CYCLIC DIONES AS HERBICIDAL COMPOUNDS

Abstract

The present invention relates to compounds of Formula (I), wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4x, R.sup.4y, m, n 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) ##STR00098## wherein R.sup.1 is selected from the group consisting of 1-propynyl, phenyl and a 5 or 6 membered heteroaryl which comprises one or two nitrogen heteroatoms, said phenyl and heteroaryl optionally substituted by one or two R.sup.15 substituents; R.sup.2 is methyl, ethyl, methoxy or chloro; R.sup.3 is selected from the group consisting of methyl, ethyl, methoxy and chloro; m is 0 or 1; n is 0 or 1; R.sup.4x is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl, hydroxyl, methoxy and halogen; R.sup.4y is selected from the group consisting of R4.sup.a, R4.sup.b and R4.sup.c: ##STR00099## R.sup.4aa is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl and C.sub.1-C.sub.6alkoxy-; R.sup.4ab 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, hydroxy-, hydroxyC.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkyl, —C.sub.1-C.sub.4alkoxyC.sub.1-C.sub.6alkyl, —C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.6haloalkyl, cyanoC.sub.1-C.sub.6alkyl-, C(O)R.sup.27, S(O).sub.nR.sup.27, 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.4aa and R.sup.4ab together form —(CH.sub.2).sub.q—, —CH.sub.2CH.sub.2X.sup.1CH.sub.2CH.sub.2— or —C(O)CH.sub.2X.sup.1CH.sub.2CH.sub.2— wherein X.sup.1 is selected from the group consisting of O, S(O).sub.n and N—R.sup.28; and R.sup.4ba is selected from the group consisting of hydrogen, C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.4alkoxy-; R.sup.4bb is selected from the group consisting of C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy-, C.sub.1-C.sub.4haloalkyl, —C(O)C.sub.1-C.sub.4alkyl, —C(O)C.sub.1-C.sub.4haloalkyl, hydroxyC.sub.1-C.sub.6alkyl-C(O)—, —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.n—C.sub.3-C.sub.6cycloalkyl, —C(O)C(R.sup.11)R.sup.12R.sup.13, —C(O)C.sub.2-C.sub.4alkenyl, —C(O)(CR.sup.9R.sup.10)CN, —C(O)(CR.sup.9R.sup.10)(CR.sup.9R.sup.10)CN, —C(O)CH.sub.2C(O)—C.sub.1-C.sub.6alkyl, —C(O)CH.sub.2OC(O)—C.sub.1-C.sub.6alkyl, —C(O)OC.sub.1-C.sub.6alkyl, —C(O)OC.sub.1-C.sub.6haloalkyl, —C(O)(CH.sub.2).sub.nS(O).sub.nC.sub.1-C.sub.6alkyl —C(O)C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.6alkyl, —C(O)C.sub.1-C.sub.3alkoxyC.sub.2-C.sub.6alkenyl, —C(O)C.sub.1-C.sub.3alkoxyC.sub.2-C.sub.6alkynyl, —C(O)C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.6haloalkyl, —C(O)C.sub.1-C.sub.3alkoxyC.sub.3-C.sub.6cycl ° alkyl, —C(O)OC.sub.1-C.sub.3alkoxyC.sub.1-C.sub.6alkyl, —C(O)C.sub.1-C.sub.3alkoxyC1-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.n—NR.sup.7C(O).sub.1e, —C(O)—(CH.sub.2).sub.n—O—N═CR.sup.5R.sup.5, —CN, —S(O).sub.2NR.sup.16R.sup.17, —S(O)(═NR.sup.18)R.sup.19, —C(O)C(O)R.sup.20, —C(O)C(R.sup.23)═N—O-R.sup.24 or —C(O)C(R.sup.23)═N—NR.sup.25R.sup.26, —(CH.sub.2).sub.n-phenyl, —C(O)—(CH.sub.2).sub.n-phenyl, —S(O).sub.n—(CH.sub.2).sub.n-phenyl, -heterocyclyl, —C(O)—(CH.sub.2).sub.n-heterocyclyl, —C(O)(CH.sub.2).sub.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 independently selected from the group consisting of hydrogen and C.sub.1-C.sub.6 alkyl; R.sup.6 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.6haloalkyl, hydroxyl-, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6 cycloalkyl, —C.sub.1-C.sub.4alkoxyC.sub.1-C.sub.6alkyl, —C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.6haloalkyl, —(CR.sup.9R.sup.10)C.sub.1-C.sub.6haloalkyl, —(CR.sup.9R.sup.10)C(O)NR.sup.5R.sup.5, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally substituted by one, two or three substituents independently selected from the group consisting of C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.2-C.sub.3 alkenyl, C.sub.2-C.sub.3 alkynyl, halogen, cyano and nitro; or R.sup.5 and R.sup.6 together form —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2—; and R.sup.7 is selected from the group consisting of hydrogen and C.sub.1-C.sub.6 alkyl; R.sup.8 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 cycloalkyl, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally substituted by one, two or three substituents independently selected from the group consisting of C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.2-C.sub.3 alkenyl, C.sub.2-C.sub.3 alkynyl, halogen, cyano and nitro; R.sup.9 is hydrogen or methyl; R.sup.10 is hydrogen or methyl; or R.sup.9 and R.sup.10 together form —CH.sub.2CH.sub.2—; and R.sup.11 is hydrogen or methyl; R.sup.12 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl, hydroxyl and C.sub.1-C.sub.6 alkoxy-; R.sup.13 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl, hydroxyl and C.sub.1-C.sub.6 alkoxy; or R.sup.12 and R.sup.13 together form —CH.sub.2—X.sup.2—CH.sub.2— wherein X.sup.2 is selected from the group consisting of O, S and N—R.sup.11; and R.sup.14 is selected from the group consisting of hydrogen, C.sub.1-C.sub.3 alkyl and C.sub.1-C.sub.3 alkoxy-; R.sup.15 is independently selected from the group consisting of C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, cyano and halogen; R.sup.16 is hydrogen or C.sub.1-C.sub.6alkyl; and R.sup.17 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6 alkoxy-C.sub.1-C.sub.3alkyl-, —C(O)C.sub.1-C.sub.6alkyl, —C(O)OC.sub.1-C.sub.6alkyl and CH.sub.2CN; or R.sup.16 and R.sup.17 together form —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2S(O).sub.2CH.sub.2CH.sub.2—; and R.sup.18 is hydrogen or C.sub.1-C.sub.6alkyl; R.sup.19 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6cycloalkyl, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally substituted by one, two or three substituents independently selected from the group consisting of C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.2-C.sub.3 alkenyl, C.sub.2-C.sub.3 alkynyl, halogen, cyano and nitro; R.sup.20 is selected from the group consisting of C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy-, C.sub.1-C.sub.6haloalkoxy, —NR.sup.21R.sup.22, phenyl and -pyridyl, wherein the phenyl and pyridyl are optionally substituted by one, two or three substituents independently selected from the group consisting of C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.2-C.sub.3 alkenyl, C.sub.2-C.sub.3 alkynyl, halogen, cyano and nitro; R.sup.21 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6 cycloalkyl, C.sub.1-C.sub.6haloalkyl- and C.sub.1-C.sub.6haloalkoxy-, —C(O)C.sub.1-C.sub.6alkyl, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally substituted by one, two or three substituents independently selected from the group consisting of C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.2-C.sub.3 alkenyl, C.sub.2-C.sub.3 alkynyl, halogen, cyano and nitro; R.sup.22 is hydrogen or C.sub.1-C.sub.6alkyl; or R.sup.21 and R.sup.22 together form —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2—; and R.sup.23 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy- and C.sub.1-C.sub.6haloalkoxy-; R.sup.24 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6cycloalkyl, —CH.sub.2CN, tetrahydropyranyl-, phenyl and -pyridyl, wherein the phenyl and pyridyl are optionally substituted by one, two or three substituents independently selected from the group consisting of C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3alkoxy, C.sub.2-C.sub.3alkenyl, C.sub.2-C.sub.3alkynyl, halogen, cyano and nitro; R.sup.25 is hydrogen or C.sub.1-C.sub.6 alkyl; R.sup.26 is hydrogen or C.sub.1-C.sub.6 alkyl; and R.sup.4ca is selected from 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.6cycloalkyl, —C.sub.1-C.sub.4alkoxyC.sub.1-C.sub.6alkyl, —C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.6haloalkyl, cyanoC.sub.1-C.sub.6alkyl-. C(O)R.sup.27, S(O).sub.nR.sup.27, 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.4cb is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl and C.sub.1-C.sub.6alkoxy-; or R.sup.4ca and R.sup.4cb together form —(CH.sub.2).sub.q—, —CH.sub.2CH.sub.2X.sup.1CH.sub.2CH.sub.2— or —C(O)CH.sub.2X.sup.1CH.sub.2CH.sub.2— wherein X.sup.1 is selected from the group consisting of O, S(O).sub.n and N—R.sup.28; R.sup.27 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, 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.28 is selected from the group consisting of hydrogen, C.sub.1-C.sub.3 alkyl, —C(O)C.sub.1-C.sub.3alkyl and C.sub.1-C.sub.3 alkoxy-; q is 3, 4 or 5; and G is selected from the group consisting of hydrogen, —(CH.sub.2).sub.n—R.sup.a, —C(O)—R.sup.a, —C(O)—(CR.sup.cR.sup.d).sub.n—O—R.sup.b, —C(O)—(CR.sup.cR.sup.d).sub.n—S—R.sup.b, —C(O)NR.sup.aR.sup.a, —S(O).sub.2—R.sup.a and C.sub.1-C.sub.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. The compound according to claim 1, wherein R.sup.1 is 1-propynyl.

