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

摘要

While iso-amyl nitrite reacts with chlorotrimethylsilane to give NOCl, iso-amyl nitrate does not yield NO 2Cl 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 NO 2Cl is generated in presence of cycloalkenes, the corresponding 1,2-dichlorocycloalkanes are obtained. Considering the evidence in hand, it is proposed that NO 2Cl, initially formed by chlorotrimethylsilane- acetyl nitrate reaction, decomposes to Cl 2, and N 2O 4. Then chlorine reacts with oximes to produce first gemchloronitroso compounds, which are oxidized by NO 2Cl or N 2O 4 to gem-chloronitro compounds, and with cycloalkenes it gives dichlorocycloalkanes. © Indian Academy of Sciences.