Abstract: The present invention relates to a cost-effective and environmentally friendly process for the preparation of chlorantranihprole of formula I. The present invention further relates to novel Intermediate I and Intermediate II and process for the preparation of Intermediate-I and Intermediate II, used for the preparation of Formula I.
1. A process for the preparation of 3-Bromo-N-[4-chloro-2-methyl-6-(methyl carbamoyl) phenyl]-l-(3-chloropyridin-2-yl)-lH-pyrazole-5-carboxamide, comprising the steps of- a. reacting a compound of formula II Foir.iula -11 with a compound of formula III Formula -ill in presence of a catalyst in a solvent to provide a compound of formula IV: K>. J^V FoimuU -IV b. chlorinating the compound of formula IV with an agent in a solvent to provide a compound of formula V; Y>tjr Fonnula-Y c. reacting compound of formula VI 0 0 Foimula-VI with compound of formula VII &' Formula-VEI in presence of a catalyst in a solvent to provide a compound of formula VIII: d. treating the compound of formula VIII in presence of a catalyst to provide a compound of formula IX; M &' Formula-IX e. treating the compound of formula IX in presence of NaN02, CuCl, an acid, and a base to provide a compound of formula X; ;■ MJ; Foimula-X f reacting a compound of formula X with Ru04 or Ru02, NaOCl in presence of cetyl trimethyl ammonium chloride, in a solution of toluene tri phosgene to provide a compound formula XI; vcf Foimula-XI g. reacting the compound of formula V and compound of formula XI in presence of a base to provide a compound of formula XII; Foimula-Xn h. reacting the compound of formula XII with a primary amine in a solvent to provide 3-Bromo-N-[4-chloro-2-methyl-6-(methyl carbamoyl) phenyl]-l-(3-chloropyridin-2-yl)-lH-pyrazole-5- carboxamide.
2. The process as claimed in claim 1, wherein the compound of formula V and formula XII can either be isolated or further reacted in next step without isolation.
3. The process as claimed in claim 1, wherein the catalyst used in step (a) is selected from the group consisting of p-toluenesulfonic acid (PTSA), Methane sulfonic acid or Ambarlyst-15.
4. The process as claimed in claim 1, wherein the solvent used in step a) and step c) is toluene.
5. The process as claimed in claim 1, wherein the agent used in step b) is selected from sulfuric acid, hydrogen peroxide or hydrochloric acid, o-Xylene and dimethyl sulfoxide.
6. The process as claimed in claim 1, wherein the solvent used in step b) is selected from acetone, N, N-Dimethyl formamide, acetonitrile, dimethyl Sulfoxide, chloro-solvents like Potassium Chloride, methylene chloride, chloroform, mono-chlorobenzene and ethylene chloride; or hydrocarbon solvents like toluene, xylene, heptane, cyclohexane, 2-methyl Cyclohexane and 2-Ethyl cyclohexane and hexane, methylene chloride, ethylene chloride, chloroform, dimethyl formamide or mixtures thereof.
7. The process as claimed in claim 1, wherein the catalyst used in step c) is p-toluene sulfonic acid (PTSA).
8. The process as claimed in claim 1, wherein the catalyst of step d) is selected from palladium, Nickel or phase transfer catalyst like Tetra butyl ammonium bromide, Tetra butyl ammonium chloride.
9. The process as claimed in claim 1, wherein the acid in step e) is selected from Hydrochloric acid or sulphuric acid in presence of water as solvent, and Hydrochloric acid or sulphuric acid in presence of water as solvent; and base is selected from sodium hydroxide or potassium hydroxide.
10. The process as claimed in claimed in claim 1, wherein the base used in step g) and h) is sodium bicarbonate.
11. The process as claimed in claim 1, wherein the primary amine used in step h) is methyl amine.
12. The process as claimed in claim 1, wherein the solvent used in step h) is selected from acetone, N, N-Dimethyl formamide, acetonitrile, Dimethyl Sulfoxide, Isopropyl alcohol, methanol and or mixtures thereof.
13. The process as claimed in claim 1, wherein the yield of 3-Bromo-N-[4-chloro-2-methyl-6-(methyl carbamoyl) phenyl]-l-(3-chloropyridin-2-yl)-lH-pyrazole-5-carboxamide is atleast about 92 % to atleast about 98%.
14. A process for preparation of 3-Bromo-N-[4-chloro-2-methyl-6-(methyl carbamoyl) phenyl]-l-(3-chloropyridin-2-yl)-lH-pyrazole-5-carboxamide, comprising the steps of- a. reacting the compound of formula V Y^T Fonnula-V in presence of a base to provide a compound of formula XII; and and the compound of formula XI Foimula-Xn b. reacting the compound of formula XII with a primary amine to provide 3-Bromo-N- [4-chloro-2-methyl-6-(methyl carbamoyl) phenyl]-l-(3-chloropyridin-2-yl)-lH-pyrazole-5-carboxamide.
15. The process as claimed in claim 14, wherein the primary amine is methyl amine and base is sodium bicarbonate.
16. The process as claimed in claim 14, wherein the compound of formula V, is prepared by chlorinating the compound of formula IV, with an agent in a solvent to provide a compound of formula V.
