Sulfonation of polyhydroxyaromatics

• US 8,492,581 B2
• Filed: 08/20/2010
• Issued: 07/23/2013
• Est. Priority Date: 08/21/2009
• Status: Expired due to Fees

• Current Assignee: Amyris Inc.
• Original Assignee: Amyris Inc.
• Inventors: Frost, John W, Bui, Vu
• Primary Examiner(s): NAZARIO GONZALEZ, PORFIRIO
• Application Number:
  US12/859,922
• Publication Number:
  US 20110046412A1
• Time in Patent Office: 1,068 Days
• Field of Search: 562/45, 562/99
• US Class Current: 562/99
• CPC Class Codes: C07B 2200/05 Isotopically modified compounds, e.g. labelled
• CPC Class Codes: C07C 303/06 by reaction with sulfuric acid or sulfur trioxide
• CPC Class Codes: C07C 309/60 the carbon skeleton being further substituted by singly-bound oxygen atoms
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials

Abstract

The present invention provides improved process for the sulfonation of hydroxyaromatics amenable to direct isolation of the sulfonylated hydroxyaromatics in their free-acid forms. The process allows for the recyclization of sulfuric acid and minimizes waste. The starting materials are from a renewal resource, e.g., biomass, and contain detectable ¹⁴C up to a ¹⁴C content of 0.0000000001% (one part per trillion). The products made include sulfonated catechol, disulfonated pyrogallol and sulfonated protocatechuic acid.

Claims

1. A process for preparing a sulfonated hydroxyaromatic compound of formula I:

2. The process of claim 1 wherein the reacting step is performed under a N₂ atmosphere.

3. The process of claim 1 wherein the separating step is performed in the presence of a solvent.

4. The process of claim 1 wherein in Formula I R¹ is SO₃Na and R² is H, and the sulfonated hydroxyaromatic compound is sulfonated catechol;

and wherein in Formula II R¹ and R² are both H, and the compound of Formula II is catechol.

5. The process of claim 1 wherein in Formula I R¹ is SO₃Na and R² is OH, and the sulfonated hydroxyaromatic compound is disulfonated pyrogallol;

and wherein in Formula II R¹ is H and R² is OH, and the compound of Formula II is pyrogallol.

6. The process of claim 1 wherein in Formula I R¹ is CO₂Na and R² is H, and the sulfonated hydroxyaromatic compound is sulfonated protocatechuic acid;

and wherein in Formula II R¹ is CO₂H and R² is H, and the compound of Formula II is protocatechuic acid.

7. The process of claim 1 wherein the compound of Formula II is derived from biomass-derived renewable carbon atoms by fermentation methods.

17. The process of claim 1 wherein the compound of Formula II contains carbon atoms derived from biomass by fermentation.

8. A sulfonated hydroxyaromatic compound of formula I:

9. The sulfonated hydroxyaromatic compound of claim 8 wherein X is H, R¹ is CO₂H and R² is H, and the sulfonated hydroxyaromatic compound is 3,4-dihydroxy-5-sulfobenzoic acid.

10. A process for preparing a sulfonated hydroxyaromatic compound of formula I:

11. The process of claim 10 further comprising precipitating a free acid of said sulfonated hydroxyaromatic compound.

12. The process of claim 11 wherein the precipitating step is performed in the presence of a solvent.

13. The process of claim 10 wherein the reacting step is performed under a N₂ atmosphere.

14. The process of claim 10 wherein the sulfonated hydroxyaromatic compound of Formula I is sulfonated catechol;

and the compound of Formula II is catechol.

15. The process of claim 10 the sulfonated hydroxyaromatic compound of Formula I is disulfonated pyrogallol;

and the compound of Formula II is pyrogallol.

16. The process of claim 10 wherein the sulfonated hydroxyaromatic compound is sulfonated protocatechuic acid;

and the compound of Formula II is protocatechuic acid.