Synthesis of 2-mesityl-3-methylpyrrole via the Trofimov reaction for a new BODIPY with hindered internal rotation

The reaction of E-ethylmesitylketoxime with acetylene in the system KOH/DMSO (the Trofimov reaction) (70-74 °C, 3 h, atmosphere pressure) affords 2-mesityl-3-methylpyrrole (23%), 2-mesityl-3-methyl-1-vinylpyrrole (8%), Z- (5%) and E- (2%) isomers of O-vinylethylmesitylketoxime. Initial ethylmesitylketoxime was prepared in two ways: via very slow oximation of ethylmesitylketone in 30% yield after 8 months, and, more efficiently, by oximation of ethylmesitylketimine hydrochloride derived from bromomesitylene in several steps. 2-Mesityl-3-methylpyrrole was used for the synthesis of 4,4-difluoro-2,6-dimethyl-3,5,8-trimesityl-4-bora-3a,4a-diaza-s-indacene with mesityl substituents having hindered internal rotation and preventing π-stacking at high concentrations. The latter factor enables the fluorescence of crystals of the prepared BODIPY, a feature that was not previously documented for such molecules.

Graphical AbstractDownload full-size image