# US 2014/0155570 A1 · Process of biologically producing terephthalic acid and derivative thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2014/0155570 A1 - Document ID: US20140155570A1 - Status: Published application - Kind: A1 - Application number: 14/091,478 - Filed: 2013-11-27 - Published: 2014-06-05 - Earliest claimed: 2012-11-30 - Assignees: Samsung Electronics Co., Ltd. - Applicants: Samsung Electronics Co., Ltd. - Inventors: Won Jae CHOI; Jin Ho AHN; Jong Won BYUN; Young Wan HA - Web page: https://patentgrep.com/patent/US20140155570A1 ## CPC - C12P 7/44: Polycarboxylic acids - C08G 63/00: Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule (polyester-amides C08G69/44; polyester-imides C08G73/16) - C08G 63/183: Terephthalic acids - C12P 7/40: containing a carboxyl group {including Peroxycarboxylic acids} - C12P 7/42: Hydroxy-carboxylic acids - C12P: FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE {(brewing of beer C12C; producing vinegar C12J; producing specific peptides or proteins C07K; producing enzymes C12N9/00; DNA or RNA concerning genetic engineering, vectors, e.g. plasmids, or their isolation, preparation or purification C12N15/00; measuring or testing processes involving enzymes or microorganisms C12Q; measuring or testing processes involving nucleic acid amplification reactions C12Q1/6844; fermentation processes to form a food composition, A21 or A23; compounds in general, see the relevant compound class, e.g. C01, C07)} - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS ## Abstract A method of biologically producing an terephthalic acid or a derivative thereof by contacting a substrate containing an aromatic carboxylic acid with a biocatalyst that adds a carboxyl group at the para-position of the aromatic carboxylic acid. ## Claims ### Claim 1 A method of biologically producing an terephthalic acid or a derivative thereof represented by Chemical Formula 1, comprising contacting a substrate containing an aromatic carboxylic acid represented by Chemical Formula 2 with a biocatalyst that adds a carboxyl group at para-position of the aromatic carboxylic acid: wherein, X and Y are independently hydrogen, hydroxy, or C1-C4 alkoxy. ### Claim 2 (depends on 1) The method of claim 1, wherein X and Y are not simultaneously hydrogen in Chemical Formula 2, and the method further comprises contacting the substrate with a biocatalyst that removes a substituent selected from the group consisting of a hydroxyl group and a C1-C4 alkoxy group located at position 3, position 5, or both of positions 3 and 5 of the benzene ring, before, simultaneously with, or after contacting with the biocatalyst that adds a carboxyl group at para-position of the aromatic carboxylic acid. ### Claim 3 (depends on 1) The method of claim 1, wherein the substrate also comprises an aromatic carboxylic acid of Chemical Formula 3 having a para-hydroxy group, and the method further comprises contacting the substrate with a biocatalyst that removes the para-hydroxy group from the aromatic carboxylic acid of Chemical Formula 3, before, simultaneously with, or after contacting with the biocatalyst that adds a carboxyl group at para-position of the aromatic carboxylic acid of Chemical Formula 2: wherein, X and Y are independently hydrogen, hydroxy, or C1-C4 alkoxy. ### Claim 4 (depends on 3) The method of claim 3, wherein X and Y are not both hydrogen in Chemical Formula 3, and the method further comprises contacting the substrate with a biocatalyst that removes a substituent selected from the group consisting of hydroxy and C1-C4 alkoxy located at position 3, position 5, or both of positions 3 and 5 of the benzene ring, before, simultaneously with, or after contacting with the biocatalyst that removes the hydroxy group at para-position. ### Claim 5 (depends on 1) The method of claim 1, wherein the biocatalyst is an enzyme, a microorganism that produces the enzyme, a lysate of the microorganism, or an extract from the lysate of the microorganism. ### Claim 6 (depends on 5) The method of claim 5, wherein the biocatalyst is a wild-type microorganism or a recombinant microorganism. ### Claim 7 (depends on 1) The method of claim 1, wherein contacting the substrate with the biocatalyst is comprises