89825-36-5

Upstream product

• 50-70-4 D-sorbitol 
• 9004-34-6 cellulose 
• 50-70-4 sorbitol 
• 641-74-7 1,4:3,6-dianhydro-D-mannitol 
• 652-67-5 Isosorbide 
• 3014-56-0 (3S,3aR,6S,6aR)-6-(benzoyloxy)hexahydrofuro[3,2-b]furan-3-yl benzoate 
• 67-56-1 methanol 
• 2914-23-0 barium methoxide 
• 54522-28-0 1,4:3,6-dianhydro-2,5-di-O-p-tosyl-D-iditol 
• 470-15-5 α-L-sorbopyranose 
• 488-45-9 L-iditol 
• 7664-93-9 sulfuric acid 
• 54522-28-0 (3R,3aS,6R,6aS)-hexahydrofuro[3,2-b]furan-3,6-diyl bis(4-methylbenzenesulfonate) 
• 616-38-6 carbonic acid dimethyl ester 

Downstream Products

• 196812-16-5 1,6-dichloro-1,6-dideoxy-mannitol 
• 1384071-73-1 isosorbide bis(diphenyl phosphate) 
• 104-80-3 tetrahydrofuran-2,5-dimethanol 
• 629-11-8 1,6-hexanediol 
• 928-40-5 hexane-1,5-diol 
• 100-72-1 Tetrahydropyran-2-methanol 
• 3014-56-0 (3S,3aR,6S,6aR)-6-(benzoyloxy)hexahydrofuro[3,2-b]furan-3-yl benzoate 
• 24808-19-3 (3S,3aS,6S,6aS)-6-[(methylsulfonyl)oxy]hexahydrofuro[3,2-b]furan-3-yl methanesulfonate 
• 54522-28-0 1,4:3,6-dianhydro-2,5-di-O-p-tosyl-D-iditol 
• 103617-84-1 2-O-allyl-1,4:3,6-dianhydro-L-iditol 
• 6338-34-7 (3S,3aR,6S,6aR)-3,6-Bis-allyloxy-hexahydro-furo[3,2-b]furan 
• 1201908-67-9 (3S,3aS,6S,6aR)-6-hydroxyhexahydrofuro[3,2-b]furan-3-yl 4-methylbenzenesulfonate 

Relevant academic research and scientific papers

One-Pot Preparation of Dimethyl Isosorbide from d-Sorbitol via Dimethyl Carbonate Chemistry

Direct synthesis of dimethyl isosorbide (DMI) from d-sorbitol via dimethyl carbonate (DMC) chemistry is herein first reported. High yield of DMI was achieved using the nitrogen superbase 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst and performing the reaction in a stainless steel autoclave by increasing the temperature from 90 to 200 °C. In this procedure, DMC features its full capacity acting in the different steps of the process as carboxymethylating, leaving-group (cyclization), and methylating agent; DMC is also employed as the reaction media.

Direct Amination of Isohexides via Borrowing Hydrogen Methodology: Regio- and Stereoselective Issues

The regio and diastereoselective direct mono or diamination of bio-based isohexides (isosorbide and isomannide) has been developed through borrowing hydrogen (BH) methodology using a cooperative catalysis between an iridium complex and a Br?nsted acid. The access to chiral amino-alcohol (NH2-OH) and diamine (NH2-NH2), interesting optically pure bio-based monomers, was also proposed using BH strategy as a sustainable route for their obtention.

Unravelling the Mechanism of the Ru/C-Catalysed Isohexide and Ether Isomerization by Hydrogen Isotope Exchange

In this article we show that the catalytic isomerization of isohexide sugar alcohols as well as their respective ethers can occur by a hydride-based mechanism rather than a dehydrogenation/re-hydrogenation. C?H bonds in α-position to hydroxy and ether groups are activated using Ru/C as solid catalyst at temperatures as high as 160 °C and above. Hydrogen isotope exchange experiments proved that a full hydride exchange and isomerization is possible for isohexides but unexpectedly also for their methyl ethers. This is of great importance as it proves the co-existence of the both mechanisms for reactions that were so far assumed to occur solely by a dehydrogenation/re-hydrogenation. Hence, this co-existence should be taken into account for kinetic investigations of such reaction systems especially in the conversion of biomass-based chemicals under hydrogenation conditions. (Figure presented.).

Is water a suitable solvent for the catalytic amination of alcohols?

The catalytic conversion of biomass and biogenic platform chemicals typically requires the use of solvents. Water is present already in the raw materials and in most cases a suitable solvent for the typically highly polar substrates. Hence, the development of novel catalytic routes for further processing would profit from the optimization of the reaction conditions in the aqueous phase mainly for energetic reasons by avoiding the initial water separation. Herein, we report the amination of biogenic alcohols in aqueous solutions using solid Ru-based catalysts and ammonia as a reactant. The influence of different support materials and bimetallic catalysts is investigated for the amination of isomannide as a biogenic diol. Most importantly, the transferability of the reaction conditions to various other primary and secondary alcohols is successfully proved. Hence, water appears to be a suitable solvent for the sustainable production of biogenic amines and offers great potential for further process development.