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

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

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

6. The compound according to claim 1, wherein R.sup.4 is R.sup.4a.

7. The compound according to claim 1, wherein R.sup.4 is R.sup.4b.

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

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

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

13. The 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 3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-N-methyl-2,4-dioxo-spiro[5.5]undecane-9-carboxamide (Compound 1.002)

[0133] ##STR00017##

Step 1: Synthesis of N-methyl-4-oxo-cyclohexanecarboxamide

[0134] ##STR00018##

To a stirred solution of 4-oxocyclohexanecarboxylic acid (1.00 g, 7.03 mmol) in DCM (24.0 mL) was added methylamine solution (9.8 M in MeOH, 2.15 mL, 21.1 mmol), HOAt (1.44 g, 10.6 mmol), EDC-HCl (1.64 g, 10.6 mmol) and DIPEA (3.68 mL, 21.1 mmol). The reaction mixture was stirred at room temperature for 17 hours, diluted with water and extracted with DCM. The combined organic layer was washed with brine, dried over Na.sub.2SO.sub.4, concentrated and purified by flash column chromatography (0-50% acetone in hexane) to give N-methyl-4-oxo-cyclohexanecarboxamide as a white solid (230 mg, 1.48 mmol, 21% yield). 1H NMR (400 MHz, CD.sub.3Cl) δ ppm=5.58 (br s, 1H), 2.83-2.82 (d, 3H), 2.54-2.47 (m, 3H), 2.36-2.28 (m, 2H), 2.17-2.12 (m, 2H), 2.03-1.93 (m, 2H)

Step 2: Synthesis of 4-acetonylidene-N-methyl-cyclohexanecarboxamide

[0135] ##STR00019##

To a stirred solution of potassium hydroxide (0.253 g, 4.51 mmol) in ethanol (7.0 mL) and water (1.8 mL) was added 1-dimethoxyphosphorylpropan-2-one (0.624 mL, 4.51 mmol) drop wise at 5° C. To this mixture was added N-methyl-4-oxo-cyclohexanecarboxamide (0.500 g, 3.22 mmol) portion wise at the same temperature. The resulting reaction mixture was stirred at room temperature for 22 hours before being concentrated, diluted with water and extracted with DCM. The combined organics were washed with brine, dried over Na.sub.2SO.sub.4 and concentrated to obtain crude material. The crude was triturated with 20% EtOAc:Hexane to obtain 4-acetonylidene-N-methyl-cyclohexanecarboxamide as an off white solid (470 mg, 2.35 mmol, 73% yield). 1H NMR (400 MHz, CD.sub.3Cl) δ ppm=6.02 (s, 1H), 5.50 (s, 1H), 2.78 (d, 3H), 2.34-1.93 (m, 12H).

Step 3: Synthesis of N-methyl-2,4-dioxo-spiro[5.5]undecane-9-carboxamide

[0136] ##STR00020##

To a stirred solution of 4-acetonylidene-N-methyl-cyclohexanecarboxamide (4.10 g, 21.0 mmol) in ethanol (26.0 mL) was added diethyl propanedioate (3.20 mL, 21.0 mmol) followed by drop-wise addition of sodium ethoxide (21.0%, 61 mL, 3.61 mmol). The reaction mixture was stirred at room temperature for 3 hours then heated to reflux for 4 hours before being allowed to stand at room temperature overnight. The reaction mixture was concentrated, diluted with water and washed with ethyl acetate. The aqueous layer was then acidified with aqueous citric acid and extracted with DCM. The combined organics were washed with brine, dried over Na.sub.2SO.sub.4 and concentrated to give ethyl 9-(methylcarbamoyl)-2,4-dioxo-spiro[5.5]undecane-5-carboxylate (3.80 g) as a brown gummy liquid. Crude ethyl 9-(methylcarbamoyl)-2,4-dioxo-spiro[5.5]undecane-5-carboxylate (3.80 g, 12.3 mmol) was taken up in ethanol (10.0 mL). Sodium hydroxide (12.0 M, 21.7 mL, 260 mmol) was added at room temperature and the reaction mixture was stirred at room temperature for 23 hours. The reaction mixture was concentrated, acidified with citric acid solution and extracted with ethyl acetate. The combined organics were dried over Na.sub.2SO.sub.4, concentrated and purified by flash column chromatography (MeOH-DCM) to give N-methyl-2,4-dioxo-spiro[5.5]undecane-9-carboxamide as an off white foam (2.3 g, 9.69 mmol, 79% yield). 1H NMR (400 MHz, CD.sub.3OD) δ ppm=2.92-2.88 (m, 2H), 2.80-2.76 (m, 2H), 2.69 (s, 3H), 2.16-2.30 (m, 1H), 1.82-1.78 (m, 2H), 1.66-1.62 (m, 4H), 1.28-1.23 (m, 2H)

Step 4: Synthesis of [diacetoxy-(4-bromo-2,6-dimethyl-phenyl)plumbyl] acetate

[0137] ##STR00021##

Lead (IV) acetate (2.32 g, 5.24 mmol) and mercuric acetate (0.139 g, 0.437 mmol) were dissolved in chloroform (20 mL) and the solution was warmed to 40° C. for 10 minutes. (4-bromo-2,6-dimethyl-phenyl)boronic acid (1.00 g, 4.37 mmol) was added and the mixture was heated at 40° C. for 3 hours. The reaction mixture was cooled to 0° C. and potassium carbonate (4.52 g, 32.7 mmol) was added. The reaction mixture was then stirred vigorously for 1 hour at room temperature. The reaction was filtered through celite-pad, washing through with chloroform. The filtrate was concentrated and the resulting solid was triturated with hexane to give [diacetoxy-(4-bromo-2,6-dimethyl-phenyl)plumbyl] acetate as a white solid (1.94 g, 3.41 mmol, 78% yield). 1H NMR (400 MHz, CD.sub.3Cl) δ ppm=7.33 (s, 2H), 2.62-2.54 (m, 6H), 2.08 (s, 9H).

Step 5: Synthesis of 3-(4-bromo-2,6-dimethyl-phenyl)-N-methyl-2,4-dioxo-spiro[5.5]undecane-9-carboxamide

[0138] ##STR00022##

[0139] To a stirred solution of compound N-methyl-2,4-dioxo-spiro[5.5]undecane-9-carboxamide (0.810 g, 3.41 mmol) in chloroform (28 mL) was added 4,4-dimethylaminopyridine (2.08 g, 17.1 mmol). The reaction mixture was stirred under nitrogen for 15 min at room temperature, then toluene (6 mL) was added followed by the addition of [diacetoxy-(4-bromo-2,6-dimethyl-phenyl)plumbyl] acetate (1.94 g, 3.41 mmol). The reaction mixture was stirred at 80° C. for 3 hours before being allowed to stand at room temperature overnight. The reaction mixture was cooled over ice, acidified with citric acid solution and filtered through celite. The aqueous layer was extracted with chloroform and the combined organics were washed with brine, dried over Na.sub.2SO.sub.4, evaporated and purified by flash column chromatography (acetone-hexane) to give 3-(4-bromo-2,6-dimethyl-phenyl)-N-methyl-2,4-dioxo-spiro[5.5]undecane-9-carboxamide as an off-white solid (125 mg, 0.275 mmol, 8% yield). 1H NMR (400 MHz, CD.sub.3OD) δ ppm=7.18 (s, 2H), 2.71-2.67 (m, 5H), 2.40 (s, 2H), 2.19-2.14 (m, 1H), 2.02 (s, 6H), 1.96-1.93 (m, 2H), 1.72-1.63 (m, 4H), 1.41-1.24 (m, 2H).

