Synlett 2017; 28(06): 705-706
DOI: 10.1055/s-0036-1588391
© Georg Thieme Verlag Stuttgart · New York

Improved Synthesis of Pinacol Dimethyl Ether – A Superior Solvent for Lithium–Oxygen Batteries

Elisabeth Jaskulska
Institut für Chemie, Carl von Ossietzky Universität Oldenburg, 26111 Oldenburg, Germany   Email:
Gunther Wittstock
Institut für Chemie, Carl von Ossietzky Universität Oldenburg, 26111 Oldenburg, Germany   Email:
Jens Christoffers*
Institut für Chemie, Carl von Ossietzky Universität Oldenburg, 26111 Oldenburg, Germany   Email:
› Author Affiliations
Further Information

Publication History

Received: 31 October 2016

Accepted after revision: 13 December 2016

Publication Date:
10 January 2017 (online)


Pinacol dimethyl ether (2,3-dimethoxy-2,3-dimethylbutane) was reported to be a superior solvent for lithium-oxygen batteries because of lacking α-H-atoms, thus, shutting down the major decomposition pathway in such devices. An improved Williamson ether synthesis of this solvent is reported starting from pinacol and methyl iodide. Crucial for the success of this double alkylation reaction was the choice of methyl lithium as the base.

Supporting Information

  • References and Notes

  • 1 Gröger O, Gasteiger HA, Suchsland J.-P. J. Electrochem. Soc. 2015; 162: A2605
    • 2a Ogasawara T, Debart A, Holzapfel M, Novak P, Bruce PG. J. Am. Chem. Soc. 2006; 128: 1390
    • 2b Geng D, Ding N, Hor TS. A, Chien SW, Liu Z, Wuu D, Sun X, Zong Y. Adv. Energy Mater. 2016; 6: 1502164
    • 3a Li Y, Wang X, Dong S, Chen X, Cui G. Adv. Energy Mater. 2016; 6: 1600751
    • 3b Ganapathy S, Adams BD, Stenou G, Anastasaki MS, Goubitz K, Miao X.-F, Nazar LF, Wagemaker M. J. Am. Chem. Soc. 2014; 136: 16335
    • 3c Vivek JP, Berry N, Papageorgiou G, Nichols RJ, Hardwick LJ. J. Am. Chem. Soc. 2016; 138: 3745
    • 3d Schwager P, Dongmo S, Fenske D, Wittstock G. Phys. Chem. Chem. Phys. 2016; 18: 10774
  • 4 Adelhelm P, Hartmann P, Bender CL, Busche M, Eufinger C, Janek J. Beilstein J. Nanotechnol. 2015; 6: 1016
    • 5a Freunberger SA, Chen Y, Drewett NE, Hardwick LJ, Bardé F, Bruce PG. Angew. Chem. 2011; 123: 8786 ; Angew. Chem. Int. Ed. 2011, 50, 8609
    • 5b Black R, Shyamsunder A, Adeli P, Kundu P, Murphy GK, Nazar LF. ChemSusChem 2016; 9: 1795
  • 6 Harding JR, Amanchukwu CV, Hammond PT, Shao-Horn Y. J. Phys. Chem. C 2015; 119: 6947
  • 7 Adams BD, Black R, Williams Z, Fernandes R, Cuisinier M, Berg EJ, Novak P, Murphy GK, Nazar LF. Adv. Energy Mater. 2015; 5: 1400867
  • 8 Hay BP, Zhang D, Rustad JR. Inorg. Chem. 1996; 35: 2650
  • 9 Lindner J. Monatsh. Chem. 1911; 32: 403
  • 10 Hanson SK, Baker RT, Gordon JC, Scott BL, Thorn DL. Inorg. Chem. 2010; 49: 5611
  • 11 2,3-Dimethoxy-2,3-dimethylbutane (PDE) Under exclusion of air and moisture (N2 atmosphere) and cooling (ice-water bath), a solution of MeLi (55 mL of a 3 mol/L solution in diethoxymethane, 165 mmol, 2 equiv) was added over a period of 10 min to a solution of pinacol (10.0 g, 84.6 mmol) in abs. THF (50 mL). Towards the end of this period, gas evolution is observed. The cooling bath was removed, and the mixture was stirred for further 1 h at ambient temperature. After addition of MeI (26.3 mL, 60.0 g, 422 mmol, 5 equiv) the mixture was heated to reflux (oil-bath temperature 70 °C) for 20 h. After cooling to ambient temperature, a sat. aq Na2S2O3 solution (90 mL) was added, and the mixture extracted with Et2O (3 × 90 mL). The combined organic layers were dried ­(Na2SO4) and evaporated to yield a crude material, which consists to 25% of the monoether together with 75% of the title compound (by GLC analysis). The mixture was transferred to a small distillation flask and treated with NaH (2.0 g of a 60% dispersion in mineral oil, 50 mmol). After stirring for 2 h at ambient temperature, the mixture was distilled at 50 mbar through a 10 cm Vigreux column to yield 5.80 g (39.7 mmol, 47%) of the title compound in the main fraction (bp 60 °C at 50 mbar). All spectroscopic data are in accordance with the literature.7