HERBICIDAL COMPOUNDS

Abstract

Compound of formula (I) or an agronomically acceptable salt thereof: (I) wherein the substituents are as defined in claim 1, useful as a pesticides, especially as herbicides.

##STR00001##

Claims

1. A compound of formula (I) or an agronomically acceptable salt thereof: ##STR00033## wherein each X.sup.1, X.sup.2 and X.sup.3 is independently selected from oxygen and sulfur; Y is CH or nitrogen; B is O, S, or NR.sup.5; D is (CR.sup.6R.sup.7).sub.n; m is an integer from 0 to 2; n is an integer from 1 to 4; R.sup.1 is hydrogen or C.sub.1-C.sub.6alkyl; R.sup.2 is hydrogen, amino, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6alkenyl, or C.sub.3-C.sub.6alkynyl; R.sup.3 is hydrogen, halogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, or C.sub.1-C.sub.4alkylsulfonyl; R.sup.4 is hydrogen, halogen, cyano, nitro, aminocarbonyl, aminothiocarbonyl, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, or C.sub.1-C.sub.4alkylsulfonyl; R.sup.5 is hydrogen, hydroxy, C.sub.1-C.sub.6alkyl, or C.sub.1-C.sub.4alkoxy; Each R.sup.6 and R.sup.7 is independently selected from hydrogen, halogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, hydroxy, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkoxycarbonyl, or CH.sub.2OR.sup.12; provided that R.sup.6 and R.sup.7 are not both hydroxy on the same carbon atom; or two groups R.sup.6 and R.sup.7, on the same or different carbon atoms, together form a C.sub.1-C.sub.5alkylene chain, which contain 0, 1 or 2 oxygen atoms, substituted by 1-3 groups R.sup.5; or two groups R.sup.6 and R.sup.7, on the same carbon atom, together with the carbon to which they are attached, form a C.sub.2alkene; R.sup.8 is OR.sup.9, SR.sup.9, or NR.sup.10R.sup.11; R.sup.9 is hydrogen, C.sub.1-C.sub.10alkyl, C.sub.1-C.sub.10haloalkyl, C.sub.3-C.sub.6alkenyl, C.sub.3-C.sub.6haloalkenyl, C.sub.3-C.sub.6alkynyl, C.sub.1-C.sub.4alkoxyC.sub.1-C.sub.6alkyl, C.sub.1-C.sub.4haloalkoxyC.sub.1-C.sub.6alkyl, C.sub.6-C.sub.10arylC.sub.1-C.sub.3alkyl, C.sub.6-C.sub.10arylC.sub.1-C.sub.3alkyl substituted by 1-4 groups R.sup.13, heteroarylC.sub.1-C.sub.3alkyl, or heteroarylC.sub.1-C.sub.3alkyl substituted by 1-3 groups R.sup.3; R.sup.10 is hydrogen, C.sub.1-C.sub.6alkyl, or SO.sub.2R.sup.14; R.sup.11 is hydrogen or C.sub.1-C.sub.6alkyl; or R.sup.10 and R.sup.11 together with the nitrogen to which they are attached form a 3- to 6-membered heterocyclyl ring, which optionally contains an oxygen atom; R.sup.12 is hydrogen, C.sub.1-C.sub.4alkyl, or C.sub.1-C.sub.4alkylcarbonyl; each R.sup.13 is independently selected from halogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, cyano, and C.sub.1-C.sub.4alkylsulfonyl; R.sup.14 is C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, or C.sub.1-C.sub.4alkyl(C.sub.1-C.sub.4alkyl)amino; each R.sup.15 is independently selected from hydrogen, halogen, C.sub.1-C.sub.4alkyl, and C.sub.1-C.sub.4haloalkyl; R.sup.16 and R.sup.17 are independently selected from hydrogen, halogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.4alkoxy, and CH.sub.2OR.sup.12; or two groups R.sup.16 and R.sup.17, together form a C.sub.2-C.sub.5alkylene chain, which contains 0, 1 or 2 oxygen atoms, substituted by 1-3 groups R.sup.15; or two groups R.sup.16 and R.sup.17 together with the carbon to which they are attached form a C.sub.2alkene; or a salt or N-oxide thereof.

