On the protonation and deuteration of N,N-disubstituted 2-aminothiophenes, 2-aminothiazoles, and some 3-amino substituted analogues

In contrast to their carbocyclic aniline analogues, N,N-diarylsubtituted 2-aminothiophenes are not protonated at their N-atoms but at the 5-position or, to a smaller extent, at the 3-position of the thiophene nucleus giving rise to cationic species of the Wheland type. However, 5-formyl and 5-acetyl-substituted 2-(N,N-diarylamino)thiophenes are protonated at the corresponding carbonyl moieties. This finding not only enables insight into the mechanism of electrophilic substitution of N,N-disubstituted 2-aminothiophenes but also allows to prepare deurated 2-aminothiophenes by treatment their non-deuterated parent compounds with CF3COOD.

Automated summary

N,N-diarylsubstituted 2-aminothiophenes are protonated at specific positions, while 5-formyl and 5-acetyl-substituted compounds are protonated at the corresponding carbonyl groups, facilitating the preparation of deuterated derivatives of amino thiophenes.