Step 6: Synthesis of 3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-N-methyl-2,4-dioxo-spiro[5.5]undecane-9-carboxamide (Compound 1.002)

[0140] ##STR00023##

3-(4-bromo-2,6-dimethyl-phenyl)-N-methyl-2,4-dioxo-spiro[5.5]undecane-9-carboxamide (0.125 g, 0.297 mmol), 4-diphenylphosphanylbutyl(diphenyl)phosphane (0.0253 g, 0.0594 mmol), bis(triphenylphosphine)palladium(II) chloride (0.0209 g, 0.0297 mmol) and 2-butynoic acid (0.0750 g, 0.892 mmol) were placed into a round-bottomed flask. Dimethyl sulfoxide (2.00 mL) and DBU (0.272 g, 1.78 mmol) were added and the reaction mixture was stirred at 110° C. for 20 hours. The reaction mixture was acidified with 10% citric acid solution and extracted with EtOAc. The combined organics were dried over Na.sub.2SO.sub.4, concentrated and purified by prep-HPLC to give 3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-N-methyl-2,4-dioxo-spiro[5.5]undecane-9-carboxamide as a white solid (24 mg, 0.063 mmol, 21% yield). 1H NMR (400 MHz, CD.sub.3OD) δ ppm=7.81 (br s, 1H), 7.02 (s, 2H), 2.71-2.67 (m, 5H), 2.39 (br s, 2H), 2.20-2.14 (m, 1H), 2.03-1.98 (m, 10H), 1.94 (m, 1H), 1.69-1.67 (m, 4H), 1.40-1.33 (m, 2H).

EXAMPLE 2

Synthesis of N-[3-[4-(5-chloro-2-pyridyl)-2,6-dimethyl-phenyl]-2,4-dioxo-spiro[5.5]undecan-9-yl]acetamide (Compound 2.026)

[0141] ##STR00024##

Step 1: Synthesis of tert-butyl N-(4-acetonylidenecyclohexyl)carbamate

[0142] ##STR00025##

To a stirred solution of potassium hydroxide (1.5 equiv., 70.333 mmol) in ethanol (20 equiv., 937.78 mmol) and water (5 equiv., 234.44 mmol) at 0° C., was added dimethyl (2-oxopropyl)phosphonate (1.4 equiv., 65.644 mmol) dropwise and the reaction mixture was stirred for 5 minutes. Then, tert-butyl N-(4-oxocyclohexyl)carbamate (10 g, 46.889 mmol) was added and the reaction mixture was allowed to stir at room temperature for 2 hours before being extracted with EtOAc, washed with brine, and dried over MgSO.sub.4. The volatiles were removed in vacuo and the residues were purified by flash column chromatography (0-100% ethyl acetate in iso-hexane) to give tert-butyl N-(4-acetonylidenecyclohexyl)carbamate as a white solid (10.3 g, 40.7 mmol, 87% yield). 1H NMR (400 MHz, CD.sub.3Cl) δ ppm=6.07-5.97 (m, 1H), 3.63-3.52 (m, 1H), 2.46-2.38 (m, 2H), 2.28-2.21 (m, 2H), 2.18 (s, 3H), 1.48-1.42 (m, 13H).

Step 2: Synthesis of tert-butyl N-(2,4-dioxospiro[5.5]undecan-9-yl)carbamate

[0143] ##STR00026##

To a stirred solution of sodium methoxide in methanol (1 equiv., 19.65 mmol, 25 mass %) at 0° C. was added dimethyl propanedioate (1.05 equiv., 20.63 mmol) dropwise and the mixture was stirred for 1 hour. Then, a solution of tert-butyl N-(4-acetonylidenecyclohexyl)carbamate (4.977 g, 19.65 mmol) in methanol (20 mL, 490 mmol) was added dropwise at 0° C. and the mixture was stirred at room temperature for 10 minutes and heated to 60° C. overnight. On cooling, a solution of potassium hydroxide (5 equiv., 98.25 mmol) in water (0.3 mL/mmol, 327.2 mmol) was added and the reaction mixture was stirred at 60° C. for 24 hours. The mixture was cooled, acidified to pH=5 with aqueous citric acid and extracted with ethyl acetate. The combined organics were dried over Na.sub.2SO.sub.4, filtered and concentrated to give tert-butyl N-(2,4-dioxospiro[5.5]undecan-9-yl)carbamate as a brown solid (4.164 g, 14.10 mmol, 72% yield). 1H NMR (400 MHz, CD.sub.3OD) δ ppm=3.37-3.32 (m, 1H), 2.41 (s, 2H), 2.26-2.20 (m, 2H), 1.79-1.69 (m, 4H), 1.43 (s, 9H), 1.40-1.32 (m, 4H).

Step 3: Synthesis of tert-butyl N-[2,4-dioxo-3-(phenyl-$I{circumflex over ( )}{3}-iodanylidene)spiro[5.5]undecan-9-yl]carbamate

[0144] ##STR00027##

Sodium carbonate (2 equiv., 24.04 mmol) was dissolved in a mixture of water (15 mL/g) and ethanol (3 mL/g). Tert-butyl N-(2,4-dioxospiro[5.5]undecan-9-yl)carbamate (3.551 g, 12.02 mmol) was added in one portion and the mixture was stirred at room temperature until dissolution of the dione (5 minutes). The solution was cooled to 5° C. and (diacetoxyiodo)benzene (1 equiv., 12.02 mmol) was added portionwise. The reaction mixture was stirred for 15 minutes at 5° C. and then at room temperature for 3 hours. The mixture was diluted with water and extracted with DCM. The combined organics were washed with brine, dried over MgSO.sub.4, concentrated and triturated in diethyl ether to give tert-butyl N-[2,4-dioxo-3-(phenyl-$I″{3}-iodanylidene)spiro[5.5]undecan-9-yl]carbamate as a brown solid (2.040 g, 4.10 mmol, 34% yield). 1H NMR (400 MHz, CDCl.sub.3) δ ppm=7.88-7.78 (m, 2H), 7.58-7.50 (m, 1H), 7.42-7.31 (m, 2H), 4.50-4.35 (m, 1H), 3.47-3.36 (m, H), 2.67-2.57 (m, 2H), 2.54-2.44 (m, 2H), 1.86-1.77 (m, 2H), 1.72-1.69 (m, 2H), 1.47-1.41 (m, 9H), 1.38-1.27 (m, 4H).

Step 4: Synthesis of tert-butyl N-[3-(4-bromo-2,6-dimethyl-phenyl)-2,4-dioxo-spiro[5.5]undecan-9-yl]carbamate

[0145] ##STR00028##

Tert-butyl N-[2,4-dioxo-3-(phenyl-$I{circumflex over ( )}{3}-iodanylidene)spiro[5.5]undecan-9-yl]carbamate (2.04 g, 4.10 mmol, 100 mass %) was dissolved in 1,2-dimethoxyethane (8 mL/mmol, 312 mmol) and the mixture was treated with (4-bromo-2,6-dimethyl-phenyl)boronic acid (1.2 equiv., 4.92 mmol) and palladium(II) acetate (0.05 equiv., 0.205 mmol). The reaction mixture was stirred at room temperature for 5 min and a solution of lithium hydroxide (3 equiv., 12.3 mmol) in water (2 mL/mmol, 442 mmol) was finally added. The mixture was stirred at 50° C. for 20 hours, cooled, diluted with aqueous citric acid and extracted with ethyl acetate. The organics were dried over MgSO.sub.4, concentrated and purified by flash column chromatography (0-100% EtOAc in iso-hexane) to give tert-butyl N-[3-(4-bromo-2,6-dimethyl-phenyl)-2,4-dioxo-spiro[5.5]undecan-9-yl]carbamate as a pale yellow solid (594 mg, 1.24 mmol, 30% yield). 1H NMR (400 MHz, CD.sub.3OD) δ ppm=7.19-7.16 (m, 2H), 2.60-2.56 (m, 2H), 2.44-2.40 (m, 2H), 2.04-2.01 (m, 6H), 1.93-1.85 (m, 2H), 1.81-1.72 (m, 2H) 1.47-1.41 (m, 13H).

