Crystal structure and anomalous chemical shift of 10-(prop-1-yn-1-yl)-10H-phenothiazine 5,5-dioxide: Intramolecular Sa=N transannular effect

The novel ynamine compounds, 10-(prop-1-yn-1-yl)-10H-phenothiazine 5-oxide (2) and 10-(prop-1-yn-1-yl)-10H-phenothiazine 5,5-dioxide (3), were prepared by MCPBA oxidation of 10-(prop-1-yn-1-yl)-10H-phenothiazine (1). These compounds were characterized successfully by crystallographical analyses, 1H and 13C NMR. The 1H NMR signals of 2 showed downfield shifts compared with 1 as expected. However two kinds of signals, methyl and 1,9-position of 3, indicated upfield shifts compared with 2. These anomalous upfield shifts were reasonably explained by trans-annular Sa=N interaction and by increase of electron density on the nitrogen atom.