Michigan State University

Purdue Research Foundation

Amyris, Inc.

Genencor International, Inc.

John Wesley Frost

Karen M Frost

Vu Bui

Dirk Schweitzer

Karen M Draths

Adeline Miermont

Douglas A Wicks

David R Knop

Kristi D Snell

Edward E Paschke

Peng Zhang

Laetitia Coudray

Jiantao Guo

Chad A Hansen

Timothy L Ward

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. BOBL&#x2003;&#x2003;Formula II

Born-based cycloaddition catalysts and methods for the production of bio-based terephthalic acid, isophthalic acid and poly (ethylene terephthalate)

Methods for producing bio-terephthalic acid and bio-isophthalic acid are provided. The methods comprise a cycloaddition reaction to produce bio-4-methyl-3-cyclohexene-1-carboxylic acid, and bio-3-methyl-3-cyclohexene-1-carboxylic from bio-isoprene and bio-acrylic acid. An aromatization reaction produces bio-para-toluic acid and bio-meta-toluic acid from the bio-4-methyl-3-cyclohexene-1-carboxylic acid, and bio-3-methyl-3-cyclohexene-1-carboxylic. An oxidation reaction produces the bio-terephthalic acid and iso-phthalic acid from the bio-para-toluic acid and bio-meta-toluic acid.

Synthesis of biobased and substituted terephthalic acids and isophthalic acids

Provided herein are processes for preparing caprolactam from a starting material such as one or more of the cis,cis-, cis,trans- and trans,trans-double-bond isomers of muconamide, muconic acid ester, or muconic acid. The starting material, intermediates, and caprolactam prepared therefrom can contain carbon atoms derived from biomass containing detectableC content determined according to ASTM D6866 and optionally containing aC content up to 0.0000000001% (one part per trillion). Caprolactam so prepared can be used to make various polyamides.

Process for preparing caprolactam and polyamides therefrom

The present invention provides improved process for the sulfonation of hydroxyaromatics amenable to direct isolation of the sulfonylated hydroxyaromatics in their free-acid forms. The process allows for the recyclization of sulfuric acid and minimizes waste. The starting materials are from a renewal resource, e.g., biomass, and contain detectableC up to aC content of 0.0000000001% (one part per trillion). The products made include sulfonated catechol, disulfonated pyrogallol and sulfonated protocatechuic acid.

Sulfonation of polyhydroxyaromatics

The present invention relates to the isomerization of cis,cis and/or cis,trans muconic acid or esters thereof to trans,trans muconic acid or esters thereof and to the esterification of such muconic acids.

Preparation of trans, trans muconic acid and trans, trans muconates

The present invention relates to polyesters prepared from benzene, cyclohexene and cyclohexane compounds having carboxylic acid groups at the 1 and 4, and optionally the 2, positions, such as terephthalic acid or dimethyl terephthalates, and alkylene glycols, such ethylene glycol or 1,4-butane diol. The invention also relates to processes for preparing such polyesters. The invention also relates to such polyesters derived from starting materials derived from renewable resources.

Biobased polyesters

Novel enzymes and novel enzymatic pathways for the pyruvate-based synthesis of shikimate or at least one intermediate thereto or derivative thereof, nucleic acids encoding the enzymes, cells transformed therewith, and kits containing said enzymes, cells, or nucleic acid. A KDPGal aldolase is used to perform condensation of pyruvate with D-erythrose 4-phosphate to form 3-deoxy-D-arabino-heptulosonate-7-phosphate (DAHP); a 3-dehydroquinate synthase is used to convert the DAHP to 3-dehydroquinate (DHQ); DHQ dehydratase can then convert DHQ to the key shikimate intermediate, 3-dehydroshikimate.

Methods and materials for the production of shikimic acid

The present invention relates to cyclohexanes having carboxylate derivatives at the 1 and 4, and optionally the 2, position. The invention also relates to processes for preparing such compounds wherein a portion of the starting materials utililzed is derived from renewable resources.