Step 5: Synthesis of tert-butyl N-[3-[2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-2,4-dioxo-spiro[5.5]undecan-9-yl]carbamate

[0146] ##STR00029##

Tert-butyl N-[3-(4-bromo-2,6-dimethyl-phenyl)-2,4-dioxo-spiro[5.5]undecan-9-yl]carbamate (261 mg, 0.5456 mmol) and bis(pinacolato)diboron (3 equiv., 1.637 mmol) were dissolved in de-gassed 1,4-dioxane (5 mL). To the mixture was added 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.2 equiv., 0.1091 mmol), tri(dibenzylideneacetone)dipalladium(0) (0.1 equiv., 0.05456 mmol) and potassium acetate (3 equiv., 1.637 mmol). The mixture was stirred at 85° C. for 24 hours, concentrated and purified by flash column chromatography (0-100% ethyl acetate in cyclohexane) to give tert-butyl N-[3-[2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-2,4-dioxo-spiro[5.5]undecan-9-yl]carbamate (264 mg, 0.467 mmol, 86% yield). 1H NMR (400 MHz, CD.sub.3OD) δ ppm=7.44 (s, 2H), 3.43-3.37 (m, 1H), 2.63 (s, 2H), 2.48 (s, 2H), 2.09-2.06 (m, 6H), 1.98-1.89 (m, 2H), 1.84-1.77 (m, 2H), 1.51-1.47 (m, 4H), 1.47-1.45 (m, 9H), 1.35 (s, 12H).

Step 6: Synthesis of tert-butyl N-[3-[4-(5-chloro-2-pyridyl)-2,6-dimethyl-phenyl]-2,4-dioxo-spiro[5.5]undecan-9-yl]carbamate

[0147] ##STR00030##

To a mixture of tert-butyl N-[3-[2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-2,4-dioxo-spiro[5.5]undecan-9-yl]carbamate (0.264 g, 0.5024 mmol), 2-bromo-5-chloro-pyridine (0.1257 g, 0.6531 mmol) and 1,1′-bis(diphenylphosphino)ferrocene-palladium(II) dichloride dichloromethane complex (0.08459 g, 0.1005 mmol) at room temperature was added 1,2-dimethoxyethane (10 mL) followed by a solution of potassium phosphate tribasic (0.4266 g, 2.010 mmol) in water (5 mL). The reaction mixture was stirred at 100° C. for 18 hours. On cooling, the mixture was diluted with 10% aqueous citric acid and extracted with ethyl acetate. The combined organics were dried over Na.sub.2SO.sub.4, passed through a phase-separator cartridge, concentrated and purified by flash column chromatography (0-100% ethyl acetate DCM) to give tert-butyl N-[3-[4-(5-chloro-2-pyridyl)-2,6-dimethyl-phenyl]-2,4-dioxo-spiro[5.5]undecan-9-yl]carbamate as a brown solid (100 mg, 0.180 mmol, 36% yield). 1H NMR (400 MHz, CD.sub.3OD) δ ppm=8.54 (d, 1H), 7.87-7.76 (m, 2H), 7.62 (s, 2H), 3.43-3.33 (m, 1H), 2.62 (s, 2H), 2.47 (s, 2H), 2.13 (s, 6H), 1.96-1.86 (m, 2H), 1.84-1.73 (m, 2H), 1.52-1.37 (m, 13H).

Step 7: Synthesis of N-[3-[4-(5-chloro-2-pyridyl)-2,6-dimethyl-phenyl]-2,4-dioxo-spiro[5.5]undecan-9-yl]acetamide (Compound 2.026)

[0148] ##STR00031##

Tert-butyl N-[3-[4-(5-chloro-2-pyridyl)-2,6-dimethyl-phenyl]-2,4-dioxo-spiro[5.5]undecan-9-yl]carbamate (122 mg, 0.2387 mmol) was dissolved in dichloromethane (0.2 M, 18.5 mmol) at room temperature and 4.0 M hydrogen chloride in dioxane (5 equiv., 1.194 mmol, 4.0 mol/L) was added dropwise. The mixture was stirred at room temperature for 2.5 hours before being concentrated. The resulting solids were re-dissolved in isopropenyl acetate (0.1 M, 20.3 mmol) and triethylamine (3 equiv., 0.6705 mmol) was added. The mixture was stirred at room temperature overnight, concentrated and purified by flash column chromatography (0-30% methanol in DCM) to afford N-[3-[4-(5-chloro-2-pyridyl)-2,6-dimethyl-phenyl]-2,4-dioxo-spiro[5.5]undecan-9-yl]acetamide (60 mg, 0.1325 mmol, 59% yield). 1H NMR (400 MHz, CD.sub.3OD) δ ppm=8.59-8.53 (m, 1H), 7.90-7.80 (m, 2H), 7.67-7.60 (m, 2H), 3.73-3.64 (m, 1H), 2.65 (s, 2H), 2.49 (s, 2H), 2.14 (s, 6H), 1.98 (s, 2H), 1.93 (s, 3H), 1.85-1.75 (m, 2H), 1.55-1.42 (m, 4H)

EXAMPLE 3

Synthesis of N-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-2,4-dioxo-spiro[5.5]undecan-9-yl]acetamide (Compound 2.001)

[0149] ##STR00032##

Step 1: Synthesis of tert-butyl N-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-2,4-dioxo-spiro[5.5]undecan-9-yl]carbamate

[0150] ##STR00033##

Dimethyl sulfoxide (6 mL/mmol) was added to a mixture of tert-butyl N-[3-(4-bromo-2,6-dimethyl-phenyl)-2,4-dioxo-spiro[5.5]undecan-9-yl]carbamate (237 mg, 0.4954 mmol), 1,4-bis(diphenylphosphino)butane (0.1 equiv., 0.04954 mmol), and but-2-ynoic acid (1.2 equiv., 0.5945 mmol). The reaction mixture was de-gassed and bis(triphenylphosphine)palladium(II) dichloride (0.05 equiv., 0.02477 mmol) was added, followed by DBU (3 equiv., 1.486 mmol). The reaction mixture was stirred at 100° C. for 2.5 hours. On cooling, the reaction mixture was adjusted to pH=6 with aqueous citric acid and extracted with ethyl acetate. The organics were dried over Na.sub.2SO.sub.4, concentrated and purified by flash column chromatography (20-100% EtOAc in iso-hexane) to give tert-butyl N-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-2,4-dioxo-spiro[5.5]undecan-9-yl]carbamate as a pale yellow oil (125 mg, 0.286 mmol, 58% yield). 1H NMR (400 MHz, CD.sub.3OD) δ ppm=7.04-7.01 (m, 2H), 3.42-3.32 (m, 1H), 2.64-2.56 (m, 2H), 2.48-2.42 (m, 2H), 2.00 (s, 6H), 1.99-1.98 (m, 3H), 1.94-1.85 (m, 2H), 1.82-1.74 (m, 2H), 1.45-1.45 (m, 4H), 1.44-1.43 (m, 9H).

