Herbicidal uracilpyrid

Abstract

The present invention relates to uracilpyridines of formula (I) ##STR00001##
or their agriculturally acceptable salts or derivatives, wherein the variables are defined according to the description, processes and intermediates for preparing the uracilpyryidines of the formula (I), compositions comprising them and their use as herbicides, i.e. for controlling harmful plants, and also a method for controlling unwanted vegetation which comprises allowing a herbicidal effective amount of at least one urycilpyridine of the formula (I) to act on plants, their seed and/or their habitat.

Claims

1. A compound of formula (I) ##STR00105## wherein the variables have the following meanings: R.sup.1 hydrogen, NH.sub.2, C.sub.1-C.sub.6-alkyl or C.sub.3-C.sub.6-alkynyl; R.sup.2 hydrogen, C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-haloalkyl; R.sup.3 hydrogen or C.sub.1-C.sub.6-alkyl; R.sup.4 H or halogen; R.sup.5 halogen, CN, NO.sub.2, NH.sub.2, CF.sub.3 or C(═S)NH.sub.2; R.sup.6 H, halogen, CN, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-haloalkyl, C.sub.1-C.sub.3-alkoxy, C.sub.1-C.sub.3-haloalkoxy, C.sub.1-C.sub.3-alkylthio, (C.sub.1-C.sub.3-alkyl)amino, di(C.sub.1-C.sub.3-alkyl)amino, C.sub.1-C.sub.3-alkoxy-C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-alkoxycarbonyl; R.sup.7 H, halogen, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-alkoxy; R.sup.8 OR.sup.9, SR.sup.9, NR.sup.10R.sup.11, NR.sup.9OR.sup.9, NR.sup.9S(O).sub.2R.sup.10 or NR.sup.9S(O).sub.2NR.sup.10R.sup.11, wherein R.sup.9 is hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-haloalkenyl, C.sub.3-C.sub.6-haloalkynyl, C.sub.1-C.sub.6-cyanoalkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl, di(C.sub.1-C.sub.6-alkoxy)C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkoxy-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyloxy-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-haloalkenyloxy-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyloxy-C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkylsulfinyl-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkylsulfonyl-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkylcarbonyl-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxycarbonyl-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkoxycarbonyl-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyloxycarbonyl-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkynyloxycarbonyl-C.sub.1-C.sub.6-alkyl, amino, (C.sub.1-C.sub.6-alkyl)amino, di(C.sub.1-C.sub.6-alkyl)amino, (C.sub.1-C.sub.6-alkylcarbonyl)amino, amino-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)amino-C.sub.1-C.sub.6-alkyl, di(C.sub.1-C.sub.6-alkyl)amino-C.sub.1-C.sub.6-alkyl, aminocarbonyl-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)aminocarbonyl-C.sub.1-C.sub.6-alkyl, di(C.sub.1-C.sub.6-alkyl)aminocarbonyl-C.sub.1-C.sub.6-alkyl, —N═CR.sup.12R.sup.13, wherein R.sup.12 and R.sup.13 independently of one another are H, C.sub.1-C.sub.4-alkyl or phenyl; C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-heterocyclyl, C.sub.3-C.sub.6-heterocyclyl-C.sub.1-C.sub.6-alkyl, phenyl, phenyl-C.sub.1-C.sub.4-alkyl or a 5- or 6 membered heteroaryl, wherein each cycloalkyl, heterocyclyl, phenyl or heteroaryl ring can be substituted by one to four substituents selected from R.sup.14 or a 3- to 7-membered carbocyclus,  which carbocyclus optionally has in addition to carbon atoms one or two ring members selected from the group consisting of —N(R.sup.12)—, —N═N—, —C(═O)—, —O— and —S—, and  which carbocyclus is optionally substituted with one to four substituents selected from R.sup.14;  wherein R.sup.14 is halogen, NO.sub.2, CN, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-alkoxy-carbonyl; R.sup.10, R.sup.11 independently of one another are R.sup.9, or together form a 3- to 7-membered carbocyclus, which carbocyclus optionally has in addition to carbon atoms one or two ring members selected from the group consisting of —N(R.sup.12)—, —N═N—, —C(═O)—, —O— and —S—, and which carbocyclus is optionally substituted with one to four substituents selected from R.sup.14; n 1 to 3; Q CH.sub.2, O, S, SO, SO.sub.2, NH or (C.sub.1-C.sub.3-alkyl)N; W O or S; X NH, NCH.sub.3, O or S; Y O or S Z phenyl, pyridyl, pyridazinyl, pyrimidinyl or pyrazinyl, each of which is optionally substituted by 1 to 4 substituents selected from the group consisting of halogen, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy; or an agriculturally acceptable salt or derivative, provided the compounds of formula (I) have a carboxyl group.

2. The compound of claim 1 wherein R.sup.1 is C.sub.1-C.sub.6-alkyl, R.sup.2 is C.sub.1-C.sub.4-haloalkyl, R.sup.3 is H and Y is O.

3. The compound of claim 1, wherein R.sup.4 is H or F, and R.sup.5 is F, Cl, Br or CN.

4. The compound of claim 1, wherein R.sup.6 is H, C.sub.1-C.sub.3-alkyl or C.sub.1-C.sub.3-alkoxy, and R.sup.7 is H.

5. The compound of claim 1 wherein R.sup.8 is OR.sup.9,NR.sup.9S(O).sub.2R.sup.10 or NR.sup.9S(O).sub.2NR.sup.10R.sup.11, wherein R.sup.9 is hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl, di(C.sub.1-C.sub.6-alkoxy)C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkylcarbonyl-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxycarbonyl-C.sub.1-C.sub.6-alkyl or C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.6-alkyl; and R.sup.10R.sup.11 are C.sub.1-C.sub.6-alkyl.

6. The compound of claim 1, wherein n is 1.

7. The compound of claim 1, wherein Q, W and X are O.

8. The compound of claim 1, wherein Z is phenyl or pyridyl, each of which is optionally substituted by 1 to 4 substituents selected from the group consisting of halogen, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy.

9. Acid halides of formula (II) ##STR00106## wherein R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, n, Q, W, X, Y and Z are as defined in claim 1, and L.sup.1 is halogen.

10. An intermediate of formula (int-1) ##STR00107## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, Q, X, Y and Z are as defined in claim 1, and I.sup.1 is H or PG, wherein PG is a protecting group selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-cyanoalkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl, (tri-C.sub.1-C.sub.6-alkyl)silyl-C.sub.1-C.sub.4-alkyl, (tri-C.sub.1-C.sub.6-alkyl)silyl-C.sub.1-C.sub.4-alkyoxy-C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cylcloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.5-C.sub.6-cycloalkenyl, tetrahydropyranyl, (tri-C.sub.1-C.sub.6-alkyl)silyl, [(diphenyl)(C.sub.1-C.sub.4-alkyl)]silyl, formyl, C.sub.1-C.sub.6-alkyl-carbonyl, C.sub.1-C.sub.6-alkyl-O-carbonyl, C.sub.2-C.sub.6-alkenyl-O-carbonyl, [(diphenyl)(C.sub.1-C.sub.4-alkyl)]silyl-C.sub.1-C.sub.4-alkyl, phenyl-C.sub.1-C.sub.4-alkyl, phenylthio-C.sub.1-C.sub.6-alkyl, phenylcarbonyl, wherein each phenyl ring can be substituted by one to three substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.4-alkyl and C.sub.1-C.sub.4-alkoxy; or a salt thereof.

11. An intermediate of formula (int-2) ##STR00108## wherein R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, n, Q, W, X, Y and Z are as defined in claim 1, and I.sup.2 is H; and I.sup.3 is H or C(═Y)L.sup.2, wherein Y is O or S, and L.sup.2 is C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylthio or aryloxy, wherein the aryl moiety may itself be partly or fully halogenated and/or may be substituted by from one to three substituents from the group of cyano, nitro, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy and C.sub.1-C.sub.4-alkylthio; or I.sup.2 and I.sup.3 together with the N-atom, to which they are attached, form a group “YCN”, wherein Y is O or S, or a group “PGN”, which is a protected amine substituent selected from the group consisting of N.sub.3, aliphatic or aromatic carbamates, aliphatic or aromatic amides, N-C.sub.1-C.sub.6-alkyl-amines, N-aryl-amines or heteroarylamides, or a salt thereof.

