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2,4′:2′,4 Dianhydride of 3-keto-glucoside, a precursor to chromophores of aged, yellow cellulose, and its weak interactions

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Abstract

Studies of cellulose aging and yellowing that involved a 1,4-dimethyl 3-keto β-d-glucoside (compound 1) model of oxidized cellulose led to a hemi-hydrated crystal of title compound 2 (1,6-dihydroxy-3,8-bis-hydoxymethyl-5,10-dimethoxy-4,9-dioxa-tricyclo [5,3,1,1,2,6] dodecane-11,12-dione). The same compound 2 was isolated in low yield from “real-world” oxidized and aged cellulosic pulp. Formation of compound 2 implies cellulose chain cleavage and, unexpectedly, cross-linking during aging. X-ray diffraction revealed an encompassing 10-membered ring whose two carbonyl group bridges define two eight-membered rings and three six-membered rings. The central six-membered ring is antecedent to 2,5-dihydroxy-1,4-benzoquinone (compound 3), a potent and nearly ubiquitous chromophore in aged cellulose; the outer rings derive from the keto-glucosides and have 4C1 and 1C4 shapes with gt and rare tg O-6 positions. Weak trans-annular interactions between >C=O carbon and ring oxygen atoms were confirmed with Atoms-in-Molecules theory. That theory was also used to analyze a questionable cyclic hydrogen bond and bonds between adjacent O–H and carbonyl oxygens.

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Authors and Affiliations

  1. Division of Chemistry of Renewable Resources, Department of Chemistry, University of Natural Resources and Life Sciences (BOKU), Muthgasse 18, 1190, Vienna, Austria

    Thomas Rosenau, Antje Potthast, Takashi Hosoya & Ute Henniges

  2. Division of Organic Chemistry, Department of Chemistry, University of Natural Resources and Life Sciences (BOKU), Muthgasse 18, 1190, Vienna, Austria

    Paul Kosma

  3. Department of Chemistry, Vienna University of Technology, Getreidemarkt 9, 1060, Vienna, Austria

    Kurt Mereiter

  4. U.S. Department of Agriculture, Southern Regional Research Center, New Orleans, LA, 70124, USA

    Alfred D. French

Authors
  1. Thomas Rosenau
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  2. Antje Potthast
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  3. Paul Kosma
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  4. Takashi Hosoya
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  5. Ute Henniges
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  6. Kurt Mereiter
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  7. Alfred D. French
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Corresponding authors

Correspondence to Thomas Rosenau or Alfred D. French.

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Rosenau, T., Potthast, A., Kosma, P. et al. 2,4′:2′,4 Dianhydride of 3-keto-glucoside, a precursor to chromophores of aged, yellow cellulose, and its weak interactions. Cellulose 24, 1227–1234 (2017). https://doi.org/10.1007/s10570-017-1198-9

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  • DOI: https://doi.org/10.1007/s10570-017-1198-9

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