2. A compound as claimed in claim 1, in which X.sup.1 is sulfur.

3. A compound as claimed in claim 1, in which X.sup.2 is oxygen.

4. A compound as claimed in claim 1, in which X.sup.3 is oxygen.

5. A compound as claimed in m claim 1, in which Y is CH.

6. A compound as claimed in claim 1, in which B is O, NH, or NMe.

7. A compound as claimed in claim 1, in which n is an integer from 1 to 2.

8. A compound as claimed in claim 7, in which n is 2.

9. A compound as claimed in claim 1, in which R.sup.r is hydrogen or C.sub.1-C.sub.4alkyl.

10. A compound as claimed in claim 1, in which R.sup.2 is hydrogen, C.sub.1-C.sub.4alkyl, or C.sub.3-C.sub.4alkynyl.

11. A compound as claimed in claim 1, in which R.sup.3 is hydrogen, chloro, or fluoro.

12. A compound as claimed in claim 1, in which R.sup.4 is hydrogen, chloro, bromo, cyano, or aminothiocarbonyl.

13. A compound as claimed in claim 1, in which each R.sup.6 and R.sup.7 is independently selected from hydrogen, halogen, C.sub.1-C.sub.4alkyl, and C.sub.1-C.sub.4alkoxycarbonyl.

14. An agrochemical composition comprising a herbicidally effective amount of a compound of formula (I) as defined in claim 1 and an agrochemically-acceptable diluent or carrier.

15. A method of controlling or preventing undesirable plant growth, wherein a herbicidally effective amount of a compound of formula (I) as defined in claim 1 is applied to the plants, to parts thereof or to the locus thereof.

Description

EXAMPLES

[0229] The Examples which follow serve to illustrate, but do not limit, the invention.

Synthesis Examples

Example 1 Preparation of (3-methoxy-3-oxo-propyl) 2-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]sulfanylpropanoate (Compound 9-245)

Step 1: Synthesis of 2-chloro-4-fluoro-5-nitro-benzoic acid

##STR00019##

[0230] Fuming nitric acid (2.8 ml, 43 mmol) was added to a stirred solution of 2-chloro-4-fluoro-benzoic acid (5.0 g, 29 mmol) in concentrated sulphuric acid (20 ml) at 0 C. The mixture was stirred for 20 minutes then poured carefully into iced water. The resulting mixture was filtered and the solid washed with acetonitrile to provide 2-chloro-4-fluoro-5-nitro-benzoic acid (6.4 g). .sup.1H NMR (400 MHz, CDCl.sub.3) 8.6 (d, 1H), 7.05 (d, 1H), 5.9 (br s, 1H) ppm.

Step 2: Synthesis of ethyl 2-chloro-4-fluoro-5-nitro-benzoate

##STR00020##

[0231] Oxalyl chloride (0.88 ml, 9.9 mmol) was added dropwise to a solution of 2-chloro-4-fluoro-5-nitro-benzoic acid (1.5 g, 6.6 mmol) in dichloromethane (15 ml). The solution was stirred for 15 minutes then dimethylformamide (3 drops) was added and stirring continued until the evolution of gas ceased. Ethanol (4 ml, 67 mmol) was added and the resulting solution stirred for 17 hours, then the solvent evaporated under reduced pressure to provide ethyl 2-chloro-4-fluoro-5-nitro-benzoate (1.7 g) as a solid. .sup.1H NMR (400 MHz, CDCl.sub.3) 8.7 (d, 1H), 7.5 (d, 1H), 4.45 (q, 2H), 1.45 (t, 3H) ppm.

