Aerobic Oxidative Esterification of Sugar-Derived 1,4-Disubstituted Benzene for Direct Synthesis of Dimethylterephthalate

Patent metadata

Field	Value
Publication number	US-2016115113-A1
Application number	US-201514877545-A
Country	US
Kind code	A1
Filing date	Oct 7, 2015
Priority date	Oct 28, 2014
Publication date	Apr 28, 2016
Grant date	—

Abstract

This invention relates to a dimethylterephthalate production process comprising reacting substituted furan with ethylene under cycloaddition reaction conditions and in the presence of a cycloaddition catalyst to produce a bicyclic ether, dehydrating the bicyclic ether to produce a substituted phenyl, dissolving said substituted phenyl in methanol, and oxidizing and esterifying the substituted phenyl in the presence of an oxidative esterification catalyst to form dimethylterephthalate. Importantly, the process does not include oxidizing the substituted phenyl to form terephthalic acid.

First claim

What is claimed is:

1 . A dimethylterephthalate production process comprising:
reacting substituted furan with ethylene under cycloaddition reaction conditions and in the presence of a cycloaddition catalyst to produce a bicyclic ether; wherein the substituted furan is represented by the formula:

wherein R and R* are separately selected from CH 3 , HC═O and —CH 2 OH, and the bicyclic ether is represented by the formula:

dehydrating the bicyclic ether to produce a substituted phenyl of the formula:

dissolving said substituted phenyl in methanol; and
oxidizing and esterifying the substituted phenyl in the presence of an oxidative esterification catalyst to form dimethylterephthalate.

2 . The process of claim 1 , wherein both R and R* are HC═O.

3 . The process of claim 1 , wherein both R and R* are —CH 2 OH.

4 . The process of claim 1 , wherein one of R and R* is HC═O and the other is —CH 2 OH.

5 . The process of claim 1 , wherein both R and R* are CH 3 .

6 . The process of claim 1 , wherein one of R and R* is CH 3 and the other is —CH 2 OH.

7 . The process of claim 1 , wherein one of R and R* is CH 3 and the other is HC═O.

8 . The process of claim 1 , wherein said oxidative esterification is conducted at a temperature from −50° C. to 100° C.

9 . The process of claim 1 , wherein the oxidative esterification catalyst is a heterogeneous catalyst bearing metal compromising at least one of cobalt, gold, palladium, platinum, and combinations thereof.

10 . The process of claim 9 , wherein the oxidative esterification catalyst is supported on materials compromising at least one of carbon, alumina, titania, silica, and metal-organic framework.

11 . The process of claim 1 , wherein said oxidative esterification is conducted at a substantially neutral pH or in the presence of a recoverable solid base catalyst.

12 . The process of claim 1 , wherein said substituted furan is derived from conversion of glucose or fructose.

13 . The process of claim 1 , which does not include oxidizing the substituted phenyl such that it forms terephthalic acid.

14 . A carbohydrate based process for producing dimethylterephthalate comprising:
(a) converting a hexose to 5-hydroxymethylfurfural; (b) reacting the 5-hydroxymethylfurfural with ethylene under cycloaddition reaction conditions and in the presence of a catalyst to produce a bicyclic ether, then dehydrating the bicyclic ether to produce a compound represented by the formula (I):

and
(c) dissolving the compound represented by the formula (I) in methanol and contacting the solution with oxygen in the presence of an oxidative esterification catalyst to produce dimethylterephthalate,

wherein the compound of formula (I) is not converted to terephthalic acid prior to step (c).

15 . A carbohydrate based process for producing dimethylterephthalate comprising:
(a) converting a hexose to 5-hydroxymethylfurfural; (b) hydrogenating 5-hydroxymethylfurfural to form 2,5-bis hydroxymethylfuran; (c) reacting the 2,5-bis hydroxymethylfuran with ethylene under cycloaddition reaction conditions and in the presence of a catalyst to produce a bicyclic ether, then dehydrating the bicyclic ether to produce a compound represented by the following formula (II):

and
(d) dissolving the compound represented by the formula (II) in methanol and contacting the solution with oxygen in the presence of an oxidation/esterification catalyst to produce dimethylterephthalate,

wherein the compound of formula (II) is not converted to terephthalic acid prior to step (d).

16 . A carbohydrate based process for producing dimethylterephthalate comprising:
(a) converting a hexose to 5-hydroxymethylfurfural; (b) partially oxidizing the 5-hydroxymethylfurfural to form diformyl furan; (c) reacting the diformyl furan with ethylene under cycloaddition reaction conditions and in the presence of a catalyst to produce a bicyclic ether, then dehydrating the bicyclic ether to produce a compound represented by the following formula (III):

and
(d) dissolving the compound represented by the formula (III) in methanol and contacting the solution with oxygen in the presence of an oxidative esterification catalyst to produce dimethylterephthalate,

wherein the compound of formula (III) is not converted to terephthalic acid prior to step (d).

17 . A carbohydrate based process for producing dimethylterephthalate comprising:
(a) converting a hexose to 5-hydroxymethylfurfural; (b) reducing the 5-hydroxymethylfurfural to form dimethyl furan; (c) reacting the dimethyl furan with ethylene under cycloaddition reaction conditions and in the presence of a catalyst to produce a bicyclic ether, then dehydrating the bicyclic ether to produce a compound represented by the following formula (IV):

and
(d) dissolving the compound represented by the formula (IV) in methanol and contacting the solution with oxygen in the presence of an oxidative esterification catalyst to produce dimethylterephthalate,

wherein the compound of formula (IV) is not converted to terephthalic acid prior to step (d).

Assignees

• Exxonmobil Chem Patents Inc

Inventors

• Shiramizu Mika
• Lattner James R
• Kandel Kapil

Classifications

• C07C37/52

  by splitting polyaromatic compounds, e.g. polyphenolalkanes · CPC title

• C07C67/03 Primary

  by reacting an ester group with a hydroxy group · CPC title

• C07C45/69

  by addition to carbon-to-carbon double or triple bonds · CPC title

• C07C67/40

  by oxidation of primary alcohols · CPC title

• C07C67/39

  by oxidation of groups which are precursors for the acid moiety of the ester · CPC title