17. The process as claimed in claim 16, wherein the wherein the agent used is selected from sulfuric acid, hydrogen peroxide or hydrochloric acid, o-Xylene and dimethyl sulfoxide; and solvent is selected from acetone, N, N-Dimethyl formamide, acetonitrile, dimethyl Sulfoxide, chloro-solvents like Potassium Chloride, methylene chloride, chloroform, mono-chlorobenzene and ethylene chloride; or hydrocarbon solvents like toluene, xylene, heptane, cyclohexane, 2-methyl Cyclohexane and 2-Ethyl cyclohexane and hexane, methylene chloride, ethylene chloride, chloroform, dimethyl
18. The process as claimed in claim 16, wherein the compound of formula IV is prepared by reacting compound of formula II Formula -II with a compound of formula III = NM2 Formula -III in a solvent to provide a compound of formula IV.
19. The process as claimed in claim 18, wherein the solvent is toluene.
20. The process as claimed in claim 14, wherein the compound of formula XI is prepared by treating a compound of formula X & Fomiula-X with Ru04 or Ru02, NaOCl in presence of cetyl trimethyl ammonium chloride, in a solution of toluene tri phosgene to provide a compound formula XI.
21. The process as claimed in claim 20, wherein the compound of formula X is prepared by treating the compound of formula IX & Foimula-IX in presence of NaN02, CuCl, an acid, and a base to provide a compound of formula X.
22. The process as claimed in claim 21, wherein the acid is selected from Hydrochloric acid or sulphuric acid in presence of water as solvent, and Hydrochloric acid or sulphuric acid in presence of water as solvent; and base is selected from sodium hydroxide or potassium hydroxide.
23. The process as claimed in claim 21, wherein the compound of formula IX is prepared by treating the compound of formula VIII &"■ Formula VIE in presence of a catalyst to provide a compound of formula IX.
24. The process as claimed in claim 23, wherein the catalyst is selected from palladium, Nickel or phase transfer catalyst like Tetra butyl ammonium bromide, Tetra butyl ammonium chloride.
25. The process as claimed in claim 23, wherein the compound of formula VIII is prepared by reacting compound of formula VI o o Foimula-VI with compound of formula VII ^Hi I Formula-VII in presence of a catalyst in a solvent to provide a compound of formula VIII.
26. The process as claimed in claim 25, wherein the solvent is toluene and catalyst is p-toluene sulfonic acid (PTSA).
27. A novel compound represented by formula XII Fomiula-Xn
28. The compound as claimed in claim 27, wherein the compound of formula XII is obtained by reacting the compound of formula V Foimula-V and compound of formula XI " &' Foimula-XI in presence of a base to provide a compound of formula XII; and wherein the base is sodium bicarbonate. Fonnula-Xn
29. The compound as claimed in claim 28, wherein the compound of formula XII can either be isolated or further reacted in next step without isolation.
30. A novel compound represented by formula V: Fonnula-Y
31. The compound as claimed in claim 30, wherein the compound of formula V is prepared by chlorinating the compound of formula IV, FoimuU JV with an agent in a solvent to provide a compound of formula V; wherein the agent used is selected from sulfuric acid, hydrogen peroxide or hydrochloric acid, o-Xylene and dimethyl sulfoxide; and wherein the ,1„„+„J f ™ „„„+ „ "NT "NT T"\:™„+U»»l f„ chloride, chloroform, mono-chlorobenzene and ethylene chloride; or hydrocarbon solvents like toluene, xylene, heptane, cyclohexane, 2-methyl Cyclohexane and 2-Ethyl cyclohexane and hexane, methylene chloride, ethylene chloride, chloroform, dimethyl formamide or mixtures thereof.
32. The process as claimed in claim 1, wherein the purity of obtained 3-Bromo-N-[4-chloro-2-methyl-6-(methyl carbamoyl) phenyl]-l-(3-chloropyridin-2-yl)-lH-pyrazole-5-carboxamide, is at least about 94.0% to at least about 96.0%.
| # | Name | Date |
|---|---|---|
| 1 | 202111031718-STATEMENT OF UNDERTAKING (FORM 3) [14-07-2021(online)].pdf | 2021-07-14 |
| 2 | 202111031718-PROVISIONAL SPECIFICATION [14-07-2021(online)].pdf | 2021-07-14 |
| 3 | 202111031718-POWER OF AUTHORITY [14-07-2021(online)].pdf | 2021-07-14 |
| 4 | 202111031718-FORM FOR SMALL ENTITY(FORM-28) [14-07-2021(online)].pdf | 2021-07-14 |
| 5 | 202111031718-FORM FOR SMALL ENTITY [14-07-2021(online)].pdf | 2021-07-14 |
| 6 | 202111031718-FORM 1 [14-07-2021(online)].pdf | 2021-07-14 |
| 7 | 202111031718-EVIDENCE FOR REGISTRATION UNDER SSI(FORM-28) [14-07-2021(online)].pdf | 2021-07-14 |
| 8 | 202111031718-DRAWINGS [14-07-2021(online)].pdf | 2021-07-14 |
| 9 | 202111031718-DECLARATION OF INVENTORSHIP (FORM 5) [14-07-2021(online)].pdf | 2021-07-14 |
| 10 | 202111031718-DRAWING [14-07-2022(online)].pdf | 2022-07-14 |
| 11 | 202111031718-COMPLETE SPECIFICATION [14-07-2022(online)].pdf | 2022-07-14 |