Synthesis and reduction of 2-nitroalkyl polysaccharide ethers

A. Heeres, F. F. Spoelma, H. A. Van Doren, K. F. Gotlieb, R. M. Kellogg, Ido Pieter Bleeker

Research output: Contribution to journalArticleAcademicpeer-review

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 Na2S2O4or Na2S2O4/NaBH4leads to complex polysaccharide ethers. The products obtained are most likely mixtures of starting material, nitroso compounds, hydroxylamines, hydroxypropyl ethers and sulfamates.
Original languageEnglish
Pages (from-to)33-43
JournalCarbohydrate polymers
Volume42
Issue number1
DOIs
Publication statusPublished - 2000

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Ethers
Polysaccharides
Cellulose
Hydroxylamines
Nitroso Compounds
Oximes
Inulin
Alkenes
Butenes
Sepharose
Olefins
Propylene
Suspensions
Acetates
Derivatives
Acids
pullulan

Cite this

Heeres, A., Spoelma, F. F., Van Doren, H. A., Gotlieb, K. F., Kellogg, R. M., & Bleeker, I. P. (2000). Synthesis and reduction of 2-nitroalkyl polysaccharide ethers. Carbohydrate polymers, 42(1), 33-43. https://doi.org/10.1016/S0144-8617(99)00123-X
Heeres, A. ; Spoelma, F. F. ; Van Doren, H. A. ; Gotlieb, K. F. ; Kellogg, R. M. ; Bleeker, Ido Pieter. / Synthesis and reduction of 2-nitroalkyl polysaccharide ethers. In: Carbohydrate polymers. 2000 ; Vol. 42, No. 1. pp. 33-43.
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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 Na2S2O4or Na2S2O4/NaBH4leads to complex polysaccharide ethers. The products obtained are most likely mixtures of starting material, nitroso compounds, hydroxylamines, hydroxypropyl ethers and sulfamates.",
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Heeres, A, Spoelma, FF, Van Doren, HA, Gotlieb, KF, Kellogg, RM & Bleeker, IP 2000, 'Synthesis and reduction of 2-nitroalkyl polysaccharide ethers', Carbohydrate polymers, vol. 42, no. 1, pp. 33-43. https://doi.org/10.1016/S0144-8617(99)00123-X

Synthesis and reduction of 2-nitroalkyl polysaccharide ethers. / Heeres, A.; Spoelma, F. F.; Van Doren, H. A.; Gotlieb, K. F.; Kellogg, R. M.; Bleeker, Ido Pieter.

In: Carbohydrate polymers, Vol. 42, No. 1, 2000, p. 33-43.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Synthesis and reduction of 2-nitroalkyl polysaccharide ethers

AU - Heeres, A.

AU - Spoelma, F. F.

AU - Van Doren, H. A.

AU - Gotlieb, K. F.

AU - Kellogg, R. M.

AU - Bleeker, Ido Pieter

PY - 2000

Y1 - 2000

N2 - 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 Na2S2O4or Na2S2O4/NaBH4leads to complex polysaccharide ethers. The products obtained are most likely mixtures of starting material, nitroso compounds, hydroxylamines, hydroxypropyl ethers and sulfamates.

AB - 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 Na2S2O4or Na2S2O4/NaBH4leads to complex polysaccharide ethers. The products obtained are most likely mixtures of starting material, nitroso compounds, hydroxylamines, hydroxypropyl ethers and sulfamates.

U2 - 10.1016/S0144-8617(99)00123-X

DO - 10.1016/S0144-8617(99)00123-X

M3 - Article

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