Herbicidal compounds

Abstract

The present invention relates to compounds of Formula (I), (I) wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 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) ##STR00099## wherein R.sup.1 is 1-propynyl, R.sup.2 is methyl; R.sup.3 is methyl; R.sup.4 is selected from the group consisting of D4, D5, D6, D12, D13, D14, D23, D28 and D30: ##STR00100## ##STR00101## ##STR00102## ##STR00103## Y is selected from the group consisting of O, CR.sup.27R.sup.28 and N-R.sup.29; R.sup.4c is selected from the group consisting of hydrogen, 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.nC(R.sup.11)R.sup.12R.sup.13, C(O) H, C(O)(CH.sub.2).sub.nC.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.nNR.sup.5R.sup.6, C(O)(CH.sub.2).sub.nNR.sup.7C(O)R.sup.8, C(O)(CH.sub.2).sub.nONCR.sup.5R.sup.5, CN, S(O).sub.2NR.sup.16R.sup.17S(O)(NR.sup.18)R.sup.19, C(O)C(O)R.sup.20, C(O)C(R.sup.23)NOR.sup.24 or C(O)C(R.sup.23)NNR.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.nheterocyclyl, C(O)(CH.sub.2).sub.nO(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 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.11 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.2XCH.sub.2; and X is selected from the group consisting of O, S and NR.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.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.6 cycloalkyl, 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.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.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-CoalkoxyC.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.6 alkoxy- 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.6 cycloalkyl, 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; R.sup.27 is hydrogen or C.sub.1-C.sub.4alkyl; R.sup.28 is hydrogen or C.sub.1-C.sub.4alkyl; R.sup.29 is selected from the group consisting of hydrogen, 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; and G is selected from the group consisting of hydrogen, (CH.sub.2).sub.nR.sup.a, C(O)R.sup.a, C(O)(CR.sup.cR.sup.4).sub.nOR.sup.b, C(O)(CR.sup.cR.sup.4).sub.nSR.sup.b, C(O) NR.sup.aR.sup.a, S(O).sub.2R.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.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.2-C.sub.3alkenyl, C.sub.2-C.sub.3alkynyl, 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.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.2-C.sub.3alkenyl, C.sub.2-C.sub.3alkynyl, 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.4 is D4 or D6.

3. A compound according to claim 1, wherein R.sup.4c is selected from the group consisting of C(O)C.sub.1-C.sub.4alkyl, S(O).sub.nC.sub.1-C.sub.6alkyl, C(O)C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.6alkyl and C(O) phenyl.

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

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

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

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

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

9. A herbicidal composition according to claim 8, further comprising at least one additional pesticide.

10. A herbicidal composition according to claim 9, wherein the additional pesticide is a herbicide or herbicide safener.

11. A method of controlling weeds at a locus comprising application to the locus of a weed controlling amount of the compound according to claim 1.

12. A method of controlling weeds at a locus comprising application to the locus of the herbicide composition of claim 8.

13. A method of controlling weeds at a locus comprising application to the locus of herbicide the composition of claim 8.

14. A compound selected from: ##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116##

Description

EXAMPLE 1: 3-ACETYL-9-(2,6-DIMETHYL-4-PROP-1-YNYL-PHENYL)-3-AZASPIRO[5.5]UNDEC-4-ENE-8,10-DIONE (EXAMPLE A1)

(1) ##STR00018##

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

(2) ##STR00019##

(3) 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

(4) ##STR00020##

(5) 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

(6) ##STR00021##

(7) 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

(8) ##STR00022##

(9) 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). 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

(10) ##STR00023##

(11) Tert-butyl 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (0.235 g, 0.555 mmol) was suspended in acetone (10 mL) then potassium carbonate (1.500 equiv., 0.832 mmol) was added followed by iodomethane (5 equiv., 2.77 mmol). The reaction mixture was stirred at room temperature for 24 hours and was then concentrated on the rotavap and then quenched by diluting cautiously into 2M HCl (effervescence) and extracted2 with EtOAc. The organics were dried and vacced down to leave an orange foam which was pre-absorbed onto silica and purified by flash chromatography to give tert-butyl 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8-methoxy-10-oxo-3-azaspiro[5.5]undec-8-ene-3-carboxylate (0.18 g, 74%)