Step 3: Synthesis of ethyl 5-amino-2-chloro-4-fluoro-benzoate

##STR00021##

[0232] Tin dichloride hydrate (4.7 g, 24 mmol) was added to a stirred solution of ethyl 2-chloro-4-fluoro-5-nitro-benzoate (2.1 g, 8.1 mmol) in ethyl acetate (21 ml) and the mixture then heated at reflux for 1.5 hours, allowed to cool and the solvent evaporated under reduce pressure. The residue was purified by column chromatography to provide ethyl 5-amino-2-chloro-4-fluoro-benzoate (1.2 g). .sup.1H NMR (400 MHz, CDCl.sub.3) 7.3 (d, 1H), 7.1 (d, 1H), 4.35 (q, 2H), 3.35 (br s, 2H), 1.4 (t, 3H) ppm.

Step 4: Synthesis of ethyl 2-chloro-4-fluoro-5-isocyanato-benzoate

##STR00022##

[0233] Diphosgene (0.8 ml, 6.6 mmol) was added to a stirred solution of ethyl 5-amino-2-chloro-4-fluoro-benzoate (1.2 g, 5.5 mmol) in dry toluene (24 ml). The resulting mixture was heated at reflux for 2 hours, allowed to cool and concentrated under reduced pressure to provide ethyl 2-chloro-4-fluoro-5-isocyanato-benzoate.

Step 5: Synthesis of ethyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzoate

##STR00023##

[0234] A solution of 1,3-dimethylthiourea (0.26 g, 2.5 mmol) and triethylamine (0.37 ml, 2.7 mmol) in toluene (10 ml) was added to ethyl 2-chloro-4-fluoro-5-isocyanato-benzoate (500 mg, 2.1 mmol) and the resulting solution heated to reflux. Carbonyl diimidazole (520 mg, 3.1 mmol) was added portionwise over 15 minutes and the resulting solution heated at reflux for a further 3 hours, then cooled and the solvent evaporated under reduced pressure. The residue was purified by column chromatography to provide ethyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzoate (550 mg) as a gum. .sup.1H NMR (400 MHz, CDCl.sub.3) 7.95 (d, 1H), 7.45 (d, 1H), 4.4 (q, 2H), 3.8 (s, 6H), 1.45 (t, 3H) ppm.

Step 6: Synthesis of 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzoic acid

##STR00024##

[0235] Concentrated sulphuric acid (2.6 ml, 45 mmol) was added to a stirred solution of ethyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzoate (1.7 g, 4.5 mmol) in glacial acetic acid (17 ml). The mixture was heated at 110 C. for 6 hours, allowed to cool to ambient temperature and carefully poured into iced water. The resulting mixture was filtered and the solid dried to provide 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzoic acid (1.5 g). 1H NMR (400 MHz, DMSO-d.sub.6) 8.15 (d, 1H), 7.85 (d, 1H), 3.6 (s, 6H), 3.35 (br s, 1H) ppm.

Step 7: Synthesis of tert-butyl N-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]carbamate

##STR00025##

[0236] A solution of dicyclohexylcarbodiimide (0.64 g, 3.0 mmol) in chlorobenzene (6 ml) was added dropwise to a stirred solution of 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzoic acid (1.0 g, 2.9 mmol) and tert-butyl N-hydroxycarbamate (0.37 g, 2.7 mmol) in chlorobenzene (6 ml) at 15 C. The resulting mixture was stirred for 30 minutes, then palladium dichloride triphenylphosphine complex (0.1 g, 0.15 mmol) and caesium carbonate (1.9 g, 5.8 mmol) was added and the mixture heated at 85 C. for one hour. The mixture was cooled, extracted with ethyl acetate and the organic phase dried and evaporated to leave a residue which was purified by column chromatography to provide tert-butyl N-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]carbamate (0.8 g). .sup.1H NMR (400 MHz, CDCl.sub.3) 8.3 (d, 1H), 7.3 (d, 1H), 3.8 (s, 6H), 1.5 (s, 9H) ppm (NH not observed).

