EP-4739679-A1 - CRYSTALLINE FORMS OF A HERBICIDE AND THEIR COMPOSITIONS

Abstract

The present invention relates to solid forms of the compound of formula (I): compositions comprising the solid forms, and methods for their use as herbicides.

Inventors

• KEATES, Adam
• HALLAM-BARNES, Gemma

Assignees

• Syngenta Crop Protection AG

Dates

Publication Date

20260513

Application Date

20240704

Claims (1)

1. CLAIMS 1 . A crystalline polymorph of the compound of formula (I) designated Form 1 , which has the following lattice parameters: a = 55.3 A ± 0.5 A, b = 9.4 A ± 0.5 A, c=24.9 A ± 0.5 A, a = 90° ± 0.1 °, p = 98.6° ± 0.1 °, y = 90° ± 0.1 °, and volume = 12728 A 3 ± 127 A 3 . 2. The crystalline polymorph according to claim 1 , wherein the polymorph is characterized by a powder X-ray diffraction pattern expressed in terms of 20 angles, wherein the powder X-ray diffraction pattern comprises: a) at least one 20 angle value at 6.5 ± 0.2, b) at least one 20 angle value at 7.2 ± 0.2, c) at least one 20 angle value at 7.4 ± 0.2, and d) at least one, preferably two, more preferably three, yet more preferably more than four 20 angle values selected from the group comprising: 8.9 ± 0.2, 12.9 ± 0.2, 14.3 ± 0.2, 14.8 ± 0.2, 16.1 ± 0.2, 17.3 ± 0.2, 19.4 ± 0.2, 20.5 ± 0.2, 23.5 ± 0.2, 25.0 ± 0.2, 26.2 ± 0.2, 28.2 ± 0.2, and 29.4 ± 0.2. 3. The crystalline polymorph according to claim 1 or claim 2, which has a melting point of 81 °C ± 5°C. 4. A crystalline polymorph of the compound of formula (I) designated Form 2, which has the following lattice parameters: a = 57.7 A ± 0.5 A, b = 9.5 A ± 0.5 A, c = 24.9 A ± 0.5 A, a = 90° ± 0.1 °, p = 96.0° ± 0.5°, y = 90° ± 0.1 °, and volume = 13532 A 3 ± 135 A 3 , and is characterized in that is prepared by the following steps: ix) Adding a mixture of methylcyclohexane and toluene to the compound of formula (I); x) Heating and stirring the resulting mixture until the solids of the compound of formula (I) are dissolved; xi) Cooling the mixture gradually such that an oil phase is formed; and xii) Stirring the resulting oil phase until a crystalline polymorph is formed. 5. The crystalline polymorph according to claim 4, wherein the polymorph is further characterized by a powder X-ray diffraction pattern expressed in terms of 20 angles, wherein the powder X-ray diffraction pattern comprises: a) at least one 20 angle value at 6.1 ± 0.2, b) at least one 20 angle value at 7.0 ± 0.2, and c) at least one, preferably two, more preferably three 20 angle values selected from the group comprising 10.9 ± 0.2, 12.3 ± 0.2, 13.5 ± 0.2, 14.1 ± 0.2, 14.7 ± 0.2, 15.3 ± 0.2, 15.9 ± 0.2, 16.9 ± 0.2, 17.1 ± 0.2, 19.4 ± 0.2, 19.7 ± 0.2, 20.1 ± 0.2, 20.4 ± 0.2, 20.8 ± 0.2, 21 .4 ± 0.2, 23.4 ± 0.2, 24.1 ± 0.2, 25.0 ± 0.2, and 26.0 ± 0.2. 6. The crystalline polymorph according to claim 4 or claim 5, which has a melting point of 70°C ± 5°C. 7. An agricultural composition comprising: i) a polymorph designated Form 1 according to any one of claims 1 to 3; and ii) a polymorph designated Form 2 according to any one of claims 4 to 6. 8. An agricultural composition comprising at least one polymorph according to any one of claims 1 to 6, further comprising an amorphous form of the compound of formula (I). 9. An agricultural composition according to claim 7, further comprising an amorphous form of the compound of formula (I). 10. An agricultural composition comprising a polymorph according to any one of claims 1 to 6, and at least one agriculturally acceptable carrier or diluent. 11 . The composition of claim 10, which further comprises at least one herbicide. 12. An agricultural composition according to any one of claims 7 to 11 , wherein the agricultural composition is a suspension concentrate formulation. 13. Use of a polymorph according to any one of claims 1 to 6, or a composition according to any one of claims 7 to 12 over crops that are resistant to the compound of formula (I). 14. Use of a polymorph according to any one of claims 1 to 6, or a composition according to any one of claims 7 to 12 to control weeds that are resistant to PPO herbicides except the compound of formula (I). 15. A method for combating weeds in crops of useful plants, which comprises treating the useful plants, seeds or cuttings thereof or the locus of the useful plants simultaneously or at separate times with a composition comprising a polymorph according to any one of claims 1 to 6, or a composition according to any one of claims 7 to 12.

