Transformation of meso-lactide

Patent metadata

Field	Value
Publication number	US-10174161-B2
Application number	US-201615756670-A
Country	US
Kind code	B2
Filing date	Sep 2, 2016
Priority date	Sep 2, 2015
Publication date	Jan 8, 2019
Grant date	Jan 8, 2019

Abstract

B/N Lewis pairs have been discovered to catalyze rapid epimerization of meso-lactide (LA) or LA diastereomers quantitatively into rac-LA. The obtained rac-LA can be kinetically polymerized into poly( L -lactide) and optically resolved D -LA, with a high stereoselectivity factor k L /k D of 53 and an ee value of 91% at 50.6% monomer conversion, by a bifunctional chiral catalyst. The epimerization and enantioselective polymerization can be coupled into a one-pot process for transforming meso-LA directly into poly( L -lactide) and D -LA.

First claim

What is claimed is:

1. A method to epimerize meso-lactide into racemic lactide comprising contacting meso-lactide and a Lewis acid/base pair for a period of time sufficient to epimerize meso-lactide to racemic lactide, wherein at least about 0.001 mol % of the Lewis acid/base pair is present with respect to the initial molar amount of meso-lactide.

2. The method of claim 1 wherein the Lewis acid/base pair is a boron/nitrogen Lewis acid/base pair.

3. The method of claim 1 wherein the Lewis acid of the Lewis acid/base pair is B(C 6 F 5 ) 3 .

4. The method of claim 1 wherein the Lewis base of the Lewis acid/base pair is 1,4-diazabicyclo [2.2.2]octane (DABCO) or triethylamine.

5. The method of claim 1 wherein at least about 80% of the meso-lactide is epimerized into racemic lactide.

6. The method of claim 1 wherein the contacting is carried out in the presence of solvent, wherein meso-lactide is soluble in the solvent at 25° C. and racemic lactide is not soluble in the solvent at 25° C.

7. The method of claim 6 wherein the initial concentration of the meso-lactide in the solvent is at least about 0.2 M.

8. The method of claim 6 wherein the initial concentration of the meso-lactide in the solvent is about 1 M to about 3 M.

9. The method of claim 6 wherein the method is carried out at about 0° C. to about 100° C.

10. The method of claim 1 wherein the contacting is carried out in the absence of solvent.

11. The method of claim 10 wherein the meso-lactide is heated to at least about 54° C. but not more than about 116° C.

12. The method of claim 1 wherein the concentration of the Lewis acid/base pair is about 10 ppm to about 5 mol % with respect to the meso-lactide.

13. The method of claim 1 further comprising isolating substantially pure racemic lactide after meso-lactide has been epimerized into racemic lactide, wherein the isolating comprises one or more of filtering, washing, and chromatographing the racemic lactide.

14. The method of claim 1 further comprising kinetic resolution of the racemic lactide by contacting the racemic lactide with a compound of Formula I:

wherein X is —NH—C(═O)—R, wherein R is —CH 3 , —CF 3 , 2-propenyl, or optionally substituted aryl;
under suitable conditions to initiate ring-opening polymerization of L -lactide to provide a mixture of isotactic poly( L -lactide) and D -lactide.

15. The method of claim 14 wherein the compound of Formula I is compound 4:

16. The method of claim 14 further comprising separating the isotactic poly( L -lactide) and D -lactide.

17. The method of claim 1 wherein the meso-lactide prior to epimerization is in a composition that comprises one or more impurities selected from racemic lactide, lactic acid, lactic acid salts, and oligomers of lactide.

18. The method of claim 17 wherein the composition that comprises one or more impurities is treated, prior to epimerization, by a method comprising contacting the composition with about 1 mol % to about 10 mol % of AlCl 3 prior to contacting the meso-lactide with the Lewis acid/base pair.

19. The method of claim 18 wherein the composition, after having been contacted with the AlCl 3 , is purified prior to epimerization.

20. A compound of Formula I:

wherein X is —NH—C(═O)—R, wherein R is —CH 3 , —CF 3 , 2-propenyl, or optionally substituted aryl.

Assignees

• Univ Colorado State Res Found

Inventors

• Chen Eugene Y
• Zhu jian-bo

Classifications

• C08G63/08

  Lactones or lactides · CPC title

• C07D515/08

  Bridged systems · CPC title

• C07D405/04

  directly linked by a ring-member-to-ring-member bond · CPC title

• C08G63/823 Primary

  for the preparation of polylactones or polylactides · CPC title

• C08L67/04

  Polyesters derived from hydroxycarboxylic acids, e.g. lactones (C08L67/06 takes precedence) · CPC title