12. An intermediate of formula (int-3) ##STR00109## wherein R.sup.4, Q, X and Z are as defined in claim 1, R.sup.5 is a halogen or CN; and PG is a protecting group selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-cyanoalkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl, (tri-C.sub.1-C.sub.6-alkyl)silyl-C.sub.1-C.sub.4-alkyl, (tri-C.sub.1-C.sub.6-alkyl)silyl-C.sub.1-C.sub.4-alkyoxy-C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cylcloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.5-C.sub.6-cycloalkenyl, tetrahydropyranyl, (tri-C.sub.1-C.sub.6-alkyl)silyl, [(diphenyl)(C.sub.1-C.sub.4-alkyl)]silyl, formyl, C.sub.1-C.sub.6-alkyl-carbonyl, C.sub.1-C.sub.6-alkyl-O-carbonyl, C.sub.2-C.sub.6-alkenyl-O-carbonyl, [(diphenyl)(C.sub.1-C.sub.4-alkyl)]silyl-C.sub.1-C.sub.4-alkyl, phenyl-C.sub.1-C.sub.4-alkyl, phenylthio-C.sub.1-C.sub.6-alkyl, phenylcarbonyl, wherein each phenyl ring can be substituted by one to three substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.4-alkyl and C.sub.1-C.sub.4-alkoxy; I.sup.2 H; and I.sup.3 H or C(═Y)L.sup.2, wherein Y is O or S, and L.sup.2 is C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylthio or aryloxy, wherein the aryl moiety may itself be partly or fully halogenated and/or may be substituted by from one to three substituents from the group of cyano, nitro, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy and C.sub.1-C.sub.4-alkylthio; or I.sup.2 and I.sup.3 together with the N-atom, to which they are attached, form a group “YCN”, wherein Y is O or S, or a group “PGN”, which is a protected amine substituent selected from the group consisting of C.sub.1-C.sub.6-alkyl-O(CO)NH—, fluorenylmethyl-O(CO)NH—, H(CO)N—, C.sub.1-C.sub.6-alkyl-(CO)—NH—, C.sub.1-C.sub.6-haloalkyl-(CO)—NH—, N-phthalimide, phenyl-O(CO)NH—, phenyl-C.sub.1-C.sub.4-alkyl-O(CO)NH—, phenyl-C.sub.1-C.sub.4-alkyl-NH—, di(phenyl-C1-C4-alkyl)N—, wherein each phenyl ring can be substituted by one to three C.sub.1-C.sub.4-alkoxy substituents, or a salt thereof.

13. A herbicidal composition comprising an herbicidally active amount of at least one uracilpyridine of formula (I) as claimed in claim 1 and at least one inert liquid and/or solid carrier and, optionally, at least one surface-active substance.

14. A process for the preparation of herbicidal active compositions, which comprises mixing an herbicidally active amount of at least one uracilpyridine of formula (I) as claimed in claim 1 and at least one inert liquid and/or solid carrier and, optionally, at least one surface-active substance.

15. A method of controlling undesired vegetation, which comprises allowing an herbicidally active amount of at least one uracilpyridine of formula (I) as claimed in claim 1 to act on plants, their environment or on seed.

16. The method of claim 15, wherein R.sup.1 is C.sub.1-C.sub.6-alkyl, R.sup.2 is C1-C4-haloalkyl, R.sup.3 is H and Y is O.

17. The method of claim 15, wherein R.sup.4 is H or F, and R.sup.5 is F, Cl, Br or CN.

18. The method of claim 15, wherein R.sup.6 is H, C.sub.1-C.sub.3-alkyl or C.sub.1-C.sub.3-alkoxy, and R.sup.7 is H.

19. The method of claim 15, wherein R.sup.8 is OR.sup.9,NR.sup.9S(O).sub.2R.sup.10 or NR.sup.9S(O).sub.2NR.sup.10R.sup.11, wherein R.sup.9 is hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl, di(C.sub.1-C.sub.6-alkoxy)C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkylcarbonyl-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxycarbonyl-C.sub.1-C.sub.6-alkyl or C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.6-alkyl; and R.sup.10, R.sup.11 are C.sub.1-C.sub.6-alkyl.

20. The method of claim 15, wherein n is 1.

21. The method of claim 15, wherein Q, W and X are O.

22. The method of claim 15, wherein Z is phenyl or pyridyl, each of which is optionally substituted by 1 to 4 substituents selected from the group consisting of halogen, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy.

Description

A Preparation Examples

Example 1

Ethyl 2-[2-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]phenoxy]acetate

(1) ##STR00072##

Example 1.1: 2-Azido-6-(2-benzyloxyphenoxy)-5-chloro-3-fluoro-pyridine

(2) ##STR00073##

(3) To a solution of 5.0 g (29 mmol) 3-chloro-2,5,6-trifluoropyridine (CAS 2879-42-7) in 50 mL DMSO was added 2.1 g (33 mmol) NaN.sub.3 and the solution was stirred at room temperature for 3 hours. Then 19.5 g (60 mmol) Cs.sub.2CO.sub.3 was added followed by a solution of 6.2 g (31 mmol) 2-(Benzyloxy)phenol) in 40 mL DMSO. The mixture was stirred at room temperature for 16 hours, water was added and the mixture was extracted with ethyl acetate. The organic layer was separated, washed with brine, dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure. The crude material (15 g) was used without further purification in the next step.

(4) [M+H]=371.0; Rt=1.368 min

Example 1.2: 2-Amino-6-(2-benzyloxyphenoxy)-5-chloro-3-fluoro-pyridine

(5) ##STR00074##

(6) To a solution of 15 g of compound 1.1 in THF was added 9.7 g (150 mmol) zinc and 100 mL semi-saturated aq. NH.sub.4Cl dropwise at 0° C. The mixture was stirred for 16 hours at room temperature, filtered and the filter cake was washed with ethyl acetate. The filtrate was extracted with ethyl acetate, the combined organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure. The crude material was purified by silica gel column (petrol ether/ethyl acetate) to give 8.8 g (25.6 mmol, 88% over 2 steps from 3-chloro-2,5,6-trifluoropyridine) of the desired product 1.2.

(7) [M+H]=345.0; Rt=1.232 min

Example 1.3: Ethyl N-[6-(2-benzyloxyphenoxy)-5-chloro-3-fluoro-2-pyridyl]carbamate

(8) ##STR00075##

(9) To a solution of 8.8 g (25.6 mmol) of compound 1.2 in 80 ml dichloromethane was added 3 g (38 mmol) pyridine followed by 4 g (37.5 mmol) ethyl chloroformate. The mixture was stirred at 25° C. for 20 hours, diluted with water and extracted with dichloromethane. The combined organic layer was washed with brine, dried over anhydrous Na.sub.2SO.sub.4 and concentrated to give 14.4 g of a mixture of carbamate 1.3 and the di-substituted derivative. The crude mixture (12.4 g) was dissolved in 200 mL ethanol and aqueous NaOH (1M) was added dropwise at 0° C. with stirring. The mixture was stirred at 15° C. for 6 hours, diluted with brine and extracted with ethyl acetate. The combined organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica (petrol ether/ethyl acetate) to give 6.6 g (15.9 mmol, 62%) of the desired compound 1.3.

(10) [M+H]=417.1; Rt=1.293 min

Example 1.4: 3-[6-(2-benzyloxyphenoxy)-5-chloro-3-fluoro-2-pyridyl]-6-(trifluoromethyl)-1H-pyrimidine-2,4-dione

(11) ##STR00076##

(12) To a solution of 1.7 g (43 mmol) NaH in NMP (N-Methyl-2-pyrrolidone) (60 mL) at 0° C. was added 6 g (14 mmol) of compound 1.3 and the mixture was stirred for 30 minutes at 35° C. Then 3.9 g (21 mmol) of ethyl (E)-3-amino-4,4,4-trifluoro-but-2-enoate (CAS: 372-29-2) was added and the reaction mixture was stirred at 100° C. for 3 days. The resulting mixture was quenched with ice water, acidified to pH=2 by using 6N HCl and extracted with ethyl acetate. The combined organic layer was washed with brine, dried over anhydrous Na.sub.2SO.sub.4, concentrated and directly used in the next step.

