4358-64-9Relevant academic research and scientific papers
Silicate complexes of sugars in aqueous solution
Lambert, Joseph B.,Lu, Gang,Singer, Stephanie R.,Kolb, Vera M.
, p. 9611 - 9625 (2004)
Certain sugars react readily with basic silicic acid to form soluble 2/1 (sugar/silicic acid) silicate complexes. Failure of monohydroxy compounds to give soluble products under these conditions indicates that the sugar silicates are chelates: five-membered diolato rings. Only furanose forms react. Pyranose sugars are stable under these conditions. Because all glycosides fail to react with silicic acid under these conditions, reaction appears to involve the anomeric position (C1 in aldoses, C2 in ketoses), which has a more acidic hydroxy group. Reaction is completed only when the anomeric hydroxy group is cis to an adjacent hydroxy group. The appropriate furanose form must have sufficient natural abundance and solubility to provide an observable product, as measured by 29Si and 13C NMR spectroscopy. These structural and practical constraints rationalize the successful reaction of the monosaccharides ribose, xylose, lyxose, talose, psicose, fructose, sorbose, and tagatose and the disaccharides lactulose, maltulose, and palatinose. Glucose, mannose, galactose, and sucrose, among others, failed to form complexes. This high selectivity for formation of sugar silicates may have ramifications in prebiotic chemistry.
Dehydration of erythritol in high-temperature carbonated water
Taniguchi, Kenkichi,Nanao, Hidetaka,Sato,Yamaguchi, Aritomo,Shirai, Masayuki
, (2019)
Intramolecular dehydration of erythritol to 1,4-anhydroerythritol proceeded in liquid water at 573 K. The initial formation rate and final yield of 1,4-anhydroerythritol were 0.50 mmol h?1 and 71%, respectively. Addition of carbon dioxide up to the pressure of 17.7 and 24.8 MPa to water solvent at 573 K, the initial product formation rates dramatically increased to 1.45 and 2.10 mmol h?1, respectively; however, the final yields were almost the same as 73 and 71%, respectively. These results showed that the protons derived from carbonic acid catalyzed the intramolecular dehydration and the concentration of proton increased with an increase in the carbon dioxide pressure introduced.
A practical and scaleable preparation of 1,4-anhydroerythritol
Childers, Karla G.,Dreher, Spencer D.,Lee, Jaemoon,Williams, J. Michael
, p. 934 - 936 (2006)
A practical and efficient kilogram-scale preparation of 1,4-anhydroerythritol from meso-erythritol is described. A novel silica gel and sodium bicarbonate slurry/filtration protocol is utilized to purify the product, giving commercial-grade material in 60-65% yield.
Hydrido-bis(meso-oxolanylen-3,4-dioxy)-λ5-phosphane
Betz, Richard,Kluefers, Peter
, p. 1615 - 1629 (2008)
The symmetric hydrido-spiro-λ5-phosphane derived from anhydroerythritol (meso-oxolane-3,4-diol, AnEryt), HP(AnErytH- 2)2(3), was prepared by two different synthetic protocols. One route involves a three step synthesis starting from phosphorus trichloride via 2-chloro-tetrahydro-furo[3,4- d][1,3,2]dioxaphosphole (1) and diethyl-(tetrahydro-furo[3,4-d][1,3,2] dioxaphosphol-2-yl)-amine (2) as intermediates. The first intermediate, P(AnErytH- 2)Cl (1), was isolated as a crystalline solid and its structure was determined by single crystal X-ray diffraction. 1 is the first example of a halogeno substituted phosphane derived from an aliphatic diol whose molecular structure in the solid state was determined by X-ray diffraction studies. Alternatively, the title compound can also be obtained in a one-pot procedure starting from tris(N,N-dimethylamino)phosphane. All new compounds were characterized by their physical constants (melting point, refractory index), NMR, IR, Raman, UV/VIS, mass spectrometry, as well as elemental analysis. Some spectroscopic proofs for the spiro nature of the title compound are given. Copyright Taylor & Francis Group, LLC.
METHODS AND COMPOSITIONS FOR BIORENEWABLE POLYESTERS DERIVED FROM CAMPHORIC ACID
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Paragraph 0180, (2020/08/28)
In one aspect, the disclosure relates to biorenewable polyesters and polyester copolymers derived from camphoric acid, methods of making same, and articles comprising same. The disclosed biorenewable polyesters can have a Mn of from about 5,000 Da to about 500,000 Da. Also disclosed herein is the preparation of various monomers useful in the reactions disclosed herein, e.g., cis-1,4-anhydroerythritol and bis(2-hydroxyethyl) camphorate. In various aspects, the disclosed biorenewable polyesters and polyester copolymers can be used to the production of various articles utilizing a conventional polyester or polyester copolymer, that is, to replace, in part or in whole, a conventional nonbiorenewable polyester or polyester copolymer. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.
