Abstract: Processes for the oxidation of carbohydrate dehydration products, such as furanics that can be oxidized to the bio-based monomer 2,5-furandicarboxylic acid (FDCA), are disclosed, according to which certain co-feeds, having been discovered to impart a beneficial reaction stabilizing effect, are oxidized together with the carbohydrate dehydration products. This can advantageously counteract, in whole or in part, detrimental effects of humin impurities present in oxidation feed, with such impurities having been generated as byproducts of the upstream dehydrating step. An important co-feed is para-xylene that can be co-oxidized to form the petroleum-based monomer terephthalic acid (TPA), such that co-processing can beneficially yield two valuable monomers, while improving performance, particularly in terms of reaction stability, over comparable processes in which only the first monomer is produced.

Abstract: Sugar-based mono and diesters are prepared by esterification of 2,5-furan-dicarboxylic acid (FDCA) with an alcohol in the presence of low loadings of a homogeneous organotin (IV) catalyst.

Abstract: Sugar-based mono and diesters are prepared by esterification of 2,5-furan-dicarboxylic acid (FDCA) with an alcohol in the presence of low loadings of a homogeneous organotin (IV) catalyst.

Abstract: A method for preparing sugar-based mono and diesters is described. The process entails the esterification of 2,5-furan-dicarboxylic acid (FDCA) with an alcohol in the presence of low loadings of a homogeneous organotin (IV) catalyst.

Abstract: A method for preparing sugar-based mono and diesters is described. The process entails the esterification of 2,5-furan-dicarboxylic acid (FDCA) with an alcohol in the presence of low loadings of a homogeneous organotin (IV) catalyst.

Abstract: Disclosed herein are methods for synthesizing 1,2,5,6-hexanetetrol (HTO), 1,6 hexanediol (HDO) and other reduced polyols from C5 and C6 sugar alcohols or R glycosides. The methods include contacting the sugar alcohol or R-glycoside with a copper catalyst, most desirably a Raney copper catalyst with hydrogen for a time, temperature and pressure sufficient to form reduced polyols having 2 to 3 fewer hydoxy groups than the starting material. When the starting compound is a C6 sugar alcohol such as sorbitol or R-glycoside of a C6 sugar such as methyl glucoside, the predominant product is HTO. The same catalyst can be used to further reduce the HTO to HDO.

Abstract: A method of making a furan dicarboxylate by means of reacting 2,5-furan dicarboxylic acid (FDCA) with an alcohol or mixture of alcohols in a CO2-predominant atmosphere without the presence of any other acid catalyst is described. The reaction is conducted under conditions that correspond to either supercritical, critical or near-critical temperatures and pressures for the alcohol species and/or CO2 gas.

Abstract: A process for producing biofuels compounds directly from carboxylic acid esters recovered from a fermentation system is described. The process involves taking a fermentation broth that has been reduced to a dry powder containing free organic acids; reacting the carboxylic acid in the powder with an alcohol solvent under a CO2-containing atmosphere in substantial absence of any other acid catalyst at a reaction temperature and pressure that corresponds to supercritical, critical or near critical conditions for at least one of the alcohol or CO2 to synthesize an ester, then subjecting the ester to either hydrogenolysis or hydrogenation to form a biofuel.

Abstract: An improved process for acid-catalyzed acylation using water-tolerant Lewis acid catalysts is described. The method involves reacting a reduction products of 5-(hydroxylmethyl)-furfural (HMF), in particular either furan-2,5-dimethanol (FDM) or bis-2,5-(hydroxymethyl)-tetrahydrofuran (bHMTHFs), with an excess of an organic acid in the presence of a Lewis acid metal triflate at a temperature and time sufficient to produce esters. The conversions of the reduction products of HMF to corresponding diesters can be quantitative with certain favored Lewis acids catalysts.

Abstract: Disclosed herein are methods for synthesizing 1,2,5,6-hexanetetrol (HTO), 1,6 hexanediol (HDO) and other reduced polyols from C5 and C6 sugar alcohols or R glycosides. The methods include contacting the sugar alcohol or R-glycoside with a copper catalyst, most desirably a Raney copper catalyst with hydrogen for a time, temperature and pressure sufficient to form reduced polyols having 2 to 3 fewer hydoxy groups than the starting material. When the starting compound is a C6 sugar alcohol such as sorbitol or R-glycoside of a C6 sugar such as methyl glucoside, the predominant product is HTO. The same catalyst can be used to further reduce the HTO to HDO.