(12) 1NMR: 1H NMR (400 MHz, CDCl.sub.3) =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 tert-butyl 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8-methoxy-4,10-dioxo-3-azaspiro[5.5]undec-8-ene-3-carboxylate

(13) ##STR00024##

(14) Tert-butyl 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8-methoxy-10-oxo-3-azaspiro[5.5]undec-8-ene-3-carboxylate (0.1800 g, 0.4113 mmol) was taken up into nitromethane (2 mL) and bisacetoxy-iodobenzene (3 equiv., 1.234 mmol) was added. The reaction mixture was cooled to 0 C. and 2-hydroperoxy-2-methyl-propane was added dropwise (4 equiv., 1.645 mmol), maintaining the temperature by the rate of addition. The reaction mixture was stirred for 4 hours at 0 C. and then at room temperature for 36 hours then quenched by the addition of sodium metabisulfite solution then extracted2 with EtOAc. The organics were dried and vacced down to leave an orange foam which was pre-absorbed onto silica and purified by flash chromatography to give crude tert-butyl 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8-methoxy-4,10-dioxo-3-azaspiro[5.5]undec-8-ene-3-carboxylate (0.011 g, 0.024 mmol). 1NMR: 1H NMR (400 MHz, CDCl.sub.3) =7.13-6.91 (m, 2H), 3.85-3.60 (m, 2H), 3.56-3.48 (m, 3H), 2.67-2.49 (m, 6H), 2.07-1.98 (m, 9H), 1.57-1.51 (m, 9H), 1.50-1.40 (m, 2H)

Step 7: Synthesis of tert-butyl 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8-methoxy-10-oxo-3-azaspiro[5.5]undeca-4,8-diene-3-carboxylate

(15) ##STR00025##

(16) To a solution of tert-butyl 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8-methoxy-4,10-dioxo-3-azaspiro[5.5]undec-8-ene-3-carboxylate (0.230 g, 0.509 mmol) in anhydrous toluene (2.00 mL) at 70 C. was added Super-Hydride (1M in THF)(1M, 0.560 mL, 0.560 mmol) dropwise. After stirring at 70 C. for 30 minutes N,N-Diisopropylethylamine (0.375 g, 2.90 mmol), 4,4-Dimethylaminopyridine (0.00124 g, 0.0102 mmol) and trifluoroacetic anhydride (0.128 g, 0.611 mmol) were added. The mixture was warmed to room temperature and stirred for 2 h. Water (4 mL) was added. The organic layer was separated and the aqueous layer extracted with EtOAc (3). The combined organics were washed with brine solution, dried over Na.sub.2SO.sub.4, filtered and concentrated to obtain crude material, which was purified by silica gel column chromatography using EtOAc-Hexane as eluent to give the desired product.

(17) 1H NMR (CDCl.sub.3, 400 MHz): =7.18-7.07 (2H), 6.93-6.76 (m, 1H), 4.85-4.80 (m, 1H), 3.61-3.56 (5H), 2.70-2.62 (m, 2H), 2.56-2.52 (1H), 2.45-2.41 (1H), 2.03-2.01 (9H), 1.86 (2H), 1.49 (s, 9H)

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

(18) ##STR00026##

(19) Tert-butyl 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8-methoxy-10-oxo-3-azaspiro[5.5]undeca-4,8-diene-3-carboxylate (400 mg, 0.918 mmol) was stirred at 0 C. in HCl in Dioxane (4M, 2.30 mL, 9.18 mmol) for 1 h then stirred at RT overnight. Reaction mixture was concentrated and triturated with pentane, decanted and dried to obtain product as a greenish solid, 300 mg. This is used crude in the next step. LCMS (NH4OAc: CH3CN): M+H=322

Step 9: Synthesis of [3-acetyl-9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-10-oxo-3-azaspiro[5.5]undeca-4,8-dien-8-yl] acetate

(20) ##STR00027##

(21) 9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-8-hydroxy-3-azaspiro[5.5]undeca-4,8-dien-10-one hydrochloride (195 mg, 0.545 mmol) was taken up in dichloromethane (10 mL) and acetyl chloride (0.156 mL, 2.18 mmol was added at 0 C. followed by triethylamine (0.608 mL, 4.36 mmol) upon which all solids went immediately into solution. The reaction was stirred at room temperature for 1 h. The reaction mixture was diluted with DCM and washed with water. The aqueous layer extracted with DCM (2). The combined organics were dried over Na.sub.2SO.sub.4, filtered and concentrated to obtain crude product.

