Methods of Making Cyclic Amide Monomers and Related Derivatives

• US 20110190488A1
• Filed: 07/24/2009
• Published: 08/04/2011
• Est. Priority Date: 07/24/2008
• Status: Abandoned Application

• Current Assignee: Amyris Inc.
• Original Assignee: Amyris Inc.
• Inventors: Wicks, Douglas A.
• Application Number:
  US13/055,668
• Publication Number:
  US 20110190488A1
• Time in Patent Office: Days
• US Class Current: 540/528
• CPC Class Codes: C07D 223/12 Nitrogen atoms not forming part of a nitro radical

Abstract

The present invention relates to methods of making a cyclic amide. The methods include the step of heating a fermentation broth in a manner effective to produce a cyclic amide, wherein the fermentation broth includes an amino acid or salt thereof. The cyclic amide monomers can be polymerized in a manner effective to form a polyamide. One advantage of the present invention is that lysine and/or salt thereof can be heated to form α-amino-ε-caprolactam while the lysine is still in the fermentation broth. The lysine and/or salt thereof do not need to be purified from the fermentation broth prior to being heated to form α-amino-ε-caprolactam. For example, the fermentation broth does not need to be subjected to an ion exchange process prior to being heated to form α-amino-ε-caprolactam. Avoiding such an ion exchange process can substantially reduce manufacturing costs.

Claims

1-7. -7. (canceled)

8. A process for synthesizing α

-amino-ε

-caprolactam, the process comprising the step of heating a mixture comprising a fermentation broth and an alcohol, without the presence of a catalyst, at a temperature of about 99°

C. to about 250°

C. to produce α

-amino-ε

-caprolactam, wherein the fermentation broth comprises lysine.

10. A process according to claim 8, wherein the alcohol has from 2 to 6 carbons.

11. A process according to claim 10, wherein the alcohol comprises a diol, a triol, and/or a glycol.

14. A process according to claim 10, wherein the alcohol is from the group consisting of ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1,2-propanediol, and mixtures thereof.

15. A process according to claim 10, wherein the alcohol is 1,2-propanediol.

16. A process according to claim 8, wherein the heating is below the temperature of polymerization of ε

-caprolactam.

17. A process according to claim 8, wherein the heating allows removal of water.

9. (canceled)

12-13. -13. (canceled)

18. (canceled)

19. A process for the synthesis of ε

-caprolactam, the process comprising;

a) heating a mixture comprising a fermentation broth and an alcohol at a temperature of about 99°

C. to about 250°

C. to produce α

-amino-ε

-caprolactam, wherein the fermentation broth comprises lysine; and

b) deaminating the α

-amino-ε

-caprolactam by a method comprising contacting the α

-amino-ε

-caprolactam at least once with a deamination catalyst in a manner effective to remove the α

-amino group and provide ε

-caprolactam.

20. A process according to claim 19, wherein the yield of ε

-caprolactam is greater than about 70%.

22. A process according to claim 19, wherein the temperature in step (b) is from about −

5°

C. to about −

20°

C.

23. A process according to claim 19, wherein the process further comprises removing an amine, produced by the deaminating step (b), using a washing step.

26. A process according to claim 19, wherein the heating step (a) comprises heating in the presence of a catalyst.

27. A process according to claim 26, wherein the catalyst is Al₂O₃.

28. A process according to claim 19, wherein the alcohol has from 2 to 6 carbons.

29. A process according to claim 28, wherein the alcohol is selected from the group consisting of ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1,2-propanediol, and mixtures thereof.

30. A process according to claim 19, wherein the alcohol is 1,2-propanediol.

31. A process according to claim 19, wherein the heating step (a) is below the temperature of polymerization of ε

-caprolactam.

32. A process according to claim 19, wherein the heating allows removal of water.

34. A process according to claim 19, wherein the deaminating step (b) includes a hydrodenitrogenation catalyst.

56. A process according to claim 34, wherein the deaminating step (b) further includes contacting the α

-amino-ε

-caprolactam with a hydrogen gas to remove the α

-amino group in the presence of the hydrodenitrogenation catalyst.

21. (canceled)

24-25. -25. (canceled)

33. (canceled)

35-55. -55. (canceled)