(13) [M+H]=508.0; Rt=1.240 min

Example 1.5: 3-[6-(2-benzyloxyphenoxy)-5-chloro-3-fluoro-2-pyridyl]-1-methyl-6-(trifluoromethyl)-pyrimidine-2,4-dione

(14) ##STR00077##

(15) To a solution of 6.5 g (12.8 mmol) of compound 1.4 in 65 mL acetonitrile was added 5.3 g (38 mmol) K.sub.2CO.sub.3 followed by 7.3 g (51 mmol) methy iodide at 0° C. with stirring. The mixture was stirred at 15° C. for 16 hours, then water (80 mL) was added and the pH was adjusted to pH=5 by using 2N HCl. The mixture was extracted with ethyl acetate, the combined organic layer was washed with brine and dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure yielding 7 g of the crude product 1.5, which was used without further purification.

(16) .sup.1H-NMR (CDCl.sub.3, ppm): 7.63 (d, J=7.28 Hz, 1H); 7.21-7.25 (m, 4H); 7.12-7.17 (m, 2H); 6.98 (t, J=7.03 Hz, 3H); 6.26 (s, 1H); 4.99 (s, 2H); 3.47 (s, 3H). [M+H]=522.0; Rt=1.323 min

Example 1.6: 3-[5-Chloro-3-fluoro-6-(2-hydroxyphenoxy)-2-pyridyl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4-dione

(17) ##STR00078##

(18) To a solution of 7 g (13.4 mmol) of compound 1.5 in 70 mL xylene was added 3.6 g (26 mmol) solid AlCl.sub.3 at 15° C. with stirring. The mixture was stirred at 130° C. for 16 hours and after cooling to 15° C., ice-water was added to the mixture. After separation of the xylene layer, the water phase was extracted with ethyl acetate, the combined organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica gel (petrol ether/ethyl acetate) to give 3.2 g (7.4 mmol, 55%) of the desired product 1.6.

(19) .sup.1H-NMR (CDCl.sub.3, ppm): 7.80 (d, J=7.26 Hz, 1H); 7.03-7.19 (m, 3H); 6.93 (dt, J=7.68 Hz, J=1.7 Hz, 1H); 6.3 (s, 1H); 5.6 (s, 1H); 3.5 (s, 3H).

(20) [M+H]=431.9; Rt=1.077 min

Example 1.7: Ethyl 2-[2-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]phenoxy]acetate (=Example 1)

(21) ##STR00079##

(22) To a solution of 0.2 g (0.46 mmol) of compound 1.6 in 10 mL dry acetonitrile was added 0.19 g (1.3 mmol) K.sub.2CO.sub.3 at 0° C. followed by dropwise addition of 0.15 g (0.92 mmol) ethyl bromoacetate. The mixture was stirred at 15° C. for 16 hours, diluted with 15 ml water and extracted with ethyl acetate. The combined organic layer was washed with brine, dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure. The crude product was purified by reversed phase preparative HPLC (acetonitrile/water containing trifluoroacetic acid) to give 0.16 g (0.31 mmol, 67%) of the desired title compound.

(23) .sup.1H-NMR (CDCl.sub.3, ppm): 7.76 (d, J=7.28 Hz, 1H); 7.22 (d, J=7.72 Hz, 1H); 7.17 (t, J=7.83 Hz, 1H); 6.99-7.06 (m, 1H); 6.88 (d, J=7.94 Hz, 1H); 6.25 (s, 1H); 4.49 (s, 2H); 4.19 (q, J=7.20 Hz, 2H); 3.47 (s, 3H); 1.25 (t, J=7.17 Hz, 3H).

(24) [M+H]=518.0; Rt=1.217 min

(25) Recrystallization from ethanol provides the title compound in a crystalline form A.

(26) The crystalline form A of example 1 displays a thermogram with a characteristic melting peak in the range from 96 to 108° C. The melting point, determined as the onset of the melting peak, typically lies in the range from about 100 to 106° C. The values quoted here relate to values determined by differential calorimetry (differential scanning calorimetry, DSC). The melting points were determined using DSC with a Mettler Toledo DSC 823e/700/229 module. The samples were placed in glass standard pans. The sample size in each case was 1 to 20 mg. The heating rate was 2.50 K/min. The samples were purged with a stream of nitrogen during the experiment. The melting point was determined as the extrapolated peak onset temperature (also called onset temperature) defined by the point of intersection of the tangent at the half height of the melting peak, on the principal side of the peak with the linelarily extrapolated initial base line.

(27) The form A was investigated by powder X-ray diffraction (PXRD). PXRD was carried out with a Panalytical X'Pert Pro X-ray diffractometer using CuK.sub.α, radiation in reflection geometry (Bragg-Brentano). The powder is placed in a silicon single crystal sample holder of 0.2 mm depth and gently and precisely flattened. The tube voltage is 45 kV and current is 40 mA. The PXRD data are collected at room temperature in the range from 2θ=3.0°-40.0° with increments of e.g. 0.017° and measurement time of 19.7 s/step.

(28) The PXRD pattern is displayed in FIG. 1. Characteristic peak positions are listed in table 2:

(29) TABLE-US-00008 TABLE 2 Peak positions observed in the PXRD pattern of example 1 in its form A: °θ, Cu Kα radiation d [Å]  5.5 ± 0.2 16.2 ± 0.6   7.4 ± 0.2 12.0 ± 0.3   7.8 ± 0.2 11.4 ± 0.3  10.0 ± 0.2 8.9 ± 0.2 10.3 ± 0.2 8.6 ± 0.2 11.2 ± 0.2 7.9 ± 0.1 11.8 ± 0.2 7.5 ± 0.1 17.1 ± 0.2 5.19 ± 0.06 18.0 ± 0.2 4.92 ± 0.06 18.8 ± 0.2 4.73 ± 0.05 19.3 ± 0.2 4.59 ± 0.05 20.9 ± 0.2 4.24 ± 0.04 21.5 ± 0.2 4.13 ± 0.04 21.9 ± 0.2 4.06 ± 0.04 23.0 ± 0.2 3.87 ± 0.04 26.3 ± 0.2 3.39 ± 0.03

(30) Most prominent peaks are 5.5±0.2, 7.4±0.2, 7.8±0.2, 10.0±0.2, 11.2±0.2, 17.1±0.2, 18.0±0.2, 21.5±0.2, 21.9±0.2 and 26.3±0.2° 2θ.

(31) Studies on single crystals of form A demonstrate that the underlying crystal structure is triclinic. The unit cell has the space group P1. The characteristic data of the crystal structure (determined at 100 K) are compiled in the following table 3:

(32) TABLE-US-00009 TABLE 3 Parameter Example 1 form A class triclinic space group P1 a 11.1534(8) Å b 12.4573(9) Å c 16.8546(12) Å α 72.960(3)° β 82.651(3)° γ 83.283(3)° volume 2212.8(3) Å.sup.3 Z 4 density (calculated) 1.554 g/cm.sup.3 wavelength 1.54178 Å largest diff peak and hole 0.716/−0.362 eÅ.sup.−3 a, b, c = unit cell length α, β, γ = unit cell angle Z = number of molecules in the unit cell

Example 2

Methyl 2-[2-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]phenoxy]-2-methoxy-acetate

(33) ##STR00080##

(34) To a solution of 2.5 g (5.8 mmol) of compound 1.6 in 20 mL dry acetonitrile was added 2.2 g (16 mmol) K.sub.2CO.sub.3 over 10 minutes at 0° C. under N.sub.2 with stirring. Then 1.4 g (7.5 mmol) of methyl 2-bromo-2-methoxy-acetate (CAS: 5193-96-4) was added dropwise to the mixture, which was stirred at 15° C. for 16 hours. The reaction mixture was filtered and the filter cake was washed with ethyl acetate. The filtrate was concentrated and the crude product was purified by reversed phase preparative HPLC (acetonitrile/water containing trifluoroacetic acid) to give 0.97 g (1.8 mmol, 31%) of the desired compound 2.

(35) .sup.1H-NMR (CDCl.sub.3, ppm): 7.77 (d, J=7.03 Hz, 1H); 7.15-7.27 (m, 3H); 7.07-7.13 (m, 1H); 6.24 (s, 1H); 5.40 (d, J=8.53 Hz, 1H); 3.70 (s, 3H); 3.46 (br. s., 3H); 3.39 (s, 3H).

