IP Library Granted Patent US 9,422,226
Granted Patent B2
US 9,422,226 · App. 14/124,562 · Granted Aug 23, 2016

Process for preparing high purity and crystalline dimethyl fumarate

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Quick Facts
Patent No.
US 9,422,226
App. No.
14/124,562
Granted
Aug 23, 2016
Kind
B2
Abstract

The present invention describes a process for the preparation of dimethyl fumarate. The process involves the esterification of fumaric acid and methanol in the presence of sulfuric acid as an acid catalyst. The high purity dimethyl fumarate contains no more than trace amounts of dimethyl sulfate. The present invention also provides a process for the preparation of highly pure dimethyl fumarate with a particle size from 20 to 250μπι.

Claims (50)

1. A method for the preparation of dimethyl fumarate, which comprises:

reacting:

(a) fumaric acid; and

(b) methanol;

in the presence of sulfuric acid; in a ratio of methanol to fumaric acid of about 5.7 to about 8.6 liters of methanol per kilogram of fumaric acid;

in a reaction mixture to obtain a product mixture comprising dimethyl fumarate and dimethyl sulfate, wherein the level of dimethyl sulfate is less than 4.0 ppm.

2. The method of claim 1 , wherein the level of dimethyl sulfate is less than 3.0 ppm.

3. The method of claim 1 , wherein the level of dimethyl sulfate is less than 2.0 ppm.

4. The method of claim 1 , wherein the level of dimethyl sulfate is less than 1.0 ppm.

5. The method of claim 1 , further comprising:

reducing the particle size of the dimethyl fumarate.

6. The method of claim 5 , wherein the reduced particle size of dimethyl fumarate ranges from about 20 μm to about 250 μm.

7. The method of claim 1 , wherein the ratio of fumaric acid:sulfuric acid is in a range from about 1:0.01 to about 1:0.50 molar equivalents.

8. The method of claim 1 , wherein the reacting is for about 3.0 to about 48 hours.

9. The method of claim 1 , wherein the reacting occurs at a temperature of from about 60° C. to about 70° C.

10. The method of claim 1 ,

wherein the ratio of fumaric acid:sulfuric acid is in a range from about 1:0.01 to about 1:0.50 molar equivalents,

the reaction mixture further comprises about 2.0% to about 5.0% water,

the reacting is for about 3.0 to about 48 hours, and

the reacting occurs at a temperature of from about 60° C. to about 70° C.

11. The method of claim 2 , wherein the ratio of fumaric acid:sulfuric acid is in a range from about 1:0.01 to about 1:0.50 molar equivalents.

12. The method of claim 2 , wherein the reacting is for about 3.0 to about 48 hours.

13. The method of claim 2 , wherein the reacting occurs at a temperature of from about 60° C. to about 70° C.

14. The method of claim 2 ,

wherein the ratio of fumaric acid:sulfuric acid is in a range from about 1:0.01 to about 1:0.50 molar equivalents,

the reaction mixture further comprises about 2.0% to about 5.0% water,

the reacting is for about 3.0 to about 48 hours, and

the reacting occurs at a temperature of from about 60° C. to about 70° C.

15. The method of claim 3 , wherein the ratio of fumaric acid:sulfuric acid is in a range from about 1:0.01 to about 1:0.50 molar equivalents.

16. The method of claim 3 , wherein the reacting is for about 3.0 to about 48 hours.

17. The method of claim 3 , wherein the reacting occurs at a temperature of from about 60° C. to about 70° C.

18. The method of claim 3 ,

wherein the ratio of fumaric acid:sulfuric acid is in a range from about 1:0.01 to about 1:0.50 molar equivalents,

the reaction mixture further comprises about 2.0% to about 5.0% water,

the reacting is for about 3.0 to about 48 hours, and

the reacting occurs at a temperature of from about 60° C. to about 70° C.

19. The method of claim 4 , wherein the ratio of fumaric acid:sulfuric acid is in a range from about 1:0.01 to about 1:0.50 molar equivalents.

20. The method of claim 4 , wherein the reacting is for about 3.0 to about 48 hours.

21. The method of claim 4 , wherein the reacting occurs at a temperature of from about 60° C. to about 70° C.

22. The method of claim 4 ,

wherein the ratio of fumaric acid:sulfuric acid is in a range from about 1:0.01 to about 1:0.50 molar equivalents,

the reaction mixture further comprises about 2.0% to about 5.0% water,

the reacting is for about 3.0 to about 48 hours, and

the reacting occurs at a temperature of from about 60° C. to about 70° C.

23. The method of claim 1 , wherein the reaction mixture further comprises about 2.0% to about 5.0% water.

24. The method of claim 2 , wherein the reaction mixture further comprises about 2.0% to about 5.0% water.

25. The method of claim 3 , wherein the reaction mixture further comprises about 2.0% to about 5.0% water.

26. The method of claim 4 , wherein the reaction mixture further comprises about 2.0% to about 5.0% water.

27. The method of claim 1 , wherein the dimethyl fumarate is crystal form I of dimethyl fumarate.

28. The method of claim 22 , wherein the dimethyl fumarate is crystal form I of dimethyl fumarate.

Assignments (4)
CHANGE OF ASSIGNEE ADDRESS Recorded Apr 18, 2019
From: BIOGEN MA INC.
To: BIOGEN MA INC.
Reel/Frame 050175/0648 →
CHANGE OF NAME Recorded May 4, 2015
From: BIOGEN IDEC MA INC.
To: BIOGEN MA INC.
Reel/Frame 035571/0926 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 5, 2015
From: GUZOWSKI, JOHN; KIESMAN, WILLIAM; IRDAM, ERWIN
To: BIOGEN IDEC MA INC.
Reel/Frame 034893/0724 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 20, 2014
From: GUZOWSKI, JOHN; KIESMAN, WILLIAM; IRDAM, ERWIN
To: BIOGEN IDEC MA INC.
Reel/Frame 032933/0713 →