Jump to main content
Jump to site search

Issue 0, 1983
Previous Article Next Article

The chemistry of nitrilium salts. Part 2. The preparation of nitrilium trifluoromethanesulphonate salts and their reactions with some oxygen and sulphur nucleophiles

Abstract

The syntheses of the nitrilium salts [RC[triple bond, length half m-dash]NMe]+Ō3SCF3[R = Me, Pri, PhCH2, Ph, CH2[double bond, length half m-dash]CHCH2, NC(CH2)3, and CH2[double bond, length half m-dash]CH] by reaction of MeO3SCF3 with the corresponding nitriles are described. The similar reaction between (E)-PhCH[double bond, length half m-dash]CHCN and MeO3SCF3 gives a mixture of [(E)-PhCH[double bond, length half m-dash]CHC[triple bond, length half m-dash]NMe]+Ō3SCF3 and the s-triazinium salt [{(E)-PhCH[double bond, length half m-dash]CH}3C3N3H]+Ō3SCF3, which hydrolyzes to give (E)-PhCH[double bond, length half m-dash]CHCONHMe and the triazine. The compound CF3SO3(CH2)4CN, prepared from I(CH2)4CN and AgO3SCF3, does not form a cyclic nitrilium salt, but slowly dimerizes at room temperature to [CF3SO3(CH2)4C[triple bond, length half m-dash]N(CH2)4CN]+Ō3SCF3. Both I(CH2)4CN and CF3SO3(CH2)4CN can be converted into the salt [CF3SO3(CH2)4C[triple bond, length half m-dash]NMe]+Ō3SCF3, but this does not form a dinitrilium salt on reaction with acetonitrile. On heating benzophenone oxime with CF3SO3H Beckmann rearrangement products are obtained, but conversion of [MeC(OH)[double bond, length half m-dash]NHPh]+Ō3SCF3 into the nitrilium salt [CH3C[triple bond, length half m-dash]NPh]+Ō3SCF3 occurs in only low yield even after 8 h at 130 °C under high vacuum. The nitrilium salts with R = Ph, Me, Pri, and PhCH2 undergo rapid exothermic reactions with phenol, thiophenol, alcohols, and thiols to give the corresponding imidate and thioimidate salts in high yields. 4,4-Dimethyl-2-phenyl-1,3-oxazoline is obtained in 74% yield on heating [PhC[triple bond, length half m-dash]NMe]+Ō3SCF3 with H2NCMe2CH2OH, and both this and 2,4,4-trimethyloxazoline react with MeO3SCF3 to give almost quantitative yields of the corresponding N-methyloxazolinium salts, which can be reduced to the oxazolidines with NaBH4. N-Methyloxazolinium salts have also been obtained from the reactions of nitrilium salts (R = Ph or Me) with ethylene oxide.

Back to tab navigation
Please wait while Download options loads

Article type: Paper
DOI: 10.1039/P19830001067
Citation: J. Chem. Soc., Perkin Trans. 1, 1983, 1067-1073
  •   Request permissions

    The chemistry of nitrilium salts. Part 2. The preparation of nitrilium trifluoromethanesulphonate salts and their reactions with some oxygen and sulphur nucleophiles

    B. L. Booth, K. O. Jibodu and M. F. J. R. P. Proença, J. Chem. Soc., Perkin Trans. 1, 1983, 1067
    DOI: 10.1039/P19830001067

Search articles by author