Step 2: Synthesis of 9-amino-3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)spiro[5.5]undecane-2,4-dione hydrochloride

[0151] ##STR00034##

Tert-butyl N-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-2,4-dioxo-spiro[5.5]undecan-9-yl]carbamate (125 mg, 0.2856 mmol) was suspended in dichloromethane (1 mL/mmol, 4.42 mmol) and then 4.0 M hydrogen chloride in 1,4-dioxane (5 equiv., 1.428 mmol) was added dropwise. The reaction mixture was stirred at room temperature for 20 hours then at 40° C. for 4 hours. The reaction mixture was concentrated, re-dissolved in acetone (5 mL) and treated with additional 4.0 M hydrogen chloride in 1,4-dioxane (5 equiv., 1.428 mmol). The mixture was stirred at 60° C. for 5 hours and concentrated to give 9-amino-3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)spiro[5.5]undecane-2,4-dione hydrochloride as a gummy yellow solid (95 mg, 0.254 mmol, 89% yield). 1H NMR (400 MHz, CD.sub.3OD) δ ppm=7.07-7.01 (m, 2H), 3.19-3.08 (m, 1H), 2.67-2.61 (m, 2H), 2.51-2.48 (m, 2H), 2.01 (s, 6H), 2.00-1.99 (m, 3H), 1.98-1.85 (m, 4H), 1.67-1.56 (m, 2H), 1.54-1.43 (m, 2H).

Step 3: Synthesis of N-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-2,4-dioxo-spiro[5.5]undecan-9-yl]acetamide (Compound 2.001)

[0152] ##STR00035##

[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-2,4-dioxo-spiro[5.5]undecan-9-yl]ammonium hydrochloride (100 mg, 0.208 mmol) was dissolved in DCM (1.040 mL, 0.2 M), cooled to 0° C. and treated with triethylamine (0.117 mL, 4 equiv.) and acetyl chloride (0.0379 mL, 2.5 equiv.). The mixture was allowed to stir at room temperature for 3 hours, acidified with dilute hydrochloric acid and extracted with DCM. The organics were concentrated, re-dissolved in methanol (2.081 mL, 0.1 M) and treated with potassium carbonate (0.05751 g, 2.0 equiv.). The mixture was stirred at room temperature for 20 hours, diluted with 2 M HCl and extracted with ethyl acetate. The organics were dried over Na.sub.2SO.sub.4, concentrated and purified by flash column chromatography (0-30% methanol in DCM) to give N-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-2,4-dioxo-spiro[5.5]undecan-9-yl]acetamide as a white solid (47 mg, 0.124 mmol, 60% yield). 1H NMR (400 MHz, CD.sub.3OD) δ ppm=8.04-7.98 (m, 1H), 7.03 (s, 2H), 3.72-3.64 (m, 1H), 2.62 (s, 2H), 2.46 (s, 2H), 2.00 (s, 6H), 1.99 (s, 3H), 1.92 (s, 3H), 1.92-1.88 (m, 2H), 1.82-1.73 (m, 2H) 1.53-1.41 (m, 4H).
Examples of herbicidal compounds of the present invention.

TABLE-US-00001 TABLE 1 CMP Structure NMR 1.001 [00036] 1H NMR (MeOD, 400 MHz): δ = 7.00 (s, 2H), 3.10 (s, 3H), 2.92 (s, 3H), 2.72-2.66 (m, 1H), 2.64 (s, 2H), 2.37 (s, 2H), 2.00-1.96 (m, 11H), 1.72-1.62 (m, 4H), 1.45- 1.37 (m, 2H) 1.002 [00037] 1HNMR (MeOD, 400 MHz): δ = 7.81 (br s, 1H), 7.02 (s, 2H), 2.71-2.67 (m, 5H), 2.39 (br s, 2H), 2.20-2.14 (m, 1H), 2.03- 1.98 (m, 10H), 1.94 (m, 1H), 1.69-1.67 (m, 4H), 1.40-1.33 (m, 2H) 1.003 [00038] 1H NMR (MeOD, 400 MHz): δ = 8.69-8.68 (m, 1H), 8.22-8.20 (m, 1H), 8.05-8.00 (m, 1H), 7.66- 7.63 (m, 1H), 7.01 (s, 2H), 3.06 (m, 1H), 2.66-2.64 (s, 2H), 2.44 (s, 2H), 2.00-1.90 (m, 13H), 1.81-1.74 (m, 2H), 1.51- 1.45 (m, 2H) 1.004 [00039] 1H NMR (MeOD, 400 MHz): δ = 8.27 (d, 1H), 8.07 (d, 1H), 7.77- 7.72 (m, 1H), 7.10-7.07 (m, 1H), 7.02 (s, 2H), 2.69 (2H), 2.49 (m, 1H), 2.42 (s, 2H), 2.01-1.98 (m, 11H), 1.83- 1.77 (m, 4H), 1.48-1.41 (m, 2H) 1.005 [00040] 1H NMR (MeOD, 400 MHz): δ = 7.01 (s, 2H), 4.24 (s, 2H), 3.91- 3.89 (m, 2H), 3.71-3.69 (m, 2H), 3.51-3.47 (m, 1H), 2.63 (s, 2H), 2.40 (s, 2H), 2.00-1.94 (m, 11H), 1.86-1.83 (m, 2H), 1.72- 1.66 (m, 2H), 1.44-1.36 (m, 2H) 1.006 [00041] 1H NMR (MeOD, 400 MHz): δ = 7.01 (s, 2H), 3.64-3.54 (m, 8H), 2.72 (m, 1H), 2.67 (s, 2H), 2.40 (s, 2H), 2.12 (s, 3H), 2.00-1.96 (m, 11H), 1.74-1.67 (m, 4H), 1.47-1.41 (m, 2H) 1.007 [00042] 1H NMR (MeOD, 400 MHz): δ = 7.01 (s, 2H), 4.04-3.97 (m, 4H), 3.17 (m, 2H), 3.10 (m, 2H), 2.77- 2.74 (m, 1H), 2.66 (s, 2H), 2.41 (s, 2H), 2.02-1.95 (m, 11H), 1.74-1.69 m, (4H), 1.49-1.42 (m, 2H) 1.008 [00043] 1H NMR (MeOD, 400 MHz): δ = 7.01 (s, 2H), 3.64-3.63 (m, 4H), 3.58 (m, 4H), 2.67 (m, 3H), 2.40 2H), 1.99-1.95 (m, 11H), 1.74-1.62 (m, 4H), 1.46-1.40 (m, 2H) 1.009 [00044] 1H NMR (MeOD, 400 MHz): δ = 7.01 (s, 2H), 3.69-3.64 (m, 2H), 3.53-3.64 (m, 2H), 3.16-2.94 (2 × s, 3H), 2.85-2.67 (m, 3H), 2.39- 2.38 (m, 2H), 1.99-1.94 (m, 11H), 1.75-1.67 (m, 4H), 1.43- 1.41 (m, 2H) 1.010 [00045] 1H NMR (MeOD, 400 MHz): δ = 7.02 (s, 2H), 3.66 (s, 3H), 2.67 (s, 2H), 2.40 (s, 2H), 1.99-1.98 (m, 12H), 1.79-1.65 (m, 4H), 1.40- 1.33 (m, 2H) 1.011 [00046] 1H NMR (MeOD, 400 MHz): δ = 7.01(s, 2H), 3.45-3.42 (m, 2H), 3.33-3.30 (m, 5H), 2.65 (s, 2H), 2.38 (s, 2H), 2.22-2.20 (m, 1H), 2.00-1.94 (m, 11H), 1.70- 1.68 (m, 4H), 1.40-1.33 (m, 2H) 1.012 [00047] 1H NMR (MeOD, 400 MHz): δ = 7.89 (m, 1H), 7.01 (s, 2H), 3.59- 3.56 (m, 2H), 3.29-3.23 (m, 2H), 2.65 (s, 2H), 2.38 (s, 2H), 2.24- 2.20 (m, 1H), 1.99-1.94 (m, 11H), 1.71 (m, 4H), 1.41-1.33 (m, 2H) 1.013 [00048] 1H NMR (MeOD, 400 MHz): δ = 7.39 (m, 1H), 7.01 (s, 2H), 2.66 (s, 2H), 2.37 (s, 2H), 2.16- 2.13 (m, 1H), 1.99-1.93 (m, 11H), 1.69-1.63 (m, 4H), 1.38- 1.28 (m, 11H) 1.014 [00049] 1H NMR (MeOD, 400 MHz): δ = 7.01 (s, 2H), 2.67-2.64 (s, 2H), 2.39 (s, 2H), 2.25 (m, 1H), 2.02- 1.90 (m, 13H), 1.70 (m, 4H), 1.58 (s, 3H), 1.40- 1.36 (m, 2H), 1.06-1.03 (t, 3H) 1.015 [00050] 1H NMR (MeOD, 400 MHz): δ = 6.82 (s, 1H), 6.74 (s, 1H), 3.65 (s, 3H), 3.10 (s, 3H), 2.92 (s, 3H), 2.72-2.58 (m, 3H), 2.35 (m, 2H), 2.09-2.05 (m, 1H), 2.00-1.99 (m, 6H), 1.93-1.90 (m, 1H), 1.71- 1.64 (m, 4H), 1.45-1.32 (m, 2H) 1.016 [00051] 1H NMR (MeOD, 400 MHz): δ = 7.80 (m, 1H), 6.82 (s, 1H), 6.75 (s, 1H), 3.65 (s, 3H), 2.71-2.61 (m, 5H), 2.39-2.31 (m, 2H), 2.21-2.13 (m, 1H), 2.08- 2.04 (m, 1H), 1.99 (m, 6H), 1.93- 1.90 (m, 1H), 1.68-1.66 (m, 4H), 1.39-1.28 (m, 2H) 1.017 [00052] 1H NMR (MeOD, 400 MHz): δ = 7.78 (br s, 1H), 7.01 (s, 2H), 3.10-3.06 (m, 1H), 2.72- 2.67 (m, 7H), 2.21-2.11 (m, 4H), 1.98-1.96 (m, 9H) 1.018 [00053] 1H NMR (MeOD, 400 MHz): δ = 6.97 (s, 2H), 2.83-2.79 (m, 1H), 2.69 (s, 3H), 2.53-2.43 (m, 2H), 2.39 (s, 2H), 2.01 (s, 6H), 1.97 (s, 3H), 1.95-1.68 (m, 6H) 1.019 [00054] .sup.1H NMR (400 MHz, MeOD) δ = 8.74 (s, 2H), 8.05 (s, 2H), 2.72 (s, 5H), 2.44 (s, 2H), 2.21 (s, 1H), 2.14 (s, 6H), 2.00 (br d, 2H), 1.77 − 1.67 (m, 4H), 1.47 − 1.35 (m, 2H) 1.020 [00055] .sup.1H NMR (400 MHz, MeOD) δ = 8.92 (d, 1H), 8.17 (dd, 8.4 Hz, 1H), 8.07 − 8.02 (m, 1H), 7.77 (s, 2H), 2.72 (s, 5H), 2.44 (s, 2H), 2.26 − 2.18 (m, 1H), 2.15 (s, 6H), 2.00 (br d, 2H), 1.76 − 1.68 (m, 4H), 1.47 − 1.34 (m, 2H) 1.021 [00056] .sup.1H NMR (400 MHz, MeOD) δ = 8.94 − 8.91 (m, 1H), 8.17 (dd, 1H), 8.04 (d, 1H), 7.77 (s, 2H), 3.12 (s, 3H), 2.94 (s, 3H), 2.79 − 2.68 (s, 2H), 2.45 (s, 2H), 2.16 (s, 6H), 2.04 − 1.97 (m, 2H), 1.76 − 1.64 (m, 4H), 1.52 − 1.42 (m, 2H) 1.022 [00057] .sup.1H NMR (400 MHz, MeOD) δ = 8.61 (d, 1H), 7.96 (dd, 1H), 7.89 (d, 1H), 7.63 (s, 2H), 2.72 (s, 5H), 2.44 (s, 2H), 2.25 − 2.18 (m, 1H), 2.15 (s, 6H), 2.00 (br d, 2H), 1.78 − 1.67 (m, 4H), 1.47 − 1.35 (m, 2H) 1.023 [00058] .sup.1H NMR (400 MHz, MeOD) δ = 8.44 (d, 1H), 7.65 (ddd, 1H), 7.53 (s, 2H), 2.74 − 2.67 (m, 5H), 2.46 − 2.39 (m, 2H), 2.26 − 2.16 (m, 1H), 2.13 (s, 6H), 2.02 − 1.96 (m, 2H), 1.77 − 1.65 (m, 4H), 1.45 − 1.34 (m, 2H) 1.024 [00059] .sup.1H NMR (400 MHz, MeOD) δ = 8.54 (d, 1H), 7.95 (dd, 1H), 7.78 1H), 7.59 (s, 2H), 2.72 − (s, 5H), 2.44 (s, 2H), 2.27 − 2.18 (m, 1H), 2.15 (s, 6H), 2.05 − 1.96 (m, 2H), 1.77 − 1.68 (m, 4H), 1.47 − 1.35 (m, 2H) 1.025 [00060] .sup.1H NMR (400 MHz, MeOD) δ = 7.63 − 7.57 (m, 2H), 7.25 (s, 2H), 7.16 − 7.09 (m, 2H), 2.73 − 2.69 (m, 5H), 2.43 (s, 2H), 2.28 − 2.15 (m, 1H), 2.11 (s, 6H), 2.04 − 1.95 (m, 2H), 1.77 − 1.67 (m, 4H), 1.46 − 1.34 (m, 2H) P1.001 [00061] 1H NMR (MeOD, 400 MHz): δ = 7.00 (s, 2H), 3.67-3.64 (m, 3H), 2.90 (s, 1H), 2.72-2.68 (m, 5H), 2.47 (s, 1H), 2.20-2.19 (m, 1H), 1.99-1.95 (m, 11H), 1.75-1.70 (m, 4H), 1.49-1.45 (m, 1H), 1.37- 1.33 (m, 1H)