(36) [M+H]=534.1; Rt=1.233 min

Example 3

2-[2-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]phenoxy]acetic acid

(37) ##STR00081##

(38) A solution of 3.5 g (6.8 mmol) of ethyl 2-[2-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]phenoxy]acetate (example 1) in 20 ml aqueous conc. HCl and 20 mL of glacial acetic acid was stirred at 60° C. for 3 hours. Water was added and the mixture was extracted with ethyl acetate. The combined organic layer was washed with water and brine, dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure to give 2.3 g (4.7 mmol, 69%) of 2-[2-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]phenoxy]acetic acid.

(39) .sup.1H-NMR (CDCl.sub.3, ppm): 7.77 (d, J=7.21 Hz, 1H); 7.15-7.25 (m, 2H); 7.06 (dt, J=7.74 Hz, J=1.46 Hz, 1H); 6.91 (dd, J=8.15 Hz, J=1.44 Hz, 1H); 6.25 (s, 1H); 4.55 (s, 2H), 3.45 (s, 3H).

(40) [M+H]=490.0; Rt=1.189 min

Example 4

2-[2-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]phenoxy]-N-methylsulfonyl-acetamide

(41) ##STR00082##

(42) To a solution of 0.7 g (1.5 mmol) 2-[2-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]phenoxy]acetic acid in 20 mL dry THF under an Argon atmosphere was added 1.0 g (7.4 mmol) diisopropylethyl amine followed by 0.8 g (3.0 mmol) 2-chloro-1-methyl-pyridinium chloride (CAS: 112277-86-8) and 0.2 g (2.2 mmol) methansulfonamide (CAS: 3144-09-0). The suspension was stirred at room temperature for 16 hours. Then water was added, the mixture was extracted with ethyl acetate, the combined organic layer was washed with water and brine, dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica (cyclohexane/ethyl acetate) to give 0.1 g (0.24 mmol, 16%) of the desired product.

(43) .sup.1H-NMR (CDCl.sub.3, ppm): 8.6 (s, 1H); 7.8 (d, 1H); 7.2-7.3 (m, 2H); 7.1 (m, 1H); 6.9 (d, 1H); 6.3 (s, 1H); 4.5 (s, 2H); 3.5 (s, 3H); 3.1 (s, 3H).

(44) [M+H]=567.1; Rt=1.123 min

Example 5

ethyl 2-[2-[[3,5-difluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]phenoxy]acetate

(45) ##STR00083##

Example 5.1: Ethyl (Z)-3-(dimethylcarbamoylamino)-4,4,4-trifluoro-but-2-enoate

(46) ##STR00084##

(47) To a solution of 104 g (2.73 mol) NaH in 600 mL dry DMF under a N.sub.2-atmosphere was added 233 g (2.18 mol) N,N-dimethylcarbamoyl chloride (CAS: 79-44-7) dissolved in 200 mL dry DMF dropwise over 1 hour at 0-5° C. with stirring. Then 200 g (1.09 mol) ethyl (Z)-3-amino-4,4,4-trifluoro-but-2-enoate (CAS: 372-29-2) dissolved in 200 mL dry DMF was added dropwise at a temperature of 0-5° C. over 1 hour with stirring. The mixture was stirred at room temperature for another 2 hours and then poured into ice-water. The mixture was extracted with ethyl acetate, the combined organic layer was washed with brine, dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica (petrol ether/ethyl acetate) to give 170 g (0.67 mol, 64%) of the desired product 5.1.

Example 5.2: 2-(dimethylamino)-4-(trifluoromethyl)-1,3-oxazin-6-one

(48) ##STR00085##

(49) To a solution of 170 g (0.67 mol) of compound 5.1 in 102 mL POCl.sub.3 was added 139 g (0.67 mol) PCl.sub.5 at 0° C. in three portions with 15 minutes stirring in between and the mixture was stirred another hour at 0° C. The mixture was then stirred at room temperature for another 3 hours. The reaction mixture was poured into 250 mL ice water and the precipitate was collected via filtration and dried to give 84 g (0.40 mol, 60%) of the desired product 5.2.

(50) .sup.1H-NMR (CDCl.sub.3, ppm): 5.9 (s, 1H); 3.2 (d, J=19.58 Hz, 6H).

(51) [M+H]=209.1; Rt=0.980 min

Example 5.3: 6-(trifluoromethyl)-3-(3,5,6-trifluoro-2-pyridyl)-1H-pyrimidine-2,4-dione

(52) ##STR00086##

(53) A solution of 1.5 g (15.2 mmol) 2-amino-3,5,6-trifluoropyridine (CAS 3534-50-7) and 3.1 g (15.2 mmol) of compound 5.2 in 15 mL glacial acetic acid was stirred at 95° C. for 16 hours. Then water was added and the mixture was extracted with ethyl acetate. The combined organic layer was washed with water and brine, dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure to give 3.9 g (12.5 mmol, 82%) of the desired product 5.3.

(54) .sup.1H-NMR (CDCl.sub.3, ppm): 7.6 (m, 1H); 6.25 (s, 1H).

(55) [M+H]=312.0; Rt=0.873 min

Example 5.4: 1-methyl-6-(trifluoromethyl)-3-(3,5,6-trifluoro-2-pyridyl)pyrimidine-2,4-dione

(56) ##STR00087##

(57) To a solution of 35 g (0.11 mol) of compound 5.3 in 400 mL DMF was added 31 g (0.23 mol) K.sub.2CO.sub.3 followed by 32 g (0.23 mol) methyl iodide at 0° C. and the mixture was stirred at room temperature for 16 hours. Then water was added, the mixture was extracted with ethyl acetate, the combined organic layer was washed with water and brine, then dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica (petrol ether/ethyl acetate) to give 15 g (46 mmol, 42%) of the desired product 5.4.

(58) .sup.1H-NMR (CDCl.sub.3, ppm): 7.6 (q, J=7.06 Hz, 1H); 6.4 (s, 1H); 3.6 (s, 3H).

(59) [M+H]=325.9; Rt=1.058 min

Example 5.5: 3-[3,5-Difluoro-6-(2-methoxyphenoxy)-2-pyridyl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4-dione

(60) ##STR00088##

(61) To a solution of 5 g (0.04 mol) of 2-methoxyphenol (CAS: 90-05-1) in 400 mL THF was added 6.9 g (0.06 mol) KO.sup.tBu at 0° C. over 5 minutes with stirring. Then 10 g (31 mmol) of compound 5.4 was added, the mixture was heated to 80° C. for 2 hours and then poured into ice water. The mixture was extracted with ethyl acetate, the combined organic layer was washed with brine, dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica (petrol ether/ethyl acetate) to give 9.3 g (22 mmol, 71%) of the desired product 5.5.

(62) .sup.1H-NMR (CDCl.sub.3, ppm): 7.5 (t, J=7.78 Hz, 1H); 7.2-7.3 (m, 2H); 6.9-7.0 (m, 2H); 6.3 (s, 1H); 3.7 (s, 3H).

(63) [M+H]=430.0; Rt=1.197 min

Example 5.6: 3-[3,5-Difluoro-6-(2-hydroxyphenoxy)-2-pyridyl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4-dione

(64) ##STR00089##

(65) To a solution of 9 g (20 mmol) of compound 5.5 in 200 mL dichloromethane cooled to −78° C. was added 7.9 g (30 mmol) BBr.sub.3 in 50 mL dichloromethane. The mixture was warmed to room temperature over 5 hours, poured into ice water and extracted with dichloromethane. The combined organic layer was washed with brine, dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure to give the desired product 5.6 which was used without further purification in the next step.

(66) .sup.1H-NMR (CDCl.sub.3, ppm): 7.54 (m, 1H); 7.09-7.18 (m, 2H); 7.00-7.08 (m, 1H); 6.87-6.96 (m, 1H); 6.3 (s, 1H); 5.7 (br. s., 1H); 3.5 (s, 3H).

(67) [M+H]=416.0; Rt=1.117 min

Example 5.7: Ethyl 2-[2-[[3,5-difluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]phenoxy]acetate

(68) ##STR00090##

(69) To a solution of 9.5 g (22.8 mmol) of compound 5.6 in 300 mL acetonitrile was added 6.3 g (45.7 mmol) K.sub.2CO.sub.3 at 0° C. with stirring. Then 7.6 g (45.7 mmol) ethyl bromoacetate (CAS: 105-36-2) was added and the mixture was stirred at 80° C. for 16 hours. Water was added, the mixture was extracted with ethyl acetate, the combined organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica (petrol ether/ethyl acetate) and recrystallized from methyl tert-butyl ether and n-hexanes to give 3.9 g (7.8 mmol, 34%) of the desired product 5.7.

