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The neighboring effect of isosorbide and its epimers in their reactions with dimethyl carbonate

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      Abstract

      The reactions of isosorbide and its epimers, isomannide and isoidide, with dimethyl carbonate have been herein investigated as easy access to bio-based products by a free-halogen chemistry approach. Isosorbide and its epimers show a different reactivity in bimolecular nucleophilic substitution with dimethyl carbonate (DMC). Carboxymethylation reaction was carried out in the presence of DMC and a weak base resulting in the high-yielding synthesis of dicarboxymethyl derivatives. Isomannide was the most reactive anydro sugar due to the less sterically hindered exo position of the OH groups. On the other hand, methylation of isosorbide and its epimers, conducted in the presence of a strong base and DMC, showed the higher reactivity of the endo hydroxyl group, isoidide being the most reactive epimer. This result has been ascribed to the neighboring effect due to the combination of the oxygen in β-position and the intramolecular hydrogen bond within the anhydro sugar structure. Methylation reactions were also conducted in autoclave at high temperature with the amphoteric catalyst hydrotalcite using DMC as reagent and solvent. In this case, the reactivity of the epimers resulted quite differently with isosorbide being the most reactive reagent possibly as a result of the structure of hydrotalcite comprising of both acidic and basic sites. The neighboring effect was observed with good evidence in these methylation reactions.

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            Author and article information

            Affiliations
            [1 ]Dipartimento Scienze Ambientali, Informatica e Statistica, Università Ca' Foscari di Venezia, Dorsoduro 2137, 30123, Venice, Italy
            Author notes
            [* ]Corresponding author's e-mail address: tundop@ 123456unive.it
            Contributors
            Journal
            SOR-CHEM
            ScienceOpen Research
            ScienceOpen
            2199-1006
            20 October 2014
            : 0 (ID: febec666-00fe-4463-9a7b-91cc0ee0bcab )
            : 0
            : 1-11
            1952:XE
            10.14293/S2199-1006.1.SORCHEM.AB3R7E.v1
            © 2014 F. Aricò et al.
            Counts
            Figures: 8, Tables: 6, References: 65, Pages: 11
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