TABLE-US-00002 TABLE 2 CMP Structure NMR 2.001 [00062] 1H NMR (MeOD, 400 MHz): δ = 7.02 (s, 2H), 3.64-3.72 (m, 1H), 2.60 (s, 2H), 2.44 (s, 2H), 1.99-2.02 (m, 6H), 1.98-1.99 (m, 3H), 1.92-1.93 (m, 3H), 1.88-1.92 (m, 2H), 1.73-1.82 (m, 2H), 1.41-1.53 (m, 4H) 2.002 [00063] 1H NMR (MeOD, 400 MHz δ = 7.03 (s, 2H), 4.36 and 3.73 (2 × m, 1H), 2.95 and 2.84 (2 × s, 3H), 2.69-2.65 (m, 2H), 2.44 (s, 2H), 2.14 and 2.09 (2 × s, 3H), 2.05-1.95 (m, 11H), 1.91-1.41 (m, 6H) 2.003 [00064] 1H NMR (MeOD, 400 MHz): δ = 8.00-7.99 (m, 1H), 6.83 (s, 1H), 6.75 (s, 1H), 3.65 (m, 4H), 2.59-2.41 (m, 4H), 1.99- 1.77 (m, 13H), 1.49-1.41 (m, 4H) 2.004 [00065] 1H NMR (MeOD, 400 MHz): δ = 7.03 (s, 2H), 3.69 (br s, 1H), 2.63 (s, 2H), 2.46 (s, 2H), 2.00 (s, 6H), 1.99 (s, 3H), 1.88- 1.95 (m, 2H), 1.75-1.83 (m, 2H), 1.52-1.58 (m, 1H), 1.42- 1.52 (m, 4H), 0.79-0.86 (m, 2H), 0.69-0.76 (m, 2H) 2.005 [00066] 1H NMR (MeOD, 400 MHz): δ = 7.03 (s, 2H), 3.63-3.76 (m, 1H), 2.64 (s, 2H), 2.44 (s, 2H), 2.00 (s, 6H), 1.99 (s, 3H), 1.93 (br d, 2H), 1.72 (br dd, 2H), 1.43-1.57 (m, 4H), 1.17 (s, 9H) 2.006 [00067] 1H NMR (MeOD, 400 MHz): δ = 8.59-8.65 (m, 1H), 8.09 (dt, 1H), 7.95 (td, 1H), 7.54 (ddd, 1H), 7.03 (s, 2H), 3.88-3.99 (m, 1H), 2.69 (s, 2H), 2.49 (s, 2H), 2.02 (s, 6H), 1.99 (s, 3H), 1.96 (br s, 2H), 1.85-1.93 (m, 2H), 1.62-1.76 (m, 2H), 1.47-1.60 (m, 2H) 2.007 [00068] 1H NMR (MeOD, 400 MHz): δ = 7.03 (s, 2H), 3.66-3.77 (m, 1H), 2.81-2.82 (m, 3H), 2.66 (s, 2H), 2.46 (s, 2H), 2.00 (s, 6H), 1.99 (s, 3H), 1.94 (br d, 2H), 1.73-1.84 (m, 2H), 1.57-1.69 (m, 2H), 1.40- 1.54 (m, 2H) 2.008 [00069] 1H NMR (MeOD, 400 MHz): δ = 7.03 (s, 2H), 6.32-6.70 (m, 1H), 4.31 (s, 2H), 3.73-3.83 (m, 1H), 2.64 (s, 2H), 2.46 (s, 2H), 2.00 (s, 6H), 1.99 (s, 3H), 1.94 (br d, 2H), 1.78 (br dd, 2H), 1.42-1.63 (m, 4H) 2.009 [00070] 1H NMR (MeOD, 400 MHz): δ = 7.03 (s, 2H), 4.06 (dd, 1H), 3.98 (dd, 1H), 3.84-3.92 (m, 1H), 3.67-3.79 (m, 3H), 3.53-3.64 (m, 1H), 3.42 (dd, 1H), 2.64 (s, 2H), 2.45 (s, 2H), 2.00 (s, 6H), 1.99 (s, 3H), 1.93 (br d, 2H), 1.68-1.78 (m, 2H), 1.41-1.65 (m, 4H) 2.010 [00071] 1H NMR (MeOD, 400 MHz): δ = 7.03 (s, 2H), 3.65-3.76 (m, 1H), 3.51 (s, 2H), 2.61 (s, 2H), 2.47 (s, 2H), 2.00 (s, 6H), 1.99 (s, 3H), 1.88-1.95 (m, 2H), 1.78-1.87 (m, 2H), 1.43-1.56 (m, 4H) 2.011 [00072] 1H NMR (MeOD, 400 MHz): δ = 7.03 (s, 2H), 5.79-6.21 (m, 1H), 3.69-3.85 (m, 1H), 2.64 (s, 2H), 2.47 (s, 2H), 2.00 (s, 6H), 1.99 (s, 3H), 1.95 (br d, 2H), 1.80 (br dd, 2H), 1.34-1.68 (m, 4H) 2.012 [00073] 1H NMR (MeOD, 400 MHz): δ = 8.22 (d, 1H), 7.90-8.01 (m, 1H), 7.13 (s, 2H), 7.04 (s, 2H), 3.71- 3.79 (m, 1H), 2.65 (s, 2H), 2.51 (s, 2H), 2.01 (s, 6H), 1.99 (s, 3H), 1.92 (br d, 4H), 1.51-1.62 (m, 4H) 2.013 [00074] 1H NMR (MeOD, 400 MHz): δ = 8.11 (d, 1H), 7.02 (s, 2H), 3.71 (m, 1H), 2.68 (t, 2H), 2.62 (s, 2H), 2.51 (t, 2H), 2.46 (s, 2H), 1.99-1.91 (m, 11H), 1.80 (m, 2H), 1.52-1.48 (m, 4H) 2.014 [00075] 1H NMR (MeOD, 400 MHz): δ = 8.12 (d, 1H), 7.27 (d, 1H), 7.03 (s, 2H), 4.16 (s, 3H), 3.95-3.92 (m, 1H), 2.69 (s, 2H), 2.48 (s, 2H), 2.01-1.89 (m, 13H), 1.76- 1.68 (m, 2H), 1.57-1.51 (m, 2H) 2.015 [00076] 1H NMR (MeOD, 400 MHz): δ = 8.58 (d, 1H), 8.48 (d, 1H), 7.03 (s, 2H), 3.92 (m, 1H), 2.79 (s, 3H), 2.66 (s, 2H), 2.49 (s, 2H), 2.01-1.89 (m, 13H), 1.67-1.61 (m, 2H), 1.57-1.52 (m, 2H) 2.016 [00077] 1H NMR (MeOD, 400 MHz): δ = 8.31 (s, 1H), 7.71 (s, 1H), 7.02 (s, 2H), 3.92-3.86 (m, 1H), 2.65 (s, 2H), 2.46 (s, 2H), 2.0-1.96 (m, 11H), 1.85-1.83 (m, 2H), 1.68- 1.59 (m, 2H), 1.53-1.47 (m, 2H) 2.017 [00078] 1H NMR (MeOD, 400 MHz): δ = 7.01 (s, 2H), 