Composition of 1,5-dimethyl-6-thioxo-3-(2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2h-benzo[b][1,4]oxazin-6-yl)-1,2,5-triazinane-2,4-dione

Abstract

The present invention relates to a composition of benzoxazinone (I) comprising the benzoxazinone (I) in form of particles, wherein at most 50% per volume of the particles have a diameter below 3 m.

Claims

1. A composition of benzoxazinone (I), ##STR00009## comprising the benzoxazinone (I) in form of particles, wherein at most 50% per volume of the particles have a diameter below 3 m.

2. The composition according to claim 1, wherein at most 60% per volume of the particles have a diameter below 5 m.

3. The composition according to claim 1, wherein at most 35% per volume of the particles have a diameter below 3 m.

4. The composition according to claim 1, wherein at least 90% wt. % of the particles are crystalline.

5. The composition according to claim 1, wherein the particles are present in the crystalline form A.

6. The composition of claim 1, wherein at most 15% per volume of the particles have a diameter above 45 m.

7. A plant protection agent comprising the composition as claimed in claim 1, and water.

8. A plant protection agent comprising a herbicidally active amount of a composition of benzoxazinone (I) as claimed in claim 1 and at least one inert liquid and/or solid carrier and, optionally, at least one surface-active substance.

9. A plant protection agent as claimed in claim 8 in form of a suspension concentrate (SC), oil-dispersion (OD), wettable powder (WP) and/or wettable granule (WG).

10. A process for the preparation of a plant protection agent, which comprises mixing an herbicidally active amount of a composition of benzoxazinone (I) as claimed in claim 1 and water.

11. A process for the preparation of a plant protection agent, which comprises mixing an herbicidally active amount of a composition of benzoxazinone (I) as claimed in claim 1 and at least one inert liquid and/or solid carrier and, optionally, at least one surface-active substance.

12. A method of controlling undesired vegetation in crops, which comprises allowing an herbicidally active amount of a composition of benzoxazinone (I) as claimed in claim 1 to act on plants, their environment or on seed.

13. The method of claim 12, wherein at most 60% per volume of the particles have a diameter below 5 m.

14. The method of claim 12, wherein at most 35% per volume of the particles have a diameter below 3 m.

15. The method of claim 12, wherein at least 90% wt. % of the particles are crystalline.

16. The method of claim 12, wherein the particles are present in the crystalline form A.

17. A method of safening crops from phytotoxic injury from application of a herbicidally effective amount of a benzoxazinone (I), ##STR00010## which comprises applying the composition of claim 1.

18. The method according to claim 17, wherein the crop plant is selected from the group consisting of Avena sativa, Glycine max, Gossypium hirsutum, Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium, Helianthus annuus, Hordeum vulgare, Lens culinaris, Linum usitatissimum, Oryza sativa , Phaseolus lunatus, Phaseolus vulgaris, Pisum sativum, Saccharum officinarum, Secale cereale, Sorghum bicolor, Triticale, Triticum aestivum, Triticum durum, Vicia faba, and Zea mays.

Description

EXAMPLE 1

Reference

(1) A suspension made of 422 parts per weight water, 60 parts propylene glycol, 167 parts Pluronic PE 10500 18% Solution, 20 parts Tamol DN, 2.5 parts Wacker Silicon SRE-PFL and 508 parts crystalline benzoxazinone (I) of modification A was circulated through a beadI mill until x.sub.80<2 m. Subsequently, a suspension of 10 parts propylene glycol, 3 parts Rhodopol G, 3 parts water, 2 parts Acticide MBS and 2.5 parts Wacker Silicon SRE-PFL was added yielding a suspension concentrate (SC) containing 500 g/L benzoxazinone (I).

(2) The particle sizes according to laser scattering were x.sub.10=0.5 m, x.sub.50=1.0 m, x.sub.90=2.3 m; x.sub.95=3.0 m (i.e. 95% per volume<3 m), x.sub.99=5.0 m (i.e. 99% per volume<5 m) and no detectable particles above 45 m.