Step 8: Synthesis of 3-(5-amino-4-chloro-2-fluoro-phenyl)-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione

##STR00026##

[0237] A mixture of tert-butyl N-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]carbamate (700 mg, 1.7 mmol) and trifluoroacetic acid (10.5 ml) was stirred at ambient temperature for 1 hour, then concentrated under reduced pressure. Saturated aqueous sodium bicarbonate (30 ml) was added and the mixture extracted with ethyl acetate (280 ml). The combined organic phases were dried over sodium sulphate, filtered and evaporated under reduced pressure to provide 3-(5-amino-4-chloro-2-fluoro-phenyl)-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (500 mg) as a white solid. .sup.1H NMR (400 MHz, CDCl.sub.3) 7.25 (d, 1H), 6.7 (d, 1H), 3.8 (s, 6H) ppm (NH.sub.2 not observed).

Step 9: Synthesis of 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzenesulfonyl chloride

##STR00027##

[0238] A solution of sodium nitrite (0.24 g, 3.3 mmol) in water (12 ml) at 0 C. was added dropwise to a stirred mixture of 3-(5-amino-4-chloro-2-fluoro-phenyl)-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (0.9 g, 2.8 mmol) and hydrochloric acid (24 ml) at 5 C. and the resulting mixture stirred at 0 C. for 15 minutes. The mixture was added dropwise to a stirred mixture of thionyl chloride (12 ml) and water (48 ml) to which copper (I) chloride (6 mg, 0.06 mmol) had been added at 5 C. The resulting mixture was stirred at 0 C. for 30 minutes and ambient temperature for 1 hour, then water (30 ml) and ethyl acetate (90 ml) added. The phases were separated and the aqueous extracted with ethyl acetate (90 ml). The combined organic phases were dried over sodium sulphate, filtered and evaporated under reduced pressure to provide 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzenesulfonyl chloride (1 g) as a solid. .sup.1H NMR (400 MHz, CDCl.sub.3) 8.2 (d, 1H), 7.6 (d, 1H), 3.8 (s, 6H) ppm.

Step 10: Synthesis of 3-(4-chloro-2-fluoro-5-sulfanyl-phenyl)-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione

##STR00028##

[0239] Triphenylphosphine (0.94 g, 3.5 mmol) was added portionwise to a stirred solution of 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzenesulfonyl chloride (0.5 g, 1.0 mmol) in tetrahydrofuran (6 ml). Water (1 ml) was added and the resulting mixture stirred at ambient temperature for 18 hours. Water (20 ml) and ethyl acetate (50 ml) were added and the pashes separated. The aqueous phase was extracted with ethyl acetate (50 ml) and the combined organic phases dried over sodium sulphate, filtered and evaporated under reduced pressure to leave a residue which was purified by column chromatography to provide 3-(4-chloro-2-fluoro-5-sulfanyl-phenyl)-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (264 mg) as a solid. .sup.1H NMR (400 MHz, CDCl.sub.3) 7.35 (m, 2H), 3.9 (s, 1H), 3.8 (s, 6H) ppm.

Step 11: Synthesis of (3-methoxy-3-oxo-propyl) 2-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]sulfanylpropanoate (Compound 9-245)

##STR00029##

[0240] (3-Methoxy-3-oxo-propyl) 2-bromopropanoate (prepared as described in example 2; 70 mg, 0.29 mmol) was added to a stirred mixture of 3-(4-chloro-2-fluoro-5-sulfanyl-phenyl)-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (90 mg, 0.26 mmol), caesium carbonate (88 mg, 0.27 mmol) and acetonitrile (1.8 ml) and the resulting mixture stirred at ambient temperature for 2 hours. Ethyl acetate (40 ml) was added and the resulting mixture washed with water (210 ml), dried over sodium sulphate, filtered and evaporated to leave a residue which was purified by column chromatography to provide (3-methoxy-3-oxo-propyl) 2-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]sulfanylpropanoate (Compound 9-245) (85 mg) as an oil. .sup.1H NMR (400 MHz, CDCl.sub.3) 7.55 (d, 1H), 7.4 (d, 1H), 4.3 (m, 2H), 3.9 (m, 1H), 3.75 (s, 6H), 3.65 (s, 3H), 2.6 (m, 2H), 1.55 (d, 3H) ppm.