Abstract: A method for acid-catalyzed acylation of an isohexide is described. The method involves a reaction of an isohexide and an excess of carboxylic acid in the presence of a Lewis acid or a Brnsted acid catalyst. One or more Lewis acid or Brnsted acid can facilitate conversion of isohexides to their corresponding mono and diesters with a pronounced greater regio-selectivity of exo-OH over endo-OH of the isohexide in the product. Particular catalytic acid species include zirconium chloride (ZrCl4) and phosphonic acid (H3PO3), which manifest a ratio of exo:endo regioselectivity of about 5.0?3:1 and about 4.00.3:1, respectively.

Abstract: A process for preparing materials derived from sugar alcohols such that the dehydration products exhibit better accountability and improved color to water-clear or near water-white appearance is described. In particular, the process involves employing a reducing Brnsted acid (e.g., phosphonic acid) for the catalysis of sugar alcohols to their corresponding dehydrated-cyclized products.

Abstract: Sugar-derived tetrol, non-ionic amphiphilic amine-esters are prepared facilely and efficaciously in a few steps. The process is initiated by the esterification of a sugar-derived tetrol with a fatty acid chloride, then, undergoing triflate esterification followed by nucleophilic displacement of the aforementioned hydrophilic amine. Each synthetic pathway is efficient and affords modest to high yields of target amphiphiles, which are valorized as practicable surfactant surrogates to petroleum incumbents.

Abstract: The production of organic acids in low-cost, high-efficiency fermentation system makes available a new route to chemical production from biomass. A process for producing a hydrogenation product involving carboxylic acid esters recovered directly from a fermentation process is described.

Abstract: A method of preparing a glycol mono-ether or mono-acetate, or carbonate involving either one of two pathways from alkylene glycols, HMF or its reduction derivative products (i.e., FDM, bHMTHFs), is provided. In particular, according to one pathway, the alkylene glycol, HMF or FDM, bHMTHFs are reacted with a dialkyl carbonate in the presence of a deprotonating agent, in substantial absence of an extrinsic catalyst, to produce an ether, and subsequently reacting the ether with an acid base. According to the other pathway, alkylene glycols are reacted with an acetate donor in the presence of an acid, base, to generate an alkylene mono-acetate, and etherified with a carbonate in the presence of a deprotonating agent.

Abstract: A process for preparing cyclic dehydration products from sugar alcohols is described. The process involve using a mixed-acid catalyst reaction mixture containing a reducing acid, having a pKa of about 1.0-1.5, and at least a strong Brønsted acid or a Lewis acid, having a pKa?0, or both acids in a solution to dehydrate and ring close said sugar alcohol. Synergistically, the mixed-acid catalysis can produce greater amounts of the desired product at similar levels of compositional accountability than either of the component acid catalysts acting alone.

Abstract: A method of making a furan dicarboxylate by means of reacting 2,5-furan dicarboxylic acid (FDCA) with an alcohol or mixture of alcohols in a CO2-predominant atmosphere without the presence of any other acid catalyst is described. The reaction is conducted under conditions that correspond to either supercritical, critical or near-critical temperatures and pressures for the alcohol species and/or CO2 gas.

Abstract: A method of etherifying glycols or other diols by employing renewable reagents is disclosed. In particular, the method involves contacting a diol with an alkylating agent in an alcoholic solvent, catalyzed with a catalyst (carbonic acid) generated in situ (from CO2). The mono- and di-ether products can serve as valued precursors to an array of renewable surfactants, dispersants, and lubricants, among others.

Abstract: A method for preparing esters from isohexide compounds, and a means by which color bodies that may be made in situ during esterification of isohexide compounds are either prevented from forming or their amounts are minimized in the resultant product mixture are described.

Abstract: An improved process for acid-catalyzed acylation using water-tolerant Lewis acid catalysts is described. The method involves reacting a reduction products of 5-(hydroxylmethyl)-furfural (HMF), in particular either furan-2,5-dimethanol (FDM) or bis-2,5-(hydroxymethyl)-tetrahydrofuran (bHMTHFs), with an excess of an organic acid in the presence of a Lewis acid metal triflate at a temperature and time sufficient to produce esters. The conversions of the reduction products of HMF to corresponding diesters can be quantitative with certain favored Lewis acids catalysts.