contacting the substrate with an enzyme, a microorganism containing the enzyme, a lysate of the microorganism, or an extract from the lysate of the microorganism, or by culturing the microorganism in a medium containing the substrate. ### Claim 8 (depends on 1) The method of claim 1, wherein the biocatalyst that adds a carboxyl group at the para-position of the aromatic carboxylic acid comprises at least one enzyme selected from the group consisting of aminobenzoate decarboxylase (EC 4.1.1.24), 3-Hydroxy-2-methylpyridine-4,5-dicarboxylate 4-decarboxylase (EC 4.1.1.51), 4,5-Dihydroxyphthalate decarboxylase (EC 4.1.1.55), Orsellinate decarboxylase (EC 4.1.1.58, Gallate decarboxylase (EC 4.1.1.59), 4-hydroxybenzoate decarboxylase (EC 4.1.1.61), Protocatechuate decarboxylase (EC 4.1.1.63), 3,4-dihydroxyphthalate decarboxylase (EC 4.1.1.69) phenylphosphate carboxylase (EC 4.1.1.x); a microorganism that produces at least one of the foregoing enzymes; a lysate of a microorganism containing at least one of the foregoing enzymes; or an extract from the lysate of the microorganism containing at least one of the foregoing enzymes. ### Claim 9 (depends on 3) The method of claim 3, wherein the biocatalyst that removes para-hydroxy comprises at least one enzyme selected from the group consisting of bile-acid 7-alpha-dehydroxylase (EC 1.17.99.5), 4-hydroxybenzoyl-CoA reductase (EC 1.3.7.9), 3-dehydroquinate hydro-lyase (EC 4.2.1.10), aldos-2-ulose dehydratase (EC 4.2.1.110), o-succinylbenzoate synthase (EC 4.2.1.113), 3-dehydroshikimate hydro-lyase (EC 4.2.1.118), prephenate hydro-lyase (EC 4.2.1.51), arogenate dehydratase (EC 4.2.1.91), scytalone 7,8-hydro-lyase (EC 4.2.1.94), 16a-hydroxyprogesterone hydro-lyase (EC 4.2.1.98); a microorganism that produces at least one of the foregoing enzymes; a lysate of a microorganism containing at least one of the foregoing enzymes; or an extract from the lysate of the microorganism containing at least one of the foregoing enzymes. ### Claim 10 (depends on 2) The method of claim 2, wherein the biocatalyst that removes at least one substituent selected from the group consisting of hydroxy and C1-C4 alkoxy is at least one enzyme selected from the group consisting of anthranilate synthase (EC 4.1.3.27), aminodeoxychorismate lyase (EC 4.1.3.38), chorismate lyase (EC 4.1.3.40), 3-dehydroquinate hydro-lyase (EC 4.2.1.10), 3-dehydroshikimate hydro-lyase (EC 4.2.1.118), prephenate hydro-lyase (EC 4.2.1.51), 5-041-carboxyvinyl)-3-phosphoshikimate phosphate-lyase (EC 4.2.3.5), isochorismate lyase (EC 4.2.99.21), hydroxyphenylpyruvate synthase (EC 5.4.99.5); a microorganism that produces at least one of the foregoing enzymes; a lysate of a microorganism containing at least one of the foregoing enzymes; or an extract from the lysate of the microorganism containing at least one of the foregoing enzymes. ### Claim 11 (depends on 4) The method of claim 4 wherein the biocatalyst that removes at least one substituent selected from the group consisting of hydroxy and C1-C4 alkoxy is at least one enzyme selected from the group consisting of anthranilate synthase (EC 4.1.3.27), aminodeoxychorismate lyase (EC 4.1.3.38), chorismate lyase (EC 4.1.3.40), 3-dehydroquinate hydro-lyase (EC 4.2.1.10), 3-dehydroshikimate hydro-lyase (EC 4.2.1.118), prephenate hydro-lyase (EC 4.2.1.51), 5-041-carboxyvinyl)-3-phosphoshikimate phosphate-lyase (EC 4.2.3.5), isochorismate lyase (EC 4.2.99.21), hydroxyphenylpyruvate synthase (EC 5.4.99.5); a microorganism that produces at least one of the foregoing enzymes; a lysate of a microorganism containing at least one of the foregoing enzymes; or an extract from the lysate of the microorganism containing at least one of the foregoing enzymes. ### Claim 12 (depends on 1) The method of claim 1, wherein the substrate comprises an aromatic aldehyde of Chemical Formula 4, and the method further comprises converting the aromatic aldehyde of Chemical Formula 4 to an aromatic carboxylic acid of Chemical Formula 3 by chemical oxidation or biocatalytic oxidation; and contacting the aromatic carboxylic acid of Chemical Formula 3 with a biocatalyst that removes the para-hydroxy group from the aromatic carboxylic acid of Chemical Formula 3 to provide the aromatic