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Practical and Efficient Large-Scale Preparation of Dimethyldioxirane

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Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9/163, 1060 Vienna, Austria
*E-mail: [email protected]. Telephone: 0043-1-58801-163721. Fax: 0043-1-58801-16399.
Cite this: Org. Process Res. Dev. 2013, 17, 2, 313–316
Publication Date (Web):January 14, 2013
https://doi.org/10.1021/op300338q
Copyright © 2013 American Chemical Society
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    Abstract

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    An improved procedure for large-scale and also commercially viable preparation of dimethyldioxirane (DMDO), a common and widely used oxidation agent in organic synthesis, was developed using a conventional laboratory plant. All reaction parameters were optimized, and the stability of a freshly prepared solution of DMDO in acetone was monitored over an extended period of time to ensure long-term use after preparation, transport, and storage. This discontinuous approach, suitable for batch processing, is of interest basically to research laboratories but also to suppliers in the research and fine chemicals market.

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    47. Douglass F. Taber*, Peter W. DeMatteo, Rasha A. Hassan. Simplified Preparation of Dimethyldioxirane ( DMDO ). 2014, 350-357. https://doi.org/10.1002/0471264229.os090.33
    48. Nina Toelle, Harald Weinstabl, Tanja Gaich, Johann Mulzer. Lichtinduzierte Totalsynthese von 17‐Desoxyprovidencin. Angewandte Chemie 2014, 126 (15) , 3940-3943. https://doi.org/10.1002/ange.201400617
    49. Nina Toelle, Harald Weinstabl, Tanja Gaich, Johann Mulzer. Light‐Mediated Total Synthesis of 17‐Deoxyprovidencin. Angewandte Chemie International Edition 2014, 53 (15) , 3859-3862. https://doi.org/10.1002/anie.201400617
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    51. Florian Glöcklhofer, Daniel Lumpi, Berthold Stöger, Johannes Fröhlich. Multigram synthesis of bis[(trimethylsilyl)ethynyl]benzenes suitable for post-polymerization modification. New J. Chem. 2014, 38 (6) , 2229-2232. https://doi.org/10.1039/C4NJ00011K
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