4.09-4.07 (m, 1H), 3.70-3.69 (m, 1H), 2.64-2.62 (s, 2H), 2.44 (s, 2H), 2.00-1.98 (m, 9H), 1.93-1.90 (m, 2H), 1.75 (m, 2H), 1.56-1.44 (m, 4H), 1.33- 1.28 (d, 3H) 2.018 [00079] 1H NMR (MeOD, 400 MHz): δ = 8.32 (d, 1H), 7.65 (d, 1H), 7.42 (s, 1H), 7.03 (s, 2H), 3.94-3.88 (m, 1H), 2.67 (s, 2H), 2.48 (s, 2H), 2.01-1.99 (m, 11H), 1.89- 1.87 (m, 2H), 1.68-1.59 (m, 2H), 1.55-1.49 (m, 2H) 2.019 [00080] 1H NMR (MeOD, 400 MHz): δ = 7.81-7.79 (m, 2H), 7.53-7.49 (m, 1H), 7.46-7.42 (m, 2H), 7.03 (s, 2H), 3.91-3.90 (m, 1H), 2.67 (s, 2H), 2.48 (s, 2H), 2.01-1.98 (m, 9H), 1.89-1.86 (m, 2H), 1.66- 1.59 (m, 2H), 1.55-1.49 (m, 2H), 1.30-1.23 (m, 2H) 2.020 [00081] 1H NMR (MeOD, 400 MHz): δ = 7.02 (s, 2H), 3.85 (s, 2H), 3.76 (m, 1H), 3.40 s, (3H), 2.63 (s, 2H), 2.45 (s, 2H), 1.99-1.98 (m, 9H), 1.94-1.90 (m, 2H), 1.77- 1.74 (m, 2H), 1.58-1.46 (m, 4H) 2.021 [00082] 1H NMR (MeOD, 400 MHz): δ = 7.02 (s, 2H), 3.48 (m, 1H), 2.58 (s, 2H), 2.46 (s, 2H), 1.99-1.98 (m, 9H), 1.86-1.77 (m, 4H), 1.50- 1.44 (m, 2H), 1.40-1.34 (m, 2H), 1.28 (s, 9H) 2.022 [00083] 1H NMR (MeOD, 400 MHz): δ = 7.02 (s, 2H), 3.70 (br s, 1H), 2.62 (s, 2H), 2.47 (s, 2H), 2.00-1.98 (m, 9H), 1.88-1.86 (m, 4H), 1.53- 1.51 (m, 4H), 1.21 (s, 9H) 2.023 [00084] 1H NMR (MeOD, 400 MHz): δ = 8.69-8.68 (m, 1H), 8.22-8.21 (m, 1H), 8.05-8.01 (m, 1H), 7.66- 7.63 (m, 1H), 7.02 (s, 2H), 3.79 (m, 1H), 2.65 (s, 2H), 2.49 (s, 2H), 2.01-1.90 (m, 13H), 1.66- 1.53 (m, 4H) 2.024 [00085] 1H NMR (MeOD, 400 MHz): δ = 6.99 (s, 2H), 4.26-4.19 (m, 1H), 2.51-2.46 (m, 4H), 2.11-2.04 (m, 2H), 2.01-1.97 (m, 9H), 1.90 (s, 3H), 1.85-1.44 (m, 4H) 2.025 [00086] 1H NMR (MeOD, 400 MHz): δ = 7.01 (s, 2H), 4.33-4.31 (m, 1H), 2.73 (s, 2H), 2.62 (s, 2H), 2.41- 2.36 (m, 2H), 1.97 (m, 9H), 1.92- 1.87 (m, 5H) 2.026 [00087] δ = ppm = 8.59 − 8.53 (m, 1H), 7.90 − 7.80 (m, 2H), 7.67 − 7.60 (m, 2H), 3.73 − 3.64 (m, 1H), 2.65 (s, 2H), 2.49 (s, 2H), 2.14 (s, 6H), 1.98 (s, 2H), 1.93 (s, 3H), 1.85 − 1.75 (m, 2H), 1.55 − 1.42 (m, 4H) 2.027 [00088] 1H NMR (400 MHz, CD.sub.3OD) δ = ppm 7.57 − 7.67 (m, 2 H) 7.28 (s, 2 H) 7.15 (t, J = 8.80 Hz, 2 H) 3.71 (br s, 1 H) 2.67 (s, 2 H) 2.51 (s, 2 H) 2.11− 2.16 (m, 6 H) 1.98 (br s, 2 H) 1.95 (s, 3 H) 1.76 − 1.88 (m, 2 H) 1.45 − 1.59 (m, 4 H) 2.028 [00089] 1H NMR (400 MHz, MeOD) δ = 8.74 (s, 2H), 8.05 (s, 2H), 3.78 − 3.62 (m, 1H), 2.66 (s, 2H), 2.50 (s, 2H), 2.14 (s, 6H), 2.00 − 1.90 (m, 5H), 1.84 − 1.75 (m, 2H), 1.56- 1.44 (m, 4H) 2.029 [00090] 1H NMR (400 MHz, MeOD) δ = 8.92 (d, 1H), 8.17 (dd, 1H), 8.04 (d, 1H), 7.78 (s, 2H), 3.75 − 3.66 (m, 1H), 2.67 (s, 2H), 2.51 (s, 2H), 2.16 (s, 6H), 1.95 (br d, 2H), 1.86 − 1.76 (m, 2H), 1.59 − 1.46 (m, 5H), 0.87 − 0.81 (m, 2H), 0.77 0.69 (m, 2H) 2.030 [00091] 1H NMR (400 MHz, MeOD) δ = 8.92 (dd, 1H), 8.17 (dd, 1H), 8.04 (dd, 1H), 7.77 (s, 2H), 3.75 − 3.64 (m, 1H), 2.66 (s, 2H), 2.50 (s, 2H), 2.15 (s, 6H), 1.99 − 1.91 (m, 5H), 1.84 − 1.76 (m, 2H), 1.56 − 1.41 (m, 4H) 2.031 [00092] 1H NMR (400 MHz, MeOD) δ = 8.44 (d, 1H), 7.66 (ddd, 1H), 7.53 (s, 2H), 3.75 − 3.63 (m, 1H), 2.66 (s, 2H), 2.50 (s, 2H), 2.13 (s, 6H), 1.99 − 1.90 (m, 5H), 1.85 − 1.75 (m, 2H), 1.55 − 1.44 (m, 4H) 2.032 [00093] 1H NMR (400 MHz, MeOD) δ = 8.55 (d, 1H), 7.96 (dd, 1H), 7.80 (dt, 1H), 7.59 (s, 2H), 3.74- 3.63 (m, 1H), 2.66 (s, 2H), 2.50 (s, 2H), 2.15 (s, 6H), 2.01- 1.91 (m, 5H), 1.86 − 1.74 (m, 2H), 1.57 − 1.42 (m, 4H) 2.033 [00094] 1H NMR (400 MHz, MeOD) δ = 7.02 (s, 2H), 3.15 − 3.10 (m, 1H), 2.95 (s, 3H), 2.60 (s, 2H), 2.45 (s, 2H), 2.00 (s, 6H), 1.99 (s, 3H), 1.95 − 1.86 (m, 4H), 1.60 − 1.43 (m, 4H) 2.034 [00095]