(70) .sup.1H-NMR (CDCl.sub.3, ppm): 7.5 (t, J=7.83 Hz, 1H); 7.2 (d, J=7.50 Hz, 1H); 7.1-7.2 (m, 1H); 7.0 (t, J=7.72 Hz, 1H); 6.9 (d, J=8.16 Hz, 1H); 6.3 (s, 1H); 4.5 (s, 1H); 4.2 (q, J=7.13 Hz, 2H); 3.5 (s, 3H); 1.3 (t, J=7.17 Hz, 3H).

(71) [M+H]=502.2; Rt=1.221 min

Example 6

Ethyl 2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]propanoate

(72) ##STR00091##

(73) To a solution of 0.22 g (1.1 mmol) of ethyl 2-[(3-hydroxy-2-pyridyl)oxy]propanoate (CAS: 353292-83-8) in 4 mL DMSO was added 0.042 g (1.1 mmol) NaH at 15° C. The suspension was stirred for 10 minutes at this temperature before 0.3 g (0.88 mmol) 3-(5-chloro-3,6-difluoro-2-pyridyl)-1-methyl-6-(trifluoromethyl)pyrimidine-2,4-dione was added to the mixture at 15° C. The resulting mixture was stirred at 90-100° C. for 2 hours, poured into water and extracted with ethyl acetate. The combined organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure. The crude product was purified by reversed phase preparative HPLC (acetonitrile/water containing trifluoroacetic acid) to give 0.17 g (0.32 mmol, 36%) of the desired product.

(74) .sup.1H-NMR (CDCl.sub.3, ppm): 7.9 (d, J=4.52 Hz, 1H); 7.8 (d, J=7.28 Hz, 1H); 7.5 (d, J=7.53 Hz, 1H); 6.9 (t, J=5.52 Hz, 1H); 6.3 (d, J=3.26 Hz, 1H); 5.0-5.1 (m, 1H); 4.2 (q, J=7.11 Hz, 2H); 3.5 (d, J=4.27 Hz, 3H); 1.4 (d, J=7.03 Hz, 3H); 1.2 (t, J=7.15 Hz, 3H).

Example 7

Ethyl 2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]acetate

(75) ##STR00092##

Example 7.1: Ethyl 2-[[3-[(6-azido-3-chloro-5-fluoro-2-pyridyl)oxy]-2-pyridyl]oxy]acetate

(76) ##STR00093##

(77) To a solution of 1.8 g (10.78 mmol) 3-chloro-2,5,6-trifluoropyridine (CAS 2879-42-7) in 20 mL DMSO at room temperature was added 0.77 g (11.8 mmol) sodium azide and the mixture was stirred 3 hours at room temperature. Then a suspension of 2.2 g (11.3 mmol) ethyl 2-[(3-hydroxy-2-pyridyl)oxy]acetate (CAS: 353292-81-6) and 7 g (21.5 mmol) Cs.sub.2CO.sub.3 in 10 mL DMSO was added to the above mixture in portions. The resulting mixture was stirred at room temperature for 15 hours, diluted with water and extracted with ethyl acetate. The combined organic layer was washed with brine, dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure. The crude product 7.1 was used without further purification in the next step.

Example 7.2: Ethyl 2-[[3-[(6-amino-3-chloro-5-fluoro-2-pyridyl)oxy]-2-pyridyl]oxy]acetate

(78) ##STR00094##

(79) To a suspension of 4.8 g (13 mmol) of compound 7.1 and 4.3 g (66 mmol) zinc in 100 mL THF was added dropwise 50 mL semi-saturated aqueous NH.sub.4Cl solution at 0° C. The mixture was stirred at room temperature for 5 hours, filtered and the filter cake was washed with ethyl acetate. To the filtrate was added 200 mL water, the mixture was extracted with ethyl acetate, the organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica (petrol ether/ethyl acetate) to give 2.7 g (8 mmol, 61%) of the desired product 7.2.

(80) .sup.1H-NMR (CDCl.sub.3, ppm): 7.9 (dd, J=4.89 Hz, J=1.51 Hz, 1H); 7.4 (d, J=7.39 Hz, 1H); 7.3 (d, J=9.06 Hz, 1H); 6.9 (dd, J=7.65 Hz, J=4.89 Hz, 1H); 4.9 (s, 2H); 4.5 (s, 2H); 4.2 (q, J=7.15 Hz, 2H); 1.25 (t, J=7.15 Hz, 3H).

(81) [M+H]=428.1; Rt=1.332 min

Example 7.3: Ethyl 2-[[3-[[3-chloro-6-[2,4-dioxo-6-(trifluoromethyl)-1H-pyrimidin-3-yl]-5-fluoro-2-pyridyl]oxy]-2-pyridyl]oxy]acetate

(82) ##STR00095##

(83) A solution of 16 g (47 mmol) of compound 7.2 and 9.8 g (47 mmol) of compound 5.2 in 430 mL glacial acetic acid was stirred at 80° C. for 16 hours. Then 9.8 g (47 mmol) of compound 5.2 was added and the mixture stirred at 80° C. for 16 hours. Again 2.9 g (14 mmol) of compound 5.2 was added and the mixture stirred at 80° C. for 16 hours. Again 9.8 g (47 mmol) of compound 5.2 was added and the mixture stirred at 80° C. for 16 hours. Then water was added, the mixture was extracted with ethyl acetate, the combined organic layer was washed with water and brine, dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure. The crude product 7.3 (23 g, 46 mmol, 97%) was used in the next step without further purification.

Example 7.4: Ethyl 2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]acetate

(84) ##STR00096##

(85) To a solution of 23 g (46 mmol) of the crude compound 7.3 in 500 mL DMF was added 38 g (275 mmol) K.sub.2CO.sub.3 followed by 26.6 g (187 mmol) methyl iodide at 0° C. The reaction mixture was stirred at room temperature for 16 hours, then 38 g (275 mmol) K.sub.2CO.sub.3 was added again followed by 26.6 g (187 mmol) methyl iodide and the mixture was again stirred at room temperature for 48 hours. The mixture was poured into water, extracted with ethyl acetate, the combined organic layer was washed with water and brine, dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed under reduced pressure. The crude product was purified by reversed phase preparative HPLC (acetonitrile/water containing trifluoroacetic acid) to give 10.3 g (19.9 mmol, 43%) of the desired product ethyl 2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]-2-pyridyl]oxy]acetate.

(86) .sup.1H-NMR (CDCl.sub.3, ppm): 7.96 (d, J=3.97 Hz, 1H); 7.76 (d, J=7.50 Hz, 1H); 7.49 (d, J=7.06 Hz, 1H); 6.95 (dd, J=7.50 Hz, J=5.29 Hz, 1H); 6.26 (s, 1H) 4.79 (s, 2H); 4.19 (q, J=7.06 Hz, 2H); 3.48 (s, 3H); 1.24 (t, J=7.06 Hz, 3H).

(87) [M+H]=519.0; Rt=1.183 min

(88) The compounds listed below in tables 4 to 9 can be prepared similarly to the examples mentioned above.

