Processes for preparing pesticidal intermediates
View Patent ↗The present invention relates to processes for the preparation of a compound of the formula wherein W is nitrogen or —CR 3 ; R 1 is halogen, haloalkyl, haloalkoxy, R 4 S(O) n — or —SF 5 ; R 2 is hydrogen or halogen; R 3 is halogen; R 4 is alkyl or haloalkyl; and n is 0, 1 or 2; and processes for using a compound of the formula (I) in the synthesis of compounds of the formula
1. A process for the preparation of a compound of formula (X) or (XI):
wherein R 1 represents halogen, haloalkyl, haloalkoxy, —SF 5 , or R 4 S(O) n —, wherein R 4 represents alkyl or haloalkyl, and n represents 0, 1 or 2; R 2 represents hydrogen or halogen; and W represents CR 3 , wherein R 3 represents halogen; which process comprises reacting a compound of formula (I):
wherein R 1 , R 2 and W are as defined above, with a source of hydrogen cyanide, to produce the corresponding compound of formula (VI):
wherein R 1 , R 2 and W are as defined above; followed by oxidizing the compound of formula (VI) thus obtained and optionally reacting it with a base.
2. A process for the preparation of a compound of formula (X) or (XI):
wherein R represents halogen, haloalkyl, haloalkoxy, —SF 5 , or R 4 S(O) n —, wherein R 4 represents alkyl or haloalkyl, and n represents 0, 1 or 2; R 2 represents hydrogen or halogen; and W represents CR 3 , wherein R 3 represents halogen; which process comprises reacting a compound of formula (I):
wherein R 1 , R 2 and W are as defined above, with hydrogen cyanide prepared from a metal cyanide salt in the presence of an acid, to produce the corresponding compound of formula (VI):
wherein R 1 , R 2 and W are as defined above; followed by oxidizing the compound of formula (VI) thus obtained and optionally reacting it with a base.
3. A process for the preparation of a compound of formula (X) or (XI):
wherein R 1 represents halogen, haloalkyl, haloalkoxy, —SF 5 , or R 4 S(O) n —, wherein R 4 represents alkyl or haloalkyl, and n represents 0, 1 or 2; R 2 represents hydrogen or halogen; and W represents CR 3 , wherein R 3 represents halogen; which process comprises reacting a compound of formula (II):
wherein R 5 and R 6 independently represent alkyl or together represent an alkylene chain having two or three carbon atoms, with an acid addition salt of an arylhydrazine compound of formula (III):
wherein R 1 , R 2 and W are as defined above, to produce the corresponding compound of formula (I):
wherein R 1 , R 2 and W are as defined above; followed by reacting the compound of formula (I) thus obtained with a source of hydrogen cyanide, to produce the corresponding compound of formula (VI):
wherein R 1 , R 2 and W are as defined above; followed by oxidizing the compound of formula (VI) thus obtained and optionally reacting it with a base.
4. A process according to claim 3 , wherein the hydrogen cyanide is prepared from a metal cyanide salt in the presence of an acid.
5. A process for the preparation of a compound of formula (X) or (XI):
wherein R 1 represents halogen, haloalkyl, haloalkoxy, —SF 5 , or R 4 S(O) n —, wherein R 4 represents alkyl or haloalkyl, and n represents 0, 1 or 2; R 2 represents hydrogen or halogen; and W represents CR 3 , wherein R 3 represents halogen; which process comprises reacting a compound of formula (IV):
wherein R 7 represents alkyl, with an arylhydrazine compound of formula (III):
wherein R 1 , R 2 and W are as defined above, to produce the corresponding compound of formula (I):
wherein R 1 , R 2 and W are as defined above; followed by reacting the compound of formula (I) thus obtained with a source of hydrogen cyanide, to produce the corresponding compound of formula (VI):
wherein R 1 , R 2 and W are as defined above; followed by oxidizing the compound of formula (VI) thus obtained and optionally reacting it with a base.
6. A process according to claim 5 , wherein the hydrogen cyanide is prepared from a metal cyanide salt in the presence of an acid.
7. A process according to claim 1 , wherein R 1 represents haloalkyl, haloalkoxy or —SF 5 ; W represents —CR 3 ; and R 3 represents halogen.
8. A process according to claim 2 , wherein R 1 represents haloalkyl, haloalkoxy or —SF 5 ; W represents —CR 3 ; and R 3 represents halogen.
9. A process according to claim 3 , wherein R 1 represents haloalkyl, haloalkoxy or —SF 5 ; W represents —CR 3 ; and R 3 represents halogen.
10. A process according to claim 4 , wherein R 1 represents haloalkyl, haloalkoxy or —SF 5 ; W represents —CR 3 ; and R 3 represents halogen.
11. A process according to claim 5 , wherein R 1 represents haloalkyl, haloalkoxy or —SF 5 ; W represents —CR 3 ; and R 3 represents halogen.
12. A process according to claim 6 , wherein R 1 represents haloalkyl, haloalkoxy or —SF 5 ; W represents —CR 3 ; and R 3 represents halogen.
13. A process according to claim 7 , wherein R 1 represents trifluoromethyl, trifluoromethoxy or —SF 5 ; W represents —CR 3 ; and R 3 represents halogen.
14. A process according to claim 8 , wherein R 1 represents trifluoromethyl, trifluoromethoxy or —SF 5 ; W represents —CR 3 ; and R 3 represents halogen.