TABLE-US-00003 TABLE 3 CMP Structure NMR 3.001 [00096] 1HNMR (MeOD, 400 MHz): δ = 7.01 (s, 2H), 3.09-3.03 (m, 1H), 2.71 (s, 3H), 2.64 (s, 2H), 2.41 (s, 2H), 2.06-1.94 (m, 13H), 1.82- 1.71 (m, 2H), 1.47-1.40 (m, 2H) 3.002 [00097] 1HNMR (MeOD, 400 MHz): δ = 7.01 (s, 2H), 3.22-3.19 (m, 1H), 2.90 (s, 6H), 2.64 (s, 2H), 2.41 (s, 2H), 2.04-1.98 (m, 13H), 1.81- 1.75 (m, 2H), 1.46-1.40 (m, 2H)

Biological Examples

[0153] Seeds of a variety of test species are sown in standard soil in pots (Lolium perenne (LOLPE), Setaria faberi (SETFA), Alopecurus myosuroides (ALOMY), Echinochloa crus-galli (ECHCG), Avena fatua (AVEFA)). After cultivation for one day (pre-emergence) or after 8 days cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16° C., day/night; 14 hours light; 65% humidity), the plants are sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone/water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5). Compounds are applied at 250 g/h. The test plants are then grown in a glasshouse under controlled conditions in a glasshouse (at 24/16° C., day/night; 14 hours light; 65% humidity) and watered twice daily. After 13 days for pre and post-emergence, the test is evaluated for the percentage damage caused to the plant. The biological activities are shown in the following table on a five-point scale (5=80-100%; 4=60-79%; 3=40-59%; 2=20-39%; 1=0-19%).

TABLE-US-00004 TABLE B1 LOLPE SETFA ALOMY ECHCG AVEFA Compound PRE POST PRE POST PRE POST PRE POST PRE POST 1.001 5 5 5 5 5 5 5 5 5 5 1.002 5 5 5 5 5 5 5 5 5 5 1.003 4 5 5 5 4 5 5 5 4 5 1.004 4 4 5 4 3 4 5 4 4 5 1.005 5 5 5 5 3 4 5 5 4 5 1.007 5 5 4 5 3 5 5 5 3 5 1.008 5 5 5 4 4 5 5 5 3 5 1.009 5 5 3 5 4 5 4 5 3 5 1.010 5 5 5 5 3 4 5 5 3 5 1.011 5 5 5 5 5 5 5 5 5 5 1.012 4 4 4 5 4 4 4 5 4 4 1.013 5 5 5 5 3 5 5 5 1 4 1.014 5 5 5 5 3 5 5 5 2 5 1.016 5 5 5 5 5 5 5 5 5 5 1.017 5 5 5 5 5 5 5 5 5 5 1.018 5 5 5 5 5 5 5 5 5 5 1.020 5 5 5 5 5 5 5 5 5 5 1.021 4 5 4 5 4 5 5 5 2 5 1.022 5 5 5 5 5 5 5 5 5 5 1.023 5 5 5 5 5 5 5 5 5 5 1.024 5 5 5 5 5 5 5 5 5 5 1.025 5 5 5 5 5 5 5 5 5 5 2.001 5 5 5 5 5 5 5 5 5 5 2.003 5 5 5 5 5 5 5 5 5 5 2.004 5 5 5 5 5 5 5 5 5 5 2.005 5 5 5 5 5 5 5 5 5 5 2.006 5 5 5 5 5 5 5 5 4 5 2.007 5 5 5 5 5 5 5 5 5 5 2.008 5 5 5 5 5 5 5 5 5 5 2.009 5 5 5 5 4 4 5 5 4 5 2.010 5 5 5 5 5 5 5 5 5 5 2.011 5 5 5 5 5 5 5 5 5 5 2.012 5 5 4 4 4 4 4 4 3 5 2.013 5 5 5 5 3 5 5 5 5 5 2.014 5 5 5 5 5 5 5 5 5 5 2.015 5 5 5 5 4 5 5 5 5 5 2.016 5 5 5 5 3 4 5 5 4 5 2.017 4 5 5 5 4 5 5 5 4 5 2.018 5 5 5 5 4 5 5 5 5 5 2.019 5 5 5 5 5 5 5 5 5 5 2.020 5 5 5 5 5 5 5 5 5 5 2.021 5 5 5 5 5 5 5 5 4 5 2.022 5 5 5 5 5 5 5 5 3 5 2.023 5 5 5 5 5 5 5 5 4 5 2.024 5 5 5 5 5 5 5 5 5 5 2.025 5 5 5 5 5 5 5 5 5 5 2.027 4 5 5 5 3 5 2 5 4 5 2.028 5 5 5 5 5 5 5 5 4 5 2.029 5 5 5 5 2 5 5 5 4 5 2.030 5 5 5 5 4 5 5 5 5 5 2.031 5 5 5 5 5 5 5 5 5 5 2.032 5 5 5 5 5 5 5 5 4 5 2.033 5 5 5 5 5 5 5 5 5 5 P1.001 5 5 5 5 5 5 5 5 5 5