(22) LCMS (NH4OAc: CH.sub.3CN): M+H=406

Step 10: Synthesis of 3-acetyl-9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-3-azaspiro[5.5]undec-4-ene-8,10-dione (Example A1)

(23) ##STR00028##

(24) [3-acetyl-9-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-10-oxo-3-azaspiro[5.5]undeca-4,8-dien-8-yl] acetate was dissolved in methanol (10 mL) and to this was added K.sub.2CO.sub.3 (0.181 g, 1.31 mmol). The reaction mixture was stirred at room temperature for 1 h and then concentrated and the residue diluted with water, washed with EtOAc (2). The combined organics were washed with brine solution. The combined basic aqueous layers were acidified with 1N HCl and extracted with EtOAc (3). The combined organics were dried over Na.sub.2SO.sub.4, filtered and concentrated to obtain crude material, which was purified by prep-HPLC to give desired product as a white solid (69 mg).

(25) 1H NMR (400 MHz, Methanol-d4) =7.15 (d, 0.4H), 7.03 (s, 2H), 6.79 (d, 0.7H), 5.17-5.10 (m, 1H), 3.74-3.73 (m, 2H), 2.64-2.49 (m, 4H), 2.18 (s, 3H), 2.04-2.03 (6H), 1.99 (m, 4H), 1.90 (t, 1H)