EXAMPLE 2

(3) Using the same recipe like in example 1 a suspension concentrate containing 500 g/L crystalline benzoxazinone (I) of modification A was manufactured, but instead of a bead mill a mechanical crushing mill was used.

(4) In this SC formulation the particles are characterized as follows x.sub.10=1.0 m, x.sub.50=5.3 m, x.sub.90=49 m, x.sub.39=3.0 m (i.e. 39% per volume<3 m), x.sub.49=5.0 m (i.e. 49% per volume<5 m) and x.sub.88=45.0 m (i.e. 12% per volume>45 m).

EXAMPLE 3

(5) Using the same recipe like in example 1 a suspension concentrate containing 500 g/L crystalline benzoxazinone (I) of modification A was manufactured, but instead of a bead mill a rotor stator system was used.

(6) In this SC formulation the particles are characterized as follows x.sub.10=1.1 m, x.sub.50=7.8 m, x.sub.90=38 m, x.sub.30=3.0 m (i.e. 30% per volume<3 m), x.sub.40=5.0 m (i.e. 40% per volume<5 m) and x.sub.93=45.0 m (i.e. 7% per volume>45 m).

(7) Preparation of Form a of Benzoxazinone (I) by Crystallization from a Solution in an Organic Solvent with Evaporation

EXAMPLES 4.1 TO 4.10

(8) 50 mg of benzoxazinone (I) were dissolved in 2-3 ml of the respective solvent in a test vessel. The test vessel was placed in a greenhouse and a nitrogen flow (5 l/min) was passed over the surface of the solvent. In this manner, benzoxazinone (I) was obtained in the form of small crystalline rods, which were isolated and analyzed by X-ray powder diffraction (XRPD). On the basis of the characteristic reflections, form A was identified.

(9) TABLE-US-00009 TABLE 1 Example Solvent Form Crystal form 4.1 ethylbenzene A small rods 4.2 dichlorobenzene A small rods 4.3 chlorobenze A small rods 4.4 p-xylene A small rods 4.5 acetone A small rods 4.6 methylethylketone A small rods 4.7 methylbutylketone A small rods 4.8 methanol A small rods 4.9 ethanol A small rods 4.10 ispropanol A small rods

(10) Preparation of Form a of Benzoxazinone (I) by Crystallization from a Slurry in a Mixture of Water and Organic Solvent

EXAMPLE 4.11

(11) A mixture of forms A and B of benzoxazinone (I), obtained by comparative example 1 (500 mg) were suspended in 3 ml of a mixture of water and Ethanol (11 v/v) and the slurry was stirred for 48 h at 23 C. A slurry of crystalline material was obtained, which was filtered and analysed by XRPD and DSC. The obtained material was pure form A of benzoxazinone (I).

EXAMPLE 4.12

(12) Form B of benzoxazinone (I), obtained by example 16 (500 mg) were suspended in 3 ml of a mixture of water and tetrahydrofurane (11 v/v) and the slurry was stirred for 48 h at 23 C. A slurry of crystalline material was obtained, which was filtered and analysed by XRPD and DSC. The obtained material was pure form A of benzoxazinone (I).

EXAMPLE 4.13

(13) A mixture forms A and B of benzoxazinone (I), obtained by comparative example 1 (500 mg) were suspended in 3 ml of a mixture of toluene and the slurry was stirred for 48 h at 23 C. A slurry of crystalline material was obtained, which was filtered and analysed by XRPD and DSC. The obtained material was pure form A of benzoxazinone (I).

EXAMPLE 4.14

(14) A mixture forms A and B of benzoxazinone (I), obtained by comparative example 1 (500 mg) were suspended in 3 ml of a mixture of water and 1,3-propanediol (11 v/v) and the slurry was stirred for 48 h at 23 C. A slurry of crystalline material was obtained, which was filtered and analysed by XRPD and DSC. The obtained material was pure form A of benzoxazinone (I).