Example 2 Preparation of (3-methoxy-3-oxo-propyl) 2-bromopropanoate

##STR00030##

[0241] Triethylamine (1.3 ml, 9.1 mmol) and methyl 3-hydroxy propanoate (0.48 ml, 5.0 mmol) were added dropwise to a stirred solution of 2-bromopropanoyl bromide (0.49 ml, 4.5 mmol) in acetonitrile (15 ml) at 0 C. The resulting mixture was stirred at 0 C. for 1 hour, then ambient temperature for 2 hours. Water (20 ml) and ethyl acetate (60 ml) were added, the phases separated and the aqueous phase extracted with ethyl acetate (60 ml). The combined organic phases were dried over sodium sulphate, filtered and evaporated under reduced pressure to leave an oil, which was purified by column chromatography to provide (3-methoxy-3-oxo-propyl) 2-bromopropanoate (440 mg) as an oil. .sup.1H NMR (400 MHz, CDCl.sub.3) 4.45 (m, 2H), 4.35 (m, 1H), 3.75 (s, 3H), 2.7 (t, 2H), 1.8 (d, 3H) ppm.

Example 3 Preparation of methyl 3-[2-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]sulfanylpropanoylamino]propanoate (Compound 9-272)

Step 1: Synthesis of methyl 3-(2-bromopropanoylamino)propanoate

##STR00031##

[0242] Triethylamine (2.6 ml, 9.1 mmol) and 2-bromopropanoyl bromide (0.97 ml, 9.1 mmol) were added to a stirred mixture of (3-methoxy-3-oxo-propyl)ammonium chloride (1.42 g, 10 mmol) in acetonitrile (30 ml) at 0 C. The resulting mixture was stirred at 0 C. for 1 hour, then ambient temperature for 2 hours. Water (20 ml) and ethyl acetate (60 ml) were added, the phases separated and the aqueous phase extracted with ethyl acetate (60 ml). The combined organic phases were dried over sodium sulphate, filtered and evaporated under reduced pressure to leave an oil, which was purified by column chromatography to provide methyl 3-(2-bromopropanoylamino)propanoate (560 mg) as a solid. .sup.1H NMR (400 MHz, CDCl.sub.3) 6.95 (br s, 1H), 4.4 (q, 1H), 3.75 (s, 3H), 3.55 (m, 2H), 2.6 (m, 2H), 1.85 (d, 3H) ppm.

Step 2: Synthesis of methyl 3-[2-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]sulfanylpropanoylamino]propanoate (Compound 9-272)

##STR00032##

[0243] Methyl 3-(2-bromopropanoylamino)propanoate (78 mg, 0.32 mmol) was added to a stirred mixture of 3-(4-chloro-2-fluoro-5-sulfanyl-phenyl)-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (prepared as described in Example 1, Step 10; 100 mg, 0.29 mmol), caesium carbonate (98 mg, 0.30 mmol) and acetonitrile (2 ml) and the resulting mixture stirred at ambient temperature for 2 hours. Ethyl acetate (50 ml) was added and the resulting mixture washed with water (220 ml), dried over sodium sulphate, filtered and evaporated to leave a residue which was purified by column chromatography to provide methyl 3-[2-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]sulfanylpropanoylamino]propanoate (Compound 9-272) (36 mg) as a solid. .sup.1H NMR (400 MHz, CDCl.sub.3) 7.35 (d, 1H), 7.25 (d, 1H), 7.0 (br m, 1H), 3.8 (m, 2H), 3.75 (s, 6H), 3.65 (s, 3H), 3.55 (m, 1H), 3.4 (m, 1H), 2.45 (m, 2H), 1.6 (d, 3H) ppm.