ISOIDIDE MANUFACTURE AND PURIFICATION

Methods are provided for the conversion of isosorbide to isoidide, wherein the isosorbide contains sorbitan impurities. The impurities in the isosorbide subjected to epimerization are converted to hydrodeoxygenation products. A method for synthesizing isoidide, comprising, providing an isosorbide containing one or more sorbitans; and, epimerizing the isosorbide to form an epimerization product comprising isoidide and hydrodeoxygenation products.

Aqueous-phase hydrogenation and hydrodeoxygenation of biomass-derived oxygenates with bimetallic catalysts

The reaction rate on a per site basis for aqueous-phase hydrogenation (APH) of propanal, xylose, and furfural was measured over various alumina-supported bimetallic catalysts (Pd-Ni, Pd-Co, Pd-Fe, Ru-Ni, Ru-Co, Ru-Fe, Pt-Ni, Pt-Co, and Pt-Fe) using a high-throughput reactor (HTR). The results in this paper demonstrate that the activity of bimetallic catalysts for hydrogenation of a carbonyl group can be 110 times higher than monometallic catalysts. The addition of Fe to a Pd catalyst increased the activity for hydrogenation of propanal, xylose, and furfural. The Pd1Fe3 catalyst had the highest reaction rate for APH of propanal among all catalysts tested in the HTR. The addition of Fe to the Pd catalyst increased the reaction rate for xylose hydrogenation by a factor of 51, compared to the monometallic Pd catalyst. However, no bimetallic catalyst tested in this study was more active than the monometallic Ru catalyst for hydrogenation of xylose. The Pd1Fe 3 catalyst had the highest reaction rate for APH of furfural, which was 9 times higher than the rate of the Pd catalyst. The Pd1Fe 3/Zr-P, a bimetallic bifunctional catalyst, was 14 times more active on a per site basis than a Pd/Zr-P catalyst for aqueous-phase hydrodeoxygenation (HDO) of sorbitol in a continuous flow reactor. The addition of Fe to the Pd catalyst increased the rate of C-C cleavage reactions and promoted the conversion of sorbitan and isosorbide in HDO of sorbitol. Pd1Fe 3/Zr-P also had a higher yield of gasoline-range products than the Pd/Zr-P catalyst.

Sustainable polyacetals from isohexides

A single step synthetic protocol to access a small family of renewable diacetals was established. The resultant chiral diacetals are valuable building blocks in pharmaceuticals and materials science. To demonstrate their synthetic competence, isohexide-diacetals (2a-c) were subjected to acetal metathesis polymerization and the corresponding polymers (poly2a-c) were isolated as white solids with molecular weights in the range 3200-27 600 (g mol-1). The semi-crystalline polymers displayed glass transition temperatures between 38-65 °C and melting temperatures in the range 103-156 °C. The isohexide derived polyacetals are stable under practical washing and rinsing conditions but degrade in slightly acidic media. This journal is the Partner Organisations 2014.

METHOD FOR PREPARING TRIOLS AND DIOLS FROM BIOMASS-DERIVED REACTANTS

A method to make triols and diols is described. The method includes the steps of performing an aqueous-phase hydrodeoxygenation reaction on a feedstock containing a biomass-derived reactant in aqueous solution. The feedstock is contacted with a heterogeneous metal-containing bifunctional catalyst or a combination of two or more heterogeneous metal-containing catalysts that catalyze cleavage of C—C and C—O bonds, for a time, temperature, pressure, and weight hourly space velocity to yield a product mix comprising triols, diols, or combinations thereof.

METHOD OF MAKING ISOIDIDE

Disclosed is a process for the preparation of isoidide from isosorbide. An aqueous solution of isosorbide is subjected to epimerization in the presence of hydrogen under the influence of a catalyst comprising ruthenium on a support, preferably a carbon support. The process of the invention can be conducted using a relatively low hydrogen pressure, and leads to a desired distribution of epimers, favoring isoidide over isomannide and isosorbide.

Direct amination of bio-alcohols using ammonia

A slightly adapted catalyst system has been successfully applied in the direct amination of primary and secondary alcohols. Moreover, the applicability to diols has been shown, giving high selectivity towards the primary diamines. It was found that the Ru/P ratio as well as the amount of ammonia used are highly important in this system, especially for higher substrate loadings. The catalyst was employed on a larger batch scale for the conversion of isomannide to the corresponding diamine. Additionally, it was shown that the catalyst is stable for at least six consecutive runs. No significant loss of activity and selectivity was observed.