Description

CRYSTALLINE FORMS OF A HERBICIDE AND THEIR COMPOSITIONS The present invention relates to solid forms of 3-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4- (trifluoromethyl)-l ,3-dihydro-1 -pyrimidinyl]phenyl}-5-methyl-4,5-dihydro-5-isoxazolecarboxylic acid ethyl ester, compositions comprising these novel solid forms, to the use thereof in herbicidal compositions, and their use in controlling plants or inhibiting plant growth. Ethyl 3-[2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1 -yl]phenyl]-5-methyl-4H- isoxazole-5-carboxylate has the structure of formula (I), and is herein also referred to as “compound of formula (I)”. The compound of formula (I) as well its preparation is disclosed, for example, in WO 2016/095768 and WO 2020/063613: (I). To date, this compound has only been isolated and disclosed as an amorphous material. While the compound in its amorphous form has successfully shown a broad spectrum herbicidal activity, it was found that its physical properties make it difficult to handle and weigh. Also, in order to prepare formulations, comminuting, in particular milling of the amorphous material often resulted in comparatively large particles, and a very broad particle size distribution, making a homogenous formulation and distribution difficult. In fact, in many cases, the amorphous form could not be milled and thus this amorphous form could not be tested further. New solid forms of this compound, their compositions and methods of their preparation and use have now been discovered. Accordingly, the present invention relates to novel crystalline forms of the compound of formula (I). The novel crystalline forms of ethyl 3-[2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4- (trifluoromethyl)pyrimidin-1 -yl]phenyl]-5-methyl-4H-isoxazole-5-carboxylate are characterized by a powder X-ray diffraction pattern expressed in terms of 20 angles. These 20 angle values are derived from a powder X-ray diffraction pattern of the polymorphs are obtained using the method of Example 2, whereby the values are generated using a wavelength of 1 .54056A with a 20 step size of 0.02°. According to a first aspect of the invention, there is provided a novel crystalline form of ethyl 3-[2-chloro- 4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1 -yl]phenyl]-5-methyl-4H-isoxazole-5- carboxylate, designated Form 1 , wherein the polymorph is characterized by a powder X-ray diffraction pattern expressed in terms of 20 angles, wherein the powder X-ray diffraction pattern comprises: a) at least one 20 angle value at 6.5 ± 0.2, b) at least one 20 angle value at 7.2 ± 0.2, c) at least one 20 angle value at 7.4 ± 0.2, and d) at least one, preferably two, more preferably three, yet more preferably more than four 20 angle values selected from the group comprising: 8.9 ± 0.2, 12.9 ± 0.2, 14.3 ± 0.2, 14.8 ± 0.2, 16.1 ± 0.2, 17.3 ± 0.2, 19.4 ± 0.2, 20.5 ± 0.2, 23.5 ± 0.2, 25.0 ± 0.2, 26.2 ± 0.2, 28.2 ± 0.2, and 29.4 ± 0.2 (see Fig. 1 ). Preferably, the powder X-ray diffraction pattern for polymorph designated Form 1 comprises: a) at least one 20 angle value at 6.5 ± 0.2, b) at least one 20 angle value at 7.2 ± 0.2, c) at least one 20 angle value at 7.4 ± 0.2, d) at least one 20 angle value at 12.9 ± 0.2, and e) at least one, preferably two, more preferably three, yet more preferably more than four 20 angle values selected from the group comprising: 8.9 ± 0.2, 14.3 ± 0.2, 14.8 ± 0.2, 16.1 ± 0.2, 17.3 ± 0.2, 19.4 ± 0.2, 20.5 ± 0.2, 23.5 ± 0.2, 25.0 ± 0.2, 26.2 ± 0.2, 28.2 ± 0.2, and 29.4 ± 0.2. More preferably, the powder X-ray diffraction pattern for polymorph designated Form 1 comprises: a) at least one 20 angle value at 6.5 ± 0.2, b) at least one 20 angle value at 7.2 ± 0.2, c) at least one 20 angle value at 7.4 ± 0.2, d) at least one 20 angle value at 12.9 ± 0.2, e) at least one 20 angle value at 17.3 ± 0.2, and f) at least one, preferably two, more preferably three, yet more preferably more than four 20 angle values selected from the group comprising: 8.9 ± 0.2, 14.3 ± 0.2, 14.8 ± 0.2, 16.1 ± 0.2, 19.4 ± 0.2, 20.5 ± 0.2, 23.5 ± 0.2, 25.0 ± 0.2, 26.2 ± 0.2, 28.2 ± 0.2, and 29.4 ± 0.2. Even more preferably, the powder X-ray diffraction pattern for polymorph designated Form 1 comprises: a) at least one 20 angle value at 6.5 ± 0.2, b) at least one 20 angle value at 7.2 ± 0.2, c) at least one 20 angle value at 7.4 ± 0.2, d) at least one 20 angle value at 12.9 ± 0.2, e) at least one 20 angle value at 17.3 ± 0.2, f) at least one 20 angle value at 19.4 ± 0.2, and g) at least one, preferably two, more preferably three, yet more preferably more than four 20 angle values selected from the group comprising: 8.9 ± 0.2, 14.3 ± 0.2, 14.8 ± 0.2, 16.1 ± 0.2, 20.5 ± 0.2, 23.5 ± 0.2, 25.0 ± 0.2, 26.2 ± 0.2, 28.2 ± 0.2, and 29.4 ± 0.2. In another embodiment of the invention, the crystalline polymorph designated Form 1 of the compound of formula (I) is characterized by the unit cell parameters of its single crystal as shown in T