Cyclohexane 1,4 carboxylates

In various embodiments, the present invention can involve a method of synthesizing &#x3b1;-amino-&#x3b5;-caprolactam. The method can comprise heating a salt of L-lysine in a solvent comprising an alcohol. In other embodiments, the present invention can involve methods for synthesizing &#x3b5;-caprolactam. The methods can comprise heating a salt of L-lysine in a solvent comprising an alcohol and deaminating the reaction product. In various embodiments, the invention can include methods of converting biomass into nylon 6. The methods can comprise heating L-lysine in a solvent comprising an alcohol to produce &#x3b1;-amino-&#x3b5;caprolactam, deaminating to produce &#x3b5;-caprolactam and polymerizing into nylon 6, wherein the L-lysine is derived from the biomass. In other embodiments, the present invention can include methods of making nylon 6. The methods can comprise synthesizing &#x3b5;-caprolactam and then polymerizing, wherein the &#x3b5;-caprolactam is derived from L-lysine.

Synthesis of caprolactam from lysine

The present invention relates to novel substituted and unsubstituted terephthalic acid and carboxylate derivatives and products prepared therefrom having a significant renewable content. The invention also relates to processes for preparing substituted and unsubstituted terephthalic and carboxylate derivatives thereof wherein a portion of the starting materials utilized is derived from renewable resources. The invention also relates to novel cyclohexene based intermediates prepared in these processes and to conversion of these intermediates to substituted and unsubstituted cyclohexane-1,4-dicarboxylates and carboxylate derivatives thereof and novel forms of the resulting products having renewable content. The invention also relates to products prepared from substituted and unsubstituted terephthalic acid and carboxylate derivatives thereof derived from starting materials derived from renewable resources.

Terephthalic and trimellitic based acids and carboxylate derivatives thereof

The present invention provides methods, enzymes, and cells for the biosynthetic production of phloroglucinol from malonyl-CoA, which is ultimately obtained from simple starting materials such as glucose; also provided are methods for preparing derivatives of biosynthetic phloroglucinol, including, e.g., resorcinol.

Biosynthesis of phloroglucinol and preparation of 1,3-dihydroxybenzene therefrom

Catalytic processes for preparing caprolactam, pipecolinic acid, and their derivatives, from lysine or alpha-amino-epsilon-caprolactam starting materials, and products produced thereby. A process for preparing caprolactam or a derivative thereof, the process comprising contacting a reactant comprising lysine or alpha aminocaprolactam with a catalyst and a gas comprising hydrogen gas, in the presence of a solvent. The catalyst may be provided on a support material, such as a transition metal.

Catalytic deamination for caprolactam production

A bioengineered synthesis scheme for the production of quinic acid from a carbon source is provided. Methods of producing quinic acid from a carbon source based on the synthesis scheme as well as conversion of quinic acid to hydroquinone are also provided.

Biocatalystic synthesis of quinic acid and conversion to hydroquinone by recombinant microbes

In various embodiments, the present invention can involve a method of synthesizing &#x3b1;-amino-&#x3b5;-caprolactam. The method can comprise heating a salt of L-lysine in a solvent comprising an alcohol. In other embodiments, the present invention can involve methods for synthesizing &#x3b5;-caprolactam. The methods can comprise heating a salt of L-lysine in a solvent comprising an alcohol and deaminating the reaction product. In various embodiments, the invention can include methods of converting biomass into nylon 6. The methods can comprise heating L-lysine in a solvent comprising an alcohol to produce &#x3b1;-amino-&#x3b5;-caprolactam, deaminating to produce &#x3b5;-caprolactam and polymerizing into nylon 6, wherein the L-lysine is derived from the biomass. In other embodiments, the present invention can include methods of making nylon 6. The methods can comprise synthesizing &#x3b5;-caprolactam and then polymerizing, wherein the &#x3b5;-caprolactam is derived from L-lysine.

Enzymatic pathways for production of aminoshikimate, kanosamine, intermediates, and derivatives thereof; nucleic acid encoding and cells containing the enzymes; compositions containing aminoshikimate, kanosamine, an intermediate or derivative thereof; and use of the cells and pathways for biosynthetic production of aminoshikimate, kanosamine, intermediates, and derivatives thereof.

Growing community of inventors

Okemos, MI, United States of America

John Wesley Frost