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

(27) TABLE-US-00001 TABLE 1 CMP Structure NMR A1 1H NMR (400 MHz, Methanol-d4) = 7.15 (d, 0.4H), 7.03 (s, 2H), 6.79 (d, 0.7H), 5.17-5.10 (m, 1H), 3.74-3.73 (m, 2H), 2.64-2.49 (m, 4H), 2.18 (s, 3H), 2.04-2.03 (6H), 1.99 (m, 4H), 1.90 (t, 1H) A2 0 1H NMR (400 MHz, Methanol-d4) = 7.06- 6.98 (m, 2H), 3.43-3.36 (m, 2H), 2.69-2.50 (m, 4H), 2.47-2.33 (m, 2H), 2.06-1.99 (m, 9H), 1.94- 1.84 (m, 2H) A3 1H NMR (400 MHz, Methanol-d4) = 7.03- 7.01 (2H), 3.65-3.52 (4H), 2.55-2.47 (4H), 2.12-2.03 (6H), 1.99- 1.98 (6H), 1.73-1.64 (m, 2H) A4 1H NMR (400 MHz, Methanol-d4) = 7.04 (s, 2H), 3.67 (t, J = 7.2 Hz, 2HA), 3.57 (t, J = 7.2 Hz, 2HB), 3.52 (s, 2HB), 3.44 (s, 2HA), 2.65 (s, 4H), 2.09-1.97 (m, 14H). A5 1H NMR (400 MHz, Acetonitrile-D3) = 7.14- 7.00 (m, 2H), 3.63- 3.55 (m, 2H), 3.05-2.98 (m, 3H), 2.91-2.80 (m, 2H), 2.74-2.64 (m, 2H), 2.17-2.08 (m, 2H), 2.04- 2.02 (m, 6H), 2.02- 2.00 (m, 3H) A6 1H NMR (400 MHz, Methanol-d4) = 7.03 (s, 2H), 3.50-3.37 (m, 4H), 2.59- 2.45 (m, 4H), 2.05-1.97 (m, 9H), 1.88- 1.68 (m, 6H), 1.47 (s, 9H). A7 1H NMR (400 MHz, Methanol-d4) = 7.04- 7.00 (m, 2H), 3.55-3.49 (m, 2H), 3.35 (s, 2H), 3.15-3.06 (m, 2H), 2.64 (s, 4H), 2.06-1.97 (m, 11H), 1.34 (t, J = 7.4 Hz, 3H). A8 1H NMR (400 MHz, Methanol-d4) = 1H NMR (400 MHz, methanol) = 7.03 (s, 2H), 3.46-3.37 (m, 4H), 3.06 (q, 2H), 2.58 (s, 4H), 2.04-1.97 (m, 9H), 1.94-1.87 (m, 2H), 1.86- 1.76 (m, 4H), 1.30 (t, 3H) A9 1H NMR (400 MHz, Methanol) = 7.03 (d, J = 1.6 Hz, 2H), 3.59- 3.50 (m, 4H), 2.61-2.47 (m, 4H), 2.12 (d, J = 2.1 Hz, 3H), 2.04-1.97 (m, 9H), 1.96-1.69 (m, 6H). A10 1H NMR (400 MHz, Methanol-d4) = 7.03 (S, 2H), 2.64-2.62 (m, 5H), 2.44-2.41 (t, 2H), 2.01-1.98 (10H), 1.95- 1.94 (t, 2H) A11 1H NMR (400 MHz, CDCl3) = 7.07 (s, 2H), 5.69 (br s, 1H), 3.43 (d, 1H), 3.31 (d, 1H), 2.79 (s, 2H), 2.64 (s, 2H), 2.50 (t, 2H), 2.07-1.90 (m, 11H), 1.86 (s, 3H) A12 0 1H NMR (400 MHz, Methanol-d4) = 7.02 (s, 2H), 4.14 (s, 2H), 3.71 (s, 3H), 3.45 (s, 2H), 2.65-2.64 (d, 4H), 2.52- 2.49 (t, 2H), 2.01-1.95 (m, 11H) A13 1H NMR (400 MHz, Methanol-d4) = 7.02 (s, 2H), 4.58-4.55 (m, 1H), 3.66-3.52 (m, 1H), 2.81-2.67 (m, 3H), 2.43 (s, 2H), 2.67 (s, 2H), 2.35-2.31 (m, 2H), 2.01- 1.98 (10H), 1.93 (s, 2H), 1.85-1.82 (m, 1H), 1.71-1.70 (m, 1H), 1.55- 1.53 (m, 1H), 1.49-1.46 (m, 2H) A14 1H NMR (400 MHz, Methanol-d4) = 7.01 (s, 2H), 3.97-3.93 (m, 1H), 3.82-3.79 (m, 1H), 2.95 (t, 1H), 2.67 (s, 2H), 2.39-2.35 (m, 4H), 2.26-2.24 (m, 1H), 2.14- 2.11 (m, 1H), 2.02-1.92 (10H), 1.64-1.59 (m, 1H), 1.44-1.38 (m, 1H), 1.24 (t, 1H) A15 1H NMR (400 MHz, Methanol-d4) = 7.13 (d, 0.4H), 7.02 (s, 2H), 6.69 (d, 0.6H), 5.22 (d, 0.4H), 5.13 (d, 0.6H), 4.26 (s, 2H), 3.77-3.60 (m, 2H), 3.45-3.37 (m, 3H), 2.63-2.45 (m, 4H), 2.05-1.85 (m, 11H) A16 1H NMR (400 MHz, Methanol-d4) = 7.54- 7.49 (m, 5H), 7.28 (br s, 0.3H) 7.02 (s, 2H), 6.52- 6.49 (m, 0.7H), 5.36 (br s, 0.3H) 5.05-5.00 (m, 0.7H), 3.89 (br s, 1.5H), 3.66 (br s, 0.5H), 2.69- 2.52 (m, 4H), 2.11-1.84 (m, 11H) A17 1H NMR (400 MHz, Methanol-d4) = 7.12 (d, 1H), 7.04 (s, 2H), 5.07 (d, 1H), 3.79-3.73 (m, 2H), 2.58 (q, 4H), 2.06-1.96 (m, 9H), 1.95- 1.88 (t, 2H), 1.31 (s, 