Process for preparing 4-trifluoromethylsulfinylpyrazole derivative
View Patent ↗A process for the preparation of a compound of formula (I) comprising oxidizing a compound of formula (II) with trifluoroperacetic acid in the presence of a corrosion inhibiting compound such as boric acid. Also, a process for preparing a compound of formula (II) by adding sulfur dioxide to a mixture of the corresponding disulfide, a formate salt, trifluoromethyl bromide and a polar solvent; and a process for preparing the disulfide comprising adding S 2 Cl 2 to a solution, in an organic solvent, of the corresponding 4-unsubstituted pyrazole.
1. A process (B) for the preparation of a compound having the formula (II):
wherein:
W is —CR 3 ;
R 1 is halogen, haloalkyl, or haloalkoxy;
R 2 is hydrogen or halogen; and
R 3 is halogen;
said process comprising adding sulfur dioxide to a mixture comprising a disulfide having the formula (III):
wherein R 1 , R 2 and W are as defined above, a formate salt, trifluoromethyl bromide and a polar solvent.
2. A process according to claim 1 , wherein the solvent is N,N-dimethylformamide.
3. A process according to claim 1 , wherein the reaction temperature during the addition of the sulfur dioxide is from about 35° C. to about 55° C.
4. A process according to claim 2 , wherein the reaction temperature during the addition of the sulfur dioxide is from about 35° C. to about 55° C.
5. A process according to claim 1 , wherein the sulfur dioxide is added over a period of from about 0.5 to about 2 hours.
6. A process according to claim 2 , wherein the sulfur dioxide is added over a period of from about 0.5 to about 2 hours.
7. A process according to claim 3 , wherein the sulfur dioxide is added over a period of from about 0.5 to about 2 hours.
8. A process according to claim 4 , wherein the sulfur dioxide is added over a period of from about 0.5 to about 2 hours.
9. A process according to claim 1 , wherein the molar ratio of trifluoromethyl bromide to disulfide of formula (III) is from about 3:1 to about 5:1.
10. A process according to claim 2 , wherein the molar ratio of trifluoromethyl bromide to disulfide of formula (III) is from about 3:1 to about 5:1.
11. A process according to claim 3 , wherein the molar ratio of trifluoromethyl bromide to disulfide of formula (III) is from about 3:1 to about 5:1.
12. A process according to claim 5 , wherein the molar ratio of trifluoromethyl bromide to disulfide of formula (III) is from about 3:1 to about 5:1.
13. A process according to claim 7 , wherein the molar ratio of trifluoromethyl bromide to disulfide of formula (III) is from about 3:1 to about 5:1.
14. A process according to claim 1 , wherein the amount of sulfur dioxide employed is from about 1.2 to about 1.5 molar equivalents relative to the disulfide of formula (III).
15. A process according to claim 2 , wherein the amount of sulfur dioxide employed is from about 1.2 to about 1.5 molar equivalents relative to the disulfide of formula (III).
16. A process according to claim 3 , wherein the amount of sulfur dioxide employed is from about 1.2 to about 1.5 molar equivalents relative to the disulfide of formula (III).
17. A process according to claim 5 , wherein the amount of sulfur dioxide employed is from about 1.2 to about 1.5 molar equivalents relative to the disulfide of formula (III).
18. A process according to claim 1 , wherein the formate salt is an alkali metal or ammonium formate.
19. A process according to claim 2 , wherein the formate salt is an alkali metal or ammonium formate.
20. A process according to claim 3 , wherein the formate salt is an alkali metal or ammonium formate.
21. A process according to claim 5 , wherein the formate salt is an alkali metal or ammonium formate.
22. A process according to claim 18 , wherein the formate salt is sodium formate.
23. A process according to claim 19 , wherein the formate salt is sodium formate.
24. A process according to claim 20 , wherein the formate salt is sodium formate.
25. A process according to claim 21 , wherein the formate salt is sodium formate.
26. A process according to claim 1 , wherein the amount of formate salt employed is from about 4 to about 6 molar equivalents relative to the disulfide of formula (III).
27. A process according to claim 2 , wherein the amount of formate salt employed is from about 4 to about 6 molar equivalents relative to the disulfide of formula (III).
28. A process according to claim 3 , wherein the amount of formate salt employed is from about 4 to about 6 molar equivalents relative to the disulfide of formula (III).
29. A process according to claim 1 , wherein the disulfide of formula (III) is 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyanopyrazol-4-yl disulfide and the compound of formula (II) is 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylthiopyrazole.