Formulation Examples

TABLE-US-00003 Wettable powders a) b) c) active ingredients 25% 50% 75% sodium lignosulfonate 5% 5% sodium lauryl sulfate 3% 5% sodium diisobutylnaphthalenesulfonate 6% 10% phenol polyethylene glycol ether 2% (7-8 mol of ethylene oxide) highly dispersed silicic acid 5% 10% 10% Kaolin 62% 27%

[0244] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.

TABLE-US-00004 Emulsifiable concentrate active ingredients 10% octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3% calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether (35 mol of ethylene oxide) 4% Cyclohexanone 30% xylene mixture 50%

[0245] Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

TABLE-US-00005 Dusts a) b) c) Active ingredients 5% 6% 4% Talcum 95% Kaolin 94% mineral filler 96%

[0246] Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill.

TABLE-US-00006 Extruder granules Active ingredients 15% sodium lignosulfonate 2% carboxymethylcellulose 1% Kaolin 82%

[0247] The combination is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

TABLE-US-00007 Coated granules Active ingredients 8% polyethylene glycol (mol. wt. 200) 3% Kaolin 89%

[0248] The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

TABLE-US-00008 Suspension concentrate active ingredients 40% propylene glycol 10% nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6% Sodium lignosulfonate 10% carboxymethylcellulose 1% silicone oil (in the form of a 75% emulsion in water) 1% Water 32%

[0249] The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.

Slow Release Capsule Suspension

[0250] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.

[0251] The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns.

[0252] The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.

Biological Examples

Pre-Emergence Biological Efficacy

[0253] Seeds of weeds and/or crops were sown in standard soil in pots (Amaranthus palmeri (AMAPA), Lolium perenne (LOLPE), Euphorbia heterophylla (EPHHL), Ipomoea hederacea (IPOHE), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG)). After cultivation for one day under controlled conditions in a glasshouse (at 24/19 C., day/night; 16 hours light), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in a small amount of acetone and a special solvent and emulsifier mixture referred to as IF50 (11.12% Emulsogen EL360 TM+44.44% N-methylpyrrolidone+44.44% Dowanol DPM glycol ether), to create a 50 g/l solution which was then diluted using 0.2% Genapol XO80 as diluent to give the desired final dose of test compound.

[0254] The test plants were then grown under controlled conditions in the glasshouse (at 24/18 C., day/night; 15 hours light; 50% humidity) and watered twice daily. After 13 days the test was evaluated (100=total damage to plant; 0=no damage to plant). The results are shown in Table 2 below.

TABLE-US-00009 TABLE 2 Rate Species Compound (g/ha) AMAPA LOLPE EPHHL IPOHE SETFA ECHCG 9-245 250 100 80 100 90 100 80 9-272 250 100 90 100 100 100 80

Post-Emergence Biological Efficacy

[0255] Seeds of weeds and/or crops were sown in standard soil in pots (Amaranthus palmeri (AMAPA), Chenopodium album (CHEAL), Euphorbia heterophylla (EPHHL), Ipomoea hederacea (IPOHE), Eleusine indica (ELEIN), Lolium perenne (LOLPE), Digitaria sanguinalis (DIGSA), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG)). After cultivation for 14 days under controlled conditions in a glasshouse (at 24/19 C., day/night; 16 hours light), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in a small amount of acetone and a special solvent and emulsifier mixture referred to as IF50 (11.12% Emulsogen EL360 TM+44.44% N-methylpyrrolidone+44.44% Dowanol DPM glycol ether), to create a 50 g/l solution which was then diluted using 0.2% Genapol XO80 as diluent to give the desired final dose of test compound.

[0256] The test plants were then grown under controlled conditions in the glasshouse (at 24/18 C., day/night; 15 hours light; 50% humidity) and watered twice daily. After 13 days the test was evaluated (100=total damage to plant; 0=no damage to plant). The results are shown in Table 3 below.

TABLE-US-00010 TABLE 3 Rate Species Compound (g/ha) AMAPA CHEAL EPHHL IPOHE ELEIN LOLPE DIGSA SETFA ECHCG 9-245 250 100 100 90 100 80 100 30 40 70 9-272 250 80 90 90 100 80 100 70 90 40