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Studies on DMSO-containing carbanilation mixtures: chemistry, oxidations and cellulose integrity

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Abstract

The oxidative effect of carbanilation mixtures containing dimethylsulfoxide (DMSO) was demonstrated by means of alcohol model substances in which competitive carbanilation was prevented due to steric hindrance of the hydroxyl function, rendering those compounds specific probes for oxidation effects. Dimethylsulfonium ions and derived ylide species were shown to be the actually oxidizing species according to trapping methodology using lipophilic olefins which were converted into the corresponding cyclopropane and epoxide derivatives. The experimental data were in good agreement with DFT computations carried out on the B3LYP/6-311+G(d,p) level of theory. The direct interaction of cellulose and sulfoxide solvent was proven by means of methyl-(2-naphthyl)sulfoxide (MNSO) as a model for DMSO, which caused introduction of UV-detectable methylthionaphthyl ether moieties into the cellulose, formed in Pummerer-type side reaction paralleling the chemical behavior of DMSO. A facile color test—responding to sulfoxide-derived oxidizing species—was developed to assess the suitability of carbanilation conditions with regard to cellulose oxidation and degradation. DMSO-based carbanilation systems have to be used with great caution for determination of molecular weight parameters and for similar purposes which require complete maintenance of the cellulose integrity. Cellulose oxidation/degradation by DMSO-derived intermediates upon carbanilation can be minimized but cannot be avoided completely. Thus, if cellulose integrity is an issue as it is in cellulose analytics, it is recommended to replace DMSO by solvent components of similar solution behavior but without the inherent danger of generating oxidants, such as pyridine or DMAc, whenever possible.

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Notes

  1. Cellulosic hydroxyls were present in 10-fold molar excess relative to the alcoholic probe.

  2. The oxidation is unable to convert aldehydes to carboxylic acids. The C-6 hydroxymethyl groups are thus oxidized to the aldehyde stage only, but not further to glucuronic acid moieties. Similarly, C-2 or C-3 keto groups are introduced without any further cleavage of adjacent carbon-carbon bonds (as for instance in periodate or permanganate oxidations).

  3. The structure of this compound strongly resembles the naphthoquinones isolated as trace chromophores from cellulosic fiber material, see Rosenau et al. (2004, 2005).

  4. Intrinsic reaction coordinates. This technique gives a full picture of the occurring transition states and intermediates between a starting geometry of molecules and the corresponding product geometry, provided that all elementary steps of the reaction are known.

  5. A full set of computational data can be obtained from the authors upon request.

  6. It should be noted that a precise determination of absolute thermodynamic data (enthalpies, energies, entropies) by computations is still difficult and requires application of time-consuming and computationally demanding high-accuracy methods. However, determination of the relative thermodynamic data as in the present case—comparing similar isodesmic reactions—affords very accurate results, as possible computational systematic errors are effectively cancelled out.

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Authors and Affiliations

  1. Department of Chemistry, University of Natural Resources and Applied Life Science, Muthgasse 18, 1990, Vienna, Austria

    Ute Henniges, Elisabeth Kloser, Anjan Patel, Antje Potthast, Paul Kosma & Thomas Rosenau

  2. Institute of Wood Technology Dresden gGmbH, Zellescher Weg 24, 01217, Dresden, Germany

    Martin Fischer

  3. Institute of Wood and Plant Chemistry, Dresden University of Technology, Pienner Str. 19, 01737, Tharandt, Germany

    Klaus Fischer

Authors
  1. Ute Henniges
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  2. Elisabeth Kloser
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  3. Anjan Patel
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  4. Antje Potthast
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  5. Paul Kosma
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  6. Martin Fischer
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  7. Klaus Fischer
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  8. Thomas Rosenau
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Correspondence to Thomas Rosenau.

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Henniges, U., Kloser, E., Patel, A. et al. Studies on DMSO-containing carbanilation mixtures: chemistry, oxidations and cellulose integrity. Cellulose 14, 497–511 (2007). https://doi.org/10.1007/s10570-007-9130-3

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