(89) ##STR00097##

(90) TABLE-US-00010 TABLE 4 no R.sup.1 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8 m/z [M + H] R.sub.t [min] 8 CH.sub.3 H H Cl H H OH 472 1.015 9 CH.sub.3 H H Cl H H OCH.sub.3 486 1.11 10 CH.sub.3 H H Cl H H OCH.sub.2CH.sub.3 500 1.197 11 CH.sub.3 H F F H H OH 474 1.004 12 CH.sub.3 H F F H H OCH.sub.3 488 1.167 13 CH.sub.3 H F Cl H H NHCH.sub.2(CO)OCH.sub.3 561 1.086 14 CH.sub.3 H F Cl H H NHCH.sub.2CH.sub.2(CO)OCH.sub.3 575 1.094 15 CH.sub.3 H F Cl CH.sub.3 (S) H OCH.sub.2CH.sub.3 532 1.306 16 CH.sub.3 H F Cl CH.sub.3 (R) H OCH.sub.2CH.sub.3 532 1.306 17 CH.sub.3 H F CN H H OCH.sub.2CH.sub.3 509 1.212 18 CH.sub.3 H H Cl OCH.sub.3 H OCH.sub.3 516 1.155 19 CH.sub.3 H H Cl CH.sub.3 (S) H OCH.sub.2CH.sub.3 514 1.241 20 CH.sub.3 H H Cl CH.sub.3 (R) H OCH.sub.2CH.sub.3 514 1.241 21 CH.sub.3 H F F OCH.sub.3 H OCH.sub.2CH.sub.3 532 1.214 22 CH.sub.3 H F F CH.sub.3 (S) H OCH.sub.2CH.sub.3 516 1.241 23 CH.sub.3 H F F CH.sub.3 (R) H OCH.sub.2CH.sub.3 24 CH.sub.3 H F Cl CH.sub.3 CH.sub.3 OCH.sub.3 532 1.266 25 CH.sub.3 H F Cl F H OCH.sub.2CH.sub.3 536 1.287 26 CH.sub.3 H F Cl F CH.sub.3 OCH.sub.3 536 1.242 27 CH.sub.3 H F Cl F F OCH.sub.2CH.sub.3 554 1.239 28 CH.sub.3 H F Cl SCH.sub.3 H OCH.sub.3 29 CH.sub.3 H F Cl SCH.sub.3 H OCH.sub.2CH.sub.3 550 1.248 30 CH.sub.3 H F Cl CH.sub.2OCH.sub.3 H OCH.sub.3 548 1.195 31 CH.sub.3 H F Cl CO.sub.2CH.sub.2CH.sub.3 H OCH.sub.2CH.sub.3 590 1.324 32 CH.sub.3 H Cl Cl H H OCH.sub.3 33 CH.sub.3 H Cl Cl H H OCH.sub.2CH.sub.3 534 1.270 34 CH.sub.3 H H Br H H OCH.sub.2CH.sub.3 544 1.199 35 CH.sub.3 H F Br H H OCH.sub.2CH.sub.3 564 1.247 36 CH.sub.3 H H CF3 H H OCH.sub.2CH.sub.3 534 1.300 37 CH.sub.3 H F CF3 H H OCH.sub.2CH.sub.3 38 CH.sub.3 H H NO.sub.2 H H OCH.sub.2CH.sub.3 511 1.165 39 CH.sub.3 H F NO.sub.2 H H OCH.sub.2CH.sub.3 40 CH.sub.3 H H NH.sub.2 H H OCH.sub.2CH.sub.3 481 1.068 41 NH.sub.2 H F Cl H H OCH.sub.3 42 NH.sub.2 H F Cl H H OCH.sub.2CH.sub.3 519 1.172 43 CD.sub.3 H F Cl H H OCH.sub.2CH.sub.3 521 1.229 44 H H F Cl H H OCH.sub.2CH.sub.3 504 1.180 45 CH.sub.3 CH.sub.3 F Cl H H OCH.sub.3 46 CH.sub.3 CH.sub.3 F Cl H H OCH.sub.2CH.sub.3 532 1.294 47 CH.sub.3 H F Cl H H OCH.sub.3 504 1.186 48 CH.sub.3 H F Cl H H SCH.sub.3 520 1.278 49 CH.sub.3 H F Cl H H OCH.sub.2C≡CH 528 1.209 50 CH.sub.3 H F Cl H H OCH.sub.2CH═CH.sub.2 530 1.251 51 CH.sub.3 H F Cl H H OCH.sub.2C≡CCH.sub.3 542 1.288 52 CH.sub.3 H F Cl H H OCH.sub.2C(CH.sub.3)═CH.sub.2 544 1.334 53 CH.sub.3 H F Cl H H OCH.sub.2CH.sub.2CH.sub.3 532 1.319 54 CH.sub.3 H F Cl H H OCH(CH.sub.3).sub.2 532 1.312 55 CH.sub.3 H F Cl H H OC(CH.sub.3).sub.3 56 CH.sub.3 H F Cl H H OCH.sub.2CH(CH.sub.3).sub.2 546 1.368 57 CH.sub.3 H F Cl H H OCH.sub.2CH.sub.2Cl 552 1.242 58 CH.sub.3 H F Cl H H OCH.sub.2CCl.sub.2H 588 1.326 59 CH.sub.3 H F Cl H H OCH.sub.2CF.sub.2H 554 1.226 60 CH.sub.3 H F Cl H H O-c-C.sub.3H.sub.5 61 CH.sub.3 H F Cl H H O-c-C.sub.4H.sub.7 544 1.335 62 CH.sub.3 H F Cl H H O-c-C.sub.5H.sub.9 558 1.370 63 CH.sub.3 H F Cl H H O-c-C.sub.6H.sub.11 572 1.418 64 CH.sub.3 H F Cl H H O-phenyl 566 1.339 65 CH.sub.3 H F Cl H H O(oxetan-3-yl) 546 1.179 66 CH.sub.3 H F Cl H H O(tetrahydropyran-4-yl) 574 1.234 67 CH.sub.3 H F Cl H H OCH.sub.2-c-C.sub.3H.sub.5 544 1.283 68 CH.sub.3 H F Cl H H OCH.sub.2-c-C.sub.4H.sub.7 558 1.349 69 CH.sub.3 H F Cl H H OCH.sub.2(phenyl) 580 1.322 70 CH.sub.3 H F Cl H H OCH.sub.2(furan-2-yl) 570 1.290 71 CH.sub.3 H F Cl H H OCH.sub.2CH.sub.2OCH.sub.3 548 1.187 72 CH.sub.3 H F Cl H H OCH.sub.2CH.sub.2OCH.sub.2CH.sub.3 562 1.234 73 CH.sub.3 H F Cl H H OCH.sub.2CH.sub.2OCH(CH.sub.3).sub.2 576 1.277 74 CH.sub.3 H F Cl H H OCH.sub.2CH.sub.2CH.sub.2OCH.sub.3 562 1.253 75 CH.sub.3 H F Cl H H OCH.sub.2CH(OCH.sub.3).sub.2 600* 1.216 76 CH.sub.3 H F Cl H H OCH.sub.2CH(OCH.sub.2CH.sub.3).sub.2 628* 1.302 77 CH.sub.3 H F Cl H H OCH.sub.2CO.sub.2CH.sub.3 562 1.182 78 CH.sub.3 H F Cl H H OCH(CH.sub.3)CO.sub.2CH.sub.3 576 1.257 79 CH.sub.3 H F Cl H H OCH.sub.2CO.sub.2CH.sub.2CH.sub.3 576 1.228 80 CH.sub.3 H F Cl H H OCH.sub.2CO.sub.2CH(CH.sub.3).sub.2 590 1.272 81 CH.sub.3 H F Cl H H NHCH.sub.3 503 1.125 82 CH.sub.3 H F Cl H H N(CH.sub.3).sub.2 517 1.135 83 CH.sub.3 H F Cl H H NHOH 505 0.996 84 CH.sub.3 H F Cl H H NHOCH.sub.3 519 1.096 85 CH.sub.3 H F Cl H H N(CH.sub.3)OCH.sub.3 533 1.162 86 CH.sub.3 H F Cl H H NHCH.sub.2C≡CH 527 1.153 87 CH.sub.3 H F Cl H H NHCH.sub.2CH.sub.2CH.sub.2CO.sub.2CH.sub.3 589 1.159 88 CH.sub.3 H F Cl H H NHSO.sub.2CH(CH.sub.3).sub.2 89 CH.sub.3 H F Cl H H NHSO.sub.2N(CH.sub.3).sub.2 596 1.165 90 CH.sub.3 H F Cl H H NHSO.sub.2N(CH.sub.3)CH(CH.sub.3).sub.2 *[M + Na]

