The Beckmann fragmentation of quadricyclanone oxime |
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| Authors: | Filip Gracias Hana Dvořáková Tomáš Martinů |
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| Institution: | 1. Department of Organic Chemistry, University of Chemistry and Technology, Prague, Technická 5, 166 28 Prague, Czech Republic;2. Laboratory of NMR Spectroscopy, University of Chemistry and Technology, Prague, Technická 5, 166 28 Prague, Czech Republic |
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| Abstract: | The attempted O-tosylation of tetracyclo3.2.0.02,7.04,6]heptan-3-one (quadricyclanone) oxime with p-toluenesulfonyl chloride in dichloromethane in the presence of triethylamine/DMAP or pyridine resulted in the Beckmann fragmentation to give a mixture of 4-exo-/4-endo-tosyloxy- and 4-exo-/4-endo-chlorobicyclo3.1.0]hex-2-ene-6-endo-carbonitriles in 90% overall yield. Solvolysis of all four products in 2,2,2-trifluoroethanol afforded the corresponding 4-exo-trifluoroethoxy derivative as the sole product. Quadricyclanone itself undergoes the fragmentation reaction with hydroxylamine-O-sulfonic acid, selectively affording the 4-exo-hydroxy-6-endo-nitrile in 90% isolated yield. |
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| Keywords: | Beckmann fragmentation Cage molecules Small molecules Ring-opening reactions Reactive intermediates |
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