15. A process according to claim 9 , wherein R 1 represents trifluoromethyl, trifluoromethoxy or —SF 5 ; W represents —CR 3 ; and R 3 represents halogen.
16. A process according to claim 10 , wherein R 1 represents trifluoromethyl, trifluoromethoxy or —SF 5 ; W represents —CR 3 ; and R 3 represents halogen.
17. A processing according to claim 11 , wherein R 1 represents trifluoromethyl, trifluoromethoxy or —SF 5 ; W represents —CR 3 ; and R 3 represents halogen.
18. A process according to claim 12 , wherein R 1 represents trifluoromethyl, trifluoromethoxy or —SF 5 ; W represents —CR 3 ; and R 3 represents halogen.
19. A process according to claim 1 , wherein R 1 represents trifluoromethyl, W represents —CR 3 and each of R 2 and R 3 represents chlorine.
20. A process according to claim 2 , wherein R 1 represents trifluoromethyl, W represents —CR 3 and each of R 2 and R 3 represents chlorine.
21. A process according to claim 3 , wherein R 1 represents trifluoromethyl, W represents —CR 3 and each of R 2 and R 3 represents chlorine.
22. A process according to claim 4 , wherein R 1 represents trifluoromethyl, W represents —CR 3 and each of R 2 and R 3 represents chlorine.
23. A process according to claim 5 , wherein R 1 represents trifluoromethyl, W represents —CR 3 and each of R 2 and R 3 represents chlorine.
24. A process according to claim 6 , wherein R 1 represents trifluoromethyl, W represents —CR 3 and each of R 2 and R represents chlorine.
25. A process according to claim 1 , wherein the reaction of the compound of formula (I) with a source of hydrogen cyanide is carried out in a sealed container.
26. A process according to claim 2 , wherein the reaction of the compound of formula (I) with hydrogen cyanide prepared from a metal cyanide salt in the presence of an acid is carried out in a sealed container.
27. A process according to claim 3 , wherein the reaction of the compound of formula (I) with a source of hydrogen cyanide is carried out in a sealed container.
28. A process according to claim 4 , wherein the reaction of the compound of formula (I) with hydrogen cyanide prepared from a metal cyanide salt in the presence of an acid is carried out in a sealed container.
29. A process according to claim 5 , wherein the reaction of the compound of formula (I) with a source of hydrogen cyanide is carried out in a sealed container.
30. A process according to claim 6 , wherein the reaction of the compound of formula (I) with hydrogen cyanide prepared from a metal cyanide salt in the presence of an acid is carried out in a sealed container.
31. A process according to claim 1 , wherein the oxidation of the compound of formula (VI) is carried out with a metal salt or oxide as oxidant.
32. A process according to claim 2 , wherein the oxidation of the compound of formula (VI) is carried out with a metal salt or oxide as oxidant.
33. A process according to claim 3 , wherein the oxidation of the compound of formula (VI) is carried out with a metal salt or oxide as oxidant.
34. A process according to claim 4 , wherein the oxidation of the compound of formula (VI) is carried out with a metal salt or oxide as oxidant.
35. A process according to claim 5 , wherein the oxidation of the compound of formula (VI) is carried out with a metal salt or oxide as oxidant.
36. A process according to claim 6 , wherein the oxidation of the compound of formula (VI) is carried out with a metal salt or oxide as oxidant.
37. A process according to claim 31 , wherein the metal salt or oxide is cupric chloride or mercuric oxide.
38. A process according to claim 32 , wherein the metal salt or oxide is cupric chloride or mercuric oxide.
39. A process according to claim 33 , wherein the metal salt or oxide is cupric chloride or mercuric oxide.
40. A process according to claim 34 , wherein the metal salt or oxide is cupric chloride or mercuric oxide.
41. A process according to claim 35 , wherein the metal salt or oxide is cupric chloride or mercuric oxide.
42. A process according to claim 36 , wherein the metal salt or oxide is cupric chloride or mercuric oxide.
43. A process according to claim 31 , wherein the molar ratio of oxidant to compound of formula (VI) is from 0.01:1 to 5:1.
44. A process according to claim 32 , wherein the molar ratio of oxidant to compound of formula (VI) is from 0.01:1 to 5:1.
45. A process according to claim 33 , wherein the molar ratio of oxidant to compound of formula (VI) is from 0.01:1 to 5:1.
46. A process according to claim 34 , wherein the molar ratio of oxidant to compound of formula (VI) is from 0.01:1 to 5:1.
47. A process according to claim 35 , wherein the molar ratio of oxidant to compound of formula (VI) is from 0.01:1 to 5:1.
48. A process according to claim 36 , wherein the molar ratio of oxidant to compound of formula (VI) is from 0.01:1 to 5:1.
49. A process according to claim 43 , wherein the molar ratio of oxidant to compound of formula (VI) is from 1:1 to 3:1.
50. A process according to claim 44 , wherein the molar ratio of oxidant to compound of formula (VI) is from 1:1 to 3:1.
51. A process according to claim 45 , wherein the molar ratio of oxidant to compound of formula (VI) is from 1:1 to 3:1.
52. A process according to claim 46 , wherein the molar ratio of oxidant to compound of formula (VI) is from 1:1 to 3:1.
53. A process according to claim 47 , wherein the molar ratio of oxidant to compound of formula (VI) is from 1:1 to 3:1.
54. A process according to claim 48 , wherein the molar ratio of oxidant to compound of formula (VI) is from 1:1 to 3:1.