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Synthesis 1993; 1993(4): 426-432
DOI: 10.1055/s-1993-25876
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On the Synthesis of Nitrilium Salts from Nitriles and Chloroformates

Prativa Bade Shrestha-Dawadi* , Johannes C. Jochims
  • *Fakultät für Chemie der Universität Konstanz, Postfach 5560, D-7750 Konstanz, Germany
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Publication History

Publication Date:
17 September 2002 (online)

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Nitriles react with methyl or ethyl chloroformate (2a,b) and antimony(V) chloride to give high yields of N-methyl-, or N-ethylnitrilium hexachloroantimonates 3,4. With butyl chloroformate (2c) N-(1-methylpropyl)nitrilium salts 6 are obtained. These products arise from a 2-butyl cation, which is formed prior to alkylation of the nitrile. Isobutyl chloroformate (2d), (2-tert-butylcyclohexyl) chloroformate (2e), menthyl chloroformate (2f), 2,2-dimethylpropyl chloroformate (2g), and 3-methylbutyl chloroformate (2h) react with nitriles to give N-tert-alkylnitrilium salts, 11,13,15,19, which were characterized by hydrolysis to amides. With phenyl chloroformate (2i) benzonitriles react in a 1 :2 ratio to furnish 2-phenoxy-1,3,5-oxadiazinium salts 21.