9H) A18 A19 A20 A21 A22 0 1H NMR (400 MHz, Methanol-d4) = 7.02 (s, 2H), 4.50-4.28 (m, 1H), 3.60-3.56 (m, 1H), 3.43-3.40 (d, 0.4H), 3.20-3.18 (d, 0.6H), 2.74-2.68 (m, 2H), 2.59-2.46 (m, 3H), 2.09-1.96 (m, 12H), 1.90-1.64 (m, 3H), 1.59- 1.53 (m, 1H) Rotamers present A23 A24 A25 A26 A27 A28 A29 A30 A31 A32 0 A33 A34 A35 A36 A37 A38 A39 A40 A41 A42 0 A43 A44 A45 A46 A47 A48 1H NMR (400 MHz, Methanol-d4) = 8.61 (d, 1H), 7.98 (t, 1H), 7.69-7.67 (m, 1H), 7.53 (t, 1H), 7.30 (d, 0.4H), 7.03-7.02 (m, 2H), 6.61 (d, 0.6H), 5.40 (d, 0.4H), 5.03 (d, 0.6H), 3.97-3.89 (m, 1.2H), 3.75-3.68 (m, 0.8H), 2.71-2.49 (m, 4H), 2.10-1.88 (m, 11H) Rotamers present A49 1H NMR (400 MHz, Methanol-d4) = 7.19- 7.10 (m, 1H), 7.03 (s, 2H), 5.15 (d, 1H), 3.98- 3.92 (m, 1H), 3.74-3.67 (m, 1H), 2.63-2.49 (m, 4H), 2.08-1.86 (m, 12H), 0-93-0.88 (m, 4H) A50 1H NMR (400 MHz, Methanol-d4) = 7.15 (d, 0.5H), 7.04 (s, 2H), 6.67 (d, 0.5H), 6.50 (t, 1H), 5.20 (dd, 1H), 4.73- 4.72 (m, 2H), 3.96-3.61 (m, 2H), 2.68-2.50 (m, 4H), 2.05-1.88 (m, 11H) A51 1H NMR (400 MHz, Methanol-d4) = 7.12 (d, 0.4H), 7.03 (s, 2H), 6.64 (d, 0.6H), 5.22 (dd, 1H), 3.80-3.63 (m, 2H), 3.32-3.27 (m, 2H), 2.62- 2.48 (m, 4H), 2.05-1.87 (m, 11H) Rotamers present A52 0 1H NMR (400 MHz, Methanol-d4) = 7.88 (s, 1H), 7.04-6.96 (m, 2H), 4.55 (s, 1H), 3.72- 3.66 (m, 1H), 3.14-3.03 (m, 1H), 2.59-2.38 (m, 4H), 2.06-1.89 (m, 11H) A53 1H NMR (400 MHz, Methanol-d4) = 7.03 (s, 2H), 6.81 (d, 1H), 5.96 (br, 1H), 4.88 (d, 1H), 3.58-3.51 (m, 2H), 2.54 (q, 4H), 2.03 (d, 6H), 1.98 (s, 3H), 1.92- 1.87 (m, 2H), 1.35 (s, 9H) A54 1H NMR (400 MHz, Methanol-d4) = 7.02 (s, 2H), 6.79-6.58 (m, 1H), 5.14 (d, 1H), 3.72- 3.65 (m, 2H), 2.58 (q, 4H), 2.05-1.92 (m, 11H), 1.24 (s, 9H) A55 1H NMR (400 MHz, Methanol-d4) = 7.03 (s, 2H), 6.59 (d, 1H), 5.02 (d, 1H), 3.65-3.58 (m, 2H), 3.17 (q, 2H), 2.58 (q, 4H), 2.02-1.95 (m, 11H), 1.31 (t, 3H) A56 1H NMR (400 MHz, Methanol-d4) = 7.12 (d, 0.4H), 7.04 (s, 2H), 6.86 (d, 0.6H), 6.54 (t, 1H), 5.39 (d, 0.4H), 5.24 (d, 0.6H), 3.84-3.76 (m, 2H), 2.69-2.50 (m, 4H), 2.07-1.95 (m, 11H) A57 1H NMR (400 MHz, Methanol-d4) = 8.69 (d, 1H), 8.20 (d, 1H), 8.03 (t, 1H), 7.67-7.62 (m, 1H), 7.03 (s, 2H), 6.98-6.73 (m, 1H), 5.22 (d, 1H), 3.85-3.79 (m, 2H), 2.59 (q, 4H), 2.05- 1.96 (m, 11H) A58 1H NMR (400 MHz, Methanol-d4) = 7.03 (s, 2H), 4.58 (br s, 1H), 4.42-4.17 (m, 1H), 3.70 (br s, 1H), 3.42 (br s, 1H), 2.72 (br s, 2H), 2.52 (d, 1H), 2.37 (d, 1H), 2.11 (s, 3H), 2.01- 1.98 (m, 9H), 1.89-1.60 (m, 3H), 1.41-1.12 (m, 3H) A59 1H NMR (400 MHz, Methanol-d4) = 7.03 (s, 2H), 3.79-3.47 (m, 4H), 2.88 (d, 1H), 2.66- 2.48 (m, 2H), 2.45-2.37 (m, 1H), 2.10 (s, 3H), 2.07-1.93 (m, 9H), 1.88- 1.70 (m, 1H), 1.62-1.45 (m, 2H). 1.06-0.97 (m, 3H) A60 A61 A62 0 A63 1H NMR (400 MHz, Methanol-d4) = 7.02 (s, 2H), 4.11 (s, 2H), 3.47 (s, 2H), 2.74-2.60 (m, 4H), 2.51 (t, 2H), 2.04-1.92 (m, 11H) A64 1H NMR (400 MHz, Methanol-d4) = 7.01 (s, 2H), 4.02 (s, 2H), 3.42 (s, 2H), 2.73 (s, 3H), 2.65-2.57 (m, 4H), 2.51 (t, 2H), 2.05-1.94 (m, 11H) A65 1H NMR (400 MHz Methanol-d4) = 7.00 (s, 2H), 4.24 (s, 2H), 3.41 (s, 2H), 3.03 (s, 3H), 2.93 (s, 3H), 2.65- 2.53 (m, 4H), 2.50 (t, 2H), 2.04-1.95 (m, 11H) A66 A67