carboxylic acid of Chemical Formula 2: wherein, X and Y are independently hydrogen, hydroxy, or C1-C4 alkoxy. ### Claim 13 (depends on 12) The method of claim 12, wherein X and Y are not simultaneously hydrogen in Chemical Formula 4, and the method further comprises contacting the substrate with a biocatalyst that removes a substituent selected from the group consisting of hydroxy and C1-C4 alkoxy located at position 3, position 5, or both of positions 3 and 5 of the benzene ring before, simultaneously with, or after the oxidation of the aromatic aldehyde of Chemical Formula 4. ### Claim 14 (depends on 3) The method of claim 3, the compounds represented by Chemical Formula 3 and Chemical Formula 4 are derived from lignin. ### Claim 15 (depends on 12) The method of claim 12, the compounds represented by Chemical Formula 3 and Chemical Formula 4 are derived from lignin. ### Claim 16 (depends on 15) The method of claim 15, wherein the substrate containing an aromatic carboxylic acid represented by Chemical Formula 2, is obtained by: degrading lignin to give a lignin degradation product comprising an aromatic carboxylic acid having a para-hydroxy group of Chemical Formula 3; and contacting the lignin degradation product with the biocatalyst that removes a para-hydroxy group from the benzene ring of Chemical Formula 3 to provide an aromatic carboxylic acid represented by Chemical Formula 2. ### Claim 17 (depends on 16) The method of claim 16, wherein X and Y are not simultaneously hydrogen in Chemical Formula 3, and the method further comprises contacting the substrate with a biocatalyst that removes a substituent selected from the group consisting of hydroxy and C1-C4 alkoxy located at positions 3, position 5, or both of positions 3 and 5 of the benzene ring, before, simultaneously with, or after contacting with the biocatalyst that removes the para-hydroxy group. ### Claim 18 (depends on 16) The method of claim 16, further comprising converting an aromatic aldehyde represented by Chemical Formula 4 to the aromatic carboxylic acid of Chemical Formula 3 by chemical oxidation or biocatalytic oxidation, before or simultaneously with contacting with the biocatalyst that removes the para-hydroxy group. ### Claim 19 (depends on 16) The method of claim 16, wherein the degradation of lignin is carried out using at least one selected from the group consisting of pyrolysis, gasification, hydrogenolysis, acidolysis, alkaline lysis, chemical oxidation, hydrolysis under supercritical conditions, and enzymolysis. ### Claim 20 (depends on 1) A polyester produced from the terephthalic acid or derivatives thereof obtained in claim 1. ### Claim 21 A method of biologically producing a terephthalic acid or a derivative thereof represented by Chemical Formula 1, the method comprising contacting a substrate containing an aromatic carboxylic acid of Chemical Formula 3 having a para-hydroxy group with a biocatalyst that removes the para-hydroxy group to provide an aromatic carboxylic acid of Chemical Formula 2; and contacting the aromatic carboxylic acid of Chemical Formula 2 with a biocatalyst that adds a carboxyl group at para-position of the aromatic carboxylic acid to provide a terephthalic acid or a derivative thereof represented by Chemical Formula 1: wherein X and Y are independently hydrogen, hydroxy, or C1-C4 alkoxy. ### Claim 22 A method of biologically producing a terephthalic acid or a derivative thereof represented by Chemical Formula 1, the method comprising providing a substrate comprising an aromatic aldehyde of Chemical Formula 4; converting the aromatic aldehyde of Chemical Formula 4 to an aromatic carboxylic acid of Chemical Formula 3 by chemical oxidation or biocatalytic oxidation; contacting the aromatic carboxylic acid of Chemical Formula 3 having a para-hydroxy group with a biocatalyst that removes the para-hydroxy group to provide an aromatic carboxylic acid of Chemical Formula 2; and contacting the aromatic carboxylic acid of Chemical Formula 2 with a biocatalyst that adds a carboxyl group at para-position of the aromatic carboxylic acid to provide a terephthalic acid or a derivative thereof represented by Chemical Formula 1: wherein X and Y are independently hydrogen, hydroxy, or C1-C4 alkoxy.