Abstract: A method of making a mono-ether of an isohexide and art assemblage of novel. Song-chain isohexide mono-ethers are described. In particular, the method involves reacting an isohexide stereoisomer with a Bronsted base and an alkyl species. The resultant mono-ethers can serve as attractive antecedents or chemical scaffolds for making a derivative compound, such as various amphiphiles with potential uses as surfactants, dispersants, and lubricants, among others.

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: Amphipathic amine-esters derived from anhydropentitols are prepared through a short sequence of synthetic steps. The process is initiated by the esterification of an anhydropentitol with a fatty acid chloride or a lipase enzyme to form anhydropentitol fatty acid esters, preferably leaving at least one free hydroxyl. The free hydroxyl group(s) are then sulfonated, forming sulfonated anhydropentitol fatty acid esters. The sulfonyl moiety on the sulfonated anhydropentitol fatty acid esters are then subject to nucleophilic displacement by a hydrophilic moiety, illustrated by a primary amine such as AEE or AEEA. The synthetic pathway is efficient and affords modest to high yields of target amphiphilic compounds, which are useful at least as surfactants and plasticizer substitutes for petroleum derived compounds.

Abstract: Linear mono- and dialkyl ethers of furan-2,5-dimethanol (FDM) and/or (tetrahydrofuran-2,5-diyl)dimethanol (bHMTHF), methods for their preparation, and derivative chemical compounds thereof are described. In general, the synthesis process entails a reaction of FDM or bHMTHFs in a polar aprotic organic solvent with a permittivity (?) >8, at a temperature ranging from about ?25° C. to about 100° C., with either a) an unhindered Brønsted base with a ?pKa?15 relative to the hydroxyl groups of the FDM or bHMTHF, or b) a hindered Brønsted base having minimum pKa of about 16 and a nucleophile.

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 present disclosure is directed to methods of making non-ionic, amphiphilic surfactants from 5-hydroxymethyl-2-furfural, furan-2,5-dimethanol and bis-2,5-dihydroxymethyltetrahydrofurans and the novel compounds that are made from those methods.

Abstract: Linear mono- and dialkyl ethers of furan-2,5-dimethanol (FDM) and/or 2,5-bis(hydroxymethyl)tetrahydrofuran (bH-MTHF), methods for their preparation, and derivative chemical compounds thereof are described. In general, the synthesis process entails a reaction of FDM or bHMTHFs in a polar aprotic organic solvent having a permittivity ( )>8, at a temperature ranging from about ?25 C to about 100 C, with either a) an unhindered Brnsted base with a pKa?15 or b) a hindered Brnsted base having minimum pKa of about 16, and a nucleophile.

Abstract: A process is described for the acid-catalyzed dehydration of a sugar alcohol, wherein the catalyst comprises a water-tolerant Lewis acid. In particular embodiments, the catalyst comprises a homogeneous water-tolerant Lewis acid, especially a homogeneous Lewis acid selected from the group consisting of bismuth (III) triflate, gallium (III) triflate, scandium (III) triflate, aluminum triflate, tin (II) triflate and indium (III) triflate. Such catalysts are effective for dehydrating both of sorbitol and the 1,4-sorbitan dehydration precursor of isosorbide, and bismuth (III) triflate particularly is beneficial for dehydrating mannitol to isomannide.

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 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: 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: Dicarbamates of the reduction products of 2-hydroxymethyl-5-furfural (HMF) and a method of preparing the same are described. The method involves reacting a mixture of an isohexide and a cynate salt in a non-aqueous solvent, with a miscible acid having a pKa of about 3.7 or less. The dicarbamates of HMF-reduction products can serve as precursor materials from which various derivative compounds can be synthesized.

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 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: 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 Brønsted acid (e.g., phosphonic acid) for the catalysis of sugar alcohols to their corresponding dehydrated-cyclized products.

Abstract: A method for acid-catalyzed acylation of an isohexide is described. The method can enable direct alcohol acylation with carboxylic acids. In particular, the method involves reacting an isohexide and an excess of carboxylic acid, in the presence of a water-tolerant Lewis acid catalyst. Water-tolerant Lewis acid catalysts can furnish relatively high diester yields (e.g., ?55%-60%) at lower catalyst loads. This feature, among others, is highly desirable for cost savings, and can improve process economics.

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 Brønsted acid catalyst. One or more Lewis acid or Brønsted 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 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 monoacetate, and etherified with a carbonate in the presence of a deprotonating agent.

Abstract: A facile, straightforward method for alkylation of anhydrosugar alcohols (isohexides) using a carbonate reagent is described. The alkylation method involves: a) contacting in a solution of an isohexide with a dialkyl, diallyl, or diaryl carbonate, and the solution includes a Brønsted base; and b) producing either an alkyl ether or alkyl carbonate of the isohexide compound. The alkylation reaction is in situ, that is, performed without an extrinsic catalyst. According to the method, one can synthesize various ethers and carbonates.

Abstract: Structured, non-polar liquid oleogels comprising non-polar liquids and a derivative of an anhydrohexitol are disclosed. Processes for producing such structured, non-polar liquid oleogels are also disclosed. Also disclosed are processes for producing esters of 1,4:3,6-dianhydrohexitol.