Process to prepare sulfonamides

• US 7,169,952 B2
• Filed: 06/01/2001
• Issued: 01/30/2007
• Est. Priority Date: 06/05/2000
• Status: Expired due to Term

• Current Assignee: FMC Corporation
• Original Assignee: FMC Corporation
• Inventors: Jarrow, Harold C., Sedergran, Thomas C., Smeltz, Leland A.
• Primary Examiner(s): DAVIS, BRIAN J
• Application Number:
  US10/296,727
• Publication Number:
  US 20030236437A1
• Time in Patent Office: 2,069 Days
• Field of Search: None
• US Class Current: 564/84
• CPC Class Codes: C07C 303/38 by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
• CPC Class Codes: C07D 239/54 as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
• CPC Class Codes: C07D 249/12 Oxygen or sulfur atoms

Abstract

A process for the preparation of a sulfonamide of formula (II), comprising reacting at elevated temperature an aniline of formula (I), with a sulfonating agent A of the formula R¹—SO₂-Z in the presence of a catalytic amount of either: (i) an amide B-1, other than N,N-dimethylformamide, or (ii) a high boiling tertiary amine B-2. Also provided in accordance with the present invention are processes for preparing sulfonamides of formula (II) by reacting an aniline of formula (I) with sulfanating agent A of the formula R¹—SO₂-Z in the presence of N,N-dimethylformamide, at a temperature in the range of about 120° C. to about 160° C. for about three to about seven hours. X, Y, Z, R and R¹ are defined herein

Claims

1. A process for the preparation of a sulfonamide of formula II:

2. The process of claim 1, wherein X and Y are each halo.

3. The process of claim 1, wherein X is 2-chloro or 2-fluoro and Y is 4-chloro.

4. The process of claim 1, wherein R is a substituted or unsubstituted heterocyclyl, the substituents comprising one or more members selected from the group consisting of halo C_1-20 alkyl, C_1-20 alkoxy, nitro, amino, amido, alkylthio, aryl, arylthio, aryloxy, alkylsulfonyl, and arylsulfonyl.

5. The process of claim 4, wherein R is 4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl, 1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedion-3-yl, or 1-amino-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedion-3-yl.

6. The process of claim 1, wherein R¹ is aryl or alkyl and Z is halo or anhydridyl.

7. The process of claim 6, wherein R¹ is methyl and Z is chloro.

8. The process of claim 1, wherein X is 2-chloro;

Y is 4-chloro;

R is 4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl; and

R¹ is methyl.

9. The process of claim 1, wherein the amide B-1 and tertiary amine B-2 are independently selected from the group consisting of 1-methyl-2-pyrrolidinone, 1,1,3,3-tetramethylurea, N,N-dimethylacetamide, hexamethylphosphoramide, isoquinoline, and 1-(2,4-dichloro-5-acetamidophenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1H-1,2,4-triazol-5-one.

10. The process of claim 1, wherein the reaction is carried out in a solvent.

11. The process of claim 10, wherein the solvent is an aromatic, alkane, or alkene solvent.

12. The process of claim 11, wherein the solvent is selected from the group consisting of toluene, xylene, and diethylbenzene.

13. The process of claim 12, wherein the solvent is toluene.

14. The process of claim 1, wherein the reaction mixture is heated at about 110°

C. to about 160°

C. for about three to about 12 hours.

15. The process of claim 14, wherein the reaction mixture is heated at about 120°

C. to about 150°

C. for about three to about seven hours.

16. The process of claim 1, wherein about 1 to about 5 molar equivalents of sulfonating agent A are present per one molar equivalent of aniline I.

17. The process of claim 16, wherein about 1.3 to about 4 molar equivalents of sulfonating agent A are present per one molar equivalent of aniline I.

18. A process for the preparation of a sulfonamide of formula II:

19. The process of claim 18, wherein X and Y are each halo.

20. The process of claim 19, wherein X is 2-chloro or 2-fluoro and Y is 4-chloro.

21. The process of claim 18, wherein R is a substituted or unsubstituted heterocyclyl, the substituents comprising one or more members selected from the group consisting of halo, C_1-20 alkyl, C_1-20 alkoxy, nitro, amino, amido, alkylthio, aryloxy, aryl, arylthio, alkylsulfonyl, and arylsulfonyl.

22. The process of claim 21, wherein R is 4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl, 1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedion-3-yl, or 1-amino-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedion-3-yl.

23. The process of claim 18, wherein R¹ is alkyl and Z is halo.

24. The process of claim 23, wherein R¹ is methyl and Z is chloro.

25. The process of claim 18, wherein X is 2-chloro;

Y is 4-chloro;

R is 4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl; and

R¹ is methyl.

26. The process of claim 18, wherein the reaction is carried out in a solvent.

27. The process of claim 26, wherein the solvent is an aromatic, alkane, or alkene solvent.

28. The process of claim 27, wherein the solvent is selected from the group consisting of toluene, xylene, and diethylbenzene.

29. The process of claim 18, wherein the reaction mixture is heated at about 125°

C. to about 150°

C. for about four to about seven hours.

30. The process of claim 18, wherein about 1.5 to about 6 molar equivalents of sulfonating agent A are present per one molar equivalent of aniline I.

31. The process of claim 30, wherein about 1.5 to about 4 molar equivalents of sulfonating agent A are present per one molar equivalent of aniline I.

32. The process of claim 18, wherein about 0.001 to about 0.09 molar equivalent of N,N-dimethylformamide is present per one molar equivalent of aniline I.

33. The process of claim 32, wherein about 0.001 to about 0.05 molar equivalent of N,N-dimethylformamide is present per one molar equivalent of aniline I.