(91) ##STR00098##

(92) TABLE-US-00011 TABLE 5 no R.sup.1 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8 m/z [M + H] R.sub.t [min] 91 CH.sub.3 H F Cl H OH 491 1.052 92 NH.sub.2 H F Cl H H OCH.sub.3 93 NH.sub.2 H F Cl H H OCH.sub.2CH.sub.3 520 1.156 94 CD.sub.3 H F Cl H H OCH.sub.2CH.sub.3 522 1.215 95 CH.sub.2C≡CH H F Cl H H OCH.sub.2CH.sub.3 543 1.215 96 CH.sub.3 CH.sub.3 F Cl H H OCH.sub.3 97 CH.sub.3 CH.sub.3 F Cl H H OCH.sub.2CH.sub.3 533 1.269 98 CH.sub.3 H F Cl H H NHCH.sub.2(CO)OCH.sub.3 99 CH.sub.3 H F Cl H H NHCH.sub.2CH.sub.2(CO)OCH.sub.3 100 CH.sub.3 H F Cl CH.sub.3 (S) H OCH.sub.2CH.sub.3 101 CH.sub.3 H F Cl CH.sub.3 (R) H OCH.sub.2CH.sub.3 102 CH.sub.3 H F CN H H OCH.sub.2CH.sub.3 103 CH.sub.3 H H Cl CH.sub.3 (S) H OCH.sub.2CH.sub.3 104 CH.sub.3 H H Cl CH.sub.3 (R) H OCH.sub.2CH.sub.3 105 CH.sub.3 H F F H H OCH.sub.2CH.sub.3 503 1.171 106 CH.sub.3 H F F CH.sub.3 (S) H OCH.sub.2CH.sub.3 107 CH.sub.3 H F F CH.sub.3 (R) H OCH.sub.2CH.sub.3 108 CH.sub.3 H F Cl CH.sub.3 CH.sub.3 OCH.sub.3 109 CH.sub.3 H F Cl F H OCH.sub.2CH.sub.3 110 CH.sub.3 H F Cl F CH.sub.3 OCH.sub.3 111 CH H F Cl F F OCH.sub.2CH.sub.3 112 CH.sub.3 H F Cl SCH.sub.3 H OCH.sub.3 113 CH.sub.3 H F Cl SCH.sub.3 H OCH.sub.2CH.sub.3 114 CH.sub.3 H Cl Cl H H OCH.sub.3 115 CH.sub.3 H Cl Cl H H OCH.sub.2CH.sub.3 116 CH.sub.3 H H Br H H OCH.sub.2CH.sub.3 117 CH.sub.3 H F Br H H OCH.sub.2CH.sub.3 118 CH.sub.3 H H CF.sub.3 H H OCH.sub.2CH.sub.3 119 CH.sub.3 H F CF.sub.3 H H OCH.sub.2CH.sub.3 120 CH.sub.3 H H NO.sub.2 H H OCH.sub.2CH.sub.3 121 CH.sub.3 H F NO.sub.2 H H OCH.sub.2CH.sub.3 122 CH.sub.3 H H NH.sub.2 H H OCH.sub.2CH.sub.3 123 CH.sub.3 H F Cl H H OCH.sub.3 505 1.154 124 CH.sub.3 H F Cl H H SCH.sub.3 125 CH.sub.3 H F Cl H H OCH.sub.2C≡CH 529 1.201 126 CH.sub.3 H F Cl H H OCH.sub.2CH═CH.sub.2 531 1.226 127 CH.sub.3 H F Cl H H OCH.sub.2C≡CCH.sub.3 128 CH.sub.3 H F Cl H H OCH.sub.2C(CH.sub.3)═CH.sub.2 545 1.305 129 CH.sub.3 H F Cl H H OCH.sub.2CH.sub.2CH.sub.3 533 1.290 130 CH.sub.3 H F Cl H H OCH(CH.sub.3).sub.2 533 1.282 131 CH.sub.3 H F Cl H H OC(CH.sub.3).sub.3 132 CH.sub.3 H F Cl H H OCH.sub.2CH(CH.sub.3).sub.2 547 1.335 133 CH.sub.3 H F Cl H H OCH.sub.2CH.sub.2Cl 134 CH.sub.3 H F Cl H H OCH.sub.2CCl.sub.2H 135 CH.sub.3 H F Cl H H OCH.sub.2CF.sub.2H 555 1.255 136 CH.sub.3 H F Cl H H O-c-C.sub.3H.sub.5 137 CH.sub.3 H F Cl H H O-c-C.sub.4H.sub.7 138 CH.sub.3 H F Cl H H O-c-C.sub.5H.sub.9 139 CH.sub.3 H F Cl H H O-c-C.sub.6H.sub.11 573 1.395 140 CH.sub.3 H F Cl H H O-phenyl 141 CH.sub.3 H F Cl H H O(oxetan-3-yl) 547 1.143 142 CH.sub.3 H F Cl H H O(tetrahydropyran-4-yl) 143 CH.sub.3 H F Cl H H OCH.sub.2-c-C.sub.3H.sub.5 545 1.257 144 CH.sub.3 H F Cl H H OCH.sub.2-c-C.sub.4H.sub.7 559 1.359 145 CH.sub.3 H F Cl H H OCH.sub.2(phenyl) 581 1.330 146 CH.sub.3 H F Cl H H OCH.sub.2(furan-2-yl) 147 CH.sub.3 H F Cl H H OCH.sub.2CH.sub.2OCH.sub.3 549 1.174 148 CH.sub.3 H F Cl H H OCH.sub.2CH.sub.2OCH.sub.2CH.sub.3 563 1.228 149 CH.sub.3 H F Cl H H OCH.sub.2CH.sub.2OCH(CH.sub.3).sub.2 577 1.272 150 CH.sub.3 H F Cl H H OCH.sub.2CH.sub.2CH.sub.2OCH.sub.3 563 1.217 151 CH.sub.3 H F Cl H H OCH.sub.2CH(OCH.sub.3).sub.2 579 1.207 152 CH.sub.3 H F Cl H H OCH.sub.2CH(OCH.sub.2CH.sub.3).sub.2 629* 1.305 153 CH.sub.3 H F Cl H H OCH.sub.2CO.sub.2CH.sub.3 154 CH.sub.3 H F Cl H H OCH(CH.sub.3)CO.sub.2CH.sub.3 577 1.223 155 CH.sub.3 H F Cl H H OCH.sub.2CO.sub.2CH.sub.2CH.sub.3 577 1.220 156 CH.sub.3 H F Cl H H OCH.sub.2CO.sub.2CH(CH.sub.3).sub.2 157 CH.sub.3 H F Cl H H NHCH.sub.3 158 CH.sub.3 H F Cl H H N(CH.sub.3).sub.2 159 CH.sub.3 H F Cl H H NHOH 160 CH.sub.3 H F Cl H H NHOCH.sub.3 161 CH.sub.3 H F Cl H H N(CH.sub.3)OCH.sub.3 162 CH.sub.3 H F Cl H H NHCH.sub.2C≡CH 163 CH.sub.3 H F Cl H H NHCH.sub.2CH.sub.2CH.sub.2CO.sub.2CH.sub.3 164 CH.sub.3 H F Cl H H NHSO.sub.2CH.sub.3 568 1.052 165 CH.sub.3 H F Cl H H NHSO.sub.2CH(CH.sub.3).sub.2 596 1.126 166 CH.sub.3 H F Cl H H NHSO.sub.2N(CH.sub.3).sub.2 167 CH.sub.3 H F Cl H H NHSO.sub.2N(CH.sub.3)CH(CH.sub.3).sub.2 *[M + Na]