(28) TABLE-US-00002 TABLE 2 CMP Structure NMR P1 1H NMR (400 MHz, Methanol-d4) = 7.01 (s, 2H), 3.66-3.45 (m, 4H), 2.75 (d, 2H), 2.66- 2.51 (m, 2H), 2.12 (d, 3H), 2.06-1.67 (m, 18H) P2 1H NMR (400 MHz, Methanol-d4) = 7.04- 6.95 (m, 2H), 3.87-3.71 (m, 2H), 2.89-2.74 (m, 3H), 2.73-2.60 (m, 3H), 2.52-2.44 (m, 3H), 2.12- 2.05 (m, 1H), 2.04- 1.99 (m, 9H), 1.99-1.90 (m, 1H), 1.88-1.81 (m, 2H) P3 1H NMR (400 MHz, chloroform) = 7.11- 7.06 (m, 2H), 3.73-3.56 (m, 7H), 2.91-2.76 (m, 2H), 2.75-2.60 (m, 2H), 2.08-2.02 (m, 14H)

BIOLOGICAL EXAMPLES

(29) 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%).

(30) TABLE-US-00003 TABLE B1 LOLPE SETFA ALOMY ECHCG AVEFA Compound PRE POST PRE POST PRE POST PRE POST PRE POST A2 4 4 5 5 3 3 3 5 3 4 A3 2 5 3 5 2 5 2 5 3 5 A4 5 5 5 5 5 5 5 5 5 5 A5 5 5 5 5 3 5 5 5 3 4 A6 5 5 5 5 4 5 5 5 4 4 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 2 5 5 3 5 A13 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 A48 5 5 5 5 5 5 5 5 5 5 A49 5 5 5 5 5 5 5 5 5 5 A50 5 5 5 5 5 5 5 5 5 5 A51 5 5 5 5 5 5 5 5 5 5 A53 5 5 5 5 5 5 5 5 2 4 A54 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 5 5 5 5 5 5 A57 5 5 5 5 5 5 5 5 4 5 A58 5 5 5 5 5 5 5 5 5 5 A59 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 NT 5 5 P3 5 5 5 5 5 5 5 5 4 5 NT = Not Tested