(15) Preparation of Form B of Benzoxazinone (I) by Crystallization from a Slurry in a Mixture of Water and Organic Solvent

EXAMPLE 4.15

(16) Form A of benzoxazinone (I), obtained by example 12 (500 mg) were suspended in 3 ml of a mixture of water and ethanol (11 v/v) and the slurry was stirred for 48 h at 90 C. A slurry of crystalline material was obtained, which was filtered and analysed by XRPD and DSC. The obtained material was pure form B of benzoxazinone (I).

EXAMPLE 4.16

(17) A mixture forms A and B of benzoxazinone (I), obtained by comparative example 1 (500 mg) were suspended in 3 ml of a mixture of water and 1,3-propanediol (11 v/v) and the slurry was stirred for 48 h at 90 C. A slurry of crystalline material was obtained, which was filtered and analysed by PXRD and DSC. The obtained material was pure form B of benzoxazinone (I).

(18) Preparation of Form B of Benzoxazinone (I) by Crystallization from a Solution in an Organic Solvent with Evaporation

EXAMPLE 4.17

(19) 50 mg of benzoxazinone (I) were dissolved in 2-3 ml of toluene in a test vessel. The test vessel placed in a greenhouse and heated to 95 C. and a nitrogen flow (5 l/min) was passed over the surface of the solvent. In this manner, benzoxazinone (I) was obtained in the form of small crystalline plates, which were isolated and analyzed by X-ray powder diffraction (XRPD). On the basis of the characteristic reflections, form B was identified.

(20) Preparation of Form B of Benzoxazinone (I) by Heating Form A

EXAMPLE 4.18

(21) 500 mg of form A of benzoxazinone (I), obtained by example 12 were placed into an open vessel. The vessel was purged with nitrogen and sealed and then heated to 180 C. for 2 h. The obtained material was isolated and analyzed by X-ray powder diffraction (XRPD). On the basis of the characteristic reflections, form B was identified.

(22) Preparation of a Mixture of Forms A and B of Benzoxazinone (I)

(23) 50 mg of benzoxazinone (I) were dissolved in 2-3 ml of the respective solvent (e.g. 1-butanol, isobutanol) in a test vessel. The test vessel was placed in a greenhouse and heated to 90 C. A nitrogen flow (5 l/min) was passed over the surface of the solvent. In this manner, benzoxazinone (I) was obtained in the form of small crystalline rods, which were isolated and analyzed by X-ray powder diffraction (XRPD). On the basis of the characteristic reflections, a mixture of forms A and B was identified.

(24) FIG. 1 shows an X-ray powder diffraction diagram of form A. The X-ray diffraction diagram of form A was recorded by using Panalytical X'Pert Pro diffractometer (manufacturer Panalytical) in reflection geometry in the range from 2=335 with increments of 0.0167 C. using Cu-K radiation (at 25 C.). The recorded 2 values were used to calculate the stated interplanar spacings d. The intensity of the peaks (y-axis linear intensity counts) is plotted versus the 2 angle (x-axis in degrees 2).

(25) FIG. 2 shows an X-ray powder diffraction diagram of form B. The X-ray diffraction diagram was recorded under the conditions stated for FIG. 1.

(26) FIG. 3 shows an X-ray powder diffraction diagram of a mixture of forms A+B+C. The X-ray diffraction diagram was recorded under the conditions stated for FIG. 1.

(27) The single crystal X-ray diffraction data of Form A was collected on a Bruker AXS CCD Detector using graphite Cu-K radiation (at 173 C.). The structure was solved using direct methods, refined and expanded by using Fourier techniques with SHELX software package (G. M. Sheldrick, SHELX-97, University of Gttingen, 1997). Absorption correction was performed with SADABS software.

(28) DSC was performed on a Mettler Toledo DSC 822e module. The samples were placed in crimped but vented aluminium pans. The samples size in each case was 5 to 10 mg. The thermal behaviour was analized in the range 30-250 C. The heating rate was 5 C./min. The samples were purged with a stream of nitrogen flowing at 150 ml/during the experiment. Melting points values were confirmed by a Mettler Hot Stage in combination with a light microscope.