(93) ##STR00099##

(94) TABLE-US-00012 TABLE 6 m/z R.sub.t no R.sup.4 R.sup.5 n X Q W n R.sup.8 [M + H] [min] 168 H Cl 1 S O O 1 OCH.sub.3 169 H Cl 1 S O O 1 OCH.sub.2CH.sub.3 516 1.222 170 F F 1 S O O 1 OCH.sub.3 171 F F 1 S O O 1 OCH.sub.2CH.sub.3 172 F Cl 1 S O O 1 OCH.sub.3 173 F Cl 1 S O O 1 OCH.sub.2CH.sub.3 174 F Cl 1 O O S 1 OCH.sub.3 175 F Cl 1 O O S 1 OCH.sub.2CH.sub.3 176 F Cl 1 O NH O 1 OCH.sub.3 177 F Cl 1 O NH O 1 OCH.sub.2CH.sub.3 178 F Cl 1 O NCH.sub.3 O 1 OCH.sub.3 179 F Cl 1 O NCH.sub.3 O 1 OCH.sub.2CH.sub.3 531 1.280 180 F Cl 1 O S O 1 OCH.sub.3 181 F Cl 1 O S O 1 OCH.sub.2CH.sub.3 182 F Cl 1 O SO O 1 OCH.sub.3 183 F Cl 1 O SO O 1 OCH.sub.2CH.sub.3 184 F Cl 1 O SO.sub.2 O 1 OCH.sub.3 185 F Cl 1 O SO.sub.2 O 1 OCH.sub.2CH.sub.3 186 F Cl 1 O CH.sub.2 O 1 OCH.sub.3 502 1.243 187 F Cl 1 O CH.sub.2 O 1 OCH.sub.2CH.sub.3 188 F Cl 2 O NH O 2 OCH.sub.3 189 F Cl 2 O NH O 2 OCH.sub.2CH.sub.3 190 F Cl 2 O NCH.sub.3 O 2 OCH.sub.3 191 F Cl 2 O NCH.sub.3 O 2 OCH.sub.2CH.sub.3 192 F Cl 2 O CH.sub.2 O 2 OCH.sub.3 193 F Cl 2 O CH.sub.2 O 2 OCH.sub.2CH.sub.3 194 F Cl 3 O O O 3 OCH.sub.3 195 F Cl 3 O O O 3 OCH.sub.2CH.sub.3 546 1.300

(95) ##STR00100##

(96) TABLE-US-00013 TABLE 7 m/z R.sub.t no R.sup.4 R.sup.5 R.sup.a R.sup.b R.sup.c R.sup.d R.sup.8 [M + H] [min] 196 F Cl F H H H OCH.sub.3 197 F Cl F H H H OCH.sub.2CH.sub.3 536 1.230 198 F Cl H F H H OCH.sub.3 199 F Cl H F H H OCH.sub.2CH.sub.3 536 1.258 200 F Cl H H F H OCH.sub.3 201 F Cl H H F H OCH.sub.2CH.sub.3 536 1.258 202 F Cl H H H F OCH.sub.3 203 F Cl H H H F OCH.sub.2CH.sub.3 536 1.240 204 F Cl Cl H H H OCH.sub.3 205 F Cl Cl H H H OCH.sub.2CH.sub.3 206 F Cl H Cl H H OCH.sub.3 207 F Cl H Cl H H OCH.sub.2CH.sub.3 552 1.303 208 F Cl H H Cl H OCH.sub.3 209 F Cl H H Cl H OCH.sub.2CH.sub.3 210 F Cl H H H Cl OCH.sub.3 211 F Cl H H H Cl OCH.sub.2CH.sub.3 212 F Cl CH.sub.3 H H H OCH.sub.3 213 F Cl CH.sub.3 H H H OCH.sub.2CH.sub.3 214 F Cl H CH.sub.3 H H OCH.sub.3 215 F Cl H CH.sub.3 H H OCH.sub.2CH.sub.3 216 F Cl H H CH.sub.3 H OCH.sub.3 217 F Cl H H CH.sub.3 H OCH.sub.2CH.sub.3 218 F Cl H H H CH.sub.3 OCH.sub.3 219 F Cl H H H CH.sub.3 OCH.sub.2CH.sub.3 220 F Cl CF.sub.3 H H H OCH.sub.3 221 F Cl CF.sub.3 H H H OCH.sub.2CH.sub.3 222 F Cl H CF.sub.3 H H OCH.sub.3 223 F Cl H CF.sub.3 H H OCH.sub.2CH.sub.3 224 F Cl H H CF.sub.3 H OCH.sub.3 225 F Cl H H CF.sub.3 H OCH.sub.2CH.sub.3 586 1.331 226 F Cl H H H CF.sub.3 OCH.sub.3 227 F Cl H H H CF.sub.3 OCH.sub.2CH.sub.3

(97) ##STR00101##

(98) TABLE-US-00014 TABLE 8 no R.sup.4 R.sup.5 R.sup.8 m/z [M + H] Rt [min] 228 F Cl OCH.sub.2CH.sub.3 518 1.267

(99) ##STR00102##

(100) TABLE-US-00015 TABLE 9 no R.sup.4 R.sup.5 R.sup.8 m/z [M + N] Rt [min] 229 F Cl OCH.sub.2CH.sub.3 518 1.256

B Use Examples

(101) The herbicidal activity of the uracilpyridines of formula (I) was demonstrated by the following greenhouse experiments:

(102) The culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.

(103) For the pre-emergence treatment, the active ingredients, which had been suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the plants had rooted. This cover caused uniform germination of the test plants, unless this had been impaired by the active ingredients. For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment.

(104) Depending on the species, the plants were kept at 10-25° C. or 20-35° C., respectively. The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.

(105) Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the aerial moieties, and 0 means no damage, or normal course of growth. A good herbicidal activity is given at values of at least 70 and a very good herbicidal activity is given at values of at least 85.

(106) The plants used in the greenhouse experiments were of the following species:

(107) TABLE-US-00016 Bayer code Scientific name ALOMY Alopecurus myosuroides AMARE Amaranthus retroflexus BRADC Brachiaria decumbens CHEAL Chenopodium album ECHCG Echinocloa crus-galli LOLMU Lolium multiflorum MATCH Matricaria chamomilla SETVI Setaria viridis ZEAMX Zea mays

(108) At an application rate of 16 g/ha, the compounds 1, 2, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 20, 21, 22, 24, 25, 26, 27, 33, 34, 35, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 83, 84, 85, 86, 89, 91, 97, 125, 126, 128, 129, 130, 132, 135, 143, 145, 147, 149, 150, 151, 152, 154, 165, 169, 199, 201, 207, 228 and 229 applied by the post-emergence method, showed very good herbicidal activity against AMARE, CHEAL, ECHCG and SETVI.

(109) At an application rate of 16 g/ha, the compounds 18, 82, 87 and 155 applied by the post-emergence method, showed very good herbicidal activity against AMARE, CHEAL and SETVI.

(110) TABLE-US-00017 TABLE 10 Comparison of the herbicidal activity of example 2 of the present invention and com- pound no. 3 known from WO 11/137088 post emergence (greenhouse) Example 2 Cmpd no. 3 (WO 11/137088) compound 03 04 application rate [g/ha] 8 8 unwanted plants damages ALOMY 70 40 LOLMU 70 40 MATCH 70 60 application rate [g/ha] 2 2 unwanted plants damages BRADC 80 20 crop plants 25 40 ZEAMX application rate [g/ha] 1 1 unwanted plants damages CHEAL 90 45

(111) The data clearly demonstrate the superior herbicidal activity of the inventive compounds of formula I of the present invention over the compounds known from the prior art.

(112) The replacement of the central phenyl ring by a pyridine ring leads not only to a much better herbicidal activity, but also to a much better crop compatability as achieved by the compound known from WO 11/137088.

(113) The control of resistant weeds by the compounds of formula (I) was demonstrated by the following greenhouse experiment:

(114) The culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species and/or resistant biotype. For the pre-emergence treatment, the active ingredients, which had been suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the plants had rooted. This cover caused uniform germination of the test plants, unless this had been impaired by the active ingredients. For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment. Depending on the species, the plants were kept at 10-25° C. or 20-35° C., respectively. The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated. The evaluation was carried out by using a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the above-ground parts, and 0 means no damage, or normal course of growth.

(115) The plants used in the greenhouse experiments were of the following species and biotype:

(116) TABLE-US-00018 weed Bayer Scientific Common no. code name name Biotype w.1 AMATA Amaranthus Common Sensitive tamariscinus waterhemp w.2 AMATA Amaranthus Common PPO resistant biotype 1 that tamariscinus waterhemp was shown to contain the ΔG210 mutation w.3 AMATA Amaranthus Common PPO resistant biotype 2 that tamariscinus waterhemp was shown to contain the ΔG210 mutation

(117) The results shown in the following table demonstrate that compound 7 and compound 1 have very good activity on both sensitive (w.1) and resistant weeds containing the ΔG210 mutation (w.2, w.3) whereas the known PPO inhibitor azafenidin shows much weaker control of resistant in comparison to sensitive biotypes.

(118) TABLE-US-00019 herbicide weed control (%) compound use rate w.1 w.2 w.3 1 4 g/ha 100 100 100 1 2 g/ha 88 87 98 7 4 g/ha 100 100 100 7 2 g/ha 93 100 100 azafenidin 4 g/ha 100 78 77 azafenidin 2 g/ha 88 62 77