Born-based cycloaddition catalysts and methods for the production of bio-based terephthalic acid, isophthalic acid and poly (ethylene terephthalate)
AssigneeBoard of Trustees of Michigan State University
InventorsJohn Wesley Frost, Peng Zhang
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Abstract
Methods for producing cycloaddition products comprising: reacting a diene with a dienophile in the presence of one or more boron-based catalysts of Formula I or Formula II are provided. In particular, the methods can be used to prepare 4-methyl-3-cyclohexene-1-carboxylic acid and 3-methyl-3-cyclohexene-1-carboxylic acid, including bio-based versions thereof. The cycloaddition products can be advantageously used in the production of terephthalic acid and isophthalic acid, and ultimately, poly(ethylene terephthalate), and bio-based versions thereof. BOBL4 Formula II
Claims20
A method for producing a cycloaddition product comprising:
- reacting a diene with a dienophile in the presence of one or more catalysts of Formula I or Formula II;
- wherein a catalyst of Formula I has the following structure:
- wherein each X, Y and Z is independently H, F, Cl, Br, I, OC(═O)R1, OR1, substituted or unsubstituted C1-6 alkyl, substituted or unsubstituted C6-12 aryl;
- wherein R1 is a substituted or unsubstituted C1-6 alkyl;
- or a substituted or unsubstituted C6-12 aryl;
- wherein at least one of X, Y and Z is Cl;
- and
- wherein the catalyst is not BCl3;
- and
- wherein a catalyst of Formula II has the following structure:
- BOBL4 Formula II
- wherein each L is independently selected from the group consisting of OC(═O)R2, substituted or unsubstituted C6-12 aryl, substituted or unsubstituted C1-6 alkyl, substituted or unsubstituted C5-12 cycloalkyl;
- substituted or unsubstituted C1-6 alkylsulfonate;
- substituted or unsubstituted C6-12 arylsulfonate, and substituted or unsubstituted C5-12 heteroaryl;
- and
- wherein R2 is a substituted or unsubstituted C1-6 alkyl;
- or a substituted or unsubstituted C6-12 aryl;
- wherein the dienophile comprises a —CH═CHC(O)OH group.
A method for producing 4-methyl-3-cyclohexene-1-carboxylic acid, comprising reacting isoprene with acrylic acid in the presence of one or more catalysts of Formula I or Formula II to produce 4-methyl-3-cyclohexene-1-carboxylic acid;
- wherein a catalyst of Formula I has the following structure:
- wherein each X, Y and Z is independently H, F, Cl, Br, I, OC(═O)R1, OR1, substituted or unsubstituted C1-6 alkyl, substituted or unsubstituted C6-12 aryl;
- wherein R1 is a substituted or unsubstituted C1-6 alkyl;
- or a substituted or unsubstituted C6-12 aryl;
- and
- wherein at least one of X, Y and Z is Cl;
- and
- wherein the catalyst is not BCl3;
- and
- wherein a catalyst of Formula II has the following structure:
- BOBL4 Formula II
- wherein each L is independently selected from the group consisting of OC(═O)R2, substituted or unsubstituted C6-12 aryl, substituted or unsubstituted C1-6 alkyl, substituted or unsubstituted C5-12 cycloalkyl;
- substituted or unsubstituted C1-6 alkylsulfonate;
- substituted or unsubstituted C6-12 arylsulfonate, and substituted or unsubstituted C5-12 heteroaryl;
- and
- wherein R2 is a substituted or unsubstituted C1-6 alkyl;
- or a substituted or unsubstituted C6-12 aryl.
A method for producing terephthalic acid, isophthalic acid or a mixture thereof, comprising:
- (a) reacting isoprene with acrylic acid in the presence of one or more catalysts of Formula I or Formula II to form 4-methyl-3-cyclohexene-1-carboxylic acid, 3-methyl-3-cyclohexene-1-carboxylic acid, or a mixtures thereof;
- (b) performing an aromatization reaction on the 4-methyl-3-cyclohexene-1-carboxylic acid, 3-methyl-3-cyclohexene-1-carboxylic acid, or a mixtures thereof to form a second product selected from the group consisting of para-toluic acid, meta-toluic acid, and mixtures thereof;
- and
- (c) performing an oxidation reaction on the second product to form terephthalic acid, isophthalic acid, or mixtures thereof;
- wherein a catalyst of Formula I has the following structure:
- wherein each X, Y and Z is independently H, F, Cl, Br, I, OC(═O)R1, OR1, substituted or unsubstituted C1-6 alkyl, substituted or unsubstituted C6-12 aryl;
- wherein R1 is a substituted or unsubstituted C1-6 alkyl;
- or a substituted or unsubstituted C6-12 aryl;
- wherein at least one of X, Y and Z is Cl;
- and
- wherein the catalyst is not BCl3;
- and
- wherein a catalyst of Formula II has the following structure:
- BOBL4 Formula II
- wherein each L is independently selected from the group consisting of OC(═O)R2, substituted or unsubstituted C6-12 aryl, substituted or unsubstituted C1-6 alkyl, substituted or unsubstituted C5-12 cycloalkyl;
- substituted or unsubstituted C1-6 alkylsulfonate;
- substituted or unsubstituted C6-12 arylsulfonate, and substituted or unsubstituted C5-12 heteroaryl;
- and
- wherein R2 is a substituted or unsubstituted C1-6 alkyl;
- or a substituted or unsubstituted C6-12 aryl.
Dependencies are inferred from the claim text.