Polymorph of benzamide compound and preparation method and applications thereof

• US 11,084,799 B2
• Filed: 07/27/2017
• Issued: 08/10/2021
• Est. Priority Date: 07/27/2016
• Status: Active Grant

• Current Assignee: Shenyang Sinochem Agrochemicals R&D Co., Ltd. (Jiangsu Yangnong Chemical Company Limited)
• Original Assignee: Shenyang Sinochem Agrochemicals R&D Co., Ltd. (Jiangsu Yangnong Chemical Company Limited)
• Inventors: Yu, Haibo, Zhao, Guimin, Zhang, Guosheng, Ying, Junwu, Yang, Huibin, Li, Bin
• Primary Examiner(s): Lundgren, Jeffrey S
• Assistant Examiner(s): Simmons, Chris E
• Application Number:
  US16/306,970
• Publication Number:
  US 20190144418A1
• Time in Patent Office: 1,475 Days
• CPC Class Codes: A01N 43/40 six-membered rings
• CPC Class Codes: A01N 43/56 1,2-Diazoles; Hydrogenated 1,2-diazoles
• CPC Class Codes: C07B 2200/13 Crystalline forms, e.g. polymorphs
• CPC Class Codes: C07D 401/04 directly linked by a ring-member-to-ring-member bond

Abstract

The present invention provides a polymorph of a benzamide compound and a preparation method and applications thereof. The shown benzamide compound is 3-Bromo-N-[2,4-dichloro-6-[(methylamino)carbonyl]phenyl]-1-(3,5-dichloro-2-pyridinyl)-1H-pyrazole-5-carboxamide. The application of the polymorph of the compound in the preparation of the formulation exhibits excellent effect. The advantages of the polymorph A in aspects such as chemical stability, filterability, solubility, hygroscopicity, melting point, solid density and flowability can have a significant impact on the developments of the production method and a formulation and on the quality and efficacy of a plant treating agent.

Claims

1. A polymorph of a benzamide compound, wherein the polymorph of the benzamide compound is a polymorph A of benzamide compound of 3-bromo-N-[2,4-dichloro-6-[(methylamino)carbonyl]phenyl]-1-(3,5-dichloro-2-pyridinyl)-1H-pyrazole-5-carboxamide;

by using Cu—

Kα

radiation, the polymorph A is characterized by x-ray powder diffraction pattern having the 2θ

reflection positions;

10.24, 12.40, 17.84, 18.96, 19.12, 22.76, 23.92, 24.72, 25.92, 26.12, 28.64, 31.96, 34.00, 38.92, 42.20 and 46.24.

2. The polymorph of the benzamide compound according to claim 1, wherein the polymorph A has x-ray powder diffraction spectrum shown in FIG. 1.

8. A formulation, wherein comprises the polymorph of the benzamide compound according to claim 1 as an active component.

9. An insecticidal and fungicidal composition, which comprises the polymorph of the benzamide compound according to claim 1 as an active component.

10. An application of the polymorph of the benzamide compound according to claim 1, which is the application of the polymorph A in controlling insect and plant disease.

3. A preparation method for a polymorph of 3-bromo-N-[2,4-dichloro-6-[(methylamino)carbonyl]phenyl]-1-(3, 5-dichloro-2-pyridinyl)-1H-pyrazole-5-carboxamide, comprising mixing a solid form of the benzamide with solvent to form a slurry containing recoverable amounts of polymorph A, a crystalline polymorph characterized by x-ray powder diffraction pattern having 20 reflection positions:

10.24, 12.40, 17.84, 18.96, 19.12, 22.76, 23.92, 24.72, 25.92, 26,12, 28.64, 31,96, 34.00, 38.92, 42.20 and 46.24, using Cu—

Kα

radiation;

wherein the solid form of the benzamide includes polymorph B of 3-bromo-N42,4-dichloro-6-[(methylamino)carbonyl]phenyl]-1-(3,5-dichloro-2-pyridinyl)-1H-pyrazole-5-carboxamide;

where the polymorph B is characterized by x-ray powder diffraction pattern having the 20 reflection positions;

10.60, 11.28, 12.92, 13.56, 15.64, 16.48, 17.36, 18.48, 19.40, 20.68, 21.24, 23.68, 25.24, 27.76, 28.88 and 29.92, using Cu—

Kα

radiation.

5. The preparation method for the polymorph of the benzamide compound according to claim 3, wherein after the solid form of 3-bromo-N42,4-dichloro-6-[(methylamino)carbonyl]phenyl]-1-(3,5-dichloro-2-pyridinyl)-1H-pyrazole-5-carboxamide is mixed with the solvent to form the slurry, the slurry is heated under stirring to a temperature between 30°

C. and the boiling point of the solvent;

the mixture is heated to reflux for 1-10 h; and

then the slurry is cooled to 0-35°

C. to obtain the polymorph A.

6. The preparation method for the polymorph of the benzamide compound according to claim 5, wherein after the solid form of 3-bromo-N[2,4-dichloro-6-[(methylamino)carbonyl]phenyl]-1-(3,5-dichloro-2-pyridinyl)-1H-pyrazole-5-carboxamide is mixed with the solvent to form the slurry, and the slurry is heated under stirring to 50°

C.−

110°

C.;

the mixture is heated to reflux for 2-6h; and

then the slurry is cooled to 0-30°

C. to obtain the polymorph A.

7. The preparation method for the polymorph of the benzamide compound according to claim 3, wherein the solvent is selected from an alcohol solvent and/or water.

4. A preparation method for a polymorph of 3-bromo-N42,4-dichloro-6-[(methylamino)carbonyl]phenyl]-1-(3,5-dichloro-2-pyridinyl)-1H-pyrazole-5-carboxamide, comprising mixing a solid form of the benzamide with solvent under suitable conditions to form a slurry containing recoverable polymorph A, a crystalline polymorph characterized by x-ray powder diffraction pattern having 20 reflection positions:

10.24, 12.40, 17.84, 18.96, 19.12, 22.76, 23.92, 24.72, 25.92, 26,12, 28.64, 31,96, 34.00, 38.92, 42.20 and 46.24, using Cu—

Kα

radiation;

wherein the solid form of 3-bromo-N42,4-dichloro-6-[(methylamino)carbonyl]phenyl]-1-(3,5-dichloro-2-pyridinyl)-1H-pyrazole-5-carboxamide includes polymorph B;

where the polymorph B is characterized by x-ray powder diffraction pattern having the 20 reflection positions;

10.60, 11.28, 12.92, 13.56, 15.64, 16.48, 17.36, 18.48, 19.40, 20.68, 21.24, 23.68, 25.24, 27.76, 28.88 and 29.92, using Cu—

Kα

radiation and wherein the step of mixing the solid form of 3-bromo-N-[2,4-dichloro-6-[(methylamino)carbonyl]phenyl]-1-(3,5-dichloro-2-pyridinyl)-1H-pyrazole-5-carboxamide with the solvent to form slurry further comprises adding the polymorph A to the slurry.