-1.79 (m, 2H), 1.74- 1.57 (m, 2H)

(17) TABLE-US-00003 TABLE 3 Prior art comparator. Compound Structure C1 (Compound A-38 from WO2014/096289)

BIOLOGICAL EXAMPLES

(18) 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%).

(19) TABLE-US-00004 TABLE B1 LOLPE SETFA ALOMY ECHCG AVEFA Compound PRE POST PRE POST PRE POST PRE POST PRE POST A2 5 5 5 NT 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 A11 5 5 5 5 5 5 5 5 5 5 A12 5 5 5 5 5 5 5 5 5 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 5 5 5 5 5 5 5 5 5 5 A18 5 5 5 5 5 5 5 5 5 5 A19 5 5 5 5 5 5 5 NT 5 5 A20 5 5 5 5 5 5 5 5 5 5 A21 5 5 5 5 5 5 5 5 5 5 A22 5 5 5 5 5 5 5 5 5 5 A23 5 5 5 5 5 5 5 5 5 5 A24 5 5 5 5 5 5 5 5 5 5 A25 5 5 5 5 5 5 5 5 5 5 A26 5 5 5 5 5 5 5 5 5 5 A27 5 5 5 5 5 5 5 5 5 5 A28 5 5 5 5 5 5 5 5 5 5 A29 5 5 5 5 5 5 5 5 5 5 P1 5 5 5 5 5 5 5 5 5 5 P2 5 5 5 5 5 5 5 5 5 5 P3 5 5 5 5 5 5 5 5 5 5 P4 5 5 5 NT 5 5 5 5 5 5 P5 5 5 5 5 5 5 5 5 5 5 P7 5 5 5 5 5 5 5 5 5 5 P9 5 5 5 5 5 5 5 NT 5 5 P10 5 5 5 5 5 5 5 5 5 5 P11 5 5 5 5 5 5 5 5 5 5 P12 5 5 5 5 5 5 5 5 5 5 P13 5 5 5 5 4 5 4 5 5 5 P14 5 5 5 5 5 5 5 5 5 5 P15 5 5 5 5 5 5 5 5 5 5 P16 5 5 5 5 5 5 5 5 5 5 P17 5 5 5 5 5 5 5 NT 5 5 P18 5 5 5 5 5 5 5 NT 5 5 NT = not tested.

(20) Using procedures outlines above, wheat and barley crop plants are treated, along with two weed species Avena fatua (AVEFA) and Lolium multiflorum (LOLPE) post-emergence with compound A2 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.

(21) TABLE-US-00005 TABLE B2 Compound Rate g/ha Wheat Barley AVENA LOLMU A2 30 5 0 75 98 60 15 15 92 100 60 + CQC 5 0 92 100 C1 30 25 5 65 98 60 75 90 90 100 60 + CQC 50 18 80 100

(22) The results outlined in Table B2 above show % phytotoxicity observed and that compound A2 of the present invention is significantly less damaging to the wheat and barley crops compared to prior art compound C1.