Untersuchungen zur Synthese von Polyethern aus Anhydropolyolen

Thiem, Joachim; Häring, Thomas; Strietholt, Wilhelm A.

doi:10.1002/star.19890410103

Cited by 13 publications

(4 citation statements)

References 37 publications

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“…Various publications deal with the etherification of isosorbide by the Williamson ether synthesis, which uses organohalides as reactants (Scheme 3 b). [32,35] In addition to convenient substituents, such as aliphatic chains, more complex asymmetric benzamidine substituted isosorbide derivatives have been reported as enzyme inhibitors. [36] In comparison to the conventional method using a homogeneous solution and heating for several hours, a highly efficient synthesis for C 8 -alkyl and different aromatic diethers of isosorbide with reaction times of only a few minutes and yields > 90 % has been achieved by using phase-transfer catalysis with microwave heating.…”

Section: Fuels Solvents and Plasticizersmentioning

confidence: 99%

Isosorbide as a Renewable Platform chemical for Versatile Applications—Quo Vadis?

2011

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Isosorbide is a platform chemical of considerable importance for the future replacement of fossil resource-based products. Applications as monomers and building blocks for new polymers and functional materials, new organic solvents, for medical and pharmaceutical applications, and even as fuels or fuel additives are conceivable. The conversion of isosorbide to valuable derivatives by functionalization or substitution of the hydroxyl groups is difficult because of the different configurations of the 2- and 5-positions and the resulting different reactivity and steric hindrance of the two hydroxyl groups. Although a substantial amount of work has been published using exclusively the endo or exo derivatives isomannide and isoidide, respectively, as starting material, a considerable effort is still necessary to transfer and adapt these methods for the efficient conversion of isosorbide. This Minireview deals with all aspects of isosorbide chemistry, which includes its production by catalytic processes, special properties, and chemical transformations for its utilization in biogenic polymers and other applications of interest.

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Section: Fuels Solvents and Plasticizersmentioning

confidence: 99%

Isosorbide as a Renewable Platform chemical for Versatile Applications—Quo Vadis?

2011

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“…By treatment of trianhydromannitol (7) in solution (dichloromethane) with trifluoromethanesulfonic acid as catalyst under varous conditions (reaction temperature, amount of catalyst) oligomers such as oligo(oxydianhydro-2,5-sorbitoldiyl) were isolated (Tab. 1).…”

Section: Polymer Synthesismentioning

confidence: 99%

“…Using 1,4 : 2,5 : 3,6-trianhydro-~-mannitol (7), easily accesible from starch, as a model compound, the first ring-opening polymerization of a tricyclic trioxolane system could be effected to lead to a polyether, based on a bicyclic repeating unit. Particular properties expected for these polyethers may be connected with the notable thermostability of 1,4 : 3,6-dianhydro-~-sorbitol(l) b).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and ring‐opening polymerization of 1,4:2,5:3,6‐trianhydro‐D‐mannitol and structure studies by MNDO calculations

1991

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Base-catalyzed intramolecular nucleophilic substitution of various dianhydrosorbitol derivatives (2,4, or 6) led to formation of trianhydromannitol(7), a tricyclic system of three interlinked oxolane rings. By treatment with trifluoromethanesulfonic acid, ring-opening reactions were achievedto give oligomeric soluble material with a number-average degree of polymerization DP, = 5 -10. Molecular weights were determined by GPC, and by desorptive chemical ionization (DCI) with ammonia a molecular weight assignment gave information on the degree of crosslinking. A complex but consistent picture allows to explain the propagation reactions of protonated trianhydromannitols 8 and 9, and further reactions of the protonated intermediates 13-15 to result in crosslinked products 16 and 17. By semiempirical quantum chemical calculations, geometries, energies and charge distributions of 7 as well as its protonated species were obtained. This allowed comparisons with their chemical reactivity and ring-opening specificity.Syntheses of monomeric compounds were followed by TLC on silica gel foils GF,,, (Merck). Detection was done by UV and/or spraying with 10% ethanolic sulfuric acid with subsequent heating to about 300°C. For column chromatography silica gel 60 (70-230 mesh, Merck) was used, and 'H NMR (300 MHz) and I3C NMR (75,46 MHz) were elaborated on a Bruker spectrometer WM 300.The number-average molecular weight D,, was determined using a Knauer vapor pressure osmometer. Selective polymer fraction_s of poly(oxy-2,3-diethoxytetramethylene) were isolated and cleaned by GPC and their exact M,, measured by vapor pressure osmometry. These values served as a basis for the calibration curve which was used to establish the weight-average molecular weight a, by GPC. GPC was performed using the combined instruments: pump (Knauer, analytical), differential refractometer type 98,00 (Knauer), integrator (Spectra-Physics). The molecular weights were determined by use of the Winner system and the GPC software (Spectra-Physics) on a XT-PC (Epson).For mass spectra and GC/MS measurements the equipment CH-7A (Varian), MAT and MAT 8230 (Finnigan-MAT GC/MS coupling, 70 eV) were applied and desorptive chemical ionization (DCI) spectra were obtained with MAT 8230 (Finnigan-MAT) using ammonia as reactant gas. Syntheses

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“…By varying the substituents various properties of high-boiling compounds can be tailored including the boiling point as well as the polarity of the molecules by etherification of either one of the two hydroxyl groups or even both. In the last decades the etherification of isosorbide was investigated mainly using the Williamson method [17][18][19][20][21][22][23][24]. Thereby, organic halides are used as reactants.…”

Section: Introductionmentioning

confidence: 99%

Reaction network analysis and continuous production of isosorbide tert-butyl ethers

et al. 2014

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Untersuchungen zur Synthese von Polyethern aus Anhydropolyolen

Cited by 13 publications

References 37 publications

Isosorbide as a Renewable Platform chemical for Versatile Applications—Quo Vadis?

Isosorbide as a Renewable Platform chemical for Versatile Applications—Quo Vadis?

Synthesis and ring‐opening polymerization of 1,4:2,5:3,6‐trianhydro‐D‐mannitol and structure studies by MNDO calculations

Reaction network analysis and continuous production of isosorbide tert-butyl ethers

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