Methods for Production of Aromatic Dicarboxylic Acids and Derivatives Thereof

Abstract

Provided are methods for the production of phthalic acid (PA), isophthalic acid (IP A), terephthalic acid (TP 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.

What is claimed is: 
     
         1 . A method for the production of a compound of formula: 
       
         
           
           
               
               
           
         
         the method comprising the step of oxidizing a compound of formula: 
       
       
         
           
           
               
               
           
         
       
       wherein each R z  is selected from the group consisting of: —H, R y , optionally substituted C 1-20  aliphatic, and optionally substituted aryl; and R y  is hydrogen, or an optionally substituted moiety selected the group consisting of acyl; arylalkyl; 6- to 10-membered aryl; C 1-20  aliphatic; C 1-20  heteroaliphatic having 1-4 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having 1-2 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur; and an oxygen protecting group. 
     
     
         2 . The method of  claim 1 , wherein each R z  is —H. 
     
     
         3 . The method of  claim 1 , wherein each R z  is —CH3. 
     
     
         4 . The method of  claim 1 , wherein the compound of formula: 
       
         
           
           
               
               
           
         
         is produced by reaction of furfural with a compound having a formula: 
       
       
         
           
           
               
               
           
         
       
     
     
         5 . A method for the production of a compound of formula: 
       
         
           
           
               
               
           
         
         the method comprising the steps of reacting furfural with beta propiolactone and oxidizing the resulting adduct, where each R z  is selected from the group consisting of:
 hydrogen, or an optionally substituted moiety selected the group consisting of acyl; arylalkyl; 6- to 10-membered aryl; C 1-20  aliphatic; C 1-20  heteroaliphatic having 1-4 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having 1-2 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur; and an oxygen protecting group. 
 
       
     
     
         6 . The method of  claim 5 , wherein each R z  is —H. 
     
     
         7 . The method of  claim 5 , wherein each R z  is —CH3. 
     
     
         8 . A method for the production of a compound of formula: 
       
         
           
           
               
               
           
         
         the method comprising the steps of reacting furfural with beta propiolactone and oxidizing the resulting adduct, where each R z  is selected from the group consisting of:
 hydrogen, or an optionally substituted moiety selected the group consisting of acyl; 
 arylalkyl; 6- to 10-membered aryl; C 1-20  aliphatic; C 1-20  heteroaliphatic having 1-4 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having 1-2 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur; and an oxygen protecting group. 
 
       
     
     
         9 . The method of  claim 8 , wherein each R z  is —H. 
     
     
         10 . The method of  claim 8 , wherein each R z  is —CH3. 
     
     
         11 . An isophthalic acid composition produced via cycloaddition reaction of furfural with an alpha beta unsaturated carboxylic acid, wherein the isophthalic acid is at least partially derived from a biobased feedstock. 
     
     
         12 . The isophthalic acid composition of  claim 11 , wherein carbon atoms one through five as shown in the formula: 
       
         
           
           
               
               
           
         
         are derived from biobased furfural. 
       
     
     
         13 . An isophthalic acid composition produced via reaction of furfural with beta propiolactone, wherein the isophthalic acid is at least partially derived from a biobased feedstock. 
     
     
         14 . The isophthalic acid composition of  claim 13 , wherein carbon atoms one through five as shown in the formula: 
       
         
           
           
               
               
           
         
         are derived from biobased furfural. 
       
     
     
         15 . The isophthalic acid composition of  claim 11 , wherein carbon atoms six through eight as shown in the formula: 
       
         
           
           
               
               
           
         
         are derived from a biobased alpha beta unsaturated acid. 
       
     
     
         16 . The isophthalic acid composition of  claim 13 , wherein carbon atoms six through eight as shown in the formula: 
       
         
           
           
               
               
           
         
         are derived from a biobased beta propiolactone. 
       
     
     
         17 . A biobased polymer composition derived from an isophthalic acid composition of  claim 11 . 
     
     
         18 . The biobased polymer composition of  claim 17 , wherein the polymer comprises polyethylene isophthalate (PIT). 
     
     
         19 . The biobased polymer composition of  claim 18 , wherein the polyethylene isophthalate further comprises biobased ethylene glycol. 
     
     
         20 . A method for the production of biobased phthalic 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; and   c. oxidizing the Diels Alder adduct of step (b) to provide a product selected from phthalic acid and phthalate ester.   
     
     
         21 . The method of  claim 20 , wherein at least one of the ethylene oxide, the carbon monoxide or the furfural is biobased. 
     
     
         22 . A method for the production of biobased isophthalic 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; and   c. oxidizing the Diels Alder adduct of step (b) to provide a product selected from isophthalic acid and isophthalate ester.   
     
     
         23 . The method of  claim 22 , wherein at least one of the ethylene oxide, the carbon monoxide or the furfural is biobased. 
     
     
         24 . A method, comprising:
 feeding a first reaction zone with furfural and a compound of formula:   
       
         
           
           
               
               
           
         
         wherein R y  is 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 selected from the group consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having 1-2 heteroatoms 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: 
       
       
         
           
           
               
               
           
         
         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 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: 
       
       
         
           
           
               
               
           
         
       
     
     
         25 . The method of  claim 24  wherein R y  is —H. 
     
     
         26 . The method of  claim 24  wherein R y  is C 1-20  aliphatic. 
     
     
         27 . The method of  claim 24  wherein each R z  is —H. 
     
     
         28 . The method of  claim 24  wherein each R z  is —CH 3 . 
     
     
         29 . A method, comprising:
 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 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 selected from the group consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having 1-2 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur; and an oxygen protecting group; and; 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 selected from the group consisting of —H, R y , optionally substituted C 1-20  aliphatic, and optionally substituted aryl; and feeding the second product stream to a rearrangement reaction zone where the second product is converted to a compound of formula: 
       
       
         
           
           
               
               
           
         
       
     
     
         30 . The method of  claim 29 , wherein R y  is —H. 
     
     
         31 . The method of  claim 29 , wherein R y  is C 1-20  aliphatic. 
     
     
         32 . The method of  claim 29 , wherein each R z  is —H. 
     
     
         33 . The method of  claim 29 , wherein each R z  is —CH 3 .