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Synthesis of the perdeuterated cellulose solvents N-methylmorpholine N-oxide (NMMO-d11 and NMMO-15N-d11), N,N-dimethylacetamide (DMAc-d9 and DMAc-15N-d9), 1-ethyl-3-methylimidazolium acetate (EMIM-OAc-d14) and 1-butyl-3-methylimidazolium acetate (BMIM-OAc-d18)

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Abstract

The syntheses of several perdeuterated substances—some of them isotopically labeled (15N) in addition—are described, which act as direct solvents of cellulose either on their own, such as N-methylmorpholine N-oxide (NMMO), 1-butyl-3-methylimidazolium acetate (BMIM-OAc), or 1-ethyl-3-methylimidazolium acetate (EMIM-OAc), or in combination with auxiliaries, such as N,N-dimethylacetamide (DMAc—for the cellulose solvent DMAc/LiCl). NMMO-d11 (9) was obtained in an eight-step approach from non-labeled diglycolic acid (1) via diethylene glycol-d8 (4) and its bis-tosylate (5), which underwent ring closure with benzylamine to N-benzylmorpholine-d8 (6). Debenzylation, methylation and oxidation completed the synthetic sequence, which was also able to provide the 15N-labeled product (9a) by usage of 15N-benzylamine. DMAc-d9 (14) was obtained from deuterated acetic acid (10) and dimethylamine-d6–carbon dioxide complex (13) in a solvent-free gas-solid reaction with acidic alumina as the catalyst. Employing the CO2-complex of 15N-dimethylamine-d6 afforded the 15N-labeled product 15N-DMAc-d9 (14a) in a similar way. The two ionic liquids EMIM-OAc (21) and BMIM-OAc (22) were obtained from imidazole in three-step sequences starting with butylation and ethylation, respectively. The resulting 1-alkyl imidazoles were purified, and subsequently methylated according to a novel protocol using dimethylcarbonate-d6. Addition of acetic acid-d4 caused traceless degradation of the methylcarbonate anions and exchange for acetate. In all syntheses, the reaction steps were optimized with non-labeled compounds towards high yields and high reproducibility before entering the “hot runs” with deuterated and otherwise isotopically labeled material.

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Acknowledgement

The financial support by the Austrian Fonds zur Förderung der wissenschaftlichen Forschung, project P-17426 is gratefully acknowledged. The authors would like to thank Dr. Andreas Hofinger, Department of Chemistry at the University of Agricultural Sciences Vienna, for recording the NMR spectra. Furthermore, the authors are indebted to Dr. Hiroshi Kamitakahara, Graduate School of Agriculture, Kyoto University, and to Dr. Toshinari Kawada, Faculty of Agriculture, Kyoto Prefectural University, for their support during this project.

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Author notes

  1. Toshiyuki Takano

    Present address: Department of Chemistry, University of Natural Resources and Applied Life Sciences, Muthgasse 18, Vienna, 1190, Austria

  2. Yuko Yoneda

    Present address: Faculty of Agriculture, Kyoto Prefectural University, Kyoto, 606-8522, Japan

Authors and Affiliations

  1. Department of Chemistry, University of Natural Resources and Applied Life Sciences, Muthgasse 18, Vienna, 1190, Austria

    Christian Adelwöhrer, Yuko Yoneda & Thomas Rosenau

  2. Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan

    Toshiyuki Takano & Fumiaki Nakatsubo

Authors
  1. Christian Adelwöhrer
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  2. Yuko Yoneda
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  3. Toshiyuki Takano
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  4. Fumiaki Nakatsubo
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  5. Thomas Rosenau
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Corresponding author

Correspondence to Thomas Rosenau.

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Adelwöhrer, C., Yoneda, Y., Takano, T. et al. Synthesis of the perdeuterated cellulose solvents N-methylmorpholine N-oxide (NMMO-d11 and NMMO-15N-d11), N,N-dimethylacetamide (DMAc-d9 and DMAc-15N-d9), 1-ethyl-3-methylimidazolium acetate (EMIM-OAc-d14) and 1-butyl-3-methylimidazolium acetate (BMIM-OAc-d18). Cellulose 16, 139–150 (2009). https://doi.org/10.1007/s10570-008-9241-5

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  • DOI: https://doi.org/10.1007/s10570-008-9241-5

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