Methods for the synthesis of olefins and derivatives

Patent metadata

Field	Value
Publication number	US-10081587-B2
Application number	US-201615182245-A
Country	US
Kind code	B2
Filing date	Jun 14, 2016
Priority date	Aug 10, 2007
Publication date	Sep 25, 2018
Grant date	Sep 25, 2018

Abstract

The invention provides a method of producing acrylic acid. The method includes contacting fumaric acid with a sufficient amount of ethylene in the presence of a cross-metathesis transformation catalyst to produce about two moles of acrylic acid per mole of fumaric acid. Also provided is an acrylate ester. The method includes contacting fumarate diester with a sufficient amount of ethylene in the presence of a cross-metathesis transformation catalyst to produce about two moles of acrylate ester per mole of fumarate diester. An integrated process for process for producing acrylic acid or acrylate ester is provided which couples bioproduction of fumaric acid with metathesis transformation. An acrylic acid and an acrylate ester production also is provided.

First claim

What is claimed is:

1. A process for producing an acrylate ester comprising:
a) culturing in a sufficient amount of nutrients and media a non-naturally occurring Escherichia coli comprising a set of metabolic modification obligatorily coupling fumaric acid product to grow of said Escherichia coli , said set of metabolic modifications comprising disruption of at least one of the gene sets comprising:
(1) Fumarase (FUM), glucose-6-phosphate-1-dehydrogenase (ZWF) and formyltetrahydrofolate deformylase (PURU), and
(2) Fumarase (FUM), glucose-6-phosphate-1-dehydrogenase (ZWF) and serine hydroxymethyltransferase;

or an ortholog thereof, to produce stable growth-coupled production of fumaric acid;
b) performing diestrification of said fumaric acid to produce fumarate diester, and
c) contacting said fumarate diester with a sufficient amount of ethylene in the presence of a cross-metasthesis catalyst to produce about two moles of an acylate ester per mole of fumarate diester.

2. The process of claim 1 , wherein said genes encoding said metabolic modifications (a) Fumarase (FUM), glucose-6-phosphate-1-dehydrogenase (ZWF) and formyltetrahydrofolate defromylase (PURU) further comprises disruption of at least one gene selected from acetate kinase (ackA-pta), glutamate dehydrogenase (gdhA), transhydrogenase (pntAB) or acetate kinase (ackA-pta), 2,3-bisphosphoglycerate-independent phosphoglycerate mutase (yibO), and 6-phosphogluconolactonase(ybhE).

3. The process of claim 1 , wherein said disruption comprises a deletion of at least one gene within said gene set.

4. The process of claim 1 , wherein said nutrients and media comprise at least one carbon substrate selected from glucose, sucrose, xylose, arabinose, galactose, mannose or fructose.

5. The method of claim 1 , wherein said cross-metathesis transformation catalyst is selected from a ruthenium catalyst bearing an N-heterocyclic carbene ligand.

6. The method of claim 5 , wherein said rhuthenium catalyst comprises Cl 2 (PCy 3 ) 2 Ru═CHPh or the phosphine-free carbene ruthenium catalyst [1,3-bis(2,6-dimethylphenyl)4,5-dihydroimidazol-2-ylidene] (PCy 3 )(Cl) 2 Ru═CHPh.

7. The process of claim 1 , wherein said fumarate diester is produced by a diesterification method comprising contacting fumaric acid with an alcohol at a 1:2 molar ratio in under condensation reaction conditions sufficient to produce fumarate diester and water at a 1:2 molar ratio.

8. The process of claim 7 , further comprising addition of an esterification catalyst.

9. The process of claim 8 , wherein said esterification catalyst is sulfuric acid (H 2 SO 4 ) or p-toluene sulfonic.

10. An acrylate ester production system, comprising:
(a) a vessel comprising a culture of a non-naturally occurring Escherichia coli comprising a set of metabolic modifications obligatorily coupling fumaric acid production to growth of said Escherichia coli , said set of metabolic modifications comprising disruption of at least one of the gene sets comprising:
(1) Fumarase (FUM), glucose-6-phosphate-1-dehydrogenase (ZWF) and formyltetrahydrofolate deformylase (PURU), or (2) Fumarase (FUM), glucose-6-phosphate-1-dehydrogenase (ZWF) and serine hydroxymethyltransferase or an ortholog thereof, which confer stable growth-coupled production of fumaric acid;

(b) at least one diesterification reagent in communication with the vessel wherein the at least one diestrification reagent sufficient to produce fumarate diester from said fumaric acid, and
(c) ethylene and a cross-metathesis catalyst in communication with the vessel wherein the ethylene and a cross-metathesis catalyst sufficient to produce about two moles of an acrylate ester per mole of fumarate diester.

11. The production system of claim 10 , wherein said genes encoding said metabolic modifications (a) fumarase glucose-6-phosphate-1-dehydrogenase, formyltetrahydrofolate deformylase further comprises disruption of at least one gene selected from ackA-pta, gdhA, pntAB or ackA-pta, yibO, ythE.

12. The production system of claim 10 , wherein said disruption comprises a deletion of at least one gene within said gene set.

Assignees

• Genomatica Inc

Inventors

• Burk Mark J
• Pharkya Priti
• Van Dien Stephen J
• Burgard Anthony P
• Schilling Christophe H

Classifications

• C12P7/46

  Dicarboxylic acids having four or less carbon atoms, e.g. fumaric acid, maleic acid · CPC title

• C07C67/32

  Decarboxylation · CPC title

• C07C51/353 Primary

  by isomerisation; by change of size of the carbon skeleton · CPC title

• C07C69/54

  Acrylic acid esters; Methacrylic acid esters · CPC title

• Y02P20/125

  Cross-Sectional Technologies · mapped topic