(29) Use Examples

(30) Greenhouse Test

(31) The herbicidal action of the composition A and combinations according to the invention was demonstrated by the following greenhouse experiments

(32) The culture containers used were trays, consisting of individually separated plastic pots (each approx. 4 cm in diameter) containing loamy sand with approximately 2.5% of organic matter as substrate. The seeds of the test plants were sown separately for each species, one seed per pot was used for corn (ZEAMX), the grass species (SETFA) was broadcasted over the pot and covered with a thin layer of soil.

(33) For the pre-emergence treatment, the active compounds in the form of the respective suspension concentrate were diluted to comply with a rate of 50 g/ha benzoxazinone (I) and 200 l/ha water, and subsequently applied directly after sowing by drip application. A pipette was used, in total per pot a volume of 2 ml was applied. 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 was adversely affected by the active compounds.

(34) The plants were kept at 15-35 C. in the glasshouse.

(35) The test period was approx. 10 days. During this time, the plants were tended and their response to the individual treatments was evaluated.

(36) 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 above-ground parts, and 0 means no damage or normal course of growth. A good herbicidal activity is given at values of at least 60, and very good herbicidal activity is given at values of at least 85. In parallel the crop injury/phytotoxicity was evaluated. The activityselectivity window was calculated as quotient of activity and phytotoxicity obtained in the test.

(37) A selectivity is present if the damage to the crop plant caused by the composition of benzoxazinone (I) according to the present invention is less compared to the damage caused by application of a benzoxazinone (I), wherein the particle size distribution is not according to that according to the present invention.

EXAMPLE 5

Herbicidal Action of the Pre-Emergence Applied Benzoxazinone (I) Against SETFA and Selectivity with Regard to Corn 10 Days after Treatment in the Greenhouse

(38) TABLE-US-00010 application rate damage herbicidal action Safety benzoxazinone (I) [g/ha] to corn against SETFA window reference 50 60 88 1.47 example 1 example 2 50 18 83 4.61

(39) In this example, benzoxazinone (I) was formulated as a 500 g/l SC.

(40) Prior to application, the formulated benzoxazinone (I) was diluted into water and the aqueous solution was used for the drip application.

(41) Field Test

(42) The herbicidal action of the composition A and combinations according to the invention was demonstrated by the following field experiments

(43) A field trial was performed on a loamy sand soil with approximately 1.5-2.5% of organic matter.

(44) The test plants were sown separately for each species in rows, as crop corn (ZEAMX) was planted, as indicator weed species Brassica (BRSNW) was planted according to field trial practice.

(45) For the pre-emergence treatment, the active compounds, suspended in water, were applied directly after sowing by means of finely distributing nozzles. 200 g/ha benzoxazinone (I) in the form of the respective SC formulations were diluted with 200 l/ha water for application.

(46) To ensure adequate activation the plots were irrigated after the application with 15 mm of water. The test period was during the whole growing period of corn. After 19 days after application the response of the crop and the activity on the indicator weed species to the individual treatments were evaluated.

(47) 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 above-ground parts, and 0 means no damage or normal course of growth. A good herbicidal activity is given at values of at least 60, and very good herbicidal activity is given at values of at least 85. In parallel the crop injury/phytotoxicity was evaluated. The activityselectivity window was calculated as quotient of activity and phytotoxicity obtained in the test.

(48) A safener action is present if the damage to the crop plant caused by the composition of benzoxazinone (I) according to the present invention is less compared to the damage caused by application of a benzoxazinone (I), wherein the particle size distribution is not according to that according to the present invention.

EXAMPLE 6

Herbicidal Action of the Pre-Emergence Applied Benzoxazinone (I) Against SETFA and Selectivity with Regard to Corn 19 Days after Treatment

(49) TABLE-US-00011 application rate damage herbicidal action Safety benzoxazinone (I) [g/ha] to corn against SETFA window reference 100 7 93 13.29 example 1 example 3 100 4 93 23.25