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Synthesis and reduction of 2-nitroalkyl polysaccharide ethers

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Author: Heeres, A. · Spoelma, F.F. · Doren, H.A. van · Gotlieb, K.F. · Bleeker, I.P. · Kellogg, R.M.
Type:article
Date:2000
Institution: Centraal Instituut voor Voedingsonderzoek TNO
Source:Carbohydrate Polymers, 1, 42, 33-43
Identifier: 86983
doi: doi:10.1016/S0144-8617(99)00123-X
Keywords: Nutrition · Addition reactions · Derivatives · Graft copolymers · Nitrogen compounds · Olefins · Polyethers · Reduction · Solutions · Suspensions (fluids) · Synthesis (chemical) · Agarose · Hydroxyethyl cellulose · Inulin · Na-polyglucuronate · Nitroalkyl polysaccharide ethers · Nitroalkylation · Polysaccharides

Abstract

Several 2-nitroalkyl polysaccharide ethers (from pullulan (1), guar (2), agarose (3), inulin (4), cellulose (5), Na-α-polyglucuronate (6) and hydroxyethyl cellulose (7)) were synthesized by reaction with 2-nitro-1-alkenes (2-nitro-1-propene and 2-nitro-1-butene) formed in situ from 2-nitroalkyl acetates. Moderate to high efficiencies are obtained in concentrated aqueous solution/suspension for addition to 1-4 and 7. Analysis of this new class of polysaccharide derivatives with the aid of labeled 2-nitropropyl-2-13C pullulan revealed that the nitrogroup is a mixture of the nitroalkane and nitronic acid tautomers. Grafting of nitroalkenes is observed and, to a lesser extent, additional reactions of the nitro group (formation of carbonyl, oxime and allyl groups) take place. Reduction of 2-nitroalkyl polysaccharide ethers with Na2S2O4 or Na2S2O4/NaBH4 leads to complex polysaccharide ethers. The products obtained are most likely mixtures of starting material, nitroso compounds, hydroxylamines, hydroxypropyl ethers and sulfamates.