NUCLEAR MAGNETIC RESONANCE STUDIES OF THE PROTONATION OF WEAK BASES IN FLUOROSULPHURIC ACID: II. AMIDES, THIOAMIDES, AND SULPHONAMIDES

The proton magnetic resonance spectra of solutions of amides in fluorosulphuric acid confirm previous results which indicated that protonation of amides occurs on the carbonyl oxygen. A similar study of solutions of thioacetamide, thioacetanilide, thiourea, and N-methylthiourea provides conclusive evidence that the sulphur atom is protonated in these bases. In the case of N-methyl- and N,N′-dimethyl-p-toluenesulphonamide and sulphamide protonation occurs on nitrogen rather than on oxygen. It was not possible to obtain any conclusive evidence on the site of protonation of urea and N,N′-dimethylurea. Evidence is presented which indicates that thiourea and N-methylthiourea are diprotonated in solution in strong acids such as fluorosulphuric acid, and diprotonation of urea and N,N′-dimethylurea under the same conditions also seems very likely.