# US 8,541,615 B2 · Method for producing biphenyltetracarboxylic acid tetraester > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,541,615 B2 - Document ID: US8541615B2 - Status: Granted - Kind: B2 - Application number: 13/057,600 - Filed: 2009-08-06 - Published: 2011-06-09 - Granted: 2013-09-24 - Earliest claimed: 2008-08-06 - Assignees: Ube Industries, Ltd. - Applicants: Masayuki Nishio; Hiroaki Imajima; Takato Nakamura; Yoshihiro Yamauchi - Inventors: Masayuki Nishio; Hiroaki Imajima; Takato Nakamura; Yoshihiro Yamauchi - Web page: https://patentgrep.com/patent/US8541615B2 ## CPC - C07C 67/343: by increase in the number of carbon atoms - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract Disclosed is a method for producing a biphenyltetracarboxylic acid ester by oxidative coupling a phthalic acid ester by using a catalyst comprising at least a palladium salt, a copper salt and a β-dicarbonyl compound in the presence of a molecular oxygen, wherein the β-dicarbonyl compound is supplied into a reaction mixture liquid intermittently at an interval of less than 30 minutes, or continuously. This method allows, in particular, the selective and economical production of an asymmetric biphenyltetracarboxylic acid tetraester such as 2,3,3′,4′-biphenyltetracarboxylic acid tetraester. ## Claims ### Claim 1 A method for producing a biphenyltetracarboxylic acid tetraester comprising oxidatively coupling a phthalic acid diester with a catalyst comprising at least a palladium salt, a copper salt and a β-dicarbonyl compound in the presence of molecular oxygen, wherein the β-dicarbonyl compound is supplied into a reaction mixture liquid intermittently at an interval of less than 30 minutes, or continuously at a temperature of the reaction mixture liquid not lower than 130° C. ### Claim 2 (depends on 1) A method for producing a biphenyltetracarboxylic acid tetraester according to claim 1, wherein 2,3,3′,4′-biphenyltetracarboxylic acid tetraester is produced as a product. ### Claim 3 (depends on 1) A method for producing a biphenyltetracarboxylic acid tetraester according to claim 1, wherein a supplied amount of the β-dicarbonyl compound is 0.1 to 50-fold moles per hour relative to one mole of the palladium salt. ### Claim 4 (depends on 1) A method for producing a biphenyltetracarboxylic acid tetraester according to claim 1, wherein the β-dicarbonyl compound is denoted by a chemical formula (1), and in which a proportion of an enol form is higher than 80% at 26° C. in a solution state at a concentration of 0.1 mol/L in dimethyl phthalate ester, in which Ra, Rb are each independently an alkyl group. ### Claim 5 (depends on 1) A method for producing a biphenyltetracarboxylic acid tetraester according to claim 1, wherein the β-dicarbonyl compound is selected from the group consisting of 2,2,6,6-tetramethyl-3,5-heptanedione, 2,6-dimethyl-3,5-heptanedione, 2,8-dimethyl-4,6-nonanedione, 2-methyl-4,6-undecanedione, 2-methyl-4,6-nonanedione, 5,5-dimethyl-2,4-hexanedione, 2,2-dimethyl-3,5-heptanedione, and 5-methyl-2,4-heptanedione. ### Claim 6 (depends on 1) A method for producing a biphenyltetracarboxylic acid tetraester according to claim 1, wherein a ratio of the copper salt to the palladium salt {copper salt (mole number)/palladium salt (mole number)} is in a range of 1 to 10. ### Claim 7 (depends on 1) A method for producing a biphenyltetracarboxylic acid tetraester according to claim 1, wherein a TON represented by {product (mole number)/catalyst palladium (mole number)} is not less than 180. ### Claim 8 A method for producing a biphenyltetracarboxylic acid tetraester comprising oxidatively coupling a phthalic acid diester with a catalyst comprising at least a palladium salt, a copper salt and a β-dicarbonyl compound in the presence of molecular oxygen, wherein the β-dicarbonyl compound is supplied into a reaction mixture liquid intermittently or continuously at a temperature of the reaction mixture liquid not lower than 130° C. ### Claim 9 A method for producing a biphenyltetracarboxylic acid tetraester comprising oxidatively coupling a phthalic acid diester with a comprising at least a palladium salt, a copper salt and a β-dicarbonyl compound in the presence of molecular oxygen, wherein the β-dicarbonyl compound is a compound denoted by a chemical formula (1), and in which a proportion of an enol form is higher than 80% at 26° C. in a solution state at a concentration of 0.1 mol/L in dimethyl phthalate ester, wherein Ra, Rb are each independently an alkyl group wherein the β-dicarbonyl compound is supplied into a reaction mixture liquid intermittently or continuously at a temperature of the reaction mixture liquid not lower than 130° C. ### Claim 10 (depends on 9) A method for producing a biphenyltetracarboxylic acid tetraester according to claim 9, wherein the β-dicarbonyl compound is selected from the group consisting of 2,2,6,6-tetramethyl-3,5-heptanedione, 2,6-dimethyl-3,5-heptanedione, 2,8-dimethyl-4,6-nonanedione, 2-methyl-4,6-undecanedione, 2-methyl-4,6-nonanedione, 5,5-dimethyl-2,4-hexanedione, 2,2-dimethyl-3,5-heptanedione, and 5-methyl-2,4-heptanedione.