Methods for production of aromatic dicarboxylic acids and derivatives thereof

Patent metadata

Field	Value
Publication number	US-10252969-B2
Application number	US-201615809612-A
Country	US
Kind code	B2
Filing date	Apr 22, 2016
Priority date	Apr 23, 2015
Publication date	Apr 9, 2019
Grant date	Apr 9, 2019

Abstract

Provided are methods for the production of isophthalic acid (IP A) and derivatives thereof. The methods are based on the addition of beta propiolactone to furfural or a derivative thereof. Provided are cost effective routes to biobased IP A and derivatives thereof, including terephthalic acid.

First claim

What is claimed is:

1. A method, comprising:
continuously feeding a first reaction zone with furfural and a compound of formula:

wherein R y is independently hydrogen, or an optionally substituted moiety selected from the group consisting of acyl; arylalkyl; 6- to 10-membered aryl; C 1-20 aliphatic; C 1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and an oxygen protecting group, to provide a first product stream comprising a first product of formula:

continuously feeding the first product stream to an oxidizing reaction zone where the first product is contacted with air to form a second product stream comprising a second product having formula:

wherein each R z is independently selected from the group consisting of —H, R y , optionally substituted C 1-20 aliphatic, and optionally substituted aryl; and continuously feeding the second product stream to a rearrangement reaction zone where the second product is converted to a compound of formula:

2. A method, comprising:
continuously feeding a first reaction zone with furfural and beta propiolactone, and an alcohol of formula HOR y , to provide a first product stream comprising a first product having formula:

wherein R y is independently hydrogen, or an optionally substituted moiety selected from the group consisting of acyl; arylalkyl; 6- to 10-membered aryl; C 1-20 aliphatic; C 1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and an oxygen protecting group; and; continuously feeding the first product stream to an oxidizing reaction zone where the first product is contacted with air to form a second product stream comprising a second product having formula:

wherein each R z is independently selected from the group consisting of —H, R y , optionally substituted C 1-20 aliphatic, and optionally substituted aryl; and continuously feeding the second product stream to a rearrangement reaction zone where the second product is converted to a compound of formula:

3. The method of claim 1 or 2 , wherein R y is —H.

4. The method of claim 1 or 2 , wherein R y is C 1-20 aliphatic.

5. The method of claim 1 , wherein each R z is —H.

6. The method of claim 1 , wherein each R z is —CH 3 .

7. A method for the production of biobased terephthalic acid or an ester thereof comprising:
a) reacting ethylene oxide with carbon monoxide to provide a product selected from beta propiolactone, acrylic acid and acrylate ester;
b) reacting the product of step (a) with furfural to provide a Diels Alder adduct;
c) oxidizing the Diels Alder adduct of step (b) to provide a product selected from isophthalic acid and isophthalate ester; and
d) treating the product of (c) to convert the isophthalic acid to terephthalic acid or the isophthalate ester to a terephthalate ester.

8. The method of claim 7 , wherein one or more steps are performed in a continuous process.

9. The method of claim 7 or 8 , wherein at least one of the ethylene oxide, the carbon monoxide or the furfural is biobased.

Assignees

• Novomer Inc

Inventors

• Farmer Jay J
• Sookraj Sadesh H

Classifications

• C07C51/235 Primary

  of —CHO groups or primary alcohol groups · CPC title

• C07C67/34

  Migration of [IMAGE cpc-sch-C07C-0962.gif] groups in the molecule · CPC title

• C07C63/24

  1,3 - Benzenedicarboxylic acid · CPC title

• C07C69/82

  Terephthalic acid esters · CPC title

• C07C63/26

  1,4 - Benzenedicarboxylic acid · CPC title