METHOD FOR THE HYDRODEOXYGENATION OF OXYGENATED COMPOUNDS TO UNSATURATED PRODUCTS
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Page/Page column 11, (2021/01/23)
The invention relates to methods of hydrodeoxygenation of oxygenated compounds into compounds with unsaturated carbon-carbon bonds, comprising the steps of: a) providing a reaction mixture comprising, an oxygenated compound containing one or more of a hydroxyl, keto or aldehyde group, an ionic liquid, a homogeneous metal catalyst, and carbon monoxide or a carbon monoxide releasing compound, b) reacting said reaction mixture under a H2 atmosphere at acidic conditions at a temperature between 180 and 250 °C and a pressure between 10 and 200 bar.
Efficient synthesis of α-branched purine-based acyclic nucleosides: Scopes and limitations of the method
Dra?ínsky, Martin,Frydrych, Jan,Janeba, Zlatko,Slavětínská, Lenka Po?tová
, (2020/10/02)
An efficient route to acylated acyclic nucleosides containing a branched hemiaminal ether moiety is reported via three-component alkylation of N-heterocycle (purine nucleobase) with acetal (cyclic or acyclic, variously branched) and anhydride (preferentially acetic anhydride). The procedure employs cheap and easily available acetals, acetic anhydride, and trimethylsilyl trifluoromethanesulfonate (TMSOTf). The multi-component reaction is carried out in acetonitrile at room temperature for 15 min and provides moderate to high yields (up to 88%) of diverse acyclonucleosides branched at the aliphatic side chain. The procedure exhibits a broad substrate scope of N-heterocycles and acetals, and, in the case of purine derivatives, also excellent regioselectivity, giving almost exclusively N-9 isomers.
A versatile biobased continuous flow strategy for the production of 3-butene-1,2-diol and vinyl ethylene carbonate from erythritol
Tshibalonza, Nelly Ntumba,Gérardy, Romaric,Alsafra, Zouheir,Eppe, Gauthier,Monbaliu, Jean-Christophe M.
supporting information, p. 5147 - 5157 (2018/11/26)
A versatile, tunable and robust continuous flow procedure for the deoxydehydration (DODH) of biobased erythritol toward 3-butene-1,2-diol is described. The procedure relies on specific assets of multistep continuous flow processing. Detailed mechanistic and computational studies on erythritol show that either 3-butene-1,2-diol or butadiene are obtained in high selectivity and yield on demand, as a function of the DODH reagent/substrate ratio and of the process parameters. Short reaction times (1-15 min) at high temperature (225-275 °C) and moderate pressure are reported. 3-Butene-1,2-diol is then further converted downstream into its corresponding carbonate, i.e. 4-vinyl-1,3-dioxolan-2-one (vinyl ethylene carbonate), an important industrial building block. The carbonation step uses a supported organocatalyst, and could be directly concatenated to the first DODH step. This unprecedented procedure also relies on a unique combination of on- and off-line analytical protocols for reaction monitoring and product quantification, and offers a biobased strategy toward important industrial building blocks otherwise petrosourced.
A strategy of ketalization for the catalytic selective dehydration of biomass-based polyols over H-beta zeolite
Che, Penghua,Lu, Fang,Si, Xiaoqin,Ma, Hong,Nie, Xin,Xu, Jie
supporting information, p. 634 - 640 (2018/02/14)
Biomass contains plentiful hydroxyl groups that lead to an oxygen-rich structure compared to petroleum-based chemicals. Dehydration is the most energy-efficient technique to remove oxygen; however, multiple similar vicinal hydroxyl groups in sugar alcohols impose significant challenges for their selective dehydration. Here, we present a novel strategy to control the etherification site in sugar alcohols by the ketalization of the vicinal-diol group for the highly selective formation of tetrahydrofuran derivatives. A ketone firstly reacts with terminal vicinal hydroxyl groups to form the 1,3-dioxolane structure. This structure of the constrained 1,3-dioxolane ring would improve the accessibility of reactive groups to facilitate intramolecular etherification. As a better leaving group than water, the ketone can also promote intramolecular etherification. Consequently, a range of tetrahydrofuran derivatives are produced in excellent yields with the H-beta zeolite catalyst under mild reaction conditions. This strategy opens up new opportunities for the efficient upgrading of biomass via the modification or protection of hydroxyl groups.
Selective C?O Hydrogenolysis of Erythritol over Supported Rh-ReOx Catalysts in the Aqueous Phase
Said, Achraf,Da Silva Perez, Denilson,Perret, Noémie,Pinel, Catherine,Besson, Michèle
, p. 2768 - 2783 (2017/07/28)
Bimetallic Rh-ReOx (Re/Rh molar ratio 0.4–0.5) catalysts supported on TiO2 and ZrO2 were prepared by the successive impregnation of dried and calcined unreduced supported Rh catalysts. Their catalytic performances were evaluated in the hydrogenolysis of erythritol to butanetriols (BTO) and butanediols (BDO) in aqueous solution at 150–240 °C under 30–120 bar H2. The activity depended on the nature of the support, and the highest selectivity to BTO and BDO at 80 % conversion was 37 and 29 %, respectively, in the presence of 3.7 wt %Rh-3.5 wt %ReOx/ZrO2 at 200 °C under 120 bar. The characterization of the catalysts by CO chemisorption, TEM with energy-dispersive X-ray spectroscopy, thermogravimetric analysis with MS, and X-ray photoelectron spectroscopy suggests a different distribution and reducibility of Re species over the supported Rh nanoparticles, which depends on the support.