30. A process (B) for the preparation of a compound having the formula (II):
wherein:
W is —CR 3 ;
R 1 is halogen, haloalkyl, or haloalkoxy;
R 2 is hydrogen or halogen; and
R 3 is halogen;
said process comprising adding sulfur dioxide to a mixture comprising a disulfide having the formula (III):
wherein R 1 , R 2 and W are as defined above, sodium formate, trifluoromethyl bromide and N,N-dimethylformamide, the reaction temperature during the addition of the sulfur dioxide being from about 35° C. to about 55° C., the sulfur dioxide being added over a period of from about 0.5 to about 2 hours, the molar ratio of trifluoromethyl bromide to disulfide of formula (III) being from about 3:1 to about 5:1, the amount of sulfur dioxide employed being from about 1.2 to about 1.5 molar equivalents relative to the disulfide of formula (III) and the amount of sodium formate employed being from about 4 to about 6 molar equivalents relative to the disulfide of formula (III).
31. The process according to claim 30 , wherein the disulfide of formula (III) is 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyanopyrazol-4-yl disulfide and the compound of formula (II) is 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylthiopyrazole.
32. A process for the preparation of a compound having the formula (I):
wherein:
W is —CR 3 ;
R 1 is halogen, haloalkyl, or haloalkoxy;
R 2 is hydrogen or halogen; and
R 3 is halogen;
said process comprising:
(a) adding sulfur dioxide to a mixture comprising a disulfide having the formula (III):
wherein R 1 , R 2 and W are as defined above, a formate salt, trifluoromethyl bromide and a polar solvent, to afford a compound having the formula (II):
wherein R 1 , R 2 and W are as defined above; and
(b) oxidizing the resultant compound of formula (II) with trifluoroperacetic acid in the presence of a corrosion inhibiting compound to afford a compound having the formula (I).
33. A process for the preparation of a compound having the formula (II):
wherein:
W is —CR 3 ;
R 1 is halogen, haloalkyl, or haloalkoxy;
R 2 is hydrogen or halogen; and
R 3 is halogen;
said process comprising:
(a) adding sulfur monochloride (S 2 Cl 2 ) to a solution, in an organic solvent, of a compound having the formula (IV):
wherein R 1 , R 2 and W are as defined above, to afford a disulfide having the formula (III):
wherein R 1 , R 2 and W are as defined above; and
(b) adding sulfur dioxide to a mixture comprising the resultant disulfide having formula (III), a formate salt, trifluoromethyl bromide and a polar solvent, to afford a compound having the formula (II).
34. A process according to claim 33 , wherein the compound of formula (IV) is 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyanopyrazole, the disulfide of formula (III) is 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyanopyrazol-4-yl disulfide and the compound of formula (II) is 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylthiopyrazole.
35. A process for the preparation of a compound having the formula (I):
wherein W is —CR 3 ;
R 1 is halogen, haloalkyl, or haloalkoxy;
R 2 is hydrogen or halogen; and
R 3 is halogen;
said process comprising:
(a) adding sulfur monochloride (S 2 Cl 2 ) to a solution, in an organic solvent, of a compound having the formula (IV):
wherein R 1 , R 2 and W are as defined above, to afford a disulfide having the formula (III):
wherein R 1 , R 2 and W are as defined above;
(b) adding the sulfur dioxide to a mixture comprising the resultant disulfide having the formula (III), a formate salt, trifluoromethyl bromide and a polar solvent, to afford a compound having the formula (II):
wherein R 1 , R 2 and W are as defined above; and
(c) oxidizing the resultant compound having the formula (II) with trifluoroperacetic acid in the presence of a corrosion inhibiting compound.
36. A process according to claim 35 , wherein the compound of formula (I) is 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfinylpyrazole, the compound of formula (II) is 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylthiopyrazole, the disulfide of formula (III) is 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyanopyrazol-4-yl disulfide, and the compound of formula (IV) is 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyanopyrazole.
37. A process according to claim 1 , wherein:
R 1 is trifluoromethyl, or trifluoromethoxy;
W is —CR 3 ;
R 2 is chlorine; and
R 3 is chlorine.
38. A process according to claim 30 , wherein:
R 1 is trifluoromethyl, or trifluoromethoxy;
W is —CR 3 ;
R 2 is chlorine; and
R 3 is chlorine.
39. A process according to claim 32 , wherein:
R 1 is trifluoromethyl, or trifluoromethoxy;
W is —CR 3 ;
R 2 is chlorine; and
R 3 is chlorine.
40. A process according to claim 33 , wherein:
R 1 is trifluoromethyl, or trifluoromethoxy;
W is —CR 3 ;
R 2 is chlorine; and
R 3 is chlorine.
41. A process according to claim 35 , wherein:
R 1 is trifluoromethyl, or trifluoromethoxy;
W is —CR 3 ;
R 2 is chlorine; and
R 3 is chlorine.