• Generation of nitryl chloride from chlorotrimethylsilane-acetyl nitrate reaction: A one-pot preparation of gem-chloronitro compounds from oximes

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      https://www.ias.ac.in/article/fulltext/jcsc/122/04/0571-0577

    • Keywords

       

      Nitryl chloride; acetyl nitrate; chlorotrimethylsilane; gem-chloronitro compounds; gemchloronitroso compounds; oximes; chlorination; cycloalkenes.

    • Abstract

       

      While iso-amyl nitrite reacts with chlorotrimethylsilane to give NOCl, iso-amyl nitrate does not yield NO2Cl with silicon reagent. However, acetyl nitrate reacts successfully with chlorotrimethylsilane to give nitryl chloride, which is characterized by its UV spectrum. If it is generated in presence of ketoximes, gem-chloronitro as well as gem-chloronitroso compounds are formed in almost equal amounts, which together account for up to 80% yield. This is possibly the simplest one-pot reaction for the preparation of gem-chloronitro compounds which find several synthetic applications. If NO2Cl is generated in presence of cycloalkenes, the corresponding 1,2-dichlorocycloalkanes are obtained. Considering the evidence in hand, it is proposed that NO2Cl, initially formed by chlorotrimethylsilane-acetyl nitrate reaction, decomposes to Cl2, and N2O4. Then chlorine reacts with oximes to produce first gem-chloronitroso compounds, which are oxidized by NO2Cl or N2O4 to gem-chloronitro compounds, and with cycloalkenes it gives dichlorocycloalkanes.

    • Author Affiliations

       

      Abdulkarim H A Mohammed1 Gopalpur Nagendrappa1

      1. Department of Chemistry, Bangalore University, (Central College Campus), Bangalore 560 001
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